JP2013047715A - Manufacturing method of laminated product, laminated material, and laminated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a laminated product for accurately transferring a toner image formed on an image carrier such as a photoreceptor to a laminated material, and stably producing a laminated product that has a high-quality toner image with cold laminate.SOLUTION: A manufacturing method of a laminated product includes: superimposing an image support on which an unfixed toner image formed on an image carrier by an image forming method employing an electrophotographic system on an adhesive layer; and applying an external force to the superimposed image support to embed the unfixed toner image to the adhesive layer, and thereby forming a toner image.

Description

  The present invention relates to a laminate product manufacturing method for producing a laminate product that transfers and holds an unfixed toner image produced by electrophotographic image formation by cold lamination in which lamination is performed without performing heat treatment.

  Laminating process to paste a transparent film made of resin on the image-formed support surface is a means to prevent deterioration such as color fading and wear, and to improve the added value of image-formed products by giving aesthetics and luxury. It is effective as. In addition, an image provided in a laminate product may be required to have a high-definition finish such as a photographic image, and a toner image formed by an electrophotographic method is one of images satisfying this need. One. And examination of the technique regarding laminating to what has a toner image has been advanced until now (for example, refer to patent documents 1 and 2).

  For example, Patent Document 1 describes a technique for simultaneously fixing and laminating a toner image by laminating a laminate member on the surface of a recording member to which a toner image has been transferred, and passing the laminate through a pair of heat rollers. Has been. Patent Document 2 describes a technique for forming a laminate containing a toner image by pressure-fixing a film having an unfixed toner image transferred to a substrate coated with a solventless adhesive under a heating environment. Yes. As described above, in the technique of laminating a toner image, a hot laminating method in which laminating is performed by heat treatment has been mainly employed. Therefore, the conventional technology for laminating a toner image requires heating in laminating in addition to toner image formation, resulting in a large energy consumption.

  Under such circumstances, a cold laminating method capable of laminating without performing heat treatment has attracted attention, and a technique for forming a surface protective layer on the toner image surface by a cold laminating method has been studied (for example, Patent Document 3). reference). Patent Document 3 forms a toner image by electrophotography on a printing surface of a lenticular lens medium, and performs a laminating process to protect the formed toner image surface. A cold laminating method is one of the laminating processes. Was mentioned. Therefore, although the technology of Patent Document 3 reduces the energy consumption of the laminating process, since the fixing is performed by heating at the time of toner image formation, the energy consumption for producing the lenticular lens medium itself is greatly increased. It was not a reduction. In this way, the toner image is melted by heating, then cooled and solidified to be fixed on the image support, so that the energy consumption when producing a laminate product having a toner image is greatly reduced. It was difficult to do.

  On the other hand, although not in the field of laminating technology, a technology for fixing a toner image without performing heat treatment is also being studied. For example, a technique in which a toner image formed on a photosensitive member is transferred and embedded in a fluid expressing layer called a toner holding material layer to hold the toner image on an image support (for example, a patent is being studied). Reference 4). This technology fixes a toner image to a toner holding material layer that exhibits fluidity when an external force such as electrostatic force or pressing force is applied. When the application of the external force is stopped, the fluidity of the toner holding material layer is released and the toner is released. It is designed to hold images. Patent Document 4 describes that the formed toner image has a sufficient color depth and a good finish without white turbidity.

  By the way, it is considered that the production of a laminate product using a toner image can provide higher productivity than the production of a laminate product using an inkjet image or the like. That is, when an inkjet image is used, since the formed inkjet image contains moisture, time is required for removing moisture even in cold lamination in which lamination is performed without applying heat. On the other hand, when a toner image is used, it is not necessary to provide time for removing moisture from the image, which is considered to contribute to an improvement in productivity of the laminate product.

  Therefore, it has been considered to apply the technique described in Patent Document 3 to the laminating technique. In other words, if this technology is applied to the manufacture of laminate products, it will be possible to fix toner images without heat treatment, and it will be possible to realize the production of laminate products with significantly reduced energy consumption. It was. In addition, it was considered that a laminate product having a sufficiently finished toner image having a sufficient color depth and no white turbidity could be produced.

JP-A-5-27616 JP-A-11-65201 JP 2009-223313 A JP 2010-145440 A

  However, when the above technology is developed into a laminate product manufacturing technology, it is surprisingly difficult to accurately and directly transfer the toner image formed on the photoreceptor to the adhesive layer having a strong adhesive force constituting the laminate material. found. That is, when transfer is performed with the pressure-sensitive adhesive layer approaching the photoconductor, the photoconductor adheres to the pressure-sensitive adhesive layer, and the toner image cannot be stably transferred. As described above, it is difficult to laminate a toner image by cold lamination.

  The present invention relates to a method for producing a laminate product, in which a toner image formed on an image carrier such as a photoreceptor is accurately transferred to a laminate material, and a laminate product having a toner image with a good image quality is stably produced by cold lamination. The purpose is to provide. Specifically, a laminate product manufacturing method is provided that produces a laminate product in which the formed toner image has good color reproducibility and fine line reproducibility, and an image quality that accurately reproduces an image like a human photograph can be obtained. The purpose is to do. It is another object of the present invention to provide a method for manufacturing a laminate product for producing a laminate product having a durability that does not damage a formed toner image when the laminate product is bent. It is another object of the present invention to provide a method for manufacturing a laminate product that enables reuse of a laminate material by producing a laminate product by cold lamination.

The present inventor has found that the above-described problem can be solved by any of the configurations described below. That is, the invention described in claim 1
“At least a method for producing a laminate product having a pressure-sensitive adhesive layer having a toner image and a substrate holding the pressure-sensitive adhesive layer,
An image support on which an unfixed toner image formed on an image carrier by an electrophotographic image forming method is transferred is superimposed on the pressure-sensitive adhesive layer,
A method for producing a laminate product, wherein the unfixed toner image is embedded in the pressure-sensitive adhesive layer through a step of applying an external force in a state where the image support is superimposed on the pressure-sensitive adhesive layer. ].

The invention described in claim 2
The method for producing a laminated product according to claim 1, wherein the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer contains a resin that exhibits thixotropic properties. ].

The invention according to claim 3
The laminate product according to claim 1 or 2, wherein the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer has a hardness measured according to JIS K6253 type A of 2 or more and 10 or less. Manufacturing method. ].

The invention according to claim 4
The said adhesive layer contains a silicone resin at least, The manufacturing method of the laminated product of any one of Claims 1-3 characterized by the above-mentioned. ].

The invention described in claim 5
The external force applied in a state where the image support is superimposed on the pressure-sensitive adhesive layer is a pressing force of 1 × 10 ³ Pa or more and 1 × 10 ⁸ Pa or less. 2. A method for producing a laminated product according to item 1. ].

The invention described in claim 6
“The substrate for holding the pressure-sensitive adhesive layer is a polyester resin, The method for producing a laminated product according to any one of claims 1 to 5. ].

The invention described in claim 7
“The toner particles constituting the unfixed toner image are
The volume-based median diameter is 5 µm or more and 8 µm or less, and the average circularity is 0.850 or more and 0.990 or less, The production of a laminate product according to any one of claims 1 to 6, Method. ].

The invention according to claim 8 provides:
"at least,
An adhesive layer capable of embedding a toner image;
A substrate for holding the pressure-sensitive adhesive layer;
It has a joining member arranged along the crease formed in the adhesive layer and the base,
A laminate material used in the method for producing a laminate product according to any one of claims 1 to 7. ].

The invention according to claim 9 is:
[9] The laminate material according to claim 8, wherein the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer contains a resin that exhibits thixotropic properties. ].

The invention according to claim 10 is:
[10] The laminate according to claim 8 or 9, wherein the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer has a hardness measured according to JIS K6253 type A of 2 or more and 10 or less. . ].

The invention according to claim 11
The pressure-sensitive adhesive used in the pressure-sensitive adhesive layer contains at least a silicone resin, The laminate material according to any one of claims 8 to 10. ].

The invention according to claim 12
The laminate material according to any one of claims 8 to 11, which has a release sheet that covers the surface of the pressure-sensitive adhesive layer. ].

The invention according to claim 13
The laminate according to claim 12, wherein the release sheet is capable of transferring and holding an unfixed toner image formed by an electrophotographic image forming method. ].

The invention according to claim 14
The laminate according to claim 12 or 13, wherein the release sheet has a layer containing a silicone resin on a surface thereof. ].

The invention according to claim 15 is:
“Laminate according to any one of claims 8 to 14, wherein the substrate holding the pressure-sensitive adhesive layer is a polyester resin. ].

The invention described in claim 16
“A laminate product having at least a pressure-sensitive adhesive layer having a toner image and a substrate holding the pressure-sensitive adhesive layer,
The laminate material according to any one of claims 8 to 15 is used to produce the laminate product according to any one of claims 1 to 7. Laminated product. ].

  According to the present invention, it becomes possible to accurately transfer a toner image formed on an image carrier such as a photosensitive member to a laminate material, and a laminate product having a good quality toner image can be stably obtained by cold lamination. Made it possible to produce. Specifically, as described in the examples described later, the toner image formed has a good color reproducibility and fine line reproducibility, and a toner image having an image quality that accurately reproduces an image like a human photograph. It became possible to produce a laminate product with cold lamination.

  In addition, according to the present invention, by using an unfixed toner image, even if the laminate product is bent, the formed toner image is not damaged, and a laminate product in which durability is imparted to the toner image is produced. Made possible. Furthermore, in the present invention, by producing a laminate product by cold lamination, energy consumption at the time of production is reduced, and toner is removed from the used laminate product, so that the laminate material and the image support can be reused. Made possible.

It is a schematic diagram showing the cross-sectional shape of the laminate material used by this invention. It is a figure which shows the cross-sectional shape of the laminate product produced from the laminate material of FIG. It is a figure which shows roughly the procedure which produces the laminate product of FIG. It is a figure explaining making a laminate material and an image support body reusable from a used laminate product. It is the schematic of the image forming apparatus which forms the toner image used for the laminate product produced by this invention.

  The present invention relates to a method for manufacturing a laminate product in which an unfixed toner image formed on an image carrier is transferred to produce a laminate product, a laminate material used in the method for manufacturing the laminate product, and the manufacture of the laminate product. The present invention relates to a laminate product produced by the method.

