Image formation methods

Abstract

To provide an image forming method for allowing a toner image to be fixed to a cloth medium, improving washing resistance, obtaining sufficient chroma for a cloth in a dark color.SOLUTION: An image forming method includes: a water-repellent layer forming step of forming a water-repellent layer including a water-repellent component on an image receiving substrate; a toner image forming step of forming a toner image on a transfer medium; and a thermal transfer step of thermally transferring the toner image to a surface of the image receiving substrate on which the water-repellent layer is formed.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present invention relates to an image forming method. [Background technology]

[0002] As an image forming method, electrophotography is known, in which an electrostatic latent image is developed with a developer to form a visible image. In electrophotography, an electrostatic latent image is formed on an electrostatic latent image carrier (also called a photoreceptor) containing a photoconductive material, and the electrostatic latent image is developed with a developer containing toner to form a toner image. The toner image is then transferred to a transfer material such as paper, and fixed by applying heat and pressure to form a fixed image. To form a full-color image using electrophotography, a toner set combining cyan, magenta, yellow, and black toners, also known as process colors, is generally used.

[0003] In recent years, as electrophotographic color image forming devices have become more widespread, the applications of these printed materials have expanded to a wide variety of uses. Particularly in the field of custom-made consumer goods, there is a growing need for electrophotographic printing on materials that cannot be printed (fixed) with conventional electrophotographic toners intended for printing on paper media. Specifically, there is a growing need for printing on fabric media such as sports team uniforms, shoes, and bags.

[0004] Patent Document 1 discloses forming a full-color toner image on an image transfer sheet and transferring the full-color toner image to a retroreflective substrate. Examples of materials that can be used to form the retroreflective substrate include woven fabrics, knitted fabrics, and nonwoven fabrics. Patent Document 1 also discloses applying a silicone resin or the like to the image transfer sheet to improve releasability. Another example discloses forming a thermoplastic resin layer on the image transfer sheet and transferring the full-color toner image to the substrate together with the thermoplastic resin. Summary of the Invention [Problem to be solved by the invention]

[0005] Printed images on fabric media must be able to be fixed to uneven fabric fibers, have strong adhesion so that they do not peel off during washing, and must not impair the color of the image even on fabrics of various colors. In particular, when printing on dark-colored fabrics, it is necessary to conceal the color of the dark fabric without impairing the color of the image. To achieve an ideal state that overcomes these challenges, the selection of the image layer structure, type of medium, imaging means, and other factors is extremely important. However, prior art has yet to achieve a practical image formation method on fabric that overcomes these challenges without requiring a complex manufacturing process, and no image of sufficient quality for practical use has been provided.

[0006] SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide an image forming method that can fix a toner image on a fabric medium, can provide good washability, and can obtain sufficient saturation even on dark colored fabrics. [Means for solving the problem]

[0007] In order to solve the above problems, the image forming method of the present invention includes a water-repellent layer forming step of forming a water-repellent layer containing a water-repellent component on an image receiving substrate, a toner image forming step of forming a toner image on a transfer medium, and a thermal transfer step of thermally transferring the toner image onto the surface of the image receiving substrate on which the water-repellent layer has been formed. The water-repellent component contains at least one selected from silicone resins and fluororesins. It is characterized by: [Effects of the Invention]

[0008] According to the present invention, it is possible to provide an image forming method that can fix a toner image even on a fabric medium, can provide good washability, and can obtain sufficient saturation even on dark colored fabrics. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 10 is a diagram showing stroke displacement in flow tester measurement. [Figure 2] 1 is a schematic diagram illustrating an example of an image forming method according to the present invention. [Figure 3] 10A and 10B are schematic diagrams illustrating another example of an image forming method according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0010] The image forming method according to the present invention will be described below with reference to the drawings. The present invention is not limited to the following embodiments, and can be modified, added, modified, deleted, or otherwise altered within the scope of what a person skilled in the art can conceive. Any embodiment that achieves the functions and effects of the present invention is within the scope of the present invention.

[0011] (Image forming method) The image forming method of the present invention is characterized by comprising a water-repellent layer forming step of forming a water-repellent layer containing a water-repellent component on an image receiving substrate, a toner image forming step of forming a toner image on a transfer medium, and a thermal transfer step of thermally transferring the toner image onto the surface of the image receiving substrate on which the water-repellent layer has been formed.

[0012] In the present invention, a toner image formed on a transfer medium is thermally transferred to an image receiving substrate on which a water-repellent layer containing a water-repellent component is formed, so the toner image can be fixed on a fabric medium. Furthermore, even if the image receiving substrate contains fibers, the toner does not penetrate the fibers, preventing bleeding and enabling high-resolution image formation. In the image forming method of the present invention, the toner image can be prevented from penetrating the fibers, so bleeding of the image can be reduced compared to when an image is formed on a fabric medium using, for example, an inkjet method.

