JP2012233953A - Toner for foil bonding, manufacturing method thereof and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide toner for foil bonding to be used in an image forming method which exhibits excellent adhesion of a foil image using the toner and prevents a finish failure such as stripes on the foil image even when heat/pressure is applied for forming a visible image on an image support body to obtain a good finished foil image and a desired visible image, and to provide a manufacturing method thereof and an image forming method.SOLUTION: The toner for foil bonding is used in an image forming method which bonds a foil on a foil bonding toner image part formed by using the toner for foil bonding to form a foil image, and pressurizes and fixes a visible toner image formed by electrophotography using toner for a visible image onto the image support body where the foil image is formed, while heating at 200°C or less. The storage modulus G' in the temperature range of 160 to 180°C falls within a range of 1×10N/mto 5×10N/m.

Description

  The present invention relates to a foil adhesion used in an image forming method in which a foil image is formed on an image support by adhesion with a foil adhesion toner on an image support by electrophotography, and then a visible image is formed using a visible image toner. The present invention relates to a toner, a manufacturing method thereof, and an image forming method.

  For example, in the field of bookbinding, commercial printing, card business, or plastic molding such as cosmetic containers, a processing technique called “foil stamping” is performed. This technology, also called “hot stamping”, uses a pressure member called a metal stamping die to transfer characters and patterns made of foil onto the surface of the substrate by the action of heat and pressure, and can be expressed in general printing. A high-quality image with a difficult metallic feeling and gloss can be imparted. Recently, foil transfer technology has also been used for holograms provided for the prevention of counterfeiting and security of cash cards and credit cards.

  The foil used for foil pressing is provided as a transfer foil, and as the transfer foil, for example, a wax layer is provided on a resinous film-like substrate, and a protective layer or a transfer material layer is provided thereon, In general, a transfer material layer having a structure in which a foil made of an adhesive layer is disposed and a transfer material layer formed mainly using metal vapor deposition or ink is used. The transfer foil having such a structure has been improved as the material to be transferred and the use have been expanded. 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 are examined (for example, refer patent document 1, 2). Further, the transfer foil for the above-mentioned cash card or credit card is required to be able to transfer a precise pattern accurately and without causing defects such as burrs or chips. For example, a polymer liquid crystal material is used as a transfer material. This problem is solved by using a transfer foil contained in the layer (for example, see Patent Document 3).

On the other hand, a method of performing foil transfer without taking time and effort has been studied. For example, a technique for forming a toner image on an image support using toner and transferring the foil thereon by adhesion is being studied. . Specifically, a toner image having an intended design pattern is formed on the image support using toner, and the foil is transferred by superimposing a transfer foil on the formed toner image and thermocompression bonding. (For example, see Patent Document 4). In this technique, the image support and the foil are strongly bonded by a synergistic action of the adhesive force generated by softening or melting the toner by heating and the adhesive force generated by melting the adhesive layer of the transfer foil. Adhesive strength is obtained.
Further, the toner is fixed on the image support in advance, the transfer foil is overlaid on the image support, hot pressed with an iron from the top, and then the film-like substrate of the transfer foil is peeled off from the image support. A technique for transferring a metal foil onto a support has also been proposed (see, for example, Patent Document 5).

  As described above, in the technology of transferring foil using toner, the foil can be transferred without using a stamping die that has been required in the prior art. It is possible to simplify the apparatus for performing the transfer.

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, after transferring foil on an image support body and forming a foil image, a heat press process may be added. Specifically, a normal visible toner image is formed on the image support on which a foil image is formed, which is called follow-up printing, and a normal visible toner image is formed by applying pressure while heating to form a visible image. Sometimes.

However, when heat and pressure treatment is performed on the image support on which the foil image formed by adhesion with the toner is formed, the toner relating to the adhesion of the foil is melted or softened again by heating, and the foil image is formed by heating. In some cases, defects such as streaks may occur.
Therefore, when an image is further formed on an image support on which a foil image is formed, it has been considered to use an image forming method other than an electrophotographic method such as an inkjet method or an offset printing method. However, there are problems such as being restricted, and complicated work processes.

  The present invention has been made on the basis of the circumstances as described above, and the object thereof is to provide good adhesion of a foil image by adhesion using a toner and to form a visible image on an image support. Even when heat and pressure treatment is applied to the foil image, it is used in an image forming method in which a foil image having a good finish and a desired visible image can be obtained without causing a defective finish such as streaks in the foil image. It is an object of the present invention to provide a toner for foil adhesion, a method for producing the same, and an image forming method.

The foil adhering toner of the present invention is a foil adhering toner image part formed on an image support by electrophotography using a foil adhering toner containing a binder resin containing a thermoplastic resin. And heating to form a foil image by adhering a foil on the toner image portion for foil adhesion, and then forming at least one kind of visible image on the image support on which the foil image is formed. A foil adhesive toner used in an image forming method for forming a visible image by heating and fixing a visible toner image formed by electrophotography using a toner while being heated at 200 ° C. or lower. ,
The storage elastic modulus G ′ in the temperature range of 160 to 180 ° C. is in the range of 1 × 10 ³ N / m ^{2 to} 5 × 10 ⁴ N / m ² .

  The foil adhering toner of the present invention is preferably a clear toner.

  The foil adhering toner of the present invention may contain a binder resin in which the content ratio of the resin component having a molecular weight of 60,000 or more measured by gel permeation chromatography (GPC) is 10 to 30% by area. preferable.

The method for producing the foil adhering toner of the present invention is a method for producing the above foil adhering toner,
A step of aggregating the binder resin fine particles by adding an aggregating agent made of a metal salt into an aqueous medium in which the binder resin fine particles containing a binder resin including a thermoplastic resin are dispersed. And

The image forming method of the present invention comprises a step of forming a toner image portion for foil adhesion on an image support by electrophotography using a foil adhesion toner containing a binder resin containing a thermoplastic resin,
A foil image forming step of forming a foil image on the foil adhesive toner image portion by contacting and heating the foil on the foil adhesive toner image portion;
On the image support on which the foil image has been formed, a visible toner image is formed by electrophotography using at least one visible image toner, and is fixed by applying pressure while heating at 200 ° C. or lower. In an image forming method having a visible image forming step of forming a visible image,
The foil adhesive toner has a storage elastic modulus G ′ in a temperature range of 160 to 180 ° C. in a range of 1 × 10 ³ N / m ^{2 to} 5 × 10 ⁴ N / m ^2. Features.

  According to the foil adhering toner of the present invention, since the foil adhering toner has a specific storage elastic modulus, the adhesive property of the foil image is good, and furthermore, 200 ° C. for fixing the visible toner image. Even in the case where pressure is applied while heating, the toner image portion for foil adhesion due to the toner for foil adhesion loses elasticity due to heating, and the flow is extremely suppressed. As a result, a visible image can be formed in a state in which a desired finish state in the foil image forming process is maintained, and as a result, a good finish state is obtained. An image from which both the foil image and the desired visible image are obtained can be easily formed.

It is a graph which shows the magnitude | size of the storage elastic modulus G 'with respect to temperature about the toner for foil adhesion | attachment of this invention, and the toner for a comparison. It is sectional drawing for description which shows the cross-section of the foil used for the image forming method using the toner for foil adhesion | attachment of this invention. 1 is a cross-sectional view illustrating an example of a configuration of an image forming apparatus for performing an image forming method using a foil bonding toner of the present invention. It is sectional drawing for description which shows an example of a structure of foil transfer apparatus. It is a schematic diagram for demonstrating a foil image formation process. It is a schematic diagram of the printed matter which has the foil image and visible image which are formed in an Example.

  Hereinafter, the present invention will be specifically described.

  The foil adhering toner of the present invention is a foil adhering toner image part formed on an image support by electrophotography using a foil adhering toner containing a binder resin containing a thermoplastic resin. The foil image forming step of forming a foil image by adhering the foil onto the toner image portion for adhering the foil is carried out by heating, and then at least one kind is formed on the image support on which the foil image is formed. A visible toner image formed by electrophotography using the visible image toner is pressed and fixed while being heated at 200 ° C. or lower, thereby forming a visible image forming step for forming a visible image, a so-called reprinting step. This is a foil adhering toner used in the image forming method.

[Storage modulus]
The toner for foil adhesion of the present invention has a storage elastic modulus G ′ (hereinafter also referred to as “storage elastic modulus G ′ _160-180 ”) in the temperature range of 160 to 180 ° C. of 1 × 10 ³ N /. m ² or more and 5 × 10 ⁴ N / m ² or less.
In the present invention, “the storage elastic modulus G ′ ₁₆₀ to ₁₈₀ is in the range of 1 × 10 ³ N / m ² or more and 5 × 10 ⁴ N / m ² or less” means any temperature range of 160 to 180 ° C. The storage elastic modulus G ′ at a temperature of 1 × 10 ³ N / m ^{2 to} 5 × 10 ⁴ N / m ² is also in the range.
Usually, the storage elastic modulus G ′ shows a higher value as the temperature is lower, so that the foil adhesive toner of the present invention has a storage elastic modulus G ′ at a temperature of 160 ° C. of 5 × 10 ⁴ N / m ² or less, and The storage elastic modulus G ′ at a temperature of 180 ° C. may be 1 × 10 ³ N / m ² or more.

