Pressure-responsive particles, cartridge, device for producing printed matter, method for producing printed matter, printed matter, sheet for producing printed matter, and method for producing sheet for producing printed matter

Abstract

To provide a pressure responsive particle which easily changes the phase due to the pressure and is excellent in the adhesiveness.SOLUTION: A pressure responsive particle contains a styrene resin including styrene and other vinyl monomers in the polymerization component, and a (meth)acrylic acid ester-based resin including at least two kinds of (meth)acrylic acid ester in the polymerization component and having the mass ratio of the (meth)acrylic acid ester in the entire polymerization component equal to or greater than 90 mass%, and has at least two glass transition temperatures. The difference between the lowest glass transition temperature and the highest glass transition temperature is equal to or greater than 30°C.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to pressure responsive particles, a cartridge, a device for producing a printed matter, a method for producing a printed matter, a printed matter, a sheet for producing a printed matter, and a method for producing a sheet for producing a printed matter. [Background technology]

[0002] Patent Document 1 describes a water-dispersed pressure-sensitive adhesive composition that contains two types of acrylic polymers in an aqueous solvent.

[0003] In Patent Document 2, the formula "20°C ≦ T(1MPa)-T(10MPa)" (T(1MPa) is the viscosity of 10 at an applied pressure of 1 MPa) is 4 T(10MPa) represents the temperature at which the viscosity becomes 10 Pa s at an applied pressure of 10 MPa. 4 The adhesive material described satisfies the following requirements:

[0004] Patent Document 3 describes a pressure-fixable toner that contains a styrene resin and a (meth)acrylic ester resin having a glass transition temperature 30° C. or more lower than that of the styrene resin, has a sea-island structure composed of a sea portion containing the styrene resin and an island portion containing the (meth)acrylic ester resin, has a core portion with a major axis of the island portion of 200 nm or more and 500 nm or less, and a shell layer that covers the core portion and contains a resin having a glass transition temperature of 50° C. or more.

[0005] Patent Document 4 describes a polymerizable composition comprising an acrylic polymer (A) which is a polymer of a monomer raw material (A) and an acrylic polymer (B) which is a polymer of a monomer raw material (B), the glass transition temperature of the acrylic polymer (B) being 0° C. or higher, and the weight average molecular weight of the acrylic polymer (B) being 0.3×10 4 Larger than 5×10 4 The weight average molecular weight of the acrylic polymer (A) is 40×10 4The aqueous dispersion pressure-sensitive adhesive composition is described, in which the difference between the glass transition temperature of the acrylic polymer (B) and the glass transition temperature of the acrylic polymer (A) is 70°C or more, and the monomer raw material (B) contains a carboxyl group-containing monomer in a proportion of 3% by weight or more and 20% by weight or less.

[0006] Patent Document 5 describes a pressure-adhesive postcard paper in which the adhesive layer contains an acrylic acid / alkyl methacrylate copolymer. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2012-188512 A [Patent Document 2] JP 2018-002889 A [Patent Document 3] JP 2018-163198 A [Patent Document 4] Patent No. 646872 [Patent Document 5] JP 2007-229993 A Summary of the Invention [Problem to be solved by the invention]

[0008] The present disclosure has an objective of providing pressure-responsive particles comprising a styrene-based resin and a (meth)acrylic ester-based resin, which are more likely to undergo phase transition due to pressure and have excellent adhesiveness compared to pressure-responsive particles in which the (meth)acrylic ester-based resin is a homopolymer of (meth)acrylic ester. [Means for solving the problem]

[0009] Specific means for solving the above problems include the following aspects.

[0010] <1> a styrene-based resin containing styrene and other vinyl monomers as polymerization components; a (meth)acrylic acid ester-based resin containing at least two kinds of (meth)acrylic acid esters as polymerization components, the mass ratio of the (meth)acrylic acid esters in the total polymerization components being 90 mass% or more; It has at least two glass transition temperatures, and the difference between the lowest and highest glass transition temperatures is 30° C. or more. Pressure-responsive particles. <2> The mass ratio of styrene in the total polymerization components of the styrene-based resin is 60% by mass or more and 95% by mass or less. <1> pressure-responsive particles. <3> the mass ratio of the two (meth)acrylic esters having the largest mass ratios among the at least two (meth)acrylic esters contained as polymerization components in the (meth)acrylic ester-based resin is 80:20 to 20:80; <1> or <2> The pressure-responsive particle according to claim 1. <4> the (meth)acrylic acid ester-based resin contains at least two (meth)acrylic acid esters as polymerization components, and the two (meth)acrylic acid alkyl esters have the largest mass ratios of each of the at least two (meth)acrylic acid esters, and the difference in the number of carbon atoms in the alkyl groups of the two (meth)acrylic acid alkyl esters is 1 or more and 4 or less. <1> ~ <3> 2. The pressure-responsive particle according to claim 1 . <5> The other vinyl monomer contained as a polymerization component in the styrene-based resin includes a (meth)acrylic acid ester. <1> ~ <4> 2. The pressure-responsive particle according to claim 1 . <6> The other vinyl monomer contained as a polymerization component in the styrene-based resin includes at least one of n-butyl acrylate and 2-ethylhexyl acrylate. <1> ~ <5> 2. The pressure-responsive particle according to claim 1 . <7> The styrene-based resin and the (meth)acrylic acid ester-based resin contain the same type of (meth)acrylic acid ester as polymerization components. <1> ~ <6> 2. The pressure-responsive particle according to claim 1 . <8> The (meth)acrylic acid ester resin contains 2-ethylhexyl acrylate and n-butyl acrylate as polymerization components. <1> ~ <7> 2. The pressure-responsive particle according to claim 1 . <9> The content of the styrene-based resin is greater than the content of the (meth)acrylic acid ester-based resin. <1> ~ <8> 2. The pressure-responsive particle according to claim 1 . <10> A sea phase containing the styrene-based resin and an island phase containing the (meth)acrylic acid ester-based resin dispersed in the sea phase. <1> ~ <9> 2. The pressure-responsive particle according to claim 1 . <11> The average diameter of the island phase is 200 nm or more and 500 nm or less. <10> The pressure-responsive particle according to claim 1. <12> The polymer has a core portion containing the styrene-based resin and the (meth)acrylic acid ester-based resin, and a shell layer covering the core portion. <1> ~ <11> 2. The pressure-responsive particle according to claim 1 . <13> The shell layer contains the styrene-based resin. <12> The pressure-responsive particle according to claim 1. <14> The temperature at which it exhibits a viscosity of 10,000 Pa·s under a pressure of 4 MPa is 90°C or lower. <1> ~ <13> 2. The pressure-responsive particle according to claim 1 .

[0011] <15> <1> ~ <14> 13. A cartridge containing the pressure responsive particles according to any one of claims 1 to 12 and being detachably attached to a printing production device. <16> <1> ~ <14> a placement means for placing the pressure responsive particles on a recording medium, the placement means storing the pressure responsive particles according to any one of the above items; a pressing means for folding the recording medium and pressing the same, or for stacking the recording medium and another recording medium and pressing the same; A printing production device comprising: <17> Further comprising a color image forming means for forming a color image on a recording medium using a color material. <16> A manufacturing apparatus for printed matter according to the above item. <18> <1> ~ <14> a step of disposing the pressure responsive particles on a recording medium using the pressure responsive particles according to any one of the above items; a pressing step of folding the recording medium and pressing the same, or stacking the recording medium and another recording medium and pressing the same; A method for producing a printed matter comprising the steps of: <19> Further comprising a color image forming step of forming a color image on a recording medium using a coloring material. <17> A method for producing a printed matter according to claim 1.

[0012] <20> The folded recording medium is, on the opposing surfaces, <1> ~ <14> 2. A printed matter comprising the pressure-responsive particles according to claim 1 . <21> The overlapping recording media are arranged on opposing surfaces. <1> ~ <14> 2. A printed matter comprising the pressure-responsive particles according to claim 1 .

[0013] <22> <1> ~ <14> The pressure-responsive particle according to any one of claims 1 to 5 is used, A sheet for producing printed matter, comprising a substrate and the pressure responsive particles disposed on the substrate. <23> <1> ~ <14> 2. A process for disposing the pressure responsive particles on a substrate using the pressure responsive particles according to any one of claims 1 to 11. A method for manufacturing a sheet for producing printed matter. Effect of the Invention

[0014] <1> According to the present invention, there is provided a pressure-responsive particle comprising a styrene-based resin and a (meth)acrylic acid ester-based resin, which is more susceptible to phase transition due to pressure and has excellent adhesive properties compared to pressure-responsive particles in which the (meth)acrylic acid ester-based resin is a homopolymer of (meth)acrylic acid ester. <2> According to the present invention, pressure-responsive particles are provided which undergo a phase transition more easily due to pressure, compared to when the mass ratio of styrene in the total polymerization components of the styrene-based resin exceeds 95 mass %. <3> According to the present invention, pressure-responsive particles are provided that are more likely to undergo phase transition due to pressure and have excellent adhesiveness, compared to when the mass ratio of the two (meth)acrylic esters with the largest mass proportions among the at least two types of (meth)acrylic esters contained as polymerization components in the (meth)acrylic ester-based resin is outside the range of 80:20 to 20:80. <4> According to the present invention, pressure-responsive particles are provided that are more likely to undergo phase transition due to pressure and have excellent adhesiveness, compared to when the difference in the number of carbon atoms in the alkyl groups of the two types of (meth)acrylic acid alkyl esters is 5 or more. <5> , <6> or <7> According to the present invention, pressure-responsive particles are provided which are more likely to undergo phase transition due to pressure than pressure-responsive particles which contain polystyrene instead of a styrene-based resin. <8> According to the present invention, there is provided a pressure-responsive particle comprising a styrene-based resin and a (meth)acrylic acid ester-based resin, the pressure-responsive particle having superior adhesiveness compared to a pressure-responsive particle in which the (meth)acrylic acid ester-based resin is a homopolymer of 2-ethylhexyl acrylate. <9> According to the present invention, pressure-responsive particles are provided that maintain adhesiveness compared to when the content of the styrene-based resin is lower than the content of the (meth)acrylic acid ester-based resin. <10> According to the present invention, there is provided a pressure-responsive particle which is more likely to undergo phase transition due to pressure and has excellent adhesiveness, as compared to a particle not having the sea-island structure. <11> According to the present invention, pressure-responsive particles are provided that are more likely to undergo phase transition due to pressure, as compared with a case in which the average diameter of the island phase exceeds 500 nm. <12> According to the present invention, pressure-responsive particles are provided that are more susceptible to phase transition due to pressure than particles having a core-shell structure in which the core portion contains only a styrene-based resin or only a (meth)acrylic ester-based resin. <13> According to the present invention, pressure-responsive particles are provided that undergo phase transition more easily due to pressure, compared to when the shell layer does not contain a styrene-based resin but contains another resin. <14> According to the present invention, pressure-responsive particles are provided that are more likely to undergo phase transition due to pressure than particles that exhibit a viscosity of 10,000 Pa·s at a pressure of 4 MPa at a temperature of over 90°C.

[0015] <15> According to the invention, a cartridge is provided which contains pressure-responsive particles comprising a styrene-based resin and a (meth)acrylic ester-based resin, the (meth)acrylic ester-based resin being more susceptible to phase transition due to pressure and having excellent adhesive properties compared to pressure-responsive particles in which the (meth)acrylic ester-based resin is a homopolymer of (meth)acrylic ester. <16> or <17> According to the invention, there is provided an apparatus for manufacturing printed matter that employs pressure-responsive particles comprising a styrene-based resin and a (meth)acrylic ester-based resin, the (meth)acrylic ester-based resin being more susceptible to phase transition due to pressure and having excellent adhesiveness compared to pressure-responsive particles that are a homopolymer of (meth)acrylic ester. <18> or <19> According to the present invention, there is provided a method for producing a printed matter using pressure-responsive particles comprising a styrene-based resin and a (meth)acrylic ester-based resin, the (meth)acrylic ester-based resin being more susceptible to phase transition due to pressure and having excellent adhesiveness compared to pressure-responsive particles in which the (meth)acrylic ester-based resin is a homopolymer of (meth)acrylic ester.

[0016] <20> or <21> According to the invention, there is provided a printed material using pressure-responsive particles comprising a styrene-based resin and a (meth)acrylic ester-based resin, the (meth)acrylic ester-based resin being more susceptible to phase transition due to pressure and having excellent adhesiveness compared to pressure-responsive particles in which the (meth)acrylic ester-based resin is a homopolymer of (meth)acrylic ester.

[0017] <22> According to the invention, there is provided a sheet for producing printed matter employing pressure-responsive particles comprising a styrene-based resin and a (meth)acrylic ester-based resin, the (meth)acrylic ester-based resin being more susceptible to phase transition due to pressure and having excellent adhesiveness compared to pressure-responsive particles which are homopolymers of (meth)acrylic ester. <23> According to the invention, there is provided a method for manufacturing a sheet for producing printed matter using pressure-responsive particles comprising a styrene-based resin and a (meth)acrylic ester-based resin, the (meth)acrylic ester-based resin being more susceptible to phase transition due to pressure and having excellent adhesiveness compared to pressure-responsive particles that are a homopolymer of (meth)acrylic ester. [Brief description of the drawings]

[0018] [Figure 1] 1 is a schematic diagram illustrating an example of a printed matter production apparatus according to an embodiment of the present invention. [Diagram 2] FIG. 11 is a schematic diagram illustrating another example of a printed matter production apparatus according to the present embodiment. [Diagram 3] FIG. 11 is a schematic diagram illustrating another example of a printed matter production apparatus according to the present embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] Hereinafter, embodiments of the present disclosure will be described. These descriptions and examples are merely illustrative of the embodiments, and are not intended to limit the scope of the embodiments.

[0020] In the present disclosure, a numerical range indicated using "~" indicates a range that includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively.

[0021] In the numerical ranges described in the present disclosure in stages, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit value of the numerical range may be replaced with a value shown in the examples.

[0022] In the present disclosure, the term "step" includes not only an independent step, but also a step that cannot be clearly distinguished from other steps, as long as the intended purpose of the step is achieved.

[0023] When an embodiment of the present disclosure is described with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. In addition, the size of the members in each drawing is conceptual, and the relative relationship between the sizes of the members is not limited to this.

[0024] In the present disclosure, each component may contain multiple types of corresponding substances. When referring to the amount of each component in a composition in the present disclosure, if multiple substances corresponding to each component are present in the composition, the total amount of the multiple substances present in the composition is meant unless otherwise specified.

[0025] In the present disclosure, the particles corresponding to each component may include multiple types. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component means the value for a mixture of the multiple types of particles present in the composition, unless otherwise specified.

[0026] In the present disclosure, the term "(meth)acrylic" means either "acrylic" or "methacrylic".

[0027] In this disclosure, the "toner for developing electrostatic images" is also referred to simply as "toner", and the "electrostatic image developer" is also referred to simply as "developer".

[0028] In this disclosure, a printed matter formed by folding a recording medium and bonding the opposing surfaces together, or a printed matter formed by stacking two or more recording media and bonding the opposing surfaces together, is referred to as a "bonded printed matter".

[0029] <Pressure-responsive particles> The pressure responsive particles according to this embodiment are a styrene-based resin containing styrene and other vinyl monomers as polymerization components; a (meth)acrylic acid ester-based resin containing at least two kinds of (meth)acrylic acid esters as polymerization components, the mass ratio of the (meth)acrylic acid esters in the total polymerization components being 90 mass% or more; It has at least two glass transition temperatures, with the difference between the lowest and highest glass transition temperatures being 30° C. or more.

[0030] The pressure-responsive particles according to this embodiment undergo a phase transition due to pressure by exhibiting the thermal characteristic of "having at least two glass transition temperatures, with the difference between the lowest and highest glass transition temperatures being 30° C. or more." In this disclosure, the pressure-responsive particles that undergo a phase transition due to pressure refer to pressure-responsive particles that satisfy the following formula 1.

[0031] Formula 1...10℃≦T1-T2 In formula 1, T1 is the temperature at which the viscosity is 10,000 Pa s under a pressure of 1 MPa, and T2 is the temperature at which the viscosity is 10,000 Pa s under a pressure of 10 MPa. How to determine temperatures T1 and T2 will be described later.

[0032] The pressure-responsive particles according to the present embodiment are made of a "styrene-based resin containing styrene and other vinyl monomers as polymerization components" and a "(meth)acrylic acid ester-based resin containing at least two (meth)acrylic acid esters as polymerization components, with the (meth)acrylic acid esters accounting for 90% by mass or more of the total polymerization components", and therefore undergo phase transition due to pressure and have excellent adhesiveness. The mechanism behind this is presumed to be as follows.

