JP6287251B2 - Heating and pressing method and method for producing releasable information sheet - Google Patents

Description

  The present invention relates to a heating and pressing apparatus, a heating and pressing method, and an apparatus for manufacturing a removable information sheet.

Catalogs, covers, DM postcards, and the like are conventionally used for a predetermined purpose in which images and characters are formed by printing.
Depending on these uses, the printing surface may be protected by surface processing or a film for protection from water wetting and dirt, or for glossiness.
Surface processing includes overprinting, vinyl drawing, and press coating, which must be applied after printing. Recently, treatment with an ultraviolet curable composition has become mainstream from the viewpoint of cost and environment.

In addition, DM postcards and the like use means capable of pressure-bonding a printing surface on which information is input, concealing information, and re-peeling when necessary. As the adhesive, latex rubber, an ultraviolet curable pressure sensitive composition, or the like is used, but an ultraviolet curable pressure sensitive composition has become the mainstream, as in surface processing.
Recently, changes in information have become frequent, and there is an increasing number of systems that can output variable information, such as changing information part by part, and speeding up of print output is desired. On-demand printing is used.
As an apparatus used for on-demand printing, there are usually an electrophotographic system and an inkjet system, but an electrophotographic system using toner is mainly used for output including an image.
An image recorded by an electrophotographic method is reproduced by fixing a powder color material called toner to a recording medium with heat or pressure.

  Also, for UV curable compositions, several commercially available UV curable compositions are commonly used in offset printing. However, when these commercially available UV curable compositions are used for images recorded by electrophotography, satisfactory results may not be obtained due to incompatibility between the toner and the UV curable composition. In general, a toner is composed of a resin, a colorant such as a pigment, an additive such as silica, and a wax. The toner after fixing has a colorant, an additive, etc. present as a powder or completely. Since there is toner that is not completely dissolved, a certain amount of gap is generated. In many cases, the ultraviolet curable composition penetrates into the gap and becomes incompatible.

  The varnish composition and the adjustment method disclosed in Patent Document 1 are more suitable for the printed matter to which the fixing oil is applied by using a water-based coating agent that does not contain ammonia and has a low static surface tension. Improved. Moreover, in the resin forming apparatus disclosed in Patent Document 2 and an apparatus equipped with the apparatus, a silicon resin layer is formed on the printing surface to provide protection of the printing surface, waterproof treatment, glossing, and the like. Further, the metal container printed on the surface disclosed in Patent Document 3 and the printing method of the metal container can efficiently perform multi-variety and small-volume printing by utilizing electrophotography, and the ultraviolet curable composition. Processing provides toner layer protection and gloss.

Further, a releasable UV-curable pressure-sensitive composition used for DM postcards and the like is disclosed in Patent Document 4. Patent Document 5 discloses an ultraviolet curable pressure-sensitive adhesive composition that matches liquid toner.
In particular, the ultraviolet curable composition disclosed in Patent Document 4 has the presence of a (meth) acrylic copolymer (B) having an average molecular weight of 10,000 to 100,000 and a glass transition point of −35.2 to 20 ° C. Is very important.
The (meth) acrylic copolymer (B) is a linear polymer and has pressure-sensitive adhesiveness. On the other hand, the ultraviolet curable component (a) basically has no pressure-sensitive adhesive property even if it is cured with ultraviolet rays. The ultraviolet-cured product of the ultraviolet-curing component (a) is hard and exists so as to surround the (meth) acrylic copolymer (B), and the (meth) acrylic copolymer before pressing and when peeled again. (B) It has the function of preventing the stickiness of the surface and preventing the person from being pressure-bonded again at a pressure given by a person in normal life.
When a very strong pressure is applied to this (compression bonding), the (meth) acrylic copolymers (B) are brought into contact with each other to exhibit adhesiveness. However, since the adhesion between the (meth) acrylic copolymers (B) moves the ultraviolet-cured product of the ultraviolet-curing component (a), the ultraviolet-cured product of the ultraviolet-curing component (a) will be restored. It adheres in a state where the stress to remain is left. Therefore, if it peels off with a strong force, it can be peeled cleanly.

However, even with these techniques, in the combination of the dry toner and the ultraviolet curable composition, even if the ultraviolet curable composition can be applied, the matching between the toner image and the ultraviolet curable composition is poor, and the toner image is Sometimes it peeled off. More specifically, when the toner image is pressure-bonded with the ultraviolet curable composition disclosed in Patent Document 4, the peel strength is insufficient, and it cannot withstand vibration during transportation, or conversely, the peel strength is too high, There were many problems that one image was peeled off when peeling. In addition, even if there is no problem immediately after crimping, the adhesive strength is often insufficient during storage, or conversely, it is very high, and it is not at a practical level for toner images. It was.
In addition, UV curable pressure-sensitive compositions used as re-peelable adhesives used in DM postcards and the like also have poor matching with dry toner images, and the toner images may peel off during re-peeling. there were.

  As described above, in the above-described prior art, the combination of the toner and the ultraviolet curable composition or the ultraviolet curable pressure sensitive composition has poor matching, and the ultraviolet curable composition or the ultraviolet curable pressure sensitive sensor is applied on the toner image. The composition could not be protected by applying and curing, imparting gloss, or releasable pressure bonding.

By the way, conventionally, in an electrophotographic image, silicon oil is used as a fixing release agent, and when an image formed using silicon oil is used, peeling of the image when re-peeling is somewhat reduced (for example, (See Patent Document 6). However, it did not reach the level used for direct mail.
In recent years, so-called oil-less toner in which a wax is contained in the toner has been generally used in order to prevent contamination of the office with silicone oil and deterioration of image quality due to running out of silicone oil. Furthermore, in order to save energy, so-called low-temperature fixing toner using a resin having a low toner softening temperature has been used.

However, when an energy ray curable precursor is provided on a toner image subjected to such oilless fixing, there is a problem that the following problems occur.
(1) The wax on the surface of the toner image repels the energy ray curable precursor and the thickness of the energy ray curable precursor layer becomes very thin at a place where the image area is high, and the energy ray curable pressure sensitive adhesive is used as it is. End up. For this reason, the location which a part does not press-fit arises, and the information sheet peels off by the vibration and handling at the time of transport.
(2) The adhesiveness between the cured energy beam curable pressure sensitive adhesive and the oilless-fixed toner image is poor, and when re-peeled, the energy beam curable pressure sensitive adhesive partially adheres to one side. A problem that the image becomes unsightly because the image quality is significantly reduced due to peeling.

  By the way, the present inventors have described that the recording medium folded in half (or more than three folds) so that the surface on which the energy ray curable composition is applied on the toner image is opposed to the recording medium is passed through a heating and pressing device. It has been found that an energy beam curable composition which is recured and is insufficiently cured is thermally cured. As a result, it has been found that good re-peeling can be achieved by preventing the fixing property between the toners and between the toner and the recording medium from being lowered.

FIG. 1 shows a releasable information sheet in which an energy beam curable composition is applied and cured on a paper (recording medium) on which a toner image is fixed, folded in two and pressed, and conventional heating. It is the schematic which shows the structure of a pressurization apparatus.
Here, in order to enable good re-peeling, as shown in FIG. 1, the surface layer of paper 1 (and a coat layer coated on the surface layer; not shown) pressed in half and energy beam curing It is necessary to heat each of the interface 4a and the interface 4b with the toner image 3 into which the mold composition 2 has permeated. The heating by the heating and pressurizing apparatus heats the two interfaces 4a and 4b from both sides of the folded and pressure-bonded paper 1. That is, since the heating and pressurizing apparatus is heating in a state of being sandwiched between the thicknesses of the paper 1, heat transfer corresponding to the thickness of the paper 1 must be considered.
Accordingly, the heat of the surface of the heating roller 10 which is a conveying member of the heating and pressing apparatus is transferred in the cross-sectional direction of the paper 1 corresponding to 50 to 200 μm, and the interface 4a or the interface 4b is heated while heating the heat capacity of the paper 1. Therefore, the heating efficiency is poor.

FIG. 2 is a schematic view showing a paper on which a toner image is fixed and a configuration of a conventional heating and pressing apparatus.
On the other hand, as shown in FIG. 2, the conventional toner image heating and fixing method is such that the toner image 3 formed on the paper 1 has a heat on the surface of the heating roller 10 corresponding to several μm at the interface 4 between the toner 3 and the paper 1. Therefore, it is efficient to melt or fix the toner.

  Conventional fixing devices as disclosed in Patent Document 7 and Patent Document 8 are configured to mainly heat the image side (toner side) of toner electrostatically held on paper (recording medium). It was. Even if the heater is provided on both the toner image side and the back side, the temperature control target is a so-called fixing roller provided on the toner image side. The heater provided in the so-called pressure roller on the back side of the paper serves as an auxiliary heating member so that the temperature of the fixing machine is not lowered so that a large amount of heat is taken away by passing paper when securing the productivity of high-speed machines and handling thick paper. It is what is installed.

  For this reason, it has been difficult to heat the two interfaces 4a and 4b of the paper 1 pressed into two folds (or more than three folds) as described above while heating (heat transfer) from both sides. For example, if the surface temperatures of the fixing roller and the pressure roller in the conventional fixing device provided on both sides of the paper 1 are different, a difference due to heat transfer from each roller surface occurs, and the two interfaces 4a and 4b The temperature could not be kept the same, and clean re-peeling across both sides was not possible.

FIG. 3 shows a releasable information sheet obtained by applying and curing an energy ray curable composition on a paper having a toner image fixed on both sides, and folding and folding the paper in two, and a conventional heat and pressure. It is the schematic which shows the structure of an apparatus.
As shown in FIG. 3, a toner image 3 b may be formed on the outer surface of the paper 1 that is pressure-bonded with the surface to which the energy beam curable composition 2 is applied facing each other. This corresponds to a direct mail address or a print for confirming the hidden crimp surface information. Also in this case, the interfaces 4a and 4b between the surface layer of the paper 1 (and the coating layer coated on the surface layer; not shown) and the toner image 3a infiltrated with the energy beam curable composition 2 correspond to 50 to 200 μm. It is necessary to heat through the cross section of the paper 1.

In the method in which the heat on the surface of the heating roller 10 is heated to the interfaces 4a and 4b by transferring the thickness of the paper 1 as described above, the heat gradient in the transmission is higher when the set temperature on the surface of the heating roller 10 is set higher. The interface 4a and 4b can be heated quickly by increasing. At this time, since the toner image 3b formed on the outer surface of the paper 1 is directly transferred from the surface of the heating roller 10, it is exposed to a higher temperature than the interfaces 4a and 4b.
In such a state, there is a problem that problems such as blistering, hot offset, and blocking occur.

Blistering is a phenomenon in which image defects occur due to the toner image 3b rising or bursting due to expansion of air and gas components in the paper 1 due to rapid temperature rise.
The hot offset is a phenomenon in which the re-melted toner image 3b is fixed again on the surface of the roller 10.
Further, the blocking is a phenomenon in which toner images 3b of adjacent papers 1 are aggregated / fused and adhered when stacked after being discharged.

  The present invention has been made in view of the above problems in the prior art, and the image quality is good even when the re-peelable information sheet that has been crimped in two or more folds is peeled again, and blister, hot offset, and blocking. An object of the present invention is to provide a heating and pressurizing apparatus capable of obtaining a releasable information sheet without generation of water.

In order to solve the above problems, the heating and pressing method according to the present invention is such that an energy beam curable composition is applied and cured on a recording medium on which a toner image is fixed, and is folded into two or more folds and pressed. A heat-pressing method for heating and pressurizing the re-peelable information sheet, wherein the toner A forms a toner image on the pressure-bonding surface of the re-peelable information sheet, and the non-pressure-bonded surface of the re-peelable information sheet. The toner B is different from the toner B forming the toner image, and the glass transition temperature Tg (B) of the toner B is 65 ° C. or more.

  According to the present invention, even if a re-peelable information sheet that has been crimped into two or more folds is re-peeled, the image quality is good, and a re-peelable information sheet is obtained without causing blistering, hot offset, or blocking. The heating and pressing apparatus can be provided.

Schematic showing a releasable information sheet formed by applying and curing an energy ray curable composition on a paper on which a toner image has been fixed, folded in two, and press-bonded, and the configuration of a conventional heating and pressing apparatus. FIG. It is the schematic which shows the paper with which the toner image was fixed, and the structure of the conventional heat press apparatus. A releasable information sheet in which an energy beam curable composition is applied and cured on a paper on which toner images are fixed on both sides, folded in two and pressed, and a configuration of a conventional heating and pressing apparatus. FIG. It is the schematic which shows the structure in one Embodiment of the heating-pressing apparatus which concerns on this invention. It is explanatory drawing which shows the model in heat transfer simulation. It is a graph which shows a heat transfer simulation. It is a graph which shows the relationship between heating roller temperature and the temperature of the pressure-bonding paper (removability information sheet) at the time of discharge. It is the schematic which shows an example of a structure of the image forming apparatus in the manufacturing apparatus of the releasable information sheet which concerns on this invention. It is the schematic which shows an example of a structure of the application | coating hardening means used for the manufacturing apparatus of the releasable information sheet which concerns on this invention.

First, prior to describing the present invention, knowledge obtained by the present inventors regarding the above-mentioned problems (blister, hot offset and blocking) in the prior art will be described first.
As a result of intensive studies to eliminate the above-mentioned problems, the present inventors have determined the temperature of the heating and pressurizing means for heating and pressurizing both sides of the releasable information sheet that has been pressed into two or more folds while forming a nip. It has been found that this problem can be solved by a heating and pressing apparatus having a relatively low temperature. According to this, blistering and hot offset do not occur even when a releasable information sheet that is crimped into two or more folds and has a toner image on its surface (non-crimped surface) is heated and pressed, and re-peeled. In addition, it is possible to realize a heating and pressing apparatus capable of obtaining a removable information sheet having good image quality.
However, this method can certainly reduce the toner temperature on the outer surface of the releasable information sheet at the outlet of the heating and pressurizing device, so that it can improve the blistering and hot offset of the toner. Increasing the time may cause a problem of lowering productivity, so it is preferable to increase the productivity. Further, regarding blocking, it is desirable that the softening temperature of the low-temperature fixing toner in recent years is low and further improvement is performed. Furthermore, since the thickness of the releasable information sheet that has been crimped in two folds is thick, it takes time to dissipate the heat accumulated in the releasable information sheet via air as compared with plain paper. Therefore, when the releasable information sheet is stacked on the paper discharge tray, the accumulated heat may cause the toner on the outer surface of the releasable information sheet to slowly soften and cause blocking, which can be further improved. Is desirable.

  Therefore, the present invention has good image quality even when a re-peelable information sheet that has been crimped into two or more folds is re-peeled, does not cause blistering, hot offset, or blocking, and reduces productivity. A second object is to provide a heating and pressing apparatus that can provide a re-peelable information sheet.

Thus, the heat and pressure apparatus according to the present invention is a releasability information obtained by applying and curing an energy beam curable composition on a recording medium on which a toner image is fixed, and folding and pressing the recording medium into two or more folds. A heating and pressing apparatus for heating and pressing a sheet, wherein the toner A forms a toner image on the pressure-bonding surface of the releasable information sheet, and forms a toner image on the non-pressure-bonding surface of the removable information sheet. The toner B is different from the toner B, and the glass transition temperature Tg (B) of the toner B is 65 ° C. or higher.
According to the present invention, the image quality is good even when the re-peelable information sheet that has been crimped into two or more folds is re-peeled, blisters, hot offsets and blocking do not occur, and productivity is reduced. It is possible to provide a heating and pressing apparatus that can obtain a removable information sheet without any problems.

Next, the heating and pressing apparatus and the heating and pressing method, and the releasable information sheet manufacturing apparatus according to the present invention will be described in more detail.
Although the embodiments described below are preferred embodiments of the present invention, various technically preferable limitations are attached thereto, but the scope of the present invention is intended to limit the present invention in the following description. Unless otherwise described, the present invention is not limited to these embodiments.

(Heating and pressing equipment)
FIG. 4 is a schematic view showing a configuration in an embodiment of the heating and pressing apparatus according to the present invention.
The re-peelable information sheet is obtained by fixing a toner image 3 on a paper 1 as a recording medium, and further applying and curing an energy ray curable composition 2 thereon. In the present invention, the removable information sheet is pressure-bonded in a state of being folded into two or more folds.

