JP2012247473A - Image forming method, and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method for allowing formation of foil images tough enough to have sufficient adhesive strength between a foil and a foil transfer surface when the foil is transferred on a foil transfer surface formed with toner.SOLUTION: Provided is an image forming method for forming a foil transfer surface with toner having storage elastic modulus of 1.0×10N/mor more and 1.0×10N/mor less at 120°C, and then applying maximum pressure to the foil transfer surface during the time period after 0.6t relative to a nip part transit time t, and 1/8 or more and 1/2 or less of the maximum pressure during the time period from 0.3t to 0.5t. Also provided is an image forming apparatus.

Description

  The present invention relates to an image forming method and an image forming apparatus for forming a foil image on a substrate (image support), and forms a toner image called a foil transfer surface by electrophotography and transfers the foil onto the formed toner image. The present invention relates to an image forming method and an image forming apparatus for forming a foil image.

  For example, in the field of bookbinding, commercial printing, card business, or plastic molding such as cosmetic containers, a processing technique called “foil stamping” is performed. This technology, also called “hot stamping”, uses letters and patterns made of foil on the surface of the substrate by the action of heat and pressure using a pressing member called a metal stamping die, and is expressed in general printing. It is possible to impart a high-quality image with a metallic feeling or gloss that is difficult to achieve. Recently, foil transfer technology has also been developed for holograms provided for the purpose of preventing falsification and security of cash cards and credit cards.

  The transfer foil used for foil pressing has, for example, a structure in which a release agent layer is provided on a resinous film-like substrate surface, and a protective layer, a transfer material layer, and an adhesive layer are disposed thereon, and the foil The transfer material layer containing is mainly formed using metal vapor deposition or ink. The transfer foil having such a structure has been improved with the expansion of materials and applications for transferring the foil. For example, a protective layer containing an organosilicon compound and a reactive organic compound is provided to improve the durability of the foil image, or a strong protective layer is formed by irradiating an electron beam after peeling from the substrate. The transfer foil etc. which were made like were examined (for example, refer patent document 1, 2). Further, the transfer foil for the above-mentioned cash card or credit card is required to have a precise pattern and transfer that does not cause defects such as burrs and chipping. For example, a transfer material layer contains a polymer liquid crystal material. This problem is solved (see, for example, Patent Document 3).

  On the other hand, a method of performing foil transfer without taking time and labor has been studied, and a technique for forming a resin layer on a substrate using toner and transferring the foil thereon has been studied. This technique softens and melts the adhesive layer between the toner and the transfer foil by heating and adheres the resin layer and the transfer foil, and can exert a strong adhesive force between the substrate and the foil. As a specific technique, for example, a toner image is formed on a substrate to form a convex image or an image of a design pattern, and a transfer foil is superimposed on the formed toner image surface and heat-pressed to transfer the foil. Some form a foil image (see, for example, Patent Document 4).

  In addition, the toner is previously deposited on the base material, the vapor-deposited foil sheet is overlaid thereon, hot-pressed with an iron from the top, and then the vapor-deposited foil sheet is peeled off from the base material. There is also a technique for forming the image (for example, see Patent Document 5). In addition, the technology for transferring foil using toner allows the transfer of foil without using a stamping die that was required in the prior art, thus simplifying the device for shortening the foil transfer operation and transferring the foil. Can be

  In this way, the technology for forming a foil image by transferring the foil onto the foil transfer surface by heating the transfer foil in contact with the foil transfer surface formed using the toner is not troublesome. Since an image can be formed, the spread of a foil image on a printed matter such as a poster is promoted.

JP-A-9-1995 JP 2007-15159 A JP 2009-90464 A Japanese Patent Laid-Open No. 1-200985 JP 2000-127691 A

  A foil image produced by performing foil transfer under heating onto a foil transfer surface formed using toner has an adhesive force obtained by softening the toner and an adhesive force obtained by melting the adhesive layer of the transfer foil. Since it acts synergistically, a certain degree of strength is imparted. In addition, a printed matter using a foil image can have an eye-catching finish due to metallic luster, hologram, or the like, so that an impact finish can be expected as the area of the foil image on the substrate increases. For example, if characters or backgrounds in flyers or posters are finished with metallic luster or holograms, the portions are conspicuous and are considered to contribute greatly to the improvement of the advertising effect.

  In the future, it is fully anticipated that a system will be established for producing on-demand printed materials having a large area occupied by foil images, for example, at the level of several hundred to several thousand sheets. And in the printed matter in which the area occupied by the foil image is large, the amount of heat necessary for softening the toner image and melting the transfer foil adhesive layer is large, so from the viewpoint of securing the adhesive strength of the foil image, it is sufficient to transfer the foil. Heating is required.

  However, it is required to quickly produce a certain number of printed materials such as posters, and it is difficult to secure a sufficient heating time when transferring the foil. In addition, it is fully assumed that the printed matter including the foil image forms a toner image for the foil image to transfer the foil, and also forms a full-color image, and more than a monochrome print creation. Time is needed. From this point of view, there has been a demand for a technique that can perform foil transfer quickly and obtain a foil image having sufficient adhesive strength.

  In the present invention, when a foil is transferred onto a foil transfer surface made of toner, for example, even if the area occupied by the foil image is large, a sufficient adhesive strength is provided between the foil and the foil transfer surface. It is an object to provide an image forming method capable of forming a foil image. Specifically, the foil image occupies a large area, and it is possible to produce an eye-catching finish printed with a metallic luster or hologram, and a foil image with excellent durability that the formed foil does not peel off. An image forming method capable of being formed is provided.

The present inventor has found that the above-described problem can be solved by any of the configurations described below. That is, the invention described in claim 1
"at least,
Exposing the photoreceptor to form an electrostatic latent image;
Supplying toner to the photoconductor on which an electrostatic latent image is formed to form a foil transfer surface;
Transferring the foil transfer surface formed on the photoreceptor to a substrate;
Fixing the foil transfer surface transferred to the substrate;
Supplying a transfer foil to a substrate on which the foil transfer surface is fixed;
An image forming method comprising a step of transferring the foil to the foil transfer surface by heating the transfer foil in a state of being in contact with the foil transfer surface,
The toner used for forming the foil transfer surface has a storage elastic modulus G ′ at 120 ° C. of 1.0 × 10 ³ N / m ² or more and 1.0 × 10 ⁴ N / m ² or less,
The process of transferring the foil to the foil transfer surface is as follows:
When the transfer foil and the foil transfer surface pass through a nip formed by a heating member and a pressure member, the foil is transferred to the foil transfer surface,
When t is the time for the transfer foil and the foil transfer surface to pass through the nip portion,
A maximum pressure is applied to the transfer foil and the foil transfer surface between 0.6 t and 1.0 t; and
An image forming method, wherein pressure is applied to the transfer foil and the foil transfer surface under a heated state from 0.3 t until the maximum pressure is applied. ].

The invention described in claim 2
“The pressure applied to the transfer foil and the foil transfer surface from 0.3 t to the time when the maximum pressure is applied is 1/8 to 1/3 of the maximum pressure. The image forming method according to claim 1. ].

The invention according to claim 3
The image forming method according to claim 1, wherein the maximum pressure applied to the transfer foil and the foil transfer surface is 200 kPa or more and 450 kPa or less. ].

The invention according to claim 4
The said heating member is a heating roll, The said pressurizing member has a pressing member which presses at least a belt member and the said belt member, The any one of Claims 1-3 characterized by the above-mentioned. Image forming method. ].

The invention described in claim 5
“The binder resin contained in the toner used to form the foil transfer surface is
The image forming method according to claim 1, comprising at least a polymer formed using a vinyl monomer having a carboxy group. ].

The invention described in claim 6
“The binder resin contained in the toner used to form the foil transfer surface is
The image forming method according to claim 5, comprising at least a polymer formed using methacrylic acid. ].

The invention described in claim 7
“The toner used to form the foil transfer surface is
The image forming method according to claim 6, comprising at least a copolymer resin formed using styrene, n-butyl acrylate, and methacrylic acid. ].

The invention according to claim 8 provides:
“The toner used to form the foil transfer surface is
At least a step of producing resin fine particles through a step of performing a polymerization reaction a plurality of times;
The image forming method according to any one of claims 5 to 7, wherein the image forming method is produced through a step of aggregating and fusing the resin fine particles produced in the step in an aqueous medium. ].

The invention according to claim 9 is:
"at least,
A photoreceptor that forms an electrostatic latent image by exposure by an exposure means;
A foil transfer surface forming means for supplying a toner to the photoreceptor on which an electrostatic latent image is formed to form a foil transfer surface;
Transfer means for transferring the foil transfer surface formed on the photoreceptor to a substrate;
Fixing means for fixing the foil transfer surface transferred to the substrate;
A transfer foil supply means for supplying a transfer foil to the substrate on which the foil transfer surface is fixed by the fixing means;
Foil transfer in which the transfer foil supplied by the transfer foil supply means is brought into contact with the foil transfer surface, and heating is performed with the transfer foil in contact with the foil transfer surface to transfer the foil to the foil transfer surface. An image forming apparatus having means,
The toner supplied from the foil transfer surface forming means has a storage elastic modulus G ′ at 120 ° C. of 1.0 × 10 ³ N / m ² or more and 1.0 × 10 ⁴ N / m ² or less,
The foil transfer means is at least
It has a heating member and a pressure member that form a nip portion that allows the foil transfer surface and the transfer foil to pass in contact with each other,
The heating member and the pressure member are
When t is the time for the transfer foil and the foil transfer surface to pass through the nip portion,
Applying a maximum pressure to the transfer foil and the foil transfer surface between 0.6 t and 1.0 t; and
An image forming apparatus characterized in that a pressure is applied while heating the transfer foil and the foil transfer surface between 0.3 t and the time when the maximum pressure is applied. ].

The invention according to claim 10 is:
“The pressure applied to the transfer foil and the foil transfer surface from the time 0.3 t to the time when the maximum pressure is applied is 1/8 to 1/3 of the maximum pressure. The image forming apparatus according to claim 9. ].

The invention according to claim 11
11. The image forming apparatus according to claim 9, wherein a maximum pressure applied to the transfer foil and the foil transfer surface by the foil transfer unit is 200 kPa or more and 450 kPa or less. ].

The invention according to claim 12
“The foil transfer means
The image forming apparatus according to any one of claims 9 to 11, wherein the heating member includes a heating roll, and the pressing member includes at least a belt member and a pressing member that presses the belt member. apparatus. ].

The invention according to claim 13
“The binder resin contained in the toner used to form the foil transfer surface is
The image forming apparatus according to claim 9, comprising at least a polymer formed using a vinyl monomer having a carboxy group. ].

The invention according to claim 14
“The binder resin contained in the toner used to form the foil transfer surface is
The image forming apparatus according to claim 13, comprising at least a polymer formed using methacrylic acid. ].

The invention according to claim 15 is:
“The toner used to form the foil transfer surface is
The image forming apparatus according to claim 14, comprising at least a copolymer resin formed using styrene, n-butyl acrylate, and methacrylic acid. ].

The invention described in claim 16
“The toner used to form the foil transfer surface is
At least a step of producing resin fine particles containing the copolymer resin through a step of performing a plurality of polymerization reactions;
16. The image forming apparatus according to claim 13, wherein the image forming apparatus is manufactured through a process of aggregating and fusing the resin fine particles prepared in the process in an aqueous medium. ].

  In the present invention, sufficient adhesive strength is imparted between the foil transfer surface and the foil, and a foil image having excellent durability can be formed. That is, the storage elastic modulus of the toner that forms the foil transfer surface, the timing for applying the maximum pressure to the foil transfer surface and the transfer foil, and the configuration in which pressure is applied under the heating state before the maximum pressure is applied are combined. It has been found that the above-described effects are exhibited.

  That is, with the above configuration, since the maximum pressure is applied in a state where the heat is sufficiently transferred to the transfer foil and the image support, the foil transfer surface, a strong adhesive force is expressed between the foil and the foil transfer surface, A foil image having excellent durability can be formed. Further, there is no burr or partial omission on the formed foil image, and it is possible to form a foil image with a good finish.

  Therefore, according to the present invention, even when a printed matter having a large area occupied by a foil image is created, the foil transfer is performed by applying a maximum pressure in a state where the foil transfer surface made of toner is sufficiently softened. Therefore, it is possible to stably produce a printed matter with a foil image having a good finish.

It is the schematic of the foil transcription | transfer apparatus which has a heating roller and a seamless pressure belt. It is a schematic diagram explaining the cross-sectional shape of a pressure pad. It is a schematic diagram which shows the procedure which transfers foil on the foil transfer surface formed on the base | substrate. It is the schematic of the foil transfer surface formation apparatus which forms a foil transfer surface by an electrostatic latent image system. 1 is a cross-sectional configuration diagram of an image forming apparatus capable of forming a foil image and a full-color toner image. It is the schematic which shows the example of arrangement | positioning of an intermediate transfer belt, foil transfer apparatus, and a transfer foil supply part. It is a schematic diagram which shows the cross-section of transfer foil. It is the schematic of the pressure distribution system which measures the pressure distribution in a nip part. It is a schematic diagram which shows the foil image layout of the sample for evaluation (printed material) used in the Example.

The present invention relates to an image forming method in which a layer called a foil transfer surface is formed at a location where a foil on a substrate is transferred, and the foil is transferred onto the layer to form a foil image. In the present invention, the foil transfer surface is formed using a toner having a storage elastic modulus G ′ at 120 ° C. of 1.0 × 10 ³ N / m ² or more and 1.0 × 10 ⁴ N / m ² or less. The transfer of the foil onto the foil transfer surface is performed by passing the transfer foil and the foil transfer surface through a nip formed by a heating member and a pressure member. Then, when the time for the transfer foil and the foil transfer surface to pass through the nip portion is t, the maximum pressure is applied to the transfer foil and the foil transfer surface after 0.6 t, and the time from 0.3 t to 0.5 t In addition, a pressure of 1/8 to 1/2 of the maximum pressure is applied to the transfer foil and the foil transfer surface. In the present invention, it has been found that these problems can be solved by these configurations.

  In order to develop a strong adhesive force between the foil transfer surface and the foil when creating a printed matter in which the foil image occupies a large area, the present inventor uses a foil transfer surface made of toner even if the area is large. It was thought that it was necessary to soften it sufficiently so that the transfer foil could be crimped at the same time. Also, if the foil transfer surface and the transfer foil are crimped too strongly, the foil transfer surface may be deformed, so in order to transfer the foil evenly, it is necessary to crimp it with a strong force within a short time. Thought it would be necessary.