When a visible toner image is fixed after forming a foil image, the foil adhesive toner image portion due to the foil adhesive toner loses its elasticity due to heating, and flow occurs, or the foil adhered to the image support by pressurization In some cases, streaks due to distortion occur, and the influence becomes greater as the fixing temperature of the visible toner image is higher. That is, when the visible toner image is fixed at a high temperature, the toner image portion for foil adhesion due to the toner for foil adhesion loses elasticity and tends to flow, and streaks due to distortion of the foil are likely to occur.
Since the storage elastic modulus G ′ ₁₆₀ to ₁₈₀ of the foil adhering toner is in the above range, even when heat-pressing treatment is performed to fix the visible toner image, the foil adhering toner with the foil adhering toner is heated. Since the toner image portion loses elasticity and the flow is extremely suppressed, the foil bonded to the image support does not cause a streak due to distortion even when the toner image is pressed. A visible image can be formed in a state in which the desired finished state is maintained, and as a result, an image in which both a foil image in a good finished state and a desired visible image are obtained can be easily formed. Can do.
On the other hand, the storage elastic modulus G ′ ₁₆₀ to ₁₈₀ of the foil adhering toner is too _small , that is, the storage elastic modulus G ′ at the heating temperature of the foil adhering toner in the heat and pressure treatment for fixing the visible toner image is 1 ×. When it is less than 10 ³ N / m ² , when heat-pressing treatment is performed to fix the visible toner image, the foil-adhering toner image portion due to the foil-adhering toner loses its elasticity due to heating, and the fluid flows. As a result, a streak or the like due to distortion occurs in the foil adhered to the image support by pressurization. Further, the storage elastic modulus G ′ ₁₆₀ to ₁₈₀ of the foil adhering toner is excessive, that is, the storage elastic modulus G ′ at the temperature at which the foil adhering toner is heated in the heat and pressure treatment for fixing the visible toner image is 5 ×. If it exceeds 10 ⁴ N / m ² , sufficient adhesion cannot be obtained in the toner image portion for foil adhesion, or it is necessary to set the heating temperature for forming the foil image high and / or increase the pressure. Since this is necessary, the environmental load increases and foil defects occur. FIG. 1 shows an example (a in FIG. 1) of the viscoelasticity curve of the toner for adhesive bonding of the present invention, in which the storage elastic modulus G ′ ₁₆₀ to ₁₈₀ is in the above range, and the storage elastic modulus G ′ ₁₆₀ to ₁₈₀ is An example (b in FIG. 1) of a viscoelastic curve of a comparative toner deviating from the above range is shown.

The storage elastic modulus G ′ _{160 to 180} of the toner for foil adhesion was measured according to the following procedures (1) to (5) using “MR-500 _solid meter” (manufactured by _Rheology Co., Ltd.). It is.
(1) The foil adhering toner is placed in a measurement sample petri dish in an environment of a temperature of 20 ± 1 ° C. and a relative humidity of 50 ± 5% RH. And a 3 cm load is applied for 30 seconds to produce a 1 cm diameter pellet.
(2) The pellet is loaded on a parallel plate having a diameter of 0.977 cm.
(3) The measurement part temperature is set to a toner softening point of −20 ° C., and the parallel plate gap is set to 3 mm. With this setting, the measuring part is heated to the softening point of the toner at −20 ° C., and the pellets are compressed until the gap becomes 3 mm. Then, it cools to 35 degreeC.
(4) After setting the measurement part temperature to 35 ° C., the temperature of the measurement part was increased to 200 ° C. at a temperature increase rate of 5 ° C. per minute while applying a sinusoidal vibration with a frequency of 1.0 Hz. The complex elastic modulus G ^{* at} is measured. The strain angle is controlled by automatic strain control.
(5) The storage elastic modulus G ′ is calculated from the complex elastic modulus G ^* .

The softening point of the foil adhering toner is measured by a flow tester method.
Specifically, first, in an environment of a temperature of 20 ± 1 ° C. and a relative humidity of 50 ± 5% RH, put in a measuring sample petri dish and leave it flat for 12 hours or more. A cylindrical shaped sample having a diameter of 1 cm is prepared by applying a load of 3 t for 30 seconds using a vessel “SSP-A” (manufactured by Shimadzu Corporation). Next, this molded sample was subjected to a load of 196 N (20 kgf) and a starting temperature of 80 ° C. with a flow tester “CFT-500D” (manufactured by Shimadzu Corporation) in an environment of a temperature of 24 ± 5 ° C. and a relative humidity of 50 ± 20% RH. Extruding from the hole of the cylindrical die (1 mm diameter x 1 mm) using a 1 cm diameter piston at the preheating time of 300 seconds under the condition of a heating rate of 6 ° C / min. The offset method temperature T _offset measured at a setting of an offset value of 5 mm by the method was defined as the softening point.

[Foil adhesive toner]
The foil adhering toner of the present invention is a toner that exhibits an action as an adhesive for adhering a foil on an image support, and contains a binder resin including a thermoplastic resin, and is colored. A color toner containing an agent or a transparent clear toner may be used, but a clear toner is preferable because the influence on the visibility of a foil image and a visible image formed thereafter is small.
In the present invention, the clear toner refers to a toner whose color is not recognized by the action of light absorption or light scattering. The clear toner may be substantially colorless and transparent. For example, a toner that does not contain a colorant such as a pigment or a dye, a toner that contains a colorant such as a pigment or a dye that cannot recognize the color, a binder resin or a wax, A toner whose transparency is slightly lowered depending on the type and amount of the external additive is also included.

〔Thermoplastic resin〕
Examples of the thermoplastic resin contained in the binder resin of the foil bonding toner particles constituting the foil bonding toner of the present invention include styrene resins, (meth) acrylic resins, and styrene- (meth) acrylic copolymers. Examples include various known thermoplastic resins such as resins, vinyl resins such as olefin resins, polyester resins, polyamide resins, polycarbonate resins, polyethers, polyvinyl acetate resins, polysulfone resins and polyurethane resins. it can. These can be used alone or in combination of two or more.

In the toner for foil adhesion of the present invention, the binder resin contained in the toner particles for foil adhesion is a content ratio of a resin component having a molecular weight of 60,000 or more as measured by gel permeation chromatography (GPC) (hereinafter referred to as “the binder resin”). , Also referred to as “high molecular weight component ratio”) is preferably 10 to 30% by area. This high molecular weight component ratio means the area ratio of a resin component having a molecular weight of 60,000 or more when the area of the peak derived from the binder resin is 100% as measured by gel permeation chromatography (GPC). . The binder resin preferably has a molecular weight peak value of about 10,000 to 30,000 as measured by gel permeation chromatography (GPC).
By having the high molecular weight component ratio as described above, an appropriate adhesive property can be obtained when heat is applied in the foil image forming process, while the foil bonding with the foil bonding toner is performed by the heat applied in the follow-up printing process. Since the fluidity that deforms the toner image portion does not occur, even when pressed, the foil adhered to the image support does not cause streaks due to distortion. Therefore, in the foil image forming process A visible image can be formed in a state where the desired finished state is maintained. If the high molecular weight component ratio is too small, due to the insufficient cohesion between the resin molecules without sufficient entanglement between the resin molecular chains constituting the binder resin of the foil adhesion toner, The toner image portion for foil adhesion is likely to be deformed by heat, and there is a possibility that streaks due to the distortion of the foil may occur when the image support on which the foil image is formed is heated and pressed in the follow-up printing process. Furthermore, when the ratio of the high molecular weight component is excessive, the intermolecular cohesive force of the resin molecules constituting the binder resin of the foil adhesive toner is too strong, so it is necessary to set the heating temperature for forming the foil image high. Yes, the environmental impact increases.

The peak value of the molecular weight and the high molecular weight component ratio of the binder resin contained in the toner for foil bonding of the present invention are calculated based on the molecular weight measured as follows.
The molecular weight is measured by gel permeation chromatography (GPC) soluble in tetrahydrofuran (THF). That is, using an apparatus “HLC-8220” (manufactured by Tosoh Corporation) and a column “TSKguardcolumn + TSKgelSuperHZM-M3 series” (manufactured by Tosoh Corporation), while maintaining the column temperature at 40 ° C., tetrahydrofuran (THF) was used as a carrier solvent at a flow rate of 0. 2 ml / min, and the measurement sample (foil adhesion toner) was dissolved in tetrahydrofuran to a concentration of 1 mg / ml under a dissolution condition in which treatment was performed for 5 minutes using an ultrasonic disperser at room temperature. A sample solution is obtained by processing with a 2 μm membrane filter, and 10 μL of this sample solution is injected into the apparatus together with the carrier solvent, detected using a refractive index detector (RI detector), and the molecular weight distribution of the measurement sample. Using a calibration curve measured using monodisperse polystyrene standard particles And calculate. As a standard polystyrene sample for calibration curve measurement, molecular weights manufactured by Pressure Chemical Co., Ltd. are 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1 .1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and at least about 10 standard polystyrene samples were measured, and a calibration curve It was created. A refractive index detector was used as the detector. In addition, a boundary line was drawn at a position where the molecular weight of the obtained molecular weight chart was 60,000, and an area ratio where the molecular weight was 60,000 or more was calculated to obtain a high molecular weight component ratio.