In the present embodiment, an upper heating roller 10a and a lower heating roller 10b (a pair of heating rollers), which are heating and pressing means, are provided so as to form a nip portion N, and the removable information sheet passes through the nip portion N. By doing so, it is heated and pressurized from both sides. The upper heating roller 10a and the lower heating roller 10b not only sandwich and reheat the releasable information sheet, but also have a function of conveying it by rotating in the direction of the arrow in FIG.
Further, a nip portion N formed by the upper heating roller 10a and the lower heating roller 10b is a contact portion with the removable information sheet. And it is preferable that the contact location where the upper heating roller 10a is in contact with one surface and the contact location where the lower heating roller 10b is in contact with the other surface are at the same temperature. The upper temperature control circuit 16a and the lower temperature control circuit 16b, which are control means, control the upper heating roller 10a and the lower heating roller 10b, respectively, so that they have the same temperature.

For example, the upper heating roller 10a is provided with an elastic layer 12 such as silicon rubber or silicone sponge having heat resistance and low hardness on a metal core 11 such as aluminum or iron, and a covering layer 13 is provided on the surface thereof. It has a structure provided, and is heated by an internal upper heater 14a (heating unit). The covering layer 13 is preferably formed of a resin having a high releasability such as PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer) or PTFE (polytetrafluoroethylene). By forming the resin with a high releasability, it is possible to suppress the occurrence of hot offset of the image (toner B) formed on the non-compression surface (outer surface) of the removable information sheet.
The upper heating roller 10a shown in this embodiment has, for example, an elastic layer 12 made of silicon rubber on an aluminum core 11 having a thickness of 3 mm, and a release layer 13 made of PFA on the surface layer, and has a diameter of 50 mm. A material having a hardness of about 60 ° (Asker-C) is used.

On the other hand, the lower heating roller 10b has the same configuration as that of the upper heating roller 10a. In this embodiment, by using common components, the cost of components can be reduced, and the temporal changes of the elastic layer 12 and the coating layer 13 can be kept equal. To be able to. In particular, since the contact portions where the upper heating roller 10a and the lower heating roller 10b are in contact with the removable information sheet are made of the same material, the heat transfer behavior can be made comparable. preferable.
The upper heating roller 10a and the lower heating roller 10b make a nip portion N having a nip width of about 10 mm between them by applying a pressure of about 1200 N using a well-known and commonly used pressure mechanism. Can do.

  As for the temperatures of the upper heating roller 10a and the lower heating roller 10b, the surface temperature is detected by temperature detection elements 15a and 15b (for example, a thermistor or the like) that are in contact with the respective surfaces. Based on the detected temperature, the upper heating roller temperature control circuit 16a and the lower heating roller temperature control circuit 16b operate the upper heater 14a and the lower heater 14b intermittently (conducting / shut-off operation) by independent control, respectively. Electric power is applied from the commercial power source 17. Thus, the surface temperature of the upper heating roller 10a and the lower heating roller 10b can be controlled to a predetermined temperature.

  In the heating and pressurizing apparatus, the paper 1 press-fitted in half as shown in FIG. 3 is guided to the contact nip N between the upper heating roller 10a and the lower heating roller 10b by the inlet guide 18, and this nip portion. Heated and pressurized with N. The toner image 3a is re-cured by heating and pressurization at the nip portion N, and the energy beam curable composition 2 that is insufficiently cured is thermally cured to fix the toner image 3a between the toner particles and to the paper 1. Property deterioration can be prevented, and sufficient fixing strength can be secured. Further, at the time of re-peeling, the toner is peeled off from an appropriate peeling surface, and toner peeling can be eliminated.

  The upper heating roller 10a and the lower heating roller 10b are heated and maintained at the same set temperature by the upper temperature control circuit 16a and the lower temperature control circuit 16b. As a result, the above-mentioned re-curing can be maintained under the same conditions (and at an appropriate temperature) over both sides of the paper 1, and it can be peeled cleanly without peeling at the time of re-peeling.

  In the above embodiment, the case of the releasable information sheet folded in half has been described. However, the present invention has the same effect as the case of folding in half even if the releasable information sheet is folded in three or more. In the following description, the heating and pressing means provided in the heating and pressing apparatus is assumed to be heating rollers (upper heating roller 10a and lower heating roller 10b), but the present invention is not limited to this. .

  Next, the set temperatures of the upper heating roller 10a and the lower heating roller 10b will be described. When the following heating conditions are employed, good re-peeling results are obtained.

<Heating conditions>
Heating roller surface temperature: about 200 ° C
Heating roller conveyance speed: 110 mm / sec
Heating roller nip width: about 10mm

The temperature at the interface between the paper 1 and the toner image 3 under such conditions was estimated using a primary heat transfer simulator.
A model diagram in this simulation is shown in FIG. In addition, about the density of each material, specific heat, thermal conductivity, thickness, and preset temperature, it carried out on the conditions of following Table 1.

The press-bonded paper 1 is a type in which the toner image 3b is also formed on the outside of the press-bonding surface as shown in FIG. 3 (that is, the front and back surfaces of the paper 1; the non-press-bonding surface). 5 is a model in a state where heat is transferred in the direction of the arrow 5 in FIG. 5 and the toner image 3a provided on the pressure-bonded inner surface is heated. At this time, the pressure-bonded paper 1 is vertically symmetrical in FIG. 5 with respect to the layer of the energy beam curable composition 2. Further, if the set temperatures of the upper heating roller 10a and the lower heating roller 10b are set to the same temperature, the heat transfer from the upper heating roller 10a and the lower heating roller 10b to the interfaces 4a and 4b between the toner 3a and the paper 1 has the same behavior. Thus, both interfaces can be heated and maintained at the same temperature, and as a result, the same cured state can be obtained.
From the above, only the heat transfer results on one side will be described for the sake of simplicity.

Table 1 shows the thermophysical properties of each layer shown in FIG. Under the above heating conditions, since the nip width is about 10 mm with respect to the conveyance speed of 110 mm / sec, the heating time corresponds to (= 10/110 × 1000 =) 91 msec. Since the heating roller set temperature is 200 ° C., a simulation was performed with heating condition 1 as follows.
Heating condition 1: Set temperature 200 ° C Heating time length 91msec

The temperature of each layer after the heating time of 91 msec in the heating condition 1 was calculated using the primary heat transfer simulator with the temperature of the paper 1 and the toners 3a and 3b being 23 ° C. of the ambient temperature.
Each boundary surface temperature (temperature at a position in contact with an adjacent layer) in which heat roller 10 (elastic layer 12 made of silicon rubber + covering layer 13 made of PFA film), toner image 3b, paper 1 and toner image 3a are transferred in this order is: The result of the graph shown in FIG. 6 was obtained. In FIG. 6, “: outer” indicates an outer boundary surface (boundary surface near the heating roller 10), and “: inner” indicates an inner boundary surface (boundary surface far from the heating roller 10).
In the simulation, the temperature is derived by dividing each material layer into a plurality of layers for calculation. More specifically, since the layers of each material are divided for each predetermined thickness and the average temperature of the divided layers is derived, the predetermined distance (thickness) is also obtained with respect to adjacent (for example, inside of Si rubber and outside of PFA) temperatures. Therefore, the temperatures of both are not the same.

  From the calculation result (FIG. 6), the toner image 3b outside the crimping surface is heated to about 140 ° C., but the interface 4a between the toner image 3a and the paper 1 inside the crimping surface absorbs heat due to the thickness of the paper 1. From the delay in heat transfer, it can be seen that the heating is limited to 80 ° C. (in the pressure nip by the heating roller 10). Also, good peeling conditions are obtained under these conditions. This indicates that, if the temperature of the interface 4a reaches 80 ° C. under the pressure applied by the heating roller 10, it is sufficient to obtain good curing (peeling).

  At this time, the fixing temperature of the image forming apparatus (used for toner image formation) is set to 165 ° C. On the other hand, since the set temperature of the heating roller used in the heating and pressing apparatus is 200 ° C., the toner image 3b outside the press contact surface is caused by excessive heat, such as the above blister, hot offset, and blocking. Is likely to occur.

In view of the above problems, a similar calculation was attempted under the following heating condition 2 in which the heating temperature was lowered to increase the heating time.
Heating condition 2: Set temperature 150 ° C Heating time length 150msec

  The calculation results are plotted together with FIG. In the heating condition 2, even when the set temperature is as low as 150 ° C., the temperature of the interface 4a between the toner image 3a and the paper 1 reaches 80 ° C., which is the same as the heating condition 1. This is because the heat transfer in the cross section of the paper 1 having a large heat capacity can be increased by increasing the heating time, and thus the interface 4a is considered to be slowly heated to 80 ° C. Under these conditions, the temperature of the toner image 3b outside the pressure-bonding surface is heated only to about 110 ° C., and can be maintained at a temperature lower by about 30 ° C. than the heating condition 1, so that there are problems such as blistering, hot offset, and blocking. Can be avoided.

(toner)
As described above, the temperature of the heating and pressurizing means is maintained at a relatively low temperature, and instead, a desired amount of heat is supplied to the inside of the releasable information sheet by being conveyed at a relatively low linear speed, and The toner temperature on the outer surface (non-crimp surface) of the releasable information sheet at the outlet of the heating and pressurizing device can be lowered. For this reason, blistering and hot offset of the toner on the outer surface of the releasable information sheet can be improved, but a decrease in productivity due to a decrease in temperature and an increase in nip time is inevitable. In blocking, the temperature of the toner on the outer surface of the releasable information sheet is lowered, so that it can be improved. However, recent low-temperature fixing toner has a low softening temperature and is not sufficient as a countermeasure. The heat accumulated in the releasable information sheet is made uniform in the layer direction over time, but the releasable information sheet that has been crimped in two or more folds is thick, so it is normal to dissipate heat through the air. It takes time compared to paper. For this reason, when the releasable information sheet is stacked on the paper discharge tray, the toner image 3b on the outer surface (non-crimped surface) of the releasable information sheet is slowly softened due to accumulated heat, and blocking may occur. there were.

Here, blocking during stacking will be described in more detail.
It is assumed that the time until the re-peelable information sheet passed through the heating and pressing apparatus is stacked on the discharge tray from the heating and pressing apparatus exit is 1 second. The re-peelable information sheet was passed through a heating and pressing device under heating condition 2, and the temperature of the re-peelable information sheet when it reached the discharge tray was calculated by a heat transfer simulator. The thermophysical values used for the calculation are as shown in Table 2 below.

  At this time, the temperature of the entire releasable information sheet was 94.2 ° C. The glass transition temperature of low-temperature fixing toners in recent years is low, and it has been experimentally known that blocking occurs when the temperature of the releasable information sheet reaches around 60 ° C. Heating condition 2 is a condition under which this blocking occurs. It is. FIG. 7 shows the relationship between the heating roller temperature of the heating and pressing device and the temperature of the removability information sheet at the time of discharge, calculated by a heat transfer simulator. However, the nip time was calculated at 150 msec.

  In order to set the temperature of the releasable information sheet at the time of discharge to 60 ° C., the heating roller temperature needs to be 89 ° C. However, if the heating roller temperature is 89 ° C., the interface 4a and interface 4b between the toner image and the recording medium at the nip exit are 55 ° C., and the re-peelability of the re-peelable information sheet may be deteriorated. There is sex. In addition, the nip time can be increased in order to increase the interface temperature, but if it is extremely slow, it is disadvantageous in terms of productivity.

Therefore, the following measures were tried to suppress blocking while keeping the temperatures of the interface 4a and the interface 4b between the toner image 3a and the recording medium properly without increasing the nip time.
The toner A forming the toner image 3a on the pressure-bonding surface and the toner B forming the toner image 3b on the non-pressure-bonding surface are different, and the glass transition temperature Tg (B) of the toner B is set to 65 ° C. or higher. . By setting the glass transition temperature of toner B to 65 ° C. or higher, the softening of the toner on the outer surface (non-crimp surface) of the releasable information sheet can be suppressed even when the paper temperature during stacking is high, and blocking. Can be improved. At the same time, even when the heating roller temperature of the heating and pressing apparatus is high, the hot offset and blistering of the toner can be improved. The glass transition temperature of the toner B is more preferably 65 to 73 ° C.

・ Glass transition temperature (Tg)
The glass transition temperature (Tg) can be determined from an endothermic chart of a differential scanning calorimeter (DSC). A typical example is Q2000 manufactured by TA Instruments. A sample (toner) filled with 5 to 10 mg in a simple air-tight pan made of aluminum can be obtained by subjecting it to the following measurement flow.
The glass transition temperature is read from the 2nd Heating thermogram, and the intersection of the original baseline and the tangent at the inflection point is defined as the glass transition temperature [° C.].
1st Heating: 30 ° C. to 220 ° C., 5 ° C./min, hold for 1 minute after reaching 220 ° C. Cooling: Quench to −60 ° C. without temperature control, hold for 1 minute after reaching −60 ° C. 2nd Heating: −60 ° C. to 180 ° C. 5 ° C / min

In the present invention, the toner A that forms a toner image on the pressure-bonding surface of the removable information sheet and the toner B that forms a toner image on the non-pressure-bonded surface of the removable information sheet are different. It is preferable that the glass transition temperature Tg (A) of the toner and the glass transition temperature Tg (B) of the toner B satisfy the relationship of the following formula 1.
Tg (A) <Tg (B) (Formula 1)

The toner image after normal fixing is sufficiently fixed on the recording medium. Next, when the energy beam curable composition is applied onto the toner image, the energy beam curable composition penetrates into minute gaps in the toner image. The permeated energy beam curable composition remains in an insufficiently cured state because the toner blocks the energy beam, and the toner in the permeation portion has a low viscosity and the fixing property is lowered.
Therefore, after the surface treatment of the energy beam curable composition, the toner is re-cured by passing through a heating and pressing device through a folding process and a crimping process, which will be described in detail later, and an energy beam curable composition that is insufficiently cured. By heat curing, it is possible to prevent a decrease in fixability between the toner and the recording medium, and a sufficient fixing strength can be provided. However, if Tg (A) is high at this time, even if the toner A having a reduced viscosity due to the penetration of the energy beam curable composition passes through the heating and pressing apparatus, the recuring of the toner is suppressed, and the removability is improved. Image peeling may occur when the information sheet is peeled again. When the glass transition temperature Tg (A) of the toner A and the glass transition temperature Tg (B) of the toner B satisfy the relationship of the above formula 1, the toner B on the non-compression surface that contacts the heating roller when passing through the heating and pressing apparatus. The toner A on the pressure-bonding surface, which is the bonded inner surface, can be efficiently re-cured without hot offset or blistering.

  The glass transition temperature Tg (A) of the toner A is preferably 45 ° C. ≦ Tg (A) ≦ 55 ° C. Under heating condition 2, the temperature of the interface 4a between the toner image 3a (toner A) on the inner side of the pressure-bonding surface in FIG. 3 and the paper 1 as the recording medium is 84 ° C. When the temperature of the interface 4a reaches 84 ° C. under the pressure applied by the heating roller 10, the re-curing of the toner A proceeds and sufficient removability can be obtained. However, by setting the glass transition temperature Tg (A) of the toner A to 45 ° C. ≦ Tg (A) ≦ 55 ° C., the toner A can be efficiently recured even when the temperature of the interface 4a is lower than 84 ° C. The re-peelability can be sufficiently maintained. Therefore, the heat roller temperature can be lowered and the nip time can be shortened, so that energy saving and productivity can be improved. When Tg (A) is lower than 45 ° C., there may be an influence from the viewpoint of toner storage stability.