[0033] Generally, styrene resins and (meth)acrylic ester resins have low compatibility with each other, so it is believed that the two resins are contained in the pressure-responsive base particles in a phase-separated state. In addition, when the pressure-responsive base particles are pressurized, the (meth)acrylic ester resin, which has a relatively low glass transition temperature, becomes fluid first, and this fluidization spreads to the styrene resin, so that both resins become fluid. In addition, it is believed that the two resins in the pressure-responsive base particles, when they are fluidized by pressurization and then solidified by decompression to form a resin layer, form a phase-separated state again due to their low compatibility. It is presumed that the (meth)acrylic acid ester-based resin containing at least two kinds of (meth)acrylic acid esters in the polymerization components has at least two kinds of ester groups bonded to the main chain, and therefore has a lower degree of molecular alignment in the solid state than a homopolymer of (meth)acrylic acid ester, and therefore is more likely to be fluidized by pressure. Furthermore, when the mass ratio of (meth)acrylic acid esters in the entire polymerization components is 90 mass% or more, at least two kinds of ester groups are present at high density, so the degree of molecular alignment in the solid state is lower, and therefore it is more likely to be fluidized by pressure. Therefore, it is presumed that the pressure-responsive particles according to this embodiment are more likely to be fluidized by pressure, that is, to undergo phase transition by pressure, compared to pressure-responsive particles in which the (meth)acrylic acid ester-based resin is a homopolymer of (meth)acrylic acid ester. In addition, a (meth)acrylic acid ester-based resin containing at least two kinds of (meth)acrylic acid esters in the polymerization components, and having a mass ratio of the (meth)acrylic acid esters in the total polymerization components of 90 mass% or more, has a low degree of molecular alignment even when solidified again, so it is presumed that the phase separation with the styrene-based resin is a minute phase separation. The finer the state of phase separation between the styrene-based resin and the (meth)acrylic acid ester-based resin, the more uniform the state of the adhesion surface to the adherend will be, and the better the adhesiveness will be. Therefore, it is presumed that the pressure-responsive particles according to this embodiment have better adhesiveness than pressure-responsive particles in which the (meth)acrylic acid ester-based resin is a homopolymer of (meth)acrylic acid ester.

[0034] The components, structure, and properties of the pressure-responsive particles according to this embodiment will be described in detail below. In the following description, unless otherwise specified, "styrene resin" means "styrene resin containing styrene and other vinyl monomers as polymerization components", and "(meth)acrylic acid ester resin" means "(meth)acrylic acid ester resin containing at least two types of (meth)acrylic acid ester as polymerization components, in which the mass ratio of (meth)acrylic acid ester to the total polymerization components is 90 mass% or more".

[0035] The pressure responsive particles according to this embodiment contain at least pressure responsive base particles, and optionally contain an external additive.

[0036] [Pressure-responsive mother particles] The pressure-responsive base particles contain at least a styrene-based resin and a (meth)acrylic acid ester-based resin, and may contain a colorant, a release agent, and other additives.

[0037] From the viewpoint of maintaining adhesiveness, the pressure-responsive base particles preferably have a styrene resin content greater than the (meth)acrylic acid ester resin content. The styrene resin content 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, based on the total content of the styrene resin and the (meth)acrylic acid ester resin.

[0038] -Styrene-based resin- The pressure-responsive base particles constituting the pressure-responsive particles according to this embodiment contain a styrene-based resin that contains styrene and other vinyl monomers as polymerization components.

[0039] The mass proportion of styrene in all the polymerization components of the styrene-based resin is preferably 60 mass% or more, more preferably 70 mass% or more, and even more preferably 75 mass% or more, from the viewpoint of suppressing fluidization of the pressure-responsive particles in an unpressurized state, and is preferably 95 mass% or less, more preferably 90 mass% or less, and even more preferably 85 mass% or less, from the viewpoint of forming pressure-responsive particles that are prone to phase transition due to pressure.

[0040] Examples of vinyl monomers other than styrene that constitute the styrene-based resin include styrene-based monomers other than styrene and acrylic monomers.

[0041] Examples of styrene-based monomers other than styrene include vinylnaphthalene; alkyl-substituted styrenes such as α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, and pn-dodecylstyrene; aryl-substituted styrenes such as p-phenylstyrene; alkoxy-substituted styrenes such as p-methoxystyrene; halogen-substituted styrenes such as p-chlorostyrene, 3,4-dichlorostyrene, p-fluorostyrene, and 2,5-difluorostyrene; nitro-substituted styrenes such as m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene; etc. The styrene-based monomers may be used alone or in combination of two or more.

[0042] The acrylic monomer is preferably at least one acrylic monomer selected from the group consisting of (meth)acrylic acid and (meth)acrylic acid esters. Examples of the (meth)acrylic acid esters include (meth)acrylic acid alkyl esters, (meth)acrylic acid carboxy-substituted alkyl esters, (meth)acrylic acid hydroxy-substituted alkyl esters, (meth)acrylic acid alkoxy-substituted alkyl esters, and di(meth)acrylic acid esters. The acrylic monomers may be used alone or in combination of two or more.

[0043] Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and isobornyl (meth)acrylate. Examples of the (meth)acrylic acid carboxy-substituted alkyl ester include 2-carboxyethyl (meth)acrylate. Examples of the hydroxy-substituted alkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Examples of the alkoxy-substituted alkyl (meth)acrylate esters include 2-methoxyethyl (meth)acrylate. Examples of di(meth)acrylic acid esters include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, pentanediol di(meth)acrylate, hexanediol di(meth)acrylate, nonanediol di(meth)acrylate, and decanediol di(meth)acrylate.

[0044] Examples of the (meth)acrylic acid ester include 2-(diethylamino)ethyl (meth)acrylate, benzyl (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate.

[0045] Examples of other vinyl monomers constituting the styrene-based resin include, in addition to styrene-based monomers and acrylic monomers, (meth)acrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; and olefins such as isoprene, butene and butadiene.

[0046] From the viewpoint of forming pressure-responsive particles that easily undergo a phase transition due to pressure, the styrene-based resin preferably contains a (meth)acrylic acid ester as a polymerization component, more preferably contains a (meth)acrylic acid alkyl ester, even more preferably contains a (meth)acrylic acid alkyl ester having an alkyl group with 2 to 10 carbon atoms, even more preferably contains a (meth)acrylic acid alkyl ester having an alkyl group with 4 to 8 carbon atoms, and particularly preferably contains at least one of n-butyl acrylate and 2-ethylhexyl acrylate. From the viewpoint of forming pressure-responsive particles that easily undergo a phase transition due to pressure, the styrene-based resin and the (meth)acrylic acid ester-based resin preferably contain the same type of (meth)acrylic acid ester as a polymerization component.

[0047] The mass ratio of the (meth)acrylic acid ester to the entire polymerization components of the styrene-based resin is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less from the viewpoint of suppressing fluidization of the pressure-responsive particles in an unpressurized state, and is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more from the viewpoint of forming pressure-responsive particles that are prone to phase transition by pressure. As the (meth)acrylic acid ester here, a (meth)acrylic acid alkyl ester is preferred, a (meth)acrylic acid alkyl ester having an alkyl group with 2 to 10 carbon atoms is more preferred, and a (meth)acrylic acid alkyl ester having an alkyl group with 4 to 8 carbon atoms is even more preferred.

[0048] It is particularly preferable that the styrene-based resin contains at least one of n-butyl acrylate and 2-ethylhexyl acrylate as a polymerization component, and the total amount of n-butyl acrylate and 2-ethylhexyl acrylate in all the polymerization components of the styrene-based resin is preferably 40 mass% or less, more preferably 30 mass% or less, and even more preferably 25 mass% or less, from the viewpoint of suppressing fluidization of the pressure-responsive particles in an unpressurized state, and is preferably 5 mass% or more, more preferably 10 mass% or more, and even more preferably 15 mass% or more, from the viewpoint of forming pressure-responsive particles that are prone to phase transition due to pressure.

[0049] The weight average molecular weight of the styrene-based resin is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more, from the viewpoint of preventing the pressure-responsive particles from fluidizing when no pressure is applied, and is preferably 60,000 or less, more preferably 55,000 or less, and even more preferably 50,000 or less, from the viewpoint of forming pressure-responsive particles that are prone to undergo phase transition when subjected to pressure.

[0050] In this disclosure, the weight average molecular weight of the resin is measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC is performed using a Tosoh HLC-8120GPC as a GPC device, a Tosoh TSKgel SuperHM-M (15 cm) as a column, and tetrahydrofuran as a solvent. The weight average molecular weight of the resin is calculated using a molecular weight calibration curve prepared using a monodisperse polystyrene standard sample.

[0051] The glass transition temperature of the styrene-based resin is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher, from the viewpoint of preventing the pressure-responsive particles from fluidizing in an unpressurized state; and from the viewpoint of forming pressure-responsive particles that easily undergo a phase transition due to pressure, the glass transition temperature is preferably 110°C or lower, more preferably 100°C or lower, and even more preferably 90°C or lower.

[0052] In the present disclosure, the glass transition temperature of a resin is determined from a differential scanning calorimetry (DSC) curve obtained by performing differential scanning calorimetry (DSC). More specifically, the glass transition temperature is determined according to the "extrapolated glass transition onset temperature" described in the method for determining glass transition temperature in JIS K7121:1987 "Method for measuring transition temperature of plastics."

[0053] The glass transition temperature of the resin can be controlled by the type and polymerization ratio of the polymerization components. The higher the density of the flexible units such as methylene groups, ethylene groups, and oxyethylene groups contained in the main chain, the lower the glass transition temperature tends to be, and the higher the density of the rigid units such as aromatic rings and cyclohexane rings contained in the main chain, the higher the glass transition temperature tends to be. In addition, the higher the density of the aliphatic groups in the side chain, the lower the glass transition temperature tends to be.

[0054] In this embodiment, the mass proportion of the styrene-based resin in the entire pressure-responsive base particle is preferably 55 mass% or more, more preferably 60 mass% or more, and even more preferably 65 mass% or more, from the viewpoint of suppressing fluidization of the pressure-responsive particles in an unpressurized state, and is preferably 80 mass% or less, more preferably 75 mass% or less, and even more preferably 70 mass% or less, from the viewpoint of forming pressure-responsive particles that are prone to phase transition due to pressure.

[0055] -(Meth)acrylic ester resin- The pressure-responsive base particles that constitute the pressure-responsive particles in this embodiment contain a (meth)acrylic acid ester-based resin that contains at least two types of (meth)acrylic acid esters as polymerization components, and in which the mass proportion of the (meth)acrylic acid esters in the total polymerization components is 90 mass% or more.

[0056] The mass proportion of (meth)acrylic acid ester in all the polymerization components of the (meth)acrylic acid ester resin is 90 mass % or more, more preferably 95 mass % or more, even more preferably 98 mass % or more, and still more preferably 100 mass %.

[0057] Examples of the (meth)acrylic acid ester include (meth)acrylic acid alkyl ester, (meth)acrylic acid carboxy-substituted alkyl ester, (meth)acrylic acid hydroxy-substituted alkyl ester, (meth)acrylic acid alkoxy-substituted alkyl ester, and di(meth)acrylic acid ester.

[0058] Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and isobornyl (meth)acrylate. Examples of the (meth)acrylic acid carboxy-substituted alkyl ester include 2-carboxyethyl (meth)acrylate. Examples of the hydroxy-substituted alkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Examples of the alkoxy-substituted alkyl (meth)acrylate esters include 2-methoxyethyl (meth)acrylate. Examples of di(meth)acrylic acid esters include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, pentanediol di(meth)acrylate, hexanediol di(meth)acrylate, nonanediol di(meth)acrylate, and decanediol di(meth)acrylate.

[0059] Examples of the (meth)acrylic acid ester include 2-(diethylamino)ethyl (meth)acrylate, benzyl (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate.

[0060] The (meth)acrylic acid ester may be used alone or in combination of two or more kinds.

[0061] As the (meth)acrylic acid ester, from the viewpoint of forming pressure-responsive particles which easily undergo a phase transition due to pressure and have excellent adhesiveness, a (meth)acrylic acid alkyl ester is preferred, a (meth)acrylic acid alkyl ester having an alkyl group with 2 to 10 carbon atoms is more preferred, a (meth)acrylic acid alkyl ester having an alkyl group with 4 to 8 carbon atoms is even more preferred, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred. From the viewpoint of forming pressure-responsive particles which easily undergo a phase transition due to pressure, it is preferred that the styrene-based resin and the (meth)acrylic acid ester-based resin contain the same type of (meth)acrylic acid ester as a polymerization component.

[0062] The mass ratio of the (meth)acrylic acid alkyl ester to the entire polymerization components of the (meth)acrylic acid ester resin is preferably 90 mass% or more, more preferably 95 mass% or more, even more preferably 98 mass% or more, and even more preferably 100 mass% from the viewpoint of forming pressure-responsive particles that easily undergo phase transition by pressure and have excellent adhesiveness. As the (meth)acrylic acid alkyl ester here, a (meth)acrylic acid alkyl ester having an alkyl group with 2 to 10 carbon atoms is preferable, and a (meth)acrylic acid alkyl ester having an alkyl group with 4 to 8 carbon atoms is more preferable.

[0063] The mass ratio of the two (meth)acrylic esters having the largest mass proportions among the at least two (meth)acrylic esters contained as polymerization components in the (meth)acrylic ester-based resin is preferably 80:20 to 20:80, more preferably 70:30 to 30:70, and even more preferably 60:40 to 40:60, from the viewpoint of forming pressure-responsive particles that easily undergo phase transition due to pressure and have excellent adhesiveness.

[0064] Of the at least two (meth)acrylic esters contained as polymerization components in the (meth)acrylic ester-based resin, the two with the largest mass ratios are preferably (meth)acrylic acid alkyl esters. The (meth)acrylic acid alkyl esters herein are preferably (meth)acrylic acid alkyl esters having an alkyl group with 2 to 10 carbon atoms, and more preferably (meth)acrylic acid alkyl esters having an alkyl group with 4 to 8 carbon atoms.

[0065] When the two (meth)acrylic acid esters having the largest mass proportions among the at least two (meth)acrylic acid esters contained as polymerization components in the (meth)acrylic acid ester-based resin are (meth)acrylic acid alkyl esters, the difference in the number of carbon atoms in the alkyl groups of the two (meth)acrylic acid alkyl esters is preferably 1 or more and 4 or less, more preferably 2 or more and 4 or less, and even more preferably 3 or 4, from the viewpoint of forming pressure-responsive particles that are easily transferred by pressure and have excellent adhesiveness.

[0066] From the viewpoint of forming pressure-responsive particles that easily undergo phase transition by pressure and have excellent adhesiveness, the (meth)acrylic acid ester resin preferably contains n-butyl acrylate and 2-ethylhexyl acrylate as polymerization components, and it is particularly preferable that the two types of (meth)acrylic acid esters that have the largest mass ratios among the at least two types of (meth)acrylic acid esters contained as polymerization components in the (meth)acrylic acid ester resin are n-butyl acrylate and 2-ethylhexyl acrylate. The total amount of n-butyl acrylate and 2-ethylhexyl acrylate in the total polymerization components of the (meth)acrylic acid ester resin is preferably 90 mass% or more, more preferably 95 mass% or more, even more preferably 98 mass% or more, and even more preferably 100 mass%.

[0067] The (meth)acrylic acid ester resin may contain a vinyl monomer other than (meth)acrylic acid ester as a polymerization component. Examples of the vinyl monomer other than (meth)acrylic acid ester include (meth)acrylic acid; styrene; styrene-based monomers other than styrene; (meth)acrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; and olefins such as isoprene, butene, and butadiene. These vinyl monomers may be used alone or in combination of two or more.

[0068] When the (meth)acrylic acid ester-based resin contains a vinyl monomer other than (meth)acrylic acid ester as a polymerization component, the vinyl monomer other than (meth)acrylic acid ester is preferably at least one of acrylic acid and methacrylic acid, and more preferably acrylic acid.

[0069] The weight average molecular weight of the (meth)acrylic acid ester resin 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 suppressing fluidization of the pressure-responsive particles in an unpressurized state, and is preferably 250,000 or less, more preferably 220,000 or less, and even more preferably 200,000 or less, from the viewpoint of forming pressure-responsive particles that are prone to undergo phase transition due to pressure.

