Conveying device and image forming apparatus

Abstract

The present disclosure relates to a conveyance device and an image forming apparatus. The conveyance device includes: a conveyance member that conveys a spread medium on which pressure-responsive particles are spread, the pressure-responsive particles containing at least a binding resin and having pressure phase transition properties, and a content of sulfur element, measured by fluorescent X-ray measurement, is set to a range of 0.1 mass% or more and 0.5 mass% or less with respect to the entire pressure-responsive particles; and a removal member that removes the pressure-responsive particles remaining on the conveyance member by bringing the pressure-responsive particles into contact with the conveyance member.

Description

Technical Field

[0001] This disclosure relates to a conveying device and an image forming device. Background Technology

[0002] Japanese Patent Application Publication No. 2018-002889 discloses an adhesive material that satisfies Formula 1, "20℃≦T(1MPa)-T(10MPa)" (where T(1MPa) indicates that the viscosity becomes 10 when a pressure of 1MPa is applied). 4 The temperature at Pa·s, T(10MPa) represents the viscosity at which a pressure of 10MPa is achieved. 4 (temperature at Pa·s).

[0003] Japanese Patent Application Publication No. 2018-004966 discloses an apparatus for manufacturing press-printed materials, comprising: an adhesion section for attaching powder that exhibits adhesiveness when pressure is applied to a bonding surface; a fixing section for applying pressure to a recording medium to which the powder is attached, fixing it to the recording medium as an adhesive layer; a bending section for bending the recording medium on which the adhesive layer is formed on the bonding surface with the bonding surfaces facing each other; and an application section for applying pressure to the recording medium with the bonding surfaces facing each other, bonding the adhesive layers together, wherein the powder satisfies Formula 1.

[0004] Japanese Patent Application Publication No. 2008-155412 discloses an apparatus for producing press-printed material. This apparatus applies a powder adhesive to a sheet using an electrophotographic transfer method, and then presses the surface coated with the powder adhesive for printing hidden information. The apparatus is characterized by comprising: a first image forming unit for transferring hidden information formed from toner to the back of the sheet; a second image forming unit for transferring the powder adhesive to the transfer surface of the hidden information; a first heating and pressurizing device for fixing the hidden information on the sheet while temporarily fixing the powder adhesive; a conveying mechanism for reversing and conveying the sheet; a third image forming unit for transferring variable information to the surface of the sheet; a second heating and pressurizing device for fixing the variable information to the surface of the sheet; a first bending device for folding the back of the sheet from the center; and a third heating and pressurizing device for using heat and pressure to formally fix the temporarily fixed surface of the powder adhesive and press it together, thereby producing a folded press-printed material that can be delivered. Summary of the Invention

[0005] The purpose of this disclosure is to improve the removal of pressure-responsive particles remaining on the conveying components compared to cases where the sulfur content is less than 0.1% by mass or more than 0.5% by mass.

[0006] According to a first aspect of this disclosure, a conveying apparatus may be provided, comprising: a conveying member for conveying a dispersed medium in which pressure-responsive particles are dispersed, the pressure-responsive particles comprising at least a binding resin and having a sulfur content, as determined by fluorescence X-rays, in the range of 0.1% by mass or more and 0.5% by mass or less relative to the total amount of pressure-responsive particles, and having pressure phase change properties; and a removal member for contacting and removing the pressure-responsive particles remaining on the conveying member.

[0007] According to a second aspect of this disclosure, the removal member comprises: a support member; and an elastic member comprising a base layer engaged with the support member and a contact layer having a higher hardness than the base layer and in contact with the surface of the conveying member. The elastic member has a type A hardness of 77 or higher and 85 or lower at 23°C, a resilience coefficient of 35% or higher and 45% or lower at 23°C, an angle of contact with the surface of the conveying member of 7.0° or higher and 15.5° or lower, and a pressing force relative to the conveying member of 0.6 gf / mm². 2 Above and 6.0gf / mm 2 the following.

[0008] According to the third aspect of this disclosure, the removal component comprises silicone rubber, and the pressing pressure of the silicone rubber relative to the conveying component is set to 0.5 gf / mm. 2 Above and 5gf / mm 2 Hereinafter, the angle between the silicone rubber and the surface of the conveying component is set to be 5° or more and 20° or less.

[0009] According to the fourth aspect of this disclosure, the removal component comprises silicone rubber, wherein the silicone rubber has a 100% modulus of 4 MPa or more and 10 MPa or less at 23°C.

[0010] According to a fifth aspect of this disclosure, the removal member has: a first removal section for removing the pressure-responsive particles; and a second removal section for removing deposits attached to the surface of the conveying member, the second removal section comprising a metal scraper.

[0011] According to the sixth aspect of this disclosure, the pressure-responsive particle has at least two glass transition temperatures, with the difference between the lowest and highest glass transition temperatures being more than 30°C.

[0012] According to the seventh aspect of this disclosure, the adhesive resin comprises a styrene-based resin and a (meth)acrylate-based resin, wherein the styrene-based resin contains styrene and other vinyl monomers in its polymerization composition, and the (meth)acrylate-based resin contains at least two (meth)acrylates in its polymerization composition, wherein the (meth)acrylates account for more than 90% by mass of the total polymerization composition of the (meth)acrylate-based resin.

[0013] According to the eighth aspect of this disclosure, an image forming apparatus may be provided, comprising: the conveying device for conveying a dispersed medium; and an image forming unit for forming an image using pressure-responsive particles dispersed on the dispersed medium.

[0014] (Effect)

[0015] According to the first scheme, the removal of pressure-responsive particles remaining on the conveying component can be improved compared to cases where the sulfur content is less than 0.1% by mass or more than 0.5% by mass.

[0016] According to the second scheme, the elastic member constituting the removal member has a type A hardness of less than 77 or more than 85 at 23°C, a resilience coefficient of less than 35% or more than 45%, an angle of contact with the surface of the conveying member of less than 7.0° or more than 15.5°, and a pressing pressure relative to the conveying member of less than 0.6 gf / mm. 2 or more than 6.0gf / mm 2 Compared to the previous situation, it can improve the removal of pressure-responsive particles remaining on the conveying components.

[0017] According to the third scheme, the pressing pressure of the silicone rubber constituting the removal member relative to the conveying member is set to less than 0.5 gf / mm. 2 or more than 5gf / mm 2 Compared to situations where the angle between the silicone rubber and the surface of the conveying component is less than 5° or more than 20°, the removal of pressure-responsive particles remaining on the conveying component can be improved.

[0018] According to the fourth scheme, compared with the case where the 100% modulus of the silicone rubber constituting the removal component is less than 4 MPa or more than 10 MPa at 23°C, the removal of pressure-responsive particles remaining on the conveying component can be improved.

[0019] According to the fifth embodiment, compared to the case where the second removal section for removing deposits adhering to the surface of the conveying member includes a resin scraper, the removal of pressure-responsive particles remaining on the conveying member can be improved.

[0020] According to the sixth scheme, compared with the case where there is only one glass transition temperature or at least two glass transition temperatures, and the difference between the lowest and highest glass transition temperatures is less than 30°C, the removal of pressure-responsive particles remaining on the conveying component can be improved.

[0021] According to the seventh scheme, compared with the case where the pressure-responsive particles are homopolymers of (meth)acrylate resins, the removal of pressure-responsive particles remaining on the conveying member can be improved.

[0022] According to the eighth scheme, image defects can be suppressed compared to pressure-responsive particles with a sulfur content of less than 0.1% by mass or more than 0.5% by mass. Attached Figure Description

[0023] Figure 1 This is a schematic diagram illustrating an example of a printing apparatus according to this embodiment.

[0024] Figure 2 This is a schematic diagram showing another example of a printing apparatus according to this embodiment.

[0025] Figure 3 This is a schematic diagram showing another example of a printing apparatus according to this embodiment.

[0026] Figure 4 This is a schematic diagram illustrating an example of the photoreceptor cleaning device according to this embodiment.

[0027] Figure 5 This is a schematic diagram showing another example of the photoreceptor cleaning device of this embodiment.

[0028] Figure 6 It is Figure 5 A partial enlarged schematic diagram is shown.

[0029] Figure 7 This is a schematic diagram showing another example of the photoreceptor cleaning device of this embodiment.

[0030] Figure 8 This is a schematic diagram showing another example of the photoreceptor cleaning device of this embodiment.

[0031] Figure 9 This is a schematic diagram showing another example of the photoreceptor cleaning device of this embodiment.

[0032] Figure 10 This is a schematic diagram illustrating an example of the intermediate transfer body cleaning apparatus of this embodiment. Detailed Implementation

[0033] The embodiments of this disclosure will now be described. These descriptions and examples are illustrative and are not intended to limit the scope of the embodiments.

[0034] In this disclosure, the numerical range represented by “~” indicates the range in which the values ​​recorded before and after “~” are respectively the minimum and maximum values.

[0035] In the numerical ranges described in this disclosure in stages, the upper or lower limit value recorded in one numerical range can be replaced by the upper or lower limit value of the numerical range recorded in other stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value of the numerical range can also be replaced by the values ​​shown in the embodiments.

[0036] In this disclosure, the term "step" includes not only independent steps, but also steps that achieve the desired purpose of the step, even if they cannot be clearly distinguished from other steps.

[0037] In this disclosure, embodiments are described with reference to the accompanying drawings, but the structure of the embodiments is not limited to the structure shown in the drawings. Furthermore, the sizes of the components in the figures are conceptual sizes, and the relative sizes of the components are not limited thereto.

[0038] This disclosure may also include multiple substances corresponding to each component. When the amount of each component in the composition is mentioned in this disclosure, the presence of multiple substances corresponding to each component in the composition refers to the total amount of said multiple substances in the composition unless otherwise specified.

[0039] This disclosure may also include multiple particles corresponding to each component. In the case of multiple particles corresponding to each component present in the composition, unless otherwise specified, the particle size of each component refers to the value of a mixture of the multiple particles present in the composition.

[0040] In this disclosure, the term "(meth)acrylic acid" can also refer to either "acrylic acid" or "methacrylic acid".

[0041] In this disclosure, a printed material formed by folding a recording medium and bringing the opposing surfaces together, or a printed material formed by overlapping two or more recording media and bringing the opposing surfaces together, is referred to as a "pressed printed material".

[0042] [Pressure-responsive particles]

[0043] <First Implementation>

[0044] The pressure-responsive particles of the first embodiment contain at least an adhesive resin, and the sulfur content, as determined by fluorescence X-ray, is in the range of 0.1% by mass or more and 0.5% by mass or less relative to the total pressure-responsive particles, and they exhibit pressure phase change properties.

[0045] The sulfur content is determined by quantitative analysis of the fluorescence X-ray intensity of the pressure-responsive particles. Specifically, for example, a sulfur-free resin is first mixed with a sulfur supply source to obtain a resin mixture with a known sulfur concentration. For 200 mg of this resin mixture, a tablet former with a diameter of 13 mm is used to obtain a particle sample. The mass of the particle sample is precisely weighed, and the peak intensity is determined by measuring the fluorescence X-ray intensity of the particle sample. Similarly, particle samples with varying amounts of sulfur supply source are also measured, and calibration curves are constructed based on these results. The sulfur content in the pressure-responsive particles, the object of the measurement, is then quantitatively analyzed using these calibration curves.

[0046] In addition, "pressure-responsive particles with pressure phase change properties" refers to pressure-responsive particles that satisfy Equation 1 below.

[0047] Equation 1···10℃≦T1-T2

[0048] In Equation 1, T1 is the temperature at which the viscosity is 10000 Pa·s under a pressure of 1 MPa, and T2 is the temperature at which the viscosity is 10000 Pa·s under a pressure of 10 MPa. The methods for determining temperatures T1 and T2 will be described later.

[0049] The pressure-responsive particles of the first embodiment, by having a sulfur content within the stated range, can suppress deformation of the printed material after pressing, compared to cases with a higher or lower sulfur content. The reason for this is uncertain, but is speculated as follows.

[0050] Pressure-responsive particles with pressure phase change properties can be used, for example, in the manufacture of printed materials obtained through a lamination process. Specifically, for example, after the pressure-responsive particles are disposed on a recording medium, the recording medium with the pressure-responsive particles disposed thereon is folded, or the recording medium with the pressure-responsive particles disposed thereon is overlapped with other recording media and lamination is performed to obtain a printed material. If a printed material obtained in this manner is placed, deformation of the printed material may sometimes occur, resulting in a decrease in appearance or operability. In particular, if the printed material is placed under high humidity (e.g., in an environment with 85% humidity), the deformation becomes more pronounced. The reason for the deformation of the printed material under high humidity is uncertain, but it is presumed to be caused by the difference in hygroscopicity between the recording medium constituting the printed material and the pressure-responsive particle layer that forms the lamination layer.

[0051] On the other hand, in the pressure-responsive particles of the first embodiment, the sulfur content is within the aforementioned range. Therefore, it is believed that the pressure-responsive particle layer at the press-fit portion of the printed material is more prone to moisture absorption compared to cases where the sulfur content is less than the aforementioned range. Furthermore, it is believed that not only the recording medium but also the pressure-responsive particle layer is prone to moisture absorption, thereby reducing the difference between the expansion coefficient caused by moisture absorption of the recording medium and the expansion coefficient caused by moisture absorption of the pressure-responsive particle layer, which can suppress overall deformation of the printed material. In addition, it is believed that if the sulfur content is within the aforementioned range, compared to cases where it is more than the aforementioned range, it is less likely that the expansion coefficient of the pressure-responsive particle layer will become relatively too large due to excessive moisture absorption, thereby suppressing overall deformation of the printed material.

[0052] Based on the above reasons, it is speculated that the pressure-responsive particles of the first embodiment can suppress deformation of the printed material after pressing, compared to cases where the sulfur content is higher or lower than the stated range.

[0053] Furthermore, when the sulfur content is within the specified range, the peelability between the pressure-responsive particle layers of the press-bonded printed material is good compared to cases with a higher sulfur content. That is, when the sulfur content is within the specified range, the pressure-responsive particle layer at the press-bonded portion is more easily peeled off during the peeling process of the press-bonded printed material compared to cases with a higher sulfur content.

[0054] The reason why the peelability between pressure-responsive particle layers is good when the sulfur content is within the stated range is uncertain, but it is believed that the reason is that excessive moisture absorption by the pressure-responsive particle layers is less likely to occur compared to cases where the sulfur content is higher than the stated range. If the pressure-responsive particle layers absorb excessive moisture, their adhesion becomes high, making it difficult for the pressure-responsive particle layers to peel off during the peeling of the laminated printed material, sometimes resulting in damage to the image area, recording medium, etc. In contrast, when the sulfur content is within the stated range, excessive moisture absorption by the pressure-responsive particle layers is less likely to occur, therefore it is speculated that the peelability between the pressure-responsive particle layers is good, and damage to the image area, recording medium, etc., is less likely to occur during peeling.

[0055] There is no particular limitation on the method for setting the sulfur content within the aforementioned range. For example, methods can be used to include a sulfur-containing compound in the pressure-responsive masterbatch and adjust its content to fall within the aforementioned range. Examples of methods for including a sulfur-containing compound in the pressure-responsive masterbatch include methods for including a sulfur-containing resin in the adhesive resin and methods for including a sulfur-containing additive in the pressure-responsive masterbatch. Compounds containing sulfur will be described later.

[0056] <Second Implementation>

[0057] The pressure-responsive particles of the second embodiment contain at least an adhesive resin, have a water absorption rate of 0.2% by mass or more and 1.5% by mass or less, and exhibit pressure phase change properties.

[0058] The water absorption rate of the pressure-responsive particles refers to the rate of increase in water content of the pressure-responsive particles under high temperature and high humidity conditions (specifically, at a temperature of 28°C and a humidity of 85%) compared to the water content of the pressure-responsive particles under normal temperature and humidity conditions (specifically, at a temperature of 25°C and a humidity of 50%).

[0059] The water absorption rate was determined as follows. Specifically, 2g of pressure-responsive particles were placed in an aluminum pan and placed at 25°C and 50% humidity for 17 hours, then weighed. Afterward, the particles were placed at 28°C and 85% humidity for another 17 hours, and then weighed again. The water absorption rate (%) is expressed as Wa after the particles were placed at 25°C and 50% humidity, and as Wb after the particles were placed at 28°C and 85% humidity.