Further, it is preferable that the storage elastic modulus G ′ (180) [Pa] of the toner B at 180 ° C. is 1.0 × 10 ³ <G ′ (180) <1.0 × 10 ⁴ . When the storage elastic modulus G ′ is in the above range, even when the heating roller temperature is high, the occurrence of hot offset and blistering of the toner B to which heat is directly transferred from the heating roller can be suppressed. If the storage elastic modulus G ′ (180) [Pa] of the toner B at 180 ° C. exceeds 1.0 × 10 ⁴ , the low-temperature fixability may be deteriorated in the electrophotographic process, and the energy-saving property may be impaired.
The dynamic viscoelastic characteristic values (storage elastic modulus G ′, loss elastic modulus G ″) of the toner can be measured using a dynamic viscoelasticity measuring apparatus ARES (manufactured by TA Instruments). Molded into pellets with a diameter of 8 mm and a thickness of 1 to 2 mm, fixed to a parallel plate with a diameter of 8 mm, stabilized at 40 ° C., frequency 1 Hz (6.28 rad / s), strain amount 0.1% (strain amount control) In mode, the temperature is increased to 200 ° C. at a rate of temperature increase of 2.0 ° C./min.

  Next, the toner material used for the toner in the present invention will be described. The toner material (toner composition) shown below can be used for either toner A or toner B. The glass transition temperatures of the toner A and the toner B can be set to a desired glass transition temperature by a well-known and commonly used method, but can be easily adjusted by, for example, the thermal characteristics of the binder resin.

<Binder resin>
The binder resin is not particularly limited, and a commonly used resin can be appropriately selected and used. For example, vinyl such as styrene monomer, acrylic monomer, methacrylic monomer, etc. Polymers, copolymers of these monomers or two or more types, polyester polymers, polyol resins, phenol resins, silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, terpene resins, Coumarone indene resin, polycarbonate resin, petroleum resin and the like can be mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferable to use a polyester polymer because the affinity between the ester group of the polyester and the hydroxyl group of cellulose in the paper that is the recording medium is high, and the fixing property is good.

  Examples of the styrene monomer include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-phenyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-amyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, Examples thereof include styrene such as p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene, or derivatives thereof.

  Examples of acrylic monomers include acrylic acid, or methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, and acrylic acid. Examples include 2-ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, acrylic acid such as phenyl acrylate, or esters thereof.

  Examples of the methacrylic monomer include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, and methacrylic acid 2 -Ethylhexyl, stearyl methacrylate, phenyl methacrylate, methacrylic acid such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate or esters thereof, and the like.

  The following (1)-(18) is mentioned as an example of the other monomer which forms the said vinyl polymer or a copolymer. (1) Monoolefins such as ethylene, propylene, butylene and isobutylene; (2) Polyenes such as butadiene and isoprene; (3) Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; (4) Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; (5) Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; (6) Vinyl methyl ketone, vinyl hexyl ketone and methyl. Vinyl ketones such as isopropenyl ketone; (7) N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone; (8), vinyl naphthalenes; (9) acrylonitrile, Such as methacrylonitrile, acrylamide, etc. (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; (11) maleic anhydride, citraconic anhydride, Unsaturated dibasic acid anhydrides such as itaconic anhydride and alkenyl succinic anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester Monoesters of unsaturated dibasic acids such as citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethylmaleic acid, dimethylfumaric acid, etc. (14) α, β-unsaturated acids such as crotonic acid and cinnamic acid; (15) α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride; 16) Monomers having a carboxyl group such as anhydrides of the α, β-unsaturated acids and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof; ) Acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (18) 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1 -Hydroxy-1-methylhexyl) monomers having a hydroxy group such as styrene.

  In the toner of the present invention, the vinyl polymer or copolymer of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include aromatic vinyl vinyl compounds such as divinylbenzene and divinylnaphthalene. Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, and 1,6. And xanthdiol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylates of these compounds with methacrylate. Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, and dipropylene. Examples include glycol diacrylate and those obtained by replacing acrylate of these compounds with methacrylate.

  Other examples include diacrylate compounds and dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond. Examples of polyester diacrylates include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.).

  Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds in place of methacrylate, triallyl cyanide. Examples include nurate and triallyl trimellitate.

  These crosslinking agents are preferably used in an amount of 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, with respect to 100 parts by mass of other monomer components. Among these crosslinkable monomers, diacrylates bonded to a toner resin by a bond chain containing one aromatic divinyl compound (especially divinylbenzene), one aromatic group and an ether bond from the viewpoint of fixability and offset resistance. Preferred examples include compounds. Among these, a combination of monomers that becomes a styrene copolymer or a styrene-acrylic copolymer is preferable.

  Examples of the polymerization initiator used for the production of the vinyl polymer or copolymer include 2,2′-azobisisobutyronitrile and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile). ), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1,1 ′ -Azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-2 ', 4' -Dimethyl-4'-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohex Ketone peroxides such as non-peroxides, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide , Di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide Oxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propiate Peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, tert-butyl Peroxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexarate, tert-butylperoxylaurate, tert-butyl-oxybenzoate, tert-butylperoxyisopropylcarbonate, di- tert-butylperoxyisophthalate, tert-butylperoxyallyl carbonate, isoamylperoxy-2-ethylhexanoate, di-tert-butylperoxyhexahydroterephthalate, tert-butylperoxyase Over door, and the like.

  The acid value when the binder resin is a vinyl polymer such as styrene-acrylic resin is preferably 0.1 mgKOH / g to 100 mgKOH / g, and preferably 0.1 mgKOH / g to 70 mgKOH / g. More preferably, it is most preferably 0.1 mgKOH / g to 50 mgKOH / g.

The following are mentioned as a monomer which comprises a polyester-type polymer.
Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or diol obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide to bisphenol A, etc. Is mentioned. In order to crosslink the polyester resin, it is preferable to use a trivalent or higher alcohol together.

  Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, such as dipentaerythritol, tripentaerythritol, 1,2,4- Butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene , Etc.

  Examples of the acid component that forms the polyester polymer include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or Unsaturated dibasic acids such as anhydride, maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride And unsaturated dibasic acid anhydrides. Examples of the trivalent or higher polyvalent carboxylic acid component include trimet acid, pyromet acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylene Carboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empol trimer acid, or anhydrides thereof, partial lower alkyl esters, and the like.

  When the binder resin is a polyester resin, the acid value is preferably 0.1 mgKOH / g to 100 mgKOH / g, more preferably 0.1 mgKOH / g to 70 mgKOH / g, and 0.1 mgKOH / g. Most preferably, it is g-50 mgKOH / g.

  As the binder resin that can be used in the toner of the present invention, a resin containing a monomer component capable of reacting with both of these resin components in at least one of the vinyl polymer component and the polyester resin component can also be used. . Examples of monomers that can react with the vinyl polymer among the monomers constituting the polyester resin component include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Examples of the monomer constituting the vinyl polymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  Moreover, when using together a polyester polymer, a vinyl polymer, and another binder resin, what has 60 mass% or more of resin whose acid value of the whole binder resin has 0.1-50 mgKOH / g is preferable.

In the present invention, the acid value of the binder resin component of the toner composition is determined by the following method, and the basic operation conforms to JIS K-0070.
(1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are obtained in advance. . The sample pulverized product 0.5 to 2.0 g is precisely weighed, and the weight of the polymer component is defined as W (g). For example, when measuring the acid value of the binder resin from the toner, the acid value and content of the colorant or magnetic material are separately measured, and the acid value of the binder resin is obtained by calculation.
(2) A sample is put into a 300 (ml) beaker, and a mixed solution 150 (ml) of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / l KOH.
(4) The amount of use of the KOH solution at this time is S (ml), and a blank is measured at the same time. However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W

-Modified polyester (prepolymer) capable of reacting with active hydrogen group-containing compound-
Furthermore, the binder resin used in the present invention may contain a modified polyester capable of reacting with an active hydrogen group-containing compound (hereinafter sometimes referred to as a polyester prepolymer). The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when the polyester capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in the toner production process. When the polyester prepolymer is subjected to an extension reaction to increase the molecular weight, the heat resistant storage stability of the toner and the stickiness of the image after fixing can be effectively reduced. The polyester prepolymer in this case is not particularly limited as long as it can react with the active hydrogen group-containing compound, but examples thereof include modified polyesters having an isocyanate group, an epoxy group, a carboxylic acid, an acid chloride group, and the like. Particularly preferred are modified polyesters containing isocyanate groups.

  The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected according to the purpose. For example, when the modified polyester capable of reacting with the active hydrogen group-containing compound is an isocyanate group-containing modified polyester, the isocyanate group-containing modified polyester can be increased in molecular weight by a reaction such as an extension reaction or a crosslinking reaction. Amines are preferred.

  The amines are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, 4,4′-diamino-3,3′dimethyl. Examples include dicyclohexylmethane, diaminecyclohexane, isophoronediamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, hydroxyethylaniline, aminoethyl mercaptan, aminopropyl mercaptan, aminopropionic acid, and aminocaproic acid. . In addition, ketimine compounds, oxazolidone compounds, and the like in which these amino groups are blocked with ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) may be mentioned.

-Surfactant-
In the preparation of the toner, a surfactant may be used for the purpose of emulsifying / dispersing the constituent components. There is no restriction | limiting in particular as surfactant, Anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, etc. are mentioned. One surfactant may be used alone, or two or more surfactants may be used in combination.

As the anionic surfactant, carboxylic acid or a salt thereof, a sulfate ester salt, a salt of a carboxymethylated product, a sulfonate salt, a phosphate ester salt, or the like is used. As the cationic surfactant, a quaternary ammonium salt type surfactant, an amine salt type surfactant and the like can be used.
As the amphoteric surfactant, a carboxylate type amphoteric surfactant, a sulfate ester type amphoteric surfactant, a sulfonate type amphoteric surfactant, a phosphate ester type amphoteric surfactant and the like can be used.
As the nonionic surfactant, an AO addition type nonionic surfactant and a polyhydric alcohol type nonionic surfactant can be used.

<Release agent>
In the present invention, both toner A and toner B can contain a release agent, but it is particularly preferable that toner B contains a release agent.
By including a release agent in the toner B that is in direct contact with the heating roller of the heating and pressing apparatus, it is possible to suppress the occurrence of hot offset and blistering of the toner B formed on the non-compression surface.
There is no restriction | limiting in particular in the kind of mold release agent, According to the objective, it can select suitably, For example, waxes, waxes, etc. are mentioned suitably.

  Examples of the waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, rice wax and sunflower wax; animal waxes such as beeswax and lanolin; minerals such as ozokerite and cercin Natural waxes such as waxes; petroleum waxes such as paraffin, microcrystalline, and petrolatum; In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax; synthetic waxes such as esters, ketones and ethers; Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbons; poly-n-stearyl methacrylate and poly-n-lauryl which are low molecular weight crystalline polymer resins A homopolymer or copolymer of polyacrylate such as methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.); a crystalline polymer having a long alkyl group in the side chain, or the like may be used. These may be used alone or in combination of two or more.

  The content of the release agent in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 30% by mass, and more preferably 2 to 20% by mass. When the content exceeds 20% by mass, the fluidity of the toner may be deteriorated.

The surface mold release agent exposure amount of the toner is preferably 9 to 13 mg / g with respect to 1 g of the toner. If the exposure amount of the surface release agent is less than 9 mg / g, the release agent is not sufficiently oozed out to the image surface, and hot offset and blistering may be deteriorated. On the other hand, when the exposed amount of the surface release agent exceeds 13 mg / g, the release agent that oozes out on the image surface of the non-crimped surface may cause the images to stick to each other at the time of paper stacking, and blocking may deteriorate. .
The toner surface release agent exposure amount can be determined by a hexane extraction method. 1.0 g of the toner base particles before adding the external additive is weighed, 7 mL of n-hexane is added, and the mixture is stirred with a roll mill at 120 rpm for 1 minute. The solution is suction filtered, and n-hexane is removed by a vacuum dryer. The mass (mg) of the component that has been removed and remained can be determined as the surface release agent exposure amount.

<Other ingredients>
In the toner of the present invention, in addition to the binder resin and the release agent, the charge control agent, the colorant, the deforming agent, the inorganic fine particles, the fluidity improver, and the cleaning property are improved as long as the effects of the present invention are not impaired. Other components such as an agent and a magnetic material may be included as necessary.

-Charge control agent-
The toner in the present invention can contain a charge control agent in the toner for the purpose of controlling the chargeability of the toner. There is no restriction | limiting in particular as a charge control agent, The following each material is mentioned.

  For example, nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1627), basic dyes such as C.I. I. Basic Yellow 2 (C.I. 41000), C.I. I. Basic Yellow 3, C.I. I. Basic Red 1 (C.I. 45160), C.I. I. Basic Red 9 (C.I. 42500), C.I. I. Basic Violet 1 (C.I. 42535), C.I. I. Basic Violet 3 (C.I. 42555), C.I. I. Basic Violet 10 (C.I. 45170), C.I. I. Basic Violet 14 (C.I. 42510), C.I. I. Basic Blue 1 (C.I. 42025), C.I. I. Basic Blue 3 (C.I. 51005), C.I. I. Basic Blue 5 (C.I. 42140), C.I. I. Basic Blue 7 (C.I. 42595), C.I. I. Basic Blue 9 (C.I. 52015), C.I. I. Basic Blue 24 (C.I. 52030), C.I. I. BasicBlue 25 (C.I. 52025), C.I. I. Basic Blue 26 (C.I. 44045), C.I. I. Basic Green 1 (C.I. 42040), C.I. I. Basic Green 4 (C.I. 42000) and the like and lake pigments of these basic dyes, C.I. I. Solvent Black 8 (C.I. 26150), quaternary ammonium salts such as benzoylmethyl hexadecyl ammonium chloride, decyl trimethyl chloride, dialkyl tin compounds such as dibutyl or dioctyl, dialkyl tin borate compounds, guanidine derivatives, containing amino groups Polyamine resins such as vinyl polymers and condensation polymers containing amino groups, described in JP-B No. 41-20153, JP-B No. 43-27596, JP-B No. 44-6397, JP-B No. 45-26478 Metal complex salts of monoazo dyes, and salicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid Zn, Al, Co, Cr described in JP-B-55-42752 and JP-B-59-7385 Gold such as Fe Genus complexes, sulfonated copper phthalocyanine pigments, organic boron salts, fluorine-containing quaternary ammonium salts, calixarene compounds, and the like. Naturally, color toners other than black should avoid the use of charge control agents that impair the desired color, and white metal salts of salicylic acid derivatives are preferably used.

  The content of the charge control agent is preferably 0.01 parts by mass to 2 parts by mass and more preferably 0.02 parts by mass to 1 part by mass with respect to 100 parts by mass of the binder resin. When the content is 0.01 parts by mass or more, charge controllability is obtained, and when it is 2 parts by mass or less, the chargeability of the toner is not excessively increased and the effect of the main charge control agent is reduced. In addition, the electrostatic attraction force with the developing roller is not increased, and the fluidity of the toner and the image density are not lowered.

-Colorant-
In the present invention, the colorant is not particularly limited and may be appropriately selected from known colorants according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, La Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Irred, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, pyridian, emerald green, pigment green B, naphthol green B, green gold, reed Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Zinc Hana, Lithbon, and the like. These may be used individually by 1 type and may use 2 or more types together.

  The color of the toner colorant is not particularly limited and may be appropriately selected according to the purpose, and may be at least one selected from black toner, cyan toner, magenta toner, and yellow toner. The toner can be obtained by appropriately selecting the type of colorant, but is preferably a color toner.

  Examples of black materials include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11), titanium oxide, and the like. And organic pigments such as aniline black (CI Pigment Black 1).

  Examples of the magenta color pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 177, 179, 202, 206, 207, 209, 211; C.I. I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, and the like.

  Examples of the color pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45 and copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, Green 7, Green 36, and the like.

  Examples of the color pigment for yellow include C.I. I. Pigment Yellow 0-16, 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 151, 154, 180; C.I. I. Bat yellow 1, 3, 20, orange 36, and the like.

  The content of the colorant in the toner is preferably 1% by mass to 15% by mass and more preferably 3% by mass to 10% by mass with respect to the toner mass. When the content is less than 1% by mass, the coloring power of the toner may be reduced. When the content is more than 15% by mass, poor dispersion of the pigment in the toner occurs, and the coloring power decreases and the electrical characteristics of the toner. May be reduced.

