Pressure-sensitive toner, apparatus for producing printed matter, method for producing printed matter, and printed matter

Abstract

To provide a pressure sensitive toner that excels in adhesion, tear resistance during removal, and hot offset resistance.SOLUTION: A pressure sensitive toner includes toner particles containing a composite resin that includes a styrene-based resin and a (meth)acrylate-based resin. The difference between a lowest glass transition temperature of the composite resin and a highest glass transition temperature thereof is 30°C or more, and the toner particles have a gel fraction of from 1.0 mass% to 8.0 mass% inclusive.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present invention relates to a pressure-sensitive toner, a device for producing a printed matter, a method for producing a printed matter, and a printed matter. [Background technology]

[0002] Patent Document 1 discloses pressure-responsive particles that contain pressure-responsive base particles that contain a styrene-based resin containing styrene and other vinyl monomers as polymerization components, and a (meth)acrylic acid ester-based resin that contains at least two types of (meth)acrylic acid esters as polymerization components, with the mass ratio of the (meth)acrylic acid esters to the total polymerization components being 90 mass % or more, and an external additive that contains titanium oxide particles, and that have at least two glass transition points, with the difference between the lowest and highest glass transition temperatures being 30°C or more.

[0003] Furthermore, Patent Document 2 describes the following components (A), (B) and (C): (A) a (meth)acrylic polymer having a glass transition temperature of −40° C. or lower, which is obtained by copolymerizing at least an alkyl (meth)acrylate ester and a functional group-containing monomer; (B) a (meth)acrylic polymer having a glass transition temperature of 80°C or higher, the main component of which is an alkyl (meth)acrylate ester; (C) Crosslinker The document describes a pressure-sensitive toner for protective sheets, which is obtained by crosslinking a crosslinkable composition containing 100 parts by weight of component (A) and 5 to 20 parts by weight of component (B) to produce a gel fraction of 80% or more. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2021-018421 [Patent Document 2] Japanese Patent Application Laid-Open No. 2005-146151 Summary of the Invention [Problem to be solved by the invention]

[0005] The object of the present invention is to provide a pressure-sensitive toner having toner particles containing a composite resin made of a styrene-based resin and a (meth)acrylic acid ester-based resin, wherein the difference between the lowest and highest glass transition temperatures of the composite resin is 30°C or more, and which has excellent adhesiveness, resistance to tearing during peeling, and resistance to hot offset compared to toner particles having a gel fraction of less than 1.0% by mass or more than 8.0% by mass. [Means for solving the problem]

[0006] Means for solving the above problems include the following aspects. <1> A pressure-sensitive toner having toner particles containing a composite resin consisting of a styrene-based resin and a (meth)acrylic acid ester-based resin, wherein the difference between the lowest and highest glass transition temperatures of the composite resin is 30°C or more, and the gel fraction of the toner particles is 1.0% by mass or more and 8.0% by mass or less. <2> The melt viscosity at 100°C is 4,000 Pa·s or more and 20,000 Pa·s or less. <1> The pressure-sensitive toner according to claim 1. <3> The toner particles are fused and coalesced particles of a particle group containing at least particles of the composite resin. <1> or <2> The pressure-sensitive toner according to claim 1. <4> The mass ratio of the styrene-based resin to the (meth)acrylic acid ester-based resin in the composite resin is 20:80 to 80:20. <1> ~ <3> 10. The pressure-sensitive toner according to any one of the preceding items. <5> The ratio Y / X of the gel fraction X in the composite resin to the gel fraction Y in the toner particles satisfies 0.8≦X / Y≦80. <1> ~ <4> 10. The pressure-sensitive toner according to any one of the preceding items. <6> The weight average molecular weight of the composite resin is 50,000 or more and 500,000 or less. <1> ~ <5> 10. The pressure-sensitive toner according to any one of the preceding items. <7> The weight average molecular weight of the composite resin is 100,000 or more and 350,000 or less. <6> The pressure-sensitive toner according to claim 1. <8> The composite resin is a resin having a crosslinked structure. <1> ~ <7> 10. The pressure-sensitive toner according to any one of the preceding items. <9> The acrylic ester resin is a resin having a crosslinked structure. <8> The pressure-sensitive toner according to claim 1. <10> The content of the composite resin in the toner particles is 65% by mass or more and 90% by mass or less with respect to the total mass of the toner particles. <1> ~ <9> 10. The pressure-sensitive toner according to any one of the preceding items. <11> The toner particles have a volume average particle size of 4 μm or more and 12 μm or less. <1> ~ <10> 10. The pressure-sensitive toner according to any one of the preceding items. <12> The gel fraction of the composite resin is 0.1% by mass or more and 2% by mass or less. <1> ~ <11> 10. The pressure-sensitive toner according to any one of the preceding items. <13> <1> ~ <12> a placement means for storing the pressure-sensitive toner described in any one of the above and placing the pressure-sensitive toner on a recording medium, and a pressing means for folding and pressing the recording medium, or for stacking and pressing the recording medium and another recording medium together. <14> <1> ~ <12> 1. A method for producing a printed matter, comprising: a step of placing the pressure-sensitive toner on a recording medium using the pressure-sensitive toner described in any one of the above; and a step of folding and pressing the recording medium, or folding and pressing the recording medium and another recording medium together. <15> The folded recording medium is, on the opposing surfaces, <1> ~ <12> A printed matter adhered with the pressure-sensitive toner according to any one of the above items. <16> The stacked recording media are arranged on opposing surfaces. <1> ~ <12> A printed matter adhered with the pressure-sensitive toner according to any one of the above items. [Effects of the Invention]

[0007] <1> , <3> or <8> According to the invention, a pressure-sensitive toner is provided which has toner particles containing a composite resin made of a styrene-based resin and a (meth)acrylic acid ester-based resin, and in which the difference between the lowest and highest glass transition temperatures of the composite resin is 30°C or more, the pressure-sensitive toner having excellent adhesion, resistance to tearing during peeling, and resistance to hot offset, compared to toner particles having a gel fraction of less than 1.0% by mass or more than 8.0% by mass. <2> According to the present invention, a pressure-sensitive toner having a melt viscosity at 100°C of less than 4,000 Pa·s or more than 20,000 Pa·s is provided which has better adhesiveness, resistance to tearing during peeling, and resistance to hot offset. <4> According to the invention, a pressure-sensitive toner having superior adhesiveness and hot offset suppression properties is provided, compared to when the mass ratio of the styrene-based resin to the (meth)acrylic acid ester-based resin in the composite resin is greater than 0 and less than 20: greater than 80 and less than 100, or greater than 80 and less than 100: greater than 0 and less than 20. <5> According to the invention related to (1), a pressure-sensitive toner is provided which is superior in the ability to suppress breakage during peeling compared to a case in which the ratio Y / X of the gel fraction X in the composite resin to the gel fraction Y in the toner particles satisfies X / Y<0.8 or X / Y>80. <6> According to the present invention, a pressure-sensitive toner is provided which is superior in adhesiveness, resistance to tearing during peeling, and resistance to hot offset compared to when the weight-average molecular weight of the composite resin is less than 50,000 or more than 500,000. <7> According to the present invention, a pressure-sensitive toner is provided which is superior in adhesiveness, resistance to tearing during peeling, and resistance to hot offset compared to when the weight-average molecular weight of the composite resin is less than 100,000 or more than 350,000. <9> According to the invention, a pressure-sensitive toner is provided which is superior in adhesiveness, resistance to tearing during peeling, and resistance to hot offset compared to when the styrene-based resin alone is a resin having a crosslinked structure. <10> According to the present invention, a pressure-sensitive toner is provided which is superior in adhesion, resistance to tearing during peeling, and resistance to hot offset compared to when the content of the composite resin in the toner particles is less than 65% by mass or more than 90% by mass relative to the total mass of the toner particles. <11> According to the invention, a pressure-sensitive toner having superior adhesiveness is provided compared to when the volume average particle size of the toner particles is less than 4 μm or more than 12 μm. <12> According to the present invention, a pressure-sensitive toner is provided which is superior in adhesion, resistance to tearing during peeling, and resistance to hot offset compared to when the gel fraction of the composite resin is less than 0.1% by mass or more than 2% by mass. <13> , <14> , <15> or <16> According to the invention, there is provided a device for producing a printed matter, a method for producing a printed matter, or a printed matter that has excellent adhesion, resistance to tearing during peeling, and resistance to hot offset, compared to when a pressure-sensitive toner having a gel fraction of less than 1.0 mass % or more than 8.0 mass % of the toner particles is used, the pressure-sensitive toner having toner particles containing a composite resin made of a styrene-based resin and a (meth)acrylic acid ester-based resin, and the difference between the lowest and highest glass transition temperatures of the composite resin is 30°C or more. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a schematic diagram illustrating an example of a printed matter manufacturing apparatus according to an embodiment of the present invention. [Figure 2] FIG. 10 is a schematic diagram illustrating another example of a printed matter manufacturing apparatus according to the present embodiment. [Figure 3] FIG. 10 is a schematic diagram illustrating another example of a printed matter manufacturing apparatus according to the present embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present embodiment will be described below. These descriptions and examples are intended to illustrate the embodiment and are not intended to limit the scope of the embodiment.

[0010] In this embodiment, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively.

[0011] In the numerical ranges described in this embodiment in stages, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this embodiment, the upper or lower limit value of the numerical range may be replaced with the value shown in the examples.

[0012] In this embodiment, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.

[0013] When the present embodiment is described with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. Furthermore, the sizes of the components in each drawing are conceptual, and the relative size relationships between the components are not limited to these.

[0014] In this embodiment, each component may contain multiple types of corresponding substances. When referring to the amount of each component in the composition in this embodiment, if multiple types of substances corresponding to each component are present in the composition, the total amount of the multiple types of substances present in the composition is used unless otherwise specified.

[0015] In the present embodiment, the composition may contain multiple types of particles corresponding to each component. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component means the value for a mixture of the multiple types of particles present in the composition, unless otherwise specified.

[0016] In this embodiment, the expression "(meth)acrylic" means that it can mean either "acrylic" or "methacrylic".

[0017] In this embodiment, the "toner for developing electrostatic images" is also referred to simply as "toner," and the "electrostatic image developer" is also referred to simply as "developer."

[0018] In this embodiment, a printed matter formed by folding a recording medium and adhering the opposing surfaces together, or a printed matter formed by overlapping two or more recording media and adhering the opposing surfaces together, is referred to as a "press-bonded printed matter."

[0019] <Pressure-sensitive toner> The pressure-sensitive toner according to this embodiment has toner particles containing a composite resin made of a styrene-based resin and a (meth)acrylic acid ester-based resin, wherein the difference between the lowest and highest glass transition temperatures of the composite resin is 30°C or more, and the gel fraction of the toner particles is 1.0% by mass or more and 8.0% by mass or less.

[0020] When using electrophotography as a pressure-sensitive toner to produce pressure-bonded postcards, etc., uneven melting of the pressure-sensitive toner components occurs when fixing with a fixing machine, and in recent years, when mailing in summer environments, the peelability of the recording medium deteriorates, resulting in tearing of the recording medium. The pressure-sensitive toner according to this embodiment has excellent adhesive properties due to the toner particles containing a composite resin consisting of a styrene-based resin and a (meth)acrylic acid ester-based resin. In addition, by setting the gel fraction of the toner particles to 8.0% by mass or less, excessive adhesion does not occur when the adhesive surface is peeled off even in the extremely hot summer environment, improving peelability and suppressing tearing of the recording medium during peeling. Furthermore, it is estimated that by setting the gel fraction of the toner particles to 1.0% by mass or more, it is possible to control the melt viscosity during toner fixation and thereby suppress hot offset. Hot offset refers to a phenomenon in which toner melts excessively and adheres to the fixing member when a toner image is fixed.

[0021] The components, structure, and properties of the pressure-sensitive toner according to this embodiment will be described in detail below. In the following description, unless otherwise specified, "styrene-based resin" means "styrene-based resin containing 50% by mass or more of styrene-based monomers as polymerization components," and "(meth)acrylic acid ester-based resin" means "(meth)acrylic acid ester-based resin containing 50% by mass or more of (meth)acrylic acid ester compounds as polymerization components." The (meth)acrylic compound may be any compound having a (meth)acrylic group, and examples thereof include (meth)acrylate compounds, (meth)acrylamide compounds, (meth)acrylic acid, and (meth)acrylonitrile.

[0022] -Melt viscosity at 100℃- From the viewpoints of adhesiveness, resistance to tearing during peeling, and resistance to hot offset, the pressure-sensitive toner according to this embodiment preferably has a melt viscosity at 100°C of 4,000 Pa·s or more and 20,000 Pa·s or less, more preferably 5,000 Pa·s or more and 18,000 Pa·s or less, even more preferably 6,000 Pa·s or more and 16,000 Pa·s or less, and particularly preferably 7,000 Pa·s or more and 14,000 Pa·s or less.

[0023] The melt viscosity of the toner is measured as follows. Using a high-speed flow tester CFT-500 (Shimadzu Corporation), the diameter of the die hole was set to 0.5 mm and the pressure load was set to 0.98 MPa (10 kg / cm 2 ), and the heating rate was 1°C / min. 3 When the sample (toner) is melted and allowed to flow, the viscosity is measured at a temperature corresponding to half the height from the start point of the flow to the end point.

[0024] (toner particles) The toner particles contain a composite resin consisting of a styrene-based resin and an acrylic ester-based resin, and the difference between the lowest and highest glass transition temperatures of the composite resin is 30°C or more, and the gel fraction is 1.0% by mass or more and 8.0% by mass or less. The toner particles are preferably particles formed by at least fusing and coalescing particles of the composite resin, and more preferably particles formed by aggregating and fusing and coalescing particles of the composite resin.

