JP3520723B2 - Image forming method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method for forming an image on a molded article such as metal, glass, pottery, or plastic, particularly a container.

[0002]

2. Description of the Related Art Metal can bodies such as aluminum and steel cans are widely used as containers for filling beverages, foods, paints and the like, and in particular, there is a very high demand as a container for beverages. In recent years, beverage products have become more diverse in small quantities, and the need for notation by distribution channel is increasing. However, cans made by printing methods that require plate making such as gravure or offset using ink for metal plates. The body surface decoration method has problems in cost and productivity. The same problems as described above also occur in glass containers such as bottles for drinking water.

To address these problems, a container surface decoration method using electrophotography has been proposed. For example, JP-A-1
Japanese Patent Laid-Open No. 163747- proposes a method of forming an image by forming a toner image on the surface of a metal can having a photoconductor layer by development, fixing the toner image, and applying a finishing varnish. However, in this method, there is a problem that the toner image melts and flows in the step of applying the varnish, and problems such as deterioration of image quality and occurrence of bar code reading error are likely to occur.

Further, in Japanese Laid-Open Patent Publication No. 1-198383, a multicolor image is formed on a sheet in which a strippable film is laminated on a belt belt by an electrophotographic method, and then the film is stripped and heated and pressure-bonded to the surface of the container. A method of forming an image by doing so has been proposed. However, when this method is used, the image due to the softening of the toner image is generated in an environment that requires hot filling for sterilization or long-term high temperature storage such as Japanese tea and coffee, and an environment that requires microwave oven heating. Peeling and flow occur and there is a problem with stability of printing surface and container quality. Furthermore, JP-A-6-
Japanese Patent No. 99570 discloses that the surface of a cylinder coated with an adhesive is
Although a method of forming an image by adhering a film printed by an electrophotographic method has been disclosed, this method also cannot improve the problems due to image peeling and flow due to the softening of the toner image as described above.

In order to improve the above problems,
Japanese Patent Application Laid-Open No. 8-194325 discloses an image forming method in which a softening point is in the range of 90 to 130 ° C., a toner containing an epoxy resin as a binder resin is transferred onto the surface of a plastic container, and then fixed by irradiation with near infrared rays. Proposed.
However, in this method, since the toner is electrostatically transferred directly to the container surface, there are restrictions on the material and thickness of the container. For example, a film deposited with a metal barrier material such as aluminum, a thick plastic container, a metal container,
Not applicable to glass containers, ceramics, etc. For the above reasons, the method for decorating the surface of a container using the electrophotography is still unworkable due to many problems.

On the other hand, recently, as a souvenir or a sales promotion item, an arbitrary character on the surface of a ceramic such as a mug,
Demand for marking designs, signatures, etc. in small quantities is increasing. When the electrophotographic method is applied to such applications, the toner image is once transferred and fixed on a paper having a water-soluble release layer, which is generally called a water transfer paper, and then wetted with water to transfer the image to the ceramic surface. A method of applying a dry finish and a method of temporarily transferring and fixing a toner image on a paper having a layer that melts and separates at a temperature higher than that of the toner and then heating the image to transfer the image to the surface of the ceramics are used. However, in either case, the cost of the transfer paper is high, and in terms of quality, there is a problem in durability of the image with respect to repeated heating and cleaning operations, and it is not practical.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an image forming method for a molded product, which is improved in various drawbacks of the above-mentioned conventional techniques.
That is, the object of the present invention is (1) to form an image on a hard molded product such as metal, glass, or ceramics without requiring a printing plate and without impairing productivity, (2) under high temperature for a long period of time. However, there is no need for image deterioration due to image flow or peeling, and no error in reading distribution information records such as barcodes. (3) High-definition full-color image output with high color development is required. An object of the present invention is to provide an image forming method that satisfies the above conditions.

[0008]

A method for forming a color image by electrophotography includes yellow, magenta, cyan, and
Although any color is reproduced by stacking each black toner, the toner used is a resin in which pigments are dispersed, so the image thickness is generally thicker than that of printing ink, and The thickness varies depending on the type and thickness. Therefore, when only the toner image functions as an adhesive layer and is interposed between the molded product and the plastic film, not only the adhesive strength becomes uneven, but also minute voids are generated in the thin toner layer portion and the non-image portion. However, it is thought that this may impair the quality and cause image bleeding and peeling in a heated environment. As a result of a study by the present inventors, when sealing and fixing an image on the interface between a molded product such as a container and a plastic film that protects the surface of the molded product, a conventional electrophotographic process uses a thin toner layer portion and a non-image portion. It has been found that the above problems can be solved by adding a step of developing and transferring the heat self-curable particles to the above, and has completed the present invention.