  The colorant may be used as a master batch combined with a resin. There is no restriction | limiting in particular as such resin, According to the objective, it can select suitably from well-known things, For example, polyester, the polymer of styrene or its substitution, a styrene-type copolymer, polymethacrylic acid Methyl, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon Examples thereof include resins, alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffin, and paraffin wax. These may be used individually by 1 type and may use 2 or more types together.

  The master batch can be produced by applying a high shear force and mixing or kneading the resin and the colorant. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. The flushing method is a method in which an aqueous paste containing water of a colorant is mixed or kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove water and the organic solvent. For mixing or kneading, for example, a high shear dispersion device such as a three-roll mill can be used.

  As the usage-amount of the said masterbatch, 0.1-20 mass parts is preferable with respect to 100 mass parts of binder resin.

  The resin for the masterbatch preferably has an acid value of 30 mgKOH / g or less, an amine value of 1 to 100, and a colorant dispersed therein. The acid value is 20 mgKOH / g or less and the amine value is 10 It is more preferable that the colorant is dispersed and used at ˜50. When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity may be lowered, and the pigment dispersibility may be insufficient. Further, when the amine value is less than 1 and when the amine value exceeds 100, the pigment dispersibility may be insufficient. The acid value can be measured by the method described in JIS K0070, and the amine value can be measured by the method described in JIS K7237.

  The dispersant is preferably highly compatible with the binder resin in terms of pigment dispersibility. Specific examples of commercially available products include “Ajisper PB821” and “Azisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd.). , “DISPERBYK-2001” (manufactured by Big Chemie), “EFKA-4010” (manufactured by EFKA), and the like.

  The mass average molecular weight of the dispersant is the maximum molecular weight of the main peak in terms of styrene in gel permeation chromatography, preferably 500 to 100,000, and more preferably 3000 to 100,000 from the viewpoint of pigment dispersibility. In particular, 5000 to 50000 is preferable, and 5000 to 30000 is most preferable. When the molecular weight is less than 500, the polarity becomes high and the dispersibility of the colorant may be lowered. When the molecular weight exceeds 100,000, the affinity with the solvent is increased and the dispersibility of the colorant is lowered. There is.

  The addition amount of the dispersant is preferably 1 to 200 parts by mass, more preferably 5 to 80 parts by mass with respect to 100 parts by mass of the colorant. If it is less than 1 part by mass, the dispersibility may be lowered, and if it exceeds 200 parts by mass, the chargeability may be lowered.

-Profiler-
The deforming agent is contained for the purpose of deforming the shape of the color toner. Although it can select suitably as a deforming agent, it is preferable to contain the layered inorganic mineral which modified | denatured at least one part of the ion which the layered inorganic mineral has with the organic substance ion. As such a layered inorganic mineral, one having a smectite basic crystal structure modified with an organic cation is desirable. Moreover, a metal anion can be introduce | transduced by substituting a part of bivalent metal of a layered inorganic mineral for a trivalent metal. However, since the hydrophilicity is increased when a metal anion is introduced, a layered inorganic compound in which at least a part of the metal anion is modified with an organic anion is desirable.

There is no restriction | limiting in particular as said organic cation modifier | denaturant, A quaternary alkyl ammonium salt, a phosphonium salt, an imidazolium salt etc. are mentioned. Among them, a quaternary alkyl ammonium salt is desirable, and examples thereof include trimethyl stearyl ammonium, dimethyl stearyl benzyl ammonium, and oleyl bis (2-hydroxyethyl) methyl ammonium.
There is no restriction | limiting in particular as said organic substance anion modifier, Branched, unbranched or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-32), hydroxyalkyl (carbon) 2-22), sulfates, sulfonates, carboxylates, or phosphates having ethylene oxide, propylene oxide, and the like. Of these, carboxylic acids having an ethylene oxide skeleton are desirable.

When at least a part of the layered inorganic mineral is modified with organic ions, it becomes moderately hydrophobic, so that the oil phase containing the toner composition has a non-Nutnian viscosity and deforms the toner. Can do.
The layered inorganic mineral can be appropriately selected, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and a mixture thereof. Among them, montmorillonite or bentonite is preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the addition amount can be made small.
The content of the layered inorganic mineral partially modified with organic ions is preferably 0.05 to 10% by mass, more preferably 0.05 to 5% by mass in the toner material.

  Commercially available products of layered inorganic minerals partially modified with an organic cation include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL Quartium 18 bentonite such as (made by Southern Clay), and stearalkonium bentonite such as Bentone 27 (made by Leox), Thixogel LG (made by United catalyst), Clayton AF, Clayton APA (made by Southern Clay) Quaternium 18 / benzalkonium bentonite such as Clayton HT and Clayton PS (manufactured by Southern Clay). Among these, Clayton AF and Clayton APA are preferable.

Moreover, as the layered inorganic mineral in which the part is modified with an organic anion, a material obtained by modifying DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) with an organic anion represented by the following general formula A is preferable. As the commercial item, for example, Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.) can be mentioned.
R ¹ (OR ² ) _n OSO ₃ M: general formula A
(In the above general formula A, R ¹ represents an alkyl group having 13 carbon atoms, R ² represents an alkylene group having 2 to 6 carbon atoms, M represents a monovalent metal element, and n represents an integer of 2 to 10) .)

―Inorganic fine particles―
The toner in the present invention may have inorganic fine particles as an external additive for imparting fluidity, developability, chargeability and the like to the toner particles.

  The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate , Zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide , Silicon nitride, and the like. These may be used individually by 1 type and may use 2 or more types together. The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. The content of the inorganic fine particles in the toner is preferably 0.01% by mass to 5.0% by mass, and more preferably 0.01% by mass to 2.0% by mass. Within this range, the fluidity, developability, and chargeability of the toner are improved.

-Fluidity improver-
The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, a fluoride. Examples thereof include silane coupling agents having an alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils. Of these, silica and titanium oxide are preferably surface treated with such a fluidity improver and used as hydrophobic silica or hydrophobic titanium oxide.

-Cleaning improver-
The cleaning property improver is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium. For example, fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, polymethyl methacrylate, etc. Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 μm to 1 μm are suitable.

-Magnetic material-
There is no restriction | limiting in particular as a magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

<Method for producing toner base particles>
The method for producing the toner base particles constituting the toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a pulverization method, a monomer composition containing a specific polymerizable monomer Polymerization method (suspension polymerization method, emulsion polymerization method) in which water is directly polymerized in water phase, a method of emulsifying or dispersing a specific binder resin solution in an aqueous medium, dissolving in a solvent, removing the solvent and grinding And a melt spray method.

-Grinding method-
The pulverization method is, for example, a method of obtaining the toner base particles by melting or kneading the toner material, pulverizing, classifying or the like. In the case of the pulverization method, for the purpose of increasing the average circularity of the toner, the shape may be controlled by applying a mechanical impact force to the obtained toner base particles. In this case, the mechanical impact force can be applied to the toner base particles using a device such as a hybridizer or mechanofusion.

  In the pulverization method, the above-described toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial continuous kneader, a biaxial continuous kneader, or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel Co., Ltd., TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Casey Kay Co., Ltd., PCM type twin screw extruder manufactured by Ikegai Iron Works, Inc. A manufactured kneader or the like is preferably used. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt-kneading temperature is determined with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

In the pulverization, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing in a narrow gap between a mechanically rotating rotor and a stator is preferably used. .
In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed, for example, by removing the fine particle portion by a cyclone, a decanter, centrifugation, or the like.
After the pulverization and classification are completed, the pulverized product is classified into an air current by centrifugal force or the like to produce toner (toner base particles) having a predetermined particle size.

  The obtained toner base particles may be used as a toner as they are, but an external additive may be added as necessary to obtain a toner. This applies not only to the pulverization method but also to other production methods.

-Suspension polymerization method-
The suspension polymerization method will be described later in an aqueous medium in which a colorant, a release agent, and the like are dispersed in an oil-soluble polymerization initiator, a polymerizable monomer, and a surfactant and other solid dispersants are contained. Emulsified and dispersed by an emulsification method. Thereafter, a polymerization reaction is performed to form particles, and then wet processing for attaching inorganic fine particles to the toner particle surfaces in the present invention may be performed. At that time, it is preferable to treat the toner particles from which excess surfactant and the like are removed by washing.

Examples of the polymerizable monomer include acrylic acids, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and other acids, acrylamide, By using a part of acrylate or methacrylate having amino group such as methacrylamide, diacetone acrylamide or their methylol compounds, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, dimethylaminoethyl methacrylate, etc. Functional groups can be introduced.
Further, by selecting a dispersant having an acid group or a basic group as the dispersant to be used, the dispersant can be adsorbed and left on the particle surface to introduce a functional group.

-Emulsion polymerization method-
As the emulsion polymerization method, a water-soluble polymerization initiator and a polymerizable monomer are emulsified in water using a surfactant, and a latex is synthesized by a usual emulsion polymerization method. Separately, a dispersion in which a colorant, a release agent and the like are dispersed in an aqueous medium is prepared, and after mixing, the toner is aggregated to a toner size and heat-fused to obtain a toner. Thereafter, wet processing of inorganic fine particles described later may be performed. A functional group can be introduced on the surface of the toner particles by using a latex similar to the monomer used in the suspension polymerization method.

-Method of emulsifying or dispersing a specific binder resin solution in an aqueous medium-
As a method of emulsifying or dispersing a specific binder resin solution in the aqueous medium, a solution or dispersion of a toner material having at least a binder resin is emulsified or dispersed in an aqueous medium, and the emulsion or dispersion is obtained. After the toner is prepared, the toner is granulated (aqueous granulation). This method includes, for example, the following steps [1] to [4].

Step [1]: Preparation of toner material solution or dispersion The toner material solution or dispersion is prepared by dissolving or dispersing a toner material such as a colorant or a binder resin in an organic solvent. The organic solvent is removed during or after the toner granulation.

Step [2]: Preparation of aqueous medium The aqueous medium is not particularly limited and may be appropriately selected from known ones such as water, alcohol miscible with water, dimethylformamide, tetrahydrofuran, and cellosolve. And solvents such as lower ketones, and mixtures thereof. Among these, water is particularly preferable.
The aqueous medium can be prepared, for example, by dispersing a dispersion stabilizer such as resin fine particles in the aqueous medium. The amount of resin fine particles added to the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 0.5 to 10% by mass is preferable.

The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin. , Etc.
These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferable that it is formed of at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin in that an aqueous dispersion of fine spherical resin particles can be easily obtained.

  In addition, in the aqueous medium, if necessary, from the viewpoint of stabilizing the oil droplets of the solution or dispersion at the time of emulsification or dispersion described later, and sharpening the particle size distribution while obtaining a desired shape, It is preferable to use a dispersant. There is no restriction | limiting in particular as a dispersing agent, According to the objective, it can select suitably, For example, surfactant, a poorly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

Step [3]: Emulsification or dispersion When the solution or dispersion containing the toner material is emulsified or dispersed in the aqueous medium, the solution or dispersion containing the toner material is dispersed in the aqueous medium while stirring. It is preferable. The dispersion method is not particularly limited, but a batch type emulsifier such as a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), Ebara Mile Dar (manufactured by Aihara Seisakusho Co., Ltd.), TK Fillmix, TK Pipeline Homomixer (manufactured by Koki Kogyo Kogyo Co., Ltd.), Colloid Mill (manufactured by Shinko Pantech Co., Ltd.), Thrasher, Trigonal Wet Fine Crusher (Mitsui Miike Chemical Co., Ltd.) ), Captron (manufactured by Eurotech), continuous emulsifier such as fine flow mill (manufactured by Taiheiyo Kiko), microfluidizer (manufactured by Mizuho Kogyo), nanomizer (manufactured by Nanomizer), APV Gaurin (manufactured by Gaurin) High-pressure emulsifiers such as membrane emulsifiers such as membrane emulsifiers (manufactured by Chilling Industries Co., Ltd.) Reduction machine, an ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.). Among these, it is preferable to use APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer from the viewpoint of uniform particle size.

  In the case where a modified polyester (prepolymer) capable of reacting with an active hydrogen group-containing compound is included as the binder resin contained in the solution or dispersion, the reaction proceeds during emulsification or dispersion. The reaction conditions are not particularly limited and can be appropriately selected according to the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is 10 minutes to 40 hours is preferable, and 2 hours to 24 hours is more preferable.

Step [4]: Removal of Solvent Next, the organic solvent is removed from the emulsified slurry obtained by the emulsification or dispersion. The organic solvent is removed by (1) a method in which the temperature of the entire reaction system is gradually raised to completely evaporate and remove the organic solvent in the oil droplets, and (2) the emulsion dispersion is sprayed in a dry atmosphere, Examples thereof include a method in which the water-insoluble organic solvent in the droplets is completely removed to form toner fine particles, and the aqueous dispersant is removed by evaporation.

(Developer)
The developer in the present invention contains the above-described toner, and in the case of a two-component developer, it contains other appropriately selected components such as a carrier. In the present invention, the developer may be a one-component developer or a two-component developer. However, when the developer is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the service life is improved. In this respect, a two-component developer is preferable.
The carrier content in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. The preferable mixing ratio of the toner and the carrier is 1 to 10 parts by mass of the toner with respect to 100 parts by mass of the carrier. .

<Career>
There is no restriction | limiting in particular as a carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.
There is no restriction | limiting in particular as a material of a core material, It can select suitably from well-known things. For example, 50-90 emu / g manganese-strontium (Mn-Sr) -based material, manganese-magnesium (Mn-Mg) -based material and the like are preferable, and in terms of securing image density, iron powder (100 emu / g or more), A highly magnetized material such as magnetite (75 to 120 emu / g) is preferred. In addition, the copper-zinc (Cu-Zn) system (30 to 80 emu) is advantageous in that it can weaken the contact with the electrostatic latent image carrier (photosensitive member) in which the toner is in a spiked state, and is advantageous in improving the image quality. / G) and the like are preferred. These may be used alone or in combination of two or more.

  The particle diameter of the core material is preferably 10 to 200 μm and more preferably 40 to 100 μm in terms of mass average particle diameter (D50). When D50 is less than 10 μm, the number of fine powder systems increases in the distribution of carrier particles, and the magnetization per particle may be lowered to cause carrier scattering. On the other hand, if it exceeds 200 μm, the specific surface area may decrease and toner scattering may occur, and in the case of full color with many solid portions, reproduction of the solid portions may be particularly poor.

  There is no restriction | limiting in particular as a material of the resin layer which coat | covers a core material, According to the objective, it can select suitably from well-known resin. For example, amino resin, polyvinyl resin, polystyrene resin, halogenated olefin resin, polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene Fluoropolymers such as resins, copolymers of vinylidene fluoride and acrylic monomers, copolymers of vinylidene fluoride and vinyl fluoride, terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers Examples include terpolymer [fluorinated triple (multiple) copolymer], silicon resin, and the like. These may be used alone or in combination of two or more. Among these, a silicone resin is preferable in that the effect of preventing toner filming on the carrier is high.

There is no restriction | limiting in particular as silicon resin which comprises a resin layer, According to the objective, it can select suitably from generally known silicon resins. For example, a straight silicone resin composed only of an organosiloxane bond; a silicon resin modified with an alkyd resin, a polyester resin, an epoxy resin, an acrylic resin, a urethane resin, or the like can be given.
Examples of commercially available silicone resins include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical Co., Ltd., and SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicone.
Commercially available modified silicone resins include KR206 (alkyd modified), KR5208 (acrylic modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical Co., Ltd .; SR2115 manufactured by Toray Dow Corning Silicone Co., Ltd. Epoxy modified), SR2110 (alkyd modified), and the like.
In addition, although it is possible to use a silicon resin alone, it is also possible to simultaneously use a component that undergoes a crosslinking reaction, a charge amount adjusting component, and the like.

The resin layer covering the core material may contain conductive powder or the like as necessary, and examples thereof include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The volume average particle diameter of these conductive powders is preferably 1 μm or less. When the volume average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.
The resin layer covering the core material is prepared by, for example, dissolving a silicon resin or the like in an organic solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, followed by drying. It can be formed by baking. Examples of the application method include an immersion method, a spray method, and a brush coating method.