[0060] Formula: Water absorption rate (%) = ((Wb-Wa) / Wa) × 100

[0061] The pressure-responsive particles of the second embodiment, by virtue of having a water absorption rate within the stated range, can suppress deformation of the printed material after pressing, compared to cases with a water absorption rate greater than or less than the stated range. The reason for this is uncertain, but is speculated as follows.

[0062] As described, printed materials obtained by pressing with pressure-responsive particles that have pressure phase change properties can sometimes deform, especially when placed in high humidity (e.g., an environment with 85% humidity).

[0063] On the other hand, in the pressure-responsive particles of the second embodiment, the water absorption rate of the pressure-responsive particles is within the stated range. Therefore, it is believed that compared to cases with a lower water absorption rate than stated, the pressure-responsive particle layer at the press-fit portion of the printed material is more prone to moisture absorption, and the expansion coefficient caused by moisture absorption of the recording medium and the expansion coefficient caused by moisture absorption of the pressure-responsive particle layer are well balanced, thus suppressing overall deformation of the printed material. Furthermore, it is believed that if the water absorption rate of the pressure-responsive particles is within the stated range, compared to cases with a higher water absorption rate than stated, it is less likely that the expansion coefficient of the pressure-responsive particle layer will relatively increase due to excessive moisture absorption, thereby suppressing overall deformation of the printed material.

[0064] Based on the above reasons, it is speculated that, compared to cases where the water absorption rate of the pressure-responsive particles is greater than or less than the stated range, the pressure-responsive particles of the second embodiment can suppress the deformation of the printed material after pressing.

[0065] Furthermore, among pressure-responsive particles with a water absorption rate within the stated range, compared to cases with a higher absorption rate, the pressure-responsive particle layers of the press-bonded printed material exhibit good peelability, making it less likely to cause damage to the image area, recording medium, etc., during peeling.

[0066] There is no particular limitation on the method for setting the water absorption rate of the pressure-responsive particles to the aforementioned range. For example, a method of setting the sulfur content to the aforementioned range can be cited. Another method for setting the sulfur content to the aforementioned range can be exemplified by: containing a sulfur-containing compound in the pressure-responsive parent particles and adjusting its content to a sulfur content within the aforementioned range. As a method for containing a sulfur-containing compound in the pressure-responsive parent particles, examples include methods of containing a sulfur-containing resin in the adhesive resin, and methods of containing a sulfur-containing additive in the pressure-responsive parent particles. Compounds containing sulfur will be described later.

[0067] Hereinafter, a pressure-responsive particle that corresponds to either the pressure-responsive particle of the first embodiment or the pressure-responsive particle of the second embodiment will be referred to as "the pressure-responsive particle of this embodiment" for description. In this disclosure, an example of a pressure-responsive particle is simply a pressure-responsive particle that corresponds to at least one of the pressure-responsive particles of the first embodiment or the pressure-responsive particle of the second embodiment.

[0068] <Pressure-responsive particles with pressure phase transition properties>

[0069] The pressure-responsive particles of this embodiment, as described, exhibit pressure phase change properties.

[0070] There are no particular limitations on the pressure-responsive particles that have pressure phase change properties, as long as they satisfy the pressure-responsive particles described in Equation 1.

[0071] As a specific example of a pressure-responsive particle with pressure phase transition properties, a pressure-responsive particle having at least two glass transition temperatures, wherein the difference between the lowest and highest glass transition temperatures is more than 30°C, can be cited.

[0072] Furthermore, as a preferred example of pressure-responsive particles where the difference between the lowest and highest glass transition temperatures is 30°C or more, examples include adhesive resins comprising pressure-responsive particles of styrene-based resins and (meth)acrylate-based resins, wherein the styrene-based resin contains styrene and other vinyl monomers in its polymer composition, and the (meth)acrylate-based resin contains at least two (meth)acrylates in its polymer composition, wherein the (meth)acrylates account for 90% or more of the total mass percentage of the polymer composition.

[0073] Unless otherwise specified, "styrene-based resin" refers to "styrene-based resin containing styrene and other vinyl monomers in its polymer composition," and "(meth)acrylate-based resin" refers to "(meth)acrylate-based resin containing at least two (meth)acrylates in its polymer composition, with the (meth)acrylates accounting for more than 90% by mass of the total polymer composition."

[0074] Compared to pressure-responsive particles containing homopolymers of (meth)acrylate instead of the (meth)acrylate-based resins, adhesive resins containing pressure-responsive particles of both styrene-based and (meth)acrylate-based resins readily undergo phase transitions under pressure and exhibit excellent adhesion. The mechanism is hypothesized as follows.

[0075] It is generally believed that styrene-based resins and (meth)acrylate-based resins have low compatibility with each other, therefore the two resins are contained in a phase-separated state within the pressure-responsive masterbatch. Furthermore, it is believed that if pressure is applied to the pressure-responsive masterbatch, the (meth)acrylate-based resin, with its lower glass transition temperature, flows first, and this flow affects the styrene-based resin, resulting in the flow of both resins. Additionally, when the two resins in the pressure-responsive masterbatch, after flowing under pressure, solidify upon depressurization to form a resin layer, their low compatibility leads to a re-phase separation.

[0076] (Meth)acrylate-based resins, which contain at least two types of (meth)acrylates in their polymer composition, have at least two types of ester groups bonded to the main chain. Compared to homopolymers of (meth)acrylates, the molecular arrangement in the solid state is lower, thus it is presumed that they are more easily fluidized under pressure. Furthermore, if the mass percentage of (meth)acrylates in the total polymer composition is 90% or more, then at least two types of ester groups exist at a high density, resulting in an even lower molecular arrangement in the solid state, thus it is presumed that they are more easily fluidized under pressure. Therefore, it is presumed that compared to pressure-responsive particles of (meth)acrylate homopolymers, these pressure-responsive particles are more easily fluidized by pressure, i.e., more easily undergo a phase transition due to pressure.

[0077] Furthermore, methacrylate-based resins containing at least two types of methacrylates in their polymer composition, with the methacrylates accounting for 90% or more of the total polymer composition by mass, exhibit low molecular arrangement even upon re-curing. Therefore, it is presumed that phase separation from the styrene-based resin is minimal. It is further presumed that the smaller the phase separation between the styrene-based resin and the methacrylate-based resin, the higher the uniformity of the bonding surface relative to the substrate, and the better the adhesion. Therefore, it is presumed that the pressure-responsive particles of this embodiment exhibit superior adhesion compared to pressure-responsive particles made from homopolymers of methacrylates.

[0078] Hereinafter, as a preferred example of the pressure-responsive particles of this embodiment, the composition, structure, and characteristics of the pressure-responsive particles comprising the styrene-based resin and the (meth)acrylate-based resin in the adhesive resin will be described in detail.

[0079] The pressure-responsive particles of this embodiment include at least pressure-responsive parent particles, and may include external additives as needed.

[0080] <Pressure-responsive parent particle>

[0081] The pressure-responsive masterbatch contains at least a binder resin. The binder resin may contain, for example, styrene-based resins and (meth)acrylate-based resins.

[0082] Pressure-responsive masterbatches may also contain colorants, release agents, and other additives.

[0083] From the viewpoint of maintaining adhesion, the content of styrene-based resin in the adhesive resin is preferably higher than the content of (meth)acrylate-based resin. The content of styrene-based resin is preferably 55% by mass or more and 80% by mass or less, more preferably 60% by mass or more and 75% by mass or less, and even more preferably 65% ​​by mass or more and 70% by mass or less, relative to the total content of styrene-based resin and (meth)acrylate-based resin.

[0084] -Styrene-based resins-

[0085] The pressure-responsive masterbatch, for example, contains a styrene-based resin in which styrene and other vinyl monomers are included in the polymer composition.

[0086] From the viewpoint of suppressing the flow of pressure-responsive particles under unpressurized conditions, the mass percentage of styrene in the total polymeric component of styrene-based resin is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 75% by mass or more. From the viewpoint of forming pressure-responsive particles that are prone to phase change due to pressure, it is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0087] Other vinyl monomers besides styrene that constitute styrene-based resins include, for example, styrene-based monomers other than styrene and acrylic monomers.

[0088] Examples of styrene monomers other than styrene include: vinylnaphthalene; alkyl-substituted styrene such as α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, and p-n-dodecylstyrene; aryl-substituted styrene such as p-phenylstyrene; alkoxy-substituted styrene such as p-methoxystyrene; halogen-substituted styrene such as p-chlorostyrene, 3,4-dichlorostyrene, p-fluorostyrene, and 2,5-difluorostyrene; and nitro-substituted styrene such as m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene. Styrene monomers can be used alone or in combination with two or more.

[0089] The acrylic monomer is preferably at least one acrylic monomer selected from the group consisting of (meth)acrylic acid and (meth)acrylates. Examples of (meth)acrylates include: alkyl (meth)acrylates, carboxyl-substituted alkyl (meth)acrylates, hydroxyl-substituted alkyl (meth)acrylates, alkoxy-substituted alkyl (meth)acrylates, di(meth)acrylates, etc. One acrylic monomer may be used alone, or two or more may be used in combination.

[0090] Examples of alkyl methacrylates include: methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, dicyclopentyl methacrylate, and isobornyl methacrylate.

[0091] Examples of carboxyl-substituted alkyl esters of (meth)acrylic acid include 2-carboxyethyl (meth)acrylic acid.

[0092] Examples of hydroxylated alkyl esters of (meth)acrylate include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0093] Examples of alkoxy-substituted alkyl esters of (meth)acrylate include 2-methoxyethyl ester of (meth)acrylate.

[0094] Examples of di(meth)acrylates include: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, pentanediol di(meth)acrylate, hexanediol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, etc.

[0095] Examples of (meth)acrylates include: 2-(diethylamino)ethyl (meth)acrylate, benzyl (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, etc.

[0096] Other vinyl monomers constituting styrene-based resins, besides styrene-based and acrylic monomers, include, for example: (meth)acrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, and vinyl isopropenyl ketone; and olefins such as isoprene, butene, and butadiene.

[0097] From the viewpoint of forming pressure-responsive particles that readily undergo phase transitions under pressure, styrene-based resins preferably contain (meth)acrylates as polymerizing components, more preferably contain alkyl (meth)acrylates, and even more preferably contain alkyl (meth)acrylates with two or more but less than ten carbon atoms in the alkyl group, and even more preferably contain alkyl (meth)acrylates with four or more but less than eight carbon atoms in the alkyl group. Particularly preferred are those containing at least one of n-butyl acrylate and 2-ethylhexyl acrylate. From the viewpoint of forming pressure-responsive particles that readily undergo phase transitions under pressure, both styrene-based resins and (meth)acrylate-based resins preferably contain the same type of (meth)acrylate as polymerizing components.

[0098] From the viewpoint of suppressing the flow of pressure-responsive particles under unpressurized conditions, the mass percentage of (meth)acrylate in the total polymer component of the styrene-based resin is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. From the viewpoint of forming pressure-responsive particles that are prone to phase change due to pressure, it is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. The (meth)acrylate used here is preferably an alkyl (meth)acrylate, more preferably an alkyl (meth)acrylate with two or more but less than ten carbon atoms in the alkyl group, and even more preferably an alkyl (meth)acrylate with four or more but less than eight carbon atoms in the alkyl group.

[0099] The styrene-based resin is particularly preferably composed of at least one of n-butyl acrylate and 2-ethylhexyl acrylate as a polymerization component. From the viewpoint of suppressing the flow of pressure-responsive particles in an unpressurized state, the total amount of n-butyl acrylate and 2-ethylhexyl acrylate in the total polymerization component of the styrene-based resin is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. From the viewpoint of forming pressure-responsive particles that are prone to phase change due to pressure, it is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more.

[0100] From the viewpoint of suppressing the flow of pressure-responsive particles in an unpressurized state, the weight average molecular weight of the styrene-based resin is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more. From the viewpoint of forming pressure-responsive particles that are prone to phase change due to pressure, it is preferably 50,000 or less, more preferably 45,000 or less, and even more preferably 40,000 or less.

[0101] In this disclosure, the weight-average molecular weight of the resin was determined using gel permeation chromatography (GPC). The molecular weight determination using GPC employed a Tosoh HLC-8120GPC as the GPC apparatus, a Tosoh TSKgel SuperHM-M (15cm) column, and tetrahydrofuran as the solvent. The weight-average molecular weight of the resin was calculated using a molecular weight calibration curve prepared from monodisperse polystyrene standard samples.

[0102] From the viewpoint of suppressing the flow of pressure-responsive particles in an unpressurized state, the glass transition temperature of the styrene-based resin is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher. From the viewpoint of forming pressure-responsive particles that are prone to phase change due to pressure, it is preferably 110°C or lower, more preferably 100°C or lower, and even more preferably 90°C or lower.

[0103] In this disclosure, the glass transition temperature of the resin is determined based on a differential scanning calorimetry (DSC) curve obtained by performing differential scanning calorimetry (DSC). More specifically, it is determined by interpolating the glass transition initiation temperature as described in the method for determining the glass transition temperature of Japanese Industrial Standards (JIS) K7121:1987 "Method for Determining the Transition Temperature of Plastics".

[0104] The glass transition temperature of a resin is controlled by the type and ratio of polymerizing components. There is a tendency for the glass transition temperature to be lower when the density of soft units such as methylene, ethylene, and oxyethylene in the main chain is higher, and vice versa. Additionally, the glass transition temperature tends to be lower when the density of aliphatic groups in the side chains is higher.

[0105] In this embodiment, from the viewpoint of suppressing the flow of pressure-responsive particles in an unpressurized state, the mass percentage of styrene-based resin in the total pressure-responsive parent particles is preferably 55% by mass or more, more preferably 60% by mass or more, and even more preferably 65% ​​by mass or more. From the viewpoint of forming pressure-responsive particles that are prone to phase change due to pressure, it is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.

[0106] -(meth)acrylate resins-

[0107] The pressure-responsive masterbatch contains, for example, a (meth)acrylate resin, wherein the (meth)acrylate resin contains at least two (meth)acrylates in the polymer composition, and the (meth)acrylates account for more than 90% by mass of the total polymer composition.

[0108] The mass percentage of (meth)acrylate in the total polymer components of (meth)acrylate resins can be, for example, 90% by mass or more, preferably 95% by mass or more, more preferably 98% by mass or more, and even more preferably 100% by mass.

[0109] Examples of (meth)acrylates include: alkyl (meth)acrylates, carboxyl-substituted alkyl (meth)acrylates, hydroxyl-substituted alkyl (meth)acrylates, alkoxy-substituted alkyl (meth)acrylates, di(meth)acrylates, etc.

[0110] Examples of alkyl methacrylates include: methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, dicyclopentyl methacrylate, and isobornyl methacrylate.

[0111] Examples of carboxyl-substituted alkyl esters of (meth)acrylic acid include 2-carboxyethyl (meth)acrylic acid.

[0112] Examples of hydroxylated alkyl esters of (meth)acrylate include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0113] Examples of alkoxy-substituted alkyl esters of (meth)acrylate include 2-methoxyethyl ester of (meth)acrylate.

[0114] Examples of di(meth)acrylates include: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, pentanediol di(meth)acrylate, hexanediol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, etc.

[0115] Examples of (meth)acrylates include: 2-(diethylamino)ethyl (meth)acrylate, benzyl (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, etc.

[0116] (Meth)acrylates can be used alone or in combination with two or more.

[0117] From the viewpoint of forming pressure-responsive particles that readily undergo phase transition under pressure and exhibit excellent adhesion, alkyl methacrylates are preferred as (meth)acrylates. Alkyl methacrylates with two or more but less than ten carbon atoms in the alkyl group are more preferred, and alkyl methacrylates with four or more but less than eight carbon atoms in the alkyl group are even more preferred. Butyl acrylate and 2-ethylhexyl acrylate are particularly preferred. From the viewpoint of forming pressure-responsive particles that readily undergo phase transition under pressure, styrene-based resins and (meth)acrylate-based resins preferably contain the same type of (meth)acrylate as a polymerization component.

