JP2021018423A - Pressure responsive particle, cartridge, manufacturing device of printer matter and manufacturing method of printed matter - Google Patents

Abstract

To provide a pressure responsive particle in which the adhesiveness and releasability between pressure responsive particle layers are achieved when a pressure-printed matter crimped by using pressure responsive particles is obtained.SOLUTION: A pressure responsive particle includes: a pressure responsive base particle containing a styrene resin having styrene and other vinyl monomers in the polymerization component and a (meth)acrylic acid ester-based resin having 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 a silica particle having the average primary particle diameter between 50 nm and 300 nm, 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: Figure 1

Description

The present invention relates to a pressure-responsive particle, a cartridge, a printed matter manufacturing apparatus, and a printed matter manufacturing method.

Patent Document 1, formula 1 "20 ℃ ≦ T (1MPa) -T (10MPa) " (T (1MPa) represents the temperature at which the viscosity at an applied pressure 1MPa becomes ^{10 4 Pa · s, T (} 10MPa ) is adhesive material that satisfies the representative.) the temperature at which the viscosity becomes ¹⁰ 4 Pa · s at an applied pressure 10MPa is described.

In Patent Document 2, the adhesive portion for adhering a powder that develops adhesiveness when pressure is applied to the surface to be adhered and the recording medium to which the powder is adhered are subjected to pressure to form an adhesive layer. The fixed portion fixed to the recording medium and the recording medium in which the adhesive layer is formed on the adhered surface are folded so that the adhered surfaces face each other. A crimp printed matter producing device including a applying portion that applies pressure to a recording medium and adheres the adhesive layers to each other is disclosed.

Patent Document 3 describes a step of forming an image layer on a support with a colored toner containing a binder resin and a colorant, and using a transparent toner containing a binder resin and a mold release agent on the image layer. An image forming method comprising a step of forming a transparent layer and a step of forming a peelable pressure-bonding layer on the transparent layer, wherein the transparent layer has a hardness larger than that of the image layer. It is disclosed.

JP-A-2018-002889 JP-A-2018-004966 Japanese Unexamined Patent Publication No. 2014-186055

Conventionally, a crimped printed matter crimped using pressure-responsive particles tends to have difficulty in achieving both adhesiveness and peelability between pressure-responsive particle layers composed of the pressure-responsive particles.
In view of the above circumstances, the present invention contains a styrene resin containing styrene and other vinyl monomers as a polymerization component, and at least two (meth) acrylic acid esters as a polymerization component, and occupies the entire polymerization component (meth). Pressure-responsive mother particles (hereinafter, also referred to as “specific pressure-responsive mother particles”) containing (meth) acrylic acid ester-based resin having a mass ratio of acrylic acid ester of 90% by mass or more, silica particles, and In the pressure-responsive particles containing, the pressure-responsiveness when a crimped printed matter crimped using the pressure-responsive particles is obtained, as compared with the case where the average primary particle size of the silica particles is less than 50 nm or more than 300 nm. An object of the present invention is to provide pressure-responsive particles having both adhesiveness and peelability between particle layers.

Specific means for solving the above problems include the following aspects.

<1> The mass ratio of the styrene resin containing styrene and other vinyl monomers as the polymerization component and the (meth) acrylic acid ester containing at least two kinds of (meth) acrylic acid esters in the polymerization component and accounting for the entire polymerization component. A pressure-responsive mother particle containing 90% by mass or more of a (meth) acrylic acid ester resin,
Silica particles with an average primary particle diameter of 50 nm or more and 300 nm or less,
Have,
It has 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.
Pressure responsive particles.
<2> The pressure-responsive particles according to claim 1, wherein the mass ratio of styrene to the total polymerized components of the styrene resin is 60% by mass or more and 95% by mass or less.
<3> The mass ratio of the two types having the largest mass ratio among the at least two types of (meth) acrylic acid esters contained as a polymerization component in the (meth) acrylic acid ester resin is 80:20 to 20:80. The pressure-responsive particles according to <1> or <2> above.
<4> Of the at least two (meth) acrylic acid esters contained in the (meth) acrylic acid ester-based resin as a polymerization component, the two having the largest mass ratio are (meth) acrylic acid alkyl esters. The pressure-responsive particle according to any one of <1> to <3>, wherein the difference in the number of carbon atoms of the alkyl groups of the two types of (meth) acrylic acid alkyl esters is 1 or more and 4 or less.
<5> The pressure-responsive particles according to any one of <1> to <4>, wherein the other vinyl monomer contained as a polymerization component in the styrene resin contains a (meth) acrylic acid ester.
<6> In any one of <1> to <5>, wherein the other vinyl monomer contained as a polymerization component in the styrene resin contains at least one of n-butyl acrylate and 2-ethylhexyl acrylate. The pressure-responsive particles described.
<7> The pressure according to any one of <1> to <6>, wherein the styrene resin and the (meth) acrylic acid ester resin contain the same type of (meth) acrylic acid ester as a polymerization component. Responsive particles.
<8> The pressure-responsive particles according to any one of <1> to <7>, wherein the (meth) acrylic acid ester resin contains 2-ethylhexyl acrylate and n-butyl acrylate as polymerization components. ..
<9> The pressure-responsive particles according to any one of <1> to <8>, wherein the content of the styrene resin is higher than the content of the (meth) acrylic acid ester resin.
<10> In any one of <1> to <9>, which has a sea phase containing the styrene resin and an island phase containing the (meth) acrylic acid ester resin dispersed in the sea phase. The pressure-responsive particles described.
<11> The pressure-responsive particles according to claim 10, wherein the island phase has an average diameter of 200 nm or more and 500 nm or less.
<12> A core portion containing the styrene resin and the (meth) acrylic acid ester resin, and
The shell layer that covers the core portion and
The pressure-responsive particle according to any one of <1> to <11>.
<13> The pressure-responsive particles according to claim 12, wherein the shell layer contains the styrene resin.
<14> The pressure-responsive particles according to any one of <1> to <13>, wherein the temperature showing a viscosity of 10000 Pa · s under a pressure of 4 MPa is 90 ° C. or lower.
<15> The pressure-responsive particle according to any one of <1> to <14>, wherein the silica particles have an average primary particle diameter of 60 nm or more and 200 nm or less.
<16> The external addition amount of the silica particles is 0.1% by mass or more and 10% by mass or less with respect to the total mass of the pressure-responsive mother particles, any one of the above <1> to <15>. The pressure responsive particles described in.
<17> The pressure-responsive particle according to claim 16, wherein the external addition amount of the silica particles is 1% by mass or more and 3% by mass or less with respect to the total mass of the pressure-responsive mother particles.
<18> A cartridge that contains the pressure-responsive particles according to any one of <1> to <17> and is attached to and detached from a printed matter manufacturing apparatus.
<19> An arrangement means for accommodating the pressure-responsive particles according to any one of <1> to <17> and arranging them on a recording medium.
A crimping means for folding and crimping the recording medium, or stacking and crimping the recording medium and another recording medium.
Printed matter manufacturing equipment including.
<20> The apparatus for producing a printed matter according to <19>, further comprising a colored image forming means for forming a colored image on a recording medium using a coloring material.
<21> The arrangement step of arranging the pressure-responsive particles according to any one of <1> to <17> on the recording medium, and
A crimping step in which the recording medium is folded and crimped, or the recording medium and another recording medium are overlapped and crimped.
A method for manufacturing printed matter including.
<22> The method for producing a printed matter according to <21>, further comprising a colored image forming step of forming a colored image on a recording medium using a coloring material.

According to the invention according to <1>, the pressure-responsive particles are compared with the case where the pressure-responsive particles include the specific pressure-responsive mother particles and the silica particles having an average primary particle diameter of less than 50 nm or more than 300 nm. When a crimped printed matter crimped by using the method is obtained, pressure-responsive particles having both adhesiveness and peelability between pressure-responsive particle layers are provided.
According to the invention according to <2>, it is possible to provide pressure-responsive particles that are more likely to undergo a phase transition due to pressure than when the mass ratio of styrene to the total polymerization component of the styrene resin is more than 95% by mass. it can.
According to the invention according to <3>, the mass ratio of the two types having the largest mass ratio among at least two types of (meth) acrylic acid esters contained as a polymerization component in the (meth) acrylic acid ester-based resin is 80:20. It is possible to provide pressure-responsive particles which are more likely to undergo a phase transition due to pressure and have excellent adhesiveness as compared with the case where the range is out of the range of about 20:80.
According to the invention according to <4>, the phase transition is more likely to occur due to pressure and the adhesiveness is improved as compared with the case where the difference in the number of carbon atoms of the alkyl groups of the two types of (meth) acrylic acid alkyl esters is 5 or more. Excellent pressure responsive particles can be provided.
According to the invention according to <5>, <6> or <7>, it is possible to provide pressure-responsive particles that are more likely to undergo a phase transition due to pressure than pressure-responsive particles containing polystyrene instead of a styrene resin. it can.
According to the invention according to <8>, the pressure-responsive particles include a styrene resin and a (meth) acrylic acid ester resin, and the (meth) acrylic acid ester resin is a homopolymer of 2-ethylhexyl acrylate. It is possible to provide pressure-responsive particles having excellent adhesiveness as compared with certain pressure-responsive particles.
According to the invention according to <9>, it is necessary to provide pressure-responsive particles in which adhesiveness is maintained as compared with the case where the content of the styrene resin is smaller than the content of the (meth) acrylic acid ester resin. Can be done.
According to the invention according to <10>, it is possible to provide pressure-responsive particles that are more likely to undergo a phase transition due to pressure and have excellent adhesiveness than those having no sea-island structure.
According to the invention according to <11>, it is possible to provide pressure-responsive particles that are more likely to undergo a phase transition due to pressure than when the average diameter of the island phase is more than 500 nm.
According to the invention according to <12>, the pressure responsiveness is more likely to undergo a phase transition due to pressure as compared with the case where the core portion has a core-shell structure containing only a styrene resin or a (meth) acrylic acid ester resin. Particles can be provided.
According to the invention according to <13>, it is possible to provide pressure-responsive particles that are more likely to undergo a phase transition due to pressure, as compared with the case where the shell layer does not contain a styrene resin and contains other resins.
According to the invention according to <14>, it is possible to provide pressure-responsive particles that are more likely to undergo a phase transition depending on the pressure, as compared with the case where the temperature showing a viscosity of 10000 Pa · s under a pressure of 4 MPa is over 90 ° C.

According to the invention according to <15>, a pressure response is obtained when a pressure-sensitive printed matter crimped using pressure-responsive particles is obtained, as compared with the case where the average primary particle diameter of the silica particles is less than 60 nm or more than 200 nm. Provided are pressure-responsive particles having better peelability between the layers of the sex particles.

According to the invention according to <16> or <17>, when the external addition amount of the silica particles is less than 0.1% by mass or more than 10% by mass with respect to the total mass of the pressure-responsive mother particles. In comparison, when a pressure-bonded printed matter crimped using the pressure-responsive particles is obtained, the pressure-responsive particles having better peelability between the pressure-responsive particle layers are provided.

According to the invention according to <18>, pressure-sensitive particles are used for pressure bonding as compared with pressure-responsive particles containing specific pressure-responsive mother particles and silica particles having an average primary particle diameter of less than 50 nm or more than 300 nm. A cartridge containing pressure-responsive particles having both adhesiveness and peelability between pressure-responsive particle layers when the pressure-sensitive printed matter is obtained is provided.

According to the invention according to <19> or <20>, the pressure-responsive particles are compared with the pressure-responsive particles containing the specific pressure-responsive mother particles and the silica particles having an average primary particle diameter of less than 50 nm or more than 300 nm. Provided is an apparatus for producing a printed matter to which pressure-responsive particles having both adhesiveness and peelability between pressure-responsive particle layers are applied when a crimped printed matter crimped using the above is obtained.

According to the invention according to <20> or <22>, the pressure-responsive particles are compared with the pressure-responsive particles containing the specific pressure-responsive mother particles and the silica particles having an average primary particle diameter of less than 50 nm or more than 300 nm. Provided is a method for producing a printed matter to which pressure-responsive particles having both adhesiveness and peelability between pressure-responsive particle layers are applied when a crimped printed matter crimped using the above is obtained.

It is the schematic which shows an example of the manufacturing apparatus of the printed matter which concerns on this embodiment. It is the schematic which shows another example of the printed matter manufacturing apparatus which concerns on this embodiment. It is the schematic which shows another example of the printed matter manufacturing apparatus which concerns on this embodiment.

Hereinafter, embodiments of the present invention will be described. These descriptions and examples exemplify the embodiments and do not limit the scope of the embodiments.

The numerical range indicated by using "~" in the present embodiment indicates a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively.

In the numerical range described stepwise in the present embodiment, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described stepwise in another stepwise. Good. Further, in the numerical range described in the present embodiment, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the embodiment.

In the present embodiment, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. ..

When the embodiment is described in the present embodiment with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. Further, the size of the members in each figure is conceptual, and the relative relationship between the sizes of the members is not limited to this.

In the present embodiment, each component may contain a plurality of applicable substances. When referring to the amount of each component in the composition in the present embodiment, if a plurality of substances corresponding to each component are present in the composition, the plurality of species present in the composition unless otherwise specified. Means the total amount of substances in.

In the present embodiment, a plurality of types of particles corresponding to each component may be contained. When a plurality of particles corresponding to each component are present in the composition, the particle size of each component means a value for a mixture of the plurality of particles present in the composition unless otherwise specified.

In the present embodiment, the notation "(meth) acrylic" means that either "acrylic" or "methacrylic" may be used.

In the present embodiment, a printed matter formed by folding and adhering facing surfaces of recording media, or a printed matter formed by adhering two or more recording media and facing each other is referred to as a "crimped printed matter".

The pressure-responsive particles according to the present embodiment contain a styrene resin containing styrene and other vinyl monomers as a polymerization component, and at least two (meth) acrylic acid esters as a polymerization component, and occupy the entire polymerization component (meth). ) Pressure-responsive mother particles containing a (meth) acrylic acid ester resin having a mass ratio of acrylic acid ester of 90% by mass or more, and silica particles having an average primary particle diameter of 50 nm or more and 300 nm or less. However, it has 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.

Conventionally, as a technique for obtaining a crimped printed matter, a technique for crimping a recording medium using pressure-responsive particles to obtain a crimped printed matter is known. The crimped printed matter using the pressure-responsive particles has a laminated structure in which the pressure-responsive particle layer and the recording medium are laminated in this order on the recording medium, and when the crimped printed matter is peeled off, the pressure response It is peeled off between the layers of the sex particles.

However, with conventional pressure-responsive particles, it has been difficult to achieve both adhesiveness and peelability between pressure-responsive particle layers when a pressure-bonded printed matter obtained by pressure-bonding using the pressure-responsive particles is obtained. Specifically, when trying to enhance the adhesiveness of the pressure-responsive particle layer, the conventional pressure-responsive particles may be separated between the layers of the recording medium without being separated between the pressure-responsive particle layers. In particular, when an image is formed on the crimping surface of the recording medium, the image may be transferred to the crimping facing surface when the image is peeled off between the layers of the recording medium.

On the other hand, the pressure-responsive particles according to the present embodiment have the above-mentioned structure, and when a crimped printed matter crimped using the pressure-responsive particles is obtained, the pressure-responsive particles have adhesiveness and peelability between the layers. Are compatible. This mechanism of action is not always clear, but can be estimated as follows.