  In the present invention, an unfixed toner image on an image carrier formed by electrophotographic image formation is transferred to an adhesive layer of a laminate via an image support, and is embedded by applying external force to form a toner image. This makes it possible to produce a laminate product without heating.

  Here, “laminate” refers to a laminated structure formed by bonding two or more materials such as a thin plate, a sheet, and a film, and producing the laminated structure is referred to as “laminating”. In the present invention, the “laminate” refers to “the state in which the toner image is not yet held in the layer holding the toner image, and can be used for laminating, among the laminated structures described above. It is a laminated structure.

  The “laminate product” in the present invention is a “laminate structure in which a toner image is held in a layer holding a toner image and a lamination process is performed” among the above-described laminate structures. That is, the “laminate product” as used in the present invention is produced by laminating (cold laminating method) without holding the toner image on the aforementioned “laminate material” and applying heat. Here, the “cold laminating method” is one of laminating processes, and is a method for producing a laminated product that is a laminated structure by bonding materials using an adhesive or the like without performing heat treatment. is there.

  The “unfixed toner image” as used in the present invention refers to a toner image that has not been subjected to a fixing process performed in an electrophotographic image forming method in which it is melted by heating and cooled and solidified after heating. It is composed of independent powder particles.

  Hereinafter, the present invention will be described in detail.

  First, a cross-sectional structure of a laminate material that can be used in the present invention will be described with reference to FIG. FIG. 1 is a schematic diagram showing a cross-sectional structure of a laminate material used in the present invention. The laminate material 1 shown in FIG. 1 includes a pressure-sensitive adhesive layer 11 that holds a toner image T, and a substrate 12 that supports the pressure-sensitive adhesive layer 11. The release sheet 13 covering the surface of the pressure-sensitive adhesive layer 11 and the joining member 14 for forming a crease are provided.

  Although FIG. 1 shows an example of a cross-sectional structure of a laminate material 1 that can be used in the present invention, the laminate material 1 that can be used in the present invention includes those that do not use a release sheet 13. That is, the laminating material 1 shown in FIG. 1 (a) covers the surfaces of the two pressure-sensitive adhesive layers 11 with a single release sheet 13, and the laminating material 1 shown in FIG. Two release sheets 13 cover the surface of each pressure-sensitive adhesive layer 11. Furthermore, the laminate material 1 shown in FIG. 1C does not use the release sheet 13 and can be opened along a broken line in the drawing by a known method. The laminate 1 shown in FIG. 1 has a structure in which a base 12 is disposed on the outermost surface and an adhesive layer 11 in which a toner image T is embedded is disposed between two bases 12 as shown in FIG. It is possible to produce the laminate product 10.

  The pressure-sensitive adhesive layer 11 constituting the laminating material 1 holds an unfixed toner image T and also acts as an adhesive, and firmly holds constituent materials such as the base 12. The pressure-sensitive adhesive layer 11 contains a so-called thixotropic resin that develops a solid state when no external force is applied and develops fluidity when an external force is applied. In addition, the specific description about the resin material contained in the adhesive layer 11 is mentioned later.

  The substrate 12 constitutes the outermost surface of the laminate material 1 or a laminate product 10 to be described later. The substrate 12 imparts an appropriate strength and makes the toner image T transferred and held on the adhesive layer 11 visible. From the viewpoint of facilitating visual recognition, a transparent material is preferable. In addition, the specific description about the material which can be used for the base | substrate 12 is mentioned later.

  The release sheet 13 prevents dust and dust from adhering to the pressure-sensitive adhesive layer 11 by covering the surface of the pressure-sensitive adhesive layer 11, and also peels smoothly from the surface of the pressure-sensitive adhesive layer 11 during lamination. . As the release sheet 13, it is possible to use a release sheet provided with a resin layer on the surface in order to perform smooth release from the pressure-sensitive adhesive layer 11. Further, by giving the release sheet 13 the property of transferring and holding an unfixed toner image formed by an electrophotographic image forming method, it can be used as the image support 15 in the present invention. . In addition, the specific description about the material which can be used for the peeling sheet 13 is mentioned later.

  The joining member 14 is provided along the crease 16 formed in the laminate material 1 or the laminate product 10 described later, and reinforces the laminate material 1 or the laminate product 10 by being arranged along the crease 16.

  Next, a laminate product 10 that can be produced using the laminate material 1 shown in FIG. 1 will be described with reference to FIG. A laminate product 10 shown in FIG. 2 transfers an unfixed toner image formed on an image carrier constituting an electrophotographic image forming apparatus to the adhesive layer 11 of the laminate 1 shown in FIG. It is produced by cold lamination which laminates without performing. That is, the laminate product 10 shown in FIG. 2 has the following: “The image support on which the unfixed toner image formed on the image carrier by the electrophotographic image forming method is transferred is superimposed on the adhesive layer of the laminate material. Produced by a method for producing a laminate product in which an external force is applied with an image support superimposed on an adhesive layer, and an unfixed toner image is embedded in the adhesive layer to form a toner image on the adhesive layer. Is done.

  The laminate product 10 shown in FIG. 2 has the release sheet 13 from the laminate material 1 shown in FIG. 1 to release the release sheet 13 to expose the surface of the adhesive layer 11 and transfer the unfixed toner image T. The body 15 is formed to overlap the pressure-sensitive adhesive layer 11. The toner image T initially transferred onto the image support 15 is embedded in the adhesive layer 11 by the action of external force. A laminate product 10 shown in FIG. 2 is produced by forming a fold 16 in the laminate material 1 shown in FIG. 1, and a bonding member 14 is provided at a portion where the fold 16 is formed. Is reinforced.

  The laminate product 10 in FIG. 2A has a structure that does not have the image support 15. For example, the image support 15 is superimposed on the surface of one adhesive layer 11 of the laminate 1 shown in FIG. Let external force be applied in this state. After the external force is applied, the image support 15 can be removed from the surface of the pressure-sensitive adhesive layer 11 and then the other pressure-sensitive adhesive layer can be superimposed on the pressure-sensitive adhesive layer in which the toner image is embedded. The laminate product 10 in FIG. 2A can visually recognize the toner image T embedded in the pressure-sensitive adhesive layer 11 from both sides.

  In addition, the laminate product 10 shown in FIG. 2B is an image support, for example, two laminate materials 1 shown in FIG. 1A are prepared, and the toner image T is transferred to the adhesive layer 11 of the other laminate material 1. The image support 15 thus made is superimposed. Then, after the toner image T transferred to the image support 15 is embedded in the pressure-sensitive adhesive layer 11, the superimposed image support 15 is removed from the surface of the pressure-sensitive adhesive layer 11, and the other laminate material 1 is bonded thereto. It can be produced by overlapping the agent layer 11. Note that the laminate product 10 shown in FIG. 2B can also be manufactured using the laminate material 1 shown in FIG.

  Next, the laminate product 10 shown in FIGS. 2C and 2D has an image support 15 disposed in the center of the cross section, and has two adhesive layers 11 by the image support 15. Compared with the laminated product of a), the thickness is increased by the thickness. The laminated product 10 shown in FIG. 2C is for visually recognizing the toner image T embedded in the pressure-sensitive adhesive layer 11 from one side, similarly to the laminated product shown in FIG. On the other hand, the laminate product 10 shown in FIG. 2 (d) has toner images T embedded in the two adhesive layers 11, respectively, which makes it possible to provide a laminate product that is durable and has a large amount of information. ing.

  Next, a method for producing the laminate product 10 shown in FIG. 2 will be described with reference to FIG. FIG. 3 schematically shows a method for manufacturing a laminate product according to the present invention. An image support 15 having a toner image T is superimposed on the surface of the pressure-sensitive adhesive layer 11 of the laminate 1 shown in FIG. FIG. 2 shows that the laminate product 10 shown in FIG. 2 is produced. In FIG. 3, the display of the laminate product 10 that does not have the image support 15 of FIG. 2A is omitted.

  The schematic diagram of FIG. 3 outlines “manufacturing a laminate product having at least an adhesive layer having a toner image formed by transferring toner particles and a substrate holding the adhesive layer”. That is, “the image support 15 carrying the unfixed toner image T formed on the image carrier by electrophotographic image formation is superimposed on the pressure-sensitive adhesive layer 11, and the pressure-sensitive adhesive layer 11 is overlapped by the superimposed image support 15. The toner particles are embedded in the adhesive layer 11 to form a toner image ”. FIG. 3A shows a laminate product 10 in which an image support 15 having a toner image T formed on one side is superposed on the surface of the pressure-sensitive adhesive layer 11. FIG. 3B shows the toner image T on both sides. The laminate product 10 is produced using the image support 15 formed in the above.

In the present invention, a laminate product 10 is produced from the laminate material 1 through at least the following steps. That is,
(1) Step of exposing the adhesive layer 11 from the laminate 1 (2) Step of transferring the toner image T formed on the photoreceptor to the image support 15 (3) Image support 15 to which the toner image T has been transferred (4) Step of applying an external force to the laminate 1 in which the image support 15 is superimposed on the pressure-sensitive adhesive layer 11 Hereinafter, the steps (1) to (4) described above This will be described in detail with reference to FIG.

(1) Step of exposing the pressure-sensitive adhesive layer 11 of the laminate material 1 This step is not shown in FIG. 3, but the laminate material 1 having the release sheet 13 shown in FIGS. The sheet 13 is peeled off to expose the surface of the pressure-sensitive adhesive layer 11. Moreover, in the laminate material 1 which does not have the peeling sheet 13 shown in FIG.1 (c), by the well-known method, the adhesive layer 11 is opened along the broken line shown in FIG.1 (c), and the adhesive layer 11 surface is made. To be exposed.

(2) Step of transferring the toner image T formed on the photoconductor to the image support 15 In this step, the toner image T formed on the photoconductor of an electrophotographic image forming apparatus (not shown) is transferred to the image support. As shown in FIG. 3, an unfixed toner image T composed of toner particles is transferred onto the image support 15 through this process. In this step, since the toner image T is adhered on the image support 15, it is preferable to pre-process the image support 15 by a known method such as charging.