[0025] -Gel fraction of toner particles and composite resin- The gel fraction of the toner particles is 1.0% by mass or more and 8.0% by mass or less, and from the viewpoints of adhesiveness, resistance to tearing during peeling, and resistance to hot offset, it is preferably 1.5% by mass or more and 6.0% by mass or less, and more preferably 2.0% by mass or more and 5.0% by mass or less. The gel fraction of the toner particles can be easily adjusted by adjusting the amount of crosslinked structure of the composite resin, the amount of chain transfer agent used, the amount of insoluble components such as a release agent, and the amount of aggregating agent used.

[0026] From the viewpoints of adhesion, resistance to tearing during peeling, and resistance to hot offset, the gel fraction of the composite resin is preferably 0.1% by mass or more and 2% by mass or less, more preferably 0.3% by mass or more and 2% by mass or less, and particularly preferably 0.3% by mass or more and 1.5% by mass or less. The gel fraction of the composite resin can be easily adjusted by adjusting the amount of crosslinked structure in the composite resin and the amount of chain transfer agent used.

[0027] From the viewpoints of adhesiveness, resistance to tearing during peeling, and resistance to hot offset, the ratio Y / X of the gel fraction X in the composite resin to the gel fraction Y in the toner particles preferably satisfies 0.8≦X / Y≦80, more preferably 1≦X / Y≦50, and particularly preferably 1.5≦X / Y≦20.

[0028] The gel fraction is measured as follows. The gel fraction is measured in accordance with JIS K6796 (1998). Specifically, the mass of the measurement sample (toner particles, composite resin, etc.) is measured, and this is the mass before solvent extraction. Next, the measurement sample is immersed in tetrahydrofuran for 24 hours, and then the solvent is filtered, and the remaining residue is filtered and measured. This weight is the mass after extraction. Then, the gel fraction is calculated according to the following formula. Formula: Gel fraction (%) = 100 × (mass after solvent extraction) / (mass before solvent extraction) In addition, when the pressure-sensitive toner is a toner containing external additives, the external additives are removed by ultrasonic treatment for 20 minutes with a mixed solution of ion-exchanged water and a surfactant, and the measurement is performed after removing the surfactant and drying and recovering the toner particles. Note that the external additive removal treatment can be repeated until the external additives are completely removed.

[0029] -Volume average particle size of toner particles- The volume average particle size (D50v) of the toner particles is preferably 4 μm or more, more preferably 5 μm or more, and even more preferably 6 μm or more, from the viewpoint of ease of handling the toner particles, and is preferably 12 μm or less, more preferably 10 μm or less, from the viewpoint of ease of phase transition of the entire toner particles due to pressure.

[0030] The volume-average particle size (D50v) of toner particles is measured using a Coulter Multisizer II (Beckman Coulter) with a 100 μm aperture. 0.5 mg to 50 mg of toner particles are dispersed in 2 mL of a 5% by weight aqueous solution of sodium alkylbenzene sulfonate, then mixed with 100 mL to 150 mL of electrolyte (ISOTON-II, Beckman Coulter), and dispersed for 1 minute using an ultrasonic disperser. The resulting dispersion is used as the sample. The particle sizes of 50,000 particles with diameters between 2 μm and 60 μm in the sample are measured. The volume-average particle size (D50v) is defined as the particle size at which the cumulative 50% of the particle size distribution is calculated from the smallest diameter.

[0031] <<Composite resin>> The toner particles contain a composite resin made of a styrene-based resin and an acrylic ester-based resin, and the difference between the lowest and highest glass transition temperatures of the composite resin is 30° C. or more. Furthermore, the composite resin in this embodiment may be an alloy resin in which a styrene-based resin and an acrylic ester-based resin are simply mixed, or may be a resin in which a styrene-based resin and an acrylic ester-based resin are bonded by a chemical bond (such as a covalent bond).

[0032] The composite resin preferably has pressure phase transition properties. Here, "having pressure phase transition properties" means that the following formula 1 is satisfied. Formula 1...10℃≦T1-T2 In Equation 1, 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.

[0033] The temperature T1 and the temperature T2 are determined as follows. The substance to be measured is compressed to prepare a pellet-shaped sample. The pellet-shaped sample is placed in a flow tester (Shimadzu Corporation, CFT-500), and the applied pressure is fixed at 1 MPa, and the viscosity at 1 MPa is measured against temperature. From the resulting viscosity graph, the temperature T1 at which the viscosity becomes 10,000 Pa·s at an applied pressure of 1 MPa is determined. Temperature T2 is determined in the same manner as for temperature T1, except that the applied pressure of 1 MPa is changed to 10 MPa.

[0034] -Crosslinking agent- The composite resin is preferably a resin having a crosslinked structure. The crosslinked structure may be possessed by either the styrene-based resin or the (meth)acrylic acid ester-based resin. However, from the viewpoints of adhesiveness, resistance to tearing during peeling, and resistance to hot offset, it is preferable that at least the (meth)acrylic acid ester-based resin has the crosslinked structure. By adjusting the amount of crosslinked structure, the amount of gel fraction of the composite resin can be easily adjusted. The crosslinked structure is preferably formed using a crosslinking agent during polymerization. As the crosslinking agent, preferred examples include difunctional or higher ethylenically unsaturated compounds, more preferred examples include difunctional or higher (meth)acrylic acid esters or difunctional or higher styrene-based monomers, even more preferred examples include difunctional or higher (meth)acrylic acid esters, and particularly preferred examples include di(meth)acrylic acid esters. The functionality of the ethylenically unsaturated group of the crosslinking agent is preferably 2 to 6, more preferably 2 or 3, and particularly preferably 2.

[0035] Examples of the ethylenically unsaturated group include functional groups such as a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, and a (meth)acryloyl group. Among these, a (meth)acryloyl group is preferred from the viewpoint of reactivity.

[0036] As the crosslinking agent, it is preferable to use a bifunctional monomer having two ethylenically unsaturated groups. Examples of the bifunctional monomer having two ethylenically unsaturated groups include aliphatic di(meth)acrylates and aromatic di(meth)acrylates. Aliphatic di(meth)acrylate is a compound in which two hydrogen atoms of an aliphatic hydrocarbon are substituted with (meth)acryloyl groups. The structure of the aliphatic di(meth)acrylate may be either branched or linear, or may have a cyclic structure. The carbon number of the aliphatic di(meth)acrylate (excluding the carbon number of the (meth)acryloyl group) is preferably 3 or more and 20 or less, more preferably 5 or more and 15 or less, and even more preferably 8 or more and 12 or less. Specific examples of the aliphatic di(meth)acrylate 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, decanediol di(meth)acrylate, 2,2-bis(4-(meth)acryloxypolyethoxypolypropoxyphenyl)propane, and bisphenol A diglycidyl ether di(meth)acrylate.

[0037] An aromatic di(meth)acrylate is a compound containing an aromatic group and two (meth)acryloyl groups. The aromatic di(meth)acrylate may have a branched or linear structure, or may have a cyclic structure. The aromatic di(meth)acrylate preferably has 3 or more and 20 or less carbon atoms (excluding the number of carbon atoms in the (meth)acryloyl group), more preferably 5 or more and 15 or less, and even more preferably 8 or more and 12 or less. Examples of di- or higher functional styrene-based monomers include divinylbenzene.

[0038] In addition to these, tri- or higher functional monomers include trimethylolpropane triacrylate.

[0039] The amount of the crosslinking agent-derived structural units in the composite resin is not particularly limited as long as it satisfies the gel fraction range. In particular, the amount of the crosslinking agent-derived structural units in the composite resin is preferably 0.05% by mass to 1.00% by mass, more preferably 0.10% by mass to 0.65% by mass, and particularly preferably 0.15% by mass to 0.45% by mass, relative to the total mass of the composite resin. The amount of crosslinking agent added during polymerization is not particularly limited, but the ratio of the amount of crosslinking agent added to the amount of chain transfer agent added (amount of crosslinking agent added / amount of chain transfer agent added) to the amount of crosslinking agent added during polymerization to the amount of chain transfer agent added (described later) is preferably 0.1 or more and 2.0 or less, more preferably 0.3 or more and 1.0 or less, and particularly preferably 0.3 or more and 0.8 or less, from the viewpoints of adhesion, resistance to tearing during peeling, and resistance to hot offset.

[0040] - Chain transfer agent - The toner particles preferably contain a chain transfer agent. The composite resin preferably contains a resin obtained by polymerization in the coexistence of a chain transfer agent. The composite resin preferably contains a structural unit derived from a chain transfer agent. Chain transfer agents include compounds containing a thiol group (thiols). The chain transfer agent is preferably a thiol containing a hydrocarbon group having 4 to 20 carbon atoms. The hydrocarbon group contained in the thiol may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The hydrocarbon group contained in the thiol is preferably an aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be either branched or straight-chain. Specific examples of the chain transfer agent include hexylthiol, heptanethiol, octanethiol, nonanethiol, decanethiol, dodecanethiol, tetradecanethiol, and hexadecanethiol, and dodecanethiol is more preferred.

[0041] The amount of the structural units derived from the chain transfer agent in the composite resin is not particularly limited, but is preferably an amount that satisfies a preferred ratio of the amount of the crosslinking agent added to the amount of the chain transfer agent added.

[0042] -Styrene-based resin- The styrene-based resin preferably contains styrene and other vinyl monomers as polymerization components.

[0043] The mass proportion of styrene in all the polymerization components of the styrene-based resin is preferably 60 mass% or more, more preferably 70 mass% or more, and even more preferably 75 mass% or more, from the viewpoint of suppressing fluidization of the composite resin in an unpressurized state, and is preferably 95 mass% or less, more preferably 90 mass% or less, and even more preferably 85 mass% or less, from the viewpoint of forming composite resin particles that are prone to phase transition under pressure.

[0044] Examples of styrene-based 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. One type of styrene-based monomer may be used alone, or two or more types may be used in combination.

[0045] The acrylic monomer is preferably at least one acrylic monomer selected from the group consisting of (meth)acrylic acid and (meth)acrylic acid esters. Examples of the (meth)acrylic acid esters include (meth)acrylic acid alkyl esters, (meth)acrylic acid carboxy-substituted alkyl esters, (meth)acrylic acid hydroxy-substituted alkyl esters, (meth)acrylic acid alkoxy-substituted alkyl esters, and di(meth)acrylic acid esters. The acrylic monomers may be used alone or in combination of two or more.

[0046] Examples of (meth)acrylic acid alkyl esters 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 the carboxy-substituted alkyl (meth)acrylate include 2-carboxyethyl (meth)acrylate. Examples of hydroxy-substituted alkyl (meth)acrylates 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 the alkoxy-substituted alkyl (meth)acrylate include 2-methoxyethyl (meth)acrylate.

[0047] Examples of the (meth)acrylic acid ester include 2-(diethylamino)ethyl (meth)acrylate, benzyl (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate.

[0048] Examples of other vinyl monomers constituting the styrene-based resin include, in addition to styrene-based monomers and acrylic 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.

[0049] From the viewpoints of adhesiveness and resistance to tearing during peeling, the styrene-based resin preferably contains a (meth)acrylic acid ester as another vinyl monomer, more preferably a (meth)acrylic acid alkyl ester, even more preferably a (meth)acrylic acid alkyl ester having an alkyl group with 2 to 10 carbon atoms, still more preferably a (meth)acrylic acid alkyl ester having an alkyl group with 4 to 8 carbon atoms, and particularly preferably 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.

[0050] The mass proportion of the (meth)acrylic acid ester in all the 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 fluidization of the composite resin in an unpressurized state, and is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, from the viewpoint of forming a composite resin that easily undergoes phase transition under pressure. The (meth)acrylic acid ester here is preferably a (meth)acrylic acid alkyl ester, more preferably a (meth)acrylic acid alkyl ester having 2 to 10 carbon atoms in the alkyl group, and even more preferably a (meth)acrylic acid alkyl ester having 4 to 8 carbon atoms in the alkyl group.

[0051] It is particularly preferable that the styrene-based resin contains at least one of n-butyl acrylate and 2-ethylhexyl acrylate as a polymerization component, and the total amount of n-butyl acrylate and 2-ethylhexyl acrylate in all 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 fluidization of the composite resin in an unpressurized state, and is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, from the viewpoint of forming a composite resin that is prone to phase transition under pressure.

[0052] The weight average molecular weight of the styrene resin is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more, from the viewpoint of suppressing fluidization of the composite resin in an unpressurized state, and is preferably 50,000 or less, more preferably 45,000 or less, and even more preferably 40,000 or less, from the viewpoint of forming a composite resin that easily undergoes phase transition under pressure.

[0053] The weight-average molecular weight of the resin is measured by gel permeation chromatography (GPC). Molecular weight measurement by GPC is performed using a Tosoh HLC-8120GPC GPC apparatus, a Tosoh TSKgel SuperHM-M (15 cm) column, and tetrahydrofuran as the solvent. The weight-average molecular weight of the resin is calculated using a molecular weight calibration curve prepared using monodisperse polystyrene standard samples.

[0054] 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 preventing the composite resin from fluidizing when no pressure is applied; and is preferably 110°C or lower, more preferably 100°C or lower, and even more preferably 90°C or lower, from the viewpoint of forming composite resin particles that are prone to phase transition when pressure is applied.

[0055] In the present disclosure, the glass transition temperature of a resin is determined from a differential scanning calorimetry (DSC) curve obtained by DSC measurement. More specifically, it is determined according to the "extrapolated glass transition onset temperature" described in JIS K7121:1987 "Method for measuring transition temperatures of plastics."