[0070] The glass transition temperature of the (meth)acrylic acid ester resin is preferably 10°C or lower, more preferably 0°C or lower, and even more preferably -10°C or lower, from the viewpoint of forming pressure-responsive particles that easily undergo phase transition due to pressure, and is preferably -90°C or higher, more preferably -80°C or higher, and even more preferably -70°C or higher, from the viewpoint of preventing the pressure-responsive particles from fluidizing in an unpressurized state.

[0071] In this embodiment, the mass proportion of the (meth)acrylic acid ester resin in the entire pressure-responsive base particle is preferably 20 mass% or more, more preferably 25 mass% or more, and even more preferably 30 mass% or more, from the viewpoint of forming pressure-responsive particles that are prone to phase transition due to pressure, and is preferably 45 mass% or less, more preferably 40 mass% or less, and even more preferably 35 mass% or less, from the viewpoint of suppressing fluidization of the pressure-responsive particles in an unpressurized state.

[0072] In this embodiment, the total amount of the styrene-based resin and (meth)acrylic acid ester-based resin contained in the pressure-responsive base particles is preferably 70 mass% or more, more preferably 80 mass% or more, even more preferably 90 mass% or more, even more preferably 95 mass% or more, and even more preferably 100 mass% based on the entire pressure-responsive base particles.

[0073] -Other resins- The pressure-responsive base particles may contain, for example, polystyrene, non-vinyl resins such as epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, modified rosin, etc. These resins may be used alone or in combination of two or more.

[0074] -Various additives- The pressure-responsive base particles may contain, as necessary, colorants (e.g., pigments, dyes), release agents (e.g., hydrocarbon waxes; natural waxes such as carnauba wax, rice wax, candelilla wax, etc.; synthetic or mineral / petroleum-based waxes such as montan wax; ester-based waxes such as fatty acid esters, montan acid esters, etc.), charge control agents, etc.

[0075] When the pressure-responsive particles of this embodiment are to be transparent pressure-responsive particles, the amount of colorant in the pressure-responsive base particle is preferably 1.0 mass % or less relative to the entire pressure-responsive base particle, and the smaller the amount, the better from the viewpoint of increasing the transparency of the pressure-responsive particle.

[0076] -Structure of pressure-responsive mother particles- The internal structure of the pressure-responsive base particle is preferably a sea-island structure, and the sea-island structure is preferably a sea-island structure having a sea phase containing a styrene-based resin and an island phase containing a (meth)acrylic acid ester-based resin dispersed in the sea phase. The specific form of the styrene-based resin contained in the sea phase is as described above. The specific form of the (meth)acrylic acid ester-based resin contained in the island phase is as described above. The island phase not containing a (meth)acrylic acid ester-based resin may be dispersed in the sea phase.

[0077] When the pressure-responsive base particles have a sea-island structure, the average diameter of the island phase is preferably 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 base particles are easily subjected to phase transition due to pressure, and when the average diameter of the island phase is 200 nm or more, the pressure-responsive base particles have excellent mechanical strength (e.g., strength that makes it difficult to deform when stirred in a developer). From these viewpoints, the average diameter of the island phase is more preferably 220 nm or more and 450 nm or less, and even more preferably 250 nm or more and 400 nm or less.

[0078] Methods for controlling the average diameter of the island phases in the sea-island structure within the above range include, for example, increasing or decreasing the amount of (meth)acrylic acid ester-based resin relative to the amount of styrene-based resin in the method for producing pressure-responsive base particles described below, and increasing or decreasing the time for which the high temperature is maintained in the process of fusing and coalescing the aggregated resin particles.

[0079] The sea-island structure and the average diameter of the island phase are determined by the following method. The pressure-responsive particles are embedded in epoxy resin, sliced ​​using a diamond knife or similar, and stained with osmium tetroxide or ruthenium tetroxide in a desiccator. The stained slices are observed under a scanning electron microscope (SEM). The sea and island phases of the sea-island structure are distinguished by the shade of the color resulting from the degree of staining of the resin by osmium tetroxide or ruthenium tetroxide, and this is used to confirm the presence or absence of a sea-island structure. 100 island phases are randomly selected from the SEM image, and the long diameter of each island phase is measured, and the average of the long diameters of the 100 islands is taken as the average diameter.

[0080] The pressure-responsive base particles may be pressure-responsive base particles of a single layer structure, or pressure-responsive base particles of a core-shell structure having a core and a shell layer covering the core. From the viewpoint of suppressing fluidization of the pressure-responsive particles in an unpressurized state, the pressure-responsive base particles preferably have a core-shell structure.

[0081] When the pressure-responsive base particle has a core-shell structure, it is preferable that the core contains a styrene resin and a (meth)acrylic acid ester resin from the viewpoint of facilitating phase transition by pressure. Furthermore, it is preferable that the shell layer contains a styrene resin from the viewpoint of suppressing fluidization of the pressure-responsive particle in a non-pressurized state. The specific form of the styrene resin is as described above. The specific form of the (meth)acrylic acid ester resin is as described above.

[0082] When the pressure-responsive base particle has a core-shell structure, it is preferable that the core part has a sea phase containing a styrene resin and an island phase containing a (meth)acrylic acid ester resin dispersed in the sea phase. The average diameter of the island phase is preferably within the above-mentioned range. Furthermore, in addition to the above-mentioned configuration of the core part, it is preferable that the shell layer contains a styrene resin. In this case, the sea phase and the shell layer of the core part have a continuous structure, and the pressure-responsive base particle is likely to undergo a phase transition due to pressure. The specific form of the styrene resin contained in the sea phase and the shell layer of the core part is as described above. The specific form of the (meth)acrylic acid ester resin contained in the island phase of the core part is as described above.

[0083] Examples of the resin contained in the shell layer include polystyrene, non-vinyl resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, and modified rosin. These resins may be used alone or in combination of two or more.

[0084] From the viewpoint of suppressing deformation of the pressure-responsive base particles, the average thickness of the shell layer is preferably 120 nm or more, more preferably 130 nm or more, and even more preferably 140 nm or more, and from the viewpoint of facilitating phase transition of the pressure-responsive base particles due to pressure, the average thickness of the shell layer is preferably 550 nm or less, more preferably 500 nm or less, and even more preferably 400 nm or less.

[0085] The average thickness of the shell layer is measured by the following method. The pressure-responsive particles are embedded in epoxy resin, sliced ​​using a diamond knife or similar, and stained with osmium tetroxide or ruthenium tetroxide in a desiccator. The stained slices are observed under a scanning electron microscope (SEM). Ten pressure-responsive base particle cross sections are randomly selected from the SEM images, and the shell layer thickness is measured at 20 points on each pressure-responsive base particle, the average value is calculated, and the average value of the 10 pressure-responsive base particles is taken as the average thickness.

[0086] From the viewpoint of ease of handling the pressure-responsive base particles, the volume average particle size (D50v) of the pressure-responsive base particles is preferably 4 μm or more, more preferably 5 μm or more, and even more preferably 6 μm or more, and from the viewpoint of ease of phase transition of the entire pressure-responsive base particles due to pressure, it is preferably 12 μm or less, more preferably 10 μm or less, and even more preferably 9 μm or less.

[0087] The volume average particle size (D50v) of the pressure-responsive base particles is measured using a Coulter Multisizer II (manufactured by Beckman Coulter) and an aperture with an aperture diameter of 100 μm. 0.5 mg to 50 mg of pressure-responsive base particles are added and dispersed in 2 mL of a 5% by mass aqueous solution of sodium alkylbenzene sulfonate, and then mixed with 100 mL to 150 mL of electrolyte (ISOTON-II, manufactured by Beckman Coulter), and dispersed for 1 minute using an ultrasonic disperser. The resulting dispersion is used as the sample. The particle size of 50,000 particles with a particle size of 2 μm to 60 μm in the sample is measured. The particle size at which the cumulative 50% of the particle size distribution on a volume basis calculated from the small diameter side is taken as the volume average particle size (D50v).

[0088] [External additives] Examples of the external additive include inorganic particles, such as SiO2, TiO2, Al2O3, CuO, ZnO, SnO2, CeO2, Fe2O3, MgO, BaO, CaO, K2O, Na2O, ZrO2, CaO·SiO2, K2O·(TiO2)n, Al2O3·2SiO2, CaCO3, MgCO3, BaSO4, and MgSO4.

[0089] The surface of the inorganic particles as an external additive may be hydrophobized. The hydrophobization may be performed, for example, by immersing the inorganic particles in a hydrophobizing agent. The hydrophobizing agent is not particularly limited, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, and aluminum coupling agents. These may be used alone or in combination of two or more. The amount of the hydrophobizing agent is, for example, 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the inorganic particles.

[0090] Examples of external additives include resin particles (resin particles such as polystyrene, polymethyl methacrylate, and melamine resin), cleaning agents (for example, metal salts of higher fatty acids such as zinc stearate, and fluorine-based polymer particles), and the like.

[0091] The amount of the external additive added is preferably from 0.01% by mass to 5% by mass, and more preferably from 0.01% by mass to 2.0% by mass, relative to the pressure-responsive base particles.

[0092] [Characteristics of pressure-responsive particles] The pressure-responsive particles of this embodiment have at least two glass transition temperatures, one of which is presumed to be the glass transition temperature of a styrene-based resin and the other is presumed to be the glass transition temperature of a (meth)acrylic ester-based resin.

[0093] The pressure-responsive particles according to this embodiment may have three or more glass transition temperatures, but the number of glass transition temperatures is preferably 2. The form in which the number of glass transition temperatures is 2 includes a form in which the resins contained in the pressure-responsive particles are only a styrene-based resin and a (meth)acrylic acid ester-based resin, and a form in which the content of other resins other than a styrene-based resin and a (meth)acrylic acid ester-based resin is small (for example, a form in which the content of other resins is 5 mass % or less relative to the entire pressure-responsive particle).

[0094] The pressure-responsive particles according to this embodiment have at least two glass transition temperatures, and the difference between the lowest glass transition temperature and the highest glass transition temperature is 30° C. or more. From the viewpoint of facilitating phase transition of the pressure-responsive particles by pressure, the difference between the lowest glass transition temperature and the highest glass transition temperature is more preferably 40° C. or more, even more preferably 50° C. or more, and even more preferably 60° C. or more. The upper limit of the difference between the lowest glass transition temperature and the highest glass transition temperature is, for example, 140° C. or less, 130° C. or less, or 120° C. or less.

[0095] The lowest glass transition temperature exhibited by the pressure-responsive particles of this embodiment is preferably 10°C or lower, more preferably 0°C or lower, and even more preferably -10°C or lower, from the viewpoint of allowing the pressure-responsive particles to easily undergo phase transition due to pressure, and is preferably -90°C or higher, more preferably -80°C or higher, and even more preferably -70°C or higher, from the viewpoint of preventing the pressure-responsive particles from fluidizing in an unpressurized state.

[0096] The highest glass transition temperature exhibited by the pressure-responsive particles of this embodiment is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher, from the viewpoint of preventing the pressure-responsive particles from fluidizing in an unpressurized state, and is preferably 70°C or lower, more preferably 65°C or lower, and even more preferably 60°C or lower, from the viewpoint of facilitating phase transition of the pressure-responsive particles due to pressure.

[0097] In the present disclosure, the glass transition temperature of the pressure-responsive particles is determined from a differential scanning calorimetry (DSC) curve obtained by performing DSC. More specifically, the glass transition temperature is determined according to the "extrapolated glass transition onset temperature" described in the method for determining glass transition temperature in JIS K7121:1987 "Method for measuring transition temperature of plastics."

[0098] The pressure-responsive particles according to this embodiment are pressure-responsive particles that undergo a phase transition due to pressure, and satisfy the following formula 1. Formula 1...10℃≦T1-T2 In Equation 1, T1 is the temperature at which the viscosity is 10,000 Pa·s under a pressure of 1 MPa, and T2 is the temperature at which the viscosity is 10,000 Pa·s under a pressure of 10 MPa.

[0099] The temperature difference (T1-T2) is 10°C or more, preferably 15°C or more, and more preferably 20°C or more, from the viewpoint of facilitating phase transition of the pressure-responsive particles due to pressure, and is preferably 120°C or less, more preferably 100°C or less, and even more preferably 80°C or less, from the viewpoint of preventing the pressure-responsive particles from fluidizing in an unpressurized state.

[0100] The value of the temperature T1 is preferably 140° C. or less, more preferably 130° C. or less, further preferably 120° C. or less, and further preferably 115° C. or less. The lower limit of the temperature T1 is preferably 80° C. or more, and more preferably 85° C. or more. The value of the temperature T2 is preferably 40° C. or higher, more preferably 50° C. or higher, and even more preferably 60° C. or higher. The upper limit of the temperature T2 is preferably 85° C. or lower.

[0101] An index showing that the pressure-responsive particles are susceptible to phase transition due to pressure is the temperature difference (T1-T3) between the temperature T1 at which the particles exhibit a viscosity of 10,000 Pa s under a pressure of 1 MPa and the temperature T3 at which the particles exhibit a viscosity of 10,000 Pa s under a pressure of 4 MPa, and it is preferable that the temperature difference (T1-T3) is 5° C. or more. From the viewpoint of the pressure-responsive particles according to this embodiment being susceptible to phase transition due to pressure, it is preferable that the temperature difference (T1-T3) is 5° C. or more, and more preferably 10° C. or more. The temperature difference (T1-T3) is generally less than 25°C.

[0102] From the viewpoint of a temperature difference (T1-T3) of 5° C. or more, the pressure-responsive particles according to this embodiment preferably have a temperature T3 at which they exhibit a viscosity of 10,000 Pa s under a pressure of 4 MPa of 90° C. or less, more preferably 85° C. or less, and even more preferably 80° C. or less. The lower limit of the temperature T3 is preferably 60° C. or more.

[0103] The temperature T1, the temperature T2, and the temperature T3 are calculated as follows. The pressure-responsive particles are compressed to prepare a pellet-shaped sample. The pellet-shaped sample is set in a flow tester (Shimadzu Corporation, CFT-500), and the applied pressure is fixed at 1 MPa, and the viscosity at 1 MPa versus temperature is measured. From the obtained viscosity graph, it is found that the viscosity is 10 4 Determine the temperature T1 when the pressure becomes Pa·s. Determine the temperature T2 in the same manner as for temperature T1, except that the applied pressure of 1 MPa is changed to 10 MPa. Determine the temperature T3 in the same manner as for temperature T1, except that the applied pressure of 1 MPa is changed to 4 MPa. Calculate the temperature difference (T1-T2) from temperatures T1 and T2. Calculate the temperature difference (T1-T3) from temperatures T1 and T3.

[0104] [Method of manufacturing pressure-responsive particles] The pressure responsive particles according to this embodiment are obtained by producing pressure responsive base particles and then externally adding an external additive to the pressure responsive base particles.

[0105] The pressure-responsive base particles may be produced by any of a dry production method (e.g., a kneading and grinding method, etc.) and a wet production method (e.g., an aggregation and coalescence method, a suspension polymerization method, a dissolution suspension method, etc.). There are no particular limitations on these production methods, and any known production method may be used. Among these, it is preferable to obtain the pressure-responsive base particles by the aggregation and coalescence method.

[0106] When the pressure-responsive base particles are produced by the aggregation and coalescence method, for example, A step of preparing a styrene-based resin particle dispersion liquid in which styrene-based resin particles containing a styrene-based resin are dispersed (a styrene-based resin particle dispersion liquid preparation step); a step of polymerizing a (meth)acrylic acid ester-based resin in a styrene-based resin particle dispersion to form composite resin particles containing a styrene-based resin and a (meth)acrylic acid ester-based resin (composite resin particle forming step); a step of aggregating the composite resin particles in the composite resin particle dispersion liquid in which the composite resin particles are dispersed to form aggregated particles (aggregated particle forming step); The pressure-responsive base particles are manufactured through a process of heating the aggregated particle dispersion liquid in which the aggregated particles are dispersed, fusing and coalescing the aggregated particles to form pressure-responsive base particles (fusion and coalescence process).

[0107] Each step will be described in detail below. In the following, a method for obtaining pressure-responsive base particles that do not contain a colorant or a release agent will be described. Colorants, release agents, and other additives may be used as necessary. When the pressure-responsive base particles contain a colorant and a release agent, a composite resin particle dispersion, a colorant particle dispersion, and a release agent particle dispersion are mixed, and then a fusion and coalescence process is performed. The colorant particle dispersion and the release agent particle dispersion can be prepared, for example, by mixing the materials and then performing a dispersion process using a known dispersing machine.

[0108] - Preparation process of styrene-based resin particle dispersion - The styrene-based resin particle dispersion liquid is, for example, a dispersion liquid in which styrene-based resin particles are dispersed in a dispersion medium by the aid of a surfactant.