  Therefore, the present inventor thought that the foil transfer surface and the transfer foil were pressure-bonded with a weak force in the first half of the passage through the nip portion, and found to find a timing for pressure-bonding both with a strong force in the latter half of the passage through the nip portion. That is, a small pressure is applied to the foil transfer surface and the transfer foil in the first half of the nip to efficiently conduct heat, and the maximum pressure is applied when the latter foil transfer surface is sufficiently softened to avoid deformation of the foil transfer surface. However, an attempt was made to find the timing at which the foil transfer surface and the transfer foil were firmly bonded without unevenness. In addition, it has been considered that the toner forming the foil transfer surface does not deform even if it continues to be stressed while passing through the nip portion, and also has the conflicting property that it can be sufficiently softened.

  The present inventor proceeds to study from such a viewpoint, and for the toner that forms the foil transfer surface, the storage elastic modulus is specified, and the pressure applied to the foil transfer surface and the transfer foil while passing through the nip portion is applied. It has been found that the above-mentioned problems can be solved by defining the timing.

  Hereinafter, the present invention will be described in detail.

  Here, terms used in the present invention will be described. First, the “foil transfer surface” refers to a region where a foil is transferred on a substrate such as an image support or a plastic molded article, and is formed using toner in the present invention.

  Further, in the present invention, the terms “product” and “substrate” are used, and both are constituted by a support called an “image support” capable of forming an image by a known image forming method. Is. Here, “product” refers to a product that has a form in which at least a foil is transferred onto a “substrate” and is decorated with the foil, and is usable by a user. The term “substrate” refers to a material that is decorated with a foil, and specifically, what is called an image support such as paper or PET (polyethylene terephthalate) base is representative, but a three-dimensional plastic Molded products and the like are also included in the category. Furthermore, in the present invention, a substrate that is in a previous stage of a state where it can be provided to the user, such as a member having a foil transfer surface or a member having a foil transferred thereon, is also called a “substrate”.

  Furthermore, the “foil” in the present invention is also referred to as “transfer foil”, and is used to give a character or a pattern having a metallic feeling or glossiness difficult to express on general printing on an image support. Is. There are various types of transfer foils, such as gold and silver foils, color pigment foils, and hologram foils, depending on the type of expression, but the type is not limited in the present invention. By using these transfer foils, it is possible to form a golden or silver image, a color image with a metallic luster, or a hologram image. The transfer foil has a layer structure as shown in FIG. In other words, it has a structure in which a release layer, a foil layer, an adhesive layer, and the like are provided on a base support, and can be adhered to a foil transfer surface formed of toner on an image support. Is. In addition, the layer of foil is comprised from a colored layer, a vapor deposition layer, etc., and a mold release layer is also called a peeling layer.

First, an image forming method according to the present invention will be briefly described. The image forming method according to the present invention includes at least
Forming a latent electrostatic image by exposing the photoreceptor;
Supplying a toner to the photoreceptor on which the electrostatic latent image is formed to form a foil transfer surface;
Transferring the foil transfer surface formed on the photoreceptor to a substrate;
Fixing the foil transfer surface transferred to the substrate;
Supplying the transfer foil to the substrate on which the foil transfer surface is fixed;
The method includes a step of transferring the foil onto the foil transfer surface by heating the transfer foil in contact with the foil transfer surface.

The image forming method according to the present invention forms a foil transfer surface using a toner having a storage elastic modulus G ′ at 120 ° C. of 1 × 10 ³ N / m ² or more and 1 × 10 ⁴ N / m ² or less. is there. In addition, the above-mentioned “step of heating the transfer foil in contact with the foil transfer surface and transferring the foil to the foil transfer surface” is a nip portion formed by a heating member and a pressure member. Are passed through the transfer foil and the foil transfer surface. When the time for the transfer foil and the foil transfer surface to pass through the nip portion is t, the maximum pressure is applied to the transfer foil and the foil transfer surface after 0.6 t, and the maximum pressure is applied from 0.3 t. In the meantime, pressure is applied to the transfer foil and the foil transfer surface under heating.

  Here, the maximum pressure applied to the transfer foil and the foil transfer surface is preferably 200 kPa to 450 kPa, and the pressure applied between 0.3 t and the time when the maximum pressure is applied is the maximum pressure. The thing of the magnitude | size of 1/8 or more and 1/3 or less is preferable.

  Here, a foil transfer apparatus for transferring a foil onto a foil transfer surface formed of toner corresponding to the foil transfer means in the present invention will be described. The foil transfer apparatus used in the present invention heats a substrate having a foil transfer surface and a transfer foil that are conveyed to a nip formed by a heating member and a pressure member in a state where the transfer foil is overlapped. The foil is transferred onto the foil transfer surface by applying pressure. A specific example of an apparatus that heats a foil transfer surface and a transfer foil at a nip formed by a heating member and a pressure member to transfer the foil onto the foil transfer surface is used in, for example, an electrophotographic image forming apparatus. There are fixing devices and the like.

  The foil transfer device used in the present invention applies a maximum pressure to the transfer foil and the foil transfer surface between 0.6 t and 1.0 t, where t is the nip passing time between the transfer foil and the foil transfer surface. The pressure is applied under a heating state between 0.3 t and the maximum pressure is applied. In other words, at the first half of the timing when the transfer foil and the foil transfer surface pass through the nip, an environment where a strong adhesion can be achieved by applying a certain amount of pressure in an overheated state to allow the heat to spread sufficiently. Forming. In this way, by applying pressure under the heating state at the timing before applying the maximum pressure, the maximum pressure is applied under the condition that the foil transfer surface is sufficiently softened, and the transfer foil and foil transfer This makes it possible to improve the adhesive strength between the surfaces.

  Then, the transfer foil is transferred to the foil transfer surface by applying maximum pressure when the transfer foil and the foil transfer surface pass through the nip portion, that is, when the foil transfer surface made of toner is sufficiently softened. It makes it possible to bond firmly. In this way, by applying the maximum pressure at the timing after 0.6 t, the transfer foil adheres to the sufficiently softened foil transfer surface, so that both realize high strength adhesion and the foil is transferred to the foil transfer surface. It is possible to avoid the peeling of the foil due to the fact that it cannot be transferred without bonding or the transfer of the foil with weak adhesive force.

  In the present invention, the maximum pressure of the nip portion formed by the heating member and the pressure member constituting the foil transfer apparatus is specified. The maximum pressure is measured using, for example, a commercially available pressure distribution measurement system. Is possible. In a commercially available pressure distribution measurement system, for example, a detection means called a sensor sheet composed of two film-like resin sheets is set at a measurement site, and the tactile sense is detected by contacting the sensor with the measurement site and detecting a change in pressure. Measurements are made using a type of sensor.

  The pressure distribution measurement system using the sensor sheet will be further described. FIG. 8 is a schematic diagram of a pressure distribution measurement system capable of measuring the pressure distribution in the nip portion N formed by the heating member and the pressure member. FIG. 8A is a system configuration diagram, and FIG. ) Is a schematic diagram of a sensor sheet. A pressure distribution measurement system 80 shown in FIG. 8A includes a computer 81, a sensor connector 82, and a sensor sheet 83.

  In addition, as shown in FIG. 8B, the sensor sheet 83 has two resin films 831 each provided with electrodes 832 at regular intervals, and the electrode provided on one resin film and the other resin film. The provided electrodes are arranged so as to be orthogonal to each other. The electrode 832 is called a row electrode and a column electrode because of this orthogonal arrangement, and the intersection of the row electrode and the column electrode forms a measurement point. The electrode 832 arranged in this way is formed of a conductive paste layer 833 and a pressure-sensitive conductive ink layer 834.

  The resin film 831 is made of polyethylene terephthalate (PET) having a thickness of about 0.1 mm. The conductive paste layer 833 is formed of a paste in which silver particles or carbon black is dispersed as a conductive filler in a resin. The pressure-sensitive conductive ink layer 834 is a known pressure-sensitive resistance. It is formed using an ink containing a substance.

  The pressure distribution measurement performed by the pressure distribution measurement system of FIG. 7 is performed by measuring the resistance value at the measurement point that is the intersection of the row electrode and the column electrode. That is, when no load is applied to the sensor sheet 83, the pressure-sensitive conductive ink layers 834 constituting the row electrode and the column electrode are in light contact with each other at the measurement point, and the resistance value at the measurement point at this time is several MΩ level. Value. Next, when a load is applied from both sides of the sensor sheet 83, the pressure-sensitive conductive ink layers 834 are pressed against each other at the measurement point to cause conduction and a decrease in resistance value, and the applied load is large. The resistance value decreases.

  Thus, the pressure applied to each measurement point can be detected by reading the change in the electrical resistance value at the measurement point. As a specific example of the pressure distribution measurement system usable in the present invention, for example, there is a “tactile sensor system” provided by Iwata Kogyo Co., Ltd. and Nitta Co., Ltd., and the measuring device is a sensor sheet made by Nitta Co., Ltd. “PINCH A3-40” is used.

  When performing measurement of a nip portion formed by a heating member and a pressure member with a “tactile sensor system” using the sensor sheet “PINCH A3-40”, after setting the sensor sheet in the nip portion, The pressure member is placed in a pressurized state and allowed to stand for 30 seconds. Thereafter, the pressure value p (x) (unit: kPa) at the nip portion at the coordinate x (unit: mm) in the substrate transport direction is measured, and the coordinate x in the substrate transport direction is divided by the transport speed to thereby nip the substrate. The part passage time t is calculated. And let the highest pressure value be the maximum pressure, and let the time be tmax.

  FIG. 1 shows a specific example of a foil transfer apparatus that can be used in the present invention. FIG. 1A shows a foil transfer apparatus configured to form a nip portion with a heating roller and a pressure belt. The foil transfer device 50 in FIG. 1A includes a heating roll 51 as a heating member and a seamless belt (pressure belt) 52 as a pressure member, and the use of the seamless belt 52 ensures that the nip portion N is expanded. Is possible. Further, the heat from the heating roll 51 is held, and a stable heating state is formed at the nip portion N.

  Further, inside the seamless belt 52, there are a pressing member 53 constituted by pressure pads 53a and 53b and the like, and a lubricant supply member 54 that form a nip portion N by contacting and pressing the seam belt 52 to the heating roll 51. Is provided. In the figure, 56 represents a separation claw, P represents a substrate on which a foil transfer surface H is formed, and F represents a transfer foil. The separation claw 56 is provided to prevent the base P or the transfer foil F that has passed through the nip portion N from being wound around the heating roll 51.

  The heating roll 51 is formed of a heat-resistant elastic layer 51b and a release layer (heat-resistant resin layer) 51c around a metal core (cylindrical core) 51a, and a heat source is provided inside the core 51a. A halogen lamp 55 is arranged. The surface temperature of the heating roll 51 is measured by the temperature sensor 57, and the halogen lamp 55 is feedback-controlled by a temperature control (not shown) based on the measurement signal, so that the surface of the heating roll 51 is adjusted to a constant temperature.

  The metal core 51a is made of, for example, a metal such as iron, aluminum, copper, or an alloy thereof, and the thickness is preferably about 0.1 to 2 mm in consideration of the balance between energy consumption and strength. . Further, a fluororesin such as polytetrafluoroethylene (PTFE) or tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) is used on the surface of the release layer 51c, and the thickness is preferably 10 to 500 μm. The release layer 51c is made of an elastic material such as heat-resistant silicone rubber such as LTV, RTV, or HTV, or silicone sponge rubber, and the thickness is preferably 0.1 to 30 mm.

  Next, the seamless belt 52 comes into contact with the heating roll 51 to form a nip portion N. In this way, the seamless belt 52 comes into contact with the heating roll 51 so that the heat from the heating roll 51 is stably held in the nip portion N, and the foil transfer surface and the transfer foil are softened well. A state is formed. The pressing member 53 provided inside the seamless belt 52 is arranged such that pressure pads 53 a and 53 b having a low friction layer on the surface press the heating roll 51 via the seamless belt 52. The pressing member 53 in the figure is composed of a pressure pad 53a for applying a maximum pressure to the base P and a pressure pad 53b for applying a weaker pressure than the maximum pressure to the base P. These pressure pads 53a and 53b are made of metal. It is held by a holder 53c manufactured by the above method.

  A belt travel guide is attached to the holder 53c so that the seamless belt 52 slides and rotates smoothly. The belt traveling guide is preferably made of a material having a low coefficient of friction because it rubs against the inner surface of the seamless belt 52, and is preferably made of a material having low thermal conductivity so that the heat from the seamless belt 52 is not easily taken. In addition, as a specific example of the material of the seamless belt 52, polyimide etc. are mentioned, for example.

  The pressing member 53 that applies pressure to the base P will be described. The above-described pressure pad 53a constituting the pressing member 53 shown in FIG. 1 applies the maximum pressure referred to in the present invention to the base P, and the pressure pad 53a is formed by the base P having the transfer foil F and the foil transfer surface H in the nip. It arrange | positions so that the maximum pressure may be provided when the part N is conveyed. The pressure pad 53a applies the maximum pressure to the base P at a timing after the middle stage after the base P having the transfer foil F and the foil transfer surface H starts transporting the nip portion N.

  Further, the pressure pad 53b constituting the pressing member 53 shown in FIG. 1 applies pressure to the base P at an early timing after the base P having the transfer foil F and the foil transfer surface H starts conveying the nip portion N. It is.

  The pressure pad 53a constituting the pressing member 53 will be described. In the present invention, the maximum pressure is applied at a timing of 0.6 t or more and 1.0 t or less of the nip passing time t between the transfer foil and the foil transfer surface. The timing of applying the maximum pressure in the above range is, for example, the pressure pad 53a. It can be changed by a known method such as changing the cross-sectional shape. FIG. 2A schematically shows an example of a pressure pad 53a having a different cross-sectional shape. The pressure pad 53a contacts the seamless belt 52 at a portion M shown in the leftmost diagram of FIG. Thus, a pressing force is applied by contact between the portion M and the seamless belt 52. In the present invention, as shown in the three figures from the left in FIG. 2 (a), by changing the cross-sectional shape of the part M, the portion indicated by the white arrow in the figure is pressed. To give maximum pressure. Further, the seamless belt 52 is held at a portion where a thin arrow at the end of the part is shown.