[0056] The glass transition temperature of a resin is controlled by the type and polymerization ratio of the polymerization components. The glass transition temperature tends to be lower as the density of flexible units such as methylene groups, ethylene groups, and oxyethylene groups contained in the main chain increases, and tends to be higher as the density of rigid units such as aromatic rings and cyclohexane rings contained in the main chain increases. In addition, the glass transition temperature tends to be lower as the density of aliphatic groups in the side chain increases.

[0057] The mass proportion of the styrene-based resin in the entire composite resin particle is preferably 55 mass% or more, more preferably 60 mass% or more, and even more preferably 65 mass% or more, from the viewpoint of preventing the composite resin particle from fluidizing when no pressure is applied, and is preferably 80 mass% or less, more preferably 75 mass% or less, and even more preferably 70 mass% or less, from the viewpoint of forming composite resin particles that are prone to phase transition when pressure is applied.

[0058] -(Meth)acrylic ester resin- The (meth)acrylic acid ester-based resin preferably contains a (meth)acrylic acid ester as a polymerization component and an acrylic acid ester as a polymerization component. The mass proportion of the (meth)acrylic acid ester in all the polymerization components of the (meth)acrylic acid ester-based resin is, for example, 90 mass% or more, more preferably 95 mass% or more, even more preferably 98 mass% or more, and still more preferably 100 mass%.

[0059] Examples of the (meth)acrylic acid ester include (meth)acrylic acid alkyl ester, (meth)acrylic acid carboxy-substituted alkyl ester, (meth)acrylic acid hydroxy-substituted alkyl ester, (meth)acrylic acid alkoxy-substituted alkyl ester, and di(meth)acrylic acid ester.

[0060] Examples of (meth)acrylic acid alkyl esters 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 the carboxy-substituted alkyl (meth)acrylate include 2-carboxyethyl (meth)acrylate. Examples of hydroxy-substituted alkyl (meth)acrylates 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 the alkoxy-substituted alkyl (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.

[0061] Examples of the (meth)acrylic acid ester include 2-(diethylamino)ethyl (meth)acrylate, benzyl (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate.

[0062] The (meth)acrylic acid ester may be used alone or in combination of two or more kinds.

[0063] As the (meth)acrylic acid ester, from the viewpoint of forming composite resin particles that easily undergo phase transition under pressure and have excellent adhesiveness, and from the viewpoint of producing a pressure-sensitive toner that has excellent adhesiveness and releasability even when bonding thin papers together and that is less likely to contaminate the pressure bonding device used to bond the thin papers, (meth)acrylic acid alkyl esters are preferred, (meth)acrylic acid alkyl esters having an alkyl group with 2 to 10 carbon atoms are more preferred, (meth)acrylic acid alkyl esters having an alkyl group with 4 to 8 carbon atoms are even more preferred, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred. From the viewpoint of forming composite resin particles that easily 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 polymerization components.

[0064] The mass proportion of the (meth)acrylic acid alkyl ester in all the polymerization components of the (meth)acrylic acid ester-based resin is preferably 90 mass % or more, more preferably 95 mass % or more, even more preferably 98 mass % or more, and still more preferably 100 mass % from the viewpoint of forming composite resin particles that easily undergo phase transition under pressure and have excellent adhesiveness. As the (meth)acrylic acid alkyl ester here, a (meth)acrylic acid alkyl ester having an alkyl group with 2 to 10 carbon atoms is preferred, and a (meth)acrylic acid alkyl ester having an alkyl group with 4 to 8 carbon atoms is more preferred.

[0065] The (meth)acrylic acid ester resin preferably contains at least two kinds of (meth)acrylic acid esters as polymerization components. When the (meth)acrylic acid ester-based 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 having 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-based 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 viewpoints of adhesion, resistance to tearing during peeling, and resistance to hot offset.

[0066] When the (meth)acrylic acid ester-based resin contains at least two kinds of (meth)acrylic acid esters as polymerization components, it is preferable that the two kinds of (meth)acrylic acid esters having the largest mass proportions among the at least two kinds of (meth)acrylic acid esters contained as polymerization components in the (meth)acrylic acid ester-based resin are (meth)acrylic acid alkyl esters. Here, the (meth)acrylic acid alkyl esters are preferably (meth)acrylic acid alkyl esters having an alkyl group with 2 to 10 carbon atoms, and more preferably (meth)acrylic acid alkyl esters having an alkyl group with 4 to 8 carbon atoms.

[0067] When a (meth)acrylic acid ester-based resin contains at least two types of (meth)acrylic acid esters as polymerization components, and the two types of (meth)acrylic acid esters with 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-based resin are (meth)acrylic acid alkyl esters, the difference in the number of carbon atoms in the alkyl groups of the two types of (meth)acrylic acid alkyl esters is preferably 1 or more and 4 or less, more preferably 2 or more and 4 or less, and even more preferably 3 or 4, from the viewpoint of forming a composite resin that is easily rearranged under pressure and has excellent adhesiveness.

[0068] From the viewpoint of forming a composite resin that easily undergoes phase transition under pressure and has excellent adhesiveness, the (meth)acrylic acid ester resin preferably contains n-butyl acrylate and 2-ethylhexyl acrylate as polymerization components, and it is particularly preferred that the two (meth)acrylic acid esters contained in the (meth)acrylic acid ester resin as polymerization components have the largest mass proportions of 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 mass% or more, more preferably 95 mass% or more, even more preferably 98 mass% or more, and even more preferably 100 mass%.

[0069] The (meth)acrylic acid ester resin may contain a vinyl monomer other than (meth)acrylic acid ester as a polymerization component. Examples of vinyl monomers other than (meth)acrylic acid ester include (meth)acrylic acid; styrene; styrene-based 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 alone or in combination of two or more.

[0070] When the (meth)acrylic acid ester-based resin contains a vinyl monomer other than a (meth)acrylic acid ester as a polymerization component, the vinyl monomer other than a (meth)acrylic acid ester is preferably at least one of acrylic acid and methacrylic acid, and more preferably acrylic acid.

[0071] 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 fluidization of the composite resin in an unpressurized state, and is preferably 250,000 or less, more preferably 220,000 or less, and even more preferably 200,000 or less, from the viewpoint of forming a composite resin that is prone to phase transition under pressure.

[0072] 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 a composite resin that easily undergoes phase transition under pressure, and is preferably -90°C or higher, more preferably -80°C or higher, and even more preferably -70°C or higher, from the viewpoint of preventing the composite resin from fluidizing in an unpressurized state.

[0073] The mass proportion of the (meth)acrylic acid ester resin in the entire composite resin is preferably 20 mass% or more, more preferably 25 mass% or more, and even more preferably 30 mass% or more, from the viewpoint of forming a composite resin that is prone to phase transition under pressure, and is preferably 45 mass% or less, more preferably 40 mass% or less, and even more preferably 35 mass% or less, from the viewpoint of preventing the composite resin from fluidizing in an unpressurized state.

[0074] The total amount of the styrene-based resin and the (meth)acrylic acid ester-based resin contained in the composite resin is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 100% by mass, based on the total amount of the composite resin.

[0075] -Other resins- The composite resin may contain, for example, polystyrene, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, non-vinyl resin such as modified rosin, etc. These resins may be used alone or in combination of two or more.

[0076] - Mass ratio of styrene-based resin to (meth)acrylic acid ester-based resin - From the viewpoints of adhesion, resistance to tearing during peeling, and resistance to hot offset, 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 preferably 80:20 to 20:80, more preferably 75:25 to 25:75, even more preferably 70:30 to 30:70, and particularly preferably 65:35 to 35:65.

[0077] -Glass transition temperature- The difference between the lowest and highest glass transition temperatures of the composite resin is 30°C or more. Here, when the composite resin having at least two glass transition temperatures contains a styrene-based resin and a (meth)acrylic acid ester-based resin, one of the glass transition temperatures is presumed to be the glass transition temperature of the styrene-based resin, and the other is presumed to be the glass transition temperature of the (meth)acrylic acid ester-based resin.

[0078] The composite resin may have three or more glass transition temperatures, but preferably has two glass transition temperatures. Examples of the composite resin having two glass transition temperatures include a composite resin containing only a styrene resin and a (meth)acrylic acid ester resin, and a composite resin containing a small amount of other resins than the styrene resin and the (meth)acrylic acid ester resin (for example, a composite resin containing 5% by mass or less of the other resins relative to the total mass of the composite resin).

[0079] When the composite resin has at least two glass transition temperatures and the difference between the lowest and highest glass transition temperatures is 30° C. or more, the difference between the lowest and highest glass transition temperatures is preferably 40° C. or more, more preferably 50° C. or more, and even more preferably 60° C. or more, from the viewpoints of adhesion, resistance to breakage during peeling, and resistance to hot offset. The upper limit of the difference between the lowest and highest glass transition temperatures is, for example, 140° C. or less, and may be 130° C. or less, or 120° C. or less.

[0080] The lowest glass transition temperature exhibited by the composite resin is preferably 10°C or lower, more preferably 0°C or lower, and even more preferably -10°C or lower, from the viewpoints of adhesion, resistance to breakage during peeling, and resistance to hot offset; and from the viewpoint of preventing the composite resin from fluidizing in an unpressurized state, it is preferably -90°C or higher, more preferably -80°C or higher, and even more preferably -70°C or higher.

[0081] The highest glass transition temperature of the composite 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 preventing the composite resin from fluidizing when not pressurized; and is preferably 70°C or lower, more preferably 65°C or lower, and even more preferably 60°C or lower, from the viewpoint of facilitating phase transition of the composite resin when pressure is applied.

[0082] The glass transition temperature of the composite resin in this embodiment is measured as follows. The composite resin, toner particles, or pressure-sensitive toner to be measured is compressed to prepare a plate-shaped sample, which is then subjected to differential scanning calorimetry (DSC) to obtain a differential scanning calorimetry curve (DSC curve) from which the glass transition temperature is determined. More specifically, the glass transition temperature is determined in accordance with the "extrapolated glass transition onset temperature" described in JIS K7121:1987 "Method for measuring the glass transition temperature of plastics."

[0083] - Weight average molecular weight of composite resin - From the viewpoints of adhesiveness, resistance to tearing during peeling, and resistance to hot offset, the weight average molecular weight of the composite resin is preferably 50,000 or more and 500,000 or less, more preferably 80,000 or more and 400,000 or less, and even more preferably 100,000 or more and 350,000 or less.

[0084] -Composite resin content- From the viewpoints of adhesiveness, resistance to tearing during peeling, and resistance to hot offset, the content of the composite resin in the toner particles is preferably 20% by mass or more and 95% by mass or less, more preferably 50% by mass or more and 90% by mass or less, and even more preferably 65% ​​by mass or more and 90% by mass or less, relative to the total mass of the toner particles.

[0085] <<Release Agent>> The toner particles preferably contain a release agent. In addition, the pressure-sensitive toner of this exemplary embodiment may have a gel fraction of toner particles adjusted by the type and content of a release agent. Examples of release agents include hydrocarbon waxes, natural waxes such as carnauba wax, rice wax, and candelilla wax, synthetic or mineral / petroleum waxes such as montan wax, and ester waxes such as fatty acid esters and montanic acid esters, but are not limited thereto.

[0086] The melting temperature of the release agent is preferably 50°C or higher and 110°C or lower, and more preferably 60°C or higher and 100°C or lower. The melting temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC) by using the "melting peak temperature" as described in the method for determining the melting temperature in JIS K 7121-1987 "Method for measuring transition temperatures of plastics."

[0087] The content of the release agent is preferably from 0.1% by mass to 8.0% by mass, more preferably from 0.2% by mass to 5.0% by mass, and particularly preferably from 0.3% by mass to 3.0% by mass, based on the total mass of the toner particles, from the viewpoints of adhesiveness, resistance to tearing during peeling, and resistance to hot offset.

[0088] <<Coloring agent>> The toner particles may include a colorant. Examples of colorants include carbon black, chrome yellow, Hansa Yellow, benzidine yellow, threne 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, lithol red, rhodamine B lake, lake red C, pigment red, rose bengal, aniline blue, ultramarine blue, and the like. Examples of the dye include various pigments such as phosphorus blue, chalco oil blue, methylene blue chloride, phthalocyanine blue, pigment blue, phthalocyanine green, and malachite green oxalate, and various dyes such as acridine-based, xanthene-based, azo-based, benzoquinone-based, azine-based, anthraquinone-based, thioindigo-based, dioxazine-based, thiazine-based, azomethine-based, indigo-based, phthalocyanine-based, aniline black-based, polymethine-based, triphenylmethane-based, diphenylmethane-based, and thiazole-based dyes. The colorant may be used alone or in combination of two or more kinds.

[0089] The colorant may be surface-treated as needed, or may be used in combination with a dispersant. Furthermore, a plurality of colorants may be used in combination.

[0090] The content of the colorant is preferably from 0.01% by mass to 30% by mass, and more preferably from 0.1% by mass to 15% by mass, based on the total mass of the toner particles.

[0091] -Other additives- Examples of other additives include well-known additives such as magnetic materials, charge control agents, inorganic powders, etc. These additives are contained in the toner particles as internal additives.

[0092] -Characteristics of toner particles, etc.- The toner particles may be toner particles of a single layer structure, or may be toner particles of a so-called core-shell structure composed of a core part (core particle) and a coating layer (shell layer) that coats the core part. Here, the toner particles having a core-shell structure may be composed of, for example, a core containing a binder resin and, if necessary, other additives such as a colorant and a release agent, and a coating layer containing the binder resin.

[0093] Examples of other additives include well-known additives such as magnetic materials, charge control agents, inorganic powders, etc. These additives are contained in the toner particles as internal additives.

[0094] (external additives) The pressure-sensitive toner according to this embodiment contains at least toner particles, and optionally contains an external additive. Examples of external additives include inorganic particles, such as SiO2, TiO2, Al2O3, CuO, ZnO, SnO2, CeO2, Fe2O3, MgO, BaO, CaO, K2O, Na2O, ZrO2, CaO·SiO2, and K2O·(TiO2). n , Al2O3·2SiO2, CaCO3, MgCO3, BaSO4, MgSO4, etc.