[0109] Examples of the dispersion medium include aqueous media such as water, alcohols, etc. These may be used alone or in combination of two or more.

[0110] Examples of the surfactant include anionic surfactants such as sulfate salts, sulfonates, phosphates, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts; and nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. The nonionic surfactants may be used in combination with anionic surfactants or cationic surfactants. Among these, anionic surfactants are preferred. The surfactants may be used alone or in combination with two or more.

[0111] Examples of a method for dispersing styrene-based resin particles in a dispersion medium include a method in which the styrene-based resin is mixed with the dispersion medium and stirred and dispersed using a rotary shear type homogenizer, a ball mill having media, a sand mill, a dyno mill, or the like.

[0112] Another method for dispersing styrene-based resin particles in a dispersion medium is emulsion polymerization.Specifically, after mixing the polymerization components of styrene-based resin with a chain transfer agent or a polymerization initiator, further mix with an aqueous medium containing a surfactant, and stir to prepare an emulsion, and polymerize the styrene-based resin in the emulsion.At this time, it is preferable to use dodecanethiol as a chain transfer agent.

[0113] The volume average particle size of the styrene-based resin particles dispersed in the styrene-based resin particle dispersion is preferably 100 nm or more and 250 nm or less, more preferably 120 nm or more and 220 nm or less, and even more preferably 150 nm or more and 200 nm or less. The volume average particle diameter of the resin particles contained in the resin particle dispersion is measured using a laser diffraction particle size distribution measuring device (e.g., LA-700 manufactured by Horiba, Ltd.), and the particle diameter that is 50% cumulative in the volume-based particle size distribution calculated from the small diameter side is defined as the volume average particle diameter (D50v).

[0114] The content of the styrene-based resin particles in the styrene-based resin particle dispersion is preferably from 30% by mass to 60% by mass, and more preferably from 40% by mass to 50% by mass.

[0115] -Composite resin particle formation process- A styrene-based resin particle dispersion liquid and a polymerization component of a (meth)acrylic acid ester-based resin are mixed, and the (meth)acrylic acid ester-based resin is polymerized in the styrene-based resin particle dispersion liquid to form composite resin particles containing the styrene-based resin and the (meth)acrylic acid ester-based resin.

[0116] The composite resin particles are preferably resin particles containing a styrene-based resin and a (meth)acrylic acid ester-based resin in a state of microphase separation. The resin particles can be produced, for example, by the following method.

[0117] A polymerization component of a (meth)acrylic acid ester resin (a group of monomers containing at least two kinds of (meth)acrylic acid esters) is added to a styrene-based resin particle dispersion, and an aqueous medium is added as necessary. Next, the temperature of the dispersion is heated to a temperature equal to or higher than the glass transition temperature of the styrene-based resin (for example, a temperature 10°C to 30°C higher than the glass transition temperature of the styrene-based resin) while slowly stirring the dispersion. Next, while maintaining the temperature, an aqueous medium containing a polymerization initiator is slowly dripped, and stirring is continued for a long period of time within a range of 1 hour to 15 hours. At this time, it is preferable to use ammonium persulfate as the polymerization initiator.

[0118] Although the detailed mechanism is not entirely clear, it is speculated that when the above method is adopted, the monomer and the polymerization initiator are impregnated into the styrene resin particles, and the (meth)acrylic acid ester is polymerized inside the styrene resin particles. As a result, it is speculated that composite resin particles are obtained in which the (meth)acrylic acid ester resin is contained inside the styrene resin particles, and the styrene resin and the (meth)acrylic acid ester resin form a microphase separation state inside the particles.

[0119] During or after the production of the composite resin particles, the polymerization components of the styrene resin (i.e., styrene and other vinyl monomers) may be added to the dispersion in which the composite resin particles are dispersed, and the polymerization reaction may be continued. This is presumably to form a state of microphase separation between the styrene resin and the (meth)acrylic acid ester resin inside the particles, and to obtain composite resin particles in which the styrene resin is attached to the particle surface. Pressure-responsive particles produced using composite resin particles in which the styrene resin is attached to the particle surface generate relatively little coarse powder. The other vinyl monomer, which is a polymerization component of the styrene-based resin to be adhered to the surface of the composite resin particle, preferably contains at least one of the same monomers as the monomers constituting the styrene-based resin or (meth)acrylic acid ester-based resin present inside the composite resin particle, and specifically, it preferably contains at least one of n-butyl acrylate and 2-ethylhexyl acrylate.

[0120] 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.

[0121] The content of the composite resin particles in the composite resin particle dispersion is preferably from 20% by mass to 50% by mass, and more preferably from 30% by mass to 40% by mass.

[0122] -Agglomerated particle formation process- The composite resin particles are aggregated in a composite resin particle dispersion to form aggregated particles having a diameter close to that of the target pressure-responsive base particles.

[0123] Specifically, for example, an aggregating agent is added to the composite resin particle dispersion, the pH of the composite resin particle dispersion is adjusted to be acidic (e.g., pH 2 or more and 5 or less), a dispersion stabilizer is added as necessary, and then the dispersion is heated to a temperature close to the glass transition temperature of the styrene-based resin (specifically, for example, the glass transition temperature of the styrene-based resin -30°C or more and the glass transition temperature -10°C or less), to aggregate the composite resin particles and form aggregated particles.

[0124] In the aggregated particle formation process, an aggregating agent is added to the composite resin particle dispersion at room temperature (e.g., 25°C) while stirring the composite resin particle dispersion with a rotary shear homogenizer, the pH of the composite resin particle dispersion is adjusted to an acidic state (e.g., pH 2 or more and 5 or less), and a dispersion stabilizer may be added as necessary, followed by heating.

[0125] Examples of the flocculant include a surfactant having a polarity opposite to that of the surfactant contained in the composite resin particle dispersion, an inorganic metal salt, and a divalent or higher metal complex. When a metal complex is used as the flocculant, the amount of the surfactant used is reduced, and the charging characteristics are improved. If necessary, an additive that forms a complex or a similar bond with the metal ion of the flocculant may be used together with the flocculant. As this additive, a chelating agent is preferably used.

[0126] Examples of inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate; and inorganic metal salt polymers such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. The chelating agent may be a water-soluble chelating agent, for example, oxycarboxylic acid such as tartaric acid, citric acid, gluconic acid, etc., aminocarboxylic acid such as iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), etc. The amount of the chelating agent added is preferably from 0.01 to 5.0 parts by mass, and more preferably from 0.1 to less than 3.0 parts by mass, relative to 100 parts by mass of the resin particles.

[0127] -Fusion / unification process- Next, the aggregated particle dispersion liquid in which the aggregated particles are dispersed is heated, for example, to a temperature equal to or higher than the glass transition temperature of the styrene-based resin (for example, a temperature 10°C to 30°C higher than the glass transition temperature of the styrene-based resin) to fuse and coalesce the aggregated particles, thereby forming pressure-responsive base particles.

[0128] The pressure-responsive base particles obtained through the above steps usually have a sea-island structure having a sea phase containing a styrene-based resin and an island phase containing a (meth)acrylic ester-based resin dispersed in the sea phase. In the composite resin particles, the styrene-based resin and the (meth)acrylic ester-based resin are in a state of microphase separation, and it is presumed that in the fusion / coalescence step, the styrene-based resin comes together to form the sea phase, and the (meth)acrylic ester-based resin comes together to form the island phase.

[0129] The average diameter of the island phases in the sea-island structure can be controlled, for example, by increasing or decreasing the amount of the styrene-based resin particle dispersion or the amount of the at least two kinds of (meth)acrylic acid esters used in the composite resin particle formation step, or by increasing or decreasing the time for which the mixture is maintained at high temperature in the fusion / coalescence step.

[0130] Pressure-responsive core-shell particles, for example, a step of further mixing the aggregated particle dispersion and the styrene-based resin particle dispersion after obtaining the aggregated particle dispersion, and aggregating the styrene-based resin particles so as to adhere to the surfaces of the aggregated particles, thereby forming second aggregated particles; a step of heating the second aggregate particle dispersion liquid in which the second aggregate particles are dispersed to fuse and coalesce the second aggregate particles to form pressure-responsive base particles having a core-shell structure; It is manufactured through the process. The pressure-responsive base particles having a core-shell structure obtained through the above process have a shell layer containing a styrene-based resin. A shell layer containing another type of resin may be formed by using a resin particle dispersion in which another type of resin particles are dispersed instead of the styrene-based resin particle dispersion.

[0131] After the fusion / coalescence process is completed, the pressure-responsive base particles formed in the solution are subjected to a known washing process, solid-liquid separation process, and drying process to obtain pressure-responsive base particles in a dried state. From the viewpoint of chargeability, the washing process is preferably performed by thorough replacement washing with ion-exchanged water. From the viewpoint of productivity, the solid-liquid separation process is preferably performed by suction filtration, pressure filtration, etc. From the viewpoint of productivity, the drying process is preferably performed by freeze drying, air flow drying, fluidized drying, vibration-type fluidized drying, etc.

[0132] The pressure-responsive particles according to this embodiment are produced, for example, by adding an external additive to the obtained pressure-responsive base particles in a dry state and mixing them. The mixing may be performed, for example, using a V blender, a Henschel mixer, a Loedige mixer, or the like. Furthermore, if necessary, coarse particles may be removed from the pressure-responsive particles using a vibration sieve, an air sieve, or the like.

[0133] <Cartridge> The cartridge according to the present embodiment is a cartridge that contains the pressure-responsive particles according to the present embodiment and is detachably attached to a printed matter production device. When the cartridge is attached to the printed matter production device, a supply pipe connects the cartridge to a placement means of the printed matter production device that places the pressure-responsive particles on a recording medium. The pressure responsive particles are supplied to the placement means from a cartridge, and when the amount of pressure responsive particles contained in the cartridge decreases, the cartridge is replaced.

[0134] <Printed matter manufacturing apparatus, printed matter manufacturing method, printed matter> The printed matter manufacturing apparatus of this embodiment includes a placement means that contains the pressure-responsive particles of this embodiment and places the pressure-responsive particles on a recording medium, and a pressing means that folds and presses the recording medium, or stacks and presses the recording medium and another recording medium together.

[0135] The placement means may include, for example, an application device that applies the pressure responsive particles onto the recording medium, and may further include a fixing device that fixes the pressure responsive particles applied onto the recording medium onto the recording medium.

[0136] The pressing means includes, for example, a folding device that folds the recording medium on which pressure-responsive particles are arranged, or a stacking device that stacks the recording medium on which pressure-responsive particles are arranged and another recording medium, and a pressure device that applies pressure to the stacked recording media.

[0137] The pressure device of the pressure bonding means applies pressure to the recording medium on which the pressure responsive particles are arranged, which causes the pressure responsive particles to flow on the recording medium and exert adhesive properties.

[0138] The apparatus for producing a printed matter according to the present embodiment implements the method for producing a printed matter according to the present embodiment. The method for producing a printed matter according to the present embodiment uses the pressure-responsive particles according to the present embodiment and includes an arrangement step of arranging the pressure-responsive particles on a recording medium, and a compression step of folding and pressing the recording medium, or folding and pressing the recording medium and another recording medium together.

[0139] The disposing step may include, for example, a step of applying the pressure responsive particles onto the recording medium, and may further include a step of fixing the pressure responsive particles applied onto the recording medium onto the recording medium.

[0140] The pressing step includes, for example, a folding step of folding the recording medium or a stacking step of stacking the recording medium and another recording medium, and a pressurizing step of applying pressure to the stacked recording media.

[0141] The pressure-responsive particles may be disposed over the entire surface of the recording medium, or may be disposed on a portion of the recording medium. The pressure-responsive particles are disposed on the recording medium in one layer or multiple layers. The layer of pressure-responsive particles may be a continuous layer in the surface direction of the recording medium, or may be a discontinuous layer in the surface direction of the recording medium. The layer of pressure-responsive particles may be a layer in which the pressure-responsive particles are arranged as particles, or a layer in which adjacent pressure-responsive particles are fused together and arranged.

[0142] The amount of pressure-responsive particles (preferably transparent pressure-responsive particles) on the recording medium is, for example, 0.5 g / m2 in the area where the particles are disposed. 2 More than 50g / m 2 Less than or equal to 1 g / m 2 More than 40g / m 2 Less than or equal to 1.5 g / m 2 More than 30g / m 2The layer thickness of the pressure responsive particles (preferably transparent pressure responsive particles) on the recording medium is, for example, 0.2 μm to 25 μm, 0.4 μm to 20 μm, or 0.6 μm to 15 μm.

[0143] Examples of recording media that can be used with the printing device according to this embodiment include paper, coated paper in which the surface of paper is coated with a resin or the like, cloth, nonwoven fabric, resin film, resin sheet, etc. The recording media may have an image on one or both sides.

[0144] An example of a printed matter production apparatus according to the present embodiment will be described below, but the present embodiment is not limited to this.

[0145] Fig. 1 is a schematic diagram showing an example of a printed matter production apparatus according to the present embodiment. The printed matter production apparatus shown in Fig. 1 includes a placement means 100 and a pressing means 200 arranged downstream of the placement means 100. The arrow indicates the transport direction of the recording medium.

[0146] The disposing means 100 is a device that uses the pressure responsive particles according to this embodiment to dispose the pressure responsive particles on a recording medium P. The recording medium P has an image formed on one or both sides in advance.

[0147] The placement means 100 includes an application device 110 and a fixing device 120 arranged downstream of the application device 110 .

[0148] The application device 110 applies the pressure responsive particles M onto the recording medium P. Examples of application methods that the application device 110 employs include a spray method, a bar coating method, a die coating method, a knife coating method, a roll coating method, a reverse roll coating method, a gravure coating method, a screen printing method, an inkjet method, a lamination method, and an electrophotographic method. Depending on the application method, the pressure responsive particles M may be dispersed in a dispersion medium to prepare a liquid composition, and the liquid composition may be applied to the application device 110.

[0149] The recording medium P to which the pressure responsive particles M have been applied by the application device 110 is transported to a fixing device 120 .

[0150] The fixing device 120 is, for example, a heating device equipped with a heat source and heating the pressure-responsive particles M on the recording medium P as it passes, thereby fixing the pressure-responsive particles M onto the recording medium P; a pressure device equipped with a pair of pressure members (roll / roll, belt / roll) and pressurizing the recording medium P as it passes, thereby fixing the pressure-responsive particles M onto the recording medium P; a pressure / heating device equipped with a pair of pressure members (roll / roll, belt / roll) equipped with a heat source inside, pressurizing and heating the recording medium P as it passes, thereby fixing the pressure-responsive particles M onto the recording medium P; etc.

[0151] 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 more and 80°C or less, more preferably 20°C or more and 60°C or less, and even more preferably 30°C or more and 50°C or less.

[0152] When the fixing device 120 has a pressure member, the pressure applied by the pressure member to the recording medium P may be lower than the pressure applied by the pressure device 230 to the recording medium P2.

[0153] The recording medium P becomes a recording medium P1 having pressure responsive particles M applied onto an image by passing through the arrangement means 100. The recording medium P1 is transported toward the pressure bonding means 200.

[0154] In the printed matter manufacturing apparatus according to this embodiment, the placement means 100 and the pressing means 200 may be in close proximity to each other or may be spaced apart. When the placement means 100 and the pressing means 200 are spaced apart, the placement means 100 and the pressing means 200 are connected by, for example, a conveying means (for example, a belt conveyor) that conveys the recording medium P1.

[0155] The pressing means 200 includes a folding device 220 and a pressure device 230, and is a means for folding and pressing the recording medium P1.

[0156] The folding device 220 folds the recording medium P1 that passes through the device to produce a folded recording medium P2. The recording medium P2 may be folded, for example, in two, three, or four, and may be folded only partially. The recording medium P2 has pressure-responsive particles M disposed on at least a portion of at least one of two opposing surfaces.

[0157] The folding device 220 may have a pair of pressure members (e.g., roll / roll, belt / roll) that apply pressure to the recording medium P2. The pressure applied by the pressure members of the folding device 220 to the recording medium P2 may be lower than the pressure applied by the pressure device 230 to the recording medium P2.

[0158] The pressing means 200 may be provided with a stacking device for stacking the recording medium P1 and another recording medium instead of the folding device 220. The recording medium P1 and the other recording medium may be stacked in a form in which one sheet of the other recording medium is stacked on the recording medium P1, or in a form in which one sheet of the other recording medium is stacked on each of a plurality of locations on the recording medium P1. The other recording medium may be a recording medium on which an image has been formed in advance on one or both sides, a recording medium on which no image has been formed, or a press-bonded printed matter prepared in advance.