There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.
The resin layer baking means is not particularly limited and may be an external heating method or an internal heating method. For example, a method using a fixed electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, or a microwave is used. Method, etc.
The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass. If it is less than 0.01% by mass, it may not be possible to form a uniform resin layer on the surface of the core material. If it exceeds 5.0% by mass, the resin layer becomes too thick and granulates between carriers. May occur, and uniform carrier particles may not be obtained.

≪Image forming device≫
The image forming apparatus provided in the releasable information sheet manufacturing apparatus according to the present invention includes at least an image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit. Preferably, it has a cleaning means, and further has other means appropriately selected as necessary, for example, a static elimination means, a recycling means, etc. (FIG. 8).
The image forming method provided in the method for producing a releasable information sheet according to the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and preferably includes a cleaning step, Further, it includes other processes appropriately selected as necessary, for example, a static elimination process, a recycling process, and the like.

  The image forming method can be suitably performed by the image forming apparatus, the electrostatic latent image forming step can be performed by the electrostatic latent image forming unit, and the developing step is performed by the developing unit. The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

<Electrostatic latent image forming step and electrostatic latent image forming means>
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the image carrier.
-Image carrier-
The image carrier (sometimes referred to as “electrostatic latent image carrier” or “photoreceptor”) is not particularly limited in terms of material, shape, structure, size, etc., and is appropriately selected from known ones. The shape is preferably a drum shape, and examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine.

  The image carrier (photoreceptor) used in the image forming apparatus in the present invention has a conductive support and at least a photosensitive layer on the conductive support, and further has other layers as necessary. It becomes.

  As the photosensitive layer, a single layer type in which a charge generation material and a charge transport material are mixed, a forward layer type in which a charge transport layer is provided on the charge generation layer, and a charge generation layer is provided on the charge transport layer. There is a reverse layer type. In order to improve the mechanical strength, abrasion resistance, gas resistance, cleaning property, etc. of the photoreceptor, an outermost surface layer can be provided on the photosensitive layer. An undercoat layer may be provided between the photosensitive layer and the conductive support. Moreover, an appropriate amount of a plasticizer, an antioxidant, a leveling agent or the like can be added to each layer as necessary.

The conductive support is not particularly limited as long as it has a volume resistance of 1.0 × 10 ¹⁰ Ω · cm or less, and can be appropriately selected according to the purpose. For example, aluminum, Metals such as nickel, chromium, nichrome, copper, gold, silver and platinum, metal oxides such as tin oxide and indium oxide, film or cylindrical plastic, paper coated or aluminum by vapor deposition or sputtering A plate made of aluminum alloy, nickel, stainless steel or the like, and a tube processed into a drum shape by a method such as extrusion or drawing, and then subjected to surface treatment such as cutting, superfinishing, or polishing can be used.
The drum-shaped support preferably has a diameter of 20 to 150 mm, more preferably 24 to 100 mm, and still more preferably 28 to 70 mm. When the diameter of the drum-shaped support is less than 20 mm, it may be physically difficult to arrange each step of charging, exposure, development, transfer, and cleaning around the drum. When the diameter exceeds 150 mm, The image forming apparatus may become large. In particular, when the image forming apparatus is a tandem type, since it is necessary to mount a plurality of photoconductors, the diameter is preferably 70 mm or less, and more preferably 60 mm or less.
Further, an endless nickel belt or an endless stainless steel belt as disclosed in JP-A-52-36016 can also be used as the conductive support.

The undercoat layer of the photoconductor may be composed of a single layer or a plurality of layers. For example, (1) the resin is the main component, and (2) the white pigment and the resin are the main components. And (3) a metal oxide film obtained by chemically or electrochemically oxidizing the surface of a conductive substrate. Among these, those containing a white pigment and a resin as main components are preferable.
Examples of the white pigment include metal oxides such as titanium oxide, aluminum oxide, zirconium oxide, and zinc oxide. Among these, titanium oxide is particularly preferable because it is excellent in preventing injection of charges from the conductive support.
Examples of the resin include thermoplastic resins such as polyamide, polyvinyl alcohol, casein, and methyl cellulose; thermosetting resins such as acrylic, phenol, melamine, alkyd, unsaturated polyester, and epoxy. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular in the thickness of the said undercoat layer, According to the objective, it can select suitably, 0.1-10 micrometers is preferable and 1-5 micrometers is more preferable.

  Examples of the charge generation material in the photosensitive layer include monoazo pigments, bisazo pigments, trisazo pigments, tetrakisazo pigments and other azo pigments, triarylmethane dyes, thiazine dyes, oxazine dyes, xanthene dyes, Cyanine dyes, styryl dyes, pyrylium dyes, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, bisbenzimidazole pigments, indanthrone pigments, squarylium pigments, phthalocyanine pigments, etc. Organic pigments or dyes; selenium, selenium-arsenic, selenium-tellurium, cadmium sulfide, zinc oxide, titanium oxide, amorphous silicon, and other inorganic materials. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the charge transport material in the photosensitive layer include anthracene derivatives, pyrene derivatives, carbazole derivatives, tetrazole derivatives, metallocene derivatives, phenothiazine derivatives, pyrazoline compounds, hydrazone compounds, styryl compounds, styryl hydrazone compounds, enamine compounds, butadiene compounds, distyryl. Examples thereof include compounds, oxazole compounds, oxadiazole compounds, thiazole compounds, imidazole compounds, triphenylamine derivatives, phenylenediamine derivatives, aminostilbene derivatives, and triphenylmethane derivatives. These may be used individually by 1 type and may use 2 or more types together.

  As the binder resin used to form the photosensitive layer, it is electrically insulating and may be a known thermoplastic resin, thermosetting resin, photocurable resin, photoconductive resin, or the like. it can. Examples of the binder resin include polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, ethylene-vinyl acetate copolymer, polyvinyl butyral, Polyvinyl acetal, polyester, phenoxy resin, (meth) acrylic resin, polystyrene, polycarbonate, polyarylate, polysulfone, polyethersulfone, ABS resin and other thermoplastic resins, phenol resin, epoxy resin, urethane resin, melamine resin, isocyanate resin, Examples thereof include thermosetting resins such as alkyd resins, silicon resins, and thermosetting acrylic resins, polyvinyl carbazole, polyvinyl anthracene, and polyvinyl pyrene. These may be used individually by 1 type and may use 2 or more types together.

Examples of the antioxidant include phenolic compounds, paraphenylenediamines, hydroquinones, organic sulfur compounds, and organic phosphorus compounds.
Examples of the phenol compound include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-ethyl- 6-t-butylphenol), 4,4′-thiobis- (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol), 1,1,3 -Tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxy Ben ) Benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis (4′-hydroxy-3 ′) -T-butylphenyl) butyric acid] cricol ester, tocopherols and the like.
Examples of the paraphenylenediamines include N-phenyl-N′-isopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl- Examples include p-phenylenediamine, N, N′-di-isopropyl-p-phenylenediamine, N, N′-dimethyl-N, N′-di-t-butyl-p-phenylenediamine, and the like.
Examples of the hydroquinones include 2,5-di-t-octyl hydroquinone, 2,6-didodecyl hydroquinone, 2-dodecyl hydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methyl. Examples include hydroquinone and 2- (2-octadecenyl) -5-methylhydroquinone.
Examples of the organic sulfur compounds include dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate, and the like. .
Examples of the organic phosphorus compounds include triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine, and the like.
These compounds are known as antioxidants such as rubbers, plastics and fats and oils, and commercially available products can be easily obtained.
The addition amount of the antioxidant is preferably 0.01 to 10% by mass with respect to the total mass of the layer to be added.

As the plasticizer, those used as plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is about 0 to 30 parts by mass with respect to 100 parts by mass of the binder resin. Is appropriate.
Further, a leveling agent may be added to the photosensitive layer. Examples of the leveling agent include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil; polymers having a perfluoroalkyl group in the chain measurement, or oligomers. As for the usage-amount of the said leveling agent, 0-1 mass part is preferable with respect to 100 mass parts of said resin.

  Next, the formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the image carrier and then performing imagewise exposure, and by the electrostatic latent image forming unit. Can do. The electrostatic latent image forming unit includes, for example, at least a charger that uniformly charges the surface of the image carrier and an exposure unit that exposes the surface of the image carrier imagewise.

The charging can be performed, for example, by applying a voltage to the surface of the image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotrons and corotrons.
The charger preferably has voltage applying means for applying a voltage having an AC component.

The exposure can be performed, for example, by exposing the surface of the image carrier imagewise using the exposure device.
The exposure device is not particularly limited as long as it can perform image-like exposure on the surface of the image carrier charged by the charger, and can be appropriately selected according to the purpose. Examples include various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.
In the present invention, an optical back side system in which imagewise exposure is performed from the back side of the image carrier may be adopted.

<Development process and development means>
The developing step is a step of developing the electrostatic latent image using a toner or a developer to form a visualized toner image.
The formation of the visualized toner image can be performed, for example, by developing the electrostatic latent image using the toner or the developer, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer, and can be appropriately selected from known ones. For example, the toner or developer is accommodated. Preferred examples include those having at least a developing unit capable of bringing the toner or developer into contact or non-contact with the electrostatic latent image.

In the developing device, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state, thereby forming a magnetic brush. Since the magnet roller is disposed in the vicinity of the image carrier (photosensitive member), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is caused by the electric attractive force. It moves to the surface of the image carrier (photoreceptor). As a result, the electrostatic latent image is developed with the toner to form a visible image (toner image) with the toner on the surface of the image carrier (photosensitive member).
The developer accommodated in the developing device is a developer containing the toner, but the developer may be a one-component developer or a two-component developer.

<Transfer process and transfer means>
The transfer step is a step of transferring the toner image to a recording medium. An intermediate transfer member is used, and after the toner image is primarily transferred onto the intermediate transfer member, the toner image is secondarily transferred onto the recording medium. A transfer mode is preferable, and a primary transfer step of forming a composite transfer image by transferring a toner image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and recording the composite transfer image An embodiment including a secondary transfer step of transferring onto a medium is more preferable.
The transfer can be performed, for example, by charging the image carrier (photosensitive member) using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

-Intermediate transfer member-
As the intermediate transfer member, a material exhibiting conductivity of a volume resistance of 1.0 × 10 ^{5 to} 1.0 × 10 ¹¹ Ω · cm is preferable. When the volume resistance is less than 1.0 × 10 ⁵ Ω · cm, so-called transfer dust is generated in which the toner image is disturbed due to discharge when the toner image is transferred from the photosensitive member to the intermediate transfer member. If the toner image exceeds 1.0 × 10 ¹¹ Ω · cm, the counter charge of the toner image is transferred onto the intermediate transfer member after the toner image is transferred from the intermediate transfer member to a recording medium such as paper. It may remain and appear as an afterimage on the next image.

As the intermediate transfer member, for example, a metal oxide such as tin oxide or indium oxide, a conductive particle such as carbon black, or a conductive polymer, alone or in combination, kneaded with a thermoplastic resin, and then an extrusion molded belt A cylindrical or cylindrical plastic can be used. In addition to this, the above-mentioned conductive particles and conductive polymer are added to a resin solution containing a thermally crosslinkable monomer or oligomer, if necessary, and subjected to centrifugal molding while heating to obtain an intermediate transfer member on an endless belt. You can also.
A surface layer may be provided on the intermediate transfer member, and it is preferable that resistance adjustment is appropriately performed using a conductive substance.

The transfer means (the primary transfer means and the secondary transfer means) includes at least a transfer device that peels and charges the visible image formed on the image carrier (photoconductor) to the recording medium side. It is preferable to have. There may be one transfer means or two or more transfer means. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper). However, in consideration of use as direct mail, the recording medium itself may be white. Preferably, the recording medium surface has a coating layer of a white pigment such as calcium carbonate, talc, or kaolin. The size of the white pigment is an average particle diameter of 0.1 μm or more, preferably 0.5 to 5 μm. When the average particle size of the white pigment is less than 0.1 μm, the strength of the white pigment layer is extremely weak, the white pigment powder is crushed, and the white pigment layer is severely cracked. It becomes easy.
The thickness of the white pigment layer is preferably 1 μm or more, preferably 1.5 to 3 μm or more in order to maintain the appearance of the information sheet.

<Fixing process and fixing means>
The fixing step is a step of forming a toner image by fixing the toner image transferred to the recording medium using the fixing unit, and may be performed each time the toner of each color is transferred to the recording medium. Alternatively, the toners of the respective colors may be simultaneously formed in a state where they are laminated.
The fixing unit is not particularly limited, and a known unit can be used. Examples of the fixing unit include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The toner particles are preferably in the range of 10 ³ Pa · s to 10 ⁴ Pa · s by heating and pressing in the fixing unit.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the image carrier. It is done.

The cleaning step is a step of removing the electrophotographic toner remaining on the image carrier and can be suitably performed by a cleaning unit.
The cleaning unit is preferably provided downstream of the transfer unit and upstream of the charger.
The cleaning means is not particularly limited, and may be appropriately selected from known cleaners as long as the toner remaining on the image carrier can be removed. For example, a magnetic brush cleaner or an electrostatic brush A cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, a web cleaner and the like are preferable.

The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

<Energy beam curable composition coating curing step (coating curing step) and energy beam curable composition coating curing unit (coating curing unit)>
The energy ray curable composition can be applied onto a recording medium carrying a toner image at any appropriate time after the fixing step. For example, an energy beam curable composition can be applied off-line immediately after forming a toner image, or on a printing device where the printing and overcoating are different, such as an inline coating device where the printing and overcoating are performed on the same printing device. Like a coating device, it can be applied to a recording medium carrying a toner image after a short or long delay time after printing. Furthermore, the energy ray curable composition can be applied to cover the entire recording medium, the entire toner image, a part of the recording medium, or a part of the toner image. Depending on the application, printing surface protection or glossing can be provided. When performing the bending described later, it is preferable not to apply the energy ray curable composition precursor to the bent portion in order to reduce the burden on the bent portion.

In order to apply the energy ray curable composition, roll coater, flexo coater, rod coater, blade, wire bar, air knife, curtain coater, slide coater, doctor knife, screen coater, gravure coater (for example, offset gravure coater), Liquid film coating equipment can be used, including slot coaters, extrusion coaters, and ink jet coaters. Such devices can be used in well-known manners such as forward and reverse roll coating, offset gravure, curtain coating, lithographic coating, screen coating, gravure coating, and inkjet coating.
There is no restriction | limiting in particular as application | coating thickness of the said energy-beam curable composition, Although it can select suitably according to the objective, 1 micrometer-15 micrometers are preferable. When the coating thickness is less than 1 μm, repelling or gloss may be insufficient, and when it exceeds 15 μm, the texture of the image may be deteriorated.

After the application step, it is preferable to cure the applied energy ray curable composition.
The energy beam curable composition can be cured by irradiating light (mainly ultraviolet rays) from a light source.

  The light source is not particularly limited and can be appropriately selected according to the purpose. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, Tungsten lamp, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers, YAG laser, light emitting diode, CRT light source, plasma light source, electron beam, gamma ray, ArF excimer laser, KrF excimer laser, F2 A laser etc. are mentioned.

  FIG. 9 shows an example of the coating and curing means. 9 includes a coating roller 102, a metal roller 103, a pressing roller 105, a coating belt 106 for coating and curing means, a tray 107, a light source 108, and a scraper 109. The energy beam curable composition 2 is stored between the application roller 102 and the metal roller 103.

The paper 1 on which the toner image is formed passes between the application roller 102 and the pressure roller 105 while being in contact with the rotating application roller 102 and the pressure roller 105. At that time, the energy beam curable composition 2 on the surface of the application roller 102 is transferred to the paper 1, whereby the energy beam curable composition 2 is applied to the paper 1.
The paper 1 on which the energy beam curable composition 2 is applied is conveyed by the coating and curing means conveying belt 106 and passes under the light source 108. At that time, the energy ray curable composition 2 applied to the paper 1 is cured by ultraviolet rays from the light source 108. Thereafter, the paper 1 (removable information sheet) moves onto the tray 107.
Unnecessary energy beam curable composition 2 attached to the pressure roller 105 is removed by the scraper 109.

-Energy ray curable composition-
Examples of the energy beam curable composition used in the present invention include a polymerizable oligomer, a polymerizable unsaturated compound, a photopolymerization initiator, a sensitizer, a polymerization inhibitor, and a surfactant.

