JP5598277B2 - Foil transfer surface forming toner, foil transfer method, and foil transfer surface forming toner manufacturing method - Google Patents

Description

  The present invention provides a foil transfer surface forming toner (hereinafter also simply referred to as a toner) used to form a layer referred to as a foil transfer surface that is supplied to a location on a product where the foil is transferred, and the toner. The present invention relates to the foil transfer method used.

  For example, in the field of bookbinding, commercial printing, card business, or plastic molding such as cosmetic containers, a processing technique called “foil stamping” is performed. This technology, also called the “hot stamping method”, applies heat and pressure using a metal stamping die to transfer characters and patterns made of foil onto the surface of the product. A glossy high-quality image can be given. Recently, foil transfer technology has also been developed for holograms provided for the purpose of preventing falsification and security of cash cards and credit cards.

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

  On the other hand, a method of performing foil transfer without taking time and labor has been studied, and a technique for forming a resin layer on a substrate using toner and transferring the foil thereon has been studied. Specifically, a convex image or a design pattern image is formed on a substrate using a toner, a transfer foil is superimposed on the toner image surface, and thermocompression bonding is performed to transfer the foil (for example, (See Patent Document 4). In addition, a sample with toner attached to the base material is prepared, a vapor-deposited foil sheet is stacked on the sample, hot pressed with an iron from the upper layer, and then the metal foil is removed simply by peeling the vapor-deposited foil sheet from the base material. There is also a technique that enables transfer (see, for example, Patent Document 5). In these techniques, since the transfer of the foil can be performed quickly without using a metal crimping member called a pressing die, the time required for the foil transfer operation is shortened and the configuration of the foil transfer device is simplified.

JP-A-9-1995 JP 2007-157159 A JP 2009-90464 A Japanese Patent Laid-Open No. 1-200985 JP 2000-127691 A

  By the way, in the technique of transferring a foil using toner, when the foil transferred onto the toner layer is closely observed, many problems remain in the finish and strength. Specifically, the transfer foil cannot be completely peeled off from the release agent layer, and the foil has been missing in some places. was there. In this way, there was a tendency that sufficient adhesive force was not applied to the foil transferred onto the toner layer, and the cause was considered to be the influence of the wax contained in the toner.

  The wax in the toner is added to prevent the base material from being wound around the fixing roller when forming the toner layer, and is often designed to quickly elute on the surface of the toner layer during fixing. Therefore, it was considered that a wax layer was formed on the surface of the toner layer, and this wax layer hindered adhesion between the foil and the toner layer. In the technology for transferring foil using the toner described above, there is no description suggesting that the adhesiveness of the foil is affected by the effect of the wax contained in the toner. It can be said that it was hardly done.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a foil transfer surface forming toner that can firmly adhere a transfer foil to the surface of a toner layer without being affected by the wax. To do. In other words, when transferring a foil onto a foil transfer surface formed using a toner containing wax, the transfer of the foil so that a good finish can be obtained without occurrence of missing or burrs of the foil on the foil transfer surface. An object of the present invention is to provide a toner capable of performing the above. It is another object of the present invention to provide a foil transfer surface forming toner that allows the foil transferred onto the foil transfer surface to be firmly adhered over a long period of time without peeling off over time. Furthermore, when forming a foil transfer surface by electrophotographic image formation, the foil transfer surface can be appropriately leached out of the wax onto the foil transfer surface, and the foil transfer surface can be smoothly formed without causing winding or the like. An object is to provide a toner for surface formation.

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 toner for forming a foil transfer surface containing a resin and a wax,
The foil transfer surface forming toner is:
Having a phase separation structure in which a wax domain phase is dispersed in a matrix phase of the resin;
The toner for forming a foil transfer surface, wherein an average domain diameter of the wax domain phase is 0.1 μm or more and 2.0 μm or less. ].

The invention described in claim 2
2. The foil transfer surface forming toner according to claim 1, wherein the resin is formed using at least a vinyl monomer having a plurality of polar groups. ].

The invention according to claim 3
3. The foil transfer surface forming toner according to claim 1, wherein the polar group is a carboxyl group (—COOH). ].

The invention according to claim 4
The foil transfer surface according to any one of claims 1 to 3, wherein the vinyl monomer having a plurality of polar groups is any of itaconic acid, maleic acid, fumaric acid, and aconitic acid. Toner for forming. ].

The invention described in claim 5
The foil transfer surface forming toner according to any one of claims 1 to 4, wherein the vinyl monomer having a plurality of polar groups is itaconic acid. ].

The invention described in claim 6
"at least,
Exposing the photoreceptor to form an electrostatic latent image;
Supplying toner to the photoconductor on which an electrostatic latent image is formed to form a foil transfer surface;
Transferring the foil transfer surface formed on the photoreceptor to a product;
Fixing the foil transfer surface transferred to the product onto the product;
Supplying a transfer foil having at least an adhesive layer to the product on which the foil transfer surface is fixed;
Bringing the adhesive layer of the transfer foil into contact with the foil transfer surface;
Heating with the adhesive layer of the transfer foil in contact with the foil transfer surface; and
A foil transfer method comprising a step of removing the transfer foil from the product,
The toner used for forming the foil transfer surface is:
Contains at least resin and wax,
Having a phase separation structure in which a wax domain phase is dispersed in a matrix phase of the resin;
The foil transfer method, wherein an average domain diameter of the wax domain phase is 0.1 μm or more and 2.0 μm or less. ].

The invention described in claim 7
The foil transfer method according to claim 6, wherein the resin is formed using at least a vinyl monomer having a plurality of polar groups. ].

The invention according to claim 8 provides:
The foil transfer method according to claim 6 or 7, wherein the polar group is a carboxyl group (-COOH). ].

The invention according to claim 9 is:
The foil transfer method according to any one of claims 6 to 8, wherein the vinyl monomer having a plurality of polar groups is any one of itaconic acid, maleic acid, fumaric acid, and aconitic acid. . ].

The invention according to claim 10 is:
The foil transfer method according to any one of claims 6 to 9, wherein the vinyl monomer having a plurality of polar groups is itaconic acid. ].

The invention according to claim 11 is
“The method for producing a toner for forming a foil transfer surface according to claim 1, comprising at least a resin and a wax,
The foil transfer surface forming toner is at least
In an aqueous medium, the resin particles are formed through a plurality of times of polymerization and the resin particles are aggregated and fused in the aqueous medium.
The step of forming the resin particles through the plurality of times of polymerization, at least,
A step of polymerizing a polymerizable monomer containing wax to form wax-containing resin particles; and a polymerization of the polymerizable monomer in the presence of the wax-containing resin particles to form a resin on the surface of the wax-containing resin particles And a step of forming resin particles by forming a layer. A method for producing a toner for forming a foil transfer surface. ].

The invention according to claim 12
“The amount of polymerizable monomer used in the step of forming a resin layer on the surface of the wax-containing resin particles is 2.5 times the amount of polymerizable monomer used in the step of forming the wax-containing resin particles. The method for producing a toner for forming a foil transfer surface according to claim 11, wherein the toner content is 3.8 times or less. ].

The invention according to claim 13
12. The method for producing a toner for forming a foil transfer surface according to claim 11, wherein a vinyl monomer having at least a plurality of polar groups is used in the step of forming the wax-containing resin particles. ].

  In the present invention, the average domain diameter of the wax dispersed in the resin matrix phase is defined for the toner used for forming the foil transfer surface. By forming a foil transfer surface that transfers the foil using toner of such a configuration, it is possible to transfer the foil stably without being affected by wax when transferring the foil onto the foil transfer surface. I made it.

  In other words, as shown in the evaluation results of the examples described later, it becomes possible to bond the foil over the entire surface of the foil transfer surface, so that the foil can be transferred without causing local omission of the foil or generation of burrs. Became. It was also confirmed that the foil can be accurately transferred onto the line image surface composed of fine fine lines.

  In addition, after transferring the foil onto the foil transfer surface, the state where the foil is adhered to the entire surface of the foil transfer surface is stably maintained, and the foil does not detach from the transfer surface over time, and the aesthetics of the product using the foil Durability to the appearance can be greatly improved. Furthermore, when the foil transfer surface is formed by using the toner by electrophotography, an appropriate leaching of wax is obtained on the foil transfer surface, so that a necessary separation performance level can be maintained. Therefore, the substrate on which the foil transfer surface is formed does not wrap around the fixing roller and causes poor conveyance, and the foil transfer surface can be formed smoothly.

FIG. 3 is a schematic diagram showing a cross-sectional structure of a foil transfer surface forming toner having a structure in which a wax domain phase is dispersed in a resin matrix phase. It is a schematic diagram which shows the procedure which transcribe | transfers foil on the foil transcription | transfer surface formed on the product. It is the schematic of the foil transfer surface formation apparatus which forms a foil transfer surface by an electrostatic latent image system. It is a cross-sectional block diagram of the foil transfer surface formation apparatus which can form foil transfer surface and full color image formation simultaneously. FIG. 3 is a schematic diagram illustrating an arrangement example of an intermediate transfer belt, a fixing device, and a transfer foil supply unit. It is a schematic diagram which shows the cross-section of transfer foil. It is a schematic diagram of the foil image sample used by evaluation of an Example.

  The present invention provides a foil transfer surface forming toner (hereinafter simply referred to as toner) that forms a layer called a foil transfer surface at a location where a foil on a product is transferred, and that transfers the foil onto the layer and contributes to improving the aesthetic appearance. In particular, the toner contains a wax.

  The present inventor has described that the toner for forming a foil transfer surface “has a phase separation structure in which a wax domain phase is dispersed in a resin matrix phase, and an average domain diameter of the wax domain phase is 0.1 μm or more and 2.0 μm. It has been found that the above-mentioned problems can be solved by setting the following. The reason why the adhesion of the transfer foil is improved on the formed foil transfer surface by the toner according to the present invention is considered as follows. That is, by setting the average domain diameter of the wax contained in the toner within the above range, the wax that has eluted during formation of the foil transfer surface is present in a finely dispersed state on the surface of the foil transfer surface. As a result, it is considered that a large number of contact surfaces between the transfer foil and the resin phase can be secured on the surface of the foil transfer surface. In other words, because the wax is finely dispersed, the contact points between the transfer foil and the resin phase are distributed evenly and uniformly on the surface of the transfer foil, although the individual areas are small, the individual contacts are like spot welding. This is probably because the transfer foil is held on the entire surface of the foil transfer surface.

  Here, a specific method for controlling the size of the wax domain phase of the toner for forming the foil transfer surface will be described. As one of the factors that make it possible to finely disperse the wax on the surface of the foil transfer surface, for example, the presence of polar groups present in the monomer unit side chain constituting the resin molecule can be considered. That is, if there are many polar groups in the monomer unit side chain, the effect of hydrogen bonds formed between these polar groups increases, and the wax that has eluted on the surface of the foil transfer surface is united by the influence of hydrogen bonds. Be disturbed. As a result, it is considered that the wax eluted on the surface of the foil transfer surface exists in a finely dispersed state.

