Method of manufacturing thermal transfer print sheet and printing method

Abstract

To provide a method of manufacturing a thermal transfer print sheet that can print toner images which are fixed on a flexible transfer destination material with large irregularities and have sufficient flexibility and strength with high print reproducibility without a decrease in saturation in dark-colored transfer destination materials.SOLUTION: A method of manufacturing a thermal transfer print sheet using a transfer base material, a color image layer forming apparatus and an electrophotography type transfer destination material adhesive layer forming apparatus includes: a color image layer forming step of forming a color image layer by the color image layer forming apparatus; and a transfer destination material adhesive layer forming step of forming a transfer destination material adhesive layer having a thickness of 40 μm or more and 120 μm or less in one printing operation by the transfer destination material adhesive layer forming apparatus. 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 that includes a polyester resin, a polyurethane resin, and a release agent. The developing devices are used in formation of the transfer destination material adhesive layer.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a method for producing a thermal transfer printing sheet and a printing method.

Background Art

[0002] In an electrophotographic method in which an electrostatic latent image is developed with a developer to form a visible image, an electrostatic latent image is formed on an electrostatic latent image carrier containing a photoconductive substance, and the electrostatic latent image is developed with a developer containing toner to form a toner image. After transferring the toner image to a transfer material such as paper, it is fixed by heating and pressing to form a fixed image. In order to form a full-color image by the electrophotographic method, it is common to use a toner set in which a black toner is combined with cyan, magenta, and yellow toners, which are three-color process colors.

[0003] In recent years, as color image forming apparatuses using the electrophotographic method have become widely popular, the uses of printed materials have also spread in various ways. Particularly in the field of general consumer goods with made-to-order designs, there is an increasing need for printing by the electrophotographic method on materials that cannot be printed with conventional electrophotographic toners intended for printing on paper media, specifically, there is an increasing need for printing on cloth media such as sports team uniforms, shoes, or bags, and leather media.

[0004] Patent Document 1 describes a clothing printing apparatus that directly prints a design on a cloth product such as a T-shirt using an inkjet printer. Patent Document 2 describes an inkjet printing method and apparatus for directly printing desired image information on cloth, wood, or a metal plate using an inkjet printer. Patent Document 3 describes a printing apparatus that directly prints on cloth such as clothing using a thermal transfer apparatus. Patent Document 4 describes using a heat-sensitive melt transfer ink ribbon, printing a pattern on three types of transfer media using a color thermal printer, closely attaching the transfer media and the cotton fabric of a T-shirt, heating them, and then peeling off the transfer media. Patent Document 5 describes using two types of thermal transfer sheets, copying one sheet to form a toner layer, overlapping and heating and closely attaching both sheets and then peeling them off. A color layer and an adhesive layer are formed on the toner layer, and the sheet is pressed against a T-shirt or the like and heat-printed. Also, Patent Document 6 proposes a thermal transfer printing sheet that can be transferred to a black plain T-shirt by transferring and fixing a special white toner layer on a peelable sheet having a releasable surface, a printed image thermally transferable to a transfer medium formed on the peelable sheet, and the printed image.

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, Patent Documents 1 to 3 are effective when producing a large number of printed materials of the same shape or when producing a large-sized printed material. However, when the size of the fabric or leather, etc., which is the object to be printed, is as small as, for example, clothing, and when producing a variety of small quantities of objects with different shapes, the method of transporting the object to be printed to the printer will be different for each object to be printed, so it will take time to produce the printed material. Also, for printing on a dark-colored object to be printed, it is necessary to use white ink. However, in the case of inkjet printing, the maintainability of the printing device is greatly reduced due to sedimentation of white pigments, clogging of the head, etc. Also, in the case of a dark-colored object to be printed, it is necessary to apply a thick white concealing layer, so the printing speed is slower compared to printing on white or light-colored objects to be printed.

[0006] Further, Patent Document 4 discloses a method in which a design is printed on a transfer medium and then heat-transferred to a printing object such as a T-shirt. This method has no problem in that the shape of the printing object is not selected. However, since the size of the transfer medium is standard (for example, A4 or A3 is common), a shape for transfer to the printing object must be separately prepared.

[0007] The method of Patent Document 5 uses two heat transfer sheets to form a shape and then heat-prints on a printing object such as a T-shirt, which is a method that solves the above problems. However, there is a drawback in that two heat transfer sheets are used and the heat-printing operation needs to be performed twice. In practice, the temperature and pressing pressure during heat-printing differ for each produced sample, and the operation requires skill.

[0008] The printing method of Patent Document 6 solves the above problems. However, the productivity of the white toner is low, and sufficient concealability for a dark-colored material to be transferred cannot be achieved. The white concealability is insufficient, the material to be transferred is exposed, and the chroma and lightness of the color image are reduced. Also, when repeatedly printing to form a thick white concealment layer to obtain sufficient concealability, the productivity decreases with multiple prints. Furthermore, curling is likely to occur on the transfer base material each time printing is overlaid, resulting in conveyance failure and misalignment in the apparatus, making reproducible printing difficult.

[0009] An embodiment of the present invention aims to provide a method for producing a heat transfer printing sheet that can print a toner image with sufficient flexibility and strength, having high print reproducibility, without a decrease in chroma on a dark-colored material to be transferred, and sufficiently fixing on a flexible material to be transferred with large irregularities.

Means for Solving the Problems

[0010] To solve the above problems, an embodiment of the present invention is a method for producing a heat transfer printing sheet using a transfer base material, a color image layer forming apparatus, and an electrophotographic material-to-be-transferred adhesive layer forming apparatus, a color image layer forming step of forming a color image layer by the color image layer forming apparatus, A method for manufacturing a thermal transfer print sheet includes a step of forming a transfer material adhesive layer having a thickness of 40 μm or more and 120 μm or less in a single printing by the transfer material adhesive layer forming device. The transfer material adhesive layer forming device has a plurality of developing devices. Among the plurality of developing devices, two or more developing devices are provided with a white toner for a transfer material adhesive layer containing a polyester resin, a polyurethane resin, and a release agent, and is a developing device used for forming the transfer material adhesive layer.

Advantages of the Invention

[0011] According to an embodiment of the present invention, there is provided a method for manufacturing a thermal transfer print sheet that can print a toner image having sufficient flexibility and strength with high print reproducibility, which has no decrease in chroma in a dark-colored transfer material, adheres sufficiently to a flexible transfer material with large unevenness, and has sufficient flexibility and strength.

Brief Description of the Drawings

[0012]

Figure 1

Figure 2

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Figure 4

Figure 5

Embodiments for Carrying Out the Invention

[0013] Hereinafter, embodiments of the present invention will be described in detail.

[0014] (Method for producing thermal transfer printing sheet) The method for producing a thermal transfer printing sheet of the present invention is a method for producing a thermal transfer printing sheet using a transfer substrate, a color image layer forming device, and an electrophotographic transfer material adhesive layer forming device, a color image layer forming step of forming a color image layer by the color image layer forming device, a transfer material adhesive layer forming step of forming a transfer material adhesive layer having a thickness of 40 μm or more and 120 μm or less by one printing by the transfer material adhesive layer forming device, and includes the transfer material adhesive layer forming device has a plurality of developing devices, among the plurality of developing devices, two or more developing devices are provided with a white toner for a transfer material adhesive layer containing a polyester resin, a polyurethane resin, and a release agent, and is a developing device used for forming the transfer material adhesive layer, which is a method for producing a thermal transfer printing sheet. According to the present invention, there is provided a method for producing a thermal transfer printing sheet that can print a toner image having sufficient flexibility and strength with high printing reproducibility, which does not cause a decrease in chroma in a dark transfer material and is sufficiently fixed to a flexible transfer material having large unevenness.

[0015] <Transfer substrate> The transfer substrate used in the method for producing a thermal transfer printing sheet of the present invention has peelability, and is not particularly limited as long as it is a sheet-like substrate capable of transferring the color image layer and the transfer material adhesive layer to a transfer material by heat and pressure, but paper, transfer paper having a transfer layer, release paper having a release layer, a release film, or a heat-resistant plastic film sheet, etc. are preferable. It is preferable that the transfer substrate has a layer containing a thermoplastic resin and / or a higher fatty acid on the transfer substrate. When the transfer substrate has a layer containing a thermoplastic resin and / or a higher fatty acid, when the image is thermally transferred to the material to be transferred by the thermoplastic resin, the layer containing the thermoplastic resin and the higher fatty acid is formed as a release layer on the uppermost layer of the image, so that the image durability on the material to be transferred can be improved. In addition, by containing a higher fatty acid, when the image is thermally transferred to the material to be transferred, the higher fatty acid melts and diffuses into the simultaneously formed color image layer and the material-to-be-transferred adhesive layer, so that the flexibility of the image thermally transferred to the material to be transferred 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. It is preferable that the color image layer is formed directly on the transfer substrate. The image of the color image layer to be formed is preferably a mirror image obtained by horizontally inverting the original image. By forming the color image layer as a mirror image, when the image formed on the thermal transfer print sheet is thermally transferred to the material to be transferred, the image is horizontally inverted again, so that the image can be formed on the material to be transferred in the original orientation. A mirror image information horizontally inverted in advance by a PC or the like may be produced and output by a color image layer forming apparatus to form a color image layer. In the case of a color image layer forming apparatus equipped with a scanner function, after scanning the original image, an inverted image may be output to form a color image layer, or a mirror image that has already been horizontally inverted 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 it can form a color image layer as an inverted image on the transfer substrate, but an electrophotographic method or an inkjet method printer is preferable, an electrophotographic method printer is more preferable, and an electrophotographic method printer using a polyester resin-containing color toner is particularly preferable. By using an electrophotographic printer, the adhesiveness between the color image layer and the transfer material adhesive layer can be further improved, and a more durable printed matter can be obtained.

[0018] The color image layer formed on the transfer material may be formed by offset printing, letterpress printing, gravure printing, flexographic printing, screen printing, etc., in addition to on-demand printing by electrophotographic or inkjet methods.

[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 as required. 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 as required. The electrostatic latent image forming step can be preferably performed by an electrostatic latent image forming means, the developing step can be preferably performed by a developing means, and the other steps can be preferably performed by other means.

[0020] <<Electrostatic 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 as long as it is a step of forming an electrostatic latent image on the electrostatic latent image carrier of the color image layer forming apparatus, and can be appropriately selected according to the purpose. For example, it can be performed by charging the surface of the electrostatic latent image carrier and then exposing it imagewise, and can be performed using an electrostatic latent image forming means. The electrostatic latent image forming means in the color image layer forming apparatus is not particularly limited as long as it is a means for forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. For example, means having at least a charging member for charging the surface of the electrostatic latent image carrier and an exposure member for exposing the surface of the electrostatic latent image carrier imagewise can be mentioned.

[0021] -Electrostatic Latent Image Carrier- The material, structure, and size of the electrostatic latent image carrier in the color image layer forming apparatus are not particularly limited and can be appropriately selected from known ones. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Examples of the organic photoreceptor include a laminated photoreceptor having a laminated structure in which a layer (charge generation layer) in which a charge generation material such as metal-free phthalocyanine or titanyl phthalocyanine is dispersed in a binder resin and a layer (charge transport layer) in which a charge transport material is dispersed in a binder resin are stacked on a support such as an aluminum drum, and a single-layer photoreceptor having a photosensitive layer with 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. In the single-layer photoreceptor, a hole transport agent and an electron transport agent can also be added as charge transport materials to the photosensitive layer. Also, an undercoat layer may be provided between the support and the laminated charge generation layer or the single-layer photosensitive layer.

[0022] -Charging member and charging- The charging member in the color image layer forming apparatus is not particularly limited and can be appropriately selected according to the purpose. Examples include known contact chargers equipped with conductive or semiconductive rollers, brushes, films, rubber blades, etc., and non-contact chargers that utilize corona discharge such as corotrons and scorotrons. Charging in the color image layer forming apparatus can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using a charging member. As the shape of the charging member, in addition to a roller, it can take any form such as a magnetic brush or a fur brush, and can be selected according to the specifications and form of the color image layer forming apparatus. The charging member in the color image layer forming apparatus is not limited to the above-mentioned contact charging member, but since an image forming apparatus with reduced ozone generated from the charging member can be obtained, it is preferable to use a contact charging member.

[0023] -Exposure member and exposure- As the exposure member in the color image layer forming apparatus, there is no particular limitation as long as it can expose the surface of the electrostatic latent image carrier charged by the charging member in the image pattern to be formed, and it can be appropriately selected according to the purpose. For example, various exposure members such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be mentioned. There is no particular limitation on the light source used for the exposure member of the color image layer forming apparatus, and it can be appropriately selected according to the purpose. For example, various light-emitting substances such as fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light-emitting diodes (LEDs), semiconductor lasers (LDs), and electroluminescence (EL) can be mentioned. In addition, in order to irradiate only light in a desired wavelength range, various filters 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 can also be used. Exposure in the color image layer forming apparatus can be performed, for example, by exposing the surface of the electrostatic latent image carrier in the image pattern using an exposure member. In the color image layer forming apparatus, an optical backside exposure method in which exposure is performed in the image pattern from the backside of the electrostatic latent image carrier may be adopted.

[0024] <<Development Process and Developing Means>> As the development process in the color image layer forming process, there is no particular limitation as long as it is a process of developing the electrostatic latent image formed on the electrostatic latent image carrier of the color image layer forming apparatus using a color toner to form a visible image, and it can be appropriately selected according to the purpose and can be performed by the developing means of the color image layer forming apparatus. As the developing means in the color image layer forming apparatus, there is no particular limitation as long as it is a developing means equipped with a color toner that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a color image layer, and it can be appropriately selected according to the purpose. Examples of developing means in a color image layer forming apparatus include a developing device. This developing device preferably has at least a developer accommodating portion for accommodating color toner, a stirrer for frictionally stirring and charging the color toner, magnetic field generating means fixed inside, and a developer carrier that has a surface carrying a developer containing color toner and is rotatable. In the developing means in a color image layer forming apparatus, for example, color toner and a carrier are mixed and stirred, and the color toner is charged by the friction during this process. It is held in a standing state on the surface of a rotating magnetic roller, and a magnetic brush is formed. The magnetic roller is disposed near an electrostatic latent image carrier. Therefore, a part of the color toner constituting the magnetic brush formed on the surface of the magnetic roller moves to the surface of the electrostatic latent image carrier by an electric attractive force. As a result, the electrostatic latent image is developed by the color toner, and a visible image by the color toner is formed on the surface of the electrostatic latent image carrier.

[0025] <<Other Processes and Other Means>> Examples of other processes in the color image layer forming process include, for example, a transfer process, a fixing process, a cleaning process, a charge removal process, a recycling process, a control process, and the like. Examples of other means in a color image layer forming apparatus include, for example, transfer means, fixing means, cleaning means, charge removal means, recycling means, control means, and the like.

[0026] -Transfer Process and Transfer Means- The transfer process in the color image layer forming process is not particularly limited as long as it is a process of transferring the color image layer, and can be appropriately selected according to the purpose. However, a mode in which an intermediate transfer body is used, the color image layer is first transferred onto the intermediate transfer body, and then the color image layer is secondarily transferred onto a transfer substrate is preferable. The transfer process in the color image layer forming process can be performed, for example, by charging the electrostatic latent image carrier using a transfer charger, and can be performed by transfer means. As the transfer means in the color image layer forming apparatus, there is no particular limitation as long as it is a means for transferring the color image layer, and it can be appropriately selected according to the purpose. However, a mode having a first transfer means for transferring the color image layer onto an intermediate transfer body to form a composite transfer image and a second transfer means for transferring the color image layer onto a transfer substrate is preferable.