That is, in the first image forming method of the present invention, a sheet of a particle image layer comprising a chromatic color toner particle image and a thermal self-curable particle image formed on a temporary image holding member is formed. The present invention is characterized by including a step of transferring onto a sheet-like substrate and a step of heating and fixing the unfixed particle image layer on the sheet-like substrate while being pressed against the surface of the plate-like material for producing a molded article or the molded article. The second image forming method comprises the steps of transferring and fixing the particle image layer consisting of chromatic toner particle image and thermal self-curing particle image formed on the image temporary holding member onto the sheet substrate, and The method is characterized by comprising the step of heating and fixing the image layer fixed on the sheet-shaped substrate while pressing it against the surface of the plate-shaped material for forming a molded product or the molded product.

In the image forming method of the present invention, yellow, magenta, cyan and black toners can be used as the chromatic toner.

In the present invention, it is preferable to form the particle image layer by setting the developing order so that the thermal self-curable particle image is the outermost layer on the sheet-shaped substrate. In addition, the relationship between the maximum value X of the volume average particle diameter of the chromatic toner particles, that is, the maximum value of the volume average particle diameter of the toner particles of each color, and the volume average particle diameter Y of the thermal self-curable particles is 0. It is preferable that 5X ≦ Y ≦ 3.0X is satisfied. Furthermore, as the thermo-self-curable particles, those containing a phenol resin are preferable.

In the image forming method of the present invention, it is preferable to seal and fix an image at the interface between a molded article such as a container and a sheet-like substrate such as a plastic film for protecting the surface of the molded article,
In order to improve the fixing maintenance without deteriorating the toner image quality and enhance the adhesive strength between the container and the sheet-like substrate, the thermo self-curing particles are used separately from the chromatic color toner particles and developed by an electrophotographic method or the like. It has a feature in that it is transferred.
Then, the thermal self-curable particles should be closest to the container material side at the adhesive interface between the plate-shaped material for forming a molded product or the molded product and the sheet-shaped substrate, that is, the thermal self-curable particle image on the sheet-shaped substrate. By providing the development order so that is the outermost layer, in the non-image part, while increasing the adhesive strength between the plate-shaped material for forming a molded article or the container and the sheet-shaped substrate,
In the image area, the film thickness can be made uniform, and the thermal self-curing particle image can be cured while being fused with the chromatic toner with which the thermal self-curing particle image comes into contact when heated, and a strong image that does not reflow in a high temperature environment can be formed. Of.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. In the present invention, the method of forming the image temporary holding member and the particle image layer for supporting the particle image layer consisting of chromatic toner particle image and thermal self-hardening particle image is not particularly limited. For example, a particle image layer may be formed on the transfer member by an electrophotographic method using an electrophotographic photosensitive member, a dielectric recording material or the like. FIG. 1 shows a case where a particle image layer is formed on a transfer body using an electrophotographic photoreceptor, and is a schematic configuration diagram showing an example of an image forming apparatus used in the image forming method of the present invention. is there. In FIG. 1, 1 is an electrostatic latent image carrier, 2 is a charging device, 3 is an exposure device, 4-X is a developing device for heat self-curing particles, 4-K is a developing device for black toner, 4-
Y is a developing device for yellow toner, 4-M is a developing device for magenta toner, 4-C is a developing device for cyan toner, 5 is a baffle, 6-1 and 6-2 are transfer corotrons, 7 is a belt transfer member, 8 Is a drive roll, 9-1 to 9-6 is a tension roll, 10 is a heating member, 11 is a plastic film (in this figure, a roll-shaped one is shown, but the presence or absence of cutting, the cutting size and shape, etc. are limited. 12 is a plastic film conveying member, 13 is a plate material for producing a metal container (illustration is not limited to a material, and may be a molded body), 14 is a metal container raw material plate conveying member, 15 Indicates a pressure roll.

In the image forming apparatus shown in FIG. 1, the electrostatic latent image formed on the surface of the electrostatic latent image carrier 1 by the charging device 2 and the exposure device 3 is developed by the developing devices 4-X, 4-K. 4-
Y, 4-M, and 4-C are sequentially developed to form a particle image layer including a thermal self-curable particle image and a toner image, and the transfer corotron 6-1 serves as a first transfer member, which is a belt transfer member 7. Is transferred to the surface of. The electrostatic latent image carrier 1
The number of units of the developing device 4 is the total number of types of toner and the number of types of thermal self-curing particles. The particle image layer formed on the surface of the belt transfer body 7 is transferred by the transfer corotron 6-2 to the plastic film 11 which is the secondary transfer body, and the plastic film 11 on which the particle image layer is transferred is a plastic film. It is conveyed by the conveying member 12, and is fixed to the metal container manufacturing plate material 13 by the heating member 10 and the pressure roll 15 via the particle image layer. As described above, an image is formed on the metal container manufacturing plate material 13. Thereafter, for example, in the case of producing a metal can container, the container is produced by a known can manufacturing method such as a Miraseam method, a Toyo Seam method, a Cono Weld method or the like.

