Particle set for printing, apparatus for manufacturing printed materials, and method for manufacturing printed materials

Abstract

To provide a particle set for manufacturing a printed matter which can give a printed matter excellent in adhesion.SOLUTION: A particle set for manufacturing a printed matter has a chromatic toner containing toner particles A, and pressure-responsive particles containing base particles B, wherein the base particles B have a predetermined resin composition and glass transition temperature, and when a volume average particle diameter of the toner particles A is represented by D50A and a volume average particle diameter of the base particles B is represented by D50B, the D50A and the D50B satisfy the following expression 1-1. Expression 1-1: 1.5 μm<(D50B-D50A).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a particle set for producing printed materials, an apparatus for producing printed materials, and a method for producing printed materials. [Background technology]

[0002] Patent Document 1 proposes an adhesive material comprising "a styrene-based resin containing styrene and other vinyl monomers as polymerization components, and a (meth)acrylic acid ester-based resin containing at least two types of (meth)acrylic acid esters as polymerization components, wherein the mass ratio of (meth)acrylic acid esters to the total polymerization components is 90% by mass or more, the mass ratio of the styrene-based resin to the (meth)acrylic acid ester-based resin is 80:20 to 20:80, and the resin particles have at least two glass transition temperatures, the lowest glass transition temperature being -30°C or lower, and the highest glass transition temperature being 30°C or higher." [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2021-017465 [Overview of the project] [Problems that the invention aims to solve]

[0004] The object of the present invention is to provide a particle set for printing in which a printed material can be obtained with superior adhesion compared to the case where D50A and D50B satisfy the following formula C1-1, when the volume average particle size of the toner particle A is D50A and the volume average particle size of the mother particle B is D50B. Formula C1-1: 1.5μm≧(D50B-D50A) [Means for solving the problem]

[0005] The above problems will be solved by the following means: <1> It comprises a chromatic toner containing toner particles A, and pressure-responsive particles containing mother particles B, The mother particle B comprises a styrene-based resin containing styrene and other vinyl monomers as polymerization components, and a (meth)acrylic acid ester-based resin containing (meth)acrylic acid esters as polymerization components. The mass ratio of the styrene resin to the (meth)acrylic acid ester resin (styrene resin:(meth)acrylic acid ester resin) is 80:20 to 20:80. The difference between the lowest glass transition temperature and the highest glass transition temperature of the pressure-responsive particle is 30°C or more. A particle set for producing printed materials in which D50A and D50B satisfy the following formula 1-1, where D50A and D50B are the volume-average particle size of the toner particle A and the volume-average particle size of the mother particle B. Formula 1-1: 1.5μm<(D50B-D50A) <2> The toner particles A contain polyester resin <1> A set of particles for producing printed materials as described above. <3> Both the toner particles A and the mother particles B contain a release agent. The amount of release agent contained in the toner particles A is W. A The amount of release agent contained in the mother particle B relative to the amount of release agent W B The ratio (W B / W A The above is where ) is 0.01 or more and 0.8 or less. <1> or <2> A set of particles for producing printed materials as described above. <4> Content W of the aforementioned release agent B The above is characterized by being 0.1% by mass or more and 4.0% by mass or less. <3> A set of particles for producing printed materials as described above. <5> The above D50A and D50B satisfy the following formula 1-2 <1> ~ <4> A set of particles for printing, as described in one of the following: Formula 1-2: 1.5μm<(D50B-D50A)<10μm <6> The above D50B is 6.0 μm or more and 20.0 μm or less. <5> A set of particles for producing printed materials as described above. <7> The mother particle B comprises a core portion containing the styrene resin and the (meth)acrylic acid ester resin, A shell layer covering the core portion, Having the above <1> ~ <6> A set of particles for printing, as described in one of the following: <8> The aforementioned mother particle B contains a pigment, The pigment content is 5 ppm or more and 100 ppm or less relative to the total amount of the mother particles B. <1> ~ <7> A set of particles for printing, as described in one of the following: <9> The aforementioned <1> ~ <8> A chromatic toner image forming means that contains a developer containing the chromatic toner in a printmaking particle set described in any one of the above, and forms the chromatic toner image on a recording medium by electrophotography using the developer, The aforementioned <1> ~ <8> Arrangement means for containing the pressure-responsive particles in a particle set for printing described in any one of the above, and for arranging the pressure-responsive particles on a recording medium to form a pressure-responsive particle layer, A heat fixing means for heat-fixing the colored toner image onto the recording medium in a state where a fixing member is in contact with the pressure-responsive particle layer, A pressure-bonding means for folding and pressure-bonding the recording medium on which the colored toner image has been heat-fixed, or for overlapping and pressure-bonding the recording medium on which the colored toner image has been heat-fixed with another recording medium, A printing material manufacturing apparatus including the above. <10> A colored toner image forming step of forming a colored toner image on a recording medium by an electrophotographic method using a developer containing the colored toner in the particle set for manufacturing a printed matter according to any one of <1> to <8> above, An arranging step of arranging the pressure-responsive particles in the particle set for manufacturing a printed matter according to any one of <1> to <8> above on the recording medium to form a pressure-responsive particle layer, A heat fixing step of heat-fixing the colored toner image onto the recording medium in a state where a fixing member is in contact with the pressure-responsive particle layer, A pressure-bonding step of folding and pressure-bonding the recording medium on which the colored toner image has been heat-fixed, or of overlapping and pressure-bonding the recording medium on which the colored toner image has been heat-fixed with another recording medium, A method for manufacturing a printed matter including the above.

Advantages of the Invention

[0006] According to the invention according to <1>, there are provided a colored toner containing toner particles A and pressure-responsive particles containing mother particles B, wherein the mother particles B contain a styrene resin containing styrene and other vinyl monomers as polymerization components, and a (meth)acrylate resin containing a (meth)acrylate as a polymerization component, and the mass ratio of the styrene resin to the (meth)acrylate resin (styrene resin:(meth)acrylate resin) is 80:20 to 20:80, and in a particle set for producing a printed matter in which the difference between the lowest glass transition temperature and the highest glass transition temperature of the pressure-responsive particles is 30 °C or more, when the volume average particle diameter of the toner particles A is D50A and the volume average particle diameter of the mother particles B is D50B, a particle set for producing a printed matter that gives a printed matter having excellent adhesiveness is provided as compared with the case where D50A and D50B satisfy the following formula C1-1. Formula C1-1: 1.5 μm ≥ (D50B - D50A) According to the invention according to <2>, there is provided a particle set for producing a printed matter that gives a printed matter having excellent adhesiveness as compared with the case where the toner particles A contain a styrene-acrylic resin. According to the invention according to <3>, both the toner particles A and the mother particles B contain a mold release agent, and the content W of the mold release agent contained in the toner particles A A relative to the content W of the mold release agent contained in the mother particles B B ratio (W B / W A )g is less than 0.01 or exceeds 0.8, a particle set for producing a printed matter that gives a printed matter having excellent adhesiveness is provided as compared with the case thereof. According to the invention according to <4>, there is provided a particle set for producing a printed matter that gives a printed matter having excellent adhesiveness as compared with the case where the content W of the mold release agent B is less than 0.1% by mass or exceeds 4.0% by mass. According to the invention according to <5>, there is provided a particle set for producing a printed matter that gives a printed matter having excellent adhesiveness as compared with the case where D50A and D50B satisfy the following formula C1-2. Formula C1-2: 1.5 μm ≥ (D50B - D50A), or (D50B - D50A) ≥ 10 μm <6> According to the invention, a particle set for producing printed materials is provided that yields printed materials with superior adhesion compared to cases where D50B is less than 6.0 μm or greater than 20.0 μm. <7> According to the invention, a particle set for producing printed materials is provided in which the mother particle B contains the styrene resin and the (meth)acrylic acid ester resin, but has superior adhesion compared to a case where there is no shell layer. <8> According to the invention, a particle set for producing printed materials is provided in which the mother particles B contain a pigment, and compared to cases where the pigment content is less than 5 ppm or more than 100 ppm relative to the total amount of mother particles B, a printed material with superior adhesion is obtained. <9> , or <10> According to the invention, a particle set for printing, comprising a chromatic toner containing toner particles A and pressure-responsive particles containing mother particles B, wherein the mother particles B comprises a styrene-based resin containing styrene and other vinyl monomers as polymerization components, and a (meth)acrylic acid ester-based resin containing (meth)acrylic acid ester as polymerization components, the mass ratio (styrene-based resin:(meth)acrylic acid ester-based resin) of the styrene-based resin and the (meth)acrylic acid ester-based resin is 80:20 to 20:80, and the difference between the lowest glass transition temperature and the highest glass transition temperature of the pressure-responsive particles is 30°C or more, wherein when the volume average particle size of the toner particles A is D50A and the volume average particle size of the mother particles B is D50B, a printing apparatus or method for manufacturing a printed material is provided that yields a printed material with superior adhesion compared to a printing particle set that satisfies the following formula C1-1. [Brief explanation of the drawing]

[0007] [Figure 1] This is a schematic diagram showing a part of an example of a printing apparatus according to this embodiment, including the placement means and the crimping means. [Figure 2] This is a schematic diagram showing another example of a printing apparatus according to this embodiment. [Figure 3]This is a schematic diagram showing an example of a first process cartridge that constitutes the process cartridge set according to this embodiment. [Modes for carrying out the invention]

[0008] The following describes an example embodiment of the present invention. These descriptions and examples are illustrative and do not limit the scope of the invention. In numerical ranges described stepwise within this specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described stepwise. Furthermore, in numerical ranges described within this specification, the upper or lower limit of that range may be replaced with the values ​​shown in the examples.

[0009] Each component may contain multiple types of the relevant substance. When referring to the amount of each component in a composition, if there are multiple substances corresponding to each component in the composition, unless otherwise specified, it refers to the total amount of those multiple substances present in the composition.

[0010] <Particle set for printing materials> The particle set for printing according to this embodiment comprises a chromatic toner containing toner particles A and pressure-responsive particles containing mother particles B, and also satisfies the following requirements. The mother particle B comprises a styrene-based resin containing styrene and other vinyl monomers as polymerization components, and a (meth)acrylic acid ester-based resin containing (meth)acrylic acid esters as polymerization components. The mass ratio of the styrene resin to the (meth)acrylic acid ester resin (styrene resin:(meth)acrylic acid ester resin) is 80:20 to 20:80. The difference between the lowest glass transition temperature and the highest glass transition temperature of the pressure-responsive particles is 30°C or more. When the volume-average particle size of toner particle A is D50A and the volume-average particle size of mother particle B is D50B, then D50A and D50B satisfy the following formula 1-1. Formula 1-1: 1.5μm<(D50B-D50A)

[0011] The photoreceptor according to this embodiment, with the above configuration, becomes a particle set for producing printed materials that yields printed materials with excellent adhesion. The reason for this is presumed to be as follows.

[0012] A particle set for printing, comprising a chromatic toner containing toner particles A and pressure-responsive particles containing mother particles B, wherein the mother particles B comprises a styrene-based resin containing styrene and other vinyl monomers as polymerization components, and a (meth)acrylic acid ester-based resin containing (meth)acrylic acid ester as polymerization components, wherein the mass ratio of the styrene-based resin to the (meth)acrylic acid ester-based resin (styrene-based resin:(meth)acrylic acid ester-based resin) is 80:20 to 20:80, and the difference between the lowest glass transition temperature and the highest glass transition temperature of the pressure-responsive particles is 30°C or more, can be used, for example, in an electrophotographic image forming apparatus to simultaneously form an image by applying the chromatic toner onto a recording medium and form a pressure-responsive particle layer by applying the pressure-responsive particles onto the recording medium. Subsequently, the recording medium on which the image and pressure-responsive particle layer are formed can be stacked and pressed together with another recording medium, causing the pressure-responsive particle layer to undergo a phase transition and bonding the recording media together. In this case, when the recording medium is pressed, if the thickness of the image formed by the chromatic toner is equal to or greater than that of the pressure-responsive particle layer, the pressure applied to the image also increases, and the pressure applied to the pressure-responsive particles tends to decrease. Therefore, there is a need to improve the adhesion of the resulting printed material.

[0013] In the particle set for printing according to this embodiment, when the volume average particle size of the toner particles A is D50A and the volume average particle size of the mother particles B is D50B, D50A and D50B satisfy formula 1-1. In other words, the particle size of the mother particles B contained in the pressure-responsive particles is larger than the particle size of the toner particles A contained in the chromatic toner. Therefore, when an image is formed on a recording medium using chromatic toner and a pressure-responsive particle layer is formed using pressure-responsive particles simultaneously, and then the recording medium is bonded to another recording medium by pressing them together, the thickness of the pressure-responsive particle layer tends to be greater than the thickness of the image. As a result, the decrease in pressure applied to the pressure-responsive particles is suppressed.

[0014] Based on the above, it is presumed that the particle set for producing printed materials according to this embodiment will produce printed materials with excellent adhesive properties.

[0015] The particle set for printing comprises at least a chromatic toner and pressure-responsive particles having a pressure phase transition property, and may optionally contain other toners (e.g., transparent toner that does not have a pressure phase transition property). Hereinafter, pressure-responsive particles having a pressure phase transition property may simply be referred to as "pressure-responsive particles". The chromatic toner and pressure-responsive particles may be present in single units or in combination of two or more types.

[0016] Here, "chromatic toner" refers to toner in which the amount of colorant in the toner particles exceeds 1.0% by mass relative to the total amount of toner particles. "Transparent toner" refers to toner in which the toner particles do not contain colorant, or in which the amount of colorant in the toner particles is 1.0% by mass or less relative to the total amount of toner particles. "Having pressure phase transition properties" means satisfying the following equation 2. Formula 2...10℃≦T1-T2 In Equation 2, T1 is the temperature at which the viscosity is 10,000 Pa·s under a pressure of 1 MPa, and T2 is the temperature at which the viscosity is 10,000 Pa·s under a pressure of 10 MPa. The methods for determining T1 and T2 will be described later. The following describes each toner that makes up the toner set according to this embodiment.

[0017] (chromatic toner) The term "chromatic toner" is not particularly limited to any toner in which the amount of colorant in toner particle A exceeds 1.0% by mass relative to the total amount of toner particle A. Chromatic toner consists of toner particles and, if necessary, external additives.

[0018] (Toner particles A) Toner particles A are composed of, for example, a binder resin, a colorant, and optionally, a release agent and other additives.

[0019] -Binding resin- Examples of binder resins include vinyl resins consisting of monomers such as styrenes (e.g., styrene, parachlorostyrene, α-methylstyrene, etc.), (meth)acrylic acid esters (e.g., methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc.), ethylenically unsaturated nitriles (e.g., acrylonitrile, methacrylonitrile, etc.), vinyl ethers (e.g., vinyl methyl ether, vinyl isobutyl ether, etc.), vinyl ketones (vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone, etc.), and olefins (e.g., ethylene, propylene, butadiene, etc.), or copolymers of two or more of these monomers. Examples of binder resins include non-vinyl resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, and modified rosin; mixtures of these with the aforementioned vinyl resins; and graft polymers obtained by polymerizing vinyl monomers in the presence of these. These binding resins may be used individually or in combination of two or more types.

[0020] Polyester resin is preferred as the binder resin. By including polyester resin as a binder, this particle set for printing produces printed materials with superior adhesion. The reason for this is presumed to be as follows: For example, if toner particle A contains a styrene-acrylic resin, it will have a similar composition to the pressure-responsive particles, making them easily miscible during fixing and allowing the pressure-responsive particles to be easily incorporated into toner particle A, thus reducing adhesion. In contrast, if toner particle A contains a polyester resin, the particles will not be miscible with each other and will not be easily incorporated into toner particle A, making it easier for the pressure-responsive particles to remain independent. As a result, it is presumed that the pressure-responsive particles will be more easily crushed, leading to improved adhesion. Examples of polyester resins include well-known polyester resins.

[0021] Examples of polyester resins include condensation polymers of polycarboxylic acids and polyhydric alcohols. Commercially available polyester resins or synthesized polyester resins may be used.

[0022] Examples of polycarboxylic acids include aliphatic dicarboxylic acids (e.g., oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, alkenylsuccinic acid, adipic acid, sebacic acid, etc.), alicyclic dicarboxylic acids (e.g., cyclohexanedicarboxylic acid, etc.), aromatic dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, etc.), their anhydrides, or their lower alkyl esters (e.g., with 1 to 5 carbon atoms). Among these, aromatic dicarboxylic acids are preferred as polycarboxylic acids. Polycarboxylic acids may be used in combination with dicarboxylic acids, or with trivalent or higher carboxylic acids that have a cross-linked or branched structure. Examples of trivalent or higher carboxylic acids include trimellitic acid, pyromellitic acid, their anhydrides, or their lower alkyl esters (e.g., having 1 to 5 carbon atoms). Polycarboxylic acids may be used individually or in combination of two or more.

[0023] Examples of polyhydric alcohols include aliphatic diols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, etc.), alicyclic diols (e.g., cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, etc.), and aromatic diols (e.g., ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, etc.). Among these, aromatic diols and alicyclic diols are preferred as polyhydric alcohols, and aromatic diols are more preferred. As for the polyhydric alcohol, a trihydric or higher polyhydric alcohol with a cross-linked or branched structure may be used in combination with the diol. Examples of trihydric or higher polyhydric alcohols include glycerin, trimethylolpropane, and pentaerythritol. Polyhydric alcohols may be used individually or in combination of two or more types.