[0027] In addition, there is no particular limitation on the intermediate transfer body in the color image layer forming apparatus, and it can be appropriately selected from known transfer bodies according to the purpose. For example, a transfer belt and the like are preferably mentioned. The transfer means (the first transfer means and the second transfer means) in the color image layer forming apparatus preferably has at least a transfer device that peels and charges the visible image formed on the electrostatic latent image carrier toward the recording medium side. Examples of this transfer device include a corona transfer device by corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, an adhesive transfer device, and the like.

[0028] -Fixing step and fixing means- As the fixing step in the color image layer forming step, there is no particular limitation as long as it is a step of fixing the color image layer on the transfer substrate, and it can be appropriately selected according to the purpose. It can be performed simultaneously at once in a state where each layer of the color toner output from each color developing means is laminated. As the fixing means in the color image layer forming apparatus, there is no particular limitation as long as it is a means for fixing the color image layer to the recording medium, and it can be appropriately selected according to the purpose. However, a known heating and pressurizing member is preferable. Examples of this heating and pressurizing member include a combination of a heating roller and a pressurizing roller, a combination of a heating roller, a pressurizing roller, and an endless belt, and the like. The fixing step in the color image layer forming step can be performed by the fixing means in the color image layer forming apparatus. The heating in the heating and pressurizing member in the color image layer forming apparatus is usually preferably 80°C to 200°C. In addition, in the color image layer forming apparatus, depending on the purpose, a known light fixing device may be used together with or instead of the fixing means of the color image layer forming apparatus. As for the surface pressure in the fixing process, there is no particular limitation, and it can be appropriately selected according to the purpose. However, it is preferably 10 N / cm 2 ~80 N / cm 2 .

[0029] - Cleaning Process and Cleaning Means - As the cleaning process in the color image layer forming process, there is no particular limitation as long as it can remove the color toner remaining on the electrostatic latent image carrier, and it can be appropriately selected according to the purpose. For example, it can be carried out by the cleaning means in the color image layer forming apparatus. As the cleaning means in the color image layer forming apparatus, there is no particular limitation as long as it can remove the color toner remaining on the electrostatic latent image carrier, and it can be appropriately selected according to the purpose. For example, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, a web cleaner, etc. can be mentioned.

[0030] - Charge Removal Process and Charge Removal Means - As the charge removal process in the color image layer forming process, there is no particular limitation as long as it applies a charge removal bias to the electrostatic latent image carrier for charge removal, and it can be appropriately selected according to the purpose. For example, it can be carried out by the charge removal means in the color image layer forming apparatus. As the charge removal means in the color image layer forming apparatus, there is no particular limitation as long as it applies a charge removal bias to the electrostatic latent image carrier for charge removal, and it can be appropriately selected according to the purpose. For example, a charge removal lamp, etc. can be mentioned.

[0031] - Recycling Process and Recycling Means - As the recycling process in the color image layer forming process, there is no particular limitation as long as it recycles the color toner removed by this cleaning process to the developing device, and it can be appropriately selected according to the purpose. For example, it can be carried out by the recycling means in the color image layer forming apparatus. As recycling means in the color image layer forming apparatus, there are no particular restrictions as long as it is means for recycling the color toner removed in the cleaning step, and it can be appropriately selected according to the purpose. For example, known conveying means and the like can be mentioned.

[0032] - Control process and control means - As the control process in the color image layer forming process, there are no particular restrictions as long as it is a process capable of controlling the movement of each process in the color image layer forming process, and it can be appropriately selected according to the purpose. For example, it can be performed by the control means in the color image layer forming apparatus. As the control means in the color image layer forming apparatus, there are no particular restrictions as long as it is means capable of controlling the movement of each means in the color image layer forming apparatus, and it can be appropriately selected according to the purpose. For example, devices such as sequencers and computers can be mentioned.

[0033] <Color image layer> The color image layer is formed by color toner.

[0034] <<Color toner>> The color toner contains resin and a colorant, and as other constituent materials, it can contain a release agent, a charge control agent, an external additive, a fluidity improver, a cleaning property improver, and the like.

[0035] - Resin - As the resin used as the material of the color toner for use in the color image layer forming apparatus, conventionally known resins can be used. For example, styrene resins (homopolymers or copolymers containing styrene or styrene substituents) such as styrene, poly-α-methylstyrene, styrene-chlorostyrene copolymer, styrene-propylene 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-methyl α-chloroacrylate copolymer, styrene-acrylonitrile-acrylic acid ester copolymer, etc., 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, polyvinyl butyrate resins, and the like can be mentioned. Further, the production method of these resins is not particularly limited, and bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc. can be used.

[0036] The resin used in the color toner preferably contains a polyester resin. By the color toner containing the polyester resin, the adhesiveness between the color toner and the toner for the transfer material adhesive layer is improved, and a more durable printed matter can be obtained. Furthermore, from the viewpoint of higher adhesiveness to the transfer material adhesive layer and improvement of durability, the resin used in the color toner preferably contains the same polyester resin as that used in the toner for the transfer material adhesive layer.

[0037] The color toner preferably contains a polyurethane resin. By the color toner containing the polyurethane resin, a highly durable color image layer in which cracking and peeling hardly occur can be obtained. Furthermore, from the viewpoint of higher adhesiveness to the transfer material adhesive layer and improvement of durability, the resin used in the color toner preferably contains the same polyurethane resin as that used in the toner for the transfer material adhesive layer.

[0038] -Colorant- There are no particular restrictions on the color toner, and those obtained by appropriately selecting commonly used colorants can be used. For example, black toner, cyan toner, magenta toner, yellow toner, red toner, green toner, blue toner, fluorescent pink toner, fluorescent blue toner, fluorescent yellow toner, etc. can be mentioned.

[0039] There are no particular restrictions on the black toner, and the colorant can be appropriately selected according to the purpose. However, it is preferable to use carbon black alone or a mixture of carbon black as the main component and copper phthalocyanine or the like to adjust the hue and lightness.

[0040] There are no particular restrictions on the cyan toner, and the colorant can be appropriately selected according to the purpose. However, copper phthalocyanine which is Pigment Blue 15:3 or a mixture of the colorant and aluminum phthalocyanine is preferable.

[0041] There are no particular restrictions on the magenta toner, and the colorant can be appropriately selected according to the purpose. However, Pigment Red 53:1, Pigment Red 81, Pigment Red 122, Pigment Red 269 can be used alone or in combination.

[0042] There are no particular restrictions on the yellow toner, and the colorant can be appropriately selected according to the purpose. However, Pigment Yellow 74, Pigment Yellow 155, Pigment Yellow 180, Pigment Yellow 185 can be used alone or in combination. It is preferable to use Pigment Yellow 185 alone or a mixture of Pigment Yellow 185 and Pigment Yellow 74 in terms of chroma and storage stability.

[0043] There are no particular restrictions on the red toner, and the colorant can be appropriately selected according to the purpose. For example, Pigment Red 254, Pigment Red 166, Pigment Red 144, Pigment Red 48:2 can be used alone or in combination.

[0044] There are no particular restrictions on the green toner, and the colorant can be appropriately selected according to the purpose. For example, Pigment Green 7 etc. can be used, but attention needs to be paid to safety.

[0045] There are no particular restrictions on the blue toner, and the colorant can be appropriately selected according to the purpose. For example, Pigment Blue 15:1, Pigment Violet 23 etc. can be mentioned.

[0046] -Release agent- The color toner can contain a release agent. In the color toner, there are no particular restrictions on the types of release agents that can be used, and they can be appropriately selected according to the purpose. They can be used alone or in combination of two or more. There are no particular restrictions on the release agent that can be used in the color toner, and it can be appropriately selected according to the purpose. For example, liquid paraffin, microcrystalline wax, natural paraffin, synthetic paraffin, polyolefin wax, and their partial oxides, 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, carnauba wax, higher fatty alcohol·higher fatty acid such as montan wax, fatty acid amide, fatty acid bisamide, zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, zinc oleate, zinc palmitate, magnesium palmitate, zinc myristate, zinc laurate, zinc behenate and other metal soaps, fatty acid esters, polyvinylidene fluoride, etc. can be mentioned. Among these, it is preferable to contain at least an ester wax such as a fatty acid ester.

[0047] When a toner contains a maleic acid-modified polyolefin having a polypropylene block in the main chain, if the content thereof is large, there is a problem that the toner and the fixing roller or the fixing belt cannot be separated during fixing, resulting in waste paper jams. However, by adding an ester wax as a release agent, this problem can be suppressed. Furthermore, the maleic acid-modified polyolefin having a polypropylene block in the main chain can finely disperse the ester wax.

[0048] The content of the release agent in the color toner is not particularly limited and can be appropriately selected according to the purpose, but it is preferably 0.1 to 8.0% by mass, and more preferably 1.0 to 6.0% by mass. If the content of the release agent in the color toner is 0.1% by mass or more, the toner and the fixing roller or the fixing belt are likely to separate during fixing, so that waste paper jams can be suppressed. Also, if the content of the release agent in the color toner is 8.0% by mass or less, the toner can be sufficiently fixed to the plastic film.

[0049] -Charge control agent- The color toner may contain a charge control agent. As the charge control agent, if it is white or colorless, it can be appropriately selected according to the purpose. For example, onium salts such as phosphonium salts and lake pigments thereof, triphenylmethane dyes and lake pigments thereof, metal salts of higher fatty acids; dialkyltin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dialkyltin borates such as dibutyltin borate, dioctyltin borate, dicyclohexyltin borate, organometallic complexes, chelate compounds, monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, metal complexes of aromatic dicarboxylic acid systems, quaternary ammonium salts. Others include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol. These can be used alone or in combination of two or more.

[0050] When these charge control agents are internally added to the color toner, the content is not particularly limited and can be appropriately set according to the purpose. However, it is preferably added in an amount of 0.1 to 10% by mass based on the total amount of the resin.

[0051] -External additive- For the color toner, inorganic fine particles or the like can be used as an external additive. The inorganic fine particles for external addition used in the color toner are not particularly limited and can be appropriately selected according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, limestone, diatomaceous earth, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, etc. can be mentioned. Among these, silica, alumina, and titanium oxide are preferred.

[0052] Also, as the inorganic fine particles used in the color toner, those surface-treated with a hydrophobizing agent may be used. The hydrophobizing agent is not particularly limited and can be appropriately selected according to the purpose. For example, silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate-based coupling agents, aluminum-based coupling agents, etc. are mentioned as preferred surface treatment agents. Also, sufficient effects can be obtained by using silicone oil as a hydrophobizing agent.

[0053] In addition, the average diameter of the primary particles of the inorganic fine particles used in the color toner is not particularly limited and can be appropriately selected according to the purpose. However, it is preferably 5 to 500 nm, more preferably 5 to 200 nm. If the average diameter of the primary particles of the inorganic fine particles used in the color toner is 5 nm or more, aggregation of the inorganic fine particles can be suppressed, and the inorganic fine particles in the color toner can be uniformly dispersed. If the average diameter of the primary particles of the inorganic fine particles used in the color toner is 500 nm or less, the heat-resistant storage stability can be improved by the filler effect. The average diameter of the primary particles of the inorganic fine particles here is a value obtained by directly measuring the particle diameter from a photograph obtained by a transmission electron microscope, and it is preferable to observe at least 100 or more inorganic fine particles and use the average value of their major diameters.

[0054] -Flowability improver- The color toner may contain a flowability improver as an additive. The flowability improver is not particularly limited as long as it has been surface-treated to increase its hydrophobicity and can prevent deterioration of the flow characteristics and charging characteristics even under high humidity conditions, and can be appropriately selected according to the purpose. For example, silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate-based coupling agents, aluminum-based coupling agents, silicone oil, modified silicone oil, etc. can be mentioned. When the external additive is silica and titanium oxide, it is preferable to perform surface treatment with such a flowability improver and use it as hydrophobic silica and hydrophobic titanium oxide.

[0055] -Cleanability improver- The color toner may contain a cleaning property improver as an additive. The cleaning property improver is not particularly limited as long as it can be added to the color toner for removing the color toner remaining after transfer on the electrostatic latent image carrier or the primary transfer medium, and can be appropriately selected according to the purpose. For example, fatty acid metal salts such as zinc stearate, calcium stearate, and stearic acid, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles, etc. may be mentioned. The polymer fine particles preferably have a relatively narrow particle size distribution, and preferably have a volume average particle diameter of 0.01 μm or more and 1 μm or less.

[0056] In order to improve the adhesiveness between the color toner and the toner for the adherend adhesive layer and obtain a more durable printed matter, it is preferable to use the same materials as those used for the toner for the adherend adhesive layer for the release agent, charge control agent, external additive, fluidity improver, and cleaning property improver used for the color toner.

[0057] <<Developer>> The color toner may be a one-component developer or a two-component developer. However, when used in high-speed printers, etc. corresponding to the recent improvement in information processing speed, from the viewpoint of improving the lifespan, it is preferable to be a two-component developer. When the color toner is used as a one-component developer, even if toner balance is carried out, the variation in the toner particle diameter is small, there is little toner filming on the developing roller, and little toner fusion on members such as blades for thinning the toner layer. Good and stable developability and images can also be obtained during long-term agitation in the developing device. When the color toner is mixed with a carrier to be used as a two-component developer, even if toner balance is carried out over a long period, the variation in the toner particle diameter is small, and good and stable developability and images can also be obtained during long-term agitation in the developing device. The color toner can be mixed with a carrier to be a two-component developer and used in an electrophotographic image forming method of a two-component development system. As the carrier, a magnetic carrier can be used.

[0058] As the developing method, a premix developing method of supplying a premix developer in which toner and carrier are mixed in advance may be adopted. In the premix developing method, the amount of carrier increased in the developing device is discharged as surplus developer. Thereby, the developer in the developing device is gradually refreshed. Therefore, it is possible to extend the replacement cycle due to the deterioration of the developer or to save the trouble of replacing the developer.

[0059] -Magnetic carrier- When using the two-component developing method, the material of the magnetic fine particles used for the magnetic carrier is not particularly limited and can be appropriately selected according to the purpose. For example, spinel ferrites such as iron powder, magnetite, and gamma iron oxide, spinel ferrites containing one or more metals other than iron (Mn, Ni, Zn, Mg, Cu, etc.), magnetoplumbite-type ferrites such as barium ferrite, and particles of iron or alloy having an oxide layer on the surface can be mentioned. Also, considering chemical stability, it is preferable to use magnetoplumbite-type ferrites such as magnetite, spinel ferrites containing gamma iron oxide, and barium ferrite. Specifically, MFL-35S, MFL-35HS (manufactured by Powdertech Co., Ltd.), DFC-400M, DFC-410M, SM-350NV (manufactured by Douwa Iron Powder Industry Co., Ltd.), etc. are preferable. Among these, those that are white are preferable in terms of color tone. The shape of the magnetic fine particles may be any of granular, spherical, and needle-shaped. Particularly when high magnetization is required for the magnetic carrier, it is preferable to use ferromagnetic fine particles such as iron.