(Estimation of mechanism of action regarding the adhesion of pressure-responsive particles)
The pressure-responsive particles according to the present embodiment exhibit thermal characteristics that "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". As a result, the phase transitions due to pressure. In the present embodiment, the pressure-responsive particles that undergo a phase transition due to pressure mean pressure-responsive particles that satisfy the following formula 1.

Equation 1 ... 10 ° C. ≤ T1-T2
In the formula 1, T1 is a temperature showing a viscosity of 10000 Pa · s under a pressure of 1 MPa, and T2 is a temperature showing a viscosity of 10000 Pa · s under a pressure of 10 MPa. How to obtain the temperature T1 and the temperature T2 will be described later.

The pressure-responsive particles according to the present embodiment include "a styrene resin containing styrene and other vinyl monomers as the polymerization component" and "at least two kinds of (meth) acrylic acid esters in the polymerization component, and the entire polymerization component contains. By including "a (meth) acrylic acid ester-based resin" in which the mass ratio of the (meth) acrylic acid ester is 90% by mass or more, the phase transition is easy due to pressure and the adhesiveness is excellent. The following is presumed as the mechanism.

Generally, since the styrene resin and the (meth) acrylic acid ester resin have low compatibility with each other, it is considered that both resins are contained in the pressure-responsive mother particles in a phase-separated state. Further, when the pressure-responsive mother particles are pressurized, the (meth) acrylic acid ester resin having a relatively low glass transition temperature first fluidizes, and the fluidization spreads to the styrene resin, and both resins fluidize. It is thought that. Further, both resins in the pressure-responsive mother particles are considered to form a phase-separated state again due to their low compatibility when they are fluidized by pressurization and then solidified under reduced pressure to form a resin layer. ..
A (meth) acrylic acid ester-based resin containing at least two types of (meth) acrylic acid esters as a polymerization component has (meth) acrylic acid because there are at least two types of ester groups bonded to the main chain. It is presumed that the molecular alignment in the solid state is lower than that of the ester homopolymer, and therefore it is easily fluidized by pressurization. Furthermore, when the mass ratio of the (meth) acrylic acid ester to the entire polymerized component is 90% by mass or more, at least two types of ester groups are present at high density, so that the degree of molecular alignment in the solid state is high. It is presumed to be lower and therefore more fluidized by pressurization. Therefore, the pressure-responsive particles according to the present embodiment are more easily fluidized by pressure than the pressure-responsive particles in which the (meth) acrylic acid ester-based resin is a homopolymer of (meth) acrylic acid ester, that is, by pressure. It is presumed that the phase transition is likely to occur.
Then, the (meth) acrylic acid ester-based resin containing at least two kinds of (meth) acrylic acid esters in the polymerization component and having a mass ratio of the (meth) acrylic acid ester to the entire polymerization component of 90% by mass or more is again used. Since the degree of molecular alignment is low even during solidification, it is presumed that the phase separation from the styrene resin becomes a minute phase separation. It is presumed that the smaller the phase separation state between the styrene resin and the (meth) acrylic acid ester resin, the higher the uniformity of the adhesive surface with respect to the object to be adhered, and the better the adhesiveness. Therefore, it is presumed that the pressure-responsive particles according to the present embodiment are superior in adhesiveness to the pressure-responsive particles in which the (meth) acrylic acid ester-based resin is a homopolymer of the (meth) acrylic acid ester.

(Estimation of the mechanism of action that improves the peelability between pressure-responsive particles)
The pressure-responsive particles according to the present embodiment include, in addition to the pressure-responsive mother particles having the above-mentioned properties, large-diameter silica particles having an average primary particle diameter of 50 nm or more and 300 nm or less as an external additive. When pressure-responsive particles having large-diameter silica particles are transferred to two or more surfaces in a recording medium and the two or more surfaces are overlapped and crimped, the large diameter is formed at the interface between the pressure-responsive particle layers that have been crimped. Silica particles tend to intervene. The interposition of the large-diameter silica particles tends to weaken the adhesiveness between the pressure-responsive particle layers. As a result, it is presumed that when the crimped printed matter crimped using the pressure-responsive particles according to the present embodiment is peeled off, the peelability between the pressure-responsive particle layers is excellent.

Further, as the pressure-responsive particles according to the present embodiment, for example, the pressure-responsive particles having large-diameter silica particles are transferred to the recording medium 1, and the recording medium 1 and another recording medium 2 are overlapped and pressure-bonded. In this case, the large-diameter silica particles tend to intervene at the interface between the pressure-responsive particle layer that has been crimped and the recording medium 2. The interposition of the large-diameter silica particles tends to weaken the adhesiveness between the pressure-responsive particle layer and the recording medium 2. As a result, it is presumed that when the crimped printed matter crimped using the pressure-responsive particles according to the present embodiment is peeled off, the peelability between the pressure-responsive particle layer and the recording medium 2 is also excellent.

≪Pressure responsive particles≫
Hereinafter, the pressure-responsive particles according to the present embodiment will be described in detail.
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 "at least 2". It means a (meth) acrylic acid ester-based resin containing a seed (meth) acrylic acid ester as a polymerization component and having a mass ratio of the (meth) acrylic acid ester to the entire polymerization component of 90% by mass or more.

The pressure-responsive particles according to the present embodiment include at least pressure-responsive mother particles and silica particles having an average primary particle diameter of 50 nm or more and 300 nm or less. The pressure-responsive particles according to the present embodiment may contain other components.

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

From the viewpoint of maintaining adhesiveness, the pressure-responsive mother particles preferably have a higher content of the styrene resin than the content of the (meth) acrylic acid ester resin. The content of the styrene resin is preferably 55% by mass or more and 80% by mass or less, more preferably 60% by mass or more and 75% by mass or less, based on the total content of the styrene resin and the (meth) acrylic acid ester resin. , 65% by mass or more and 70% by mass or less is more preferable.

-Styrene resin-
The pressure-responsive mother particles constituting the pressure-responsive particles according to the present embodiment contain a styrene-based resin containing styrene and other vinyl monomers as a polymerization component.

The mass ratio of styrene to the total polymerized components of the styrene resin is preferably 60% by mass or more, more preferably 70% by mass or more, from the viewpoint of suppressing the fluidization of pressure-responsive particles in a non-pressurized state. It is more preferably 75% by mass or more, more preferably 95% by mass or less, still more preferably 90% by mass or less, still more preferably 85% by mass or less, from the viewpoint of forming pressure-responsive particles that easily undergo a phase transition due to pressure.

Examples of other vinyl monomers other than styrene constituting the styrene resin include styrene-based monomers other than styrene and acrylic monomers.

Examples of styrene-based monomers other than styrene include vinylnaphthalene; α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-. Alkyl-substituted styrenes such as butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene; Aryl-substituted styrene such as p-phenylstyrene; alkoxy-substituted styrene such as p-methoxystyrene; halogen-substituted styrene such as p-chlorostyrene, 3,4-dichlorostyrene, p-fluorostyrene, 2,5-difluorostyrene; m -Nitro-substituted styrenes such as nitrostyrene, o-nitrostyrene, p-nitrostyrene; and the like. One type of styrene-based monomer may be used alone, or two or more types may be used in combination.

As the acrylic monomer, at least one acrylic monomer selected from the group consisting of (meth) acrylic acid and (meth) acrylic acid ester is preferable. 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 and the like can be mentioned. One type of acrylic monomer may be used alone, or two or more types may be used in combination.

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

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

Other vinyl monomers constituting the styrene resin include, for example, (meth) acrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl ethyl ketone, and the like, in addition to the styrene monomer and the acrylic monomer. Vinyl ketones such as vinylisopropenylketone; olefins such as isoprene, butene and butadiene; are also included.

The styrene resin preferably contains a (meth) acrylic acid ester as a polymerization component, and more preferably contains a (meth) acrylic acid alkyl ester, from the viewpoint of forming pressure-responsive particles that easily undergo a phase transition due to pressure. It is more preferable to contain a (meth) acrylic acid alkyl ester having 2 or more and 10 or less carbon atoms in the alkyl group, and a (meth) acrylic acid alkyl ester having 4 or more and 8 or less carbon atoms in the alkyl group. It is more preferable to contain at least one of n-butyl acrylate and 2-ethylhexyl acrylate. The styrene resin and the (meth) acrylic acid ester resin preferably contain the same type of (meth) acrylic acid ester as a polymerization component from the viewpoint of forming pressure-responsive particles that easily undergo a phase transition due to pressure.

The mass ratio of the (meth) acrylic acid ester to the total polymerized components of the styrene resin is preferably 40% by mass or less, preferably 30% by mass or less, from the viewpoint of suppressing the fluidization of the pressure-responsive particles in the unpressurized state. More preferably, it is 5% by mass or less, more preferably 25% by mass or less, and from the viewpoint of forming pressure-responsive particles that are easily phase-shifted by pressure, 5% by mass or more is more preferable, 10% by mass or more is more preferable, and 15% by mass or more. Is more preferable. As the (meth) acrylic acid ester here, a (meth) acrylic acid alkyl ester is preferable, and a (meth) acrylic acid alkyl ester having an alkyl group having 2 or more and 10 or less carbon atoms is more preferable, and the alkyl group has an alkyl group. A (meth) acrylic acid alkyl ester having 4 or more and 8 or less carbon atoms is more preferable.

The styrene resin preferably contains at least one of n-butyl acrylate and 2-ethylhexyl acrylate as the polymerization component, and the total of n-butyl acrylate and 2-ethylhexyl acrylate in the entire polymerization component of the styrene resin. The amount is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, depending on the pressure, from the viewpoint of suppressing the fluidization of the pressure-responsive particles in the unpressurized state. From the viewpoint of forming pressure-responsive particles that easily undergo a phase transition, 5% by mass or more is preferable, 10% by mass or more is more preferable, and 15% by mass or more is further preferable.

The weight average molecular weight of the styrene resin is preferably 3000 or more, more preferably 4000 or more, further preferably 5000 or more, depending on the pressure, from the viewpoint of suppressing the fluidization of pressure-responsive particles in a non-pressurized state. From the viewpoint of forming pressure-responsive particles that easily undergo a phase transition, 60,000 or less is preferable, 55,000 or less is more preferable, and 50,000 or less is further preferable.

In this embodiment, the weight average molecular weight of the resin is measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC is performed by using HLC-8120GPC manufactured by Tosoh as a GPC device, TSKgel SuperHM-M (15 cm) manufactured by Tosoh 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 from a monodisperse polystyrene standard sample.

The glass transition temperature of the styrene resin is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, from the viewpoint of suppressing the fluidization of pressure-responsive particles in a non-pressurized state. The temperature is more preferably 50 ° C. or higher, and from the viewpoint of forming pressure-responsive particles that easily undergo a phase transition due to pressure, the temperature is preferably 110 ° C. or lower, more preferably 100 ° C. or lower, and 90 ° C. or lower. Is even more preferable.

In the present embodiment, the glass transition temperature of the resin is obtained from the differential scanning calorimetry (DSC curve) obtained by performing differential scanning calorimetry (DSC). More specifically, it is obtained according to the "external glass transition start temperature" described in the method for determining the glass transition temperature of JIS K7121: 1987 "Method for measuring the transition temperature of plastics".

The glass transition temperature of the resin can be controlled by the type of polymerization component and the polymerization ratio. The glass transition temperature is lower as the density of flexible units such as methylene group, ethylene group and oxyethylene group contained in the main chain is higher, and the density of rigid units such as aromatic ring and cyclohexane ring contained in the main chain is higher. Tends to be high. In addition, the glass transition temperature tends to be lower as the density of aliphatic groups in the side chain increases.

In the present embodiment, the mass ratio of the styrene-based resin to the total pressure-responsive mother particles is preferably 55% by mass or more, preferably 60% by mass or more, from the viewpoint of suppressing the fluidization of the pressure-responsive particles in the unpressurized state. Mass% or more is more preferable, 65% by mass or more is further preferable, and from the viewpoint of forming pressure-responsive particles that easily undergo a phase transition due to pressure, 80% by mass or less is preferable, 75% by mass or less is more preferable, and 70% by mass or less. Is more preferable.

-(Meta) acrylic acid ester resin-
The pressure-responsive mother particles constituting the pressure-responsive particles according to the present embodiment contain at least two types of (meth) acrylic acid esters in the polymerization component, and the mass ratio of the (meth) acrylic acid ester to the total polymerization component is Contains 90% by mass or more of (meth) acrylic acid ester resin.

The mass ratio of the (meth) acrylic acid ester to the total polymerization component of the (meth) acrylic acid ester resin is 90% by mass or more, more preferably 95% by mass or more, further preferably 98% by mass or more, and 100% by mass. % Is more preferable.

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 and the like can be mentioned.

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

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

One type of (meth) acrylic acid ester may be used alone, or two or more types may be used in combination.

As the (meth) acrylic acid ester, a (meth) acrylic acid alkyl ester is preferable from the viewpoint of forming pressure-responsive particles that are easily phase-shifted by pressure and have excellent adhesiveness, and the alkyl group has 2 or more carbon atoms and is 10 or more. The number of (meth) acrylic acid alkyl esters is more preferable, and the number of (meth) acrylic acid alkyl esters having 4 or more and 8 or less carbon atoms of the alkyl group is more preferable, and n-butyl acrylate and 2-acrylic acid 2-. Ethylhexyl is particularly preferred. The styrene resin and the (meth) acrylic acid ester resin preferably contain the same type of (meth) acrylic acid ester as a polymerization component from the viewpoint of forming pressure-responsive particles that easily undergo a phase transition due to pressure.

The mass ratio of the (meth) acrylic acid alkyl ester to the total polymerization component of the (meth) acrylic acid ester-based resin is 90% by mass from the viewpoint of forming pressure-responsive particles that are easily phase-transferred by pressure and have excellent adhesiveness. The above is preferable, 95% by mass or more is more preferable, 98% by mass or more is further preferable, and 100% by mass is further preferable. As the (meth) acrylic acid alkyl ester here, a (meth) acrylic acid alkyl ester having an alkyl group having 2 or more and 10 or less carbon atoms is preferable, and the alkyl group has 4 or more and 8 or less carbon atoms. Certain (meth) acrylic acid alkyl esters are more preferred.

The mass ratio of the two types having the largest mass ratio among at least two types of (meth) acrylic acid esters contained as a polymerization component in the (meth) acrylic acid ester-based resin is a pressure that easily undergoes a phase transition due to pressure and has excellent adhesiveness. From the viewpoint of forming responsive particles, it is preferably 80:20 to 20:80, more preferably 70:30 to 30:70, and even more preferably 60:40 to 40:60.

Of the at least two (meth) acrylic acid esters contained as a polymerization component in the (meth) acrylic acid ester-based resin, the two having the largest mass ratio are preferably (meth) acrylic acid alkyl esters. As the (meth) acrylic acid alkyl ester here, a (meth) acrylic acid alkyl ester having an alkyl group having 2 or more and 10 or less carbon atoms is preferable, and the alkyl group has 4 or more and 8 or less carbon atoms. Certain (meth) acrylic acid alkyl esters are more preferred.

When the two types having the largest mass ratio among at least two types of (meth) acrylic acid esters contained as a polymerization component in the (meth) acrylic acid ester-based resin are (meth) acrylic acid alkyl esters, the two types (meth) The difference in the number of carbon atoms of the alkyl group of the (meth) acrylic acid alkyl ester is preferably 1 or more and 4 or less, preferably 2 or less, from the viewpoint of forming pressure-responsive particles that are easily transferred by pressure and have excellent adhesiveness. The number is more preferably 4 or less, and further preferably 3 or 4.