[0024] The glass transition temperature (Tg) of the polyester resin is preferably 50°C to 80°C, and more preferably 50°C to 65°C. The glass transition temperature is determined from the DSC curve obtained by differential scanning calorimetry (DSC), and more specifically, it is determined by the "extracorporeal glass transition onset temperature" described in the method for determining the glass transition temperature in JIS K 7121-1987 "Method for Measuring the Transition Temperature of Plastics".

[0025] The weight-average molecular weight (Mw) of the polyester resin is preferably 5,000 to 1,000,000, and more preferably 7,000 to 500,000. The number-average molecular weight (Mn) of the polyester resin is preferably between 2,000 and 100,000. The molecular weight distribution (Mw / Mn) of the polyester resin is preferably 1.5 to 100, and more preferably 2 to 60. The weight-average molecular weight and number-average molecular weight are measured by gel permeation chromatography (GPC). GPC molecular weight measurement is performed using a Tosoh GPC-HLC-8120GPC analyzer, a Tosoh TSKgel SuperHM-M (15cm) column, and THF solvent. The weight-average molecular weight and number-average molecular weight are calculated from these measurement results using a molecular weight calibration curve prepared with monodisperse polystyrene standard samples.

[0026] Polyester resins can be obtained by well-known manufacturing methods. Specifically, for example, they can be obtained by a method in which the polymerization temperature is set to 180°C or higher and 230°C or lower, and the reaction system is subjected to reduced pressure as needed, while removing water and alcohol generated during condensation. If the monomers of the raw materials do not dissolve or become miscible at the reaction temperature, a high-boiling point solvent may be added as a solubilizer to dissolve them. In this case, the polycondensation reaction should be carried out while distilling off the solubilizer. If there are monomers with poor miscibility, it is advisable to condense the poorly miscible monomers with the acid or alcohol to be polycondensed with them beforehand, and then polycondense them together with the main component.

[0027] The binder resin content is preferably 40% to 95% by mass, more preferably 50% to 90% by mass, and even more preferably 60% to 85% by mass, relative to the total toner particles A.

[0028] -Colorants- The amount of colorant in toner particle A exceeds 1.0% by mass relative to the total amount of toner particle A. Examples of colorants include carbon black, chrome yellow, Hansa yellow, benzidine yellow, surene yellow, quinoline yellow, pigment yellow, permanent orange GTR, pyrazolone orange, balkan orange, Watch Young red, permanent red, brilliant carmine 3B, brilliant carmine 6B, DuPont oil red, pyrazolone red, risole red, rhodamine B lake, lake red C, pigment red, rose bengal, aniline blue, and ultramarine. Examples include various pigments such as phosphorus blue, chalcioyl blue, methylene blue chloride, phthalocyanine blue, pigment blue, phthalocyanine green, and malachite green oxalate, as well as various dyes such as acridine, xanthene, azo, benzoquinone, azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, and thiazole. Colorants may be used individually or in combination of two or more types.

[0029] The coloring agent may be a surface-treated coloring agent as needed, and may be used in combination with a dispersant. Furthermore, multiple types of coloring agents may be used in combination.

[0030] The colorant content is preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 15% by mass or less, relative to the total toner particles A.

[0031] -Release agent- Examples of release agents include hydrocarbon waxes; natural waxes such as carnauba wax, rice wax, and candelilla wax; synthetic or mineral / petroleum-based waxes such as montan wax; and ester waxes such as fatty acid esters and montanic acid esters. However, the release agents are not limited to these.

[0032] The melting temperature of the release agent is preferably 50°C to 110°C, and more preferably 60°C to 100°C. The melting temperature is determined from the DSC curve obtained by differential scanning calorimetry (DSC) using the "melting peak temperature" described in JIS K 7121-1987 "Method for determining the transition temperature of plastics".

[0033] The release agent content is preferably 1% to 20% by mass, and more preferably 5% to 15% by mass, relative to the total amount of toner particles A.

[0034] -Other additives- Other additives include well-known additives such as magnetic materials, charge control agents, and inorganic powders. These additives are included in toner particles A as internal additives.

[0035] -Characteristics of toner particle A- Toner particle A may be a single-layer toner particle A, or it may be a so-called core-shell toner particle A composed of a core (core particle) and a coating layer (shell layer) covering the core. Here, the core-shell structured toner particle A may consist of, for example, a core portion comprising a binder resin and, if necessary, other additives such as a colorant and a release agent, and a coating layer comprising a binder resin.

[0036] (External additive) Examples of external additives include inorganic particles. Examples of such inorganic particles include SiO2, TiO2, Al2O3, CuO, ZnO, SnO2, CeO2, Fe2O3, MgO, BaO, CaO, K2O, Na2O, ZrO2, CaO·SiO2, K2O·(TiO2)n, Al2O3·2SiO2, CaCO3, MgCO3, BaSO4, MgSO4, and the like.

[0037] The surface of the inorganic particles used as an external additive should preferably be subjected to a hydrophobic treatment. The hydrophobic treatment is carried out, for example, by immersing the inorganic particles in a hydrophobic treatment agent. The hydrophobic treatment agent is not particularly limited, but examples include silane-based coupling agents, silicone oil, titanate-based coupling agents, and aluminum-based coupling agents. These may be used individually or in combination of two or more. The amount of hydrophobic treatment agent is typically, for example, 1 to 10 parts by mass per 100 parts by mass of inorganic particles.

[0038] Examples of external additives include resin particles (such as polystyrene, polymethyl methacrylate (PMMA), and melamine resin), and cleaning activators (for example, metal salts of higher fatty acids represented by zinc stearate, and fluorine-based high molecular weight particles).

[0039] The amount of external additive is preferably 0.01% to 5% by mass, and more preferably 0.01% to 2.0% by mass, relative to toner particles A.

[0040] (Manufacturing method for chromatic toner) Next, a method for manufacturing chromatic toner according to this embodiment will be described. The chromatic toner according to this embodiment is obtained by manufacturing toner particles A and then adding an external additive to the toner particles A.

[0041] Toner particles A may be manufactured by either a dry process (e.g., kneading and grinding method) or a wet process (e.g., agglomeration, suspension polymerization, dissolution and suspension method). There are no particular restrictions on the manufacturing method of toner particles A, and any well-known method may be used. Among these methods, obtaining toner particles A by the aggregation and coalescence method is preferable.

[0042] Specifically, for example, when manufacturing toner particles A by an aggregation and coalescence method, The toner particle A is manufactured through the following steps: preparing a resin particle dispersion in which resin particles that will serve as a binder are dispersed (resin particle dispersion preparation step); a step of agglomerating resin particles (and other particles as needed) in the resin particle dispersion (and in a dispersion after mixing with other particle dispersions as needed) to form aggregated particles (aggregated particle formation step); and a step of heating the aggregated particle dispersion in which the aggregated particles are dispersed to fuse and combine the aggregated particles to form toner particles A (fusion and combination step).

[0043] The details of each step are explained below. The following explanation describes a method for obtaining toner particles A containing a colorant and a release agent, but the colorant and release agent are used as needed. Of course, other additives besides colorants and release agents may also be used.

[0044] -Resin particle dispersion preparation process- First, a resin particle dispersion containing resin particles that will act as a binder is prepared, along with, for example, a coloring agent particle dispersion containing coloring agent particles and a release agent particle dispersion containing release agent particles.

[0045] Here, the resin particle dispersion is prepared, for example, by dispersing resin particles in a dispersion medium with a surfactant.

[0046] Examples of dispersion media used in resin particle dispersions include aqueous media. Examples of aqueous media include water such as distilled water and deionized water, and alcohols. These may be used individually or in combination of two or more.

[0047] Examples of surfactants include anionic surfactants such as sulfate esters, sulfonates, phosphates, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts; and nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, anionic surfactants and cationic surfactants are particularly noteworthy. Nonionic surfactants may be used in combination with anionic or cationic surfactants. Surfactants may be used individually or in combination of two or more types.

[0048] In resin particle dispersions, common dispersion methods for dispersing resin particles in a dispersion medium include, for example, rotary shear homogenizers, ball mills with media, sand mills, and dyno mills. Depending on the type of resin particles, the resin particles may also be dispersed in the resin particle dispersion using, for example, a phase inversion emulsification method. Phase inversion emulsification is a method in which the resin to be dispersed is dissolved in a hydrophobic organic solvent in which the resin is soluble, a base is added to the organic continuous phase (O phase) to neutralize it, and then an aqueous medium (W phase) is added. This causes a conversion of the resin from W / O to O / W (so-called phase inversion), resulting in a discontinuous phase, and the resin is dispersed in the aqueous medium in particulate form.

[0049] The volume-average particle size of the resin particles dispersed in the resin particle dispersion is preferably 0.01 μm or more and 1 μm or less, more preferably 0.08 μm or more and 0.8 μm or less, and even more preferably 0.1 μm or more and 0.6 μm or less. The volume-average particle size of the resin particles is measured using a laser diffraction particle size distribution analyzer (e.g., LA-700, manufactured by Horiba, Ltd.). The particle size distribution is obtained by subtracting the cumulative distribution from the smallest particle size side for each divided particle size range (channel), and the particle size that accounts for 50% of the total particle size is measured as the volume-average particle size D50v. The volume-average particle size of particles in other dispersions is measured in the same manner.

[0050] The resin particle content in the resin particle dispersion is preferably, for example, 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 40% by mass or less.

[0051] Furthermore, colorant particle dispersions and release agent particle dispersions are prepared in the same manner as resin particle dispersions. In other words, the volume average particle size, dispersion medium, dispersion method, and particle content of the resin particle dispersions are the same for colorant particles dispersed in colorant particle dispersions and release agent particles dispersed in release agent particle dispersions.

[0052] -Agglomerated particle formation process- Next, the resin particle dispersion is mixed with the coloring agent particle dispersion and the mold release agent particle dispersion. Then, in the mixed dispersion, the resin particles, colorant particles, and release agent particles are heteroaggregated to form aggregated particles containing the resin particles, colorant particles, and release agent particles, which have a diameter close to that of the target toner particle A.

[0053] Specifically, for example, a coagulant is added to a mixed dispersion, the pH of the mixed dispersion is adjusted to be acidic (for example, pH 2 to 5), a dispersion stabilizer is added as needed, and then the mixture is heated to a temperature of the glass transition temperature of the resin particles (specifically, for example, above the glass transition temperature of the resin particles -30°C or below the glass transition temperature of -10°C) to agglomerate the particles dispersed in the mixed dispersion and form agglomerated particles. In the agglomerated particle formation step, for example, the mixed dispersion may be stirred in a rotary shear homogenizer, the above-mentioned flocculant may be added at room temperature (e.g., 25°C), the pH of the mixed dispersion may be adjusted to acidic (e.g., pH 2 to 5), a dispersion stabilizer may be added as needed, and then the above-mentioned heating may be performed.

[0054] Examples of flocculants include surfactants with opposite polarity to the surfactant used as a dispersant added to a mixed dispersion, inorganic metal salts, and metal complexes with a valency of 2 or higher. In particular, when a metal complex is used as a flocculant, the amount of surfactant used is reduced and the electrostatic properties are improved. Additives that form complexes or similar bonds with the metal ions of the flocculant may be used as needed. Chelating agents are preferably used as such additives.

[0055] Examples of inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, as well as inorganic metal salt polymers such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. As a chelating agent, a water-soluble chelating agent may be used. Examples of chelating agents include oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid, as well as iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA). The amount of chelating agent to be added is preferably 0.01 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of resin particles, and more preferably 0.1 parts by mass or more and less than 3.0 parts by mass.

[0056] -Fusion / coalescence process- Next, the dispersion of aggregated particles is heated to a temperature above the glass transition temperature of the resin particles (for example, 10 to 30°C higher than the glass transition temperature of the resin particles) to fuse and combine the aggregated particles and form toner particles A.

[0057] Toner particles A are obtained through the above process. Alternatively, after obtaining an aggregated particle dispersion in which aggregated particles are dispersed, the toner particles A may be manufactured by further mixing the aggregated particle dispersion with a resin particle dispersion in which resin particles are dispersed, and agglomerating the aggregated particles so that resin particles adhere to the surface of the aggregated particles to form second aggregated particles, and by heating the second aggregated particle dispersion in which the second aggregated particles are dispersed to fuse and combine the second aggregated particles to form toner particles A with a core / shell structure.

[0058] Here, after the fusion and combination process is completed, the toner particles A formed in the solution are subjected to known washing, solid-liquid separation, and drying processes to obtain dried toner particles A. The washing process should be thoroughly performed using ion-exchanged water for displacement washing, considering the electrostatic charge. The solid-liquid separation process is not particularly restricted, but suction filtration, pressure filtration, etc., are preferable for productivity. The drying process is also not particularly restricted, but freeze-drying, air-flow drying, fluidized bed drying, vibratory fluidized bed drying, etc., are preferable for productivity.

[0059] The chromatic toner according to this embodiment is manufactured, for example, by adding an external additive to the obtained dried toner particles A and mixing them. Mixing can be performed using, for example, a V-blender, a Henschel mixer, a Redigge mixer, etc. Furthermore, if necessary, coarse particles of the chromatic toner may be removed using a vibrating screen separator, a wind screen separator, etc.

[0060] (Pressure-responsive particles) The pressure-responsive particles include at least mother particles B and optionally include external additives.

[0061] (Mother particle B) Mother particle B contains at least a binder resin. The binder resin contains a styrene-based resin containing styrene and other vinyl monomers as polymerization components, and a (meth)acrylic acid ester-based resin containing (meth)acrylic acid esters as polymerization components. Mother particle B may contain colorants, release agents, and other additives. If mother particle B contains a coloring agent, the amount of coloring agent in mother particle B is 1.0% by mass or less relative to the total amount of mother particle B.

[0062] -Styrene resin- Styrene resins contain styrene and other vinyl monomers as polymerization components.

[0063] The mass percentage of styrene in the total polymerization components of the styrene-based resin is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 75% by mass or more, from the viewpoint of suppressing the fluidization of mother particles B when not pressurized. From the viewpoint of forming mother particles B that are prone to phase transition under pressure, it is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0064] Examples of styrene monomers other than styrene include vinylnaphthalene; alkyl-substituted styrenes such as α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, and pn-dodecylstyrene; aryl-substituted styrenes such as p-phenylstyrene; alkoxy-substituted styrenes such as p-methoxystyrene; halogen-substituted styrenes such as p-chlorostyrene, 3,4-dichlorostyrene, p-fluorostyrene, and 2,5-difluorostyrene; and nitro-substituted styrenes such as m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene. Styrene monomers may be used individually or in combination of two or more.

[0065] As the acrylic monomer, at least one acrylic monomer selected from the group consisting of (meth)acrylic acid and (meth)acrylic acid esters is preferred. Examples of (meth)acrylic acid esters include alkyl (meth)acrylates, carboxylated alkyl (meth)acrylates, hydroxylated alkyl (meth)acrylates, alkoxylated alkyl (meth)acrylates, and di(meth)acrylic acid esters. The acrylic monomer may be used alone or in combination of two or more.

[0066] Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)methacrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and isobornyl (meth)acrylate. Examples of carboxylated alkyl esters of (meth)acrylate include 2-carboxyethyl (meth)acrylate. Examples of hydroxysubstituted alkyl esters of (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Examples of alkoxy-substituted alkyl esters of (meth)acrylate include 2-methoxyethyl (meth)acrylate. Examples of di(meth)acrylic acid esters include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, pentanediol di(meth)acrylate, hexanediol di(meth)acrylate, nonanediol di(meth)acrylate, and decanediol di(meth)acrylate.

[0067] Examples of (meth)acrylic acid esters include 2-(diethylamino)ethyl (meth)acrylate, benzyl (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate.

[0068] Other vinyl monomers that constitute styrene-based resins include, in addition to styrene-based monomers and acrylic-based monomers, (meth)acrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; and olefins such as isoprene, butene, and butadiene.

[0069] The styrene-based resin preferably contains (meth)acrylic acid ester as another vinyl monomer, more preferably contains alkyl (meth)acrylic acid ester, even more preferably contains alkyl (meth)acrylic acid ester having 2 to 10 carbon atoms in the alkyl group, even more preferably contains alkyl (meth)acrylic acid ester having 4 to 8 carbon atoms in the alkyl group, and particularly preferably contains at least one of n-butyl acrylate and 2-ethylhexyl acrylate. The styrene-based resin and the (meth)acrylic acid ester-based resin preferably contain the same type of (meth)acrylic acid ester as a polymerization component.

[0070] The mass percentage of (meth)acrylic acid ester in the total polymerization components of the styrene-based resin is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less, from the viewpoint of suppressing the fluidization of mother particles B in the unpressurized state. From the viewpoint of forming mother particles B that are prone to phase transition under pressure, it is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. The (meth)acrylic acid ester here is preferably an alkyl (meth)acrylic acid ester, more preferably an alkyl (meth)acrylic acid ester with 2 to 10 carbon atoms in the alkyl group, and even more preferably an alkyl (meth)acrylic acid ester with 4 to 8 carbon atoms in the alkyl group.