[0095] The surfaces of inorganic particles as external additives are preferably 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, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, and aluminum coupling agents. These may be used alone or in combination of two or more. The amount of the hydrophobic treatment agent is usually, for example, 1 part by mass or more and 10 parts by mass or less per 100 parts by mass of the inorganic particles.

[0096] Examples of external additives include resin particles (resin particles such as polystyrene, polymethyl methacrylate (PMMA), and melamine resin), cleaning agents (for example, metal salts of higher fatty acids such as zinc stearate, and particles of fluorine-based polymers).

[0097] The amount of the external additive added is, for example, preferably 0.01% by mass to 10% by mass, and more preferably 0.01% by mass to 5.0% by mass, based on the total mass of the toner particles.

[0098] (Pressure-sensitive toner manufacturing method) The method for producing the pressure-sensitive toner according to the present embodiment is not particularly limited, but A first step of preparing a styrene-based resin particle dispersion liquid in which styrene-based resin particles containing a styrene-based resin are dispersed; a second step of polymerizing a (meth)acrylic ester-based resin in a reaction solution containing the styrene-based resin particle dispersion, a chain transfer agent, a crosslinking agent, and a polymerization component for a (meth)acrylic ester-based resin to form composite resin particles containing a styrene-based resin and a (meth)acrylic ester-based resin; a third step of aggregating the composite resin particles in the composite resin particle dispersion liquid in which the composite resin particles are dispersed to form aggregated particles; a fourth step of heating the aggregated particle dispersion in which the aggregated particles are dispersed to fuse and coalesce the aggregated particles to form toner particles; It is preferred that the compound contains:

[0099] Each step will be described in detail below. The following describes a method for obtaining toner particles that do not contain a colorant or a release agent. A colorant, a release agent, and other additives may be used as needed. When a colorant and a release agent are to be contained in the toner particles, the composite resin particle dispersion, the colorant particle dispersion, and the release agent particle dispersion are mixed together, and then the fourth step is carried out. The colorant particle dispersion and the release agent particle dispersion are prepared, for example, by mixing the materials and then performing a dispersion process using a known disperser.

[0100] -1st process- The first step is a step of preparing a styrene-based resin particle dispersion liquid in which styrene-based resin particles containing a styrene-based resin are dispersed. The 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.

[0101] Examples of the dispersion medium include the same solvents as the aqueous solvents described above.

[0102] Examples of surfactants include anionic surfactants such as sulfate ester salts, sulfonate salts, phosphate esters, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts; and nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Nonionic surfactants may be used in combination with anionic surfactants or cationic surfactants. Among these, anionic surfactants are preferred. The surfactants may be used alone or in combination of two or more.

[0103] Examples of a method for dispersing styrene-based resin particles in a dispersion medium include a method in which the styrene-based resin and the dispersion medium are mixed and stirred using a rotary shear homogenizer, a ball mill with media, a sand mill, a dyno mill, or the like to disperse the mixture.

[0104] Another method for dispersing styrene-based resin particles in a dispersion medium is emulsion polymerization. Specifically, after mixing the polymerization components of the styrene-based resin with a chain transfer agent or a polymerization initiator, an aqueous medium containing a surfactant is further mixed and stirred to prepare an emulsion, and the styrene-based resin is polymerized in the emulsion. In this case, it is preferable to use dodecanethiol as a chain transfer agent.

[0105] The volume average particle size of the styrene-based resin particles dispersed in the styrene-based resin particle dispersion is preferably 100 nm or more and 250 nm or less, more preferably 120 nm or more and 220 nm or less, and even more preferably 150 nm or more and 200 nm or less. The volume average particle diameter of the resin particles contained in the resin particle dispersion is measured using a laser diffraction particle size distribution measuring device (e.g., LA-700 manufactured by Horiba, Ltd.), and the particle diameter at the cumulative 50% in the volume-based particle size distribution calculated from the smallest diameter side is defined as the volume average particle diameter (D50v).

[0106] The content of the styrene-based resin particles contained in the styrene-based 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.

[0107] -Second process- The second step is a step of polymerizing a (meth)acrylic ester resin in a reaction solution containing a styrene-based resin particle dispersion, a chain transfer agent, a crosslinking agent, and polymerization components of a (meth)acrylic ester resin to form the composite resin particles.

[0108] The composite resin particles are preferably resin particles containing a styrene-based resin and a (meth)acrylic acid ester-based resin in a microphase-separated state. The resin particles are produced, for example, by the following method.

[0109] A chain transfer agent, a crosslinking agent, and a polymerization component of a (meth)acrylic ester resin are added to a styrene-based resin particle dispersion, and an aqueous medium is added as needed. Next, while slowly stirring the dispersion, the temperature of the dispersion is heated to a temperature equal to or higher than the glass transition temperature of the styrene-based resin (for example, a temperature 10°C to 30°C higher than the glass transition temperature of the styrene-based resin). Next, while maintaining the temperature, an aqueous medium containing a polymerization initiator is slowly added dropwise, and stirring is continued for an additional long period of time, ranging from 1 hour to 15 hours. In this case, ammonium persulfate is preferably used as the polymerization initiator.

[0110] Although the detailed mechanism is not entirely clear, it is speculated that when the above-mentioned method is adopted, the styrene-based resin particles are impregnated with the monomer and the polymerization initiator, and the (meth)acrylic acid ester is polymerized inside the styrene-based resin particles. As a result, it is speculated that composite resin particles are obtained in which the (meth)acrylic acid ester resin is contained inside the styrene-based resin particles, and the styrene-based resin and the (meth)acrylic acid ester resin form a microphase-separated state inside the particles.

[0111] The volume average particle size of the composite resin particles dispersed in the composite resin particle dispersion is preferably 140 nm or more and 300 nm or less, more preferably 150 nm or more and 280 nm or less, and even more preferably 160 nm or more and 250 nm or less.

[0112] The volume average particle diameter of the composite resin particles is measured using a laser diffraction particle size distribution analyzer (e.g., LA-700 manufactured by Horiba, Ltd.), and the particle diameter at the cumulative 50% in the volume-based particle size distribution calculated from the smallest diameter side is defined as the volume average particle diameter (D50v).

[0113] The content of the composite resin particles contained 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.

[0114] -3rd process- The third step is a step of aggregating the composite resin particles in the composite resin particle dispersion liquid in which the composite resin particles are dispersed to form aggregated particles. The composite resin particles are aggregated in the composite resin particle dispersion to form aggregated particles having a diameter close to that of the target toner particles.

[0115] Specifically, for example, an aggregating agent is added to the composite resin particle dispersion, and the pH of the composite resin particle dispersion is adjusted to be acidic (for example, pH 2 or higher and 5 or lower), and a dispersion stabilizer is added as necessary. After that, the dispersion is heated to a temperature close to the glass transition temperature of the styrene-based resin (for example, the glass transition temperature of the styrene-based resin -30°C or higher and the glass transition temperature -10°C or lower), causing the composite resin particles to aggregate and form aggregated particles.

[0116] In the aggregated particle formation process, an aggregating agent is added to the composite resin particle dispersion at room temperature (e.g., 25°C) while stirring with a rotary shear homogenizer, the pH of the composite resin particle dispersion is adjusted to an acidic value (e.g., pH 2 or more and 5 or less), and a dispersion stabilizer may be added as needed, followed by heating.

[0117] Examples of the flocculant include a surfactant having an opposite polarity to that of the surfactant contained in the composite resin particle dispersion, an inorganic metal salt, and a divalent or higher metal complex. When a metal complex is used as the flocculant, the amount of surfactant used can be reduced, and charging properties can be improved. If necessary, an additive that forms a complex or a similar bond with the metal ions of the flocculant may be used together with the flocculant, and a chelating agent is preferably used as this additive.

[0118] 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. The chelating agent may be a water-soluble chelating agent, such as hydroxycarboxylic acid (e.g., tartaric acid, citric acid, gluconic acid), or aminocarboxylic acid (e.g., iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), or ethylenediaminetetraacetic acid (EDTA). The amount of the chelating agent added is preferably 0.01 parts by mass or more and 5.0 parts by mass or less, and more preferably 0.1 parts by mass or more and less than 3.0 parts by mass, relative to 100 parts by mass of the resin particles.

[0119] -4th process- The fourth step is a step of heating the aggregated particle dispersion in which the aggregated particles are dispersed to fuse and coalesce the aggregated particles, thereby forming toner particles. The aggregated particle dispersion liquid in which the aggregated particles are dispersed is heated, for example, to a temperature equal to or higher than the glass transition temperature of the styrene-based resin (for example, a temperature 10°C to 30°C higher than the glass transition temperature of the styrene-based resin), to fuse and coalesce the aggregated particles and form toner particles.

[0120] The toner particles obtained through the above steps usually have a sea-island structure having a sea phase containing a styrene-based resin and an island phase containing a (meth)acrylic ester-based resin dispersed in the sea phase. In the composite resin particles, the styrene-based resin and the (meth)acrylic ester-based resin are in a state of microphase separation, and it is presumed that in the fusion and coalescence step, the styrene-based resins come together to form the sea phase, and the (meth)acrylic ester-based resins come together to form the island phase.

[0121] The toner particles having a core-shell structure are, for example, a step of further mixing the aggregated particle dispersion and the styrene-based resin particle dispersion after obtaining the aggregated particle dispersion, and aggregating the styrene-based resin particles so that the particles adhere to the surfaces of the aggregated particles, thereby forming second aggregated particles; a step of heating the second aggregate particle dispersion liquid in which the second aggregate particles are dispersed to fuse and coalesce the second aggregate particles, thereby forming toner particles having a core-shell structure; It is manufactured through this process. The toner particles having a core-shell structure obtained through the above process have a shell layer containing a styrene-based resin. A resin particle dispersion in which other types of resin particles are dispersed may be used instead of the styrene-based resin particle dispersion to form a shell layer containing other types of resin.

[0122] After the fusion and coalescence process is completed, the toner particles formed in the solution are subjected to a known washing process, solid-liquid separation process, and drying process to obtain dried toner particles. In the washing process, from the viewpoint of chargeability, it is preferable to perform sufficient substitution washing with ion-exchanged water. In the solid-liquid separation process, from the viewpoint of productivity, it is preferable to perform suction filtration, pressure filtration, etc. In the drying process, from the viewpoint of productivity, it is preferable to perform freeze drying, flash drying, fluidized drying, vibration-type fluidized drying, etc.

[0123] The toner is produced by, for example, adding an external additive to the obtained dry toner particles and mixing them. The mixing can be performed using, for example, a V blender, a Henschel mixer, a Loedige mixer, etc. Furthermore, if necessary, coarse particles may be removed from the toner using a vibrating sieve, an air sieve, etc.

[0124] <Cartridge> The cartridge according to the present embodiment is a cartridge that contains the pressure-sensitive toner according to the present embodiment and is detachably attached to a printing production device. When the cartridge is attached to the printing production device, a supply pipe connects the cartridge to a placement device of the printing production device that places the pressure-sensitive toner on a recording medium. Pressure-sensitive toner is supplied from the cartridge to the placement means, and when the pressure-sensitive toner contained in the cartridge runs low, the cartridge is replaced.

[0125] <Printed matter manufacturing device, printed matter manufacturing method, printed matter> The printed matter manufacturing apparatus of this embodiment includes a placement means that stores the pressure-sensitive toner of this embodiment and places the pressure-sensitive toner on a recording medium, and a pressing means that folds and presses the recording medium, or that stacks and presses the recording medium and another recording medium together. The printed matter according to this embodiment may be any printed matter that is adhered with the pressure-sensitive toner according to this embodiment. Suitable examples of printed matter according to this embodiment include a printed matter in which overlapping recording media are adhered on their opposing surfaces by the pressure-sensitive toner according to this embodiment, or a printed matter in which multiple overlapping recording media are adhered on their opposing surfaces by the pressure-sensitive toner according to this embodiment.

[0126] The placement unit may include, for example, an application device that applies pressure-sensitive toner onto the recording medium, and may further include a fixing device that fixes the pressure-sensitive toner applied onto the recording medium.

[0127] The pressing means includes, for example, a folding device that folds the recording medium on which pressure-sensitive toner is disposed, or a stacking device that stacks the recording medium on which pressure-sensitive toner is disposed and another recording medium, and a pressure device that applies pressure to the stacked recording media.

[0128] The pressure device provided in the pressure bonding means applies pressure to the recording medium on which the pressure-sensitive toner is placed, causing the pressure-sensitive toner to flow and exhibit adhesive properties on the recording medium.

[0129] The apparatus for producing printed matter according to the present embodiment implements the method for producing printed matter according to the present embodiment. The method for producing printed matter according to the present embodiment uses the pressure-sensitive toner according to the present embodiment and includes a placement step of placing the pressure-sensitive toner on a recording medium, and a pressing step of folding and pressing the recording medium or placing and pressing the recording medium and another recording medium together.

[0130] The disposing step may include, for example, a step of applying pressure-sensitive toner onto the recording medium, and may further include a step of fixing the pressure-sensitive toner applied onto the recording medium.

[0131] The pressing step includes, for example, a folding step of folding the recording medium or a stacking step of stacking the recording medium and another recording medium, and a pressurizing step of applying pressure to the stacked recording media.

[0132] The pressure-sensitive toner may be disposed over the entire surface of the recording medium, or may be disposed on a portion of the recording medium. The pressure-sensitive toner may be disposed in one layer or multiple layers on the recording medium. The pressure-sensitive toner layer may be a continuous layer in the surface direction of the recording medium, or may be a discontinuous layer in the surface direction of the recording medium. The pressure-sensitive toner layer may be a layer in which the pressure-sensitive toner particles are aligned as particles, or a layer in which adjacent pressure-sensitive toner particles are fused and aligned.