[Method for producing foil bonding toner]
The method for producing the toner for foil adhesion of the present invention is not particularly limited, and includes a kneading / pulverization method, a suspension polymerization method, an emulsion aggregation method, an emulsion association method, a miniemulsion polymerization aggregation method, and other known methods. Can be mentioned.
As a method for producing a toner for foil adhesion, particularly when a binder resin containing a styrene-acrylic resin is used, the control of the high molecular weight component ratio in the binder resin is easy. Is preferably used. An example of the emulsion association method is given below as an example.

  In the emulsion association method, a dispersion of fine particles (hereinafter referred to as “binder resin fine particles”) made of a binder resin produced by an emulsion polymerization method is added to a foil such as other colorant fine particles and wax fine particles as necessary. The dispersion of the toner particle constituents for adhesion is also mixed together, and the particles are slowly agglomerated while balancing the repulsive force of the fine particle surface by pH adjustment and the agglomeration force by adding an aggregating agent made of an electrolyte. In this method, the toner particles for foil adhesion are manufactured by performing association while controlling the distribution and simultaneously controlling the shape by fusing the fine particles by heating and stirring.

  The binder resin fine particles may have a structure of two or more layers made of binder resins having different compositions. In this case, the first resin prepared by emulsion polymerization treatment (first-stage polymerization) according to a conventional method. It is possible to employ a multistage polymerization method in which a polymerization initiator and a polymerizable monomer are added to a fine particle dispersion, and this system is polymerized (second stage polymerization).

When the binder resin fine particles are formed by a multistage polymerization method, binder resin fine particles having a desired high molecular weight component ratio are prepared depending on the type and / or addition amount of the radical polymerization initiator and chain transfer agent used. By using the binder resin fine particles, toner particles having a desired high molecular weight component ratio can be produced.
Further, toner particles having a desired high molecular weight ratio can also be produced by using a mixture of low molecular weight binder resin fine particles and high molecular weight binder resin fine particles in an arbitrary ratio.
Further, in the case of using the emulsion association method as a method for producing the toner for foil adhesion, in order to form the binder resin, the binder resin includes a resin obtained from a polymerizable monomer having an acid group. The amount of the ion crosslinking structure can be adjusted by the amount of the polymerizable monomer having an acid group in the polymerizable monomer and the amount of the flocculant added when the binder resin fine particles are aggregated, As a result, the storage elastic modulus G ′ of the foil adhering toner can be adjusted.
The ionic crosslinking structure can be formed by reacting a polyvalent metal with a resin containing a structural unit having an acid group. The ionic cross-linked structure is a cross-linked structure generated by a coordinate bond (ionic bond) between a carboxyl group and a polyvalent metal ion.

Specifically showing an example of the production process when the foil bonding toner of the present invention is obtained by an emulsion association method,
(1) a binder resin fine particle polymerization step for obtaining binder resin fine particles by allowing a radical polymerization initiator to act on a polymerizable monomer that is to form a binder resin in an aqueous medium;
(2) An association step in which coagulant is added to the aqueous medium in which the binder resin fine particles are present and the temperature is adjusted to advance the salting out and simultaneously perform aggregation and fusion to form associated particles. ,
(3) A maturing step of forming a toner for foil adhesion by controlling the shape of the associated particles,
(4) Filtration and washing step for filtering the foil adhering toner particles from the aqueous medium and removing the surfactant from the foil adhering toner particles.
(5) A drying step of drying the washed toner particles for bonding the foil,
(6) An external additive adding step of adding an external additive to the dried toner particles for bonding the foil.

  Here, the “aqueous medium” refers to a medium composed of 50 to 100% by mass of water and 0 to 50% by mass of a water-soluble organic solvent. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran, and alcohol-based organic solvents that do not dissolve the obtained resin such as methanol, ethanol, isopropanol, and butanol are preferable.

(1) Binder resin fine particle polymerization step Specifically, in this binder resin fine particle polymerization step, for example, at least a polymerizable monomer described later is added to an aqueous medium, and mechanical energy is applied and dispersed. In this state, the polymerized monomer is radically polymerized by emulsion polymerization to form binder resin fine particles having a size of, for example, a volume-based median diameter of about 50 to 300 nm. Is.

  The dispersing device for imparting mechanical energy for forming oil droplets is not particularly limited. For example, a commercially-available stirring device “CLEARMIX” (M (Technique, Inc.) is a typical example. In addition to the above-described stirring device provided with a rotor capable of rotating at high speed, devices such as an ultrasonic dispersion device, a mechanical homogenizer, a manton gourin, and a pressure homogenizer can be used.

  Although the temperature which concerns on radical polymerization reaction changes also with the kind of the polymerizable monomer and radical polymerization initiator to be used, it is preferable that it is 50-100 degreeC, for example, More preferably, it is 55-90 degreeC. The time required for the radical polymerization reaction varies depending on the kind of the polymerizable monomer used and the reaction rate of the radical from the radical polymerization initiator, but is preferably 2 to 12 hours, for example.

Examples of the polymerizable monomer for obtaining the thermoplastic resin contained in the binder resin of the foil adhering toner include the following.
・ Styrene monomers (styrene or styrene derivatives)
Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-tert-butylstyrene, pn- Hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, etc .;
・ Methacrylic acid monomers (methacrylic acid or methacrylic ester derivatives)
Methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate , Phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, etc .;
・ Acrylic acid monomers (acrylic acid or acrylic ester derivatives)
Acrylic acid, 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.
The above polymerizable monomers can be used alone or in combination of two or more.
Moreover, it is preferable to use together the polymerizable monomer which has an acid group from a viewpoint of forming an ionic crosslinked structure. Examples of the polymerizable monomer having an acid group include those having one or more of carboxylic acid group, sulfonic acid group, sulfinic acid group, phosphonic acid group, boric acid group and the like. Among these, a polymerizable monomer having a carboxylic acid group is particularly preferably used because of the strength of the acid and the ease of copolymerization. Specific examples of the polymerizable monomer having a carboxylic acid group include acrylic acid, methacrylic acid, α-ethylacrylic acid, (meth) acrylic acid such as crotonic acid, and α-alkyl derivatives or β-alkyl derivatives; fumaric acid, Unsaturated dicarboxylic acids such as maleic acid, citraconic acid and itaconic acid; unsaturated succinic acid monoacryloyloxyethyl ester, succinic acid monoacryloyloxyethylene ester, phthalic acid monoacryloyloxyethyl ester, phthalic acid monomethacryloyloxyethyl ester, etc. And dicarboxylic acid monoester derivatives. It is preferable that the usage-amount of the polymerizable monomer which has these acid groups is about 3 to 10% of a total polymerizable monomer.

In addition to the above styrene monomer and / or (meth) acrylic acid monomer, the following vinyl polymerizable monomers can also be used.
・ Olefins Ethylene, propylene, isobutylene, etc .;
・ Vinyl esters Vinyl propionate, vinyl acetate, vinyl benzoate, etc .;
・ Vinyl ethers Vinyl methyl ether, vinyl ethyl ether, etc .;
・ Vinyl ketones Vinyl methyl ketone, vinyl ethyl ketone, vinyl hexyl ketone, etc .;
N-vinyl compounds N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, etc .;
・ Others Vinyl compounds such as vinyl naphthalene and vinyl pyridine, acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

Furthermore, together with the above styrene monomer and / or (meth) acrylic acid monomer, the following polyfunctional vinyls can be used to make the thermoplastic resin have a crosslinked structure.
-Polyfunctional vinyls Ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, and the like.

[Surfactant]
In the binder resin fine particle polymerization step, an appropriate dispersion stabilizer can be added in order to stably disperse the fine particles in the 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, sulfuric acid. Examples include barium, bentonite, silica, and alumina. In addition, polyvinyl alcohol, gelatin, methylcellulose, sodium dodecylbenzenesulfonate, ethylene oxide adducts, higher alcohol sodium sulfate and the like which are generally used as surfactants can also be used as the dispersion stabilizer.
As such a surfactant, conventionally known various ionic surfactants, nonionic surfactants, and the like can be used.
Examples of ionic surfactants include sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino-8-naphthol-6-sulfonate Sulfonates such as sodium ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sulfonate;
There are sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, and the fatty acid salts include sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, oleic acid Examples thereof include sulfate ester salts such as calcium; fatty acid salts and the like.
Examples of nonionic surfactants include polyethylene oxide, polypropylene oxide, a combination of polypropylene oxide and polyethylene oxide, esters of polyethylene glycol and higher fatty acids, alkylphenol polyethylene oxide, esters of higher fatty acids and polyethylene glycol, higher fatty acids and polypropylene. Examples include oxide esters and sorbitan esters.

