Pressure-responsive particles, cartridge, printed matter, and manufacturing apparatus and manufacturing method therefor, and sheet for printed matter and manufacturing method therefor

Abstract

The present application relates to a kind of pressure responsive particles, box, printed matter and its manufacturing device and manufacturing method, printed matter manufacturing sheet and its manufacturing method.A kind of pressure responsive particles, containing: pressure responsive parent particle, containing styrene resin and (meth) acrylate resin, the styrene resin contains styrene and other vinyl monomer as polymerization component, the (meth) acrylate resin contains at least two (meth) acrylate as polymerization component and the mass ratio of (meth) acrylate in the whole polymerization component is 90 mass% or more;And first inorganic oxide particle, the ratio Db / Da of the number average particle size Db of first inorganic oxide particle and the number average particle size Da of the pressure responsive parent particle is 0.05 or more and 0.25 or less, has at least two glass transition temperatures, and the difference between the lowest glass transition temperature and the highest glass transition temperature is 30 DEG C or more.

Description

Technical Field

[0001] This invention relates to an apparatus for manufacturing pressure-responsive particles, boxes, and printed materials, a method for manufacturing printed materials, printed materials, sheets for manufacturing printed materials, and a method for manufacturing sheets for manufacturing printed materials. Background Technology

[0002] Patent document 1 describes an aqueous dispersible adhesive composition containing two acrylic polymers in an aqueous solvent.

[0003] Patent document 2 describes a method that satisfies the formula "20℃≤T(1MPa)-T(10MPa)" (T(1MPa) indicates that the viscosity becomes 10 when a pressure of 1MPa is applied). 4 The temperature at Pa·s, T(10MPa) represents the viscosity at which a pressure of 10MPa is achieved. 4 The temperature at Pa·s. ) adhesive material.

[0004] Patent document 3 describes a pressure fixing toner containing styrene resin and (meth)acrylate resin with a glass transition temperature 30°C or lower than that of the styrene resin. It has an island structure consisting of a sea portion containing styrene resin and an island portion containing (meth)acrylate resin. It has a core portion with a major diameter of 200 nm or more and 500 nm or less for the island portion and a shell portion containing resin with a glass transition temperature of 50°C or higher covering the core portion.

[0005] Patent document 4 describes a water-dispersible adhesive composition containing a polymer of monomer raw material (A), namely an acrylic polymer (A), and a polymer of monomer raw material (B), namely an acrylic polymer (B). The acrylic polymer (B) has a glass transition temperature of 0°C or higher and a weight-average molecular weight greater than 0.3 × 10⁻⁶. 4 And 5×10 4 The following acrylic polymer (A) has a weight-average molecular weight of 40 × 10⁻⁶. 4 The difference between the glass transition temperature of acrylic polymer (B) and that of acrylic polymer (A) is 70°C or more, and the monomer raw material (B) contains a carboxyl-containing monomer in a proportion of 3% to 20% by weight or more.

[0006] Patent document 5 describes a type of crimped postcard paper with an adhesive layer containing an acrylic / alkyl methacrylate copolymer.

[0007] Patent document 6 or 7 describes an aqueous emulsion-type pressure-sensitive adhesive.

[0008] Patent Document 1: Japanese Patent Application Publication No. 2012-188512

[0009] Patent Document 2: Japanese Patent Application Publication No. 2018-002889

[0010] Patent Document 3: Japanese Patent Application Publication No. 2018-163198

[0011] Patent Document 4: Japanese Patent No. 6468727

[0012] Patent Document 5: Japanese Patent Application Publication No. 2007-229993

[0013] Patent Document 6: Japanese Patent Application Publication No. 2016-190446

[0014] Patent Document 7: Japanese Patent Application Publication No. 2018-052046 Summary of the Invention

[0015] The objective of this invention is to provide pressure-responsive particles that, compared to pressure-responsive particles containing a homopolymer of a styrene-based resin and a (meth)acrylate-based resin, and wherein the (meth)acrylate-based resin is a (meth)acrylate, exhibit superior adhesion between the surfaces of a recording medium that can be peeled off, and compared to pressure-responsive particles containing inorganic oxide particles in which the ratio of the number-average particle size Db to the number-average particle size Da of the pressure-responsive parent particles is Db / Da, which is 0.04, pressure-responsive particles that expose the adhesive surfaces of the recording medium are less prone to refeeding.

[0016] The specific methods used to solve the aforementioned problem include the following.

[0017] <1> A pressure-responsive particle containing:

[0018] Pressure-responsive parent material comprising a styrene-based resin and a (meth)acrylate-based resin, wherein the styrene-based resin contains styrene and other vinyl monomers as polymerization components, and the (meth)acrylate-based resin contains at least two (meth)acrylates as polymerization components, and the (meth)acrylates account for more than 90% by mass of the total polymer components; and

[0019] The ratio of the number-average particle size Db of the first inorganic oxide particle to the number-average particle size Da of the pressure-responsive parent particle, Db / Da, is 0.05 or more and 0.25 or less.

[0020] It has at least two glass transition temperatures, and the difference between the lowest and highest glass transition temperatures is more than 30°C.

[0021] <2> According to the pressure-responsive particle described in <1>, wherein,

[0022] The ratio Db / Da of the first inorganic oxide particle is 0.08 or higher and 0.20 or lower.

[0023] <3> According to <1> or <2>, the pressure-responsive particle, wherein,

[0024] The first inorganic oxide particle contains at least one of strontium titanate particles and cerium oxide particles.

[0025] <4> The pressure-responsive particles according to any one of <1> to <3> further contain second inorganic oxide particles with a number-average particle size of less than 200 nm.

[0026] <5> According to the pressure-responsive particles described in <4>, wherein,

[0027] The second inorganic oxide particle contains silicon dioxide particles.

[0028] <6> The pressure-responsive particle according to any one of <1> to <5>, wherein,

[0029] The amount of the first inorganic oxide particles added is more than 0.05 parts by mass and less than 3 parts by mass relative to 100 parts by mass of the pressure-responsive parent particles.

[0030] <7> According to the pressure-responsive particle described in <6>, wherein,

[0031] The amount of the first inorganic oxide particles added is 0.08 parts by mass and less than 1.5 parts by mass relative to 100 parts by mass of the pressure-responsive parent particles.

[0032] <8> The pressure-responsive particle according to any one of <1> to <7>, wherein,

[0033] Styrene accounts for more than 60% by mass and less than 95% by mass in the total polymer composition of the styrene-based resin.

[0034] <9> The pressure-responsive particle according to any one of <1> to <8>, wherein,

[0035] The mass ratio of the two (meth)acrylates contained in the (meth)acrylate resin as a polymerization component, which have the largest mass proportion, is 80:20 to 20:80.

[0036] <10> A pressure-responsive particle according to any one of <1> to <9>, wherein,

[0037] The (meth)acrylate resin contains at least two (meth)acrylates as polymerizing components, the two with the largest mass proportions being (meth)acrylate alkyl esters, wherein the difference in the number of carbon atoms of the alkyl groups of the two (meth)acrylate alkyl esters is more than 1 and less than 4.

[0038] <11> Pressure-responsive particles according to any one of <1> to <10>, wherein,

[0039] The other vinyl monomers contained in the styrene-based resin as polymerizing components contain (meth)acrylates.

[0040] <12> The pressure-responsive particle according to any one of <1> to <11>, wherein,

[0041] The other vinyl monomers contained in the styrene-based resin as polymerizing components include at least one of n-butyl acrylate and 2-ethylhexyl acrylate.

[0042] <13> The pressure-responsive particle according to any one of <1> to <12>, wherein,

[0043] The styrene-based resin and the (meth)acrylate-based resin contain the same type of (meth)acrylate as a polymerization component.

[0044] <14> The pressure-responsive particle according to any one of <1> to <13>, wherein,

[0045] The (meth)acrylate resin contains 2-ethylhexyl acrylate and n-butyl acrylate as polymerizing components.

[0046] <15> The pressure-responsive particle according to any one of <1> to <14>, wherein,

[0047] In the pressure-responsive parent material, the content of the styrene-based resin is greater than the content of the (meth)acrylate-based resin.

[0048] <16> The pressure-responsive particle according to any one of <1> to <15>, wherein,

[0049] The pressure-responsive parent material has a marine phase containing the styrene-based resin and an island phase containing the (meth)acrylate-based resin dispersed in the marine phase.

[0050] <17> According to the pressure-responsive particle described in <16>, wherein,

[0051] The average diameter of the island phase is above 200 nm and below 500 nm.

[0052] <18> The pressure-responsive particle according to any one of <1> to <17>, wherein,

[0053] The pressure-responsive parent particle has a core containing the styrene-based resin and the (meth)acrylate-based resin, and a shell covering the core.

[0054] <19> According to the pressure-responsive particle described in <18>, wherein,

[0055] The shell contains the styrene-based resin.

[0056] <20> A pressure-responsive particle according to any one of <1> to <19>, wherein,

[0057] The temperature at which the viscosity of 10000 Pa·s is displayed under a pressure of 4 MPa is below 90 °C.

[0058] <21> A box containing any one of <1> to <20> pressure-responsive particles and being loaded and unloaded into a printing manufacturing apparatus.

[0059] <22> An apparatus for manufacturing printed matter, comprising:

[0060] A configuration unit, comprising any one of <1> to <20> pressure-responsive particles, and configuring the pressure-responsive particles onto a recording medium; and

[0061] A crimping unit folds and crimps the recording medium or overlaps and crimps the recording medium and another recording medium.

[0062] <23> The printing apparatus according to <22> further includes:

[0063] A color image forming unit uses pigments to form a color image on a recording medium.

[0064] <24> A method for manufacturing printed matter, comprising:

[0065] The configuration step involves configuring the pressure-responsive particles onto a recording medium using any one of <1> to <20>.

[0066] The pressing process involves folding and pressing the recording medium or overlapping and pressing the recording medium and another recording medium.

[0067] <25> The method for manufacturing printed matter according to <24> further includes:

[0068] The color image forming process uses pigments to form a color image on a recording medium.

[0069] <26> A printed material formed by bonding the opposite surfaces of a folded recording medium with pressure-responsive particles as described in any one of <1> to <20>.

[0070] <27> A printed matter formed by bonding the opposing surfaces of a plurality of recording media together using pressure-responsive particles as described in any one of <1> to <20>.

[0071] <28> A sheet material for printing, which uses any one of <1> to <20> pressure-responsive particles.

[0072] It has a substrate and pressure-responsive particles disposed on the substrate.

[0073] <29> A method for manufacturing a sheet for printing, comprising:

[0074] In the configuration process, pressure-responsive particles are configured onto a substrate using any one of <1> to <20>.

[0075] Invention Effects

[0076] According to the inventions described in <1>, <2>, <4> or <5>, a pressure-responsive particle is provided that, compared to pressure-responsive particles containing a homopolymer of styrene-based resin and (meth)acrylate-based resin, wherein the (meth)acrylate-based resin is (meth)acrylate, exhibits superior adhesion between the surfaces of a recording medium that can be peeled off, and compared to pressure-responsive particles containing inorganic oxide particles in which the ratio of number-average particle size Db to the number-average particle size Da of the pressure-responsive parent particle is Db / Da, which is 0.04, a pressure-responsive particle that exposes the adhesive surface of the recording medium is less prone to refeeding.

[0077] According to the invention described in <3>, a pressure-responsive particle is provided that, compared to the case where the first inorganic oxide particle does not contain at least one of strontium titanate particles and cerium oxide particles but contains other inorganic oxide particles, the recording medium with exposed adhesive surfaces is less prone to refeeding.

[0078] According to the invention described in <6>, a pressure-responsive particle is provided that, compared to a case where the amount of the first inorganic oxide particle added is less than 0.05 parts by mass relative to 100 parts by mass of the pressure-responsive parent particle, the recording medium with exposed adhesive surfaces is less prone to refeeding, and compared to a case where it exceeds 3 parts by mass, the pressure-responsive particle exhibits superior adhesion.

[0079] According to the invention described in <7>, a pressure-responsive particle is provided that, compared to the case where the amount of the first inorganic oxide particle added is less than 0.08 parts by mass relative to 100 parts by mass of the pressure-responsive parent particle, the recording medium with exposed adhesive surfaces is less prone to refeeding, and compared to the case where it exceeds 1.5 parts by mass, the pressure-responsive particle exhibits excellent adhesion.

[0080] According to the invention described in <8>, a pressure-responsive particle that is more prone to phase change due to pressure is provided compared to cases where the mass proportion of styrene in the total polymeric component of a styrene-based resin exceeds 95% by mass.

[0081] According to the invention described in <9>, a pressure-responsive particle is provided that is more prone to phase change due to pressure and has excellent adhesion compared to a situation where the mass ratio of the two largest (meth)acrylates contained as polymerizing components in a (meth)acrylate resin is not in the range of 80:20 to 20:80.

[0082] According to the invention described in <10>, a pressure-responsive particle is provided that is more prone to phase change due to pressure and has excellent adhesion compared to the case where the difference in the number of carbon atoms of the alkyl groups of the two (meth)acrylates is 5 or more.

[0083] According to the inventions involved in <11>, <12> or <13>, a pressure-responsive particle that is more prone to phase change due to pressure is provided compared with pressure-responsive particles containing polystyrene instead of styrene-based resins.

[0084] According to the invention involved in <14>, a pressure-responsive particle with superior adhesion is provided compared to a pressure-responsive particle containing a homopolymer of styrene-based resin and (meth)acrylate-based resin, wherein the (meth)acrylate-based resin is 2-ethylhexyl acrylate.

[0085] According to the invention described in <15>, a pressure-responsive particle that maintains adhesion compared to a case where the content of a styrene-based resin is less than that of a (meth)acrylate-based resin is provided.

[0086] According to the invention involved in <16>, a pressure-responsive particle is provided that is more prone to phase change due to pressure and has excellent adhesion compared to the case without the island structure.

[0087] According to the invention involved in <17>, a pressure-responsive particle that is more prone to phase transition due to pressure is provided compared to the case where the average diameter of the island phase exceeds 500 nm.

[0088] According to the invention described in <18>, a pressure-responsive particle that is more prone to phase change due to pressure is provided compared to a core / shell structure in which the core contains only styrene-based resin or only (meth)acrylate-based resin.

[0089] According to the invention described in <19>, a pressure-responsive particle that is more prone to phase change due to pressure is provided compared to a case where the shell does not contain styrene-based resin but contains other resins.

[0090] According to the invention described in <20>, a pressure-responsive particle is provided that is more prone to phase change due to pressure compared to a case where the viscosity at 4 MPa exceeds 10000 Pa·s and the temperature exceeds 90°C.

[0091] According to the invention described in <21>, a box is provided that contains pressure-responsive particles that are more prone to phase change due to pressure and have excellent adhesion compared to pressure-responsive particles containing a homopolymer of a styrene-based resin and a (meth)acrylate-based resin, wherein the (meth)acrylate-based resin is a (meth)acrylate.

[0092] According to the invention described in <22> or <23>, an apparatus is provided for manufacturing a printable material that is more prone to phase change due to pressure and has excellent adhesion compared to pressure-responsive particles containing a styrene-based resin and a (meth)acrylate-based resin, wherein the (meth)acrylate-based resin is a (meth)acrylate homopolymer.

[0093] According to the invention described in <24> or <25>, a method for manufacturing a printable material is provided that is suitable for pressure-responsive particles that readily undergo phase change under pressure and have excellent adhesion compared to pressure-responsive particles containing a styrene-based resin and a (meth)acrylate-based resin, wherein the (meth)acrylate-based resin is a (meth)acrylate homopolymer.

[0094] According to the invention described in <26> or <27>, a printable material is provided that is more prone to phase change due to pressure and has excellent adhesion compared to pressure-responsive particles containing a styrene-based resin and a (meth)acrylate-based resin, wherein the (meth)acrylate-based resin is a (meth)acrylate homopolymer.

[0095] According to the invention described in <28>, a sheet material for printing is provided that is suitable for pressure-responsive particles that are more prone to phase change due to pressure and have excellent adhesion compared to pressure-responsive particles containing styrene-based resins and (meth)acrylate-based resins, wherein the (meth)acrylate-based resin is (meth)acrylate.

[0096] According to the invention described in <29>, a method is provided for manufacturing a sheet for printing materials that is more prone to phase change due to pressure and has excellent adhesion compared to pressure-responsive particles that contain styrene-based resins and (meth)acrylate-based resins, wherein the (meth)acrylate-based resin is (meth)acrylate. Attached Figure Description

[0097] The embodiments of the present invention will be described in detail with reference to the following figures.

[0098] Figure 1This is a schematic diagram illustrating an example of a printing manufacturing apparatus according to this embodiment;

[0099] Figure 2 This is a schematic diagram of an inkjet recording device as an example of a color image forming unit;

[0100] Figure 3 This is a schematic diagram illustrating another example of a printing manufacturing apparatus according to this embodiment;

[0101] Figure 4 This is a schematic diagram illustrating another example of a printing apparatus according to this embodiment.

[0102] Symbol Explanation

[0103] 100 - Configuration unit, 110 - Imparting device, 120 - Fixing device, 200 - Crimping unit, 220 - Folding device, 230 - Pressing device, 231, 232 - Pressure rollers, M - Pressure-responsive particles, P - Recording medium, P1 - Recording medium with pressure-responsive particles applied to the image, P2 - Folded recording medium, P3 - Crimped printed material; 400 - Inkjet recording device, 30Y, 30M, 30C, 30K - Inkjet heads, 32Y, 32M, 32C, 32K - Ink cartridges, 34Y 34M, 34C, 34K - Drying unit; 40 - Frame; 42, 66 - Container; 44, 62 - Conveyor path; 46 - Roller; 48, 64 - Roller pair; 50 - Conveyor belt; 52 - Drive roller; 54 - Driven roller; 56 - Charged roller; 58 - Stripping plate; 101 - Photoreceptor; 102 - Charged roller (an example of a charged unit); 103 - Exposure device (an example of an electrostatic image forming unit); 104 - Developing device (an example of a developing unit); 105 - Transfer roller (an example of a transfer unit); 106 - Photoreceptor Photosensitive cleaning device (an example of a cleaning unit), 107- Fixing device (an example of a fixing unit); 300- Printing unit, 1T, 1Y, 1M, 1C, 1K- Photosensitive material, 2T, 2Y, 2M, 2C, 2K- Charged roller (an example of a charged unit), 3T, 3Y, 3M, 3C, 3K- Exposure device (an example of an electrostatic image forming unit), 4T, 4Y, 4M, 4C, 4K-Developing device (an example of a developing unit), 5T, 5Y, 5M, 5C, 5K- Primary transfer roller (a primary transfer unit). (Example), 6T, 6Y, 6M, 6C, 6K - Photoreceptor cleaning device (an example of a cleaning unit), 8T - Pressure-responsive particle box, 8Y, 8M, 8C, 8K - Toner box, 10T, 10Y, 10M, 10C, 10K - Unit, 20 - Intermediate transfer belt (an example of an intermediate transfer body), 21 - Intermediate transfer body cleaning device, 22 - Drive roller, 23 - Support roller, 24 - Opposing roller, 26 - Secondary transfer roller (an example of a secondary transfer unit), 28 - Thermal fixing device (an example of a thermal fixing unit). Detailed Implementation

[0104] The embodiments of the present invention will be described below. These descriptions and examples are for illustrative purposes only and do not limit the scope of the embodiments.