[0133] The amount of pressure-sensitive toner (preferably transparent pressure-sensitive toner) on the recording medium is, for example, 0.5 g / m 2 in the area where it is placed. 2 More than 50g / m 2 less than 1 g / m 2More than 40g / m 2 less than or equal to 1.5 g / m 2 More than 30g / m 2 The thickness of the pressure-sensitive toner (preferably transparent pressure-sensitive toner) layer on the recording medium is, for example, 0.2 μm to 25 μm, 0.4 μm to 20 μm, or 0.6 μm to 15 μm.

[0134] Examples of recording media that can be used with the printed matter production device according to this embodiment include paper, coated paper in which the surface of paper is coated with a resin or the like, cloth, nonwoven fabric, resin film, resin sheet, etc. The recording media may have an image on one or both sides.

[0135] An example of a printed matter production apparatus according to this embodiment will be described below, but this embodiment is not limited to this.

[0136] Fig. 1 is a schematic diagram showing an example of a printed matter production apparatus according to the present embodiment. The printed matter production apparatus shown in Fig. 1 includes a placement means 100 and a pressing means 200 arranged downstream of the placement means 100. The arrow indicates the transport direction of the recording medium.

[0137] The placement means 100 is a device that uses the pressure-sensitive toner according to this embodiment to place the pressure-sensitive toner on a recording medium P. The recording medium P has an image formed on one or both sides thereof in advance.

[0138] The placement means 100 includes an application device 110 and a fixing device 120 arranged downstream of the application device 110 .

[0139] The application device 110 applies the pressure-sensitive toner M onto the recording medium P. Application methods that the application device 110 employs include, for example, spraying, bar coating, die coating, knife coating, roll coating, reverse roll coating, gravure coating, screen printing, inkjet printing, lamination, and electrophotography. Depending on the application method, the pressure-sensitive toner M may be dispersed in a dispersion medium to prepare a liquid composition, and the liquid composition may be applied to the application device 110.

[0140] The recording medium P to which the pressure-sensitive toner M has been applied by the application device 110 is transported to the fixing device 120.

[0141] The fixing device 120 is, for example, a heating device that has a heating source and heats the pressure-sensitive toner M on the recording medium P that passes through, thereby fixing the pressure-sensitive toner M onto the recording medium P; a pressure device that has a pair of pressure members (roll / roll, belt / roll) and pressurizes the recording medium P that passes through, thereby fixing the pressure-sensitive toner M onto the recording medium P; a pressure and heating device that has a pair of pressure members (roll / roll, belt / roll) that has a heating source inside, and pressurizes and heats the recording medium P that passes through, thereby fixing the pressure-sensitive toner M onto the recording medium P; etc.

[0142] When the fixing device 120 has a heating source, the surface temperature of the recording medium P when heated by the fixing device 120 is preferably 10°C or higher and 80°C or lower, more preferably 20°C or higher and 60°C or lower, and even more preferably 30°C or higher and 50°C or lower.

[0143] When the fixing device 120 has a pressure member, the pressure applied by the pressure member to the recording medium P may be lower than the pressure applied by the pressure device 230 to the recording medium P2.

[0144] The recording medium P becomes a recording medium P1 having an image with pressure-sensitive toner M applied thereon by passing through the positioning means 100. The recording medium P1 is transported toward the pressing means 200.

[0145] In the printed matter manufacturing apparatus according to this embodiment, the placement means 100 and the pressing means 200 may be located close to each other or may be located apart from each other. When the placement means 100 and the pressing means 200 are located apart from each other, the placement means 100 and the pressing means 200 are connected by, for example, a conveying means (for example, a belt conveyor) that conveys the recording medium P1.

[0146] The pressing means 200 includes a folding device 220 and a pressure device 230, and is a means for folding and pressing the recording medium P1.

[0147] The folding device 220 folds the recording medium P1 that passes through the device to produce a folded recording medium P2. The recording medium P2 may be folded in half, in thirds, or in fourths, for example, or may be folded only partially. The recording medium P2 has pressure-sensitive toner M disposed on at least a portion of at least one of two opposing surfaces.

[0148] The folding device 220 may have a pair of pressure members (for example, roll / roll, belt / roll) that apply pressure to the recording medium P2. The pressure applied by the pressure members of the folding device 220 to the recording medium P2 may be lower than the pressure applied by the pressure device 230 to the recording medium P2.

[0149] The pressing means 200 may be provided with a stacking device that stacks the recording medium P1 and another recording medium instead of the folding device 220. The recording medium P1 and the other recording medium may be stacked, for example, in a form in which one sheet of the other recording medium is stacked on the recording medium P1, or in a form in which one sheet of the other recording medium is stacked at each of multiple locations on the recording medium P1. The other recording medium may be a recording medium with an image formed on one or both sides, a recording medium without an image formed on it, or a pre-prepared press-bonded printed material.

[0150] The recording medium P2 that has left the folding device 220 (or the overlapping device) is conveyed toward the pressure device 230.

[0151] The pressure device 230 includes a pair of pressure members (i.e., pressure rolls 231 and 232). The pressure rolls 231 and 232 come into contact with each other at their outer circumferential surfaces and press against each other, applying pressure to the recording medium P2 passing through. The pair of pressure members included in the pressure device 230 is not limited to a combination of pressure rolls, but may also be a combination of a pressure roll and a pressure belt, or a combination of a pressure belt and a pressure belt.

[0152] When pressure is applied to the recording medium P2 passing through the pressure device 230, the pressure-sensitive toner M on the recording medium P2 becomes fluidized by the pressure and exhibits adhesiveness.

[0153] The pressure applying device 230 may or may not have an internal heat source (e.g., a halogen heater) for heating the recording medium P2. However, the fact that the pressure applying device 230 does not have an internal heat source does not exclude the possibility that the temperature inside the pressure applying device 230 may become equal to or higher than the ambient temperature due to heat generated by a motor or the like provided in the pressure applying device 230.

[0154] As the recording medium P2 passes through the pressure device 230, the overlapping surfaces are bonded together by the fluidized pressure-sensitive toner M, producing a pressure-bonded printed matter P3. In the pressure-bonded printed matter P3, two opposing surfaces are partially or entirely bonded together.

[0155] The completed pressure-bonded printed matter P3 is carried out from the pressure device 230.

[0156] The first form of the pressure-bonded printed matter P3 is a pressure-bonded printed matter in which two folded recording media are adhered on their opposing surfaces with pressure-sensitive toner M. The pressure-bonded printed matter P3 of this form is produced by a printed matter production apparatus equipped with a folding device 220.

[0157] The second form of the pressure-bonded printed matter P3 is a pressure-bonded printed matter in which a plurality of overlapping recording media are adhered on their opposing surfaces by pressure-sensitive toner M. The pressure-bonded printed matter P3 of this form is manufactured by a pressure-bonded printed matter manufacturing apparatus equipped with a layering device.

[0158] The printed matter production device according to this embodiment is not limited to a device that continuously transports the recording medium P2 from the folding device 220 (or the overlapping device) to the pressure device 230. The printed matter production device according to this embodiment may also be a device that stores the recording medium P2 that has left the folding device 220 (or the overlapping device), and transports the recording medium P2 to the pressure device 230 after the amount of stored recording medium P2 reaches a predetermined amount.

[0159] In the printed matter manufacturing apparatus according to this embodiment, the folding device 220 (or overlapping device) and the pressing and pressuring device 230 may be located close to each other or may be located apart from each other. When the folding device 220 (or overlapping device) and the pressing and pressuring device 230 are located apart from each other, the folding device 220 (or overlapping device) and the pressing and pressuring device 230 are connected by, for example, a conveying means (for example, a belt conveyor) that conveys the recording medium P2.

[0160] The printed matter production apparatus according to this embodiment may include a cutting means for cutting the recording medium to a predetermined size. The cutting means may be, for example, a cutting means disposed between the placement means 100 and the pressing means 200, which cuts off a portion of the recording medium P1 where the pressure-sensitive toner M is not disposed; a cutting means disposed between the folding device 220 and the pressure device 230, which cuts off a portion of the recording medium P2 where the pressure-sensitive toner M is not disposed; or a cutting means disposed downstream of the pressing means 200, which cuts off a portion of the pressure-bonded printed matter P3 where the pressure-sensitive toner M is not adhered.

[0161] The printed matter manufacturing apparatus according to the present embodiment is not limited to a sheet-fed type apparatus, but may be an apparatus that performs a placement process and a pressing process on a long recording medium to form a long, pressed-on printed matter, and then cuts the long, pressed-on printed matter to predetermined dimensions.

[0162] The apparatus for producing a printed matter according to the present embodiment may further include a color image forming unit that forms a color image on a recording medium using a coloring material. Examples of the color image forming unit include a unit that forms a color ink image on a recording medium by an inkjet method using colored ink as a coloring material, and a unit that forms a color image on a recording medium by an electrophotographic method using a colored electrostatic image developer.

[0163] The manufacturing apparatus having the above-described configuration is used to carry out the method for manufacturing a printed matter according to the present embodiment, which further includes a color image forming step of forming a color image on a recording medium using a coloring material. Specific examples of the color image forming step include a step of forming a color ink image on a recording medium by an inkjet method using colored ink as a coloring material, and a step of forming a color image on a recording medium by an electrophotographic method using a colored electrostatic image developer.

[0164] <<Production of printed materials using electrophotography>> An embodiment in which the pressure-sensitive toner according to this embodiment is applied to an electrophotographic system will be described.

[0165] -Electrostatic image developer- The electrostatic image developer according to the present embodiment contains at least the pressure-sensitive toner according to the present embodiment. The electrostatic image developer according to the present embodiment may be a one-component developer containing only the pressure-sensitive toner according to the present embodiment, or may be a two-component developer in which the pressure-sensitive toner according to the present embodiment is mixed with a carrier.

[0166] The carrier is not particularly limited, and known carriers can be used. Examples of the carrier include a coated carrier in which the surface of a core material made of magnetic powder is coated with a resin; a magnetic powder dispersion type carrier in which magnetic powder is dispersed and mixed in a matrix resin; and a resin impregnated type carrier in which porous magnetic powder is impregnated with a resin. The magnetic powder dispersion type carrier and the resin impregnated type carrier may be a carrier in which the constituent particles of the carrier are used as a core material and the surface of this is coated with a resin.

[0167] Examples of magnetic powder include magnetic metals such as iron, nickel, and cobalt; and magnetic oxides such as ferrite and magnetite.

[0168] 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 resins containing organosiloxane bonds or modified products thereof, fluororesin, polyester, polycarbonate, phenolic resin, and epoxy resin. The coating resin and matrix resin may contain other additives such as conductive particles. Examples of conductive particles include particles of metals such as gold, silver, and copper, carbon black, titanium oxide, zinc oxide, tin oxide, barium sulfate, aluminum borate, and potassium titanate.

[0169] To coat the surface of the core material with a resin, a method of coating with a coating layer-forming solution prepared by dissolving the coating resin and various additives (used as needed) in an appropriate solvent can be used. The solvent is not particularly limited and may be selected taking into consideration the type of resin used, its suitability for application, etc. Specific resin coating methods include an immersion method in which the core material is immersed in a solution for forming a coating layer; a spray method in which the solution for forming a coating layer is sprayed onto the surface of the core material; a fluidized bed method in which the solution for forming a coating layer is sprayed onto the core material while it is suspended in flowing air; and a kneader coater method in which the core material of the carrier and the solution for forming a coating layer are mixed in a kneader coater and then the solvent is removed.

[0170] The mixing ratio (mass ratio) of the pressure-sensitive toner and the carrier in the two-component developer is preferably pressure-sensitive toner:carrier=1:100 to 30:100, and more preferably 3:100 to 20:100.

[0171] [Printed matter manufacturing apparatus and printed matter manufacturing method] The apparatus for manufacturing printed matter using an electrophotographic method includes a placement means for storing a developer containing the pressure-sensitive toner according to this embodiment and placing the pressure-sensitive toner on a recording medium using an electrophotographic method, and a pressing means for folding and pressing the recording medium, or for stacking and pressing the recording medium and another recording medium together.

[0172] The apparatus for producing printed matter according to the present embodiment implements a method for producing printed matter by electrophotography. The method for producing printed matter according to the present embodiment includes a placement step of electrophotographically placing the pressure-sensitive toner on a recording medium using a developer containing the pressure-sensitive toner according to the present embodiment, and a pressing step of folding and pressing the recording medium or placing and pressing the recording medium and another recording medium together.

[0173] The arrangement unit included in the printed matter manufacturing device according to the present embodiment includes, for example, A photoreceptor; a charging means for charging the surface of the photoreceptor; an electrostatic image forming means for forming an electrostatic image on the charged surface of the photoreceptor; a developing unit that contains the electrostatic image developer according to the present embodiment and develops the electrostatic image formed on the surface of the photosensitive member by the electrostatic image developer as a pressure-sensitive toner application unit; a transfer means for transferring the pressure-sensitive toner application portion formed on the surface of the photoreceptor onto the surface of a recording medium; Equipped with. It is preferable that the positioning means further comprises fixing means for fixing the pressure-sensitive toner application portion transferred onto the surface of the recording medium.

[0174] The arrangement step included in the method for producing a printed matter according to the present embodiment includes, for example, a charging step of charging the surface of the photoreceptor; an electrostatic image forming step of forming an electrostatic image on the charged surface of the photoreceptor; a developing step of developing the electrostatic image formed on the surface of the photosensitive member as a pressure-sensitive toner application portion using the electrostatic image developer according to the present embodiment; a transfer step of transferring the pressure-sensitive toner application portion formed on the surface of the photoreceptor onto the surface of a recording medium; Includes: The positioning step preferably further includes a fixing step of fixing the pressure-sensitive toner application portion transferred to the surface of the recording medium.