  Further, the ratio of the wax-containing resin layer of the resin particles constituting the toner is also considered as a factor for controlling the size of the wax domain phase of the foil transfer surface toner. That is, when resin particles are formed by a multistage polymerization method, first, monomers are polymerized in the presence of wax to form wax-containing resin particles. Subsequently, by introducing a monomer in the presence of the wax-containing resin particles and performing a polymerization reaction, a resin layer containing no wax can be formed on the surface of the wax-containing resin particles. Thus, resin particles having a structure having a wax-containing resin layer and a resin layer not containing wax can be formed using a multistage polymerization method. Then, resin particles are formed by reducing the amount of monomer used in the polymerization reaction initially performed in the presence of wax to be smaller than the amount of monomer used in the polymerization reaction performed in the presence of wax-containing resin particles. In this resin particle, since the resin layer that does not contain the wax formed in the second polymerization reaction affects the wax-containing resin layer, the more the monomer used in the second polymerization reaction, the more the wax-containing resin Since the ratio of the layers is lowered, the size of the wax domain phase of the toner formed by aggregation and fusion is considered to be small. This will be specifically described in an embodiment described later.

  For these reasons, it is considered that the adhesion of the transfer foil is improved on the surface of the foil transfer surface formed with the toner according to the present invention.

  Further, the foil transfer surface formed with the toner according to the present invention is in a state in which the wax is finely dispersed over the entire surface, so that it is considered that the releasability due to the wax is sufficiently expressed. In this manner, the foil transfer surface formed by the electrophotographic image forming method can be fixed under the condition that the releasability of the wax is sufficiently developed, so the foil transfer surface can be attached to the fixing device member. It is thought that it is difficult to cause winding.

  Hereinafter, the present invention will be described in detail.

  The “foil transfer surface forming toner” as used in the present invention is used in a region where a foil is transferred when forming a foil on a product such as an image support on which an image is formed or a plastic molded product such as an ID card. It is a resin powder. The foil transfer surface forming toner reinforces and maintains the adhesion of the transfer foil on the product via the toner layer formed on the product. Specifically, first, a toner is supplied to a photosensitive member on which an electrostatic latent image having the same shape as the shape of the foil formed on the product is formed, and the foil is transferred onto the product on the photosensitive member. A layer (foil transfer surface) is formed. The toner layer formed on the photoreceptor is transferred onto the product and subjected to a fixing process by heating. Next, the transfer foil is supplied to the product on which the toner layer fixed by the fixing process is formed, and when the heat treatment is performed in a state where the product and the transfer foil are in contact, the foil adheres to the toner layer. When the transfer foil is removed, the foil is transferred and fixed onto the toner layer, and a foil pattern is formed on the product.

  As described above, the “foil transfer surface forming toner” referred to in the present invention is supplied onto the photoreceptor to form a toner layer called a foil transfer surface. The foil transfer surface on the photoreceptor formed by the toner for forming a foil transfer surface according to the present invention is transferred and fixed onto a sheet-shaped product typified by an image support. Further, the foil transfer surface fixed on the product is supplied with the transfer foil and, when heated, adheres firmly to the foil for transfer.

  In addition, the “foil transfer surface” in the present invention is a region where a foil on a product such as an image support or a plastic molded product is transferred, and is formed using the toner according to the present invention.

  Further, in the present invention, the terms “product” and “substrate” are used, and both are constituted by a support called an “image support” capable of forming an image by a known image forming method. Is. Here, the “product” in the present invention refers to a product in which at least a foil is transferred onto a “substrate” and decorated with the foil. The “substrate” as used in the present invention refers to an image support such as paper or PET (polyethylene terephthalate) base, or a three-dimensional shape such as a plastic molded product, which is before being decorated with foil. is there.

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

  The toner for forming a foil transfer surface according to the present invention will be described. The toner according to the present invention contains at least a resin and a wax, and has a structure in which a wax domain phase having an average domain diameter of 0.1 μm or more and 2.0 μm or less is dispersed in a resin matrix phase. As the resin forming the matrix phase, at least one formed using a vinyl monomer having a plurality of polar groups is preferably used.

  FIG. 1 shows a cross-sectional structure of the toner for forming a foil transfer surface according to the present invention. The toner T shown in FIG. 1 has a so-called phase separation structure or a domain matrix structure in which a wax domain phase D is dispersed in a matrix phase M which is a continuous phase. The domain phase D of the wax dispersed in the toner particles T has an average domain diameter of 0.1 μm or more and 2.0 μm or less.

  By setting the average domain diameter within the above range, the aggregation (also referred to as coalescence) of the wax eluted on the surface of the foil transfer surface formed by the toner is suppressed, and the foil transfer surface is good for the transfer foil. This makes it possible to develop adhesive performance. In other words, the wax is dispersed finely and uniformly on the surface of the foil transfer surface, and the resin phase also appears uniformly on the entire surface of the foil transfer surface, so that the adhesion between the resin and the transfer foil is uniform on the entire surface of the foil transfer surface. Will be expressed in any state.

  As a result, when transferring the transfer foil to the surface of the foil transfer surface, the transfer foil is firmly held on the surface of the foil transfer surface, so that the transfer can be performed without losing the foil. Further, since the adhesive force between the transferred foil image and the foil transfer surface does not decrease with time, the foil image can stably maintain the adhesion over a long period of time without peeling from the foil transfer surface.

  In addition, when a foil transfer surface is formed on a substrate using the toner, it is possible to appropriately exhibit a release property on the foil transfer surface, so that the substrate does not wrap around a fixing device constituting member such as a roller. In addition, the foil transfer surface can be formed smoothly.

  As described above, the toner according to the present invention has a good finish because the transfer foil is held on the entire surface of the foil transfer surface and can be transferred without losing the foil by setting the average domain diameter of the wax component in the above range. It is possible to form a foil image. In addition, the foil image transferred to the foil transfer surface maintains its adhesiveness with the resin over a long period of time, so there is no detachment from the foil transfer surface due to a decrease in adhesive strength over time, and the product quality is maintained over a long period of time. Is possible. Furthermore, the toner according to the present invention disperses the wax finely and uniformly on the entire surface of the formed foil transfer surface when forming the foil transfer surface on the substrate, so that the releasability of the wax is sufficiently ensured, and the fixing device It is possible to form a foil transfer surface smoothly without causing winding around the member.

  In the toner according to the present invention, the average domain diameter of the wax can be controlled, for example, by adding a vinyl monomer having a plurality of polar groups described later. For example, it is possible to reduce the wax domain diameter by adding more vinyl monomers having a plurality of polar groups, and increasing the domain diameter by reducing the amount of vinyl monomers having a plurality of polar groups. Is possible.

  For example, the reason why the wax domain diameter is controlled by controlling the amount of vinyl monomer having a plurality of polar groups, etc., is that wax aggregation (also referred to as coalescence) due to the strength of hydrogen bonds formed between polar groups. ) Is affected. That is, there is an electric bias due to the polar group in the molecular chain constituting the resin, and a hydrogen bond is formed between the molecular chains constituting the resin by the action of the dipole moment resulting from this. In the region where hydrogen bonds exist, aggregation of molecular chains constituting the resin proceeds, but it is considered that the aggregation (unification) of wax acts in a direction to be inhibited.

  Therefore, it is considered that when the amount of the vinyl monomer having a plurality of polar groups is increased, the hydrogen bond density is increased, the aggregation of the wax component is inhibited, and the domain diameter is reduced. On the other hand, when the amount of the vinyl monomer having a plurality of polar groups is reduced, the hydrogen bond density is lowered, and aggregation of the wax component is promoted to increase the domain diameter. By such a mechanism, it is considered that the domain diameter of the wax is controlled by the presence of a factor that controls the hydrogen bond density, such as a vinyl monomer having a plurality of polar groups.

  The average domain diameter of the wax of the toner according to the present invention can be calculated, for example, by observing the cross-sectional structure of the toner particles with a transmission electron microscope (TEM) or the like. Here, a method for measuring and calculating the average domain diameter of the wax in the toner particles using a transmission electron microscope (TEM) will be described. Measurement of the average domain diameter of the wax of the toner for forming the foil transfer surface with a transmission electron microscope is, for example, the following procedure for preparing a sample, photographing the prepared sample with a transmission electron microscope, and taking an electron micrograph obtained by photographing It can be calculated from the image.

  First, the toner was sufficiently dispersed in a room temperature curable epoxy resin, embedded, dispersed in a styrene fine powder having a particle size of about 100 nm, and then pressure-molded to contain a toner for forming a foil transfer surface. Create a block. If necessary, the prepared block is dyed with ruthenium tetroxide or osmium tetroxide, if necessary, and then cut into a 200-nm-thick flake using a microtome with diamond teeth. To prepare a measurement sample.

  The measurement sample thus thinned is set on a transmission electron microscope (TEM), and a photograph is taken of the cross-sectional structure of the foil transfer surface forming toner. At this time, the magnification of the electron microscope is preferably set to a magnification that allows the cross section of one toner particle to enter the field of view. Specifically, photographing is performed with the negative magnification set to 280 times, and the photographed image is stretched to create a photographic image with a magnification of 12,000 times. Then, the created photographic image with a magnification of 12,000 times is analyzed using a commercially available image processing apparatus “Luzex III (manufactured by Nireco)” to calculate the average domain diameter of the wax. Here, the “average domain diameter” is equivalent to, for example, the domain diameter of each domain phase existing in 20 toner particles for forming a foil transfer surface when the created photographic image is analyzed by the image processing apparatus. The diameter is calculated, and the average value is defined as “average domain diameter”.

  In addition, as a specific model of the transmission electron microscope capable of observing the domain phase of the toner for forming the foil transfer surface, for example, “LEM-2000 type (manufactured by Topcon Corporation)” or “JEM-2000FX (manufactured by JEOL Ltd.) ) "And the like.

  Next, the “vinyl monomer having a plurality of polar groups” which is preferably used when forming the resin constituting the toner for forming a foil transfer surface according to the present invention will be described. As described above, the resin constituting the toner for forming a foil transfer surface according to the present invention is required to express a physical factor that enables control of a wax domain diameter such as a hydrogen bond density between molecular chains. For example, a resin formed using “a vinyl monomer having a plurality of polar groups” is preferable because it is considered that the wax domain diameter can be controlled by hydrogen bonding between molecular chains as described above. .

Here, the “polar group” in the “vinyl monomer having a plurality of polar groups” means that there is an electric bias between atoms due to the difference in electronegativity of each atom constituting the group. It is a functional group to be obtained. Specifically, the functional group contains an oxygen atom, a nitrogen atom, etc., and a hydroxyl group (—OH), a carbonyl group (—C═O), a carboxyl group (—COOH), an amino group (—NH ₂ ), There are a nitro group (—NO ₂ ), a sulfonyl group (—SO ₃ H), a cyano group (—CN), and the like. Further, the “vinyl monomer” means at least one pair of unsaturated bonds between carbon atoms such as a vinyl group (CH ₂ ═CH—) in the molecular structure, and this carbon atom unsaturation under a polymerization initiator. An organic compound capable of forming a polymer by performing an addition reaction through a bond.

  As the “vinyl monomer having a plurality of polar groups” preferably used in forming the foil transfer surface forming toner according to the present invention, for example, a vinyl monomer having a plurality of carboxyl groups (—COOH) is preferably used. It is representative of things. Specific examples of the vinyl monomer having a plurality of carboxyl groups (—COOH) include, for example, itaconic acid, maleic acid, fumaric acid and the like having two carboxyl groups, and aconitic acid having three carboxyl groups. Specific examples of vinyl monomers having a plurality of carboxyl groups are shown below.