Here, a description of each device and member will be given below, but any device known in the electrophotographic system can be applied to each device and member in the above process, without any limitation. It is not something that will be done.

In the present invention, the developer used in the developing device is a two-component developer composed of toner and carrier,
Any one-component developer such as a magnetic toner or the like which is used alone can be used, and as a developing method, a cascade method, a touchdown method, a magnetic brush method or the like can be applied. Among them, the two-component developer is preferably used because the carrier shares the functions of stirring, conveying, charging, etc. of the developer, and high-speed development is possible even with color toner. As a developing method, when productivity is important, a magnetic brush method using a magnetic roll as a developer transport carrier is preferable, and in order to improve developing efficiency, a method of applying an AC electric field to a developing DC bias is preferable. .

When a two-component developer is used, as a carrier, a magnetic powder-dispersed carrier, which is obtained by melting and dispersing magnetic powder in a resin and then granulated, and a magnetic powder surface such as iron powder and ferrite particles A resin-coated carrier coated with a resin or the like is used. Among them, the resin-coated carrier is preferable from the viewpoint of triboelectrification controllability and resistance controllability. Examples of the coating resin include polyolefin resins such as polyethylene and polypropylene; polyvinyl and polyvinylidene resins such as polystyrene, acrylic resins, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, and the like.
Polyvinyl chloride, polyvinyl carbazole, polyvinyl ether, polyvinyl ketone, etc .; vinyl chloride-vinyl acetate copolymers; styrene-acrylic acid copolymers; straight silicone resins consisting of organosiloxane bonds or modified products thereof; fluororesins such as polytetra Fluoroethylene, polyvinyl fluoride, polyvinylidene fluoride and polychlorotrifluoroethylene etc .; polyesters; polyurethanes; polycarbonates; phenol resins; amino resins such as urea-formaldehyde resins,
Examples thereof include melamine resin, benzoguanamine resin, urea resin and polyamide resin; and epoxy resin. These may be used alone or in combination of two or more. The average particle size of the carrier is preferably set within a range such that the carrier does not adhere to the carrier according to the copying speed.
Range of 0 to 150 μm, more preferably 30 to 100 μm
Set in the range of m.

In FIG. 1, the temporary image carrier is the belt transfer body 7 which is the primary transfer body, but the belt transfer body 7 is not an essential component. For example, the sheet-shaped substrate may be a roll-shaped continuous plastic film, or may have a thickness of 1
When the plastic sheet is 00 μm or more, it is preferable to use a belt transfer body as an intermediate transfer body. As the material of the belt transfer member, relatively hard resins are preferable, and polyamide resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin, polyvinyl ketone resin, polystyrene resin, polyacrylamide resin, polyimide resin, poly Known resins such as acrylic imide resin and polyether imide resin can be used. Further, in order to control the transferability, it is preferable to disperse a resistance controlling material in the resin, which may be carbon black, N, N '.
-Metallocene compounds such as dimethylferrocene, N, N '
-Diphenyl-N, N'-bis (3-methylphenyl)
Aromatic amine compounds such as-[1,1'-biphenyl] -4,4'-diamine, metal oxides such as antimony oxide, tin oxide, titanium oxide, indium oxide, tin oxide-antimony oxide and the like can be used. However, the invention is not limited to these. The thickness of the belt transfer body is not particularly limited, but it is necessary to have both constant strength and elasticity, so that it is preferably about 50 to 220 μm, and may be determined according to the material used.

In the present invention, in order to make the function of the thermo-self-curable particles more effectively act, as described above, the thermo-self-curable particles are used as the plate-shaped material for producing a molded article or the molded article and the sheet. At the adhesive interface with the substrate, it is preferable to provide the order of development so that it is closest to the plate-shaped material side for forming a molded article or the molded article side, that is, the thermal self-curable particle image is the outermost layer on the sheet substrate. . Therefore, when a toner image is formed on a plastic film by secondary transfer as shown in FIG.
When the toner image is formed on the plastic film by the subsequent transfer, it is preferable that the development order of the thermo-self-curable particles be at the end. Further, when toner that is not transferred and remains in the primary transfer and secondary transfer is generated, it is preferable to provide a cleaning mechanism on the electrostatic latent image carrier or the primary transfer member.