[0060] By selecting the type and content of the magnetic fine particles, a magnetic carrier having a desired magnetic charge can also be used. The magnetic characteristics of the magnetic carrier preferably have a magnetic charge strength of 30 to 150 emu / g at 1,000 Oe.

[0061] The chargeability of the magnetic carrier can be controlled by fixing positively or negatively charged fine particles or conductive fine particles on the surface of the magnetic fine particles, or by coating with a resin. Examples of the resin used as the coating material on the surface of the magnetic fine particles include silicone resin, acrylic resin, epoxy resin, fluororesin, etc. Among these, silicone resin and acrylic resin are preferred. The surface of the magnetic fine particles may be further coated to include positively or negatively charged fine particles or conductive fine particles. The magnetic carrier can be produced by spraying a melt-kneaded product of magnetic fine particles and an insulating binder resin with a spray dryer, or by reacting and curing a monomer or prepolymer in an aqueous medium in which magnetic fine particles are present to form 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 accommodated in the developing device is preferably 85% by mass or more and less than 98% by mass. When the mass ratio of the carrier in the developer is 85% by mass or more, scattering of the toner from the developing device is less likely to occur, and the occurrence of defective images can be reduced. When the mass ratio of the carrier in the developer is less than 98% by mass, it is possible to suppress an excessive increase in the charge amount of the color toner or a shortage in the supply amount of the color toner, so that a decrease in image density and the occurrence of defective images can be reduced.

[0063] <Transfer material adhesive layer forming step and transfer material adhesive layer forming apparatus> In the transfer material adhesive layer forming step, the transfer material adhesive layer forming apparatus forms a transfer material adhesive layer having a thickness of 40 μm or more and 120 μm or less in one printing. The transfer material adhesive layer forming apparatus is an electrophotographic method. By being an electrophotographic method, even if a white pigment is used for the toner for the transfer material adhesive layer, the white pigment does not settle or aggregate like ink, and the maintainability of the transfer material adhesive layer forming apparatus does not deteriorate.

[0064] It is preferable that the step of forming the transfer material adhesive layer is performed after the step of forming the color image layer. After forming the color image layer on the transfer substrate in the color image layer forming step, it is preferable to form the transfer material adhesive layer on the color image layer in the transfer material adhesive layer forming step. More preferably, a transparent transfer material adhesive layer is formed on the color image layer, and a white transfer material adhesive layer is formed on the transparent transfer material adhesive layer. By forming a transparent transfer material adhesive layer on the color image layer, even if the color image layer is embedded in the transfer material adhesive layer during thermal transfer to the transfer material, vivid print quality with no reduction in chroma and lightness can be obtained. In this specification, "toner for white transfer material adhesive layer" means toner for transfer material adhesive layer containing a white pigment, and "white transfer material adhesive layer" means a transfer material adhesive layer formed by "toner for white transfer material adhesive layer". Also, "toner for transparent transfer material adhesive layer" means toner for transfer material adhesive layer not containing a coloring material, and "transparent transfer material adhesive layer" means a transfer material adhesive layer formed by "toner for transparent transfer material adhesive layer".

[0065] Since the transfer material adhesive layer is formed by overlapping on the color image layer, when the image of the color image layer is a mirror image with the original image reversed left and right, the transfer material adhesive layer is also formed based on a mirror image with the original image reversed left and right, similar to the color image layer. A mirror image information of a color image that has been reversed left and right in advance by a PC or the like may be produced and output by a transfer material adhesive layer forming apparatus to form the transfer material adhesive layer. In the case of a transfer material adhesive layer forming apparatus equipped with a scanner function, an image obtained by scanning the original image and then performing an inversion process may be output to form the transfer material adhesive layer, or an already left-and-right reversed mirror image may be scanned and then output to form the transfer material adhesive layer.

[0066] The thickness of the transfer material adhesive layer formed by one-time printing with the transfer material adhesive layer forming apparatus is 40 μm or more and 120 μm or less, preferably 50 μm or more and 120 μm or less, and more preferably 60 μm or more and 120 μm or less. If the thickness of the transfer material adhesive layer formed by one-time printing with the transfer material adhesive layer forming apparatus is less than 40 μm, in the formation of an image on a dark transfer material, the chroma of the color image layer decreases, making it difficult to obtain a vivid image. If it is thicker than 120 μm, it becomes difficult to set the fixing conditions for suppressing hot offset and cold offset, and it becomes difficult to obtain stable quality. If the thickness of the transfer material adhesive layer formed by one-time printing with the transfer material adhesive layer forming apparatus is 50 μm or more and 120 μm or less, a clearer color image layer can be obtained. When the transfer material adhesive layer has a white transfer material adhesive layer and a transparent transfer material adhesive layer, the white transfer material adhesive layer is preferably 40 μm or more and 100 μm or less.

[0067] The transfer material adhesive layer forming apparatus includes at least an electrostatic latent image forming means and a developing means, and may further include other means as required. The transfer material adhesive layer forming step includes at least an electrostatic latent image forming step and a developing step, and may further include other steps as required. In the transfer material adhesive layer forming step, the electrostatic latent image forming step can be preferably performed by the electrostatic latent image forming means, the developing step can be preferably performed by the developing means, and the other steps can be preferably performed by the other means.

[0068] <<Electrostatic Latent Image Forming Step and Electrostatic Latent Image Forming Means>> The electrostatic latent image forming step in the transfer material adhesive layer forming step is not particularly limited as long as it is a step of forming an electrostatic latent image on an electrostatic latent image carrier, and can be appropriately selected according to the purpose. For example, it can be performed by charging the surface of the electrostatic latent image carrier and then exposing it imagewise, and can be performed using an electrostatic latent image forming means. As the electrostatic latent image forming means in the transfer material adhesive layer forming apparatus, there is no particular limitation as long as it is means for forming an electrostatic latent image on the electrostatic latent image carrier, and it can be appropriately selected according to the purpose. For example, there are means having at least a charging member for charging the surface of the electrostatic latent image carrier and an exposure member for imagewise exposing the surface of the electrostatic latent image carrier.

[0069] -Electrostatic latent image carrier- Regarding the material, structure, and size of the electrostatic latent image carrier in the transfer material adhesive layer forming apparatus, there is no particular limitation, and it can be appropriately selected from known ones. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Examples of the organic photoreceptor include a laminated photoreceptor having a laminated structure in which a layer (charge generation layer) in which a charge generation material such as metal-free phthalocyanine or titanyl phthalocyanine is dispersed in a binder resin and a layer (charge transport layer) in which a charge transport material is dispersed in a binder resin are stacked on a support such as an aluminum drum, and a single-layer photoreceptor having a single-layer photosensitive layer in which both a charge generation material and a charge transport material are dispersed in a binder resin on a support. In the single-layer photoreceptor, a hole transport agent and an electron transport agent can also be added as charge transport materials to the photosensitive layer. Also, an undercoat layer may be provided between the support and the laminated charge generation layer or the single-layer photosensitive layer.

[0070] -Charging member and charging- Regarding the charging member in the transfer material adhesive layer forming apparatus, there is no particular limitation, and it can be appropriately selected according to the purpose. For example, there are known contact chargers equipped with conductive or semiconductive rollers, brushes, films, rubber blades, etc., and non-contact chargers using corona discharge such as corotrons and scorotrons. Charging in the transfer material adhesive layer forming apparatus can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using a charging member. As the shape of the charging member, in addition to a roller, it may take any form such as a magnetic brush, a fur brush, etc., and can be selected according to the specifications and form of the transfer material adhesive layer forming apparatus. The charging member is not limited to a contact type charging member, but since a transfer material adhesive layer forming apparatus with reduced ozone generated from the charging member can be obtained, it is preferable to use a contact type charging member.

[0071] - Exposure member and exposure - The exposure member in the transfer material adhesive layer forming apparatus is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charging member in an image - like manner, and can be appropriately selected according to the purpose. For example, various exposure members such as a copying optical system, a rod lens array system, a laser optical system, a liquid crystal shutter optical system, etc. can be mentioned. The light source used for this exposure member is not particularly limited and can be appropriately selected according to the purpose. For example, various light - emitting substances such as fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light - emitting diodes (LEDs), semiconductor lasers (LDs), electroluminescence (EL), etc. can be mentioned.

[0072] In addition, in order to irradiate only light in a desired wavelength range, various filters such as a sharp - cut filter, a band - pass filter, a near - infrared cut filter, a dichroic filter, an interference filter, a color temperature conversion filter, etc. can also be used. This exposure can be performed, for example, by exposing the surface of the electrostatic latent image carrier in an image - like manner using the exposure member in the transfer material adhesive layer forming apparatus. In the transfer material adhesive layer forming apparatus, a light - back exposure method of performing image - like exposure from the back side of the electrostatic latent image carrier may be adopted.

[0073] <<Development process and developing means>> As the development process in the transfer material adhesive layer forming process, there are no particular restrictions as long as it is a process of developing the electrostatic latent image formed on the electrostatic latent image carrier of the transfer material adhesive layer forming apparatus using a toner for the transfer material adhesive layer to form a visible image, and it can be appropriately selected according to the purpose, and can be performed by the developing means in the transfer material adhesive layer forming apparatus. As the developing means in the transfer material adhesive layer forming apparatus, there are no particular restrictions as long as it is a developing means provided with a toner for the transfer material adhesive layer that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a transfer material adhesive layer, and it can be appropriately selected according to the purpose. Examples of the developing means in the transfer material adhesive layer forming apparatus include a developing device. This developing device preferably has at least a developer accommodating portion for accommodating the toner for the transfer material adhesive layer, a stirrer for frictionally stirring and charging the toner for the transfer material adhesive layer, a magnetic field generating means fixed inside, and a developer carrier that is rotatable while carrying a developer containing the toner for the transfer material adhesive layer on its surface.

[0074] In the developing means of the transfer material adhesive layer forming apparatus, for example, the toner for the transfer material adhesive layer and the carrier are mixed and stirred, and the toner is charged by the friction at that time and is held in a standing state on the surface of the rotating magnet roller to form a magnetic brush. The magnet roller is arranged near the electrostatic latent image carrier. Therefore, a part of the toner for the transfer material adhesive layer constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the electrostatic latent image carrier by an electric attractive force. As a result, the electrostatic latent image is developed by the toner and a visible image by the toner for the transfer material adhesive layer is formed on the surface of the electrostatic latent image carrier.

[0075] The transfer material adhesive layer forming apparatus has a plurality of developing devices, and among the plurality of developing devices, two or more developing devices are provided with a white toner for the transfer material adhesive layer containing a polyester resin, a polyurethane resin, and a release agent, which is used for forming the transfer material adhesive layer. A white transfer material adhesive layer is formed by this white toner. The transfer material adhesive layer forming device preferably further includes a developing device including a transparent toner containing a polyester resin, a polyurethane resin, and a release agent, which is used for forming the transfer material adhesive layer. A transparent transfer material adhesive layer is formed by this transparent toner for the transfer material adhesive layer.

[0076] Among the plurality of developing devices included in the transfer material adhesive layer forming device, two or more developing devices are provided with a white toner for the transfer material adhesive layer containing a polyester resin, a polyurethane resin, and a release agent, and the transfer material adhesive layer is formed in one printing. Thereby, a thermal transfer print sheet can be produced without the color image layer protruding outside the transfer material adhesive layer. The transfer material adhesive layer forming device preferably further includes a developing device including a transparent toner for the transfer material adhesive layer containing a polyester resin, a polyurethane resin, and a release agent, and can form a transfer material adhesive layer including a white transfer material adhesive layer and a transparent transfer material adhesive layer in one printing.

[0077] By arranging a developing device provided with a white toner for the transfer material adhesive layer and a developing device provided with a transparent toner for the transfer material adhesive layer in the transfer material adhesive layer forming device so that a transparent transfer material adhesive layer is formed on the color image layer formed on the transfer substrate, and a white transfer material adhesive layer is formed on the transparent transfer material adhesive layer, a thermal transfer print sheet in which each toner layer overlaps in the order of transfer substrate-color image layer-transparent transfer material adhesive layer-white transfer material adhesive layer can be produced.

[0078] The amount of the toner for the transfer material adhesive layer output from each developing device of the transfer material adhesive layer forming device is preferably 1.7 mg / cm 2 or more and 4.8 mg / cm 2 or less, more preferably 1.7 mg / cm 2 or more and 3.2 mg / cm 2 or less, and even more preferably 1.7 mg / cm 2 or more and 3.0 mg / cm 2 or less. When the amount of the toner for the transfer material adhesive layer output from each developing device is 1.7 mg / cm2 4.8 mg / cm or less 2 When it is 4.8 mg / cm or less, when a thermal transfer print sheet having a transfer material adhesive layer formed on a transfer substrate using a plurality of developing devices is thermally transferred to a transfer material, the image on the transfer material is not rough, and the transfer material base can be sufficiently white-concealed. The amount of toner for the transfer material adhesive layer output from each developing device is 1.7 mg / cm 2 3.2 mg / cm or more 2 When it is 3.2 mg / cm or less, generation of transfer residue of the toner for the transfer material adhesive layer can be suppressed, and when it is 1.7 mg / cm 2 3.0 mg / cm or more 2 When it is 3.0 mg / cm or less, generation of transfer residue of the toner for the transfer material adhesive layer can be further suppressed.

[0079] The thickness of the transfer material adhesive layer formed by the toner for the transfer material adhesive layer output from one developing device of the transfer material adhesive layer forming apparatus is preferably 20 μm or more and 30 μm or less. When the thickness of the transfer material adhesive layer formed by the toner for the transfer material adhesive layer output from one developing device is 20 μm or more and 30 μm or less, when a thermal transfer print sheet having a transfer material adhesive layer formed on a transfer substrate using a plurality of developing devices is thermally transferred to a transfer material, the image on the transfer material is not rough, and the transfer material base can be sufficiently white-concealed. Also, generation of transfer residue of the toner for the transfer material adhesive layer can be suppressed.

[0080] <<Other Processes and Other Means>> Examples of other processes in the transfer material adhesive layer forming process include a transfer process, a fixing process, a cleaning process, a charge elimination process, a recycling process, a control process, and the like. Examples of other means in the transfer material adhesive layer forming apparatus include a transfer means, a fixing means, a cleaning means, a charge elimination means, a recycling means, a control means, and the like.

[0081] - Transfer Process and Transfer Means - The transfer process in the process of forming the adherend adhesive layer is not particularly limited as long as it is a process of transferring the adherend adhesive layer onto the color image layer on the transfer substrate, and can be appropriately selected according to the purpose. However, a mode in which an intermediate transfer body is used, the adherend adhesive layer is primarily transferred onto the intermediate transfer body, and then the adherend adhesive layer is secondarily transferred onto the color image layer on the transfer substrate is preferable. The transfer means is not particularly limited as long as it is a means for transferring the adherend adhesive layer onto the color image layer, and can be appropriately selected according to the purpose. However, a mode having a first transfer means for transferring the image of the adherend adhesive layer onto the intermediate transfer body to form a composite transfer image and a second transfer means for transferring the composite transfer image onto the color image layer is preferable. The transfer process can be performed, for example, by charging the electrostatic latent image carrier of the adherend adhesive layer forming apparatus using a transfer charger with the adherend adhesive layer, and can be performed by the transfer means.