The (meth) acrylic acid ester resin preferably contains n-butyl acrylate and 2-ethylhexyl acrylate as polymerization components from the viewpoint of forming pressure-responsive particles that are easily phase-shifted by pressure and have excellent adhesiveness. Of the at least two (meth) acrylic acid esters contained as a polymerization component in the (meth) acrylic acid ester resin, the two having the largest mass ratio are n-butyl acrylate and 2-ethylhexyl acrylate. Is particularly preferable. The total amount of n-butyl acrylate and 2-ethylhexyl acrylate in the total polymerization component of the (meth) acrylic acid ester resin is preferably 90% by mass or more, more preferably 95% by mass or more, and 98% by mass or more. More preferably, 100% by mass is further preferable.

The (meth) acrylic acid ester-based resin may contain a vinyl monomer other than the (meth) acrylic acid ester as a polymerization component. Examples of vinyl monomers other than (meth) acrylic acid esters 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 methyl ketone, Vinyl ketones such as vinyl ethyl ketone and vinyl isopropenyl ketone; olefins such as isoprene, butene and butadiene; can be mentioned. These vinyl monomers may be used alone or in combination of two or more.

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

The weight average molecular weight of the (meth) acrylic acid ester resin is preferably 50,000 or more, more preferably 100,000 or more, and more preferably 12 or more, from the viewpoint of suppressing the fluidization of pressure-responsive particles in a non-pressurized state. More than 10,000 is more preferable, and from the viewpoint of forming pressure-responsive particles that easily undergo a phase transition due to pressure, 250,000 or less is preferable, 220,000 or less is more preferable, and 200,000 or less is further preferable.

The glass transition temperature of the (meth) acrylic acid ester resin is preferably 10 ° C. or lower, more preferably 0 ° C. or lower, from the viewpoint of forming pressure-responsive particles that easily undergo a phase transition with pressure. It is more preferably 10 ° C. or lower, and preferably −90 ° C. or higher, preferably −80 ° C. or higher, from the viewpoint of suppressing the fluidization of pressure-responsive particles in a non-pressurized state. More preferably, it is more preferably −70 ° C. or higher.

In the present embodiment, the mass ratio of the (meth) acrylic acid ester-based resin to the entire pressure-responsive mother particles is preferably 20% by mass or more, preferably 25% by mass, from the viewpoint of forming pressure-responsive particles that easily undergo a phase transition due to pressure. % Or more is more preferable, 30% by mass or more is further preferable, and from the viewpoint of suppressing fluidization of pressure-responsive particles in a non-pressurized state, 45% by mass or less is preferable, and 40% by mass or less is more preferable. , 35% by mass or less is more preferable.

In the present embodiment, the total amount of the styrene resin and the (meth) acrylic acid ester resin contained in the pressure-responsive mother particles is preferably 70% by mass or more, preferably 80% by mass or more, based on the entire pressure-responsive mother particles. Is more preferable, 90% by mass or more is further preferable, 95% by mass or more is further preferable, and 100% by mass is further preferable.

-Other resins-
The pressure-responsive mother particles may contain, for example, polystyrene; a non-vinyl resin such as an epoxy resin, a polyester resin, a polyurethane resin, a polyamide resin, a cellulose resin, a polyether resin, or a modified rosin; One of these resins may be used alone, or two or more of these resins may be used in combination.

-Various additives-
The pressure-responsive mother particles are, if necessary, a colorant (eg, pigment, dye), a mold release agent (eg, hydrocarbon wax; natural wax such as carnauba wax, rice wax, candelilla wax; montane wax; Etc. or mineral / petroleum wax; ester wax such as fatty acid ester and montanic acid ester), charge control agent and the like may be contained.

When the pressure-responsive particles according to the present embodiment are transparent pressure-responsive particles, the amount of the colorant in the pressure-responsive mother particles is 1.0% by mass or less with respect to the entire pressure-responsive mother particles. Preferably, the smaller the number, the more preferable, from the viewpoint of increasing the transparency of the pressure-responsive particles.

-Structure of pressure-responsive mother particles-
The internal structure of the pressure-responsive mother particles is preferably a sea-island structure, and the sea-island structure includes a sea phase containing a styrene resin and an island phase containing a (meth) acrylic acid ester-based resin dispersed in the sea phase. A sea-island structure having is preferable. The specific form of the styrene resin contained in the sea phase is as described above. The specific form of the (meth) acrylic acid ester resin contained in the island phase is as described above. An island phase that does not contain a (meth) acrylic acid ester resin may be dispersed in the sea phase.

When the pressure-responsive mother particle has a sea-island structure, the average diameter of the island phase is preferably 200 nm or more and 500 nm or less. When the mean diameter of the island phase is 500 nm or less, the pressure-responsive mother particles are likely to undergo a phase transition due to pressure, and when the mean diameter of the island phase is 200 nm or more, the mechanical strength required for the pressure-responsive mother particles (for example). , Strength that does not easily deform when stirred in the developer) is excellent. From these viewpoints, the average diameter of the island phase is more preferably 220 nm or more and 450 nm or less, and further preferably 250 nm or more and 400 nm or less.

As a method of controlling the mean diameter of the island phase of the sea-island structure within the above range, for example, in the method for producing pressure-responsive mother particles described later, the amount of (meth) acrylic acid ester-based resin is increased or decreased with respect to the amount of styrene-based resin. In the process of fusing and coalescing the agglomerated resin particles, the time for maintaining the high temperature is increased or decreased.

The sea-island structure is confirmed and the average diameter of the island fauna is measured by the following method.
The pressure-responsive particles are embedded in an epoxy resin, sections are prepared with a diamond knife or the like, and the prepared sections are stained with osmium tetroxide or ruthenium tetroxide in a desiccator. The stained section is observed with a scanning electron microscope (SEM). The sea phase and the island phase of the sea-island structure are distinguished by the shade due to the degree of dyeing of the resin with osmium tetroxide or ruthenium tetroxide, and the presence or absence of the sea-island structure is confirmed by using this. 100 island phases are randomly selected from the SEM image, the major axis of each island phase is measured, and the average value of 100 major axes is taken as the average diameter.

The pressure-responsive mother particle may be a pressure-responsive mother particle having a single-layer structure, or may be a pressure-responsive mother particle having a core-shell structure having a core portion and a shell layer covering the core portion. Good. From the viewpoint of suppressing the fluidization of the pressure-responsive particles in the unpressurized state, the pressure-responsive mother particles preferably have a core-shell structure.

When the pressure-responsive mother particles have a core-shell structure, the core portion preferably contains a styrene resin and a (meth) acrylic acid ester resin from the viewpoint of facilitating a phase transition due to pressure. Further, from the viewpoint of suppressing the fluidization of the pressure-responsive particles in the unpressurized state, it is preferable that the shell layer contains a styrene resin. 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.

When the pressure-responsive mother particles have a core-shell structure, it is preferable that the core portion 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 fauna is preferably in the above range. Further, in addition to the core portion having the above-mentioned structure, it is preferable that the shell layer contains a styrene resin. In this case, the sea phase of the core portion and the shell layer have a continuous structure, and the pressure-responsive mother particles are likely to undergo a phase transition due to pressure. The specific form of the styrene-based resin contained in the sea phase of the core portion and the shell layer is as described above. The specific form of the (meth) acrylic acid ester-based resin contained in the island phase of the core portion is as described above.

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

The average thickness of the shell layer is preferably 120 nm or more, more preferably 130 nm or more, further preferably 140 nm or more, from the viewpoint of suppressing deformation of the pressure-responsive mother particles, and from the viewpoint that the pressure-responsive mother particles are likely to undergo a phase transition due to pressure. It is preferably 550 nm or less, more preferably 500 nm or less, and even more preferably 400 nm or less.

The average thickness of the shell layer is measured by the following method.
The pressure-responsive particles are embedded in an epoxy resin, sections are prepared with a diamond knife or the like, and the prepared sections are stained with osmium tetroxide or ruthenium tetroxide in a desiccator. The stained section is observed with a scanning electron microscope (SEM). Ten cross sections of pressure-responsive mother particles were randomly selected from the SEM image, and the thickness of the shell layer was measured at 20 points for each pressure-responsive mother particle to calculate the average value, and the pressure-responsive mother particles were calculated. The average value of 10 particles is taken as the average thickness.

The volume average particle diameter (D50v) of the pressure-responsive mother particles is preferably 4 μm or more, more preferably 5 μm or more, further preferably 6 μm or more, and pressure-responsive depending on the pressure, from the viewpoint of ease of handling of the pressure-responsive mother particles. From the viewpoint that the entire sex mother particle is easily undergoing a phase transition, it is preferably 12 μm or less, more preferably 10 μm or less, and further preferably 9 μm or less.

The volume average particle diameter (D50v) of the pressure-responsive mother particles is measured using a Coulter Multisizer II (manufactured by Beckman Coulter) and an aperture having an aperture diameter of 100 μm. Pressure-responsive mother particles were added to 2 mL of a 5 mass% aqueous solution of sodium alkylbenzene sulfonate (0.5 mg or more and 50 mg or less) to disperse them, and then mixed with an electrolytic solution (ISOTON-II, manufactured by Beckman Coulter) of 100 mL or more and 150 mL or less. Disperse with a sonic disperser for 1 minute, and use the obtained dispersion as a sample. The particle size of 50,000 particles having a particle size of 2 μm or more and 60 μm or less in the sample is measured. The volume average particle size (D50v) is defined as the particle size that is cumulatively 50% in the volume-based particle size distribution calculated from the small diameter side.

[Silica particles]
The pressure-responsive particles according to the present embodiment are silica particles having an average primary particle diameter of 50 nm or more and 300 nm or less as an external additive (hereinafter, silica particles having an average primary particle diameter within the above range are referred to as “large-diameter silica particles”. Also referred to as). When the pressure-responsive particles contain large-diameter silica particles, the pressure-responsive particles are crimped using the pressure-responsive particles to achieve both adhesiveness and peelability between the pressure-responsive particle layers.

The large-diameter silica particles may be silica, that is, particles containing SiO ₂ as a main component, and may be crystalline or amorphous. Further, the large-diameter silica particles may be particles produced from a silicon compound such as water glass or alkoxysilane, or may be particles obtained by pulverizing quartz. Specifically, examples of the large-diameter silica particles include solgel silica particles; aqueous colloidal silica particles; alcoholic silica particles; fumed silica particles obtained by a vapor phase method and the like; molten silica particles; and the like. Among the above, the large-diameter silica particles preferably contain sol-gel silica particles from the viewpoint of further improving the peelability between the pressure-responsive particle layers.

Sol-gel silica particles are obtained, for example, as follows.
Tetraalkoxysilane (TMS) is added dropwise to an alkaline catalyst solution containing an alcohol compound and aqueous ammonia, and the tetraalkoxysilane is hydrolyzed and condensed to obtain a suspension containing sol-gel silica particles. The solvent is then removed from the suspension to give the granules. The granules are then dried to give sol-gel silica particles.

The average primary particle diameter of the large-diameter silica particles is 50 nm or more and 300 nm or less, preferably 55 nm or more and 280 nm or less, and more preferably 60 nm or more and 200 nm or less.

When a printed matter is pressure-bonded using pressure-responsive particles having large-diameter silica particles having an average primary particle diameter of 50 nm or more as an external additive, the large-diameter silica particles dispersed in the pressure-responsive particle layer allow the pressure-responsive particle layers to be laminated. It is considered that the peelability of the particles is improved.
When a printed matter is pressure-bonded using pressure-responsive particles having large-diameter silica particles having an average primary particle diameter of 300 nm or less as an external additive, the large-diameter silica particles dispersed in the pressure-responsive particle layer allow the pressure-responsive particle layers to be laminated. It is considered that the adhesiveness of the particles is easily maintained.

The method of setting the average primary particle size of the large-diameter silica particles within the above range is not particularly limited. There are methods to do this.

The particle diameter of the large-diameter silica particles is the diameter of a circle having the same area as the primary particle image (so-called circle equivalent diameter). Specifically, a pressure-responsive particle layer composed of pressure-responsive particles externally attached with large-diameter silica particles is observed with an SEM (Scanning Electron Microscope) device at an arbitrary magnification, and an electron microscope image is taken. For any silica particles in the obtained electron microscope image, the equivalent circle diameter is obtained by image analysis. This operation is performed on 100 arbitrary silica particles. Then, the particle diameter (50% diameter, D50v) that is cumulatively 50% from the small diameter side in the distribution based on the number of primary particle diameters of each large diameter silica particle is defined as the average primary particle diameter of the large diameter silica particles.

From the viewpoint of dispersibility, the average circularity of the large-diameter silica particles is preferably 0.85 or more and 0.99 or less, more preferably 0.86 or more and 0.98 or less, and 0.9 or more. It is more preferably 0.97 or less. Further, the average circularity of the large-diameter silica particles is preferably 0.99 or less from the viewpoint of manufacturing. Further, when the average circularity of the large-diameter silica particles is 0.85 or more, the large-diameter silica particles tend to be suppressed from being buried in the surface of the pressure-responsive mother particles.

The method of setting the average circularity of the large-diameter silica particles within the above range is not particularly limited. For example, when the large-diameter silica particles are sol-gel silica particles, the method is controlled by the amount of alkoxysilane added dropwise to the amount of the alkali catalyst solution. Techniques and the like can be mentioned.

The average circularity of the large-diameter silica particles is calculated by the following method.
The surface of the pressure responsive mother particle is observed at 40,000 times by a scanning electron microscope (SEM) to obtain an image of at least 100 large diameter silica particles on the outer edge of the pressure responsive mother particle. The obtained image of the large-diameter silica particles is analyzed using the image processing analysis software WinRof (manufactured by Mitani Shoji Co., Ltd.), and the circularity of each large-diameter silica particle is obtained by the following formula. In the following formula, A represents the projected area and PM represents the peripheral length. The arithmetic mean value of the circularity of each of the obtained large-diameter silica particles is defined as the average circularity of the large-diameter silica particles.
Circularity = Circle equivalent diameter Peripheral length / Peripheral length = [2 x (Aπ) ^1/2 ] / PM

The large-diameter silica particles may be hydrophobic large-diameter silica particles that have been subjected to a hydrophobic surface treatment. The hydrophobizing agent is not particularly limited, but a silicon-containing organic compound is preferable. Examples of the silicon-containing organic compound include an alkoxysilane compound, a silazane compound, and a silicone oil. These may be used alone or in combination of two or more.

Examples of the hydrophobizing agent include silazane compounds (for example, dimethyldisilazane, trimethyldisilazane, tetramethyldisilazane, pentamethyldisilazane, hexamethyldisilazane and the like). Among the above, 1,1,1,3,3,3-hexamethyldisilazane (HMDS) is preferable as the hydrophobizing agent for the sol-gel silica particles.

The amount of the hydrophobizing agent is preferably 10% by mass or more and 100% by mass or less, preferably 40% by mass or less, based on 100 parts by mass of the silica particles, for example, from the viewpoint of efficiently hydrophobizing the surface of the silica particles. More preferably, it is% or more and 80% by mass or less.