[0071] The styrene-based resin is particularly preferably composed of at least one of n-butyl acrylate and 2-ethylhexyl acrylate as polymerization components. The total amount of n-butyl acrylate and 2-ethylhexyl acrylate in the total polymerization components of the styrene-based resin is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less, from the viewpoint of suppressing the fluidization of mother particles B in the unpressurized state. From the viewpoint of forming mother particles B that are prone to phase transition under pressure, it is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more.

[0072] The weight-average molecular weight of the styrene resin is preferably 3000 or more, more preferably 4000 or more, and even more preferably 5000 or more, from the viewpoint of suppressing the fluidization of mother particles B in the unpressurized state. From the viewpoint of forming mother particles B that are prone to phase transition under pressure, it is preferably 50000 or less, more preferably 45000 or less, and even more preferably 40000 or less.

[0073] The glass transition temperature of the styrene-based resin is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher, from the viewpoint of suppressing the fluidization of the parent particles B in the unpressurized state. From the viewpoint of forming parent particles B that are easily subjected to phase transition by pressure, it is preferably 110°C or lower, more preferably 100°C or lower, and even more preferably 90°C or lower.

[0074] In this disclosure, the glass transition temperature of the resin is determined from a differential scanning calorimetry (DSC) curve obtained by performing differential scanning calorimetry (DSC). More specifically, it is determined according to the "extracorporeal glass transition onset temperature" described in the method for determining the glass transition temperature in JIS K7121:1987 "Method for Measuring the Transition Temperature of Plastics".

[0075] The glass transition temperature of a resin is controlled by the type and polymerization ratio of the polymer components. The glass transition temperature tends to be lower when the density of flexible units such as methylene groups, ethylene groups, and oxyethylene groups in the main chain is high, and higher when the density of rigid units such as aromatic rings and cyclohexane rings in the main chain is high. Furthermore, the glass transition temperature tends to be lower when the density of aliphatic groups in the side chains is high.

[0076] The mass percentage of styrene-based resin in the total mother particle B is preferably 55% by mass or more, more preferably 60% by mass or more, and even more preferably 65% ​​by mass or more, from the viewpoint of suppressing the fluidization of mother particle B when not pressurized. From the viewpoint of forming mother particle B that is prone to phase transition by pressure, it is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.

[0077] -(meth)acrylic acid ester resin- (Meth)acrylic acid ester resins contain acrylic acid ester as a polymerization component. The mass percentage of (meth)acrylic acid ester in the total polymerization components of the (meth)acrylic acid ester resin is, for example, 90% by mass or more, more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 100% by mass.

[0078] Examples of (meth)acrylic acid esters include alkyl (meth)acrylates, carboxylated alkyl (meth)acrylates, hydroxylated alkyl (meth)acrylates, alkoxylated alkyl (meth)acrylates, and di(meth)acrylic acid esters.

[0079] Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)methacrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and isobornyl (meth)acrylate. Examples of carboxylated alkyl esters of (meth)acrylate include 2-carboxyethyl (meth)acrylate. Examples of hydroxysubstituted alkyl esters of (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Examples of alkoxy-substituted alkyl esters of (meth)acrylate include 2-methoxyethyl (meth)acrylate. Examples of di(meth)acrylic acid esters include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, pentanediol di(meth)acrylate, hexanediol di(meth)acrylate, nonanediol di(meth)acrylate, and decanediol di(meth)acrylate.

[0080] Examples of (meth)acrylic acid esters include 2-(diethylamino)ethyl (meth)acrylate, benzyl (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate.

[0081] (Meth)acrylic acid esters may be used individually or in combination of two or more types.

[0082] As for the (meth)acrylic acid ester, alkyl (meth)acrylic acid esters are preferred from the viewpoint of forming mother particles B that readily undergo phase transition under pressure and have excellent adhesion, alkyl (meth)acrylic acid esters with 2 to 10 carbon atoms in the alkyl group are more preferred, alkyl (meth)acrylic acid esters with 4 to 8 carbon atoms in the alkyl group are even more preferred, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred. From the viewpoint of forming mother particles B that readily undergo phase transition under pressure, it is preferable that the styrene-based resin and the (meth)acrylic acid ester-based resin contain the same type of (meth)acrylic acid ester as a polymerization component.

[0083] The mass percentage of alkyl (meth)acrylate in the total polymerization components of the (meth)acrylic acid ester resin is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 100% by mass, from the viewpoint of forming mother particles B that are easily phase-transformed by pressure and have excellent adhesion. Here, alkyl (meth)acrylate is preferably an alkyl (meth)acrylate having 2 to 10 carbon atoms in the alkyl group, and more preferably an alkyl (meth)acrylate having 4 to 8 carbon atoms in the alkyl group.

[0084] (Meth)acrylic acid ester resins preferably contain at least two types of (meth)acrylic acid esters as polymerization components. When a (meth)acrylic acid ester resin contains at least two types of (meth)acrylic acid esters as polymerization components, the mass ratio of the two types of (meth)acrylic acid esters that make up the largest mass proportion among the at least two types of (meth)acrylic acid esters contained as polymerization components in the (meth)acrylic acid ester resin is preferably 80:20 to 20:80, more preferably 70:30 to 30:70, and even more preferably 60:40 to 40:60, from the viewpoint of forming mother particles B that are easily subjected to phase transition by pressure and have excellent adhesion.

[0085] When a (meth)acrylic acid ester resin contains at least two types of (meth)acrylic acid esters as polymerization components, it is preferable that the two types of (meth)acrylic acid esters that make up the largest mass proportion among the at least two types of (meth)acrylic acid esters contained as polymerization components in the (meth)acrylic acid ester resin are alkyl (meth)acrylic acid esters. Here, alkyl (meth)acrylic acid esters with 2 to 10 carbon atoms in the alkyl group are preferred, and alkyl (meth)acrylic acid esters with 4 to 8 carbon atoms in the alkyl group are more preferred.

[0086] When a (meth)acrylic acid ester resin contains at least two types of (meth)acrylic acid esters as polymerization components, and the two types with the highest mass proportion among the at least two types of (meth)acrylic acid esters contained as polymerization components in the (meth)acrylic acid ester resin are alkyl (meth)acrylic acid esters, the difference in the number of carbon atoms of the alkyl groups of the two alkyl (meth)acrylic acid esters is preferably 1 to 4, more preferably 2 to 4, and even more preferably 3 or 4, from the viewpoint of forming mother particles B that are easily transferred by pressure and have excellent adhesion.

[0087] (Meth)acrylic acid ester resins preferably contain n-butyl acrylate and 2-ethylhexyl acrylate as polymerization components, from the viewpoint of forming mother particles B that readily undergo phase transition under pressure and have excellent adhesion, and it is particularly preferable that the two types of (meth)acrylic acid esters that make up the largest mass proportions among the at least two types of (meth)acrylic acid esters contained as polymerization components in the (meth)acrylic acid ester resin are n-butyl acrylate and 2-ethylhexyl acrylate. The total amount of n-butyl acrylate and 2-ethylhexyl acrylate in the total polymerization components of the (meth)acrylic acid ester resin is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 100% by mass.

[0088] (Meth)acrylic acid ester resins may contain vinyl monomers other than (meth)acrylic acid esters as polymerization components. Examples of vinyl monomers other than (meth)acrylic acid esters include (meth)acrylic acid; styrene; styrene monomers other than styrene; (meth)acrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; and olefins such as isoprene, butene, and butadiene. These vinyl monomers may be used individually or in combination of two or more.

[0089] When a (meth)acrylic acid ester resin contains a vinyl monomer other than (meth)acrylic acid ester as a polymerization component, at least one of acrylic acid and methacrylic acid is preferred as the vinyl monomer other than (meth)acrylic acid ester, and acrylic acid is more preferred.

[0090] The weight-average molecular weight of the (meth)acrylic acid ester resin is preferably 100,000 or more, more preferably 120,000 or more, and even more preferably 150,000 or more, from the viewpoint of suppressing the fluidization of mother particles B in the unpressurized state, and preferably 250,000 or less, more preferably 220,000 or less, and even more preferably 200,000 or less, from the viewpoint of forming mother particles B that are prone to phase transition under pressure.

[0091] The glass transition temperature of the (meth)acrylic acid ester resin is preferably 10°C or lower, more preferably 0°C or lower, and even more preferably -10°C or lower, from the viewpoint of forming mother particles B that are prone to phase transition under pressure. From the viewpoint of suppressing the fluidization of mother particles B in the unpressurized state, it is preferably -90°C or higher, more preferably -80°C or higher, and even more preferably -70°C or higher.

[0092] The mass percentage of (meth)acrylic acid ester resin in the total mother particle B is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 30% by mass or more, from the viewpoint of forming mother particle B that is prone to phase transition under pressure, and from the viewpoint of suppressing the fluidization of mother particle B in the unpressurized state, it is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.

[0093] The total amount of styrene-based resin and (meth)acrylic acid ester-based resin contained in mother particle B is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 100% by mass, relative to the total amount of mother particle B.

[0094] -Mass ratio of styrene-based resin to (meth)acrylic acid ester-based resin- The mass ratio of styrene resin to (meth)acrylic acid ester resin (styrene resin:(meth)acrylic acid ester resin) is 80:20 to 20:80. From the viewpoint of providing a particle set for printing that yields printed materials with superior adhesion, the mass ratio of styrene resin to (meth)acrylic acid ester resin (styrene resin:(meth)acrylic acid ester resin) is preferably 75:25 to 25:75, more preferably 70:30 to 30:70, and even more preferably 65:35 to 35:65.

[0095] -Other resins- Mother particle B may contain, for example, non-vinyl resins such as polystyrene:epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, and modified rosin. These resins may be used individually or in combination of two or more.

[0096] -Colorants- Mother particle B may contain a coloring agent. Examples of colorants contained in mother particle B include pigments and dyes. From the viewpoint of obtaining a particle set for printing that produces printed materials with superior adhesion, it is preferable that the coloring agent contained in the mother particle B is a pigment.

[0097] From the viewpoint of obtaining a particle set for printing that improves interaction with the colorant contained in toner particles A and produces printed materials with better adhesion, it is preferable that the pigment contained in the mother particle B is a pigment having at least one selected from the group consisting of heterocyclic pigments, amino group pigments, amide group pigments, hydroxyl group pigments, and carboxyl group pigments.

[0098] Examples of cyan pigments include CI Pigment Blue 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 23, 60, 65, 73, 83, 180, CI Batt Cyan 1, 3, 20, etc., as well as Prussian Blue, Cobalt Blue, Alkali Blue Lake, Phthalocyanine Blue, Metal-Free Phthalocyanine Blue, Partially Chlorinated Phthalocyanine Blue, First Sky Blue, Induthlene Blue BC, etc.

[0099] From the viewpoint of creating a particle set for printing that yields printed materials with superior adhesion, it is preferable that the cyanide pigment is a cyanide pigment containing a phthalocyanine skeleton. The cyanide pigment containing the phthalocyanine skeleton is preferably at least one selected from the group consisting of CI pigment blue 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 23, 60, 65, 73, 83, 180, CI, phthalocyanine blue, metal-free phthalocyanine blue, and partially chlorinated phthalocyanine blue.

[0100] Examples of magenta colorants include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, and so on. Examples include 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 176, 184, 185, 202, 206, 207, 209, 238, 269, etc., as well as pigment violet 19, etc.

[0101] From the viewpoint of creating a particle set for printing that yields printed materials with superior adhesion, it is preferable that the magenta pigment used contains an amino group.

[0102] The magenta pigment containing an amino group preferably includes at least one selected from the group consisting of CI Pigment Red 122, CI Pigment Red 185, and CI Pigment Red 238.

[0103] Examples of yellow colorants include yellow pigments such as CI Pigment Yellow 2, 3, 15, 16, 17, 74, 97, 180, 185, and 139.

[0104] From the viewpoint of creating a particle set for printing that yields printed materials with superior adhesion, it is preferable that the yellow pigment be a magenta pigment containing an amide group. The magenta pigment containing an amide group preferably includes at least one selected from the group consisting of CI Pigment Yellow 3, 15, 16, 17, 74, 97, 180, and 185.

[0105] Examples of black pigments include carbon black, copper oxide, manganese dioxide, aniline black, and activated carbon. From the viewpoint of providing a particle set for printing that yields printed materials with superior adhesion, the black pigment is preferably a black pigment containing a pigment group having at least one selected from the group consisting of a hydroxyl group and a carboxyl group, and more preferably carbon black.

[0106] The mother particle B contains a pigment, and the pigment content in the mother particle B is preferably 5 ppm to 100 ppm relative to the total amount of mother particle B, more preferably 10 ppm to 97 ppm, and even more preferably 15 ppm to 95 ppm.

[0107] By setting the pigment content in mother particle B to between 5 ppm and 100 ppm relative to the total amount of mother particle B, it becomes easier to create a particle set for printing that produces printed materials with even better adhesion. The reason is not entirely clear, but it is thought that the interaction between the polar groups (e.g., heteroatoms in heterocycles, amino groups, amide groups, hydroxyl groups, carboxyl groups, etc.) of the pigment contained in mother particle B and the polar groups of the colorant contained in toner particle A increases the cohesive force between mother particle B and toner particle A.

[0108] The following methods can be used to measure the pigment content in mother particle B. The pigment content can be quantified by combining analyses such as GC-MS (gas chromatography-mass spectrometry), TG-DTA (thermal analysis-differential thermogravimetric analysis), IPC-OES (inductively coupled plasma emission spectrometry), IPC-AES (plasma emission spectrometry), IPC-MS (inductively coupled plasma mass spectrometry), and atomic absorption spectrometry.

[0109] - Various additives - Mother particle B may contain a mold release agent, a charge control agent, etc., as needed. Furthermore, the mold release agent is the same as that used for chromatic toners.

[0110] -Structure of parent particle B- The mother particle B may be a single-layer mother particle B, or it may be a core-shell mother particle B having a core portion and a shell layer covering the core portion. From the viewpoint of suppressing the fluidization of pressure-responsive particles when not pressurized, and from the viewpoint of providing a particle set for printing that yields printed materials with better adhesion, it is preferable that the mother particle B has a core-shell structure.

[0111] When the parent particle B has a core-shell structure, it is preferable that the core portion contains a styrene-based resin and a (meth)acrylic acid ester resin, from the viewpoint of being easily subjected to phase transition by pressure. Furthermore, it is preferable that the shell layer contains a styrene-based resin, from the viewpoint of suppressing the fluidization of pressure-responsive particles when not pressurized. The specific form of the styrene-based resin is as described above. The specific form of the (meth)acrylic acid ester resin is as described above.

[0112] Examples of resins that can be included in the shell layer include polystyrene: epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, modified rosin, and other non-vinyl resins. These resins may be used individually or in combination of two or more.

[0113] The average thickness of the shell layer is preferably 120 nm or more, more preferably 130 nm or more, and even more preferably 140 nm or more, from the viewpoint of suppressing deformation of the parent particle B. From the viewpoint of the parent particle B being more susceptible to phase transition under pressure, it is preferably 550 nm or less, more preferably 500 nm or less, and even more preferably 400 nm or less.

[0114] The average thickness of the shell layer is measured by the following method. Pressure-responsive particles are embedded in epoxy resin, sections are prepared using a diamond knife or similar tool, and the prepared sections are stained with osmium tetroxide or ruthenium tetroxide in a desiccator. The stained sections are observed using a scanning electron microscope (SEM). Ten sections of parent particle B are randomly selected from the SEM images, and the thickness of the shell layer is measured at 20 locations for each parent particle B. The average value is calculated, and the average value of 10 parent particles B is taken as the average thickness.

[0115] The weight-average molecular weight of parent particle B is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 50,000 or more, from the viewpoint of suppressing offset during thermal fixing. From the viewpoint of achieving both suppression of offset during thermal fixing and good adhesion, it is preferably 250,000 or less, more preferably 200,000 or less, and even more preferably 150,000 or less.

[0116] The number-average molecular weight of parent particles B is preferably 5000 or more, more preferably 8000 or more, and even more preferably 10000 or more, from the viewpoint of suppressing offset during thermal fixing. From the viewpoint of achieving both suppression of offset during thermal fixing and good adhesion, it is preferably 50000 or less, more preferably 40000 or less, and even more preferably 30000 or less.

[0117] (External additive) Examples of external additives include those similar to those used in chromatic toners. The amount of external additive added is preferably 0.01% by mass or more and 5% by mass or less relative to the mother particle B, and more preferably 0.01% by mass or more and 2.0% by mass or less.

[0118] (Characteristics of pressure-responsive particles) -Glass transition temperature- The pressure-responsive particles according to this embodiment have at least two glass transition temperatures, with a difference of 30°C or more between the lowest and highest glass transition temperatures. One of the glass transition temperatures is presumed to be the glass transition temperature of a styrene-based resin, and the other is presumed to be the glass transition temperature of a (meth)acrylic acid ester-based resin.