  In the present invention, among the vinyl monomers having a plurality of polar groups, a toner made of a resin formed using itaconic acid, maleic acid, and aconitic acid is more preferable, and a toner made of a resin formed using itaconic acid is more preferable. Particularly preferred.

  Further, as described above, when the addition amount of the vinyl monomer having a plurality of polar groups is small, the toner particles to be formed have a large domain phase, and when the addition amount is large, a toner having a small domain phase is formed. be able to. In the present invention, when the resin is formed using a vinyl monomer having a plurality of polar groups, the addition amount is more preferably 0.1% by mass to 5% by mass with respect to the total amount of the vinyl monomer. It is especially preferable to set it as 4 mass%-2.5 mass%.

  Next, a vinyl monomer that can be used in combination with the above-described vinyl monomer having a plurality of polar groups when producing the resin constituting the toner for forming a foil transfer surface according to the present invention will be described. When the resin constituting the toner for forming the foil transfer surface is produced, when a “vinyl monomer having a plurality of polar groups” is used, a known vinyl monomer can be used in combination.

  Specific examples of vinyl monomers that can be used are shown below, but vinyl monomers that can be used for the production of the resin constituting the toner for forming a foil transfer surface according to the present invention are limited to those shown below. is not.

(1) Styrene or styrene derivatives Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-tert- Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, etc. (2) Methacrylate derivatives Methyl methacrylate, methacryl Ethyl acetate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethyl methacrylate Aminoethyl, dimethylaminoethyl methacrylate, etc. (3) Acrylic acid ester derivatives 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. (4) olefins ethylene, propylene, isobutylene, etc. (5) vinyl esters vinyl propionate, vinyl acetate, vinyl benzoate, etc. (6) vinyl ether (7) Vinyl ketones Vinyl methyl ketone, vinyl ethyl ketone, vinyl hexyl ketone, etc. (8) N-vinyl compounds N-vinyl carbazole, N-vinyl India (9) Others Vinyl compounds such as vinyl naphthalene and vinyl pyridine, acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

It is also possible to produce a resin having a crosslinked structure using the polyfunctional vinyls shown below. Specific examples of the polyfunctional vinyls are shown below. That is,
Divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, etc. The clear toner is not particularly limited as long as it can stably exhibit the performance as a clear toner. For example, a number average molecular weight Mn of 5,000 or more and 50,000 or less is preferable. The ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn is, for example, one that is preferably 1.0 or more and 1.5 or less. When the number average molecular weight Mn and the weight average molecular weight Mw of the resin constituting the toner satisfy the above relationship, a sharp melting property is expressed at the time of fixing, which is preferable in promoting solidification by melting and cooling of the toner.

  Next, the wax used for the toner for forming a foil transfer surface according to the present invention will be described. As described above, the toner for forming a foil transfer surface according to the present invention has a phase separation structure in which a wax domain phase having an average domain diameter of 0.1 μm or more and 2.0 μm or less is dispersed, and is composed of a resin component. In this case, a domain phase composed of a wax component is dispersed in the matrix phase.

The wax that can be used in the toner for forming a foil transfer surface according to the present invention is not particularly limited as long as it can form a phase separation structure with a resin component, and a known wax is used. Is possible. Specific examples of the wax that can be used in the toner for forming a foil transfer surface according to the present invention are shown below, but the wax that can be used in the present invention is not limited to the following.
(1) Hydrocarbon wax Polyolefin wax such as paraffin wax, polyethylene wax, polypropylene wax, sazol wax, etc. (2) Ester wax Trimethylolpropane tribehenate, pentaerythritol tetramyristate, pentaerythritol tetrastearate, Pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecanediol distearate, tristearyl trimellitic acid, distearyl maleate, etc. (3) Amide wax ethylenediamine di Behenylamide, trimellitic acid tristearylamide, etc. (4) dialkyl ketone waxes, distearyl ketone, etc. (5) other carnauba wax, Down Tan wax and the like.

  Among the waxes described above, “hydrocarbon wax” is composed of a molecular chain having nonpolar properties, so that it exhibits good incompatibility with a resin phase having a polar part in some places, and has a predetermined particle size. It is considered that it acts advantageously in forming the domain phase.

  The hydrocarbon wax that can be used in the toner for forming a foil transfer surface according to the present invention includes a linear hydrocarbon compound, a branched hydrocarbon compound, and a hydrocarbon having a cyclic structure on the molecular structure. There are compounds.

  The linear hydrocarbon compound includes, for example, petroleum wax composed mainly of paraffin wax called normal paraffin, and polyolefin wax such as Fischer-Trops wax, polyethylene wax and polypropylene wax. Here, the paraffin wax is obtained by separating from a vacuum distilled oil by a known method. Fischer-Tropx wax is a hydrocarbon compound having 16 to 78 carbon atoms obtained from distillation of hydrocarbons synthesized from synthesis gas consisting of carbon monoxide and hydrogen, or hydrogenation of these. It is. Furthermore, polyethylene wax and polypropylene wax are obtained by polymerization of ethylene and propylene and thermal decomposition of polyethylene and polypropylene.

  Next, examples of the branched hydrocarbon compound and the hydrocarbon compound having a cyclic structure on the molecular structure include the following microcrystalline wax and wax mainly composed of isoparaffin. Specific examples of the microcrystalline wax include, for example, HNP-0190, Hi-Mic-1045, Hi-Mic-1070, Hi-Mic-1080, Hi-Mic-1090, Hi-Mic-2045, Hi-Mic-2065. , Hi-Mic-2095, etc. (all manufactured by Nippon Seiwa Co., Ltd.). Here, the microcrystalline wax is a wax having a high proportion of a branched hydrocarbon compound called isoparaffin or a cyclic hydrocarbon compound called cycloparaffin as a main component in petroleum wax. Since microcrystalline wax contains a large amount of low crystalline isoparaffin and cycloparaffin, it has smaller crystals and higher molecular weight than paraffin wax. The microcrystalline wax generally has 60 to 150 carbon atoms, a number average molecular weight Mn of 900 to 2,000, and a melting point of 60 to 90 ° C.

  Specific examples of the wax mainly composed of isoparaffin include EMW-0001 and EMW-0003.

  The melting point of the wax is usually preferably 40 to 160 ° C. By making the melting point of the wax within the above range, melting by heating can be performed quickly and uniformly, and a wax film having a uniform thickness is formed on the surface of the clear toner layer. Therefore, it is considered that it works advantageously. Further, by setting the melting point of the wax to 50 to 120 ° C., preferably 60 to 90 ° C., it is possible to achieve good wax melting even at a low heating temperature, and to reduce energy consumption when forming the clear toner layer. . Further, the wax content in the clear toner is preferably 1% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.

  Next, a method for producing the foil transfer surface forming toner according to the present invention will be described.

  The method for producing the toner for forming a foil transfer surface according to the present invention is not particularly limited, and a toner production method used for image formation of a known electrophotographic system can be applied. Specifically, a toner by a so-called pulverization method in which a toner is prepared through a kneading, pulverization, and classification process, or a so-called polymerization method in which a polymerizable monomer is polymerized and particles are formed while simultaneously controlling the shape and size. By applying the production method, the toner for forming a foil transfer surface according to the present invention can be produced.

  As described above, the foil transfer surface forming toner according to the present invention has the wax domain phase having the above-mentioned average domain diameter in the resin matrix phase. As a method for controlling the size of the domain phase of the wax component of the foil transfer surface forming toner, for example, as described above, the addition amount of “vinyl monomer having a plurality of polar groups” is controlled. .

  As a preferred method for producing toner particles while making the size of the domain phase of the wax uniform in the toner production process, for example, a polymerization method is exemplified. The toner production method using a polymerization method includes a step of forming resin particles by a polymerization reaction such as suspension polymerization or emulsion polymerization. Among toner production methods based on polymerization, a production method having an association step in which resin particles formed by suspension polymerization or emulsion polymerization are aggregated and fused to form toner base particles is particularly preferable.

  Hereinafter, as an example of a method for producing a toner for forming a foil transfer surface according to the present invention, a method for producing a toner for forming a foil transfer surface by an emulsion association method will be described. A method for producing a toner for forming a foil transfer surface by an emulsion association method is performed, for example, through the following steps.

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

(1) Preparation Step of Resin Particle Dispersion This step is a step of forming a resin constituting the foil transfer surface forming toner. Specifically, for example, after adding a vinyl monomer such as the vinyl monomer having a plurality of polar groups described above to an aqueous medium, dispersion treatment is performed to form oil droplets of the monomer, and emulsification is performed in this state. A polymerization reaction is performed to form resin particles having a size of about 100 nm.

  That is, after adding a vinyl monomer such as a vinyl monomer having a plurality of polar groups in an aqueous medium, an emulsion dispersion treatment is performed to form oil droplets of the vinyl monomer, and in the oil droplets formed in the aqueous medium Resin particles are formed by performing a radical polymerization reaction. In this step, it is also possible to add a vinyl monomer dissolved in a wax to an aqueous medium and perform a dispersion treatment to form oil droplets of the vinyl monomer containing the wax. Thus, it is also possible to form resin particles containing wax by carrying out radical polymerization reaction in oil droplets of vinyl monomer containing wax.

  The oil droplets of the vinyl monomer are formed by applying mechanical energy to the aqueous medium to which the vinyl monomer is added by a known method and performing a dispersion treatment. A dispersion apparatus for forming oil droplets by applying mechanical energy to an aqueous medium is not particularly limited. For example, a commercially available stirring apparatus “CLEARMIX” (M Technique Co., Ltd.) having a rotor that rotates at a high speed is used. ))) Etc. is a typical apparatus. In addition to the agitating device described above, known dispersing devices such as an ultrasonic dispersing machine, a mechanical homogenizer, a manton gourin, and a pressure homogenizer can be mentioned. By these dispersing devices, oil droplets of about 100 nm are formed in an aqueous medium. It is possible to disperse.

  The radical polymerization reaction is a method in which a polymerization initiator is contained in the above-mentioned vinyl monomer oil droplets to generate radicals, and the vinyl monomer polymerization reaction is performed in the oil droplets. Resin particles are formed by the radical polymerization reaction. It is what is done. Alternatively, there is a method in which a polymerization initiator is added to an aqueous medium, and radicals generated from the polymerization initiator are supplied into oil droplets to start a radical polymerization reaction.

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

  The above-mentioned “aqueous medium” is a liquid composed of water and an organic solvent soluble in water, and contains at least 50% by mass of water. Examples of the organic solvent that can be dissolved in water constituting the aqueous medium include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. Among these, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol are preferred because they do not cause dissolution of the formed resin.

  As described above, the resin particles forming the toner according to the present invention are polymerized for the first time in the presence of wax to form a wax-containing resin layer, and then a monomer is added in the presence of the wax-containing resin layer. And it is preferable to produce through the process of performing the 2nd polymerization. In this manner, a method of forming resin particles by performing a plurality of polymerization reactions stepwise is called multistage polymerization. By performing multistage polymerization, for example, it becomes possible to form a wax-containing region at the center of the formed resin particles and a region not containing wax on the particle surface.

  By using resin particles in which a wax-containing region is defined by a multistage polymerization method, the size of the wax domain phase of the toner can be controlled as described in Examples described later. From such a viewpoint, it is preferable to form the resin particles using a multistage polymerization method such as a two-stage polymerization method or a three-stage polymerization method. Hereinafter, the two-stage polymerization method which is one of the multistage polymerization methods will be described.