[0105] In this invention, the numerical range represented by “~” indicates the range of values ​​before and after “~” as the minimum and maximum values, respectively.

[0106] Within the numerical ranges described in stages in this invention, an upper or lower limit value within one numerical range can be replaced with an upper or lower limit value within another numerical range described in stages. Furthermore, within the numerical ranges described in this invention, the upper or lower limit value of that numerical range can be replaced with the values ​​shown in the embodiments.

[0107] In this invention, the term "process" includes not only independent processes, but also processes that can achieve their intended purpose, even if they cannot be clearly distinguished from other processes.

[0108] When describing embodiments in this invention with reference to the accompanying drawings, the structure of these embodiments is not limited to the structure shown in the drawings. Furthermore, the sizes of the components in the figures are conceptual, and the relative sizes of the components are not limited thereto.

[0109] In this invention, each component may contain a plurality of corresponding substances. Unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition, the total amount of such substances present in the composition is indicated.

[0110] In this invention, a plurality of particles corresponding to each component may be contained. When a plurality of particles corresponding to each component are present in the composition, unless otherwise specified, the particle size of each component represents a value relating to the mixture of the plurality of particles present in the composition.

[0111] In this invention, the designation "(meth)acrylic acid" indicates that it can be either "acrylic acid" or "methacrylic acid".

[0112] In this invention, a printed material formed by folding a recording medium and bonding its opposing surfaces together, or a printed material formed by overlapping two or more recording media and bonding their opposing surfaces together, is called a "pressed printed material".

[0113] <Pressure-responsive particles>

[0114] The pressure-responsive particles involved in this embodiment contain:

[0115] Pressure-responsive parent material comprising a styrene-based resin and a (meth)acrylate-based resin, wherein the styrene-based resin contains styrene and other vinyl monomers as polymerization components, and the (meth)acrylate-based resin contains at least two (meth)acrylates as polymerization components, and the (meth)acrylates account for more than 90% by mass of the total polymer components; and

[0116] The ratio of the number-average particle size Db of the first inorganic oxide particle to the number-average particle size Da of the pressure-responsive parent particle, Db / Da, is 0.05 or more and 0.25 or less.

[0117] It has at least two glass transition temperatures, and the difference between the lowest and highest glass transition temperatures is more than 30°C.

[0118] The pressure-responsive particles involved in this embodiment are pressure-responsive particles that can peelably bond the surfaces of a recording medium together by softening under pressure.

[0119] The pressure-responsive particles involved in this embodiment exhibit thermal properties of "having at least two glass transition temperatures, with the difference between the lowest and highest glass transition temperatures being 30°C or more," and undergo a phase transition due to pressure. In this invention, pressure-responsive particles that undergo a phase transition due to pressure represent pressure-responsive particles that satisfy Equation 1 below.

[0120] Equation 1……10℃≤T1-T2

[0121] In Equation 1, T1 is the temperature at which the viscosity is 10000 Pa·s under a pressure of 1 MPa, and T2 is the temperature at which the viscosity is 10000 Pa·s under a pressure of 10 MPa. The method for determining temperatures T1 and T2 will be described later.

[0122] The pressure-responsive particles involved in this embodiment readily undergo phase transitions under pressure and exhibit excellent adhesion by using a styrene-based resin containing "styrene and other vinyl monomers as polymerizing components" and a "(meth)acrylate-based resin containing at least two types of (meth)acrylates as polymerizing components, with the (meth)acrylates accounting for 90% or more of the total mass of the polymerizing components." The mechanism behind this is speculated to be as follows.

[0123] Typically, styrene-based resins and (meth)acrylate-based resins have low compatibility with each other; therefore, it is assumed that the pressure-responsive masterbatch contains both resins in a phase-separated state. Furthermore, it is believed that when the pressure-responsive masterbatch is pressurized, the (meth)acrylate-based resin, with its lower glass transition temperature, fluidizes first, and this fluidization extends to the styrene-based resin, causing both resins to fluidize uniformly. Moreover, it is believed that when the two resins in the pressure-responsive masterbatch solidify upon depressurization after pressurization to form a resin layer, their low compatibility will cause them to reform into a phase-separated state.

[0124] Hypothesis: In (meth)acrylate resins containing at least two types of (meth)acrylates as polymerizing components, at least two types of ester groups are bonded to the main chain. Therefore, compared to homopolymers of (meth)acrylates, the molecular alignment in the solid state is lower, making them easier to fluidize under pressure. Furthermore, it is hypothesized that:

[0125] When the (meth)acrylate accounts for 90% or more of the total mass percentage of the polymer component, at least two ester groups will exist in high density. Therefore, the alignment of the molecules in the solid state becomes lower, making them easier to fluidize under pressure. Thus, it is speculated that the pressure-responsive particles involved in this embodiment are more prone to fluidization under pressure, i.e., more prone to phase transition under pressure, compared to pressure-responsive particles of homopolymers of (meth)acrylate-based resins.

[0126] Furthermore, methacrylate-based resins containing at least two types of (meth)acrylates as polymerizing components, with the (meth)acrylates accounting for 90% or more of the total polymerizing components, exhibit low molecular alignment during re-curing. Therefore, it is speculated that phase separation with the styrene-based resin will be minimal. It is speculated that the smaller the phase separation between the styrene-based and (meth)acrylate-based resins, the higher the uniformity of the bonding surface relative to the adhered material, and the better the adhesion. Therefore, it is speculated that the pressure-responsive particles involved in this embodiment exhibit superior adhesion compared to pressure-responsive particles where the (meth)acrylate-based resin is a homopolymer of (meth)acrylate.

[0127] In this embodiment, when the pressure-responsive particles, which contain first inorganic oxide particles with a number-average particle size Db to a number-average particle size Da of the pressure-responsive parent particles, are successively conveyed from a recording medium in which multiple sheets are overlapped in a manner that exposes the adhesive surface, the recording medium is less prone to retransmission.

[0128] Hypothesis: The first inorganic oxide particles, due to their inorganic oxide raw material, possess a certain degree of hardness and a relatively large particle size (1 / 4 to 1 / 20 of the parent particles). Therefore, the resin layer exposed at the bonding surface generates appropriate friction between the overlapping recording media. Hypothesis: As a result, the recording media other than the sheet being transmitted utilize this friction to resist the transmission force of the transmission unit, suppressing retransmission.

[0129] Inorganic oxide particles with a Db / Da ratio less than 0.05 will be buried by the resin on the bonding surface or have a small exposed area, making it difficult to achieve the above-mentioned effects.

[0130] On the other hand, inorganic oxide particles with a Db / Da ratio exceeding 0.25 form larger protrusions containing inorganic oxides on the bonding surface, which can sometimes weaken the adhesive force of the bonding surface.

[0131] The composition, structure, and characteristics of the pressure-responsive particles involved in this embodiment will be described in detail below. In the following description, unless otherwise specified, "styrene-based resin" means "styrene-based resin containing styrene and other vinyl monomers as polymerizing components", and "(meth)acrylate-based resin" means "(meth)acrylate-based resin containing at least two (meth)acrylates as polymerizing components and the (meth)acrylates account for 90% or more of the total mass of the polymerizing components".

[0132] [Pressure-responsive parent particle]

[0133] The pressure-responsive masterbatch contains at least styrene-based resins and (meth)acrylate-based resins. The pressure-responsive masterbatch may also contain colorants, release agents, and other additives.

[0134] From the viewpoint of maintaining adhesion, the content of styrene-based resin in the pressure-responsive masterbatch is preferably greater than that of (meth)acrylate-based resin. The content of styrene-based resin relative to the total content of styrene-based resin and (meth)acrylate-based resin is preferably 55% by mass or more and 80% by mass or less, more preferably 60% by mass or more and 75% by mass or less, and even more preferably 65% ​​by mass or more and 70% by mass or less.

[0135] -Styrene-based resins-

[0136] The pressure-responsive parent particles constituting the pressure-responsive particles involved in this embodiment contain a styrene-based resin, which contains styrene and other vinyl monomers as polymerizing components.

[0137] Regarding the mass percentage of styrene in the overall polymer composition of styrene-based resins, from the viewpoint of suppressing the fluidization of pressure-responsive particles in an unpressurized state, it is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 75% by mass or more. From the viewpoint of forming pressure-responsive particles that are prone to phase change due to pressure, it is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0138] Other vinyl monomers besides styrene that constitute styrene-based resins include, for example, styrene-based monomers other than styrene and acrylic monomers.

[0139] Examples of styrene monomers other than styrene include: vinylnaphthalene; alkyl-substituted styrene such as α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, and p-n-dodecylstyrene; aryl-substituted styrene such as p-phenylstyrene; alkoxy-substituted styrene such as p-methoxystyrene; halogen-substituted styrene such as p-chlorostyrene, 3,4-dichlorostyrene, p-fluorostyrene, and 2,5-difluorostyrene; and nitro-substituted styrene such as m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene. Styrene monomers can be used alone or in combination with two or more.

[0140] As an acrylic monomer, at least one acrylic monomer selected from the group consisting of (meth)acrylic acid and (meth)acrylates is preferred. Examples of (meth)acrylates include alkyl (meth)acrylates, carboxyl-substituted alkyl (meth)acrylates, hydroxyl-substituted alkyl (meth)acrylates, alkoxy-substituted alkyl (meth)acrylates, and di(meth)acrylates. An acrylic monomer may be used alone or in combination with two or more monomers.

[0141] Examples of alkyl methacrylates include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, dicyclopentyl methacrylate, and isobornyl methacrylate.

[0142] Examples of carboxyl-substituted alkyl esters of (meth)acrylic acid include 2-carboxyethyl methacrylate.

[0143] Examples of hydroxylated alkyl esters of (meth)acrylate include 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, 3-carboxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0144] Examples of alkoxy-substituted alkyl esters of (meth)acrylate include 2-methoxyethyl ester of (meth)acrylate.

[0145] Examples of di(meth)acrylates 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.

[0146] Examples of (meth)acrylates include 2-(diethylamino)ethyl (meth)acrylate, benzyl (meth)acrylate, and methoxy polyethylene glycol (meth)acrylate.

[0147] Other vinyl monomers constituting styrene-based resins, besides styrene-based monomers and acrylic monomers, include, for example: (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.

[0148] From the viewpoint of forming pressure-responsive particles that readily undergo phase transitions under pressure, styrene-based resins preferably contain (meth)acrylates, more preferably alkyl (meth)acrylates, even more preferably alkyl (meth)acrylates containing alkyl groups with 2 or more but less than 10 carbon atoms, and even more preferably alkyl (meth)acrylates containing alkyl groups with 4 or more but less than 8 carbon atoms. Particularly preferred are those containing at least one of n-butyl acrylate and 2-ethylhexyl acrylate. From the viewpoint of forming pressure-responsive particles that readily undergo phase transitions under pressure, styrene-based resins and (meth)acrylate-based resins preferably contain the same type of (meth)acrylate as polymerizing components.

[0149] Regarding the mass percentage of (meth)acrylate in the overall polymer composition of the styrene-based resin, from the viewpoint of suppressing the fluidization of pressure-responsive particles in an unpressurized state, it 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 forming pressure-responsive particles that readily undergo phase change due to pressure, it is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. As the (meth)acrylate used here, alkyl (meth)acrylate is preferred, for example, more preferably an alkyl (meth)acrylate with 2 or more and 10 or less carbon atoms in the alkyl group, and even more preferably an alkyl (meth)acrylate with 4 or more and 8 or less carbon atoms in the alkyl group.

[0150] Styrene-based resins, for example, particularly preferably contain at least one of n-butyl acrylate and 2-ethylhexyl acrylate as a polymerization component. Regarding the total amount of n-butyl acrylate and 2-ethylhexyl acrylate in the overall polymerization component of the styrene-based resin, from the viewpoint of suppressing the fluidization of pressure-responsive particles in an unpressurized state, it 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 forming pressure-responsive particles that are prone to phase change due to pressure, it is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more.

[0151] Regarding the weight-average molecular weight of the styrene-based resin, from the viewpoint of suppressing the fluidization of pressure-responsive particles in an unpressurized state, it is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more. From the viewpoint of forming pressure-responsive particles that are prone to phase change due to pressure, it is preferably 60,000 or less, more preferably 55,000 or less, and even more preferably 50,000 or less.

[0152] In this invention, the weight-average molecular weight of the resin was determined using gel permeation chromatography (GPC). In the GPC determination, a TOSOH CORPORATION HLC-8120 GPC was used as the GPC apparatus, a TOSOH CORPORATION TSKgel SuperHM-M (15 cm) column was used as the column, and tetrahydrofuran was used as the solvent. The weight-average molecular weight of the resin was calculated using a molecular weight calibration curve prepared from monodisperse polystyrene standard samples.

[0153] Regarding the glass transition temperature of styrene-based resins, from the viewpoint of suppressing the fluidization of pressure-responsive particles in an unpressurized state, it is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher. From the viewpoint of forming pressure-responsive particles that are prone to phase change due to pressure, it is preferably 110°C or lower, more preferably 100°C or lower, and even more preferably 90°C or lower.

[0154] In this invention, the glass transition temperature of the resin is determined based on a differential scanning calorimetry (DSC) curve obtained by performing differential scanning calorimetry (DSC). More specifically, it is determined by extrapolating the glass transition onset temperature as described in JIS K7121:1987 "Method for determining the transition temperature of plastics".

[0155] The glass transition temperature of a resin can be controlled by the type and ratio of polymerizing components. A higher density of flexible units such as methylene, ethylene, and oxyethylene in the main chain tends to result in a lower glass transition temperature, while a higher density of rigid units such as aromatic rings and cyclohexane rings in the main chain tends to result in a higher glass transition temperature. Furthermore, a higher density of aliphatic groups in the side chains tends to result in a lower glass transition temperature.

[0156] In this embodiment, regarding the mass percentage of styrene-based resin in the total pressure-responsive master particles, from the viewpoint of suppressing the fluidization of pressure-responsive particles in an unpressurized state, it is preferably 55% by mass or more, more preferably 60% by mass or more, and even more preferably 65% ​​by mass or more. From the viewpoint of forming pressure-responsive particles that are prone to phase change due to pressure, it is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.

[0157] -(meth)acrylate resins-

[0158] The pressure-responsive parent particles constituting the pressure-responsive particles involved in this embodiment contain a (meth)acrylate resin, which contains at least two (meth)acrylates as polymerizing components and the (meth)acrylates account for 90% or more of the total mass of the polymerizing components.

[0159] The mass percentage of (meth)acrylate in the total polymer component of (meth)acrylate resin is, for example, 90% by mass or more, more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 100% by mass.

[0160] Examples of (meth)acrylates include alkyl (meth)acrylates, carboxyl-substituted alkyl (meth)acrylates, hydroxyl-substituted alkyl (meth)acrylates, alkoxy-substituted alkyl (meth)acrylates, and di(meth)acrylates.

[0161] Examples of alkyl methacrylates include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, dicyclopentyl methacrylate, and isobornyl methacrylate.

[0162] Examples of carboxyl-substituted alkyl esters of (meth)acrylic acid include 2-carboxyethyl methacrylate.

[0163] Examples of hydroxylated alkyl esters of (meth)acrylate include 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, 3-carboxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0164] Examples of alkoxy-substituted alkyl esters of (meth)acrylate include 2-methoxyethyl ester of (meth)acrylate.

[0165] Examples of di(meth)acrylates 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.

[0166] Examples of (meth)acrylates include 2-(diethylamino)ethyl (meth)acrylate, benzyl (meth)acrylate, and methoxy polyethylene glycol (meth)acrylate.

[0167] (Meth)acrylates can be used alone or in combination with two or more.

[0168] From the viewpoint of forming pressure-responsive particles that readily undergo phase change under pressure and exhibit excellent adhesion, alkyl methacrylates are preferred, more preferably alkyl methacrylates with 2 or more but less than 10 carbon atoms in the alkyl group, and even more preferably alkyl methacrylates with 4 or more but less than 8 carbon atoms in the alkyl group. Especially preferred are n-butyl acrylate and 2-ethylhexyl acrylate. From the viewpoint of forming pressure-responsive particles that readily undergo phase change under pressure, styrene-based resins and methacrylate-based resins preferably contain the same type of methacrylate as a polymerization component.

[0169] From the viewpoint of forming pressure-responsive particles that readily undergo phase change under pressure and exhibit excellent adhesion, the mass percentage of (meth)acrylate alkyl esters in the overall polymer composition of (meth)acrylate-based resins is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 100% by mass. As for the (meth)acrylate alkyl esters used here, for example, alkyl acrylates with 2 or more and 10 or less carbon atoms in the alkyl group are preferred, and alkyl acrylates with 4 or more and 8 or less carbon atoms in the alkyl group are more preferred.

[0170] From the viewpoint of forming pressure-responsive particles that readily undergo phase change under pressure and exhibit excellent adhesion, the mass ratio of the two (meth)acrylates contained in the (meth)acrylate resin as polymerizing components, which have the largest mass proportions, is preferably 80:20 to 20:80, more preferably 70:30 to 30:70, and even more preferably 60:40 to 40:60.

[0171] In a meth)acrylate resin, the two meth)acrylates containing the largest mass proportion of at least two types as polymerizing components are preferably alkyl meth)acrylates. As the alkyl meth)acrylates used here, alkyl meth)acrylates with 2 or more but less than 10 carbon atoms in the alkyl group are preferred, and alkyl meth)acrylates with 4 or more but less than 8 carbon atoms in the alkyl group are more preferred.

[0172] When the two (meth)acrylates contained as polymerizing components in a (meth)acrylate resin are alkyl (meth)acrylates with the largest mass proportions, from the viewpoint of forming pressure-responsive particles that are easily transformed by pressure and have excellent adhesion, the difference in the number of carbon atoms of the alkyl groups of the two (meth)acrylates is preferably, for example, 1 or more and 4 or less, more preferably 2 or more and 4 or less, and even more preferably 3 or 4.

[0173] From the viewpoint of forming pressure-responsive particles that readily undergo phase transitions under pressure and exhibit excellent adhesion, (meth)acrylate resins preferably contain, for example, n-butyl acrylate and 2-ethylhexyl acrylate as polymerization components. More preferably, among the at least two (meth)acrylates contained as polymerization components in the (meth)acrylate resin, n-butyl acrylate and 2-ethylhexyl acrylate are the two with the largest mass proportions. The total amount of n-butyl acrylate and 2-ethylhexyl acrylate in the overall polymerization components of the (meth)acrylate resin is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 98% by mass or more, and even more preferably 100% by mass.

[0174] (Meth)acrylate resins may contain vinyl monomers other than (meth)acrylates as polymerization components. Examples of vinyl monomers other than (meth)acrylates include: (meth)acrylic acid; styrene; styrene monomers other than styrene; (meth)acrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, and vinyl isopropenyl ketone; and olefins such as isoprene, butene, and butadiene. These vinyl monomers may be used individually or in combination with two or more.