  In this manner, the pressure pad 53a that constitutes the pressing member 53 of the foil transfer device 50 has a cross-sectional shape that is in contact with the seamless belt 52, and applies maximum pressure at the location of the convex portion. The timing for applying the maximum pressure can be changed depending on the position. This will be described with reference to three figures on the right side of the second figure from the left in FIG. The pressure pad 53aa shown at the second from the left in FIG. 2A has a convex portion for applying the maximum pressure arranged at substantially the center of the portion M, and is 0.6 t when set on the foil transfer device 50. This is an example of applying the maximum pressure at an arbitrary timing later than 1.0 t later. Further, the pressure pad 53ab shown in the second from the right in FIG. 2 (a) has a convex portion for applying the maximum pressure arranged at the right end of the part M, and is set in the foil transfer device 50 in FIG. This is an example of applying the maximum pressure at a timing of 0.6 t. Further, the pressure pad 53ac shown on the right side of FIG. 2 (a) has a convex portion arranged at the left end of the portion M. When the pressure pad 53ac is set in the foil transfer device 50 of FIG. It is an example of what gives.

  Next, the pressure pad 53b constituting the pressing member 53 will be described. In the present invention, the pressure is applied at a timing until the maximum pressure is applied from 0.3t of the nip passing time t between the transfer foil and the foil transfer surface. As a specific means for applying pressure to the foil transfer surface and the transfer foil at the timing in the above range, for example, a method of pressing the seamless belt 52 using a pressure pad 53b having a cross-sectional shape shown in FIG. is there. The pressure application timing at the nip portion N can be controlled by pressing from the pressure pad 53b.

  As shown in FIG. 1, the pressure pad 53 b is a member that presses the nip portion N at a relatively early timing when the base P having the transfer foil F and the foil transfer surface H passes through the nip portion N. FIG. 2B schematically shows an example of the cross-sectional shape of the pressure pad 53b that can be used in the foil transfer device 50 shown in FIG. 1, and the contact form with the seamless belt 52 depends on the cross-sectional shape of the pressure pad 53b. By changing the pressure, it is possible to change the timing and size of pressure application.

  The timing of applying the pressing force and the magnitude of the pressing force will be described with reference to the pressure pad 53b shown in FIG. A portion Q of the pressure pad 53 b shown in FIG. 2B is a portion that contacts the seamless belt 52, and a pressing force is applied by the contact between the portion Q and the seamless belt 52. And the timing and magnitude | size which give pressing force are controlled by the width | variety and area of the site | part Q. FIG. That is, when the width of the part Q is widened, it is possible to apply a pressing force at an early timing, and when the area of the part Q is large, it is possible to apply a strong pressing force.

  The relationship between the pressure pads 53b (53ba to 53bf) shown in FIG. Here, when the pressure pad 53ba shown in the upper left of FIG. 2 (b) is set in the foil transfer device 50 of FIG. It is designed to apply a pressure that is 1/2 of the maximum pressure at a timing of 4 t. First, comparing the pressure pad 53bb and the pressure pad 53ba shown in the upper center of FIG. 2 (b), the pressure pad 53bb has the same width of the portion Q, but the area that can contact the seamless belt 52 is small. Yes. When the pressure pad 53bb is set in the foil transfer device 50 of FIG. 1 in the embodiment described later, the transfer foil and the foil transfer surface are ¼ of the maximum pressure at the timing of 0.4 t after the passage of the nip portion N starts. It is designed to apply pressure.

  Next, comparing the pressure pad 53bc shown in the upper right of FIG. 2 (b) with the pressure pad 53ba, the width of the portion Q of the pressure pad 53bc is wide, and the area that can contact the seamless belt 52 is set to the same level. is there. When the pressure pad 53bc is set in the foil transfer device 50 of FIG. 1 in an embodiment described later, the pressure foil is half the maximum pressure at a timing of 0.3 t after the transfer foil and the foil transfer surface pass through the nip portion N. It is designed to give Further, comparing the pressure pad 53bd and the pressure pad 53ba shown in the lower left of FIG. 2B, the width of the portion Q of the pressure pad 53bd is wide, and the area that can contact the seam belt 52 is smaller than 53ba. It is. When the pressure pad 53bd is set in the foil transfer device 50 of FIG. 1 in the embodiment described later, the transfer foil and the foil transfer surface are 1/8 the maximum pressure at the timing of 0.3 t after passing the nip portion N. It is designed to apply a certain pressure.

  Next, comparing the pressure pad 53be and the pressure pad 53ba shown in the lower center of FIG. 2B, the pressure pad 53be has a width of the portion Q narrower than 53ba, but the area that can contact the seamless belt 52 is as follows. The level is the same as 53ba. When the pressure pad 53be is set in the foil transfer device 50 of FIG. 1 in the embodiment described later, the transfer foil and the foil transfer surface are half the maximum pressure at the timing of 0.5 t after passing the nip portion N. It is designed to apply a certain pressure. Furthermore, comparing the pressure pad 53bf and the pressure pad 53ba shown in the lower right of FIG. 2B, the width of the portion Q of the pressure pad 53bf is narrower than 53ba, and the area that can contact the seamless belt 52 is also greater than 53ba. Is also made smaller. When the pressure pad 53bf is set in the foil transfer device 50 of FIG. 1 in an embodiment described later, the transfer foil and the foil transfer surface are ¼ of the maximum pressure at a timing of 0.5 t after passing the nip portion N. It is designed to apply a certain pressure.

  As described above, by changing the contact form with the seamless belt 52 according to the cross-sectional shape of the pressure pad 53b, it is possible to change the timing and magnitude of applying pressure to the transfer foil and the foil transfer surface.

Next, the storage elastic modulus G ′ of the toner for forming the foil transfer surface used in the image forming method according to the present invention will be described. As described above, the toner used in the present invention has a storage elastic modulus G ′ at 120 ° C. of 1 × 10 ³ N / m ² or more and 1 × 10 ⁴ N / m ² or less. In the present invention, by using a toner whose storage elastic modulus G ′ at 120 ° C. falls within the above range, the foil transfer surface is not deformed even when heated when transferring the foil, and the foil is firmly bonded. This makes it possible to develop softening properties.

In this way, the present inventor pays attention to the viscoelasticity of the toner forming the foil transfer surface, and by defining the value of the storage elastic modulus G ′ at 120 ° C. of the toner forming the foil transfer surface as described above, It has been found that a foil transfer surface that does not deform due to stress applied during foil transfer can be obtained. Therefore, when a toner having a storage elastic modulus G ′ at 120 ° C. of less than 1 × 10 ³ N / m ² is used, the formed foil transfer surface may be deformed by stress applied when transferring the foil, Fine foil images such as fine lines and fine dots cannot be formed accurately. In addition, when a toner having a storage elastic modulus G ′ larger than 1 × 10 ⁴ N / m ² is used, the formed foil transfer surface is not likely to be deformed by the stress applied when transferring the foil, but is sufficient. Softness cannot be obtained, and good adhesion between the foil and the foil transfer surface cannot be obtained. For example, the foil does not adhere to the foil transfer surface in the process of transferring the foil, or even if the foil can be adhered to the foil transfer surface in the process of transferring the foil, the adhesive force is weak, so the user can use the foil during use. It is assumed that there will be fluttering.

  The storage elastic modulus G ′ at 120 ° C. of the toner used in the present invention can be measured by a known viscoelasticity measuring device. As a specific example, for example, a solid meter “MR-500 type” described below ) Manufactured by Rheology).

  The storage elastic modulus G ′ will be further described. The storage elastic modulus G ′ of the toner used in the present invention is based on the concept relating to the dynamic viscoelasticity of the toner as described below. Dynamic viscoelasticity is to evaluate the viscoelasticity of a sample by giving the sample a strain or stress that changes with time, such as sinusoidal vibration, and measuring the stress or strain corresponding thereto. Thus, viscoelasticity obtained through sinusoidal vibration is called dynamic viscoelasticity, and the elastic modulus obtained by sinusoidal vibration is usually expressed in the form of a complex number.

The elastic modulus G is a physical quantity representing the difficulty of deformation of the object, and is represented by the ratio of the applied stress σ and the strain γ generated by the action of the stress σ. The elastic modulus in the dynamic viscoelasticity is called the complex modulus G ^*, the complex modulus G ^* is the dynamic viscoelasticity, ^* stress ^sigma, the strain and gamma ^*,
G ^* = σ ^* / γ ^*
It is represented by

The real part of the complex elastic modulus G ^* is referred to as storage elastic modulus, and the imaginary part is referred to as loss elastic modulus. Hereinafter, the concept of storage elastic modulus, which is a factor for specifying the toner used in the present invention, will be described.

When a sample is given a sinusoidal distortion γ having an amplitude γ ₀ and an angular frequency ω, the sinusoidal distortion γ is expressed as follows. That is,
γ = γ ₀ cos ωt
At this time, a stress having the same angular frequency is generated in the sample. The stress σ is expressed as follows because the phase advances by δ from the strain γ.

σ = σ ₀ cos (ωt + δ)
Here, when these equations are expressed in complex numbers using Euler's formula exp (iωt) = cosωt + isinωt, the sinusoidal distortion γ ^* is γ ^* = γ ₀ exp (iωt), and the stress σ ^* caused thereby is , Σ ^* = σ ₀ exp (i (ωt + δ)).

When the above formula is put into the above-described complex elastic modulus G ^* = σ ^* / γ ^* ,
G ^* = (σ ₀ / γ ₀ ) expδ
= (Σ ₀ / γ ₀ ) (cos δ + isin δ)
Here, when the complex elastic modulus G ^* is expressed by a real part and an imaginary part, that is, G ^* = G ′ + iG ″,
G ′ = (σ ₀ / γ ₀ ) cos δ
G ″ = (σ ₀ / γ ₀ ) sin δ
It becomes. This means that the elastic energy stored in the viscoelastic body during one period is proportional to G ′, and the energy that the viscoelastic body loses as heat is proportional to G ″. From this, the real part G ′ is called storage elastic modulus, and G ″ which is an imaginary part is called loss elastic modulus.

The storage elastic modulus G ′ of the toner used in the present invention can be calculated, for example, by performing measurement according to the following procedure.
(1) 0.5 g of toner for forming a foil transfer surface is loaded into a compression molding machine, and a 3 t load is applied for 30 seconds to form pellets having a diameter of 1 cm.
(2) The pellet is loaded on a parallel plate having a diameter of 1 cm.
(3) The measurement part temperature is set to 120 ° C. and the parallel plate gap is set to 3 mm. With this setting, the measuring part is heated to 120 ° C., and the pellet is compressed until the gap is 3 mm. Then, it cools to -20 degreeC with liquid nitrogen.
(4) After setting the measurement part temperature to −20 ° C. with liquid nitrogen, the measurement part was heated to 200 ° C. at a temperature increase rate of 5 ° C. per minute while applying a sinusoidal vibration with a frequency of 1.0 Hz. The complex elastic modulus G ^* at the temperature of is measured. The strain angle is controlled by automatic strain control. Automatic strain control checks the measurement state about every 2 to 4 cycles after the start of reading measurement data, and adjusts the strain angle based on the torque peak at that time (average of torque waveform values from 0 to peak) To do.

In summary, the storage modulus G ′ of the toner used in the present invention can be obtained by measuring under the following conditions. That is,
Measuring device: MR-500 solid meter (manufactured by Rheology Co., Ltd.)
Frequency: 1.0Hz
Plate diameter: 1.0cm (parallel plate)
Gap: 3.0mm
Strain angle: Set to automatic strain control Measurement temperature range: -20 ° C to 200 ° C
In the above measuring device, the storage modulus G 'is measured in units of dyn / cm ^2, is converted to ^{1dyn / cm 2 = 1 × 10} -1 N / m 2.

  A toner whose storage elastic modulus G 'at 120 ° C. falls within the range specified in the present invention is, for example, in the binder resin constituting the toner, for example, a weight average molecular weight of 300,000, as described in Examples below. This can be realized by including a high molecular weight component at a level. This is because the presence of a high molecular weight component in the binder resin constituting the toner enhances the entanglement between the molecular chains constituting the binder resin and improves the cohesive force between the molecular chains. It is believed that the layer improves durability and does not deform when heated.

  Further, in addition to adding a high molecular weight component to the binder resin, it is also possible to prepare by controlling the reaction conditions when polymerizing the binder resin by a known method. For example, in the examples described later, the toner is prepared by an emulsion association method in which resin fine particles are produced through multi-stage polymerization, and the resin fine particles are aggregated and fused to produce toner base particles. The toner is prepared by adjusting the amount of each compound added. That is, when preparing resin fine particles by multistage polymerization, the addition amount of a compound such as a polymerizable monomer, a polymerization initiator, a chain transfer agent, or the addition amount of a flocculant when aggregating resin fine particles is adjusted. Preparation and the like.

  In addition, when preparing toner particles, resin fine particles are often prepared using a plurality of types of polymerizable monomers. Therefore, adjusting the composition ratio of these polymerizable monomers is one of the realizing methods. Can be mentioned. Furthermore, since resin fine particles are produced by a polymerization reaction of a polymerizable monomer, adjusting the temperature and time during the polymerization reaction is also one of the realizing methods.

  Next, the resin constituting the toner used in the present invention will be described. The resin constituting the toner used in the present invention is, for example, a vinyl-based polymerizable monomer such as a copolymer resin formed using a styrene monomer or a (meth) acrylic acid monomer. The thermoplastic resin represented by the well-known resin formed using a body is mentioned. Specific examples include vinyl resins such as styrene resins, (meth) acrylic acid resins, styrene (meth) acrylic acid copolymer resins, polyvinyl acetate resins, and polyolefin resins. In the present invention, a resin formed by using a vinyl polymerizable monomer having a “carboxy group (—COOH)” together with the styrene monomer or (meth) acrylic acid monomer is preferable. Used. It is also possible to use thermoplastic resins such as polyester resins, polyamide resins, polycarbonate resins, polyether resins, polysulfone resins, and polyurethane resins.

  Here, specific examples of the “polymerizable monomer having a carboxyl group (—COOH)” that can be used for the production of the toner for forming a foil transfer surface include, for example, molecules such as acrylic acid and methacrylic acid. Examples include compounds having one carboxy group in the structure. Examples of the vinyl monomer having two carboxy groups include itaconic acid, maleic acid, and fumaric acid. Examples of the vinyl monomer having three carboxy groups include aconitic acid. Below, the specific example of the vinyl-type monomer which has a carboxy group (-COOH) is shown.

  By using the polymerizable monomer having the carboxy group (-COOH), it is presumed to be due to the polarity of the carboxy group in the binder resin, but the transfer foil is moved along the shape of the foil transfer surface during foil transfer. Easy to transfer. Therefore, when forming a foil image of a complicated design in which many thin lines are used, it is possible to faithfully reproduce a design having a complicated shape with the foil without worrying about missing of a foil or generation of burrs. In addition, although the foil image of the thin line has a narrow contact area with the foil and it is difficult to ensure the adhesive strength, the formed foil image exhibits a strong adhesive strength and is from the foil transfer surface. There is no risk of the foil peeling off. In this way, by using a toner containing a binder resin formed using a polymerizable monomer having a carboxy group, a foil image having a complicated shape can be accurately obtained without worrying about the occurrence of burrs and chips. It can be formed and maintained on the product with strong adhesive strength. Therefore, it can be said that it is most suitable for producing a hologram for an identification card used for recording personal information as well as a high-class aesthetic appearance.