<Two-stage polymerization method>
The two-stage polymerization method is a method for producing resin particles having two regions, for example, resin particles having a central portion composed of a resin containing wax and an outer layer composed of a resin not containing wax. is there. In the two-stage polymerization method, resin particles are formed by performing two polymerization reactions of first-stage polymerization and second-stage polymerization.

  For example, when a toner that defines the size of the wax domain phase is prepared, a polymerizable monomer to which a wax is first added is prepared in order to form resin particles used for the preparation of the toner. Then, mechanical energy is imparted to the aqueous medium to form oil droplets of the polymerizable monomer. Then, the oil droplets of the polymerizable monomer containing the wax are polymerized as described above (first-stage polymerization) to produce a resin particle dispersion containing the wax.

  Next, a polymerization initiator and a polymerizable monomer are added to the produced wax-containing resin particle dispersion, and polymerization of the polymerizable monomer (second-stage polymerization) is performed in the presence of the wax-containing resin particles. . In this way, the resin phase having no wax can be coated on the surface of the wax-containing resin particles to form resin particles having a two-layer structure.

(2) Aggregation / fusion process of resin particles (association process)
In this step, the resin particles formed in the above-described step are aggregated in an aqueous medium to form particles, and the particles formed by aggregation are heated and fused to form particles (base of clear toner before external addition treatment) This is a process for producing particles) and is also called an association process. In other words, particles are produced by agglomerating and fusing resin particles formed by emulsion polymerization of a vinyl monomer having a plurality of polar groups and another vinyl monomer.

  In this step, the resin particles are aggregated by adding an aggregating agent such as an alkali metal salt or an alkaline earth metal salt typified by magnesium chloride into the aqueous medium in which the resin particles are present. Next, the water-based medium is heated to a temperature equal to or higher than the glass transition temperature of the resin particles to advance the aggregation, and at the same time, the aggregated resin particles are fused together. And when aggregation is advanced and the particle | grain size becomes a target, salt, such as salt, is added and aggregation is stopped.

  When the toner for forming a foil transfer surface according to the present invention is produced, it is necessary to include a wax component in the toner particles. When the resin particles containing the wax component described above are used, the resin particles are aggregated and fused as they are to form particles. When using the resin particles not containing the wax component, both the resin particles are waxed together. Aggregation and fusion are performed by adding particles. In this case, a wax particle dispersion is prepared in advance, and this is added to the resin particle dispersion for aggregation and fusion. The wax particle dispersion is formed by adding a wax to an aqueous medium and then carrying out a dispersion process by the action of mechanical energy by a known method, as in the case of forming the above-mentioned vinyl monomer oil droplets. It is a dispersion of wax particles of about 100 nm.

(3) Ripening step This step is a so-called shape control step in which the reaction system is heat-treated subsequent to the aggregation / fusion step to ripen the particle shape to a desired average circularity.

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

(5) Washing step This step includes a step of solid-liquid separation of the particles from the particle dispersion liquid cooled to a predetermined temperature in the above step, and a cake-like aggregate called a wet toner cake that has been solid-liquid separated. It comprises a washing step for removing deposits such as surfactants and coagulants from the particles.

  In the washing treatment, the filtrate is washed with water until the electric conductivity of the filtrate becomes, for example, about 10 μS / cm. Examples of the solid-liquid separation method include a centrifugal separation method, a vacuum filtration method using Nutsche and the like, a filtration method using a filter press and the like, and are not particularly limited in the present invention.

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

  The moisture of the dried particles is preferably 5% by mass or less, more preferably 2% by mass or less. In addition, when the dried particles are aggregated due to weak interparticle attractive force, the aggregate may be crushed. Here, as the crushing processing apparatus, a mechanical crushing apparatus such as a jet mill, a Henschel mixer, a coffee mill, or a food processor can be used.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Next, a foil transfer method (hereinafter also referred to as a foil transfer method according to the present invention) performed using the toner for forming a foil transfer surface according to the present invention will be described. The foil transfer method according to the present invention includes at least the following steps (1) to (7). That is,
(1) Step of forming an electrostatic latent image by exposing the photoconductor (2) Forming a foil transfer surface by supplying the foil transfer surface forming toner according to the present invention to the photoconductor on which the electrostatic latent image is formed (3) The process of transferring the foil transfer surface formed on the photoreceptor to the product (4) The process of heating and fixing the foil transfer surface transferred onto the product (5) The foil transfer surface subjected to the fixing process (6) The step of bringing the adhesive layer of the supplied transfer foil into contact with the product (7) Heating the adhesive layer of the transfer foil and the foil transfer surface in contact with each other Process (8) It has the process of removing the transfer foil of the contacted state from the product. As described above, in the foil transfer method according to the present invention, first, an electrostatic latent image having the shape of the foil transfer surface formed on the product is formed by exposing the photoconductor to form the electrostatic latent image. The foil transfer surface forming toner according to the present invention is supplied to form a foil transfer surface. Then, the foil transfer surface formed on the photoreceptor is transferred to the product, and the foil transfer surface is heated and fixed, and the transfer foil is supplied and brought into contact with the product. Transfer the foil.

  The foil transfer method according to the present invention will be specifically described with reference to the drawings. FIG. 2 is a schematic diagram showing the procedure of the foil transfer method reflecting the steps (4) to (7) among the steps (1) to (7). That is, the transfer foil F is supplied to the product P in which the foil transfer surface H is formed on the base P manufactured through the steps (1) to (3) not shown in FIG. 2, and the supplied transfer foil F is supplied. Is brought into contact with the foil transfer surface H and heated in this state to transfer the foil f2 to the foil transfer surface H. Hereinafter, (a) to (d) shown in FIG. 2 will be specifically described.

  FIG. 2A is a cross-sectional view of a product P in which a foil transfer surface manufactured using the toner according to the present invention is formed on a sheet-like substrate P. A method for forming the foil transfer surface H on the substrate P through the steps (1) to (3) will be described later.

  Next, FIG. 2B shows a state in which the transfer foil F having at least the adhesive layer f1 is supplied to the product P, and the transfer foil F is formed so that the adhesive layer f1 is in contact with the foil transfer surface H. Supplied. At this time, the adhesive layer f1 of the supplied transfer foil F is assumed to be in contact with the entire surface of the product P, and a contact state is formed at least on the foil transfer surface H formed in a convex shape on the product surface. It can be said that. On the surface of the foil transfer surface H formed using the toner according to the present invention, it is presumed that a state of being easily attached to the adhesive layer f1 of the transfer foil F is formed by the action of the carboxyl group described above. The transfer foil F used in the present invention has at least an adhesive layer f1 and a foil layer f2 on a base film f0. Here, the layer configuration other than the adhesive layer f1 and the foil layer f2 is omitted. is there. A detailed description of the transfer foil F usable in the present invention will be given later.

  FIG. 2 (c) shows a state in which the transfer foil F is in contact with the product P and passes between the heating and pressure rollers R1 and R2 as heating means, and the adhesive layer f1 of the transfer foil F is the product. In the state where it is in contact with the foil transfer surface H on P, it passes between the heating and pressure rollers R1 and R2, which are heating means. By passing between the heating and pressing rollers R1 and R2, the adhesive layer f1 of the transfer foil F is melted, and after passing, the adhesive layer f1 is cooled and cured. At this time, the adhesive layer f <b> 1 in the region of the transfer foil F that is in contact with the foil transfer surface H forms a strong adhesive state with the foil transfer surface H. Thus, in the present invention, the transfer foil F forms an adhesive state with the foil transfer surface H through the adhesive layer f1 in contact with the foil transfer surface H formed in a convex shape on the product P. It is possible to transfer the foil layer f <b> 2 from the transfer foil F into a shape that faithfully corresponds to the shape of the foil transfer surface H.

  Next, FIG. 2D shows a state in which the transfer foil F is removed from the product P. When the transfer foil F is removed, the foil layer f2 is adhered only on the foil transfer surface H on the product P. It is transcribed with. Here, the foil layer f2 can be transferred to a shape corresponding to the shape of the foil transfer surface H by using the foil transfer surface forming toner according to the present invention, and without using a metal stamping die. It is possible to accurately transfer the foil layer f2 having a predetermined shape without causing chipping or burrs.

  Therefore, according to the present invention, a foil transfer device having a simple and compact configuration that does not have a metal stamping die can perform foil transfer of a predetermined shape without burrs or chips, and a high-quality foil can be obtained by a simple foil transfer device. It is possible to produce a product P having an image.

  Next, an example of a foil transfer surface forming apparatus capable of forming a foil transfer surface on a product performed by the foil transfer method according to the present invention will be described with reference to FIG. The foil transfer surface forming apparatus 1 in FIG. 3 is capable of performing the steps (1) to (3) among the steps (1) to (7) described above, and forms an electrostatic latent image by exposure. A foil transfer surface corresponding to the electrostatic latent image is formed by supplying a foil transfer surface forming toner according to the present invention to the photoconductor. Then, the formed foil transfer surface is transferred from the photoreceptor to the product.

  In the foil transfer surface forming apparatus 1 shown in FIG. 3, the exposure light L is irradiated onto the photoconductor 11H charged by the charging roller 12H in the drawing to form an electrostatic latent image. The electrostatic latent image formed on the photoconductor 11H is supplied with the foil transfer surface forming toner from the foil transfer surface forming toner supply device 21H disposed in the vicinity of the photoconductor 11H. Form. At this time, the toner supply roller 14 built in the foil transfer surface forming toner supply device 21H rotates, and the toner attached to the toner supply roller 14 is supplied to the photoconductor 11H, and the foil is transferred onto the photoconductor 11H. Form a surface.

  Next, when the charge on the photoconductor 11H is neutralized by the static elimination lamp 22, the foil transfer surface on the photoconductor 11H is on the substrate p1 constituting the product P at the transfer portion where the photoconductor 11H and the transfer roller 13H are close to each other. Is transferred to. The substrate p1 shown in FIG. 3 has a sheet shape typified by transfer paper, and is transported to a transfer portion by a transport roller 23 from a paper feed cassette (not shown), and has a charge opposite in polarity to the foil transfer surface forming toner by the transfer roller 13H. Is granted. The base p1 can transfer the foil transfer surface from the photoconductor 11H by the electrostatic action of the charge having the reverse polarity applied by the transfer roller 13H.

  The substrate p1 to which the foil transfer surface has been transferred is separated from the photoconductor 11H and then conveyed to a fixing device (not shown) by the conveyance belt 24. The fixing device has fixing means composed of, for example, a heating roller and a pressure roller, and melts and fixes the foil transfer surface formed on the substrate p1.

  With the above procedure, in the foil transfer surface forming apparatus 1 of FIG. 3, an electrostatic latent image corresponding to the shape of the foil is formed on the photoreceptor 11H, and the foil transfer surface forming toner is supplied to the foil on the photoreceptor 11H. A transfer surface is formed. The foil transfer surface formed on the photoconductor 11H is transferred to the base p1 constituting the product P by the transfer roller 13H.

  The charging roller 12H in the drawing can charge the photoconductor 11H, for example, by the following procedure. That is, the charging roller 12H is charged with the bias voltage composed of a direct current (DC) component and an alternating current (AC) component from the power source 27 to charge the photosensitive drum 11H. Charging using the charging roller 12 shown in FIG. 3 is called a so-called contact method. In the present invention, in addition to the charging method shown in FIG. 3, non-contact charging used in the apparatus shown in FIG. It is also possible to do this. Examples of the bias voltage applied to the charging roller 12H include a DC bias of ± 500 to 1000 V that is a DC component and an AC bias of 100 Hz to 10 kHz and 200 to 3500 V that are AC components. .