[0175] When a (meth)acrylate resin contains a vinyl monomer other than (meth)acrylate as a polymerization component, the vinyl monomer other than (meth)acrylate is preferably at least one of acrylic acid and methacrylic acid, and more preferably acrylic acid.

[0176] Regarding the weight-average molecular weight of (meth)acrylate resins, from the viewpoint of suppressing the fluidization of pressure-responsive particles in an unpressurized state, it is preferably 50,000 or more, more preferably 100,000 or more, even more preferably 120,000 or more, and even more preferably 150,000 or more. From the viewpoint of forming pressure-responsive particles that are prone to phase change due to pressure, it is preferably 250,000 or less, more preferably 220,000 or less, and even more preferably 200,000 or less.

[0177] Regarding the glass transition temperature of (meth)acrylate resins, from the viewpoint of forming pressure-responsive particles that readily undergo phase change due to pressure, it is preferably 10°C or less, more preferably 0°C or less, and even more preferably -10°C or less. From the viewpoint of suppressing the fluidization of pressure-responsive particles in an unpressurized state, it is preferably -90°C or more, more preferably -80°C or more, and even more preferably -70°C or more.

[0178] In this embodiment, regarding the mass percentage of (meth)acrylate resin in the total pressure-responsive master particles, from the viewpoint of forming pressure-responsive particles that are prone to phase change due to pressure, it is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 30% by mass or more. From the viewpoint of suppressing the fluidization of pressure-responsive particles in an unpressurized state, it is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.

[0179] In this embodiment, the total amount of styrene-based resin and (meth)acrylate-based resin contained in the pressure-responsive masterbatch is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 100% by mass, relative to the total amount of the pressure-responsive masterbatch.

[0180] -Other Resins-

[0181] Pressure-responsive parent materials may contain, for example, polystyrene; epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, modified rosin, and other non-vinyl resins; etc. These resins may be used alone or in combination with two or more.

[0182] -Various additives-

[0183] Pressure-responsive parent particles may contain colorants (e.g., pigments, dyes), release agents (e.g., hydrocarbon waxes; natural waxes such as carnauba wax, rice bran wax, and candelilla wax; synthetic or mineral / petroleum waxes such as lignite wax; ester waxes such as fatty acid esters and lignite esters), charge control agents, etc., as needed.

[0184] When the pressure-responsive particles involved in this embodiment are made into transparent pressure-responsive particles, the coloring dose in the pressure-responsive parent particles is preferably 1.0% by mass or less relative to the total pressure-responsive parent particles. From the viewpoint of improving the transparency of the pressure-responsive particles, for example, the less the better.

[0185] -Structure of pressure-responsive parent particles-

[0186] The internal structure of the pressure-responsive parent particle is preferably an island structure, for example. As an island structure, a preferred structure is one containing a marine phase with a styrene-based resin and an island phase containing a (meth)acrylate resin dispersed within that marine phase. The specific morphology of the styrene-based resin contained in the marine phase is as described above. The specific morphology of the (meth)acrylate resin contained in the island phase is as described above. An island phase without (meth)acrylate resin may also be dispersed in the marine phase.

[0187] When the pressure-responsive parent particle has an island structure, the average diameter of the island phase is preferably, for example, 200 nm or more and 500 nm or less. When the average diameter of the island phase is 500 nm or less, the pressure-responsive parent particle is more prone to phase transition due to pressure, and when the average diameter of the island phase is 200 nm or more, the required mechanical strength of the pressure-responsive parent particle (e.g., the strength to resist deformation during stirring in a developer) is excellent. From these viewpoints, the average diameter of the island phase is more preferably, for example, 220 nm or more and 450 nm or less, and even more preferably 250 nm or more and 400 nm or less.

[0188] As a method for controlling the average diameter of the island phase in the island structure within the aforementioned range, examples include: increasing or decreasing the amount of (meth)acrylate resin relative to the amount of styrene-based resin in the method for manufacturing pressure-responsive master particles described later; increasing or decreasing the time of maintaining at high temperature in the process of melting / assembling the aggregated resin particles; etc.

[0189] The confirmation of island structures and the determination of the average diameter of island facies are carried out by the following methods.

[0190] Pressure-responsive particles were embedded in epoxy resin, and sections were prepared using a diamond scalpel. The sections were then stained with osmium tetroxide or ruthenium tetroxide in a desiccator. The stained sections were observed using a scanning electron microscope (SEM). The intensity of the resin staining (using osmium tetroxide or ruthenium tetroxide) was used to distinguish between marine and island facies with island structures, and this was used to confirm the presence or absence of island structures. One hundred island facies were randomly selected from the SEM images, and the major axis of each island facies was measured. The average of the 100 major axes was taken as the average diameter.

[0191] The pressure-responsive parent particle can be a monolayer structure or a core / shell structure with a core and a shell covering the core. From the viewpoint of suppressing the fluidization of the pressure-responsive particle in an unpressurized state, a core / shell structure is preferred, for example.

[0192] When the pressure-responsive parent particle has a core / shell structure, from the viewpoint that it is easy to undergo a phase transition due to pressure, it is preferable, for example, that the core contains a styrene-based resin and a (meth)acrylate-based resin. Furthermore, from the viewpoint of suppressing the fluidization of the pressure-responsive particle in an unpressurized state, it is preferable, for example, that the shell contains a styrene-based resin. The specific forms of the styrene-based resin are as described above. The specific forms of the (meth)acrylate-based resin are as described above.

[0193] When the pressure-responsive parent particle has a core / shell structure, it is preferable, for example, that the core has a marine phase containing a styrene-based resin and an island phase containing a (meth)acrylate-based resin dispersed in the marine phase. The average diameter of the island phase is preferably within the range described above. Furthermore, in addition to the core having the above structure, it is also preferable, for example, that the shell contains a styrene-based resin. In this case, the marine phase and shell of the core have a continuous structure, and the pressure-responsive parent particle is prone to phase transition due to pressure. The specific morphology of the styrene-based resin contained in the marine phase of the core and the shell is as described above. The specific morphology of the (meth)acrylate-based resin contained in the island phase of the core is as described above.

[0194] Examples of resins contained in the shell include: polystyrene; epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, modified rosin, and other non-ethylene resins; etc. These resins can be used alone or in combination with two or more.

[0195] Regarding the average thickness of the shell, from the viewpoint of suppressing deformation of pressure-responsive parent particles, it is preferably 120 nm or more, more preferably 130 nm or more, and even more preferably 140 nm or more. From the viewpoint that pressure-responsive parent particles are prone to phase transition due to pressure, it is preferably 550 nm or less, more preferably 500 nm or less, and even more preferably 400 nm or less.

[0196] The average thickness of the shell was determined by the following method.

[0197] Pressure-responsive particles were embedded in epoxy resin, and sections were prepared using a diamond scalpel. The sections were then stained with osmium tetroxide or ruthenium tetroxide in a desiccator. The stained sections were observed using a scanning electron microscope (SEM). Ten cross-sections of pressure-responsive parent particles were randomly selected from the SEM images. The shell thickness at 20 locations was measured for each pressure-responsive parent particle, and the average value was calculated. The average thickness of the ten pressure-responsive parent particles was taken as the mean thickness.

[0198] Regarding the number-average particle size of the pressure-responsive parent particles, from the viewpoint of the ease of handling the pressure-responsive parent particles, it is preferably 5 μm or more, more preferably 5.5 μm or more, and even more preferably 6 μm or more. From the viewpoint that the pressure-responsive parent particles as a whole are prone to phase transition due to pressure, it is preferably 12 μm or less, more preferably 10 μm or less, and even more preferably 9 μm or less.

[0199] The particle size of a pressure-responsive parent particle refers to the diameter of a circle with the same area as the particle image (the so-called equivalent circle diameter). The number-average particle size of a pressure-responsive parent particle refers to the particle size that accumulates from the smallest diameter side to 50% in a distribution based on the number of particles. The number-average particle size of a pressure-responsive parent particle is determined by taking SEM (scanning electron microscope) images of pressure-responsive parent particles and performing image analysis on at least 300 pressure-responsive parent particles in the SEM images.

[0200] [First inorganic oxide particle]

[0201] Examples of first inorganic oxide particles include CeO2, SrTiO3, SiO2, TiO2, Al2O3, CuO, ZnO, SnO2, Fe2O3, MgO, BaO, CaO, K2O, Na2O, ZrO2, CaO·SiO2, and K2O·(TiO2). n Al₂O₃·2SiO₂, etc. These inorganic oxide particles can be used alone or in combination with two or more.

[0202] As the first inorganic oxide particle, at least one of strontium titanate particles (SrTiO3) and cerium oxide particles (CeO2) is preferred. Strontium titanate is the common name for strontium titanium trioxide (IV).

[0203] Strontium titanate particles and cerium oxide particles have a certain degree of hardness and are angular in shape, thus generating appropriate friction between overlapping recording media, which easily suppresses the retransmission of the recording media.

[0204] The surface of the first inorganic oxide particles is preferably subjected to a hydrophobic treatment, for example. The hydrophobic treatment is performed, for example, by immersing the inorganic oxide particles in a hydrophobic treatment agent. There are no particular limitations on the hydrophobic treatment agent; examples include silane-based coupling agents, silicone oils, titanate-based coupling agents, and aluminum-based coupling agents. One or more of these can be used simultaneously. The amount of the hydrophobic treatment agent is, for example, more than 1 part by mass and less than 10 parts by mass relative to 100 parts by mass of the inorganic oxide particles.

[0205] From the viewpoint of suppressing the retransmission of the recording medium, the ratio of the number-average particle size Db of the first inorganic oxide particles to the number-average particle size Da of the pressure-responsive parent particles, Db / Da, is, for example, 0.05 or more, preferably 0.06 or more, and more preferably 0.08 or more.

[0206] From the viewpoint of excellent adhesion of pressure-responsive particles, the ratio of the number-average particle size Db of the first inorganic oxide particle to the number-average particle size Da of the pressure-responsive parent particle, Db / Da, is, for example, 0.25 or less, preferably 0.22 or less, and more preferably 0.20 or less.

[0207] From the viewpoint of suppressing the retransmission of the recording medium, the average primary particle size Db of the first inorganic oxide particles is preferably 0.5 μm or more, more preferably 0.6 μm or more, and even more preferably 0.8 μm or more.

[0208] From the viewpoint of excellent adhesion of pressure-responsive particles, the average primary particle size Db of the first inorganic oxide particles is preferably 2.5 μm or less, more preferably 2.0 μm or less, and even more preferably 1.5 μm or less.

[0209] The primary diameter of the first inorganic oxide particle refers to the diameter of a circle with the same area as the primary particle image (the so-called equivalent circle diameter). The average primary diameter of the first inorganic oxide particles refers to the particle diameter accumulated from the smallest diameter side to 50% in the distribution of primary diameters. The primary diameter of the first inorganic oxide particles is determined by taking SEM (scanning electron microscope) images of pressure-responsive particles exfoliated with the first inorganic oxide particles and performing image analysis on the inorganic oxide particles on the pressure-responsive parent particles in the SEM images. Inorganic oxide particles with an equivalent circle diameter exceeding 250 nm are randomly extracted, and the average primary diameter based on the number of equivalent circle diameters is determined.

[0210] The primary particle size of the first inorganic oxide particles can be adjusted through crushing and grading of the inorganic oxide particles.

[0211] From the viewpoint of suppressing the retransmission of the recording medium, the amount of the first inorganic oxide particles added is preferably 0.05 parts by mass or more, more preferably 0.08 parts by mass or more, and even more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the pressure-responsive parent particles.

[0212] From the viewpoint of excellent adhesion of pressure-responsive particles, the amount of the first inorganic oxide particles added is preferably 3 parts by mass or less, more preferably 1.5 parts by mass or less, and even more preferably 1 part by mass or less.

[0213] [Second inorganic oxide particle]

[0214] From the viewpoint of suppressing the aggregation of the particles and having excellent fluidity, pressure-responsive particles are preferably, for example, containing second inorganic oxide particles with a number-average particle size of 200 nm or less.

[0215] The number-average particle size of the second inorganic oxide particles is preferably 150 nm or less, more preferably 120 nm or less. The number-average particle size of the second inorganic oxide particles is preferably 10 nm or more, more preferably 20 nm or more, and even more preferably 30 nm or more.

[0216] The primary particle size of the second inorganic oxide particle refers to the diameter of a circle with the same area as the primary particle image (the so-called equivalent circle diameter). The average primary particle size of the second inorganic oxide particle refers to the particle size accumulated from the smallest diameter side to 50% in the distribution of primary particle sizes based on the number of particles. The primary particle size of the second inorganic oxide particle is determined by taking SEM (scanning electron microscope) images of pressure-responsive particles exfoliated with the second inorganic oxide particle and performing image analysis on the inorganic oxide particles on the pressure-responsive parent particle in the SEM images. Inorganic oxide particles with an equivalent circle diameter of less than 250 nm are randomly extracted, and the average primary particle size based on the number of particles is determined from at least 300 equivalent circle diameters.

[0217] Examples of second inorganic oxide particles include SiO2, TiO2, Al2O3, CuO, ZnO, SnO2, Fe2O3, MgO, BaO, CaO, K2O, Na2O, ZrO2, CaO·SiO2, and K2O·(TiO2). n Materials such as Al2O3·2SiO2, etc. Among these, silicon dioxide particles (SiO2), titanium dioxide particles (TiO2), and aluminum oxide particles (Al2O3) are preferred, with silicon dioxide particles being more preferred. These inorganic oxide particles can be used individually or in combination with two or more.

[0218] The surface of the second inorganic oxide particles is preferably subjected to a hydrophobic treatment, for example. The hydrophobic treatment is performed, for example, by immersing the inorganic oxide particles in a hydrophobic treatment agent. There are no particular limitations on the hydrophobic treatment agent; examples include silane-based coupling agents, silicone oils, titanate-based coupling agents, and aluminum-based coupling agents. One or more of these can be used simultaneously. The amount of the hydrophobic treatment agent is, for example, more than 1 part by mass and less than 10 parts by mass relative to 100 parts by mass of the inorganic oxide particles.

[0219] From the viewpoint of suppressing the aggregation of pressure-responsive particles, the amount of the second inorganic oxide particles added is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1.0 parts by mass or more, relative to 100 parts by mass of the pressure-responsive parent particles.

[0220] From the viewpoint of excellent adhesion of pressure-responsive particles, the amount of the second inorganic oxide particles added is preferably 7 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less.

[0221] [Other additives]

[0222] Examples of additives include resin particles (such as polystyrene, polymethyl methacrylate, and melamine resin) and cleaning aids (such as metal salts of higher fatty acids, such as zinc stearate, and particles of fluorinated high molecular weight compounds).

[0223] [Properties of pressure-responsive particles]

[0224] When the pressure-responsive particles involved in this embodiment have at least two glass transition temperatures, it is presumed that one of the glass transition temperatures is the glass transition temperature of a styrene-based resin and the other is the glass transition temperature of a (meth)acrylate-based resin.

[0225] The pressure-responsive particles involved in this embodiment may also have three or more glass transition temperatures, and the number of glass transition temperatures is preferably two, for example. A form with two glass transition temperatures is one in which the resin contained in the pressure-responsive particles is only styrene-based resin and (meth)acrylate-based resin; or in a form where the content of other resins besides styrene-based resin and (meth)acrylate-based resin is low (for example, the content of other resins is 5% by mass or less relative to the total weight of the pressure-responsive particles).

[0226] The pressure-responsive particles involved in this embodiment have at least two glass transition temperatures, and the difference between the lowest and highest glass transition temperatures is 30°C or more. From the viewpoint that pressure-responsive particles readily undergo phase transitions due to pressure, the difference between the lowest and highest glass transition temperatures is more preferably 40°C or more, further preferably 50°C or more, and even more preferably 60°C or more. The upper limit of the difference between the lowest and highest glass transition temperatures is, for example, 140°C or less, 130°C or less, or 120°C or less.

[0227] Regarding the lowest glass transition temperature exhibited by the pressure-responsive particles involved in this embodiment, from the viewpoint that pressure-responsive particles are prone to phase transition due to pressure, it is preferably 10°C or less, more preferably 0°C or less, and even more preferably -10°C or less. From the viewpoint of suppressing the fluidization of pressure-responsive particles in an unpressurized state, it is preferably -90°C or more, more preferably -80°C or more, and even more preferably -70°C or more.

[0228] Regarding the highest glass transition temperature exhibited by the pressure-responsive particles involved in this embodiment, from the viewpoint of suppressing the fluidization of pressure-responsive particles in an unpressurized state, it is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher. From the viewpoint that pressure-responsive particles are prone to phase transition due to pressure, it is preferably 70°C or lower, more preferably 65°C or lower, and even more preferably 60°C or lower.

[0229] In this invention, the glass transition temperature of the pressure-responsive particles is determined based on a differential scanning calorimetry (DSC) curve obtained by performing differential scanning calorimetry (DSC). More specifically, it is determined by extrapolating the glass transition onset temperature as described in JIS K7121:1987 "Method for determining the transition temperature of plastics".

[0230] The pressure-responsive particles involved in this embodiment are pressure-responsive particles that undergo a phase change due to pressure, and they satisfy the following formula 1.

[0231] Equation 1……10℃≤T1-T2

[0232] In Equation 1, T1 is the temperature at which the viscosity is 10000 Pa·s under a pressure of 1 MPa, and T2 is the temperature at which the viscosity is 10000 Pa·s under a pressure of 10 MPa.

[0233] Regarding the temperature difference (T1-T2), from the viewpoint that pressure-responsive particles are prone to phase change due to pressure, it is, for example, 10°C or more, preferably 15°C or more, and more preferably 20°C or more. From the viewpoint of suppressing the fluidization of pressure-responsive particles in an unpressurized state, it is, for example, preferably 120°C or less, more preferably 100°C or less, and even more preferably 80°C or less.

[0234] The value of temperature T1 is preferably 140°C or less, more preferably 130°C or less, even more preferably 120°C or less, and even more preferably 115°C or less. The lower limit of temperature T1 is preferably 80°C or more, more preferably 85°C or more.

[0235] The value of temperature T2 is preferably 40°C or higher, more preferably 50°C or higher, and even more preferably 60°C or higher. The upper limit of temperature T2 is preferably 85°C or lower.

[0236] As an indicator of the ease with which pressure-responsive particles undergo a phase transition due to pressure, the temperature difference (T1-T3) between temperature T1, which displays a viscosity of 10000 Pa·s at a pressure of 1 MPa, and temperature T3, which displays a viscosity of 10000 Pa·s at a pressure of 4 MPa, can be used. The temperature difference (T1-T3) is preferably 5°C or more. From the viewpoint of ease with which a phase transition occurs due to pressure, the pressure-responsive particles involved in this embodiment preferably have a temperature difference (T1-T3) of 5°C or more, and more preferably 10°C or more.

[0237] The temperature difference (T1-T3) is usually below 25℃.