(3) Step of superimposing the image support 15 to which the toner image T has been transferred to the adhesive layer 11 of the laminate material 1 This process is schematically shown in FIG. In this step, the image support 15 is superimposed on the laminate material 1 so as to face the surface of the pressure-sensitive adhesive layer 11 of the laminate material 1. Through this step, the toner image T transferred to the image surface of the image support 15 and the pressure-sensitive adhesive layer 11 of the laminate 1 are brought into contact with each other.

(4) Step of applying an external force to the laminate 1 in which the image support 15 is superimposed on the pressure-sensitive adhesive layer 11 This step is indicated by a white arrow in FIG. By applying an external force to the laminate material 1 on which 15 is superimposed, the pressure-sensitive adhesive layer 11 exhibits fluidity and the toner image T on the image support 15 is buried in the pressure-sensitive adhesive layer 11. The pressure-sensitive adhesive layer 11 is solidified by releasing the application of external force, and the buried toner image T is held and fixed in the pressure-sensitive adhesive layer 11. That is, through this process, the toner image T held on the image support 15 that has been in contact with the surface of the pressure-sensitive adhesive layer 11 is embedded in the pressure-sensitive adhesive layer 11 that has been fluidized by the action of the pressing force. The toner image T is held on the solidified pressure-sensitive adhesive layer 11 by releasing the pressure. In this way, it is possible to produce a laminate product 10 having a configuration in which the toner image T is held on the pressure-sensitive adhesive layer 11.

The pressing force applied to the laminate material 1 with the image support 15 to which the toner image T has been transferred applied to the pressure-sensitive adhesive layer 11 is, for example, from 1 × 10 ³ Pa to 1 × 10 ^{8 as} shown in the examples described later. A range of Pa is preferable. By applying a pressing force in the above range, the toner image T on the image surface 16 of the image support 15 can be stably held by the adhesive layer 11.

  As described above, in the present invention, a laminate product 10 in which the toner image T is held in the pressure-sensitive adhesive layer 11 as shown in FIG. 3 is produced through at least the steps (1) to (4). It is possible.

  For example, the laminate product 10 capable of visually recognizing the toner image T embedded in the pressure-sensitive adhesive layer 11 from both sides shown in FIG. 2A can be manufactured by the following procedure. First, a laminate material 1 shown in FIG. 1 is prepared, and the image support 15 is superimposed on the exposed pressure-sensitive adhesive layer 11 surface through the steps (1) to (4). To be buried. Next, the other pressure-sensitive adhesive layer 11 is exposed, and the image support 15 is removed from the surface of the pressure-sensitive adhesive layer 11 of the laminate 1 in which the toner image T is embedded. Then, by laminating the surface of the pressure-sensitive adhesive layer 11 in which the toner image T is embedded and the pressure-sensitive adhesive layer 11 surface of the remaining laminate material 1, it is possible to produce a laminate product 10 shown in FIG. .

  Moreover, the laminated product 10 shown in FIGS. 2B and 2C uses the laminate material 1 shown in FIG. 1 as described in the above (1) to (4) as shown in FIGS. 3A and 3B. Through this process, the image support 15 is superimposed on the pressure-sensitive adhesive layer 11, and an external force is further applied to embed the toner image T in the pressure-sensitive adhesive layer 11.

  The laminate product 10 having the toner images T on both sides shown in FIG. 2 (c), for example, transfers the toner images T formed on an image carrier such as a photoconductor to both sides of the image support 15 to obtain the image support 15 Both surfaces are sandwiched between two pressure-sensitive adhesive layers 11 and overlapped with each pressure-sensitive adhesive layer 11. Then, the image support 15 having the toner image T transferred on both sides thereof is produced by applying an external force with the two adhesive layers 11 being sandwiched.

  Next, reuse of the members constituting the laminate product produced in the present invention will be described with reference to FIG. FIG. 4 is a diagram schematically showing that the reusable laminate 1 and the image support 15 are produced from the used laminate product 10 ′ produced in the present invention. FIG. 4 (a) shows the recovered used laminate product 10 ′, and FIG. 4 (b) shows the recovered used laminate product 10 ′ as used laminate material 1 ′ and used image support 15 ′. Shows the state of disassembly. In the present invention, since the unfixed toner image T is transferred to the image support 15 and the toner image T is embedded in the adhesive layer 11 to form an image, the used laminate material of FIG. The toner image T is buried in the 1 ′ pressure-sensitive adhesive layer 11, and the toner image T hardly exists on the used image support 15 ′. Therefore, the used image support 15 ′ shown in FIG. 4B can transfer and hold an unfixed toner image only by wiping with a non-woven fabric impregnated with methanol, as shown in Examples described later. It can be reused as the image support 15.

  Next, FIG. 4C shows a used laminate material 1 ′ including the pressure-sensitive adhesive layer 11 from which the toner image T has been removed, the base 12, and the bonding member 14. That is, in FIG. 4, the toner embedded in the pressure-sensitive adhesive layer 11 by wiping off the pressure-sensitive adhesive layer 11 with, for example, a non-woven fabric impregnated with methanol at a position indicated by a white arrow between (b) and (c). Can be removed. That is, since the pressure-sensitive adhesive layer 11 has thixotropy, the pressure-sensitive adhesive layer 11 is fluidized by the action of external force generated when wiping with a nonwoven fabric or the like, and the buried toner particles are discharged out of the pressure-sensitive adhesive layer 11. It is thought that it is easy.

  In addition, it is possible to form the form shown in FIG. 4C by removing the adhesive layer 11 in which the toner particles are embedded from the substrate 12 and newly providing the adhesive layer 11.

  And the laminated material 1 of the form shown to FIG. 1 (a), (b) can be produced by coat | covering the adhesive layer of used laminate material 1 'shown in FIG.4 (c) with the peeling sheet 13. FIG. Is possible. Further, it is possible to produce the laminate material 1 having the form shown in FIG. 1C by bending the pressure-sensitive adhesive layer 11 and the substrate 12 along the crease 16.

  Thus, the used laminate material 1 ′ and the used image support 15 ′ constituting the laminate product 10 produced in the present invention can be reused.

  Next, the pressure-sensitive adhesive layer 11, the substrate 12, the bonding member 14, the image support 15, and the release sheet 13 constituting the laminate material 1 shown in FIG. 1 and the laminate product shown in FIG. 2 will be described.

  First, the adhesive layer 11 will be described. The pressure-sensitive adhesive layer 11 is composed of a pressure-sensitive adhesive. Here, the pressure-sensitive adhesive will be described. The pressure-sensitive adhesive used in the present invention is not particularly limited as long as it has transparency that allows the toner image T to be sufficiently visually recognized and exhibits good adhesion to the substrate 12. Is not to be done. As a material exhibiting such a property, for example, a gel-like substance exhibiting viscoelastic behavior called thixotropy is preferable. Here, thixotropy refers to a viscoelastic behavior that does not exhibit fluidity when no external force is applied, and exhibits fluidity when an external force is applied. That is, the pressure-sensitive adhesive layer 11 causes the toner image T to be buried inside due to the fluidity when the external force is applied, and does not develop the fluidity when the external force is not applied. It is possible to hold on.

  In the present invention, the toner image T is embedded in the pressure-sensitive adhesive layer 11 exhibiting thixotropy as described above, so that the toner image formed by the electrophotographic image forming method is not melted in the laminate material 1. Can be fixed. Further, by generating fluidity when an external force is applied, the toner particles are surely embedded in the pressure-sensitive adhesive layer 11, and when a full color image is formed, a plurality of types of toners are appropriately mixed to start secondary colors. The color reproducibility to be good. As a result, it is possible to produce a laminated product having a beautifully finished full color toner image.

  The pressure-sensitive adhesive exhibiting thixotropy preferably has a hardness measured according to JIS K6253 type A of 2 or more and 10 or less, and more preferably 2 or more and 5 or less. Specifically, the hardness measurement method performed according to JIS K6253 type A is to measure the adhesive on the adhesive layer 11 using a commercially available “Durometer GS-719N” (manufactured by Teclock Corporation). Is done. At this time, in the case of a laminate product having a toner image, the pressure-sensitive adhesive in the non-image area where no toner particles are present is the object of measurement.

  The pressure-sensitive adhesive having a hardness in the above range can be formed by a known method. For example, in addition to a method of using a gel material, an elastomer material, or a rubber material having a hardness in the above range as they are, they are listed below. It can be formed by a known method. That is, a method of blending and forming gel materials, elastomer materials, rubber materials, etc. having different hardnesses at a predetermined ratio, and a method of adjusting the amount of curing agent added to reactive gel materials, elastomer materials, rubber materials, etc. Alternatively, there is a method of adjusting the curing conditions when using a thermosetting material.

  In addition, the adhesive that can be used in the present invention is incompatible with the resin constituting the toner particles while having a certain degree of affinity for the toner particles from the viewpoint of reliably burying the toner particles. What has is preferable.

  Specific examples of pressure-sensitive adhesives that exhibit the above performance include, for example, a silicone resin having a crosslinked structure, a polymer compound such as an acrylic resin having a crosslinked structure, a vinyl resin, and a urethane resin, and a water-soluble property represented by a polysaccharide. Examples include gel materials such as polymers. In addition, since the above-described polymer compound is used in a gel form, for example, a gel or sol of these polymer compound and an organic solvent or oil, an aqueous emulsion of the polymer compound, or the polymer compound and water-soluble There are sols and gels in which a polymer is dissolved and dispersed in a hydrophilic solvent.

  Hereinafter, specific examples of the silicone resin, acrylic resin, vinyl resin, and urethane resin will be described.

First, the silicone resin can be formed, for example, by polymerizing the following compounds. That is,
Dimethylsiloxane, diphenylsiloxane, methylvinylsiloxane, methylphenylsiloxane, fluorosiloxane, trifluorosiloxane, trifluoropropylsiloxane, chloromethylsiloxane, cyanoethylsiloxane, ether siloxane, fluoroethersiloxane, aminosiloxane, etc. For example, it can be formed by polymerizing the following compounds. That is, 2-ethylhexyl acrylate, n-butyl acrylate, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, acrylamide derivatives, hydroxyethyl acrylate, glycidyl acrylate, and the like. As shown in these compounds, acrylic resins have a carboxy group (—COOH) in the side chain, a carboxylic acid ester group in the side chain, and a carboxy group and a carboxylic acid ester group in the side chain. There is something.