[0013] When fixing toner to an image-receiving substrate such as cloth, the surface of the cloth has unevenness due to fibers, making it difficult for the toner to wet and spread. In conventional techniques, the toner was unable to wet and spread on the cloth, resulting in areas that were not covered, resulting in insufficient hiding power for the image and making it impossible to form a high-resolution toner image on the cloth. Furthermore, in conventional techniques, the toner was unable to wet and spread on the cloth, resulting in an image that was not robust, and the toner image easily peeled off, for example, when washed.

[0014] On the other hand, the present invention can form a toner image on an image receiving substrate such as fabric, and can provide good washability. Furthermore, the present invention can wet and spread the toner on the fabric, thereby suppressing areas on the fabric that are not covered with the toner, improving the fabric's hiding power, and providing sufficient saturation even on dark-colored fabrics.

[0015] <Water-repellent layer formation process> In the water-repellent layer forming step, a water-repellent layer containing a water-repellent component is formed on the image-receiving substrate. The method for forming the water-repellent layer is not particularly limited and can be selected appropriately. For example, a method of applying a water-repellent component can be used. The area where the water-repellent layer is formed can be changed appropriately, and may be the entire surface or a part of the image-receiving substrate.

[0016] The image receiving substrate can be appropriately selected, and can be, for example, any so-called fabric made of artificial or natural fibers such as cotton, polyester, silk, etc. The image receiving substrate in the present invention includes any so-called fabric made of artificial or natural fibers such as cotton, polyester, silk, etc.

[0017] The image receiving substrate is preferably made of fibers, preferably selected from polyester fibers and cotton fibers, which have the advantages of high affinity with the toner and high heat resistance to heat applied during thermal fixing.

[0018] The water-repellent component can be appropriately selected, and for example, a water-repellent agent that can be applied to fabric can be used. As the water-repellent component, for example, a water-repellent agent containing a silicone resin as a main component or a water-repellent agent containing a fluororesin as a main component can be used. Generally, waterproof sprays available on the market as "waterproof spray for clothing" or "waterproof spray for shoes" can be obtained and used.

[0019] Silicone resins and fluororesins are preferably used as the water-repellent component, as they have an increased affinity for fibers and can promote the wetting and spreading of the heat-melted toner on the fibers.

[0020] The inventors conducted repeated trials of forming toner images on cloth and, from the results of observing the toner images, found that applying a water-repellent component to an image-receiving substrate such as cloth can impart uniform toner wettability to the image-receiving substrate. It was found that applying a water-repellent component significantly reduces uneven toner adhesion and image defects, even with the same amount of toner adhesion. Furthermore, when cloth is used as the image-receiving substrate, applying a water-repellent component significantly reduces fiber exposure, increasing the degree of toner concealment of the image-receiving substrate surface.

[0021] The amount of the water-repellent component to be applied can be selected as appropriate, for example, an amount that allows the water-repellent effect to be exerted. The method for applying the water-repellent component can be selected as appropriate, for example, a method in which the water-repellent component is sprayed evenly onto the surface of the image-receiving substrate from a distance of about 10 cm for about 10 seconds.

[0022] <Toner image forming process> In the toner image forming process, a toner image is formed on a transfer medium. The method for forming the toner image is not particularly limited and can be selected appropriately. For example, a method can be used in which a toner layer is transferred to a transfer medium, followed by thermal fixing to form a toner image on the transfer medium. The toner layer may be a single layer or multiple layers. The toner used in the toner image forming process will be described in detail later.

[0023] In the present invention, an undercoat layer may be formed when a toner image is formed on a transfer medium. The undercoat layer can conceal the background color of the image-receiving substrate, thereby improving the saturation of the image formed on the image-receiving substrate. Furthermore, by forming a water-repellent layer on the image-receiving substrate and then forming an undercoat layer, it is possible to improve washability. The toner for the undercoat layer can be appropriately selected, and for example, a white toner can be used. The undercoat layer may also be referred to as a concealing layer, etc.

[0024] In the present invention, for example, it is preferable to form a white toner layer as the uppermost layer on the transfer medium. In this case, when the toner image is thermally transferred onto the image receiving substrate in the thermal transfer process, it is preferable to perform the thermal transfer so that the white toner layer is the lowermost layer of the toner image on the image receiving substrate. In this way, a white toner image is formed under the color toner image on the image receiving substrate, and the white toner image can function as an undercoat layer. By providing an undercoat layer, the hiding power is improved and an even higher resolution image can be obtained.

[0025] The ability of white toner to conceal background color is affected by the toner adhesion amount and the wetting and spreading properties of the toner. In the present invention, a water-repellent layer is formed on the image-receiving substrate, so when a toner layer such as white toner is formed, the concealing properties are improved and an even higher-resolution image can be obtained. This is thought to be because the toner wets and spreads evenly over the image-receiving substrate. For this reason, the present invention can improve image quality (improve saturation) without increasing the toner adhesion amount.