The heating member 10 and the pressure roll 15 shown in FIG.
For the fixing device configured as described above, all of the techniques known as the electrophotographic method can be applied. For example, as the heating member, a heating fixing roll type in which an elastic layer is provided on a substrate roll having a heating source such as a Colts lamp inside, and a heating fixing roller type 3 in the vicinity of the heating source to increase a heating area and fixing efficiency are provided. A belt type supported by a supporting roll having a number of dots or more, a type of heating with an infrared radiation lamp in a non-contact state, and the like can all be used. In addition, image-formed films and molded products (or plate-shaped materials for molding products)
A mechanism for preliminarily heating the toner image may be provided before the adhesion with the toner.

Next, the plastic film which is the sheet-like substrate used in the present invention will be described. As the plastic film, any of those known as a packaging material such as a cellulose resin, a polyolefin resin including polyethylene and polypropylene, a polyester resin, a polycarbonate resin, a polyamide resin and the like can be used. In addition, as a film processing method, in the case of a cellulose film, a solution film forming method called a coagulation method or a casting method can be mentioned. In the case of polyethylene, polypropylene, polyester, polycarbonate, polyamide, a T-die method and a ring-die method can be used. Examples of the so-called melt film forming method include, but are not limited to. Further, these films can be used as a single layer, and may have a multi-layer structure in order to add performances such as gas barrier property and moisture proof property. Furthermore, a surface treatment method known as a method for increasing the adhesiveness in the packaging material laminating technique, for example, a method for increasing the critical surface tension of the film surface by a corona discharge treatment, an oxidation treatment, a plasma treatment, or the like is used. It is also effective to apply it to the film surface side to which the thermal self-curable particles are transferred.

Next, the molded article and the plate-shaped material for producing the molded article used in the present invention will be described. Materials used for molded products and plate-shaped materials for producing molded products include metals such as aluminum, steel and tin, polyethylene terephthalate, polyethylene, polypropylene, plastics such as polyvinyl carbonate, glass, ceramics and wood. A relatively hard material is preferable. The molded product is formed of these materials, but the molded product may be processed by forming an image on the plate-shaped material for manufacturing a molded product according to the present invention, or a molded product that is previously molded and processed. The surface of the may be subjected to the image forming treatment according to the present invention, and can be selected according to the material and shape of the molded product. In addition, in order to improve the image adhesion efficiency, the surface of the molded product or the plate-shaped material for forming the molded product may be pre-treated with a coating material, surface treatment, film laminating, vapor deposition of a barrier material, etc. before image formation. Alternatively, the molded product or the plate-shaped material for producing the molded product may be preheated.

Next, the chromatic color toner particles used in the present invention will be described. Examples of chromatic color toner particles include toner particles such as yellow toner, magenta toner, cyan toner, and black toner. Examples of colorants used for these chromatic toner particles include carbon black, nigrosine, aniline blue, calcoil blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, and lamp. Black, Rose Bengal, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 1
22, C.I. I. Pigment Red 57: 1, C.I. I.
Pigment Yellow 97, C.I. I. Pigment Yellow 12, C.I. I. Pigment Blue 15: 1, C.I.
I. Pigment Blue 15: 3 and the like can be illustrated as a typical example. The toner particles used in the present invention are yellow, magenta, cyan, and black particles in order to obtain a full-color image.
To reproduce colors such as gold, silver, and white, which are difficult to obtain by so-called subtractive methods, a toner containing metallic pigments such as copper-zinc alloy powder and aluminum powder, and white pigment such as titanium oxide powder is prepared separately. Can be used.

The binder resin used for the chromatic toner particles includes styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene, vinyl acetate, vinyl propionate, vinyl benzoate and vinyl acetate. Vinyl ester, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate,
Α-methylene aliphatic monocarboxylic acid ester such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate, vinyl ether such as vinyl methyl ether, vinyl ethyl ether, vinyl butyl ether, vinyl methyl ketone, vinyl hexyl ketone, vinyl Homopolymers or copolymers of vinyl ketone and the like such as isopropenyl ketone can be exemplified, and particularly typical binder resins include polystyrene and styrene.
Examples thereof include an alkyl acrylate copolymer, a styrene-alkyl methacrylate copolymer, a styrene-acrylonitrile copolymer, a styrene-butadiene copolymer, a styrene-maleic anhydride copolymer, polyethylene and polypropylene. Furthermore, polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin and waxes can be mentioned. Among these, it is particularly effective when polyester is used as the binder resin. For example, a linear polyester resin composed of a polycondensate containing bisphenol A and a polyvalent aromatic carboxylic acid as main monomer components can be preferably used.

A resin which can be used particularly preferably has a softening point of 9
0 to 150 ° C., glass transition point 50 to 70 ° C., number average molecular weight 2000 to 6000, weight average molecular weight 8000 to 15
It is a resin showing 0000, an acid value of 5 to 30, and a hydroxyl value of 5 to 40.