  Examples of the vinyl resin include the following. That is, polyvinyl acetate, ethylene-vinyl acetate copolymer, acrylic-vinyl acetate copolymer, polyvinyl acetal, polyvinyl butyral, phenol-vinyl butyral copolymer, polyvinyl pyrrolidone, polyvinyl chloride and the like.

Examples of the urethane resin include a polyurethane prepolymer obtained by reacting a polyol compound and a polyisocyanate compound. Specific examples of the polyol compound and the polyisocyanate compound include the following. That is,
Polyol compound; 1,2-polybutadiene polyol, 1,4-polybutadiene polyol, poly (pentadiene butadiene) polyol, poly (butadiene styrene) polyol, poly (butadiene acrylonitrile) polyol, etc. Polyisocyanate compound; diphenylmethane diisocyanate , Tolylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl isocyanate, xylylene diisocyanate, lysine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, methylene bis (cyclohexyl isocyanate) and the like.

Furthermore, examples of the water-soluble polymer include the following natural polymer polysaccharides, natural low-molecular polysaccharides, and water-soluble vinyl polymers. That is,
Natural polymer polysaccharides: xanthan gum, carrageenan, pullulan, furseleran, curdlan, gelatin, collagen, etc. Natural low molecular polysaccharides: sodium alginate, calcium alginate, etc. Water-soluble vinyl polymers; polyacrylic acid, sodium polyacrylate, Polyvinyl alcohol, etc. Further, water-based solvents include water, methanol, ethanol, ethylene glycol, propylene glycol, polyethylene glycol, glycerin and the like.

  In the present invention, among the above-mentioned pressure-sensitive adhesives, a silicone resin having a crosslinked structure and an acrylic resin having a crosslinked structure are preferable, and a silicone resin having a crosslinked structure is particularly preferable.

  Next, the base 12 constituting the laminate 1 shown in FIG. 1 or the laminate product 10 shown in FIG. 2 will be described. The base 12 holds the pressure-sensitive adhesive layer 11 and imparts strength to the laminate 1 or the laminate product 10, and further has a property of not hindering visual recognition from the outside of the toner image T formed of toner particles. It is what has. The substrate 12 may be light-transmitting (transparent) or non-translucent (opaque) as long as it does not hinder the visibility of the toner image T from the outside. There may be.

  Whether the substrate 12 is transparent or opaque is selected based on the fact that stable visibility is exhibited under the conditions of use of the produced laminate product. This is preferable because it is effective for use in an environment where it is difficult to visually recognize the image.

  When the substrate 12 is transparent, its transmission density is preferably 0.15 or less, more preferably 0.10 or less. By using a base material having a transmission density of 0.15 or less, the density of the image T formed by the toner particles becomes relatively high. Thus, a laminate product having excellent image visibility with a good contrast is produced. Is possible.

  Here, the transmission density is obtained by expressing the transmittance t as a common logarithm, and is calculated from the equation of transmission density D = log (1 / t). Specifically, the transmission density D can be measured using a commercially available densitometer “X-Rite 310TR” (manufactured by X-Rite). When the above densitometer is used, the measurement aperture diameter is φ3 mm, and calibration is performed. After the calibration with the calibration wedge, the visual density is measured and calculated from the measurement result.

  Specific examples of the transparent substrate 12 include known resin films such as a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, a polystyrene (PS) sheet, a polyimide film, and a cellulose film.

  Moreover, as a specific example of the base | substrate 12 which does not have translucency, well-known paper, cloth, a resin film etc. are mentioned, for example.

  The thickness of the substrate 12 is preferably 10 μm to 1 mm, more preferably 30 μm to 200 μm.

  Next, the joining member 14 constituting the laminate material 1 shown in FIG. 1 or the laminate product 10 shown in FIG. 2 will be described. 1 is a laminate product 10 shown in FIG. 2 in which a fold 16 is formed in an adhesive layer 11 and a substrate 12, and a crease 16 is formed on the crease 16 in order to reinforce strength reduction due to the formation of the fold 16. The joining member 14 is provided along. The joining member 14 can be installed along the crease 16 to reinforce the laminate material 1 or the laminate product 10, has a certain degree of elasticity, and does not affect the visibility of the toner image T. Well-known resin films and elastic bodies that exhibit rubber elasticity can be mentioned.

  Specific examples of a resin film that can be used as the bonding member 14 and an elastic body that exhibits rubber elasticity are given below. First, examples of the resin film include polyethylene, polypropylene, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyethylene terephthalate (PET), and polyethylene naphthalate (PEN). Examples of elastic bodies that exhibit rubber elasticity include silicone rubber, acrylic rubber, butadiene rubber, isoprene rubber, styrene butadiene copolymer rubber (SBR), nitrile rubber, and urethane rubber. Among these, silicone rubber is particularly preferable.

  Next, the image support 15 on which the toner image T is transferred while being superimposed on the pressure-sensitive adhesive layer 11 constituting the laminate 1 when the laminate product 10 shown in FIG. 2 is produced will be described. As described above, the image support 15 used in the present invention transfers an unfixed toner image T formed on an image carrier such as a photoreceptor or an intermediate transfer member of an electrophotographic image forming apparatus. The toner particles are electrostatically attached to the toner particles. Then, the surface on which the toner image T is transferred (image surface) is superimposed so as to face the surface of the pressure-sensitive adhesive layer 11 of the laminate 1, and further, an external force is applied and pressed in this state, whereby an image support is provided. The toner image T on 15 is embedded and held in the adhesive layer 11.

  As described above, the image support 15 used in the present invention transfers an unfixed toner image T formed on an image carrier such as a photosensitive member constituting an electrophotographic image forming apparatus and transfers the image. The toner image T is electrostatically carried. Further, the surface having the unfixed toner image T and the surface of the pressure-sensitive adhesive layer 11 are overlapped to have a strength that can withstand pressing by an external force. Examples of such a material include papers and films used for electrophotographic image formation, and specifically, coatings such as plain paper, high-quality paper, art paper, or coated paper. Printed paper, OHP plastic film, cloth and the like.

  Next, the release sheet 13 that can be used for the laminate material 1 shown in FIG. 1 will be described. The release sheet 13 covers the pressure-sensitive adhesive layer 11 constituting the laminate material 1 and has a performance of smoothly peeling from the surface of the pressure-sensitive adhesive layer 11 when the laminate product 10 is manufactured. Moreover, the adhesiveness which does not peel from the adhesive layer 11 is expressed at the time of unused before producing a laminate product.

  As the release sheet 13 having such performance, for example, a sheet having a release layer obtained by coating a resin on a paper or resin film substrate is preferably used. As a specific resin for forming the release layer, for example, a silicone resin, an acrylic resin, a fluororesin or the like is preferably used, and among these, a silicone resin is particularly preferable. The thickness of the release layer is not particularly limited, but is preferably 0.5 μm to 10 μm, and more preferably 1 μm to 5 μm.

  Specific examples of the base material for the release sheet 13 include various papers and coated papers coated with polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), or polystyrene (PS). It is done. Further, a sheet film made of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), or polystyrene (PS) can be used. In addition, the thickness of the base material for the release sheet 13 is preferably 10 μm to 200 μm, and more preferably 25 μm to 100 μm.

  As described above, the release sheet 13 is required to be smoothly peeled off from the pressure-sensitive adhesive layer 11 when the laminate product 10 is manufactured, and not to peel off from the pressure-sensitive adhesive layer 11 when not in use. The release sheet 13 satisfying this performance preferably has a peel strength of 0.05 N / 20 mm to 8 N / 20 mm according to a peel test measured according to JIS Z2307, and is preferably 0.05 N / 20 mm to 5 N / 20 mm. More preferable is one that provides peel strength. In addition, the peeling test according to JIS Z2307 is a 180 ° peeling test performed under conditions of a peeling speed of 300 mm / min, a peeling distance of 150 mm, and an adhesive layer width of 20 mm.

  The release sheet 13 having a peel strength in the above range peels more smoothly than the pressure-sensitive adhesive layer when producing a laminated product, and does not peel off from the pressure-sensitive adhesive layer surface when not in use. The performance of can be maintained stably.

  In the present invention, as described in the embodiments described later, an unfixed toner image T formed on an image carrier such as a photoconductor can be transferred, and the transferred toner image T is electrostatically carried. It is also possible to use the above-mentioned image support 15 having such a property as the release sheet 13. When the above-mentioned image support 15 is used as the release sheet 13, for example, a laminate product 10 containing the image support 15 as shown in FIGS. 2 (a), (c) and (d) is prepared. Therefore, when producing such a laminate product, it is preferable to use the release sheet 13 having no release layer from the viewpoint of durability.

  Next, the toner used when the laminate product according to the present invention is produced will be described. The toner particles forming the toner image T constituting the laminate product according to the present invention contain at least a binder resin and, if desired, a colorant, a charge control agent, magnetic powder, a release agent and the like. It is possible to make it. Here, the aggregate of toner particles used for image formation is called toner. Hereinafter, toner particles usable in the present invention will be described.

  First, the particle diameter of the toner particles constituting the toner used in the present invention is preferably 4 to 10 μm, more preferably 6 to 9 μm, for example, as a volume-based median diameter. By setting the volume-based median diameter of the toner particles in the above range, reproducibility of fine lines and high image quality of photographic images are achieved, and it is possible to produce high-quality seal products with excellent design.

  The volume-based median diameter of toner particles is measured and calculated using a measuring device in which a computer system equipped with data processing software “Software V3.51” is connected to “Coulter Multisizer 3” (manufactured by Beckman Coulter). It is what is done.