[0119] The above-mentioned pressure-responsive particles may have three or more glass transition temperatures, but it is preferable that the number of glass transition temperatures be two. Examples of forms having two glass transition temperatures include: a form in which the resin contained in the pressure-responsive particles consists only of styrene-based resin and (meth)acrylic acid ester resin; and a form in which the content of other resins other than styrene-based resin and (meth)acrylic acid ester resin is low (for example, a form in which the content of other resins is 5% by mass or less relative to the total pressure-responsive particles).

[0120] The difference between the lowest and highest glass transition temperatures is more preferably 40°C or higher, even more preferably 50°C or higher, and even more preferably 60°C or higher, from the viewpoint of making pressure-responsive particles more susceptible to phase transitions under pressure. The upper limit of the difference between the lowest and highest glass transition temperatures may be, for example, 140°C or lower, 130°C or lower, or 120°C or lower.

[0121] The lowest glass transition temperature exhibited by pressure-responsive particles is preferably 10°C or lower, more preferably 0°C or lower, and even more preferably -10°C or lower, from the viewpoint of the pressure-responsive particles being easily subjected to a phase transition. From the viewpoint of suppressing the fluidization of pressure-responsive particles in the unpressurized state, it is preferably -90°C or higher, more preferably -80°C or higher, and even more preferably -70°C or higher.

[0122] The highest glass transition temperature exhibited by pressure-responsive particles is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher, from the viewpoint of suppressing the fluidization of pressure-responsive particles in the unpressurized state. From the viewpoint of the pressure-responsive particles being more susceptible to phase transitions, it is preferably 70°C or lower, more preferably 65°C or lower, and even more preferably 60°C or lower.

[0123] In this disclosure, the glass transition temperature of pressure-responsive particles is determined from a differential scanning calorimetry (DSC) curve obtained by compressing the pressure-responsive particles to prepare a plate-shaped sample and performing differential scanning calorimetry (DSC) on this sample. More specifically, it is determined according to the "extracorporeal glass transition onset temperature" described in the method for determining the glass transition temperature in JIS K7121:1987 "Method for Measuring the Transition Temperature of Plastics".

[0124] - Pressure phase transition - Pressure-responsive particles are particles that undergo a phase transition due to pressure and satisfy the following equation 2. Formula 2...10℃≦T1-T2 In Equation 2, T1 is the temperature at which the viscosity is 10,000 Pa·s under a pressure of 1 MPa, and T2 is the temperature at which the viscosity is 10,000 Pa·s under a pressure of 10 MPa.

[0125] The temperature difference (T1-T2) is preferably 10°C or more, more preferably 15°C or more, and more preferably 20°C or more, from the viewpoint of making it easier for pressure-responsive particles to undergo a phase transition due to pressure. From the viewpoint of suppressing the fluidization of pressure-responsive particles in the unpressurized state, it is preferably 120°C or less, more preferably 100°C or less, and even more preferably 80°C or less. The temperature T1 is preferably 140°C or lower, more preferably 130°C or lower, even more preferably 120°C or lower, and particularly preferably 115°C or lower. The temperature T2 is preferably 40°C or higher, more preferably 50°C or higher, and even more preferably 60°C or higher. The upper limit of the temperature T2 is preferably 85°C or lower.

[0126] As an indicator of how easily pressure-responsive particles undergo a phase transition due to pressure, the temperature difference (T1-T3) between the temperature T1 at which a viscosity of 10,000 Pa·s is observed under a pressure of 1 MPa and the temperature T3 at which a viscosity of 10,000 Pa·s is observed under a pressure of 4 MPa is used, and it is preferable that the temperature difference (T1-T3) is 5°C or more. From the viewpoint of how easily transparent toner undergoes a phase transition due to pressure, it is preferable that the temperature difference (T1-T3) is 5°C or more, and more preferably 10°C or more. The temperature difference (T1-T3) is generally 25°C or less.

[0127] From the viewpoint of ensuring a temperature difference (T1-T3) of 5°C or more, it is preferable that the temperature T3 at which a viscosity of 10,000 Pa·s is observed under a pressure of 4 MPa is 90°C or lower, more preferably 85°C or lower, and even more preferably 80°C or lower. The lower limit of temperature T3 is preferably 60°C or higher.

[0128] The method for determining temperatures T1, T2, and T3 is as follows: The particles to be measured are compressed to create a pellet-shaped sample. The pellet-shaped sample is placed in a flow tester (Shimadzu Corporation, CFT-500), the applied pressure is fixed at 1 MPa, and the viscosity as a function of temperature at 1 MPa is measured. From the obtained viscosity graph, the viscosity at an applied pressure of 1 MPa is 10 4 Determine the temperature T1 when the temperature reaches Pa·s. Determine the temperature T2 in the same manner as the method for temperature T1, except that the applied pressure is changed from 1 MPa to 10 MPa. Determine the temperature T3 in the same manner as the method for temperature T1, except that the applied pressure is changed from 1 MPa to 4 MPa. Calculate the temperature difference (T1-T2) from temperatures T1 and T2. Calculate the temperature difference (T1-T3) from temperatures T1 and T3.

[0129] -Other characteristics- In this case, the pressure-responsive particles are preferably transparent. Because the pressure-responsive particles are transparent, even when the pressure-responsive particles are applied to the image portion of the recording medium and formed, the visibility of the image portion is ensured. Furthermore, "transparent" means that the average transmittance of light in the visible region (400 nm to 700 nm) of the region where the pressure-responsive particles are fixed is 10% or more, preferably 50% or more, more preferably 80% or more, and even more preferably 90% or more. The above average transmittance is measured using a V700 spectrophotometer (manufactured by JASCO Corporation).

[0130] (Method for manufacturing pressure-responsive particles) The above-mentioned pressure-responsive particles are obtained by manufacturing mother particles B and then adding an external additive to mother particles B.

[0131] Mother particle B may be produced by either a dry method (e.g., kneading and grinding method) or a wet method (e.g., agglomeration, suspension polymerization, dissolution and suspension method). There are no particular restrictions on these methods, and known methods can be used. Among these, it is preferable to obtain mother particle B by the agglomeration method.

[0132] When producing parent particle B by an aggregation and coalescence method, for example, The process involves preparing a styrene resin particle dispersion in which styrene resin particles containing styrene resin are dispersed (styrene resin particle dispersion preparation process), A step of polymerizing a (meth)acrylic acid ester resin in a styrene resin particle dispersion to form composite resin particles containing styrene resin and (meth)acrylic acid ester resin (composite resin particle formation step), The process involves agglomerating composite resin particles in a composite resin particle dispersion liquid to form aggregated particles (aggregated particle formation process), The process involves heating a dispersion of aggregated particles to fuse and combine the aggregated particles, thereby forming mother particles B (fusion and combination step), and ultimately producing mother particles B.

[0133] The details of each step are explained below. The following description explains a method for obtaining mother particles B that do not contain colorants or release agents. Colorants, release agents, and other additives may be used as needed. When mother particles B contain colorants and release agents, a fusion / combination process is performed after mixing the composite resin particle dispersion, the colorant particle dispersion, and the release agent particle dispersion. The colorant particle dispersion and the release agent particle dispersion can be prepared, for example, by mixing the materials and then performing a dispersion process using a known disperser.

[0134] -Preparation process for styrene resin particle dispersion- A styrene-based resin particle dispersion is, for example, a dispersion in which styrene-based resin particles are dispersed in a dispersion medium using a surfactant.

[0135] Examples of dispersion media include aqueous media such as water and alcohols. These may be used individually or in combination of two or more.

[0136] Examples of surfactants include anionic surfactants such as sulfate esters, sulfonates, phosphates, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts; and nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Nonionic surfactants may be used in combination with anionic or cationic surfactants. Among these, anionic surfactants are preferred. Surfactants may be used individually or in combination of two or more.

[0137] Methods for dispersing styrene resin particles in a dispersion medium include, for example, mixing the styrene resin with the dispersion medium and then stirring and dispersing it using a rotary shear homogenizer, a ball mill with media, a sand mill, a dyno mill, or the like.

[0138] Another method for dispersing styrene resin particles in a dispersion medium is emulsion polymerization. Specifically, the polymerization components of the styrene resin are mixed with a chain transfer agent or polymerization initiator, and then an aqueous medium containing a surfactant is further mixed and stirred to prepare an emulsion, in which the styrene resin is polymerized. In this case, it is preferable to use dodecanethiol as the chain transfer agent.

[0139] The volume-average particle size of the styrene-based resin particles dispersed in the styrene-based resin particle dispersion is preferably 100 nm to 250 nm, more preferably 120 nm to 220 nm, and even more preferably 150 nm to 200 nm. The volume-average particle size of resin particles contained in a resin particle dispersion is determined by measuring the particle size using a laser diffraction particle size distribution analyzer (e.g., LA-700 manufactured by Horiba, Ltd.). The volume-average particle size (D50v) is defined as the particle size at which the cumulative 50% of the volume-based particle size distribution, calculated from the smallest diameter side, occurs.

[0140] The content of styrene resin particles in the styrene resin particle dispersion is preferably 30% by mass or more and 60% by mass or less, and more preferably 40% by mass or more and 50% by mass or less.

[0141] -Composite resin particle formation process- A dispersion of styrene-based resin particles and a polymerization component of (meth)acrylic acid ester resin are mixed, and the (meth)acrylic acid ester resin is polymerized in the dispersion of styrene-based resin particles to form composite resin particles containing styrene-based resin and (meth)acrylic acid ester resin.

[0142] The composite resin particles are preferably resin particles containing a styrene-based resin and a (meth)acrylic acid ester-based resin in a state of microphase separation. These resin particles are manufactured, for example, by the following method.

[0143] A polymerization component of a (meth)acrylic acid ester resin (a group of monomers containing at least two (meth)acrylic acid esters) is added to a dispersion of styrene resin particles, and an aqueous medium is added as needed. Next, the dispersion is heated to a temperature above the glass transition temperature of the styrene resin (for example, 10°C to 30°C higher than the glass transition temperature of the styrene resin) while slowly stirring. Then, while maintaining the temperature, an aqueous medium containing a polymerization initiator is slowly added dropwise, and stirring is continued for a long period of time, ranging from 1 hour to 15 hours. In this case, ammonium persulfate is preferably used as the polymerization initiator.

[0144] Although the detailed mechanism is not entirely clear, it is presumed that when the above method is employed, monomers and polymerization initiators are impregnated into the styrene resin particles, and (meth)acrylic acid ester polymerizes inside the styrene resin particles. As a result, it is presumed that composite resin particles are obtained in which (meth)acrylic acid ester resin is contained inside the styrene resin particles, and the styrene resin and (meth)acrylic acid ester resin form a state of microphase separation inside the particles.

[0145] The volume-average particle size of the composite resin particles dispersed in the composite resin particle dispersion is preferably 140 nm to 300 nm, more preferably 150 nm to 280 nm, and even more preferably 160 nm to 250 nm.

[0146] The content of composite resin particles in the composite resin particle dispersion is preferably 20% by mass or more and 50% by mass or less, and more preferably 30% by mass or more and 40% by mass or less.

[0147] -Agglomerated particle formation process- The composite resin particles are aggregated in a composite resin particle dispersion to form aggregated particles with a diameter close to that of the target mother particle B.

[0148] Specifically, for example, a flocculant is added to a composite resin particle dispersion, the pH of the composite resin particle dispersion is adjusted to be acidic (for example, pH 2 to 5), a dispersion stabilizer is added as needed, and then the mixture is heated to a temperature close to the glass transition temperature of the styrene resin (specifically, for example, above -30°C or below the glass transition temperature of the styrene resin, and below -10°C) to flocce the composite resin particles and form flocculated particles.

[0149] In the aggregated particle formation process, the composite resin particle dispersion is stirred in a rotary shear homogenizer, a flocculant is added at room temperature (e.g., 25°C), the pH of the composite resin particle dispersion is adjusted to acidic (e.g., pH 2 to 5), a dispersion stabilizer is added as needed, and then heating may be performed.

[0150] Examples of flocculants include surfactants with opposite polarity to the surfactant contained in the composite resin particle dispersion, inorganic metal salts, and metal complexes with a valency of 2 or higher. When a metal complex is used as a flocculant, the amount of surfactant used is reduced and the electrostatic properties are improved. Along with the flocculant, an additive that forms a complex or similar bond with the metal ions of the flocculant may be used as needed. A chelating agent is preferably used as this additive.

[0151] Examples of inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate; and inorganic metal salt polymers such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. As a chelating agent, a water-soluble chelating agent may be used. Examples of chelating agents include oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid; and aminocarboxylic acids such as iminodiacid acetic acid (IDA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA). The amount of chelating agent added is preferably 0.01 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of resin particles, and more preferably 0.1 parts by mass or more and less than 3.0 parts by mass.

[0152] -Fusion / coalescence process- Next, the dispersion of aggregated particles is heated to a temperature above the glass transition temperature of the styrene resin (for example, 10°C to 30°C higher than the glass transition temperature of the styrene resin) to fuse and combine the aggregated particles and form mother particles B.

[0153] The parent particle B of the core-shell structure is, for example, After obtaining an aggregated particle dispersion, the aggregated particle dispersion and the styrene-based resin particle dispersion are further mixed to aggregate the aggregated particles so that styrene-based resin particles adhere to the surface of the aggregated particles, thereby forming second aggregated particles. A step of heating a second aggregate particle dispersion containing second aggregate particles to fuse and combine the second aggregate particles to form a core-shell structured mother particle B, It is manufactured through the following process. The core-shell structure mother particle B obtained through the above process has a shell layer containing a styrene-based resin. Instead of a styrene-based resin particle dispersion, a resin particle dispersion containing other types of resin particles may be used to form a shell layer containing other types of resins.

[0154] After the fusion and coalescence process is complete, the mother particles B formed in the solution are subjected to known washing, solid-liquid separation, and drying processes to obtain dried mother particles B. From the viewpoint of electrostatic properties, the washing process should be performed thoroughly by displacement washing with ion-exchanged water. From the viewpoint of productivity, the solid-liquid separation process should be performed by suction filtration, pressure filtration, etc. From the viewpoint of productivity, the drying process should be performed by freeze-drying, air-flow drying, fluidized bed drying, vibratory fluidized bed drying, etc.

[0155] The pressure-responsive particles are then produced, for example, by adding an external additive to the obtained dry mother particles B and mixing them. Mixing can be performed using, for example, a V-blender, a Henschel mixer, a Redigge mixer, etc. Furthermore, if necessary, coarse particles of the pressure-responsive particles may be removed using a vibrating screen separator, a wind screen separator, etc.

[0156] (Relationship between toner particle A and mother particle B) -Volume-average particle size- When the volume-average particle size of toner particle A is D50A and the volume-average particle size of mother particle B is D50B, then D50A and D50B satisfy the following formula 1-1. Formula 1-1: 1.5μm<(D50B-D50A)

[0157] From the viewpoint of providing a particle set for printing that yields printed materials with superior adhesion, it is preferable that D50A and D50B satisfy the following formula 1-2, more preferably that they satisfy the following formula 1-3, and even more preferably that they satisfy the following formula 1-4. Formula 1-2: 1.5μm<(D50B-D50A)<15μm Formula 1-3: 1.5μm<(D50B-D50A)<10μm Formula 1-4: 1.5μm<(D50B-D50A)<7.0μm

[0158] From the viewpoint of increasing the pressure applied to the layer formed by pressure-responsive particles during bonding by increasing the difference in thickness between the layer formed by pressure-responsive particles and the layer (image) formed by chromatic toner, the thickness of D50B is preferably 6.0 μm or more and 20.0 μm or less, more preferably 7.0 μm or more and 15.0 μm or less, and even more preferably 8.0 μm or more and 13.0 μm or less.

[0159] The average particle sizes and particle size distribution indices of toner particles A and mother particles B are measured using a Coulter Multisizer II (manufactured by Beckman Coulter), and the electrolyte is measured using ISOTON-II (manufactured by Beckman Coulter). For measurement, add 0.5 mg to 50 mg of the sample to be measured in 2 ml of a 5% aqueous solution of a surfactant (preferably sodium alkylbenzenesulfonate) as a dispersant. Add this to 100 ml to 150 ml of electrolyte. The electrolyte containing the suspended sample is dispersed in an ultrasonic disperser for 1 minute. The particle size distribution of particles with a diameter of 2 μm to 60 μm is then measured using a Coulter Multisizer II with an aperture diameter of 100 μm. The number of particles sampled is 50,000. Based on the measured particle size distribution, a cumulative distribution of volume and number is drawn for each divided particle size range (channel) from the smallest diameter side. The particle size at which the cumulative total reaches 16% is defined as the volume particle size D16v and the number particle size D16p, the particle size at which the cumulative total reaches 50% is defined as the volume average particle size D50v and the cumulative number average particle size D50p, and the particle size at which the cumulative total reaches 84% ​​is defined as the volume particle size D84v and the number particle size D84p. Using these, the volume particle size distribution index (GSDv) is (D84v / D16v) 1 / 2 The GSDp index is (D84p / D16p) 1 / 2 It is calculated as follows.

[0160] Furthermore, the average circularity of toner particles A and mother particles B is preferably 0.94 or more and 1.00 or less, and more preferably 0.95 or more and 0.98 or less.