[0082] Here, when the image secondarily transferred onto the color image layer is an adherend adhesive layer composed of two types of toners for the adherend adhesive layer, transparent and white, the toner for the adherend adhesive layer is sequentially superposed on the intermediate transfer body by the transfer means to form the adherend adhesive layer on the intermediate transfer body, and the adherend adhesive layer on the intermediate transfer body is secondarily transferred onto the color image layer all at once by the intermediate transfer means.

[0083] The intermediate transfer body in the adherend adhesive layer forming apparatus is not particularly limited and can be appropriately selected from known transfer bodies according to the purpose. For example, a transfer belt is preferably mentioned. The transfer means (the first transfer means and the second transfer means) in the adherend adhesive layer forming apparatus preferably has at least a transferrer for peeling and charging the visible image formed on the electrostatic latent image carrier toward the recording medium side. Examples of this transferrer include a corona transferrer by corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, an adhesive transferrer, and the like.

[0084] -Fixing process and fixing means- The fixing step in the step of forming the transfer material adhesive layer is not particularly limited as long as it is a step of fixing the transfer material adhesive layer transferred onto the transfer base material, and can be appropriately selected according to the purpose. It can be performed simultaneously at once in a state where each layer formed by the toner for the transfer material adhesive layer output from a plurality of respective developing means is laminated. The fixing means in the transfer material adhesive layer forming apparatus is not particularly limited as long as it is a means for fixing the transfer material adhesive layer transferred onto the transfer base material, and can be appropriately selected according to the purpose. However, a known heating and pressurizing member is preferable. Examples of the heating and pressurizing member in the transfer material adhesive layer forming apparatus include a combination of a heating roller and a pressurizing roller, and a combination of a heating roller, a pressurizing roller, and an endless belt. This fixing step can be performed by the fixing means in the transfer material adhesive layer forming apparatus. The heating in the heating and pressurizing member of the transfer material adhesive layer forming apparatus is usually preferably 80°C to 200°C. In the transfer material adhesive layer forming apparatus, depending on the purpose, a known light fixing device may be used together with or instead of the fixing means. The surface pressure in the fixing step is not particularly limited and can be appropriately selected according to the purpose, but it is preferably 2 ~80 N / cm 2 .

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

[0086] -Charge removal process and charge removal means- As the charge removal process in the transfer material adhesive layer forming process, there is no particular limitation as long as it is a process of applying a charge removal bias to the electrostatic latent image carrier of the transfer material adhesive layer forming apparatus to remove charge, and it can be appropriately selected according to the purpose. For example, it can be performed by a charge removal means. As the charge removal means in the transfer material adhesive layer forming apparatus, there is no particular limitation as long as it is a means of applying a charge removal bias to the electrostatic latent image carrier to remove charge, and it can be appropriately selected according to the purpose. For example, a charge removal lamp and the like can be mentioned.

[0087] -Recycling process and recycling means- As the recycling process in the transfer material adhesive layer forming process, there is no particular limitation as long as it is a process of recycling the toner for the transfer material adhesive layer removed by the cleaning process to the developing device in the transfer material adhesive layer forming apparatus, and it can be appropriately selected according to the purpose. For example, it can be performed by a recycling means. As the recycling means in the transfer material adhesive layer forming apparatus, there is no particular limitation as long as it is a means of recycling the toner for the transfer material adhesive layer removed by the cleaning process to the developing device, and it can be appropriately selected according to the purpose. For example, known conveying means and the like can be mentioned.

[0088] -Control process and control means- As the control process in the transfer material adhesive layer forming process, there is no particular limitation as long as it is a process capable of controlling the movement of each process in the transfer material adhesive layer forming process, and it can be appropriately selected according to the purpose. For example, it can be performed by a control means. As the control means in the transfer material adhesive layer forming apparatus, there is no particular limitation as long as it is a means capable of controlling the movement of each means in the transfer material adhesive layer forming apparatus, and it can be appropriately selected according to the purpose. For example, devices such as a sequencer and a computer can be mentioned.

[0089] <Transfer material adhesive layer> The transfer material adhesive layer is a layer that adheres to the transfer material when the thermal transfer print sheet is thermally transferred to the transfer material. The transfer material is not particularly limited as long as it adheres to the transfer material adhesive layer, and may be a flexible transfer material having flexibility or a non-flexible transfer material not having flexibility. Examples of the flexible transfer material include cloth, leather, plastic film, and the like. Examples of the non-flexible transfer material include tiles, pottery, easels, and the like. The transfer material adhesive layer is formed by toner for the transfer material adhesive layer. The white transfer material adhesive layer is formed by white toner for the transfer material adhesive layer, and the transparent transfer material adhesive layer is formed by transparent toner for the transfer material adhesive layer. The structure of the transfer material adhesive layer is not particularly limited as long as it has a white transfer material adhesive layer, but it is preferably formed such that the white transfer material adhesive layer is in contact with the transfer material, and more preferably, a transparent transfer material adhesive layer is formed on the white transfer material adhesive layer.

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

[0091] -Polyester Resin- The polyester resin used in the toner for the transfer material adhesive layer is preferably obtained by polycondensation of an alcohol and a carboxylic acid. There are no particular restrictions on the alcohol used, and it can be appropriately selected according to the purpose. For example, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol, 1,4-bis(hydroxymethyl)cyclohexane, etherified bisphenols such as bisphenol A, and other divalent alcohol monomers, trivalent or higher polyhydric alcohol monomers, etc. can be mentioned.

[0092] Also, there are no particular restrictions on the carboxylic acid, and it can be appropriately selected according to the purpose. For example, 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 acid monomers 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, 1,3-dicarboxyl-2-methylenecarboxypropane, and 1,2,7,8-octanetetracarboxylic acid can be mentioned.

[0093] - Polyurethane resin - Polyurethane resin is generally suitable for the toner for the transfer material adhesive layer because it is excellent in tensile strength, abrasion resistance, elasticity, and oil resistance. In terms of the composition of polyurethane, it is preferable to use a polyurethane resin composed of 1,4-butanediol (1,6-hexanediol), adipic acid, diphenylmethane diisocyanate, etc. Also, there are no particular restrictions on the specific trade name of the polyurethane resin used, and it can be appropriately selected according to the purpose. For example, Hot Melt Powder ECOFREEN POWDER (manufactured by ECOFREEN), T8175N (manufactured by DIC Covestro Polymer), P22MBRNAT (manufactured by Nippon Milk Industry Co., Ltd.), etc. can be mentioned. Since the toner for the transfer material adhesive layer contains a polyurethane resin, the transfer material adhesive layer can have rubber elasticity, so that the image thermally transferred to the transfer material is less likely to crack even when pulled, bent, washed, etc.

[0094] It is preferable that both the softening temperature and the glass transition temperature of the polyurethane resin are 45°C or lower. If both the softening temperature and the glass transition temperature of the polyurethane resin are 45°C or lower, the flexibility of the transfer material adhesive layer after fixing can be ensured. Also, it is preferable that both the softening temperature and the glass transition temperature of the polyester resin are 55°C or higher. If both the softening temperature and the glass transition temperature of the polyester are 55°C or higher, the heat storage stability of the transfer material adhesive layer can be ensured.

[0095] The toner for the transfer material adhesive layer contains a polyester resin and a polyurethane resin. The polyester resin and the polyurethane resin are preferably incompatible, and by combining and using the polyester resin and the polyurethane resin, an incompatible sea-island structure of the polyester resin and the polyurethane resin can be formed in the cross-section of the toner for the transfer material adhesive layer. In this sea-island structure of the toner cross-section, it is preferable that the domain serving as the island part contains the polyurethane resin and the matrix serving as the sea part contains the polyester resin.

[0096] The weight average molecular weight of the polyurethane resin is preferably 20,000 to 100,000, more preferably 20,000 to 80,000, and even more preferably 20,000 to 60,000. If the weight average molecular weight is 20,000 or more, there is no risk of the transfer material adhesive layer melting out when thermally transferred to the transfer material, and if the weight average molecular weight is 100,000 or less, the melting and kneading of other toner components and the adhesive are easy during toner formation.

[0097] The content of the polyurethane resin is not particularly limited and can be appropriately selected according to the purpose. However, when the toner for the transfer material adhesive layer contains a release agent, it is preferably in the range of 10 to 50% by mass, more preferably in the range of 20 to 40% by mass, based on the total mass of the resin and the release agent. If the content of the polyurethane resin is 10% by mass or more based on the total mass of the resin and the release agent, sufficient fixability to a flexible transfer material such as a toner cloth and the flexibility of the transfer material adhesive layer after fixing can be obtained. If it is 50% by mass or less, the heat storage stability of the toner does not deteriorate and there is no risk of aggregation of toner particles.

[0098] Also, as all or part of the polyurethane resin, any one of polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, polybutylene isophthalate, and styrene-butadiene rubber having the same characteristics as the above polyurethane resin can be substituted.

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

[0100] The release agent that can be used in the toner for the transfer material adhesive layer is not particularly limited and can be appropriately selected according to the purpose. For example, liquid paraffin, microcrystalline wax, natural paraffin, synthetic paraffin, polyolefin wax, and their partial oxides, 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, carnauba wax, higher fatty alcohols and higher fatty acids such as montan wax, fatty acid amides, fatty acid bisamides, zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, zinc oleate, zinc palmitate, magnesium palmitate, zinc myristate, zinc laurate, zinc behenate and other metal soaps, fatty acid esters, polyvinylidene fluoride, etc. can be mentioned. Among these, it is preferable to contain at least an ester wax such as a fatty acid ester.

[0101] When a maleic acid-modified polyolefin having a polypropylene block in the main chain is contained in the toner for the transfer material adhesive layer, if the content is large, there is a problem that the toner and the fixing roller (or fixing belt) cannot be separated during fixing, resulting in a waste paper jam. However, by adding an ester wax as a release agent, this problem can be suppressed. Furthermore, the maleic acid-modified polyolefin having a polypropylene block in the main chain can finely disperse the ester wax.

[0102] The content of the release agent in the toner for the transfer material adhesive layer is not particularly limited and can be appropriately selected according to the purpose, but it is preferably 0.1 to 8.0% by mass, and more preferably 1.0 to 6.0% by mass. If the content of the release agent in the toner for the transfer material adhesive layer is 0.1% by mass or more, the toner and the fixing roller (or fixing belt) can be separated during fixing, suppressing waste paper jams. Also, if the content of the release agent in the toner for the transfer material adhesive layer is 8.0% by mass or less, the toner can be sufficiently fixed to the plastic film.

[0103] -White pigment- The white pigment that can be included in the toner for the transfer material adhesive layer is not particularly limited and can be appropriately selected according to the purpose. Titanium dioxide, lead white, talc, kaolin, zinc sulfide, barium sulfate, calcium carbonate, zinc oxide, hollow silica, etc. can be used. Also, those obtained by subjecting the white pigment to surface treatment may be used. For example, those obtained by surface treatment with organics such as silicon, zirconia, aluminum, polyol, etc. can be used. Specifically, those obtained by subjecting titanium dioxide to surface treatment with organics such as aluminum and polyol are preferred. It is presumed that by this surface treatment, the release agent in the toner for the transfer material adhesive layer wets the white pigment, thereby relaxing the hardness of the transfer material adhesive layer and obtaining a white transfer material adhesive layer that is less likely to crack.

[0104] -Charge control agent- The toner for the transfer material adhesive layer can contain a charge control agent. As the charge control agent, if it is white or colorless, it can be appropriately selected according to the purpose. For example, onium salts such as phosphonium salts and their lake pigments, triphenylmethane dyes and their lake pigments, metal salts of higher fatty acids; dialkyltin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dialkyltin borates such as dibutyltin borate, dioctyltin borate, dicyclohexyltin borate, organometallic complexes, chelate compounds, monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, metal complexes of aromatic dicarboxylic acid systems, quaternary ammonium salts can be mentioned. In addition, aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, phenol derivatives such as bisphenol can be mentioned. These can be used alone or in combination of two or more.

[0105] When these charge control agents are internally added to the toner for the transfer material adhesive layer, the content is not particularly limited and can be appropriately set according to the purpose, but it is preferably added in an amount of 0.1 to 10% by mass based on the total amount of the resin.

[0106] -External additive- For the toner for the transfer material adhesive layer, inorganic fine particles or the like can be used as an external additive. The inorganic fine particles for external addition used in the present invention are not particularly limited and can be appropriately selected according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, limestone, diatomaceous earth, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, etc. can be mentioned. Among these, silica, alumina, and titanium oxide are preferable.

[0107] Also, inorganic fine particles that have been surface-treated with a hydrophobizing agent may be used. The hydrophobizing agent is not particularly limited and can be appropriately selected according to the purpose. For example, silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate-based coupling agents, aluminum-based coupling agents, etc. are mentioned as preferable surface treatment agents. Also, sufficient effects can be obtained by using silicone oil as a hydrophobizing agent.

[0108] Also, the average diameter of the primary particles of the inorganic fine particles is not particularly limited and can be appropriately selected according to the purpose, but 5 to 500 nm is preferable, and 5 to 200 nm is more preferable. If the average diameter of the primary particles of the inorganic fine particles is 5 nm or more, aggregation of the inorganic fine particles can be suppressed, and the inorganic fine particles in the toner can be uniformly dispersed. If the average diameter of the primary particles of the inorganic fine particles is 500 nm or less, the heat-resistant storage stability can be improved by the filler effect. Here, the average diameter of the primary particles of the inorganic fine particles is a value obtained by directly measuring the particle diameter from a photograph obtained by a transmission electron microscope, and it is preferable to observe at least 100 or more inorganic fine particles and use the average value of their major axes.

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

[0110] - Cleaning property improver - The toner for the transfer material adhesive layer may contain a cleaning property improver as an additive. The cleaning property improver is not particularly limited as long as it can be added to the toner for the transfer material adhesive layer in order to remove the toner after transfer remaining on the electrostatic latent image carrier or the primary transfer medium, and can be appropriately selected according to the purpose. For example, fatty acid metal salts such as zinc stearate, calcium stearate, and stearic acid, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles, and the like can be mentioned. The polymer fine particles preferably have a relatively narrow particle size distribution, and preferably have a volume average particle diameter of 0.01 μm or more and 1 μm or less.

[0111] The toner for the transfer material adhesive layer preferably has a sea-island structure in the toner cross-section. The "sea-island structure" means that when the continuous phase of one component is expressed as the "sea", other components different from the sea part exist in the "sea" in an "island" shape in a non-compatible manner with the sea part. The island part in the toner cross-section is called the "domain", and the sea part is called the "matrix". From the viewpoint of the crack resistance of the transfer material adhesive layer after fixing, the toner for the transfer material adhesive layer has a cross-sectional area of 100 μm 2 per, the aspect ratio is 2 or more, and the area is 0.1 μm 2 or more, and it is preferable that an average of 3 or more domains exist, and more preferably an average of 5 or more domains exist.