[0118] From the viewpoint of forming pressure-responsive particles that readily undergo phase transition under pressure and exhibit excellent adhesion, the mass percentage of (meth)acrylate alkyl esters in the overall polymer composition of (meth)acrylate-based resins is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more, and even more preferably 100% by mass. The (meth)acrylate alkyl esters used here are preferably (meth)acrylate alkyl esters with two or more but less than ten carbon atoms in the alkyl group, and more preferably (meth)acrylate alkyl esters with four or more but less than eight carbon atoms in the alkyl group.

[0119] From the viewpoint of forming pressure-responsive particles that are prone to phase change due to pressure and have excellent adhesion, the mass ratio of the two (meth)acrylates included as polymerizing components in the (meth)acrylate resin is preferably 80:20 to 20:80, more preferably 70:30 to 30:70, and even more preferably 60:40 to 40:60.

[0120] Of the at least two (meth)acrylates included as polymerizing components in a (meth)acrylate resin, the two with the highest mass proportion are preferably alkyl (meth)acrylates. As the alkyl (meth)acrylates herein, alkyl (meth)acrylates with two or more but less than ten carbon atoms in the alkyl group are preferred, and alkyl (meth)acrylates with four or more but less than eight carbon atoms in the alkyl group are more preferred.

[0121] In the case where the two alkyl methacrylates contained as polymerizing components in a (meth)acrylate resin are alkyl methacrylates and have the highest mass proportion among the at least two (meth)acrylates, from the viewpoint of forming pressure-responsive particles that are prone to phase change due to pressure and have excellent adhesion, the difference in the number of carbon atoms of the alkyl groups of the two (meth)acrylates is preferably one or more and four or less, more preferably two or more and four or less, and even more preferably three or four.

[0122] From the viewpoint of forming pressure-responsive particles that readily undergo phase transitions under pressure and exhibit excellent adhesion, (meth)acrylate resins preferably contain n-butyl acrylate and 2-ethylhexyl acrylate as polymerization components. Particularly preferred are n-butyl acrylate and 2-ethylhexyl acrylate, which constitute the majority of the mass percentages of the at least two (meth)acrylates included as polymerization components in the (meth)acrylate resin. The total mass percentage of n-butyl acrylate and 2-ethylhexyl acrylate in the total polymerization components of the (meth)acrylate resin is preferably 90% by mass or more, more preferably 95% by mass or more, more preferably 98% by mass or more, and more preferably 100% by mass.

[0123] (Meth)acrylate resins may contain vinyl monomers other than (meth)acrylates in their polymer composition. Examples of vinyl monomers other than (meth)acrylates include: (meth)acrylic acid; styrene; styrene monomers other than styrene; (meth)acrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, and vinyl isopropenyl ketone; and olefins such as isoprene, butene, and butadiene. These vinyl monomers may be used alone or in combination with two or more.

[0124] In the case where the (meth)acrylate resin contains vinyl monomers other than (meth)acrylate in its polymerization composition, the vinyl monomer other than (meth)acrylate is preferably at least one of acrylic acid and methacrylic acid, and more preferably acrylic acid.

[0125] From the viewpoint of suppressing the flow of pressure-responsive particles in an unpressurized state, the weight average molecular weight of the (meth)acrylate resin is preferably 50,000 or more, more preferably 100,000 or more, and even more preferably 120,000 or more. From the viewpoint of forming pressure-responsive particles that are prone to phase change due to pressure, it is preferably 250,000 or less, more preferably 220,000 or less, and even more preferably 200,000 or less.

[0126] From the viewpoint of forming pressure-responsive particles that are prone to phase change due to pressure, the glass transition temperature of the (meth)acrylate resin is preferably 10°C or less, more preferably 0°C or less, and even more preferably -10°C or less. From the viewpoint of suppressing the flow of pressure-responsive particles in an unpressurized state, it is preferably -90°C or more, more preferably -80°C or more, and even more preferably -70°C or more.

[0127] From the viewpoint of forming pressure-responsive particles that are prone to phase change due to pressure, the mass percentage of (meth)acrylate resin in the total pressure-responsive master particles is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 30% by mass or more. From the viewpoint of suppressing the flow of pressure-responsive particles in an unpressurized state, it is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.

[0128] The total amount of styrene-based resin and (meth)acrylate-based resin contained in the pressure-responsive parent particle is preferably 70% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 100% by mass, relative to the overall pressure-responsive parent particle.

[0129] -Other Resins-

[0130] Pressure-responsive parent materials may also contain, for example, polystyrene; epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, modified rosin, and other non-vinyl resins. These resins may be used alone or in combination of two or more.

[0131] As described above, for the purpose of setting the sulfur content within the aforementioned range, the adhesive resin may contain a resin containing sulfur. The sulfur-containing resin may be included in the adhesive resin as a styrene-based resin, as a (meth)acrylate-based resin, or as one of the other resins.

[0132] As a resin containing sulfur, examples include resins with thiol groups, specifically, examples include styrene resins and acrylic resins that use octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, tridecanethiol, tetradecanethiol, pentadecanethiol, hexadecanethiol, etc., as one of their monomer components.

[0133] -Various additives-

[0134] Pressure-responsive parent particles may also contain colorants (e.g., pigments, dyes), release agents (e.g., hydrocarbon waxes; natural waxes such as palm wax, rice wax, and candelilla wax; synthetic or mineral and / or petroleum waxes such as lignite wax; ester waxes such as fatty acid esters and lignite esters), charge control agents, etc., as needed.

[0135] When the pressure-responsive particles of this embodiment are made into transparent pressure-responsive particles, it is preferable that the pressure-responsive parent particles do not contain colorants, or that the amount of colorant in the pressure-responsive parent particles is 1.0% by mass or less relative to the entire pressure-responsive parent particles. From the viewpoint of improving the transparency of the pressure-responsive particles, the less the colorant, the better.

[0136] As described above, for the purpose of setting the sulfur content within the range, the pressure-responsive parent material may contain an additive containing sulfur.

[0137] As additives containing sulfur, examples include compounds with thiol groups, such as: dodecanethiol, octanethiol, nonanethiol, decanethiol, undecanethiol, tridecanethiol, tetradecanethiol, pentadecanethiol, hexadecanethiol, etc.

[0138] -Structure of pressure-responsive parent particles-

[0139] The internal structure of the pressure-responsive parent particle is preferably an island structure. As an island structure, it is preferably a structure comprising a marine phase containing a styrene-based resin and an island phase containing a (meth)acrylate-based resin dispersed within the marine phase. The specific morphology of the styrene-based resin contained in the marine phase is as described above. The specific morphology of the (meth)acrylate-based resin contained in the island phase is as described above. Alternatively, an island phase not containing a (meth)acrylate-based resin may be dispersed within the marine phase.

[0140] When the pressure-responsive parent particle has an island structure, the average diameter of the island phase is preferably 200 nm or more and 500 nm or less. If the average diameter of the island phase is 500 nm or less, the pressure-responsive parent particle is prone to phase transition due to pressure. If the average diameter of the island phase is 200 nm or more, the required mechanical strength of the pressure-responsive parent particle (e.g., the strength to resist deformation when stirred in a developer) is excellent. From these perspectives, the average diameter of the island phase is more preferably 220 nm or more and 450 nm or less, and even more preferably 250 nm or more and 400 nm or less.

[0141] As a method for controlling the average diameter of the island phase in the island structure within the specified range, examples include: increasing or decreasing the amount of (meth)acrylate resin relative to the amount of styrene-based resin, increasing or decreasing the time of maintaining a high temperature in the step of fusing and / or combining the aggregated resin particles, etc., in the method for manufacturing pressure-responsive parent particles described later.

[0142] The confirmation of island structures and the determination of the average diameter of island facies are carried out using the following methods.

[0143] Pressure-responsive particles were embedded in epoxy resin, and sections were prepared using a diamond scalpel. The sections were then stained with osmium tetroxide or ruthenium tetroxide in a desiccator. The stained sections were observed using a scanning electron microscope (SEM). Marine and island facies with island structures were distinguished by the intensity of osmium tetroxide or ruthenium tetroxide staining of the resin, and this distinction was used to confirm the presence or absence of island structures. One hundred island facies were randomly selected from the SEM images, and the major axis of each island facies was measured. The average of the 100 major axes was taken as the average diameter.

[0144] The pressure-responsive parent particle can be a single-layer structure or a core-shell structure with a core and a shell covering the core. From the viewpoint of suppressing the flow of pressure-responsive particles in an unpressurized state, the pressure-responsive parent particle is preferably a core-shell structure.

[0145] In the case where the pressure-responsive parent particle has a core-shell structure, from the viewpoint that it is easy to undergo a phase transition due to pressure, it is preferable that the core contains a styrene-based resin and a (meth)acrylate-based resin. Furthermore, from the viewpoint of suppressing the flow of pressure-responsive particles in an unpressurized state, it is preferable that the shell contains a styrene-based resin. The specific form of the styrene-based resin is as described above. The specific form of the (meth)acrylate-based resin is as described above.

[0146] When the pressure-responsive parent particle has a core-shell structure, for the purpose of setting the sulfur content within the aforementioned range, a sulfur-containing compound (e.g., a sulfur-containing resin, a sulfur-containing additive, etc.) may be contained in the core, in the shell, or in both the core and the shell. Preferably, the sulfur-containing compound is contained at least in the shell, and more preferably in both the core and the shell.

[0147] When the pressure-responsive parent particle has a core-shell structure, it is preferable that the core has a marine phase containing a styrene-based resin and an island phase containing a (meth)acrylate-based resin dispersed in the marine phase. The average diameter of the island phase is preferably within the range described above. Furthermore, it is preferable that not only the core has the aforementioned structure, but the shell also contains a styrene-based resin. In this case, the marine phase forming the core and the shell are continuous, and the pressure-responsive parent particle is more likely to undergo a phase transition due to pressure. The specific morphology of the marine phase in the core and the styrene-based resin contained in the shell is as described above. The specific morphology of the (meth)acrylate-based resin contained in the island phase in the core is as described above.

[0148] Examples of resins included in the shell layer include: polystyrene; epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, modified rosin, and other non-vinyl resins. These resins can be used alone or in combination of two or more.

[0149] From the viewpoint of suppressing the deformation of pressure-responsive parent particles, the average thickness of the shell is preferably 120 nm or more, more preferably 130 nm or more, and even more preferably 140 nm or more. From the viewpoint that pressure-responsive parent particles are prone to phase transition due to pressure, it is preferably 550 nm or less, more preferably 500 nm or less, and even more preferably 400 nm or less.

[0150] The average thickness of the shell was determined using the following method.

[0151] Pressure-responsive particles were embedded in epoxy resin, and sections were prepared using a diamond scalpel. The sections were then stained with osmium tetroxide or ruthenium tetroxide in a desiccator. The stained sections were observed using a scanning electron microscope (SEM). Ten pressure-responsive parent particle profiles were randomly selected from the SEM images. The thickness of the shell at 20 locations was measured for each pressure-responsive parent particle, and the average value was calculated. The average value of the ten pressure-responsive parent particles was taken as the average thickness.

[0152] From the viewpoint of ease of handling pressure-responsive parent particles, the volume average particle size (D50v) of the pressure-responsive parent particles is preferably 4 μm or more, more preferably 5 μm or more, and even more preferably 6 μm or more. From the viewpoint of the ease with which the pressure-responsive parent particles as a whole undergo a phase transition due to pressure, it is preferably 12 μm or less, more preferably 10 μm or less, and even more preferably 9 μm or less.

[0153] The volume average particle size (D50v) of the pressure-responsive parent particles was determined using a Coulter Multisizer II (Beckman-Coulter) with a 100 μm pore size. 0.5 mg to 50 mg of pressure-responsive parent particles were added to 2 mL of a 5% (w / w) aqueous solution of alkylbenzene sulfonate and dispersed. This was then mixed with 100 mL to 150 mL of electrolyte (ISOTON-II, Beckman-Coulter) and dispersed using an ultrasonic disperser for 1 minute. The resulting dispersion was used as the sample. The particle size of 50,000 particles with a diameter of 2 μm to 60 μm in the sample was measured. The particle size distribution on a volume basis, measured from the smallest diameter side, was defined as the cumulative 50% of the particle size distribution, which was then set as the volume average particle size (D50v).

[0154] <External Additives>

[0155] As external additives, inorganic particles can be listed as examples. Examples of inorganic particles include: SiO2, TiO2, Al2O3, CuO, ZnO, SnO2, CeO2, Fe2O3, MgO, BaO, CaO, K2O, Na2O, ZrO2, CaO·SiO2, K2O·(TiO2)n, Al2O3·2SiO2, CaCO3, MgCO3, BaSO4, MgSO4, etc.

[0156] The surface of the inorganic particles, used as an external additive, can be hydrophobically treated. Hydrophobic treatment can be performed, for example, by impregnating the inorganic particles with a hydrophobic agent. There are no particular limitations on the hydrophobic agent; examples include silane-based coupling agents, silicone oils, titanate-based coupling agents, and aluminum-based coupling agents. These can be used alone or in combination with two or more. For example, the amount of hydrophobic agent relative to 100 parts by mass of inorganic particles is 1 part by mass or more and 10 parts by mass or less.

[0157] Examples of external additives include: resin particles (resin particles of polystyrene, polymethyl methacrylate, melamine resin, etc.), cleaning and activating agents (e.g., metal salts of higher fatty acids represented by zinc stearate, particles of fluorine-based high molecular weight substances), etc.

[0158] The amount of external additive added relative to the pressure-responsive parent particles is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.01% by mass or more and 3.0% by mass or less.

[0159] <Properties of Pressure-Responsive Particles>

[0160] -Sulfur content, water absorption rate of pressure-responsive particles-

[0161] The sulfur content in the pressure-responsive particles of this embodiment is preferably 0.1% by mass or more and 0.5% by mass or less. From the viewpoint of suppressing deformation after pressing, it is more preferably 0.15% by mass or more and 0.4% by mass or less, and even more preferably 0.2% by mass or more and 0.3% by mass or less.

[0162] The water absorption rate of the pressure-responsive particles in this embodiment is preferably 0.2% by mass or more and 1.5% by mass or less. From the viewpoint of suppressing deformation after pressing, it is more preferably 0.3% by mass or more and 1.2% by mass or less, and even more preferably 0.4% by mass or more and 0.8% by mass or less.

[0163] -Pressure phase change-

[0164] The pressure-responsive particles in this embodiment are pressure-responsive particles that undergo a phase change due to pressure, satisfying the following equation 1.

[0165] Equation 1···10℃≦T1-T2

[0166] In Equation 1, T1 is the temperature at which the viscosity is 10000 Pa·s under a pressure of 1 MPa, and T2 is the temperature at which the viscosity is 10000 Pa·s under a pressure of 10 MPa.

[0167] From the viewpoint that pressure-responsive particles are prone to phase transition due to pressure, the temperature difference T1-T2 is 10°C or more, preferably 15°C or more, more preferably 20°C or more. From the viewpoint of suppressing the flow of pressure-responsive particles in an unpressurized state, it is preferably 120°C or less, more preferably 100°C or less, and even more preferably 80°C or less.

[0168] The temperature T1 is preferably below 140°C, more preferably below 130°C, even more preferably below 120°C, and particularly preferably below 115°C. The lower limit of temperature T1 is preferably above 80°C, even more preferably above 85°C.

[0169] 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 temperature T2 is preferably 85°C or lower.

[0170] As an indicator of whether pressure-responsive particles are prone to undergoing a phase transition due to pressure, the temperature difference (T1-T3) between temperature T1, which displays a viscosity of 10,000 Pa·s at a pressure of 1 MPa, and temperature T3, which displays a viscosity of 10,000 Pa·s at a pressure of 4 MPa, can be cited. The temperature difference (T1-T3) is preferably 5°C or more. From the viewpoint of easy phase transition due to pressure, the temperature difference (T1-T3) of the pressure-responsive particles in this embodiment is preferably 5°C or more, and more preferably 10°C or more.

[0171] The temperature difference (T1-T3) is generally below 25℃.

[0172] From the viewpoint that the temperature difference (T1-T3) is 5°C or more, the temperature T3 at which the viscosity is 10000 Pa·s under a pressure of 4 MPa is preferably 90°C or less, more preferably 85°C or less, and even more preferably 80°C or less. The lower limit of temperature T3 is preferably 60°C or more.

[0173] The method for determining temperature T1, temperature T2, and temperature T3 is as follows.