[0159] The recording medium P2 that has left the folding device 220 (or the overlapping device) is conveyed toward the pressure device 230.

[0160] The pressure device 230 includes a pair of pressure members (i.e., pressure rolls 231 and 232). The pressure rolls 231 and 232 come into contact with each other at their outer circumferential surfaces and press against each other to apply pressure to the recording medium P2 passing through. The pair of pressure members included in the pressure device 230 is not limited to a combination of a pressure roll and a pressure roll, and may also be a combination of a pressure roll and a pressure belt, or a combination of a pressure belt and a pressure belt.

[0161] When pressure is applied to the recording medium P2 passing through the pressure device 230, the pressure responsive particles M on the recording medium P2 become fluidized by the pressure and exert adhesive properties.

[0162] The pressure applying device 230 may or may not have a heat source (e.g., a halogen heater) for heating the recording medium P2 inside. The fact that the pressure applying device 230 does not have a heat source inside does not exclude the case where the temperature inside the pressure applying device 230 becomes equal to or higher than the ambient temperature due to heat generated by a motor or the like provided in the pressure applying device 230.

[0163] As the recording medium P2 passes through the pressure device 230, the overlapping surfaces are bonded together by the fluidized pressure-responsive particles M, producing a pressure-bonded printed matter P3. In the pressure-bonded printed matter P3, two opposing surfaces are partially or entirely bonded together.

[0164] The completed pressure-bonded printed matter P3 is conveyed out of the pressure device 230.

[0165] The first form of the laminated printed matter P3 is a laminated printed matter in which the opposing surfaces of folded recording media are bonded together by pressure-responsive particles M. The laminated printed matter P3 of this form is produced by a printed matter production apparatus including a folding device 220.

[0166] The second form of the laminated printed matter P3 is a laminated printed matter in which a plurality of overlapping recording media are bonded on opposing surfaces by pressure-responsive particles M. The laminated printed matter P3 of this form is manufactured by a manufacturing apparatus for a laminated printed matter that includes a laminating device.

[0167] The printed matter production device according to the present embodiment is not limited to a device in a form that continuously transports the recording medium P2 from the folding device 220 (or the overlapping device) to the pressure device 230. The printed matter production device according to the present embodiment may be a device in a form that stores the recording medium P2 that has left the folding device 220 (or the overlapping device), and transports the recording medium P2 to the pressure device 230 after the amount of the recording medium P2 stored reaches a predetermined amount.

[0168] In the printed matter manufacturing apparatus according to this embodiment, the folding device 220 (or overlapping device) and the pressing and pressurizing device 230 may be in close proximity to each other or may be spaced apart. When the folding device 220 (or overlapping device) and the pressing and pressurizing device 230 are spaced apart, the folding device 220 (or overlapping device) and the pressing and pressurizing device 230 are connected by, for example, a conveying means (for example, a belt conveyor) that conveys the recording medium P2.

[0169] The printing production device according to the present embodiment may include a cutting means for cutting the recording medium to a predetermined size. The cutting means may be, for example, a cutting means arranged between the arrangement means 100 and the bonding means 200, which cuts off a part of the recording medium P1 in an area where the pressure-responsive particles M are not arranged; a cutting means arranged between the folding device 220 and the pressurizing device 230, which cuts off a part of the recording medium P2 in an area where the pressure-responsive particles M are not arranged; a cutting means arranged downstream of the bonding means 200, which cuts off a part of the bonded printed matter P3 in an area where the pressure-responsive particles M are not bonded; etc.

[0170] The apparatus for producing printed matter according to the present embodiment is not limited to a sheet-fed type apparatus, but may be an apparatus that performs a placement process and a pressing process on a long recording medium to form a long-length pressed-on printed matter, and then cuts the long-length pressed-on printed matter to a predetermined size.

[0171] The apparatus for producing a printed matter according to the present embodiment may further include a color image forming unit that forms a color image on the recording medium using a coloring material. Examples of the color image forming unit include a unit that forms a color ink image on the recording medium by an inkjet method using colored ink as a coloring material, and a unit that forms a color image on the recording medium by an electrophotographic method using a colored electrostatic image developer.

[0172] The manufacturing apparatus having the above-described configuration is used to carry out the method for manufacturing a printed matter according to the present embodiment, which further includes a colored image forming step of forming a colored image on a recording medium using a coloring material. Specific examples of the colored image forming step include a step of forming a colored ink image on a recording medium by an inkjet method using colored inks as coloring materials, and a step of forming a colored image on a recording medium by an electrophotographic method using a colored electrostatic image developer.

[0173] <Sheet for producing printed matter, and method for producing sheet for producing printed matter> The sheet for producing printed matter according to the present embodiment has a substrate and pressure-responsive particles arranged on the substrate. The sheet for producing printed matter according to the present embodiment is produced using the pressure-responsive particles according to the present embodiment. The pressure-responsive particles on the substrate may or may not retain the particle shape they had before they were arranged on the substrate.

[0174] The sheet for producing printed matter according to this embodiment is applicable, for example, to a masking sheet that is laminated and adhered to a recording medium when it is desired to conceal information recorded on the recording medium; a release sheet that is used to provide an adhesive layer on a recording medium when laminated and adhering recording media together; and the like.

[0175] Examples of substrates applicable to the sheet for producing printed matter according to the present embodiment include paper, coated paper in which the surface of paper is coated with a resin or the like, cloth, nonwoven fabric, resin film, resin sheet, etc. An image may be formed on one or both sides of the substrate.

[0176] In the sheet for producing printed matter according to this embodiment, the pressure responsive particles may be disposed over the entire surface of the substrate, or may be disposed on a portion of the substrate. The pressure responsive particles are disposed in one layer or multiple layers on the substrate. The layer of pressure responsive particles may be a continuous layer in the surface direction of the substrate, or may be a discontinuous layer in the surface direction of the substrate. The layer of pressure responsive particles may be a layer in which the pressure responsive particles are arranged as particles, or a layer in which adjacent pressure responsive particles are fused and arranged.

[0177] The amount of pressure-responsive particles on the substrate may be, for example, 0.5 g / m2 in the area where the particles are disposed. 2 More than 50g / m 2 Less than or equal to 1 g / m 2 More than 40g / m 2 Less than or equal to 1.5 g / m 2 More than 30g / m 2 The layer 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.

[0178] The sheet for producing printed matter according to this embodiment is produced, for example, by using the pressure responsive particles according to this embodiment and by a production method including a step of arranging the pressure responsive particles on a substrate.

[0179] The disposing step may include, for example, an applying step of applying the pressure responsive particles onto a substrate, and may further include a fixing step of fixing the pressure responsive particles applied onto the substrate onto the substrate.

[0180] The application step is realized by an application method such as, for example, a spray method, a bar coating method, a die coating method, a knife coating method, a roll coating method, a reverse roll coating method, a gravure coating method, a screen printing method, an inkjet method, a lamination method, an electrophotographic method, etc. Depending on the application method in the application step, the pressure responsive particles may be dispersed in a dispersion medium to prepare a liquid composition, and the liquid composition may be applied to the application step.

[0181] The fixing process includes, for example, a heating process in which the pressure-responsive particles on the substrate are heated with a heat source to fix the pressure-responsive particles onto the substrate; a pressurizing process in which the substrate to which the pressure-responsive particles have been applied is pressurized with a pair of pressurizing members (roll / roll, belt / roll) to fix the pressure-responsive particles onto the substrate; and a pressurizing and heating process in which the substrate to which the pressure-responsive particles have been applied is pressurized and heated with a pair of pressurizing members (roll / roll, belt / roll) having a heat source inside to fix the pressure-responsive particles onto the substrate.

[0182] <Production of printed matter using electrophotography> An embodiment in which the pressure responsive particles according to this embodiment are applied to an electrophotographic system will be described below. In the electrophotographic system, the pressure responsive particles are used as toner.

[0183] [Electrostatic image developer] The electrostatic image developer according to the present embodiment contains at least the pressure responsive particles according to the present embodiment. The electrostatic image developer according to the present embodiment may be a one-component developer containing only the pressure responsive particles according to the present embodiment, or may be a two-component developer in which the pressure responsive particles according to the present embodiment are mixed with a carrier.

[0184] The carrier is not particularly limited, and may be a known carrier. For example, the carrier may be a coated carrier in which the surface of a core material made of magnetic powder is coated with a resin; a magnetic powder dispersion type carrier in which magnetic powder is dispersed and mixed in a matrix resin; a resin impregnated type carrier in which porous magnetic powder is impregnated with a resin; etc. The magnetic powder dispersion type carrier and the resin impregnated type carrier may be a carrier in which the constituent particles of the carrier are used as a core material, and the surface of the core material is coated with a resin.

[0185] Examples of the magnetic powder include magnetic metals such as iron, nickel, and cobalt; magnetic oxides such as ferrite and magnetite; and the like.

[0186] Examples of the resin and matrix resin for coating include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic acid ester copolymer, straight silicone resin or its modified product containing organosiloxane bonds, fluororesin, polyester, polycarbonate, phenolic resin, epoxy resin, etc. The resin and matrix resin for coating may contain other additives such as conductive particles. Examples of the conductive particles include particles of metals such as gold, silver, copper, carbon black, titanium oxide, zinc oxide, tin oxide, barium sulfate, aluminum borate, potassium titanate, etc.

[0187] Examples of methods for coating the surface of the core material with a resin include a method of coating with a coating layer-forming solution in which the coating resin and various additives (used as necessary) are dissolved in a suitable solvent. The solvent is not particularly limited and may be selected taking into consideration the type of resin used, suitability for application, etc. Specific resin coating methods include an immersion method in which the core material is immersed in a solution for forming a coating layer; a spray method in which the solution for forming a coating layer is sprayed onto the surface of the core material; a fluidized bed method in which the solution for forming a coating layer is sprayed onto the core material while it is suspended in flowing air; and a kneader coater method in which the carrier core material and the solution for forming a coating layer are mixed in a kneader coater and then the solvent is removed.

[0188] The mixing ratio (mass ratio) of the pressure responsive particles to the carrier in the two-component developer is preferably pressure responsive particles:carrier=1:100 to 30:100, and more preferably 3:100 to 20:100.

[0189] [Printed matter production equipment, printed matter production method] The apparatus for producing printed matter using an electrophotographic method includes a placement means for storing a developer containing the pressure-responsive particles according to this embodiment and placing the pressure-responsive particles on a recording medium using an electrophotographic method, and a pressing means for folding and pressing the recording medium, or for stacking and pressing the recording medium and another recording medium together.

[0190] The apparatus for producing a printed matter according to the present embodiment is used to carry out a method for producing a printed matter by electrophotography. The method for producing a printed matter according to the present embodiment includes a step of arranging pressure-responsive particles on a recording medium by electrophotography using a developer containing the pressure-responsive particles according to the present embodiment, and a step of folding and pressing the recording medium, or folding and pressing the recording medium and another recording medium together.

[0191] The arrangement unit included in the printed matter production device according to the present embodiment includes, for example, A photoconductor; A charging means for charging the surface of the photoreceptor; an electrostatic image forming means for forming an electrostatic image on the charged surface of the photoreceptor; a developing unit that contains the electrostatic image developer according to the present embodiment and develops the electrostatic image formed on the surface of the photoconductor by the electrostatic image developer as a pressure responsive particle application unit; a transfer means for transferring the pressure responsive particle application portion formed on the surface of the photoreceptor onto a surface of a recording medium; Equipped with. It is preferable that the positioning means further comprises a fixing means for fixing the pressure responsive particle application portion transferred to the surface of the recording medium.

[0192] The arrangement step included in the method for producing a printed matter according to the present embodiment includes, for example, a charging step of charging the surface of the photoconductor; an electrostatic image forming step of forming an electrostatic image on the charged surface of the photoreceptor; a developing step of developing the electrostatic image formed on the surface of the photoconductor as a pressure responsive particle application portion by using the electrostatic image developer according to the present embodiment; a transfer step of transferring the pressure responsive particle application portion formed on the surface of the photoreceptor onto a surface of a recording medium; Includes. It is preferable that the positioning step further includes a fixing step of fixing the pressure responsive particle-applied portion transferred to the surface of the recording medium.

[0193] The arrangement means may be, for example, a direct transfer type device that directly transfers the pressure responsive particle application portion formed on the surface of the photoreceptor to a recording medium; an intermediate transfer type device that primarily transfers the pressure responsive particle application portion formed on the surface of the photoreceptor to the surface of an intermediate transfer body, and secondarily transfers the pressure responsive particle application portion transferred to the surface of the intermediate transfer body to the surface of the recording medium; a device equipped with a cleaning means that cleans the surface of the photoreceptor before charging after the transfer of the pressure responsive particle application portion; a device equipped with a discharging means that irradiates the surface of the photoreceptor with discharging light to discharge before charging after the transfer of the pressure responsive particle application portion; etc. When the arrangement means is an intermediate transfer type device, the transfer means has, for example, an intermediate transfer body on whose surface the pressure responsive particle application portion is transferred, a primary transfer means that primarily transfers the pressure responsive particle application portion formed on the surface of the photoreceptor to the surface of the intermediate transfer body, and a secondary transfer means that secondarily transfers the pressure responsive particle application portion transferred to the surface of the intermediate transfer body to the surface of the recording medium.

[0194] The arrangement means may have a cartridge structure (so-called process cartridge) in which a portion including the developing means is detachably attached to the arrangement means. As the process cartridge, for example, a process cartridge that contains the electrostatic image developer according to the present embodiment and has the developing means is preferably used.

[0195] The pressure bonding means included in the printed matter manufacturing apparatus according to the present embodiment applies pressure to the recording medium on which the pressure responsive particles according to the present embodiment are arranged. This causes the pressure responsive particles according to the present embodiment to fluidize on the recording medium and exert adhesive properties. The pressure applied by the pressure bonding means to the recording medium for the purpose of fluidizing the pressure responsive particles according to the present 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.

[0196] The pressure-responsive particles according to this embodiment may be disposed on the entire surface of the recording medium, or on a part of the recording medium. The pressure-responsive particles according to this embodiment are disposed on the recording medium in one or more layers. The layer of the pressure-responsive particles according to this embodiment may be a continuous layer in the surface direction of the recording medium, or may be a discontinuous layer in the surface direction of the recording medium. The layer of the pressure-responsive particles according to this embodiment may be a layer in which the pressure-responsive particles are arranged as particles, or may be a layer in which adjacent pressure-responsive particles are fused together and arranged.

[0197] The amount of the pressure-responsive particles according to this embodiment (preferably transparent pressure-responsive particles) on the recording medium is, for example, 0.5 g / m in the area where the particles are arranged. 2 More than 50g / m 2 Less than or equal to 1 g / m 2 More than 40g / m 2 Less than or equal to 1.5 g / m 2 More than 30g / m 2 The layer thickness of the pressure responsive particles according to this embodiment (preferably transparent pressure responsive particles) on the recording medium is, for example, 0.2 μm to 25 μm, 0.4 μm to 20 μm, or 0.6 μm to 15 μm.

[0198] Examples of recording media that can be used with the printing device according to this embodiment include paper, coated paper in which the surface of paper is coated with a resin or the like, cloth, nonwoven fabric, resin film, resin sheet, etc. The recording media may have an image on one or both sides.

[0199] An example of a production apparatus for printed matter according to the present embodiment that employs an electrophotographic method will be described below, but the present embodiment is not limited to this.

[0200] Fig. 2 is a schematic diagram showing an example of a printed matter production apparatus according to the present embodiment. The printed matter production apparatus shown in Fig. 2 includes a placement means 100 and a pressing means 200 arranged downstream of the placement means 100. The arrows indicate the rotation direction of the photoconductor or the transport direction of the recording medium.

[0201] The placement means 100 is a direct transfer type device that uses a developer containing the pressure responsive particles according to this embodiment to place the pressure responsive particles according to this embodiment on a recording medium P by an electrophotographic method. An image is formed on one or both sides of the recording medium P in advance.

[0202] The arrangement means 100 has a photoreceptor 101. Around the photoreceptor 101, there are sequentially arranged a charging roll (an example of a charging means) 102 that charges the surface of the photoreceptor 101, an exposure device (an example of an electrostatic image forming means) 103 that exposes the charged surface of the photoreceptor 101 to a laser beam to form an electrostatic image, a development device (an example of a development means) 104 that supplies pressure responsive particles to the electrostatic image to develop it, a transfer roll (an example of a transfer means) 105 that transfers the developed pressure responsive particle application portion onto a recording medium P, and a photoreceptor cleaning device (an example of a cleaning means) 106 that removes the pressure responsive particles remaining on the surface of the photoreceptor 101 after transfer.