[0026] The device for performing the toner image forming process can be appropriately selected, and a known image forming device (which may also be called a printing device, recording device, copier, etc.) can be used. For example, a device equipped with an electrostatic latent image carrier, an exposure unit, a charging unit, a developing unit, a transfer unit, a fixing unit, etc. can be used. For example, a RICOH Pro C7200S manufactured by Ricoh Co., Ltd. can be used. The device for performing the toner image forming process may be improved so that the toner for the undercoat layer and the developer can be set in one of the color stations.

[0027] The transfer medium can be selected appropriately, and examples thereof include transfer paper or release paper that has been surface-treated to have suitable fixability and releasability for use in the toner image forming process and the thermal transfer process, such as WOW Light 8.0, WOWi Sheet 7A, and WOWm Sheet 7 manufactured by Piotek Corporation, and CLAPp-MULT manufactured by Europort.

[0028] <Thermal transfer process> In the thermal transfer process, a toner image is thermally transferred onto the surface of an image receiving substrate on which a water-repellent layer has been formed. The thermal transfer step can be appropriately selected, and examples thereof include a method in which the image receiving substrate and the transfer medium are overlapped so that the surface of the image receiving substrate on which the water-repellent layer is formed faces the surface of the transfer medium on which the toner image is formed, and then heat and pressure are applied, and the transfer medium is peeled off.

[0029] In the thermal transfer step, for example, a heat press fixing machine is used to perform the thermal transfer. The heat press fixing machine can be appropriately selected, and may be any machine capable of applying the temperature and pressure required to fix the toner to the image receiving substrate. For example, Model HTP234PS1, Model 728, and Model 201 manufactured by Piotec Corporation, and Hercules PH-4634, Hercules Wide PH-5040, Gaia PGA-5040, and Zeus PZ-130110D manufactured by Europort, etc. may be used. An iron may also be used instead of the heat press machine.

[0030] Thermal transfer temperature P in the thermal transfer process T can be selected appropriately. For example, when using a toner for the undercoat layer, P T It is preferable that the following formula (1) is satisfied: In this case, for example, the toner for the undercoat layer does not penetrate too far into the interior of the image receiving substrate, but remains on the surface, and good hiding power and adhesiveness can be exhibited. UT fb <P T ≦UT 1 / 2 ··· Equation (1)

[0031] In the above formula (1), UT fb represents the temperature at which the toner that forms the undercoat layer begins to flow. 1 / 2 represents the half-flow temperature of the toner that forms the undercoat layer. Note that the "U" is added for convenience to indicate that it is an undercoat layer, and is used to mean "Under."

[0032] The outflow start temperature and half outflow temperature are measured, for example, as follows. Using a flow tester (Shimadzu CFT-500D), 1.0 g of sample was heated at a temperature increase rate of 6°C / min, while a load of 1.96 MPa was applied by the plunger, and the sample was extruded from a nozzle with a diameter of 1.0 mm and a length of 1.0 mm. This produced a plot of the plunger stroke of the flow tester versus temperature. An example of this plot is shown in Figure 1. From this plot, two points, as shown in Figure 1, were determined as the outflow start temperature T fb , 1 / 2 outlet temperature T 1 / 2 The example shown in FIG. 1 is an example of measurement of the toner for the undercoat layer, and the flow-out starting temperature T fb UT fb and 1 / 2 outflow temperature T 1 / 2 UT 1 / 2 is shown.

[0033] FIG. 1 will be explained in more detail. In the obtained plot, the inflection point where the change in the plunger downstroke (stroke) changes from a stable region of zero to an increasing region is the outflow start temperature T fb In the example shown in the figure, the change in stroke is zero between about 65°C and about 105°C, and the stroke starts to increase from about 105°C. Therefore, in this example, the outflow start temperature T fb The temperature at which half the sample flows out is taken as the half-outflow temperature. In the example shown in the figure, the half-outflow temperature T 1 / 2 can be said to be about 145°C.

[0034] In the thermal transfer process, for example, an image receiving substrate and a transfer medium are placed on top of each other, and then heat and pressure are applied. The conditions for heating and pressure are not particularly limited and can be selected appropriately. For example, taking into consideration the thermal conductivity, thickness, surface roughness, etc. of the image receiving substrate, the pressure is set to 100 g / cm. 2 ~800g / cm 2 The time is preferably 5 to 60 seconds.