[0238] From the viewpoint that the temperature difference (T1-T3) is 5°C or more, the pressure-responsive particles involved in this embodiment preferably exhibit a viscosity of 10000 Pa·s at a pressure of 4 MPa at a temperature T3 of 90°C or less, more preferably 85°C or less, and even more preferably 80°C or less. The lower limit of temperature T3 is preferably 60°C or more, for example.

[0239] The method for determining temperatures T1, T2, and T3 is as follows.

[0240] Compressed pressure-responsive particles were used to prepare granular samples. The granular samples were placed in a flow meter (Shimadzu Corporation, CFT-500), and the applied pressure was fixed at 1 MPa. The viscosity at 1 MPa relative to temperature was measured. Based on the obtained viscosity graph, the viscosity at the applied pressure of 1 MPa was determined to be 10. 4Temperature T1 is determined at a pressure of 1 MPa per 10 MPa. Temperature T2 is determined using the same method as for temperature T1, except that the applied pressure is set to 10 MPa. Temperature T3 is determined using the same method as for temperature T1, except that the applied pressure is set to 4 MPa. The temperature difference (T1-T2) is calculated from temperatures T1 and T2. The temperature difference (T1-T3) is calculated from temperatures T1 and T3.

[0241] [Methods for manufacturing pressure-responsive particles]

[0242] The pressure-responsive particles involved in this embodiment can be obtained by adding an additive to the pressure-responsive master particles after manufacturing them.

[0243] Pressure-responsive parent particles can be manufactured by any of the following methods: dry preparation (e.g., mixing and pulverizing) or wet preparation (e.g., agglomeration polymerization, suspension polymerization, dissolution suspension polymerization). There are no particular limitations on these methods, and well-known methods can be used. For example, agglomeration polymerization is preferred for obtaining pressure-responsive parent particles.

[0244] In the case of manufacturing pressure-responsive parent particles by agglomeration, the pressure-responsive parent particles are manufactured, for example, through the following steps:

[0245] The process of preparing a styrene-based resin particle dispersion containing styrene-based resin particles (styrene-based resin particle dispersion preparation process).

[0246] The process of polymerizing (meth)acrylate resin in a styrene-based resin particle dispersion to form composite resin particles containing styrene-based resin and (meth)acrylate resin (composite resin particle formation process).

[0247] The process of agglomerating composite resin particles in a composite resin particle dispersion to form aggregated particles (agglomerated particle formation process); and

[0248] The process of heating a dispersion of agglomerated particles to melt / aggregate the agglomerated particles and form pressure-responsive parent particles (melting / aggregation process).

[0249] The details of each process are explained below.

[0250] The following description illustrates a method for obtaining pressure-responsive masterbatch free of colorants and release agents. Colorants, release agents, and other additives may be used as needed. When the pressure-responsive masterbatch contains colorants and release agents, a melt / assembly process is performed after mixing the composite resin particle dispersion, the colorant particle dispersion, and the release agent particle dispersion. The colorant particle dispersion and the release agent particle dispersion can be prepared, for example, by dispersing the materials using a known disperser after mixing.

[0251] -Preparation process for styrene-based resin particle dispersion-

[0252] Styrene-based resin particle dispersions are, for example, dispersions in which styrene-based resin particles are dispersed in a dispersion medium using surfactants.

[0253] Examples of suitable dispersion media include aqueous media such as water and alcohols. They can be used alone or in combination with two or more.

[0254] Examples of surfactants include: anionic surfactants such as sulfate esters, sulfonates, 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 polyols. Nonionic surfactants can be used simultaneously with anionic or cationic surfactants. Anionic surfactants are preferred, for example. A single surfactant can be used, or two or more can be used simultaneously.

[0255] As a method for dispersing styrene-based resin particles in a dispersion medium, for example, a method of mixing styrene-based resin and a dispersion medium and then dispersing them by stirring using a rotary shear homogenizer or a ball mill, sand mill, bead mill, or similar media.

[0256] Another method for dispersing styrene-based resin particles in a dispersion medium is emulsion polymerization.

[0257] Specifically, after mixing the polymerization components of the styrene-based resin with a chain transfer agent or polymerization initiator, an aqueous medium containing a surfactant is further mixed and stirred to prepare an emulsion, in which the styrene-based resin is polymerized. At this time, dodecanethiol is preferably used as a chain transfer agent, for example.

[0258] 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.

[0259] The volume average particle size of the resin particles contained in the resin particle dispersion was determined using a laser diffraction particle size distribution measuring device (e.g., HORIBA, Ltd. LA-700), and the particle size accumulated to 50% of the volume-based particle size distribution from the smallest diameter side was taken as the volume average particle size (D50v).

[0260] The content of styrene-based resin particles in the styrene-based resin particle dispersion is preferably 30% by mass or more and 60% by mass or less, more preferably 40% by mass or more and 50% by mass or less.

[0261] -Composite resin particle formation process-

[0262] A styrene-based resin particle dispersion and a (meth)acrylate resin polymerization component are mixed, and the (meth)acrylate resin is polymerized in the styrene-based resin particle dispersion to form composite resin particles containing styrene-based resin and (meth)acrylate resin.

[0263] The composite resin particles are preferably resin particles containing styrene-based resin and (meth)acrylate-based resin in a micro-phase separated state. These resin particles can be manufactured, for example, by the following method.

[0264] Add the polymerization component of a (meth)acrylate resin (containing at least two (meth)acrylate monomers) to a styrene-based resin particle dispersion, and add an aqueous medium as needed. Then, while slowly stirring the dispersion, heat the dispersion to above the glass transition temperature of the styrene-based resin (e.g., a temperature 10°C to 30°C higher than the glass transition temperature of the styrene-based resin). Next, while maintaining the temperature, slowly add the aqueous medium containing a polymerization initiator dropwise, and continue stirring for a prolonged period of 1 hour to 15 hours. At this time, ammonium persulfate is preferably used as the polymerization initiator, for example.

[0265] The detailed mechanism is unclear, but it is speculated that, using the above method, monomers and polymerization initiators are impregnated in styrene-based resin particles, causing (meth)acrylate to polymerize inside the styrene-based resin particles. It is speculated that this results in composite resin particles containing (meth)acrylate resin inside the styrene-based resin particles, with the styrene-based resin and (meth)acrylate resin forming a microscopic phase separation within the particles.

[0266] The polymerization components of styrene-based resins (i.e., styrene and other vinyl monomers) can be added to the dispersion containing the composite resin particles during or after the manufacture of the composite resin particles, and the polymerization reaction can be continued. It is speculated that this will result in composite resin particles in which styrene-based resins and (meth)acrylate resins form a microscopic phase separation within the particles, with the styrene-based resin adhering to the particle surface. Pressure-responsive particles manufactured using composite resin particles with styrene-based resin adhering to the particle surface produce less coarse powder.

[0267] Other vinyl monomers that are polymeric components of the styrene-based resin attached to the surface of the composite resin particles preferably contain, for example, at least one of the monomers that constitute the styrene-based resin or (meth)acrylate-based resin present inside the composite resin particles, specifically, for example, at least one of n-butyl acrylate and 2-ethylhexyl acrylate.

[0268] 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.

[0269] The content of composite resin particles in the composite resin particle dispersion is preferably 20% by mass or more and 50% by mass or less, more preferably 30% by mass or more and 40% by mass or less.

[0270] -Agglomerated particle formation process-

[0271] The composite resin particles are agglomerated in the composite resin particle dispersion to form agglomerated particles with a diameter close to that of the target pressure-responsive parent particles.

[0272] Specifically, for example, a coagulant is added to the composite resin particle dispersion, and the pH of the composite resin particle dispersion is adjusted to acidic (e.g., pH above 2 and below 5). After adding a dispersing stabilizer as needed, the dispersion is heated to a temperature close to the glass transition temperature of the styrene-based resin (specifically, for example, above -30°C and below -10°C of the glass transition temperature of the styrene-based resin) to cause the composite resin particles to agglomerate and form aggregated particles.

[0273] In the process of forming aggregated particles, a rotary shear homogenizer can also be used to stir the composite resin particle dispersion, add a coagulant at room temperature (e.g., 25°C), adjust the pH of the composite resin particle dispersion to acidic (e.g., pH above 2 and below 5), and then heat after adding a dispersing stabilizer as needed.

[0274] Examples of flocculants include surfactants with polarity opposite to that of the surfactants contained in the composite resin particle dispersion, inorganic metal salts, and metal complexes with a polarity of two or higher. When metal complexes are used as flocculants, the amount of surfactant used can be reduced, and the charging properties can be improved.

[0275] Additives that form complexes or similar bonds with the metal ions of the flocculant can be used as needed. Chelating agents can be used as such additives.

[0276] Examples of inorganic metal salts include: calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, aluminum sulfate, etc.; inorganic metal salt polymers such as polyaluminum chloride, polyaluminum hydroxide, calcium polysulfide, etc.

[0277] Water-soluble chelating agents can be used. Examples of chelating agents include: hydroxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid; aminocarboxylic acids such as iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA); etc.

[0278] The amount of chelating agent added is preferably 0.01 parts by mass or more and 5.0 parts by mass or less relative to 100 parts by mass of resin particles, and more preferably 0.1 parts by mass or more and less than 3.0 parts by mass.

[0279] -Melting / Assembly Process-

[0280] Next, the dispersion of agglomerated particles containing the agglomerated particles is heated, for example, to a temperature above the glass transition temperature of the styrene-based resin (e.g., a temperature 10°C to 30°C higher than the glass transition temperature of the styrene-based resin) to melt / agglomerate the agglomerated particles and form pressure-responsive master particles.

[0281] The pressure-responsive parent particles obtained through the above processes typically possess an island structure consisting of a marine phase containing styrene-based resin and an island phase containing (meth)acrylate resin dispersed within this marine phase. In the composite resin particles, when the styrene-based resin and the (meth)acrylate resin are in a micro-phase-separated state, it is presumed that during the melt / assemble process, the styrene-based resin aggregates to form the marine phase, and the (meth)acrylate resin aggregates to form the island phase.

[0282] The average diameter of the island phase in the island structure can be controlled, for example, by increasing or decreasing the amount of styrene-based resin particle dispersion or at least two (meth)acrylates used in the composite resin particle forming process; increasing or decreasing the time of maintaining high temperature in the melting / combining process; etc.

[0283] Core / shell structured pressure-responsive parent particles are manufactured, for example, through the following processes:

[0284] After obtaining the agglomerated particle dispersion, the agglomerated particle dispersion and the styrene-based resin particle dispersion are further mixed, causing the styrene-based resin particles to further agglomerate on the surface of the agglomerated particles in an adherent manner, forming a second agglomerated particle process; and

[0285] The process of heating a dispersion of second aggregated particles containing second aggregated particles to melt / aggregate the second aggregated particles and form a core / shell structured pressure-responsive parent particle.

[0286] The core / shell structured pressure-responsive parent particles obtained through the above process have a shell containing a styrene-based resin. Alternatively, a resin particle dispersion containing other types of resin particles can be used instead of a styrene-based resin particle dispersion to form a shell containing other types of resin.

[0287] After the melting / combining process, the pressure-responsive parent particles formed in the solution are subjected to known cleaning, solid-liquid separation, and drying processes to obtain dry pressure-responsive parent particles. From the viewpoint of charge, the cleaning process preferably involves thorough displacement cleaning with deionized water, for example. From the viewpoint of productivity, the solid-liquid separation process preferably involves suction filtration, pressure filtration, etc. For productivity, the drying process preferably involves freeze drying, airflow drying, fluidized bed drying, vibrating fluidized bed drying, etc.

[0288] Furthermore, the pressure-responsive particles involved in this embodiment are manufactured, for example, by adding an additive to and mixing the obtained dry pressure-responsive parent particles. Mixing is preferably performed using, for example, a V-mixer, a Henschel mixer, or a Rhodes mixer. Moreover, coarse particles in the pressure-responsive particles can be removed as needed using a vibrating screen, a pneumatic screen, or the like.

[0289] <Box>

[0290] The cartridge involved in this embodiment is a cartridge that contains the pressure-responsive particles involved in this embodiment and is mounted and dismounted from a printing manufacturing apparatus. When the cartridge is mounted on the printing manufacturing apparatus, the cartridge is connected to the configuration unit of the printing manufacturing apparatus that configures the pressure-responsive particles onto the recording medium via a supply pipe.

[0291] Replace the box when the supply of pressure-responsive particles from the box to the configuration unit results in a decrease in the number of pressure-responsive particles contained within the box.

[0292] <Printing apparatus, printing method, printed matter>

[0293] The printing apparatus according to this embodiment includes: a placement unit that accommodates the pressure-responsive particles according to this embodiment and places the pressure-responsive particles onto a recording medium; and a pressing unit that folds and presses the recording medium or overlaps and presses the recording medium and another recording medium.

[0294] The configuration unit may include, for example, an applicator for applying pressure-responsive particles to a recording medium, and a fixing device for fixing the pressure-responsive particles applied to the recording medium onto the recording medium.

[0295] The crimping unit includes, for example, a folding device for folding a recording medium in which pressure-responsive particles are arranged, or an overlapping device for overlapping a recording medium in which pressure-responsive particles are arranged and another recording medium; and a pressurizing device for pressurizing the overlapping recording medium.

[0296] The pressurizing device in the crimping unit applies pressure to the recording medium containing pressure-responsive particles. As a result, the pressure-responsive particles fluidize on the recording medium, exerting adhesive properties.

[0297] The method for manufacturing printed matter according to this embodiment is implemented using the printing apparatus according to this embodiment. The method for manufacturing printed matter according to this embodiment includes: a configuration step, using the pressure-responsive particles according to this embodiment and configuring the pressure-responsive particles onto a recording medium; and a pressing step, folding and pressing the recording medium or overlapping and pressing the recording medium and another recording medium.

[0298] The configuration process may include, for example, the process of applying pressure-responsive particles to a recording medium, and may also include the process of fixing the pressure-responsive particles applied to the recording medium onto the recording medium.

[0299] The crimping process includes, for example, a folding process of folding a recording medium or an overlapping process of overlapping a recording medium and another recording medium; and a pressing process of applying pressure to the overlapping recording media.

[0300] Pressure-responsive particles can be disposed on the entire surface of the recording medium or on a portion of the recording medium. One or more layers of pressure-responsive particles can be disposed on the recording medium. The layers of pressure-responsive particles can be continuous or discontinuous along the surface direction of the recording medium. The layers of pressure-responsive particles can be layers where the pressure-responsive particles are directly arranged in particle form, or layers where adjacent pressure-responsive particles are fused together and arranged.

[0301] The amount of pressure-responsive particles (e.g., preferably transparent pressure-responsive particles) on the recording medium is, for example, 0.5 g / m² in the configured region.2 Above and 50g / m 2 Below, 1g / m 2 Above and 40g / m 2 Below, 1.5g / m 2 Above and 30g / m 2 The thickness of the pressure-responsive particles (e.g., preferably transparent pressure-responsive particles) on the recording medium is, for example, 0.2 μm or more and 25 μm or less, 0.4 μm or more and 20 μm or less, or 0.6 μm or more and 15 μm or less.

[0302] Recording media suitable for the printing apparatus of this embodiment include, for example, paper, coated paper formed by coating the surface of paper with resin, cloth, nonwoven fabric, resin film, resin sheet, etc. The recording media has an image on one or both sides.

[0303] The following is an example of a printing manufacturing apparatus according to this embodiment, but this embodiment is not limited thereto.

[0304] Figure 1 This is a schematic structural diagram illustrating an example of a printing manufacturing apparatus according to this embodiment. Figure 1 The illustrated printing apparatus includes a configuration unit 100 and a pressing unit 200 disposed downstream of the configuration unit 100. Arrows indicate the direction of transport of the recording medium.

[0305] The configuration unit 100 is an apparatus that uses the pressure-responsive particles according to this embodiment and configures the pressure-responsive particles onto the recording medium P. The recording medium P has an image pre-formed on one or both sides.

[0306] The configuration unit 100 includes a feeding device 110 and a fixing device 120 disposed downstream of the feeding device 110.

[0307] The applicator 110 applies pressure-responsive particles M onto the recording medium P. Examples of applicator methods employed by the applicator 110 include spraying, bar coating, die coating, doctor blade coating, roller coating, reverse roller coating, gravure coating, screen printing, inkjet printing, lamination, and electrophotography. A liquid composition can be prepared by dispersing the pressure-responsive particles M in a dispersion medium according to the applicator method, and the liquid composition can be applied to the applicator 110.

[0308] The recording medium P, which is given pressure-responsive particles M by the imparting device 110, is transmitted to the stationary device 120.

[0309] The fixing device 120 may be, for example, a heating device that has a heating source and heats the pressure-responsive particles M on the recording medium P, thereby fixing the pressure-responsive particles M on the recording medium P; a pressure device that has a pair of pressure-applying components (rollers / rollers, belts / rollers) and pressurizes the recording medium P, thereby fixing the pressure-responsive particles M on the recording medium P; a pressure heating device that has a pair of pressure-applying components (rollers / rollers, belts / rollers) with a heating source inside, and pressurizes and heats the recording medium P, thereby fixing the pressure-responsive particles M on the recording medium P; etc.

[0310] 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.

[0311] When the fixing device 120 has a pressurizing component, the pressure applied by the pressurizing component to the recording medium P can be lower than the pressure applied by the pressurizing device 230 to the recording medium P2.

[0312] The recording medium P is transformed into a recording medium P1 with pressure-responsive particles M applied to the image via the configuration unit 100. The recording medium P1 is then conveyed toward the crimping unit 200.

[0313] In the printing apparatus according to this embodiment, the placement unit 100 and the pressing unit 200 can be in a close proximity or in a far proximity. When the placement unit 100 and the pressing unit 200 are far apart, the placement unit 100 and the pressing unit 200 are connected, for example, by a transport unit (e.g., a conveyor belt) that transports the recording medium P1.

[0314] The crimping unit 200 includes a folding device 220 and a pressing device 230, and is a unit for folding and crimping the recording medium P1.

[0315] The folding device 220 folds the recording medium P1 to create a folded recording medium P2. The folding method of the recording medium P2 can be, for example, folding in half, tripling, or quadrupling, or it can be a method of folding only a portion of the recording medium P2. The recording medium P2 is in a state where pressure-responsive particles M are disposed on at least a portion of at least one of its two opposing surfaces.

[0316] The folding device 220 may have a pair of pressurizing components (e.g., roller / roller, belt / roller) that apply pressure to the recording medium P2. The pressure applied to the recording medium P2 by the pressurizing components of the folding device 220 may be lower than the pressure applied to the recording medium P2 by the pressurizing device 230.

[0317] The crimping unit 200 may replace the folding device 220 with an overlapping device that overlaps the recording medium P1 and another recording medium. The overlapping method between the recording medium P1 and the other recording medium may be, for example, overlapping one of the other recording media onto the recording medium P1, or overlapping one of the other recording media at multiple positions on the recording medium P1. The other recording medium may be a recording medium with an image pre-formed on one or both sides, a recording medium without an image, or a pre-made crimped print.

[0318] The recording medium P2, which leaves the folding device 220 (or overlapping device), is conveyed toward the pressurizing device 230.