[0203] The operation of the arranging means 100 for arranging the pressure responsive particles according to this embodiment on the recording medium P will be described. First, the surface of the photoconductor 101 is charged by the charging roll 102. The exposure device 103 irradiates the charged surface of the photoconductor 101 with a laser beam in accordance with image data sent from a control unit (not shown). As a result, an electrostatic charge image of the arrangement pattern of the pressure responsive particles according to this embodiment is formed on the surface of the photoconductor 101.

[0204] The electrostatic image formed on the photoconductor 101 rotates to a development position as the photoconductor 101 travels. Then, at the development position, the electrostatic image on the photoconductor 101 is developed by a developing device 104 and becomes a pressure responsive particle application portion.

[0205] The developing device 104 contains a developer containing at least the pressure responsive particles according to this embodiment and a carrier. The pressure responsive particles according to this embodiment are triboelectrically charged by being stirred together with the carrier inside the developing device 104, and are held on the developer roll. As the surface of the photoconductor 101 passes through the developing device 104, the pressure responsive particles electrostatically adhere to the electrostatic charge image on the surface of the photoconductor 101, and the electrostatic charge image is developed by the pressure responsive particles. The photoconductor 101 on which the pressure responsive particle application portion has been formed continues to travel, and the pressure responsive particle application portion on the photoconductor 101 is transported to the transfer position.

[0206] When the pressure-responsive particle application portion on the photoreceptor 101 is transported to the transfer position, a transfer bias is applied to the transfer roll 105, and an electrostatic force from the photoreceptor 101 to the transfer roll 105 acts on the pressure-responsive particle application portion, causing the pressure-responsive particle application portion on the photoreceptor 101 to be transferred onto the recording medium P.

[0207] The pressure responsive particles remaining on the photoreceptor 101 are removed and collected by the photoreceptor cleaning device 106. The photoreceptor cleaning device 106 is, for example, a cleaning blade, a cleaning brush, etc. The photoreceptor cleaning device 106 is preferably a cleaning brush from the viewpoint of suppressing the phenomenon in which the pressure responsive particles according to the present embodiment remaining on the surface of the photoreceptor are fluidized by pressure and adhere to the surface of the photoreceptor in the form of a film.

[0208] The recording medium P to which the pressure responsive particle application portion has been transferred is transported to a fixing device (an example of a fixing means) 107. The fixing device 107 is, for example, a pair of fixing members (roll / roll, belt / roll). The arrangement means 100 does not need to include the fixing device 107, but it is preferable that the fixing device 107 is included from the viewpoint of preventing the pressure responsive particles according to this embodiment from falling off from the recording medium P. The pressure applied by the fixing device 107 to the recording medium P may be lower than the pressure applied by the pressure device 230 to the recording medium P2, and specifically, it is preferable that the pressure is 0.2 MPa or more and 1 MPa or less.

[0209] Fixing device 107 may or may not have an internal heating source (e.g., a halogen heater) for heating recording medium P. If fixing device 107 has an internal heating source, the surface temperature of 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. Note that the fact that fixing device 107 does not have an internal heating source does not exclude the temperature inside fixing device 107 becoming equal to or higher than the ambient temperature due to heat generated by a motor or the like provided in arrangement means 100.

[0210] The recording medium P becomes a recording medium P1 having the pressure responsive particles according to this embodiment applied onto the image by passing through the arrangement means 100. The recording medium P1 is transported towards the pressure bonding means 200.

[0211] In the printed matter manufacturing apparatus according to this embodiment, the placement means 100 and the pressing means 200 may be in close proximity to each other or may be spaced apart. When the placement means 100 and the pressing means 200 are spaced apart, the placement means 100 and the pressing means 200 are connected by, for example, a conveying means (for example, a belt conveyor) that conveys the recording medium P1.

[0212] The pressing means 200 includes a folding device 220 and a pressure device 230, and is a means for folding and pressing the recording medium P1.

[0213] The folding device 220 folds the recording medium P1 that passes through the device to produce a folded recording medium P2. The recording medium P2 may be folded, for example, in two, three, or four, and may be folded only partially. The recording medium P2 has pressure-responsive particles according to this embodiment disposed on at least a portion of at least one of two opposing surfaces.

[0214] The folding device 220 may have a pair of pressure members (e.g., roll / roll, belt / roll) that apply pressure to the recording medium P2. The pressure applied by the pressure members of the folding device 220 to the recording medium P2 may be lower than the pressure applied by the pressure device 230 to the recording medium P2, and specifically, is preferably 1 MPa or more and 10 MPa or less.

[0215] The pressing means 200 may be provided with a stacking device for stacking the recording medium P1 and another recording medium instead of the folding device 220. The recording medium P1 and the other recording medium may be stacked in a form in which one sheet of the other recording medium is stacked on the recording medium P1, or in a form in which one sheet of the other recording medium is stacked on each of a plurality of locations on the recording medium P1. The other recording medium may be a recording medium on which an image has been formed in advance on one or both sides, a recording medium on which no image has been formed, or a press-bonded printed matter prepared in advance.

[0216] The recording medium P2 that has left the folding device 220 (or the overlapping device) is conveyed toward the pressure device 230.

[0217] The pressure device 230 includes a pair of pressure members (i.e., pressure rolls 231 and 232). The pressure rolls 231 and 232 come into contact with each other at their outer circumferential surfaces and press against each other to apply pressure to the recording medium P2 passing through. The pair of pressure members included in the pressure device 230 is not limited to a combination of a pressure roll and a pressure roll, and may also be a combination of a pressure roll and a pressure belt, or a combination of a pressure belt and a pressure belt.

[0218] When pressure is applied to the recording medium P2 passing through the pressure device 230, the pressure-responsive particles according to this embodiment are fluidized by the pressure on the recording medium P2 and exert adhesiveness. The pressure applied by the pressure device 230 to the recording medium P2 is preferably 3 MPa or more and 300 MPa or less, more preferably 10 MPa or more and 200 MPa or less, and even more preferably 30 MPa or more and 150 MPa or less.

[0219] The pressurizing device 230 may or may not have an internal heat source (e.g., a halogen heater) for heating the recording medium P2. If the pressurizing device 230 has an internal heat source, the surface temperature of the recording medium P2 when heated by the heat source is preferably 30° C. or higher and 120° C. or lower, more preferably 40° C. or higher and 100° C. or lower, and even more preferably 50° C. or higher and 90° C. or lower. Note that the fact that the pressurizing device 230 does not have an internal heat source does not exclude the temperature inside the pressurizing device 230 becoming equal to or higher than the ambient temperature due to heat generated by a motor or the like provided in the pressurizing device 230.

[0220] As the recording medium P2 passes through the pressure device 230, the overlapping surfaces are bonded together by the fluidized pressure-responsive particles according to this embodiment, producing a pressure-bonded printed matter P3. In the pressure-bonded printed matter P3, opposing surfaces are partially or entirely bonded together.

[0221] The completed pressure-bonded printed matter P3 is conveyed out of the pressure device 230.

[0222] The first form of the laminated printed matter P3 is a laminated printed matter in which the opposing surfaces of folded recording media are bonded by the pressure-responsive particles according to the present embodiment. The laminated printed matter P3 of this embodiment is manufactured by a printing matter manufacturing apparatus equipped with a folding device 220.

[0223] The second form of the pressure-bonded printed matter P3 is a pressure-bonded printed matter in which a plurality of overlapping recording media are bonded on their opposing surfaces by pressure-responsive particles according to the present embodiment. The pressure-bonded printed matter P3 of this form is manufactured by a pressure-bonded printed matter manufacturing apparatus equipped with a stacking device.

[0224] The printed matter production device according to the present embodiment is not limited to a device in a form that continuously transports the recording medium P2 from the folding device 220 (or the overlapping device) to the pressure device 230. The printed matter production device according to the present embodiment may be a device in a form that stores the recording medium P2 that has left the folding device 220 (or the overlapping device), and transports the recording medium P2 to the pressure device 230 after the amount of the recording medium P2 stored reaches a predetermined amount.

[0225] In the printed matter manufacturing apparatus according to this embodiment, the folding device 220 (or overlapping device) and the pressing and pressurizing device 230 may be in close proximity to each other or may be spaced apart. When the folding device 220 (or overlapping device) and the pressing and pressurizing device 230 are spaced apart, the folding device 220 (or overlapping device) and the pressing and pressurizing device 230 are connected by, for example, a conveying means (for example, a belt conveyor) that conveys the recording medium P2.

[0226] The printing production device according to the present embodiment may include a cutting means for cutting the recording medium to a predetermined size. The cutting means may be, for example, a cutting means arranged between the arrangement means 100 and the pressure bonding means 200, which cuts off a part of the recording medium P1 in an area where the pressure responsive particles according to the present embodiment are not arranged; a cutting means arranged between the folding device 220 and the pressure device 230, which cuts off a part of the recording medium P2 in an area where the pressure responsive particles according to the present embodiment are not arranged; a cutting means arranged downstream of the pressure bonding means 200, which cuts off a part of the pressure-bonded printed matter P3 in an area where the pressure responsive particles according to the present embodiment are not bonded; etc.

[0227] The apparatus for producing printed matter according to the present embodiment is not limited to a sheet-fed type apparatus, but may be an apparatus that performs a placement process and a pressing process on a long recording medium to form a long-length pressed-on printed matter, and then cuts the long-length pressed-on printed matter to a predetermined size.

[0228] The apparatus for producing a printed matter according to the present embodiment may further include a color image forming unit that forms a color image on a recording medium by an electrophotographic method using a color electrostatic image developer. A photoconductor; A charging means for charging the surface of the photoreceptor; an electrostatic image forming means for forming an electrostatic image on the charged surface of the photoreceptor; a developing means for storing a color electrostatic image developer and developing the electrostatic image formed on the surface of the photoconductor into a color toner image by the color electrostatic image developer; a transfer means for transferring the color toner image formed on the surface of the photoreceptor to a surface of a recording medium; and a heat fixing means for heat fixing the color toner image transferred onto the surface of the recording medium.

[0229] The manufacturing apparatus having the above-described configuration is used to carry out a method for manufacturing a printed matter according to the present embodiment, which further includes a color image forming step of forming a color image on a recording medium by an electrophotographic method using a color electrostatic image developer. a charging step of charging the surface of the photoconductor; an electrostatic image forming step of forming an electrostatic image on the charged surface of the photoreceptor; a developing step of developing the electrostatic image formed on the surface of the photoconductor into a color toner image by a color electrostatic image developer; a transfer step of transferring the color toner image formed on the surface of the photoreceptor onto a surface of a recording medium; and a heat fixing step of heat fixing the color toner image transferred onto the surface of the recording medium.

[0230] The color image forming means included in the printed matter manufacturing apparatus according to the present embodiment is, for example, a direct transfer type device that directly transfers a colored toner image formed on the surface of a photoreceptor to a recording medium; an intermediate transfer type device that primarily transfers a colored toner image formed on the surface of a photoreceptor to the surface of an intermediate transfer body, and then secondarily transfers the colored toner image transferred to the surface of the intermediate transfer body to the surface of a recording medium; a device equipped with a cleaning means that cleans the surface of the photoreceptor before charging after the transfer of the colored toner image; a device equipped with a discharging means that irradiates the surface of the photoreceptor with discharging light to discharge the surface before charging after the transfer of the colored toner image. When the color image forming means is an intermediate transfer type device, the transfer means includes, for example, an intermediate transfer body onto whose surface a colored toner image is transferred, a primary transfer means that primarily transfers the colored toner image formed on the surface of the photoreceptor to the surface of the intermediate transfer body, and a secondary transfer means that secondarily transfers the colored toner image transferred to the surface of the intermediate transfer body to the surface of a recording medium.

[0231] In the printed matter manufacturing apparatus of this embodiment, when the placement means for the developer containing the pressure-responsive particles of this embodiment and the color image forming means adopt an intermediate transfer method, the placement means and the color image forming means may share the intermediate transfer body and secondary transfer means.

[0232] In the apparatus for producing printed matter according to this embodiment, the means for placing the image developer containing the pressure responsive particles according to this embodiment and the color image forming means may share the thermal fixing means.

[0233] An example of a printing device according to the present embodiment that includes a color image forming unit will be described below, but the present embodiment is not limited to this example. In the following description, the main parts shown in the drawings will be described, and the description of the rest will be omitted.

[0234] Fig. 3 is a schematic diagram showing an example of a production apparatus for a printed matter according to the present embodiment using an electrophotographic method. The production apparatus for a printed matter shown in Fig. 3 includes a printing means 300 that simultaneously performs the arrangement of pressure-responsive particles according to the present embodiment on a recording medium and the formation of a colored image, and a pressing means 200 that is disposed downstream of the printing means 300.

[0235] The printing means 300 is a 5-tandem type and intermediate transfer type printing means. The printing means 300 includes a unit 10T that arranges pressure-responsive particles (T) according to the present embodiment, and units 10Y, 10M, 10C, and 10K that form images of each color of yellow (Y), magenta (M), cyan (C), and black (K). The unit 10T is an arrangement means that arranges the pressure-responsive particles according to the present embodiment on the recording medium P using a developer containing the pressure-responsive particles according to the present embodiment. The units 10Y, 10M, 10C, and 10K are means that form color images on the recording medium P using a developer containing color toner. The units 10T, 10Y, 10M, 10C, and 10K adopt an electrophotographic system.

[0236] The units 10T, 10Y, 10M, 10C, and 10K are arranged in parallel and spaced apart from one another in the horizontal direction. The units 10T, 10Y, 10M, 10C, and 10K may be process cartridges that are detachably attached to the printing means 300.

[0237] An intermediate transfer belt (an example of an intermediate transfer body) 20 is provided below the units 10T, 10Y, 10M, 10C, and 10K and extends through each unit. The intermediate transfer belt 20 is provided wrapped around a drive roll 22, a support roll 23, and an opposing roll 24, which are in contact with the inner surface of the intermediate transfer belt 20, and runs in a direction from the unit 10T to the unit 10K. An intermediate transfer body cleaning device 21 is provided on the image bearing surface side of the intermediate transfer belt 20, facing the drive roll 22.

[0238] The units 10T, 10Y, 10M, 10C, and 10K respectively include developing devices (examples of developing means) 4T, 4Y, 4M, 4C, and 4K. The developing devices 4T, 4Y, 4M, 4C, and 4K are supplied with the pressure responsive particles according to the present embodiment housed in a pressure responsive particle cartridge 8T, or with yellow toner, magenta toner, cyan toner, and black toner housed in toner cartridges 8Y, 8M, 8C, and 8K.

[0239] Units 10T, 10Y, 10M, 10C and 10K have the same configuration and operation, so unit 10T, which arranges pressure responsive particles according to this embodiment on a recording medium, will be described as a representative.

[0240] The unit 10T has a photoconductor 1T. Around the photoconductor 1T, a charging roll (an example of a charging means) 2T that charges the surface of the photoconductor 1T, an exposure device (an example of an electrostatic image forming means) 3T that exposes the surface of the charged photoconductor 1T to a laser beam to form an electrostatic image, a developing device (an example of a developing means) 4T that supplies pressure responsive particles to the electrostatic image to develop the electrostatic image, a primary transfer roll (an example of a primary transfer means) 5T that transfers the developed pressure responsive particle application portion onto the intermediate transfer belt 20, and a photoconductor cleaning device (an example of a cleaning means) 6T that removes the pressure responsive particles remaining on the surface of the photoconductor 1T after the primary transfer are arranged in this order. The primary transfer roll 5T is arranged inside the intermediate transfer belt 20 and is provided at a position facing the photoconductor 1T.

[0241] Hereinafter, the operation of arranging the pressure responsive particles according to this embodiment on the recording medium P and forming a color image will be described while illustrating the operation of the unit 10T. First, the surface of the photoconductor 1T is charged by the charging roll 2T. The charged surface of the photoconductor 1T is irradiated with a laser beam by the exposure device 3T in accordance with image data sent from a control unit (not shown). As a result, an electrostatic charge image of the arrangement pattern of the pressure-responsive particles according to this embodiment is formed on the surface of the photoconductor 1T.

[0242] The electrostatic image formed on the photoconductor 1T rotates to a development position as the photoconductor 1T travels. At the development position, the electrostatic image on the photoconductor 1T is developed by a developing device 4T and becomes a pressure responsive particle application portion.