[0035] <Example of image formation> An example of the present invention will now be described with reference to FIG. 2A, a color toner layer 12 is formed on the transfer medium 10. Next, the transfer medium 10 is subjected to thermal fixing, and the color toner layer 12 is fixed to the transfer medium 10. In Fig. 2(B), a water-repellent component is applied to the image receiving substrate 20 to form a water-repellent layer 22. The order in which Fig. 2(B) is performed can be changed as appropriate, and it may be performed after Fig. 2(A) or before Fig. 2(A). 2(C), the image receiving substrate 20 and the transfer medium 10 are stacked so that the surface of the image receiving substrate 20 on which the water-repellent layer 22 is formed faces the surface of the transfer medium 10 on which the toner image is formed, and then heat and pressure are applied. Next, the transfer medium 10 is peeled off. As a result, a toner image can be formed on the image receiving substrate 20 as shown in FIG. 2(D).

[0036] In the present invention, the toner image may be formed in a plurality of layers, for example, an image formed by color toners and an image formed by toner for an undercoat layer, for example, a white toner, etc. may be used as the toner for the undercoat layer.

[0037] Another example of the present invention will be described with reference to Fig. 3. The example shown in Fig. 3 is an example in which a white toner layer (undercoat layer) is formed. By forming an undercoat layer, the hiding power of the image receiving substrate is improved, and the saturation of the image on the image receiving substrate can be improved. In FIG. 3A, a color toner layer 12 is formed on a transfer medium 10. In FIG. 3B, a white toner layer 14 is formed on the color toner layer 12. Next, the transfer medium 10 is subjected to thermal fixing, so that the color toner layer 12 and the white toner layer 14 are fixed to the transfer medium 10 . In Fig. 3(C), a water-repellent component is applied to the image receiving substrate 20 to form a water-repellent layer 22. The order in which Fig. 3(C) is performed can be changed as appropriate, and it may be performed after Fig. 3(A) or Fig. 3(B), or before Fig. 3(A) or Fig. 3(B). 3(D), the image receiving substrate 20 and the transfer medium 10 are stacked so that the surface of the image receiving substrate 20 on which the water-repellent layer 22 is formed faces the surface of the transfer medium 10 on which the toner image is formed, and then heat and pressure are applied. Next, the transfer medium 10 is peeled off. As a result, a toner image can be formed on the image receiving substrate 20 as shown in FIG. 3(E).

[0038] <Toner> The toner used in the toner image forming process is not particularly limited and can be selected appropriately. In the toner image forming process, a toner layer is transferred to a transfer medium and fixed to the transfer medium, thereby forming a toner image on the transfer medium. The toner layer can be selected appropriately, and for example, a layer of color toner and an undercoat layer on the color toner layer can be provided.

[0039] The color toner used in the toner image forming process is not particularly limited, and for example, a process color toner used in printing with an electrophotographic printer can be used. One color or multiple colors may be used. The color toner may also be referred to as a process color toner.

[0040] The toner used in the undercoat layer is not particularly limited and can be selected appropriately. The toner used in the undercoat layer is sometimes called a toner for the undercoat layer. The reason for calling it an undercoat layer is that it is assumed that the undercoat layer will be formed as the uppermost layer on the transfer medium, and that when the toner image on the transfer medium is thermally transferred to the image receiving substrate, the undercoat layer will be below the layer of color toner.

[0041] The toner for the undercoat layer can be one made of the same material as the color toner. The color of the toner for the undercoat layer may be any color, but a colorless transparent toner containing no colorant such as a pigment is preferred, or a white toner using a white pigment as a colorant is preferred. The use of a white toner is particularly preferred, because when the image receiving substrate is a dark color such as black or navy blue, the color of the image receiving substrate can be concealed and the color of the color toner can be prevented from being impaired.

[0042] The half-flow temperature of the undercoat layer toner is preferably higher than the half-flow temperature of the color toners, so that the undercoat layer toner adheres well to the color toners and color mixing of the undercoat layer toner and the color toners can be prevented.

[0043] Next, the materials constituting the toner will be described. The following description applies to both the toner for the undercoat layer and the color toner unless otherwise specified.

[0044] <<Binder resin>> The binder resin (also referred to as a fixing resin) used in the toner may be a conventionally known resin. Examples include styrene-based resins (homopolymers or copolymers containing styrene or styrene substitutes) such as styrene, poly-α-styrenestyrene, styrene-chlorostyrene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-α-methyl chloroacrylate copolymer, and styrene-acrylonitrile-acrylate copolymer; epoxy resin, vinyl chloride resin, rosin-modified maleic acid resin, phenolic resin, polyethylene resin, polypropylene resin, petroleum resin, polyurethane resin, ketone resin, ethylene-ethyl acrylate copolymer, xylene resin, and polyvinyl butyrate resin. The method for producing these resins is not particularly limited, and any of bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization can be used.

[0045] In the present invention, it is preferable that the binder resin (fixing resin) contains a polyester resin, and it is particularly preferable that the binder resin contains a polyester resin as the main component. Polyester resins are generally suitable for the present invention because they can be fixed at low temperatures while maintaining heat-resistant storage stability compared to other resins.