〔wax〕
The wax used when the wax-bonding toner particles of the present invention contain a wax is not particularly limited, and examples thereof include polyethylene wax, oxidized polyethylene wax, polypropylene wax, oxidized polypropylene wax, and carnauba wax. Sazol wax, rice wax, candelilla wax, jojoba oil wax, beeswax wax and the like.

  As a method for incorporating the wax into the toner particles for foil adhesion, as described above, in the method for forming the binder resin fine particles as containing wax, or in the association step for forming the toner particles for foil adhesion, in the aqueous medium And a method of adding a dispersion liquid in which wax fine particles are dispersed to salt out, agglomerate, and fuse the binder resin fine particles, the colorant fine particles, and the wax fine particles. Good.

  The content ratio of the wax in the toner particles for foil adhesion is usually 0.5 to 5 parts by mass, preferably 1 to 3 parts by mass with respect to 100 parts by mass of the binder resin. When the content ratio of the wax is less than 0.5 parts by mass with respect to 100 parts by mass of the binder resin, a sufficient offset prevention effect cannot be obtained, and on the other hand, it is larger than 5 parts by mass with respect to 100 parts by mass of the binder resin. As a result, the obtained foil adhering toner has low translucency and color reproducibility. Further, the adhesion of the foil 80c (see FIG. 5) may be hindered by the bleeding of the wax.

[Charge control agent]
The charge control agent used in the case of incorporating the charge control agent in the toner particles for adhesive bonding of the present invention is a substance that can give positive or negative charge by frictional charging and is colorless. There is no particular limitation, and various known positively chargeable charge control agents and negatively chargeable charge control agents can be used.
The content ratio of the charge control agent in the foil adhesion toner particles is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin. .
Examples of the method for containing the charge control agent in the foil bonding toner particles include the same method as the method for containing the wax described above.

(Polymerization initiator)
As a polymerization initiator used in the binder resin fine particle polymerization step, an appropriate oil-soluble or water-soluble polymerization initiator can be used.
Specific examples of the oil-soluble polymerization initiator include, for example,
(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 and the like;
(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 and the like.
Specific examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and its salts, and hydrogen peroxide. .

[Chain transfer agent]
In the binder resin fine particle polymerization step, a commonly used chain transfer agent can be used for the purpose of adjusting the molecular weight of the binder resin. The chain transfer agent is not particularly limited. For example, n-octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, n-octyl-3-mercaptopropionic acid ester, terpinolene, carbon tetrabromide, α-methylstyrene dimer And so on.

(2) Association step to (6) The external additive addition step of adding the external additive to the dried toner particles for foil bonding can be performed according to various conventionally known methods.

[Flocculant]
The aggregating agent used in the association step includes monovalent, divalent or trivalent metal ions. From the viewpoint of forming an ionic cross-linked structure, it is preferable to use divalent or trivalent metal ions. Examples of such metal ions include magnesium ions, calcium ions, strontium ions, barium ions, zinc ions, and aluminum ions. Among these, magnesium ions and aluminum ions are particularly preferably used. A combination of these metal ions can also be used. In addition, chlorides, bromides, sulfides, and hydrates of the above metal ions can be used.
Moreover, it is preferable that the addition amount of a flocculant is 40-100 mass parts with respect to 450 mass parts of binder resin fine particles.

(External additive)
The above foil adhesion toner particles can constitute the foil adhesion toner of the present invention as it is, but in order to improve fluidity, chargeability, cleaning properties, etc., the foil adhesion toner particles are referred to as so-called foil adhesion toner particles. The foil adhering toner of the present invention may be constituted by adding external additives such as a fluidizing agent and a cleaning aid as post-treatment agents.

Examples of the external additive include inorganic oxide fine particles composed of silica fine particles, alumina fine particles, titanium oxide fine particles, inorganic stearate compound fine particles such as aluminum stearate fine particles and zinc stearate fine particles, strontium titanate, titanium, and the like. Inorganic titanic acid compound fine particles such as zinc acid are listed. These can be used individually by 1 type or in combination of 2 or more types.
These inorganic fine particles are preferably subjected to surface treatment with a silane coupling agent, a titanium coupling agent, a higher fatty acid, silicone oil or the like in order to improve heat-resistant storage stability and environmental stability.
As the external additive, spherical organic fine particles having a number average primary particle diameter of about 10 to 2000 nm can also be used. As such organic fine particles, specifically, fine particles composed of homopolymers such as styrene and methyl methacrylate or copolymers thereof can be used.

  The total amount of these various external additives added is 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass, with respect to 100 parts by mass of the foil bonding toner. In addition, various external additives may be used in combination.

[Toner for visible image]
The visible image toner used in the image forming method using the foil adhering toner of the present invention is not particularly limited as long as it can be suitably fixed at a heating temperature of 200 ° C. or lower. An image developing toner can be used.

The visible image toner is not particularly limited as long as a desired image can be obtained, and may be a color toner containing a colorant or a clear toner. A toner is preferable.
When the toner particles are configured to contain a colorant, organic or inorganic pigments of various colors as exemplified below can be used as the colorant.
That is, as a colorant for black toner, carbon black, magnetic material, iron / titanium composite oxide black, etc. can be used. As carbon black, channel black, furnace black, acetylene black, thermal black, lamp Black and the like can be mentioned, and examples of the magnetic material include ferrite and magnetite.
As a colorant for yellow toner, C.I. I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162, etc., and C.I. I. Pigment Yellow 14, 17, 74, 93, 94, 138, 155, 180, 185, etc. can be used, and mixtures thereof can also be used.
As a colorant for magenta toner, C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 122, etc. I. Pigment Red 5, 48: 1, 53: 1, 57: 1, 122, 139, 144, 149, 166, 177, 178, 222, etc. can be used. Mixtures of these can also be used.
As a colorant for cyan toner, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95, etc. I. Pigment Blue 1, 7, 15, 15, 60, 62, 66, 76, etc. can be used, and a mixture thereof can also be used.
The content ratio of the colorant is preferably 0.5 to 20% by mass, more preferably 2 to 10% by mass in the toner particles of the visible image toner.

[Method for producing visible image toner]
The visible image toner according to the present invention has a softening point so that it can be suitably fixed at a heating temperature of 200 ° C. or less by selecting the type and amount of the binder resin in the above-described method for producing the foil adhesive toner. It can be produced in the same manner except that the glass transition point is adjusted and a colorant is appropriately contained.
Specifically, when the visible image toner is prepared by using the emulsion association method, for example, in the association step (2) in the method for preparing the foil adhering toner, the binder resin fine particles are contained in the aqueous medium. In the aqueous medium in which the binder resin fine particles and the colorant fine particles are present, the dispersion obtained by dispersing the colorant fine particles in a separately prepared aqueous medium is added to and mixed with the dispersion. In addition, a toner for visible image can be produced by adding a flocculant and adjusting the temperature to advance salting-out and at the same time agglomerate and fuse to form colored associated particles. .
Further, for example, in the binder resin fine particle polymerization step (1) in the above method for producing a toner for foil adhesion, a liquid in which a colorant is added to a polymerizable monomer that should form a binder resin is added to an aqueous medium. In this state, the droplets are formed, and in this state, the polymerizable monomer is subjected to radical polymerization reaction by emulsion polymerization to produce colored binder resin fine particles, thereby producing a visible image toner. can do.

[Particle size of toner particles]
The particle diameter of the toner particles constituting the toner for foil adhesion and the visible image toner as described above is preferably 4 to 10 μm, and more preferably 6 to 9 μm, for example, on a volume basis median diameter.
The volume-based median diameter of the toner particles is connected to a computer system (Beckman Coulter) equipped with data processing software "Software V3.51" to "Coulter Counter Multisizer 3" (Beckman Coulter 3). Measure and calculate using the device.
As a measurement procedure, 0.02 g of a measurement sample (foil adhesion toner or visible image toner) and 20 mL of a surfactant solution (for the purpose of dispersing the measurement sample, for example, a neutral detergent containing a surfactant component is purified water. (10% diluted surfactant solution), and ultrasonic dispersion is performed for 1 minute to prepare a toner dispersion. This toner dispersion is poured into a beaker containing “ISOTON II” (manufactured by Beckman Coulter) in a sample stand with a pipette until the display density of the measuring instrument becomes 5% to 10%. By setting this concentration range, a reproducible measurement value can be obtained. In the measuring machine, the measurement particle count number is 25000, the aperture diameter is 100 μm, the frequency range is calculated by dividing the measurement range of 2.0 to 60 μm into 256, and the volume integrated fraction is larger. The 50% particle diameter is defined as a volume-based median diameter (volume D ₅₀ % diameter).