[0112] The toner for the transfer material adhesive layer is not particularly limited in the particle size distribution based on volume%, and can be appropriately selected according to the purpose. However, it preferably has a peak in the range of 5 to 30 μm, and more preferably has a peak in the range of 10 to 20 μm. Here, the "peak" of the particle size distribution means that the peak top of the particle size distribution is within the above particle size range. Also, the volume average particle size of the toner for the transfer material adhesive layer is not particularly limited and can be appropriately selected according to the purpose. However, it is preferably 5 μm or more and 30 μm or less, and more preferably 10 μm or more and 20 μm or less. For the toner for the transfer material adhesive layer as described above, by increasing the toner particle size, the developing ability can be improved, the toner development amount in one development can be increased, the pile height of the toner layer can be increased, and it is possible to easily fill the unevenness on the surface of the flexible transfer material such as cloth. Also, in view of the balance with the transferability which is a trade-off, the toner for the transfer material adhesive layer more preferably has a particle size distribution having a peak in the range of 10 to 20 μm in the particle size distribution based on volume%. For the same reason, the toner for the transfer material adhesive layer more preferably has a volume average particle size of 10 μm or more and 20 μm or less.

[0113] For the release agent, charge control agent, external additive, fluidity improver, and cleaning property improver used in the toner for the transfer material adhesive layer, in order to improve the adhesiveness between the color toner and the toner for the transfer material adhesive layer and obtain a more durable printed matter, it is preferable to use the same materials as those used in the color toner.

[0114] [Observation of Incompatible Domains in the Cross-Section of Toner for Transfer Material Adhesive Layer] Regarding the sea-island structure in the cross-section of the toner for the transfer material adhesive layer and the size and shape of the island part (domain), it can be confirmed by observing the reflected electron image using a scanning electron microscope (SEM). Due to the color difference between the island part (domain) and the sea part (matrix) in the sea-island structure of the cross-section of the toner for the transfer material adhesive layer, the presence of the sea part (matrix) and the island part (domain) can be confirmed, and it can also be confirmed that the sea part and the island part are incompatible. In order to enhance the contrast and facilitate the discrimination between the island part and the sea part, staining with ruthenium tetroxide may be performed as necessary. As an example of the observation of the reflected electron image using a scanning electron microscope, the following procedures and conditions are given.

[0115] The sea-island structure of the present invention can be observed in the same way for both the toner particles for the transfer material adhesive layer and the crushed product of the molten kneaded mixture of the toner components for the transfer material adhesive layer. Particles of the toner for the transfer material adhesive layer or the crushed product of the molten kneaded mixture of the toner components for the transfer material adhesive layer are embedded in an epoxy resin. After cross-sectioning, observations can be made under the following conditions using a scanning electron microscope (SU8230, manufactured by Hitachi, Ltd.). At this time, since the non-stained part is observed as a dark part, it can be distinguished from the stained part (bright part). ·Acceleration voltage: 5 kV ·Emission current: 10 μA ·Probe current: Norm ·Condenser lens 1: 5.0 ·W.D.: 8.0 mm ·Observation mode: SE ·Magnification: ×2,000 or ×5,000

[0116] [Aspect ratio and area of the domain in the cross-section of the toner for the transfer material adhesive layer] The ratio of the length of the longest side to the length of the shortest side of the island part (domain) of the sea-island structure in the SEM image when observing the cross-section of the toner for the transfer material adhesive layer by a scanning electron microscope is defined as the aspect ratio of the domain. The larger this value, the higher the anisotropy. Also, the area of the island part (domain) of the sea-island structure in the SEM image when observing the cross-section of the toner for the transfer material adhesive layer by a scanning electron microscope can be defined as the area of the domain.

[0117] [Average number of specific domains per 100 μm of the cross-section of the toner for the adherend bonding layer 2 For the cross-section of the toner for the adherend bonding layer at 100 μm 2 The average number of domains with an aspect ratio of 2 or more and an area of 0.1 μm 2 or more is obtained as follows. An example is shown below.

[0118] Prepare at least 10 toner particles for the adherend bonding layer with a particle size of 10 to 20 μm, and for each toner particle, take an SEM image of the toner cross-section at a position approximately half of the particle size. Among the domains present in the SEM image of the toner cross-section, by obtaining the number of domains with an aspect ratio of 2 or more and an area of 0.1 μm 2 or more and the toner cross-sectional area, the number of domains with an aspect ratio of 2 or more and an area of 0.1 μm 2 or more per 100 μm 2 of the cross-section can be obtained. By summing up the number of domains with an aspect ratio of 2 or more and an area of 0.1 μm 2 or more per 100 μm 2 of each toner particle and dividing by the number of toner cross-sections used, the average number of domains with an aspect ratio of 2 or more and an area of 0.1 μm 2 or more per 100 μm 2 of the SEM image of the toner cross-section can be obtained.

[0119] [Taking an SEM image of the fixed image of the toner for the adherend bonding layer Regarding taking an SEM image of the fixed image of the toner for the adherend bonding layer, it can be taken in the same manner as the method of [incompatible domain observation] described above, except that the fixed image of the toner for the adherend bonding layer is used as the sample.

[0120] [Method for measuring the particle size and particle size distribution of the toner for the adherend bonding layer based on volume% ​As a method for measuring the particle size distribution and particle size of the toner for the transfer material adhesive layer based on volume%, for example, a particle size analyzer ("Multi-Sizer III", manufactured by Beckman Coulter, Inc.) can be used to measure at an aperture diameter of 100 μm, and it can be analyzed with analysis software (Beckman Coulter Mutlisizer 3 Version 3.51). An example is shown below. Add 0.5 ml of a 10 mass% surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) to a 100 ml glass beaker, add 0.5 g of each toner, stir with a microspatula, and then add 80 ml of ion-exchanged water to obtain a dispersion. The obtained dispersion is subjected to dispersion treatment with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.) for 10 minutes to obtain a sample dispersion of the toner for the transfer material adhesive layer. Regarding the sample dispersion of the toner for the transfer material adhesive layer, measurement is performed using the Multi-Sizer III and isotonic III (manufactured by Beckman Coulter, Inc.) as the measurement solution. From the viewpoint of measurement reproducibility, the sample dispersion of the toner is dropped so that there is no error in the particle size and the concentration indicated by the apparatus becomes 8 ± 2%, and the volume average particle size of the toner is measured.

[0121] [Confirmation and Quantification of the Presence of Resin in the Toner for the Transfer Material Adhesive Layer] Regarding the resin contained in the toner for the transfer material adhesive layer, the presence can be confirmed and quantified preferably by gas chromatograph mass spectrometer (GC-MS) or NMR (Nuclear Magnetic Resonance). Specifically, it can be performed according to the following procedures, apparatus, and conditions.

[0122] [Component Analysis by Gas Chromatograph Mass Spectrometer (GC-MS)] - Sample Preparation - The toner for the adherent layer of the transfer material is dispersed in chloroform and stirred for one day and night to obtain a dispersion. Subsequently, this dispersion is centrifuged, and only the supernatant is recovered. The recovered supernatant is evaporated to dryness and subjected to composition analysis using a gas chromatograph-mass spectrometer (GC-MS). An example of the measurement conditions by GC-MS is shown below. Note that a mixture obtained by dropping approximately 1 μL of a methylating agent (tetramethylammonium hydroxide 20% methanol solution: TMAH) into a sample of about 1 mg is used as the sample.

[0123] -Measurement Conditions- · Pyrolysis-Gas Chromatograph Mass Spectrometry (Py-GCMS) Analyzer: QP2010 (manufactured by Shimadzu Corporation) · Heating Furnace: Py2020D (manufactured by Frontier Lab Co., Ltd.) · Heating Temperature: 320 °C · Column: Ultra ALLOY-5 (L = 30 m, I.D = 0.25 mm, Film = 0.25 μm, manufactured by GL Sciences Inc.) · Column Temperature: 50 °C (holding time: 1 minute) ~ temperature increase (10 °C / min) ~ 340 °C (holding time: 7 minutes) · Split Ratio: 1:100 · Column Flow Rate: 1.0 ml / min · Ionization Method: EI method (70 eV) · Measurement Mode: Scan Mode · Search Data: NIST 20 MASS SPECTRAL LIB.

[0124] [Component Analysis by NMR] -Sample Preparation- The toner for the adherent layer of the transfer material is dispersed in chloroform and stirred for one day and night to obtain a dispersion. Subsequently, this dispersion is centrifuged, and only the supernatant is recovered. The recovered supernatant is evaporated to dryness and used as 1 a sample for 1H-NMR and 13 a sample for 13C-NMR, and the composition is analyzed by NMR. 1 An example of the preparation method of the sample for 1H-NMR, 13 the preparation method of the sample for 13C-NMR, and the measurement conditions are shown below.

[0125] (1) 1 Preparation method of sample for H-NMR To 100 mg of the sample, add 1 mL of d8-toluene (manufactured by Fujifilm Wako Pure Chemical Corporation), warm it with a dryer to dissolve it, 1 and prepare a sample for H-NMR. (2) 13 Preparation method of sample for C-NMR To 100 mg of the sample, add 1 mL of deuterated 1,2-dichlorotoluene (manufactured by Fujifilm Wako Pure Chemical Corporation), warm it with a dryer to dissolve it, 13 and prepare a sample for C-NMR.

[0126] -Measurement conditions- · NMR apparatus: ECX-500 (manufactured by JEOL Ltd.) · Measured nucleus = 1 H (500 MHz), measurement pulse file = single pulse dec.jxp( 1 H), 45 °C pulse, integration 20,000 times, Relaxation Delay - 4 s, data point 32K, Offset 100 ppm, observation width = 250 ppm, measurement temperature 70 °C · Measured nucleus = 13 C (125 MHz), measurement pulse file = single pulsedec.jxp( 13 C), 45 °C pulse, integration 64 times, Relaxation Delay 5 s, data point 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 the transfer material adhesive layer can be obtained by measuring the molecular weight distribution of the THF (tetrahydrofuran) soluble fraction with a gel permeation chromatography (GPC) measuring device. There is no particular limitation on the GPC measuring device, and it can be appropriately selected according to the purpose. For example, under the trade name, GPC-150C (manufactured by Waters Corporation) etc. 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 the purpose. For example, by trade name, KF801 (column for organic solvent-based SEC (GPC)), KF802 (column for organic solvent-based SEC (GPC)), KF803 (column for organic solvent-based SEC (GPC)), KF804 (column for organic solvent-based SEC (GPC)), KF805 (column for organic solvent-based SEC (GPC)), KF806 (column for organic solvent-based SEC (GPC)), KF807 (column for organic solvent-based SEC (GPC)) (all manufactured by Showa Denko K.K.) and the like can be mentioned.

[0129] The method for measuring the weight-average molecular weight of the resin used in the toner for the transfer material adhesive layer is not particularly limited and can be appropriately selected according to the purpose. For example, it can be carried out by the following method. Stabilize the column in a heat chamber at 40 °C and flow THF as a solvent at a flow rate of 1 mL per minute. Next, after completely dissolving 0.05 g of the sample in 5 g of THF, filter it through a pretreatment filter (for example, trade name: Chromatodisk, pore size: 0.45 μm, manufactured by Kuraray Co., Ltd.), and finally adjust the sample concentration to 0.05 mass% to 0.6 mass%. Inject 50 μL to 200 μL of the THF sample solution prepared with the sample concentration into the column, separate the THF-soluble components contained in the THF sample solution, and then use a detector (for example, a differential refractive index (RI) detector (device name: GPC-150C, manufactured by Waters Corporation)) to convert to molecular weight, whereby the weight-average molecular weight (Mw) of the THF-soluble components contained in the THF sample solution can be measured.

[0130] The measurement of the weight-average molecular weight Mw and the number-average molecular weight Mn of the THF-soluble components contained in the sample is calculated from the relationship between the logarithmic value of the calibration curve created by several monodisperse polystyrene standard samples and the count number of the molecular weight distribution of the sample. As the standard polystyrene sample for creating the calibration curve, for example, those manufactured by Pressure Chemical or Toyo Soda Industry Co., Ltd., with molecular weights of 6×10 2 , 2.1×10 2 , 4×10 2 , 1.75×10 4 , 5.1×10 4, 1.1×10 5 , 3.9×10 5 , 8.6×10 5 , 2×10 6 , and 4.48×10 6 It is preferable to use at least about 10 standard polystyrene samples. Also, it is preferable to use an RI (refractive index) detector as the detector.

[0131] [Method for Measuring Softening Temperature] In measuring the softening temperature (Tm) of the resin used for the toner for the transfer material adhesive layer, for example, it can be measured using a flow tester (manufactured by Shimadzu Corporation, CFT-500D), and the temperature at which the sample first deforms (= the temperature at which the sample begins to deform as it changes from a solid state to a rubbery state) can be determined as the softening temperature. For example, using the said flow tester, while heating a 1.0 g sample at a heating rate of 6 °C / min, applying a load of 1.96 MPa with a plunger, extruding from a nozzle with a diameter of 1.0 mm and a length of 1.0 mm, plotting the plunger drop amount of the flow tester against the temperature, obtaining an S-shaped curve regarding temperature (°C) / stroke (mm), taking the maximum value of the stroke in the S-shaped curve as S 1 Let it be, and the stroke value of the baseline on the low temperature side be S 2 Let it be, and in the S-shaped curve, the temperature at which the value of the stroke is (S 1 + S 2 ) / 2 can be determined as the softening temperature (Tm).

[0132] [Method for Measuring Glass Transition Temperature] In measuring the glass transition temperature (Tg) of the resin used in the toner for the transfer material adhesive layer, for example, it can be measured using a differential scanning calorimeter (manufactured by Seiko Instruments Inc., DSC210). Specifically, for example, with the differential scanning calorimeter, 0.01 to 0.02 g of the sample is weighed into an aluminum pan at room temperature, cooled to -20 °C at a temperature decrease rate of 10 °C / min, and then the sample is heated to 200 °C at a temperature increase rate of 10 °C / min. The temperature at the intersection of the extension line of the baseline and the tangent showing the maximum slope from the rising part of the peak to the apex of the peak can be determined as the glass transition temperature (Tg).

[0133] <<Developer>> The toner for the transfer material adhesive layer may be a one-component developer or a two-component developer. However, when used in high-speed printers, etc. that respond to the recent improvement in information processing speed, from the viewpoint of improving the life, it is preferably a two-component developer. When the toner for the transfer material adhesive layer is used as a one-component developer, even if the toner balance is maintained, the variation in the toner particle diameter is small, and there is little toner filming on the developing roller and little toner fusion on members such as a blade for thinning the toner layer. Good and stable developability and images can be obtained even in long-term stirring in the developing device. When the toner for the transfer material adhesive layer is mixed with a carrier to form a two-component developer and used, even if the toner balance is maintained over a long period, the variation in the toner particle diameter is small, and good and stable developability and images can be obtained even in long-term stirring in the developing device. The toner for the transfer material adhesive layer can be mixed with a carrier to form a two-component developer and used in an electrophotographic image forming method using a two-component development system. As this carrier, a magnetic carrier can be used. The magnetic carrier that can be used is the same as 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 the transfer material adhesive layer, the mass ratio of the carrier in the developer accommodated in the developing device is preferably 85% by mass or more and less than 98% by mass. When the mass ratio of the carrier in the developer is 85% by mass or more, toner scattering from the developing device is less likely to occur, and the occurrence of defective images can be reduced. When the mass ratio of the carrier in the developer is less than 98% by mass, it is possible to suppress an excessive increase in the charge amount of the toner for the transfer material adhesive layer or a shortage in the supply amount of the toner for the transfer material adhesive layer. Therefore, it is possible to reduce a decrease in image density and the occurrence of defective images.