[0175] The arrangement means may be, for example, a direct transfer type device that directly transfers a pressure-sensitive toner application portion formed on the surface of a photoreceptor to a recording medium; an intermediate transfer type device that primarily transfers a pressure-sensitive toner application portion formed on the surface of a photoreceptor to the surface of an intermediate transfer body and then secondarily transfers the pressure-sensitive toner application portion transferred to the surface of the intermediate transfer body to the surface of a recording medium; a device equipped with a cleaning means that cleans the surface of the photoreceptor after the transfer of the pressure-sensitive toner application portion and before charging; or a device equipped with a charge-removing means that irradiates the surface of the photoreceptor with charge-removing light to remove charge after the transfer of the pressure-sensitive toner application portion and before charging. When the arrangement means is an intermediate transfer type device, the transfer means may include, for example, an intermediate transfer body onto whose surface the pressure-sensitive toner application portion is transferred, a primary transfer means that primarily transfers the pressure-sensitive toner application portion formed on the surface of the photoreceptor to the surface of the intermediate transfer body, and a secondary transfer means that secondarily transfers the pressure-sensitive toner application portion transferred to the surface of the intermediate transfer body to the surface of a recording medium.

[0176] The arrangement means may have a cartridge structure (so-called process cartridge) in which a portion including the developing means is detachably attached to the arrangement means. As the process cartridge, for example, a process cartridge that contains the electrostatic image developer according to the present embodiment and is equipped with the developing means is preferably used.

[0177] The pressure-bonding device included in the printed matter production apparatus according to this embodiment applies pressure to the recording medium on which the pressure-sensitive toner according to this embodiment is disposed. This causes the pressure-sensitive toner according to this embodiment to fluidize and exhibit adhesiveness on the recording medium. The pressure applied by the pressure-bonding device to the recording medium in order to fluidize the pressure-sensitive toner according to this embodiment 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.

[0178] The pressure-sensitive toner according to this embodiment may be disposed over the entire surface of the recording medium, or may be disposed on only a portion of the recording medium. The pressure-sensitive toner according to this embodiment is disposed in one or more layers on the recording medium. The pressure-sensitive toner layer according to this embodiment may be a continuous layer in the surface direction of the recording medium, or may be a discontinuous layer in the surface direction of the recording medium. The pressure-sensitive toner layer according to this embodiment may be a layer in which the pressure-sensitive toner particles are aligned as they are, or a layer in which adjacent pressure-sensitive toner particles are fused and aligned.

[0179] The amount of the pressure-sensitive toner (preferably transparent pressure-sensitive toner) according to this embodiment on the recording medium is, for example, 0.5 g / m in the area where it is placed. 2 More than 50g / m 2 less than 1 g / m 2 More than 40g / m 2 less than or equal to 1.5 g / m 2 More than 30g / m 2 The thickness of the pressure-sensitive toner (preferably transparent pressure-sensitive toner) layer on the recording medium according to this embodiment is, for example, 0.2 μm to 25 μm, 0.4 μm to 20 μm, or 0.6 μm to 15 μm.

[0180] Examples of recording media that can be used with the printed matter production device according to this embodiment include paper, coated paper in which the surface of paper is coated with a resin or the like, cloth, nonwoven fabric, resin film, resin sheet, etc. The recording media may have an image on one or both sides.

[0181] An example of a printed matter production apparatus according to this embodiment that employs an electrophotographic method will be described below, but this embodiment is not limited to this.

[0182] Fig. 2 is a schematic diagram showing an example of a printed matter production apparatus according to the present embodiment. The printed matter production apparatus shown in Fig. 2 includes a placement unit 100 and a pressing unit 200 disposed downstream of the placement unit 100. The arrows indicate the rotation direction of the photosensitive member or the transport direction of the recording medium.

[0183] The placement means 100 is a direct transfer type device that uses a developer containing the pressure-sensitive toner according to the present embodiment to place the pressure-sensitive toner according to the present embodiment on a recording medium P by an electrophotographic method. An image has been formed on one or both sides of the recording medium P in advance.

[0184] The arrangement means 100 has a photoreceptor 101. Around the photoreceptor 101, there are arranged in this order: a charging roll (an example of a charging means) 102 that charges the surface of the photoreceptor 101; an exposure device (an example of an electrostatic image forming means) 103 that exposes the surface of the charged photoreceptor 101 to a laser beam to form an electrostatic image; a developing device (an example of a developing means) 104 that supplies pressure-sensitive toner to the electrostatic image to develop it; a transfer roll (an example of a transfer means) 105 that transfers the developed pressure-sensitive toner application portion onto a recording medium P; and a photoreceptor cleaning device (an example of a cleaning means) 106 that removes pressure-sensitive toner remaining on the surface of the photoreceptor 101 after transfer.

[0185] The operation of the placement means 100 for placing the pressure-sensitive toner according to this embodiment on the recording medium P will be described. First, the surface of the photoconductor 101 is charged by the charging roll 102. The exposure device 103 irradiates the charged surface of the photoconductor 101 with a laser beam in accordance with image data sent from a control unit (not shown). As a result, an electrostatic charge image of the arrangement pattern of the pressure-sensitive toner according to this embodiment is formed on the surface of the photoconductor 101.

[0186] The electrostatic image formed on the photoconductor 101 rotates to the development position as the photoconductor 101 travels. At the development position, the electrostatic image on the photoconductor 101 is developed by the developing device 104 and becomes a pressure-sensitive toner application portion.

[0187] Developing device 104 contains a developer containing at least the pressure-sensitive toner according to this embodiment and a carrier. The pressure-sensitive toner according to this embodiment is frictionally charged by being stirred together with the carrier inside developing device 104, and is held on a developer roll. As the surface of photoconductor 101 passes through developing device 104, the pressure-sensitive toner electrostatically adheres to the electrostatic charge image on the surface of photoconductor 101, and the electrostatic charge image is developed with the pressure-sensitive toner. Photoconductor 101, on which the pressure-sensitive toner application portion has been formed, continues to travel, and the pressure-sensitive toner application portion on photoconductor 101 is transported to the transfer position.

[0188] When the pressure-sensitive toner application portion on the photosensitive body 101 is transported to the transfer position, a transfer bias is applied to the transfer roll 105, and an electrostatic force from the photosensitive body 101 toward the transfer roll 105 acts on the pressure-sensitive toner application portion, causing the pressure-sensitive toner application portion on the photosensitive body 101 to be transferred onto the recording medium P.

[0189] The pressure-sensitive toner remaining on the photoreceptor 101 is removed and collected 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 pressure-sensitive toner according to this embodiment remaining on the surface of the photoreceptor becomes fluidized by pressure and adheres to the surface of the photoreceptor in the form of a film.

[0190] The recording medium P onto which the pressure-sensitive toner application portion has been transferred is transported to a fixing device 107 (an example of a fixing means). The fixing device 107 is, for example, a pair of fixing members (roll / roll, belt / roll). The placement means 100 does not necessarily have to include the fixing device 107, but it is preferable that the fixing device 107 be included in order to prevent the pressure-sensitive toner according to this embodiment from falling off from the recording medium P. The pressure applied to the recording medium P by the fixing device 107 may be lower than the pressure applied to the recording medium P2 by the pressure device 230, and specifically, is preferably 0.2 MPa or more and 1 MPa or less.

[0191] The fixing device 107 may or may not have an internal heat source (e.g., a halogen heater) for heating the recording medium P. If the fixing device 107 has an internal heat source, the surface temperature of the recording medium P when heated by the heat source is preferably 150°C or higher and 220°C or lower, more preferably 155°C or higher and 210°C or lower, and even more preferably 160°C or higher and 200°C or lower. Note that the fact that the fixing device 107 does not have an internal heat source does not exclude the possibility that the temperature inside the fixing device 107 will become equal to or higher than the ambient temperature due to heat generated by a motor or the like provided in the placement means 100.

[0192] The recording medium P becomes a recording medium P1 having an image on which the pressure-sensitive toner according to this embodiment is applied by passing through the placement means 100. The recording medium P1 is transported toward the pressure bonding means 200.

[0193] In the printed matter manufacturing apparatus according to this embodiment, the placement means 100 and the pressing means 200 may be located close to each other or may be located apart from each other. When the placement means 100 and the pressing means 200 are located apart from each other, the placement means 100 and the pressing means 200 are connected by, for example, a conveying means (for example, a belt conveyor) that conveys the recording medium P1.

[0194] The pressing means 200 includes a folding device 220 and a pressure device 230, and is a means for folding and pressing the recording medium P1.

[0195] The folding device 220 folds the recording medium P1 that passes through the device to produce a folded recording medium P2. The recording medium P2 may be folded, for example, in half, in thirds, or in fourths, or may be folded only partially. The recording medium P2 has the pressure-sensitive toner according to this embodiment disposed on at least a portion of at least one of two opposing surfaces.

[0196] The folding device 220 may have a pair of pressure members (for example, roll / roll, belt / roll) that apply pressure to the recording medium P2. The pressure applied by the pressure members of the folding device 220 to the recording medium P2 may be lower than the pressure applied by the pressure device 230 to the recording medium P2, and specifically, is preferably 1 MPa or more and 10 MPa or less.

[0197] The pressing means 200 may be provided with a stacking device that stacks the recording medium P1 and another recording medium instead of the folding device 220. The recording medium P1 and the other recording medium may be stacked, for example, in a form in which one sheet of the other recording medium is stacked on the recording medium P1, or in a form in which one sheet of the other recording medium is stacked at each of multiple locations on the recording medium P1. The other recording medium may be a recording medium with an image formed on one or both sides, a recording medium without an image formed on it, or a pre-prepared press-bonded printed material.

[0198] The recording medium P2 that has left the folding device 220 (or the overlapping device) is conveyed toward the pressure device 230.

[0199] The pressure device 230 includes a pair of pressure members (i.e., pressure rolls 231 and 232). The pressure rolls 231 and 232 come into contact with each other at their outer circumferential surfaces and press against each other, applying pressure to the recording medium P2 passing through. The pair of pressure members included in the pressure device 230 is not limited to a combination of pressure rolls, but may also be a combination of a pressure roll and a pressure belt, or a combination of a pressure belt and a pressure belt.

[0200] When pressure is applied to the recording medium P2 passing through the pressure device 230, the pressure-sensitive toner according to this embodiment becomes fluidized and exhibits adhesiveness on the recording medium P2. The pressure applied to the recording medium P2 by the pressure device 230 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.

[0201] The pressure applying device 230 may or may not have an internal heat source (e.g., a halogen heater) for heating the recording medium P2. If the pressure applying 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 or higher and 120°C or lower, more preferably 40°C or higher and 100°C or lower, and even more preferably 50°C or higher and 90°C or lower. Note that the fact that the pressure applying device 230 does not have an internal heat source does not exclude the possibility that the temperature inside the pressure applying device 230 will become higher than the ambient temperature due to heat generated by a motor or the like provided in the pressure applying device 230.

[0202] As the recording medium P2 passes through the pressure device 230, the overlapping surfaces are adhered together by the fluidized pressure-sensitive toner according to this embodiment, producing a pressure-bonded printed matter P3. In the pressure-bonded printed matter P3, the opposing surfaces are partially or entirely adhered together.

[0203] The completed pressure-bonded printed matter P3 is carried out from the pressure device 230.

[0204] The first form of the bonded printed matter P3 is a bonded printed matter in which two overlapping recording media are bonded on their opposing surfaces with the pressure-sensitive toner according to this embodiment. The bonded printed matter P3 of this embodiment is produced by a printed matter production apparatus equipped with a folding device 220.

[0205] The second form of the laminated printed matter P3 is a laminated printed matter in which a plurality of overlapping recording media are bonded on their opposing surfaces with the pressure-sensitive toner according to this embodiment. The laminated printed matter P3 of this form is produced by a laminated printed matter production apparatus equipped with a stacking device.

[0206] The printed matter production device according to this embodiment is not limited to a device that continuously transports the recording medium P2 from the folding device 220 (or the overlapping device) to the pressure device 230. The printed matter production device according to this embodiment may also be a device that stores the recording medium P2 that has left the folding device 220 (or the overlapping device), and transports the recording medium P2 to the pressure device 230 after the amount of stored recording medium P2 reaches a predetermined amount.

[0207] In the printed matter manufacturing apparatus according to this embodiment, the folding device 220 (or overlapping device) and the pressing and pressuring device 230 may be located close to each other or may be located apart from each other. When the folding device 220 (or overlapping device) and the pressing and pressuring device 230 are located apart from each other, the folding device 220 (or overlapping device) and the pressing and pressuring device 230 are connected by, for example, a conveying means (for example, a belt conveyor) that conveys the recording medium P2.

[0208] The printed product manufacturing apparatus according to the present embodiment may include a cutting device that cuts the recording medium to a predetermined size. The cutting device may be, for example, a cutting device that is disposed between the placement device 100 and the pressing device 200 and cuts off a portion of the recording medium P1 that is not coated with the pressure-sensitive toner according to the present embodiment; a cutting device that is disposed between the folding device 220 and the pressure device 230 and cuts off a portion of the recording medium P2 that is not coated with the pressure-sensitive toner according to the present embodiment; or a cutting device that is disposed downstream of the pressing device 200 and cuts off a portion of the pressure-bonded printed product P3 that is not bonded with the pressure-sensitive toner according to the present embodiment.

[0209] The printed matter manufacturing apparatus according to the present embodiment is not limited to a sheet-fed type apparatus, but may be an apparatus that performs a placement process and a pressing process on a long recording medium to form a long, pressed-on printed matter, and then cuts the long, pressed-on printed matter to predetermined dimensions.