  As a measurement procedure, 0.02 g of toner is added to 20 ml of a surfactant solution (for example, a surfactant solution in which a neutral detergent containing a surfactant component is diluted 10 times with pure water for the purpose of dispersing the toner). Then, ultrasonic dispersion is performed for 1 minute to prepare a toner dispersion. This toner dispersion is pipetted into a beaker containing “ISOTON II (manufactured by Beckman Coulter)” in a sample stand until the measured concentration is 5% to 10%. By setting this concentration range, reproducible measurement values can be obtained. In the measuring apparatus, the measurement particle count is set to 25000 and the aperture diameter is set to 50 μm, the frequency range is calculated by dividing the measurement range of 1 μm to 30 μm into 256, and the volume integrated fraction is 50 % Particle diameter is defined as the volume-based median diameter.

  The toner particles preferably have an average circularity value defined by the following formula of 0.700 to 1.000, more preferably 0.850 to 1.000.

Average circularity = peripheral length of circle determined from equivalent circle diameter / perimeter length of projected particle image The method for producing toner particles usable in the present invention is not particularly limited, and a pulverization method, an emulsification dispersion method, Suspension polymerization method, dispersion polymerization method, emulsion polymerization method, emulsion polymerization aggregation method, and other known methods can be exemplified.

  When the toner particles are prepared by a pulverization method, an emulsification dispersion method, or the like, for example, the following can be used as the binder resin. That is, styrene resins, (meth) acrylic resins, styrene- (meth) acrylic copolymer resins, vinyl resins such as olefin resins, polyester resins, polyamide resins, polycarbonate resins, polyether resins, poly Known resins such as vinyl acetate resins, polysulfone resins, epoxy resins, polyurethane resins and urea resins can be used. These can be used alone or in combination of two or more.

  On the other hand, when the toner particles are prepared by a polymerization method, that is, when the toner particles are prepared by the above-described suspension polymerization method, dispersion polymerization method, emulsion polymerization method, emulsion polymerization aggregation method, etc., in order to prepare a binder resin, Vinyl-based polymerizable monomers as shown are used. Examples of the polymerizable monomer used when the toner particles are prepared by a polymerization method include the following styrene monomers, methacrylic acid ester monomers, acrylic acid ester monomers, and olefin monomers. And monomers.

  First, specific examples of the styrene monomer include styrene and styrene derivatives as shown below. That is, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-phenylstyrene, p-ethylstyrene, 2,4- Dimethyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, and the like.

  Further, specific examples of the methacrylic acid ester monomer include, for example, the methacrylic acid ester derivatives shown below. That is, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, Phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate and the like.

  Specific examples of the acrylate ester monomer include, for example, the acrylate derivative shown below. That is, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, Phenyl acrylate, etc.

  Specific examples of the olefin monomer include, for example, ethylene, propylene, isobutylene and the like.

  In addition to the above vinyl monomers, there are the following vinyl halide monomers, vinyl ester monomers, vinyl ether monomers, vinyl ketone monomers, and the like. Specific examples of the vinyl halide monomer include, for example, vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, and vinylidene fluoride. Specific examples of the vinyl ester monomer include, for example, vinyl propionate, vinyl acetate, and vinyl benzoate. Specific examples of vinyl ether monomers include, for example, vinyl methyl ether and vinyl ethyl ether. Specific examples of vinyl ketone monomers include, for example, vinyl methyl ketone, vinyl ethyl ketone, and vinyl hexyl ketone. Etc.

  Further, N-vinyl compound monomer compounds such as N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone, vinyl compounds such as vinyl naphthalene and vinyl pyridine, and acrylic acids such as acrylonitrile, methacrylonitrile and acrylamide Alternatively, there are vinyl monomers such as methacrylic acid derivatives. These vinyl monomers can be used alone or in combination of two or more.

  It is also possible to use a combination of polymerizable monomers having an ionic dissociation group. The polymerizable monomer having an ionic dissociation group has, for example, a substituent such as a carboxy group, a sulfonic acid group, or a phosphoric acid group as a constituent group. Specifically, acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester, styrene sulfonic acid, allyl sulfosuccinic acid, 2-acrylamide-2- Examples include methylpropane sulfonic acid, acid phosphooxyethyl methacrylate, and 3-chloro-2-acid phosphooxypropyl methacrylate.

  Furthermore, as a polymerizable monomer, divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl A resin having a crosslinked structure can also be obtained using polyfunctional vinyls such as glycol diacrylate.

  Next, colorants, waxes and the like that can be used for the toner used in the present invention will be described.

  In the present invention, since a seal product having a good finish is produced, it is possible to contain the following colorant in the toner particles. First, examples of the black colorant include carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black, and magnetic powder such as magnetite and ferrite can also be used.

  Examples of colorants for magenta or red include C.I. I. Pigment Red 2, 3, 5, 6, 7, 15, 15, 48: 1, 53: 1, 57: 1, 60, 63, 64, 68, the same 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 139, 144, 149, 150, 163, 166, 170, 177, 178, 184, 202, 206, 207, 209, 222, 238, 269, and the like. In addition, as a dye, C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 122, etc.

  Examples of the colorant for orange or yellow include C.I. I. Pigment Orange 31 and 43, C.I. I. Pigment Yellow 12, 14, 15, 17, 74, 83, 93, 94, 138, 155, 162, 180, 185, and the like. In addition, as a dye, C.I. I. Solvent Yellow 2, 6, 14, 15, 16, 19, 21, 21, 33, 44, 56, 61, 77, 79, 80, 81, 82, the same 93, 98, 103, 104, 112, 162, and the like.

  Further, examples of the colorant for green or cyan include C.I. I. Pigment Blue 2, 3, 15, 15, 15: 2, 15: 3, 15: 4, 16, 17, 17, 60, 62, 66, C.I. I. Pigment Green 7 etc. In addition, as a dye, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95, etc.

  In the present invention, it is also possible to use a dye in order to obtain a high-definition image using yellow, magenta, and cyan toners. These colorants can be used alone or in combination of two or more as required. The content of the colorant is preferably 0.5% by mass to 20% by mass in the toner particles, and more preferably 2% by mass to 10% by mass.

  The toner used in the present invention can contain a wax in the toner particles, and a known wax can be used. Specific examples of the wax include polyolefin waxes such as low molecular weight polypropylene and polyethylene and oxidized polypropylene and polyethylene. The content of the wax in the toner particles is preferably 1% by mass to 30% by mass, and more preferably 3% by mass to 15% by mass.

  In order to improve the chargeability of the toner, a charge control agent (also referred to as a charge control agent) can be contained in the toner particles. The charge control agent is not particularly limited as long as it can impart positive or negative charge by frictional charging, and a known one can be used.

  Examples of the positive charge control agent that positively charges the toner by frictional charging include nigrosine dyes, quaternary ammonium salts, alkoxylated amines, alkylamides, molybdate acid chelate pigments, and imidazole compounds. And as a commercially available nigrosine dye, "Nigrosine Base EX (produced by Orient Chemical Industry Co., Ltd.)", etc., as a commercially available quaternary ammonium salt, "quaternary ammonium salt (produced by Orient Chemical Industries Ltd.)", "Copy Charge PX VP435 (Made by Hoechst Japan) ". Furthermore, as a commercially available imidazole compound, there is “PLZ1001 (manufactured by Shikoku Kasei Kogyo Co., Ltd.)” and the like.

  Examples of the negative charge control agent that negatively charges the toner by frictional charging include, for example, metal complexes, thioindigo pigments, quaternary ammonium salts, calixarene compounds, boron compounds, fluorine such as magnesium fluoride and carbon fluoride. There are compounds. Examples of commercially available metal complexes include “Bontron S-22”, “Bontron S-34”, and “Bontron E-81” manufactured by Orient Chemical Industries, and “Spiron Black TRH” manufactured by Hodogaya Chemical Co., Ltd. . In addition, as commercially available boron compounds such as “Copy Charge NX VP434 (manufactured by Hoechst Japan)” as a commercially available quaternary ammonium salt, “Bontron E-81 (manufactured by Orient Chemical Industries)” as a commercially available calixarene compound, etc. “LR147 (made by Nippon Carlit)” and the like. Furthermore, in addition to the above-mentioned commercially available products, the metal complexes used as negative charge control agents include oxycarboxylic acid metal complexes, dicarboxylic acid metal complexes, amino acid metal complexes, diketone metal complexes, diamine metal complexes, azo group-containing benzene- A benzene derivative skeleton metal complex, an azo group-containing benzene-naphthalene derivative skeleton metal complex, or the like can be used.

  The content of the charge control agent is preferably 0.01% by mass to 30% by mass in the toner particles, and more preferably 0.1% by mass to 10% by mass.

  Further, the toner used in the present invention can be a toner in which an external additive is added to and mixed with the surface of the toner particles as necessary, and the addition of the external additive can improve fluidity, chargeability, cleaning properties, etc. Can be improved. Typical external additives include inorganic fine particles such as the following inorganic oxide fine particles, inorganic stearic acid compound fine particles, and inorganic titanic acid compound particles.

Inorganic oxide fine particles: silica fine particles, alumina fine particles, titanium oxide fine particles, etc. Inorganic stearic acid compound fine particles: aluminum stearate fine particles, zinc stearate fine particles, etc. Inorganic titanate compound fine particles: strontium titanate, zinc titanate, etc. These inorganic fine particles are In order to improve heat resistant storage stability and environmental stability, those subjected to surface treatment with a silane coupling agent, a titanium coupling agent, a higher fatty acid, silicone oil or the like are preferable.

  The total amount of external additives added is preferably from 0.05 to 5 parts by weight, more preferably from 0.1 to 3 parts by weight, based on 100 parts by weight of the toner. It is also possible to use a combination of a plurality of types of external additive particles.

  The toner used in the present invention can be used as a magnetic or non-magnetic one-component developer composed only of toner, but can also be used as a two-component developer composed of carrier and toner. . When the toner is used as a two-component developer, as the carrier, for example, metals such as iron, ferrite, and magnetite, alloys of these metals with metals such as aluminum and lead, etc., conventionally known materials are used as magnetic particles. It is possible to use. Among these, ferrite particles are preferable.

  Also, a coat carrier in which the surface of magnetic particles is coated with a resin or the like, or a binder type carrier in which a magnetic fine powder is dispersed in a binder resin can be used. The coating resin constituting the coat carrier is not particularly limited, and examples thereof include olefin resins, styrene resins, styrene acrylic copolymer resins, silicone resins, polyester resins, and fluorine resins. In addition, the resin constituting the binder type carrier is not particularly limited, and a known one can be used. For example, use of a styrene acrylic copolymer resin, a polyester resin, a fluorine resin, a phenol resin, etc. Is possible.