When the large-diameter silica particles are hydrophobic large-diameter silica particles that have been subjected to a hydrophobic surface treatment, the average primary particle size of the large-diameter silica particles is the hydrophobic sol-gel silica particles after the hydrophobic surface treatment. Refers to the average primary particle size of.

The external addition amount of the large-diameter silica particles is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 5% by mass or less, based on the total mass of the pressure-responsive mother particles. More preferably, it is by mass% or more and 3% by mass or less.
When the external addition amount of the large-diameter silica particles is 0.1% by mass or more, the peelability between the pressure-responsive particle layers tends to be further improved. On the other hand, when the external addition amount of the large-diameter silica particles is 10% by mass or less, the decrease in adhesiveness between the pressure-responsive particle layers tends to be further suppressed.

[Other external additives]
Examples of the external additive other than the large-diameter silica particles (hereinafter, also simply referred to as “other external additives”) include inorganic particles. As inorganic particles, silica particles having an average primary particle diameter of less than 50 nm, TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO ₂ , CeO ₂ , Fe ₂ O ₃ , MgO, BaO, CaO, K ₂ O, Na _{2 O, ZrO 2, CaO · SiO} 2, K 2 O · (TiO 2) n, Al 2 O 3 · 2SiO 2, CaCO 3, MgCO 3, BaSO 4, MgSO 4 , and the like.

The surface of the inorganic particles as other external additives should be hydrophobized. The hydrophobizing treatment is performed, for example, by immersing the inorganic particles in the hydrophobizing agent. The hydrophobizing agent is not particularly limited, and examples thereof include a silane-based coupling agent, a silicone oil, a titanate-based coupling agent, and an aluminum-based coupling agent. These may be used alone or in combination of two or more. The amount of the hydrophobizing agent may be, 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.

Other external additives include resin particles (resin particles such as polystyrene, polymethylmethacrylate, and melamine resin), cleaning activators (for example, metal salts of higher fatty acids typified by zinc stearate, and fluoropolymers. Particles) and the like.

The amount of the external additive added is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.01% by mass or more and 2.0% by mass or less, based on the pressure-responsive mother particles.

[Characteristics of pressure-responsive particles]
When the pressure-responsive particles according to the present embodiment have at least two glass transition temperatures, one of the glass transition temperatures is presumed to be the glass transition temperature of the styrene resin, and the other is the (meth) acrylic acid ester-based. It is presumed to be the glass transition temperature of the resin.

The pressure-responsive particles according to the present embodiment may have three or more glass transition temperatures, but the number of glass transition temperatures is preferably two. The form in which the number of glass transition temperatures is two is that the resin contained in the pressure-responsive particles is only a styrene resin and a (meth) acrylic acid ester resin; a styrene resin and a (meth) acrylic acid ester. A form in which the content of other resins other than the styrene resin is low (for example, a form in which the content of the other resin is 5% by mass or less with respect to the total pressure-responsive particles);

The pressure-responsive particles according to the present 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. The difference between the lowest glass transition temperature and the highest glass transition temperature is more preferably 40 ° C. or higher, still more preferably 50 ° C. or higher, still more preferably 50 ° C. or higher, from the viewpoint that pressure-responsive particles are likely to undergo a phase transition due to pressure. Is 60 ° C. or higher. The upper limit of the difference between the lowest glass transition temperature and the highest glass transition temperature is, for example, 140 ° C. or lower, 130 ° C. or lower, and 120 ° C. or lower.

The lowest glass transition temperature exhibited by the pressure-responsive particles according to the present embodiment is preferably 10 ° C. or lower, more preferably 0 ° C. or lower, from the viewpoint that the pressure-responsive particles are likely to undergo a phase transition due to pressure. , −10 ° C. or lower, and preferably −90 ° C. or higher, preferably −80 ° C. or higher, from the viewpoint of suppressing the fluidization of pressure-responsive particles in a non-pressurized state. More preferably, it is more preferably −70 ° C. or higher.

The highest glass transition temperature exhibited by the pressure-responsive particles according to the present embodiment is preferably 30 ° C. or higher, preferably 40 ° C. or higher, from the viewpoint of suppressing the fluidization of the pressure-responsive particles in the unpressurized state. The temperature is more preferably 70 ° C. or higher, more preferably 50 ° C. or higher, and from the viewpoint that pressure-responsive particles are likely to undergo a phase transition due to pressure, the temperature is preferably 70 ° C. or lower, more preferably 65 ° C. or lower. It is preferably 60 ° C. or lower, and more preferably 60 ° C. or lower.

In the present embodiment, the glass transition temperature of the pressure-responsive particles is obtained from the differential scanning calorimetry (DSC curve) obtained by performing differential scanning calorimetry (DSC). More specifically, it is obtained according to the "external glass transition start temperature" described in the method for determining the glass transition temperature of JIS K7121: 1987 "Method for measuring the transition temperature of plastics".

The pressure-responsive particles according to the present embodiment are pressure-responsive particles that undergo a phase transition due to pressure, and satisfy the following formula 1.
Equation 1 ... 10 ° C. ≤ T1-T2
In the formula 1, T1 is a temperature showing a viscosity of 10000 Pa · s under a pressure of 1 MPa, and T2 is a temperature showing a viscosity of 10000 Pa · s under a pressure of 10 MPa.

The temperature difference (T1-T2) is 10 ° C. or higher, preferably 15 ° C. or higher, more preferably 20 ° C. or higher, and the pressure in a non-pressurized state from the viewpoint that pressure-responsive particles are easily phase-translated by pressure. From the viewpoint of suppressing the fluidization of the responsive particles, 120 ° C. or lower is preferable, 100 ° C. or lower is more preferable, and 80 ° C. or lower is further preferable.

The value of the temperature T1 is preferably 140 ° C. or lower, more preferably 130 ° C. or lower, further preferably 120 ° C. or lower, still more preferably 115 ° C. or lower. The lower limit of the temperature T1 is preferably 80 ° C. or higher, more preferably 85 ° C. or higher.
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.

As an index showing that pressure-responsive particles are likely to undergo a phase transition due to pressure, the temperature difference (T1-) between the temperature T1 having a viscosity of 10000 Pa · s under a pressure of 1 MPa and the temperature T3 having a viscosity of 10000 Pa · s under a pressure of 4 MPa (T1- T3) is mentioned, and the temperature difference (T1-T3) is preferably 5 ° C. or higher. The pressure-responsive particles according to the present embodiment preferably have a temperature difference (T1-T3) of 5 ° C. or higher, more preferably 10 ° C. or higher, from the viewpoint of easy phase transition due to pressure.
The temperature difference (T1-T3) is generally 25 ° C. or lower.

The pressure-responsive particles according to the present embodiment preferably have a temperature T3 of 90 ° C. or lower, which exhibits a viscosity of 10000 Pa · s under a pressure of 4 MPa, from the viewpoint that the temperature difference (T1-T3) is 5 ° C. or higher. It is more preferably ° C. or lower, and even more preferably 80 ° C. or lower. The lower limit of the temperature T3 is preferably 60 ° C. or higher.

The method for obtaining the temperature T1, the temperature T2 and the temperature T3 is as follows.
The pressure-responsive particles are compressed to prepare a pellet-shaped sample. A pellet-shaped sample is set in a flow tester (CFT-500 manufactured by Shimadzu Corporation), the applied pressure is fixed at 1 MPa, and the viscosity with respect to the temperature at 1 MPa is measured. From the graph of the resulting viscosity, at an applied pressure 1MPa to determine the temperature T1 at which becomes ¹⁰ 4 Pa · s. The temperature T2 is determined in the same manner as the method related to the temperature T1 except that the applied pressure of 1 MPa is 10 MPa. The temperature T3 is determined in the same manner as the method related to the temperature T1 except that the applied pressure of 1 MPa is 4 MPa. The temperature difference (T1-T2) is calculated from the temperature T1 and the temperature T2. The temperature difference (T1-T3) is calculated from the temperature T1 and the temperature T3.

[Manufacturing method of pressure-responsive particles]
The pressure-responsive particles according to the present embodiment can be obtained by externally adding an external additive to the pressure-responsive mother particles after producing the pressure-responsive mother particles.

The pressure-responsive mother particles may be produced by any of a dry production method (for example, a kneading and pulverizing method) and a wet production method (for example, an agglomeration coalescence method, a suspension polymerization method, a dissolution suspension method, etc.). There are no particular restrictions on these manufacturing methods, and known manufacturing methods are adopted. Among these, it is preferable to obtain pressure-responsive mother particles by the aggregation and coalescence method.

When the pressure-responsive mother 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 (styrene-based resin particle dispersion liquid preparation step) and
A step of polymerizing a (meth) acrylic acid ester resin in a styrene resin particle dispersion to form composite resin particles containing the styrene resin and the (meth) acrylic acid ester resin (composite resin particle forming step). ,
A step of aggregating the composite resin particles in a composite resin particle dispersion liquid in which the composite resin particles are dispersed to form agglomerated particles (aggregated particle forming step).
The pressure-responsive mother particles are formed through a step of heating the agglomerated particle dispersion liquid in which the agglomerated particles are dispersed and fusing and coalescing the agglomerated particles to form a pressure-responsive mother particle (fusion and coalescence step). To manufacture.

The details of each step will be described below.
In the following description, a method for obtaining pressure-responsive mother particles containing no colorant and release agent will be described. Colorants, mold release agents, and other additives may be used as needed. When the pressure-responsive mother particles contain a colorant and a mold release agent, the composite resin particle dispersion liquid, the colorant particle dispersion liquid, and the release agent particle dispersion liquid are mixed, and then the fusion / coalescence step is performed. The colorant particle dispersion and the release agent particle dispersion can be produced, for example, by mixing the materials and then performing a dispersion treatment using a known disperser.

-Styrene-based resin particle dispersion preparation process-
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 with a surfactant.

Examples of the dispersion medium include water-based media such as water and alcohols. These may be used alone or in combination of two or more.

Examples of the surfactant include anionic surfactants such as sulfate ester type, sulfonate type, phosphoric acid ester type and soap type; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol. Examples thereof include nonionic surfactants such as systems, alkylphenol ethylene oxide adducts, and polyhydric alcohols. The nonionic surfactant may be used in combination with an anionic surfactant or a cationic surfactant. Among these, anionic surfactants are preferable. The surfactant may be used alone or in combination of two or more.

As a method of dispersing the styrene resin particles in the dispersion medium, for example, the styrene resin and the dispersion medium are mixed and stirred and dispersed using a rotary shear type homogenizer, a ball mill having a medium, a sand mill, a dyno mill, or the like. The method can be mentioned.

As another method of dispersing the styrene resin particles in the dispersion medium, an emulsion polymerization method can be mentioned. Specifically, after mixing the polymerization component of the styrene resin with the chain transfer agent or the polymerization initiator, an aqueous medium containing a surfactant is further mixed and stirred to prepare an emulsion, which is contained in the emulsion. Polymerize the styrene resin in. At this time, it is preferable to use dodecanethiol as the chain transfer agent.

The volume average particle size of the styrene resin particles dispersed in the styrene 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 further preferably 150 nm or more and 200 nm or less.
The volume average particle size of the resin particles contained in the resin particle dispersion is measured by a laser diffraction type particle size distribution measuring device (for example, LA-700 manufactured by Horiba Seisakusho), and the particle size is based on the volume calculated from the small diameter side. The particle size that is cumulatively 50% in the distribution is defined as the volume average particle size (D50v).

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

-Composite resin particle forming process-
The styrene resin particle dispersion liquid and the polymer component of the (meth) acrylic acid ester resin are mixed, and the (meth) acrylic acid ester resin is polymerized in the styrene resin particle dispersion liquid to form the styrene resin and the (meth) resin. Form composite resin particles containing an acrylic acid ester resin.

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

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

Although the detailed mechanism is not always clear, when the above method is adopted, the monomer and the polymerization initiator are impregnated in the styrene resin particles, and the (meth) acrylic acid ester is polymerized inside the styrene resin particles. It is presumed that. As a result, the (meth) acrylic acid ester-based resin is contained inside the styrene-based resin particles, and the styrene-based resin and the (meth) acrylic acid ester-based resin form a microphase-separated state inside the particles. It is presumed that the composite resin particles are obtained.

The volume average particle diameter 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 further preferably 160 nm or more and 250 nm or less.

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

-Agglomerated particle formation process-
The composite resin particles are agglomerated in the composite resin particle dispersion to form agglomerated particles having a diameter close to the diameter of the target pressure-responsive mother particles.

Specifically, for example, a flocculant was added to the composite resin particle dispersion, the pH of the composite resin particle dispersion was adjusted to acidic (for example, pH 2 or more and 5 or less), and a dispersion stabilizer was added as necessary. After that, the composite resin particles are agglomerated by heating to a temperature close to the glass transition temperature of the styrene resin (specifically, for example, the glass transition temperature of the styrene resin is -30 ° C or higher and the glass transition temperature is -10 ° C or lower). , Form agglomerated particles.

In the agglomerated particle forming step, the composite resin particle dispersion is stirred with a rotary shear type homogenizer, a flocculant is added at room temperature (for example, 25 ° C.), and the pH of the composite resin particle dispersion is acidic (for example, pH 2 or more and 5 or less). If necessary, a dispersion stabilizer may be added, and then heating may be performed.

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 valent 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.
An additive that forms a complex or a similar bond with the metal ion of the flocculant may be used together with the flocculant, if necessary. As this additive, a chelating agent is preferably used.

Examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride and aluminum sulfate; and inorganic metal salts such as polyaluminum chloride, polyaluminum hydroxide and calcium polysulfide. Polymers; and the like.
As the chelating agent, a water-soluble chelating agent may be used. Examples of the chelating agent include oxycarboxylic acids such as tartaric acid, citric acid and gluconic acid; aminocarboxylic acids such as iminodioic acid vinegar (IDA), nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid (EDTA); Be done.
The amount of the chelating agent added is preferably 0.01 parts by mass or more and 5.0 parts by mass or less, and more preferably 0.1 parts by mass or more and less than 3.0 parts by mass with respect to 100 parts by mass of the resin particles.

-Fusion / unification process-
Next, the agglomerated particle dispersion liquid in which the agglomerated particles are dispersed is heated to, for example, a temperature equal to or higher than the glass transition temperature of the styrene resin (for example, a temperature 10 ° C. to 30 ° C. higher than the glass transition temperature of the styrene resin) to obtain the agglomerated particles. Are fused and united to form a pressure-responsive mother particle.

The pressure-responsive mother particles obtained through the above steps usually have a sea-island structure having a sea phase containing a styrene resin and an island phase containing a (meth) acrylic acid ester-based resin dispersed in the sea phase. Have. In the composite resin particles, the styrene resin and the (meth) acrylic acid ester resin were in a microphase-separated state, but in the fusion / union step, the styrene resins gathered together to form a sea phase (meth). ) It is presumed that the acrylic acid ester resins gather together to form an island phase.

The average diameter of the island phase of the sea-island structure is, for example, increasing or decreasing the amount of the styrene-based resin particle dispersion liquid used in the composite resin particle forming step or the amount of at least two (meth) acrylic acid esters, fusion and coalescence. It can be controlled by increasing or decreasing the time for maintaining the high temperature in the process.