[0135] <<Method for manufacturing toner for transfer material adhesive layer>> The method for manufacturing the toner for the transfer material adhesive layer is not particularly limited and can be appropriately selected according to the purpose. Hereinafter, an example of the method for manufacturing the toner for the transfer material adhesive layer will be described. As a method for manufacturing the toner for the transfer material adhesive layer having a transfer material base hiding function containing a white pigment, the melt-kneading pulverization method is preferable. This is because the white pigment has a larger specific gravity compared to other toner constituent materials, making it difficult to granulate by chemical methods such as the dissolution suspension method, and a step of cooling and rolling the melt-kneaded product of the toner components is necessary to form a domain having an aspect ratio of 2 or more in the toner cross-section.

[0136] On the other hand, chemical methods such as the dissolution suspension method can be used for the toner for the transfer material adhesive layer if a toner material configuration and manufacturing process that enable internal dispersion of the white pigment and can form a domain having an aspect ratio of 2 or more in the toner cross-section are adopted. The shape and size of the domain in the toner cross-section are determined by the compatibility of the domain material and the matrix material and the stretching force applied during the cooling and rolling of the melt-kneaded product. Therefore, the easiest method for controlling the domain diameter and shape is to use incompatible materials, determine the relationship between the domain size, shape, and rolling thickness in advance, reduce the thickness of the melt-kneaded product of the toner material to an appropriate thickness, preferably adjusted to 1 mm or less, to obtain a toner having a large domain and an aspect ratio of 2 or more. The compatibility of the domain material and the matrix material is determined by the molecular weight and composition of each material.

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

[0138] - Step of obtaining a resin mixture (mixing step)- First, a polyester resin, a polyurethane resin, and a release agent, and, if necessary, a charge control agent, etc. are mixed by a mixer to obtain a mixture (mixing step). When producing a white toner for a transfer material adhesive layer, a white pigment is added as described above to obtain a mixture. The mixer is not particularly limited and can be appropriately selected according to the purpose. For example, a Henschel mixer (trade name: FM20B, manufactured by Nippon Coke & Engineering Co., Ltd.), a Super mixer (SMV-20Ba, manufactured by Kawata Co., Ltd.), etc. can be mentioned.

[0139] - Step of obtaining a kneaded product of the mixture (melt kneading step)- Next, the obtained mixture is melt kneaded using a hot melt kneader to obtain a kneaded product (melt kneading step). The hot melt kneader is not particularly limited and can be appropriately selected according to the purpose. For example, by trade name, a twin screw extruder PCM series (manufactured by Ikegai Corporation), a TEM type extruder (manufactured by Shibaura Machine Co., Ltd.), a twin screw extruder PCM conical kneader (manufactured by Buss), an open roll type continuous kneader Neodeck (manufactured by Nippon Coke & Engineering Co., Ltd.), etc. can be mentioned.

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

[0141] - Step of obtaining a pulverized product of the solid (fine pulverization step)- Next, the obtained solid is finely pulverized to obtain a pulverized product (fine pulverization step). The solid can be pulverized using a known pulverization method. For example, a jet mill method in which toner is included in a high-speed air stream and the solid is pulverized by the energy when the toner collides with a collision plate, an inter-particle collision method in which toner particles collide with each other in an air stream, a mechanical pulverization method in which toner is supplied between a rotor rotating at high speed and a narrow gap and pulverized, etc. can be used.

[0142] - Step of classifying and recovering the pulverized product (classification step)- Next, the pulverized product is classified to recover a pulverized product having a predetermined volume average particle diameter. Thereby, the toner for the transfer material adhesive layer can be obtained (classification step). The classification method is not particularly limited and can be appropriately selected according to the purpose. For example, any appropriate method can be used.

[0143] In addition, the toner for the transfer material adhesive layer can be manufactured using the dissolution suspension method. When manufacturing the toner using the dissolution suspension method, an oil phase in which a toner material such as a polyester resin, a polyurethane resin, and a release agent, and optionally a charge control agent, is dissolved or dispersed in an organic solvent is dispersed in an aqueous medium (aqueous phase), and the resin is reacted. Thereby, a dispersion liquid containing a dispersion (oil droplets) containing a prepolymer in which the toner material is emulsified or dispersed is obtained. When producing a white toner for the transfer material adhesive layer, a white pigment is added as described above and the same operation is performed. Then, the organic solvent is removed from the dispersion liquid, filtration, washing, and drying are performed, and further classification or the like is performed as necessary to produce the mother particles of the toner for the transfer material adhesive layer. By granulating the mother particles obtained using the dissolution suspension method, the toner for the transfer material adhesive layer can be obtained. The organic solvent used in the dissolution suspension method is not particularly limited and can be appropriately selected according to the purpose. However, an organic solvent having a boiling point of less than 150°C is preferable in terms of easy removal.

[0144] The organic solvent with a boiling point of less than 150°C is not particularly limited and can be appropriately selected according to the purpose. For example, 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, methyl isobutyl ketone, etc. can be mentioned. These may be used alone or in combination of two or more. Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferred, and ethyl acetate is more preferred.

[0145] The aqueous medium used in the dissolution-suspension method is not particularly limited and can be appropriately selected according to the purpose. For example, water, a solvent miscible with water, a mixture thereof, etc. can be mentioned. These may be used alone or in combination of two or more. Among these, water is preferred. The solvent miscible with water is not particularly limited and can be appropriately selected according to the purpose. For example, alcohol, lower ketones, dimethylformamide, tetrahydrofuran, cellosolves, etc. can be mentioned. The alcohol is not particularly limited and can be appropriately selected according to the purpose. For example, methanol, isopropanol, ethylene glycol, etc. can be mentioned. The lower ketones are not particularly limited and can be appropriately selected according to the purpose. For example, acetone, methyl ethyl ketone, etc. can be mentioned.

[0146] The method for removing the organic solvent from the dispersion in the dissolution-suspension method is not particularly limited and can be appropriately selected according to the purpose. For example, a method of gradually raising the temperature of the entire reaction system to evaporate the organic solvent in the oil droplets, a method of spraying the dispersion in a dry atmosphere to remove the organic solvent in the oil droplets, etc. can be mentioned.

[0147] The classification in the dissolution and suspension method may be performed by removing the fine particle portion by means of a cyclone, a decanter, centrifugation, etc. in a liquid, or the classification operation may be performed after drying.

[0148] <<Process Cartridge>> A process cartridge using toner for the transfer material adhesive layer is detachably molded to various transfer material adhesive layer forming apparatuses, and includes at least an electrostatic latent image carrier that carries an electrostatic latent image, and developing means that develops the electrostatic latent image carried on the electrostatic latent image carrier with a developer of toner for the transfer material adhesive layer to form a toner image. Note that the process cartridge may further include other means as necessary. As developing means in the process cartridge, a developing device includes at least a developer storage unit that stores a developer of toner for the transfer material adhesive layer, and a developer carrier that carries and conveys the stored developer. Note that the developing means in the process cartridge may further include a regulating member or the like for regulating the thickness of the developer to be carried.

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

[0150] The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of the arrow by three rollers 51 disposed inside thereof and stretching it. A part of the three rollers 51 also functions as a transfer bias roller capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. A cleaning device 90 having a cleaning blade is disposed near the intermediate transfer member 50. Further, near the intermediate transfer member 50, a transfer roller 80 as transfer means capable of applying a transfer bias for transferring (secondary transfer) a transfer material adhesive layer to the color image layer formed transfer substrate 95 which is a recording medium is disposed facing the intermediate transfer member 50. Around the intermediate transfer member 50, a corona charger 58 for charging the toner image on the intermediate transfer member 50 is disposed between the contact portion of the electrostatic latent image carrier 10 and the intermediate transfer member 50 and the contact portion of the intermediate transfer member 50 and the color image layer formed transfer substrate 95 in the rotational direction of the intermediate transfer member 50.

[0151] The developing device 40 is composed of a developing belt 41 as the developer carrier, and a first developer 45K, a second developer 45Y, a third developer 45M, and a fourth developer 45C provided around the developing belt 41. The first developer 45K includes a developer storage portion 42K, a developer supply roller 43K, and a developing roller 44K. The second developer 45Y includes a developer storage portion 42Y, a developer supply roller 43Y, and a developing roller 44Y. The third developer 45M includes a developer storage portion 42M, a developer supply roller 43M, and a developing roller 44M. The fourth developer 45C includes a developer storage portion 42C, a developer supply roller 43C, and a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched by a plurality of belt rollers, and a part thereof is in contact with the electrostatic latent image carrier 10.

[0152] FIG. 1 is a schematic configuration diagram of an example of a transfer material adhesive layer forming apparatus used in a method for manufacturing a thermal transfer print sheet according to an embodiment of the present invention. In the transfer material adhesive layer forming apparatus 100A shown in FIG. 1, for example, the charging roller 20 uniformly charges the electrostatic latent image carrier 10. The exposure device 30 performs imagewise exposure L on the electrostatic latent image carrier 10 to form an electrostatic latent image. The electrostatic latent image formed on the electrostatic latent image carrier 10 is developed by supplying toner for forming a transfer material adhesive layer from the developing device 40 to form a transfer material adhesive layer. The transfer material adhesive layer is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer substrate 95 on which the color image layer has been formed. As a result, a transfer material adhesive layer is formed on the transfer substrate 95 on which the color image layer has been formed. The remaining toner for forming the transfer material adhesive layer on the electrostatic latent image carrier 10 is removed by the cleaning device 60, and the charging on the electrostatic latent image carrier 10 is once removed by the discharging lamp 70.

[0153] FIG. 2 is a schematic configuration diagram of another example of the transfer material adhesive layer forming apparatus used in the method for producing a thermal transfer print sheet according to an embodiment of the present invention. The transfer material adhesive layer forming apparatus 100B has the same configuration as the transfer material adhesive layer forming apparatus 100A shown in FIG. 1, except that a developing belt 41 is not provided and the first developing device 45K, the second developing device 45Y, the third developing device 45M, and the fourth developing device 45C are directly opposed and arranged around the electrostatic latent image carrier 10.

[0154] FIG. 3 is a schematic configuration diagram of another example of the transfer material adhesive layer forming apparatus used in the method for producing a thermal transfer print sheet according to an embodiment of the present invention. FIG. 4 is a partially enlarged view of the transfer material adhesive layer forming apparatus of FIG. 3.

[0155] The transfer material adhesive layer forming apparatus shown in FIG. 3 includes a copying machine main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400. An endless belt-shaped intermediate transfer member 50 is provided at the center of the copying machine main body 150. The intermediate transfer member 50 is stretched over the support rollers 14, 15, and 16 and is rotatable clockwise in FIG. 3. Near the support roller 15, an intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed. Opposite to the intermediate transfer member 50 stretched by the support rollers 14 and 15, a tandem type developing device 120 is disposed. In the tandem type developing device 120, four developing devices 18, namely the first, second, third, and fourth, are juxtaposed opposite to each other along the conveyance direction of the intermediate transfer member 50. Toner for forming an adherent layer on the material to be transferred is output in the order from the first developing device to the fourth developing device. Near the tandem type developing device 120, an exposure device 21 which is the exposure member is disposed. On the side of the intermediate transfer member 50 opposite to the side where the tandem type developing device 120 is disposed, a secondary transfer device 22 is disposed. In the secondary transfer device 22, a secondary transfer belt 24 which is an endless belt is stretched over a pair of rollers 23, and the color image layer formed transfer substrate conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 can be brought into contact with each other. Near the secondary transfer device 22, a fixing device 25 which is the fixing means is disposed. The fixing device 25 includes a fixing belt 26 which is an endless belt and a pressure roller 27 disposed to be pressed against the fixing belt 26.

[0156] In this embodiment, an elastic intermediate transfer belt can also be used as the intermediate transfer member 50. As the elastic intermediate transfer belt, for example, a belt in which a flexible elastic layer is laminated on a rigid base layer having relatively good flexibility can be used. Also, in order to prevent the intermediate transfer member 50 from meandering, a centering guide member may be provided on the inner peripheral surface of the intermediate transfer member 50.

[0157] In FIG. 3, the intermediate transfer member cleaning device 17 is disposed to clean the outer peripheral surface of the intermediate transfer member 50, but an intermediate transfer member cleaning device for cleaning the inner peripheral surface of the intermediate transfer member 50 may be separately provided. In addition, as the cleaning means of the intermediate transfer body cleaning device 17, a blade-shaped one, a brush-shaped one, or the like can be used. Further, a collecting means for receiving the toner or the like removed by the cleaning means may be provided. As the collecting means, a dish-shaped tray or the like can be used.

[0158] In the transfer material adhesive layer forming device of FIG. 3, a sheet reversing device 28 for reversing the transfer substrate in order to form images on both sides of the transfer substrate is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25.

[0159] Next, the formation of the transfer material adhesive image using the tandem type developing device 120 will be described. First, a color image original is set on the original platen 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the color image original is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed. When the start switch is pressed, when a color image original is set in the automatic document feeder 400, after the original is conveyed and moved onto the contact glass 32, the scanner 300 is driven. On the other hand, when a color image original is set on the contact glass 32, immediately, the scanner 300 is driven. Then, the first traveling body 33 and the second traveling body 34 travel. At this time, the first traveling body 33 irradiates light from the light source, and the reflected light from the color image original surface is reflected by the mirror in the second traveling body 34 and received by the reading sensor 36 through the imaging lens 35, and the image information of the color image original is read, becoming the image information of black, yellow, magenta, and cyan, and further becoming the solid image information with a uniform deposition amount of all colors.

[0160] Then, the solid image information is transmitted to each developing device (the first developing device, the second developing device, the third developing device, and the fourth developing device) in the tandem developing device 120. And in each developing device, an image unified for all developing devices is formed by each developing unit. That is, each developing device 18 (the first developing device, the second developing device, the third developing device, and the fourth developing device) in the tandem developing device 120, as shown in FIG. 4, respectively includes an electrostatic latent image carrier 10 (the electrostatic latent image carrier 10K for the first transfer material adhesion layer, the electrostatic latent image carrier 10Y for the second transfer material adhesion layer, the electrostatic latent image carrier 10M for the third transfer material adhesion layer, and the electrostatic latent image carrier 10C for the fourth transfer material adhesion layer), a charging device 160 which is a charging means for uniformly charging the electrostatic latent image carrier 10, an exposure device which exposes the electrostatic latent image carrier in the form corresponding to the solid image based on the solid image information (L in FIG. 4) to form an electrostatic latent image corresponding to the solid image information on the electrostatic latent image carrier, a developing unit 61 which is a developing means for developing the electrostatic latent image using each toner for forming a transfer material adhesion layer (toner for the white transfer material adhesion layer, toner for the transparent transfer material adhesion layer) to form a transfer material adhesion layer with each toner for forming a transfer material adhesion layer, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, and a discharging device 64. And each developing device 18 forms a single-color transfer material adhesion layer (the first transfer material adhesion layer, the second transfer material adhesion layer, the third transfer material adhesion layer, and the fourth transfer material adhesion layer) based on the image information of each color. The first transfer material adhesion layer, the second transfer material adhesion layer, the third transfer material adhesion layer, and the fourth transfer material adhesion layer thus formed are respectively transferred (primary transfer) onto the intermediate transfer member 50 rotated and moved by the support rollers 14, 15, and 16, that is, the first transfer material adhesion layer formed on the electrostatic latent image carrier 10K for the first transfer material adhesion layer, the second transfer material adhesion layer formed on the electrostatic latent image carrier 10Y for the second transfer material adhesion layer, the third transfer material adhesion layer formed on the electrostatic latent image carrier 10M for the third transfer material adhesion layer, and the fourth transfer material adhesion layer formed on the electrostatic latent image carrier 10C for the fourth transfer material adhesion layer.Then, on the intermediate transfer member 50, a transfer material adhesive layer is formed by laminating and synthesizing the first transfer material adhesive layer, the second transfer material adhesive layer, the third transfer material adhesive layer, and the fourth transfer material adhesive layer.