[0161] The average circularity of toner particle A and mother particle B is determined by (circular equivalent perimeter) / (perimeter) [(perimeter of a circle with the same projected area as the particle image) / (perimeter of the particle projection image)]. Specifically, it is a value measured by the following method. First, the toner particles to be measured are collected by suction, a flattened flow is formed, and a still image of the particles is captured by instantaneous strobe flashing. This particle image is then analyzed using a flow-type particle image analyzer (FPIA-3000 manufactured by Sysmex Corporation). The number of samples used to determine the average circularity is 3500. If the toner contains external additives, the toner (developer) to be measured is dispersed in water containing a surfactant, and then ultrasonic treatment is performed to obtain toner particles from which the external additives have been removed.

[0162] - Release agent content - Both toner particles A and mother particles B contain a release agent, and the amount of release agent contained in toner particles A is W. A The amount of release agent contained in the mother particle B relative to the amount of release agent W B The ratio (W B / W A Preferably, the value is 0.01 or more and 0.8 or less, more preferably 0.05 or more and 0.7 or less, and even more preferably 0.1 or more and 0.6 or less. Here, the content W A This is "the amount of release agent contained in toner particles A relative to the total amount of toner particles A." Also, the content W B This is "the amount of release agent contained in mother particle B relative to the total amount of mother particle B".

[0163] By having both toner particles A and mother particles B contain a release agent, and by keeping the release agent content within the above numerical range, a particle set for producing printed materials with superior adhesion is obtained. The reason for this is presumed to be as follows. Ratio of release agent content (W B / W A When the ratio of the release agent content (W) is 0.01 or higher, the amount of release agent in the pressure-responsive particles increases, suppressing the occurrence of offset during heat fixing. By suppressing the occurrence of offset, the decrease in the amount of pressure-responsive particles is suppressed, and as a result the adhesive strength is improved. Ratio of release agent content (W) B / W A When the ratio is 0.8 or less, the amount of release agent does not become too large relative to the amount of resin in the pressure-responsive particles, and the amount of release agent present on the image surface does not become too large during heat fixing. As a result, the phenomenon of reduced adhesion due to the release agent getting into the spaces between the pressure-responsive particles that exert adhesive force is suppressed.

[0164] From the perspective of creating a particle set for printing that yields printed materials with superior adhesion, the release agent content W B The amount is preferably 0.1% by mass or more and 4.0% by mass or less, more preferably 0.2% by mass or more and 3.0% by mass or less, and even more preferably 0.5% by mass or more and 2.5% by mass or less.

[0165] Content W A and content W B This is done using a differential scanning calorimeter (Shimadzu Corporation: DSC60, with an automatic tangential processing system) and the amount of heat absorbed in the melting temperature range is determined by the ASTM method, with the amount of heat absorbed by the same weight of release agent set to 100. If the particles to be measured contain external additives, the particles to be measured are dispersed in water containing a surfactant, and then the external additives are removed by sonication before measurement.

[0166] <Developer Kit> The developer set according to this embodiment will be described below. In describing the developer set, an example in which the pressure-responsive particles according to this embodiment are used as toner will be explained. In the description of the developer set, the "particle set for printmaking" will be referred to as the "toner set," and the "pressure-responsive particles" will be referred to as the "transparent toner."

[0167] The developer set according to this embodiment comprises a developer containing at least a chromatic toner (hereinafter sometimes referred to as an electrostatic image developer) and a developer containing at least a transparent toner. In this case, the chromatic toner according to this embodiment is used as the chromatic toner. Furthermore, the pressure-responsive particles according to this embodiment are used as the transparent toner. The electrostatic image developer constituting the developer set according to this embodiment may be a one-component developer containing only the toner, or a two-component developer containing a mixture of the toner and a carrier. If both the electrostatic image developer containing chromatic toner and the electrostatic image developer containing transparent toner are two-component developers, the type and content of the carrier contained in these developers may be the same or different.

[0168] There are no particular restrictions on the carriers, and known carriers can be used. Examples of carriers include coated carriers in which a resin is coated on the surface of a core material made of magnetic powder; magnetic powder dispersed carriers in which magnetic powder is dispersed in a matrix resin; and resin-impregnated carriers in which resin is impregnated into porous magnetic powder. In the case of magnetic powder dispersed carriers and resin-impregnated carriers, the constituent particles of the carrier may be used as the core material, and the surface of this core material may be coated with resin.

[0169] Examples of magnetic powders include magnetic metals such as iron, nickel, and cobalt; and magnetic oxides such as ferrite and magnetite.

[0170] Examples of coating resins and matrix resins include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic acid ester copolymer, straight silicone resin or modified thereof containing organosiloxane bonds, fluororesin, polyester, polycarbonate, phenolic resin, epoxy resin, etc. The coating resin and matrix resin may also contain conductive particles and other additives. Examples of conductive particles include metals such as gold, silver, and copper, carbon black, titanium dioxide, zinc oxide, tin oxide, barium sulfate, aluminum borate, and potassium titanate.

[0171] To coat the surface of the core material with resin, one method is to coat it with a coating layer-forming solution prepared by dissolving the coating resin and various additives (used as needed) in a suitable solvent. The solvent is not particularly limited and should be selected considering the type of resin used and its suitability for coating. Specific resin coating methods include the immersion method, in which the core material is immersed in a coating layer forming solution; the spray method, in which the coating layer forming solution is sprayed onto the surface of the core material; the fluidized bed method, in which the coating layer forming solution is sprayed onto the core material while it is suspended by fluidized air; and the kneader coater method, in which the carrier core material and the coating layer forming solution are mixed in a kneader coater, and then the solvent is removed.

[0172] In a two-component developer, the mixing ratio (mass ratio) of toner and carrier is preferably toner:carrier = 1:100 to 30:100, and more preferably 3:100 to 20:100.

[0173] <Equipment for manufacturing printed materials, methods for manufacturing printed materials> The printing apparatus according to this embodiment includes a chromatic toner image forming means that contains a developer containing chromatic toner in the particle set for printing according to this embodiment, and forms a chromatic toner image on a recording medium by electrophotography using the first developer, The particle set for printing according to this embodiment includes an arrangement means for containing the pressure-responsive particles and arranging the pressure-responsive particles on a recording medium to form a pressure-responsive particle layer, A thermal fixing means comprising a fixing member, wherein the fixing member is in contact with the pressure-responsive particle layer, and the chromatic toner image is thermally fixed to the recording medium. A pressing means for folding and pressing together a recording medium on which the chromatic toner image has been heat-fixed, or for overlapping and pressing together a recording medium on which the chromatic toner image has been heat-fixed and another recording medium, Includes.

[0174] The printing method according to this embodiment is carried out using the printing apparatus according to this embodiment.

[0175] The method for manufacturing a printed material according to this embodiment includes a chromatic toner image formation step in which a chromatic toner image is formed on a recording medium by an electrophotographic method using a developer containing chromatic toner in the particle set for printing material according to this embodiment, A placement step of arranging pressure-responsive particles in the particle set for printing according to this embodiment on a recording medium to form a pressure-responsive particle layer, A thermal fixing step in which the fixing member is in contact with the pressure-responsive particle layer and the chromatic toner image is thermally fixed to the recording medium, A pressing step of folding and pressing together a recording medium on which the chromatic toner image has been heat-fixed, or overlapping and pressing together a recording medium on which the chromatic toner image has been heat-fixed with another recording medium, Includes.

[0176] The chromatic toner image forming means included in the printing apparatus according to this embodiment is, for example, Photoreceptor and A charging means for charging the surface of the photoreceptor, A means for forming an electrostatic image on the surface of the charged photoreceptor, A developing means comprising a particle set for printing according to this embodiment, containing an electrostatic image developer containing chromatic toner, and developing the electrostatic image formed on the surface of the photoreceptor as a chromatic toner image using the electrostatic image developer, A transfer means for transferring a toner image formed on the surface of the photoreceptor to the surface of a recording medium, It is equipped with.

[0177] The arrangement means included in the printing apparatus according to this embodiment is, for example, Photoreceptor and A charging means for charging the surface of the photoreceptor, A means for forming an electrostatic image on the surface of the charged photoreceptor, A developing means comprising a particle set for printing according to this embodiment, containing an electrostatic image developer containing pressure-responsive particles as toner, and developing the electrostatic image formed on the surface of the photoreceptor as a pressure-responsive particle layer using the electrostatic image developer, A transfer means for transferring the pressure-responsive particle layer formed on the surface of the photoreceptor to the surface of a recording medium, It is equipped with.

[0178] The arrangement means included in the printing apparatus according to this embodiment is not limited to the electrophotographic method described above, but can also be applied to spray method, bar coating method, die coating method, knife coating method, roll coating method, reverse roll coating method, gravure coating method, screen printing method, inkjet method, lamination method, etc.

[0179] The color toner image formation step included in the printing method according to this embodiment is, for example, A charging process in which the surface of the photoreceptor is charged, A step of forming an electrostatic image on the surface of the charged photoreceptor, The development step of developing the electrostatic image formed on the surface of the photoreceptor as a chromatic toner image using an electrostatic image developer containing chromatic toner in the particle set for printing according to this embodiment, A transfer step of transferring a chromatic toner image formed on the surface of the photoreceptor to the surface of a recording medium, Includes.

[0180] The arrangement step included in the method for manufacturing printed materials according to this embodiment is, for example, A charging process in which the surface of the photoreceptor is charged, A step of forming an electrostatic image on the surface of the charged photoreceptor, A developing step in which the electrostatic image formed on the surface of the photoreceptor is developed as a pressure-responsive particle layer using an electrostatic image developer containing pressure-responsive particles as toner in the particle set for printing according to this embodiment, A transfer step of transferring the pressure-responsive particle layer formed on the surface of the photoreceptor to the surface of a recording medium, Includes.

[0181] The arrangement step included in the printing method according to this embodiment is not limited to the electrophotographic method described above, but can also be applied to spray method, bar coating method, die coating method, knife coating method, roll coating method, reverse roll coating method, gravure coating method, screen printing method, inkjet method, lamination method, etc.

[0182] The chromatic toner image forming means is, for example, a direct transfer type device that directly transfers a chromatic toner image formed on the surface of a photoreceptor to a recording medium; an intermediate transfer type device that first transfers a chromatic toner image formed on the surface of a photoreceptor to the surface of an intermediate transfer body, and then secondarily transfers the chromatic toner image transferred to the surface of the intermediate transfer body to the surface of a recording medium; a device equipped with a cleaning means for cleaning the surface of the photoreceptor before charging after the transfer of the chromatic toner image; a device equipped with a static elimination means for irradiating the surface of the photoreceptor with static elimination light before charging after the transfer of the chromatic toner image; and the like. In the case of an intermediate transfer type device, the transfer means includes, for example, an intermediate transfer body on which a chromatic toner image is transferred; a primary transfer means for first transferring the chromatic toner image formed on the surface of the photoreceptor to the surface of the intermediate transfer body; and a secondary transfer means for secondarily transferring the chromatic toner image transferred to the surface of the intermediate transfer body to the surface of a recording medium.

[0183] When electrophotography is employed, the arrangement means may include, for example, a direct transfer device that directly transfers a pressure-responsive particle layer formed on the surface of a photoreceptor to a recording medium on which a chromatic toner image is formed; an intermediate transfer device that first transfers a pressure-responsive particle layer formed on the surface of a photoreceptor to the surface of an intermediate transfer body, and then secondarily transfers the pressure-responsive particle layer transferred to the surface of the intermediate transfer body to the surface of the recording medium; a device equipped with a cleaning means for cleaning the surface of the photoreceptor after the transfer of the pressure-responsive particle layer and before charging; or a device equipped with a static elimination means for irradiating the surface of the photoreceptor with static elimination light to eliminate static charge after the transfer of the pressure-responsive particle layer and before charging. When the arrangement means is an intermediate transfer device, the transfer means may include, for example, an intermediate transfer body on which a pressure-responsive particle layer is transferred; a primary transfer means for first transferring the pressure-responsive particle layer formed on the surface of a photoreceptor to the surface of the intermediate transfer body; and a secondary transfer means for secondarily transferring the pressure-responsive particle layer transferred to the surface of the intermediate transfer body to the surface of the recording medium.

[0184] The chromatic toner image forming means and the placement means may each be a cartridge structure (so-called process cartridge) in which the portion including the developing means is attached to and detached from the chromatic toner image forming means and the placement means. As the process cartridge, for example, a process cartridge that houses each electrostatic image developer in the developer set according to this embodiment and is equipped with a developing means is preferably used. The process cartridge may constitute a process cartridge set having a first process cartridge equipped with a first developing means that houses an electrostatic image developer containing chromatic toner, and a second process cartridge equipped with a second developing means that houses an electrostatic image developer containing pressure-responsive particles as toner.

[0185] The crimping means included in the printing apparatus according to this embodiment applies pressure to the recording medium on which the pressure-responsive particles in the particle set for printing according to this embodiment are arranged. As a result, the pressure-responsive particles on the recording medium become fluid and exhibit adhesive properties. The pressure applied by the crimping means to the recording medium for the purpose of fluidizing the pressure-responsive particles is preferably 3 MPa to 300 MPa, more preferably 10 MPa to 200 MPa, and even more preferably 30 MPa to 150 MPa.

[0186] In the particle set for printing according to this embodiment, the pressure-responsive particles may be arranged on the entire surface of the recording medium or on a part of the recording medium. In the particle set for printing according to this embodiment, the pressure-responsive particles are arranged in one or more layers on the recording medium. In the particle set for printing according to this embodiment, the pressure-responsive particle layer may be a continuous layer in the planar direction of the recording medium or a discontinuous layer in the planar direction of the recording medium.

[0187] The amount of pressure-responsive particles on the recording medium is, for example, 0.5 g / m² in the area where they are placed. 2 More than 50g / m 2 The following applies: 1 g / m 2 More than 40g / m 2 The following is true: 1.5 g / m 2 More than 30g / m 2 The following applies: The layer thickness of the pressure-responsive particles on the recording medium is, for example, 0.2 μm to 25 μm, 0.4 μm to 20 μm, and 0.6 μm to 15 μm.

[0188] Examples of recording media to be used in the printing apparatus according to this embodiment include paper, coated paper (paper surface coated with resin, etc.), cloth, nonwoven fabric, resin film, and resin sheet. The recording media may have images on one side or both sides.

[0189] The following is an example of a printing apparatus according to this embodiment, but this embodiment is not limited to this example. In the following description of an example of a printing equipment, the "particle set for printing" will be referred to as the "toner set," and the "pressure-responsive particles" will be referred to as the "transparent toner."

[0190] Figure 1 is a schematic diagram showing a part of an example of a printing apparatus according to this embodiment, including the placement means and the crimping means. The printing apparatus shown in Figure 1 comprises a placement means 100 and a crimping means 200 located downstream of the placement means 100. The arrows indicate the rotation direction of the photoreceptor or the transport direction of the recording medium.

[0191] The placement means 100 is a direct transfer device that uses a developer containing the transparent toner in the toner set according to this embodiment to place the transparent toner on a recording medium P on which a chromatic toner image has been formed by electrophotography. The recording medium P has a chromatic toner image pre-formed on one or both sides.

[0192] The arrangement means 100 has a photoreceptor 101. Around the photoreceptor 101, the following are arranged in order: a charging roll (an example of a charging means) 102 for charging the surface of the photoreceptor 101; an exposure device (an example of a static charge image forming means) 103 for exposing the surface of the charged photoreceptor 101 with a laser beam to form a static charge image; a developing device (an example of a developing means) 104 for supplying toner to the static charge image to develop the static charge image; a transfer roll (an example of a transfer means) 105 for transferring the developed toner image onto the recording medium P; and a photoreceptor cleaning device (an example of a cleaning means) 106 for removing toner remaining on the surface of the photoreceptor 101 after transfer.

[0193] The operation of the placement means 100 in which transparent toner is placed on the recording medium P will be described. First, the surface of the photoreceptor 101 is charged by the charging roll 102. The exposure device 103 irradiates the charged surface of the photoreceptor 101 with a laser beam according to image data sent from a control unit (not shown). As a result, an electrostatic charge image of the transparent toner arrangement pattern is formed on the surface of the photoreceptor 101.

[0194] The electrostatic charge image formed on the photoreceptor 101 rotates as the photoreceptor 101 moves to the development position. At the development position, the electrostatic charge image on the photoreceptor 101 is developed by the developing device 104 and becomes a transparent toner layer.

[0195] The developing device 104 contains a developer containing at least transparent toner and a carrier. The transparent toner is agitated together with the carrier inside the developing device 104, becoming triboelectrically charged and held on the developer roll. As the surface of the photoreceptor 101 passes through the developing device 104, the transparent toner electrostatically adheres to the electrostatic charge image on the surface of the photoreceptor 101, and the electrostatic charge image is developed by the transparent toner. The photoreceptor 101, on which a transparent toner layer has been formed, continues to move, and the transparent toner layer developed on the photoreceptor 101 is transported to the transfer position.

[0196] When the transparent toner layer on the photoreceptor 101 is transported to the transfer position, a transfer bias is applied to the transfer roll 105, and an electrostatic force acts on the transparent toner layer from the photoreceptor 101 toward the transfer roll 105, transferring the transparent toner layer on the photoreceptor 101 onto the recording medium P.