  Among the polymers formed using the polymerizable monomer having a carboxy group (—COOH), a copolymer resin formed using methacrylic acid is preferable. In particular, a copolymer resin formed using a polymerizable monomer having two or more carboxy groups such as itaconic acid and aconitic acid in addition to methacrylic acid is more preferable.

  The “styrene monomer” here is a vinyl polymerizable monomer having a benzene ring in the side chain in the molecular structure. In addition to styrene, a methyl group, a phenyl group, etc. And styrene derivatives having various functional groups such as hydrocarbon groups and halogen groups. The “(meth) acrylic acid monomer” means a vinyl polymerizable monomer containing either a carboxy group (—COOH) or a carboxylic acid ester structure (—COOR) as a functional group in the molecular structure. It is a mass.

In addition, “(meth) acryl” means that the monomer structure is one of a methacryl group (CH ₂ ═C (CH ₃ ) COO—) and an acryl group (CH ₂ ═CHCOO—). Is classified into “methacrylic acid monomer” and “acrylic acid monomer”. Therefore, specific examples of the “methacrylic acid monomer” include the methacrylic acid (CH ₂ ═C (CH ₃ ) COOH) described above and the methacrylic acid ester derivatives shown below. Specific examples of the “acrylic acid monomer” include the above-mentioned acrylic acid (CH ₂ ═CHCOOH) and the following acrylic ester derivatives.

  Hereinafter, specific examples of the vinyl polymerizable monomer for producing the toner used in the present invention will be shown. The vinyl polymerizable monomer capable of producing the toner usable in the present invention is as follows. It is not limited to those.

(1) Styrene monomers (styrene or styrene derivatives)
Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-tert-butylstyrene, pn- Hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, etc. (2) Methacrylic acid ester derivative monomers Methyl methacrylate, ethyl methacrylate, N-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, methacryl Acid di Methylaminoethyl etc. (3) Acrylic acid ester derivative monomer Methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, acrylic 2-ethylhexyl acid, stearyl acrylate, lauryl acrylate, phenyl acrylate, and the like.

The following vinyl-based polymerizable monomers are used in combination with the above-mentioned polymerizable monomers having a carboxy group, styrene-based monomers, and (meth) acrylic acid ester derivative-based monomers. It is also possible to form. That is,
(4) Olefins Ethylene, propylene, isobutylene, etc. (5) Vinyl esters Vinyl propionate, vinyl acetate, vinyl benzoate, etc. (6) Vinyl ethers Vinyl methyl ether, vinyl ethyl ether, etc. (7) Vinyl ketones Vinyl methyl ketone, Vinyl ethyl ketone, vinyl hexyl ketone, etc. (8) N-vinyl compounds N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone, etc. (9) Others Vinyl compounds such as vinyl naphthalene and vinyl pyridine, acrylonitrile, methacrylo Acrylic acid or methacrylic acid derivatives such as nitrile and acrylamide.

Furthermore, it is also possible to produce a resin having a crosslinked structure using the following polyfunctional vinyls. Specific examples of the polyfunctional vinyls are shown below. That is,
Ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, and the like.

  Next, a method for producing a toner that can be used for forming a foil transfer surface in the present invention will be described.

The toner that can be used in the present invention can be produced by a known production method for producing a toner used for known electrophotographic image formation. Specifically, a so-called pulverization method for producing a toner through kneading, pulverization, and classification steps, a so-called polymerization method for polymerizing a polymerizable monomer, and simultaneously forming particles while controlling the shape and size, etc. It is possible to produce a toner for forming a foil transfer surface. That is, by these known methods, a toner having a storage elastic modulus G ′ at 120 ° C. of 1 × 10 ³ N / m ² or more and 1 × 10 ⁴ N / m ² or less can be produced.

  Among them, the polymerization method is an advantageous method for producing toner particles having a uniform size and shape, and the toner particles are produced through a resin particle formation step by a polymerization reaction such as suspension polymerization or emulsion polymerization. is there. Among the polymerization methods, a production method based on an association method is preferred, in which resin fine particles of about 100 nm, for example, are produced by a polymerization reaction, and toner base particles are produced by agglomerating and fusing the resin fine particles.

  Hereinafter, as an example of a method for producing a toner that can be used in the present invention, resin fine particles are produced by an emulsion association method, that is, emulsion polymerization, and the toner fine particles obtained by aggregating and fusing the produced resin fine particles are obtained. A manufacturing method will be described. Production of the toner for forming the foil transfer surface by the emulsion association method is performed, for example, through the following steps.

(1) Production process of resin fine particle dispersion (2) Aggregation / fusion process of resin fine particles (association process)
(3) Aging step (4) Cooling step (5) Washing step (6) Drying step (7) External additive treatment step Hereinafter, each step will be described.

(1) Production Step of Resin Fine Particle Dispersion This step is a step of forming a binder resin constituting the foil transfer surface forming toner. Specifically, for example, at least the vinyl polymerizable monomer described above is added and dispersed in an aqueous medium, and the vinyl polymerizable monomer is polymerized by emulsion polymerization in this state. Thus, resin fine particles having a size of about 100 nm are formed.

  In this step, first, the above-mentioned vinyl polymerizable monomer is added to the aqueous medium, and the emulsion medium is subjected to an emulsifying dispersion treatment to disperse oil droplets of the vinyl polymerizable monomer. Is formed. In the oil droplets dispersed in the aqueous medium, a radical polymerization reaction is performed to form resin fine particles.

  In this step, in addition to the vinyl polymerizable monomer used in the polymerization reaction, a toner constituent material such as wax is added to the aqueous medium, and the polymerizable single component in which the toner constituent material such as wax is dissolved by a dispersion treatment. It is also possible to form a monomeric oil droplet and subject it to a radical polymerization reaction. By subjecting such oil droplets to radical polymerization reaction, it is possible to form resin fine particles containing a toner constituent material such as wax.

  A radical polymerization reaction is one in which a polymerization initiator is taken into oil droplets, radicals are generated from the polymerization initiator by the action of heat or light, and this radical initiates the polymerization reaction of the vinyl polymerizable monomer. The polymerization reaction proceeds in a chain reaction, and resin fine particles are formed. Alternatively, there is also a method in which radicals generated from a polymerization initiator present in an aqueous medium are taken into oil droplets and radical polymerization starts to form resin fine particles.

  The temperature at which radical polymerization is performed depends on the type of vinyl polymerizable monomer and the type of polymerization initiator that generates radicals, but is usually preferably 50 ° C to 100 ° C, more preferably 55 ° C to 90 ° C. preferable. The polymerization reaction time is preferably 2 to 12 hours, although it depends on the reaction rate of the vinyl polymerizable monomer and radical.

  In this step, after adding a vinyl polymerizable monomer to the aqueous medium, mechanical energy is imparted to the aqueous medium to perform dispersion treatment to form oil droplets of the polymerizable monomer. The dispersion apparatus which forms the oil droplets of the polymerizable monomer by applying mechanical energy is not particularly limited. For example, a commercially available stirring apparatus “CLEARMIX” (M・ Technique Co., Ltd.) ”is a typical dispersion device. In addition to the above-described stirring device provided with a rotor capable of rotating at high speed, there are devices such as an ultrasonic dispersion device, a mechanical homogenizer, a manton gourin, and a pressure homogenizer. By these dispersing devices, dispersed particles of oil droplets of around 100 nm are formed in the aqueous medium.

  Here, the “aqueous medium” is a liquid composed of water and an organic solvent that can be dissolved in water, and contains at least 50% by mass of water. Examples of the “organic solvent soluble in water” constituting the aqueous medium include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. Among these, alcohol-based organic solvents exhibiting stability with respect to resins such as methanol, ethanol, isopropanol, and butanol are preferable.

  Since the resin fine particles constituting the toner for forming the foil transfer surface have a certain molecular weight distribution, the resin fine particles are subjected to a polymerization reaction in a plurality of times so as to form a plurality of phases having different molecular weight distributions. It is preferable. In this way, a method of forming resin fine particles by performing a plurality of polymerization reactions stepwise is called multistage polymerization. By performing multistage polymerization, it is possible to impart a molecular weight change such as a gradient from the particle center toward the particle surface, for example, to the formed resin fine particles. It is also possible to form a low molecular weight surface layer by first preparing a high molecular weight resin particle dispersion and then adding a polymerizable monomer and a chain transfer agent to the resin particle dispersion. is there.

  When producing resin fine particles, multiple times of polymerization such as two-stage polymerization method or three-stage polymerization method from the viewpoint of stability in production, imparting sufficient crushing strength to the formed toner, and reliable addition of wax etc. It is preferable to adopt a method called a multistage polymerization method in which a reaction is performed to form resin fine particles. Hereinafter, the two-stage polymerization method and the three-stage polymerization method, which are representative forms of the multistage polymerization method, will be described.

<Two-stage polymerization method>
The two-stage polymerization method is a method for producing resin fine particles having two regions, for example, resin fine particles having a central portion made of a high molecular weight resin and an outer layer made of a low molecular weight resin. In the two-stage polymerization method, resin fine particles are formed by performing two polymerization reactions of first-stage polymerization and second-stage polymerization.

  For example, when forming resin fine particles with different molecular weight distribution, first prepare a polymerizable monomer to produce high molecular weight resin fine particles, add this to the aqueous medium, and then give mechanical energy to the aqueous medium Thus, oil droplets of the polymerizable monomer are formed. Then, the polymer monomer oil droplets are polymerized (first-stage polymerization) as described above to prepare a high molecular weight resin fine particle dispersion.

  Next, a polymerization initiator and a polymerizable monomer for forming a low molecular weight resin are added to the prepared resin fine particle dispersion, and polymerization of the polymerizable monomer in the presence of high molecular weight resin fine particles ( Second stage polymerization) is performed. In this manner, the resin fine particles having a two-layer structure can be formed by coating the surface of the high molecular weight resin fine particles with the low molecular weight resin phase.

<Three-stage polymerization method>
The three-stage polymerization method is, for example, a resin fine particle having a central portion composed of a high molecular weight resin, an intermediate layer composed of a resin containing a toner constituent material such as wax, and an outer layer composed of a low molecular weight resin. In this way, resin fine particles having three regions are produced. In the three-stage polymerization method, resin fine particles are formed by performing three polymerization reactions of first-stage polymerization, second-stage polymerization, and third-stage polymerization.

  For example, when forming resin fine particles having different molecular weight distributions and containing a toner constituent material such as wax, a polymerizable monomer for preparing high molecular weight resin fine particles is first prepared, Similarly to the polymerization, a first polymerization reaction (first-stage polymerization) is performed to prepare a high molecular weight resin fine particle dispersion.

  Next, the resin fine particle dispersion prepared is added to an aqueous medium, and a polymerizable monomer solution in which a toner constituent material such as wax is dissolved is also added to the aqueous medium to disperse the monomer solution in oil droplets. In this state, the second polymerization reaction (second stage polymerization) is performed. In this manner, a dispersion liquid of resin fine particles having a composite structure (hereinafter referred to as composite resin fine particles) in which an intermediate layer of a resin phase containing a toner constituent material such as wax is formed on the surface of high molecular weight resin fine particles.

  Next, a polymerization initiator and a polymerizable monomer for forming a low molecular weight resin are added to the dispersion of the composite resin fine particles formed through the second stage polymerization, and the polymerization is performed in the presence of the composite resin particles. Monomer polymerization (third-stage polymerization) is performed. In this manner, resin particles having a three-layer structure can be formed by coating the surface of the composite resin particles with a low molecular weight resin phase.

(2) Aggregation / fusion process of resin fine particles (association process)
In this step, the resin fine particles formed in the above step are aggregated in an aqueous medium to form particles, and the particles formed by aggregation are heated and fused to form particles (base particles of toner before external addition treatment). ) Is also referred to as an association step. That is, it is a step of producing toner base particles by agglomerating and fusing resin fine particles formed by polymerizing a vinyl polymerizable monomer by the emulsion polymerization method described above.

  In this step, an aggregating agent such as an alkali metal salt or an alkaline earth metal salt typified by magnesium chloride is added to the aqueous medium containing the resin fine particles to aggregate the resin fine particles. Next, the aqueous medium is heated to a temperature equal to or higher than the glass transition temperature of the resin fine particles to advance the aggregation, and the aggregated resin particles are fused together. When the size of the resin particles becomes the target due to the progress of aggregation, a salt such as salt is added to stop the aggregation.

(3) Aging process This process is a process in which the shape of the resin particles is aged until the desired average circularity is obtained by heat-treating the reaction system subsequent to the above-described aggregation / fusion process, and is also called a shape control process. It is.

(4) Cooling step This step is a step of cooling (rapid cooling) the dispersion of the resin particles. As a cooling treatment condition, cooling is performed at a cooling rate of 1 ° C./min to 20 ° C./min. The cooling treatment method is not particularly limited, and the treatment can be performed by introducing a refrigerant from the outside of the reaction vessel and cooling it, or by directly introducing cold water into the reaction system and cooling it.

(5) Washing step This step includes a step of solid-liquid separation of the resin particles from the resin particle dispersion liquid cooled to a predetermined temperature in the above step, and a cake-like aggregate called a wet toner cake that has been solid-liquid separated. It has a washing process which removes deposits, such as a surface active agent and a flocculant, from the resin particle surface which became.

  In the washing treatment, the filtrate is washed with water until the electric conductivity of the filtrate becomes, for example, about 10 μS / cm. Examples of the solid-liquid separation method include a centrifugal separation method, a vacuum filtration method using Nutsche and the like, a filtration method using a filter press and the like.

(6) Drying step This step is a step of drying the washed resin particles. Examples of the dryer used in this step include a spray dryer, a vacuum freeze dryer, and a vacuum dryer, and a stationary shelf dryer, a mobile shelf dryer, a fluidized bed dryer, and a rotary dryer. It is preferable to use a stirring dryer or the like.

  Moreover, it is preferable that the water | moisture content of the dried resin particle is 5 mass% or less, More preferably, it is 2 mass% or less. In addition, when the resin particles subjected to the drying treatment are aggregated with a weak interparticle attractive force, the aggregate may be crushed. Here, a mechanical crushing device such as a jet mill, a Henschel mixer, a coffee mill, or a food processor can be used as the crushing treatment device.