[0210] The apparatus for producing a printed matter according to the present embodiment may further include a color image forming unit that forms a color image on a recording medium by an electrophotographic method using a color electrostatic image developer. A photoreceptor; a charging means for charging the surface of the photoreceptor; an electrostatic image forming means for forming an electrostatic image on the charged surface of the photoreceptor; a developing means containing a color electrostatic image developer and developing the electrostatic image formed on the surface of the photosensitive member into a color toner image by using the color electrostatic image developer; a transfer means for transferring the color toner image formed on the surface of the photoreceptor to the surface of a recording medium; and a thermal fixing means for thermally fixing the color toner image transferred onto the surface of the recording medium.

[0211] The manufacturing apparatus having the above-described configuration is used to carry out a method for manufacturing a printed matter according to the present embodiment, which further includes a color image forming step of forming a color image on a recording medium by an electrophotographic method using a color electrostatic image developer. a charging step of charging the surface of the photoreceptor; an electrostatic image forming step of forming an electrostatic image on the charged surface of the photoreceptor; a developing step of developing the electrostatic image formed on the surface of the photoreceptor into a color toner image using a color electrostatic image developer; a transfer step of transferring the color toner image formed on the surface of the photoreceptor to the surface of a recording medium; and a heat fixing step of heat fixing the color toner image transferred onto the surface of the recording medium.

[0212] The color image forming means included in the printed matter production apparatus according to this embodiment may be, for example, a direct transfer type device that directly transfers a color toner image formed on the surface of a photoreceptor to a recording medium; an intermediate transfer type device that primarily transfers a color toner image formed on the surface of a photoreceptor to the surface of an intermediate transfer body and then secondarily transfers the color toner image transferred to the surface of the intermediate transfer body to the surface of a recording medium; a device equipped with a cleaning unit that cleans the surface of the photoreceptor after the transfer of the color toner image and before charging; or a device equipped with a charge eliminating unit that irradiates the surface of the photoreceptor with charge eliminating light to eliminate charge after the transfer of the color toner image and before charging. When the color image forming means is an intermediate transfer type device, the transfer unit may include, for example, an intermediate transfer body onto whose surface the color toner image is transferred, a primary transfer unit that primarily transfers the color toner image formed on the surface of the photoreceptor to the surface of the intermediate transfer body, and a secondary transfer unit that secondarily transfers the color toner image transferred to the surface of the intermediate transfer body to the surface of a recording medium.

[0213] In the printed matter manufacturing apparatus of this embodiment, if the developer placement means containing the pressure-sensitive toner of this embodiment and the color image forming means adopt an intermediate transfer method, the placement means and the color image forming means may share the intermediate transfer body and secondary transfer means.

[0214] In the apparatus for producing printed matter according to this embodiment, the means for placing the image developer containing the pressure-sensitive toner according to this embodiment and the color image forming means may share the thermal fixing means.

[0215] An example of a printed matter production apparatus according to the present embodiment, which is equipped with a color image forming unit, will be described below, but the present embodiment is not limited to this. In the following description, the main parts shown in the drawings will be described, and descriptions of the rest will be omitted.

[0216] Fig. 3 is a schematic diagram showing an example of a printed matter production apparatus according to the present embodiment, which employs an electrophotographic method. The printed matter production apparatus shown in Fig. 3 includes a printing unit 300 that simultaneously performs the deposition of pressure-sensitive toner according to the present embodiment on a recording medium and the formation of a color image, and a pressing unit 200 that is disposed downstream of the printing unit 300.

[0217] The printing means 300 is a five-tandem type printing means of an intermediate transfer type. The printing means 300 includes a unit 10T that applies the pressure-sensitive toner (T) according to the present embodiment, and units 10Y, 10M, 10C, and 10K that form images of yellow (Y), magenta (M), cyan (C), and black (K) colors. The unit 10T is a applying unit that applies the pressure-sensitive toner according to the present embodiment onto the recording medium P using a developer containing the pressure-sensitive toner according to the present embodiment. The units 10Y, 10M, 10C, and 10K are units that form color images on the recording medium P using developers containing color toners, respectively. The units 10T, 10Y, 10M, 10C, and 10K employ an electrophotographic system.

[0218] The units 10T, 10Y, 10M, 10C, and 10K are arranged side by side and spaced apart from one another in the horizontal direction. The units 10T, 10Y, 10M, 10C, and 10K may be process cartridges that are detachably attached to the printing means 300.

[0219] An intermediate transfer belt (an example of an intermediate transfer body) 20 is provided below units 10T, 10Y, 10M, 10C, and 10K and extends through each unit. The intermediate transfer belt 20 is provided wrapped around a drive roll 22, a support roll 23, and an opposing roll 24, which are in contact with the inner surface of the intermediate transfer belt 20, and runs in a direction from unit 10T to unit 10K. An intermediate transfer body cleaning device 21 is provided on the image bearing surface side of the intermediate transfer belt 20, facing the drive roll 22.

[0220] Units 10T, 10Y, 10M, 10C, and 10K are equipped with developing devices (examples of developing means) 4T, 4Y, 4M, 4C, and 4K, respectively. Developing devices 4T, 4Y, 4M, 4C, and 4K are supplied with the pressure-sensitive toner according to this embodiment housed in a pressure-sensitive toner cartridge 8T, or yellow toner, magenta toner, cyan toner, and black toner housed in toner cartridges 8Y, 8M, 8C, and 8K, respectively.

[0221] Since units 10T, 10Y, 10M, 10C, and 10K have the same configuration and operation, unit 10T, which places pressure-sensitive toner according to this embodiment on a recording medium, will be described as a representative.

[0222] The unit 10T has a photoreceptor 1T. Around the photoreceptor 1T, there are arranged in this order: a charging roll (an example of a charging means) 2T that charges the surface of the photoreceptor 1T; an exposure device (an example of an electrostatic image forming means) 3T that exposes the surface of the charged photoreceptor 1T to a laser beam to form an electrostatic image; a developing device (an example of a developing means) 4T that supplies pressure-sensitive toner to the electrostatic image to develop it; a primary transfer roll (an example of a primary transfer means) 5T that transfers the developed pressure-sensitive toner application portion onto the intermediate transfer belt 20; and a photoreceptor cleaning device (an example of a cleaning means) 6T that removes pressure-sensitive toner remaining on the surface of the photoreceptor 1T after the primary transfer. The primary transfer roll 5T is arranged inside the intermediate transfer belt 20, facing the photoreceptor 1T.

[0223] Hereinafter, the operation of disposing the pressure-sensitive toner according to this embodiment on the recording medium P and forming a color image will be described, taking the operation of the unit 10T as an example. First, the surface of the photoreceptor 1T is charged by the charging roll 2T. The exposed surface of the photoreceptor 1T is irradiated with a laser beam by the exposure device 3T in accordance with image data sent from a control unit (not shown). As a result, an electrostatic charge image of the pressure-sensitive toner arrangement pattern according to this embodiment is formed on the surface of the photoreceptor 1T.

[0224] The electrostatic image formed on the photoreceptor 1T rotates to the development position as the photoreceptor 1T moves. At the development position, the electrostatic image on the photoreceptor 1T is developed by the developing device 4T and becomes a pressure-sensitive toner application portion.

[0225] The developing device 4T contains a developer containing at least the pressure-sensitive toner according to this embodiment and a carrier. The pressure-sensitive toner according to this embodiment is frictionally charged by being stirred together with the carrier inside the developing device 4T, and is held on a developer roll. As the surface of the photoreceptor 1T passes through the developing device 4T, the pressure-sensitive toner electrostatically adheres to the electrostatic charge image on the surface of the photoreceptor 1T, and the electrostatic charge image is developed with the pressure-sensitive toner. The photoreceptor 1T, with the pressure-sensitive toner application portion formed, continues to travel, and the pressure-sensitive toner application portion on the photoreceptor 1T is transported to the primary transfer position.

[0226] When the pressure-sensitive toner application portion on the photoreceptor 1T is transported to the primary transfer position, a primary transfer bias is applied to the primary transfer roll 5T, and an electrostatic force from the photoreceptor 1T toward the primary transfer roll 5T acts on the pressure-sensitive toner application portion, causing the pressure-sensitive toner application portion on the photoreceptor 1T to be transferred onto the intermediate transfer belt 20. Pressure-sensitive toner remaining on the photoreceptor 1T is removed and collected by the photoreceptor cleaning device 6T. The photoreceptor cleaning device 6T is, for example, a cleaning blade or a cleaning brush, and is preferably a cleaning brush.

[0227] In units 10Y, 10M, 10C, and 10K, the same operation as in unit 10T is performed using a developer containing color toner. The intermediate transfer belt 20, onto which the pressure-sensitive toner application portion has been transferred in unit 10T, passes through units 10Y, 10M, 10C, and 10K in order, and toner images of each color are transferred onto the intermediate transfer belt 20 in multiple layers.

[0228] The intermediate transfer belt 20, onto which the pressure-sensitive toner application portions and toner images have been multiply transferred through units 10T, 10Y, 10M, 10C, and 10K, reaches a secondary transfer portion composed of the intermediate transfer belt 20, an opposing 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 arranged on the image bearing surface side of the intermediate transfer belt 20. Meanwhile, a recording medium P is fed via 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 opposing roll 24. At this time, an electrostatic force directed from the intermediate transfer belt 20 toward the recording medium P acts on the pressure-sensitive toner application portions and the toner images, and the pressure-sensitive toner application portions and the toner images on the intermediate transfer belt 20 are transferred onto the recording medium P.

[0229] The recording medium P onto which the pressure-sensitive toner application unit and the toner image have 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 heat 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 or higher and 220°C or lower, more preferably 155°C or higher and 210°C or lower, and even more preferably 160°C or higher and 200°C or lower. By passing through the thermal fixing device 28, the colored toner image is thermally fixed onto the recording medium P.

[0230] From the viewpoint of preventing the pressure-sensitive toner according to this embodiment from falling off from the recording medium P and from the viewpoint of improving the fixability of the color image to the recording medium P, the thermal fixing device 28 is preferably a device that applies pressure as well as heat, and may be, for example, a pair of fixing members (roll / roll, belt / roll) equipped with an internal heat source. 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 pressure device 230 applies to the recording medium P2, and specifically, it is preferably 0.2 MPa or more and 1 MPa or less.

[0231] The recording medium P becomes a recording medium P1 to which a color image and the pressure-sensitive toner according to this embodiment are applied by passing through the printing means 300. The recording medium P1 is transported toward the pressing means 200.

[0232] The configuration of the crimping means 200 in FIG. 3 may be the same as that of the crimping means 200 in FIG. 2, and detailed description of the configuration and operation of the crimping means 200 will be omitted.

[0233] In the printed matter manufacturing apparatus according to this embodiment, the printing means 300 and the pressing means 200 may be located close to each other or may be located apart from each other. When the printing means 300 and the pressing means 200 are located apart from each other, the printing means 300 and the pressing means 200 are connected by, for example, a conveying means (for example, a belt conveyor) that conveys the recording medium P1.

[0234] The apparatus for producing printed matter according to this embodiment may include a cutting device that cuts the recording medium to a predetermined size. The cutting device may be, for example, a cutting device that is disposed between the printing device 300 and the bonding device 200 and cuts off a portion of the recording medium P1 that is not coated with the pressure-sensitive toner according to this embodiment; a cutting device that is disposed between the folding device 220 and the pressure device 230 and cuts off a portion of the recording medium P2 that is not coated with the pressure-sensitive toner according to this embodiment; or a cutting device that is disposed downstream of the bonding device 200 and cuts off a portion of the bonded printed matter P3 that is not bonded with the pressure-sensitive toner according to this embodiment.

[0235] The printed matter manufacturing apparatus according to the present embodiment is not limited to a sheet-fed type apparatus, but may be an apparatus that performs a color image forming process, a positioning process, and a pressing process on a long recording medium to form a long, pressed-on printed matter, and then cuts the long, pressed-on printed matter to predetermined dimensions.

[0236] [Process cartridge] A process cartridge applied to an electrophotographic printing device will be described. The process cartridge according to this embodiment contains the electrostatic image developer according to this embodiment, and is equipped with a developing means that uses the electrostatic image developer to develop an electrostatic image formed on the surface of a photosensitive element as a pressure-sensitive toner application section, and is a process cartridge that is detachably attached to a printed matter manufacturing device.

[0237] The process cartridge according to this embodiment may be configured to include a developing unit, and, if necessary, at least one selected from a photosensitive member, a charging unit, an electrostatic image forming unit, a transfer unit, and the like.

[0238] An example of an embodiment of a process cartridge is a cartridge in which a photosensitive member, a charging roll (an example of a charging means) provided around the photosensitive member, a developing device (an example of a developing means), and a photosensitive member cleaning device (an example of a cleaning means) are integrated into a housing. The housing has an opening for exposure. The housing has mounting rails, and the process cartridge is attached to a printing product production device via the mounting rails.

[0239] 2 is an image forming apparatus having a configuration in which toner cartridges 8Y, 8M, 8C, and 8K can be attached and detached, and developing devices 4Y, 4M, 4C, and 4K are connected to the toner cartridges corresponding to each developing device (color) by toner supply pipes (not shown). When the toner stored in a toner cartridge runs low, the toner cartridge is replaced. [Example]

[0240] Examples will be described below, but the present invention is not limited to these examples. In the following description, unless otherwise specified, all "parts" and "%" are by mass.