[0046] The polyester resin used in the present invention is obtained by condensation polymerization of an alcohol and a carboxylic acid. Examples of the alcohol that can be used include glycols such as ethylene glycol, diene glycol, triethylene glycol, and propylene glycol, etherified bisphenols such as 1,4-bis(hydroxymeta)cyclohexane and bisphenol A, other dihydric alcohol monomers, and trihydric or higher polyhydric alcohol monomers.

[0047] Examples of the carboxylic acid include divalent organic acid monomers such as maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and malonic acid, and trivalent or higher polyvalent carboxylic acid monomers such as 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, and 1,2,7,8-octanetetracarboxylic acid.

[0048] <<Release Agent>> The release agent used in the toner is not particularly limited and can be appropriately selected depending on the purpose. One type may be used alone, or two or more types may be used in combination.

[0049] Examples of release agents that can be used include liquid paraffin, microcrystalline wax, natural paraffin, synthetic paraffin, polyolefin wax, and partial oxides of these, as well as aliphatic hydrocarbons such as fluorides and chlorides, animal oils such as beef tallow and fish oil, vegetable oils such as coconut oil, soybean oil, rapeseed oil, rice bran wax, and carnauba wax, higher aliphatic alcohols and higher fatty acids such as montan wax, fatty acid amides, fatty acid bisamides, metal soaps such as zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, zinc oleate, zinc palmitate, magnesium palmitate, zinc myristate, zinc laurate, and zinc behenate, fatty acid esters, and polyvinylidene fluoride.

[0050] <<Coloring agent>> The colorant used in the toner is not particularly limited, and any commonly used colorant can be appropriately selected and used.

[0051] As the black toner, for example, carbon black alone or a toner containing carbon black as a main component and mixed with copper phthalocyanine or the like, with the hue and brightness adjusted, is preferred.

[0052] As the cyan toner, for example, copper phthalocyanine pigment blue 15:3 or a mixture of aluminum phthalocyanine and a colorant is preferable.

[0053] As the magenta toner, for example, Pigment Red 53:1, Pigment Red 81, Pigment Red 122, Pigment Red 269 can be used alone or in combination.

[0054] As the yellow toner, for example, Pigment Yellow 74, Pigment Yellow 155, Pigment Yellow 180, and Pigment Yellow 185 can be used alone or in mixture. From the viewpoints of saturation and storage stability, Pigment Yellow 185 alone or a mixture of Pigment Yellow 185 and Pigment Yellow 74 is preferred.

[0055] The white pigment used in the white toner can be appropriately selected, and for example, titanium dioxide that has been surface-treated with silicon, zirconia, aluminum, polyol, or the like can be used.

[0056] As the green toner, for example, Pigment Green 7 or the like can be used, but safety considerations must be taken into account.

[0057] Examples of blue toners include Pigment Blue 15:1 and Pigment Violet 23.

[0058] <<Charge control agent>> The toner may contain a charge control agent (CCA). Examples of charge control agents include nigrosine and fatty acid metal salts modified with phosphonium salts and their lake pigments, triphenylmethane dyes and their lake pigments, metal salts of higher fatty acids, diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, and dicyclohexyltin oxide, diorganotinborates such as dibutyltin borate, dioctyltin borate, and dicyclohexyltin borate, organometallic complexes, chelate compounds, monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, metal complexes of aromatic dicarboxylic acids, and quaternary ammonium salts. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenols. While not limited to these, zirconium salicylate is preferred. These can be used alone or in combination.

[0059] <<External additives>> An external additive may be used in the toner, and examples of the external additive include inorganic fine particles. Examples of inorganic fine particles for external addition include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Silica, alumina, and titanium oxide are particularly preferred.

[0060] In addition, inorganic fine particles may be surface-treated with a hydrophobic treatment agent. Examples of the hydrophobic treatment agent include silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, and aluminum coupling agents. Furthermore, sufficient effects can be obtained by using silicone oil as a hydrophobic treatment agent.

[0061] <Developer> In the toner image forming process, either a one-component development system in which toner is used as a developer or a two-component development system in which toner is mixed with a carrier and used as a two-component developer can be used.

[0062] When a two-component developer system is used, the magnetic particles used in the magnetic carrier can be, for example, magnetite, spinel ferrite such as gamma iron oxide, spinel ferrite containing one or more metals other than iron (Mn, Ni, Zn, Mg, Cu, etc.), magnetoplumbite ferrite such as barium ferrite, or iron or alloy particles having an oxide layer on their surface. The shape of the particles may be granular, spherical, or needle-like. When particularly high magnetization is required, it is preferable to use ferromagnetic particles such as iron. Furthermore, considering chemical stability, it is preferable to use magnetite, spinel ferrite containing gamma iron oxide, or magnetoplumbite ferrite such as barium ferrite.