[0197] The transparent toner remaining on the photoreceptor 101 is removed and recovered by the photoreceptor cleaning device 106. The photoreceptor cleaning device 106 is, for example, a cleaning blade or a cleaning brush. The photoreceptor cleaning device 106 is preferably a cleaning brush, from the viewpoint of suppressing the phenomenon in which the transparent toner remaining on the surface of the photoreceptor becomes fluid due to pressure and adheres to the surface of the photoreceptor in a film-like manner.

[0198] The recording medium P onto which the transparent toner layer has been transferred is transported to a fixing device (an example of a fixing means) 107. The fixing device 107 is, for example, a pair of fixing members (roll / roll, belt / roll). The pressure applied to the recording medium P by the fixing device 107 may be lower than the pressure applied to the recording medium P by the pressurizing device 230, and specifically, 0.2 MPa or more and 1 MPa or less is preferred.

[0199] The fixing device 107 may or may not have an internal heating source (e.g., a halogen heater) for heating the recording medium P. If the fixing device 107 has an internal heating source, the surface temperature of the recording medium P when heated by the heating source is preferably 150°C to 220°C, more preferably 155°C to 210°C, and even more preferably 160°C to 200°C. Note that the absence of an internal heating source in the fixing device 107 does not exclude the possibility that the temperature inside the fixing device 107 may exceed the ambient temperature due to heat generated by the motor or other components of the placement means 100.

[0200] The recording medium P becomes a recording medium P1 with transparent toner applied to the image by passing through the placement means 100. The recording medium P1 is then transported toward the crimping means 200.

[0201] In the printing apparatus according to this embodiment, the placement means 100 and the crimping means 200 may be in close proximity or separated. When the placement means 100 and the crimping means 200 are separated, they are connected, for example, by a transport means (e.g., a belt conveyor) that transports the recording medium P1.

[0202] The crimping means 200 comprises a folding device 220 and a pressing device 230, and is a means for folding and crimping the recording medium P1.

[0203] The folding device 220 folds the recording medium P1 as it passes through the device to produce a folded recording medium P2. The way the recording medium P2 is folded can be, for example, a two-fold, a three-fold, or a four-fold, and it may also be a form in which only a part of the recording medium P2 is folded. The recording medium P2 is in a state in which transparent toner is placed on at least a part of at least one of two opposing surfaces.

[0204] The folding device 220 may have a pair of pressing members (for example, roll / roll, belt / roll) that apply pressure to the recording medium P2. The pressure applied by the pressing members of the folding device 220 to the recording medium P2 may be lower than the pressure applied by the pressing device 230 to the recording medium P2. Specifically, it is preferably 1 MPa or more and 10 MPa or less.

[0205] Instead of the folding device 220, the crimping means 200 may include a stacking device that stacks the recording medium P1 and another recording medium. The form of the overlap between the recording medium P1 and another recording medium is, for example, a form in which another recording medium overlaps on the recording medium P1, or a form in which another recording medium overlaps one by one at a plurality of locations on the recording medium P1. Another recording medium may be a recording medium on which an image is previously formed on one or both sides, a recording medium on which no image is formed, or a previously prepared pressure-sensitive printed matter.

[0206] The recording medium P2 that exits the folding device 220 (or stacking device) is conveyed toward the pressing device 230.

[0207] The pressing device 230 includes a pair of pressing members (that is, pressing rolls 231 and 232). The pressing roll 231 and the pressing roll 232 contact and press against each other on their outer peripheral surfaces, and apply pressure to the passing recording medium P2. The pair of pressing members included in the pressing device 230 is not limited to the combination of a pressing roll and a pressing roll, and may also be a combination of a pressing roll and a pressing belt, or a combination of a pressing belt and a pressing belt.

[0208] When pressure is applied to the recording medium P2 passing through the pressing device 230, the transparent toner on the recording medium P2 becomes fluidized by the pressure and exhibits adhesiveness. The pressure applied by the pressing device 230 to the recording medium P2 is preferably 3 MPa or more and 300 MPa or less, more preferably 10 MPa or more and 200 MPa or less, and even more preferably 30 MPa or more and 150 MPa or less.

[0209] The pressurizing device 230 may or may not have an internal heat source (e.g., a halogen heater) for heating the recording medium P2. If the pressurizing device 230 has an internal heat source, the surface temperature of the recording medium P2 when heated by the heat source is preferably 30°C to 120°C, more preferably 40°C to 100°C, and even more preferably 50°C to 90°C. Note that the absence of an internal heat source in the pressurizing device 230 does not rule out the possibility that the temperature inside the pressurizing device 230 may exceed the ambient temperature due to heat generated by the motor or other components of the pressurizing device 230.

[0210] As the recording medium P2 passes through the pressurizing device 230, the overlapping surfaces are bonded together by the fluidized transparent toner, and a pressure-sensitive printed material P3 is produced. The pressure-sensitive printed material P3 has opposing surfaces that are partially or completely bonded together.

[0211] The completed pressure-pressed printed material P3 is discharged from the pressure device 230.

[0212] The first form of the pressure-sensitive printed material P3 is a pressure-sensitive printed material in which folded recording media are bonded together on opposing surfaces with transparent toner. This form of pressure-sensitive printed material P3 is manufactured by a printing apparatus equipped with a folding device 220.

[0213] The second form of the pressure-sensitive printed material P3 is a pressure-sensitive printed material in which multiple overlapping recording media are bonded together on opposing surfaces with transparent toner. This form of pressure-sensitive printed material P3 is manufactured by a pressure-sensitive printed material manufacturing apparatus equipped with an overlapping device.

[0214] The printing apparatus according to this embodiment is not limited to an apparatus that continuously transports the recording medium P2 from the folding device 220 (or stacking device) to the pressurizing device 230. The printing apparatus according to this embodiment may also be an apparatus that stores the recording medium P2 after it has exited the folding device 220 (or stacking device), and after the amount of stored recording medium P2 reaches a predetermined amount, transports the recording medium P2 to the pressurizing device 230.

[0215] In the printing apparatus according to this embodiment, the folding device 220 (or stacking device) and the pressing device 230 may be located close together or separated. When the folding device 220 (or stacking device) and the pressing device 230 are separated, they are connected, for example, by a transport means (e.g., a belt conveyor) that transports the recording medium P2.

[0216] The printing apparatus according to this embodiment may include cutting means for cutting a recording medium to predetermined dimensions. Examples of cutting means include: cutting means positioned between the placement means 100 and the crimping means 200 to cut off a portion of the recording medium P1 where transparent toner is not present; cutting means positioned between the folding device 220 and the pressing device 230 to cut off a portion of the recording medium P2 where transparent toner is not present; cutting means positioned downstream of the crimping means 200 to cut off a portion of the crimped print P3 where transparent toner is not bonded; and so on.

[0217] The printing apparatus according to this embodiment is not limited to a sheet-fed apparatus. The printing apparatus according to this embodiment may be an apparatus that performs a placement process and a pressing process on a long recording medium to form a long pressed printed material, and then cuts the long pressed printed material to predetermined dimensions.

[0218] The following describes another example of a printing apparatus according to this embodiment that includes a chromatic toner image forming means, but this embodiment is not limited to this example. In the following description, the main parts shown in the figures will be described, and other parts will be omitted from the description.

[0219] Figure 2 is a schematic diagram showing another example of a printing apparatus according to this embodiment. The printing apparatus shown in Figure 2 comprises a printing means 300 that performs the placement of transparent toner on a recording medium and the formation of a chromatic toner image in a single operation, and a pressing means 200 located downstream of the printing means 300.

[0220] The printing means 300 is a five-tandem and intermediate transfer printing means. The printing means 300 comprises a unit 10T for arranging transparent toner (T), and units 10Y, 10M, 10C, and 10K for forming chromatic toner images of yellow (Y), magenta (M), cyan (C), and black (K). Unit 10T is an arrangement means for arranging transparent toner on the recording medium P using a developer containing transparent toner. Units 10Y, 10M, 10C, and 10K are means for forming chromatic toner images on the recording medium P using a developer containing chromatic toner. Units 10T, 10Y, 10M, 10C, and 10K employ an electrophotographic method.

[0221] Units 10T, 10Y, 10M, 10C, and 10K are arranged side by side, spaced apart from each other in the horizontal direction. Units 10T, 10Y, 10M, 10C, and 10K may also be process cartridges that can be attached to and detached from the printing means 300.

[0222] Below units 10T, 10Y, 10M, 10C, and 10K, an intermediate transfer belt (an example of an intermediate transfer body) 20 extends through each unit. The intermediate transfer belt 20 is wound around a drive roll 22, a support roll 23, and an opposing roll 24 that are in contact with the inner surface of the intermediate transfer belt 20, and is configured to travel in the direction from unit 10T to unit 10K. On the image holding surface side of the intermediate transfer belt 20, an intermediate transfer body cleaning device 21 is provided opposite the drive roll 22.

[0223] Units 10T, 10Y, 10M, 10C, and 10K are each equipped with a developing device (an example of a developing means) 4T, 4Y, 4M, 4C, and 4K, respectively. Each of the developing devices 4T, 4Y, 4M, 4C, and 4K is supplied with transparent toner, yellow toner (a chromatic toner), magenta toner (a chromatic toner), cyan toner (a chromatic toner), and black toner (a chromatic toner), which are contained in toner cartridges 8T, 8Y, 8M, 8C, and 8K, respectively.

[0224] Since units 10T, 10Y, 10M, 10C, and 10K have equivalent configurations and operations, unit 10T, which places the transparent toner on the recording medium, will be described as representative.

[0225] Unit 10T has a photoreceptor 1T. Around the photoreceptor 1T are arranged in order: a charging roll (an example of a charging means) 2T for charging the surface of the photoreceptor 1T; an exposure device (an example of a static charge image forming means) 3T for exposing the charged surface of the photoreceptor 1T with a laser beam to form a static charge image; a developing device (an example of a developing means) 4T for supplying toner to the static charge image to develop the static charge image; a primary transfer roll (an example of a primary transfer means) 5T for transferring the developed toner image onto the intermediate transfer belt 20; and a photoreceptor cleaning device (an example of a cleaning means) 6T for removing toner remaining on the surface of the photoreceptor 1T after primary transfer. The primary transfer roll 5T is located inside the intermediate transfer belt 20 and is positioned opposite the photoreceptor 1T.

[0226] The following describes the operation of placing transparent toner and forming a chromatic toner image on the recording medium P, using the operation of unit 10T as an example. First, the surface of the photoreceptor 1T is charged by the charging roll 2T. The exposure device 3T irradiates the charged surface of the photoreceptor 1T with a laser beam according to image data sent from a control unit (not shown). As a result, an electrostatic charge image of the transparent toner arrangement pattern is formed on the surface of the photoreceptor 1T.

[0227] The electrostatic charge image formed on the photoreceptor 1T rotates as the photoreceptor 1T moves to the development position. At the development position, the electrostatic charge image on the photoreceptor 1T is developed and visualized by the developing device 4T, becoming a toner image.

[0228] In the developing device 4T, a developer containing at least a transparent toner and a carrier is accommodated. The transparent toner is triboelectrically charged by being agitated together with the carrier inside the developing device 4T and is held on the developer roll. As the surface of the photoreceptor 1T passes through the developing device 4T, toner is electrostatically attached to the electrostatic charge image on the surface of the photoreceptor 1T, and the electrostatic charge image is developed with toner. The photoreceptor 1T on which the toner image of the toner is formed continues to run, and the toner image developed on the photoreceptor 1T is conveyed to the primary transfer position.

[0229] When the toner image on the photoreceptor 1T is conveyed to the primary transfer position, a primary transfer bias is applied to the primary transfer roll 5T, and an electrostatic force directed from the photoreceptor 1T toward the primary transfer roll 5T acts on the toner image, and the toner image on the photoreceptor 1T is transferred onto the intermediate transfer belt 20. The toner remaining on the photoreceptor 1T is removed and recovered by the photoreceptor cleaning device 6T. The photoreceptor cleaning device 6T is, for example, a cleaning blade, a cleaning brush, etc., and is preferably a cleaning brush.

[0230] In the units 10Y, 10M, 10C, and 10K as well, the same operation as that of the unit 10T is performed using a developer containing a color toner. The intermediate transfer belt 20 onto which the transparent toner layer of the transparent toner is transferred in the unit 10T passes through the units 10Y, 10M, 10C, 10K in sequence, and color toner images of each color are multi-transferred onto the intermediate transfer belt 20.

[0231] The intermediate transfer belt 20, on which five toner images (i.e., a transparent toner layer and four chromatic toner images) have been multiple-transferred through units 10T, 10Y, 10M, 10C, and 10K, proceeds to a secondary transfer section consisting of the intermediate transfer belt 20, a counter roll 24 in contact with the inner surface of the intermediate transfer belt, and a secondary transfer roll (an example of a secondary transfer means) 26 positioned on the image-holding side of the intermediate transfer belt 20. Meanwhile, the recording medium P is fed through a supply mechanism into the gap where the secondary transfer roll 26 and the intermediate transfer belt 20 are in contact, and a secondary transfer bias is applied to the counter roll 24. At this time, an electrostatic force from the intermediate transfer belt 20 toward the recording medium P acts on the toner images, and the toner images on the intermediate transfer belt 20 are transferred onto the recording medium P.

[0232] The recording medium P onto which the toner image has been transferred is transported to a thermal fixing device (an example of a thermal fixing means) 28. The thermal fixing device 28 is equipped with a heating source such as a halogen heater and heats the recording medium P. The surface temperature of the recording medium P when heated by the thermal fixing device 28 is preferably 150°C to 220°C, more preferably 155°C to 210°C, and even more preferably 160°C to 200°C. By passing through the thermal fixing device 28, the chromatic toner image is thermally fixed onto the recording medium P.

[0233] The thermal fixing device 28 is preferably a device that applies heat and pressure, from the viewpoint of suppressing the detachment of transparent toner from the recording medium P and improving the fixation of the chromatic toner image to the recording medium P. For example, it may be a pair of fixing members (roll / roll, belt / roll) equipped with a heating source inside. When the thermal fixing device 28 applies pressure, the pressure that the thermal fixing device 28 applies to the recording medium P may be lower than the pressure that the pressurizing device 230 applies to the recording medium P2. Specifically, it is preferably 0.2 MPa or more and 1 MPa or less.

[0234] The recording medium P becomes a recording medium P1 with a chromatic toner image and transparent toner applied to it by passing through the printing means 300. The recording medium P1 is then transported toward the crimping means 200.

[0235] The configuration of the crimping means 200 in Figure 2 is the same as that of the crimping means 200 in Figure 1, and a detailed explanation of the configuration and operation of the crimping means 200 is omitted.

[0236] In the printed material manufacturing apparatus according to this embodiment, the printing means 300 and the crimping means 200 may be in close proximity or separated. When the printing means 300 and the crimping means 200 are separated, they are connected, for example, by a transport means (e.g., a belt conveyor) that transports the recording medium P1.

[0237] The printing apparatus according to this embodiment may include cutting means for cutting a recording medium to predetermined dimensions. Examples of cutting means include: cutting means positioned between the printing means 300 and the crimping means 200 to cut off a portion of the recording medium P1 where transparent toner is not present; cutting means positioned between the folding device 220 and the pressing device 230 to cut off a portion of the recording medium P2 where transparent toner is not present; cutting means positioned downstream of the crimping means 200 to cut off a portion of the crimped print P3 where transparent toner is not bonded; and so on.

[0238] The printing apparatus according to this embodiment is not limited to a sheet-fed apparatus. The printing apparatus according to this embodiment may be an apparatus that performs a color toner image formation process, a placement process, and a pressure pressing process on a long recording medium to form a long pressure-pressed printed material, and then cuts the long pressure-pressed printed material to predetermined dimensions.

[0239] <Processing Cartridge Set> A process cartridge set according to this embodiment will be described. The process cartridge set according to this embodiment comprises: a first process cartridge containing an electrostatic image developer containing chromatic toner in the particle set for printing according to this embodiment, and equipped with a first developing means for developing the electrostatic image for the chromatic toner image formed on the surface of the photoreceptor as a chromatic toner image using the electrostatic image developer containing chromatic toner; and a second process cartridge containing an electrostatic image developer containing pressure-responsive particles as toner in the particle set for printing according to this embodiment, and equipped with a second developing means for developing the electrostatic image for the pressure-responsive particle layer formed on the surface of the photoreceptor as a pressure-responsive particle layer using the electrostatic image developer containing pressure-responsive particles as toner, and is a process cartridge set that can be attached to and detached from a printing apparatus.

[0240] Each process cartridge constituting the process cartridge set according to this embodiment may be configured to include a developing means and, if necessary, at least one selected from a photoreceptor, a charging means, an electrostatic image forming means, a transfer means, etc.

[0241] An example of a process cartridge set according to this embodiment is shown below, but this embodiment is not limited to this example. In the following description, the main parts shown in the figures will be described, and other parts will not be described.

[0242] Figure 3 is a schematic diagram showing an example of a first process cartridge that constitutes the process cartridge set according to this embodiment. The process cartridge 500 shown in Figure 3 can be attached to, for example, the printing equipment shown in Figure 1 or Figure 2.