  The volume-based median diameter of the carrier is preferably 20 μm to 100 μm, and more preferably 20 μm to 60 μm. The volume-based median diameter of the carrier can be measured by a laser diffraction particle size analyzer “HELOS (manufactured by Sympatec Corporation)” equipped with a wet disperser.

  Next, an image forming apparatus capable of forming a toner image used in the present invention will be described. FIG. 5 is a schematic diagram illustrating the configuration of the image forming apparatus 3 capable of forming a toner image used in the present invention. As described above, in the present invention, the unfixed toner image formed on the image carrier is transferred to the image support, and the image support onto which the toner image has been transferred is superimposed on the adhesive layer 15 of the laminate material. By applying an external force in the state, the toner image is embedded in the adhesive layer.

  5 includes a photosensitive drum 31 that is a drum-shaped image carrier, and a charging unit 32, a developing unit 34, a transfer unit 35, a separation unit 36, and a cleaning unit arranged along the circumferential surface thereof. 37 and the like.

  The arrow a in the figure indicates the optical path of the laser beam of an image writing unit (not shown) that scans and exposes the peripheral surface, which is the photosensitive surface of the photosensitive drum 31, and the arrow b indicates the image support before the toner image is transferred. The arrow c indicates the course of the image support 15 to which the transferred toner image is transferred. An arrow r indicates the rotation direction of the photosensitive drum 31.

  First, the photosensitive drum 31 is uniformly charged by corona discharge of the charging unit 32, and the uniformly charged photosensitive drum 31 is subjected to scanning exposure by beam light carrying image information by an image writing unit (not shown). As a result, a latent image is formed on the photosensitive drum 31. The formed latent image is developed with toner supplied from the developing unit 34 at a position facing the developing unit 34 by the rotation of the photosensitive drum 31, and a toner image T is formed on the photosensitive drum 31.

  Corresponding to the position of the developed image, the image support 15 is sent out by the timing roller 52, and the toner image T on the photosensitive drum 31 is transferred onto the image support 15 by the action of the transfer unit 35.

  The image support 15 carrying the toner image T is separated from the photosensitive drum 31 by the action of the separation unit 36. A separation claw 38 is disposed in the vicinity of the photosensitive drum 31, and the front end of the separation claw 38 is brought into contact with the surface of the photosensitive drum 31 so that the image support 15 can be reliably detached from the photosensitive drum 31. ing.

  Then, after the image support 15 carrying the toner image T is separated, the toner remaining on the surface of the photosensitive drum 31 is removed by the cleaning unit 37. The cleaning unit 37 is provided with a resin cleaning blade 371 having elasticity such as polyurethane resin, for example, and the remaining toner is removed by rubbing the surface of the photosensitive drum 31 that is rotationally driven by the tip of the cleaning blade 371. Is done.

  Through such a procedure, the image forming apparatus 3 shown in FIG. 5 receives the toner image T formed of a collection of toner particles on the surface of the image support 15 to be superimposed on the adhesive layer 11 of the laminate material 11. Can be formed.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited only to the form shown in an Example.

1. 1. Production of “laminates 1 to 12” 1-1. Preparation of “Peeling Sheets (Image Supports) A to F” (1) Preparation of “Peeling Sheets (Image Supports) A to D” Transfer and carry unfixed toner images formed by an electrophotographic image forming method Commercially available papers shown below were prepared as image supports that can be used as “release sheets C and D”. Further, a commercially available low-temperature curable silicone elastomer material “SE1740” (manufactured by Dow Corning Toray) is applied to the surface of the paper with a bar coater, and heat-cured at 80 ° C. for 1 hour to have a resin layer having a thickness of 5 μm. “Peeling sheets A and B” were prepared. Here, the paper used for the “peeling sheets A and C” is “J paper” (manufactured by Konica Minolta Business Solutions), and the paper used for the production of the “peeling sheets B and D” is “POD gloss coated paper” ( Oji Paper Co., Ltd.).

(2) Preparation of “Peeling Sheets E and F” Next, as an image support capable of transferring and carrying an unfixed toner image formed by an electrophotographic image forming method, a commercially available 50 μm-thick is available. A transparent polyethylene terephthalate (PET) film was prepared, and this PET film was designated as “Peeling Sheet F”. On the PET film, the commercially available low-temperature curable silicone elastomer material “SE1740” (manufactured by Toray Dow Corning Co., Ltd.) is applied with a bar coater and heat-cured at 80 ° C. for 1 hour to give a resin having a thickness of 5 μm. A “release sheet E” having a layer was prepared.

  “Release sheets A to F” produced by the above procedure are shown in Table 1 below. In Table 1 below, “J paper” is referred to as “J paper”, and “POD gloss coated paper” is referred to as “gloss coated paper”.

1-2. Production of “Adhesive Sheets 1-6” (1) Production of “Adhesive Sheet 1” A commercially available transparent polyethylene terephthalate film base (thickness: 100 μm, transmission density: 0.05) was prepared as a substrate constituting the laminate material. This was cut into a B5 plate size to obtain a substrate for a laminate material.

  Next, an adhesive layer was formed on the substrate. Specifically, a commercially available silicone gel material A “CY52-276” (manufactured by Dow Corning Toray Co., Ltd.) was applied with a bar coater and heat-cured at 70 ° C. for 1 hour to obtain a thickness including the substrate thickness. Produced an “adhesive sheet 1” having a thickness of 200 μm. In addition, what provided the adhesive layer on the base | substrate which comprises a laminate material is called "adhesive sheet." The “pressure-sensitive adhesive sheet 1” produced by the above procedure had a hardness measured according to JIS K6253 type A of less than 1.

(2) Production of “Adhesive Sheet 2” Instead of silicone gel material A used in the production of “adhesive sheet 1”, commercially available silicone gel material B “SE1891H” (manufactured by Toray Dow Corning Co., Ltd.) The “adhesive sheet 2” was prepared by taking the same procedure except that was used. The “pressure-sensitive adhesive sheet 2” produced by the above procedure had a hardness of less than 1 as measured according to JIS K6253 type A, similarly to the “pressure-sensitive adhesive sheet 1”.

(3) Production of “Adhesive Sheet 3” In the production of “Adhesive Sheet 1”, 1% by mass of the aforementioned silicone gel material B as a material for the adhesive, commercially available silicone elastomer material A “SE1740” (Toray Industries, Inc.) -What was mixed and prepared so that it might become 99 mass% was used. Moreover, it changed into what performs a heat-hardening process at the temperature of 120 degreeC for 1 hour. Otherwise, the same procedure was used to prepare “Adhesive Sheet 3” with a hardness of 2 measured according to JIS K6253 Type A.

(4) Production of “Adhesive Sheet 4” In the production of “Adhesive Sheet 3”, the silicone gel material B is 1% by mass, the silicone elastomer material A is 90% by mass, and commercially available silicone. Elastomer material B “Sylguard 184” mixed and prepared to 9% by mass was used. Otherwise, the same procedure was used to prepare “adhesive sheet 4” having a hardness of 5 measured according to JIS K6253 type A.

(5) Production of “Adhesive Sheets 5 and 6” In the production of the “Adhesive Sheet 3”, 84 mass% of the silicone elastomer material A and 16 mass% of the silicone elastomer material B were used as the adhesive material. What was mixed and prepared as described above was used. Otherwise, the same procedure was used to prepare “Adhesive Sheet 5” having a hardness of 10 measured according to JIS K6253 Type A. Further, in the production of the “pressure-sensitive adhesive sheet 3”, a material prepared by mixing and preparing the pressure-sensitive adhesive material so that the silicone elastomer material A was 80% by mass and the silicone elastomer material B was 20% by mass was used. . Otherwise, the same procedure was used to prepare “Adhesive Sheet 6” having a hardness of 12 measured according to JIS K6253 Type A.

  Regarding the “adhesive sheets 1 to 6” produced by the above procedure, the mass ratio of each material used when producing the adhesive material and the hardness measured according to JIS K6253 type A are shown in Table 2 below. Show.

1-3. Production of “laminates 1-12” B5 plate size as shown in Table 3 below by combining “Peeling Sheets A to F” shown in Table 1 and “Adhesive Sheets 1 to 6” shown in Table 2 “Laminates 1-12” were prepared. The “laminates 1 to 12” are in the form of using two release sheets shown in FIG. 1 (b), and the base side of the two adhesive sheet ends is connected by a commercially available silicone rubber bonding member. By doing so, a crease is formed. Among these, the “laminate material 7” does not have a release sheet and transfers an unfixed toner image directly from the photoreceptor to the adhesive sheet.

1-4. Evaluation of handling properties of laminate materials Among the above-mentioned laminate materials, for "laminate materials 1 to 6, 8 to 12", the ease of peeling of the release sheet from the adhesive sheet is evaluated as handleability, and the evaluation criteria are as follows. Of these, ○ and △ were accepted. That is,
○: The release sheet could be peeled off smoothly from the adhesive sheet. Δ: It took some time to peel off, but the adhesive layer was not damaged. ×: Difficult to peel, damage to the adhesive layer such as scratches or breakage. Was generated.

  As shown in Table 3, it was confirmed that “laminates 1 to 6 and 8 to 12” can peel the release sheet without damaging the adhesive layer.

2. Production of “Toner Particles 1 to 4” “Toner Particles 1 to 3” were produced by an emulsion association method, and “Toner Particle 4” was produced by a pulverization method. That is,
2-1. Preparation of “Toner Particle 1” (1) First-stage polymerization 8 parts by mass of sodium dodecyl sulfate was dissolved in 3000 parts by mass of ion-exchanged water in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introduction device. A surfactant solution was prepared, and the internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream. After raising the temperature, a solution prepared by dissolving 10 parts by mass of potassium persulfate (KPS) in 200 parts by mass of ion-exchanged water was added to the surfactant solution, and the temperature was again adjusted to 80 ° C. The polymerizable monomer mixture to be added was dropped over 1 hour.