[0241] Example 1 (First step: Preparation of styrene-based resin particle dispersion) Styrene (as a polymerization component): 370 parts n-Butyl acrylate (as a polymerization component): 115 parts Acrylic acid (as a polymerization component): 15 parts Dodecanethiol (as a chain transfer agent): 7.5 parts The above materials were mixed and dissolved to prepare a monomer solution (1). Eight parts of an anionic surfactant (DOWFAX2A1, manufactured by The Dow Chemical Company) was dissolved in 205 parts of ion-exchanged water, and the monomer solution (1) was added and dispersed to obtain an emulsion. 1.8 parts of the anionic surfactant was dissolved in 462 parts of ion-exchanged water and charged into a polymerization flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube. The mixture was heated to 73°C with stirring and maintained at that temperature. 3 parts of ammonium persulfate was dissolved in 21 parts of ion-exchanged water and added dropwise to the polymerization flask via a metering pump over 15 minutes, followed by the addition of the emulsion via a metering pump over 160 minutes. The polymerization flask was then maintained at 75°C for 3 hours with continued slow stirring and then returned to room temperature. This resulted in a styrene-based resin particle dispersion (St1) having a volume average particle size (D50v) of 198 nm, a weight average molecular weight of 45,000 as determined by GPC (UV detection), a glass transition temperature of 53° C., and a solid content of 42%.

[0242] (Second step: Preparation of pressure-sensitive toner) Styrene-based resin particle dispersion (St1): 980 parts n-Butyl acrylate (as a polymerization component): 200 parts 2-Ethylhexyl acrylate (as a polymerization component): 150 parts Dodecanethiol (as a chain transfer agent): 4.3 parts 1,10-Decanediol diacrylate (A-DOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd., as a crosslinking agent): 2.2 parts Ion-exchanged water: 1,200 parts The above materials were charged into a polymerization flask to prepare a monomer solution (2). After stirring the monomer solution (2) at 25°C for 1 hour, it was heated to 70°C. 2.5 parts of ammonium persulfate was dissolved in 75 parts of ion-exchanged water and added dropwise to the polymerization flask over 60 minutes via a metering pump. The polymerization flask was then maintained at 70°C for 3 hours with slow stirring. Furthermore, a monomer solution (3) prepared by mixing and dissolving 85 parts of styrene and 15 parts of n-butyl acrylate as a polymerization component was added dropwise over 30 minutes. Furthermore, 2.5 parts of ammonium persulfate was dissolved in 75 parts of ion-exchanged water and added dropwise to the polymerization flask over 60 minutes via a metering pump. After the addition, the mixture was maintained at 75°C for 3 hours and then returned to room temperature. This resulted in a composite resin particle dispersion containing composite resin particles, with a volume average particle size (D50v) of 265 nm, a weight average molecular weight of 250,000 as determined by GPC (UV detection), and a solids content of 33%.

[0243] (Preparation of Release Agent Particle Dispersion) Polyalkylene wax (FNP0100, melting point 100°C, manufactured by Nippon Seiro Co., Ltd.): 45 parts by mass Anionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 5 parts by mass Ion-exchanged water: 200 parts by mass The above components were heated to 110°C and thoroughly dispersed using an Ultra Turrax T50 manufactured by IKA, and then dispersed using a pressure discharge Gaulin homogenizer to obtain a release agent dispersion having a center diameter of 220 nm and a solid content of 18%.

[0244] (Toner Preparation) ·Composite resin particle dispersion: 504 parts Ion-exchanged water: 710 parts Release agent particle dispersion: 10 parts Anionic surfactant (Dow Chemical Company, Dowfax2A1): 1 part

[0245] The above materials were placed in a reaction vessel equipped with a thermometer and pH meter. A 1.0% aqueous nitric acid solution was added at 25°C to adjust the pH to 3.0. Then, 23 parts of a 2.0% aqueous aluminum sulfate solution were added while dispersing with a homogenizer (IKA Ultra Turrax T50) at 5,000 rpm. The reaction vessel was then equipped with a stirrer and a mantle heater. The temperature was increased at a rate of 0.5°C / min up to 50°C, and then at a rate of 0.05°C / min after exceeding 50°C. The particle size was measured every 10 minutes using a Multisizer II (aperture diameter 50 μm, Beckman Coulter). The temperature was maintained when the volume average particle size reached 8.7 μm, and 170 parts of a styrene-based resin particle dispersion (St1) were added over 5 minutes. After the addition, the mixture was maintained at 50°C for 30 minutes, and then a 1.0% aqueous sodium hydroxide solution was added to adjust the pH of the slurry to 6.0. Next, the temperature was raised to 94°C at a rate of 1°C / min while adjusting the pH to 6.0 every 5°C, and then maintained at 94°C for 4 hours. When the particle shape and surface properties were observed using an optical microscope and a field emission scanning electron microscope (FE-SEM), particle coalescence was confirmed, so the container was cooled to 30°C over 5 minutes with cooling water.

[0246] After cooling, the slurry was passed through a nylon mesh with 20 μm openings to remove coarse particles, and the slurry that passed through the mesh was filtered under reduced pressure using an aspirator. The solids remaining on the filter paper were added to ion-exchanged water (30°C) in an amount 30 times the solids volume and stirred for 30 minutes. The mixture was then filtered under reduced pressure using an aspirator, and the solids remaining on the filter paper were vacuum-dried in an oven at 25°C for 48 hours to obtain toner particles. The toner particles had a volume average particle size of 9.0 μm.

[0247] 100 parts of the toner particles and 1.5 parts of hydrophobic silica (RY50, manufactured by Nippon Aerosil Co., Ltd.) were mixed and mixed for 30 seconds at a rotation speed of 13,000 rpm using a sample mill. The mixture was sieved using a vibrating sieve with 45 μm openings to obtain a pressure-sensitive toner.

[0248] (Preparation of electrostatic image developer) 10 parts of the pressure-sensitive toner and 100 parts of the following resin-coated carrier (1) were placed in a V-blender and stirred for 20 minutes, and then sieved through a vibrating sieve with 212 μm openings to obtain electrostatic image developers.

[0249] -Resin coated carrier (1)- Mn-Mg-Sr ferrite particles (average particle size 40 μm): 100 parts Toluene: 14 parts Polymethyl methacrylate: 2 parts Carbon black (VXC72: manufactured by Cabot Corporation): 0.12 parts

[0250] The above materials except for the ferrite particles were mixed with glass beads (1 mm in diameter, the same amount as toluene) and stirred for 30 minutes at a rotation speed of 1,200 rpm using a sand mill manufactured by Kansai Paint Co., Ltd. to obtain a dispersion liquid. This dispersion liquid and the ferrite particles were placed in a vacuum degassing kneader and dried under reduced pressure while stirring to obtain a resin-coated carrier (1).

[0251] <Examples 2 to 11 and Comparative Examples 1 and 2> A pressure-sensitive toner and an electrostatic image developer were obtained in the same manner as in Example 1, except that the type of styrene-based resin, the type of (meth)acrylic acid ester-based resin, the mass ratio of the styrene-based resin to the (meth)acrylic acid ester-based resin (mass ratio of St / Ac), the type and amount of chain transfer agent, the type and amount of crosslinking agent, the mass ratio of the crosslinking agent to the chain transfer agent (crosslinking agent / chain transfer agent), the type of release agent, and the amount of coagulant used were changed as shown in Table 1.

[0252] <Evaluation of Pressure-Sensitive Toner> (Adhesion evaluation) A character image was printed using an electrophotographic printer, and C2 paper (manufactured by Fujifilm Business Innovation Co., Ltd., basis weight 82 gsm) was cut into V-fold postcard size. The resulting pressure-sensitive toner was applied to the paper using a bar coater at a rate of 2.5 g / m. 2The pressure-sensitive toner was then fixed to the paper using the fixing bench of the multifunction printer and dried, after which the paper was folded in half and passed through a sealer (Pressle multi2, manufactured by Toppan Forms Co., Ltd.) to apply pressure (Gap 10, pressure 90 MPa). After leaving it overnight, the paper was cut into 15 mm wide specimens and used for a 90-degree peel test. The peel speed for the 90-degree peel test was 20 mm / min, and the 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 to evaluate the adhesive strength. Evaluation standard C indicates insufficient adhesive strength and did not achieve the target value. The evaluation results are shown in Table 1. A: 0.8N or more B: 0.4N or more and less than 0.8N C: Less than 0.4N

[0253] (Paper tear prevention (tear prevention when peeled) evaluation) The sheets were subjected to pressure with a sealer in the same manner as in the adhesive strength evaluation, and then stored in a chamber at 30°C and 90% RH for one week. The adhesive was then manually peeled off, and the presence or absence of tearing of the sheets was evaluated according to the following criteria. The evaluation results are shown in Table 1. A: No tears B: Slight paper tearing (image is fine) C: Large tears in the paper (tears extend to the image area)

[0254] (Hot offset suppression evaluation) A modified DocuCentre C7550 (manufactured by Fujifilm Business Innovation Co., Ltd.) was used with a toner amount of 15.0 g / m 2 A 4cm x 4cm image was created using C2 paper. The process speed was fixed at 600mm / sec, and the image was fixed using a fixing machine modified to fix the fixing temperature at 190°C and 230°C. Ten prints were made and evaluated according to the following criteria. The evaluation results are shown in Table 1. A: No hot offset occurred at fixing temperatures of 190°C and 230°C. B: Hot offset occurred on 3 sheets or less at a fixing temperature of 230°C, and no hot offset occurred at a fixing temperature of 190°C. C: Hot offset occurred on 4 or more sheets at a fixing temperature of 230°C, or on at least 1 sheet at a fixing temperature of 190°C.

[0255] [Table 1]

[0256] In Table 1, St in the type column of the styrene-based resin component represents styrene, BA represents n-butyl acrylate, AA represents acrylic acid, and MAA represents methacrylic acid. The "mass ratio of St / Ac" in Table 1 represents the mass ratio of the styrene-based resin to the (meth)acrylic acid ester-based resin. FNP0085 (melting point 85°C) in Table 1 represents polyalkylene wax (manufactured by Nippon Seiro Co., Ltd.).

[0257] From the above results, it can be seen that the present example is superior to the comparative example in adhesiveness, resistance to tearing during peeling, and resistance to hot offset. [Explanation of symbols]

[0258] 100 Placement means 110 Applicator 120 Fixation device 200 Crimping means 220 Folding device 230 Pressure Device 231, 232 Pressure roll M Pressure Sensitive Toner P Recording medium P1: Recording medium with pressure-sensitive toner applied to the image P2 Folded recording media P3 Pressed Printed Material

[0259] 101 Photoreceptor 102 Charging roll (an example of charging means) 103 Exposure device (an example of electrostatic image forming means) 104 Developing device (an example of developing means) 105 Transfer roll (an example of transfer means) 106 Photosensitive member cleaning device (an example of cleaning means) 107 Fixing device (an example of fixing means)

[0260] 300 Printing means 1T, 1Y, 1M, 1C, 1K photoconductor 2T, 2Y, 2M, 2C, 2K Charging roll (an example of charging means) 3T, 3Y, 3M, 3C, 3K exposure equipment (an example of electrostatic image forming means) 4T, 4Y, 4M, 4C, 4K developing device (an example of developing means) 5T, 5Y, 5M, 5C, 5K Primary transfer roll (an example of a primary transfer means) 6T, 6Y, 6M, 6C, 6K Photoconductor cleaning device (an example of a cleaning means) 8T Pressure Sensitive Toner Cartridge 8Y, 8M, 8C, 8K toner cartridges 10T, 10Y, 10M, 10C, 10K units 20 Intermediate transfer belt (an example of an intermediate transfer body) 21 Intermediate transfer body cleaning device 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 thermal fixing means)

Claims

1. The toner particles contain a composite resin made of a styrene-based resin and a (meth)acrylic acid ester-based resin, the difference between the lowest glass transition temperature and the highest glass transition temperature of the composite resin is 30°C or more; the gel fraction of the toner particles is 1.0% by mass or more and 8.0% by mass or less, The pressure-sensitive toner, wherein the mass ratio of the styrene-based resin to the (meth)acrylic acid ester-based resin in the composite resin is 65:35 to 35:

65.

2. 2. The pressure-sensitive toner according to claim 1, wherein the melt viscosity at 100[deg.] C. is 4,000 Pa.s or more and 20,000 Pa.s or less.

3. 3. The pressure-sensitive toner according to claim 1, wherein the toner particles are fused and coalesced particles of a particle group containing at least particles of the composite resin.

4. 4. The pressure-sensitive toner according to claim 1, wherein the ratio Y / X of the gel fraction X in the composite resin to the gel fraction Y in the toner particles satisfies 0.8≦Y / X≦80.

5. 5. The pressure-sensitive toner according to claim 1, wherein the composite resin has a weight average molecular weight of 50,000 or more and 500,000 or less.

6. 6. The pressure-sensitive toner according to claim 5, wherein the composite resin has a weight average molecular weight of 100,000 or more and 350,000 or less.

7. 7. The pressure-sensitive toner according to claim 1, wherein the composite resin is a resin having a crosslinked structure.

8. 8. The pressure-sensitive toner according to claim 7, wherein the (meth)acrylic acid ester resin is a resin having a crosslinked structure.

9. 9. The pressure-sensitive toner according to claim 1, wherein the content of the composite resin in the toner particles is 65% by mass or more and 90% by mass or less with respect to the total mass of the toner particles.

10. 10. The pressure-sensitive toner according to claim 1, wherein the toner particles have a volume average particle size of 4 [mu]m or more and 12 [mu]m or less.

11. 11. The pressure-sensitive toner according to claim 1, wherein the composite resin has a gel fraction of 0.1% by mass or more and 2% by mass or less.

12. a step of using the pressure-sensitive toner according to any one of claims 1 to 11 and disposing the pressure-sensitive toner on a recording medium; a pressing step of folding the recording medium and pressing it together, or of placing the recording medium and another recording medium together and pressing them together. Methods for producing printed materials.

Images