[0161] On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet of the transfer substrate with the color image layer formed from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. The sheet is separated one by one by the separation roller 145, sent out to the paper feed path 146, conveyed by the conveying roller 147, guided to the paper feed path 148 in the copying machine main body 150, and stopped by abutting against the registration roller 49. Alternatively, the paper feed roller 142 is rotated to feed out the sheet on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual paper feed path 53, and also stopped by abutting against the registration roller 49. The registration roller 49 is generally used while being grounded, but it may also be used in a state where a bias is applied for removing paper dust and the like on the sheet. Then, the registration roller 49 is rotated at a timing such that the transfer material adhesive layer synthesized on the intermediate transfer member 50 is transferred onto the color image layer on the transfer substrate, and a sheet of the transfer substrate with the color image layer formed is sent out between the intermediate transfer member 50 and the secondary transfer device 22, and the secondary transfer device 22 transfers (secondary transfer) the transfer material adhesive layer onto the transfer substrate with the color image layer formed. By doing so, the transfer material adhesive layer is transferred onto the transfer substrate with the color image layer formed, and the transfer material adhesive layer is formed on the color image layer. The toner for forming the transfer material adhesive layer remaining on the intermediate transfer member 50 after the transfer of the transfer material adhesive layer is cleaned by the intermediate transfer member cleaning device 17.

[0162] The sheet of the color image layer-formed transfer substrate on which the transfer material adhesive layer is transferred and the transfer material adhesive layer is formed is conveyed by the secondary transfer device 22 and sent out to the fixing device 25. In the fixing device 25, the transfer material adhesive layer is fixed on the sheet by heat and pressure. Thereafter, the sheet is switched by the switching claw 55 and discharged by the discharge roller 56, and stacked on the paper discharge tray 57. Alternatively, the sheet is switched by the switching claw 55, reversed by the sheet reversing device 28, guided back to the transfer position, the transfer material adhesive layer is also recorded on the back surface, and then discharged by the discharge roller 56 and stacked on the paper discharge tray 57.

[0163] Since the fourth developing device in the tandem type developing device 120 outputs and develops the toner for the transfer material adhesive layer on the intermediate transfer body 50 last and forms the first transfer material adhesive layer in contact with the color image layer on the transfer substrate, it is preferable to provide a transparent toner for the transfer material adhesive layer. When the fourth developing device is provided with a transparent toner for the transfer material adhesive layer, the transparent transfer material adhesive layer directly contacts the color image layer. When the fourth transfer material adhesive layer in contact with the color image layer is a transparent transfer material adhesive layer, when thermally transferring the color image layer and the transfer material adhesive layer laminated on the thermal transfer print sheet to the transfer material, it is possible to suppress the decrease in the chroma of the color image layer when a part of the color image layer is embedded in the transfer material adhesive layer, and a more vivid image with higher reproducibility can be formed.

[0164] FIG. 5 is a schematic view of an example of a process cartridge in a transfer material adhesive layer forming device used in the method for manufacturing a thermal transfer print sheet according to an embodiment of the present invention. The process cartridge 110 has an electrostatic latent image carrier 10, a corona charger 58, a developing device 40, a transfer roller 80, and a cleaning device 90.

[0165] (Printing method) An embodiment of the present invention provides a printing method for printing a thermal transfer print sheet manufactured by the method for manufacturing the thermal transfer print sheet on a flexible transfer material using a thermal transfer device. The flexible transfer material is not particularly limited as long as it can transfer the image of the thermal transfer print sheet using a thermal transfer device, but cloth, leather, plastic film, etc. are preferred.

[0166] <Thermal transfer device> A thermal transfer device is a device that thermally transfers a thermal transfer print sheet to a transfer material such as cloth or leather, and is a device that can apply heat at a uniform pressure on the press surface for a certain period of time. Specifically, for example, an iron press, a heat press, a thermal press, etc. can be mentioned, but from the point that heat can be applied uniformly and at a constant pressure, it is preferable to use a thermal press. Also, thermal transfer may be performed with a commercially available iron or the like. The thermal transfer device used in the printing method of the present invention may be a generally sold thermal transfer device. Specifically, for example, GFH-380, GHP-300 (above, System Graphy Co., Ltd.), HPT234PS1, HSP-5400, HP-4536A-12, HP-54A, HP-84A, HSP-1513PV-AT, HSP-1010 (above, HASHIMA), TS-ONE (Sister), TP630M, TP700A (Horizon), etc. can be mentioned.

[0167] Since uniform heat and pressure can be applied to the entire surface of the transfer material and an image after thermal transfer can be obtained without leaving a press mark on the transfer material, it is preferable that the area of the press surface of the thermal transfer device is larger than the area of the transfer material. This is the same when performing thermal transfer using a thermal transfer print sheet in which a color image layer and a transfer material adhesive layer are formed on a transfer material such as a T-shirt. The temperature for thermal transfer varies depending on the material and thickness of the transfer material, but it is preferably higher than the softening point Ts of the toner for the transfer material adhesive layer and lower than Th - 20°C, which is lower than the heat-resistant temperature Th of the transfer material. The pressure for thermal transfer is preferably low as long as transfer is possible, 1000 g / cm 2 The following is preferable, 600 g / cm 2 The following is more preferable, 300 g / cm 2 The following is even more preferable.

Examples

[0168] Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0169] (Preparation of toner for transfer material adhesive layer) [Production Example of Toner 1 for Transfer Material Adhesive Layer] - Raw materials of toner 1 for transfer material adhesive layer- · Polyurethane resin ECOFREEN POWDER (manufactured by ECOFREEN, softening point 120 °C, glass transition temperature -29 °C) 30 parts by mass · Polyester resin RN-306SF (manufactured by Kao Corporation, softening temperature 100 °C, glass transition temperature 60 °C) 60 parts by mass · Wax dispersant (EXD-001, manufactured by Sanyo Chemical Industries, Ltd.) 5 parts by mass · Ester wax (LW-13, manufactured by Sanyo Chemical Industries, Ltd.) 5 parts by mass · Titanium oxide white pigment PF-739 (manufactured by Ishihara Sangyo Co., Ltd.) 80 parts by mass

[0170] The raw materials of the above toner 1 for transfer material adhesive layer were preliminarily mixed using a Henschel mixer (FM20B, manufactured by Nippon Coke & Engineering Co., Ltd.), and then melted and kneaded at a temperature of 100 to 130 °C using a single-screw kneader (manufactured by Buss, co-kneader, BUSS co-kneader "MDK46-11D"). The obtained kneaded product was cooled and rolled to a thickness of 1 mm or less while being cooled by a rolling roll, and coarsely pulverized to 200 to 300 μm using a rotorplex (manufactured by Toa Machinery Co., Ltd.). What was obtained in this coarsely pulverizing step is a coarsely pulverized product of the toner component melt-kneaded product. Next, using a counter jet mill (100AFG, manufactured by Hosokawa Micron Corporation), it was finely pulverized while appropriately adjusting the pulverizing air pressure so that the volume average particle diameter became 10 to 15 μm, and then classified using an air classifier (EJ-LABO, manufactured by Matsubo Co., Ltd.) while appropriately adjusting the louver opening so that the volume average particle diameter was in the range of 11.0 ± 0.5 μm, to obtain toner mother particles 1 for transfer material adhesive layer. Next, 1.0 part by mass of Additive 1 (HDK-2000, manufactured by Clariant Corporation, substance name: silica) and 1.0 part by mass of Additive 2 (H05TD, manufactured by Clariant Corporation, substance name: silica) were stirred and mixed with 100 parts by mass of the obtained toner base particles for the transfer material adhesive layer using a Henschel mixer to produce Toner 1 for the transfer material adhesive layer.

[0171] [Production Example of Toner 2 for Transfer Material Adhesive Layer] -Raw Materials for Toner 2 for Transfer Material Adhesive Layer- · 40 parts by mass of polyurethane resin E780M128 (manufactured by Nippon Milk Industry Co., Ltd., 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.) Except for using the above raw materials for Toner 2 for the transfer material adhesive layer, Toner 2 for the transfer material adhesive layer was produced in the same manner as Toner 1 for the transfer material adhesive layer.

[0172] [Production Example of Toner 3 for Transfer Material Adhesive Layer] -Raw Materials for Toner 3 for Transfer 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.) Except for using the above raw materials for Toner 3 for the transfer material adhesive layer, Toner 3 for the transfer material adhesive layer was produced in the same manner as Toner 1 for the transfer material adhesive layer.

[0173] [Production Example of Toner 4 for Transfer Material Adhesive Layer] -Raw materials for the toner 4 for the transfer 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 Co., Ltd.) The toner 4 for the transfer material adhesive layer was manufactured in the same manner as the toner 1 for the transfer material adhesive layer, except that the above raw materials for the toner 4 for the transfer material adhesive layer were used.

[0174] [Production example of toner 5 for transfer material adhesive layer] The toner 5 for the transfer material adhesive layer was manufactured in the same manner as the toner 1 for the transfer material adhesive layer, except that the volume average particle diameter after air classification of the above toner 1 for the transfer material adhesive layer was set to 15 μm.

[0175] [Preparation of carrier 1] -Raw materials for the carrier- · 710 parts by mass of IP solvent · 220 parts by mass of mixed fine particles of aluminum oxide, tin acid value, and phosphorus pentoxide (ECF-800, manufactured by Titanium Industry Co., Ltd.) · 40 parts by mass of silicone·acrylic resin·toluene solution (R5T, manufactured by Toray Dow Coating Co., Ltd.) · 400 parts by mass of polyalkenylsiloxane·toluene solution (RCF-2130, manufactured by 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 raw materials of the above carrier 1 were dispersed with a homomixer for 20 minutes to prepare a resin layer coating solution. Using a fluidized bed type coating apparatus, the resin layer coating solution was applied to the surface of 7,200 parts by mass of spherical manganese-magnesium ferrite with an average particle diameter of 50 μm to produce carrier 1.

[0177] <Production of developer for transfer material adhesive layer> Using a ball mill, 5 parts by mass of the toner 1 for the transfer material adhesive layer and 95 parts by mass of carrier 1 were mixed to produce developer 1 for the transfer material adhesive layer. Regarding the toners 2 to 5 for the transfer material adhesive layer, they were each mixed with carrier 1 in the same manner as developer 1 for the transfer material adhesive layer to produce developers 2 to 5 for the transfer material adhesive layer. Next, transfer printed sheets were produced using each of the produced developers for the transfer material adhesive layer.

[0178] <Formation of color image layer> As a color image layer forming apparatus, a production printer RICOH Pro C7200S manufactured by Ricoh was used. For the transfer substrates 1 and 2 described later, color toner was output and printed using mirror image information in which a color chart of CMYRGB gradation printing patches was reversed left and right to form a color image layer. The standard adhesion amount of each toner was set to 0.45 mg / cm 2 Thereby. Incidentally, the toner (RICOH Pro toner C7200 series) installed in the production printer RICOH Pro C7200S manufactured by Ricoh is a toner containing a polyester resin, a thermoplastic elastomer, and wax. As transfer substrates, transfer substrate 1 (WoW Light 8.0 A3 sheet manufactured by Paiotech) and transfer substrate 2 (CRV-4 A3 sheet manufactured by Cowatechnoa) were used.

[0179] <Formation of transfer material adhesive layer> As a transfer material adhesive layer forming apparatus, a Ricoh MFP IM C6000 (Ricoh Company, Ltd.) capable of mounting four developing units was used. On each of five sheets of each of the transfer substrates 1 and 2 on which a color image layer was formed, a transfer material adhesive layer was formed on the color image layer according to the following output conditions 1 to 12 so that the shape and position of the transfer material adhesive layer were the same as those of the color image layer, and a thermal transfer print sheet was produced. In the thermal transfer print sheet, the transfer material adhesive layer was formed so that the edge of the transfer material adhesive layer protruded 0.68 mm outward from the edge of the color image layer.

[0180] (Output condition 1) All four developing units (in the order of outputting developer to the intermediate transfer body: first developing unit - second developing unit - third developing unit - fourth developing unit) that can be mounted on the transfer material adhesive layer forming apparatus were equipped with the developer 1 for the transfer material adhesive layer, printed using all four developing units, and the transfer material adhesive layer was formed in one printing. The developing amount from each developing unit was at most 3.2 mg / cm 2 The thickness of the white transfer material adhesive layer formed by being output from the four developing units was 80 μm.

[0181] (Output condition 2) All four developing units that can be mounted on the transfer material adhesive layer forming apparatus were equipped with the developer 2 for the transfer material adhesive layer, printed using all four developing units, and the transfer material adhesive layer was formed in one printing. The developing amount from each developing unit was at most 3.2 mg / cm 2 The thickness of the white transfer material adhesive layer formed by being output from the four developing units was 80 μm.

[0182] (Output condition 3) All four developing units that can be mounted on the transfer material adhesive layer forming apparatus were equipped with the developer 5 for the transfer material adhesive layer, printed using all four developing units, and the transfer material adhesive layer was formed in one printing. The developing amount from each developing unit was at most 4.8 mg / cm 2It was 120 μm in thickness of the white transfer material adhesive layer formed by being output from the four developing devices.

[0183] (Output condition 4) All four developing devices that can be mounted on the transfer material adhesive layer forming device were made to be provided with the developer 2 for the transfer material adhesive layer. In the transfer material adhesive layer forming device, printing was performed using three developing devices, the first developing device - the second developing device - the third developing device, at a developing voltage of 800 V, which is a developing condition where carrier adhesion does not occur and the developing amount of toner is maximized, and the transfer material adhesive layer was formed in one printing. The formed white transfer material adhesive layer was 60 μm.

[0184] (Output condition 5) All four developing devices that can be mounted on the transfer material adhesive layer forming device were made to be provided with the developer 2 for the transfer material adhesive layer. In the transfer material adhesive layer forming device, printing was performed using two developing devices, the first developing device - the second developing device, at a developing voltage of 800 V, which is a developing condition where carrier adhesion does not occur and the developing amount of toner is maximized, and the transfer material adhesive layer was formed in one printing. The formed white transfer material adhesive layer was 40 μm.