  The transfer roller 13H in FIG. 3 is also formed on the photoconductor 11H at the transfer site upon application of a bias voltage comprising a direct current (DC) component and an alternating current (AC) component from the power source 28, similarly to the charging roller 12H. The foil transfer surface is transferred onto the substrate p1. As a specific example of the bias voltage applied to the transfer roller 13H, as in the specific example of the bias voltage applied to the charging roller 12H, a DC bias of DC component ± 500 to 1000 V and an AC component of 100 Hz to 10 kHz, 200 to There is a superposition of 3500V AC bias.

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

  The photoconductor 11H having transferred the foil transfer surface to the base p1 is removed by the cleaning blade 25b provided in the cleaning device 25, so that the next foil transfer surface is formed.

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

  FIG. 4 is a cross-sectional configuration diagram of a foil transfer surface forming apparatus capable of forming the above-described foil transfer surface of FIG. 3 and forming an electrophotographic full-color image. The foil transfer surface forming apparatus shown in FIG. 4 has substantially the same configuration as the foil transfer surface forming apparatus 1 shown in FIG. 3, and includes a fixing device 50 that cures the formed foil transfer surface H by heating and pressing. It is what is installed.

  A foil transfer surface forming apparatus 1 shown in FIG. 4 has the same configuration as an electrophotographic image forming apparatus called a so-called “tandem color image forming apparatus”, and includes a foil transfer surface forming unit 20H and a plurality of sets of toner images. The forming units 20Y, 20M, 20C, and 20Bk, a belt-shaped intermediate transfer belt 26, a paper feeding device 40, a fixing device 50, and the like are included. In particular, the foil transfer surface forming apparatus 1 of FIG. 4 is provided with a transfer foil supply unit 70 below the intermediate transfer belt 26, and the foil transfer surface H fixed by the fixing device 50 is transferred onto the fixed substrate p1. The foil is supplied and passes through the fixing device 50 again, whereby the foil is transferred onto the foil transfer surface H.

  As described above, in the foil transfer surface forming apparatus 1 shown in FIG. 4, the foil transfer surface H can be formed on the substrate p1 constituting the product P, and the transfer foil can be transferred onto the formed foil transfer surface H. A full color image can be formed on the substrate p1 to which the foil has been transferred using color toner. In the foil transfer surface forming apparatus 1 of FIG. 4, the transfer foil supply unit 70 is arranged below the intermediate transfer belt 26, but the arrangement location of the transfer foil supply unit is not limited to this, and the transfer foil is not limited thereto. Any portion where foil transfer can be performed by heating and pressurizing with the fixing device 50 after the supply is performed.

  For the arrangement of the intermediate transfer belt 26, the fixing device 50, and the transfer foil supply unit 70, for example, the arrangement shown in FIG. In the foil transfer surface forming apparatus 1 of FIG. 6, an intermediate transfer belt 26, a fixing device 50, and a transfer foil supply unit 70 are sequentially arranged. Moreover, the arrow in the figure represents the conveyance direction of the base | substrate p1. 5 includes a transfer foil supply roll 71, foil transfer rollers 73a and 73b, and a transfer foil take-up roller 72. The transfer foil F is supplied from the transfer foil supply roll 71, and foil transfer is performed. The used transfer foil F is wound around the transfer foil winding roller 72. In FIG. 5, the foil transfer surface forming unit 20H, the toner image forming units 20Y, 20M, 20C, 20Bk, etc. are omitted. Further, FIG. 5 will be described in detail later.

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

  In FIG. 4, the constituent elements are collectively indicated by reference numerals with alphabetic suffixes omitted, and H (for foil transfer surface), Y (yellow), and M (magenta) are indicated when referring to individual constituent elements. , C (cyan), and Bk (black).

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

  The photoconductor 11 is made of, for example, an organic photoconductor in which a photosensitive layer made of a resin containing an organic photoconductor is formed on the outer peripheral surface of a drum-shaped metal base, and the base p1 constituting the product P to be conveyed. Are arranged in a state of extending in the width direction (perpendicular to the paper surface in FIG. 4). As the resin constituting the photosensitive layer, for example, a known photosensitive layer forming resin such as a polycarbonate resin is used. In the embodiment shown in FIG. 4, the configuration example using the drum-shaped photoconductor 11 is described. However, the configuration is not limited thereto, and a belt-shaped photoconductor may be used.

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

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

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

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

  Then, the substrate p1 to which the foil transfer surface H is fixed is once transported through the paper transport path having the paper discharge rollers 47, and then transported to the transfer foil supply path 51 via the transport path 48, where transfer is performed. Transfer foil is supplied from the foil supply unit 70. Further, the substrate p1 passes through the fixing device 50 again with the transfer foil supplied thereto, and the foil is transferred onto the foil transfer surface H by heating and pressurization of the fixing device 50.

  In this way, the base p1 on which the foil transfer surface H is formed and the foil is transferred is conveyed in front of the intermediate transfer belt 26 via the double-sided conveyance path 48, and this time, toner image formation is performed. Is done. First, the primary transfer rollers 13Y, 13M on the intermediate transfer belt 26 on which the respective color toner images formed on the photoreceptors 11Y, 11M, 11C, 11Bk are also rotated by the respective color toners from the toner supply devices 21Y, 21M, 21C, 21Bk. , 13C, and 13Bk, and a combined full-color image is formed on the intermediate transfer belt 26. On the other hand, the residual toner is removed by the cleaning devices 25 (25H, 25Y, 25M, 25C, and 25Bk) of the photosensitive member 11H that has transferred the foil transfer surface H and the photosensitive members 11Y, 11M, 11C, and 11Bk that have transferred the toner image. .

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

  Note that the three-stage substrate storage portions 41 arranged vertically in the vertical direction at the bottom of the foil transfer surface forming apparatus 1 have substantially the same configuration, and thus are denoted by the same reference numerals. Further, since the three-stage sheet feeding units 42 have almost the same configuration, the same reference numerals are given. The substrate storage unit 41 and the sheet supply unit 42 are collectively referred to as a sheet feeding device 40.

  The foil transfer surface H and the full-color image transferred onto the substrate p1 constituting the product P are fixed on the substrate p1 by a fixing device 50 that heats, pressurizes, melts and cures the foil transfer surface H and the full-color image. The substrate p1 is nipped and conveyed by the conveyance roller pair 57, is discharged from the discharge roller 47 provided in the discharge conveyance path, and is placed on the discharge tray 90 outside the apparatus.

  On the other hand, the intermediate transfer belt 26 in which the foil transfer surface H and the full-color toner image are transferred onto the base p1 by the secondary transfer roller 13A and the base p1 is separated by the curvature remains by the cleaning device 261 for the intermediate transfer belt. Toner is removed.

  In addition, when forming the foil transfer surface H and a full color image on both surfaces of the base | substrate p1 which comprises the product P, the foil transfer surface and the full color image were formed in the 1st surface of the base | substrate p1, and also these were fuse | melted and hardened. Thereafter, the base p1 is branched from the paper discharge conveyance path by the branch plate 49. Then, the paper is introduced into the double-sided conveyance path 48 and turned upside down and conveyed again to the paper feed roller 45B. The base p1 forms a foil transfer surface H and a full color toner image on the second surface by the foil transfer surface forming portion 20H and the image forming portions 20Y, 20M, 20C, and 20Bk for each color, and is heated and pressurized by the fixing device 50. Then, the paper is discharged out of the apparatus by the paper discharge roller 47. In this way, a full-color toner image in which the foil transfer surface is provided on both surfaces of the product P can be formed.

In addition, as shown in FIG. 5, the foil transfer surface forming apparatus 1 in which the intermediate transfer belt 26, the fixing device 50, and the transfer foil supply unit 70 are arranged, for example, forms the foil transfer surface H, transfers the foil, and the toner in the following procedure. Image formation can be performed. That is,
(1) The foil transfer surface H formed on the intermediate transfer belt 26 at the location of the secondary transfer roller 13A is transferred to the base p1.
(2) The base p1 is passed through the fixing device 50 to fix the foil transfer surface H.
(3) Transfer foil F is supplied onto the base p1 by the transfer foil supply unit 70, and the foil is transferred.
(4) The substrate p1 to which the foil is transferred via the conveyance path 48 is conveyed to the intermediate transfer belt 26, and the full color toner image is transferred onto the substrate p1.
(5) The base p1 is passed through the fixing device 50 to fix the full color toner image.
(6) The substrate p1 passes through the transfer foil supply unit 70 as it is, and is discharged out of the apparatus via the discharge roller 47.

  With the above procedure, the foil transfer surface forming apparatus 1 shown in FIG. 4 or 5 forms the foil transfer surface H on the base p1 constituting the product P, and transfers the transfer foil onto the formed foil transfer surface H. . Then, it is possible to form a full color image using color toner on the base p1 to which the foil is transferred.

  Next, a transfer foil that can be used in the present invention will be described with reference to FIG. FIG. 6 is a schematic diagram showing a cross-sectional structure of a typical transfer foil that can be used in the present invention. The transfer foil F that can be used in the present invention includes at least a film-like support f0 made of a resin, a foil layer f2 containing a colorant, a metal, and the like, and an adhesive layer f1 containing an organic material that exhibits adhesiveness. The foil layer f2 and the adhesive layer f1 are transferred onto the product P. The adhesive layer f1 is provided on the outermost surface of the transfer foil F, and is arranged so that the foil layer f2 is firmly attached to the surface of the product P by directly contacting the surface of the product P by transfer. Further, the transfer foil F shown in FIG. 5 has a release layer f3 between the support f0 and the foil layer f2. Hereinafter, each layer of the support f0, the foil layer f2, and the adhesive layer f1 will be described.

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

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

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

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

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

  Hereinafter, although an example is given and an embodiment of the present invention is explained concretely, the present invention is not limited to this. In addition, although there is a part described as "part" in the following sentence, it represents "mass part".

1. Preparation of “Foil Transfer Surface Forming Toners 1 to 18” As shown below, 18 types of foil transfer surface forming toners were prepared by a polymerization method and a pulverization method.

1-1. Preparation of “resin fine particle dispersion A1” (1) First stage polymerization A monomer composition was prepared by charging the following compound into a vessel equipped with a stirrer:
Styrene 90 parts by mass n-butyl acrylate 50 parts by mass Acrylic acid 35 parts by mass Itaconic acid 10 parts by mass n-octyl mercaptan 2.6 parts by mass Further, in the monomer composition comprising the above compound,
70 parts by mass of paraffin wax “HNP-57” (manufactured by Nippon Seiki Co., Ltd.) was added, and the mixture was heated to 80 ° C. and dissolved to prepare “mixed solution 1”.

  On the other hand, an anionic surfactant (polyoxy (2) dodecyl ether sulfate sodium salt 1.5 mass parts was dissolved in ion-exchanged water 650 mass parts to prepare a surfactant aqueous solution, which was heated to 90 ° C. Then, the “mixed solution 1” was added, and then mixed and dispersed for 3 hours using a mechanical disperser “CLEAMIX (manufactured by M Technique Co., Ltd.)” having a circulation path, and emulsified particles having a dispersed particle size of 210 nm A dispersion containing was prepared.