  Through the steps up to the above drying step, toner base particles are formed.

(7) External additive treatment step This step is a step of adding an external additive or a lubricant to the toner base particles obtained through the drying treatment. The base particles obtained through the drying step can be used as they are as toner particles for forming the foil transfer surface, but the addition of external additives further improves the chargeability, fluidity and cleaning properties of the toner. Can be made. As these external additives, known inorganic fine particles, organic fine particles, and aliphatic metal salts can be used, and the addition amount thereof is 0.1 to 10.0% by mass, preferably 0.5% with respect to the whole toner. It is -4.0 mass%. In addition, various external additives can be added in combination. In addition, as a mixing apparatus used when adding an external additive, there exist well-known mechanical mixing apparatuses, such as a turbula mixer, a Henschel mixer, a Nauta mixer, a V-type mixer, a coffee mill, for example.

  Examples of known inorganic fine particles include silica, titania, alumina, and strontium titanate fine particles. In addition, it is also possible to use those obtained by hydrophobizing these inorganic fine particles.

  Specific examples of the silica fine particles include commercially available products R-805, R-976, R-974, R-972, R-812, R-809 manufactured by Nippon Aerosil Co., Ltd., HVK-2150 manufactured by Hoechst, H -200, commercially available products TS-720, TS-530, TS-610, H-5, MS-5, etc. manufactured by Cabot Corporation.

  As the titania fine particles, for example, commercially available products T-805 and T-604 manufactured by Nippon Aerosil Co., Ltd., commercially available products MT-100S, MT-100B, MT-500BS, MT-600, MT-600SS, JA- 1. Commercial products TA-300SI, TA-500, TAF-130, TAF-510, TAF-510T manufactured by Fuji Titanium Co., Ltd. Commercial products IT-S, IT-OA, IT-OB, IT- manufactured by Idemitsu Kosan Co., Ltd. OC etc.

  Examples of the alumina fine particles include commercial products RFY-C and C-604 manufactured by Nippon Aerosil Co., Ltd., and commercial products TTO-55 manufactured by Ishihara Sangyo Co., Ltd.

  As the organic fine particles, spherical organic fine particles having a number average primary particle diameter of about 10 to 2000 nm can be used. Specifically, homopolymers such as styrene and methyl methacrylate and copolymers thereof can be used.

  The addition amount of these external additives is preferably 0.1 to 10.0% by mass with respect to the whole toner.

  Through the above steps, the toner for forming a foil transfer surface according to the present invention can be produced by an emulsion association method.

  Next, a polymerization initiator, a dispersion stabilizer, a surfactant and the like used when the foil transfer surface forming toner is produced by the above-described emulsion association method will be described.

The binder resin constituting the toner for forming the foil transfer surface is formed by polymerizing a known polymerizable monomer, and a known oil-soluble or water-soluble polymerization initiator is used for the polymerization. It is possible. Specific examples of the oil-soluble polymerization initiator include the following azo or diazo polymerization initiators and peroxide polymerization initiators. That is,
(1) Azo or diazo polymerization initiator 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1 -Carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, etc. (2) peroxide-based polymerization initiators benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl Peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis- (4 4-t-butylperoxycyclohexyl) propane, tris (T-butylperoxy) triazine In the case of forming the resin particles by emulsion polymerization is a water-soluble radical polymerization initiators can be used. Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and its salts, hydrogen peroxide and the like.

  A known chain transfer agent can also be used for adjusting the molecular weight of the resin particles. Specific examples include n-octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, n-octyl-3-mercaptopropionic acid ester, terpinolene, carbon tetrabromide, and α-methylstyrene dimer.

  Further, in the present invention, as described above, polymerization is performed in a state where a vinyl monomer having a plurality of polar groups and another vinyl monomer are dispersed in an aqueous medium, and the resin particles obtained by polymerization are dispersed in the aqueous medium. Then, this is agglomerated and fused to produce a toner for forming a foil transfer surface. It is preferable to use a dispersion stabilizer that stably disperses these toner materials in an aqueous medium. Examples of the dispersion stabilizer include tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, Examples include barium sulfate, bentonite, silica, and alumina. In addition, polyvinyl alcohol, gelatin, methylcellulose, sodium dodecylbenzenesulfonate, ethylene oxide adduct, higher alcohol sodium sulfate and the like which are generally used as surfactants can also be used as the dispersion stabilizer.

  Further, when polymerization is performed using a polymerizable monomer in an aqueous medium, it is necessary to uniformly disperse oil droplets of the polymerizable monomer in the aqueous medium using a surfactant. In this case, usable surfactants are not particularly limited, but for example, the following ionic surfactants can be used as preferable ones. Examples of the ionic surfactant include a sulfonate, a sulfate ester salt, and a fatty acid salt. Examples of the sulfonate include sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, and 3,3-disulfonediphenyl. Urea-4,4-diazo-bis-amino-8-naphthol-6-sulfonate sodium, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4 -Sodium diazo-bis-β-naphthol-6-sulfonate.

  Examples of sulfate salts include sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, and sodium octyl sulfate. Fatty acid salts include sodium oleate, sodium laurate, sodium caprate, sodium caprylate, Examples include sodium caproate, potassium stearate, and calcium oleate.

  Nonionic surfactants can also be used. Specifically, polyethylene oxide, polypropylene oxide, a combination of polypropylene oxide and polyethylene oxide, esters of polyethylene glycol and higher fatty acids, alkylphenol polyethylene oxide, higher fatty acids and Examples include polyethylene glycol esters, higher fatty acid and polypropylene oxide esters, sorbitan esters, and the like.

Next, the above-described image forming method according to the present invention will be described in detail. More specifically, the image forming method according to the present invention includes the following steps (1) to (6). That is,
(1) Step of forming an electrostatic latent image by exposing the photosensitive member (2) Step of forming a foil transfer surface by supplying toner for forming a foil transfer surface to the photosensitive member on which the electrostatic latent image has been formed. 3) Step of transferring the foil transfer surface formed on the photoreceptor to the substrate (4) Step of heating and fixing the foil transfer surface transferred onto the substrate (5) At least an adhesive layer on the substrate having the foil transfer surface (6) A step of bringing the adhesive layer of the supplied transfer foil into contact with the substrate and heating in this state to transfer the foil onto the foil transfer surface. That is, in the image forming method according to the present invention, first, an electrostatic latent image having the shape of a foil transfer surface to be formed on a product is formed by exposing the photosensitive member, and the electrostatic latent image is formed on the photosensitive member. A foil transfer surface is formed by supplying toner for forming the foil transfer surface. Next, the foil transfer surface formed on the photoconductor is transferred to a substrate, and the transferred foil transfer surface is heated and fixed to form a foil transfer surface on the substrate. Then, the transfer foil is supplied to the substrate, the foil transfer surface and the transfer foil are brought into contact, and heated in this state to transfer the foil onto the foil transfer surface.

  Each of the above steps will be specifically described with reference to FIGS. FIG. 3 is a schematic diagram illustrating the steps (5) and (6) in detail among the steps (1) to (6) described above, and supplying the transfer foil F to the base P on which the foil transfer surface H is formed. Then, it is explained that the foil f2 is brought into contact with the foil transfer surface H and heated in this state to transfer the foil f2 onto the foil transfer surface H. Hereinafter, (a) to (e) of FIG. 3 will be described. The steps (1) to (4) will be described with reference to FIG.

  FIG. 3A is a cross-sectional view of the substrate P showing a state in which the foil transfer surface H is formed on the sheet-like substrate P using toner. The formation of the foil transfer surface H on the substrate P is performed through the above steps (1) to (4), but the description thereof is omitted here. Next, FIG. 3B shows a state in which the transfer foil F having at least the adhesive layer f1 is supplied to the base P, and the transfer foil F is formed so that the adhesive layer f1 is in contact with the foil transfer surface H. Supplied. Here, the adhesive layer f1 of the supplied transfer foil F forms a contact state on the foil transfer surface H that exists in a convex shape on the substrate surface.

  The transfer foil F used in the present invention has at least an adhesive layer f1 and a foil layer f2 on a base film f0, and the layer configuration other than the adhesive layer f1 and the foil layer f2 is omitted here. A detailed description of the transfer foil F usable in the present invention will be given later.

  3C is formed between the heating and pressurizing means R1 and R2 provided also in the foil transfer apparatus shown in FIGS. 1 and 2 described above with the transfer foil F in contact with the base P. FIG. It shows a state of passing through the nip portion. As described above, when the substrate P having the transfer foil F and the foil transfer surface H is passed through the nip portion formed between the heating and pressurizing means R1 and R2, it contacts the foil transfer surface H of the transfer foil F. A bonding state is formed between the adhesive layer f <b> 1 in the region and the foil transfer surface H. And the foil layer f2 of the area | region which formed the adhesive state between foil transfer surfaces H is transcribe | transferred to the shape corresponding to the shape of the foil transfer surface H faithfully.

  Next, FIG. 3D shows a state in which the transfer foil F is removed from the substrate P. When the transfer foil F is removed, the foil transfer surface H on the substrate P as shown in FIG. Only on top, the foil layer f2 is transferred together with the adhesive layer f1. In this way, in the present invention, the foil transfer surface is made of toner, whereby the foil layer f2 is transferred to a shape corresponding to the shape of the foil transfer surface H, and chipping and burrs are eliminated without using a metal mold. It is possible to accurately form the foil layer f2 having a predetermined shape without being generated.

  Next, a method for forming the foil transfer surface H on the substrate P performed by the image forming method according to the present invention will be described with reference to FIG. FIG. 4 shows an example of an image forming apparatus that can be used in the present invention. The image forming apparatus 1 in FIG. 4 performs the steps (1) to (4) among the steps (1) to (6) for forming a foil image, and forms a latent image by exposure. A foil transfer surface corresponding to the electrostatic latent image is formed by supplying toner for forming the foil transfer surface to the photoconductor. Then, the formed foil transfer surface is transferred from the photoreceptor to the substrate P, and further, the foil transfer surface on the substrate P is heated and fixed.

  In the image forming apparatus 1 shown in FIG. 4, the exposure light L is irradiated onto the photoconductor 11H charged by the charging roller 12H in the figure, thereby forming an electrostatic latent image. The electrostatic latent image formed on the photoconductor 11H is supplied with the foil transfer surface forming toner from the foil transfer surface forming toner supply device 21H disposed in the vicinity of the photoconductor 11H. Form. At this time, the toner supply roller 14 built in the foil transfer surface forming toner supply device 21H rotates, and the toner attached to the toner supply roller 14 is supplied to the photoconductor 11H, and the foil is transferred onto the photoconductor 11H. Form a surface.

  Next, when the charge on the photoconductor 11H is discharged by the charge eliminating lamp 22, the foil transfer surface on the photoconductor 11H is transferred onto the substrate P at the transfer portion where the photoconductor 11H and the transfer roller 13H are close to each other. The substrate P shown in FIG. 4 has a sheet shape typified by transfer paper, and is transported to a transfer portion by a transport roller 23 from a paper feed cassette (not shown), and has a polarity opposite to that of the toner for forming the foil transfer surface by the transfer roller 13H. Charge is applied. The base P can transfer the foil transfer surface from the photoreceptor 11H by the electrostatic action of the charge having the reverse polarity applied by the transfer roller 13H.

  The substrate P to which the foil transfer surface has been transferred is separated from the photoconductor 11H, and then conveyed to a fixing device (not shown) by the conveyance belt 24. The fixing device includes known fixing means such as a roller fixing device composed of a heating roller and a pressure roller. The foil transfer surface formed on the substrate P is heated, melted, and fixed.

  According to the above procedure, in the image forming apparatus 1 in FIG. 4, an electrostatic latent image corresponding to the shape of the foil is formed on the photoreceptor 11H, and the foil transfer surface is formed on the photoreceptor 11H by supplying the toner for forming the foil transfer surface. Is formed. The foil transfer surface formed on the photoreceptor 11H is transferred to the base P by the transfer roller 13H, and heated and melted by a fixing device (not shown) to form the foil transfer surface H.

  The charging roller 12H in the drawing can charge the photoconductor 11H, for example, by the following procedure. That is, the charging roller 12H is charged with the bias voltage composed of a direct current (DC) component and an alternating current (AC) component from the power source 27 to charge the photosensitive drum 11H. Charging using the charging roller 12 shown in FIG. 4 is a so-called contact method. In the present invention, in addition to the charging method shown in FIG. 4, non-contact charging used in the apparatus shown in FIG. It is also possible to do this. Examples of the bias voltage applied to the charging roller 12H include a DC bias of ± 500 to 1000 V that is a DC component and an AC bias of 100 Hz to 10 kHz and 200 to 3500 V that are AC components. .

  The transfer roller 13H in FIG. 4 is also formed on the photoconductor 11H at the transfer site upon application of a bias voltage composed of a direct current (DC) component and an alternating current (AC) component from the power source 28, similarly to the charging roller 12H. The foil transfer surface is transferred onto the substrate p1. As a specific example of the bias voltage applied to the transfer roller 13H, as in the specific example of the bias voltage applied to the charging roller 12H, a DC bias of DC component ± 500 to 1000 V and an AC component of 100 Hz to 10 kHz, 200 to There is a superposition of 3500V AC bias.

The charging roller 12H and the transfer roller 13H are driven or forcibly rotated while being in pressure contact with the photoconductor 11H. The pressing force of these rollers to the photosensitive drum 11H is, for example, 9.8 × 10 ^{−2 to} 9.8 × 10 ⁻¹ N / cm, and the rotational speed of the rollers is, for example, the peripheral speed of the photosensitive member 11. 1-8 times. The pressing force of the roller to the photoconductor 11H can be realized by applying a pressing force of about 1N to 10N to both ends of the charging roller 12, for example.

  The photoconductor 11H having transferred the foil transfer surface to the substrate P is removed by a cleaning blade 25b provided in the cleaning device 25, so that the next foil transfer surface is formed.

  In the present invention, it is also possible to form a foil image and a visible image on the product forming the foil transfer surface. The method for forming a visible image on the product is not particularly limited, and can be produced by using a known image forming method such as an electrophotographic method, a printing method, an ink jet method, or a silver salt photographic method. It is. For example, after a foil transfer surface is formed on a product and the foil is transferred onto the foil transfer surface, a toner image can be formed around the transferred foil by an electrophotographic image forming method. It is also possible to create an image with a different color by placing a color toner on the foil. By these methods, it is possible to give further bright expression to the product to which the foil is transferred.