[0174] Pressure-responsive particles were compressed to create granular samples. These granular samples were placed in a flow testing apparatus (Shimadzu CFT-500), and the applied pressure was fixed at 1 MPa. The viscosity at 1 MPa relative to temperature was measured. Based on the obtained viscosity graph, it was determined that the viscosity reached 10 at an applied pressure of 1 MPa. 4 Temperature T1 is determined at a pressure of 1 MPa per 10 MPa. Temperature T2 is determined using the same method as for temperature T1, except that the applied pressure is set from 1 MPa to 4 MPa. The temperature difference (T1-T2) is calculated from temperatures T1 and T2. The temperature difference (T1-T3) is calculated from temperatures T1 and T3.

[0175] -Glass transition temperature-

[0176] As described above, examples of pressure-responsive particles exhibiting pressure phase transition properties include pressure-responsive particles having at least two glass transition temperatures, with the difference between the lowest and highest glass transition temperatures being 30°C or more. Furthermore, when the pressure-responsive particle having at least two glass transition temperatures is a pressure-responsive particle comprising a styrene-based resin and a (meth)acrylate-based resin, one of the glass transition temperatures is presumed to be the glass transition temperature of the styrene-based resin, and the other is presumed to be the glass transition temperature of the (meth)acrylate-based resin.

[0177] The pressure-responsive particles of this embodiment may have three or more glass transition temperatures, preferably two. A form with two glass transition temperatures is either a form in which the resin contained in the pressure-responsive particles consists only of styrene-based resins and (meth)acrylate-based resins, or a form in which the content of other resins besides styrene-based resins and (meth)acrylate-based resins is low (e.g., the content of other resins is 5% by mass or less relative to the total weight of the pressure-responsive particles).

[0178] When the pressure-responsive particle has at least two glass transition temperatures, and the difference between the lowest and highest glass transition temperatures is 30°C or more, from the viewpoint that the pressure-responsive particle is prone to phase transition due to pressure, the difference between the lowest and highest glass transition temperatures is more preferably 40°C or more, more preferably 50°C or more, and more preferably 60°C or more. The upper limit of the difference between the lowest and highest glass transition temperatures is, for example, 140°C or less, but can be 130°C or less, or 120°C or less.

[0179] From the viewpoint that pressure-responsive particles are prone to phase transition due to pressure, the lowest glass transition temperature exhibited by the pressure-responsive particles is preferably 10°C or less, more preferably 0°C or less, and even more preferably -10°C or less. From the viewpoint of suppressing the flow of pressure-responsive particles in an unpressurized state, it is preferably -90°C or more, more preferably -80°C or more, and even more preferably -70°C or more.

[0180] From the viewpoint of suppressing the flow of pressure-responsive particles in an unpressurized state, the highest glass transition temperature exhibited by the pressure-responsive particles is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher. From the viewpoint that pressure-responsive particles are prone to phase transition due to pressure, it is preferably 70°C or lower, more preferably 65°C or lower, and even more preferably 60°C or lower.

[0181] In this disclosure, a plate-shaped sample is prepared by compressing pressure-responsive particles, and the sample is used for differential scanning calorimetry (DSC). The glass transition temperature of the pressure-responsive particles is determined based on the obtained DSC curve. More specifically, it is determined by "extrapolation of the glass transition initiation temperature" as described in the method for determining the glass transition temperature of JIS K7121:1987 "Method for determination of transition temperature of plastics".

[0182] <Methods for Manufacturing Pressure-Responsive Particles>

[0183] The pressure-responsive particles of this embodiment can be obtained by adding an external additive to the pressure-responsive master particles after manufacturing them.

[0184] Pressure-responsive parent particles can be manufactured using either dry methods (e.g., mixing and pulverizing) or wet methods (e.g., coagulation polymerization, suspension polymerization, dissolution suspension polymerization). There are no particular limitations on these methods, and well-known methods can be employed. Among these, coagulation polymerization can be used to obtain pressure-responsive parent particles.

[0185] In the case of using the condensation-unification method to produce pressure-responsive parent particles, the pressure-responsive parent particles are produced, for example, through the following steps:

[0186] Steps for preparing a styrene-based resin particle dispersion containing styrene-based resin particles (Styrene-based resin particle dispersion preparation steps).

[0187] The step of polymerizing (meth)acrylate resin in a styrene-based resin particle dispersion to form composite resin particles containing styrene-based resin and (meth)acrylate resin (composite resin particle formation step).

[0188] The step of agglomerating composite resin particles in a dispersion of composite resin particles to form aggregated particles (agglomerated particle formation step); and

[0189] The step of heating a dispersion of agglomerated particles to fuse and / or merge the agglomerated particles into pressure-responsive parent particles (fusion and / or merging step).

[0190] The details of each step are explained below.

[0191] The following description illustrates a method for obtaining pressure-responsive masterbatch free of colorants and release agents. Colorants, release agents, and other additives may be used as needed. When the pressure-responsive masterbatch contains colorants and release agents, a fusion and / or unification step is performed after mixing a composite resin particle dispersion with a colorant particle dispersion and a release agent particle dispersion. The colorant particle dispersion and the release agent particle dispersion are prepared, for example, by dispersing the mixed materials using a known disperser.

[0192] -Preparation steps for styrene-based resin particle dispersion-

[0193] Styrene-based resin particle dispersions are, for example, dispersions formed by dispersing styrene-based resin particles in a dispersion medium using surfactants.

[0194] Examples of dispersion media include water, alcohols, and other aqueous media. These can be used individually or in combination with two or more.

[0195] Examples of surfactants include: anionic surfactants such as sulfate esters, sulfonates, phosphate esters, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts; and nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyols. Nonionic surfactants can also be used in combination with anionic or cationic surfactants. Anionic surfactants are preferred among these. A surfactant can be used alone or in combination with two or more surfactants.

[0196] Methods for dispersing styrene-based resin particles in a dispersion medium include, for example, mixing styrene-based resin with a dispersion medium and dispersing it by stirring using a rotary shear homogenizer, or a ball mill, sand mill, dynomill, or similar media.

[0197] Another method for dispersing styrene-based resin particles in a dispersion medium is emulsion polymerization. Specifically, the polymerizable component of the styrene-based resin is mixed with a chain transfer agent or polymerization initiator, and then mixed with an aqueous medium containing a surfactant. The mixture is stirred and an emulsion is prepared, in which the styrene-based resin is polymerized. In this case, dodecyl mercaptan is preferably used as the chain transfer agent.

[0198] The volume average particle size of the styrene-based resin particles dispersed in the styrene-based resin particle dispersion is preferably 100 nm or more and 250 nm or less, more preferably 120 nm or more and 220 nm or less, and even more preferably 150 nm or more and 200 nm or less.

[0199] Regarding the volume average particle size of the resin particles contained in the resin particle dispersion, the particle size is measured using a laser diffraction particle size distribution measuring device (e.g., the LA-700 manufactured by Horiba Manufacturing Co., Ltd.), and the particle size that accumulates to 50% in the volume-based particle size distribution measured from the smallest diameter side is set as the volume average particle size (D50v).

[0200] The content of styrene-based resin particles in the styrene-based resin particle dispersion is preferably 30% by mass or more and 60% by mass or less, more preferably 40% by mass or more and 50% by mass or less.

[0201] -Composite resin particle formation steps-

[0202] A styrene-based resin particle dispersion is mixed with the polymerizing component of a (meth)acrylate resin, and the (meth)acrylate resin is polymerized in the styrene-based resin particle dispersion to form composite resin particles containing styrene-based resin and (meth)acrylate resin.

[0203] The composite resin particles are preferably resin particles comprising styrene-based resin and (meth)acrylate-based resin in a microphase-separated state. These resin particles are manufactured, for example, using the methods described below.

[0204] Add the polymerization component of a (meth)acrylate resin (containing at least two (meth)acrylate monomer groups) to a styrene-based resin particle dispersion, and add an aqueous medium if necessary. Then, while slowly stirring the dispersion, heat the dispersion to above the glass transition temperature of the styrene-based resin (e.g., a temperature 10°C to 30°C higher than the glass transition temperature of the styrene-based resin). Next, while maintaining the temperature, slowly add the aqueous medium containing the polymerization initiator, and continue stirring for a prolonged period of 1 hour to 15 hours. Ammonium persulfate is preferably used as the polymerization initiator.

[0205] The detailed mechanism may not be clear, but it is speculated that when the method described above is used, the styrene-based resin particles contain monomers and polymerization initiators, and (meth)acrylate polymerizes inside the styrene-based resin particles. Therefore, it is speculated that by including (meth)acrylate resin inside the styrene-based resin particles, composite resin particles in a microphase-separated state between the styrene-based resin and the (meth)acrylate resin can be obtained.

[0206] The volume average particle size of the composite resin particles dispersed in the composite resin particle dispersion is preferably 140 nm or more and 300 nm or less, more preferably 150 nm or more and 280 nm or less, and even more preferably 160 nm or more and 250 nm or less.

[0207] The content of composite resin particles in the composite resin particle dispersion is preferably 20% by mass or more and 50% by mass or less, more preferably 30% by mass or more and 40% by mass or less.

[0208] -Steps of condensed particle formation-

[0209] The composite resin particles are aggregated in the composite resin particle dispersion to form aggregated particles with a diameter close to that of the target pressure-responsive parent particles.

[0210] Specifically, for example, a coagulant is added to the composite resin particle dispersion, and the pH value of the composite resin particle dispersion is adjusted to acidic (e.g., pH value above 2 and below 5). If necessary, a dispersing stabilizer is added, and the mixture is heated at a temperature close to the glass transition temperature of the styrene-based resin (specifically, for example, the glass transition temperature of the styrene-based resin is above -30°C and below -10°C) to cause the composite resin particles to coagulate and form aggregated particles.

[0211] In the particle formation step, a coagulant can also be added to the composite resin particle dispersion using a rotary shear homogenizer under stirring at room temperature (e.g., 25°C) to adjust the pH of the composite resin particle dispersion to acidic (e.g., pH above 2 and below 5). If necessary, a dispersant stabilizer can be added, followed by heating.

[0212] Examples of coagulants include surfactants with the opposite polarity to the surfactants contained in the composite resin particle dispersion, inorganic metal salts, and metal complexes with a valence of two or higher. When using metal complexes as coagulants, the amount of surfactant used can be reduced, and the charging properties are improved.

[0213] Additives that form metal ions and complexes with the coagulant or similar bonds may also be used in conjunction with the coagulant, depending on the need. Chelating agents are preferably used as such additives.

[0214] Examples of inorganic metal salts include: calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, aluminum sulfate, etc.; and inorganic metal salt polymers such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide.

[0215] Water-soluble chelating agents can also be used as chelating agents. Examples of chelating agents include: hydroxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid; and aminocarboxylic acids such as iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA).

[0216] The amount of chelating agent added relative to 100 parts by weight of resin particles is preferably 0.01 parts by weight or more and 5.0 parts by weight or less, more preferably 0.1 parts by weight or more and less than 3.0 parts by weight.

[0217] -Integration and / or unification steps-

[0218] Secondly, the dispersion of agglomerated particles containing the agglomerated particles is heated to, for example, above the glass transition temperature of a styrene-based resin (e.g., a temperature 10°C to 30°C higher than the glass transition temperature of a styrene-based resin) to cause the agglomerated particles to fuse and / or merge, thereby forming pressure-responsive parent particles.

[0219] The pressure-responsive parent particles obtained through the above steps typically possess an island structure, comprising a marine phase containing styrene-based resins and island phases containing (meth)acrylate-based resins dispersed within the marine phase. In the composite resin particles, the styrene-based resins and (meth)acrylate-based resins are in a microphase-separated state; however, it is presumed that during the fusion and / or unification steps, the styrene-based resins aggregate to form the marine phase, and the (meth)acrylate-based resins aggregate to form the island phase.

[0220] The average diameter of the island phase in the island structure can be controlled, for example, by increasing or decreasing the amount of styrene-based resin particle dispersion or at least two (meth)acrylates used in the composite resin particle formation step, increasing or decreasing the time maintained at high temperature in the fusion and / or integration steps, etc.

[0221] Core-shell structured pressure-responsive parent particles are manufactured, for example, through the following steps:

[0222] After obtaining the agglomerated particle dispersion, the agglomerated particle dispersion is further mixed with a styrene-based resin particle dispersion to agglomerate the styrene-based resin particles onto the surface of the agglomerated particles, thereby forming second agglomerated particles; and

[0223] The step of heating a dispersion of second aggregated particles containing second aggregated particles to fuse and / or merge the second aggregated particles to form a core-shell structured pressure-responsive parent particle.

[0224] The core-shell structured pressure-responsive parent particles obtained through the above steps have a shell containing a styrene-based resin. Alternatively, a resin particle dispersion containing other types of resin particles can be used instead of a styrene-based resin particle dispersion to form a shell containing other types of resin.

[0225] After the fusion and / or unification step, the pressure-responsive parent particles formed in the solution are subjected to known washing, solid-liquid separation, and drying steps to obtain dry pressure-responsive parent particles. From the viewpoint of charge, the washing step can be performed by displacement washing using ion-exchanged water. From a production perspective, the solid-liquid separation step can be performed by suction filtration, pressure filtration, etc. From a production perspective, the drying step can be performed by freeze drying, airflow drying, flow drying, vibrating flow drying, etc.

[0226] Furthermore, the pressure-responsive particles of this embodiment can be manufactured, for example, by adding an external additive to the obtained dry pressure-responsive master particles and mixing them. Mixing can be carried out using, for example, a V-type stirrer, a Henschel mixer, or a Loedige mixer. Furthermore, if necessary, a vibrating screen, a pneumatic screen, or the like can be used to remove coarse particles from the pressure-responsive particles.

[0227] [box]

[0228] The cartridge in this embodiment is a cartridge that houses the pressure-responsive particles of this embodiment and is detachably mounted in a printing manufacturing apparatus. When the cartridge is mounted in the printing manufacturing apparatus, the cartridge is connected to a configuration component of the printing manufacturing apparatus that positions the pressure-responsive particles onto a recording medium via a supply pipe.

[0229] When the pressure-responsive particles supplied from the box to the configuration component decrease in number, the box is replaced.

[0230] [Apparatus for manufacturing printed matter, method for manufacturing printed matter, printed matter]

[0231] The printing apparatus of this embodiment includes: a placement member for receiving the pressure-responsive particles of this embodiment and placing the pressure-responsive particles on a recording medium; and a pressing member for folding and pressing the recording medium or overlapping and pressing the recording medium with other recording media.

[0232] The configuration components include, for example, an applicator for applicating pressure-responsive particles onto a recording medium, and a fixing device for fixing the pressure-responsive particles applicated onto the recording medium onto the recording medium.

[0233] The crimping component includes, for example, a bending device for folding a recording medium equipped with pressure-responsive particles, or an overlapping device for overlapping a recording medium equipped with pressure-responsive particles with other recording media; and a pressing device for pressing the overlapping recording media.

[0234] The pressure-applying device included in the crimping component applies pressure to the recording medium in which pressure-responsive particles are disposed. As a result, the pressure-responsive particles flow onto the recording medium and exert adhesion.

[0235] The pressure applied to the recording medium by the crimping member is preferably 3 MPa or more and 300 MPa or less, more preferably 10 MPa or more and 200 MPa or less, and even more preferably 30 MPa or more and 150 MPa or less.

[0236] The printing method of this embodiment is implemented using the printing apparatus of this embodiment. The printing method of this embodiment includes: a placement step, using the pressure-responsive particles of this embodiment and placing the pressure-responsive particles on a recording medium; and a pressing step, folding and pressing the recording medium, or overlapping and pressing the recording medium with other recording media.

[0237] The configuration steps may include, for example, the step of applying pressure-responsive particles to the recording medium, and may also include the step of fixing the pressure-responsive particles applied to the recording medium to the recording medium.

[0238] The crimping step may include, for example, a bending step of folding the recording medium or an overlapping step of overlapping the recording medium with other recording media; and a pressing step of pressing the overlapping recording media.

[0239] Pressure-responsive particles can be disposed on the entire surface of the recording medium or on a portion of the recording medium. One or more layers of pressure-responsive particles can be disposed on the recording medium. A layer of pressure-responsive particles can be a continuous layer in the planar direction of the recording medium or a discontinuous layer in the planar direction of the recording medium. A layer of pressure-responsive particles can be formed by maintaining the particle's state of alignment, or it can be formed by adjacent pressure-responsive particles fused together.