[0319] The pressurizing device 230 includes a pair of pressurizing components (i.e., pressurizing rollers 231 and 232). Pressurizing rollers 231 and 232 contact each other with their outer peripheral surfaces and press against each other to apply pressure to the recording medium P2. The pair of pressurizing components included in the pressurizing device 230 is not limited to a combination of pressurizing rollers, but may also be a combination of pressurizing rollers and pressurizing belts, or a combination of pressurizing belts.

[0320] When pressure is applied to the recording medium P2 via the pressurization device 230, the pressure-responsive particles M flow onto the recording medium P2 due to the pressure, thus exhibiting adhesive properties.

[0321] The pressurizing device 230 may or may not have an internal heating source (e.g., a halogen heater) for heating the recording medium P2. Furthermore, the absence of an internal heating source in the pressurizing device 230 does not preclude the possibility that the temperature inside the pressurizing device 230 may exceed ambient temperature due to heat generated by the motor or other components within the pressurizing device 230.

[0322] By passing the recording medium P2 through the pressurizing device 230, pressure-responsive particles M are used to bond the folded surfaces together to create a press-printed material P3. In the press-printed material P3, part or all of the two opposing surfaces are bonded together.

[0323] The completed press-printed material P3 is conveyed from the pressurizing device 230.

[0324] The first method of press-printed material P3 is to form a press-printed material by bonding the opposing surfaces of a folded recording medium using pressure-responsive particles M. This type of press-printed material P3 is manufactured using a printing apparatus equipped with a folding device 220.

[0325] The second method of press-printed material P3 is to form a press-printed material by bonding the opposing surfaces of a plurality of overlapping recording media using pressure-responsive particles M. The press-printed material P3 of this method is manufactured using a press-printed material manufacturing apparatus equipped with an overlapping device.

[0326] The printing apparatus described in this embodiment is not limited to an apparatus that continuously transfers the recording medium P2 from the folding device 220 (or the overlapping device) to the pressurizing device 230. The printing apparatus described in this embodiment may also be an apparatus that stores the recording medium P2 after it leaves the folding device 220 (or the overlapping device), and transfers the recording medium P2 to the pressurizing device 230 after the stored amount of the recording medium P2 reaches a predetermined amount.

[0327] In the printing apparatus according to this embodiment, the folding device 220 (or overlapping device) and the pressing device 230 can be in a close-to-close or far-away configuration. When the folding device 220 (or overlapping device) and the pressing device 230 are far apart, they are connected, for example, via a transport unit (e.g., a conveyor belt) that transports the recording medium P2.

[0328] The printing apparatus according to this embodiment may include a cutting unit for cutting recording media into a predetermined size. Examples of cutting units include: a cutting unit disposed between the placement unit 100 and the pressing unit 200 to cut off a portion of the recording medium P1, i.e., the area where pressure-responsive particles M are not disposed; a cutting unit disposed between the folding device 220 and the pressing device 230 to cut off a portion of the recording medium P2, i.e., the area where pressure-responsive particles M are not disposed; a cutting unit disposed downstream of the pressing unit 200 to cut off a portion of the pressed printed material P3, i.e., the area not bonded by pressure-responsive particles M; and so on.

[0329] The printing apparatus described in this embodiment is not limited to a sheet-fed apparatus. The printing apparatus described in this embodiment may also be an apparatus that, after performing a configuration process and a pressing process on a strip of recording medium to form a strip of pressed printed material, cuts the strip of pressed printed material into a predetermined size.

[0330] The printing apparatus according to this embodiment may further include a color image forming unit that forms a color image on a recording medium using pigments. Examples of color image forming units include units that form color ink images on a recording medium by inkjet printing using colored ink as pigments, and units that form color images on a recording medium by electrophotography using a color electrostatic image developer.

[0331] The manufacturing apparatus described above, when used in this embodiment, includes a color image forming process that uses pigments to form a color image on a recording medium, and the method for manufacturing printed matter also includes this embodiment. Specifically, examples of the color image forming process include forming a color ink image on a recording medium by inkjet printing using colored ink as a pigment, and forming a color image on a recording medium by electrophotography using a color electrostatic image developer.

[0332] As a color image forming unit, the inkjet color image forming unit is described using the accompanying drawings. Figure 2 The diagram illustrates an example of an inkjet recording device 400. The inkjet recording device 400, for example, is... Figure 1 The printing apparatus shown is located upstream of the configuration unit 100.

[0333] The inkjet recording apparatus 400 includes, inside the housing 40, a container 42 for holding the recording medium P before image recording, an annular conveyor belt 50 mounted on the drive roller 52 and the driven roller 54, inkjet heads 30Y, 30M, 30C and 30K (collectively referred to as inkjet heads 30), drying units 34Y, 34M, 34C and 34K (collectively referred to as drying units 34), and a container 66 for holding the recording medium P after image recording.

[0334] Between container 42 and conveyor belt 50 is a transport path 44 for the recording medium P before it records an image. The transport path 44 is equipped with rollers 46 that sequentially remove the recording medium P from container 42 and multiple pairs of rollers 48 that transport the recording medium P. An electrified roller 56 is positioned upstream of conveyor belt 50. Driving the electrified roller 56 simultaneously clamps the conveyor belt 50 and the recording medium P between it and a driven roller 54, creating a potential difference between the electrified roller 56 and the grounded driven roller 54. This applies a charge to the recording medium P, causing it to electrostatically adhere to conveyor belt 50.

[0335] The inkjet head 30 is positioned above the conveyor belt 50, opposite to the flat portion of the conveyor belt 50. The area where the inkjet head 30 faces the conveyor belt 50 is the area from which ink droplets are ejected from the inkjet head 30.

[0336] Inkjet heads 30Y, 30M, 30C, and 30K are respectively the printhead for recording images of color Y (yellow), color M (magenta), color C (blue-green), and color K (black). For example, inkjet heads 30Y, 30M, 30C, and 30K are arranged sequentially from the upstream side to the downstream side of conveyor belt 50. Inkjet heads 30Y, 30M, 30C, and 30K are connected to ink cartridges 32Y, 32M, 32C, and 32K of each color, which are mounted and dismounted in the inkjet recording device 400, via supply pipes (not shown), and ink of each color is supplied from the ink cartridges to the inkjet heads.

[0337] Examples of inkjet heads 30 include: an elongated printhead whose effective recording area (the configuration area of ​​the printhead that ejects ink) is greater than or equal to the width of the recording medium P (the length in a direction orthogonal to the transport direction of the recording medium P); and a carriage-type printhead whose effective recording area is shorter than the width of the recording medium P and moves in the width direction of the recording medium P to eject ink.

[0338] Examples of inkjet methods used in the inkjet head 30 include: piezoelectric methods that utilize the vibration pressure of piezoelectric elements; charge control methods that utilize electrostatic induction to eject ink; acoustic inkjet methods that convert electrical signals into sound beams to irradiate ink and use radiation pressure to eject ink; and thermal inkjet methods that heat ink to form bubbles and utilize the resulting pressure.

[0339] The inkjet head 30 includes, for example, a low-resolution recording head (e.g., a 600 dpi recording head) that ejects ink droplets in a droplet volume range of 10 pL or more and 15 pL or less, and a high-resolution recording head (e.g., a 1200 dpi recording head) that ejects ink droplets in a droplet volume range of less than 10 pL. dpi stands for "dots per inch".

[0340] The inkjet recording device 400 is not limited to having four inkjet heads. The inkjet recording device 400 may also be: having four or more inkjet heads for YMCK and intermediate colors; or having one inkjet head and recording an image of only one color.

[0341] Downstream of the inkjet head 30, above the conveyor belt 50, drying units 34Y, 60M, 60C, and 60K are provided for each color inkjet head. Examples of drying units 34 include contact heating units and warm air supply units. The inkjet recording device 400 is not limited to having drying units for each color inkjet head; it may also have only one drying unit downstream of the most downstream inkjet head.

[0342] Downstream of the drying unit 34, a stripping plate 58 is disposed opposite to the drive roller 52. The stripping plate 58 strips the recording medium P from the conveyor belt 50.

[0343] Between the conveyor belt 50 and the container 66 is a transport path 62 for the recording medium P after the recorded image is transported, and a plurality of roller pairs 64 for transporting the recording medium P are arranged on the transport path 62.

[0344] The operation of the inkjet recording device 400 will be explained.

[0345] Before recording an image, the recording media P is removed one by one from the container 42 via roller 46 and conveyed to the conveyor belt 50 via a plurality of roller pairs 48. Next, the recording media P is electrostatically attracted to the conveyor belt 50 via charged roller 56 and conveyed to the area below the inkjet head 30 by the rotation of the conveyor belt 50. Then, ink is ejected from the inkjet head 30 onto the recording media P, recording an image. Next, the ink on the recording media P is dried by the drying unit 34. Finally, the ink-dried recording media P with the image fixed on it is peeled off from the conveyor belt 50 by a peeling plate 58 and conveyed to the container 66 via a plurality of roller pairs 64.

[0346] <Sheets for Printing and Methods for Manufacturing Sheets for Printing>

[0347] The sheet for printing according to this embodiment has a substrate and pressure-responsive particles disposed on the substrate. The sheet for printing according to this embodiment is manufactured using the pressure-responsive particles according to this embodiment. The pressure-responsive particles on the substrate may or may not maintain the particle shape previously disposed on the substrate.

[0348] The printing sheet involved in this embodiment can be applied, for example, to: concealment sheets that are overlapped and bonded to a recording medium when information recorded on the recording medium is to be concealed; release sheets used to provide an adhesive layer on the recording medium when overlapping recording media are bonded to each other; and so on.

[0349] Examples of substrates suitable for the printed matter manufacturing sheets described in this embodiment include paper, coated paper formed by coating the surface of paper with resin, cloth, nonwoven fabric, resin film, and resin sheet. Images may be formed on one or both sides of the substrate.

[0350] In the sheet material for printing production according to this embodiment, pressure-responsive particles can be disposed on the entire surface of the substrate or on a portion of the substrate. One or more layers of pressure-responsive particles are disposed on the substrate. The layer of pressure-responsive particles can be a continuous layer in the surface direction of the substrate or a discontinuous layer in the surface direction of the substrate. The layer of pressure-responsive particles can be a layer in which the pressure-responsive particles are directly arranged in the form of particles, or a layer in which adjacent pressure-responsive particles are fused together and arranged.

[0351] The amount of pressure-responsive particles on the substrate is, for example, 0.5 g / m² in the configured area. 2 Above and 50g / m 2 Below, 1g / m 2 Above and 40g / m 2 Below, 1.5g / m 2 Above and 30g / m 2The thickness of the pressure-responsive particles on the substrate is, for example, 0.2 μm or more and 25 μm or less, 0.4 μm or more and 20 μm or less, or 0.6 μm or more and 15 μm or less.

[0352] The sheet material for printing involved in this embodiment is manufactured, for example, by a manufacturing method including a configuration step, which uses the pressure-responsive particles involved in this embodiment and configures the pressure-responsive particles onto a substrate.

[0353] The configuration process may include, for example, an application process of applying pressure-responsive particles to a substrate, and a fixing process of fixing the pressure-responsive particles applied to the substrate to the substrate.

[0354] The coating process can be achieved through methods such as spraying, bar coating, mold coating, doctor blade coating, roller coating, reverse roller coating, gravure coating, screen printing, inkjet printing, lamination, and electrophotography. A liquid composition can be prepared by dispersing pressure-responsive particles in a dispersion medium according to the coating method used in the coating process, and the liquid composition can then be applied to the coating process.

[0355] The fixing process includes, for example: a heating process that heats the pressure-responsive particles on the substrate using a heating source to fix the pressure-responsive particles on the substrate; a pressure-pressurizing process that pressurizes the substrate to which the pressure-responsive particles are applied using a pair of pressure-pressurizing components (rollers / rollers, belts / rollers) to fix the pressure-responsive particles on the substrate; a pressure-heating process that pressurizes and heats the substrate to which the pressure-responsive particles are applied using a pair of pressure-pressurizing components (rollers / rollers, belts / rollers) with internal heating sources to fix the pressure-responsive particles on the substrate; etc.

[0356] <The manufacture of printed materials by electrophotography>

[0357] An example of applying the pressure-responsive particles described in this embodiment to an electrophotographic method will be described. In the electrophotographic method, the pressure-responsive particles are used as a toner for electrostatic image development (also simply referred to as "toner").

[0358] [Electrostatic Image Developer]

[0359] The electrostatic image developer (also referred to simply as "developer") involved in this embodiment contains at least the pressure-responsive particles involved in this embodiment. The electrostatic image developer involved in this embodiment may be a single-component developer containing only the pressure-responsive particles involved in this embodiment, or it may be a two-component developer formed by mixing the pressure-responsive particles involved in this embodiment and a carrier.

[0360] There are no particular limitations on the carrier, and known carriers can be cited. Examples of carriers include: a coated carrier formed by coating the surface of a core material containing magnetic powder with resin; a magnetic powder dispersion carrier formulated by dispersing magnetic powder in a matrix resin; and a resin-impregnated carrier formed by impregnating porous magnetic powder with resin; etc. Magnetic powder dispersion carriers and resin-impregnated carriers can be carriers in which the structural particles of the carrier are used as the core material and the surface is coated with resin.

[0361] Examples of magnetic powders include: magnetic metals such as iron, nickel, and cobalt; magnetic oxides such as ferrite and magnetite; etc.

[0362] Examples of coating resins and matrix resins include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyethylene ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylate copolymer, linear silicone resins containing organosiloxane bonds or their modified products, fluoropolymers, polyesters, polycarbonates, phenolic resins, and epoxy resins. The coating resins and matrix resins may contain conductive particles and other additives. Examples of conductive particles include metals such as gold, silver, and copper, carbon black, titanium dioxide, zinc oxide, tin oxide, barium sulfate, aluminum borate, and potassium titanate.

[0363] Examples of resin-coated core materials include coating with a solution formed by dissolving a coating resin and various additives (as needed) in a suitable solvent. There are no particular limitations on the solvent; it can be selected based on the type of resin used and its suitability for coating.

[0364] Specific resin coating methods include: immersion method in which the core material is immersed in a coating layer forming solution; spraying method in which a coating layer forming solution is sprayed onto the surface of the core material; fluidized bed method in which a coating layer forming solution is sprayed while the core material is suspended by flowing air; kneading coating method in which the core material and coating layer forming solution are mixed in a kneading coating machine and then the solvent is removed; etc.

[0365] The mixing ratio (mass ratio) of pressure-responsive particles to carrier in a two-component developer is preferably from 1:100 to 30:100, more preferably from 3:100 to 20:100.

[0366] [Apparatus for manufacturing printed materials, methods for manufacturing printed materials]

[0367] An apparatus for manufacturing printed matter using an electrophotographic method includes: a placement unit that contains a developer containing pressure-responsive particles as described in this embodiment, and places the pressure-responsive particles onto a recording medium by an electrophotographic method; and a pressing unit that folds and presses the recording medium or overlaps and presses the recording medium and another recording medium.

[0368] The printing apparatus of this embodiment is used to implement a printing method by electrophotography. The printing method of this embodiment includes: a preparation step, in which pressure-responsive particles containing pressure-responsive particles according to this embodiment are prepared onto a recording medium by electrophotography; and a pressing step, in which the recording medium is folded and pressed or the recording medium and another recording medium are overlapped and pressed.

[0369] The configuration unit included in the printing apparatus according to this embodiment includes, for example:

[0370] Photoreceptor;

[0371] The charging unit charges the surface of the photoreceptor.

[0372] An electrostatic image forming unit forms an electrostatic image on the surface of the charged photoreceptor;

[0373] The developing unit contains the electrostatic image developer according to this embodiment, and develops an electrostatic image formed on the surface of the photoreceptor using the electrostatic image developer as a pressure-responsive particle delivery part; and

[0374] The transfer unit transfers pressure-responsive particle-imparting portions formed on the surface of the photoreceptor onto the surface of the recording medium.

[0375] The configuration unit preferably also includes a fixing unit for fixing a pressure-responsive particle transfer portion onto the surface of the recording medium.

[0376] The configuration steps included in the method for manufacturing printed materials according to this embodiment include, for example:

[0377] The charging process charges the surface of the photoreceptor.

[0378] The electrostatic image forming process forms an electrostatic image on the surface of the charged photoreceptor;

[0379] In the development process, the electrostatic image formed on the surface of the photoreceptor by the electrostatic image developer according to this embodiment is used as a pressure-responsive particle delivery part; and

[0380] The transfer process transfers the pressure-responsive particle-imparting portion formed on the surface of the photoreceptor onto the surface of the recording medium.

[0381] The configuration process preferably further includes, for example, a fixing process for fixing the pressure-responsive particle-imparting portion transferred to the surface of the recording medium.

[0382] The configuration unit may be, for example, a direct transfer method apparatus that directly transfers pressure-responsive particle-applying portions formed on the surface of a photoreceptor to a recording medium; an intermediate transfer method apparatus that first transfers pressure-responsive particle-applying portions formed on the surface of a photoreceptor to the surface of an intermediate transfer body, and then secondly transfers the pressure-responsive particle-applying portions transferred to the surface of the intermediate transfer body to the surface of the recording medium; an apparatus equipped with a cleaning unit that cleans the surface of the photoreceptor before it becomes charged after transferring the pressure-responsive particle-applying portions; an anti-static unit that irradiates the surface of the photoreceptor with anti-static light to remove static electricity after transferring the pressure-responsive particle-applying portions but before it becomes charged; and so on. In the case where the configuration unit is an intermediate transfer method apparatus, the transfer unit may include, for example, an intermediate transfer body that transfers pressure-responsive particle-applying portions to a surface; a first transfer unit that first transfers pressure-responsive particle-applying portions formed on the surface of a photoreceptor to the surface of an intermediate transfer body; and a second transfer unit that secondly transfers pressure-responsive particle-applying portions transferred to the surface of the intermediate transfer body to the surface of the recording medium.

[0383] The portion of the configuration unit that includes the developing unit can be a cartridge structure (so-called a processing cartridge) that is detachable from the configuration unit. For example, a processing cartridge containing the electrostatic image developer according to this embodiment and having a developing unit can be used.

[0384] The printing apparatus of this embodiment includes a pressing unit that applies pressure to a recording medium on which the pressure-responsive particles of this embodiment are disposed. As a result, the pressure-responsive particles of this embodiment fluidize on the recording medium, exhibiting adhesive properties. The pressure applied to the recording medium by the pressing unit for the purpose of fluidizing the pressure-responsive particles of 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.

[0385] The pressure-responsive particles involved in this embodiment can be disposed on the entire surface of the recording medium or on a portion of the recording medium. The pressure-responsive particles involved in this embodiment are disposed in one or more layers on the recording medium. The layer of pressure-responsive particles involved in this embodiment can be a continuous layer in the planar direction of the recording medium or a discontinuous layer in the planar direction of the recording medium. The layer of pressure-responsive particles involved in this embodiment can be a layer in which the pressure-responsive particles are directly arranged in the form of particles, or a layer in which adjacent pressure-responsive particles are fused together and arranged.