[0243] The developing device 4T contains a developer containing at least the pressure-responsive particles according to this embodiment and a carrier. The pressure-responsive particles according to this embodiment are triboelectrically charged by being stirred together with the carrier inside the developing device 4T, and are held on the developer roll. As the surface of the photoconductor 1T passes through the developing device 4T, the pressure-responsive particles electrostatically adhere to the electrostatic charge image on the surface of the photoconductor 1T, and the electrostatic charge image is developed by the pressure-responsive particles. The photoconductor 1T on which the pressure-responsive particle-applied portion has been formed continues to travel, and the pressure-responsive particle-applied portion on the photoconductor 1T is transported to the primary transfer position.

[0244] When the pressure responsive particle applied portion on the photoreceptor 1T is transported to the primary transfer position, a primary transfer bias is applied to the primary transfer roll 5T, and an electrostatic force from the photoreceptor 1T toward the primary transfer roll 5T acts on the pressure responsive particle applied portion, and the pressure responsive particle applied portion on the photoreceptor 1T is transferred onto the intermediate transfer belt 20. The pressure responsive particles remaining on the photoreceptor 1T are removed and collected by the photoreceptor cleaning device 6T. The photoreceptor cleaning device 6T is, for example, a cleaning blade, a cleaning brush, etc., and is preferably a cleaning brush.

[0245] In units 10Y, 10M, 10C, and 10K, the same operation as in unit 10T is performed using a developer containing color toner. The intermediate transfer belt 20 to which the pressure responsive particle application portion has been transferred in unit 10T passes through units 10Y, 10M, 10C, and 10K in sequence, and the toner images of each color are transferred onto the intermediate transfer belt 20 in multiple layers.

[0246] The intermediate transfer belt 20 onto which the pressure responsive particle providing portion and the toner image have been transferred in multiple layers through the units 10T, 10Y, 10M, 10C, and 10K reaches a secondary transfer portion including the intermediate transfer belt 20, an opposing roll 24 in contact with the inner surface of the intermediate transfer belt, and a secondary transfer roll (an example of a secondary transfer means) 26 arranged on the image bearing surface side of the intermediate transfer belt 20. Meanwhile, the recording medium P is fed into the gap between the secondary transfer roll 26 and the intermediate transfer belt 20 via a supply mechanism, and a secondary transfer bias is applied to the opposing roll 24. At this time, an electrostatic force directed from the intermediate transfer belt 20 toward the recording medium P acts on the pressure responsive particle providing portion and the toner image, and the pressure responsive particle providing portion and the toner image on the intermediate transfer belt 20 are transferred onto the recording medium P.

[0247] The recording medium P to which the pressure responsive particle application unit and the toner image have been transferred is transported to a thermal fixing device (one example of a thermal fixing means) 28. The thermal fixing device 28 is equipped with a heating source such as a halogen heater, and heats the recording medium P. The surface temperature of the recording medium P when heated by the thermal fixing device 28 is preferably 150° C. or higher and 220° C. or lower, more preferably 155° C. or higher and 210° C. or lower, and even more preferably 160° C. or higher and 200° C. or lower. By passing through the thermal fixing device 28, the colored toner image is thermally fixed onto the recording medium P.

[0248] From the viewpoint of preventing the pressure-responsive particles according to this embodiment from falling off the recording medium P and from the viewpoint of improving the fixability of the color image to the recording medium P, the thermal fixing device 28 is preferably a device that applies pressure as well as heat, and may be, for example, a pair of fixing members (roll / roll, belt / roll) equipped with an internal heat source. When the thermal fixing device 28 applies pressure, the pressure that the thermal fixing device 28 applies to the recording medium P may be lower than the pressure that the pressure device 230 applies to the recording medium P2, and specifically, it is preferably 0.2 MPa or more and 1 MPa or less.

[0249] The recording medium P becomes a recording medium P1 to which a colored image and pressure responsive particles according to this embodiment are applied by passing through the printing means 300. The recording medium P1 is transported toward the pressing means 200.

[0250] The configuration of the crimping means 200 in FIG. 3 may be the same as that of the crimping means 200 in FIG. 2, and detailed description of the configuration and operation of the crimping means 200 will be omitted.

[0251] In the printed matter manufacturing apparatus according to this embodiment, the printing means 300 and the pressing means 200 may be in close proximity to each other or may be spaced apart from each other. When the printing means 300 and the pressing means 200 are spaced apart from each other, the printing means 300 and the pressing means 200 are connected to each other by, for example, a conveying means (for example, a belt conveyor) that conveys the recording medium P1.

[0252] The printing production device according to the present embodiment may include a cutting means for cutting the recording medium to a predetermined size. The cutting means may be, for example, a cutting means arranged between the printing means 300 and the bonding means 200, which cuts off a part of the recording medium P1 in an area where the pressure-responsive particles according to the present embodiment are not arranged; a cutting means arranged between the folding device 220 and the pressing device 230, which cuts off a part of the recording medium P2 in an area where the pressure-responsive particles according to the present embodiment are not arranged; a cutting means arranged downstream of the bonding means 200, which cuts off a part of the bonded printed matter P3 in an area where the pressure-responsive particles according to the present embodiment are not attached; etc.

[0253] The printed matter production apparatus according to the present embodiment is not limited to a sheet-fed type apparatus, but may be an apparatus that performs a color image forming process, a positioning process, and a pressing process on a long recording medium to form a long pressed printed matter, and then cuts the long pressed printed matter to a predetermined size.

[0254] [Process cartridge] A process cartridge for use in an electrophotographic printing device will now be described. The process cartridge according to this embodiment is a process cartridge that contains the electrostatic image developer according to this embodiment, is equipped with a developing means that uses the electrostatic image developer to develop an electrostatic image formed on the surface of a photosensitive member as a pressure-responsive particle application section, and is detachably attached to a printed matter production device.

[0255] The process cartridge according to the present embodiment may be configured to include a developing unit, and, as necessary, at least one selected from a photoconductor, a charging unit, an electrostatic image forming unit, a transfer unit, and the like.

[0256] An example of an embodiment of the process cartridge is a cartridge in which a photoconductor, a charging roll (an example of a charging means) provided around the photoconductor, a developing device (an example of a developing means), and a photoconductor cleaning device (an example of a cleaning means) are integrated into a housing. The housing has an opening for exposure. The housing has a mounting rail, and the process cartridge is attached to a production device for printed matter via the mounting rail. EXAMPLES

[0257] Hereinafter, the embodiments of the present invention will be described in detail with reference to examples, but the embodiments of the present invention are not limited to these examples. In the following description, unless otherwise specified, "parts" and "%" are based on mass.

[0258] <Preparation of Dispersion Containing Styrene-Based Resin Particles> [Preparation of styrene-based resin particle dispersion (St1)] Styrene: 390 parts n-Butyl acrylate: 100 parts Acrylic acid: 10 parts Dodecanethiol: 7.5 parts The above materials were mixed and dissolved to prepare a monomer solution. 8 parts of anionic surfactant (Dowfax2A1, manufactured by Dow Chemical Company) was dissolved in 205 parts of ion-exchanged water, and the monomer solution was added thereto and dispersed and emulsified to obtain an emulsion. 2.2 parts of anionic surfactant (Dowfax2A1, manufactured by The Dow Chemical Company) was dissolved in 462 parts of ion-exchanged water, and the solution was charged into a polymerization flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, and the mixture was heated to 73°C with stirring and maintained at that temperature. 3 parts of ammonium persulfate was dissolved in 21 parts of ion-exchanged water and added dropwise to the polymerization flask via a metering pump over 15 minutes, and then the emulsion was added dropwise to the solution via a metering pump over 160 minutes. The polymerization flask was then kept at 75° C. for 3 hours with continued slow stirring, and then allowed to cool to room temperature. This resulted in a styrene-based resin particle dispersion (St1) containing styrene-based resin particles, with a volume average particle size (D50v) of 174 nm, a weight average molecular weight measured by GPC (UV detection) of 49,000, a glass transition temperature of 54°C, and a solid content of 42%.

[0259] The styrene resin particle dispersion (St1) was dried to extract the styrene resin particles, and the thermal behavior was analyzed in the temperature range of -100°C to 100°C using a differential scanning calorimeter (Shimadzu Corporation, DSC-60A). One glass transition temperature was observed. Table 1 shows the glass transition temperatures.

[0260] [Preparation of styrene-based resin particle dispersions (St2) to (St13)] In the same manner as in the preparation of the styrene-based resin particle dispersion liquid (St1), except that the monomers were changed as shown in Table 1, styrene-based resin particle dispersion liquids (St2) to (St13) were prepared.

[0261] The composition and physical properties of the styrene-based resin particle dispersion (St1) and the like are shown in Table 1. In Table 1, the monomers are represented by the following abbreviations. 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

[0262] [Table 1]

[0263] <Preparation of Dispersion Containing Composite Resin Particles> [Preparation of composite resin particle dispersion (M1)] Styrene-based resin particle dispersion (St1): 1,190 parts (solids: 500 parts) 2-Ethylhexyl acrylate: 250 parts -n-Butyl acrylate: 250 parts Ion-exchanged water: 982 parts The above materials were charged into a polymerization flask and stirred at 25°C for 1 hour, then heated to 70°C. 2.5 parts of ammonium persulfate was dissolved in 75 parts of ion-exchanged water, and the solution was added dropwise to the polymerization flask over 60 minutes via a metering pump. The polymerization flask was then kept at 70° C. for 3 hours with continued slow stirring, and then allowed to cool to room temperature. This resulted in a composite resin particle dispersion (M1) containing composite resin particles, the resin particles having a volume average particle size (D50v) of 219 nm, a weight average molecular weight measured by GPC (UV detection) of 219,000, and a solid content of 32%.

[0264] The composite resin particle dispersion (M1) was dried to take out the composite resin particles, and their thermal behavior was analyzed in the temperature range of -150°C to 100°C using a differential scanning calorimeter (Shimadzu Corporation, DSC-60A). Two glass transition temperatures were observed. The glass transition temperatures are shown in Table 2.

[0265] [Preparation of Composite Resin Particle Dispersions (M2) to (M21) and (cM1) to (cM3)] Composite resin particle dispersions (M2) to (M21) and (cM1) to (cM3) were prepared in the same manner as in the preparation of the composite resin particle dispersion (M1), except that the styrene-based resin particle dispersion (St1) was changed as shown in Table 2, or the polymerization components of the (meth)acrylic ester-based resin were changed as shown in Table 2.

[0266] [Preparation of Composite Resin Particle Dispersions (M22) to (M27)] Composite resin particle dispersions (M22) to (M27) were prepared in the same manner as in the preparation of composite resin particle dispersion (M1), except that the amounts of 2-ethylhexyl acrylate and n-butyl acrylate used were adjusted.

[0267] The composition and physical properties of the composite resin particle dispersion (M1) and the like are shown in Table 2. In Table 2, the monomers are represented by the following abbreviations. 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, Propyl acrylate: PA

[0268] [Table 2]

[0269] [Preparation of Composite Resin Particle Dispersions (M28) to (M30)] Composite resin particle dispersions (M28) to (M30) having different weight average molecular weights of the composite resin particles were prepared in the same manner as in the preparation of composite resin particle dispersion (M1), except that the amount of ammonium persulfate was changed as shown in Table 3.

[0270] [Table 3]

[0271] The composition and physical properties of the composite resin particle dispersion (M28) etc. are shown in Table 4. In Table 4, the monomers are represented by the following abbreviations. Styrene: St, n-butyl acrylate: BA, acrylic acid: AA, 2-ethylhexyl acrylate: 2EHA

[0272] [Table 4]

[0273] <Preparation of pressure-responsive particles> [Preparation of pressure-responsive particles (1)] ·Composite resin particle dispersion (M1): 504 parts Ion-exchanged water: 710 parts Anionic surfactant (Dow Chemical Company, Dowfax2A1): 1 part

[0274] The above materials were placed in a reaction vessel equipped with a thermometer and a pH meter, and a 1.0% aqueous nitric acid solution was added at a temperature of 25°C to adjust the pH to 3.0. Then, 23 parts of a 2.0% aqueous aluminum sulfate solution was added while dispersing with a homogenizer (Ultra Turrax T50, manufactured by IKA) at a rotation speed of 5000 rpm. Next, a stirrer and a mantle heater were installed in the reaction vessel, and the temperature was increased at a rate of 0.2°C / min up to 40°C, and at a rate of 0.05°C / min after exceeding 40°C, and the particle size was measured every 10 minutes with a Multisizer II (aperture diameter 50 μm, manufactured by Beckman Coulter). When the volume average particle size reached 5.0 μm, the temperature was maintained, and 170 parts of a styrene-based resin particle dispersion (St1) was added over 5 minutes. After the addition was completed, the mixture was held at 50°C for 30 minutes, and then a 1.0% aqueous sodium hydroxide solution was added to adjust the pH of the slurry to 6.0. Next, the temperature was increased to 90°C at a rate of 1°C / min while adjusting the pH to 6.0 every 5°C, and then maintained at 90°C. When the particle shape and surface properties were observed using an optical microscope and a field emission scanning electron microscope (FE-SEM), coalescence of the particles was confirmed after 10 hours, so the container was cooled to 30°C over 5 minutes with cooling water.

[0275] The cooled slurry was passed through a nylon mesh with a mesh size of 15 μm to remove coarse particles, and the slurry that passed through the mesh was filtered under reduced pressure with an aspirator. The solids remaining on the filter paper were crushed as finely as possible by hand, and then added to ion-exchanged water (temperature 30°C) with 10 times the amount of solids, and stirred for 30 minutes. Next, the mixture was filtered under reduced pressure with an aspirator, and the solids remaining on the filter paper were crushed as finely as possible by hand, and then added to ion-exchanged water (temperature 30°C) with 10 times the amount of solids, and then stirred for 30 minutes, and then filtered under reduced pressure again with an aspirator, and the electrical conductivity of the filtrate was measured. This operation was repeated until the electrical conductivity of the filtrate was 10 μS / cm or less, and the solids were washed.

[0276] The washed solid content was finely crushed with a wet-dry type granulator (Comil) and vacuum-dried in an oven at 25° C. for 36 hours to obtain pressure-responsive base particles (1). The pressure-responsive base particles (1) had a volume average particle size of 8.0 μm.

[0277] 100 parts of pressure-responsive base particles (1) and 1.5 parts of hydrophobic silica (RY50, manufactured by Nippon Aerosil Co., Ltd.) were mixed and mixed for 30 seconds at a rotation speed of 13,000 rpm using a sample mill. The mixture was sieved using a vibrating sieve with 45 μm openings to obtain pressure-responsive particles (1).

[0278] When the thermal behavior of the pressure-responsive particle (1) sample was analyzed in the temperature range of -150°C to 100°C using a differential scanning calorimeter (Shimadzu Corporation, DSC-60A), two glass transition temperatures were observed. The glass transition temperatures are shown in Table 5.

[0279] When the temperatures T1 and T2 of the pressure-responsive particles (1) were determined by the above-mentioned measurement method, it was found that the pressure-responsive particles (1) satisfied the formula 1 "10° C.≦T1−T2".

[0280] When the cross section of the pressure-responsive particle (1) was observed with a scanning electron microscope (SEM), a sea-island structure was observed. The pressure-responsive particle (1) had a core portion in which an island phase existed, and a shell layer in which no island phase existed. The sea phase contained a styrene-based resin, and the island phase contained a (meth)acrylic ester-based resin. The average diameter of the island phase was determined by the measurement method described above. Table 5 shows the average diameter of the island phase.

[0281] [Preparation of pressure-responsive particles (2)-(27)] Pressure responsive particles (2) to (27) were prepared in the same manner as in the preparation of pressure responsive particles (1), except that the composite resin particle dispersion and the styrene-based resin particle dispersion were changed as shown in Table 5.

[0282] When the temperatures T1 and T2 of the pressure-responsive particles (2) to (27) were determined by the above-mentioned measurement method, all of the pressure-responsive particles (2) to (27) satisfied the formula 1 "10° C.≦T1−T2".

[0283] [Preparation of pressure-responsive particles (28)-(30)] In the same manner as in the preparation of pressure responsive particles (1), except that the composite resin particle dispersion liquid was changed as shown in Table 6, pressure responsive particles (28) to (30) were prepared.

[0284] The temperatures T1 and T2 of the pressure-responsive particles (28) to (30) were determined by the above-mentioned measurement method, and all of the pressure-responsive particles (28) to (30) satisfied the formula 1 "10° C.≦T1−T2".

[0285] [Preparation of pressure-responsive particles (31)] Pressure-responsive base particles were prepared by the following grinding method. The composite resin particle dispersion (M1) was dried to obtain composite resin particles (M31). The composite resin particles (M31) were kneaded by heat in an extruder set at a temperature of 100°C, cooled, pulverized and classified to obtain pressure-responsive base particles (31) having a volume average particle size of 8.0 μm.