[0240] The amount of pressure-responsive particles (preferably transparent pressure-responsive particles) on the recording medium is, for example, 0.5 g / m³ in the configured area. 2 Above and 50g / m 2 Below, 1g / m2 Above and 40g / m 2 Below, 1.5g / m 2 Above and 30g / m 2 The 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, or 0.6 μm or more and 15 μm or less.

[0241] Examples of recording media used in the printing apparatus of this embodiment include: paper, coated paper (made by coating the surface of paper with resin or the like), cloth, nonwoven fabric, resin film, resin sheet, etc. The recording medium may have images on one or both sides.

[0242] The recording medium is preferably at least one selected from the group consisting of paper and coated paper. The water absorption rate of the recording medium is not particularly limited, but examples include 0.2% by mass or more and 1.5% by mass or less, preferably 0.3% by mass or more and 1.5% by mass or less, and more preferably 0.3% by mass or more and 1.2% by mass or less. The water absorption rate of the recording medium is the rate of increase in water content of the recording medium under high temperature and high humidity conditions (temperature 28°C, humidity 85%) relative to the water content of the recording medium under normal temperature and humidity conditions (temperature 25°C, humidity 50%), determined using the same method as for the water absorption rate of the pressure-responsive particles.

[0243] The following describes an example of a printing apparatus according to this embodiment, but this embodiment is not limited thereto.

[0244] Figure 1 This is a schematic structural diagram illustrating an example of a printing apparatus according to this embodiment. Figure 1 The illustrated printing apparatus includes a mounting component 100 and a pressing component 200 disposed downstream of the mounting component 100. Arrows indicate the direction of transport of the recording medium.

[0245] The configuration component 100 is an apparatus that uses pressure-responsive particles according to this embodiment and configures the pressure-responsive particles on the recording medium P. An image is pre-formed on one or both sides of the recording medium P.

[0246] The configuration component 100 includes a feeding device 110 and a fixing device 120 disposed downstream of the feeding device 110.

[0247] The applicator 110 applies pressure-responsive particles M onto the recording medium P. Examples of applicator methods used in the applicator 110 include: spray coating, bar coating, die coating, doctor blade coating, roller coating, reverse roller coating, gravure coating, screen printing, inkjet printing, lamination, and electrophotography. Depending on the applicator method, the pressure-responsive particles M can be dispersed in a dispersion medium to prepare a liquid composition, which is then applied to the applicator 110.

[0248] The recording medium P, which has been given pressure-responsive particles M by the imparting device 110, is transported to the fixing device 120.

[0249] The fixing device 120 may be, for example, a heating device including a heating source, for heating the pressure-responsive particles M on the passing recording medium P, thereby fixing the pressure-responsive particles M onto the recording medium P; a pressurizing device including a pair of pressurizing members (roller / roller, belt / roller) for pressurizing the passing recording medium P, thereby fixing the pressure-responsive particles M onto the recording medium P; or a pressurizing and heating device including a pair of pressurizing members (roller / roller, belt / roller) containing a heating source inside, for pressurizing and heating the passing recording medium P, thereby fixing the pressure-responsive particles M onto the recording medium P, etc.

[0250] When the fixing device 120 has a heating source, the surface temperature of the recording medium P when heated by the fixing device 120 is preferably 10°C or higher and 80°C or lower, more preferably 20°C or higher and 60°C or lower, and even more preferably 30°C or higher and 50°C or lower.

[0251] When the fixing device 120 has a pressure member, the pressure applied to the recording medium P by the pressure member can be lower than the pressure applied to the recording medium P2 by the pressure device 230.

[0252] The recording medium P is configured by the configuration component 100, thereby becoming a recording medium P1 that imparts pressure-responsive particles M to the image. The recording medium P1 is then conveyed to the crimping component 200.

[0253] In the printing apparatus of this embodiment, the placement member 100 and the pressing member 200 may be in a close proximity or in a separate configuration. When the placement member 100 and the pressing member 200 are separate, they are connected, for example, by a conveying member (e.g., a belt conveyor) that conveys the recording medium P1.

[0254] The crimping component 200 is a component that includes a bending device 220 and a pressing device 230, and folds and crimps the recording medium P1.

[0255] The bending device 220 folds the recording medium P1 through the device to create a folded recording medium P2. The folding method of the recording medium P2 is, for example, folding in half, tripling, or quadrupling, and may be a form in which only a portion of the recording medium P2 is folded. The recording medium P2 is in a state in which pressure-responsive particles M are disposed on at least a portion of at least one of at least two opposing surfaces.

[0256] The bending device 220 may have a pair of pressure members (e.g., rollers / rollers, belts / rollers) that apply pressure to the recording medium P2. The pressure applied to the recording medium P2 by the pressure members of the bending device 220 may be lower than the pressure applied to the recording medium P2 by the pressure device 230.

[0257] The crimping component 200 may also include an overlapping device instead of the bending device 220 for overlapping the recording medium P1 with other recording media. The overlapping of the recording medium P1 with other recording media can be, for example, overlapping one other recording medium onto the recording medium P1, or overlapping one other recording medium at multiple locations on the recording medium P1. The other recording media may be recording media with images pre-formed on one or both sides, recording media without images, or pre-made crimped prints.

[0258] The recording medium P2 output from the bending device 220 (or the overlay device) is transferred to the pressurizing device 230.

[0259] The pressurizing device 230 includes a pair of pressurizing components (i.e., pressurizing roller 231 and pressurizing roller 232). Pressurizing roller 231 and pressurizing roller 232 contact and press against each other on their outer peripheral surfaces, applying pressure to the passing recording medium P2. The pair of pressurizing components included in the pressurizing device 230 is not limited to a combination of pressurizing rollers, but may also be a combination of pressurizing rollers and pressurizing belts, or a combination of pressurizing belts.

[0260] If pressure is applied to the recording medium P2 via the pressurizing device 230, the pressure-responsive particles M on the recording medium P2 will flow due to the pressure and exhibit adhesion.

[0261] The pressurizing device 230 may or may not have an internal heating source (e.g., a halogen heater) for heating the recording medium P2. Furthermore, the absence of an internal heating source in the pressurizing device 230 does not preclude the possibility that the temperature inside the pressurizing device 230 may reach above the ambient temperature due to heat generated by the motor or other components included in the pressurizing device 230.

[0262] The recording medium P2 is pressurized by a pressurizing device 230, thereby bonding the folded surfaces together using fluidized pressure-responsive particles M to create a press-printed material P3. In the press-printed material P3, two opposing surfaces are partially or completely bonded together.

[0263] Remove the completed press-printed material P3 from the self-pressurizing device 230.

[0264] The first form of the press-printed material P3 is a press-printed material formed by bonding folded recording media on opposite surfaces using pressure-responsive particles M. This form of press-printed material P3 is manufactured by a printing apparatus including a bending device 220.

[0265] The second form of the overprinted material P3 is an overprinted material formed by bonding multiple overlapping recording media on opposite surfaces using pressure-responsive particles M. This form of overprinted material P3 is manufactured by an overprinted material manufacturing apparatus including an overlay device.

[0266] The printing apparatus of this embodiment is not limited to an apparatus that continuously transports the recording medium P2 from the bending device 220 (or the overlay device) to the pressurizing device 230. The printing apparatus of this embodiment may also be an apparatus that stores the recording medium P2 output from the bending device 220 (or the overlay device) and transports the recording medium P2 to the pressurizing device 230 after the storage amount of the recording medium P2 reaches a predetermined amount.

[0267] In the printing apparatus of this embodiment, the bending device 220 (or overlapping device) and the pressurizing device 230 may be in a close proximity or in a separate configuration. When the bending device 220 (or overlapping device) and the pressurizing device 230 are separate, they are connected, for example, via a conveying component (e.g., a belt conveyor) that conveys the recording medium P2.

[0268] The printing apparatus of this embodiment may include a cutting member for cutting a recording medium to a predetermined size. Examples of cutting members include: a cutting member disposed between the placement member 100 and the pressing member 200 that cuts off areas that are part of the recording medium P1 and where pressure-responsive particles M are not disposed; a cutting member disposed between the bending device 220 and the pressing device 230 that cuts off areas that are part of the recording medium P2 and where pressure-responsive particles M are not disposed; and a cutting member disposed downstream of the pressing member 200 that cuts off areas that are part of the pressed printed material P3 and where pressure-responsive particles M are not applied.

[0269] The printing apparatus of this embodiment is not limited to a single-sheet apparatus. The printing apparatus of this embodiment can be an apparatus that, after forming a strip of laminated printed material by performing a configuration step and a lamination step on a strip of recording medium, cuts the strip of laminated printed material into a predetermined size and pattern.

[0270] The printing apparatus (image forming apparatus) of this embodiment may further include a colored image forming component (image forming unit) that forms a colored image on a recording medium using a color material. Examples of colored image forming components include: a component that forms a colored ink image on a recording medium by inkjet printing using colored ink as a color material, and a component that forms a colored image on a recording medium by electrophotography using a colored electrostatic image developer.

[0271] The manufacturing apparatus with the described structure allows for the implementation of a manufacturing method for printed materials according to this embodiment, which further includes a colored image forming step of forming a colored image on a recording medium using a color material. Specifically, the colored image forming step can be exemplified by, for example, forming a colored ink image on a recording medium using colored ink as a color material via inkjet printing, or forming a colored image on a recording medium using a colored electrostatic image developer via electrophotography.

[0272] [Printing sheet, manufacturing method of printing sheet]

[0273] The printing sheet of this embodiment has a substrate and pressure-responsive particles disposed on the substrate. The printing sheet of this embodiment is manufactured using the pressure-responsive particles of this embodiment. The pressure-responsive particles on the substrate may or may not maintain the particle shape they had before being disposed on the substrate.

[0274] The printing sheet of this embodiment can be used, for example, as a mask sheet that overlaps with a recording medium when it is desired to hide information recorded on the recording medium; or as a release sheet for setting an adhesive layer on a recording medium when recording media are overlapped together.

[0275] Examples of substrates for the printed matter manufacturing sheet used in this embodiment include: paper, coated paper made by coating the surface of paper with resin, cloth, non-woven fabric, resin film, resin sheet, etc. Images can be formed on one or both sides of the substrate.

[0276] In the printing sheet of this embodiment, pressure-responsive particles can be disposed on the entire surface of the substrate or on a portion of the substrate. One or more layers of pressure-responsive particles are disposed on the substrate. The layer of pressure-responsive particles can be a continuous layer in the surface direction of the substrate or a discontinuous layer in the surface direction of the substrate. The layer of pressure-responsive particles can be a layer in which the pressure-responsive particles maintain their individual particle arrangement, or a layer in which adjacent pressure-responsive particles are fused together and arranged.

[0277] The amount of pressure-responsive particles on the substrate is, for example, 0.5 g / m² in the configured area. 2Above and 50g / m 2 Below, 1g / m 2 Above and 40g / m 2 Below, 1.5g / m 2 Above and 30g / m 2 The thickness of the pressure-responsive particles on the substrate is, for example, 0.2 μm or more and 25 μm or less, 0.4 μm or more and 20 μm or less, or 0.6 μm or more and 15 μm or less.

[0278] The printing sheet of this embodiment is manufactured, for example, using a manufacturing method that includes a configuration step of using the pressure-responsive particles of this embodiment and configuring the pressure-responsive particles on a substrate.

[0279] The configuration steps include, for example, an assignment step, in which pressure-responsive particles are assigned to a substrate; and a fixing step, in which the pressure-responsive particles assigned to the substrate are fixed to the substrate.

[0280] The assemblage step can be achieved through methods such as spraying, bar coating, mold coating, doctor blade coating, roller coating, reverse roller coating, gravure coating, screen printing, inkjet printing, lamination, and electrophotography. Depending on the assemblage method used, pressure-responsive particles can be dispersed in a dispersion medium to prepare a liquid composition, which is then applied to the assemblage step.

[0281] The fixing steps include, for example: a heating step, in which the pressure-responsive particles on the substrate are heated using a heating source and the pressure-responsive particles are fixed to the substrate; a pressurizing step, in which a pair of pressurizing members (rollers / rollers, belts / rollers) are used to pressurize the substrate to which the pressure-responsive particles are applied and to fix the pressure-responsive particles to the substrate; and a pressurizing and heating step, in which a pair of pressurizing members (rollers / rollers, belts / rollers) including a heating source inside are used to pressurize and heat the substrate to which the pressure-responsive particles are applied and to fix the pressure-responsive particles to the substrate, etc.

[0282] <Manufacturing of Printed Materials Using Electrophotography>

[0283] An example of applying the pressure-responsive particles of this embodiment to an electrophotographic method will be described. In the electrophotographic method, the pressure-responsive particles are equivalent to toners.

[0284] (Electrostatic imaging developer)

[0285] The electrostatic imaging developer of this embodiment contains at least the pressure-responsive particles of this embodiment. The electrostatic imaging developer of this embodiment may be a single-component developer containing only the pressure-responsive particles of this embodiment, or it may be a two-component developer in which the pressure-responsive particles of this embodiment are mixed with a carrier.

[0286] There are no particular limitations on the carrier, and known carriers can be listed. Examples of carriers include: a coated carrier in which resin is coated on the surface of a core material containing magnetic powder; a magnetic powder dispersion carrier in which magnetic powder is dispersed in a matrix resin and then formulated; and a resin impregnating carrier in which resin is impregnated in porous magnetic powder. Magnetic powder dispersion carriers and resin impregnating carriers can also be carriers in which the structural particles of the carrier are used as the core material and the surface is coated with resin.

[0287] Examples of magnetic powders include: magnetic metals such as iron, nickel, and cobalt; magnetic oxides such as ferrite and magnetite.

[0288] Examples of coating resins and matrix resins include: polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylate copolymer, pure silicone resins or their modifications containing organosiloxane bonds, fluororesins, polyesters, polycarbonates, phenolic resins, epoxy resins, etc. Other additives, such as conductive particles, may also be included in the coating resins and matrix resins. Examples of conductive particles include: metals such as gold, silver, and copper, carbon black, titanium dioxide, zinc oxide, tin oxide, barium sulfate, aluminum borate, potassium titanate, etc.

[0289] When coating the surface of a core material with resin, methods such as coating with a coating layer forming solution obtained by dissolving the coating resin and various additives (as needed) in a suitable solvent can be cited. There are no particular limitations on the solvent; it can be selected based on factors such as the type of resin used and its coating compatibility.

[0290] Specific resin coating methods include: immersion method in which the core material is immersed in a coating layer forming solution; spraying method in which the coating layer forming solution is sprayed onto the surface of the core material; fluidized bed method in which the coating layer forming solution is sprayed while the core material is floating using flowing air; and kneading coating machine method in which the core material of the carrier is mixed with the coating layer forming solution in a kneading coating machine and then the solvent is removed.

[0291] The mixing ratio (mass ratio) of pressure-responsive particles to carrier in the two-component developer is preferably from 1:100 to 30:100, more preferably from 3:100 to 20:100.

[0292] (Apparatus for manufacturing printed materials, methods for manufacturing printed materials)

[0293] An apparatus for manufacturing printed matter using an electrophotographic method includes: a placement component for storing a developer containing pressure-responsive particles of this embodiment, and for placing the pressure-responsive particles onto a recording medium using an electrophotographic method; and a pressing component for folding and pressing the recording medium or overlapping and pressing the recording medium with other recording media.

[0294] The printing apparatus of this embodiment is used to implement a method for manufacturing printed matter using an electrophotographic method.

[0295] The method for manufacturing printed matter according to this embodiment includes: a configuration step, using a developer containing pressure-responsive particles of this embodiment, configuring the pressure-responsive particles onto a recording medium by an electrophotographic method; and a lamination step, folding and laminating the recording medium, or overlapping and laminating the recording medium with other recording media.

[0296] The configuration components included in the printing apparatus of this embodiment include, for example:

[0297] Photoreceptor;

[0298] A charged component that charges the surface of the photoreceptor;

[0299] The electrostatic image forming component forms an electrostatic image on the surface of the charged photoreceptor;

[0300] The developing unit houses the electrostatic image developer of this embodiment, and uses the electrostatic image developer to develop the electrostatic image formed on the surface of the photoreceptor as a pressure-responsive particle layer, i.e., a pressure-responsive particle imparting portion; and

[0301] The transfer component transfers the pressure-responsive particle imparting portion formed on the surface of the photoreceptor to the surface of the recording medium.