Styrene 480 parts by weight n-butyl acrylate 250 parts by weight Methacrylic acid 68 parts by weight n-octyl-3-mercaptopropionate 16 parts by weight After dropwise addition, the system is heated and stirred at 80 ° C. for 2 hours. Polymerization (first stage polymerization) was performed to prepare “resin particle dispersion 1h” containing “resin particles 1h”.

(2) Second-stage polymerization In a flask equipped with a stirrer, was added and heated to 90 ° C. to dissolve to prepare a monomer solution.

On the other hand, a surfactant solution in which 7 parts by mass of sodium polyoxyethylene-2-dodecyl ether sulfate was dissolved in 800 parts by mass of ion-exchanged water was heated to 98 ° C. To this surfactant solution, 260 parts by mass of the above-mentioned “resin particles 1h” in terms of solid content and a polymerizable monomer mixed solution containing the following compound were added. That is,
Styrene 245 parts by mass n-butyl acrylate 120 parts by mass n-octyl-3-mercaptopropionate 1.5 parts by mass Wax “HNP-11 (Nippon Seiki Co., Ltd.)” 67 parts by mass A machine having a circulation path after addition A dispersion liquid containing emulsified particles was prepared by carrying out a mixing dispersion treatment for 1 hour using a type disperser “CLEAMIX” (manufactured by M Technique Co., Ltd.).

  Next, a solution prepared by dissolving 6 parts by mass of potassium persulfate in 200 parts by mass of ion-exchanged water is added to this dispersion, and the system is heated and stirred at 82 ° C. for 1 hour (second stage polymerization). And “resin particle dispersion 1HM” containing “resin particle 1HM” was produced.

(3) Third-stage polymerization After adding an initiator solution in which 11 parts by mass of potassium persulfate is dissolved in 400 parts by mass of ion-exchanged water to the above “resin particle dispersion AHM”, and the temperature of the liquid is 80 ° C., A polymerizable monomer mixture containing the following compound was added dropwise over 1 hour. That is,
Styrene 435 parts by weight n-butyl acrylate 130 parts by weight Methacrylic acid 33 parts by weight n-octyl-3-mercaptopropionate 8 parts by weight After completion of dropping, polymerization is performed by heating and stirring for 2 hours (third stage polymerization). Then, it was cooled to 28 ° C., and “resin particle dispersion A” containing “resin particles a” was produced. When the particle diameter of the “resin particle A” contained in the “resin particle dispersion A” was measured using an electrophoretic light scattering photometer “ELS-800 (manufactured by Otsuka Electronics Co., Ltd.)”, the volume-based median diameter was It was 150 nm. Moreover, it was 45 degreeC when the glass transition temperature was measured by the well-known method.

(4) Preparation of “Colorant Particle Dispersion” While stirring 900 parts by mass of 10% by weight aqueous solution of sodium dodecyl sulfate, 100 parts by mass of a commercially available colorant (carbon black; “Regal 330R (manufactured by Cabot)”) was gradually added. Added to. Subsequently, a black “colorant dispersion liquid K” was prepared by performing a dispersion treatment using a stirring device “Claremix (M Technique Co., Ltd.)”. The average dispersion diameter of the colorant particles in the colorant dispersion was measured with a commercially available dynamic light scattering particle size distribution analyzer “Microtrac UPA150 (manufactured by Microtrac)” and found to be 150 μm.

  Further, in the preparation of the “Colorant Dispersion Liquid K”, the same procedure was followed except that the colorant was changed to the commercially available pigment “CI Pigment Yellow 74”. Was prepared. Similarly, in the preparation of the above “colorant dispersion K”, the same procedure was followed except that the colorant was changed to the commercially available pigment “CI Pigment Red 48: 1”. Dispersion M "was prepared. Further, by preparing the above “Colorant Dispersion Liquid K”, the same procedure was followed except that the colorant was changed to a commercially available pigment “CI Pigment Blue 15: 3”. Liquid C "was prepared. The average dispersion diameter of the colorant particles in these colorant dispersions was 150 nm.

(5) Preparation of “toner base particle 1 (1K, 1Y, 1M, 1C)” In a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device,
"Resin particle dispersion A" 300 parts by mass (solid content conversion)
Ion-exchanged water 1400 parts by weight “Colorant particle dispersion K” 120 parts by weight (in terms of solid content)
Was introduced. Further, a solution of 3 parts by mass of sodium polyoxyethylene-2-dodecyl sulfate in 120 parts by mass of ion-exchanged water was added, the temperature of the solution was adjusted to 30 ° C., and then a 5 mol / liter sodium hydroxide aqueous solution was added. The pH was adjusted to 10.

  Next, an aqueous solution in which 35 parts by mass of magnesium chloride hexahydrate is dissolved in 35 parts by mass of ion-exchanged water is added over 10 minutes at 30 ° C. with stirring, and the temperature is raised for 3 minutes. Started. The temperature was raised to 90 ° C. over 60 minutes, and the particles were aggregated and fused while maintaining the temperature at 90 ° C. In this state, using “Multisizer 3 (manufactured by Beckman Coulter)”, the particle size of the particles growing in the reaction vessel was measured, and when the volume-based median diameter reached 6.5 μm, 150 parts by mass of sodium chloride Was added to an aqueous solution of 600 parts by mass of ion-exchanged water to stop particle growth. Further, as a ripening treatment, the liquid temperature was set to 98 ° C., and the mixture was heated and stirred, and particle fusion was advanced until the average circularity was 0.930 as measured by “FPIA-2100 (manufactured by Sysmex Corporation)”.

  Thereafter, the liquid temperature was cooled to 30 ° C., the pH of the liquid was adjusted to 2 using hydrochloric acid, and stirring was stopped. In this way, “toner base particle dispersion 1K” was produced.

  The “toner base particle dispersion 1K” produced through the above steps is subjected to solid-liquid separation with a basket-type centrifuge “MARK III model number 60 × 40 (manufactured by Matsumoto Kikai Co., Ltd.)” to wet the “toner base particle 1K”. A cake was formed.

  This wet cake was washed with ion exchange water at 45 ° C. until the electric conductivity of the filtrate reached 5 μS / cm with the basket type centrifuge, and then transferred to “Flash Jet Dryer (manufactured by Seishin Enterprise Co., Ltd.)”. Then, a “toner base particle 1K” was produced by performing a drying process until the water content reached 0.5% by mass.

  Further, in the production of the “toner base particle 1K”, the “colorant particle dispersion Y”, “colorant particle dispersion M”, “colorant particles” described above are used instead of the “colorant particle dispersion K”. “Toner base particles 1Y, 1M, 1C” were prepared in the same manner except that “Dispersion C” was used.

(6) Production of “Toner Particles 1 (1K, 1Y, 1M, 1C)” 3.5 masses of hydrophobic silica fine particles having a number average primary particle size of 80 nm with respect to 100 mass parts of the produced “toner base particles 1K”. %, Hydrophobic titania fine particles having a number average primary particle size of 10 nm were added so as to be 0.6% by mass. Then, by using a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.) for 25 seconds at a peripheral speed of 35 m / s, “toner particles 1K” having a volume-based median diameter of 6.5 μm and an average circularity of 0.930 are obtained. Produced. The same processing was performed on “toner base particles 1Y, 1M, 1C” to produce “toner particles 1Y, 1M, 1C” having a volume-based median diameter of 6.5 μm and an average circularity of 0.930. .

2-2. Preparation of “Toner Particles 2 and 3” When preparing the toner base particles in the preparation of “Toner Particles 1”, the sodium chloride aqueous solution was added when the volume-based median diameter of the particles reached 5.0 μm. Grain growth was stopped. Further, during the aging treatment, the particles were fused until the average circularity became 0.990 as measured by “FPIA-2100 (manufactured by Sysmex Corporation)”. Otherwise, the same procedure was used to produce “toner particles 2 (2K, 2Y, 2M, 2C)” having a volume-based median diameter of 5.0 μm and an average circularity of 0.990.

  Further, when producing the toner base particles, the sodium chloride aqueous solution was added to stop the particle growth when the volume-based median diameter of the particles reached 8.0 μm. In addition, the particles were fused until the average circularity reached 0.850 as measured by “FPIA-2100 (manufactured by Sysmex Corporation)” during the aging treatment. Otherwise, the same procedure was used to prepare “toner particles 3 (3K, 3Y, 3M, 3C)” having a volume-based median diameter of 8.0 μm and an average circularity of 0.850.

2-3. Production of “Toner Particle 4” The same binder resin and colorant that form the above “toner particles 1 to 3” were charged into a commercially available biaxial kneader, and kneaded and pulverized to obtain a volume standard. “Toner particles 4 (4K, 4Y, 4M, 4C)” having a median diameter of 8.5 μm and an average circularity of 0.700 were produced.

3. Production of “laminate products 1 to 21” (1) Production of “laminate products 1 to 3 and 8 to 12” The release sheet is peeled off from the “laminate materials 1 to 3 and 8 to 12” of B5 size produced in the above procedure. The release sheet was used as an image support, and the image forming apparatus “bizhub C253” (manufactured by Konica Minolta Business Technologies, Inc.) from which the fixing device was removed was set. On the release sheet, using “toner particles 1”, a full-color portrait image, a single color of yellow / magenta / cyan, and a solid image (2 cm × 2 cm) of R / G / B, a thin line image (8 Toner images having a line / mm, 6 lines / mm, and 4 lines / mm) were formed. Here, the solid image is formed using “toner particles 1Y, 1M, 1C”, and the thin line image is formed using “toner particles 1K”.

The release sheet on which the toner image is formed is superimposed on the pressure-sensitive adhesive layer surface of each of the “laminate materials 1 to 3 and 8 to 12”, and a pressing force of 5 × 10 ⁵ Pa is applied, whereby FIG. “Laminated products 1-3, 8-12” having the laminated structure shown in FIG.

(2) Production of “Laminate Product 7” “Laminate 7” is set in the image forming apparatus from which the fixing device has been removed, and the above-mentioned full-color portrait photograph image, yellow / magenta / cyan single color, and , R / G / B solid images and fine line images were formed. “Peeling sheet C” is superimposed on the surface of the pressure-sensitive adhesive layer carrying the toner image, and a pressing force of 5 × 10 ⁵ Pa is applied to produce “laminate product 7” having the laminated structure shown in FIG. did.