[0386] The amount of pressure-responsive particles (e.g., preferably transparent pressure-responsive particles) involved in this embodiment on the recording medium is, for example, 0.5 g / m³ in the configured area. 2 Above and 50g / m 2 Below, 1g / m 2 Above and 40g / m 2 Below, 1.5g / m 2 Above and 30g / m 2 The following describes the layer thickness of the pressure-responsive particles (e.g., preferably transparent pressure-responsive particles) involved in this embodiment on the recording medium, for example, 0.2 μm or more and 25 μm or less, 0.4 μm or more and 20 μm or less, or 0.6 μm or more and 15 μm or less.

[0387] Recording media suitable for the printing apparatus of this embodiment include, for example, paper, coated paper formed by coating the surface of paper with resin, cloth, nonwoven fabric, resin film, resin sheet, etc. The recording media has an image on one or both sides.

[0388] The following is an example of a printing apparatus according to this embodiment that is applicable to electrophotography, but this embodiment is not limited thereto.

[0389] Figure 3 This is a schematic structural diagram illustrating an example of a printing manufacturing apparatus according to this embodiment. Figure 3 The illustrated printing apparatus includes a configuration unit 100 and a pressing unit 200 disposed downstream of the configuration unit 100. Arrows indicate the rotation direction of the photosensitive element or the transport direction of the recording medium.

[0390] The configuration unit 100 is a direct transfer apparatus that uses a developer containing pressure-responsive particles according to this embodiment to configure the pressure-responsive particles according to this embodiment onto a recording medium P via an electrophotographic method. The recording medium P has an image pre-formed on one or both sides.

[0391] The configuration unit 100 includes a photoreceptor 101. Around the photoreceptor 101 are arranged sequentially a charging roller (an example of a charging unit) 102 for charging the surface of the photoreceptor 101, an exposure apparatus (an example of an electrostatic image forming unit) for forming an electrostatic image by exposing the surface of the charged photoreceptor 101 with a laser beam, a developing apparatus (an example of a developing unit) for developing the electrostatic image by supplying pressure-responsive particles to it, a transfer roller (an example of a transfer unit) 105 for transferring the developed pressure-responsive particle imparting portion onto a recording medium P, and a photoreceptor cleaning apparatus (an example of a cleaning unit) 106 for removing pressure-responsive particles remaining on the surface of the photoreceptor 101 after the transfer.

[0392] The operation of the configuration unit 100 in configuring the pressure-responsive particles involved in this embodiment onto the recording medium P will be described.

[0393] First, the surface of the photoreceptor 101 is charged by the charging roller 102. The exposure apparatus 103 irradiates the charged surface of the photoreceptor 101 with a laser beam based on image data sent from a control unit (not shown). As a result, an electrostatic image of the configuration pattern of pressure-responsive particles according to this embodiment is formed on the surface of the photoreceptor 101.

[0394] The electrostatic image formed on the photoreceptor 101 rotates to the developing position as the photoreceptor 101 moves. Then, at the developing position, the electrostatic image on the photoreceptor 101 is developed by the developing apparatus 104 and becomes a pressure-responsive particle delivery section.

[0395] The developing apparatus 104 contains at least a developer containing the pressure-responsive particles and a carrier as described in this embodiment. The pressure-responsive particles, as described in this embodiment, become triboelectrically charged by being stirred together with the carrier inside the developing apparatus 104 and are held on the developer roller. By passing the surface of the photoreceptor 101 through the developing apparatus 104, the pressure-responsive particles electrostatically attach to an electrostatic image on the surface of the photoreceptor 101, and the electrostatic image is developed by the pressure-responsive particles. The photoreceptor 101, to which the pressure-responsive particle application portion is formed, continues to travel, conveying the pressure-responsive particle application portion on the photoreceptor 101 to the transfer position.

[0396] When the pressure-responsive particle delivery portion on the photoreceptor 101 is conveyed to the transfer position, a transfer bias is applied to the transfer roller 105, and an electrostatic force from the photoreceptor 101 toward the transfer roller 105 acts on the pressure-responsive particle delivery portion, transferring the pressure-responsive particle delivery portion on the photoreceptor 101 onto the recording medium P.

[0397] Pressure-responsive particles remaining on the photoreceptor 101 are removed and recycled by the photoreceptor cleaning device 106. The photoreceptor cleaning device 106 is, for example, a cleaning scraper, a cleaning brush, etc. From the viewpoint of suppressing the phenomenon of film-like adhesion to the surface of the photoreceptor by utilizing pressure fluidization of the pressure-responsive particles remaining on the surface of the photoreceptor as described in this embodiment, the photoreceptor cleaning device 106 is preferably, for example, a cleaning brush.

[0398] The recording medium P, to which pressure-responsive particle-imparting portions are transferred, is conveyed to a fixing device (an example of a fixing unit) 107. The fixing device 107 is, for example, a pair of fixing components (roller / roller, belt / roller). The configuration unit 100 may not include the fixing device 107, but from the viewpoint of suppressing the pressure-responsive particles involved in this embodiment from falling off the recording medium P, it is preferable, for example, to include the fixing device 107. The pressure applied by the fixing device 107 to the recording medium P is only required to be lower than the pressure applied by the pressurizing device 230 to the recording medium P2; specifically, it is preferably 0.2 MPa or more and 1 MPa or less.

[0399] The mounting device 107 may or may not have an internal heating source (e.g., a halogen heater) for heating the recording medium P. When the mounting device 107 has an internal heating source, the surface temperature of the recording medium P when heated by the heating source is preferably 150°C 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. Furthermore, even if the mounting device 107 does not have an internal heating source, it is possible that the temperature inside the mounting device 107 may exceed ambient temperature due to heat generated by the motor or the like in the mounting unit 100.

[0400] The recording medium P is transformed into a recording medium P1, which is imbued with pressure-responsive particles as described in this embodiment, via the configuration unit 100. The recording medium P1 is then conveyed toward the crimping unit 200.

[0401] In the printing apparatus according to this embodiment, the placement unit 100 and the pressing unit 200 can be in a close proximity or in a far proximity. When the placement unit 100 and the pressing unit 200 are far apart, the placement unit 100 and the pressing unit 200 are connected, for example, by a transport unit (e.g., a conveyor belt) that transports the recording medium P1.

[0402] The crimping unit 200 includes a folding device 220 and a pressing device 230, and is a unit for folding and crimping the recording medium P1.

[0403] The folding device 220 folds the recording medium P1 to create a folded recording medium P2. The folding method of the recording medium P2 can be, for example, folding in half, tripling, or quadrupling, or it can be a method of folding only a portion of the recording medium P2. The recording medium P2 is in a state where at least a portion of at least one of its two opposing surfaces is disposed with the pressure-responsive particles according to this embodiment.

[0404] The folding device 220 may have a pair of pressure-applying components (e.g., rollers / rollers, belts / rollers) that apply pressure to the recording medium P2. The pressure applied to the recording medium P2 by the pressure-applying components of the folding device 220 may be lower than the pressure applied to the recording medium P2 by the pressure-applying device 230, specifically, preferably 1 MPa or more and 10 MPa or less.

[0405] The crimping unit 200 may replace the folding device 220 with an overlapping device that overlaps the recording medium P1 and another recording medium. The overlapping method between the recording medium P1 and the other recording medium may be, for example, overlapping one of the other recording media onto the recording medium P1, or overlapping one of the other recording media at multiple positions on the recording medium P1. The other recording medium may be a recording medium with an image pre-formed on one or both sides, a recording medium without an image, or a pre-made crimped print.

[0406] The recording medium P2, which leaves the folding device 220 (or overlapping device), is conveyed toward the pressurizing device 230.

[0407] The pressurizing device 230 includes a pair of pressurizing components (i.e., pressurizing rollers 231 and 232). Pressurizing rollers 231 and 232 contact each other with their outer peripheral surfaces and press against each other to apply pressure to the recording medium P2. The pair of pressurizing components included in the pressurizing device 230 is not limited to a combination of pressurizing rollers, but may also be a combination of pressurizing rollers and pressurizing belts, or a combination of pressurizing belts.

[0408] When pressure is applied to the recording medium P2 via the pressurizing device 230, the pressure-responsive particles involved in this embodiment flow onto the recording medium P2 due to the pressure, exhibiting adhesive properties. The pressure applied to the recording medium P2 by the pressurizing 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.

[0409] The pressurizing device 230 may or may not have an internal heating source (e.g., a halogen heater) for heating the recording medium P2. When the pressurizing device 230 has an internal heating source, the surface temperature of the recording medium P2 when heated by the heating 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. Furthermore, if the pressurizing device 230 does not have an internal heating source, it is possible that the temperature inside the pressurizing device 230 may exceed ambient temperature due to heat generated by the motor or other components included in the pressurizing device 230.

[0410] By passing the recording medium P2 through the pressurizing device 230, the folded surfaces are bonded together using pressure-responsive particles according to this embodiment through fluidization, thus creating a press-printed material P3. In the press-printed material P3, some or all of the opposing surfaces are bonded together.

[0411] The completed press-printed material P3 is conveyed from the pressurizing device 230.

[0412] The first method of press-printed material P3 is to form a press-printed material by bonding the opposing surfaces of a folded recording medium with pressure-responsive particles as described in this embodiment. The press-printed material P3 of this method is manufactured by a printing material manufacturing apparatus equipped with a folding device 220.

[0413] The second method of press-printed material P3 is to form a press-printed material by bonding the opposing surfaces of a plurality of overlapping recording media using pressure-responsive particles as described in this embodiment. The press-printed material P3 of this method is manufactured using a press-printed material manufacturing apparatus equipped with an overlapping device.

[0414] The printing apparatus described in this embodiment is not limited to an apparatus that continuously transfers the recording medium P2 from the folding device 220 (or the overlapping device) to the pressurizing device 230. The printing apparatus described in this embodiment may also be an apparatus that stores the recording medium P2 after it leaves the folding device 220 (or the overlapping device), and transfers the recording medium P2 to the pressurizing device 230 after the stored amount of the recording medium P2 reaches a predetermined amount.

[0415] In the printing apparatus according to this embodiment, the folding device 220 (or overlapping device) and the pressing device 230 can be in a close-to-close or far-away configuration. When the folding device 220 (or overlapping device) and the pressing device 230 are far apart, they are connected, for example, via a transport unit (e.g., a conveyor belt) that transports the recording medium P2.

[0416] The printing apparatus according to this embodiment may include a cutting unit for cutting recording media to a predetermined size. Examples of cutting units include: a cutting unit disposed between the placement unit 100 and the pressing unit 200 to cut off a portion of the recording media P1, i.e., the area where the pressure-responsive particles according to this embodiment are not placed; a cutting unit disposed between the folding device 220 and the pressing device 230 to cut off a portion of the recording media P2, i.e., the area where the pressure-responsive particles according to this embodiment are not placed; a cutting unit disposed downstream of the pressing unit 200 to cut off a portion of the pressed printed material P3, i.e., the area not bonded by the pressure-responsive particles according to this embodiment; and so on.

[0417] The printing apparatus described in this embodiment is not limited to a sheet-fed apparatus. The printing apparatus described in this embodiment may also be an apparatus that, after performing a configuration process and a pressing process on a strip of recording medium to form a strip of pressed printed material, cuts the strip of pressed printed material into a predetermined size.

[0418] The printing apparatus according to this embodiment may further include a color image forming unit that forms a color image on a recording medium using a color electrostatic image developer via electrophotography. The color image forming unit may include, for example:

[0419] Photoreceptor;

[0420] The charging unit charges the surface of the photoreceptor.

[0421] An electrostatic image forming unit forms an electrostatic image on the surface of the charged photoreceptor;

[0422] The developing unit contains a color electrostatic image developer, and the electrostatic image formed on the surface of the photoreceptor by the color electrostatic image developer is used as a color toner image.

[0423] The transfer unit transfers a color toner image formed on the surface of the photoreceptor onto the surface of the recording medium; and

[0424] The thermal fixing unit thermally fixes the color toner image transferred onto the surface of the recording medium.

[0425] The manufacturing apparatus with the above-described structure further implements the method for manufacturing printed matter according to this embodiment, which includes a color image forming step of forming a color image on a recording medium using a color electrostatic image developer via electrophotography. Specifically, the color image forming step includes:

[0426] The charging process charges the surface of the photoreceptor.

[0427] The electrostatic image forming process forms an electrostatic image on the surface of the charged photoreceptor;

[0428] In the developing process, an electrostatic image formed on the surface of the photoreceptor is developed using a color electrostatic image developer as a color toner image.

[0429] The transfer process transfers a color toner image formed on the surface of the photoreceptor onto the surface of the recording medium; and

[0430] The heat fixing process involves heat fixing the color toner image transferred onto the surface of the recording medium.

[0431] The color image forming unit included in the printing apparatus according to this embodiment is, for example, a direct transfer method apparatus that directly transfers a color toner image formed on the surface of a photoreceptor to a recording medium; an intermediate transfer method apparatus that first transfers a color toner image formed on the surface of a photoreceptor to the surface of an intermediate transfer body, and then transfers the color toner image transferred to the surface of the intermediate transfer body to the surface of the recording medium a second time; an apparatus equipped with a cleaning unit that cleans the surface of the photoreceptor before it becomes charged after transferring the color toner image; an apparatus equipped with a de-energizing unit that irradiates the surface of the photoreceptor with de-energizing light to de-energize it after transferring the color toner image but before it becomes charged; and so on. In the case of an apparatus in which the color image forming unit is an intermediate transfer method, the transfer unit includes, for example: an intermediate transfer body that transfers a color toner image onto a surface; a primary transfer unit that transfers a color toner image formed on the surface of a photoreceptor onto the surface of the intermediate transfer body in a primary transfer; and a secondary transfer unit that transfers the color toner image transferred to the surface of the intermediate transfer body onto the surface of the recording medium in a secondary transfer.

[0432] In the printing apparatus according to this embodiment, when the preparation unit containing the developer containing the pressure-responsive particles according to this embodiment and the color image forming unit adopt the intermediate transfer method, the preparation unit and the color image forming unit can share the intermediate transfer body and the secondary transfer unit.

[0433] In the printing apparatus according to this embodiment, the image developer preparation unit containing the pressure-responsive particles according to this embodiment and the color image forming unit may also share the thermal fixing unit.

[0434] The following describes an example of a printing apparatus according to this embodiment, which includes a color image forming unit; however, this embodiment is not limited to this. In the following description, the main parts shown in the figures will be described, and the description of other parts will be omitted.

[0435] Figure 4This is a schematic structural diagram illustrating an example of a printing apparatus according to this embodiment that employs an electrophotographic method. Figure 4 The printing apparatus shown includes a printing unit 300 that performs the configuration of pressure-responsive particles and the formation of a color image on a recording medium in one step, and a crimping unit 200 disposed downstream of the printing unit 300.

[0436] The printing unit 300 comprises five sets of printing units connected in series and using an intermediate transfer method. The printing unit 300 includes: a unit 10T for configuring the pressure-responsive particles (T) according to this embodiment; and units 10Y, 10M, 10C, and 10K for forming images of yellow (Y), magenta (M), cyan (C), and black (K). Unit 10T is a configuration unit for configuring the pressure-responsive particles according to this embodiment on the recording medium P using a developer containing the pressure-responsive particles according to this embodiment. Units 10Y, 10M, 10C, and 10K are units for forming color images on the recording medium P using a developer containing a color toner. Units 10T, 10Y, 10M, 10C, and 10K employ an electrophotographic method.

[0437] Units 10T, 10Y, 10M, 10C, and 10K are arranged side-by-side in a horizontal direction, spaced apart from each other. Units 10T, 10Y, 10M, 10C, and 10K can be processing cartridges that are mounted and dismounted from the printing unit 300.

[0438] Below units 10T, 10Y, 10M, 10C, and 10K, an intermediate transfer belt (an example of an intermediate transfer body) 20 extends through each unit. The intermediate transfer belt 20 is configured to be wound around a drive roller 22, a support roller 23, and an opposing roller 24 that are in contact with the inner surface of the intermediate transfer belt 20, and travels in a direction from unit 10T toward unit 10K. On the image holding surface side of the intermediate transfer belt 20, an intermediate transfer body cleaning device 21 is provided opposite to the drive roller 22.

[0439] Units 10T, 10Y, 10M, 10C, and 10K are each equipped with developing apparatus (an example of a developing unit) 4T, 4Y, 4M, 4C, and 4K, respectively. The developing apparatuses 4T, 4Y, 4M, 4C, and 4K are respectively supplied with pressure-responsive particles as described in this embodiment, contained in the pressure-responsive particle cartridge 8T, or with yellow toner, magenta toner, blue-green toner, and black toner contained in the toner cartridges 8Y, 8M, 8C, and 8K.

[0440] Units 10T, 10Y, 10M, 10C, and 10K have the same structure and operation, so unit 10T, which is configured with pressure-responsive particles according to this embodiment onto a recording medium, will be used as an example for description.

[0441] Unit 10T includes a photoreceptor 1T. Around the photoreceptor 1T are arranged sequentially a charging roller (an example of a charging unit) 2T for charging the surface of the photoreceptor 1T, an exposure device (an example of an electrostatic image forming unit) 3T for forming an electrostatic image by exposing the surface of the charged photoreceptor 1T with a laser beam, a developing device (an example of a developing unit) 4T for developing the electrostatic image by supplying pressure-responsive particles, a primary transfer roller (an example of a primary transfer unit) 5T for transferring the developed pressure-responsive particles onto an intermediate transfer belt 20, and a photoreceptor cleaning device (an example of a cleaning unit) 6T for removing pressure-responsive particles remaining on the surface of the photoreceptor 1T after the primary transfer. The primary transfer roller 5T is disposed inside the intermediate transfer belt 20, positioned opposite the photoreceptor 1T.

[0442] Hereinafter, the operation of the example unit 10T will be described to illustrate the operation of configuring the pressure-responsive particles and forming a color image on the recording medium P as described in this embodiment.

[0443] First, the surface of the photoreceptor 1T is charged by the charged roller 2T. The exposure apparatus 3T then irradiates the charged surface of the photoreceptor 1T with a laser beam based on image data sent from a control unit (not shown). As a result, an electrostatic image of the configuration pattern of pressure-responsive particles according to this embodiment is formed on the surface of the photoreceptor 1T.

[0444] The electrostatic image formed on the photoreceptor 1T rotates to the developing position as the photoreceptor 1T moves. Then, at the developing position, the electrostatic image on the photoreceptor 1T is developed by the developing apparatus 4T, becoming a pressure-responsive particle delivery unit.

[0445] The developing apparatus 4T contains at least a developer containing the pressure-responsive particles and a carrier as described in this embodiment. The pressure-responsive particles, as described in this embodiment, become triboelectrically charged by being stirred together with the carrier inside the developing apparatus 4T and are held on the developer roller. By passing the surface of the photoreceptor 1T through the developing apparatus 4T, the pressure-responsive particles electrostatically attach to an electrostatic image on the surface of the photoreceptor 1T, and the electrostatic image is developed by the pressure-responsive particles. The photoreceptor 1T, to which the pressure-responsive particle application portion is formed, continues to travel, conveying the pressure-responsive particle application portion on the photoreceptor 1T to a primary transfer position.