If desired, these chromatic color toner particles may contain known additives such as a charge control agent and a fixing aid. Further, for the purpose of imparting fluidity, controlling charging, imparting cleaning property on the electrostatic latent image carrier, etc., inorganic fine particles such as SiO ₂ , TiO ₂ , Al ₂ O ₃ , SnO, and fatty acid metal are formed on the toner particle surface. Organic fine particles such as salt, polymethylmethacrylate, and polyvinylidene fluoride may be added. The chromatic color toner particles preferably have a smaller particle size in order to improve the image quality, and preferably have a particle size of 3 to 12 μm.
Those having an average particle diameter of m, more preferably 4 to 10 μm are used.

The thermal self-hardening particles used in the present invention are:
It can be selected and used from the compositions known as powder coating materials or powder adhesive materials. For example, epoxy resin including polyglycidyl ether having polyhydric alcohol and epoxy group-containing acrylic polymer, guanamine resin, benzoguanamine resin, melamine resin, urea resin, polyurethane resin, polyimide resin, carboxylic acid functional polyester resin, carboxylic acid Examples thereof include functional acrylic resin and phenol resin. When an organic photoconductor is used as the electrostatic latent image carrier and an electrophotographic system in which a latent image is formed by a laser or an LED is applied, a phenol resin is preferable among the above materials because it has excellent developability.

Further, in order to control the melt flow rate and the curing rate at the time of heating to adhere an image having an excellent appearance to a molded article such as a container, it is preferable that the thermoself-curable particles contain a heat fluidity modifier. It is effective. Examples of heat fluidity modifiers include methyl methacrylate, 2-ethylhexyl acrylate,
A resin having a relatively high hydroxyl value and a low glass transition temperature obtained by polymerization of isodecyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, etc. is preferable.

These heat self-curing particles may optionally contain known additives such as a charge control agent and a fixing aid. Further, in order to impart powder fluidity, charge control, and cleaning property on the electrostatic latent image bearing member, SiO ₂ , Ti
Inorganic fine particles such as O ₂ , Al ₂ O ₃ and SnO, organic fine particles such as fatty acid metal salt, polymethylmethacrylate, polyvinylidene fluoride and the like may be added to the surface of the heat self-curing particles.

The development of the thermal self-hardening particles is shown in FIG. 2 when the thickness of the particle image layer transferred onto the sheet-like substrate (the thickness of the layer formed from the chromatic color toner particles and the thermal self-hardening particles). It is preferable to adjust the developing amount in the image output machine so that the amount can be kept constant. In FIG. 2, 21 is a sheet-shaped substrate, 22 is chromatic color toner particles, and 23 is thermo-self-curable particles. At that time, regarding the particle diameter of the heat self-curable particles, X is the maximum volume average particle diameter of the volume average particle diameters of the chromatic toner particles of each color, and Y is the volume average particle diameter of the heat self-curable particles. At this time, it is preferable to satisfy 0.5X ≦ Y ≦ 3.0X. When Y is less than 0.5X, it becomes difficult to control the development amount of the heat self-curable particles, and the thickness of the image layer of the particles transferred onto the sheet-like substrate becomes uneven, resulting in image quality and sheet-like substrate and molded products. Poor adhesion strength between and is likely to occur. Also, when Y exceeds 3.0X, similarly, it becomes difficult to control the development amount of the thermal self-curable particles, and the thickness of the particle image layer transferred onto the sheet-like substrate becomes uneven, resulting in image quality and sheet-like shape. Poor adhesion strength between the substrate and the molded product is likely to occur.

In the present invention, first, a particle image layer consisting of a chromatic color toner particle image and a thermal self-curable particle image formed on an image temporary holding member formed by electrophotography or the like is provided with a sheet-like substrate. Although transferred to the above, the unfixed particle image layer may be fixed onto the sheet-like substrate by heating at the same time as the transfer or after the transfer. The unfixed particle image layer transferred onto the sheet-like substrate or the image layer fixed onto the sheet-like substrate is then heated while being brought into pressure contact with the surface of the plate-shaped material for producing a molded article or the molded article. As a result, the on-sheet substrate and the plate-shaped material for producing a molded article or the molded article are bonded and fixed in a form in which an image is formed by the toner particle image and the thermal self-curable particle image . The fixing in this case can be carried out by using the fixing device in the electrophotographic method as described above. Regarding the pressure contact force and heating temperature at that time, the pressure contact force is usually 0.5 to ¹⁰ kg / cm ² , preferably 1 to 5 kg / c.
in the range of m ^2, heating temperature, 100 to 250 ° C., preferably preferably in the range of 130 to 200 ° C..