  FIG. 5 is a cross-sectional configuration diagram of an image forming apparatus capable of performing the above-described foil transfer surface formation of FIG. 3 and electrophotographic full-color image formation. The image forming apparatus shown in FIG. 5 performs fixing for heating and pressurizing and curing the formed foil transfer surface H, as well as the foil transfer surface forming apparatus 1 shown in FIG. A foil transfer device 50 for transferring the foil is mounted.

  An image forming apparatus 1 shown in FIG. 5 has the same configuration as an electrophotographic image forming apparatus called a so-called “tandem color image forming apparatus”, and includes a foil transfer surface forming unit 20H and a plurality of sets of toner image forming units. 20Y, 20M, 20C, 20Bk, a belt-like intermediate transfer belt 26, a paper feeding device 40, a foil transfer device 50, and the like. In particular, the image forming apparatus 1 shown in FIG. 5 is provided with a transfer foil supply unit 70 below the intermediate transfer belt 26, and the transfer foil F is supplied onto the base P on which the foil transfer surface H is fixed. The foil is transferred onto the foil transfer surface H by passing through the transfer device 50.

  As described above, in the image forming apparatus 1 shown in FIG. 5, the foil transfer surface H can be formed on the base P constituting the product Q, and the transfer foil can be transferred onto the formed foil transfer surface H. A full color image can be formed on the substrate p1 to which the foil has been transferred using color toner. In the image forming apparatus 1 shown in FIG. 5, the transfer foil supply unit 70 is disposed below the intermediate transfer belt 26. However, the arrangement of the transfer foil supply unit is not limited to this, and the transfer foil is supplied. After that, it may be a place where foil transfer is possible by heating and pressurization by the foil transfer device 50. Further, the foil transfer device 50 provided in the image forming apparatus 1 shown in FIG. 5 and FIG. 6 described later is also used as a fixing device for fixing the foil transfer surface and the toner image on the substrate P.

  For the arrangement of the intermediate transfer belt 26, the foil transfer device 50, and the transfer foil supply unit 70, in addition to the image forming apparatus shown in FIG. 5, for example, the arrangement shown in FIG. In the foil transfer surface forming apparatus 1 of FIG. 6, the intermediate transfer belt 26, the foil transfer device 50, and the transfer foil supply unit 70 are sequentially arranged. In addition, the arrows in the figure indicate the transport direction of the substrate P. 6 includes a transfer foil supply roll 71, foil transfer rollers 73a and 73b, and a transfer foil take-up roller 72. The transfer foil F is supplied from the transfer foil supply roll 71, and foil transfer is performed. The used transfer foil F is wound around the transfer foil winding roller 72. In FIG. 6, the foil transfer surface forming unit 20H, the toner image forming units 20Y, 20M, 20C, 20Bk, etc. are omitted. Further, FIG. 6 will be described in detail later.

  An image reading unit 60 is installed on the upper part of the image forming apparatus 1. The document placed on the document table is scanned and exposed by the optical system of the document image scanning exposure apparatus of the image reading unit 60 and read by the line image sensor. The analog signal photoelectrically converted by the line image sensor is subjected to analog processing, A / D conversion, shading correction, image compression processing, and the like in the control means, and then input to the exposure units 30H, 30Y, 30M, 30C, and 30Bk. .

  In FIG. 5, the constituent elements are collectively indicated by reference numerals with alphabetic suffixes omitted, and H (for foil transfer surface), Y (yellow), and M (magenta) are indicated when referring to individual constituent elements. , C (cyan), and Bk (black).

Foil transfer surface forming toner supply unit 21H for supplying foil transfer surface forming toner, yellow image forming unit 20Y for forming yellow toner image, magenta image forming unit 20M for forming magenta toner image, cyan color The cyan image forming unit 20C that forms a toner image and the black image forming unit 20Bk that forms a black toner image each have the following configuration. That is,
(1) Drum-shaped photoconductor 11 (11H, 11Y, 11M, 11C, 11Bk)
(2) Band electrode 12 (12H, 12Y, 12M, 12C, 12Bk)
(3) Exposure unit 30 (30H, 30Y, 30M, 30C, 30Bk)
(4) Foil transfer surface forming toner supply device 21H and developing device 21 (21Y, 21M, 21C, 21Bk)
(5) Cleaning device 25 (25H, 25Y, 25M, 25C, 25Bk).

  The photoconductor 11 is made of, for example, an organic photoconductor in which a photosensitive layer made of a resin containing an organic photoconductor is formed on the outer peripheral surface of a drum-shaped metal base, and the base P constituting the product Q to be conveyed. Are arranged in a state extending in the width direction (perpendicular to the paper surface in FIG. 5). As the resin constituting the photosensitive layer, for example, a known photosensitive layer forming resin such as a polycarbonate resin is used. In the embodiment shown in FIG. 5, the configuration example using the drum-shaped photoconductor 11 has been described. However, the configuration is not limited thereto, and a belt-shaped photoconductor may be used.

  The foil transfer surface forming toner supply device 21H contains a two-component foil transfer surface forming agent comprising the foil transfer surface forming toner (T) according to the present invention and a carrier. Further, the developing device 21 contains two-component developers composed of toners and carriers of different colors of yellow toner (Y), magenta toner (M), cyan toner (C) and black (Bk). The two-component foil transfer surface forming agent is composed of a carrier in which ferrite is used as a core and an insulating resin is coated around the core and a foil transfer surface forming toner. In addition, the two-component developer includes a carrier having a ferrite core and an insulating resin coated around it, a known binder resin, a known pigment, a colorant such as carbon black, a charge control agent, silica, titanium oxide, and the like. And a toner of each color contained.

  For example, the carrier has an average particle diameter of 10 to 50 μm, a saturation magnetization of 10 to 80 emu / g, and the toner has a particle diameter of 4 to 10 μm. Further, the charging characteristics of the toners used in the foil transfer surface forming apparatus shown in FIG. 3 including the clear toner according to the present invention are negative charging characteristics, and the average charge amount is −20 to −60 μC / g. Preferably there is. The two-component foil transfer surface forming agent and the two-component developer are prepared by mixing and adjusting the carrier and the toner so that the toner concentration becomes 4% by mass to 10% by mass.

The intermediate transfer belt 26 that is an intermediate transfer member is rotatably supported by a plurality of rollers. The intermediate transfer belt 26 is an endless belt having a volume resistance of 10 ⁶ to 10 ¹² Ω · cm, for example. The intermediate transfer belt 26 is made of a known resin material such as polycarbonate (PC), polyimide (PI), polyamideimide (PAI), polyvinylidene fluoride (PVDF), tetrafluoroethylene-ethylene copolymer (ETFE). Can be formed. The thickness of the intermediate transfer belt 26 is preferably 50 to 200 μm.

  The foil transfer surface H formed on the photoreceptor 11H from the foil transfer surface forming toner supply device 21H is transferred onto the rotating intermediate transfer belt 26 by the primary transfer roller 13H (primary transfer). The foil transfer surface H transferred onto the intermediate transfer belt 26 is transferred onto a substrate p1 supplied from a sheet feeding device 40 described later (secondary transfer), and the substrate p1 onto which the foil transfer surface H is transferred will be described later. The foil transfer surface H is fixed by passing through the foil transfer device 50.

  Then, the base P on which the foil transfer surface H is fixed is once transported through a paper transport path having a paper discharge roller 47, and then transported to a transfer foil supply path 51 via a transport path 48. Transfer foil is supplied from the foil supply unit 70. Further, the substrate P passes through the foil transfer device 50 again with the transfer foil being supplied, and the foil is transferred onto the foil transfer surface H by heating and pressurization of the foil transfer device 50.

  In this way, the substrate P on which the foil transfer surface H is formed and the foil is transferred is conveyed in front of the intermediate transfer belt 26 via the double-sided conveyance path 48, and this time, toner image formation is performed. Is done. First, the primary transfer rollers 13Y, 13M on the intermediate transfer belt 26 on which the respective color toner images formed on the photoreceptors 11Y, 11M, 11C, 11Bk are also rotated by the respective color toners from the toner supply devices 21Y, 21M, 21C, 21Bk. , 13C, and 13Bk, and a combined full-color image is formed on the intermediate transfer belt 26. On the other hand, the residual toner is removed by the cleaning devices 25 (25H, 25Y, 25M, 25C, and 25Bk) of the photosensitive member 11H that has transferred the foil transfer surface H and the photosensitive members 11Y, 11M, 11C, and 11Bk that have transferred the toner image. .

  The substrate p1 constituting the product P accommodated in the substrate storage unit (tray) 41 constituting the sheet feeding device 40 is fed by the first sheet feeding unit 42 and fed by the sheet feeding rollers 43, 44, 45A, 45B, The sheet is conveyed to the secondary transfer roller 13A through the registration roller (second paper feed unit) 46 and the like, and the foil transfer surface H and the color image are transferred onto the base p1 (secondary transfer).

  It should be noted that the three-stage base storage portions 41 arranged in a vertical column in the lower part of the image forming apparatus 1 have substantially the same configuration, and thus are denoted by the same reference numerals. Further, since the three-stage sheet feeding units 42 have almost the same configuration, the same reference numerals are given. The substrate storage unit 41 and the sheet supply unit 42 are collectively referred to as a sheet feeding device 40.

  The foil transfer surface H and the full-color image transferred onto the substrate P constituting the product Q are fixed on the substrate P by a foil transfer device 50 that heats, pressurizes, melts and cures the foil transfer surface H and the full-color image. . The substrate P is nipped and conveyed by the conveyance roller pair 57, is discharged from the paper discharge roller 47 provided in the paper discharge conveyance path, and is placed on a paper discharge tray 90 outside the apparatus.

  On the other hand, the intermediate transfer belt 26 in which the foil transfer surface H and the full-color toner image are transferred onto the substrate P by the secondary transfer roller 13A and the substrate P is separated by the curvature remains by the cleaning device 261 for the intermediate transfer belt. Toner is removed.

  In addition, when forming the foil transfer surface H and a full-color image on both surfaces of the base | substrate P which comprises the product Q, the foil transfer surface and the full-color image were formed in the 1st surface of the base | substrate P, and also these were fuse | melted and hardened. Thereafter, the base P is branched from the paper discharge conveyance path by the branch plate 49. Then, the sheet is introduced into the conveyance path 48 and turned upside down and conveyed again to the paper feed roller 45B. The substrate P forms a foil transfer surface H and a full color toner image on the second surface by the foil transfer surface forming unit 20H and the image forming units 20Y, 20M, 20C, and 20Bk for each color, and is heated and pressurized by the fixing device 50. Then, the paper is discharged out of the apparatus by the paper discharge roller 47. In this way, a full color image having a foil image on both sides of the substrate P can be formed.

Further, as shown in FIG. 6, the image forming apparatus 1 in which the intermediate transfer belt 26, the foil transfer device 50, and the transfer foil supply unit 70 are arranged, for example, forms the foil transfer surface H, transfers the foil, and the toner image by the following procedure. Formation can be performed. That is,
(1) The foil transfer surface H formed on the intermediate transfer belt 26 is transferred to the base P at the location of the secondary transfer roller 13A.
(2) The foil transfer device 50 is used as a fixing device, and the foil transfer surface H is fixed through the substrate P.
(3) The transfer foil F is supplied onto the substrate P by the transfer foil supply unit 70, and the foil is transferred by the foil transfer device 50 via the conveyance path 48.
(4) The substrate P to which the foil has been transferred via the conveyance path 48 is conveyed to the intermediate transfer belt 26, and the full color toner image is transferred onto the substrate P.
(5) The foil transfer device 50 is used as a fixing device, and the full color toner image is fixed through the substrate P.
(6) The substrate P passes through the transfer foil supply unit 70 as it is, and is discharged out of the apparatus via the discharge roller 47.

  With the above procedure, the image forming apparatus 1 shown in FIG. 5 or 6 forms the foil transfer surface H on the base P constituting the product Q, and transfers the foil onto the formed foil transfer surface H. Then, it is possible to form a full color image using color toner on the base P to which the foil has been transferred.

  Next, a transfer foil that can be used in the present invention will be described with reference to FIG. FIG. 7 is a schematic diagram showing a cross-sectional structure of a typical transfer foil that can be used in the present invention. The transfer foil F that can be used in the present invention includes at least a film-like support f0 made of a resin, a foil layer f2 containing a colorant, a metal, and the like, and an adhesive layer f1 containing an organic material that exhibits adhesiveness. The foil layer f2 and the adhesive layer f1 are transferred onto the product P. The adhesive layer f1 is provided on the outermost surface of the transfer foil F, and is disposed so as to be in direct contact with the surface of the substrate P by transfer and firmly adhere the foil layer f2 to the surface of the substrate P. In addition, the transfer foil F shown in FIG. 7 has a release layer f3 between the support f0 and the foil layer f2. Hereinafter, each layer of the support f0, the foil layer f2, and the adhesive layer f1 will be described.

  First, the support f0 is a film or sheet made of a resin or the like. Examples of the material for the support f0 include known resin materials such as polyethylene terephthalate (PET) resin, polyethylene naphthalate (PEN) resin, polypropylene (PP) resin, polyethersulfone resin, and polyimide resin. In addition to these resin materials, materials such as paper can be used.

  Further, as the support f0, one having a single layer structure or a multilayer structure can be used. In the case of adopting a multilayer structure for the support f0, the support f0 preferably includes a release layer f3 that can be used for adjusting the peeling resistance as the outermost surface layer on the foil layer f2 side. As the material of the release layer f3, for example, a thermosetting resin using melamine or isocyanate as a curing agent, an ultraviolet ray containing an acrylate or epoxy resin, or a known release agent added to an electron beam curable resin. Can be mentioned. Examples of known release agents that can be added to the release layer f3 include fluorine-based or silicon-based monomers or polymers.

  The foil layer f2 contains a colorant, a metal material, and the like, and expresses an aesthetic appearance after being transferred onto the product P. When transferred onto the product P, the foil layer f2 is required to have a performance of peeling more smoothly than the support f0. Since the outermost surface of the product P is formed after the transfer, durability is also required. The foil layer f2 can be formed by applying a known resin satisfying the above performance on the support f0 using a coater such as a gravure coater, a micro gravure coater, and a roll coater. Examples of such a known resin include an acrylic resin, a styrene resin, a melamine resin, and the like, and the resin can be colored by adding a known dye or pigment.