[0243] The process cartridge 500 is a cartridge in which a photoreceptor 501, a charging roll 502 (an example of a charging means), a developing device 504 (an example of a developing means), and a photoreceptor cleaning device 506 (an example of a cleaning means) are integrated by a housing 517. The housing 517 has an opening 518 for exposure. The housing 517 has a mounting rail 516, and the process cartridge 500 is mounted on a printing machine via the mounting rail 516.

[0244] Figure 3 also shows the exposure device 503 and transfer device 505, which are arranged around the process cartridge 500 when the process cartridge 500 is installed in the printing equipment, as well as the recording medium P.

[0245] <Cartridge Set> The cartridge set according to this embodiment comprises a first cartridge containing chromatic toner in the printmaking particle set according to this embodiment, and a second cartridge containing pressure-responsive particles in the printmaking particle set according to this embodiment, and is a cartridge set that can be attached to and detached from a printmaking apparatus. Each cartridge constituting the cartridge set contains replenishment toner for supply to a developing means provided in the printmaking apparatus.

[0246] The printing means 300 shown in Figure 2 has a configuration in which a cartridge set consisting of cartridges 8T, 8Y, 8M, 8C, and 8K can be attached and detached. The developing devices 4T, 4Y, 4M, 4C, and 4K are connected to cartridges 8T, 8Y, 8M, 8C, and 8K, respectively, by supply pipes (not shown). Cartridge 8T, which is the first cartridge constituting the cartridge set according to this embodiment, contains pressure-responsive particles. On the other hand, cartridges 8Y, 8M, 8C, and 8K, which are the second cartridges constituting the cartridge set according to this embodiment, contain yellow, magenta, cyan, and black chromatic toners, respectively. When the amount of toner contained in the cartridges becomes low, these cartridges are replaced. [Examples]

[0247] Examples are described below, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "parts" and "%" all refer to mass.

[0248] <Fabrication of pressure-responsive particles> (Fabrication of pressure-responsive particles (B1)) -Preparation of mold release agent dispersion (1)- Fischer-Tropsch wax: 270 parts (Manufactured by Nippon Seiro Co., Ltd., Product name: FNP-0090, Melting temperature = 90℃) • Anionic surfactant: 1.0 part (Manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK) • Ion-exchanged water: 400 copies The above components were mixed and heated to 95°C, dispersed using a homogenizer (IKA, Ultra-Turrax T50), and then dispersed for 360 minutes using a Manton-Gorin high-pressure homogenizer (Gorin) to prepare a release agent dispersion (1) (solid content concentration: 20% by mass) in which release agent particles with a volume average particle size of 0.23 μm were dispersed.

[0249] -Preparation process for styrene resin particle dispersion- • Styrene (as polymerization component): 370 parts n-butyl acrylate (as polymerization component): 115 parts • Acrylic acid (as polymerization component): 15 parts Dodecanethiol (as a chain transfer agent): 7.5 parts The above materials were mixed and dissolved to prepare monomer solution (1). Eight parts of anionic surfactant (Dow Chemical Company, DOWFAX2A1) were dissolved in 205 parts of deionized water, and the monomer solution (1) was added and dispersed to obtain an emulsion. 2.2 parts of the anionic surfactant were dissolved in 462 parts of deionized water and placed in a polymerization flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube. The mixture was heated to 73°C while stirring and maintained at that temperature. 3 parts of ammonium persulfate were dissolved in 21 parts of deionized water and added dropwise to the polymerization flask via a metering pump over 15 minutes. The emulsion was then added dropwise via a metering pump over 160 minutes. The polymerization flask was then kept at 75°C for 3 hours while continuing to stir slowly, and then returned to room temperature. This resulted in a styrene-based resin particle dispersion (St1) with a volume-average particle size (D50v) of 220 nm, a weight-average molecular weight of 33,000 determined by GPC (UV detection), a glass transition temperature of 53°C, and a solid content of 42%.

[0250] -Composite resin particle formation process- • Styrene resin particle dispersion (St1): Amount resulting in a solid content of 600 parts • 2-ethylhexyl acrylate: 250 parts n-butyl acrylate: 150 parts • Ion-exchanged water: 1080 units The above materials were placed in a polymerization flask to prepare monomer solution (2). The solution was slowly stirred for 2 hours. Then, while continuing to stir, the temperature was raised to 70°C, and 4.5 parts of ammonium persulfate and 100 parts of deionized water were added dropwise over 30 minutes using a metering pump. After that, the mixture was held for 3 hours while continuing to stir to complete the polymerization. Through the above steps, composite resin particles with a volume-average particle size of 219 nm and a weight-average molecular weight of 220,000 were dispersed, and a composite resin particle dispersion SM1 was obtained, with the solid content adjusted to 30% by mass by adding deionized water.

[0251] The resin particles of the obtained composite resin particle dispersion SM1 were dried, and the glass transition temperature (Tg) behavior of the dried resin particles was analyzed from -150°C to 100°C using a differential scanning calorimeter (DSC) manufactured by Shimadzu Corporation. A glass transition due to low Tg (meth)acrylic acid ester resin was observed at -50°C. In addition, a glass transition due to high Tg styrene resin was observed at 54°C (glass transition temperature difference: 104°C).

[0252] -Agglomerated particle formation process / fusion / coalescence process- ·Composite resin particle dispersion SM1: 840 parts • Release agent dispersion (1): 10.5 parts • Colloidal silica aqueous solution: 13 parts (Manufactured by Nissan Chemical Corporation, Snowtex OS) • Ion-exchanged water: 800 units • Anionic surfactants: Part 1 (Dowfax 2A1, manufactured by Dow Chemical Co., Ltd.) As a material for forming the core, the above components were placed in a 3-liter reaction vessel equipped with a thermometer, pH meter, and stirrer. At a temperature of 25°C, 1.0% by mass nitric acid was added to adjust the pH to 3.0. Then, while dispersing at 5,000 rpm using a homogenizer (IKA Japan Co., Ltd., Ultra-Turrax T50), 0.3 parts of the prepared 10% by mass aqueous solution of polyaluminum chloride were added and dispersed for a further 6 minutes.

[0253] Subsequently, a stirrer and mantle heater were installed in the reaction vessel, and the temperature was increased at a rate of 0.2°C / min up to 40°C, and then at a rate of 0.05°C / min above 40°C, while adjusting the stirrer's rotation speed to ensure the slurry was thoroughly mixed. The particle size was measured every 10 minutes using a Multisizer II (aperture diameter: 50 μm, manufactured by Coulter). When the volume-average particle size of the aggregated particles reached 10 μm, the temperature was maintained, and 150 parts of styrene-based resin particle dispersion (St1) were added over 5 minutes as the material for forming the shell. After holding for 30 minutes, the pH was adjusted to 6.0 using a 1% by mass sodium hydroxide aqueous solution. Thereafter, the temperature was increased to 90°C at a rate of 1°C / min, while adjusting the pH to 6.0 every 5°C in the same manner, and then maintained at 96°C. Particle shape and surface properties were observed using an optical microscope and a scanning electron microscope (FE-SEM). Particle coalescence was confirmed 2.0 hours after the start of holding at 96°C, so the container was cooled to 30°C in cooling water over 5 minutes.

[0254] The cooled slurry was passed through a 30 μm nylon mesh to remove coarse powder, and the slurry that passed through the mesh was filtered under reduced pressure using an aspirator. The particles remaining on the filter paper were crushed as finely as possible by hand, and the particles were washed with deionized water at 30°C. The washed toner was finely crushed in a wet-dry granulator (Cormill), and then vacuum-dried in a 25°C dryer for 36 hours to obtain mother particles (B1). The obtained mother particles (B1) had a volume-average particle size of 10.5 μm and a circularity of 0.965.

[0255] - Fabrication of pressure-responsive particles (B1) - To 100 parts of the obtained pressure-responsive particles (B1), 0.5 parts of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) was added and mixed for 30 seconds at 13,000 rpm using a sample mill. Subsequently, the mixture was sieved using a vibrating sieve with a mesh size of 106 μm to prepare the pressure-responsive particles (B1).

[0256] (Preparation of pressure-responsive particles B2-B8) Except for changing the composition of the monomer solution (2) charged into the polymerization flask during the composite resin particle formation process and the volume-average particle size of the aggregated particles produced during the aggregated particle formation process, as shown in Table 1, pressure-responsive particles B2 to B8 were prepared in the same manner as pressure-responsive particles (B1). The abbreviations used in Table 1 are as follows: • 2EHA: 2-ethylhexyl acrylate BA: n-butyl acrylate

[0257] (Preparation of pressure-responsive particles B9-B16) Except for changing the amount of release agent dispersion (1) added during the preparation process and the volume-average particle size of the aggregated particles produced in the aggregated particle formation process as shown in Table 1, pressure-responsive particles B9 to B16 were produced in the same manner as pressure-responsive particles (B1).

[0258] (Preparation of pressure-responsive particle B17) In the aggregated particle formation process / fusion and unification process, pressure-responsive particles B17 were prepared in the same manner as pressure-responsive particles (B1), except that the temperature was maintained when the volume-average particle size of the aggregated particles reached 10.2 μm, and then styrene-based resin particle dispersion (St1) was not added as a material for forming the shell.

[0259] (Preparation of pressure-responsive particles B18-B22) Pressure-responsive particles B18 to B22 were prepared in the same manner as pressure-responsive particles (B1), except that in the aggregated particle formation process / fusion and coalescence process, instead of adding 150 parts of styrene-based resin particle dispersion (St1) as the material for forming the shell, a dispersion of 150 parts of styrene-based resin particle dispersion (St1) and the coloring agent particle dispersion described in Table 1 was added as the material for forming the shell. The amount of colorant particle dispersion to be mixed with the styrene resin particle dispersion (St1) was as shown in Table 1.

[0260] The colorant particle dispersions used to produce pressure-responsive particles B18-B22 were prepared using the following procedure.

[0261] <Preparation of Pigment Dispersion C> • Cyan pigment (CI Pigment Blue 15:3): 50 copies • Ionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 5 parts • Ion-exchanged water: 195 units The above components were mixed and dispersed for 10 minutes using a homogenizer (IKA Ultra-Turrax). Then, the dispersion treatment was performed for 15 minutes at a pressure of 250 MPa using an ultimateizer (opposing impact type wet pulverizer: manufactured by Sugino Machine Co., Ltd.). Deionized water was added to adjust the mixture, and a cyanide pigment dispersion (solid content 2%) was prepared, in which cyanide pigment with a volume average particle size of 126 nm was dispersed.

[0262] <Preparation of Pigment Dispersion M> • Magenta pigment (CI Pigment Red 122): 50 copies • Ionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 5 parts • Ion-exchanged water: 195 units The above components were mixed and dispersed for 10 minutes using a homogenizer (IKA Ultra-Turrax). Then, the dispersion was treated for 15 minutes at a pressure of 250 MPa using an ultimateizer (opposing impact type wet pulverizer: manufactured by Sugino Machine Co., Ltd.). Deionized water was added to adjust the mixture, and a magenta pigment dispersion (solid content 2%) was prepared, in which magenta pigment with a volume average particle size of 146 nm was dispersed.

[0263] <Preparation of Pigment Dispersion Y> • Yellow pigment (CI Pigment Yellow 74): 50 copies • Ionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 5 parts • Ion-exchanged water: 195 units The above components were mixed and dispersed for 10 minutes using a homogenizer (IKA Ultra-Turrax). Then, the mixture was dispersed for 15 minutes at a pressure of 250 MPa using an ultimateizer (opposing impact type wet pulverizer: manufactured by Sugino Machine Co., Ltd.). Deionized water was added to adjust the mixture, and a yellow pigment dispersion (solid content 2%) was prepared, in which yellow pigment with a volume average particle size of 130 nm was dispersed.

[0264] <Preparation of Pigment Dispersion B> • Black pigment (carbon black, manufactured by Cabot, Regal 330): 50 copies • Ionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 5 parts • Ion-exchanged water: 195 units The above components were mixed and dispersed for 10 minutes using a homogenizer (IKA Ultra-Turrax). Then, the dispersion was treated for 15 minutes at a pressure of 250 MPa using an ultimateizer (opposing impact type wet pulverizer: manufactured by Sugino Machine Co., Ltd.). Deionized water was added to adjust the mixture, and a black pigment dispersion (solid content 2%) was prepared, in which black pigment with a volume average particle size of 135 nm was dispersed.

[0265] Furthermore, the volume-average particle size of the pigments in the pigment dispersion was measured using a laser diffraction particle size distribution analyzer (for example, LA-700 manufactured by Horiba, Ltd.). The particle size at which the cumulative total of 50% of the volume-based particle size distribution, calculated from the smallest diameter side, was determined as the volume-average particle size (D50v).

[0266] When T1 and T2 for pressure-responsive particles B1 to B22 were determined by the method described above, they satisfied Equation 2, "10°C ≤ T1 - T2". The pigment content (ppm) in the parent particle B relative to the total parent particle B, contained in pressure-responsive particles B1 to B22, is shown in Table 1.

[0267] [Table 1]

[0268] <Production of chromatic toner> (Preparation of chromatic toner (A1)) -Preparation of amorphous polyester resin dispersion (A1)- • Ethylene glycol: 37 parts • Neopentyl glycol: 65 parts • 1,9-nonanediol: 32 parts Terephthalic acid: 96 parts The above materials were placed in a flask, and the temperature was raised to 200°C over 1 hour. After confirming that the reaction system was uniformly stirred, 1.2 parts of dibutyltin oxide were added. The temperature was raised to 240°C over 6 hours while distilling off the generated water, and stirring was continued at 240°C for 4 hours to obtain amorphous polyester resin (acid value 9.4 mg KOH / g, weight-average molecular weight 13,000, glass transition temperature 62°C). The amorphous polyester resin, in its molten state, was transferred to an emulsifier / disperser (Cavitron CD1010, Eurotech) at a rate of 100 g per minute. Separately, a 0.37% dilute ammonia water solution, obtained by diluting reagent ammonia water with deionized water, was placed in a tank and transferred to the emulsifier / disperser simultaneously with the amorphous polyester resin at a rate of 0.1 liters per minute while being heated to 120°C in a heat exchanger. The emulsifier / disperser was operated at a rotor speed of 60 Hz and a pressure of 5 kg / cm². 2The system was operated under the specified conditions to obtain an amorphous polyester resin dispersion (A1) with a volume-average particle size of 160 nm and a solid content of 20%.

[0269] - Preparation of crystalline polyester resin dispersion (C1) - Decandioic acid: 81 parts Hexanediol: 47 parts The above materials were placed in a flask, and the temperature was raised to 160°C over 1 hour. After confirming that the reaction system was uniformly stirred, 0.03 parts of dibutyltin oxide were added. The temperature was raised to 200°C over 6 hours while distilling off the water produced, and stirring was continued at 200°C for 4 hours. Next, the reaction mixture was cooled, solid-liquid separation was performed, and the solid was dried at 40°C under reduced pressure to obtain crystalline polyester resin (C1) (melting point 64°C, weight-average molecular weight 15,000).

[0270] • Crystalline polyester resin (C1): 50 parts • Anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 2 parts • Ion-exchanged water: 200 bottles The above materials were heated to 120°C and thoroughly dispersed in a homogenizer (Ultra-Turrax T50, IKA Corporation), followed by dispersion treatment in a pressure-discharge homogenizer. When the volume-average particle size reached 180 nm, the mixture was collected to obtain a crystalline polyester resin dispersion (C1) with a solid content of 20%.

[0271] -Preparation of mold release agent particle dispersion (W1)- • Paraffin wax (HNP-9, manufactured by Nippon Seiro Co., Ltd.): 100 units • Anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 1 part • Ion-exchanged water: 350 units The above materials were mixed and heated to 100°C, dispersed using a homogenizer (IKA Ultra-Turrax T50), and then dispersed again using a pressure-discharge type Gorin homogenizer to obtain a release agent particle dispersion containing release agent particles with a volume-average particle size of 200 nm. Deionized water was added to this release agent particle dispersion to adjust the solid content to 20%, resulting in release agent particle dispersion (W1).

[0272] -Preparation of a colorant particle dispersion (M1)- • Magenta pigment (Pigment Red 122, DIC Corporation): 50 copies • Anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 5 parts • Ion-exchanged water: 195 units The above materials were mixed and dispersed for 60 minutes using a high-pressure impact disperser (Ultimizer HJP30006, Sugino Machine Co., Ltd.) to obtain a colorant particle dispersion (M1) with a solid content of 20%.