  Next, 700 parts by mass of ion-exchanged water heated to 90 ° C. is added to the dispersion, and further a solution in which 3 parts by mass of potassium persulfate (KPS) is dissolved in 120 parts by mass of ion-exchanged water is added. After the temperature of this system was 82 ° C., the polymerization reaction was carried out by heating and stirring for 3 hours. In this way, “resin fine particle dispersion a1” was produced.

(2) Second-stage polymerization A solution prepared by dissolving 3 parts by mass of potassium persulfate (KPS) in 120 parts by mass of ion-exchanged water was added to the “resin fine particle dispersion a1”, and the mixture was heated to 80 ° C. “Mixed solution 1-2” was added dropwise over 1 hour.

Styrene 248 parts by mass n-butyl acrylate 82 parts by mass n-octyl mercaptan 3.5 parts by mass After completion of dropping, the mixture was heated and stirred at 80 ° C. for 3 hours, and then cooled to 28 ° C. Thus, “resin fine particle dispersion A1” was prepared. The proportion of each vinyl monomer used in preparing “resin fine particle A1” constituting “resin fine particle dispersion A1” was 65.6 mass% for styrene and 25.6 mass% for n-butyl acrylate. The acrylic acid was 6.8% by mass and itaconic acid was 2.0% by mass.

1-2. Preparation of “resin fine particle dispersions A2 to A14” (1) Preparation of “resin fine particle dispersion A2” In preparing “resin fine particle dispersion A1”, when preparing “mixed solution 1” of the first stage polymerization, “Resin fine particle dispersion A2” was prepared in the same procedure except that the addition amount of acrylic acid was changed to 39.8 parts by mass and the addition amount of itaconic acid was changed to 5.2 parts by mass. The mass ratio of each vinyl monomer used when producing “resin fine particle A2” constituting “resin fine particle dispersion A2” was 65.6 mass% for styrene and 25.6 mass for n-butyl acrylate. %, Acrylic acid was 7.7% by mass, and itaconic acid was 1.1% by mass.

(2) Preparation of “resin fine particle dispersion A3” In preparing “resin fine particle dispersion A1”, when preparing “mixed solution 1” of the first stage polymerization, the amount of acrylic acid added was 17.5 parts by mass. “Resin fine particle dispersion A3” was prepared in the same procedure except that the amount of itaconic acid was changed to 28.5 parts by mass. The mass ratio of each vinyl monomer used in preparing the “resin fine particle dispersion A3” constituting the “resin fine particle dispersion A3” was 65.5 mass% for styrene and 25.6 mass for n-butyl acrylate. %, Acrylic acid was 3.4% by mass, and itaconic acid was 5.5% by mass.

(3) Production of “resin fine particle dispersion A4” The content of the monomer composition constituting “mixed solution 1” used when the first stage polymerization was performed in the production of “resin fine particle dispersion A1”. “Mixed solution 4” was prepared in the same procedure except for the following changes. That is,
Styrene 92 parts by mass n-butyl acrylate 48 parts by mass Methacrylic acid 30 parts by mass Cis-2-butenediol 14.5 parts by mass n-octyl mercaptan 2.6 parts by mass The above “resin” was used except that “mixed solution 4” was used. The first stage polymerization and the second stage polymerization were performed in the same procedure as the preparation of the “fine particle dispersion A1” to prepare the “resin fine particle dispersion A4”. The mass ratio of each vinyl monomer used in preparing “resin fine particle A4” constituting “resin fine particle dispersion A4” was 66.1% by mass of styrene and 25.3 mass of n-butyl acrylate. %, Methacrylic acid was 5.8% by mass, and cis-2-butenediol was 2.8% by mass.

(4) Production of “resin fine particle dispersion A5” In the production of “resin fine particle dispersion A4”, when preparing “mixed solution 4” of the first stage polymerization, the addition amount of methacrylic acid was 37 parts by mass, cis. “Resin fine particle dispersion A5” was prepared in the same procedure except that the amount of 2-butenediol added was changed to 7.7 parts by mass. The mass ratio of each vinyl monomer used in preparing the “resin fine particle dispersion A5” constituting the “resin fine particle dispersion A5” was 66.1 mass% for styrene and 25.3 mass for n-butyl acrylate. %, Methacrylic acid was 7.1% by mass, and cis-2-butenediol was 1.5% by mass.

(5) Preparation of “resin fine particle dispersion A6” In preparing “resin fine particle dispersion A1”, when preparing “mixed solution 1” of the first stage polymerization, 35 parts by weight of methacrylic acid was used instead of acrylic acid. “Resin fine particle dispersion A6” was prepared in the same procedure except that the “mixed solution 6” was changed. The mass ratio of each vinyl monomer used in producing “resin fine particle A6” constituting “resin fine particle dispersion A6” was 65.6% by mass of styrene and 25.6% by mass of n-butyl acrylate. %, Methacrylic acid was 6.8% by mass, and itaconic acid was 2.0% by mass.

(6) Preparation of “resin fine particle dispersion A7” In preparing “resin fine particle dispersion A6”, when preparing “mixed solution 6” of the first stage polymerization, 10 parts by mass of maleic acid was used instead of itaconic acid. “Resin fine particle dispersion A7” was prepared in the same procedure except that the “mixed solution 7” was changed. The mass ratio of each vinyl monomer used when producing “resin fine particle A7” constituting “resin fine particle dispersion A7” was 65.6% by mass of styrene and 25.6% by mass of n-butyl acrylate. %, Methacrylic acid was 6.8% by mass, and maleic acid was 2.0% by mass.

(7) Preparation of “resin fine particle dispersion A8” In preparing “resin fine particle dispersion A6”, when preparing “mixed solution 6” of the first stage polymerization, 10 parts by mass of fumaric acid was used instead of itaconic acid. “Resin fine particle dispersion A8” was prepared in the same procedure except that the “mixed solution 8” was changed. The mass ratio of each vinyl monomer used in preparing the “resin fine particle dispersion A8” constituting the “resin fine particle dispersion A8” was 65.6 mass% for styrene and 25.6 mass for n-butyl acrylate. %, Methacrylic acid was 6.8% by mass, and fumaric acid was 2.0% by mass.

(8) Preparation of “resin fine particle dispersion A9” In preparing “resin fine particle dispersion A6”, when preparing “mixed solution 6” of the first stage polymerization, 10 parts by weight of aconitic acid was used instead of itaconic acid. “Resin fine particle dispersion A9” was prepared in the same procedure except that the “mixed solution 9” was changed. The mass ratio of each vinyl monomer used in preparing the “resin fine particle dispersion A9” constituting the “resin fine particle dispersion A9” was 65.6 mass% for styrene and 25.6 mass for n-butyl acrylate. %, Methacrylic acid was 6.8% by mass, and aconitic acid was 2.0% by mass.

(9) Preparation of “resin fine particle dispersion A10” In preparing “resin fine particle dispersion A6”, when preparing “mixed solution 6” of the first stage polymerization, the amount of itaconic acid added was changed to 4 parts by mass. In addition, “resin fine particle dispersion A10” was prepared in the same procedure except that 6 parts by mass of aconitic acid was added to obtain “mixed solution 10”. The mass ratio of each vinyl monomer used in preparing the “resin fine particle dispersion A10” constituting the “resin fine particle dispersion A10” was 65.6 mass% for styrene and 25.6 mass for n-butyl acrylate. %, Methacrylic acid was 6.8% by mass, itaconic acid was 0.8% by mass, and aconitic acid was 1.2% by mass.

(10) Preparation of “resin fine particle dispersion A11” In preparing “resin fine particle dispersion A6”, when preparing “mixed solution 6” of the first stage polymerization, the amount of itaconic acid added was changed to 6 parts by mass. In addition, “resin fine particle dispersion A11” was prepared in the same procedure except that 4 parts by mass of cis-2-butenediol was added to obtain “mixed solution 11”. The mass ratio of each vinyl monomer used in preparing “resin fine particle A11” constituting “resin fine particle dispersion A11” was 65.6 mass% for styrene and 25.6 mass for n-butyl acrylate. %, Methacrylic acid was 6.8% by mass, itaconic acid was 1.2% by mass, and cis-2-butenediol was 0.8% by mass.

(11) Preparation of “resin fine particle dispersion A12” When preparing “mixed solution 1” of the first stage polymerization in the preparation of “resin fine particle dispersion A1”, itaconic acid was not added and other compounds were added. The “mixed solution 12” was prepared while keeping the addition amount as it was, and “resin fine particle dispersion A12” was prepared by using the same other manufacturing steps. The mass ratio of each vinyl monomer used in producing “resin fine particle A12” constituting “resin fine particle dispersion A12” was 66.9 mass% for styrene and 26.1 mass for n-butyl acrylate. %, And acrylic acid was 7.0% by mass. Further, in the production of “resin fine particle dispersion A12”, the sum of the polymerizable monomers used in the first stage polymerization was 175 parts by mass, and the sum of the polymerizable monomers used in the second stage polymerization was 330. The ratio of the amount of monomer used in both polymerizations, “the amount of monomer used in the second stage polymerization / the amount of monomer used in the first stage polymerization” was 1.89 in parts by mass.

(12) Preparation of “resin fine particle dispersion A13” In preparing “resin fine particle dispersion A6”, when preparing “mixed solution 6” of the first stage polymerization, itaconic acid was not added and The amount of body added was changed as follows to prepare “mixed solution 13”. That is,
Styrene 129.5 parts by mass n-butyl acrylate 72.0 parts by mass Methacrylic acid 50.4 parts by mass n-octyl mercaptan 3.74 parts by mass Liquid a13 "was produced.

Moreover, the addition amount of the monomer used by the second stage polymerization was changed as follows. That is,
Styrene 190.1 parts by mass n-butyl acrylate 62.9 parts by mass n-octyl mercaptan 2.65 parts by mass The polymerization was carried out under the same conditions as in the second stage polymerization to prepare “resin fine particle dispersion A13”. . The mass ratio of each vinyl monomer used in producing “resin fine particle A13” constituting “resin fine particle dispersion A13” was 63.3 mass% for styrene and 26.7 mass for n-butyl acrylate. %, And methacrylic acid was 10.0% by mass. In addition, in the production of “resin fine particle dispersion A13”, the sum of the polymerizable monomers used in the first stage polymerization is 252 parts by mass, and the sum of the polymerizable monomers used in the second stage polymerization is 253. The ratio of the amount of monomer used in both polymerizations, “the amount of monomer used in the second stage polymerization / the amount of monomer used in the first stage polymerization”, was 1.00 in parts by mass.

(13) Preparation of “resin fine particle dispersion A14” In preparing “resin fine particle dispersion A1”, when preparing “mixed solution 1” of the first stage polymerization, the amount of acrylic acid added was 7 parts by mass; “Resin fine particle dispersion A14” was prepared in the same procedure except that 38 parts by mass of fumaric acid was added in place of the acid. The mass ratio of each vinyl monomer used when producing “resin fine particle A14” constituting “resin fine particle dispersion A14” was 65.5% by mass of styrene and 25.6% by mass of n-butyl acrylate. %, Acrylic acid was 1.4% by mass, and fumaric acid was 7.5% by mass.