  Moreover, when forming the finished foil which has metallic luster, it is possible to form by providing a reflection layer in the above-mentioned resin by a well-known method using a metal etc. As a metal material for forming the reflective layer, for example, a nickel-chromium-iron alloy, an alloy such as bronze, aluminum bronze or the like can be used in addition to a carrier such as aluminum, tin, silver, chromium, nickel, and gold. It is. Examples of the method for forming the reflective layer using the metal material include known methods such as vapor deposition, sputtering, and ion plating, and a reflective layer having a thickness of about 10 nm to about 100 nm is formed. Is possible. In addition, the reflective layer can be subjected to a patterning process for imparting a regular pattern by using a known processing method such as, for example, water-washed celite processing, etching processing, or laser processing.

  The adhesive layer f1 includes, for example, a layer containing a heat-sensitive adhesive called a so-called hot melt type that develops tackiness by heating. Examples of the heat-sensitive adhesive include known thermoplastic resins that can be used for hot-melt type adhesives such as acrylic resin, vinyl chloride-vinyl acetate copolymer, epoxy resin, and ethylene-vinyl alcohol copolymer. Can be mentioned. The adhesive layer f1 can be formed, for example, by applying the above-described resin on the foil layer f2 using a coater such as a gravure coater, a micro gravure coater, or a roll coater.

  Examples of the present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In addition, although there is a part described as "part" in the following sentence, it represents "mass part".

1. Preparation of “Foil Transfer Surface Forming Toners A to I” and “Foil Transfer Surface Forming Developers A to I” Through the above-described resin fine particle preparation process by the multistage polymerization method and the aggregation and fusion processes by the emulsion association method, Eight types of “foil transfer surface forming toners A to I” having different storage elastic moduli G ′ at 120 ° C. were prepared. Further, these foil transfer surface forming toners were mixed with a resin-coated carrier in the procedure described later to prepare “Foil transfer surface forming developers A to I”.

1-1. Production of “Toner A for Foil Transfer Surface Formation” (1) Production of “Resin Fine Particle A2” As shown below, “resin fine particle A3” was produced through a three-stage polymerization reaction, that is, by a multistage polymerization method.

(First stage polymerization)
4 parts by mass of sodium polyoxyethylene-2-dodecyl ether sulfate and 3000 parts by mass of ion-exchanged water are put into a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device, and the stirring speed is 230 rpm under a nitrogen stream. The liquid temperature was raised to 80 ° C. while stirring. After the temperature increase, an initiator solution in which 5 parts by mass of potassium persulfate (KPS) was dissolved in 200 parts by mass of ion-exchanged water was added, the temperature of the liquid was set to 75 ° C., and a monomer mixed solution containing the following compound was added to 1 It was added dropwise over time. That is,
Styrene 567 parts by mass n-butyl acrylate 165 parts by mass Methacrylic acid 68 parts by mass After the above monomer mixed solution was dropped, a polymerization reaction was carried out by heating and stirring at a liquid temperature of 75 ° C. for 2 hours to obtain “resin fine particles”. A dispersion of “A1” was prepared. In addition, it was 300,000 when the weight average molecular weight of "resin fine particle A1" was measured by the gel permeation chromatography method.

(Second stage polymerization)
2 parts by mass of sodium polyoxyethylene-2-dodecyl ether sulfate and 1270 parts by mass of ion-exchanged water are put into a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction device, and the stirring speed is 230 rpm under a nitrogen stream. The liquid temperature was raised to 80 ° C. while stirring. After the temperature rise, a mixed solution containing 40 parts by mass of the above-mentioned “resin fine particle A1” dispersion and the following compound was added, and a mechanical disperser “CLEARMIX (M Technique Co., Ltd.) having a circulation path was added. Manufactured)) for 1 hour to prepare a dispersion containing emulsified particles. The compounds contained in the mixed solution are as follows. That is,
Styrene 123 parts by mass n-butyl acrylate 45 parts by mass Methacrylic acid 10 parts by mass Acrylic acid 10 parts by mass n-Octyl mercaptan 0.5 parts by mass Paraffin wax “HNP-57” (manufactured by Nippon Seiki Co., Ltd.) 82 parts by mass The above dispersion Into this, an initiator solution in which 5 parts by mass of potassium persulfate (KPS) is dissolved in 100 parts by mass of ion-exchanged water is added, and the polymerization reaction is performed by heating and stirring for 1 hour at a liquid temperature of 80 ° C. A dispersion of “resin fine particles A2” was prepared.

(Third stage polymerization)
After adding an initiator solution in which 10 parts by mass of potassium persulfate (KPS) is dissolved in 200 parts by mass of ion-exchanged water to the dispersion of “resin fine particles A2”, the following compound is obtained under a temperature condition of 80 ° C. The mixed solution in which was dissolved was added dropwise over 1 hour. The compounds contained in the mixed solution are as follows. That is,
Styrene 390 parts by weight n-butyl acrylate 143 parts by weight Methacrylic acid 37 parts by weight n-octyl mercaptan 13 parts by weight After completion of the dropwise addition, the mixture was heated and stirred for 2 hours at a liquid temperature of 80 ° C. Cooling to 28 ° C. produced a dispersion of “resin fine particles A3”.

(2) Preparation of “Foil transfer surface forming toner A” (Aggregation / fusion process)
In a reaction vessel equipped with a stirrer, temperature sensor, cooling pipe, nitrogen introduction device,
"Resin fine particles A3" 450 parts by mass (solid content conversion)
Ion-exchanged water 1100 parts by mass Polyoxyethylene-2-dodecyl ether sodium sulfate 2 parts by mass was added and stirred. After adjusting the temperature in the reaction vessel to 30 ° C., the pH was adjusted to 10 by adding a 5 mol / liter sodium hydroxide aqueous solution.

  Next, an aqueous solution obtained by dissolving 60 parts by mass of magnesium chloride hexahydrate as a flocculant in 60 parts by mass of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. After the addition, the temperature was started after standing for 3 minutes, and the temperature of the system was raised to 85 ° C. over 60 minutes, and the aggregation and fusion of the “resin fine particles A3” were continued while maintaining the temperature at 85 ° C. did. In this state, the particle size of the formed particles was measured using “Multisizer 3 (manufactured by Beckman Coulter)”, and when the volume-based median diameter of the particles became 6.7 μm, 200 parts by mass of sodium chloride was used. An aqueous solution in which 860 parts by mass of ion-exchanged water was dissolved was added to stop aggregation.

  After agglomeration is stopped, the liquid temperature is set to 95 ° C. for 8 hours as a ripening treatment, and the mixture is heated for 8 hours. Then, “toner base particle A” was formed. After the aging treatment, the liquid temperature was cooled to 30 ° C., the pH in the liquid was adjusted to 2 using hydrochloric acid, and the stirring was stopped.

  The “toner base particle A” produced through the above steps is subjected to solid-liquid separation with a basket-type centrifuge “MARK III model number 60 × 40 (manufactured by Matsumoto Kikai Co., Ltd.)”, and a wet cake of “toner base particle A” is obtained. Formed. The wet cake was washed with ion exchanged water at 40 ° C. until the electric conductivity of the filtrate reached 5 μS / cm with the basket-type centrifuge, and then transferred to “Flash Jet Dryer (manufactured by Seishin Enterprise Co., Ltd.)” A “toner base particle A” was produced by performing a drying process until the water content became 0.5 mass%.

(External processing)
The following external additive is added in an amount of 100 parts by mass to the “toner base particle A” thus prepared, and external addition processing is performed with a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.). Was made.

Hexamethylsilazane-treated silica (average primary particle size 12 nm, hydrophobicity 68)
1.0 part by mass n-octylsilane-treated titanium dioxide (average primary particle size 20 nm, hydrophobicity 63)
0.3 parts by mass The external addition treatment by the Henschel mixer was performed under the conditions of a peripheral speed of the stirring blade of 35 m / second, a treatment temperature of 35 ° C., and a treatment time of 15 minutes.

By the above procedure, “foil transfer surface forming toner A” was prepared. The “foil transfer surface forming toner A” produced by the above procedure has a volume-based median diameter of 6.7 μm, and a storage elastic modulus G ′ at 120 ° C. measured by the measurement method is 4.4 × 10 ³ N / It was m ^2.

1-2. Production of “Foil Transfer Surface Forming Toners B to I” (1) Production of “Foil Transfer Surface Formation Toner B” In the production of “Foil Transfer Surface Formation Toner A”, “Resin Fine Particle A1” is produced. 68 parts by mass of methacrylic acid used in the one-stage polymerization was changed to 68 parts by mass of itaconic acid. In addition, the methacrylic acid and acrylic acid used in the second stage polymerization for producing the “resin fine particles A2”
Itaconic acid 10 parts by weight Methacrylic acid 5 parts by weight Acrylic acid 5 parts by weight. Otherwise, the same procedure was followed to produce “foil transfer surface forming toner B”. The produced “foil transfer surface forming toner B” had a volume-based median diameter of 6.7 μm and a storage elastic modulus G ′ measured at 120 ° C. of 5.4 × 10 ³ N / m ^{2 according} to the measurement method. .

(2) Production of “Foil Transfer Surface Forming Toner C” In the production of “Foil Transfer Surface Formation Toner A”, 68 parts by mass of methacrylic acid used in the first stage polymerization for producing “resin fine particles A1” is as follows. The compound was changed. That is,
Itaconic acid 28 parts by mass Aconitic acid 40 parts by mass In addition, methacrylic acid and acrylic acid used in the second stage polymerization for producing “resin fine particles A2”
Itaconic acid 6 parts by weight Aconitic acid 4 parts by weight Methacrylic acid 5 parts by weight Acrylic acid 5 parts by weight Otherwise, the same procedure was followed to produce “foil transfer surface forming toner C”. The produced “foil transfer surface forming toner C” had a volume-based median diameter of 6.7 μm and a storage elastic modulus G ′ at 120 ° C. of 6.3 × 10 ³ N / m ² as measured by the measurement method. .

(3) Production of “Foil Transfer Surface Forming Toner D” In the production of “Foil Transfer Surface Formation Toner A”, 68 parts by mass of methacrylic acid used in the first stage polymerization for producing “resin fine particles A1” is as follows. The compound was changed. That is,
34 parts by weight of fumaric acid 34 parts by weight of aconitic acid In addition, the methacrylic acid and acrylic acid used in the second stage polymerization for producing “resin fine particles A2”
Fumaric acid 5 parts by weight Aconitic acid 5 parts by weight Methacrylic acid 5 parts by weight Acrylic acid 5 parts by weight Otherwise, the same procedure was followed to produce “Foil transfer surface forming toner D”. The produced “foil transfer surface forming toner D” had a volume-based median diameter of 6.6 μm and a storage elastic modulus G ′ measured at 120 ° C. of 6.1 × 10 ³ N / m ^{2 according} to the measurement method. .

(4) Production of “Foil Transfer Surface Forming Toner E” In the production of “Foil Transfer Surface Formation Toner A”, the amount of n-octyl mercaptan added was 4 in the second-stage polymerization for producing “resin fine particles A2.” The polymerization reaction was carried out in the same procedure except that the content was changed to 0.0 parts by mass. Further, the addition amount of the compound constituting the mixed solution added to the resin fine particle dispersion in the third stage polymerization for producing “resin fine particles A3”,
Styrene 428 parts by mass n-butyl acrylate 131 parts by mass Methacrylic acid 11 parts by mass n-octyl mercaptan 13 parts by mass Otherwise, the same procedure was followed to produce “foil transfer surface forming toner E”. The “foil transfer surface forming toner E” produced by the above procedure has a volume-based median diameter of 6.7 μm and a storage elastic modulus G ′ at 120 ° C. measured by the measurement method of 1.0 × 10 ³ N / m ^2. Met.

(5) Production of “Foil Transfer Surface Forming Toner F” In the production of “Foil Transfer Surface Formation Toner A”, the addition of “resin fine particle A1” dispersion in the second stage polymerization for producing “resin fine particle A2” The amount was changed to 200 parts by mass in terms of solid content. Further, the addition amount of the compound constituting the mixed solution added to the resin fine particle dispersion in the third stage polymerization for producing “resin fine particles A3”,
Styrene 353 parts by weight n-butyl acrylate 148 parts by weight Methacrylic acid 68 parts by weight n-octyl mercaptan 13 parts by weight Otherwise, the same procedure was used to prepare “Foil transfer surface forming toner F”. The “foil transfer surface forming toner F” produced by the above procedure has a volume-based median diameter of 6.6 μm. When the storage elastic modulus G ′ at 120 ° C. is measured by the measurement method, 1.0 × 10 ⁴ N / m ² Met.

(6) Preparation of “Foil Transfer Surface Forming Toner G” In the preparation of “Foil Transfer Surface Forming Toner A”, the amount of n-octyl mercaptan added was 5 in the second stage polymerization for preparing “resin fine particles A2.” Changed to 0.0 parts by mass. Further, the addition amount of the monomer constituting the mixed solution to be added to the resin fine particle dispersion in the third stage polymerization for producing the “resin fine particles A3”,
Styrene 430 parts by weight n-butyl acrylate 131 parts by weight Methacrylic acid 9 parts by weight n-octyl mercaptan 13 parts by weight Otherwise, the same procedure was followed to produce “foil transfer surface forming toner G”. The “foil transfer surface forming toner G” produced by the above procedure has a volume-based median diameter of 6.7 μm, and a storage elastic modulus G ′ at 120 ° C. measured by the measurement method is 5.5 × 10 ² N / m ^2. was.

(7) Preparation of “Foil Transfer Surface Forming Toner H” In the preparation of “Foil Transfer Surface Forming Toner A”, the addition of “resin fine particle A1” dispersion in the second stage polymerization for preparing “resin fine particle A2” While changing the amount to 200 parts by mass in terms of solid content, the amount of n-octyl mercaptan added was changed to 0.2 parts by mass. Further, the addition amount of the monomer constituting the mixed solution to be added to the resin fine particle dispersion in the third stage polymerization for producing the “resin fine particles A3”,
Styrene 331 parts by mass n-butyl acrylate 154 parts by mass Methacrylic acid 86 parts by mass n-octyl mercaptan 13 parts by mass Otherwise, the same procedure was followed to produce “foil transfer surface forming toner H”. The “foil transfer surface forming toner H” produced by the above procedure has a volume-based median diameter of 6.5 μm, and the storage elastic modulus G ′ measured at 120 ° C. by the above-described measurement method is 4.3 × 10 ⁴ N / m. ² .

(8) Preparation of “Foil Transfer Surface Forming Toner I” In the preparation of “Foil Transfer Surface Forming Toner A”, methacrylic acid 20 was used without using acrylic acid in the second-stage polymerization for preparing “resin fine particles A2.” A “foil transfer surface forming toner I” was produced by following the same procedure except that the mass part was changed. The “foil transfer surface forming toner I” produced by the above procedure has a volume-based median diameter of 6.7 μm, and the storage elastic modulus G ′ at 120 ° C. measured by the measurement method is 4.9 × 10 ³ N / m. ² .