(3) Preparation of “Laminated Products 13 to 15” By using the same procedure except that the toner particles for image formation were changed to “Toner Particles 2 to 4” in the preparation of “Laminated Product 1”, FIG. “Laminated products 13 to 15” having the laminated structure shown in FIG.

(4) Production of “laminate products 16 and 17” In the production of “laminate product 11”, the pressing force applied when the release sheet (image support) carrying the toner image is superimposed on the pressure-sensitive adhesive layer surface is applied. Except for changing to 1 × 10 ³ Pa, the same procedure was followed to produce “laminate product 16” having a laminated structure shown in FIG. Further, in the production of the “laminate product 12”, the pressing force applied when the release sheet (image support) carrying the toner image is superimposed on the pressure-sensitive adhesive layer surface is changed to 1 × 10 ⁸ Pa. In the same procedure, “laminate product 17” having a laminated structure shown in FIG.

(5) Production of “laminate product 18” In the production of “laminate product 7”, the pressing force when “peeling sheet C” is superimposed on the surface of the pressure-sensitive adhesive layer carrying the toner image is set to 1 × 10 ⁸ Pa. The “laminate product 18” having the laminated structure shown in FIG.

(6) Production of “laminate product 19” A predetermined fixing device is attached to the image forming apparatus, and the “release sheet C” peeled off from the “laminate material 1” is mounted on the image forming apparatus. A fixing toner image composed of the above-described full-color human photographic image, solid image, and fine line image was formed. The “release sheet C” on which the toner image is formed is superimposed on the pressure-sensitive adhesive layer surface of the “laminate material 1”, and a pressing force of 5 × 10 ⁵ Pa is applied, whereby “ A laminate product 19 "was produced.

(7) Production of “Laminate Product 20” A release sheet on which a toner image is formed is superimposed on one adhesive layer surface of the “laminate material 1”, and a pressing force of 5 × 10 ⁵ Pa is applied to embed the toner image. It was. Next, the “release sheet C” is removed from the surface of the adhesive layer in which the toner image is embedded, and then the other adhesive layer surface is superimposed on the surface of the adhesive layer in which the toner image is embedded and pressed by hand. Thus, a “laminate product 20” having a laminated structure shown in FIG.

(8) Production of “Laminate Product 21” An unfixed toner image composed of the above-mentioned full-color human photograph image, solid image, and fine line image formed on the image carrier of the image forming apparatus from which the above-described fixing device is removed is referred to as “ When the image was transferred to the release sheet of “Laminate 1”, the unfixed toner images were formed on both sides of the release sheet. Except for using “Release Sheet C” having an unfixed toner image transferred on both sides, the same procedure as that for producing “Laminate Product 1” was adopted, whereby toner images on both sides shown in FIG. A laminate product 21 "was produced.

  Table 4 shows the laminated structure of “laminate products 1 to 3 and 7 to 21” produced by the above procedure, the laminate material used for the production, the image support, the toner particles, and the pressing force.

4). Evaluation Experiment Regarding “laminate products 1 to 3 and 7 to 21” shown in Table 4 above, color reproducibility of formed images, human photograph image finish, fine line reproducibility, toner image durability, and reusability of laminate materials are as follows. It was evaluated as follows. Here, the evaluation about “laminate products 1-3, 8-17, 20, 21” is “Examples 1-15”, and the evaluation about “laminate products 7, 18, 19” is “comparative examples 1-3”. It was.

<Evaluation of color reproducibility of formed image>
The color gamut area is calculated by measuring the color gamut of each of the above-described single colors of yellow / magenta / cyan and R / G / B solid images (2 cm × 2 cm), and the calculated gamut area value and reference The color reproducibility was evaluated by comparing the color gamut area of the printing Japan color used in the above. Here, the color gamut area of the Japan color for printing was set to 100, and the color gamut area of the formed toner image exceeded 100.

<Toner image finish evaluation>
The above-described portrait photograph image, the monochrome solid image of yellow / magenta / cyan, and each solid image of R / G / B (2 cm × 2 cm) are visually observed to determine whether density unevenness occurs on the solid image, The toner image finish was evaluated by evaluating the skin color of the photographic image and the finish of the hair as “excellent”, “good” or “impossible”. A solid image in which density unevenness did not occur and the person photo image finished was “excellent” or “good” was accepted.

<Reproducibility of thin lines>
The above-mentioned thin line images (8 lines / mm, 6 lines / mm, 4 lines / mm) were observed with the naked eye and with a magnifying glass, and the presence / absence of crushing / cutting of lines and occurrence of unevenness was evaluated as follows. . That is,
Rank A: The above image defects were not observed in both the magnifying glass and the naked eye. Rank B: Although some defects were observed in the magnifying glass, the above defects were not observed in the macroscopic observation. Rank C determined to be none; the occurrence of the above-mentioned defect was observed by naked eye observation, and the three thin line images that were determined to have practical problems were evaluated as having passed no rank C.

<Toner image durability>
The laminate product was held with both hands, the folding operation was continuously performed 50 times, the toner image in the laminated product subjected to the bending operation was visually observed, and the damage state of the toner image was visually evaluated. A solid image or a portrait image that did not have cracks and the thin line image was not cut was regarded as acceptable. The bending was performed so that the substrate constituting the laminated product did not become cloudy.

<Reuseability of laminate material>
In the evaluation of the reusability of the laminate material, first, the produced laminate product is opened by a known method to expose the adhesive layer in which the toner image is embedded, and the “release sheet C” as the image support is superimposed. Was separated from the adhesive layer surface. Next, using a nonwoven fabric impregnated with methanol, the pressure-sensitive adhesive layer and the “release sheet C” were wiped off to evaluate whether or not the toner can be removed. The case where the toner could be removed was evaluated as ◯, and the case where the toner could not be removed as x.

  The results are shown in Table 5 below.

  As shown in Table 5, “Examples 1 to 15” in which laminate products produced by the production method having the configuration of the present invention were evaluated were color reproducibility, human photograph image finish, fine line reproducibility, and toner image durability. Good results were obtained for both the reusability of the substrate and the image support. Also, a laminate product 3 (Example 3) using a transparent PET film as an image support, and a laminate product 20 (Example) having a structure in which a formed toner image is sandwiched between two adhesive layers without using an image support. In 14), in addition to the above results, the toner image was visible on both sides.

  It was confirmed that “Comparative Examples 1 to 3” which evaluated the laminate products produced by the production method not having the configuration of the present invention did not give the results as obtained in the above “Examples 1 to 15”. . That is, Comparative Examples 1 and 2 in which a laminate product in which a toner image was transferred to an adhesive layer without using an image support were evaluated gave good results in color reproducibility, human photograph image finish, and fine line reproducibility. There wasn't. In Comparative Example 3 in which a laminate product using a toner image heated and melted and solidified was evaluated, the durability of the toner image was inferior and the image support could not be reused.

DESCRIPTION OF SYMBOLS 1 Laminating material 1 'Used laminating material 10 Laminated product 10' Used laminated product 11 Adhesive layer 12 Base | substrate 13 Release sheet 14 Joining member 15 Image support body 16 Folding 3 Image forming apparatus 31 Photosensitive drum 32 Charging part 34 Developing part 35 Transfer section 36 Separation section 37 Cleaning section T Toner image

Claims (16)

A method for producing a laminate product having at least a pressure-sensitive adhesive layer having a toner image and a substrate for holding the pressure-sensitive adhesive layer,
An image support on which an unfixed toner image formed on an image carrier by an electrophotographic image forming method is transferred is superimposed on the pressure-sensitive adhesive layer,
A method for producing a laminate product, wherein the unfixed toner image is embedded in the pressure-sensitive adhesive layer through a step of applying an external force in a state where the image support is superimposed on the pressure-sensitive adhesive layer.   The method for producing a laminated product according to claim 1, wherein the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer contains a resin that exhibits thixotropic properties.   The laminate product according to claim 1 or 2, wherein the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer has a hardness measured according to JIS K6253 type A of 2 or more and 10 or less. Production method.   The method for producing a laminate product according to any one of claims 1 to 3, wherein the pressure-sensitive adhesive layer contains at least a silicone resin. 5. The external force applied in a state where the image support is superimposed on the pressure-sensitive adhesive layer is a pressing force of 1 × 10 ³ Pa or more and 1 × 10 ⁸ Pa or less. A method for producing a laminate product according to Item.   The method for producing a laminated product according to any one of claims 1 to 5, wherein the substrate holding the pressure-sensitive adhesive layer is a polyester resin. The toner particles constituting the unfixed toner image are:
The volume-based median diameter is 5 µm or more and 8 µm or less, and the average circularity is 0.850 or more and 0.990 or less, The production of a laminate product according to any one of claims 1 to 6, Method. at least,
An adhesive layer capable of embedding a toner image;
A substrate for holding the pressure-sensitive adhesive layer;
It has a joining member arranged along the crease formed in the adhesive layer and the base,
A laminate material used in the method for producing a laminate product according to any one of claims 1 to 7.   The laminate material according to claim 8, wherein the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer contains a resin that exhibits thixotropic properties.   10. The laminate according to claim 8, wherein the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer has a hardness measured according to JIS K6253 type A of 2 or more and 10 or less.   The pressure-sensitive adhesive used in the pressure-sensitive adhesive layer contains at least a silicone resin, and the laminate material according to any one of claims 8 to 10.   It has a peeling sheet which coat | covers the surface of the said adhesive layer, The laminate material of any one of Claims 8-11 characterized by the above-mentioned.   13. The laminate material according to claim 12, wherein the release sheet is capable of transferring and holding an unfixed toner image formed by an electrophotographic image forming method.   The laminate according to claim 12 or 13, wherein the release sheet has a layer containing a silicone resin on a surface thereof.   The laminate according to any one of claims 8 to 14, wherein the substrate holding the pressure-sensitive adhesive layer is a polyester resin. At least a laminate product having a pressure-sensitive adhesive layer having a toner image and a substrate for holding the pressure-sensitive adhesive layer,
The laminate material according to any one of claims 8 to 15 is used to produce the laminate product according to any one of claims 1 to 7. Laminated product.

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