[0063] By selecting the type and content of ferromagnetic fine particles, a resin carrier having the desired magnetization can be used. In this case, the magnetic properties of the carrier are preferably, for example, a magnetization strength of 30 to 150 emu / g at 1,000 oersted.

[0064] The carrier used in the present invention may be produced, for example, by spraying a melt-kneaded mixture of magnetic fine particles and an insulating binder resin using a spray dryer. Alternatively, a carrier in which magnetic fine particles are dispersed in a condensation binder may be produced by reacting and curing a monomer or prepolymer in an aqueous medium in the presence of magnetic fine particles. Furthermore, the chargeability may be controlled by adhering positively or negatively charged fine particles or conductive fine particles to the surface of the magnetic carrier, or by coating the carrier with a resin.

[0065] Examples of the coating material (resin) that can be used on the surface of the magnetic fine particles include silicone resin, acrylic resin, epoxy resin, and fluorine-based resin. Furthermore, the coating can include positively or negatively charged fine particles or conductive fine particles. Silicone resin and acrylic resin are preferred resins for use in this case.

[0066] <Toner manufacturing method> The method for producing the toner used in the present invention is not particularly limited and can be appropriately selected. An example will be described below. First, a binder resin, a colorant, a release agent, and optionally a charge control agent are combined and thoroughly mixed in a mixer such as a Henschel mixer or a super mixer, and then the materials are melt-kneaded using a heat melt kneader such as a heating roll, a kneader, or an extruder to thoroughly mix the materials.The mixture is then cooled and solidified, and then finely pulverized and classified to obtain a toner.

[0067] Examples of the pulverization method include a jet mill method in which the toner is entrained in a high-speed airflow and pulverized by the energy generated by the collision of the toner with a collision plate. Other methods include a particle-to-particle collision method in which toner particles collide with each other in an airflow. Furthermore, other methods such as a mechanical pulverization method in which the toner is supplied between a narrow gap and a rotor rotating at high speed and pulverized can also be used.

[0068] The method for producing the toner is not limited to the above. A solution suspension method is also possible, in which an oil phase in which toner materials are dissolved or dispersed in an organic solvent phase is dispersed in an aqueous medium phase, and after the resin reaction is carried out, the solvent is removed, and the resulting mixture is filtered, washed, and dried to produce toner base particles.

[0069] (Toner storage unit) In the toner image forming process, a toner storage unit may be used. In the present invention, the toner storage unit refers to a unit having a function of storing toner and storing the toner. Here, examples of the toner storage unit include a toner storage container, a developing unit, and a process cartridge. The toner container refers to a container that stores toner. The developing device is a device that contains toner and has means for developing. A process cartridge is a device that integrates at least an image carrier and a developing unit, contains toner, and is detachably mountable to an image forming apparatus. The process cartridge may further include at least one selected from a charging unit, an exposure unit, and a cleaning unit. The use of a toner storage unit enables good image formation. [Example]

[0070] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.

[0071] (Toner production) <White Toner 1 Manufacturing Example> [Toner raw materials] Polyester resin RN-290 (Kao Corporation) 94.7 parts by weight Carnauba wax WA-05 (Cerarica Noda Co., Ltd.) 5.3 parts by weight Zirconium salicylate (CCA) TN-105 (manufactured by Hodogaya Chemical Co., Ltd.) 0.5 parts by weight Titanium oxide white pigment PF-739 (Ishihara Sangyo Kaisha) 60 parts by weight

[0072] The above toner raw materials were premixed using a Henschel mixer (FM20B, manufactured by Nippon Coke & Engineering Co., Ltd.) and then melted and kneaded at 100-130°C using a single-screw kneader (Ko-Kneader, manufactured by Buss). The resulting kneaded mixture was cooled to room temperature and coarsely pulverized to 200-300 μm using a Rotoplex. It was then finely pulverized using a counter jet mill (100AFG, manufactured by Hosokawa Micron Corporation) while adjusting the pulverization air pressure appropriately to achieve the desired number-average particle size distribution. The mixture was then classified using an air classifier (EJ-LABO, manufactured by Matsubo Corporation) while adjusting the louver opening appropriately to achieve the desired number-average particle size distribution, yielding toner base particles. Next, 3.0 parts of an additive (HDK-2000, manufactured by Clariant) were added to 100 parts of the toner base particles and mixed with them using a Henschel mixer to produce [White Toner 1].