[0032]

EXAMPLES The present invention will now be described by way of examples, which should not be construed as limiting the invention. In the examples, “part” means part by weight. <Production of Yellow Toner> Polyester Resin 100 Parts [Linear Polyester by Polycondensation of Ethylene Oxide Adduct of Bisphenol A / Cyclohexanedimethanol / Terephthalic Acid (Tg = 67 ° C., Mw = 12000)] Yellow Pigment (C.I. Pigment Yellow 12) 5 parts The above mixture was kneaded with an extruder, pulverized with a jet mill, and then classified with a wind-powered classifier to obtain yellow colored particles with d50 = 8 μm. This particle has an average particle size of 12 nm
Of TiO ₂ particles of 0.8% by weight, and an average particle size of 50 nm of S
A yellow toner was obtained by adding and mixing the iO ₂ particles with a 0.5 wt% Henschel mixer.

<Production of Magenta Toner> Polyester Resin 100 Parts [Linear Polyester by Polycondensation of Ethylene Oxide Adduct of Bisphenol A / Cyclohexanedimethanol / Terephthalic Acid (Tg = 67 ° C., Mw = 12000)] Magenta Pigment ( CI Pigment Red 57) 5 parts The above mixture was kneaded with an extruder, ground with a jet mill, and then classified with a wind classifier to obtain magenta colored particles with d50 = 8 μm. This particle has an average particle size of 12 nm
Of TiO ₂ particles of 0.8% by weight, and an average particle size of 50 nm of S
Magnesium toner was obtained by adding and mixing the iO ₂ particles with a 0.5 wt% Henschel mixer.

<Production of Cyan Toner> 100 parts of polyester resin [linear polyester (Tg = 67 ° C., Mw = 12000) by polycondensation of ethylene oxide adduct of bisphenol A / cyclohexanedimethanol / terephthalic acid] Cyan pigment ( CI Pigment Blue 15: 3) 5 parts The above mixture was kneaded with an extruder, pulverized with a jet mill, and then classified with an air classifier to obtain magenta colored particles having d50 = 8 µm. This particle has an average particle size of 12 nm
Of TiO ₂ particles of 0.8% by weight, and an average particle size of 50 nm of S
The cyan toner was obtained by adding and mixing the iO ₂ particles with a 0.5 wt% Henschel mixer.

<Production of Black Toner> Polyester Resin 100 Parts [Linear Polyester (Tg = 67 ° C., Mw = 12000) by Polycondensation of Ethylene Oxide Adduct of Bisphenol A / Cyclohexanedimethanol / Terephthalic Acid] Carbon Black ( (Mogal L; made by Cabot) 6 parts The above mixture was kneaded with an extruder, pulverized with a jet mill and then classified with a wind-powered classifier to obtain black particles of d50 = 8 μm. TiO 2 with an average particle size of 12 nm
_Two particles were added by 0.8% by weight, and SiO ₂ particles having an average particle size of 50 nm were added and mixed by a Henschel mixer by 0.5% by weight to obtain a black toner.

<Preparation of Thermal Self-Curing Particles a> Methylol group-containing phenol particles (S-870; manufactured by Kanebo Co., Ltd., average particle diameter 18 μm) were mixed with SiO ₂ particles having an average particle diameter of 12 nm.
The mixture was added and mixed with a 2 wt% Henschel mixer to obtain thermal self-curable particles a. <Preparation of Thermal Self-Curing Particles b> A bisphenol A type epoxy resin (Epicoat 1003; manufactured by Yuka Shell Co., Ltd.) was pulverized and classified to have an average particle size of 15 μm, and then 0.2% by weight of SiO ₂ particles having an average particle size of 12 nm. The mixture was added and mixed with a Henschel mixer to obtain thermal self-curable particles b. <Preparation of Thermal Self-Curing Particles c> A bisphenol A type epoxy resin (Epicoat 1003; made by Yuka Shell Co., Ltd.) was pulverized and classified to have an average particle size of 21 μm, and then 0.2% by weight of SiO ₂ particles having an average particle size of 12 nm. The mixture was added and mixed with a Henschel mixer to obtain thermosetting particles c.

<Preparation of Thermally Self-Curing Particles d> A bisphenol A type epoxy resin (Epicoat 1003; made by Yuka Shell Co., Ltd.) was pulverized and classified to have an average particle size of 15 μm, and then SiO ₂ particles having an average particle size of 12 nm were prepared. 2% by weight and finely ground product of methacrylate / 2-ethylhexyl acrylate / hydroxypropyl acrylate copolymer (average particle size 3
μm) 5% by weight is added and mixed with a Henschel mixer,
Thermal self-curing particles d were obtained. <Preparation of Thermal Self-Curing Particles e> Epoxy group-containing acrylate (KAYARAD R-205; manufactured by Nippon Kayaku Co., Ltd.) was pulverized and classified to have an average particle size of 5 μm, and then 0.6% by weight of SiO 2 particles having an average particle size of 12 nm. The mixture was added and mixed with a Henschel mixer to obtain thermal self-curable particles e.