[0446] When the pressure-responsive particle delivery section on the photoreceptor 1T is conveyed to the primary transfer position, a primary transfer roller 5T is applied with a primary transfer bias. An electrostatic force from the photoreceptor 1T toward the primary transfer roller 5T acts on the pressure-responsive particle delivery section, transferring the pressure-responsive particles from the photoreceptor 1T onto the intermediate transfer belt 20. The pressure-responsive particles remaining on the photoreceptor 1T are removed and recycled by the photoreceptor cleaning device 6T. The photoreceptor cleaning device 6T is, for example, a cleaning scraper or a cleaning brush, preferably a cleaning brush.

[0447] In units 10Y, 10M, 10C, and 10K, a developer containing color toner is used to perform the same operation as in unit 10T. The intermediate transfer belt 20, following the pressure-responsive particle transfer section of unit 10T, sequentially passes through units 10Y, 10M, 10C, and 10K, transferring the toner images of each color multiple times onto the intermediate transfer belt 20.

[0448] After passing through units 10T, 10Y, 10M, 10C, and 10K for multiple transfers of the pressure-responsive particle delivery unit and toner image, the intermediate transfer belt 20 reaches the secondary transfer section, which consists of the intermediate transfer belt 20, an opposing roller 24 in contact with the inner surface of the intermediate transfer belt, and a secondary transfer roller (an example of a secondary transfer unit) 26 disposed on the image-retaining side of the intermediate transfer belt 20. Meanwhile, the recording medium P is supplied via a supply mechanism to the gap between the secondary transfer roller 26 and the intermediate transfer belt 20, causing a secondary transfer bias to be applied to the opposing roller 24. At this time, an electrostatic force from the intermediate transfer belt 20 toward the recording medium P acts on the pressure-responsive particle delivery unit and toner image, transferring the pressure-responsive particle delivery unit and toner image on the intermediate transfer belt 20 onto the recording medium P.

[0449] A recording medium P, on which a pressure-responsive particle transfer portion and a toner image are transferred, is conveyed to a thermal fixing apparatus (an example of a thermal fixing unit) 28. The thermal fixing apparatus 28 is equipped with a heating source such as a halogen heater, which heats the recording medium P. The surface temperature of the recording medium P when heated by the thermal fixing apparatus 28 is preferably, for example, 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. Through the thermal fixing apparatus 28, the color toner image is thermally fixed onto the recording medium P.

[0450] From the viewpoint of suppressing the detachment of pressure-responsive particles from the recording medium P as described in this embodiment, and from the viewpoint of improving the fixing properties of color images on the recording medium P, the thermal fixing apparatus 28 is preferably a device that applies pressure while heating, for example, it can be a pair of fixing components (roller / roller, belt / roller) with a heating source inside. When the thermal fixing apparatus 28 applies pressure, the pressure applied by the thermal fixing apparatus 28 to the recording medium P only needs to be lower than the pressure applied by the pressure applying device 230 to the recording medium P2, specifically, preferably 0.2 MPa or more and 1 MPa or less.

[0451] After passing through the printing unit 300, the recording medium P becomes a recording medium P1 imbued with a color image and pressure-responsive particles as described in this embodiment. The recording medium P1 is then conveyed toward the crimping unit 200.

[0452] Figure 4 The structure of the crimping unit 200 can be compared with... Figure 3 The crimping unit 200 is the same as that in the previous version, and the detailed description of the structure and operation of the crimping unit 200 is omitted.

[0453] In the printing apparatus according to this embodiment, the printing unit 300 and the pressing unit 200 can be arranged close to each other or far apart. When the printing unit 300 and the pressing unit 200 are far apart, they are connected, for example, by a transport unit (e.g., a conveyor belt) that transports the recording medium P1.

[0454] The printing apparatus according to this embodiment may include a cutting unit for cutting the recording medium to a predetermined size. Examples of cutting units include: a cutting unit disposed between the printing unit 300 and the pressing unit 200 to cut off a portion of the recording medium P1, i.e., the area where the pressure-responsive particles according to this embodiment are not disposed; a cutting unit disposed between the folding device 220 and the pressing device 230 to cut off a portion of the recording medium P2, i.e., the area where the pressure-responsive particles according to this embodiment are not disposed; a cutting unit disposed downstream of the pressing unit 200 to cut off a portion of the pressed printed material P3, i.e., the area not bonded by the pressure-responsive particles according to this embodiment; and so on.

[0455] The printing apparatus described in this embodiment is not limited to a sheet-fed apparatus. The printing apparatus described in this embodiment may also be an apparatus that, after forming a strip of laminated printed material by performing a color image forming process, a placement process, and a lamination process on a strip of recording medium, cuts the strip of laminated printed material into a predetermined size.

[0456] [Processing Box]

[0457] A processing box suitable for an apparatus for manufacturing printed materials by electrophotography is described.

[0458] The processing box involved in this embodiment is as follows: it contains the electrostatic image developer involved in this embodiment, and has a developing unit that uses the electrostatic image developer to develop an electrostatic image formed on the surface of a photoreceptor as a pressure-responsive particle imparting part, and is mounted and dismounted in a printing manufacturing apparatus.

[0459] The processing box involved in this embodiment may also be configured to include: a developing unit; and at least one selected from a photoreceptor, a charged unit, an electrostatic image forming unit, a transfer unit, etc., as needed.

[0460] As an example of a processing cartridge, a cartridge that integrates a photoreceptor, a charged roller (an example of a charged unit) disposed around the photoreceptor, a developing apparatus (an example of a developing unit), and a photoreceptor cleaning apparatus (an example of a cleaning unit) using a frame. The frame has an opening for exposure. The frame has a mounting rail, and the processing cartridge is mounted to a printing manufacturing apparatus via the mounting rail.

[0461] Example

[0462] The following detailed description of the embodiments of the invention is provided through examples, but the embodiments of the invention are not limited to these examples. In the following description, unless otherwise specified, "parts" and "%" are based on mass.

[0463] <Preparation of dispersions containing styrene-based resin particles>

[0464] [Preparation of styrene-based resin particle dispersion (St1)]

[0465]

[0466] The above materials were mixed and dissolved to prepare a monomer solution.

[0467] Eight parts of anionic surfactant (Dowfax2A1 manufactured by The Dow Chemical Company) were dissolved in 205 parts of deionized water, and the monomer solution was added for dispersion and emulsification to obtain an emulsion.

[0468] 2.2 parts of anionic surfactant (manufax2A1 manufactured by The Dow Chemical Company) were dissolved in 462 parts of deionized water and placed in a polymerization flask equipped with a stirrer, thermometer, reflux cooling tube and nitrogen inlet tube. The mixture was stirred and heated to 73°C and maintained.

[0469] Three parts of ammonium persulfate were dissolved in 21 parts of deionized water and added dropwise to the polymerization flask over 15 minutes using a metering pump. Then, the emulsion was added dropwise over 160 minutes using a metering pump.

[0470] Next, while stirring slowly and continuously, the polymerization flask was kept at 75°C for 3 hours before being brought back to room temperature.

[0471] Thus, a styrene-based resin particle dispersion (St1) containing styrene-based resin particles was obtained, with a volume average particle size (D50v) of 174 nm, a weight average molecular weight of 49,000 as detected by GPC (UV detection), a glass transition temperature of 54 °C, and a solid content of 42%.

[0472] The styrene-based resin particle dispersion (St1) was dried, and the styrene-based resin particles were removed. The thermal behavior in the temperature range of -100°C to 100°C was analyzed using a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation), and a glass transition temperature was observed. The glass transition temperatures are shown in Table 1.

[0473] [Preparation of styrene-based resin particle dispersions (St2) to (St13)]

[0474] Except for the monomer changes as described in Table 1, styrene-based resin particle dispersions (St2) to (St13) were prepared in the same manner as the preparation of styrene-based resin particle dispersion (St1).

[0475] The composition and physical properties of styrene-based resin particle dispersions (St1) are shown in Table 1. In Table 1, monomers are referred to by the following abbreviations.

[0476] Styrene: St, n-Butyl acrylate: BA, 2-Ethylhexyl acrylate: 2EHA, Ethyl acrylate: EA, 4-Hydroxybutyl acrylate: 4HBA, Acrylic acid: AA, Methacrylic acid: MAA, 2-Carboxyethyl acrylate: CEA

[0477] [Table 1]

[0478]

[0479] <Preparation of dispersions containing composite resin particles>

[0480] [Preparation of composite resin particle dispersion (M1)]

[0481]

[0482] The above materials were placed in a polymerization flask, stirred at 25°C for 1 hour, and then heated to 70°C.

[0483] Dissolve 2.5 parts of ammonium persulfate in 75 parts of deionized water and add the solution dropwise to the polymerization flask over 60 minutes using a metering pump.

[0484] Next, while stirring slowly and continuously, the polymerization flask was kept at 70°C for 3 hours before being brought back to room temperature.

[0485] Thus, a composite resin particle dispersion (M1) containing composite resin particles was obtained, with a volume average particle size (D50v) of 219 nm, a weight average molecular weight of 219,000 as detected by GPC (UV detection), and a solid content of 32%.

[0486] The composite resin particle dispersion (M1) was dried and the composite resin particles were removed. The thermal behavior in the temperature range of -150°C to 100°C was analyzed using a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation), and two glass transition temperatures were observed. The glass transition temperatures are shown in Table 2.

[0487] [Preparation of composite resin particle dispersions (M2)~(M21) and (cM1)~(cM3)]

[0488] Except for changing the styrene-based resin particle dispersion (St1) as described in Table 2 or changing the polymerization composition of the (meth)acrylate-based resin as described in Table 2, composite resin particle dispersions (M2) to (M21) and (cM1) to (cM3) were prepared in the same manner as the preparation of composite resin particle dispersion (M1).

[0489] [Preparation of composite resin particle dispersions (M22) to (M27)]

[0490] Except for adjusting the amount of 2-ethylhexyl acrylate and n-butyl acrylate used, composite resin particle dispersions (M22) to (M27) were prepared in the same manner as the preparation of composite resin particle dispersion (M1).

[0491] The composition and physical properties of the composite resin particle dispersion (M1), etc., are shown in Table 2. In Table 2, monomers are referred to by the following abbreviations.

[0492] Styrene: St, n-Butyl acrylate: BA, 2-Ethylhexyl acrylate: 2EHA, Ethyl acrylate: EA, 4-Hydroxybutyl acrylate: 4HBA, Acrylic acid: AA, Methacrylic acid: MAA, 2-Carboxyethyl acrylate: CEA, Hexyl acrylate: HA, Propylene acrylate: PA

[0493] [Table 2]

[0494]

[0495] [Preparation of composite resin particle dispersions (M28) to (M30)]

[0496] Except for changing the amount of ammonium persulfate as described in Table 3, composite resin particle dispersions (M28) to (M30) with different weight-average molecular weights of composite resin particles were prepared in the same manner as the preparation of composite resin particle dispersion (M1).

[0497] [Table 3]

[0498] ammonium persulfate M28 3.0 copies M29 5.0 copies M30 7.5 copies

[0499] The composition and physical properties of composite resin particle dispersions (M28), etc., are shown in Table 4. In Table 4, monomers are referred to by the following abbreviations.

[0500] Styrene: St, n-Butyl acrylate: BA, Acrylic acid: AA, 2-Ethylhexyl acrylate: 2EHA

[0501] [Table 4]

[0502]

[0503] <Preparation of Pressure-Responsive Particles>

[0504] [Preparation of pressure-responsive particles (1)]

[0505] • Composite resin particle dispersion (M1): 504 parts

[0506] • Deionized water: 710 parts

[0507] • Anionic surfactant (manufactured by The Dow Chemical Company, Dowfax2A1): 1 part

[0508] The above materials were placed in a reaction vessel equipped with a thermometer and a pH meter. A 1.0% nitric acid aqueous solution was added at 25°C to adjust the pH to 3.0. While dispersing using a homogenizer (IKA, ULTRA-TURRAX T50) at 5000 rpm, 23 parts of a 2.0% aluminum sulfate aqueous solution were added. Next, a stirrer and a covered heater were installed in the reaction vessel, and the temperature was increased to 40°C at a rate of 0.2°C / min. After exceeding 40°C, the temperature was increased at a rate of 0.05°C / min. Particle size was measured every 10 minutes using a MULTISIZER II (50 μm pore size, Beckman Coulter, Inc.). The temperature was maintained at 5.0 μm for 5 minutes, and 170 parts of a styrene-based resin particle dispersion (St1) were added. After the addition was complete, the mixture was maintained at 50°C for 30 minutes, and then a 1.0% sodium hydroxide aqueous solution was added to adjust the pH of the slurry to 6.0. Next, the pH was adjusted to 6.0 every 5°C, while the temperature was increased to 90°C at a rate of 1°C / min and maintained at 90°C. The particle shape and surface properties were observed using an optical microscope and a field emission scanning electron microscope (FE-SEM). The aggregation of particles was confirmed at the 10th hour, so the container was cooled to 30°C with cooling water for 5 minutes.

[0509] The cooled slurry was passed through a 15μm nylon sieve to remove coarse particles. The slurry after passing through the sieve was then filtered under reduced pressure using a suction device. The remaining solids on the filter paper were manually crushed into fine particles and added to 10 times the volume of the solids in deionized water (30°C), and stirred for 30 minutes. Next, reduced pressure filtration was performed using a suction device, and the remaining solids on the filter paper were manually crushed into fine particles and added to 10 times the volume of the solids in deionized water (30°C), and stirred for 30 minutes. The filtrate was then filtered under reduced pressure again using a suction device, and the conductivity of the filtrate was measured. This process was repeated until the conductivity of the filtrate was below 10μS / cm, and the solids were washed away.

[0510] The washed solid components were pulverized into fine particles using a wet-dry granulator (COMIL) and then vacuum dried in an oven at 25°C for 36 hours to obtain pressure-responsive parent particles (1). The number-average particle size of the pressure-responsive parent particles (1) was 8.0 μm.

[0511] 100 parts of pressure-responsive parent particles (1), 0.25 parts of the first inorganic oxide particles, namely strontium titanate particles (number average particle size 1.45 μm), and 1.5 parts of the second inorganic oxide particles, namely hydrophobic silica (manufactured by NIPPON AEROSIL CO.,LTD., RY50), were mixed using a sample mill at a speed of 13000 rpm for 30 seconds. The mixture was then sieved using a vibrating sieve with a mesh size of 45 μm to obtain pressure-responsive particles (1).

[0512] Using pressure-responsive particles (1) as samples, the thermal behavior in the temperature range of -150°C to 100°C was analyzed using a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation), and two glass transition temperatures were observed. The glass transition temperatures are shown in Table 5.

[0513] The temperature T1 and temperature T2 of the pressure-responsive particle (1) were determined by the above measurement method. The pressure-responsive particle (1) satisfies Equation 1 "10℃≤T1-T2".

[0514] The cross-section of the pressure-responsive particle (1) was observed using scanning electron microscopy (SEM), revealing an island structure. The pressure-responsive particle (1) has a core containing an island phase and a shell without an island phase. The marine phase contains styrene-based resin, and the island phase contains (meth)acrylate-based resin. The average diameter of the island phase was determined using the methods described above. The average diameter of the island phase is shown in Table 5.

[0515] [Preparation of pressure-responsive particles (2) to (27)]

[0516] Except for the changes to the composite resin particle dispersion and the styrene-based resin particle dispersion as described in Table 5, pressure-responsive particles (2) to (27) were prepared in the same manner as the preparation of pressure-responsive particles (1).

[0517] The temperatures T1 and T2 of the pressure-responsive particles (2) to (27) were determined by the above measurement method. All the pressure-responsive particles (2) to (27) satisfy Equation 1 "10℃≤T1-T2".

[0518] [Preparation of pressure-responsive particles (28) to (30)]

[0519] Except for the changes to the composite resin particle dispersion as described in Table 6, pressure-responsive particles (28) to (30) were prepared in the same manner as the preparation of pressure-responsive particles (1).

[0520] The temperatures T1 and T2 of the pressure-responsive particles (28) to (30) were determined by the above measurement method. All the pressure-responsive particles (28) to (30) satisfy Equation 1 "10℃≤T1-T2".

[0521] [Preparation of pressure-responsive particles (31)]

[0522] Pressure-responsive parent particles were prepared by the following pulverization method.

[0523] The composite resin particle dispersion (M1) was dried to obtain composite resin particles (M31). The composite resin particles (M31) were hot-mixed using an extruder at a set temperature of 100°C. After cooling, they were pulverized and classified to obtain pressure-responsive master particles (31) with a number average particle size of 8.0 μm.

[0524] 100 parts of pressure-responsive parent particles (31), 0.25 parts of the first inorganic oxide particles, namely strontium titanate particles (number average particle size 1.45 μm), and 1.5 parts of the second inorganic oxide particles, namely hydrophobic silica (manufactured by NIPPON AEROSIL CO.,LTD., RY50), were mixed using a sample mill at a speed of 13000 rpm for 30 seconds. The mixture was then sieved using a vibrating sieve with a mesh size of 45 μm to obtain pressure-responsive particles (31).

[0525] Using pressure-responsive particles (31) as samples, the thermal behavior in the temperature range of -150°C to 100°C was analyzed using a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation), and two glass transition temperatures were observed. The glass transition temperatures are shown in Table 6.

[0526] The temperature T1 and temperature T2 of the pressure-responsive particle (31) were obtained by the above measurement method. The pressure-responsive particle (31) satisfies Equation 1 "10℃≤T1-T2".

[0527] [Comparative preparation of pressure-responsive particles (c1) to (c3)]

[0528] Except for the changes to the composite resin particle dispersion and the styrene-based resin particle dispersion as described in Table 5, pressure-responsive particles (c1) to (c3) were prepared in the same manner as the preparation of pressure-responsive particles (1).

[0529] [Evaluation of pressure-responsive phase transitions]

[0530] The temperature difference (T1-T3) was determined as an indicator of how easily pressure-responsive particles undergo a phase transition under pressure. Using each pressure-responsive particle as a sample, temperatures T1 and T3 were measured using a flow meter (Shimadzu Corporation, CFT-500), and the temperature difference (T1-T3) was calculated. Tables 5 and 6 show the temperature difference (T1-T3).

[0531] [Evaluation of Adhesion]

[0532] As the recording medium, Fuji Xerox Co., Ltd. postcard paper V424 was prepared. Using the Fuji Xerox Co., Ltd. image forming apparatus DocuCentre C7550I and commercially available yellow, magenta, blue-green, and black toners, an image with an area density of 30% consisting of black characters and a full-color photographic image was formed on one side of the postcard paper, and the image was then fixed.

[0533] Pressure-responsive particles are dispersed across the entire image-forming surface of the postcard paper to achieve an amount of 3 g / m². 2 The pressure-responsive particles are then fixed onto the image-forming surface of the postcard paper by a roller-type fixing machine, forming a layer of pressure-responsive particles.

[0534] Using the PRESSLE multiII sealing machine manufactured by TOPPAN FORMS CO.,LTD., postcard paper with a layer of pressure-responsive particles on the image forming surface is folded in such a way that the image forming surface is the inside. Pressure is applied to the folded postcard paper to bond the inner image forming surfaces together at a pressure of 90 MPa.