Pressure-responsive mother particles of core-shell structure are, for example,
After obtaining the agglomerated particle dispersion, the agglomerated particle dispersion and the styrene resin particle dispersion are further mixed and aggregated so that the styrene resin particles are further adhered to the surface of the agglomerated particles to form the second agglomerated particles. The process of forming and
A step of heating the second agglomerated particle dispersion liquid in which the second agglomerated particles are dispersed to fuse and coalesce the second agglomerated particles to form a pressure-responsive mother particle having a core-shell structure.
Manufactured via.
The pressure-responsive mother particles having a core-shell structure obtained through the above steps have a shell layer containing a styrene resin. Instead of the styrene-based resin particle dispersion liquid, a resin particle dispersion liquid in which other types of resin particles are dispersed may be used to form a shell layer containing another type of resin.

After completion of the fusion / coalescence step, the pressure-responsive mother particles formed in the solution are subjected to a known washing step, solid-liquid separation step, and drying step to obtain a dried pressure-responsive mother particles. In the cleaning step, from the viewpoint of chargeability, it is preferable to sufficiently perform replacement cleaning with ion-exchanged water. In the solid-liquid separation step, suction filtration, pressure filtration and the like may be performed from the viewpoint of productivity. From the viewpoint of productivity, the drying step may be freeze-dried, air-flow-dried, fluid-dried, vibrating fluid-dried or the like.

The pressure-responsive particles according to the present embodiment are produced, for example, by adding an external additive to the obtained dry pressure-responsive mother particles and mixing them. The mixing may be carried out by, for example, a V blender, a Henschel mixer, a Ladyge mixer or the like. Further, if necessary, coarse particles of pressure-responsive particles may be removed by using a vibration sieving machine, a wind sieving machine, or the like.

<Printed matter manufacturing equipment, printed matter manufacturing method, printed matter>
The printed matter manufacturing apparatus according to the present embodiment accommodates the pressure-responsive particles according to the present embodiment, and folds and crimps the recording medium with an arrangement means for arranging the pressure-responsive particles on the recording medium. Alternatively, the crimping means for superimposing and crimping the recording medium and another recording medium is included.

The arranging means includes, for example, an applying device for applying pressure-responsive particles on the recording medium and a fixing device for fixing the pressure-responsive particles applied on the recording medium on the recording medium.

The crimping means includes, for example, a folding device for folding a recording medium on which pressure-responsive particles are arranged, or a stacking device for stacking a recording medium on which pressure-responsive particles are arranged and another recording medium, and an overlapping recording medium. It is provided with a pressurizing device for pressurizing.

The pressurizing device provided by the crimping means applies pressure to a recording medium on which pressure-responsive particles are arranged. As a result, the pressure-responsive particles are fluidized on the recording medium and exhibit adhesiveness.
The pressure applied to the recording medium by the crimping means is preferably 3 MPa or more and 300 MPa or less, more preferably 10 MPa or more and 200 MPa or less, and further preferably 30 MPa or more and 150 MPa or less.

The printed matter manufacturing apparatus according to the present embodiment implements the printed matter manufacturing method 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, arranges the pressure-responsive particles on a recording medium, and folds and crimps the recording medium. Alternatively, the crimping step of superimposing and crimping the recording medium and another recording medium is included.

The arrangement step includes, for example, a step of applying the pressure-responsive particles on the recording medium and a step of fixing the pressure-responsive particles applied on the recording medium on the recording medium.

The crimping step includes, for example, a folding step of folding the recording medium, a stacking step of stacking the recording medium and another recording medium, and a pressurizing step of pressurizing the overlapping recording media.

The pressure-responsive particles may be arranged on the entire surface of the recording medium or may be arranged on a part of the recording medium. The pressure-responsive particles are arranged in one or more layers on the recording medium. The layer of the pressure-responsive particles may be a layer continuous in the plane direction of the recording medium or a layer discontinuous in the plane direction of the recording medium. The layer of the pressure-responsive particles 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 and arranged.

The amount of pressure-responsive particles (preferably transparent pressure-responsive particles) on the recording medium is, for example, 0.5 g / m ² or more and 50 g / m ² or less and 1 g / m ² or more in the arranged region. It is 40 g / m ² or less, and 1.5 g / m ² or more and 30 g / m ² or less. The layer thickness of the pressure-responsive particles (preferably transparent pressure-responsive particles) on the recording medium is, for example, 0.2 μm or more and 25 μm or less, 0.4 μm or more and 20 μm or less, and 0.6 μm or more and 15 μm or less. is there.

Examples of the recording medium applied to the printed matter manufacturing apparatus according to the present embodiment include paper, coated paper in which the surface of the paper is coated with resin or the like, cloth, non-woven fabric, resin film, resin sheet, and the like. The recording medium may have an image on one side or both sides.

Hereinafter, an example of a printed matter manufacturing apparatus according to the present embodiment will be shown, but the present embodiment is not limited to this.

FIG. 1 is a schematic configuration diagram showing an example of a printed matter manufacturing apparatus according to the present embodiment. The printed matter manufacturing apparatus shown in FIG. 1 includes an arrangement means 100 and a crimping means 200 arranged downstream of the arrangement means 100. The arrow indicates the transport direction of the recording medium.

The arranging means 100 is an apparatus for arranging the pressure responsive particles on the recording medium P by using the pressure responsive particles according to the present embodiment. An image is formed in advance on one side or both sides of the recording medium P.

The arranging means 100 includes a granting device 110 and a fixing device 120 arranged downstream of the granting device 110.

The applying device 110 applies the pressure-responsive particles M onto the recording medium P. Examples of the applying method adopted by the applying device 110 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, and a laminating method. Examples include 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.

The recording medium P to which the pressure-responsive particles M are attached by the applying device 110 is conveyed to the fixing device 120.

The fixing device 120 includes, for example, a heating device that includes a heating source, heats the pressure-responsive particles M on the passing recording medium P, and fixes the pressure-responsive particles M on the recording medium P; a pair of pressurizing members ( A pressurizing device provided with a roll / roll, a belt / roll, pressurizing a passing recording medium P, and fixing pressure-responsive particles M on the recording medium P; a pair of pressurizing members (rolls) having a heating source inside. / Roll, belt / roll), a pressure heating device that pressurizes and heats the passing recording medium P, and fixes the pressure-responsive particles M on the recording medium P; and the like.

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

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

By passing through the arrangement means 100, the recording medium P becomes the recording medium P1 to which the pressure-responsive particles M are added on the image. The recording medium P1 is conveyed toward the crimping means 200.

In the printed matter manufacturing apparatus according to the present embodiment, the arranging means 100 and the crimping means 200 may be in close proximity to each other or may be separated from each other. When the arrangement means 100 and the crimping means 200 are separated from each other, the arrangement means 100 and the crimping means 200 are connected by, for example, a conveying means (for example, a belt conveyor) that conveys the recording medium P1.

The crimping means 200 includes a folding device 220 and a pressurizing device 230, and is a means for folding and crimping the recording medium P1.

The folding device 220 folds the recording medium P1 that passes through the device to produce the folded recording medium P2. The folding method of the recording medium P2 is, for example, two-fold, three-fold, or four-fold, and a form in which only a part of the recording medium P2 is folded may be used. The recording medium P2 is in a state in which the pressure-responsive particles M are arranged on at least a part of at least one of the two opposing surfaces.

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

The crimping means 200 may include a stacking device for stacking the recording medium P1 and another recording medium instead of the folding device 220. The overlapping form of the recording medium P1 and another recording medium is, for example, a form in which one other recording medium is overlapped on the recording medium P1, and another recording medium is placed at a plurality of locations on the recording medium P1. These are overlapping forms. The other recording medium may be a recording medium in which an image is formed in advance on one side or both sides, a recording medium in which an image is not formed, or a pressure-bonded printed matter prepared in advance.

The recording medium P2 exiting the folding device 220 (or the stacking device) is conveyed toward the pressurizing device 230.

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

When pressure is applied to the recording medium P2 passing through the pressurizing device 230, the pressure-responsive particles M are fluidized by the pressure on the recording medium P2 to exhibit adhesiveness.

The pressurizing device 230 may or may not have a heating source (for example, a halogen heater) for heating the recording medium P2 inside. The fact that the pressurizing device 230 does not have a heating source inside does not exclude that the temperature inside the pressurizing device 230 becomes equal to or higher than the ambient temperature due to heat generated by the motor or the like included in the pressurizing device 230.

When the recording medium P2 passes through the pressurizing device 230, the folded surfaces are adhered to each other by the fluidized pressure-responsive particles M, and the crimped printed matter P3 is produced. In the pressure-bonded printed matter P3, two facing surfaces are partially or wholly adhered to each other.

The completed crimped printed matter P3 is carried out from the pressurizing device 230.

The first form of the crimped printed matter P3 is a crimped printed matter in which the folded recording medium is adhered by the pressure-responsive particles M on the facing surfaces. The crimped printed matter P3 of this embodiment is manufactured by a printed matter manufacturing apparatus including a folding device 220.

A second form of the crimped printed matter P3 is a crimped printed matter in which a plurality of overlapping recording media are adhered to each other by pressure-responsive particles M on opposite surfaces. The crimped printed matter P3 of this embodiment is manufactured by a crimped printed matter manufacturing apparatus including a stacking device.

The printed matter manufacturing apparatus according to the present embodiment is not limited to the apparatus in which the recording medium P2 is continuously conveyed from the folding device 220 (or the stacking device) to the pressurizing device 230. The printed matter manufacturing apparatus according to the present embodiment stores the recording medium P2 that has exited the folding device 220 (or the stacking device), and after the storage amount of the recording medium P2 reaches a predetermined amount, the recording medium P2 is stored. The device may be in the form of being conveyed to the pressurizing device 230.

In the printed matter manufacturing apparatus according to the present embodiment, the folding apparatus 220 (or the stacking apparatus) and the crimping pressurizing apparatus 230 may be in close proximity to each other or may be separated from each other. When the folding device 220 (or the stacking device) and the crimping pressurizing device 230 are separated from each other, the folding device 220 (or the stacking device) and the crimping pressurizing device 230 are, for example, a transport means for transporting the recording medium P2. For example, they are connected by a belt conveyor).

The printed matter manufacturing apparatus according to the present embodiment may include a cutting means for cutting the recording medium to a predetermined size. The cutting means is arranged, for example, between the arranging means 100 and the crimping means 200, and cuts off a region which is a part of the recording medium P1 and where the pressure-responsive particles M are not arranged; the folding device 220 and the addition. Cutting means arranged between the pressure device 230 and a part of the recording medium P2 where the pressure-responsive particles M are not arranged; a cutting means arranged downstream of the crimping means 200 and a part of the crimping printed matter P3. A cutting means for cutting off a region that is not adhered by the pressure-responsive particles M; and the like.

The printed matter manufacturing apparatus according to the present embodiment is not limited to the sheet-fed type apparatus. The printed matter manufacturing apparatus according to the present embodiment performs an arrangement step and a crimping step on a long recording medium to form a long crimped printed matter, and then cuts the long crimped printed matter to a predetermined size. It may be a device in the style of

The printed matter manufacturing apparatus according to the present embodiment may further include a colored image forming means for forming a colored image on a recording medium using a coloring material. The colored image forming means is, for example, a means for forming a colored ink image on a recording medium by an inkjet method using a colored ink as a coloring material, or a means for forming a colored ink image on a recording medium by an electrophotographic method using a colored electrostatic charge image developer. Means for forming a colored image and the like can be mentioned.

With the manufacturing apparatus having the above configuration, the manufacturing method according to the present embodiment, further including a colored image forming step of forming a colored image on a recording medium using a coloring material, is carried out. Specifically, the colored image forming step is, for example, a step of forming a colored ink image on a recording medium by an inkjet method using a colored ink as a coloring material, and an electrophotographic method using a colored electrostatic charge image developer. Examples thereof include a step of forming a colored image on a recording medium.

<Manufacturing printed matter by electrophotographic method>
An example of an embodiment in which the pressure-responsive particles according to the present embodiment are applied to the electrophotographic method will be described. In electrophotographic schemes, pressure responsive particles correspond to toner.

(Static charge image developer)
The electrostatic charge image developer according to the present embodiment contains at least the pressure-responsive particles according to the present embodiment. The electrostatic charge 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 the pressure-responsive particles according to the present embodiment and carriers are mixed. It may be a two-component developer.

The carrier is not particularly limited, and examples thereof include known carriers. As the carrier, for example, a coating 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 the magnetic powder is dispersed in a matrix resin; and a porous magnetic powder is impregnated with the resin. Resin-impregnated carrier; etc. The magnetic powder dispersion type carrier and the resin impregnation type carrier may be carriers in which the constituent particles of the carrier are used as a core material and the surface thereof is coated with a resin.

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

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

Examples of coating the surface of the core material with a resin include a method of coating with a coating resin and a coating layer forming solution in which various additives (used if necessary) are dissolved in an appropriate solvent. The solvent is not particularly limited, and may be selected in consideration of the type of resin used, coating suitability, and the like.
Specific resin coating methods include a dipping method in which the core material is immersed in a coating layer forming solution; a spray method in which the coating layer forming solution is sprayed onto the core material surface; and the core material is suspended by flowing air. Examples thereof include a fluidized bed method in which a coating layer forming solution is sprayed; a kneader coater method in which a carrier core material and a coating layer forming solution are mixed in a kneader coater, and then the solvent is removed.

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

(Printed matter manufacturing equipment, printed matter manufacturing method)
The printed matter manufacturing apparatus according to the present embodiment accommodates a developing agent containing the pressure-responsive particles according to the present embodiment, and arranges the pressure-responsive particles on a recording medium by an electrophotographic method, and the recording. The medium includes a crimping means for folding and crimping the medium, or stacking and crimping the recording medium and another recording medium.

The printed matter manufacturing apparatus according to the present embodiment implements a printed matter manufacturing method by an electrophotographic method.

The method for producing a printed matter according to the present embodiment includes an arrangement step of arranging the pressure-responsive particles on a recording medium by an electrophotographic method using a developer containing the pressure-responsive particles according to the present embodiment, and the recording. It includes a crimping step of folding and crimping a medium, or stacking and crimping the recording medium and another recording medium.

The arrangement means included in the printed matter manufacturing apparatus according to the present embodiment is, for example,
Photoreceptor and
A charging means for charging the surface of the photoconductor and
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged photoconductor, and
A developing means that accommodates the electrostatic charge image developer according to the present embodiment and develops the electrostatic charge image formed on the surface of the photoconductor as a pressure-responsive particle imparting portion by the electrostatic charge image developer.
A transfer means for transferring the pressure-responsive particle-imparting portion formed on the surface of the photoconductor to the surface of the recording medium, and
To be equipped.
It is preferable that the arranging means further includes a fixing means for fixing the pressure-responsive particle-imparting portion transferred to the surface of the recording medium.

The arrangement step included in the method for producing a printed matter according to the present embodiment is, for example,
The charging process that charges the surface of the photoconductor,
A static charge image forming step of forming an electrostatic charge image on the surface of the charged photoconductor, and
A developing step of developing an electrostatic charge image formed on the surface of the photoconductor as a pressure-responsive particle-imparting portion by using the electrostatic charge image developer according to the present embodiment.
A transfer step of transferring the pressure-responsive particle-imparting portion formed on the surface of the photoconductor to the surface of the recording medium, and
including.
It is preferable that the arrangement step further includes a fixing step of fixing the pressure-responsive particle-imparting portion transferred to the surface of the recording medium.