<Preparation of Thermal Self-Curing Particles f> A bisphenol A type epoxy resin (Epicoat 1003; manufactured by Yuka Shell Co., Ltd.) was pulverized and classified to have an average particle size of 26 μm, and then SiO ₂ particles having an average particle size of 12 nm were added to 0.2%. The mixture was added and mixed with a 2 wt% Henschel mixer to obtain thermal self-curable particles f. <Preparation of Thermal Self-Curing Particles g> Epoxy group-containing polyacrylate (KAYARAD R-205; manufactured by Nippon Kayaku Co., Ltd.) was pulverized and classified to have an average particle size of 3.5 μm, and then SiO ₂ particles having an average particle size of 12 nm were used as 1 particle. The mixture was added and mixed with a 0.0 wt% Henschel mixer to obtain thermal self-curable particles g.

<Production of Carrier Particles> Cu-Zn ferrite particles (average particle diameter; 60 μm) 100 parts by weight Toluene 10 parts by weight Styrene-methyl methacrylate copolymer 0.5 parts by weight (copolymerization ratio 30:70, weight average (Molecular weight 60,000) The above components except ferrite particles are stirred with a stirrer for 10 minutes to prepare a coating layer forming liquid, and the coating layer forming liquid and ferrite particles are put into a vacuum degassing type kneader and the temperature is 60 ° C. for 30 minutes. After stirring, the toluene was removed while drying under reduced pressure, and the coating layer was formed to obtain carrier particles.

100 parts of the above-mentioned carrier particles and 6 parts by weight of each of yellow toner, magenta toner, cyan toner, black toner and thermal self-curing particles a to g are mixed by a V-type mixer to prepare a developer, Yellow developer, magenta developer, cyan developer, black developer and thermal self-curing particle developers a to g were obtained.

Electrophotographic color printer (Docuc
color 4040, manufactured by Fuji Xerox Co., Ltd.) was modified into the form shown in FIG. 1, and the following output test was carried out by selectively using the above-mentioned developer. The environment in which the output test was performed was controlled at 22 ° C. and 55% RH, and the image input was performed by a processing method in which an image created on a personal computer was directly connected to a printer with a LAN cable and transmitted.

Example 1 A thermal self-curing particle developer a, a black developer, a yellow developer, a magenta developer, and a cyan developer were developed in this order, and a carbon black-dispersed polyimide belt having a thickness of 80 μm (see FIG. 1) was used. (Corresponding to the belt transfer body 7 of No. 1). After that, it was collectively transferred onto a 45 μm-thick polyethylene terephthalate film (corresponding to the plastic film 11 in FIG. 1) that had been subjected to corona discharge treatment, and the heating member 10 and the pressure roll 15 in FIG. 180 ° C polyethylene terephthalate film
The color image was fixed on the steel plate by heating under pressure. Note that the image also includes character information generally referred to as an OCR method, which conforms to JIS standard X9001 “character shape for optical character recognition”. The steel plate on which the color image was formed was processed into a metal container by the known Toyo Seam method.

Example 2 Thermal self-curable particle developer a was replaced with thermal self-curable particle developer b.
Except that it is replaced with
A steel plate on which a color image was formed was obtained. Example 3 Thermal self-curable particle developer a was replaced with thermal self-curable particle developer c.
Except that it is replaced with
A steel plate on which a color image was formed was obtained. Example 4 Thermal self-curable particle developer a was replaced with thermal self-curable particle developer d.
Except that it is replaced with
A steel plate on which a color image was formed was obtained. Example 5 A color image is formed by performing the same operations as in Example 1 except that development is performed in the order of black developer, yellow developer, magenta developer, cyan developer, and thermal self-curable particle developer a. Got a steel plate.

Example 6 A thermal self-curing particle developer d, a black developer, a yellow developer, a magenta developer, and a cyan developer were developed in this order, and a carbon black-dispersed polyimide belt having a thickness of 80 μm (see FIG. 1) was used. (Corresponding to the belt transfer body 7 of No. 1). After that, the particles are collectively transferred onto a 45 μm-thick polyethylene terephthalate film (corresponding to the plastic film 11 in FIG. 1) that has been subjected to corona discharge treatment, and the titanium oxide is dispersed in the heating member 10 and the pressure roll 15 in FIG. 20 Polyethylene terephthalate film is placed on a ceramic plate laminated with 12 nylon film.
The color image was fixed by heating under pressure at 0 ° C.
A bar code record known as a JAN symbol is also shown on the image. The pottery plate after image formation was processed as a container lid.