  The type of polymerizable monomer having a carboxy group (—COOH) used in the production of “foil transfer surface forming toners A to I” produced by the above procedure and the storage elastic modulus G ′ at 120 ° C. Table 1 shows.

1-3. Preparation of “Foil Transfer Surface Forming Developers A to I” Each of the “Foil Transfer Surface Forming Toners A to I” and an acrylic resin-coated ferrite carrier having a volume average particle size of 40 μm were mixed using a V-type mixer. Thus, “developers A to I for forming a foil transfer surface” in the form of a two-component developer having a toner concentration of 6% by mass were prepared.

2. Evaluation Equipment Evaluation was carried out by mounting the foil transfer device 50 shown in FIG. 1 on a commercially available digital color multifunction peripheral “bizhub C353 (manufactured by Konica Minolta Business Technologies, Inc.)” having the configuration of the image forming apparatus of FIG. . The pressure application to the transfer foil and the foil transfer surface was set by combining the pressure pads 53a (53aa to 53ab) and 53b (53ba to 53bf) shown in FIG. That is, the pressure pad 53a applies a maximum pressure to the transfer foil and the foil transfer surface, and the pressure pad 53b applies a pressure to the transfer foil and the foil transfer surface before the maximum pressure is applied. Table 2 shows the pressure application timing and application pressure of each pressure pad.

  The specifications, heating conditions, and pressure conditions of the heating roller and pressure belt of the foil transfer apparatus 50 mounted on the image forming apparatus are as follows.

(1) Specifications of heating roller and pressure belt Heating roller: 357 mm wide, 62 mm outer diameter, 5 mm thick aluminum substrate with 1.5 mm thick silicone rubber layer arranged Pressure belt; 357 mm width, A silicone rubber layer having a thickness of 10 μm arranged on a polyimide resin substrate having a thickness of 50 μm. Nip width: 7.5 mm
Nip passing time t: 0.1 sec
In addition, the polyimide resin base | substrate which comprises a pressurization belt was produced in the following procedures. A polyimide precursor solution having a viscosity of 150 Pa · s obtained by dissolving “U varnish S (trade name) manufactured by Ube Industries, Ltd.”, which is a commercially available polyimide precursor, in dimethylacetamide / naphtha (9/1) is aluminum. A die coat was applied to the surface of the core. Then, the core body coated with the polyimide precursor solution was heat-treated at a temperature of 250 ° C. for 25 minutes to prepare a polyimide resin substrate having a thickness of 50 μm. Further, the same silicone rubber layer as that used for the heating roller was formed on the surface of the polyimide resin substrate by a known method so as to have a thickness of 10 μm.

(2) Heating conditions A heat source (thermistor temperature control) is placed inside the heating roller, pressure belt, and pressure roller.
Heating roller surface temperature: set at 160 ° C. Pressure belt, pressure roller surface temperature: set at 100 ° C. (3) Pressurizing condition Variable by spring load and applied from pressing member (pressing member 53) (maximum pressure at 980 N) Set to be 390 kPa)
3. Evaluation experiment 3-1. Evaluation Conditions (1) Settings of “Examples 1 to 14” and “Comparative Examples 1 to 4” “Foil Transfer Surface Forming Developers A to I”, Foil Transfer Device Used for Evaluation, Timing to Apply Maximum Pressure The pressure values were combined as shown in Table 3 below and mounted on the commercially available digital color multifunction peripheral. Here, a combination of a developer and a foil transfer device in which the storage elastic modulus of toner, the maximum pressure application timing, and the pressure application before the maximum pressure application are all within the range defined by the present invention is referred to as “Example 1”. To 14 ”, and combinations that do not satisfy the configuration of the present invention are referred to as“ Comparative Examples 1 to 4 ”. Note that the pressure applied before the maximum pressure is given as a preliminary pressure in Table 3.

(2) Evaluation Image First, an image support P for forming a foil image is a commercially available B4 size image support “OK top coat + (basis weight 157 g / m ² , paper thickness 131 μm)” (Oji Paper Co., Ltd.) Made) ”. Further, the supply amount of toner for forming the foil transfer surface is set to 4 g / m ^2, and the transfer foil “BL No. 2 Gold 2.8 (Murata Gold Foil Co., Ltd.) having the layer configuration of FIG. 7 is used for the transfer foil. )"It was used.

  In addition, the image support conveyance direction during image formation for evaluation is the B4 size image support vertical direction, the image support conveyance speed is 73 mm / sec, under a normal temperature and humidity environment (temperature 20 ° C., relative humidity 50% RH). An image for evaluation was formed.

  The image for evaluation formed on the image support P is as shown in FIG. 9, and the foil image S is arranged above eleven character images Sa to Sm marked “Japanese boy's intention and romance”, above the human image. It is the image Sn of the speech balloon which put the dialogue which is done. Then, after forming the foil image, a toner image T is formed on the image support P by the toner image forming unit 20 constituting the image forming apparatus described above. The toner image T is a person image Ta shown in the figure, a character image Tb written as “Oira is not Ishimatsu, Edokko, and sushi,” in a balloon, and a thin monochromatic image with a reflection density of 0.1. The background image Tc.

(3) Evaluation items For each example and each comparative example, 100 continuous prints were made, 10 prints were arbitrarily selected from the created 100 prints, and burrs were generated on the transfer surface. The presence or absence of partial omission of the transfer foil was evaluated to evaluate the finish of the foil image. Moreover, the adhesive strength of the formed foil image was evaluated.

<Film image finish evaluation (existence of burrs and partial omission)>
About the selected 10 printed materials, the foil images Sa to Sm of 11 characters and the foil image Sn of the balloon on the printed material are visually observed using the naked eye and a magnifying glass of 10 times magnification, and are classified into the following ranks. , And evaluated how many of each rank. That is,
Rank A: No burr generation or partial omission observed in all 11 characters and balloon foil images in both macroscopic and magnifier observations Rank B: All 11 characters and balloon foil images in macroscopic observation No burrs or partial omissions were observed, and there were 1 to 2 characters with slight burrs or partial omissions observed by magnifying glass. Rank C; No burrs or partial omissions were observed in all, and there were 3 to 5 characters with slight burrs or partial omissions observed by magnifying glass. Rank D; 11 characters and balloon foil for macroscopic observation There were no burrs or partial omissions in all images, and there were 6 or more characters with slight burrs or partial omissions observed by magnifying glass. Rank E; One or more characters were found to be generated or partially missing. Based on the above rank, the following evaluation was made. That is,
Excellent; all 10 are of rank A and rank B Good; rank C is 1 to 3 in 10 and the rest is rank A and rank B Pass; rank C is 4 or more in 10 The rest are those of rank A and rank B. Rejected: 10 out of 10 rank D and rank E.

<Evaluation of adhesive strength of foil image>
For the selected 10 prints, after tape was applied to the balloon image Sn, the tape was peeled off by hand, and the state of the foil image from which the tape was peeled off was observed with the naked eye and a 10 × magnification loupe. It was evaluated in the same way. The tape used was “Scotch Mending Tape MP-18 (manufactured by Sumitomo 3M Limited)”.

○: There was no peeling that could be confirmed by magnifying observation. △: There was peeling that could be confirmed by loupe observation, but it was judged that there was no problem with the naked eye. Based on the above rank, it was evaluated as follows. That is,
Excellent: All 10 sheets are good. Good: △ is less than 5 in 10 sheets and the rest is ○ Passed; △ is 6 to 10 in 10 sheets and the rest is ○ Fail: 10 sheets There is even one x inside.

  The above results are shown in Table 4 below.

  As shown in Table 4, “Examples 1 to 14” having the configuration of the present invention are foils that have a good finish without any burrs or foil partial loss, and have a strong adhesive force. It was confirmed that an image was obtained. On the other hand, “Comparative Examples 1 to 4” not having the configuration of the present invention resulted in the formed foil images having a predetermined level of finish and adhesive strength.

1 Image forming apparatus 11 (11H, 11Y, 11M, 11C, 11Bk) Photoconductor 12 (12H, 12Y, 12M, 12C, 12Bk) Charging roller, band electrode 13 (13A, 13H, 13Y, 13M, 13C, 13Bk) Transfer Roller 14 Toner supply roller 20H Foil transfer surface forming portion 20Y, 20M, 20C, 20Bk Toner image forming portion 21H Toner supply device for forming foil transfer surface 21Y, 21M, 21C, 21Bk Toner supply device (developing device)
23 Transport roller 25 (25H, 25Y, 25M, 25C, 25Bk) Cleaning device 26 Intermediate transfer belt 30 (30H, 30Y, 30M, 30C, 30Bk) Exposure unit 50 Foil transfer device 51 (R1) Heating roll 52 (R2) Seamless Belt 53 Press member 53a, 53b Pressure pad N Nip part 60 Image reading part 70 Transfer foil supply part 71 Transfer foil supply roller 72 Transfer foil winding roller 73a, 73b Foil transfer roller 80 Pressure distribution measuring system 81 Computer 82 Sensor connector 83 Sensor Sheet 831 Resin sheet 832 Electrode (row electrode, column electrode)
833 conductive paste layer 834 conductive ink layer F transfer foil f0 support f1 adhesive layer f2 foil layer f3 release layer H foil transfer surface P substrate (image support)
R1, R2 Heating and pressing means

Claims (16)

at least,
Exposing the photoreceptor to form an electrostatic latent image;
Supplying toner to the photoconductor on which an electrostatic latent image is formed to form a foil transfer surface;
Transferring the foil transfer surface formed on the photoreceptor to a substrate;
Fixing the foil transfer surface transferred to the substrate;
Supplying a transfer foil to a substrate on which the foil transfer surface is fixed;
An image forming method comprising a step of transferring the foil to the foil transfer surface by heating the transfer foil in a state of being in contact with the foil transfer surface,
The toner used for forming the foil transfer surface has a storage elastic modulus G ′ at 120 ° C. of 1.0 × 10 ³ N / m ² or more and 1.0 × 10 ⁴ N / m ² or less,
The process of transferring the foil to the foil transfer surface is as follows:
When the transfer foil and the foil transfer surface pass through a nip formed by a heating member and a pressure member, the foil is transferred to the foil transfer surface,
When t is the time for the transfer foil and the foil transfer surface to pass through the nip portion,
A maximum pressure is applied to the transfer foil and the foil transfer surface between 0.6 t and 1.0 t; and
An image forming method, wherein pressure is applied to the transfer foil and the foil transfer surface under a heated state from 0.3 t until the maximum pressure is applied.   The pressure applied to the transfer foil and the foil transfer surface between 0.3 t and the time when the maximum pressure is applied is 1/8 or more and 1/3 or less of the maximum pressure. The image forming method according to claim 1.   The image forming method according to claim 1, wherein a maximum pressure applied to the transfer foil and the foil transfer surface is 200 kPa or more and 450 kPa or less.   The image according to claim 1, wherein the heating member is a heating roll, and the pressure member has at least a belt member and a pressing member that presses the belt member. Forming method. The binder resin contained in the toner used for forming the foil transfer surface is:
The image forming method according to claim 1, comprising at least a polymer formed using a vinyl monomer having a carboxy group. Binder resin contained in the toner used for forming the foil transfer surface,
The image forming method according to claim 5, comprising at least a polymer formed using methacrylic acid. The toner used for forming the foil transfer surface is:
The image forming method according to claim 6, comprising at least a copolymer resin formed using styrene, n-butyl acrylate, and methacrylic acid. The toner used for forming the foil transfer surface is:
At least a step of producing resin fine particles through a step of performing a polymerization reaction a plurality of times;
The image forming method according to any one of claims 5 to 7, wherein the image forming method is produced through a step of aggregating and fusing the resin fine particles produced in the step in an aqueous medium. at least,
A photoreceptor that forms an electrostatic latent image by exposure by an exposure means;
A foil transfer surface forming means for supplying a toner to the photoreceptor on which an electrostatic latent image is formed to form a foil transfer surface;
Transfer means for transferring the foil transfer surface formed on the photoreceptor to a substrate;
Fixing means for fixing the foil transfer surface transferred to the substrate;
A transfer foil supply means for supplying a transfer foil to the substrate on which the foil transfer surface is fixed by the fixing means;
Foil transfer in which the transfer foil supplied by the transfer foil supply means is brought into contact with the foil transfer surface, and heating is performed with the transfer foil in contact with the foil transfer surface to transfer the foil to the foil transfer surface. An image forming apparatus having means,
The toner supplied from the foil transfer surface forming means has a storage elastic modulus G ′ at 120 ° C. of 1.0 × 10 ³ N / m ² or more and 1.0 × 10 ⁴ N / m ² or less,
The foil transfer means is at least
It has a heating member and a pressure member that form a nip portion that allows the foil transfer surface and the transfer foil to pass in contact with each other,
The heating member and the pressure member are
When t is the time for the transfer foil and the foil transfer surface to pass through the nip portion,
Applying a maximum pressure to the transfer foil and the foil transfer surface between 0.6 t and 1.0 t; and
An image forming apparatus characterized in that a pressure is applied while heating the transfer foil and the foil transfer surface between 0.3 t and the time when the maximum pressure is applied.   The pressure applied to the transfer foil and the foil transfer surface between 0.3 t and the maximum pressure is 1/8 or more and 1/3 or less of the maximum pressure. Item 10. The image forming apparatus according to Item 9.   11. The image forming apparatus according to claim 9, wherein a maximum pressure applied to the transfer foil and the foil transfer surface by the foil transfer unit is 200 kPa or more and 450 kPa or less. The foil transfer means is
The image forming apparatus according to any one of claims 9 to 11, wherein the heating member includes a heating roll, and the pressing member includes at least a belt member and a pressing member that presses the belt member. apparatus. The binder resin contained in the toner used for forming the foil transfer surface is:
The image forming apparatus according to claim 9, comprising at least a polymer formed using a vinyl monomer having a carboxy group. Binder resin contained in the toner used for forming the foil transfer surface,
The image forming apparatus according to claim 13, comprising at least a polymer formed using methacrylic acid. The toner used for forming the foil transfer surface is:
The image forming apparatus according to claim 14, comprising at least a copolymer resin formed using styrene, n-butyl acrylate, and methacrylic acid. The toner used for forming the foil transfer surface is:
At least a step of producing resin fine particles containing the copolymer resin through a step of performing a plurality of polymerization reactions;
16. The image forming apparatus according to claim 13, wherein the image forming apparatus is manufactured through a process of aggregating and fusing the resin fine particles prepared in the process in an aqueous medium.

Images