[0073] <Production example of color toner 1> [Toner raw materials] Polyester resin RN-290 (Kao Corporation) 94.7 parts by weight Carnauba wax WA-05 (Cerarica Noda Co., Ltd.) 5.3 parts by weight Zirconium salicylate (CCA) TN-105 (manufactured by Hodogaya Chemical Co., Ltd.) 0.1 parts by weight Copper phthalocyanine cyan pigment FG-7351 (manufactured by Toyo Ink Co., Ltd.) 10 parts by weight

[0074] [Color Toner 1] was produced in the same manner as [White Toner 1], except that the above toner raw materials were changed.

[0075] <Production example of color toner 2> [Toner raw materials] Polyester resin RN-290 (Kao Corporation) 94.7 parts by weight Carnauba wax WA-05 (Cerarica Noda Co., Ltd.) 5.3 parts by weight Zirconium salicylate (CCA) TN-105 (manufactured by Hodogaya Chemical Co., Ltd.) 0.5 parts by weight Copper phthalocyanine cyan pigment FG-7351 (manufactured by Toyo Ink Co., Ltd.) 10 parts by weight

[0076] [Color Toner 2] was produced in the same manner as [White Toner 1], except that the above-mentioned toner raw materials were used.

[0077] (Example of manufacturing two-component developer) <Creating the carrier> Silicone resin (organo straight silicone) 100 parts by weight Toluene 100 parts by weight γ-(2-aminoethyl)aminopropyltrimethoxysilane 5 parts by weight Carbon black 10 parts by weight

[0078] The mixture was dispersed in a homomixer for 20 minutes to prepare a coating layer forming solution. This coating layer forming solution was applied to Mn ferrite particles with a weight average particle size of 35 μm as the core material, and the temperature in the fluidized bed coating device was controlled to 70°C in order to obtain an average film thickness of 0.20 μm on the core material surface, and then dried. The obtained carrier was fired in an electric furnace at 180°C for 2 hours to obtain [Carrier A].

[0079] <Preparation of two-component developer> The prepared [White Toner 1], [Color Toner 1], [Color Toner 2], and [Carrier A] were mixed uniformly for 5 minutes at 48 rpm in a Turbler mixer (manufactured by Willy & Bachofen (WAB)) and charged to prepare two-component developers. The toner and carrier mixing ratio was adjusted to match the toner concentration (7% by mass) of the initial developer for the evaluation machine.

[0080] (measurement) The flow-out start temperature and half flow-out temperature of the produced toner were measured as follows. Using a flow tester (Shimadzu CFT-500D), 1.0 g of sample was heated at a temperature increase rate of 6°C / min, while applying a load of 1.96 MPa with the plunger, and extruded from a nozzle with a diameter of 1.0 mm and a length of 1.0 mm. This resulted in a plot of the plunger stroke of the flow tester versus temperature, as shown in Figure 1. From this plot, the outflow start temperatures T fb , 1 / 2 outlet temperature T 1 / 2 asked for. The measurement results are shown in Table 1. In Table 1, the following are indicated: UT 1 / 2 : 1 / 2 flow temperature of white toner (toner for undercoat layer) UT fb : Flow start temperature of white toner (toner for undercoat layer) CT 1 / 2 : 1 / 2 the outflow temperature of color toner CT fb :Color toner flow start temperature

[0081] (evaluation) The resulting developer was used to form an image and was evaluated. The evaluation results are shown in Table 2. The evaluation methods and conditions were as follows.

[0082] <Creating evaluation images> <<Example 1>> The developer using [Color Toner 1] was set in the cyan station of a RICOH Pro C7200S (manufactured by Ricoh Co., Ltd.). The toner adhesion amount was 0.40 mg / cm 2 The development and transfer conditions were adjusted using a process controller so that the image was as shown below, and an unfixed solid cyan image was printed on transfer paper (Piotec WOW Light 8.0). The developer using [White Toner 1] was set in the fifth station of a RICOH Pro C7200S (manufactured by Ricoh Co., Ltd.). The toner adhesion amount was 1.0 mg / cm 2 The developing and transferring conditions were adjusted by a process controller so that the above-mentioned unfixed solid image of cyan was superimposed on the unfixed solid image of cyan on the transfer paper, and an unfixed solid image serving as an undercoat layer was output. The transfer paper was then heat-fixed to form a toner image on the transfer paper. Next, the toner image on the transfer paper was placed on a 100% polyester cloth (black T-shirt) as an image receiving substrate, and the resulting material was placed in a heat press (Model HTP234PS1 manufactured by Piotec Corporation). T at 140°C for 20 seconds at a pressure of 600g / cm 2 After applying heat and pressure, the transfer paper was peeled off and the toner image was thermally fixed onto the T-shirt. Here, a black 100% polyester fabric (T-shirt) was sprayed with Konishi's "Bond Long-lasting Waterproof Spray," which contains silicone resin and fluororesin components, from a distance of 10 cm from the T-shirt for 10 seconds, and then allowed to dry. In this way, an evaluation image of Example 1 was prepared.