(Developer)
The foil adhering toner and visible image toner of the present invention can be used as a magnetic or non-magnetic one-component developer, but may be mixed with a carrier and used as a two-component developer. In the case of using the toner for foil adhesion and the toner for visible image of the present invention as a two-component developer, the carrier includes metals such as iron, ferrite and magnetite, alloys of these metals with metals such as aluminum and lead, etc. Magnetic particles made of conventionally known materials can be used, and ferrite particles are particularly preferable. Further, as the carrier, a coat carrier in which the surface of the magnetic particles is coated with a coating agent such as a resin, a binder type carrier in which a magnetic fine powder is dispersed in a binder resin, or the like may be used.
The coating resin constituting the coat carrier is not particularly limited, and examples thereof include olefin resins, styrene resins, styrene-acrylic resins, silicone resins, ester resins, and fluorine resins. Moreover, it does not specifically limit as resin which comprises a resin dispersion type carrier, A well-known thing can be used, For example, a styrene-acrylic-type resin, a polyester resin, a fluororesin, a phenol resin etc. can be used.

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

[Foil]
In the present invention, the “foil” is used for providing a character or a pattern having a metallic feeling or glossiness difficult to express by general printing on an image support. As the foil, various kinds of foil such as a gold-silver foil for obtaining a golden or silver image, a color pigment foil for obtaining a color image having a metallic luster, a hologram foil for obtaining a hologram image, etc. Although there are some, the kind of foil used in the present invention is not particularly limited.

  The foil is subjected to a foil image forming process as a transfer foil. Specifically, for example, as shown in FIG. 2, the transfer foil 80 has a layer structure in which a foil 80c is formed on a film-like support 80a made of resin or the like via a release layer 80b. Is. Specifically, the foil 80c includes a foil layer 80d containing a colorant or a metal formed on the release layer 80b, and an adhesive layer 80e formed on the foil layer 80d and exhibiting adhesiveness. Become.

The support 80a is made of a film made of resin or the like, a sheet, or paper. When the support 80a is made of a resin, examples of the resin material include polyethylene terephthalate (PET) resin, polyethylene naphthalate (PEN) resin, polypropylene (PP) resin, polyether sulfone resin, and polyimide resin. A well-known resin material is mentioned.
The support 80a may have a single layer structure or a multilayer structure.

  The release layer 80b is for ensuring good releasability from the support 80a of the foil 80c made of the foil layer 80d and the adhesive layer 80e. The material constituting the release layer 80b is, for example, , A thermosetting resin using melamine or isocyanate as a curing agent, an ultraviolet ray or electron beam curable resin containing an acrylate or an epoxy resin, for example, a known wax such as a fluorine-based or silicon-based monomer or polymer Etc.

The foil layer 80d contains a colorant, a metal material, and the like, and exhibits an aesthetic appearance after being transferred onto the image support.
The foil layer 80d is specifically composed of a colored layer or a layer obtained by laminating a metal layer on the colored layer,
As the colored layer, a known dye or pigment is added to a known resin having desired performance such as good releasability from the release layer 80b and durability after formation of a foil image, if necessary. For example, a coating composition formed by applying the coating composition onto the release layer 80b on the support 80a with a gravure coater, a micro gravure coder, a roll coater, and the like, and drying the coating composition can be used. Examples of the resin for forming the foil layer 80d include an acrylic resin, a styrene resin, and a melamine resin.
The metal layer is a layer having a metallic luster, and can be formed using a metal by a known method such as a vapor deposition method, a sputtering method, or an ion plating method. As a metal material for forming the metal layer, for example, in addition to a simple substance such as aluminum, tin, silver, chromium, nickel, gold, an alloy such as nickel-chromium-iron alloy, bronze, aluminum bronze is used. it can. The metal layer can be about 10-100 nm thick. Moreover, as a metal layer, the patterning process which provides a regular pattern using well-known processing methods, such as washing | cleaning celite processing, an etching process, and laser processing, for example can also be given.

The adhesive layer 80e can be made of, for example, a so-called hot melt type heat-sensitive adhesive that develops binding properties by heating. Examples of heat-sensitive adhesives include various known hot-melt adhesives such as acrylic resins, vinyl chloride-vinyl acetate copolymers, epoxy resins, and ethylene-vinyl alcohol copolymers. A thermoplastic resin is mentioned.
The adhesive layer 80e can be formed by applying a thermoplastic resin that forms a heat-sensitive adhesive onto the foil layer 80d using, for example, a gravure coater, a micro gravure coater, a roll coater, or the like.

(Image support)
The image support used in the image forming method using the foil adhering toner of the present invention may be any image support as long as it can hold a foil image and a visible image. Specifically, for example, from thin paper to thick paper Examples include, but are not limited to, plain paper, high-quality paper, coated printing paper such as art paper or coated paper, and various printing paper such as commercially available Japanese paper and postcard paper. It is not a thing.

[Image forming apparatus]
In the image forming method using the foil adhering toner of the present invention, the foil image forming step and the reprinting step may be performed separately by separate image forming apparatuses or may be performed continuously by one image forming apparatus. .

FIG. 3 is an explanatory sectional view showing an example of the configuration of an image forming apparatus for performing the image forming method using the foil adhering toner of the present invention.
This image forming apparatus is a tandem type color image forming apparatus capable of continuously executing a foil image forming process using a foil adhering toner and a reprinting process using a visible image toner.

  This image forming apparatus includes a foil bonding toner image forming unit 20H that forms a foil bonding toner image on which a foil image is to be formed, and a colored toner image forming unit 20Y that forms a yellow, magenta, cyan, or black toner image, respectively. , 20M, 20C, and 20Bk, and the intermediate transfer unit 10 that transfers the toner images formed in the toner image forming unit 20H for foil adhesion or the colored toner image forming units 20Y, 20M, 20C, and 20Bk onto the image support P. And a fixing device 50 that fixes the toner image by applying pressure while heating the image support P, and a foil transfer device 70 that supplies a foil 80c (see FIG. 5) to the image support P.

  The colored toner image forming unit 20Y forms a yellow toner image, the colored toner image forming unit 20M forms a magenta toner image, and the colored toner image forming unit 20C forms a cyan toner image. Then, a black toner image is formed in the colored toner image forming unit 20Bk.

  The foil adhesion toner image forming unit 20H includes a photoreceptor 11H that is an electrostatic latent image carrier, a charging unit 23H that applies a uniform potential to the surface of the photoreceptor 11H, and a uniformly charged photoreceptor 11H. An exposure unit 22H that forms an electrostatic latent image of a desired shape thereon, a developing unit 21H that transports the foil adhering toner onto the photoconductor 11H to visualize the electrostatic latent image, and a photoconductor after primary transfer. 11H, and a cleaning unit 25H that collects residual toner remaining on 11H.

  The colored toner image forming portions 20Y, 20M, 20C, and 20Bk are uniform on the surfaces of the photoreceptors 11Y, 11M, 11C, and 11Bk that are electrostatic latent image carriers and the photoreceptors 11Y, 11M, 11C, and 11Bk. Charging means 23Y, 23M, 23C, and 23Bk for providing an appropriate potential, and exposure means 22Y, 22M, and 22C for forming electrostatic latent images of a desired shape on the uniformly charged photoreceptors 11Y, 11M, 11C, and 11Bk. , 22Bk, developing means 21Y, 21M, 21C, 21Bk for conveying the color toner onto the photoconductors 11Y, 11M, 11C, 11Bk to visualize electrostatic latent images, and photoconductors 11Y, 11M, Cleaning means 25Y, 25M, 25C, and 25Bk for collecting residual toner remaining on 11C and 11Bk are provided.

The intermediate transfer unit 10 includes an intermediate transfer member 16, a primary transfer roller 13H for transferring the foil bonding toner image formed by the foil bonding toner image forming unit 20H to the intermediate transfer member 16, and a colored toner image forming unit. The colored toner images formed by 20Y, 20M, 20C, and 20Bk were transferred onto the intermediate transfer body 16 by the primary transfer rollers 13Y, 13M, 13C, and 13Bk for transferring to the intermediate transfer body 16 and the primary transfer roller 13H. A secondary transfer roller that transfers the toner image for foil adhesion or the visible toner image transferred onto the intermediate transfer body 16 by the primary transfer rollers 13Y, 13M, 13C, and 13Bk onto the image support P on which the foil image is formed. 13A and a cleaning unit 12 that collects residual toner remaining on the intermediate transfer member 16.
The intermediate transfer body 16 has an endless belt shape that is stretched by a plurality of support rollers 16a to 16d and is rotatably supported.

  The fixing device 50 is provided in a state in which a pair of heat and pressure rollers 51 and 52 are in pressure contact with each other and a nip portion N is formed in the pressure contact portion.

As shown in FIG. 4, the foil transfer device 70 includes a foil transfer roller 73a that is driven by appropriate driving means and rotated clockwise, and a foil transfer roller 73b that is rotated by being driven by the foil transfer roller 73a. The conveying means 79 is provided so as to be in pressure contact with each other via a long sheet-shaped transfer foil 80 having a foil 80c to be supplied to the image support P, and to move the transfer foil 80. Is provided.
The foil transfer device 70 is provided with a separation mechanism (not shown) in which the foil transfer rollers 73a and 73b are separated from each other, and the separation mechanism is removed from the fixing device 50 through a reprinting process. When the discharged foil image S and the image support P on which the visible image is formed pass through the foil transfer device 70, the foil transfer rollers 73a and 73b are changed to be separated from each other.