[0302] The configuration component preferably includes a fixing component that fixes the pressure-responsive particle imparting portion transferred to the surface of the recording medium.

[0303] The configuration steps included in the method for manufacturing printed matter according to this embodiment include, for example:

[0304] The charging step charges the surface of the photoreceptor.

[0305] The electrostatic charge image formation step involves forming an electrostatic charge image on the surface of the charged photoreceptor;

[0306] The development step involves developing the electrostatic image formed on the surface of the photoreceptor as a pressure-responsive particle-imparting portion using the electrostatic image developer of this embodiment; and

[0307] The transfer step involves transferring the pressure-responsive particle-imparting portion formed on the surface of the photoreceptor to the surface of the recording medium.

[0308] The configuration step preferably includes a fixing step of fixing the pressure-responsive particle imparting portion transferred to the surface of the recording medium.

[0309] The configuration component may be, for example, a device for a direct transfer method that directly transfers pressure-responsive particle-imparting portions formed on the surface of a photoreceptor to a recording medium; a device for an intermediate transfer method that first transfers pressure-responsive particle-imparting portions formed on the surface of a photoreceptor to the surface of an intermediate transfer body, and then secondly transfers the pressure-responsive particle-imparting portions transferred to the surface of the intermediate transfer body to the surface of the recording medium; a device including a cleaning component that cleans the surface of the photoreceptor before it becomes charged after the transfer of the pressure-responsive particle-imparting portions; and a device including a de-energizing component that irradiates the surface of the photoreceptor with de-energizing light after the transfer of the pressure-responsive particle-imparting portions but before it becomes charged to de-energize it. In the case where the configuration component is an intermediate transfer method device, the transfer component may include, for example, an intermediate transfer body that transfers pressure-responsive particle-imparting portions to a surface; a primary transfer component that firstly transfers pressure-responsive particle-imparting portions formed on the surface of a photoreceptor to the surface of an intermediate transfer body; and a secondary transfer component that secondly transfers pressure-responsive particle-imparting portions transferred to the surface of the intermediate transfer body to the surface of the recording medium.

[0310] The portion of the configuration component that includes the developing component can be a cassette structure (so-called a processing cassette) that is detachably mounted to the configuration component. As a processing cassette, for example, a processing cassette that houses the electrostatic imaging developer of this embodiment and includes the developing component can preferably be used.

[0311] The printing apparatus of this embodiment includes a pressing member that applies pressure to a recording medium on which the pressure-responsive particles of this embodiment are disposed. As a result, the pressure-responsive particles of this embodiment flow onto the recording medium and exhibit adhesion. For the purpose of flowing the pressure-responsive particles of this embodiment, the pressure applied to the recording medium by the pressing member is preferably 3 MPa or more and 300 MPa or less, more preferably 10 MPa or more and 200 MPa or less, and even more preferably 30 MPa or more and 150 MPa or less.

[0312] The pressure-responsive particles of this embodiment can be disposed on the entire surface of the recording medium or on a portion of the recording medium. One or more layers of pressure-responsive particles are disposed on the recording medium. The layer of pressure-responsive particles in this embodiment can be a continuous layer in the surface direction of the recording medium or a discontinuous layer in the surface direction of the recording medium.

[0313] The amount of pressure-responsive particles of this embodiment on the recording medium is, for example, 0.5 g / m³ in the configured area. 2 Above and 50g / m 2 Below, 1g / m 2 Above and 40g / m 2 Below, 1.5g / m 2 Above and 30g / m 2 The thickness of the pressure-responsive particles in this 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, or 0.6 μm or more and 15 μm or less.

[0314] Examples of recording media used in the printing apparatus of this embodiment include: paper, coated paper (made by coating the surface of paper with resin, etc.), cloth, non-woven fabric, resin film, resin sheet, etc. The recording medium may have an image on one or both sides. The recording medium is preferably at least one selected from the group consisting of paper and coated paper. The water absorption rate of the recording medium is not particularly limited, but examples include 0.2% by mass or more and 1.5% by mass or less, preferably 0.3% by mass or more and 1.5% by mass or less, and more preferably 0.3% by mass or more and 1.2% by mass or less. The water absorption rate of the recording medium is the rate of increase in water content of the recording medium under high temperature and high humidity conditions (temperature 28°C, humidity 85%) relative to the water content of the recording medium under normal temperature and humidity conditions (temperature 25°C, humidity 50%), calculated using the same method as the water absorption rate of the pressure-responsive particles.

[0315] The following describes an example of a printing apparatus of this embodiment that uses an electrophotographic method, but this embodiment is not limited to this.

[0316] Figure 2 This is a schematic structural diagram illustrating an example of a printing apparatus according to this embodiment. Figure 2 The illustrated printing apparatus includes a mounting component 100 and a pressing component 200 disposed downstream of the mounting component 100. Arrows indicate the rotation direction of the photoreceptor or the transport direction of the recording medium.

[0317] The configuration component 100 is a direct transfer apparatus that uses a developer containing the pressure-responsive particles of this embodiment to configure the pressure-responsive particles of this embodiment onto a recording medium P using an electrophotographic method. An image is pre-formed on one or both sides of the recording medium P.

[0318] The configuration component 100 includes a photoreceptor 101. Around the photoreceptor 101 are arranged sequentially the following: a charging roller (an example of a charging component) 102, which charges the surface of the photoreceptor 101; an exposure device (an example of a static charge image forming component) 103, which uses laser light to expose the charged surface of the photoreceptor 101 to form a static charge image; a developing device (an example of a developing component) 104, which supplies pressure-responsive particles to the static charge image and develops the static charge image; a transfer roller (an example of a transfer component) 105, which transfers the developed pressure-responsive particles onto the recording medium P; and a photoreceptor cleaning device (an example of a cleaning component) 106, which removes the pressure-responsive particles remaining on the surface of the photoreceptor 101 after the transfer.

[0319] The operation of the configuration component 100 in configuring the pressure-responsive particles of this embodiment onto the recording medium P will be described.

[0320] First, the surface of the photoreceptor 101 is charged using the charged roller 102. Based on image data sent from a control unit (not shown), the exposure apparatus 103 irradiates the surface of the charged photoreceptor 101 with laser light. As a result, an electrostatic charge image of the arrangement pattern of pressure-responsive particles according to this embodiment is formed on the surface of the photoreceptor 101.

[0321] The electrostatic charge image formed on the photoreceptor 101 rotates to the developing position as the photoreceptor 101 moves. Then, at the developing position, the electrostatic charge image on the photoreceptor 101 is developed by the developing apparatus 104 to become a pressure-responsive particle delivery section.

[0322] The developing apparatus 104 contains a developer that includes at least the pressure-responsive particles of this embodiment and a carrier. The pressure-responsive particles of this embodiment are agitated and triboelectrically charged together with the carrier inside the developing apparatus 104 and held on the developer roller. As the surface of the photoreceptor 101 passes through the developing apparatus 104, the pressure-responsive particles electrostatically attach to the electrostatically charged image on the surface of the photoreceptor 101, and this electrostatically charged image is developed using the pressure-responsive particles. The photoreceptor 101 with the pressure-responsive particle application portion is then moved, and the pressure-responsive particle application portion developed on the photoreceptor 101 is transported to the transfer position.

[0323] When the pressure-responsive particle-imparting portion on the photoreceptor 101 is transported to the transfer position, a transfer bias is applied to the transfer roller 105. The electrostatic force from the photoreceptor 101 toward the transfer roller 105 acts on the pressure-responsive particle-imparting portion, thereby transferring the pressure-responsive particle-imparting portion on the photoreceptor 101 onto the recording medium P.

[0324] Pressure-responsive particles remaining on the photoreceptor 101 are removed and recycled by the photoreceptor cleaning device 106. The photoreceptor cleaning device 106 is, for example, a cleaning scraper, a cleaning brush, etc. From the viewpoint of suppressing the phenomenon that the pressure-responsive particles remaining on the surface of the photoreceptor in this embodiment flow due to pressure and adhere to the surface of the photoreceptor in a film form, the photoreceptor cleaning device 106 is preferably a cleaning brush.

[0325] The recording medium P, on which the pressure-responsive particle transfer portion is transferred, is conveyed to the fixing device (an example of a fixing member) 107. The fixing device 107 is, for example, a pair of fixing members (roller / roller, belt / roller). The configuration member 100 may not include the fixing device 107, but from the viewpoint of suppressing the pressure-responsive particles of this embodiment from falling off the recording medium P, it is preferable to include the fixing device 107. The pressure applied to the recording medium P by the fixing device 107 may be lower than the pressure applied to the recording medium P by the pressurizing device 230, specifically, preferably 0.2 MPa or more and 1 MPa or less.

[0326] The fixing device 107 may or may not have an internal heating source (e.g., a halogen heater) for heating the recording medium P. When the fixing device 107 has an internal heating source, the surface temperature of the recording medium P when heated by the heating source is preferably 150°C or higher and 220°C or lower, more preferably 155°C or higher and 210°C or lower, and even more preferably 160°C or higher and 200°C or lower. Furthermore, even when the fixing device 107 does not have an internal heating source, it does not preclude the possibility that the temperature inside the fixing device 107 may reach or exceed the ambient temperature due to heat generated by the motor or the like included in the mounting components 100.

[0327] The recording medium P is configured by the configuration member 100, thereby becoming a recording medium P1 on which the pressure-responsive particles of this embodiment are imparted to the image. The recording medium P1 is then conveyed to the crimping member 200.

[0328] In the printing apparatus of this embodiment, the placement member 100 and the pressing member 200 may be in a close proximity or in a separate configuration. When the placement member 100 and the pressing member 200 are separate, they are connected, for example, by a conveying member (e.g., a belt conveyor) that conveys the recording medium P1.

[0329] The crimping component 200 is a component that includes a bending device 220 and a pressing device 230, and folds and crimps the recording medium P1.

[0330] The bending device 220 folds the recording medium P1 through the device to create a folded recording medium P2. The folding method of the recording medium P2 can be, for example, a fold in half, a third fold, a fourth fold, or a fold where only a portion of the recording medium P2 is folded. The recording medium P2 is in a state where at least a portion of at least one of at least two opposing surfaces is provided with the pressure-responsive particles of this embodiment.

[0331] The bending device 220 may have a pair of pressure members (e.g., roller / roller, belt / roller) that apply pressure to the recording medium P2. The pressure applied to the recording medium P2 by the pressure members of the bending device 220 may be lower than the pressure applied to the recording medium P2 by the pressure device 230, specifically, preferably 1 MPa or more and 10 MPa or less.

[0332] The crimping component 200 may also include an overlapping device instead of the bending device 220 for overlapping the recording medium P1 with other recording media. The overlapping of the recording medium P1 with other recording media can be, for example, overlapping one other recording medium onto the recording medium P1, or overlapping one other recording medium at multiple locations on the recording medium P1. The other recording media may be recording media with images pre-formed on one or both sides, recording media without images, or pre-made crimped prints.

[0333] The recording medium P2 output from the bending device 220 (or the overlay device) is transferred to the pressurizing device 230.

[0334] The pressurizing device 230 includes a pair of pressurizing components (i.e., pressurizing roller 231 and pressurizing roller 232). Pressurizing roller 231 and pressurizing roller 232 contact and press against each other on their outer peripheral surfaces, applying pressure to the passing recording medium P2. The pair of pressurizing components included in the pressurizing device 230 is not limited to a combination of pressurizing rollers, but may also be a combination of pressurizing rollers and pressurizing belts, or a combination of pressurizing belts.

[0335] If pressure is applied to the recording medium P2 via the pressurizing device 230, the pressure-responsive particles of this embodiment flow and exhibit adhesion on the recording medium P2 due to the pressure. The pressure applied to the recording medium P2 by the pressurizing device 230 is preferably 3 MPa or more and 300 MPa or less, more preferably 10 MPa or more and 200 MPa or less, and even more preferably 30 MPa or more and 150 MPa or less.

[0336] The pressurizing device 230 may or may not have an internal heating source (e.g., a halogen heater) for heating the recording medium P2. When the pressurizing device 230 has an internal heating source, the surface temperature of the recording medium P2 when heated by the heating source is preferably 30°C or higher and 120°C or lower, more preferably 40°C or higher and 100°C or lower, and even more preferably 50°C or higher and 90°C or lower. Furthermore, even if the pressurizing device 230 does not have an internal heating source, it does not preclude the possibility that the temperature inside the pressurizing device 230 may reach or exceed the ambient temperature due to heat generated by the motor or other components included in the pressurizing device 230.

[0337] The recording medium P2 is pressurized by a pressurizing device 230, thereby bonding the folded surfaces together using fluidized pressure-responsive particles of this embodiment to produce a press-printed material P3. Partial or all of the opposing surfaces in the press-printed material P3 are bonded together.

[0338] Remove the completed press-printed material P3 from the self-pressurizing device 230.

[0339] The first form of the press-printed material P3 is a press-printed material formed by bonding folded recording media on opposite surfaces using pressure-responsive particles according to this embodiment. This type of press-printed material P3 is manufactured by a printing apparatus including a bending device 220.

[0340] The second form of the overprinted material P3 is an overprinted material formed by bonding multiple overlapping recording media on opposite surfaces using pressure-responsive particles according to this embodiment. This type of overprinted material P3 is manufactured by an overprinted material manufacturing apparatus including an overlay device.

[0341] The printing apparatus of this embodiment is not limited to an apparatus that continuously transports the recording medium P2 from the bending device 220 (or the overlay device) to the pressurizing device 230. The printing apparatus of this embodiment may also be an apparatus that stores the recording medium P2 output from the bending device 220 (or the overlay device) and transports the recording medium P2 to the pressurizing device 230 after the storage amount of the recording medium P2 reaches a predetermined amount.

[0342] In the printing apparatus of this embodiment, the bending device 220 (or overlapping device) and the pressurizing device 230 may be in a close proximity or in a separate configuration. When the bending device 220 (or overlapping device) and the pressurizing device 230 are separate, they are connected, for example, via a conveying component (e.g., a belt conveyor) that conveys the recording medium P2.

[0343] The printing apparatus of this embodiment may include a cutting member for cutting a recording medium to a predetermined size. Examples of cutting members include: a cutting member disposed between the placement member 100 and the pressing member 200 that cuts off areas that are part of the recording medium P1 and are not configured with the pressure-responsive particles of this embodiment; a cutting member disposed between the bending device 220 and the pressing device 230 that cuts off areas that are part of the recording medium P2 and are not configured with the pressure-responsive particles of this embodiment; and a cutting member disposed downstream of the pressing member 200 that cuts off areas that are part of the pressed printed material P3 and are not bonded using the pressure-responsive particles of this embodiment.

[0344] The printing apparatus of this embodiment is not limited to a single-sheet apparatus. The printing apparatus of this embodiment can be an apparatus that, after forming a strip of laminated printed material by performing a configuration step and a lamination step on a strip of recording medium, cuts the strip of laminated printed material into a predetermined size and pattern.

[0345] The printing apparatus of this embodiment may further include a color image forming unit, which forms a color image on a recording medium using a colored electrostatic image developer and by electrophotography. The color image forming unit includes, for example:

[0346] Photoreceptor;

[0347] A charged component that charges the surface of the photoreceptor;

[0348] The electrostatic image forming component forms an electrostatic image on the surface of the charged photoreceptor;

[0349] The developing unit contains a colored electrostatic image developer and uses the colored electrostatic image developer to develop the electrostatic image formed on the surface of the photoreceptor as a colored toner image.

[0350] The transfer unit transfers a colored toner image formed on the surface of the photoreceptor to the surface of the recording medium; and

[0351] A thermal fixing unit performs thermal fixing on a colored toner image transferred to the surface of the recording medium.

[0352] The manufacturing apparatus using the described structure is used to implement a manufacturing method for printed matter according to this embodiment, which further includes a colored image forming step of forming a colored image on a recording medium using a colored electrostatic image developer and by electrophotography. The colored image forming step specifically includes:

[0353] The charging step charges the surface of the photoreceptor.