[0083] <<Example 2>> An evaluation image was prepared in the same manner as in Example 1, except that [Color Toner 1] in Example 1 was changed to [Color Toner 2].

[0084] <<Comparative Example 1>> An evaluation image was prepared in the same manner as in Example 1, except that no water-repellent component was applied to the image-receiving substrate in Example 1. That is, in Comparative Example 1, Bond Waterproof Spray Long-lasting was not applied to a black 100% polyester fabric (T-shirt).

[0085] <<Example 3>> An evaluation image was prepared in the same manner as in Example 1, except that the image receiving substrate was changed from "black 100% polyester fabric" to "black cotton fabric."

[0086] <<Example 4>> An evaluation image was prepared in the same manner as in Example 2, except that the image receiving substrate was changed from "black 100% polyester fabric" to "black cotton fabric."

[0087] <<Comparative Example 2>> An evaluation image was prepared in the same manner as in Comparative Example 1, except that the image receiving substrate was changed from "black 100% polyester fabric" to "black cotton fabric."

[0088] <<Example 5>> An evaluation image was prepared in the same manner as in Example 1, except that the image receiving substrate in Example 1 was changed from "black 100% polyester fabric" to "white 100% polyester fabric."

[0089] <<Example 6>> An evaluation image was prepared in the same manner as in Example 5, except that the white toner was not used.

[0090] <<Comparative Example 3>> An evaluation image was prepared in the same manner as in Example 6, except that no water-repellent component was added to the image-receiving substrate.

[0091] <Image color evaluation> The saturation of the obtained evaluation image was visually evaluated according to the following criteria. [Evaluation criteria] ◎: The image colors are vivid 〇: The image color is vivid, but only the yellow image part is △ rank △: There are some darker areas in the image (only when using a black T-shirt) or some lighter areas in the image (common to both black and white T-shirts). ×: Dark areas in the image (only when using a black T-shirt) or lighter areas in the image due to unevenness of the fabric fibers are clearly visible (common to both black and white T-shirts)

[0092] <Washing durability evaluation> The obtained evaluation images were subjected to a washing fastness test according to the test method of JIS0844:2011, and were evaluated according to the following criteria. [Evaluation criteria] ◎: JIS0844 discoloration grayscale rank 5 ○: JIS0844 discoloration grayscale rank 4 △: JIS0844 discoloration grayscale rank 3 ×: JIS0844 discoloration grayscale rank 2-1

[0093] The formulations and evaluation results are shown in Tables 1 and 2. As can be seen from the evaluation results, according to the present invention, it is possible to form a toner image even on fabric, and to form an image with good wash resistance and good saturation. In addition, the reason why Examples 1 and 3 show better results than Examples 2 and 4 is that the half outflow temperature UT of the white toner 1 / 2 is the half outflow temperature CT of color toner 1 / 2 This is because it is higher than

[0094] [Table 1]

[0095] [Table 2] [Explanation of symbols]

[0096] 10 Transfer Media 12 color toner layers 14 White toner layer 20 Image receiving substrate 22 Water-repellent layer [Prior art documents] [Patent documents]

[0097] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-006747

Claims

1. a water-repellent layer forming step of forming a water-repellent layer containing a water-repellent component on an image-receiving substrate; a toner image forming step of forming a toner image on a transfer medium; a thermal transfer step of thermally transferring the toner image onto the surface of the image receiving substrate on which the water-repellent layer is formed, The image forming method according to claim 1, wherein the water-repellent component contains at least one material selected from the group consisting of silicone resins and fluorine resins.

2. 2. The image forming method according to claim 1, wherein the thermal transfer step includes stacking the image receiving substrate and the transfer medium so that the surface of the image receiving substrate on which the water-repellent layer is formed faces the surface of the transfer medium on which the toner image is formed, applying heat and pressure, and peeling off the transfer medium.

3. 3. The image forming method according to claim 1, wherein the toner image forming step comprises transferring a toner layer onto the transfer medium, and then performing thermal fixing to form a toner image on the transfer medium.

4. 4. The image forming method according to claim 1, wherein the image receiving substrate is made of fiber.

5. 5. The image forming method according to claim 1, wherein the image receiving substrate contains at least one fiber selected from the group consisting of polyester fiber and cotton fiber.

6. The toner image forming step includes forming a white toner layer on the transfer medium as a top layer, 6. The image forming method according to claim 1, wherein the thermal transfer step is performed such that, when the toner image is thermally transferred onto the image receiving substrate, the white toner layer is the bottom layer in the toner image on the image receiving substrate.

7. The toner image forming step includes forming a layer of color toner and a layer of white toner on the color toner layer, 1 / 2 outflow temperature UT of the white toner １／２ is the half outflow temperature CT of the color toner １／２ 7. The image forming method according to claim 1, wherein the surface tension is higher than 1000 nm.

Images