The arrangement means is, for example, a direct transfer type device that directly transfers the pressure-responsive particle-imparting portion formed on the surface of the photoconductor to a recording medium; the pressure-responsive particle-imparting portion formed on the surface of the photoconductor is intermediate. An intermediate transfer type device that first transfers to the surface of the transfer body and secondarily transfers the pressure-responsive particle-imparting portion transferred to the surface of the intermediate transfer body to the surface of the recording medium; after the transfer of the pressure-responsive particle-imparting portion, A device equipped with a cleaning means for cleaning the surface of the photoconductor before charging; a device provided with a static elimination means for irradiating the surface of the photoconductor with static elimination light after transfer of the pressure-responsive particle-imparting portion and before charging; It is a device of. When the arrangement means is an intermediate transfer type apparatus, the transfer means includes, for example, an intermediate transfer body in which the pressure-responsive particle-imparting portion is transferred to the surface and a pressure-responsive particle-imparting portion formed on the surface of the photoconductor. It has a primary transfer means for primary transfer to the surface of the intermediate transfer body, and a secondary transfer means for secondary transfer of the pressure-responsive particle-imparting portion transferred to the surface of the intermediate transfer body to the surface of the recording medium.

The arrangement means may have a cartridge structure (so-called process cartridge) in which a portion including the developing means is attached to and detached from the arrangement means. As the process cartridge, for example, a process cartridge containing the electrostatic charge image developer according to the present embodiment and provided with developing means is preferably used.

The crimping 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. As a result, the pressure-responsive particles according to the present embodiment flow on the recording medium and exhibit adhesiveness. The pressure applied to the recording medium by the pressure-bonding means 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 further preferably 30 MPa or more and 150 MPa or less.

The pressure-responsive particles according to the present embodiment may be arranged on the entire surface of the recording medium or may be arranged on a part of the recording medium. The pressure-responsive particles according to the present embodiment are arranged in one layer or a plurality of layers on a recording medium. The layer of the pressure-responsive particles according to the present embodiment may be a layer continuous in the plane direction of the recording medium or a layer discontinuous in the plane direction of the recording medium. The layer of the pressure-responsive particles according to the present embodiment may be a layer in which the pressure-responsive mother particles are arranged as particles, or may be a layer in which adjacent pressure-responsive mother particles are fused and arranged. Good.

The amount of the pressure-responsive particles according to the present embodiment on the recording medium, in the arrangement region, for example, 0.5 g / ^{m 2} or more 50 g / ^{m 2} or less, 1 g / ^{m 2} or more 40 g / ^{m 2} or less It is 1.5 g / m ² or more and 30 g / m ² or less. The layer thickness of the pressure-responsive particles according to the present embodiment on the recording medium is, for example, 0.2 μm or more and 25 μm or less, 0.4 μm or more and 20 μm or less, and 0.6 μm or more and 15 μm or less.

Examples of the recording medium applied to the printed matter manufacturing apparatus according to the present embodiment include paper, coated paper in which the surface of the paper is coated with resin or the like, cloth, non-woven fabric, resin film, resin sheet, and the like. The recording medium may have an image on one side or both sides.

Hereinafter, an example of a printed matter manufacturing apparatus according to the present embodiment to which the electrophotographic method is applied will be shown, but the present embodiment is not limited to this.

FIG. 2 is a schematic configuration diagram showing an example of a printed matter manufacturing apparatus according to the present embodiment. The printed matter manufacturing apparatus shown in FIG. 2 includes an arrangement means 100 and a crimping means 200 arranged downstream of the arrangement means 100. The arrow indicates the rotation direction of the photoconductor or the transport direction of the recording medium.

The arranging means 100 is a direct transfer type apparatus for arranging the pressure responsive particles according to the present embodiment on the recording medium P by an electrophotographic method using a developer containing the pressure responsive particles according to the present embodiment. .. An image is formed in advance on one side or both sides of the recording medium P.

The arranging means 100 has a photoconductor 101. Around the photoconductor 101, a charging roll (an example of charging means) 102 that charges the surface of the photoconductor 101, and an exposure apparatus (static) that exposes the surface of the charged photoconductor 101 with a laser beam to form a static charge image. Example of charge image forming means) 103, a developing device (an example of developing means) 104 that supplies pressure-responsive particles to an electrostatic charge image to develop an electrostatic charge image, and a developed pressure-responsive particle imparting portion on a recording medium P. A transfer roll (an example of a transfer means) 105 to be transferred to, and a photoconductor cleaning device (an example of a cleaning means) 106 for removing pressure-responsive particles remaining on the surface of the photoconductor 101 after transfer are arranged in this order.

The operation of the arranging means 100 arranging the pressure-responsive particles according to the present 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 surface of the charged photoconductor 101 with a laser beam according to image data sent from a control unit (not shown). As a result, an electrostatic charge image of the arrangement pattern of the pressure-responsive particles according to the present embodiment is formed on the surface of the photoconductor 101.

The electrostatic charge image formed on the photoconductor 101 rotates to the developing position as the photoconductor 101 travels. Then, at the developing position, the electrostatic charge image on the photoconductor 101 is developed and visualized by the developing device 104 to become a pressure-responsive particle imparting portion.

The developing apparatus 104 contains at least a developing agent containing pressure-responsive particles and carriers according to the present embodiment. The pressure-responsive particles according to the present embodiment are triboelectrically charged by being stirred together with the carrier inside the developing apparatus 104 and are held on the developing agent roll. As the surface of the photoconductor 101 passes through the developing device 104, the pressure-responsive particles are electrostatically attached 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-imparting portion of the pressure-responsive particles is formed continues to run, and the pressure-responsive particle-imparting portion developed on the photoconductor 101 is conveyed to the transfer position.

When the pressure-responsive particle-imparting portion on the photoconductor 101 is conveyed to the transfer position, a transfer bias is applied to the transfer roll 105, and an electrostatic force from the photoconductor 101 toward the transfer roll 105 acts on the pressure-responsive particle-imparting portion. Then, the pressure-responsive particle-imparting portion on the photoconductor 101 is transferred onto the recording medium P.

The pressure-responsive particles remaining on the photoconductor 101 are removed by the photoconductor cleaning device 106 and recovered. The photoconductor cleaning device 106 is, for example, a cleaning blade, a cleaning brush, or the like. The photoconductor cleaning device 106 is a cleaning brush from the viewpoint of suppressing the phenomenon that the pressure-responsive particles according to the present embodiment remaining on the surface of the photoconductor are fluidized by pressure and adhere to the surface of the photoconductor in the form of a film. Is preferable.

The recording medium P on which the pressure-responsive particle-imparting portion is transferred is conveyed to a fixing device (an example of fixing means) 107. The fixing device 107 is, for example, a pair of fixing members (roll / roll, belt / roll). The arranging means 100 may not be provided with the fixing device 107, but is preferably provided with the fixing device 107 from the viewpoint of suppressing the pressure-responsive particles according to the present embodiment from falling off from the recording medium P. .. The pressure applied to the recording medium P by the fixing device 107 may be lower than the pressure applied to the recording medium P2 by the pressurizing device 230, and specifically, it is preferably 0.2 MPa or more and 1 MPa or less.

The fixing device 107 may or may not have a heating source (for example, a halogen heater) for heating the recording medium P inside. When the fixing device 107 has a heating source inside, the surface temperature of the recording medium P when heated by the heating source is preferably 150 ° C. or higher and 220 ° C. or lower, more preferably 155 ° C. or higher and 210 ° C. or lower, and 160 ° C. or higher. More preferably 200 ° C. or lower. The fact that the fixing device 107 does not have a heating source inside does not exclude that the temperature inside the fixing device 107 becomes equal to or higher than the environmental temperature due to heat generated by the motor or the like included in the arrangement means 100.

By passing through the arrangement means 100, the recording medium P becomes the recording medium P1 to which the pressure-responsive particles according to the present embodiment are imparted on the image. The recording medium P1 is conveyed toward the crimping means 200.

In the printed matter manufacturing apparatus according to the present embodiment, the arranging means 100 and the crimping means 200 may be in close proximity to each other or may be separated from each other. When the arrangement means 100 and the crimping means 200 are separated from each other, the arrangement means 100 and the crimping means 200 are connected by, for example, a conveying means (for example, a belt conveyor) that conveys the recording medium P1.

The crimping means 200 includes a folding device 220 and a pressurizing device 230, and is a means for folding and crimping the recording medium P1.

The folding device 220 folds the recording medium P1 that passes through the device to produce the folded recording medium P2. The folding method of the recording medium P2 is, for example, two-fold, three-fold, or four-fold, and a form in which only a part of the recording medium P2 is folded may be used. The recording medium P2 is in a state in which the pressure-responsive particles according to the present embodiment are arranged on at least a part of at least one of the two opposing surfaces.

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

The crimping means 200 may include a stacking device for stacking the recording medium P1 and another recording medium instead of the folding device 220. The overlapping form of the recording medium P1 and another recording medium is, for example, a form in which one other recording medium is overlapped on the recording medium P1, and another recording medium is placed at a plurality of locations on the recording medium P1. These are overlapping forms. The other recording medium may be a recording medium in which an image is formed in advance on one side or both sides, a recording medium in which an image is not formed, or a pressure-bonded printed matter prepared in advance.

The recording medium P2 exiting the folding device 220 (or the stacking device) is conveyed toward the pressurizing device 230.

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

When pressure is applied to the recording medium P2 passing through the pressurizing device 230, the pressure-responsive particles according to the present embodiment are fluidized by the pressure on the recording medium P2 to exhibit adhesiveness. The pressure applied by the pressurizing 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 further preferably 30 MPa or more and 150 MPa or less.

The pressurizing device 230 may or may not have a heating source (for example, a halogen heater) for heating the recording medium P2 inside. When the pressurizing device 230 has a heating source inside, the surface temperature of the recording medium P2 when heated by the heating source is preferably 30 ° C. or higher and 120 ° C. or lower, more preferably 40 ° C. or higher and 100 ° C. or lower, and more preferably 50 ° C. More preferably 90 ° C. or lower. The fact that the pressurizing device 230 does not have a heating source inside does not exclude that the temperature inside the pressurizing device 230 becomes equal to or higher than the ambient temperature due to heat generated by the motor or the like included in the pressurizing device 230.

When the recording medium P2 passes through the pressurizing device 230, the folded surfaces are adhered to each other by the fluidized pressure-responsive particles according to the present embodiment, and the crimped printed matter P3 is produced. In the pressure-bonded printed matter P3, the facing surfaces are partially or wholly adhered to each other.

The completed crimped printed matter P3 is carried out from the pressurizing device 230.

The first form of the crimped printed matter P3 is a crimped printed matter in which the folded recording media are adhered to each other on the facing surfaces by the pressure-responsive particles according to the present embodiment. The crimped printed matter P3 of this embodiment is manufactured by a printed matter manufacturing apparatus including a folding device 220.

A second form of the crimped printed matter P3 is a crimped printed matter in which a plurality of overlapping recording media are adhered to each other on facing surfaces by the pressure-responsive particles according to the present embodiment. The crimped printed matter P3 of this embodiment is manufactured by a crimped printed matter manufacturing apparatus including a stacking device.

The printed matter manufacturing apparatus according to the present embodiment is not limited to the apparatus in which the recording medium P2 is continuously conveyed from the folding device 220 (or the stacking device) to the pressurizing device 230. The printed matter manufacturing apparatus according to the present embodiment stores the recording medium P2 that has exited the folding device 220 (or the stacking device), and after the storage amount of the recording medium P2 reaches a predetermined amount, the recording medium P2 is stored. The device may be in the form of being conveyed to the pressurizing device 230.

In the printed matter manufacturing apparatus according to the present embodiment, the folding apparatus 220 (or the stacking apparatus) and the crimping pressurizing apparatus 230 may be in close proximity to each other or may be separated from each other. When the folding device 220 (or the stacking device) and the crimping pressurizing device 230 are separated from each other, the folding device 220 (or the stacking device) and the crimping pressurizing device 230 are, for example, a transport means for transporting the recording medium P2. For example, they are connected by a belt conveyor).

The printed matter manufacturing apparatus according to the present embodiment may include a cutting means for cutting the recording medium to a predetermined size. The cutting means is arranged, for example, between the arranging means 100 and the crimping means 200, and cuts off a portion of the recording medium P1 in which the pressure-responsive particles according to the present embodiment are not arranged; folding. Cutting means arranged between the device 220 and the pressurizing device 230 to cut off a part of the recording medium P2 in which the pressure-responsive particles according to the present embodiment are not arranged; arranged downstream of the crimping means 200. A cutting means for cutting off a region which is a part of the pressure-bonded printed matter P3 and is not adhered by the pressure-responsive particles according to the present embodiment; and the like.

The printed matter manufacturing apparatus according to the present embodiment is not limited to the sheet-fed type apparatus. The printed matter manufacturing apparatus according to the present embodiment performs an arrangement step and a crimping step on a long recording medium to form a long crimped printed matter, and then cuts the long crimped printed matter to a predetermined size. It may be a device in the style of

The printed matter manufacturing apparatus according to the present embodiment may further include a colored image forming means for forming a colored image on a recording medium by an electrophotographic method using a colored electrostatic charge image developer. The colored image forming means is, for example,
Photoreceptor and
A charging means for charging the surface of the photoconductor and
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged photoconductor, and
A developing means that contains a colored electrostatic charge image developer and develops the electrostatic charge image formed on the surface of the photoconductor as a colored toner image by the colored electrostatic charge image developer.
A transfer means for transferring a colored toner image formed on the surface of the photoconductor to the surface of a recording medium, and
A heat fixing means for heat-fixing a colored toner image transferred to the surface of the recording medium is provided.

The method for producing a printed matter according to the present embodiment further includes a colored image forming step of forming a colored image on a recording medium by an electrophotographic method using a colored electrostatic charge image developer by the manufacturing apparatus having the above configuration. The manufacturing method is carried out. Specifically, the colored image forming process is described.
The charging process that charges the surface of the photoconductor,
A static charge image forming step of forming an electrostatic charge image on the surface of the charged photoconductor, and
A developing step of developing an electrostatic charge image formed on the surface of the photoconductor as a colored toner image with a colored electrostatic charge image developer.
A transfer step of transferring a colored toner image formed on the surface of the photoconductor to the surface of a recording medium, and
It includes a heat fixing step of heat fixing a colored toner image transferred to the surface of the recording medium.

The colored image forming means included in the printed matter manufacturing apparatus according to the present embodiment is, for example, a direct transfer type apparatus for directly transferring a colored toner image formed on the surface of the photoconductor to a recording medium; formed on the surface of the photoconductor. An intermediate transfer type device that primary transfers the colored toner image to the surface of the intermediate transfer body and secondarily transfers the colored toner image transferred to the surface of the intermediate transfer body to the surface of the recording medium; colored toner image. A device equipped with a cleaning means for cleaning the surface of the photoconductor after the transfer and before charging; a device provided with a static elimination means for irradiating the surface of the photoconductor with static elimination light after the transfer of a colored toner image and before charging. ; And so on. When the colored image forming means is an intermediate transfer type apparatus, the transfer means transfers, for example, an intermediate transfer body in which a colored toner image is transferred to the surface and a colored toner image formed on the surface of the photoconductor. It has a primary transfer means for primary transfer to the surface of the intermediate transfer body and a secondary transfer means for secondary transfer of a colored toner image transferred to the surface of the intermediate transfer body to the surface of a recording medium.