-Polymerizable oligomer-
There is no restriction | limiting in particular as said polymerizable oligomer, According to the objective, it can select suitably, For example, polyester acrylate, epoxy acrylate, urethane acrylate etc. are mentioned.
There is no restriction | limiting in particular as said polyester acrylate, According to the objective, it can select suitably, For example, the acrylic ester of the polyester polyol obtained from a polyhydric alcohol and a polybasic acid is mentioned. The polyester acrylate exhibits excellent reactivity.
There is no restriction | limiting in particular as said epoxy acrylate, According to the objective, it can select suitably, For example, the epoxy acrylate obtained by reaction of bisphenol-type epoxy, novolak-type epoxy, alicyclic epoxy, etc. and acrylic acid is mentioned. It is done. The epoxy acrylate is excellent in hardness, flexibility, and curability.
There is no restriction | limiting in particular as said urethane acrylate, According to the objective, it can select suitably, For example, the urethane acrylate obtained by reacting polyester polyol, polyether polyol, etc., acrylic acid ester with a diisocyanate and a hydroxyl group Is mentioned. When the urethane acrylate is used, a flexible and strong film can be obtained.
The said polymerizable oligomer may be used individually by 1 type, and may use 2 or more types together.

  There is no restriction | limiting in particular as content of the said polymerizable oligomer in the said energy-beam curable composition, Although it can select suitably according to the objective, 5 mass%-60 mass% are preferable, and 10 mass%-50 % By mass is more preferable, and 20% by mass to 45% by mass is particularly preferable. When the content is less than 5% by mass, poor curing may occur, the viscosity may be too low, or the flexibility after curing may be impaired. When the content exceeds 60% by mass, the adhesion is deteriorated. Or the viscosity becomes too high. When the content is within the particularly preferable range, it is advantageous in terms of viscosity optimization, curability, flexibility of the coating layer of the energy beam curable composition after curing, and strength.

-Polymerizable unsaturated compound-
The polymerizable unsaturated compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a monofunctional polymerizable unsaturated compound, a bifunctional polymerizable unsaturated compound, and a trifunctional polymerizable compound. Examples thereof include unsaturated compounds and tetrafunctional or higher polymerizable unsaturated compounds.
Examples of the monofunctional polymerizable unsaturated compound include 2-ethylhexyl acrylate, 2-hydroxylethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, benzyl acrylate, phenyl glycol monoacrylate, and cyclohexyl acrylate. It is done.
Examples of the bifunctional polymerizable unsaturated compound include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, tripropylene glycol diacrylate, and tetraethylene glycol. Examples include diacrylate.
Examples of the trifunctional polymerizable unsaturated compound include trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, and the like.
Examples of the tetrafunctional or higher polymerizable unsaturated compound include pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hydroxypentaacrylate, and dipentaerythritol hexaacrylate.
The said polymerizable unsaturated compound may be used individually by 1 type, and may use 2 or more types together.

  There is no restriction | limiting in particular as content of the said polymerizable unsaturated compound in the said energy-beam curable composition, Although it can select suitably according to the objective, 35 mass%-90 mass% are preferable, and 40 mass% -85 mass% is more preferable, and 45 mass%-75 mass% is especially preferable. When the content is less than 35% by mass, the viscosity may be too high, and when it exceeds 90% by mass, the curing may be poor, the viscosity may be too low, or the flexibility after curing may be increased. It may be damaged. When the content is within the particularly preferable range, it is advantageous in terms of viscosity optimization, curability, and the coating layer of the energy beam curable composition after curing.

A polyfunctional one is faster than a monofunctional one and has a faster curing speed and is suitable for high-speed fixing, but has a large volume shrinkage. In the case of a polymerizable unsaturated compound that greatly shrinks due to a curing reaction, curling is likely to occur. Therefore, it is desirable to use a polymerizable unsaturated compound having a volumetric shrinkage as low as possible and its polymer.
The polymerizable unsaturated compound preferably has a volume shrinkage of 15% or less.

P. of the polymerizable unsaturated compound and the polymerizable oligomer. I. I. There is no restriction | limiting in particular as (skin irritation), Although it can select suitably according to the objective, 1.0 or less is preferable. P. I. I. If it is 5.0 or more, irritation to the skin is too strong, which may cause safety problems.
Further, the hue of the polymerizable unsaturated compound and the polymerizable oligomer is preferably as colorless and transparent as possible, and preferably 2 or less in the Gardner gray scale. When the Gardner gray scale exceeds 2, the color of the image portion may change, and the discoloration of the background portion may become conspicuous.

-Photopolymerization initiator-
The photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include benzophenone, benzoin ethyl ether, benzoin isopropyl ether, and benzyl. A commercial item can be used as said photoinitiator. Examples of the commercially available photopolymerization initiator include Irgacure 1300, Irgacure 369, Irgacure 907 manufactured by Ciba Specialty Chemicals, Inc., and Lucilin TPO manufactured by BASF.

  When the mixture of the polymerizable oligomer or the polymerizable unsaturated compound and the photopolymerization initiator is irradiated with ultraviolet rays, the photopolymerization initiator is represented by the following formulas (I) and (II): Generate radicals. The radical causes an addition reaction of the polymerizable oligomer or the polymerizable unsaturated compound to the polymerizable double bond. Further radicals are generated by the addition reaction, and by repeating the addition reaction to the polymerizable double bond of the other polymerizable oligomer or the polymerizable unsaturated compound, the polymerization reaction is performed as shown in the following formula (III). proceed.

(I) Hydrogen drawing type

(II) Photocleavage type

(III) Polymerization

  The photopolymerization initiator includes (i) high ultraviolet absorption efficiency, (ii) high solubility in the polymerizable oligomer or polymerizable unsaturated compound, (iii) odor, yellowing, and toxicity. Those having good characteristics such as low and (iv) no dark reaction are preferred.

  There is no restriction | limiting in particular as content of the said photoinitiator in the said energy-beam curable composition, Although it can select suitably according to the objective, 1 mass%-10 mass% are preferable, and 2 mass%- 5 mass% is more preferable.

-Sensitizer-
In the case of using the hydrogen abstraction type benzophenone photopolymerization initiator of the formula (I), the reaction may be slowed only by the photopolymerization initiator. It is preferable to improve the property. By containing an amine sensitizer, there is an effect of supplying hydrogen to the photopolymerization initiator by a hydrogen abstraction action and an effect of preventing reaction inhibition due to oxygen in the air.
The amine-based sensitizer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include triethanolamine, triisopropanolamine, 4,4-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid. , Ethyl 4-dimethylaminobenzoate, isoacyl 4-dimethylaminobenzoate and the like.

  There is no restriction | limiting in particular as content of the said sensitizer in the said energy-beam curable composition, Although it can select suitably according to the objective, 1 mass%-15 mass% are preferable, and 3 mass%-8 The mass% is more preferable.

-Polymerization inhibitor-
The polymerization inhibitor is used to increase the storage stability of the energy beam curable composition.
The polymerization inhibitor is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 2,6-ditert-butyl-p-cresol (BHT), 2,3-dimethyl-6-tert. -Butylphenol (IA), anthraquinone, hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ) and the like.

  There is no restriction | limiting in particular as content of the said polymerization inhibitor in the said energy-beam curable composition, Although it can select suitably according to the objective, 0.5-3 mass% is preferable.

-Surfactant-
By including the surfactant in the energy beam curable composition, the interface between the toner and the energy beam curable composition is imparted with adsorptivity, or the surface tension of the energy beam curable composition is lowered and wettability is achieved. Improve the performance.

There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably, For example, anionic surfactant, nonionic surfactant, silicon surfactant, fluorosurfactant etc. are mentioned.
Examples of the anionic surfactant include sulfosuccinate, disulfonate, phosphate ester, sulfate, sulfonate, and mixtures thereof.
Examples of the nonionic surfactant include polyvinyl alcohol, polyacrylic acid, isopropyl alcohol, acetylenic diol, ethoxylated octylphenol, ethoxylated branched secondary alcohol, bellfluorobutane sulfonate, alkoxylated alcohol, and the like. .
Examples of the silicon surfactant include polyether-modified polydimethyldimethylsiloxane.
Examples of the fluorosurfactant include ethoxylated nonylphenol.

  There is no restriction | limiting in particular as content of the said surfactant in the said energy-beam curable composition, Although it can select suitably according to the objective, 0.1 mass%-5 mass% are preferable, 0.5 A mass% to 3 mass% is more preferable. When the content is less than 0.1% by mass, wettability may not be obtained, and when it exceeds 5% by mass, curability may be inhibited. When the content is within the more preferable range, it is advantageous in terms of improving wettability.

  The other components further include leveling agents, matting agents, waxes for adjusting film physical properties, tackifiers (adhesives that do not inhibit polymerization) to improve adhesion to recording media such as polyolefin and PET. Property-imparting agent).

Further, it is preferable to contain a polymer that is compatible with the polymerizable oligomer and the polymerizable unsaturated compound. Due to the presence of the polymer, the energy ray curable composition layer is not destroyed or moved with respect to the pressure bonding during the production of the protective agent sheet, and the pressure bonding can be reliably performed. As a preferable polymer, a (meth) acrylic copolymer having a weight average molecular weight of 10,000 to 100,000 and a glass transition temperature of −60 ° C. to 20 ° C. is the polymerizable oligomer and the polymerizable unsaturated. The compatibility with the compound is high, the pressure-bonding property is good, and the removability is also most preferable.
The (meth) acrylic copolymer in the present invention is obtained by polymerizing a monomer component composed of an acrylic acid alkyl ester or a methacrylic acid alkyl ester using an organic solvent as a polymerization solvent.

  Examples of the acrylic acid alkyl ester or methacrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, n-decyl (meth) acrylate and glycol di (meth) acrylate, such as ethylene glycol di (meth) acrylate, Examples include butylene glycol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate.

  When producing a (meth) acrylic copolymer, if necessary, an ethylenically unsaturated monomer copolymerizable with a (meth) acrylic acid ester, for example, a carboxylic acid-containing ethylene such as acrylic acid, methacrylic acid, and itaconic acid Unsaturated monomers, and hydroxyalkyl (meth) acrylates such as 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and alkylamino (meth) acrylates such as Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and glycidyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylate Ethylenically unsaturated monomer having a functional group as such Ruamido, vinyl acetate, vinyl propionate, styrene, can be copolymerized α- methyl styrene.

As the polymerization solvent for the (meth) acrylic copolymer, each organic solvent can be used, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol. Alcohols such as cellosolve acetate, methyl cellosolve, ethyl cellosolve, n-butyl cellosolve, i-butyl cellosolve, n-propyl cellosolve, etc., propylene glycol-n-butyl ether, propylene glycol methyl ether, propylene glycol phenyl ether, dipropylene Propylene glycol ethers such as glycol methyl ether and propylene glycol methyl ether acetate, toluene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone Aromatic (petroleum fractions) solvents, phthalate ester plasticizers, such as alkyl phosphates.
In preparing the varnish composition (energy ray curable composition), the (meth) acrylic copolymer (B) solution dissolved in the solvent may be blended as it is, and in that case, from the composition Finally, the solvent may be removed.

  The (meth) acrylic copolymer synthesized as described above can find particularly effective use in a specific molecular weight range and a specific glass transition temperature range.

The weight average molecular weight of the (meth) acrylic copolymer is required to be 10,000 to 100,000, preferably 20,000 to 50,000.
When this component has a weight average molecular weight of less than 10,000, the cohesive force is insufficient, the adhesiveness is low, and an appropriate removable adhesiveness is not exhibited.
Further, when the weight average molecular weight of this component exceeds 100,000, the compatibility with the polymerizable oligomer and the polymerizable unsaturated compound is lowered. In such a case, it is necessary to use a large amount of a diluent for blending the component into the polymerizable oligomer and the polymerizable unsaturated compound, which causes a decrease in curing speed and a decrease in surface gloss due to ultraviolet rays, Sanitary problems due to the deterioration of the working environment due to solvents and fire-fighting law problems will increase.

Next, the glass transition temperature of the (meth) acrylic copolymer needs to be in the range of −60 to 20 ° C., preferably −50 to 10 ° C.
When this component has a glass transition temperature lower than −60 ° C., the sticky feeling is strong and the adhesive strength is not sufficiently obtained.
Moreover, if this component (B) has a glass transition temperature higher than 20 degreeC, re-peeling adhesiveness will not be obtained.

  The glass transition temperature referred to in the present invention is a general polymer as described in, for example, Eizo Omori, “Acrylic acid ester and its polymer (II)”, pages 110-115 issued by Shojido Co., Ltd. In the case of a copolymer, it is the calculated glass transition temperature described on page 120 of the same document.

  The above (meth) acrylic copolymer has good compatibility with the polymerizable oligomer and the polymerizable unsaturated compound, and the energy beam curable varnish composition in which the component (B) is uniformly dissolved. You can get things.

The blending ratio of the (meth) acrylic copolymer to the polymerizable oligomer and the polymerizable unsaturated compound is not particularly limited, but a particularly preferable range is the total of the polymerizable oligomer and the polymerizable unsaturated compound. It is 5 to 80 parts by weight with respect to 100 parts by weight.
When the blending ratio is less than 5 parts by weight, the varnish composition may not be provided with sufficient removable adhesiveness or may have poor adhesiveness.
On the other hand, when the amount exceeds 80 parts by weight, the resulting varnish composition has a strong stickiness and lowers the original gloss of the varnish. There is also a possibility that the blocking resistance of the paper is insufficient.
In addition, the said mixture ratio (weight part) of this component says the quantity of only a copolymer component, and does not contain the solvent etc. which were used for superposition | polymerization.

Since the (meth) acrylic copolymer in the present invention is uniformly mixed with other components in the composition to form a solution state, the coating surface has excellent gloss, and in an atmosphere under a normal living environment. , Blocking resistance will be imparted.
As physical conditions at the time of bonding, the varnish composition surfaces coated and cured on the paper surface are combined with each other, for example, a linear pressure of about 10 to 50 kg / cm, or about 0.1 to 10 kg / cm When a combination of pressurization by linear pressure and heating at a temperature of 50 to 150 ° C. is used, the components ooze out to the surface, an adhesive layer is formed on the surface of the varnish coating layer, and the varnish composition surfaces are peeled again. Adhesive bonding becomes possible.
Adhesive strength can be adjusted as appropriate by selecting the physical conditions and mixing ratio of the components, glass transition temperature and average molecular weight, and is weaker than the adhesive strength between the printed and varnished surfaces. Appropriate peelability can be imparted without imparting.

There is no restriction | limiting in particular as a viscosity of the said energy-beam curable composition, Although it can select suitably according to the objective, The viscosity in 25 degreeC is 10 mPa * s-800 mPa * s. If the viscosity is less than 10 mPa · s or exceeds 800 mPa · s, it may be difficult to control the coating thickness.
The viscosity can be measured by, for example, a B-type viscometer (manufactured by Toyo Seiki Seisakusho).

  The energy ray curable composition can be prepared by an oily type using a solvent, but in the case of an energy ray curable type (photocuring type) using UV, safety ensuring, environmental protection, energy saving and high It is preferable from the viewpoint of productivity.

<Folding process, crimping process and folding means, crimping means>
After the coating and curing process, if necessary, it is cut into a desired size, and for example, a folding process for folding more than two folds such as bi-fold (V-fold), tri-fold (Z-fold), etc. Match the processed surfaces of the composition. An adhesive having removability can be obtained by laminating the surfaces of the energy beam curable composition by roller pressure bonding. The amount of pressure applied when crimping is generally in the range of 50 to 1000 N / cm ² .
In this way, productivity is increased by bending and pressing one sheet.
In addition, it is preferable not to apply the energy beam curable composition to the bent portion, because the bent portion is not damaged when it is peeled again.