[0286] 100 parts of the pressure-responsive base particles (31) and 1.5 parts of hydrophobic silica (RY50, manufactured by Nippon Aerosil Co., Ltd.) were mixed and mixed for 30 seconds at a rotation speed of 13,000 rpm using a sample mill. The mixture was sieved using a vibrating sieve with an opening of 45 μm to obtain pressure-responsive particles (31).

[0287] When the thermal behavior of the pressure-responsive particle (31) sample was analyzed in the temperature range of -150°C to 100°C using a differential scanning calorimeter (Shimadzu Corporation, DSC-60A), two glass transition temperatures were observed. The glass transition temperatures are shown in Table 6.

[0288] When temperatures T1 and T2 of the pressure-responsive particles (31) were determined by the above-mentioned measurement method, it was found that the pressure-responsive particles (31) satisfied formula 1 "10° C.≦T1−T2".

[0289] [Preparation of pressure-responsive particles (c1) to (c3) for comparison] Pressure-responsive particles (c1) to (c3) were prepared in the same manner as in the preparation of pressure-responsive particles (1), except that the composite resin particle dispersion and the styrene-based resin particle dispersion were changed as shown in Table 5.

[0290] [Evaluation of pressure-responsive phase transition] The temperature difference (T1-T3), which is an index showing the ease with which pressure-responsive particles undergo phase transition due to pressure, was determined. Using each pressure-responsive particle as a sample, the temperatures T1 and T3 were measured using a flow tester (Shimadzu Corporation, CFT-500), and the temperature difference (T1-T3) was calculated. Tables 5 and 6 show the temperature difference (T1-T3).

[0291] [Adhesion evaluation] As a recording medium, postcard paper V424 manufactured by Fuji Xerox Co., Ltd. was prepared. An image with an area density of 30% in which black text and a full-color photographic image were mixed was formed on one side of the postcard paper using an image forming apparatus DocuCentre C7550I manufactured by Fuji Xerox Co., Ltd. and commercially available yellow toner, magenta toner, cyan toner, and black toner manufactured by Fuji Xerox Co., Ltd., and the image was fixed. Pressure-responsive particles are applied to the entire image-forming surface of postcard paper at a rate of 3 g / m 2 The pressure-responsive particles were then fixed to the image-forming surface of the postcard paper by passing through a belt roll type fixing machine, thereby forming a layer of pressure-responsive particles. A postcard having a layer of pressure-responsive particles on its image-forming surface was folded in half with the image-forming surface facing inward using a sealer, PRESSLE multiII, manufactured by Toppan Forms Co., Ltd., and pressure was applied to the folded postcard to bond the inner image-forming surfaces together at a pressure of 90 MPa. Using the above-mentioned device and conditions, ten postcards were continuously produced, each folded in half with the image-formed surface facing inward and with the image-formed surfaces glued together. The tenth postcard was cut in the long direction to a width of 15 mm to prepare a rectangular test piece, and a 90-degree peel test was performed. The peel speed for the 90-degree peel test was 20 mm / min, and the load (N) was collected at 0.4 mm intervals from 10 mm to 50 mm after the start of the measurement, and the average was calculated, and the load (N) of three test pieces was also averaged. The load (N) required for peeling was classified as follows. The results are shown in Tables 5 and 6.

[0292] A: 0.8N or more B: 0.6N or more, less than 0.8N C: 0.4N or more, less than 0.6N D: 0.2N or more, less than 0.4N E: Less than 0.2N

[0293] [Table 5]

[0294] [Table 6]

[0295] <Preparation of Dispersion Containing Composite Resin Particles> [Preparation of composite resin particle dispersion (M50)] Styrene-based resin particle dispersion (St1): 1,190 parts (solids: 500 parts) 2-Ethylhexyl acrylate: 200 parts -n-Butyl acrylate: 200 parts Ion-exchanged water: 1,360 parts The above materials were charged into a polymerization flask and stirred at 25°C for 1 hour, then heated to 70°C. 2.5 parts of ammonium persulfate was dissolved in 75 parts of ion-exchanged water, and the solution was added dropwise to the polymerization flask over 60 minutes via a metering pump. Next, the polymerization flask was kept at 70°C for 2 hours while continuing to slowly stir, and then a mixture of 85 parts of styrene and 15 parts of n-butyl acrylate was added dropwise over 60 minutes. After the dropwise addition, the temperature was kept at 75°C for 3 hours, and then the temperature was returned to room temperature. This resulted in a composite resin particle dispersion (M50) containing composite resin particles, with a volume average particle size (D50v) of the resin particles of 223 nm, a weight average molecular weight by GPC (UV detection) of 220,000, and a solid content of 32%.

[0296] The composite resin particle dispersion (M50) was dried to extract the composite resin particles, and their thermal behavior was analyzed in the temperature range of -150°C to 100°C using a differential scanning calorimeter (Shimadzu Corporation, DSC-60A). Two glass transition temperatures were observed. The glass transition temperatures are shown in Table 7.

[0297] [Preparation of Composite Resin Particle Dispersions (M51) to (M55)] Composite resin particle dispersions (M51) to (M55) were prepared in the same manner as in the preparation of composite resin particle dispersion (M50), except that the materials were changed to those shown in Table 7.

[0298] The composition and physical properties of the composite resin particle dispersion (M50) and the like are shown in Table 7. In Table 7, the monomers are represented by the following abbreviations. Styrene: St, n-butyl acrylate: BA, acrylic acid: AA, 2-ethylhexyl acrylate: 2EHA

[0299] [Table 7]

[0300] <Preparation of pressure-responsive particles> [Preparation of pressure-responsive particles (50)-(55)] Pressure responsive particles (50) to (55) were prepared in the same manner as in the preparation of pressure responsive particles (1), except that the materials were changed to those shown in Table 8.

[0301] Pressure-responsive particles (50) to (55) were used as samples, and their thermal behavior was analyzed in the temperature range of -150°C to 100°C using a differential scanning calorimeter (Shimadzu Corporation, DSC-60A). Two glass transition temperatures were observed. The glass transition temperatures are shown in Table 8.

[0302] When the temperatures T1 and T2 of the pressure-responsive particles (50) to (55) were determined by the above-mentioned measurement method, all of the pressure-responsive particles (50) to (55) satisfied the formula 1 "10° C.≦T1−T2".

[0303] When the cross sections of the pressure-responsive particles (50) to (55) were observed with a scanning electron microscope (SEM), a sea-island structure was observed. The pressure-responsive particles (50) to (55) had a core portion in which an island phase existed and a shell layer in which no island phase existed. The sea phase contained a styrene-based resin, and the island phase contained a (meth)acrylic ester-based resin. The average diameter of the island phase was determined by the measurement method described above. The average diameter of the island phase is shown in Table 8.

[0304] [Evaluation of pressure-responsive phase transition] Using each pressure-responsive particle as a sample, the temperatures T1 and T3 were measured using a flow tester (Shimadzu Corporation, CFT-500), and the temperature difference (T1-T3) was calculated. Table 8 shows the temperature difference (T1-T3).

[0305] [Adhesion evaluation] The adhesiveness was evaluated by the above-mentioned evaluation method of [Evaluation of adhesiveness] in the same manner as the pressure-responsive particles (1) etc. The results are shown in Table 8.

[0306] [Table 8]

[0307] <Production of printed matter using electrophotography> 10 parts of any of the pressure responsive particles (1) to (31), (c1) to (c3), and (50) to (55) and 100 parts of the resin-coated carrier (1) described below were placed in a V-type blender and stirred for 20 minutes, and then sieved through a vibrating sieve with 212 μm openings to obtain developers (1) to (31), (c1) to (c3), and (50) to (55), respectively.

[0308] -Resin-coated carrier (1)- Mn-Mg-Sr ferrite particles (average particle size 40 μm): 100 parts Toluene: 14 parts Polymethylmethacrylate: 2 parts Carbon black (VXC72: manufactured by Cabot): 0.12 parts The above materials except for the ferrite particles were mixed with glass beads (diameter 1 mm, same amount as toluene) and stirred for 30 minutes at a rotation speed of 1200 rpm using a sand mill manufactured by Kansai Paint Co., Ltd. to obtain a dispersion liquid. The dispersion liquid and the ferrite particles were placed in a vacuum degassing kneader, and the mixture was dried under reduced pressure while stirring to obtain a resin-coated carrier (1).

[0309] As a printing device, an apparatus shown in Fig. 3 was prepared. That is, a printing device was prepared that includes a 5-tandem type intermediate transfer type printing means that simultaneously performs the arrangement of pressure-responsive particles according to this embodiment on a recording medium and the formation of a color image, and a pressing means having a folding device and a pressing device. The developer according to the present embodiment (or a comparative developer), a yellow developer, a magenta developer, a cyan developer, and a black developer were placed in each of the five developing devices of the printing means. Commercially available products manufactured by Fuji Xerox Co., Ltd. were used as the developers of each color, including yellow. As a recording medium, postcard paper V424 manufactured by Fuji Xerox was prepared. The image formed on the postcard paper was a mixture of black text and a full-color photographic image with an area density of 30%, and was formed on one side of the postcard paper. The amount of pressure-responsive particles according to this embodiment (or pressure-responsive particles for comparison) applied to the image forming area on the image forming surface of the postcard paper is 3 g / m 2 It was decided. The folding device was a device that folded postcards in half so that the image-formed surface was on the inside. The pressure in the pressurizing device was set to 90 MPa. Using the above-mentioned device and conditions, ten postcards were continuously produced, each folded in half with the image-formed surface facing inward and with the image-formed surfaces glued together. The tenth postcard was cut in the long direction to a width of 15 mm to prepare a rectangular test piece, and a 90-degree peel test was performed. The peel speed for the 90-degree peel test was 20 mm / min, and the load (N) was collected at 0.4 mm intervals from 10 mm to 50 mm after the start of the measurement, and the average was calculated, and the load (N) of three test pieces was also averaged. The load (N) required for peeling was classified as follows. The results are shown in Tables 9, 10, and 11.

[0310] A: 0.8N or more B: 0.6N or more, less than 0.8N C: 0.4N or more, less than 0.6N D: 0.2N or more, less than 0.4N E: Less than 0.2N

[0311] [Table 9]

[0312] [Table 10]

[0313] [Table 11] [Explanation of symbols]

[0314] 100 Placement means 110 Applicator 120 Fixation device 200 Crimping means 220 Folding device 230 Pressurizing device 231, 232 Pressure roll M Pressure-Responsive Particles P Recording medium P1: A recording medium having pressure-responsive particles applied to an image P2 Folded recording media P3 Pressure-bonded Printed Material

[0315] 101 Photoreceptor 102 Charging roll (an example of a charging means) 103 Exposure device (an example of an electrostatic image forming means) 104 Developing device (an example of developing means) 105 Transfer roll (an example of a transfer means) 106 Photoconductor cleaning device (an example of a cleaning means) 107 Fixing device (an example of fixing means)

[0316] 300 Printing means 1T, 1Y, 1M, 1C, 1K photoconductor 2T, 2Y, 2M, 2C, 2K Charging roll (an example of charging means) 3T, 3Y, 3M, 3C, 3K exposure equipment (an example of electrostatic image forming means) 4T, 4Y, 4M, 4C, 4K developing device (an example of developing means) 5T, 5Y, 5M, 5C, 5K Primary transfer roll (an example of a primary transfer means) 6T, 6Y, 6M, 6C, 6K Photoconductor cleaning device (an example of a cleaning means) 8T Pressure Responsive Particle Cartridge 8Y, 8M, 8C, 8K toner cartridges 10T, 10Y, 10M, 10C, 10K units 20 Intermediate transfer belt (an example of an intermediate transfer body) 21 Intermediate transfer body cleaning device 22 Driving Roll 23 Support roll 24 Opposing Roll 26 Secondary transfer roll (an example of a secondary transfer means) 28 Thermal fixing device (an example of a thermal fixing means)

Claims

1. a styrene-based resin containing styrene and other vinyl monomers as polymerization components; a (meth)acrylic acid ester-based resin containing at least two kinds of (meth)acrylic acid alkyl esters as polymerization components, the mass ratio of the (meth)acrylic acid alkyl esters in the total polymerization components being 90 mass% or more; the other vinyl monomer contained as a polymerization component in the styrene-based resin includes at least one of n-butyl acrylate and 2-ethylhexyl acrylate; the at least two kinds of (meth)acrylic acid alkyl esters contained as polymerization components in the (meth)acrylic acid ester-based resin include 2-ethylhexyl acrylate and at least one selected from the group consisting of n-butyl acrylate, hexyl acrylate, and propyl acrylate; the mass ratio of the two (meth)acrylic acid alkyl esters having the largest mass ratios among the at least two (meth)acrylic acid alkyl esters contained as polymerization components in the (meth)acrylic acid ester-based resin is 80:20 to 20:80; a core portion containing the styrene-based resin and the (meth)acrylic acid ester-based resin, and a shell layer containing the styrene-based resin and covering the core portion, It has at least two glass transition temperatures, the difference between the lowest glass transition temperature and the highest glass transition temperature being 30° C. or more; The temperature difference (T1-T2) is 10°C or more and 120°C or less. Pressure-responsive particles. Here, T1 is the temperature at which the viscosity is 10,000 Pa·s under a pressure of 1 MPa, and T2 is the temperature at which the viscosity is 10,000 Pa·s under a pressure of 10 MPa.

2. 2. The pressure-responsive particle according to claim 1, wherein a mass ratio of styrene to all of the polymerization components of the styrene-based resin is 60 mass % or more and 95 mass % or less.

3. A pressure-responsive particle as described in claim 1 or claim 2, wherein the difference in the number of carbon atoms in the alkyl groups of the two (meth)acrylic acid alkyl esters having the largest mass proportions among the at least two (meth)acrylic acid alkyl esters contained as polymerization components in the (meth)acrylic acid ester-based resin is 1 or more and 4 or less.

4. 4. The pressure-responsive particle according to claim 1, wherein the styrene-based resin and the (meth)acrylic acid ester-based resin contain the same type of (meth)acrylic acid alkyl ester as polymerization components.

5. 5. The pressure-responsive particle according to claim 1, wherein the (meth)acrylic ester resin contains 2-ethylhexyl acrylate and n-butyl acrylate as polymerization components.

6. 6. The pressure-responsive particle according to claim 1, wherein the content of the styrene-based resin is greater than the content of the (meth)acrylic acid ester-based resin.

7. 7. The pressure-responsive particle according to claim 1, comprising a sea phase containing the styrene-based resin and an island phase containing the (meth)acrylic ester-based resin dispersed in the sea phase.

8. The pressure-responsive particle according to claim 7 , wherein the average diameter of the island phase is 200 nm or more and 500 nm or less.

9. 9. The pressure-responsive particle according to claim 1, wherein the temperature at which the particle shows a viscosity of 10,000 Pa·s under a pressure of 4 MPa is 90° C. or lower.

10. A cartridge containing the pressure responsive particles according to any one of claims 1 to 9, the cartridge being detachably attached to a printing production device.

11. A placement means for storing the pressure responsive particles according to any one of claims 1 to 9 and placing the pressure responsive particles on a recording medium; a pressing means for folding the recording medium and pressing the same, or for stacking the recording medium and another recording medium and pressing the same; A printing production device comprising:

12. The apparatus for producing a printed matter according to claim 11, further comprising a color image forming means for forming a color image on the recording medium using a coloring material.

13. a step of disposing the pressure responsive particles on a recording medium using the pressure responsive particles according to any one of claims 1 to 9; a pressing step of folding the recording medium and pressing the same, or stacking the recording medium and another recording medium and pressing the same; A method for producing a printed matter comprising the steps of:

14. The method for producing a printed matter according to claim 13, further comprising a color image forming step of forming a color image on the recording medium using a coloring material.

15. A printed matter comprising two folded recording media, the opposing surfaces of which are bonded together by the pressure responsive particles according to any one of claims 1 to 9.

16. A printed matter comprising a plurality of overlapping recording media, the opposing surfaces of which are bonded together by the pressure responsive particles according to any one of claims 1 to 9.

17. The pressure-responsive particle according to any one of claims 1 to 9 is used, A sheet for producing printed matter, comprising a substrate and the pressure responsive particles disposed on the substrate.

18. The method includes a step of disposing the pressure responsive particles on a substrate using the pressure responsive particles according to any one of claims 1 to 9. A method for manufacturing a sheet for producing printed matter.

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