The conveying means 79 for running the transfer foil 80 includes an original winding portion 71 having an original winding roller 71A around which the transfer foil 80 is wound and reverse tension is applied to prevent the transfer foil 80 from being loosened, and a drive source. And the winding portion 72 having the winding roller 72A rotated counterclockwise (arrow direction in FIG. 4), and the traveling direction of the transfer foil 80 is the same as the moving direction of the surface of the foil transfer roller 73a. It is arranged as follows.
The rotational speed of the take-up roller 72A of the transport means 79 is such that the transport speed of the transfer foil 80 at the press contact portion of the foil transfer rollers 73a and 73b is the same as the transport speed of the image support P at the press contact portion. .

  The foil transfer rollers 73a and 73b have the same function as the heat and pressure roller, and at least one of the foil transfer rollers 73a and 73b is provided with a heating source (not shown).

[Foil image forming process]
In such an image forming apparatus, first, in the foil adhesion toner image forming unit 20H, the photosensitive member 11H is charged by the charging unit 23H and exposed by the exposure unit 22H, thereby forming an electrostatic latent image. The electrostatic latent image is developed with the foil adhering toner in the developing means 21H to form a foil adhering toner image, and the foil adhering toner image is transferred onto the intermediate transfer member 16 by the primary transfer roller 13H. On the other hand, the image support P accommodated in the paper feed cassette 41 is fed by the paper feed transport means 42 and transported by a plurality of paper feed rollers 44a, 44b, 44c, 44d and registration rollers 46, and is subjected to secondary transfer. The foil bonding toner image on the intermediate transfer member 16 is transferred onto the image support P by the roller 13A. Thereafter, the toner image for foil bonding transferred onto the image support P is fixed by pressing and heating in the fixing device 50 to form a toner image portion H for foil bonding.

The fixing conditions of the fixing device 50 in the foil image forming process vary depending on the type of foil adhesion toner used and the type of visible image toner used in the next follow-up printing process, but can be as follows, for example.
-Heating temperature: 150-230 ° C
・ Nip time: 50-500msec
The nip time is calculated from the length in the conveyance direction (mm) / linear velocity (mm / sec) × 1000 of the nip portion of the heat and pressure rollers 51 and 52.
Further, the heating temperature in the foil image forming step refers to the surface temperature of the heating and pressing roller 51 that contacts the surface of the image support P to which the foil bonding toner image has been transferred.

In the foil transfer device 70, the image support P on which the toner image portion H for bonding the foil is formed is transferred to the transfer foil 80 in a state of being wound around the original winding roller 71A by the conveying means 79. By being driven and rotated and wound up, it is conveyed along the conveying path so as to pass through the pressure contact portions of the foil transfer rollers 73a and 73b.
At the pressure contact portions of the foil transfer rollers 73a and 73b, as shown in FIG. 5, the transfer foil conveyed onto the image support P (FIG. 5 (a)) on which the foil bonding toner image portion H is formed. 80 are stacked in contact with each other (FIG. 5B), and heated in this state by the foil transfer rollers 73a and 73b (FIG. 5C) and naturally cooled after passing through the pressure contact portions of the foil transfer rollers 73a and 73b. As a result, the foil 80c is adhered onto the foil adhesion toner image portion H, and the portion of the transfer foil 80 that is not in contact with the foil adhesion toner image portion H is peeled off (FIG. 5D). ), A foil image S having a shape that coincides with the shape of the toner image portion H for foil adhesion is formed (FIG. 5E).
The portion of the transfer foil 80 that is not in contact with the foil adhesion toner image portion H of the foil 80c is taken up by the take-up roller 72A together with the support 80a and the release layer 80b.

The fixing conditions in the foil transfer device 70 vary depending on the type of foil adhesion toner used, but can be as follows, for example.
・ Heating temperature: 100-180 ° C
・ Nip time: 50-500msec
The nip time is calculated from the length (mm) / linear velocity (mm / sec) × 1000 in the conveyance direction of the pressure contact portions of the foil transfer rollers 73a and 73b.
The heating temperature is the surface temperature of the foil transfer roller 73a that contacts the surface of the image support P on which the toner image portion H for foil adhesion is formed.

[Reprint process]
The image support P on which the foil image S is formed is once transported to the paper discharge transport path having the paper discharge rollers 47, then transported in the reverse direction, and is branched from the paper discharge transport path by the branch plate 49. The toner is conveyed to the secondary transfer roller 13A via the paths 48a and 48b, and the visible toner image is transferred.
Specifically, in the colored toner image forming units 20Y, 20M, 20C, and 20Bk, the photosensitive members 11Y, 11M, 11C, and 11Bk are charged by the charging units 23Y, 23M, 23C, and 23Bk, and the exposure units 22Y, 22M, and 22C. , 22Bk to form an electrostatic latent image, and the electrostatic latent image is developed with visible image toner in the developing means 21Y, 21M, 21C, and 21Bk to form a visible toner image of each color. The visible toner images of the respective colors are sequentially superimposed and transferred onto the intermediate transfer member 16 by the primary transfer rollers 13Y, 13M, 13C, and 13Bk, and transferred onto the intermediate transfer member 16 by the secondary transfer roller 13A. The visible toner images of the respective colors are collectively transferred onto the image support P on which the foil image S is formed.
The visible toner images of the respective colors transferred onto the image support P on which the foil image S is formed are fixed by a heating and pressing process in which pressure is applied while being heated in the fixing device 50 to form a visible image. The image support P on which the foil image S and the visible image are formed passes between the foil transfer rollers 73a and 73b in the separated state of the foil transfer device 70, and is further discharged to the outside by the paper discharge roller 47. And placed on the paper discharge tray 60.
In the follow-up printing process, the visible image may be formed in a region where the foil image S on the image support P is not formed, or may be formed on the foil image S on the image support P.

The fixing condition of the fixing device 50 in the follow-up printing process is that the heating temperature is 200 ° C. or less, preferably 120 to 190 ° C., and the nip time is preferably 10 to 300 msec, more preferably 20 to 70 msec. It is.
The heating temperature in the follow-up printing process refers to the surface temperature of the heating and pressing roller 51 that contacts the surface of the image support P to which the visible toner image has been transferred.
When the heating temperature and the nip time in the follow-up printing process are in the above ranges, fluidity is generated such that the toner image portion H for bonding the foil 80 adhering the foil 80c is deformed by the heat applied in the follow-up printing process. Is reliably prevented. On the other hand, when the heating time in the follow-up printing process is excessively low or the nip time is excessively short, there is a possibility that a fixing defect may occur in the visible image. Further, when the heating time in the follow-up printing process is excessively high or the nip time is excessively long, the foil bonding toner image portion H to which the foil 80c is bonded is softened and deformed, so that the image is pressed. There is a possibility that streaks due to distortion may occur in the foil 80c adhered to the support P.

After the foil adhesion toner image is transferred to the intermediate transfer member 16, the toner remaining on the photoreceptor 11H is removed by the cleaning means 25H, and then used for forming the next foil adhesion toner image. The
The photoreceptors 11Y, 11M, 11C, and 11Bk after the visible toner images of the respective colors are transferred to the intermediate transfer member 16 are respectively cleaned by the cleaning units 25Y, 25M, 25C, and 25Bk. After the toner remaining in the toner is removed, it is used to form visible toner images of the following colors.
On the other hand, the intermediate transfer body 16 after the foil adhesion toner image or the visible toner image of each color is transferred onto the image support P by the secondary transfer roller 13A is the toner remaining on the intermediate transfer body 16 by the cleaning means 12. Then, the toner image is subjected to intermediate transfer of the next foil adhesion toner image or each color visible toner image.

  According to the foil adhering toner as described above, since the foil adhering toner has a specific storage elastic modulus, the adhesive property of the foil image is good, and furthermore, in order to fix the visible toner image, 200 is used. Even when the pressure is applied while heating to below ℃, the foil adhesion toner image portion H due to the foil adhesion toner loses elasticity due to the heating, and the flow is extremely suppressed. There is no occurrence of streaks due to distortion in the foil 80c bonded to the support P, and therefore, a visible image can be formed in a state in which the desired finished state in the foil image forming process is maintained. An image in which both a foil image S in a good finished state and a desired visible image are obtained can be easily formed.

  As mentioned above, although embodiment of this invention was described concretely, embodiment of this invention is not limited to said example, A various change can be added.

  For example, in the above description, the case where the foil image S and the visible image are formed on the surface of the image support P has been described. However, the foil image and the visible image can be formed on both surfaces of the image support, respectively. In this case, after forming the foil image (S1) and the visible image (T1) on the surface of the image support, the foil image (S2) and the visible image (T2) may be formed on the back surface of the image support. First, a foil image (S1) is formed on the surface of the image support, then a foil image (S2) is formed on the back surface of the image support, and then a visible image (T1) is formed on the surface of the image support. It is preferable to form and finally form a visible image (T2) on the back surface of the image support.