Example 7 Thermal self-curable particle developer d was replaced with thermal self-curable particle developer e.
The same operation as in Example 6 is performed except that
An image-formed ceramic plate was obtained. Example 8 Thermal self-curable particle developer d is replaced with thermal self-curable particle developer f
The same operation as in Example 6 is performed except that
An image-formed ceramic plate was obtained. Example 9 Thermal self-curable particle developer d was replaced with thermal self-curable particle developer g
The same operation as in Example 6 is performed except that
An image-formed ceramic plate was obtained.

Comparative Example 1 A steel plate on which a color image was formed was obtained in the same manner as in Example 1 except that the thermal self-curable particle developer a was not used. Comparative Example 2 The same operation as in Example 6 was carried out except that the thermal self-curable particle developer d was not used to obtain an image-formed ceramic plate.

The results of evaluation of the output image are shown in Table 1.

[Table 1]

The evaluation criteria are based on the following. (Image quality) ⊚: Bubbles are not recognized in the image, which is a very good image. ◯: The resolution is relatively inferior to ◎, but a good image. Δ: Bubbles are slightly recognized in the image when staring. ,
Practical image ×: An image corresponding to at least one of the image partially flowing and bleeding, the film partially peeling, and color unevenness (circulation information reading accuracy) ◎: Using a commercially available reading device, the probability that readability will be less than 0.1% ○: Using a commercially available reading device, the probability that readability will be less than 0.1 to 1.0% △: Using a commercially available reading device , Probability of readability is 1.0 to less than 5.0% x: Probability of readability is 5.0% or more using a commercially available reading device

[0049]

As described above, the image forming method of the present invention uses the thermal self-hardening particles to form an image on a molded product such as a container or a plate-shaped material for molding a molded product, thereby forming a conventional image. The various drawbacks in are improved. That is, it is possible to form an image on a hard container such as metal, glass, and ceramics without requiring printing plate making and without impairing productivity, and also image deterioration due to image flow or peeling even under high temperature for a long period of time. It is possible to form an image that does not cause a reading error of a distribution information record such as a barcode. Furthermore, there is an effect that it is possible to output a full-color image with high clarity and high color development.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of an image forming apparatus for carrying out an image forming method of the present invention.

FIG. 2 is a schematic sectional view of a particle image layer.

[Explanation of reference numerals] 1 ... Electrostatic latent image carrier, 2 ... Charging device, 3 ... Exposure device, 4
-X ... Thermal self-curing particle developing device, 4-K ... Black toner developing device, 4-Y ... Yellow toner developing device, 4-
M ... Magenta toner developing device, 4-C ... Cyan toner developing device, 5 ... Baffles, 6-1 and 6-2 ... Transfer corotron, 7 ... Belt transfer member, 8 ... Driving roll, 9-
1-9-6 ... Tension roll, 10 ... Heating member, 11 ... Plastic film, 12 ... Plastic film conveying member, 13 ... Metal container manufacturing plate material, 14 ... Metal container raw material plate conveying member, 15 ... Pressure roll, 21 ... Sheet-like substrate, 2
2 ... Chromatic color toner particles, 23 ... Thermal self-curable particles.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Chiaki Suzuki 1600 Takematsu, Minamiashigara-shi, Kanagawa Fuji Zerox Co., Ltd. (56) References JP-A-6-35239 (JP, A) JP-A-7-72695 ( JP, A) JP 5-281863 (JP, A) JP 63-151962 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03G 15/16 101 G03G 15 / 01 114 G03G 15/20 102 B41J 29/00

Claims (3)

(57) [Claims] 1. A step of transferring the particle image layer consisting of image chromatic formed on a temporary carrier color toner particle image, and thermally self-hardening particle image on the sheet substrate, and the unfixed on the sheet substrate An image forming method comprising a step of heating and fixing the particle image layer while pressing it against the surface of a plate-shaped material for producing a molded article or a molded article. 2. A process of transferring and fixing the particle image layer consisting of image chromatic formed on a temporary carrier color toner particle image, and thermally self-hardening particle image on the sheet substrate, and the sheet substrate on An image forming method comprising a step of heating and fixing the fixed image layer to the surface of a plate-shaped material for producing a molded article or the surface of a molded article. 3. The relationship between the maximum volume average particle diameter X of the volume average particle diameters of the chromatic color toner particles of each color and the volume average particle diameter Y of the thermal self-curable particles satisfies the following expression (1). The image forming method according to claim 1, further comprising: 0.5X ≦ Y ≦ 3.0X (1)