[0273] -Production of chromatic toner particles (A1)- • Ion-exchanged water: 200 bottles • Amorphous polyester resin dispersion (A1): 150 parts • Crystalline polyester resin dispersion (C1): 10 parts • Release agent particle dispersion (W1): 22.5 parts • Coloring agent particle dispersion (M1): 15 parts • Anionic surfactant (TaycaPower): 2.8 parts The above materials were placed in a round stainless steel flask, and 0.1N nitric acid was added to adjust the pH to 3.5. Then, an aqueous solution of aluminum chloride (Oji Paper Co., Ltd., 30% powder) was added, prepared by dissolving 2 parts of aluminum chloride in 30 parts of deionized water. The mixture was dispersed at 30°C using a homogenizer (IKA Ultra-Turrax T50), and then heated in a heating oil bath to 45°C, holding until the volume-average particle size reached 5.0 μm. Next, 60 parts of amorphous polyester resin dispersion (A1) were added and held for 30 minutes. When the volume-average particle size reached 5.2 μm, another 60 parts of amorphous polyester resin dispersion (A1) were added and held for 30 minutes. Subsequently, 20 parts of a 10% NTA (nitrilotriacetic acid) metal salt aqueous solution (Kirest 70, Kirest Co., Ltd.) were added, and a 1N sodium hydroxide aqueous solution was added to adjust the pH to 9.0. Next, 1 part of anionic surfactant (TaycaPower) was added, and the mixture was heated to 85°C while continuing to stir, and held for 5 hours. Then, it was cooled to 20°C at a rate of 20°C / min. Finally, it was filtered, thoroughly washed with deionized water, and dried to obtain chromatic toner particles (A1) with a volume-average particle size of 5.0 μm and an average circularity of 0.971.

[0274] (Preparation of chromatic toner (A1)) 100 parts of chromatic toner particles (A1) and 1.3 parts of hydrophobic silica (NY50, manufactured by Nippon Aerosil Co., Ltd.) with an average particle size of 30 nm were mixed and blended for 10 minutes at a peripheral speed of 32 m / s using a Henschel mixer. After that, coarse particles were removed using a sieve with a 45 μm mesh to obtain chromatic toner (A1).

[0275] (Preparation of chromatic toner (A2)) -Preparation of resin particle dispersion (A2)- Styrene (manufactured by Wako Pure Chemical Industries, Ltd.): 330 parts by mass n-butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.): 60 parts by mass Dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd.): 3.1 parts by mass The above components were mixed and dissolved, and then emulsified and dispersed in a flask in a solution of 6 parts by mass of a nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical Industries, Ltd.) and 10 parts by mass of an anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) dissolved in 550 parts by mass of deionized water. While slowly mixing for 10 minutes, 50 parts by mass of deionized water containing 4 parts by mass of ammonium persulfate was added. After nitrogen purging, the contents of the flask were heated in an oil bath while stirring until they reached 70°C, and emulsion polymerization was continued for 5 hours. As a result, a resin particle dispersion (A2) was obtained in which styrene acrylic resin particles with a volume average particle size D50v = 104 nm, a glass transition temperature Tg = 59°C, and a weight average molecular weight of 34,000 were dispersed.

[0276] -Preparation of resin particle dispersion (A2-2)- Styrene: 300 parts by mass n-butyl acrylate: 90 parts by mass • Acrylic acid: 0.1 parts by mass Dodecanethiol: 2.8 parts by mass • 2-(dimethylaminoester) methacrylic acid: 1.0 part by mass The above components were mixed and dissolved, and then emulsified and dispersed in a flask in a solution of 6 parts by mass of a nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical Industries, Ltd.) and 10 parts by mass of an anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) dissolved in 550 parts by mass of deionized water. While slowly mixing for 10 minutes, 50 parts by mass of deionized water containing 4 parts by mass of ammonium persulfate was added. After nitrogen purging, the contents of the flask were heated in an oil bath while stirring until they reached 70°C, and emulsion polymerization was continued for 5 hours. As a result, a resin particle dispersion (A2-2) was obtained in which resin particles with a volume-average particle size D50v = 120 nm, a glass transition temperature Tg = 52°C, and a weight-average molecular weight of 35,000 were dispersed.

[0277] -Production of chromatic toner particles (A2)- ·Resin particle dispersion (A2): 402.5 parts • Coloring agent particle dispersion (M1): 12.5 parts • Release agent particle dispersion (W1): 50 parts • Anionic surfactant (manufactured by Tayca Co., Ltd., TaycaPower): 2 parts The above materials were placed in a round stainless steel flask, and 0.1 mol / L nitric acid was added to adjust the pH to 3.5. Then, 30 parts of a 10% polyaluminum chloride aqueous solution of nitric acid were added. Subsequently, the mixture was dispersed at 30°C using a homogenizer (IKA Ultra-Turrax T50), and then heated in a heating oil bath to 45°C until the volume-average particle size reached 5.2 μm. After that, 100 parts of resin particle dispersion (A2-2) were added and held for 1 hour. Then, 0.1 mol / L sodium hydroxide aqueous solution was added to adjust the pH to 8.5, and the mixture was heated to 78°C while continuing to stir, and held for 10 hours. After that, it was cooled to 30°C at a rate of 20°C / min, 0.1 mol / L nitric acid was added to adjust the pH to 4.0, and then heated again in a heating oil bath to 60°C and held for 3 hours. Subsequently, the mixture was cooled to 20°C at a rate of 20°C / min, filtered, thoroughly washed with deionized water, and dried to obtain chromatic toner particles (A2) with a volume-average particle size of 6.2 μm.

[0278] -Creation of chromatic toner (A2)- Using the same procedure as for preparing the chromatic toner (A1), hydrophobic silica was added to the chromatic toner particles (A2) and coarse particles in the toner were removed to obtain the chromatic toner (A2).

[0279] (Creation of chromatic toner (A3) to (A6)) Release agent content W A Chromatic toners (A3) to (A6) were obtained using the same procedure as for chromatic toner (A1), except that the amount of release agent particle dispersion (W1) added was adjusted so that the values ​​shown in Table 2 were obtained.

[0280] <Career Creation> A coating layer-forming solution was prepared by mixing 14 parts toluene, 2 parts styrene-methyl methacrylate copolymer (mass ratio: 80 / 20, weight-average molecular weight: 70000), and 0.6 parts zinc oxide (Titanium Industry, MZ500) and stirring with a stirrer for 10 minutes to disperse the zinc oxide. Next, this coating layer-forming solution and 100 parts ferrite particles (volume-average particle size: 38 μm) were placed in a vacuum degassing kneader, stirred at 60°C for 30 minutes, and then degassed by reducing the pressure while heating, followed by drying to produce a carrier.

[0281] <Examples 1-21, Comparative Examples 1 and 2> (Preparation of a developer containing chromatic toner) Eight parts of the chromatic toner and 100 parts of the carrier listed in Table 2 were mixed in a V-blender to prepare a developer containing the chromatic toner.

[0282] (Preparation of a developer containing pressure-responsive particles) Eight parts of the pressure-responsive particles and 100 parts of the carrier listed in Table 2 were mixed in a V-blender to prepare a developer containing the pressure-responsive particles as toner.

[0283] <Rating> (Evaluation of adhesive properties) As a printing apparatus, we prepared an apparatus (Iridesse production press) in the configuration shown in Figure 2. Specifically, we prepared a printing apparatus that includes an intermediate transfer printing method that performs the placement of pressure-responsive particles onto a recording medium and the formation of a colored image in a single step, and a crimping method that has a folding device and a pressing device. Developers containing chromatic toners and pressure-responsive particles, as obtained in each example, were introduced into the developing machine. Recording paper (OK Prince high-quality paper, manufactured by Oji Paper Co., Ltd.) was set in the printing machine, and a full-surface halftone image with an image density of 40% was developed with the chromatic toner. Simultaneously, a halftone image with an image density of 50% was developed on top of that image with the pressure-responsive particles to obtain a printed image. After that, the recording paper was folded in half to align the images, and then passed through a sealer (Pressle multi2, manufactured by Toppan Forms Co., Ltd.) and pressure was applied (Gap 10 setting (equivalent to a pressure of 95 MPa)). After being left overnight, the paper was cut into 15 mm wide pieces and used as test pieces for a 90-degree peel test. The peeling speed for the 90-degree peel test was set to 20 mm / min. Load (N) was measured at 0.4 mm intervals from 10 mm to 50 mm after the start of measurement, and the average was calculated. The load (N) required for peeling was classified as follows, and the adhesive strength was evaluated. The evaluation results are shown in Table 2. A(〇): 0.8N or higher B(△): 0.6N or higher, less than 0.8N C(Δ-): 0.4N or higher, less than 0.6N D(×): Less than 0.4N

[0284] (Evaluation of storage properties of dispersion) The dispersion was sealed and stored in a 30°C chamber for one month, after which the particle size distribution was measured using an LS coulter. If aggregated particles occurred, the volume-average particle size distribution would show a bimodal distribution with a peak on the coarser side. The storage stability of the dispersion was evaluated based on the following evaluation criteria. The evaluation results are shown in Table 2. A(〇): No change, the distribution remains unchanged (single-peak distribution). B(△): Initially a bimodal distribution, but becomes a unimodal distribution after redispersion. C(×): Remains a bimodal distribution even after redispersion.

[0285] (Image missing evaluation) Image whiteout evaluation was performed using an Iridesse Production Press (manufactured by Fuji Xerox Co., Ltd.). Pressure-responsive particles were introduced into the first developing unit, and 1000 full-screen halftone images with 50% image density and 1000 full-screen halftone images with 40% image density using magenta toner were printed simultaneously. The whiteout occurrence rate was counted. Image whiteout evaluation was performed based on the evaluation criteria below. The evaluation results are shown in Table 2. A(〇): Incidence rate 0% to less than 2% B(△): Incidence rate between 2% and less than 5% C(×): Incidence rate 5% or higher

[0286] (Transparency assessment) Transparency evaluation was performed using an Iridesse Production Press (manufactured by Fuji Xerox Co., Ltd.). Pressure-responsive particles were introduced into the first developing unit, and an image consisting of pressure-responsive particles with an image density of 50% was formed on a transparent film (manufactured by Panac Co., Ltd., product name: PETG media film). The light transmittance of the area where the image was formed was measured using the procedure described below, and transparency was evaluated based on the obtained light transmittance. The evaluation results are shown in Table 2. -Method for measuring light transmittance- The light transmittance of the film in the visible light range (400-700 nm) was measured using a Hitachi U-4100 spectrophotometer. -Evaluation Criteria- A(〇): Light transmittance of 80% or more in the 400-700nm range. B(△): Light transmittance between 400 and 700 nm is 50% or more but less than 80%. C(×): Light transmittance less than 50% in the 400-700nm range.

[0287] [Table 2]

[0288] The abbreviations used in Table 2 are as follows: St: Styrene BA: n-butyl acrylate AA: Acrylic acid • 2EHA: 2-ethylhexyl acrylate BA: n-butyl acrylate • MinTg (°C): Lowest glass transition temperature of pressure-responsive particles • MaxTg (°C): Highest glass transition temperature of pressure-responsive particles

[0289] From the above results, it can be seen that the particle set for printing in this embodiment can produce printed materials with excellent adhesion. [Explanation of Symbols]

[0290] 100 Placement means 101 Photoreceptor 102 Charging Roll (Example of Charging Method) 103 Exposure apparatus (an example of a means for forming electrostatic images) 104 Developing apparatus (an example of a developing means) 105 Transfer Roll (Example of Transfer Means) 106 Photoreceptor cleaning device (an example of a cleaning method) 107 Fixing device (an example of a fixing means) 200 Crimping means 220 folding device 230 Pressurizing device 231, 232 Pressure Roll P recording medium P1 A recording medium on which transparent toner has been applied to the image. P2 Overlapping recording media P3 Pressure-sensitive printed materials

[0291] 300 Printing means 1T, 1Y, 1M, 1C, 1K photoconductor 2T, 2Y, 2M, 2C, 2K Charging Rolls (Example of Charging Method) 3T, 3Y, 3M, 3C, 3K exposure equipment (an example of electrostatic image forming means) 4T, 4Y, 4M, 4C, 4K developing equipment (an example of a developing method) 5T, 5Y, 5M, 5C, 5K Primary Transfer Rolls (Example of Primary Transfer Method) 6T, 6Y, 6M, 6C, 6K Photoconductor Cleaning Device (Example of Cleaning Method) 8T, 8Y, 8M, 8C, 8K Toner Cartridges 10T, 10Y, 10M, 10C, 10K units 20. Intermediate transfer belt (an example of an intermediate transfer material) 21 Intermediate Transfer Body Cleaning Apparatus 22 Drive Roll 23 Support Roll 24 Opposing Roll 26. Secondary transfer roll (an example of a secondary transfer means) 28. Thermal fixing device (an example of a thermal fixing means)

[0292] 500 Process Cartridges 501 Photoreceptor 502 Charging Roll (Example of Charging Method) 503 Exposure apparatus (an example of electrostatic image formation means) 504 Developing apparatus (an example of a developing means) 505 Transfer device (an example of a transfer means) 506 Photoconductor Cleaning Apparatus (Example of Cleaning Method) 516 Mounting Rail 517 cabinets 518 Aperture for exposure

Claims

1. It comprises a chromatic toner consisting of toner particles A, or toner particles A to which an external additive has been added, and a group of pressure-responsive particles consisting of mother particles B, or mother particles B to which an external additive has been added. The toner particles A are It comprises at least a binder resin and a coloring agent, The content of the binder resin is 40% by mass or more and 95% by mass or less relative to the total amount of toner particles A. The amount of colorant in the toner particles A is greater than 1.0% by mass relative to the total amount of toner particles A. The aforementioned parent particle B is This includes styrene-based resins containing styrene and other vinyl monomers as polymerization components, and (meth)acrylic acid ester-based resins containing (meth)acrylic acid esters as polymerization components. The particles have a mass ratio (styrene resin:(meth)acrylic acid ester resin) of 80:20 to 20:80 between the styrene resin and the (meth)acrylic acid ester resin. The pressure-responsive particle group satisfies the following equation 2, The difference between the lowest glass transition temperature and the highest glass transition temperature of the pressure-responsive particle group is 30°C or more. A particle set for producing printed materials in which D50A and D50B satisfy the following formula 1-1, where D50A and D50B are the volume-average particle size of the toner particle A and the volume-average particle size of the mother particle B. Formula 1-1: 1.5μm<(D50B-D50A) Formula 2...10℃≦T1-T2 In Equation 1, the volume-average particle size D50A is the particle size at which the cumulative distribution of toner particles A is subtracted from the smallest particle size side, and the cumulative distribution is 50% of the total particle size. The volume-average particle size D50B is the particle size at which the cumulative distribution of the volume of parent particles B is subtracted from the smallest particle size, and the cumulative distribution is 50% of the total particle size. In Equation 2, T1 is the temperature at which the viscosity is 10,000 Pa·s at a pressure of 1 MPa, and T2 is the temperature at which the viscosity is 10,000 Pa·s at a pressure of 10 MPa.

2. The particle set for producing printed materials according to claim 1, wherein the toner particles A contain polyester resin.

3. Both the toner particles A and the mother particles B contain a release agent. The amount of release agent contained in the toner particles A is W. Ａ The amount of release agent contained in the mother particle B relative to the amount of release agent W Ｂ The ratio (W Ｂ / W Ａ A particle set for producing printed materials according to claim 1 or claim 2, wherein the ratio is 0.01 or more and 0.8 or less.

4. Content W of the aforementioned release agent Ｂ The particle set for producing printed materials according to claim 3, wherein the amount is 0.1% by mass or more and 4.0% by mass or less.

5. A particle set for producing printed materials according to any one of claims 1 to 4, wherein D50A and D50B satisfy the following formula 1-2. Formula 1-2: 1.5μm<(D50B-D50A)<10μm

6. The particle set for producing printed materials according to claim 5, wherein the D50B is 6.0 μm or more and 20.0 μm or less.

7. The mother particle B comprises a core portion containing the styrene resin and the (meth)acrylic acid ester resin, A shell layer covering the core portion, A particle set for producing printed materials according to any one of claims 1 to 6, comprising:

8. The aforementioned mother particle B contains a pigment, The particle set for producing printed materials according to any one of claims 1 to 7, wherein the content of the pigment is 5 ppm or more and 100 ppm or less relative to the total amount of the mother particles B.

9. A chromatic toner image forming means for containing a developer containing the chromatic toner in a particle set for printing according to any one of claims 1 to 8, and for forming the chromatic toner image on a recording medium by electrophotography using the developer, Arrangement means for containing the pressure-responsive particle group in the printmaking particle set according to any one of claims 1 to 8, and for arranging the pressure-responsive particle group on a recording medium to form a pressure-responsive particle layer, A thermal fixing means comprising a fixing member, wherein the fixing member is in contact with the pressure-responsive particle layer, and the chromatic toner image is thermally fixed to the recording medium. A pressing means for folding and pressing together a recording medium on which the chromatic toner image has been heat-fixed, or for overlapping and pressing together a recording medium on which the chromatic toner image has been heat-fixed and another recording medium, A manufacturing apparatus for printed materials, including those containing printed materials.

10. A chromatic toner image formation step of forming a chromatic toner image on a recording medium by electrophotography using a developer containing the chromatic toner in the printmaking particle set according to any one of claims 1 to 8, Arrangement step of arranging the pressure-responsive particle group in the printmaking particle set according to any one of claims 1 to 8 on a recording medium to form a pressure-responsive particle layer, A thermal fixing step in which the fixing member is in contact with the pressure-responsive particle layer and the chromatic toner image is thermally fixed to the recording medium, A pressing step of folding and pressing together a recording medium on which the chromatic toner image has been heat-fixed, or overlapping and pressing together a recording medium on which the chromatic toner image has been heat-fixed with another recording medium, A method for manufacturing printed materials that include [the specified material].

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