<Heating and pressing step and heating and pressing means>
The heating and pressurizing step in the present invention is performed in a step subsequent to the folding step and the crimping step. In the next step of the folding step, the component of the heating and pressurizing step does not come into contact with the energy ray curable composition processed surface, so that the processed surface is not damaged or stained. In addition, when the energy ray curable composition processed surface has tackiness, there is a possibility that the conveyance performance may be lowered, but this can be prevented. In the next step of the crimping step, the processed surface of the energy beam curable composition is in a bonded state, so that it can be conveyed in any direction of the removable information sheet, and the conveyance design is further facilitated.
In the present invention, this heating and pressing step is performed by the heating and pressing method described above, and the heating and pressing means uses the aforementioned heating and pressing apparatus.

<Image formation>
Next, a basic configuration of the copying machine 100B using each of the above means will be described.
FIG. 7 is a schematic configuration diagram showing the configuration of the copying machine 100B. The copying machine 100B is a tandem color image forming apparatus, and includes a printer unit 150, which is a main body of the image forming apparatus, a paper feeding device 200, a scanner 300, and an automatic document feeder (ADF) 400.

The printer unit 150 is provided with an endless belt-shaped intermediate transfer belt 50 at the center. The intermediate transfer belt 50 is stretched around three support rollers including a belt driving roller 14, a cleaning counter roller 15, and a secondary transfer counter roller 16, and can rotate clockwise in FIG. In the vicinity of the cleaning counter roller 15, an intermediate transfer belt cleaning device 17 that is an intermediate transfer belt cleaning unit for removing residual toner on the intermediate transfer belt 50 is disposed.
The printer unit 150 also includes four yellow, cyan, magenta, and black colors along the transport direction so as to face the stretched surface between the belt driving roller 14 and the cleaning facing roller 15 in the intermediate transfer belt 50. A tandem-type image forming unit 120 in which two image forming units 18 are arranged to face each other is arranged.

  An exposure device 21 is disposed above the tandem type image forming unit 120. The secondary transfer device 22 is disposed on the opposite side (below the intermediate transfer belt 50) to the side where the tandem image forming unit 120 is disposed with the intermediate transfer belt 50 interposed therebetween. In the secondary transfer device 22, a transfer conveyance belt 24 that is an endless belt is stretched around a pair of transfer conveyance support rollers 23, and one of the pair of transfer conveyance support rollers 23 is rotationally driven as a drive roller. The transfer conveyance belt 24 is driven to rotate counterclockwise in FIG. Also, the transfer conveyance support roller 23 on the right side in FIG. 8 and the secondary transfer counter roller 16 are in contact with each other with the intermediate transfer belt 50 and the transfer conveyance belt 24 sandwiched therebetween. A contact portion with the conveyance belt 24 becomes a secondary transfer nip.

A fixing device 25 that fixes the toner image on the recording medium S is disposed on the downstream side in the conveyance direction of the recording medium S of the secondary transfer device 22 in the printer unit 150 (left side in FIG. 8). The fixing device 25 includes a heating unit 26 provided with a heater (not shown) therein, and a pressure roller 27 that is pressed by a spring (not shown) and presses against the heating unit 26 to form a nip portion as a press-contact portion. ing.
Below the secondary transfer device 22 and the fixing device 25 in the printer unit 150, a reversing device 28 for reversing the recording medium S when an image is formed on both sides of the recording medium S is disposed.

  Next, formation of a full color image (color copy) using the copying machine 100B will be described. First, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and a document is set on the contact glass 32 of the scanner 300. close up.

  When the user presses a start switch on an operation panel (not shown), when a document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32. As soon as the document is set on the scanner 300, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, the light from the light source is irradiated by the first traveling body 33 so that the light is reflected by the document surface, and the reflected light is reflected by the mirrors in the first traveling body 33 and the second traveling body 34, Light is received by the reading sensor 36 through the imaging lens 35. As a result, a color original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta, and cyan is transmitted to the exposure device 21, and exposure light corresponding to each image information is directed to each photoreceptor 10 of each image forming unit 18 in the tandem type image forming unit 120. Each is irradiated. As a result, black, yellow, magenta, and cyan toner images are formed in each image forming unit 18.

  The four image forming units 18 (Y, C, M, and K) have substantially the same configuration except that the colors of the toners to be used are different. Therefore, in FIG. , M, and K are omitted. The image forming unit 18 includes a drum-shaped photoconductor 10, and around the photoconductor 10, a charging device as a charging unit, a developing device, a primary transfer roller 62 as a primary transfer unit, a photoconductor cleaning device, and a charge eliminating device. Etc.

  Each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image forming unit) in the printer unit 150 is based on the image information of each corresponding color. Images (black image, yellow image, magenta image, and cyan image) can be formed on the surface of each photoconductor 10.

  The black image, yellow image, magenta image, and cyan image formed by each image forming unit 18 are respectively transferred onto the intermediate transfer belt 50 that is rotationally moved by the belt driving roller 14, the cleaning facing roller 15, and the secondary transfer facing roller 16. A black image formed on the black photoconductor 10K, a yellow image formed on the yellow photoconductor 10Y, a magenta image formed on the magenta photoconductor 10M, and a cyan photoconductor 10C. Cyan images are sequentially transferred (primary transfer).

  Then, a black image, a yellow image, a magenta image, and a cyan image are superimposed on the intermediate transfer belt 50 to form a composite color image (color transfer image).

On the other hand, in the paper feeding device 200, one of the paper feeding rollers 142 is selectively rotated to feed out the recording medium S from one of the paper feeding cassettes 144 provided in multiple stages in the paper bank 143, and one sheet is separated by the separation roller 145. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the main body side paper feed path 148 in the printer unit 150, and abutted against the registration roller 49 and stopped. Alternatively, the manual feed roller 51 is rotated to feed out the recording medium S on the manual tray 54, separated one by one by the manual separation roller 52, and put into the manual feed path 53, and abutted against the registration roller 49 as described above. Stop.
The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the recording medium S.

  After abutting against the registration roller 49 and stopping, the registration roller 49 is rotated in time with the synthesized color image (color transfer image) synthesized on the intermediate transfer belt 50, and the recording medium is directed toward the secondary transfer nip. S is sent out. A composite color image (color transfer image) on the intermediate transfer belt 50 is recorded by a transfer electric field formed between the transfer conveyance support roller 23 on the secondary transfer device 22 side and the secondary transfer counter roller 16 in the secondary transfer nip. Transfer (secondary transfer) is performed on the medium S, and a color image is formed on the recording medium S. The transfer residual toner on the intermediate transfer belt 50 after passing through the secondary transfer nip is cleaned by the intermediate transfer belt cleaning device 17.

  The recording medium S on which the color image is transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25. In the fixing device 25, the composite color image (color transfer image) is fixed on the recording medium S by applying heat and pressure at a nip formed by the heating unit 26 and the pressure roller 27. The

  The recording medium S that has passed through the fixing device 25 is given conveyance force by the conveyance roller pair 56 after fixing and reaches the position of the switching claw 55. The recording medium S is discharged by the discharge roller pair 156 by being switched in the transport direction by the switching claw 55 and stacked on the discharge tray 57. Alternatively, the conveying direction is switched by the switching claw 55 to reach the reversing device 28, where the reversing device 28 is reversed and guided to a position where it again hits the registration roller 49, and an image is also formed on the back surface at the secondary transfer nip. After fixing at 25, the paper is discharged by the discharge roller pair 156 and stacked on the paper discharge tray 57.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

-Production of unmodified polyester (low molecular weight polyester)-
(Production Example 1) Production of unmodified polyester 1 In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 2765 parts of bisphenol A ethylene oxide 2 mol adduct, 480 parts of bisphenol A propylene oxide 2 mol adduct, 1100 parts of terephthalic acid, 225 parts of adipic acid and 10 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure.
Next, after reacting the reaction solution under a reduced pressure of 10 to 15 mmHg for 5 hours, 130 parts of trimellitic anhydride was put into a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours, [Unmodified Polyester 1] Got.
[Non-modified polyester 1] had a glass transition temperature Tg of 43 ° C.

(Production Example 2) Production of unmodified polyester 2 In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 1210 parts of bisphenol A ethylene oxide 2 mol adduct, 2750 parts of bisphenol A propylene oxide 3 mol adduct, 910 parts of terephthalic acid, 190 parts of adipic acid and 10 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure.
Next, after reacting the reaction solution under a reduced pressure of 10 to 15 mmHg for 5 hours, 220 parts of trimellitic anhydride was put into a reaction vessel and reacted for 2 hours at 180 ° C. under normal pressure, [unmodified polyester 2] Got.
[Non-modified polyester 2] had a glass transition temperature Tg of 49 ° C.

(Production Example 3) Production of unmodified polyester 3 In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 229 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 529 parts by mass of bisphenol A propylene oxide 3 mol adduct 100 parts by mass of isophthalic acid, 108 parts by mass of terephthalic acid, 46 parts by mass of adipic acid, and 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure.
Next, the reaction solution was reacted for 5 hours under a reduced pressure of 10 to 15 mmHg, and then 30 parts by weight of trimellitic anhydride was placed in the reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours, [Unmodified Polyester 3] Got.
[Non-modified polyester 3] had a glass transition temperature Tg of 55 ° C.

(Production Example 4) Production of unmodified polyester 4 In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 229 parts of bisphenol A ethylene oxide 2 mol adduct, 400 parts of bisphenol A propylene oxide 2 mol adduct, 208 parts of terephthalic acid, 46 parts of adipic acid and 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure.
Next, the reaction solution was reacted for 7 hours under a reduced pressure of 10 to 15 mmHg, and then 20 parts of trimellitic anhydride was placed in the reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours. ] Was obtained.
[Non-modified polyester 4] had a glass transition temperature Tg of 63 ° C.

-Production of master batch (MB)-
(Production Example 5) Production of master batch 1 1000 parts by mass of water and carbon black “Printex35”; manufactured by Degussa, DBP oil absorption = 42 ml / 100 g, pH = 9.5) 540 parts by mass, and the unmodified polyester 1 1200 parts by mass were mixed using a Henschel mixer (manufactured by Mitsui Mining).
The mixture was kneaded at 150 ° C. for 30 minutes with two rolls, then cooled with rolling and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to obtain a master batch 1.

(Manufacture example 6) Manufacture of masterbatch 2 Masterbatch 2 was obtained by the same method except having used unmodified polyester 2 instead of unmodified polyester 1 in manufacture of the said masterbatch 1.

(Manufacture example 7) Manufacture of masterbatch 3 Masterbatch 3 was obtained by the same method except having used unmodified polyester 3 instead of unmodified polyester 1 in manufacture of the above-mentioned masterbatch 1.

(Manufacture example 8) Manufacture of master batch 4 Master batch 4 was obtained by the same method except having used unmodified polyester 4 instead of unmodified polyester 1 in manufacture of the above-mentioned master batch 1.

-Synthesis of prepolymer-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, trimellitic anhydride 22 parts by mass of acid and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure.
Subsequently, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester was synthesize | combined.
The obtained intermediate polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,600, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, and a hydroxyl value of 49.

Next, 411 parts by mass of the intermediate polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are charged in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Thus, a prepolymer (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized.
The free isocyanate content of the obtained prepolymer was 1.60% by mass, and the solid content concentration of the prepolymer (after standing at 150 ° C. for 45 minutes) was 50% by mass.

-Synthesis of ketimine (the active hydrogen group-containing compound)-
In a reaction vessel equipped with a stir bar and a thermometer, 30 parts by mass of isophoronediamine and 70 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (the active hydrogen group-containing compound).
The amine value of the obtained ketimine compound (the active hydrogen machine-containing compound) was 423.

-Synthesis of styrene-acrylic copolymer resin-
Into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 300 parts by mass of ethyl acetate was charged, and a styrene-acrylic monomer mixture (styrene / 2-ethylhexyl acrylate / acrylic acid / hydroxylethyl acrylate = 75/15 / 5/5) 300 parts by mass and 10 parts by mass of azobisisobutylnitrile were added and reacted at 60 ° C. for 15 hours under a normal pressure nitrogen atmosphere.
Next, 200 parts by mass of methanol was added to the reaction solution, and after stirring for 1 hour, the supernatant was removed and dried under reduced pressure to synthesize the styrene-acrylic copolymer resin.

-Dissolution of toner material and adjustment of dispersion-
In a beaker, the prepolymer and the unmodified polyester were put in the number of parts described in Table 3 below, and further 100 parts by mass of ethyl acetate and 30 parts by mass of a styrene-acrylic copolymer were stirred and dissolved.
Next, a petroleum-based wax (cycloparaffin 15% mass, average molecular weight = 650) as a release agent, the master batch was charged in the number of parts described in Table 3, and a bead mill (“Ultra Visco Mill”; manufactured by Imex Corporation) was used. The raw material solution was prepared by three passes under the condition of 1 kg / hr of the liquid feeding speed, 6 m / s of the disk peripheral speed, and 80% by volume of 0.5 mm zirconia beads, and the ketimine described in Table 3 below. In addition, it was dissolved to prepare [Dissolution or Dispersion 1 to 12 of toner material].

-Preparation of aqueous medium phase-
An aqueous medium phase was prepared by mixing and stirring 306 parts by mass of ion-exchanged water, 265 parts by mass of a 10% by mass tricalcium phosphate suspension, and 0.2 parts by mass of sodium dodecylbenzenesulfonate, and dissolving them uniformly.

-Preparation of emulsion or dispersion-
150 parts by mass of the aqueous medium phase is put in a container, and stirred at a rotational speed of 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 100 parts by mass were added and mixed for 10 minutes to prepare [Emulsification or Dispersion (Emulsion Slurry) 1-12].

-Removal of organic solvent-
In a Kolben equipped with a stirrer and a thermometer, 100 parts by mass of the [emulsified slurry 1-12] were charged, and the solvent was removed at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min.

-Cleaning and drying-
After filtering 100 parts by mass of [Dispersion Slurries 1 to 12] under reduced pressure, 100 parts by mass of ion-exchanged water was added to the filter cake, followed by mixing with a TK homomixer (rotating at 12,000 rpm for 10 minutes) and filtration. did.
To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice.
To the obtained filter cake, 20 parts by mass of a 10% by mass aqueous sodium hydroxide solution was added, mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered.
To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice.
Furthermore, 20 mass parts of 10 mass% hydrochloric acid was added to the obtained filter cake, mixed with a TK homomixer (at a rotation speed of 12,000 rpm for 10 minutes) and then filtered.
To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at a rotation speed of 12,000 rpm), and then filtered twice to obtain a final filter cake.
The obtained final filter cake was dried with a circulating dryer at 45 ° C. for 48 hours, and sieved with a mesh having an opening of 75 μm to obtain [toner base particles 1 to 12].

-External treatment-
Furthermore, with respect to 100 parts by mass of [Toner Base Particles 1 to 12], 0.6 part by mass of hydrophobic silica having an average particle diameter of 100 nm, 1.0 part by mass of titanium oxide having an average particle diameter of 20 nm, and an average particle diameter 0.8 parts of 15 nm hydrophobic silica fine powder was mixed with a Henschel mixer to obtain toners A1 to A4 and toners B1 to B8.

  The physical property list prepared as described above is shown in Table 4 below.

  The toner particle size distribution, glass transition temperature, storage elastic modulus G ′ (180), and toner surface release agent exposure amount are measured as follows.

<< Measurement of Volume Average Particle Size (Dv), Number Average Particle Size and Ratio (Dv / Dn) >>
The particle size distribution of the toner (toner base particles) was performed using a Coulter Multisizer.
That is, Coulter Multisizer III (manufactured by Coulter Inc.) is used as a measuring device, and an interface (manufactured by Nikkaki Co., Ltd.) for outputting number distribution and volume distribution is connected to a personal computer. Was used to prepare a 1 mass% NaCl aqueous solution. As a measurement method, 0.1 to 5 mL of a surfactant (alkylbenzene sulfonate) is added as a dispersant to 100 to 150 mL of the aqueous solution as the electrolytic solution, and 2 to 20 mg of a measurement sample is further added. Dispersion treatment was performed for about 1 to 3 minutes. Further, 100 to 200 mL of an electrolytic aqueous solution is put into another beaker, and the sample dispersion is added to a predetermined concentration therein, and 50,000 particles are used by the Coulter Multisizer III using a 100 μm aperture as an aperture. The average of was measured. From the obtained volume average particle diameter (Dv) and number average particle diameter (Dn), the ratio (Dv / Dn) between them was determined.