In the printed matter manufacturing apparatus according to the present embodiment, when the developing agent containing the pressure-responsive particles and the colored image forming means according to the present embodiment employ an intermediate transfer method, the placing means and the colored image forming means. The means may share an intermediate transfer body and a secondary transfer means.

In the printed matter manufacturing apparatus according to the present embodiment, the heat fixing means may be shared between the means for arranging the image developer containing the pressure-responsive particles and the means for forming a colored image according to the present embodiment.

Hereinafter, an example of a printed matter manufacturing apparatus according to the present embodiment including the colored image forming means will be shown, but the present embodiment is not limited to this. In the following description, the main parts shown in the figure will be described, and the description thereof will be omitted for the others.

FIG. 3 is a schematic configuration diagram showing an example of a printed matter manufacturing apparatus according to the present embodiment to which the electrophotographic method is applied. The printed matter manufacturing apparatus shown in FIG. 3 includes a printing means 300 for collectively arranging pressure-responsive particles and forming a colored image according to the present embodiment on a recording medium, and a crimping means arranged downstream of the printing means 300. It is equipped with 200.

The printing means 300 is a 5-series tandem type and intermediate transfer type printing means. The printing means 300 includes a unit 10T for arranging the pressure-responsive particles (T) according to the present embodiment and a unit for forming each color image of yellow (Y), magenta (M), cyan (C), and black (K). It has 10Y, 10M, 10C and 10K. The unit 10T is an arrangement means for arranging the pressure-responsive particles according to the present embodiment on the recording medium P using the developer containing the pressure-responsive particles according to the present embodiment. Units 10Y, 10M, 10C, and 10K are means for forming a colored image on the recording medium P by using a developing agent containing colored toner, respectively. Units 10T, 10Y, 10M, 10C and 10K employ an electrophotographic method.

The units 10T, 10Y, 10M, 10C and 10K are arranged side by side so as to be separated from each other in the horizontal direction. The units 10T, 10Y, 10M, 10C, and 10K may be process cartridges attached to and detached from the printing means 300.

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

Units 10T, 10Y, 10M, 10C and 10K include developing devices (an example of developing means) 4T, 4Y, 4M, 4C and 4K, respectively. Each of the developing devices 4T, 4Y, 4M, 4C, and 4K has a pressure-responsive particle cartridge 8T, and the pressure-responsive particles and yellow toner according to the present embodiment contained in the toner cartridges 8Y, 8M, 8C, and 8K. , Magenta toner, cyan toner, and black toner are supplied.

Since the units 10T, 10Y, 10M, 10C and 10K have the same configuration and operation, the unit 10T in which the pressure-responsive particles according to the present embodiment are arranged on the recording medium will be described as a representative.

The unit 10T has a photoconductor 1T. Around the photoconductor 1T, a charging roll (an example of charging means) 2T that charges the surface of the photoconductor 1T, and an exposure apparatus (static) that exposes the surface of the charged photoconductor 1T with a laser beam to form a static charge image. Example of charge image forming means) 3T, developing device (example of developing means) 4T that supplies pressure-responsive particles to the electrostatic charge image to develop the electrostatic charge image, and the developed pressure-responsive particle imparting portion is attached to the intermediate transfer belt 20. A primary transfer roll (an example of a primary transfer means) 5T to be transferred onto the photoconductor and a photoconductor cleaning device (an example of a cleaning means) 6T for removing pressure-responsive particles remaining on the surface of the photoconductor 1T after the primary transfer are arranged in order. ing. The primary transfer roll 5T is arranged inside the intermediate transfer belt 20 and is provided at a position facing the photoconductor 1T.

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

The electrostatic charge image formed on the photoconductor 1T rotates to the developing position as the photoconductor 1T travels. Then, at the developing position, the electrostatic charge image on the photoconductor 1T is developed and visualized by the developing device 4T to become a pressure-responsive particle imparting portion.

The developing apparatus 4T contains at least a developing agent containing pressure-responsive particles and carriers according to the present embodiment. The pressure-responsive particles according to the present embodiment are triboelectrically charged by being stirred together with the carrier inside the developing apparatus 4T and are held on the developing agent roll. As the surface of the photoconductor 1T passes through the developing device 4T, the pressure-responsive particles are electrostatically attached 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-imparting portion of the pressure-responsive particles is formed continues to run, and the pressure-responsive particle-imparting portion developed on the photoconductor 1T is conveyed to the primary transfer position.

When the pressure-responsive particle-imparting portion on the photoconductor 1T is conveyed to the primary transfer position, a primary transfer bias is applied to the primary transfer roll 5T, and the electrostatic force from the photoconductor 1T toward the primary transfer roll 5T is the pressure-responsive particles. It acts on the imparting portion, and the pressure-responsive particle imparting portion on the photoconductor 1T is transferred onto the intermediate transfer belt 20. The pressure-responsive particles remaining on the photoconductor 1T are removed by the photoconductor cleaning device 6T and recovered. The photoconductor cleaning device 6T is, for example, a cleaning blade, a cleaning brush, or the like, and is preferably a cleaning brush.

In units 10Y, 10M, 10C and 10K, the same operation as in unit 10T is performed using a developing agent containing colored toner. The intermediate transfer belt 20 to which the pressure-responsive particle imparting portion according to the present embodiment is transferred by the unit 10T sequentially passes through the units 10Y, 10M, 10C, and 10K, and the toner images of each color are multiplexed on the intermediate transfer belt 20. Transcribed.

The intermediate transfer belt 20 in which the pressure-responsive particle imparting portion and the toner image are multiple-transferred through the units 10T, 10Y, 10M, 10C and 10K is intermediate between the intermediate transfer belt 20 and the opposing roll 24 in contact with the inner surface of the intermediate transfer belt. It leads to a secondary transfer unit composed of a secondary transfer roll (an example of the secondary transfer means) 26 arranged on the image holding surface side of the transfer belt 20. On the other hand, the recording medium P is fed to the gap where the secondary transfer roll 26 and the intermediate transfer belt 20 are in contact with each other via the supply mechanism, and the secondary transfer bias is applied to the opposing roll 24. At this time, the electrostatic force from the intermediate transfer belt 20 toward the recording medium P acts on the pressure-responsive particle-imparting portion and the toner image, and the pressure-responsive particle-imparting portion and the toner image on the intermediate transfer belt 20 act on the recording medium P. Transferred.

The pressure-responsive particle-imparting portion and the recording medium P on which the toner image is transferred are conveyed to a heat fixing device (an example of heat fixing means) 28. The heat fixing device 28 includes 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 heat 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 further preferably 160 ° C. or higher and 200 ° C. or lower. By passing through the heat fixing device 28, the colored toner image is heat-fixed on the recording medium P.

The heat fixing device 28 pressurizes with heating from the viewpoint of suppressing the pressure-responsive particles according to the present embodiment from falling off from the recording medium P and improving the fixability of the colored image to the recording medium P. It is preferable that the device performs the above, and for example, it may be a pair of fixing members (roll / roll, belt / roll) having a heating source inside. When the heat fixing device 28 pressurizes, the pressure applied by the heat fixing device 28 to the recording medium P may be lower than the pressure applied by the pressurizing device 230 to the recording medium P2. It is preferably 0.2 MPa or more and 1 MPa or less.

By passing through the printing means 300, the recording medium P becomes the recording medium P1 to which the colored image and the pressure-responsive particles according to the present embodiment are attached. The recording medium P1 is conveyed toward the crimping means 200.

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.

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

The printed matter manufacturing apparatus according to the present embodiment may include a cutting means for cutting the recording medium to a predetermined size. The cutting means is arranged, for example, between the printing means 300 and the crimping means 200, and cuts off a part of the recording medium P1 in which the pressure-responsive particles according to the present embodiment are not arranged; A cutting means arranged between the apparatus 220 and the pressurizing apparatus 230 to cut off a region which is a part of the recording medium P2 and where the pressure-responsive particles according to the present embodiment are not arranged; arranged downstream of the crimping means 200. A cutting means for cutting off a region which is a part of the crimped printed matter P3 and is not adhered by the pressure-responsive particles according to the present embodiment; and the like.

The printed matter manufacturing apparatus according to the present embodiment is not limited to the sheet-fed type apparatus. The printed matter manufacturing apparatus according to the present embodiment performs a colored image forming step, an arrangement step, and a crimping step on a long recording medium to form a long crimped printed matter, and then determines a long crimped printed matter in advance. It may be a device in a style of cutting to the specified dimensions.

<Cartridge>
The cartridge according to the present embodiment is a cartridge that contains the pressure-responsive particles according to the present embodiment and is attached to and detached from the printed matter manufacturing apparatus. The cartridge contains the pressure-responsive particles for replenishment for supplying the pressure-responsive particles provided in the printed matter manufacturing apparatus to the arrangement means arranged on the recording medium.

When the cartridge is mounted on the printed matter manufacturing apparatus, the cartridge and the arrangement means for arranging the pressure-responsive particles on the recording medium, which the printed matter manufacturing apparatus has, are connected by a supply pipe.
When the pressure-responsive particles are supplied from the cartridge to the placement means and the pressure-responsive particles contained in the cartridge are reduced, the cartridge is replaced.

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

<Preparation of dispersion containing styrene 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.
Eight parts of an anionic surfactant (Dowfax2A1 manufactured by Dow Chemical Co., Ltd.) was dissolved in 205 parts of ion-exchanged water, and the monomer solution was added to disperse and emulsify to obtain an emulsion.
2.2 parts of an anionic surfactant (Dowfax2A1 manufactured by Dow Chemical Co., Ltd.) was dissolved in 462 parts of ion-exchanged water and charged into a polymerization flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube. It was heated to 73 ° C. with stirring and held.
3 parts of ammonium persulfate was dissolved in 21 parts of ion-exchanged water and added dropwise to the polymerization flask over 15 minutes via a metering pump, and then the emulsion was dropped over 160 minutes via a metering pump.
Then, the polymerization flask was kept at 75 ° C. for 3 hours while continuing to stir slowly, and then returned to room temperature.
As a result, styrene-based resin particles are contained, the volume average particle size (D50v) of the resin particles is 174 nm, the weight average molecular weight by GPC (UV detection) is 49 k, the glass transition temperature is 54 ° C., and the solid content is 42%. A resin particle dispersion (St1) was obtained.

The styrene resin particle dispersion (St1) is dried to take out the styrene resin particles, and the thermal behavior in the temperature range of -100 ° C to 100 ° C is observed with a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation). Upon analysis, one glass transition temperature was observed. Table 1 shows the glass transition temperature.

[Preparation of Styrene-based Resin Particle Dispersion Liquids (St2) to (St14)]
Styrene-based resin particle dispersions (St2) to (St14) were prepared in the same manner as in the preparation of the styrene-based resin particle dispersion (St1), except that the monomers were changed as shown in Table 1.

In Table 1, the monomers are listed by the following abbreviations.
Styrene: St, n-butyl acrylate: BA, 2-ethylhexyl acrylate: 2EHA, ethyl acrylate: EA, 4-hydroxybutyl acrylate: 4HBA, acrylate: AA, methacrylic acid: MAA, 2-carboxylate acrylate Ethyl: CEA

<Preparation of dispersion containing composite resin particles>
[Preparation of composite resin particle dispersion (M1)]
-Styrene-based resin particle dispersion (St1): 1190 parts (solid content 500 parts)
-2-Ethylhexyl acrylate: 250 parts-n-Butyl acrylate: 250 parts-Ion-exchanged water: 982 parts The above materials were placed in a polymerization flask, stirred at 25 ° C. for 1 hour, and then heated to 70 ° C.
2.5 parts of ammonium persulfate was dissolved in 75 parts of ion-exchanged water and added dropwise to the polymerization flask over 60 minutes via a metering pump.
Then, the polymerization flask was kept at 70 ° C. for 3 hours while continuing to stir slowly, and then returned to room temperature.
As a result, a composite resin particle dispersion (M1) containing composite resin particles, having a volume average particle size (D50v) of 219 nm, a weight average molecular weight of 219 k by GPC (UV detection), and a solid content of 32% is obtained. It was.

The composite resin particle dispersion (M1) was dried to take out the composite resin particles, and the thermal behavior in the temperature range of −150 ° C. to 100 ° C. was analyzed with a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation). However, two glass transition temperatures were observed. Table 2 shows the glass transition temperature.

[Preparation of composite resin particle dispersions (M2) to (M21), (M28) to (M32) and (cM1) to (cM3)]
Similar to the preparation of the composite resin particle dispersion (M1), except that the styrene resin particle dispersion (St1) is changed as shown in Table 2 or the (meth) acrylic acid ester resin is polymerized. The components were changed as shown in Table 2 to prepare composite resin particle dispersions (M2) to (M21), (M28) to (M32) and (cM1) to (cM3).

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

In Table 2, the monomers are described by the following abbreviations.
Styrene: St, n-butyl acrylate: BA, 2-ethylhexyl acrylate: 2EHA, ethyl acrylate: EA, 4-hydroxybutyl acrylate: 4HBA, acrylate: AA, methacrylic acid: MAA, 2-carboxylate acrylate Ethyl: CEA, hexyl acrylate: HA, propyl acrylate: PA

<Preparation of release agent dispersion>
-Fischer-Tropsch wax: 270 parts (manufactured by Nippon Seiro Co., Ltd., trade name: FNP-0090, melting temperature = 90 ° C)
-Anionic surfactant: 1.0 part (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Neogen RK)
-Ion-exchanged water: 400 parts The above components are mixed, heated to 95 ° C., dispersed using a homogenizer (Ultratarax T50 manufactured by IKA), and then dispersed with a manton Gorin high-pressure homogenizer (Gorin) for 360 minutes. The treatment was carried out to prepare a release agent dispersion liquid (solid content concentration: 20%) prepared by dispersing a release agent having a volume average particle size of 0.23 μm.

<Preparation of large-diameter silica particles>
(Preparation of large-diameter silica particles (S1))
-Preparation of large-diameter silica particle dispersion-
To a 1.5 L glass reaction vessel equipped with a stirrer, a dropping nozzle and a thermometer, 300 parts of methanol and 70 parts of 10% aqueous ammonia were added and mixed to obtain an alkaline catalyst solution. After the temperature of this alkaline catalyst solution is set to 30 ° C., 169 parts of tetramethoxysilane (TMS) and 45 parts of 8.0% ammonia water are simultaneously added dropwise to the stirred alkaline catalyst solution to make it highly hydrophilic. A dia-silica particle dispersion (solid content concentration 12.0%) was obtained. Here, the dropping time was 29 minutes. Then, the obtained large-diameter silica particle dispersion was condensed to a solid content concentration of 40% with a rotary filter R-fine (manufactured by Kotobuki Kogyo Co., Ltd.). This condensed product was used as a large-diameter silica particle dispersion.

-Preparation of large-diameter silica particles whose surface has been hydrophobized-
To 250 parts of the above-mentioned large-diameter silica particle dispersion liquid, 62 parts of hexamethyldisilazane (HMDS) was added as a hydrophobizing agent, and the mixture was reacted at 130 ° C. for 2 hours. Then, it was cooled and dried by spray drying to obtain hydrophobic large-diameter silica particles (S1) in which the surface of the large-diameter silica particles was hydrophobized.