  Further, for example, the intermediate transfer unit 10 is not limited to a configuration commonly used in the foil image forming process and the follow-up printing process, and an intermediate transfer unit may be provided for each. In such a configuration, the same fixing device is not used for forming the toner image portion for foil adhesion and the visible image, and a fixing device may be provided separately for each.

Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto. The molecular weight of the resin fine particles, the volume-based median diameter of the toner for foil adhesion, and the storage elastic modulus G ′ _{160 to 180} were measured as described above.

[Foil Adhesive Preparation Example A: Emulsion Association Method Toner]
(1) Production of resin fine particles A (first stage polymerization)
4 parts by mass of polyoxyethylene (2) sodium dodecyl ether sulfate and 3000 parts by mass of ion-exchanged water are charged into a reaction vessel equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introducing device, and the stirring speed is 230 rpm under a nitrogen stream. The temperature was raised to 80 ° C. with stirring.
After the temperature increase, an initiator solution in which 4 parts by mass of potassium persulfate (KPS) was dissolved in 200 parts by mass of ion-exchanged water was added, and the liquid temperature was adjusted to 75 ° C.
Styrene 567 mass parts n-butyl acrylate 165 mass parts Methacrylic acid 68 mass parts was dripped over 1 hour. After the dropwise addition, the resin fine particle dispersion [A1] in which the resin fine particles [A1] are dispersed was prepared by heating and stirring at 75 ° C. for 2 hours to perform a polymerization reaction. It was 300,000 when the weight average molecular weight of resin fine particle [A1] was measured.

(Second stage polymerization)
Next, 2 parts by mass of polyoxyethylene (2) sodium dodecyl ether sulfate and 1270 parts by mass of ion-exchanged water are put into a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device, and the temperature is raised to 80 ° C. Heated. After heating, the resin fine particle dispersion [A1] is 40 parts by mass in terms of solid content,
Styrene 129 parts by weight n-butyl acrylate 47 parts by weight Methacrylic acid 15 parts by weight n-octyl mercaptan 0.5 parts by weight “WEP-5” (manufactured by NOF Corporation) 80 parts by weight at 80 ° C. 5 "is dissolved in a monomer mixture and emulsified by mixing and dispersing for 1 hour using a mechanical dispersion device" CLEAMIX "(M Technique Co., Ltd.) having a circulation path. After preparing a particle dispersion and adding an initiator solution in which 6 parts by mass of potassium persulfate (KPS) is dissolved in 100 parts by mass of ion-exchanged water to the emulsified particle dispersion, the mixture is heated at 80 ° C. for 1 hour. By performing a polymerization reaction with stirring, a resin fine particle dispersion [A2] in which the resin fine particles [A2] are dispersed was prepared. The high molecular weight component ratio of the resin fine particles [A2] was 52 area%.

(Third stage polymerization)
Next, after adding an initiator in which 10 parts by mass of potassium persulfate (KPS) was dissolved in 200 parts by mass of ion-exchanged water in the resin fine particle dispersion [A2], the liquid temperature was brought to 80 ° C.,
Styrene 386 parts by weight n-butyl acrylate 140 parts by weight Methacrylic acid 45 parts by weight n-octyl mercaptan 13 parts by weight were added dropwise over 1 hour, and then heated and stirred at 80 ° C. for 2 hours to conduct a polymerization reaction. Thereafter, by cooling to 28 ° C., a resin fine particle dispersion [A3] in which the resin fine particles [A3] are dispersed was prepared.

(2) Preparation of foil adhesion toner A In a reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introduction device, 450 parts by mass of resin fine particle dispersion [A3] (in terms of solid content), 1100 mass of ion-exchanged water And 2 parts by mass of sodium dodecyl sulfate were added and stirred. After adjusting the temperature in the reaction vessel to 30 ° C., the pH was adjusted to 10 by adding a 5 mol / L aqueous sodium hydroxide solution.
Next, an aqueous solution in which 70 parts by mass of magnesium chloride hexahydrate was dissolved in 75 parts by mass of ion-exchanged water was added over 10 minutes at 30 ° C. under a stirring frame. The temperature was raised after standing for 3 minutes, and the temperature of the system was raised to 85 ° C. over 60 minutes, and the aggregation and fusion of the resin fine particles [A3] were continued while maintaining the temperature at 85 ° C. In this state, the particle size of the aggregated particles formed using “Multisizer 3” (manufactured by Beckman Coulter, Inc.) is measured, and when the volume-based median diameter of the aggregated particles becomes 6.7 μm, Aggregation was stopped by adding an aqueous solution in which 200 parts by mass was dissolved in 860 parts by mass of ion-exchanged water.
After the flocculation was stopped, the liquid temperature was set to 98 ° C. as a ripening treatment, and the mixture was heated and stirred for 8 hours to advance the fusion between the flocculated particles, thereby forming toner base particles [A]. After the aging treatment, the liquid temperature was cooled to 30 ° C., the pH in the liquid was adjusted to 2 using hydrochloric acid, and stirring was stopped.
The obtained toner base particles [A] are subjected to solid-liquid separation using a basket type centrifuge “MARK III model number 60 × 40 (manufactured by Matsumoto Kikai Co., Ltd.)” to form a wet cake of toner base particles [A]. The wet cake was washed with ion-exchanged water at 40 ° C. until the electric conductivity of the filtrate reached 5 μS / cm using the basket-type centrifuge, and then “flash jet dryer” (manufactured by Seishin Enterprise Co., Ltd.) The toner base particles [A] were obtained by carrying out a drying treatment until the water content reached 0.5% by mass.
1.0 part by mass of hexamethylsilazane-treated silica (average primary particle size 12 nm, hydrophobization degree 68) and n-octylsilane-treated titanium dioxide (average primary particle size) with respect to 100 parts by mass of the toner base particles [A] Toner [A] was prepared by adding an external additive consisting of 0.3 parts by mass of 20 nm, hydrophobizing degree 63) and performing an external addition treatment with a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.).
The external addition process using a Henschel mixer was performed under the conditions of a peripheral speed of a stirring blade of 35 m / second, a processing temperature of 35 ° C., and a processing time of 15 minutes.
Table 1 shows the storage elastic modulus G ′ (storage elastic modulus G ′ _160-180 ), softening point, and high molecular weight component ratio in the temperature range of 160 to 180 ° C. of the above toner for foil bonding [A].

[Foil Adhesive Preparation Examples B to E, G, H: Emulsion Association Method Toner]
In Preparation Example A of the foil adhering toner, the addition amount of the resin fine particle dispersion [A1] and n-octyl mercaptan used in the second stage polymerization in the preparation process of the resin fine particles A, and the preparation process of the foil adhering toner A are used. Foil adhesive toners [B] to [E], [G] and [H] were prepared in the same manner except that the amount of magnesium chloride hexahydrate added was changed according to Table 1. Table 1 shows the storage elastic moduli G ′ _{160 to 180} , softening point and high molecular weight component ratio of these toners [B] to [E], [G] and [H].

[Foil Adhesive Preparation Example F: Crushing Toner]
(1) Mixing step A mixture was obtained by mixing the following materials with a “Henschel mixer” (manufactured by Mitsui Mining Co., Ltd.) for 5 minutes under the condition that the peripheral speed of the stirring blade was 25 m / sec.
Polyester resin (bisphenol A-ethylene oxide adduct, terephthalic acid, trimellitic acid condensate: weight average molecular weight 20,000): 95 parts by mass Polyester resin (bisphenol A-ethylene oxide adduct, terephthalic acid, trimellitic Acid condensate: weight average molecular weight 80,000): 5 parts by mass Wax (pentaerythritol tetrastearate): 6 parts by mass Charge control agent (boron dibenzylate): 1 part by mass (2) Kneading step The mixture was kneaded while being heated to 110 ° C. with a twin screw kneader to obtain a kneaded product, and then the kneaded product was cooled.
(3) Grinding step The obtained kneaded material was coarsely pulverized with a “hammer mill” (manufactured by Hosokawa Micron) and then finely pulverized with a “turbo mill T-400 type” (manufactured by Turbo Kogyo Co., Ltd.) to obtain a fine powder.
(4) Classifying Step Toner base particles [F] were obtained by classifying the obtained fine powder with an air classifier.
(5) External Addition Step As for the toner base particles [F], in the same manner as the toner base particles [A], hexamethylsilazane-treated silica (average primary particle size of 12 nm) is added to 100 parts by weight of the toner base particles [F]. An external additive consisting of 1.0 part by mass of hydrophobization degree 68) and 0.3 part by mass of titanium dioxide treated with n-octylsilane (average primary particle size 20 nm, hydrophobization degree 63) was added to a Henschel mixer (Mitsui The foil adhering toner [F] was prepared by external addition treatment by Miike Mining Co., Ltd. Table 1 shows the storage elastic modulus G ′ _{160 to 180} , the softening point, and the high molecular weight component ratio of the toner for foil adhesion [F].

[Developer Preparation Examples A to H]
With respect to the manufactured foil bonding toners [A] to [H], a ferrite carrier having a volume-based median diameter of 60 μm coated with a silicone resin is used, and the concentration of the foil bonding toner is 6 mass using a V-type mixer. % To prepare a foil adhesive developer [A] to [H].