<< Measurement of glass transition temperature >>
The glass transition temperature (Tg) can be determined from an endothermic chart of a differential scanning calorimeter (DSC). As a measuring device, Q2000 manufactured by TA Instruments was used. The toner was obtained by filling 5 to 10 mg of toner in a simple air-tight pan made of aluminum for the following measurement flow.
The glass transition temperature is read from the 2nd Heating thermogram, and the intersection of the original baseline and the tangent at the inflection point is defined as the glass transition temperature [° C.].
1st Heating: 30 ° C. to 220 ° C., 5 ° C./min, hold for 1 minute after reaching 220 ° C. Cooling: Quench to −60 ° C. without temperature control, hold for 1 minute after reaching −60 ° C. 2nd Heating: −60 ° C. to 180 ° C. 5 ° C / min

<< Measurement of storage elastic modulus G '>>
The dynamic viscoelastic characteristic values (storage elastic modulus G ′, loss elastic modulus G ″) of the toner were measured using a dynamic viscoelasticity measuring device ARES (manufactured by TA Instruments). Molded into pellets with a thickness of 1 to 2 mm, fixed to a parallel plate with a diameter of 8 mm, stabilized at 40 ° C., frequency 1 Hz (6.28 rad / s), strain amount 0.1% (strain amount control mode) The temperature was raised to 200 ° C. at a rate of temperature rise of 2.0 ° C./min.

<< Measurement of exposure amount of toner surface release agent >>
The exposure amount of the surface release agent of the toner was measured by a hexane extraction method. 1.0 g of the toner base particles before adding the external additive is weighed, 7 ml of n-hexane is added, and the mixture is stirred with a roll mill at 120 rpm for 1 minute. The solution is suction filtered, and n-hexane is removed by a vacuum dryer. The mass (mg) of the component that was removed and remained was defined as the surface release agent exposure amount.

-Production of carrier-
[Carrier coating film forming solution formulation]
Acrylic resin solution (solid content 50 wt%) 21.0 parts by mass Guanamine solution (solid content 70 wt%) 6.4 parts by mass Alumina particles 7.6 parts by mass [0.3 μm, specific resistance 10 ¹⁴ (Ω · cm ]]
・ Silicon resin solution 65.0 parts by mass [solid content 23 wt% (SR2410: manufactured by Toray Dow Corning Silicone)]
Aminosilane 1.0 part by mass [solid content 100 wt% (SH6020: manufactured by Toray Dow Corning Silicone)]
・ Toluene 60 parts by mass ・ Butyl cellosolve 60 parts by mass

The said formulation was disperse | distributed for 10 minutes with the homomixer, and the blend coating film formation solution of the acrylic resin and silicon resin containing an alumina particle was obtained.
A sintered ferrite powder [(MgO) _1.8 (MnO) _49.5 (Fe ₂ O ₃ ) _48.0 : average particle size; 35 μm] was used as the core material, and the carrier coating film forming solution was applied to the core material surface. It was applied with a Spira coater (Okada Seiko Co., Ltd.) so as to have a film thickness of 0.15 μm and dried.
The obtained carrier was baked by standing in an electric furnace at 150 ° C. for 1 hour.
After cooling, the ferrite powder bulk was crushed using a sieve having an aperture of 106 μm to obtain a carrier 1 having a weight average particle diameter of 35 μm.

  Each developer is uniformly mixed and charged using a turbuler mixer of a type in which the container rolls and stirs at a ratio of 7 parts by mass of toners A1 to A4 and B1 to B8 with respect to 100 parts by mass of carrier 1. Was made.

-UV curable pressure sensitive composition-
(UV curable pressure sensitive composition 1)
[Monomer composition of (meth) acrylic copolymer]
10 parts by mass of 2-ethylhexyl acrylate, 30 parts by mass of 2-hydroxyethyl acrylate, 50 parts by mass of butyl methacrylate and 10 parts by mass of acrylic acid are mixed with stirring to obtain a monomer composition A of a (meth) acrylic copolymer. It was.

[Production example of intermediate product]
40 parts by mass of lipoxy SP-1509 (epoxy acrylate oligomer manufactured by Showa Polymer Co., Ltd.), 40 parts by mass of tripropylene glycol diacrylate, 20 parts by mass of Aronix M-400 (dipentaerythritol hexaacrylate manufactured by Toagosei Co., Ltd.) Parts, Irgacure 184 (Hydroxycyclohexyl phenyl ketone, manufactured by Ciba-Gaykey) and 0.1 part by weight of methoquinone were mixed with stirring to obtain intermediate product A.

In a 500 ml reaction vessel equipped with a stirrer, nitrogen gas inlet, thermometer, and reflux condenser, a total of 100 parts by weight of monomers related to monomer composition A, 100 parts by weight of isopropyl alcohol as a polymerization solvent, and azobis as a polymerization initiator 1 part by mass of isobutylnitrile was added, and polymerization was performed at 82 ° C. for 6 hours under reflux of isopropyl alcohol in a nitrogen gas stream to obtain a resin solution containing 50% by weight of a transparent and viscous resin component.
Next, the resin solution was added in an amount of 60 parts by mass (of which the solid content was 105.1 parts by mass of the intermediate product A (of which 100 parts by mass of the UV-curable monomer and oligomer having a (meth) acryloyl group). Was 30 parts by mass) to obtain a UV-curable pressure-sensitive composition 1 in a transparent solution state.

-Heating and pressurizing device-
(Heating and pressing device 1)
Halogen lamps were provided as heat sources on both the upper and lower rolls of the heating and pressing apparatus of FIG. The surface pressure of the pair of heating and pressing rolls was set to 40 N / cm ² , and the linear velocity of the heating and pressing apparatus 1 was set to 67 mm / sec. The upper and lower roll temperatures were set to 150 ° C. The nip width was 10 mm.

(Heating and pressing device 2)
Halogen lamps were provided as heat sources on both the upper and lower rolls of the heating and pressing apparatus of FIG. The surface pressure of the pair of heating and pressing rolls was set to 40 N / cm ² , and the linear velocity of the heating and pressing apparatus 1 was set to 125 mm / sec. The upper and lower roll temperatures were set to 150 ° C. The nip width was 10 mm.

(Heating and pressing device 3)
Halogen lamps were provided as heat sources on both the upper and lower rolls of the heating and pressing apparatus of FIG. The surface pressure of the pair of heating and pressing rolls was set to 40 N / cm ² , and the linear velocity of the heating and pressing apparatus 1 was set to 143 mm / sec. The upper and lower roll temperatures were set to 180 ° C. The nip width was 10 mm.

(Heating and pressing device 4)
Halogen lamps were provided as heat sources on both the upper and lower rolls of the heating and pressing apparatus of FIG. The surface pressure of the pair of heating and pressing rolls was set to 40 N / cm ² , and the linear velocity of the heating and pressing apparatus 1 was set to 159 mm / sec. The upper and lower roll temperatures were set to 200 ° C. The nip width was 10 mm.

<Example 1>
-Creation of evaluation samples-
(Evaluation sample 1)
Using a Ricoh color MFP RICOH Pro C751, an image with an image area ratio of 20% is printed with toner A1 on the surface of an A4 plate of OK topcoat 110 kg paper. Further, an image with an image area ratio of 5% is printed on the back surface with the toner B1.
The UV curable pressure-sensitive composition 1 is coated only on the surface of the printed matter with a film thickness of 5 to 6 g / cm 2 using a UV varnish coater (SAC-18E) manufactured by Hirose Tekko. The ultraviolet curable pressure sensitive composition 1 is cured by the coater.
Then, the sample cut | judged in width 150mm and length 150mm is created, and the surface processing surfaces of the ultraviolet curable pressure sensitive composition 1 of a sample are match | combined. The sample was crimped by applying a load of Yuri Roll desktop super calender and gauge pressure of 100 N / cm ² , and the sample was further passed through the heating and pressing apparatus 1.
The produced evaluation sample 1 (removable information sheet) is folded in two, and a toner image made of toner A1 is formed on the pressure-bonding surface, and a toner image made of toner B1 is formed on the non-pressure-bonded surface.

<Examples 2-12, Comparative Examples 1-3>
(Evaluation samples 2 to 15)
Evaluation samples 2 to 15 are the same as evaluation sample 1 except that the toner to be printed on the front and back surfaces of the OK top coat 110 kg paper and the heating and pressurizing device to be passed are changed as shown in Table 5 below. Created.

  According to the following methods, the prepared samples were evaluated for fixing at peeling, non-bonded surface hot offset evaluation, non-bonded surface blister evaluation, and blocking evaluation at stacking.

<Fixability evaluation at peeling>
The prepared crimped paper (evaluation sample; re-peelable information sheet) was peeled off at 6 cm / sec, and the printed surface after peeling was visually observed and evaluated according to the following criteria (hereinafter referred to as fixability test at peeling). ).

[Feeling fixability test criteria]
A: There is no toner peeling. O: A part of the toner image is peeled off in fine dots.
Δ: The entire toner image is peeled into fine dots.
X: The toner image is largely peeled off.

<Hot offset evaluation of non-crimped surface>
After the pressure-bonded paper (removable information sheet) passes through the heating and pressing device, continuously pass one A4 plate of OK topcoat 110 kg paper, and visually observe the amount of toner transferred to the paper. Evaluation was performed according to the following criteria.

[Hot offset evaluation criteria]
A: No toner is transferred to the paper.
○: A part of the toner image is thinly transferred to the paper.
Δ: The entire toner image is thinly transferred to the paper.
X: Most of the toner image is clearly transferred onto the paper.

<Non-crimp surface blister evaluation>
The non-compression surface (the surface in contact with the heating roller) of the pressure-bonded paper (removable information sheet) passed through the heating and pressurizing device is 85 μm in length × width with a scanning electron microscope with an acceleration voltage of 5.0 kV and a magnification of 1000 times. Three regions of 110 μm were observed, the number of foam marks (holes) generated when passing through the heating and pressing apparatus was counted, the average of the three locations was calculated, and evaluation was performed according to the following criteria.

[Blister evaluation criteria]
A: No foaming marks are observed on the image surface.
○: 1 to 5 foaming marks are confirmed on the image surface.
Δ: 6 to 10 foaming marks are confirmed on the image surface.
X: 11 or more foam marks are confirmed on the image surface.

<Blocking evaluation>
With 350 sheets of pressure-sensitive paper (removable information sheet) that has passed through the heating and pressing device stacked on the paper discharge unit, after leaving for 3 hours, between the 100th and 120th discharged sheets of the stacked sheets The sticking of the paper (removable information sheet) was visually observed and evaluated according to the following criteria.

[Blocking evaluation criteria]
A: There was no sticking of the paper.
○: 1 or more and 3 or less sheets stuck.
Δ: 4 or more and 9 or less sheets stuck.
X: Ten or more sheets stuck.

  The evaluation results of Examples 1 to 12 and Comparative Examples 1 to 3 are shown in Table 6 below.

From the results shown in Table 6, in the heating and pressurizing apparatus that heats and presses the pressure-sensitive paper (removable information sheet), the toner A that forms an image on the pressure-bonding surface and the toner B that forms an image on the non-pressure-bonding surface By making the glass transition temperature Tg (B) of toner B 65 ° C. or higher, the blister, hot offset and blocking can be maintained well while having good removability and productivity. It was.
In Comparative Examples 1 to 3, the Tg (B) was 65 ° C. or lower, so the toner on the non-bonded surface was softened slowly by the amount of heat accumulated at the time of discharge, and the blocking property was greatly deteriorated. Further, in Comparative Example 2, G ′ (180) of the toner B was out of the specified range, so it could not withstand the heat from the heating roller, the elastic modulus decreased, and the hot offset and blister deteriorated. Since Comparative Example 3 did not contain a release agent in the toner B, the hot offset deteriorated.

(About FIGS. 1-7 and FIG. 9)
1 paper (recording medium)
2 Energy ray curable composition 3, 3a, 3b Toner, toner image 4, 4a, 4b Interface 10 Heating roller 10a Upper heating roller 10b Lower heating roller 11 Core metal 12 Elastic layer 13 Cover layer 14a Upper heater 14b Lower heater 15a, 15b Temperature detection element 16a Temperature control circuit for upper heating roller 16b Temperature control circuit for lower heating roller 17 Commercial power supply 18 Inlet guide 21a, 21b Driven roller 20a, 20b Belt 102 Application roller 103 Metal roller 105 Pressure roller 106 Conveyance for application curing means Belt 107 Tray 108 Light source 109 Scraper N Nip (for FIG. 8)
DESCRIPTION OF SYMBOLS 10 Photosensitive drum 10K Black photoconductor 10Y Yellow photoconductor 10M Magenta photoconductor 10C Cyan photoconductor 14, 15, 16 Support roller 17 Intermediate transfer belt cleaning device 18 Image forming means 21 Exposure device 22 Secondary transfer device 23 Transfer conveying support roller 24 Transfer conveying belt 25 Fixing device 26 Heating means (fixing belt)
27 pressure roller 28 reversing device 32 contact glass 33 first traveling body 34 second traveling body 35 imaging lens 36 reading sensor 49 registration roller 50 intermediate transfer belt 51 sheet feeding roller 52 manual separation roller 53 manual sheet feeding path 54 manual tray 55 switching claw 57 paper discharge tray 62 primary transfer roller 100B image forming apparatus 120 tandem developing device 130 document table 142 paper feed roller 143 paper bank 144 paper feed cassette 145 separation roller 146 paper feed path 147 transport roller 148 main body side paper feed path 150 Printer unit 156 Discharge roller pair 200 Paper feed table 300 Scanner 400 Automatic document feeder L Exposure light

JP 2007-277547 A Japanese Patent No. 3708853 Japanese Patent No. 2522333 Japanese Patent No. 3827124 Japanese Patent No. 4471334 JP 2009-169337 A JP 07-219383 A JP 2004-205988 A

Claims (8)

A heating and pressing method in which an energy beam curable composition is applied and cured on a recording medium on which a toner image is fixed, and a releasable information sheet formed by being folded into two or more folds and press-bonded is heated and pressed. ,
The toner A forming a toner image on the pressure-bonding surface of the removable information sheet and the toner B forming a toner image on the non-pressure-bonding surface of the removable information sheet are different.
The heating and pressing method, wherein the toner B has a glass transition temperature Tg (B) of 65 ° C. or higher. 2. The heating and pressing method according to claim 1, wherein the glass transition temperature Tg (A) of the toner A and the glass transition temperature Tg (B) of the toner B satisfy the relationship of the following formula 1.
Tg (A) <Tg (B) (Formula 1) 3. The heating and pressing method according to claim 1, wherein a glass transition temperature Tg (A) of the toner A satisfies 45 ° C. ≦ Tg (A) ≦ 55 ° C. 4. The storage elastic modulus G ′ (180) [Pa] of the toner B at 180 ° C. satisfies 1.0 × 10 ³ <G ′ (180) <1.0 × 10 ⁴ . 4. The heating and pressing method according to any one of 3 above. The heating and pressing method according to claim 1, wherein the toner B contains a release agent. 6. The heating and pressurizing method according to claim 5, wherein the exposure amount of the surface release agent of the toner B is 9 to 13 mg / g with respect to 1 g of the toner. Heat pressurizing method according to claim 1, by heating roller having a coating layer releasability on the front surface contains a high resin and wherein the pressurized heating. An electrostatic latent image forming step for forming an electrostatic latent image on the image carrier, a developing step for visualizing the electrostatic latent image with toner to form a toner image, and recording the toner image from the image carrier. An image forming method comprising: a transfer step of transferring onto a medium; and a fixing step of fixing the toner image transferred onto the recording medium onto the recording medium to form a toner image;
Wherein the energy ray-curable composition precursor was applied to a recording medium on which the toner image is fixed, and cured, the coating cure step of coating an energy beam curable composition,
A folding step of folding the recording medium into two or more folds;
A pressure bonding step in which the recording medium folded by the folding means is pressure-bonded to form a releasable information sheet;
A heating and pressurizing step for heating and pressurizing the re-peelable information sheet,
The said heat pressurization process is performed with the heat pressurization method in any one of Claims 1-7, The manufacturing method of the releasable information sheet characterized by the above -mentioned .