(Preparation of large-diameter silica particles (S2) to (S7))
Large-diameter silica particles (S2) to (S7) are the same as those of the large-diameter silica particles (S1), except that the conditions for preparing the large-diameter silica particle dispersion and the conditions for the hydrophobization treatment are as shown in Table 3. Was produced. Table 3 shows the results of measuring the average primary particle diameter (D50v) and the average circularity of each large-diameter silica particle by the method described above.

<Preparation of pressure-responsive particles>
[Preparation of pressure-responsive mother particles (1)]
-Composite resin particle dispersion (M1): 504 parts-Release release agent dispersion: 7.5 parts-Ion exchange water: 710 parts-Anionic surfactant (Dowfax2A1 manufactured by Dow Chemical Co., Ltd.): 1 part

Put the above materials in a reaction vessel equipped with a thermometer and a pH meter, add a 1.0% aqueous nitric acid solution at a temperature of 25 ° C. to adjust the pH to 3.0, and then homogenizer (Ultrata manufactured by IKA). Twenty-three parts of a 2.0% aqueous aluminum sulfate solution was added while dispersing at a rotation speed of 5000 rpm with Lux T50). Next, a stirrer and a mantle heater are installed in the reaction vessel, and the temperature is raised at a rate of 0.2 ° C./min up to a temperature of 40 ° C. and at a rate of 0.05 ° C./min after exceeding 40 ° C. The particle size was measured every 10 minutes with a multi-sizer II (aperture diameter 50 μm, manufactured by Beckman-Coulter). The temperature was maintained when the volume average particle size reached 5.0 μm, and 170 parts of the styrene resin particle dispersion (St1) was added over 5 minutes. After completion of charging, the mixture was kept 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. Then, while adjusting the pH to 6.0 every 5 ° C., the temperature was raised to 90 ° C. at a heating rate of 1 ° C./min and maintained at 90 ° C. When the particle shape and surface properties were observed with an optical microscope and a field emission scanning electron microscope (FE-SEM), the coalescence of the particles was confirmed at 10 hours, so the container was cooled to 30 ° C. for 5 minutes. It was cooled over.

The cooled slurry was passed through a nylon mesh having an opening of 15 μm to remove coarse particles, and the slurry passed through the mesh was vacuum-filtered with an aspirator. The solid content remaining on the filter paper was crushed as finely as possible by hand, put into ion-exchanged water (temperature 30 ° C.) 10 times the solid content, and stirred for 30 minutes. Next, it is vacuum-filtered with an ejector, the solid content remaining on the filter paper is crushed as finely as possible by hand, put into ion-exchanged water (temperature 30 ° C.) 10 times the solid content, stirred for 30 minutes, and then again with an ejector. The filtrate was filtered under reduced pressure, and the electrical conductivity of the filtrate was measured. This operation was repeated until the electrical conductivity of the filtrate became 10 μS / cm or less, and the solid content was washed.

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

100 parts of pressure-responsive mother particles (1), 1.5 parts of large-diameter silica particles (S1), and 0.5 parts of silica particles (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., RY50) with an average primary particle diameter of 40 nm. And were mixed and mixed for 30 seconds at a rotation speed of 13000 rpm using a sample mill. Pressure-responsive particles (1) were obtained by sieving with a vibrating sieve having a mesh size of 45 μm.

Pressure-responsive particles (1) are sprayed on the postcard paper V424 manufactured by Fuji Xerox Co., Ltd. so that the amount of pressure-responsive particles (1) applied is 6 g / m ^{2 over} the entire image forming surface of the postcard, and the particles are passed through a belt roll type fixing machine. , The pressure-responsive particles (1) were fixed on the image-forming surface of the postcard to form a layer of the pressure-responsive particles. A postcard having a layer of pressure-responsive particles on the image-forming surface is folded in half using a sealer PRESSLE multiII manufactured by Toppan Foams Co., Ltd. so that the image-forming surface is on the inside, and pressure is applied to the folded postcard. Was applied, and the inner image-forming surfaces were bonded to each other at a pressure of 90 MPa.
Under the above equipment and conditions, 10 postcards were continuously produced, which were folded in half so that the image forming surfaces were on the inside and the image forming surfaces were adhered to each other. As a result of evaluating the adhesiveness and peelability of the obtained postcard, the postcard crimped using the pressure-responsive particles (1) has both adhesiveness and peelability between the pressure-responsive particle layers. I understood.

Using the pressure-responsive particles (1) as a sample, the thermal behavior in the temperature range of -150 ° C to 100 ° C was analyzed with a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation). Two were observed. Table 4 shows the glass transition temperature.

When the temperature T1 and the temperature T2 of the pressure-responsive particles (1) were determined by the above-mentioned measuring method, the pressure-responsive particles (1) satisfied the formula 1 “10 ° C. ≦ T1-T2”.

When the cross section of the pressure-responsive particles (1) was observed with a scanning electron microscope (SEM), a sea-island structure was observed. The pressure-responsive particles (1) had a core portion in which the island phase was present and a shell layer in which the island phase was not present. The sea phase contained a styrene resin, and the island phase contained a (meth) acrylic acid ester resin. The average diameter of the island phase was determined by the measurement method described above. Table 4 shows the average diameter of the island fauna.

10 parts of the pressure-responsive particles (1) and 100 parts of the following resin-coated carrier were placed in a V-type blender and stirred for 20 minutes, and then sieved with a vibrating sieve having a mesh size of 212 μm to obtain a developer (1). ..

-Mn-Mg-Sr-based ferrite particles (average particle size 40 μm): 100 parts-Toluene: 14 parts-Polymethyl methacrylate: 2 parts-Carbon black (VXC72: manufactured by Cabot): 0.12 parts Excluding ferrite particles The material and glass beads (diameter 1 mm, the same amount as toluene) were mixed and stirred at a rotation speed of 1200 rpm for 30 minutes 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 type kneader, and the pressure was reduced while stirring to dry the mixture to obtain a resin-coated carrier.

[Preparation of pressure-responsive particles (2) to (40) and developing agents (2) to (40)]
Similar to the preparation of the pressure-responsive particles (1), however, the types and amounts of the composite resin particle dispersion, the styrene resin particle dispersion, and the large-diameter silica particle dispersion are changed as shown in Tables 4 and 5. Then, pressure-responsive particles (2) to (40) and developer (2) to (40) were prepared.

When the temperatures T1 and T2 of the pressure-responsive particles (2) to (40) were determined by the above-mentioned measuring method, all the pressure-responsive particles (2) to (40) were given by Equation 1 "10 ° C.≤T1-T2". Was satisfied.

[Preparation of pressure-responsive particles (c1) to (c5) and developing agents (c1) to (c5) for comparison]
Similar to the preparation of the pressure responsive particles (1), however, the composite resin particle dispersion and the styrene resin particle dispersion are changed as shown in Tables 4 and 5, and the pressure responsive particles (c1) to (C5) and developers (c1) to (c5) were prepared.

[Evaluation of pressure-responsive phase transition]
The temperature difference (T1-T3), which is an index indicating that the pressure-responsive particles are likely to undergo a phase transition due to pressure, was determined. Using each pressure-responsive particle as a sample, the temperature T1 and the temperature T3 were measured with a flow tester (CFT-500 manufactured by Shimadzu Corporation), and the temperature difference (T1-T3) was calculated. Tables 4 and 5 show the temperature difference (T1-T3).

[Evaluation of adhesiveness and peelability, and evaluation of image transfer to face-to-face printed matter]
As a printed matter manufacturing apparatus, an apparatus having the form shown in FIG. 3 was prepared. That is, a five-series tandem and intermediate transfer printing means for collectively arranging pressure-responsive particles and forming a colored image according to the present embodiment on a recording medium, and a crimping means having a folding device and a pressurizing device. A printed matter manufacturing apparatus equipped with the above was prepared.
The pressure-responsive particles (or pressure-responsive particles for comparison), yellow toner, magenta toner, cyan toner, and black toner according to the present embodiment were placed in each of the five developing machines of the printing means. As the yellow toner, magenta toner, cyan toner and black toner, commercially available products manufactured by Fuji Xerox Co., Ltd. were used.
The image formed on the postcard paper was an image having an area density of 20% in which black characters and a full-color photographic image were mixed, and was formed on one side of the postcard paper.
The amount of the pressure-responsive particles (or pressure-responsive particles for comparison) according to the present embodiment was set to 3 g / m ² in the image-forming region of the image-forming surface of the postcard paper.
The folding device is a device that folds the postcard paper in half so that the image forming surface is on the inside.
The pressure of the pressurizing device was 90 MPa.
Under the above equipment and conditions, 10 postcards were continuously produced, which were folded in half so that the image forming surfaces were on the inside and the image forming surfaces were adhered to each other.
The tenth postcard was cut in the long side direction with a width of 15 mm to prepare a rectangular test piece, and a 90-degree peeling test was performed. The peeling speed of the 90-degree peeling test was set to 20 mm / min, and after the start of measurement, loads (N) from 10 mm to 50 mm were collected at 0.4 mm intervals, the average was calculated, and the load (N) of three test pieces was further calculated. Was averaged. The load (N) required for peeling was classified as follows. The results are shown in Tables 4 and 5. In addition, it was visually observed whether or not the image formed on the postcard paper on the pressure-bonding facing surface was transferred to the postcard paper after peeling. Then, the case where the image transfer occurred was evaluated as "occurred", and the case where the image transfer did not occur was evaluated as "not generated".

A: 1.6N or more B: 1.4N or more and less than 1.6N C: 1.0N or more and less than 1.4N D: 0.5N or more and less than 1.0N E: less than 0.5N

As shown in Tables 4 and 5, the pressure-responsive particles of the examples are more pressure-responsive than the pressure-responsive particles of the comparative example when a crimped printed matter crimped with the pressure-responsive particles is obtained. It was found that both the adhesiveness between the layers of the sex particles and the peelability are compatible.

100 Arrangement means 101 Photoreceptor 102 Charging roll (an example of charging means)
103 Exposure device (an example of static charge image forming means)
104 Developing device (an example of developing means)
105 Transfer roll (an example of transfer means)
106 Photoreceptor cleaning device (an example of cleaning means)
107 Fixing device (an example of fixing means)
120 Fixing device 110 Applying device 200 Crimping means 220 Folding device 230 Pressurizing device 231 and 232 Pressurizing roll M Pressure-responsive particles P Recording medium P1 Recording medium P2 to which the pressure-responsive particles according to the present embodiment are applied on an image. Folded recording medium P3 crimp printed matter

300 Printing means 1T, 1Y, 1M, 1C, 1K Photoreceptor 2T, 2Y, 2M, 2C, 2K Charging roll (an example of charging means)
3T, 3Y, 3M, 3C, 3K exposure equipment (an example of electrostatic charge image forming means)
4T, 4Y, 4M, 4C, 4K developing equipment (an example of developing means)
5T, 5Y, 5M, 5C, 5K primary transfer roll (example of primary transfer means)
6T, 6Y, 6M, 6C, 6K Photoreceptor cleaning device (an example of cleaning means)
8T Pressure Responsive Particle Cartridge 8Y, 8M, 8C, 8K Toner Cartridge 10T, 10Y, 10M, 10C, 10K Unit 20 Intermediate Transfer Belt (Example of Intermediate Transfer)
21 Intermediate transfer body cleaning device 22 Drive roll 23 Support roll 24 Opposing roll 26 Secondary transfer roll (an example of secondary transfer means)
28 Heat fixing device (an example of heat fixing means)

Claims (22)

90% by mass of a styrene resin containing styrene and other vinyl monomers as a polymerization component, and a (meth) acrylic acid ester containing at least two kinds of (meth) acrylic acid esters in the polymerization component and accounting for the entire polymerization component. The pressure-responsive mother particles containing the (meth) acrylic acid ester-based resin described above,
Silica particles with an average primary particle diameter of 50 nm or more and 300 nm or less,
Have,
It has 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.
Pressure responsive particles. The pressure-responsive particles according to claim 1, wherein the mass ratio of styrene to the total polymerized components of the styrene resin is 60% by mass or more and 95% by mass or less. Claimed that the mass ratio of the two types having the largest mass ratio among the at least two types of (meth) acrylic acid esters contained as a polymerization component in the (meth) acrylic acid ester-based resin is 80:20 to 20:80. The pressure-responsive particle according to claim 1 or 2. Of the at least two (meth) acrylic acid esters contained in the (meth) acrylic acid ester-based resin as a polymerization component, the two having the largest mass ratio are (meth) acrylic acid alkyl esters, and the two types are The pressure-responsive particle according to any one of claims 1 to 3, wherein the difference in the number of carbon atoms of the alkyl group of the (meth) acrylic acid alkyl ester is 1 or more and 4 or less. The pressure-responsive particles according to any one of claims 1 to 4, wherein the other vinyl monomer contained in the styrene resin as a polymerization component contains a (meth) acrylic acid ester. The pressure response according to any one of claims 1 to 5, wherein the other vinyl monomer contained as a polymerization component in the styrene resin contains at least one of n-butyl acrylate and 2-ethylhexyl acrylate. Sex particles. The pressure-responsive particles according to any one of claims 1 to 6, wherein 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. The pressure-responsive particles according to any one of claims 1 to 7, wherein the (meth) acrylic acid ester-based resin contains 2-ethylhexyl acrylate and n-butyl acrylate as polymerization components. The pressure-responsive particles according to any one of claims 1 to 8, wherein the content of the styrene resin is higher than the content of the (meth) acrylic acid ester resin. The pressure response according to any one of claims 1 to 9, which has a sea phase containing the styrene resin and an island phase containing the (meth) acrylic acid ester resin dispersed in the sea phase. Sex particles. The pressure-responsive particles according to claim 10, wherein the island phase has an average diameter of 200 nm or more and 500 nm or less. A core portion containing the styrene resin and the (meth) acrylic acid ester resin, and
The shell layer that covers the core portion and
The pressure-responsive particle according to any one of claims 1 to 11. The pressure-responsive particles according to claim 12, wherein the shell layer contains the styrene resin. The pressure-responsive particles according to any one of claims 1 to 13, wherein the temperature showing a viscosity of 10000 Pa · s under a pressure of 4 MPa is 90 ° C. or lower. The pressure-responsive particles according to any one of claims 1 to 14, wherein the silica particles have an average primary particle diameter of 60 nm or more and 200 nm or less. The pressure according to any one of claims 1 to 15, wherein the external addition amount of the silica particles is 0.1% by mass or more and 10% by mass or less with respect to the total mass of the pressure-responsive mother particles. Responsive particles. The pressure-responsive particles according to claim 16, wherein the external addition amount of the silica particles is 1% by mass or more and 3% by mass or less with respect to the total mass of the pressure-responsive mother particles. A cartridge that contains the pressure-responsive particles according to any one of claims 1 to 17, and is attached to and detached from a printed matter manufacturing apparatus. An arrangement means for accommodating the pressure-responsive particles according to any one of claims 1 to 17 and arranging them on a recording medium.
A crimping means for folding and crimping the recording medium, or stacking and crimping the recording medium and another recording medium.
Printed matter manufacturing equipment including. The printed matter manufacturing apparatus according to claim 19, further comprising a colored image forming means for forming a colored image on a recording medium using a coloring material. The arrangement step of arranging the pressure-responsive particles according to any one of claims 1 to 17 on a recording medium, and
A crimping step in which the recording medium is folded and crimped, or the recording medium and another recording medium are overlapped and crimped.
A method for manufacturing printed matter including. The method for producing a printed matter according to claim 21, further comprising a colored image forming step of forming a colored image on a recording medium using a coloring material.