[0354] The electrostatic charge image formation step involves forming an electrostatic charge image on the surface of the charged photoreceptor;

[0355] The developing step involves developing the electrostatic image formed on the surface of the photoreceptor as a colored toner image using a colored electrostatic image developer.

[0356] The transfer step involves transferring a colored toner image formed on the surface of the photoreceptor to the surface of the recording medium; and

[0357] The thermal fixing step involves thermally fixing the colored toner image transferred to the surface of the recording medium.

[0358] The colored image forming component included in the printing apparatus of this embodiment is, for example, the following apparatus: a direct transfer method apparatus that directly transfers a colored toner image formed on the surface of a photoreceptor to a recording medium; an intermediate transfer method apparatus that transfers a colored toner image formed on the surface of a photoreceptor to the surface of an intermediate transfer body in one step, and then transfers the colored toner image transferred to the surface of the intermediate transfer body to the surface of the recording medium in a second step; an apparatus including a cleaning component that cleans the surface of the photoreceptor before it becomes charged after the colored toner image is transferred; and an anti-static component that removes static electricity by irradiating the surface of the photoreceptor with anti-static light before it becomes charged after the colored toner image is transferred, etc. In the case of an apparatus in which the color image forming component is an intermediate transfer method, the transfer component includes, for example: an intermediate transfer body that transfers a colored toner image to a surface; a primary transfer component that transfers a colored toner image formed on the surface of a photoreceptor to the surface of the intermediate transfer body in a primary transfer; and a secondary transfer component that transfers a colored toner image transferred to the surface of the intermediate transfer body to the surface of a recording medium in a secondary transfer.

[0359] In the printing apparatus of this embodiment, when the placement component of the developer containing the pressure-responsive particles of this embodiment and the color image forming component adopt an intermediate transfer method, the placement component and the color image forming component may share an intermediate transfer body and a secondary transfer component.

[0360] In the printing apparatus of this embodiment, the dispensing unit of the developer containing the pressure-responsive particles of this embodiment and the color image forming unit may share a thermal fixing unit. That is, the thermal fixing unit in the color image forming unit may also serve as the fixing unit in the dispensing unit.

[0361] The following describes an example of a printing apparatus according to this embodiment, which includes a colored image forming component; however, this embodiment is not limited to this. In the following description, the main parts shown in the figures will be described, and the description of other parts will be omitted.

[0362] Figure 3This is a schematic structural diagram illustrating an example of a printing apparatus according to this embodiment that applies an electrophotographic method. Figure 3 The apparatus for manufacturing printed matter shown includes: a printing unit 300, which performs the configuration of pressure-responsive particles and the formation of a colored image on a recording medium in this embodiment; and a pressing unit 200, which is disposed downstream of the printing unit 300.

[0363] The printing unit 300 is a five-string serial printing unit with an intermediate transfer method. The printing unit 300 includes: a unit 10T for configuring the pressure-responsive particles (T) of this embodiment, and units 10Y, 10M, 10C, and 10K for forming images of yellow (Y), magenta (M), cyan (C), and black (K). Unit 10T is a configuration unit that configures the pressure-responsive particles of this embodiment on the recording medium P using a developer containing the pressure-responsive particles of this embodiment. Units 10Y, 10M, 10C, and 10K are respectively units that form colored images on the recording medium P using a developer containing colored toner. Units 10T, 10Y, 10M, 10C, and 10K are produced using an electrophotographic method.

[0364] Units 10T, 10Y, 10M, 10C, and 10K are arranged side-by-side, spaced apart from each other in the horizontal direction. Units 10T, 10Y, 10M, 10C, and 10K may also be processing boxes that are detachably mounted on the printing component 300.

[0365] An intermediate transfer belt (an example of an intermediate transfer body) 20 is provided extending below units 10T, 10Y, 10M, 10C, and 10K through each unit. The intermediate transfer belt 20 is provided wound around a drive roller 22, a support roller 23, and an opposing roller 24 that are in contact with the inner surface of the intermediate transfer belt 20, and moves in the direction from unit 10T toward unit 10K. An intermediate transfer body cleaning device 21 is included on the image holding surface side of the intermediate transfer belt 20, facing the drive roller 22.

[0366] Furthermore, as an intermediate transfer body cleaning device 21, for example, Figure 10 As shown, a structure in which a doctor blade 72 (an example of a removal component) and a squeegee 74 are arranged relative to the intermediate transfer belt 20 can also be adopted. The doctor blade 72 and the squeegee 74 are each formed as a flat plate extending axially along the drive roller 22, and one end (fixed end) of the doctor blade 72 and the squeegee 74 is connected to and fixed to a squeegee bracket (not shown) containing a metal plate.

[0367] Furthermore, the other end (free end) of the doctor blade 72 is configured to contact the outer peripheral surface of the intermediate transfer belt 20. Specifically, the free end of the doctor blade 72 contacts the upstream end of the portion of the intermediate transfer belt 20 wound on the drive roller 22 in the direction of movement at a contact angle β.

[0368] On the other hand, the squeegee 74 contacts the planar portion 20A on the upstream side of the moving direction of the intermediate transfer belt 20, which is further upstream than the squeegee blade 72, at a contact angle γ. Furthermore, an opposing roller 76 is provided on the inner circumferential surface of the intermediate transfer belt 20 to prevent the intermediate transfer belt 20 from slipping off due to the contact pressure of the squeegee 74. In addition, the contact pressure and contact angle of the squeegee 74 are set to be greater than those of the squeegee blade 72.

[0369] Thus, if the intermediate transfer cleaning device 21 is made into a multi-segment scraper with a scraper blade 72 and a squeegee 74, the squeegee 74 can be used to evenly level the pressure-responsive particles and other residues remaining on the intermediate transfer belt 20, and the scraper blade 72 can be used to scrape off the evenly leveled residues, thereby improving the removal of the residues (removal efficiency).

[0370] Furthermore, a brush roller (not shown) can be used instead of the squeegee 74. Alternatively, a cooling mechanism (not shown) for cooling the intermediate transfer belt 20 can be provided upstream of the squeegee blade 72 in the direction of movement. This cooling mechanism may include, for example, a cooling pipe (not shown) that contacts the inner circumferential surface of the intermediate transfer belt 20.

[0371] Specifically, the configuration is as follows: a temperature detection component detects the surface temperature of the intermediate transfer belt 20, and a control component controls a flow control component based on the detected temperature, thereby adjusting the flow rate of the coolant circulating in the cooling pipe. Accordingly, residues remaining on the intermediate transfer belt 20 are cooled and hardened by the cooling pipe, thus improving the scraping performance (cleanability) of the doctor blade 72.

[0372] On the other hand, units 10T, 10Y, 10M, 10C, and 10K respectively include developing apparatuses (an example of a developing component) 4T, 4Y, 4M, 4C, and 4K. Each of the developing apparatuses 4T, 4Y, 4M, 4C, and 4K is supplied with pressure-responsive particles, yellow pigment, magenta pigment, cyan pigment, and black pigment of this embodiment, which are housed in cartridges 8T, 8Y, 8M, 8C, and 8K.

[0373] Furthermore, since units 10T, 10Y, 10M, 10C, and 10K have the same structure and operation, the following description will focus on unit 10T, which is configured with pressure-responsive particles on a recording medium according to this embodiment.

[0374] Unit 10T includes a photoreceptor 1T (an example of a conveying member). Around the photoreceptor 1T are arranged sequentially: a charging roller (an example of a charging component) 2T, which charges the surface of the photoreceptor 1T; an exposure device (an example of an electrostatic image forming component) 3T, which exposes the charged surface of the photoreceptor 1T using laser light to form an electrostatic image; a developing device (an example of a developing component) 4T, which supplies pressure-responsive particles to the electrostatic image and develops the image; a primary transfer roller (an example of a primary transfer component) 5T, which transfers the developed pressure-responsive particles onto an intermediate transfer belt 20; and a photoreceptor cleaning device (an example of a cleaning component) 6T, which removes the pressure-responsive particles remaining on the surface of the photoreceptor 1T after the primary transfer. The primary transfer roller 5T is disposed inside the intermediate transfer belt 20 and is positioned opposite the photoreceptor 1T.

[0375] Here, specific examples are given to illustrate the photoreceptor cleaning device 6T.

[0376] First, let's explain the first specific example. For example... Figure 4 As shown, the photoreceptor cleaning device 6T includes: a cleaning scraper 32 (an example of a removal component) that contacts the surface of the rotating photoreceptor 1T to remove residual particles such as pressure-responsive particles remaining after transfer; and a recovery spiral conveyor 33 that carries the recovered residue to a recovery box (not shown) disposed outside the image forming unit (not shown).

[0377] The cleaning scraper 32 includes a support member 34 and an elastic member 35 engaged with the support member 34. The elastic member 35 includes a base layer 36 engaged with the support member 34 and a contact layer 38 with a greater hardness than the base layer 36 and in contact with the surface of the photoreceptor 1T.

[0378] Furthermore, the contact angle α between the elastic member 35 of the cleaning scraper 32 and the surface of the photoreceptor 1T is set to be 7.0° or more and 15.5° or less, and the pressing pressure N relative to the surface of the photoreceptor 1T is set to 0.6 gf / mm. 2 Above and 6.0gf / mm 2 the following.

[0379] The contact angle α between the elastic member 35 of the cleaning scraper 32 and the photoreceptor 1T refers to the angle formed by the side of the cleaning scraper 32 contact layer 38 opposite to the surface of the photoreceptor 1T, and the downstream side of the tangent Q at the position where the cleaning scraper 32 contact layer 38 and the surface of the photoreceptor 1T are in the direction of rotation, as viewed from the rotation axis of the photoreceptor 1T.

[0380] In addition, the pressing pressure N of the elastic member 35 of the cleaning scraper 32 relative to the photoreceptor 1T refers to the pressure applied towards the center of the photoreceptor 1T at the position where the contact layer 38 of the cleaning scraper 32 contacts the surface of the photoreceptor 1T.

[0381] The support member 34 can support the elastic member 35 by means of an adhesive or the like, and at a ratio of 0.6 gf / mm. 2 Above and 6.0gf / mm 2 The following pressure presses the elastic member 35 against the surface of the photosensitive element 1T. Examples of materials that constitute this support member 34 include metals such as aluminum and stainless steel.

[0382] On the other hand, the elastic member 35 is an elastic member with a hardness of 77 or higher and 85 or lower using a Type A hardness tester at 23°C, and a resilience coefficient of 35% or higher and 45% or lower. Here, the Type A hardness of the elastic member 35 refers to the value obtained by measuring it using a Type A hardness tester specified in JISK 7215 according to the hardness test method shown in JISK 7311.

[0383] Furthermore, the resilience of the elastic member 35 is determined according to the Lupke-style resilience test of JIS K6255, the Resilience Test Method for Vulcanized Rubber and Thermoplastic Rubber. Ideally, the sample to be tested should be placed sufficiently at the stated temperature (23°C in the case of testing resilience at 23°C) beforehand to ensure it meets the testing conditions. Additionally, materials for the elastic member 35 may include, for example, elastomers such as polyurethane rubber, silicone rubber, and chloroprene rubber.

[0384] According to the cleaning scraper 32 in the first specific example above, the hardness of the contact portion with the surface of the photoreceptor 1T can be increased, the wear resistance of the cleaning scraper 32 can be improved, and the removal of residues such as pressure-responsive particles remaining on the surface of the photoreceptor 1T can be improved.

[0385] Secondly, the second specific example will be explained. For example... Figure 5 , Figure 6As shown, a cleaning scraper 40 (an example of a removal member) is provided on the downstream side of the frame 30, further downstream of the sealing member 46 in the direction of rotation of the photoreceptor 1T (arrow A direction). Specifically, a base 42, serving as one end of the cleaning scraper 40, is fixedly supported on the lower outer surface of a metal plate 48, which is a support substrate with an approximately "L"-shaped cross-section arranged along the axial direction of the photoreceptor 1T, by means of attachment. Furthermore, the metal plate 48 is fixed to the upper outer surface of the frame 30 by a locking screw 49.

[0386] The cleaning scraper 40 comprises an elastic material and is formed in a plate shape (scraper shape). For example, its thickness (t) is set to 2.0 mm, and its free length (width not fixed to the metal plate 48 (length in the vertical direction): L) is set to 10.0 mm. Furthermore, examples of the elastic material include thermosetting polyurethane rubber, silicone rubber, fluororubber, and ethylene-propylene-diene rubber, which possess excellent mechanical properties such as wear resistance, chip resistance, and creep resistance. Here, the cleaning scraper 40 is constructed from silicone rubber.

[0387] like Figure 5 , Figure 6 As shown, the cleaning scraper 40 is configured such that its tip (lower end) 44 faces the opposite side of the rotation direction (arrow A direction) of the photoreceptor 1T, with its edge 45 in contact with the surface of the photoreceptor 1T. Furthermore, the contact angle α of the cleaning scraper 40 is adjusted to be 5° or more and 20° or less.

[0388] The contact angle α of the cleaning scraper 40 is given by α = θ - tan -1 The formula [3d / 2L] (θ: scraper setting angle, d: scraper cutting depth, L: scraper free length) is used to calculate the angle, and these values ​​are adjusted for control. Furthermore, the contact angle α of the cleaning scraper 40 is preferably adjusted to 5° or more and 20° or less, more preferably to 10° or more and 15° or less. Additionally, the scraper setting angle θ is preferably adjusted to 10° or more and 45° or less, more preferably to 15° or more and 30° or less.

[0389] The pressure (pressing pressure) N of the cleaning scraper 40 is determined to be a value that can maintain cleanliness over a long period of time, given by N = dEt. 3 / 4L 3 The force N is calculated using the formula (L: free length of the scraper, t: scraper thickness, E: Young's modulus (hardness) of the scraper material, d: scraper cutting depth). That is, the applied pressure N is controlled by adjusting these values.

[0390] Furthermore, the Young's modulus is adjusted by selecting the material used in the cleaning scraper 40, but for each material, a generally known value can be used, and values ​​described in literature can be applied. Additionally, the scraper thickness is preferably adjusted to 1.0 mm or more and 10.0 mm or less, more preferably to 1.5 mm or more and 4.0 mm or less. Furthermore, the free length of the scraper is preferably adjusted to 3.0 mm or more and 30.0 mm or less, more preferably to 5.0 mm or more and 30.0 mm or less.

[0391] Furthermore, the pressure N of the cleaning scraper 40 is controlled to be 0.5 gf / mm. 2 Above and 5gf / mm 2 The following range applies when the applied pressure N is less than 0.5 gf / mm. 2 In certain situations, pressure-responsive particles and other residues remain unswept at the contact points with the cleaning scraper 40 (passing through) and become adhered, resulting in streaky contamination on the photoreceptor 1T. On the other hand, when the applied pressure N exceeds 5 gf / mm... 2 In such cases, the cleaning scraper 40 is easily worn due to the friction between the cleaning scraper 40 and the surface of the photosensitive material 1T.

[0392] Since the contact angle α and the applied pressure N of the cleaning blade 40 in the second embodiment are set within the aforementioned range, when cleaning pressure-responsive particles and other residues remaining on the surface of the photoreceptor 1T, the residues can be prevented from passing through the cleaning blade 40, thereby suppressing the formation of streaky contamination on the photoreceptor 1T. In other words, the removal efficiency of pressure-responsive particles and other residues remaining on the photoreceptor 1T can be improved. Furthermore, wear on the cleaning blade 40 can be suppressed.

[0393] Secondly, the third specific example will be explained. For example... Figure 7 As shown, the cleaning scraper 50 (an example of a removal component) has: a contact corner 52 that contacts and cleans the surface of the photoreceptor 1T; a front end face 54, where the contact corner 52 forms an edge and faces upstream in the rotation direction of the photoreceptor 1T (arrow A direction); a ventral face 56, where the contact corner 52 forms an edge and faces downstream in the rotation direction of the photoreceptor 1T; and a back face 58 that shares an edge with the front end face 54 and faces the ventral face 56.

[0394] Furthermore, the cleaning blade 50 is attached to and supported by a rigid plate-shaped support member (not shown). Additionally, the cleaning blade 50, including the contact corner 52 that contacts the surface of the photoreceptor 1T, is constructed entirely of a single material. For example, the cleaning blade 50 is made of silicone rubber.