<Examples 1-6, Comparative Examples 1-2>
According to Table 1, foil adhesive developers [A] to [H] with foil adhesive toners [A] to [H], and commercially available cyan toner [C] or commercially available black toner [Bk] as visible image toner The prints [1] to [8] on which the test images having the design foil images Sa, Sb, Sc and the visible image Ta shown in FIG. 6 were formed were produced, and the prints were evaluated. The thickness of the lines of the foil images Sa and Sb is 0.5 mm, and the character size of the visible image Ta is 10.5 points.
Specifically, the printed matter has a toner image forming part for foil adhesion on a commercially available digital image forming apparatus “bizhub Pro C6500” (manufactured by Konica Minolta Business Technologies) having the same configuration as the image forming apparatus shown in FIG. It was formed using a modified machine.
As the image support (P), a commercially available B4-size image support “OK topcoat +” (manufactured by Oji Paper Co., Ltd., basis weight: 157 g / m ² , paper thickness: 131 μm) was used.
The toner supply amount in each toner image forming unit was set to 4 g / m ² .
As the transfer foil, “BL No. 2 Gold 2.8” manufactured by Murata Gold Leaf Co., Ltd. was used.
Cyan toner [C] is a commercial product corresponding to “bizhub C6500”.
The black toner [Bk] is a commercially available product corresponding to “bizhub C6500”.
The fixing device includes an upper heating and pressure roller in which a 3 mm thick silicone rubber layer and a polytetrafluoroethylene (PTFE) coating layer are arranged in this order on an aluminum base having an outer diameter of 100 mm and a thickness of 10 mm; And a lower heating pressure roller in which a silicone rubber layer having a thickness of 3 mm is disposed on an aluminum substrate having an outer diameter of 80 mm and a thickness of 10 mm. A halogen lamp is provided as a heating source in each heating pressure roller. The temperature is controlled by a thermistor.

The conditions in the fixing device in the foil image forming process are as follows.
・ Surface temperature of upper heating pressure roller: Set to 190 ° C ・ Surface temperature of lower heating pressure roller: Set to 100 ° C
-Conveyance speed (linear speed) of image support: 100 mm / sec
・ Nip time: 70msec
-Image carrier transport direction: Longitudinal direction-Environment: Normal temperature and humidity environment (temperature 20 ° C, relative humidity 50% RH)

The conditions in the foil transfer apparatus in the foil image forming process are as follows.
-Surface temperature of the foil transfer roller (upper): set to 150 ° C-Surface temperature of the foil transfer roller (lower): set to 100 ° C-Nip width (length in the conveyance direction of the nip portion): 7 mm
-Conveyance speed (linear speed) of image support: 100 mm / sec
・ Nip time: 70msec
-Image carrier transport direction: Longitudinal direction-Environment: Normal temperature and humidity environment (temperature 20 ° C, relative humidity 50% RH)

The conditions in the reprinting process are as follows.
・ Surface temperature of upper heating and pressure roller: set to 180 ° C. ・ Surface temperature of lower heating and pressure roller: set to 100 ° C. ・ Nip width (length in nip transport direction): 7 mm
・ Nip time: 40 msec
-Image carrier transport direction: Longitudinal direction-Environment: Normal temperature and humidity environment (temperature 20 ° C, relative humidity 50% RH)

  The obtained prints [1] to [8] were evaluated for the adhesiveness of the transfer foil, the transferability of the visible image on the foil image, and the presence or absence of streaks after the reprinting process. The results are shown in Table 1.

<Adhesiveness of transfer foil>
After applying the tape “Scotch Mending Tape MP-18” (manufactured by Sumitomo 3M) on the two types of foil images Sa and Sb of the test image shown in FIG. 6, the tape is peeled off by hand, and the tape is peeled off. The state of the foil image was observed with the naked eye and a magnifier with a magnification of 10 times, and evaluated according to the following evaluation criteria. In addition, the case where it is rank 3 or rank 2 is judged to have no practical problem.
-Evaluation criteria-
Rank 3: There is no fine peeling that can be confirmed by loupe observation.
Rank 2: Although there is a fine peeling that can be confirmed by magnifying glass observation, it can be judged that there is no problem with the naked eye.
Rank 1: There is one in which peeling can be confirmed with the naked eye.

<Fixability of visible image on foil image>
The fixed toner is rubbed on the visible visible image Ta formed on the foil image Sc of the test image shown in FIG. And it confirmed with the magnifier of 10 time magnification, and evaluated according to the following evaluation criteria. In addition, the case where it is rank 3 or rank 2 is judged to have no practical problem.
-Evaluation criteria-
Rank 3: There is no fine peeling that can be confirmed by loupe observation.
Rank 2: Although there is a fine peeling that can be confirmed by magnifying observation, it can be determined that there is no problem in visual observation.
Rank 1: Some can be confirmed by naked eye observation.

<Occurrence of streaks>
The foil image Sc of the test image shown in FIG. 6 was observed with the naked eye and a magnifier with a magnification of 10 times, and evaluated according to the following evaluation criteria. In addition, it is judged that the case of rank 5 or rank 4 is not a problem practically.
-Evaluation criteria-
Rank 5: No streak is observed in both the naked eye observation and the magnifying glass observation.
Rank 4: No streak is observed with the naked eye, and one or two streaks are observed with the magnifying glass.
Rank 3: No streaking was observed in the naked eye observation, and 3-5 streaks were observed in the loupe observation.
Rank 2: No streaking was observed with the naked eye, but 6 or more streaks were observed with the magnifying glass.
Rank 1: The occurrence of one or more streaks is observed by visual observation.

DESCRIPTION OF SYMBOLS 10 Intermediate transfer part 11H, 11Y, 11M, 11C, 11Bk Photoconductor 12 Cleaning means 13H, 13Y, 13M, 13C, 13Bk Primary transfer roller 13A Secondary transfer roller 16 Intermediate transfer body 16a-16d Support roller 20H Foil adhesion toner image Forming portions 20Y, 20M, 20C, 20Bk Colored toner image forming portions 21H, 21Y, 21M, 21C, 21Bk Developing means 22H, 22Y, 22M, 22C, 22Bk Exposure means 23H, 23Y, 23M, 23C, 23Bk Charging means 25H, 25Y , 25M, 25C, 25Bk Cleaning means 41 Paper feed cassette 42 Paper feed transport means 44a, 44b, 44c, 44d Paper feed roller 46 Registration roller 47 Paper discharge rollers 48a, 48b, 48c Transport path 49 Branch plate 50 Fixing devices 51, 52 Heating and pressing roller 60 Paper discharge tray 70 Foil transfer device 71 Original winding portion 71A Original winding roller 72 Winding portion 72A Winding rollers 73a and 73b Foil transfer roller 79 Conveying means 80 Transfer foil 80a Support body 80b Release layer 80c Foil 80d Foil layer 80e Adhesive layer N Nip part P Image support H Foil adhesion toner image part S, Sa, Sb Foil image Ta, Tb, Tc Visible image

Claims (5)

The foil is brought into contact with the foil-adhering toner image portion formed on the image support by electrophotography using a foil-adhering toner containing a binder resin including a thermoplastic resin, and the foil is heated. A foil image is formed by adhering a foil on the adhesive toner image portion, and then formed by electrophotography using at least one visible image toner on the image support on which the foil image is formed. A foil adhering toner used in an image forming method for forming a visible image by pressing and fixing the resulting visible toner image while heating at 200 ° C. or lower,
A toner for foil bonding, wherein a storage elastic modulus G ′ in a temperature range of 160 to 180 ° C. is in a range of 1 × 10 ³ N / m ^{2 to} 5 × 10 ⁴ N / m ² .   The foil adhering toner according to claim 1, wherein the toner is a clear toner.   3. A binder resin containing a resin component having a molecular weight of 60,000 or more as measured by gel permeation chromatography (GPC) of 10 to 30 area%. The toner for foil adhesion described in 1. A method for producing the foil adhering toner according to any one of claims 1 to 3,
A step of aggregating the binder resin fine particles by adding an aggregating agent made of a metal salt into an aqueous medium in which the binder resin fine particles containing a binder resin including a thermoplastic resin are dispersed. A method for producing a foil adhering toner. Forming a toner image portion for foil adhesion on an image support by electrophotography using a foil adhesion toner containing a binder resin including a thermoplastic resin;
A foil image forming step of forming a foil image on the foil adhesive toner image portion by contacting and heating the foil on the foil adhesive toner image portion;
On the image support on which the foil image has been formed, a visible toner image is formed by electrophotography using at least one visible image toner, and is fixed by applying pressure while heating at 200 ° C. or lower. In an image forming method having a visible image forming step of forming a visible image,
The foil adhesive toner has a storage elastic modulus G ′ in a temperature range of 160 to 180 ° C. in a range of 1 × 10 ³ N / m ^{2 to} 5 × 10 ⁴ N / m ^2. An image forming method.

Images