  The mass ratio of vinyl monomers having a plurality of polar groups such as styrene, n-butyl acrylate, acrylic acid or methacrylic acid, and itaconic acid constituting “resin fine particles A1 to A14” produced by the above procedure is shown in Table 1 below. .

1-3. Production of “Resin Fine Particle Dispersion A15 and Resin Fine Particle Dispersion A16” (1) Production of “Resin Fine Particle Dispersion A15” In the production of “Resin Fine Particle Dispersion A12”, “Mixed Mixture Containing First Stage Polymerization Wax” When preparing “Solution 12”, the amount of each compound added was changed as follows to prepare “Mixed Solution 15”. That is,
Styrene 74.3 parts by mass n-butyl acrylate 41.3 parts by mass Acrylic acid 28.9 parts by mass n-octyl mercaptan 2.6 parts by mass Paraffin wax “HNP-57” (manufactured by Nippon Seiki Co., Ltd.) 70 parts by mass A “resin fine particle dispersion a15” was produced by conducting a polymerization reaction under the same conditions as the first stage polymerization conducted in the production of the “resin fine particle dispersion A12” except that the mixed solution 15 was used.

Next, in the second-stage polymerization for forming a resin region not containing wax, when preparing a mixed solution to be dropped into the “resin fine particle dispersion a15”, the addition amount of each compound is changed as follows: This was designated as “mixed solution (15)”. That is,
Styrene 271 parts by mass n-butyl acrylate 90 parts by mass n-octyl mercaptan 3.8 parts by mass The “mixed solution (15)” containing the compound in the above-mentioned addition amount was added dropwise to the “resin fine particle dispersion a15”. A “resin fine particle dispersion A15” was produced by performing a polymerization reaction and a post-reaction treatment under the same conditions as the second-stage polymerization performed in the production of the “resin fine particle dispersion A12”. In the preparation of “resin fine particle dispersion A15”, the sum of the polymerizable monomers used in the first stage polymerization was 144.5 parts by mass, and the sum of the polymerizable monomers used in the second stage polymerization. Was 361 parts by mass, and the ratio of the amount of monomer used in both polymerizations, “the amount of monomer used in the second stage polymerization / the amount of monomer used in the first stage polymerization” was 2.50.

(2) Preparation of “resin fine particle dispersion A16” In preparing “resin fine particle dispersion A12”, when preparing “mixed solution 12” containing the first stage polymerization wax, the amount of each compound added is as follows: In this manner, “mixed solution 16” was prepared. That is,
Styrene 63.6 parts by mass n-butyl acrylate 35.4 parts by mass Acrylic acid 24.8 parts by mass n-octyl mercaptan 1.83 parts by mass Paraffin wax “HNP-57” (manufactured by Nippon Seiki Co., Ltd.) 70 parts by mass A “resin fine particle dispersion a16” was produced by carrying out a polymerization reaction under the same conditions as the first stage polymerization conducted in the production of the “resin fine particle dispersion A12” except that the mixed solution 16 was used.

Next, in the second-stage polymerization for forming a resin region not containing wax, when preparing a mixed solution to be dropped into the “resin fine particle dispersion a16”, the addition amount of each compound is changed as follows: This was designated as “mixed solution (16)”. That is,
Styrene 286.7 parts by mass n-butyl acrylate 94.8 parts by mass n-octyl mercaptan 4.0 parts by mass “Mixed solution (16)” containing the above-mentioned amount of the compound added dropwise to the “resin fine particle dispersion a16” Otherwise, the “resin fine particle dispersion A16” was produced by performing the polymerization reaction and the post-reaction treatment under the same conditions as the second stage polymerization conducted in the production of the “resin fine particle dispersion A12”. In the preparation of “resin fine particle dispersion A16”, the sum of the polymerizable monomers used in the first stage polymerization was 123.8 parts by mass, and the sum of the polymerizable monomers used in the second stage polymerization was. Was 381.5 parts by mass, and the ratio of the amount of monomer used in both polymerizations, “the amount of monomer used in the second stage polymerization / the amount of monomer used in the first stage polymerization” was 3.80.

1-4. Preparation of “Foil Transfer Surface Forming Toner 1” (1) Preparation of “Toner Base Particle 1” (Aggregation / Fusion Process)
In a reaction vessel equipped with a stirrer, temperature sensor, cooling pipe, nitrogen introduction device,
"Resin fine particle dispersion A1" 400 parts by mass (in terms of solid content)
Ion-exchanged water 1250 parts by mass Sodium dodecyl sulfate 8.5 parts by mass was added and stirred. After adjusting the temperature in the reaction vessel to 30 ° C., a 5 mol / liter aqueous sodium hydroxide solution was added to adjust the pH to 10.

  Next, an aqueous solution in which 60 parts by mass of magnesium chloride hexahydrate was dissolved in 60 parts by mass of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. The temperature was raised after standing for 3 minutes, and the temperature of the system was raised to 80 ° C. over 60 minutes, and the aggregation and fusion of the “resin fine particles A1” were continued while maintaining the temperature at 80 ° C. In this state, the particle size of the formed particles was measured using “Multisizer 3 (manufactured by Beckman Coulter)”, and when the volume-based median diameter of the particles became 6.5 μm, 190 parts by mass of sodium chloride Was added to an aqueous solution obtained by dissolving 760 parts by mass of ion-exchanged water to stop aggregation.

  After the agglomeration was stopped, the liquid temperature was set to 80 ° C. as a ripening treatment, and the mixture was heated and stirred for 3 hours to continue fusing to form “toner base particles 1”. Thereafter, the liquid temperature was cooled to 30 ° C., the pH was adjusted to 2 using hydrochloric acid, and stirring was stopped.

  The “toner base particle dispersion 1” produced through the above steps is subjected to solid-liquid separation with a basket type centrifuge “MARKIII model number 60 × 40 (manufactured by Matsumoto Kikai Co., Ltd.)”, and the “toner base particle 1” is wet. 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.)” A “toner base particle 1” was produced by performing a drying process until the water content became 1.0 mass%.

(2) External Addition Treatment The following external additives are added to the produced “toner base particle 1” and subjected to external addition treatment with a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.). Was made.

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

  By the above procedure, “Foil transfer surface forming toner 1” was produced. The volume-based median diameter of “Foil transfer surface forming toner 1” produced by the above procedure was 6.5 μm.

1-5. Preparation of “Foil Transfer Surface Forming Toners 2-16” In the preparation of “Foil Transfer Surface Forming Toner 1”, “resin fine particle dispersions A2 to A16” were used instead of “resin fine particle dispersions A1”. Otherwise, “Foil transfer surface forming toners 2 to 16” were prepared in the same procedure. The volume-based median diameter of the “foil transfer surface forming toners 2 to 16” produced by the above procedure was 6.5 μm.

1-6. Preparation of “Foil Transfer Surface Forming Toners 17 and 18” (1) Preparation of “Foil Transfer Surface Forming Toner 17” After thoroughly mixing the following compounds with “Henschel Mixer (Mitsui Miike Mining Co., Ltd.)”, biaxial extrusion A kneading machine “PCM-30 (manufactured by Ikegai Iron Works Co., Ltd.)” was used, and the mixture was cooled after melt kneading using the one from which the discharge part was removed. That is,
Vinyl resin (formed by a known polymerization method using styrene / n-butyl acrylate / methacrylic acid / itaconic acid (mass ratio = 25: 10: 3: 2)
100 parts by mass Paraffin wax “HNP-57” (manufactured by Nippon Seiki Co., Ltd.) 8.7 parts by mass The obtained kneaded product was cooled with a cooling belt and then roughly pulverized with a feather mill. Thereafter, the mixture is pulverized to an average particle size of 9 to 10 μm by a mechanical pulverizer “KTM (manufactured by Kawasaki Heavy Industries, Ltd.)”, and further an average particle size of 6. Grinding and coarse powder classification were performed until the thickness became 5 μm. Thereafter, using a rotor type classifier (Teplex type classifier type “100 ATP (manufactured by Hosokawa Micron Corporation))” from the coarse powder classifier, a “toner base particle 17” having a volume-based median diameter of 6.5 μm is obtained. Produced.

  The following external additives were added to the produced “toner base particles 17” and subjected to external addition treatment with a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.) to produce “foil transfer surface forming toner 17”.

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

(2) Production of “Foil Transfer Surface Forming Toner 18” In place of the vinyl resin used when producing “toner base particle 17” in the production of “foil transfer surface formation toner 17”,
Vinyl-based resin (formed by a known polymerization method using styrene / n-butyl acrylate / methacrylic acid (mass ratio = 5: 2: 3)) “Toner base particles” using the same procedure except that 100 parts by mass were used. 18 ”was prepared, and the“ foil transfer surface forming toner 18 ”was prepared by performing the above-described external addition process.

  By the above procedure, 18 types of toner for forming a foil transfer surface were produced.

2. Structural analysis of “foil transfer surface forming toners 1 to 18” Using a commercially available transmission electron microscope (TEM) “JEM-2000FX (manufactured by JEOL)”, structural analysis of each of the above foil transfer surface forming toner particles was performed. It was. First, each of the produced “foil transfer surface forming toners 1 to 15” was sufficiently dispersed in a room temperature curable epoxy resin, embedded, dispersed in a styrene fine powder having a particle size of about 100 nm, and then added. A block containing toner for forming a foil transfer surface was formed by pressure molding. Next, a block prepared by a microtome equipped with diamond teeth was cut into a thin piece having a thickness of 200 nm to obtain a measurement sample.

  The prepared flaky sample for measurement was set on a transmission electron microscope (TEM), and a cross-sectional structure of the foil transfer surface forming toner was photographed. At this time, photographing was performed with the negative magnification set to 280 times, and a photographic image with a magnification of 1200 times was created by enlargement. The photograph image thus created was analyzed with a commercially available image processing apparatus “Luxex III (manufactured by Nireco Corporation)”, and the size of the domain phase (average domain diameter) formed in the toner particles for forming the foil transfer surface ) Was calculated. The “domain phase size” is calculated by calculating the equivalent circle diameter for each domain existing in 20 foil transfer surface forming toner particles when the created photographic image is analyzed by the image processing apparatus. The arithmetic average value was defined as “domain phase size (average domain diameter)”. Table 2 shows the size of the domain phase of “foil transfer surface forming toners 1 to 18” calculated by the above procedure.

2. Evaluation experiment 2-1. Preparation of Toner Developer for Forming Foil Transfer Surface A ferrite carrier having a volume average particle diameter of 40 μm formed by coating a methyl methacrylate resin with respect to the “foil transfer surface forming toners 1 to 18” is 6% by mass. Then, “foil transfer surface forming toner developers 1 to 18” taking the form of a two-component developer were prepared.

2-2. Evaluation Experiment (1) Evaluation Conditions “Foil transfer surface forming toner developers 1 to 18” are respectively mounted on the foil transfer surface forming toner supply device 21H of the foil transfer surface forming apparatus 1 having the configuration shown in FIG. A surface was formed. The foil transfer surface was formed on a commercially available image support “OK topcoat + (basis weight 157 g / m ² , paper thickness 131 μm) (manufactured by Oji Paper Co., Ltd.)”. In the foil transfer surface forming apparatus 1, the foil transfer surface was formed by setting the supply amount of the foil transfer surface forming toner to 4 g / m ² .

  The fixing speed of the image support in the fixing device 50 was set to 230 mm / sec, the surface material of the heating roller was set to polytetrafluoroethylene (PTFE), and the surface temperature of the heating roller was set to 135 ° C.