[0535] Under the aforementioned apparatus and conditions, 10 postcards are continuously produced by folding them in half with the image-forming surfaces facing inwards and then bonding the image-forming surfaces together.

[0536] The 10th postcard was cut to a width of 15mm along its length to create a rectangular test piece, which was then subjected to a 90-degree peel test. The peeling speed for the 90-degree peel test was set to 20mm / min. The load (N) was measured at 0.4mm intervals from 10mm to 50mm after the start of the measurement, and the average was calculated. The load (N) of the three test pieces was then averaged. The required peel load (N) is categorized below. The results are shown in Tables 5 and 6.

[0537] A: 0.8N or more

[0538] B: 0.6N or more and less than 0.8N

[0539] C: 0.4N or higher and less than 0.6N

[0540] D: 0.2N or more and less than 0.4N

[0541] E: less than 0.2N

[0542] [Table 5]

[0543]

[0544] [Table 6]

[0545]

[0546] ※The pressure-responsive particles (31) are manufactured by pulverizing composite resin particles (M31) obtained by drying composite resin particle dispersion (M1).

[0547] The postcards made using pressure-responsive particles (1) to (31) were evaluated in the same way as the [evaluation of retransmission suppression] described later, and the pressure-responsive particles (1) to (31) were classified as A.

[0548] <Preparation of dispersions containing composite resin particles>

[0549] [Preparation of composite resin particle dispersion (M50)]

[0550]

[0551] The above materials were placed in a polymerization flask, stirred at 25°C for 1 hour, and then heated to 70°C.

[0552] Dissolve 2.5 parts of ammonium persulfate in 75 parts of deionized water and add the solution dropwise to the polymerization flask over 60 minutes using a metering pump.

[0553] Next, while stirring continuously and slowly, the polymerization flask was kept at 70°C for 2 hours. Then, a mixture of 85 parts styrene and 15 parts n-butyl acrylate was added dropwise over a period of 60 minutes. After the addition, the mixture was kept at 75°C for 3 hours and then allowed to return to room temperature.

[0554] Thus, a composite resin particle dispersion (M50) containing composite resin particles was obtained, with a volume average particle size (D50v) of 223 nm, a weight average molecular weight of 220,000 as detected by GPC (UV detection), and a solid content of 32%.

[0555] The composite resin particle dispersion (M50) was dried and the composite resin particles were removed. The thermal behavior in the temperature range of -150°C to 100°C was analyzed using a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation), and two glass transition temperatures were observed. The glass transition temperatures are shown in Table 7.

[0556] [Preparation of composite resin particle dispersions (M51) to (M55)]

[0557] Except for changing the materials to the specifications listed in Table 7, composite resin particle dispersions (M51) to (M55) were prepared in the same manner as the preparation of composite resin particle dispersion (M50).

[0558] The composition and physical properties of composite resin particle dispersions (M50), etc., are shown in Table 7. In Table 7, monomers are referred to by the following abbreviations.

[0559] Styrene: St, n-Butyl acrylate: BA, Acrylic acid: AA, 2-Ethylhexyl acrylate: 2EHA

[0560] [Table 7]

[0561]

[0562] <Preparation of Pressure-Responsive Particles>

[0563] [Preparation of pressure-responsive particles (50) to (55)]

[0564] Except for changing the material to the specifications listed in Table 8, pressure-responsive particles (50) to (55) were prepared in the same manner as the preparation of pressure-responsive particles (1).

[0565] Using pressure-responsive particles (50) to (55) as samples, the thermal behavior in the temperature range of -150°C to 100°C was analyzed using a differential scanning calorimeter (Shimadzu Corporation, DSC-60A), and two glass transition temperatures were observed. The glass transition temperatures are shown in Table 8.

[0566] The temperatures T1 and T2 of the pressure-responsive particles (50) to (55) were determined by the above measurement method. All the pressure-responsive particles (50) to (55) satisfy Equation 1 "10℃≤T1-T2".

[0567] The cross-sections of pressure-responsive particles (50) to (55) were observed using scanning electron microscopy (SEM), revealing an island structure. The pressure-responsive particles (50) to (55) possess a core containing an island phase and a shell without an island phase. The marine phase contains styrene-based resin, and the island phase contains (meth)acrylate-based resin. The average diameter of the island phase was determined using the methods described above. The average diameter of the island phase is shown in Table 8.

[0568] [Evaluation of pressure-responsive phase transitions]

[0569] Each pressure-responsive particle was used as a sample, and temperatures T1 and T3 were measured using a flow meter (Shimadzu Corporation, CFT-500). The temperature difference (T1-T3) was calculated. Table 8 shows the temperature difference (T1-T3).

[0570] [Evaluation of Adhesion]

[0571] Similar to pressure-responsive particles (1), the adhesion was evaluated using the evaluation method described above for [adhesion evaluation]. The results are shown in Table 8.

[0572] [Table 8]

[0573]

[0574] The postcards made using pressure-responsive particles (50) to (55) were evaluated in the same way as the evaluation of retransmission suppression described later, and the pressure-responsive particles (50) to (55) were classified as A.

[0575] <The manufacture of printed materials by electrophotography>

[0576] Ten parts of any one of the pressure-responsive particles (1) to (31), (c1) to (c3) and (50) to (55) and 100 parts of the resin-coated carrier (1) were placed in a V-type mixer and stirred for 20 minutes. Then, the mixture was sieved using a vibrating sieve with a mesh size of 212 μm to obtain the developer (1) to (31), (c1) to (c3) and (50) to (55).

[0577] -Resin-coated carrier (1)-

[0578]

[0579] The above materials, excluding ferrite particles, and glass beads (1 mm in diameter, in the same amount as toluene) were mixed and stirred for 30 minutes at 1200 rpm using a KANSAI PAINT CO.,LTD. sand mill to obtain a dispersion. The dispersion and ferrite particles were then placed in a vacuum degassing kneader and dried under reduced pressure while stirring, thereby obtaining the resin-coated carrier (1).

[0580] As a manufacturing apparatus for printed materials, it was prepared Figure 4 The apparatus described herein is a printing unit that prepares a printing unit having a tandem configuration of five sets of pressure-responsive particles and a color image formation method as described in this embodiment, which simultaneously performs the configuration of pressure-responsive particles and the formation of color images on a recording medium, as well as an intermediate transfer method, and a pressing unit having a folding device and a pressing device.

[0581] The five developers of the printing unit are respectively placed with the developer (or comparative developer), yellow developer, magenta developer, blue-green developer, and black developer according to this embodiment. The developers of the various colors, such as yellow, are commercially available products manufactured by Fuji Xerox Co., Ltd.

[0582] As the recording medium, we prepared Fuji Xerox Co., Ltd.'s V424 postcard paper.

[0583] The image formed on the postcard paper is an image with an area density of 30% that is a mixture of black characters and full-color photographic images, and is formed on one side of the postcard paper.

[0584] In this embodiment, the amount of pressure-responsive particles (or comparative pressure-responsive particles) imparted is set to 3 g / m² in the image-forming area of ​​the image-forming surface of the postcard paper. 2 .

[0585] The folding device is configured to fold the postcard paper in such a way that the image forming surface is the inside.

[0586] The pressure of the pressurizing device is set to 90 MPa.

[0587] Under the aforementioned apparatus and conditions, 10 postcards are continuously produced by folding them in half with the image-forming surfaces facing inwards and then bonding the image-forming surfaces together.

[0588] The 10th postcard was cut with a width of 15mm along its length to create a rectangular test piece, which was then subjected to a 90-degree peel test. The peeling speed for the 90-degree peel test was set to 20mm / min. The load (N) was measured at 0.4mm intervals from 10mm to 50mm after the start of the measurement, and the average was calculated. The load (N) of the three test pieces was then averaged. The required peel load (N) is categorized below. The results are shown in Tables 9, 10, and 11.

[0589] A: 0.8N or more

[0590] B: 0.6N or more and less than 0.8N

[0591] C: 0.4N or higher and less than 0.6N

[0592] D: 0.2N or more and less than 0.4N

[0593] E: less than 0.2N

[0594] [Table 9]

[0595]

[0596] [Table 10]

[0597]

[0598] [Table 11]

[0599]

[0600] The postcards produced using developers (1) to (31) and (50) to (55) were evaluated in the same way as described later in the evaluation of [retransmission inhibition]. Developers (1) to (31) and (50) to (55) were classified as A.

[0601] <Study on the First Inorganic Oxide Particles>

[0602] [Preparation of pressure-responsive particles (60)]

[0603] Except for adjusting the melting / combining process time, pressure-responsive master particles (60) with a number average particle size of 8.5 μm were prepared in the same manner as the preparation of pressure-responsive master particles (1).

[0604] 100 parts of pressure-responsive parent particles (60), 0.25 parts of the first inorganic oxide particles, namely strontium titanate particles (number average particle size 1.45 μm), and 1.5 parts of the second inorganic oxide particles, namely hydrophobic silica (manufactured by NIPPON AEROSIL CO.,LTD., RX50), were mixed using a sample mill at 13000 rpm for 30 seconds. The mixture was then sieved using a vibrating sieve with a mesh size of 45 μm to obtain the pressure-responsive particles (60).

[0605] Using pressure-responsive particles (60) as samples, the thermal behavior in the temperature range of -150°C to 100°C was analyzed using a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation). Two glass transition temperatures were observed: -52°C and 54°C.

[0606] The temperature T1 and temperature T2 of the pressure-responsive particle (60) were determined by the above measurement method. The pressure-responsive particle (60) satisfies Equation 1 "10℃≤T1-T2".

[0607] [Preparation of pressure-responsive particles (61)~(73) and (c4)~(c6)]

[0608] Except for changing the first inorganic oxide particles to the specifications listed in Table 12, pressure-responsive particles (61) to (73) and (c4) to (c6) were prepared in the same manner as the preparation of pressure-responsive particles (60).

[0609] The temperatures T1 and T2 of the pressure-responsive particles (61) to (73) were determined by the above measurement method. All the pressure-responsive particles (61) to (73) satisfy Equation 1 "10℃≤T1-T2".

[0610] [Evaluation of Adhesion]

[0611] As the recording medium, Fuji Xerox Co., Ltd. postcard paper V424 was prepared. Using the Fuji Xerox Co., Ltd. image forming apparatus DocuCentre C7550I and commercially available yellow, magenta, blue-green, and black toners, an image with an area density of 30% consisting of black characters and a full-color photographic image was formed on one side of the postcard paper, and the image was then fixed.

[0612] Pressure-responsive particles are dispersed across the entire image-forming surface of the postcard paper to achieve an amount of 3 g / m². 2The pressure-responsive particles are then fixed onto the image-forming surface of the postcard paper by a roller-type fixing machine, forming a layer of pressure-responsive particles.

[0613] Using the PRESSLE multiII sealing machine manufactured by TOPPAN FORMS CO.,LTD., postcard paper with a layer of pressure-responsive particles on the image forming surface is folded in such a way that the image forming surface is the inside. Pressure is applied to the folded postcard paper to bond the inner image forming surfaces together at a pressure of 90 MPa.

[0614] Under the aforementioned apparatus and conditions, 10 postcards are continuously produced by folding them in half with the image-forming surfaces facing inwards and then bonding the image-forming surfaces together.

[0615] The 10th postcard was cut to a width of 15mm along its length to create a rectangular test piece, which was then subjected to a 90-degree peel test. The peeling speed for the 90-degree peel test was set to 20mm / min. The load (N) was collected at 0.4mm intervals from 10mm to 50mm after the start of the measurement, and the average was calculated. The load (N) of the three test pieces was then averaged. The required peel load (N) is categorized below. The results are shown in Table 12.

[0616] A: 0.8N or more

[0617] B: 0.6N or more and less than 0.8N

[0618] C: 0.4N or higher and less than 0.6N

[0619] D: 0.2N or more and less than 0.4N

[0620] E: less than 0.2N

[0621] [Evaluation of resuppression]

[0622] A modified version of the Color 1000Press image forming apparatus manufactured by Fuji Xerox Co., Ltd. was used for a transport test at a processing speed equivalent to 120 sheets / minute for A4 size. The test quantity was 50,000 sheets, and Ncolor209 paper (manufactured by Fuji Xerox Co., Ltd.) was used. The images were evaluated based on adhesion. The evaluation environment was set at a temperature of 30°C and a relative humidity of 80%. The number of re-feedings in the test quantity is categorized below. The results are shown in Table 12.

[0623] A: No resend occurred.

[0624] B: The number of resends is 1 to 3 times.

[0625] C: The number of resends is 4 to 6.

[0626] D: The number of resends is 7 to 10.

[0627] E: The number of resends has exceeded 11.

[0628] [Table 12]

[0629]

[0630] The embodiments of the present invention described above are provided for illustrative purposes. Furthermore, these embodiments do not exhaustively encompass the present invention, nor do they limit the invention to the disclosed methods. It will be apparent to those skilled in the art that various modifications and variations will be readily understood. These embodiments were chosen and described to most readily explain the principles and applications of the invention. Thus, those skilled in the art can understand the invention through various modifications that are assumed to be optimized for specific uses of various embodiments. The scope of the invention is defined by the foregoing claims and their equivalents.

Claims

1. A pressure-responsive particle comprising: A pressure-responsive parent particle containing a styrene-based resin and a (meth)acrylate-based resin, the pressure-responsive parent particle having a core containing the styrene-based resin and the (meth)acrylate-based resin and a shell covering the core, the styrene-based resin containing styrene and other vinyl monomers as polymerizing components, the (meth)acrylate-based resin containing at least two (meth)acrylate alkyl esters as polymerizing components and the (meth)acrylate alkyl esters accounting for more than 90% by mass of the total polymerizing components, the at least two (meth)acrylate alkyl esters including at least 2-ethylhexyl acrylate and linear (meth)acrylate alkyl esters, wherein the linear (meth)acrylate alkyl ester is selected from one of n-butyl acrylate, hexyl acrylate and propyl acrylate, the two (meth)acrylate alkyl esters with the largest mass proportions being 2-ethylhexyl acrylate and the linear (meth)acrylate alkyl ester, and the mass ratio of 2-ethylhexyl acrylate and the linear (meth)acrylate alkyl ester in the at least two (meth)acrylate alkyl esters is 80:20 to 20:80; and The ratio of the number-average particle size Db of the first inorganic oxide particle to the number-average particle size Da of the pressure-responsive parent particle, Db / Da, is 0.05 or more and 0.25 or less. The pressure-responsive particle has at least two glass transition temperatures, and the difference between the lowest and highest glass transition temperatures is more than 30°C.

2. The pressure-responsive particle according to claim 1, wherein, The ratio of the number-average particle size Db of the first inorganic oxide particle to the number-average particle size Da of the pressure-responsive parent particle, Db / Da, is greater than 0.08 and less than 0.

20.

3. The pressure-responsive particle according to claim 1 or 2, wherein, The first inorganic oxide particle contains at least one of strontium titanate particles and cerium oxide particles.

4. The pressure-responsive particles according to claim 1 or 2, further comprising second inorganic oxide particles with a number-average particle size of less than 200 nm.

5. The pressure-responsive particle according to claim 4, wherein, The second inorganic oxide particle contains silicon dioxide particles.

6. The pressure-responsive particle according to claim 1 or 2, wherein, The amount of the first inorganic oxide particles added is more than 0.05 parts by mass and less than 3 parts by mass relative to 100 parts by mass of the pressure-responsive parent particles.

7. The pressure-responsive particle according to claim 6, wherein, The amount of the first inorganic oxide particles added is 0.08 parts by mass and less than 1.5 parts by mass relative to 100 parts by mass of the pressure-responsive parent particles.

8. The pressure-responsive particle according to claim 1 or 2, wherein, Styrene accounts for more than 60% by mass and less than 95% by mass in the total polymer composition of the styrene-based resin.

9. The pressure-responsive particle according to claim 1 or 2, wherein, The difference in the number of carbon atoms of the alkyl groups of the two (meth)acrylate alkyl esters that have the largest mass proportion in the polymerizing component of the (meth)acrylate resin is 2 or 4.

10. The pressure-responsive particle according to claim 1 or 2, wherein, The other vinyl monomers contained in the styrene-based resin as polymerizing components contain (meth)acrylates.

11. The pressure-responsive particle according to claim 1 or 2, wherein, The other vinyl monomers contained in the styrene-based resin as polymerizing components include at least one of n-butyl acrylate and 2-ethylhexyl acrylate.

12. The pressure-responsive particle according to claim 1 or 2, wherein, The styrene-based resin and the (meth)acrylate-based resin contain the same type of (meth)acrylate alkyl ester as a polymerization component.

13. The pressure-responsive particle according to claim 1 or 2, wherein, The (meth)acrylate resin contains linear (meth)acrylate alkyl esters of 2-ethylhexyl acrylate and n-butyl acrylate as polymerization components.

14. The pressure-responsive particle according to claim 1 or 2, wherein, In the pressure-responsive parent material, the content of the styrene-based resin is greater than the content of the (meth)acrylate-based resin.

15. The pressure-responsive particle according to claim 1 or 2, wherein, The pressure-responsive parent material has a marine phase containing the styrene-based resin and an island phase containing the (meth)acrylate-based resin dispersed in the marine phase.

16. The pressure-responsive particle according to claim 15, wherein, The average diameter of the island phase is above 200 nm and below 500 nm.

17. The pressure-responsive particle according to claim 1, wherein, The shell contains the styrene-based resin.

18. The pressure-responsive particle according to claim 1 or 2, wherein, The temperature at which the viscosity of 10000 Pa·s is displayed under a pressure of 4 MPa is below 90 °C.

19. A box containing pressure-responsive particles according to any one of claims 1 to 18, and detachable from a printing manufacturing apparatus.

20. An apparatus for manufacturing printed matter, comprising: A configuration unit, comprising a pressure-responsive particle as claimed in any one of claims 1 to 18, and configuring the pressure-responsive particle onto a recording medium; and A crimping unit folds and crimps the recording medium or overlaps and crimps the recording medium and another recording medium.

21. The apparatus for manufacturing printed matter according to claim 20, further comprising: A color image forming unit uses pigments to form a color image on a recording medium.

22. A method for manufacturing printed matter, comprising: The configuration step involves configuring the pressure-responsive particles onto a recording medium using any one of claims 1 to 18. and The pressing process involves folding and pressing the recording medium or overlapping and pressing the recording medium and another recording medium.

23. The method for manufacturing printed matter according to claim 22, further comprising: The color image forming process uses pigments to form a color image on a recording medium.

24. A printed material formed by bonding the opposite surfaces of a folded recording medium with pressure-responsive particles according to any one of claims 1 to 18.

25. A printed material formed by bonding the opposing surfaces of a plurality of overlapping recording media using pressure-responsive particles according to any one of claims 1 to 18.

26. A sheet for printing, comprising the use of pressure-responsive particles according to any one of claims 1 to 18. It has a substrate and pressure-responsive particles disposed on the substrate.

27. A method for manufacturing a sheet for printing, comprising: The configuration step involves configuring the pressure-responsive particles onto a substrate using any one of claims 1 to 18.

Images