[0185] (Output condition 6) Among the four developing devices that can be mounted on the transfer material adhesive layer forming device, three developing devices, the first developing device - the second developing device - the third developing device, were made to be provided with the developer 1 for the transfer material adhesive layer, and the fourth developing device was made to be provided with the developer 3 for the transfer material adhesive layer. Printing was performed using all four developing devices, and the transfer material adhesive layer was formed in one printing. The developing amount of the first developing device was at most 2.7 mg / cm 2 and the transparent transfer material adhesive layer formed by the output of the first developing device alone was 20 μm. The total thickness of the transfer material adhesive layer output using all the developing devices was 80 μm, the transparent transfer material adhesive layer was 20 μm, and the white transfer material adhesive layer was 60 μm.

[0186] (Output condition 7) All four developing devices that can be mounted on the transfer material adhesive layer forming apparatus are provided with the developer 4 for the transfer material adhesive layer, and printing is performed using all four developing devices, and the transfer material adhesive layer is formed in a single printing. The developing amount from each developing device is at most 3.2 mg / cm 2 and the thickness of the white transfer material adhesive layer formed by being output from the four developing devices was 80 μm.

[0187] (Output condition 8) All four developing devices that can be mounted on the transfer material adhesive layer forming apparatus were made to be provided with the developer 4 for the transfer material adhesive layer. In the transfer material adhesive layer forming apparatus, printing was performed using two developing devices, the first developing unit - the second developing unit, at a developing voltage of 800 V, which is a developing condition where carrier adhesion does not occur and the developing amount of toner is maximized, and the transfer material adhesive layer was formed in a single printing. The formed white transfer material adhesive layer was 40 μm.

[0188] (Output condition 9) All four developing devices that can be mounted on the transfer material adhesive layer forming apparatus were made to be provided with the developer 2 for the transfer material adhesive layer. In the transfer material adhesive layer forming apparatus, printing was performed using only one developing device, the first developing device, at a developing voltage of 800 V, which is a developing condition where carrier adhesion does not occur and the developing amount of toner is maximized, and the transfer material adhesive layer was formed in a single printing. The formed white transfer material adhesive layer was 20 μm.

[0189] (Output condition 10) All four developing devices that can be mounted on the transfer material adhesive layer forming apparatus were made to be provided with the developer 2 for the transfer material adhesive layer. The developing amount from each developing unit was set to 2.4 mg / cm 2 respectively, and printing was performed using two developing devices, the first developing device - the second developing device, and the transfer material adhesive layer was formed in a single printing. The formed white transfer material adhesive layer was 30 μm.

[0190] (Output condition 11) All four developing devices that can be mounted on the transfer material adhesive layer forming apparatus were equipped with the developer 1 for the transfer material adhesive layer. In the transfer material adhesive layer forming apparatus, after forming the transfer material adhesive layer by printing using only the first developing device at a developing voltage of 800 V, which is the developing condition where the amount of toner development is maximized without carrier adhesion, the printed thermal transfer print sheet was set again in the transfer material adhesive layer forming apparatus and printed in the same manner, and this was repeated so that it was printed a total of 4 times. However, a misregistration occurred where the color image layer protruded from the range where the transfer material adhesive layer was formed at the second time, a large misregistration also occurred at the third time, and a jam occurred at the fourth time, so the output was aborted.

[0191] (Output condition 12) All four developing devices that can be mounted on the transfer material adhesive layer forming apparatus were equipped with the developer 1 for the transfer material adhesive layer. The developing amount from each developing unit was set to 1.6 mg / cm 2 After forming the transfer material adhesive layer by printing using only two developing devices, the first developing device and the second developing unit, the printed thermal transfer print sheet was set again in the transfer material adhesive layer forming apparatus and printed in the same manner, and this was repeated so that it was printed a total of 3 times. However, a misregistration occurred where the color image layer protruded from the range where the transfer material adhesive layer was formed at the second time, and a large misregistration also occurred at the third time. Also, offset occurred during fixing at the portion where the transfer material adhesive layer could be formed in three layers.

[0192] Note that for each output condition, 5 consecutive thermal transfer print sheets using the transfer substrate 1 were printed, and then 5 consecutive thermal transfer print sheets using the transfer substrate 2 were printed.

[0193] For the thermal transfer printed sheets obtained under output conditions 1 to 12, for each transfer substrate and each output condition, 2 out of 5 sheets were randomly selected. For each thermal transfer printed sheet, at an arbitrary position on a black T-shirt (4.7 ounces, dry silk touch T-shirt, lovely bleed, manufactured by United Athle) as the material to be transferred, place it such that the adhesive layer for the material to be transferred is in contact with the surface of the T-shirt, and set it on a heat press machine (Model HTP234PS1 manufactured by Pyrotech). Apply heat and pressure at a temperature of 130 °C for 20 seconds and a pressure of 300 g / cm 2 After applying heat and pressure, peel off the transfer substrate, and thermally transfer and fix the color image layer and the adhesive layer for the material to be transferred onto the black T-shirt. Furthermore, place a release paper on the color image layer, and again apply heat and pressure at a temperature of 130 °C for 20 seconds and a pressure of 300 g / cm 2 After applying heat and pressure, peel off the release paper to complete the printed T-shirt. Examples 1 to 6 were cases where thermal transfer was performed on a black T-shirt using the thermal transfer printed sheets prepared under output conditions 1 to 6, and Comparative Examples 1 to 6 were cases where thermal transfer was performed on a black T-shirt using the thermal transfer printed sheets prepared under output conditions 7 to 12.

[0194] [Evaluation] [Printing reproducibility] For 5 thermal transfer printed sheets using transfer substrate 1 and 5 thermal transfer printed sheets using transfer substrate 2, each output under output conditions 1 to 12, the misalignment of the color image layer and the adhesive layer for the material to be transferred was visually evaluated. The results of the evaluation according to the following evaluation criteria are shown in Table 1. [Evaluation criteria] Among all 10 thermal transfer printed sheets, in all sheets, the color image layer is completely included within the printing range of the adhesive layer for the material to be transferred: A (good) Among all 10 thermal transfer printed sheets, if there is one or more sheets where the color image layer protrudes outside the adhesive layer for the material to be transferred: B (unacceptable)

[0195] [Fixing property] The color bleeding and peeling of the color image layers of each printed T-shirt thermally transferred and fixed using two thermal transfer printing sheets with a transfer substrate 1 and two thermal transfer printing sheets with a transfer substrate 2 were evaluated. Table 1 shows the results evaluated according to the following evaluation criteria. (Evaluation Criteria) For all printed T-shirts, no color bleeding or peeling of the color image layer: A (Good) For some of the printed T-shirts, there is color bleeding and peeling of the color image layer: B (Poor)

[0196] <Chroma> Regarding the chroma of the color image layers of the printed T-shirts thermally transferred and fixed with two thermal transfer printing sheets using transfer substrate 1 and two thermal transfer printing sheets using transfer substrate 2 respectively, the chroma of the R solid patches of C100% and M100% in the color chart was measured using X-rite eXact (manufactured by X-Rite) under the conditions of m0, UV komi / ISO 13655:2017. Table 1 shows the results evaluated according to the following evaluation criteria. (Evaluation Criteria) The chroma *C of the color image layers of all printed T-shirts is 60 or more: A (Excellent) The chroma *C of the color image layers of all printed T-shirts is 50 or more and less than 60: B (Good) The chroma *C of the color image layers of all printed T-shirts is 45 or more and less than 50: C (Acceptable) The chroma *C of the color image layers of all printed T-shirts is less than 45: D (Poor)

[0197] <Washing Fastness Evaluation Method> For the printed T-shirts produced in the examples and comparative examples, a washing fastness test was conducted according to the test method of JIS0844:2011 and evaluated according to the following evaluation criteria. The results are shown in Table 1. (Evaluation Criteria) For all printed T-shirts, the gray scale rank for JIS0844 color fading of the color image layer is 5, and there are no cracks in the color image layer and the adhered layer of the material to be transferred even after repeating washing 10 times: A (Excellent) In all printed T-shirts, the gray scale rank for JIS0844 fading of the color image layer is 5, and when 10 washings are repeated, cracks occur in a part of the color image layer and the transfer material adhesion layer: B (Good) In all printed T-shirts, the gray scale rank for JIS0844 fading of the color image layer is 4 to 3: C (Acceptable) In all printed T-shirts, the gray scale rank for JIS0844 fading of the color image layer is 2 to 1: D (Unacceptable)

[0198]

Table 1

[0199] Those with an evaluation result of A for printing reproducibility and fixability, and an evaluation result of A to C for chroma and washing fastness were judged to be feasible as the present invention and were judged as "qualified". Others were judged as "unqualified".

[0200] In Examples 1 to 6, the evaluation results for printing reproducibility and fixability were all A, and the evaluation results for chroma and washing fastness were A to C. Therefore, they were feasible as the present invention and were judged as "qualified".

[0201] In Comparative Examples 1 and 2, since the toner for the transfer material adhesion layer does not contain a polyurethane resin, the color image layer on the printed T-shirt is likely to fade, and the fixability and washing fastness are inferior. Therefore, they were judged as "unqualified" as the present invention.

[0202] In Comparative Examples 3 and 4, since the thickness of the transfer material adhesion layer was less than 40 μm and the chroma of the color image layer on the printed T-shirt was low, they were judged as "unqualified" as the present invention.

[0203] In Comparative Examples 5 and 6, since the adhesive layer for the material to be transferred was formed by printing multiple times, the print reproducibility was poor. Also, in Comparative Example 5, jamming occurred during the fourth printing, so the fixability could not be evaluated. In Comparative Example 6, offset occurred during fixing and the fixability was poor. Therefore, Comparative Examples 5 and 6 were judged as "failed" as the present invention. Thus, for Comparative Examples 5 and 6, the evaluation of color density and washing fastness was not performed.

[0204] As described above, the embodiments have been explained. However, the above embodiments are presented as examples, and the present invention is not limited by the above embodiments. The above embodiments can be implemented in various other forms, and can be changed within the scope that those skilled in the art can conceive, such as addition, modification, deletion, etc. As long as the functions and effects of the present invention are achieved in any aspect, they are included in the scope of the present invention. Also, various combinations, omissions, replacements, changes, etc. can be made without departing from the gist of the invention. These embodiments and their modifications are included in the scope and gist of the invention, and are included in the invention described in the claims and its equivalent scope.

[0205] From the above, it has been shown that the method for producing a thermal transfer print sheet of the present invention is a method for producing a thermal transfer print sheet that can print a toner image having sufficient flexibility and strength with high print reproducibility, which does not reduce the color density in a dark-colored material to be transferred and is sufficiently fixed to a flexible material to be transferred with large unevenness.

[0206] As an aspect of the present invention, for example, it is as follows. <1>A method for producing a thermal transfer print sheet using a transfer base material, a color image layer forming device, and an electrophotographic adhesive layer forming device for the material to be transferred, comprising: A color image layer forming step of forming a color image layer by the color image layer forming device; An adhesive layer forming step for the material to be transferred of forming an adhesive layer for the material to be transferred having a thickness of 40 μm or more and 120 μm or less by one printing by the adhesive layer forming device for the material to be transferred, The adhesive layer forming device for the material to be transferred has a plurality of developing devices, Of the plurality of developing devices, two or more developing devices are provided with a toner for a white transfer material adhesive layer containing a polyester resin, a polyurethane resin, and a release agent, and are developing devices used for forming the transfer material adhesive layer. A method for producing a thermal transfer print sheet. <2>The method for producing a thermal transfer print sheet according to <1>, wherein the transfer material adhesive layer forming device further includes a developing device provided with a transparent toner for a transfer material adhesive layer containing a polyester resin, a polyurethane resin, and a release agent, and is used for forming the transfer material adhesive layer. <3>The method for producing a thermal transfer print sheet according to <1> or <2>, wherein the thickness of the white layer in the transfer material adhesive layer is 40 μm or more. <4>In the color image layer forming step, after forming the color image layer on the transfer base material, <8>The method for producing a thermal transfer print sheet according to any one of <1> to <3>, wherein in the transfer material adhesive layer forming step, the transfer material adhesive layer is formed on the color image layer. <5>In the transfer material adhesive layer forming step, a transparent transfer material adhesive layer is formed on the color image layer, <12>The method for producing a thermal transfer print sheet according to <4>, wherein a white transfer material adhesive layer is formed on the transparent transfer material adhesive layer. <6>The method for producing a thermal transfer print sheet according to any one of <1> to <5>, wherein the volume average particle diameter of the toner for the transfer material adhesive layer is 10 μm or more and 20 μm or less. <7>A printing method of printing a thermal transfer print sheet produced by the method for producing a thermal transfer print sheet according to any one of <1> to <6> on a flexible transfer material using a thermal transfer device. <8>The printing method according to <7>, wherein the flexible transfer material is cloth, leather, or a plastic film.

[0207] According to the method for producing a thermal transfer print sheet according to any one of <1> to <6> above and the printing method according to <7> or <8> above, various conventional problems can be solved and the object of the present invention can be achieved.

Explanation of Signs

[0208] 45K First Developer 45Y Second Developer 45M Third Developer 45C Fourth Developer 61 Developer 95 Transfer Substrate with Color Image Layer Formed 100A Transfer Material Adhesive Layer Forming Device 100B Transfer Material Adhesive Layer Forming Device

Prior Art Documents

Patent Documents

[0209]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Claims

1. A method for producing a thermal transfer print sheet using a transfer substrate, a color image layer forming device, and an electrophotographic transfer material adhesive layer forming device, comprising: a color image layer forming step of forming a color image layer by the color image layer forming device; a transfer-receiving material adhesive layer forming step of forming a transfer-receiving material adhesive layer having a thickness of 40 μm or more and 120 μm or less in one printing by the transfer-receiving material adhesive layer forming device, The transfer material adhesive layer forming device has a plurality of developing units, A method for producing a thermal transfer print sheet, wherein two or more of the multiple developing devices are equipped with a white toner for a transfer material adhesive layer containing a polyester resin, a polyurethane resin, and a release agent, and are developing devices used to form the transfer material adhesive layer.

2. The method for producing a thermal transfer print sheet according to claim 1, wherein the transfer material adhesive layer forming device is provided with a transparent transfer material adhesive layer toner containing a polyester resin, a polyurethane resin, and a release agent, and further has a developing device used to form the transfer material adhesive layer.

3. 3. The method for producing a thermal transfer print sheet according to claim 1, wherein the thickness of the white layer in the adhesive layer for the transfer material is 40 [mu]m or more.

4. In the color image layer forming step, after the color image layer is formed on the transfer substrate, 3. The method for producing a thermal transfer print sheet according to claim 1, wherein in the transfer-receiving material adhesive layer forming step, the transfer-receiving material adhesive layer is formed on the color image layer.

5. In the transfer-receiving-material adhesive layer forming step, a transparent transfer-receiving-material adhesive layer is formed on the color image layer, 5. The method for producing a thermal transfer print sheet according to claim 4, further comprising forming a white adhesive layer for a transfer material on said transparent adhesive layer for a transfer material.

6. 3. The method for producing a thermal transfer print sheet according to claim 1, wherein the toner for the adhesive layer of the transfer-receiving material has a volume average particle size of 10 [mu]m or more and 20 [mu]m or less.

7. 3. A printing method, comprising printing a thermal transfer print sheet produced by the method for producing a thermal transfer print sheet according to claim 1 or 2 on a flexible material to be printed with a thermal transfer device.

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

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