  After forming the foil transfer surface with each toner on the image support using the foil transfer surface forming apparatus 1, the image support is manufactured according to the procedure shown in FIG. 2 and has a layer structure shown in FIG. The foil was transferred onto a foil transfer surface formed on the image support using the transfer foil. As the transfer foil, a commercially available gold foil “BL No. 2 Gold 2.8” and a hologram foil “KP015YPP” (all manufactured by Murata Gold Foil Co., Ltd.) were used.

The foil transfer was performed under the conditions shown below by the procedure shown in FIG. That is,
-Heating roll: a 3 mm thick silicone rubber layer placed on an aluminum base with an outer diameter of 100 mm and a thickness of 10 mm, and the surface temperature set to 150 ° C-Pressurizing roll: an outer diameter of 80 mm, with a thickness of 10 mm A silicone rubber layer with a thickness of 3mm is placed on an aluminum substrate, and the surface temperature is set to 100 ° C. Heat source: Halogen lamps are placed inside the heating roll and pressure roll, respectively (temperature controlled by a thermistor)
・ Nip width between heating roll and pressure roll: 7mm
-Image support conveyance speed: 73 mm / sec-Image support conveyance direction: A4 size image support is conveyed in the vertical direction-Evaluation environment: normal temperature and normal humidity environment (temperature 20 ° C, relative humidity 50% RH)
When transferring the hologram foil, the surface temperature of the heating roll was changed to 135 ° C., the surface temperature of the pressure roll was changed to 85 ° C., and the other conditions were the same.

  Here, the evaluation of the samples formed using “foil transfer surface forming toners 1 to 11 and 15 to 17” and the commercially available foil “BL No. 2 Gold 2.8” is referred to as “Examples 1 to 14”. Evaluations of samples formed with foils using “foil transfer surface forming toners 12 to 14 and 18” were referred to as “Comparative Examples 1 to 4”. The evaluation of a sample formed using “foil transfer surface forming toner 1” and the above-mentioned hologram foil “KP015YPP” was defined as “Example 15”.

(2) Evaluation experiment According to the following procedure, the presence or absence of winding around the fixing device during the formation of the foil transfer surface, the finished evaluation of the prepared foil image, and the foil image left in a high-temperature and high-humidity environment The durability was evaluated.

<Winding around fixing device components>
The occurrence of winding around the fixing device constituent member (heating roll) is carried out by transporting 100 sheets of the A4 size image support body in the horizontal direction under the above-mentioned creation conditions, and winding the image support body around the heating roll or pressure roll. The state of occurrence was visually observed and evaluated as follows. That is,
(Evaluation criteria)
◯: No winding of 100 sheets occurred, and no phenomenon that the image support adhered to the heating roll was lifted. Δ: No winding of all 100 sheets occurred, but the image support became a heating roll. The phenomenon of adhesion and lifting was observed in 1 to 3 sheets, but it was evaluated that there was no problem. X: Winding occurred, and the lifting phenomenon due to adhesion of the image support to the heating roll frequently occurred and judged to be defective. .

  Next, a sample was prepared for evaluation of the finish of the foil image under the above-mentioned creation conditions. Six types of foil image samples shown in FIG. 7 were formed on the image support. In the figure, Sa and Sb are thin line images, Sa is a line drawing with a width of 2 mm arranged vertically and horizontally at 1.5 mm width intervals, and Sb is a line drawing with a width of 0.5 mm arranged at 1 mm width intervals. It is. Sc is a circle, Sd is a square, Se is a regular triangle, and Sf is a star-shaped foil image. Five foil image samples are prepared for each toner type, and the foil images thus prepared are visually observed as follows. Sex was evaluated.

<Foil missing on the foil transfer surface>
The foil images of Sc to Sf formed on each sample were visually observed with the naked eye and a magnifying glass having a magnification of 10 times, and the presence or absence of the lack of foil on the foil transfer surface was evaluated as follows. ○ and Δ were accepted and x was rejected. That is,
(Evaluation criteria)
○: Even when all the foil images were observed by magnifying glass observation, no foil loss was observed. △: There was a foil image having a minute chipping formed by magnifying glass. It was judged that there was no problem at a level where there was no problem in the observation. X: One of five sheets was formed with a foil image in which a lack of foil was observed by visual observation.

<Burr generation>
The edge portion of the Sc-Sf foil image formed on each sample was visually observed with the naked eye and a magnifying glass with a magnification of 10 times, and the presence or absence of burrs was evaluated as follows. ○ and Δ were accepted and x was rejected. That is,
(Evaluation criteria)
○: No burrs were observed even when all the foil image edges were observed with a magnifying glass for all five samples. △: Some burrs were observed with the magnifying glass. Then, it was judged that there was no problem at a level where there was no problem. X: One of five sheets was found to have burrs by visual observation.

<Foil fine line reproducibility>
The above-mentioned two thin line images formed on each sample are visually observed with the naked eye and a magnifying glass with a magnification of 10 times, and the absence of excess foil between the thin lines and the absence or absence of the foil on the thin lines are as follows. evaluated. ○ and Δ were accepted and x was rejected. That is,
(Evaluation criteria)
○: In both two thin line images, it was confirmed by loupe observation that all the five samples had no excess foil between the thin lines and that there was no lack of foil on the thin line. Although a minute chip was seen on the thin line image, it was at a level that does not cause any problem in the naked eye observation. In addition, in all five samples, there was no excess foil between the fine lines of the two fine line images. X: Five sheets in which the extra foil remained between the fine lines were found by visual observation. There was at least one of them.

<Peeling resistance>
Two samples with better finishes than 5 samples are selected and left for 48 hours in an environment of temperature 30 ° C. and relative humidity 80% RH, and then a fine line image, equilateral triangle, square, star shape formed on the sample After sticking a tape on each foil image of, the tape was peeled off by hand. The state of the foil image after peeling the tape was observed with the naked eye and a magnifier with a magnification of 10 times, and evaluated as follows. The tape used was “Scotch Mending Tape MP-18 (manufactured by Sumitomo 3M Limited)”. That is,
(Evaluation criteria)
○: No peeling was observed by loupe observation for both of the two samples. △: There was a fine peeling that could be confirmed by loupe observation. At least one of the two sheets was confirmed to be peeled.

  The above results are shown in Table 3.

  As shown in Table 3, in Examples 1 to 15 in which foil images were formed using the toner for forming a foil transfer surface having the configuration of the present invention, the image support was used as a fixing device when the foil transfer surface was formed. It was confirmed that no wrapping occurred and the prepared foil image had a good finish and had excellent durability. On the other hand, in “Comparative Examples 1 to 4” using the toner for forming a foil transfer surface that does not have the configuration of the present invention, the image support causes the fixing device to wrap around the foil transfer surface, or the prepared foil image In some cases, good adhesive strength was not obtained due to the effect of wax, and foils were lost or burrs occurred, or the durability was inferior. From these results, "Examples 1 to 15" using the foil transfer surface forming toner having the configuration of the present invention and "Comparative Examples 1 to 1" using the foil transfer surface forming toner not satisfying the configuration of the present invention. It was confirmed that there was a clear performance difference between “4”.

DESCRIPTION OF SYMBOLS 1 Foil transfer surface formation apparatus 11 (11H, 11Y, 11M, 11C, 11Bk) Photoconductor 12 (12H, 12Y, 12M, 12C, 12Bk) Charging roller, belt electrode 13 (13A, 13H, 13Y, 13M, 13C, 13Bk) ) Transfer roller 14 Toner supply roller 20H Foil transfer surface forming portion 20Y, 20M, 20C, 20Bk Toner image forming portion 21H Toner supply device for forming foil transfer surface 21Y, 21M, 21C, 21Bk Toner supply device (developing device)
23 Conveying roller 25 (25H, 25Y, 25M, 25C, 25Bk) Cleaning device 26 Intermediate transfer belt 30 (30H, 30Y, 30M, 30C, 30Bk) Exposure unit 50 Fixing device 51 Transfer foil supply path 60 Image reading unit 70 Transfer foil Supply unit 71 Transfer foil supply roller 72 Transfer foil take-up roller 73a, 73b Foil transfer roller F Transfer foil f0 Support body f1 Adhesive layer f2 Foil layer f3 Release layer H Foil transfer surface P Product p1 Substrate (image support body)
R1, R2 Heating pressure roller S Foil image sample Sa, Sb Line drawing foil image sample Sc Circle foil image sample Sd Square foil image sample Se Equilateral triangle foil image sample Sf Star-shaped foil image sample T Foil transfer surface formation Toner (toner)
D domain phase M matrix phase U charge measurement device u1 conductive sleeve u2 magnet roll u3 bias power source u4 cylindrical electrode

Claims (7)

at least,
Exposing the photoreceptor to form an electrostatic latent image;
Supplying toner to the photoconductor on which an electrostatic latent image is formed to form a foil transfer surface;
Transferring the foil transfer surface formed on the photoreceptor to a product;
Fixing the foil transfer surface transferred to the product onto the product;
Supplying a transfer foil having at least an adhesive layer to the product on which the foil transfer surface is fixed;
Bringing the adhesive layer of the transfer foil into contact with the foil transfer surface;
Heating with the adhesive layer of the transfer foil in contact with the foil transfer surface; and
A foil transfer method comprising a step of removing the transfer foil from the product,
The toner used for forming the foil transfer surface is:
Contains at least resin and wax,
Having a phase separation structure in which a wax domain phase is dispersed in a matrix phase of the resin;
The foil transfer method, wherein an average domain diameter of the wax domain phase is 0.1 μm or more and 2.0 μm or less. The foil transfer method according to claim 1 , wherein the resin is formed using at least a vinyl monomer having a plurality of polar groups. Foil transferring method according to claim 1 or 2, wherein the polar group is a carboxyl group (-COOH). The foil transfer method according to any one of claims 1 to 3 , wherein the vinyl monomer having a plurality of polar groups is any one of itaconic acid, maleic acid, fumaric acid, and aconitic acid. The foil transfer method according to any one of claims 1 to 4 , wherein the vinyl monomer having a plurality of polar groups is itaconic acid. At least a resin and a wax, having a phase separation structure in which a wax domain phase is dispersed in a matrix phase of the resin, and an average domain diameter of the domain phase of the wax is 0.1 μm to 2.0 μm A method for producing a toner for forming a foil transfer surface,
The foil transfer surface forming toner is at least
In an aqueous medium, the resin particles are formed through a plurality of times of polymerization and the resin particles are aggregated and fused in the aqueous medium.
The step of forming the resin particles through the plurality of times of polymerization, at least,
A step of polymerizing a polymerizable monomer containing wax to form wax-containing resin particles; and a polymerization of the polymerizable monomer in the presence of the wax-containing resin particles to form a resin on the surface of the wax-containing resin particles all SANYO and a step of forming a layer to form a resin particles,
Wherein in the step of forming a wax-containing resin particles, method for producing a toner for forming a foil transferring layer, wherein Rukoto using a vinyl monomer having at least a plurality of polar groups. The amount of polymerizable monomer used in the step of forming a resin layer on the surface of the wax-containing resin particles is at least 2.5 times the amount of polymerizable monomer used in the step of forming the wax-containing resin particles. The method for producing a toner for forming a foil transfer surface according to claim 6 , wherein the toner is 3.8 times or less.

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