[0395] The M100 / Re ratio (the ratio of 100% modulus (M100 [MPa]) to resilience coefficient (Re [%))) of the cleaning scraper 50 is set to 0.25 or more, preferably 0.28 or more, and more preferably 0.3 or more. Furthermore, from the viewpoint of resistance to defects, the upper limit of the M100 / Re ratio of the contact corner 52 is preferably 1.0 or less, and more preferably 0.9 or less.

[0396] The resilience coefficient (Re[%) of the cleaning scraper 50 is 25% or more, but preferably 28% or more, and more preferably 30% or more. Furthermore, from the viewpoint of suppressing scraper noise and improving wear resistance, the upper limit of the resilience coefficient (Re[%) of the contact corner 52 is preferably 60% or less, and more preferably 40% or less.

[0397] In terms of wear resistance and resistance to defects, the 100% modulus (M100 [MPa]) of the cleaning scraper 50 at 23°C is preferably 4 MPa or more and 10 MPa or less, more preferably 5 MPa or more and 9 MPa or less.

[0398] If the 100% modulus of the cleaning blade 50 is less than 4 MPa, the hardness decreases, the dynamic bending of the cleaning blade 50 increases, and the cleaning blade 50 is prone to uneven wear. On the other hand, if the 100% modulus of the cleaning blade 50 is greater than 10 MPa, the following performance of the cleaning blade 50 relative to the photoreceptor 1T will deteriorate, raising concerns about reduced cleaning performance.

[0399] In the third specific example, the 100% modulus of the cleaning blade 50 is set within the aforementioned range, thus the cleaning blade 50 is less prone to uneven wear, improving cleaning performance (removal of pressure-responsive particles and other residues remaining on the surface of the photoreceptor 1T). Furthermore, the 100% modulus is measured according to J1SK6251. Additionally, regarding the cleaning blade 50, it has been confirmed that it maintains its cleaning function even in an environment with a temperature of 28°C and a humidity of 80%.

[0400] In addition, such as Figure 8 As shown, the cleaning blade 50 can also be configured as the first removal part, and the metal cleaning blade 60 (an example of a removal member) that contacts the surface of the photoreceptor 1T can be configured as the second removal part. That is, the cleaning blade 50 can be used to remove residues such as pressure-responsive particles, and the cleaning blade 60 can be used to remove deposits attached to the surface of the photoreceptor 1T.

[0401] in addition, Figure 4 , Figure 5 The cleaning blades 32 and 40 shown are pressurized relative to the photoreceptor 1T using a simple and low-cost constant displacement method, but are not limited to the constant displacement method. A constant load method with almost no pressure and time-varying constant load can also be used.

[0402] That is, for example, Figure 9 As shown, a structure can be adopted where a pressing spring 66 is positioned at the rotation fulcrum 64, away from the rotating scraper support member 62. The pressing spring 66 applies a load by contacting the cleaning housing 68 only when the cleaning scraper 70 (an example of a removal member) moves away from the surface of the photosensitive element 1T. This maintains a stable contact pressure, thus ensuring adequate removal performance and extending the lifespan of the cleaning scraper 70.

[0403] Hereinafter, while demonstrating the operation of the unit 10T, the operation of configuring the pressure-responsive particles and forming a colored image on the recording medium P according to this embodiment will be explained.

[0404] First, the surface of the photoreceptor 1T is charged using the charged roller 2T. Based on image data sent from a control unit (not shown), the exposure apparatus 3T irradiates the charged surface of the photoreceptor 1T with laser light. As a result, an electrostatic charge image of the arrangement pattern of pressure-responsive particles according to this embodiment is formed on the surface of the photoreceptor 1T.

[0405] The electrostatic charge image formed on the photoreceptor 1T rotates to the developing position as the photoreceptor 1T moves. Then, at the developing position, the electrostatic charge image on the photoreceptor 1T is developed by the developing apparatus 4T to become a pressure-responsive particle imparting part.

[0406] The developing apparatus 4T contains a developer that includes at least the pressure-responsive particles and a carrier of this embodiment. The pressure-responsive particles of this embodiment are agitated and triboelectrically charged together with the carrier inside the developing apparatus 4T and held on the developer roller. The surface of the photoreceptor 1T passes through the developing apparatus 4T, whereby the pressure-responsive particles electrostatically attach to the electrostatically charged image on the surface of the photoreceptor 1T, and the electrostatically charged image is developed using the pressure-responsive particles. The photoreceptor 1T, on which the pressure-responsive particle dispensing portion is formed, then moves, and the pressure-responsive particle dispensing portion developed on the photoreceptor 1T is transported to the primary transfer position.

[0407] When the pressure-responsive particle-imparting portion on the photoreceptor 1T is conveyed to the primary transfer position, a primary transfer bias is applied to the primary transfer roller 5T. The electrostatic force from the photoreceptor 1T towards the primary transfer roller 5T acts on the pressure-responsive particle-imparting portion, thereby transferring the pressure-responsive particle-imparting portion on the photoreceptor 1T onto the intermediate transfer belt 20. Pressure-responsive particles remaining on the photoreceptor 1T are removed and recovered by the photoreceptor cleaning device 6T. The photoreceptor cleaning device 6T may include cleaning blades 32, 40, 50, and 60, as well as cleaning brushes, etc.

[0408] In units 10Y, 10M, 10C, and 10K, the same operation as in unit 10T is performed using a developer containing colored toner. In unit 10T, the intermediate transfer belt 20, on which the pressure-responsive particle delivery section of this embodiment is transferred, sequentially passes through units 10Y, 10M, 10C, and 10K, transferring the toner images of each color multiple times onto the intermediate transfer belt 20.

[0409] An intermediate transfer belt 20, through units 10T, 10Y, 10M, 10C, and 10K, which has multiple transfers of pressure-responsive particle delivery portions and toner images, reaches a secondary transfer section comprising the intermediate transfer belt 20, an opposing roller 24 in contact with the inner surface of the intermediate transfer belt, and a secondary transfer roller (an example of a secondary transfer component) 26 disposed on the image-retaining side of the intermediate transfer belt 20. Meanwhile, a recording medium P is supplied via a supply mechanism to the gap between the secondary transfer roller 26 and the intermediate transfer belt 20, and a secondary transfer bias is applied to the opposing roller 24. At this time, an electrostatic force from the intermediate transfer belt 20 toward the recording medium P acts on the pressure-responsive particle delivery portions and toner images, thereby transferring the pressure-responsive particle delivery portions and toner images on the intermediate transfer belt 20 onto the recording medium P.

[0410] A recording medium P, on which a pressure-responsive particle transfer portion and a toner image are transferred, is conveyed to a thermal fixing apparatus (an example of a thermal fixing unit) 28. The thermal fixing apparatus 28 includes a heating source such as a halogen heater and heats the recording medium P. The surface temperature of the recording medium P during heating by the thermal fixing apparatus 28 is preferably 150°C or higher and 220°C or lower, more preferably 155°C or higher and 210°C or lower, and even more preferably 160°C or higher and 200°C or lower. Passing through the thermal fixing apparatus 28, the colored toner image is thermally fixed onto the recording medium P, and the pressure-responsive particle transfer portion is fixed onto the recording medium P.

[0411] From the viewpoint of suppressing the detachment of pressure-responsive particles from the recording medium P in this embodiment, and from the viewpoint of improving the fixing performance of the color image on the recording medium P, the thermal fixing apparatus 28 is preferably a device that applies pressure together with heating, for example, it may be a pair of fixing members (roller / roller, belt / roller) that include a heating source inside. When the thermal fixing apparatus 28 applies pressure, the pressure applied by the thermal fixing apparatus 28 to the recording medium P can be lower than the pressure applied by the pressure applying device 230 to the recording medium P2, specifically, preferably 0.2 MPa or more and 1 MPa or less.

[0412] The recording medium P passes through the printing member 300, thereby becoming a recording medium P1 that imparts a colored image and pressure-responsive particles according to this embodiment. The recording medium P1 is then conveyed to the crimping member 200.

[0413] Figure 3 The structure of the crimping component 200 can be compared with... Figure 2 The crimping component 200 is the same as that in the previous example, and detailed descriptions of its structure and operation are omitted for the crimping component 200.

[0414] In the printing apparatus of this embodiment, the printing component 300 and the pressing component 200 may be in a close proximity or in a separate configuration. When the printing component 300 and the pressing component 200 are separate, they are connected, for example, by a conveying component (e.g., a belt conveyor) that conveys the recording medium P1.

[0415] The printing apparatus of this embodiment may include a cutting member for cutting a recording medium to a predetermined size. Examples of cutting members include: a cutting member disposed between the printing member 300 and the pressing member 200 that cuts off a region that is part of the recording medium P1 and is not provided with the pressure-responsive particle delivery portion of this embodiment; a cutting member disposed between the bending device 220 and the pressing device 230 that cuts off a region that is part of the recording medium P2 and is not provided with the pressure-responsive particle delivery portion of this embodiment; and a cutting member disposed downstream of the pressing member 200 that cuts off a region that is part of the pressed printed material P3 and is not joined by the pressure-responsive particle delivery portion of this embodiment.

[0416] The printing apparatus of this embodiment is not limited to a single-piece apparatus. The printing apparatus of this embodiment can be an apparatus that, after forming a strip of laminated printed material by performing a color image forming step, a placement step, and a lamination step on a strip of recording medium, cuts the strip of laminated printed material into a predetermined size and pattern.

[0417] <Processing Box>

[0418] The processing box used in the manufacturing apparatus for printed materials using electrophotography is described.

[0419] The processing box of this embodiment is a processing box that can be detachably installed in a printing manufacturing apparatus: it includes a developing component that holds the electrostatic image developer of this embodiment, and the electrostatic image formed on the surface of the photoreceptor is developed as a pressure-responsive particle imparting part using the electrostatic image developer.

[0420] The processing box of this embodiment may have the following structure: including a developing component, and at least one selected from a photoreceptor, a charged component, an electrostatic image forming component, a transfer component, etc., as needed.

[0421] As an example of a processing cartridge, one can exemplify a cartridge in which a photoreceptor, a charged roller (an example of a charged component) surrounding the photoreceptor, a developing apparatus (an example of a developing component), and a photoreceptor cleaning apparatus (an example of a cleaning component) are integrally formed by a frame. The frame has an opening for exposure. The frame has a mounting rail, via which the processing cartridge is mounted to a printing manufacturing apparatus.

[0422] [Example]

[0423] The disclosed implementation methods are described in detail below using examples, but the disclosed implementation methods are not limited to these examples. In the following description, unless otherwise specified, "parts" and "%" are based on mass.

[0424] [Example A]

[0425] <Preparation of Resin Particle Dispersion for Core>

[0426] (Preparation of resin particle dispersion (A1) for the core)

[0427] Styrene: 440 parts

[0428] • n-Butyl acrylate: 130 parts

[0429] Acrylic acid: 20 parts

[0430] • Dodecanethiol: 5 parts

[0431] Solution A is prepared by mixing and dissolving the components.

[0432] On the other hand, 10 parts of anionic surfactant (manufactured by Dow Chemical, DOWFAX 2A1) were dissolved in 250 parts of ion-exchanged water, and the solution A was added to a flask for dispersion and emulsification (monovolume emulsion A).

[0433] Next, 1 part of the same anionic surfactant (manufactured by Dow Chemical, DOWFAX 2A1) was dissolved in 555 parts of deionized water and poured into a polymerization flask. A reflux tube was installed in the polymerization flask, and nitrogen was added while stirring slowly. At the same time, the polymerization flask was heated to 75°C using a water bath and maintained thereafter.

[0434] Dissolve 9 parts of ammonium persulfate in 43 parts of ion-exchanged water, and add the solution dropwise over 20 minutes to a polymerization flask containing an aqueous solution of an anionic surfactant. Then, add monolithic emulsion A dropwise over 200 minutes using a metering pump.

[0435] Subsequently, the polymerization flask was kept at 75°C for 3 hours while continuously stirring to end the first stage of polymerization. Thus, a resin particle dispersion (A1) precursor containing styrene-based resin particles with a volume average particle size of 195 nm, a glass transition temperature of 53°C, and a weight average molecular weight of 32,000 was obtained for the core.

[0436] Next, after lowering the temperature to room temperature (25°C), 240 parts of 2-ethylhexyl acrylate, 160 parts of n-butyl acrylate, 7 parts of decanethiol, and 1200 parts of deionized water were added to a polymerization flask containing the core-type resin particle dispersion (A1). The mixture was slowly stirred for 2 hours. Then, while continuing to stir, the temperature was raised to 70°C, and 4.5 parts of ammonium persulfate and 100 parts of deionized water were added dropwise over 20 minutes using a metering pump. The polymerization was then stopped by continuing to stir for 3 hours. Through these steps, a core-type resin particle dispersion (A1) was obtained, containing composite resin particles with a volume average particle size of 240 nm, a weight average molecular weight of 133,000, and a number average molecular weight of 18,000, and adjusted to a solid content of 30% by mass by adding deionized water.

[0437] The obtained core was dried using a resin particle dispersion (A1) to prepare a sample in which the dried resin particles were embedded in epoxy resin. The sample was then cut with a diamond scalpel to create cross-sectional sections of the resin particles. The cut surfaces of the samples were then stained in ruthenium tetroxide vapor and observed using a transmission electron microscope for confirmation. The cross-sectional observation of the resin particles confirmed that the structure consisted of multiple regions of low-Tg (meth)acrylate resin dispersed within a high-Tg styrene resin matrix.

[0438] Furthermore, when analyzing the glass transition temperature (Tg) behavior of dried resin particles using a differential scanning calorimeter (DSC) manufactured by Shimadzu Corporation from -150°C to 100°C, a glass transition caused by low-Tg (meth)acrylate resin was observed at -59°C. Additionally, a glass transition caused by high-Tg styrene resin was observed at 53°C (glass transition temperature difference: 112°C).

[0439] (Preparation of core-grade resin particle dispersions (A2-A6))

[0440] In the preparation of the core resin particle dispersion (A1) precursor, the amount of dodecyl mercaptan added was changed as shown in Table 1, and the amounts of 2-ethylhexyl acrylate and n-butyl acrylate added after the preparation of the core resin particle dispersion (A1) precursor were also changed as shown in Table 1. Otherwise, the same as the core resin particle dispersion (A1) was obtained, in which composite resin particles with a volume average particle size in the range of 200 nm to 240 nm were dispersed, and the solid content of the core resin particle dispersion (A2) to core resin particle dispersion (A6) was adjusted to 30% by mass by adding ion-exchanged water.

[0441] The weight-average molecular weight, number-average molecular weight, and glass transition temperature difference of the composite resin particles contained in the core resin particle dispersions (A2) to (A6) are shown in Table 1.

[0442] [Table 1]

[0443]

[0444] <Preparation of Resin Particle Dispersion for Shell Part>

[0445] (Preparation of the shell-type resin particle dispersion (B1))

[0446] Styrene: 450 parts

[0447] • n-Butyl acrylate: 135 parts

[0448] Acrylic acid: 10 parts

[0449] • Dodecanethiol: 5 parts

[0450] Solution B is prepared by mixing and dissolving the components.

[0451] On the other hand, 10 parts of anionic surfactant (manufactured by Dow Chemical, DOWFAX 2A1) were dissolved in 250 parts of ion-exchanged water, and the solution B was added to a flask for dispersion and emulsification (monovolume emulsion B).

[0452] Next, 1 part of the same anionic surfactant (manufactured by Dow Chemical, DOWFAX 2A1) was dissolved in 555 parts of deionized water and poured into a polymerization flask. A reflux tube was installed in the polymerization flask, and nitrogen was added while stirring slowly. At the same time, the polymerization flask was heated to 75°C using a water bath and maintained thereafter.

[0453] Dissolve 9 parts of ammonium persulfate in 43 parts of ion-exchanged water, and add the solution dropwise over 20 minutes to a polymerization flask containing an aqueous solution of an anionic surfactant. Then, add monolithic emulsion B dropwise over 200 minutes using a metering pump.

[0454] Subsequently, the polymerization flask was kept at 75°C for 3 hours while continuously stirring to end the first stage of polymerization. This yielded a shell-type resin particle dispersion (B1) containing styrene-based resin particles with a volume average particle size of 200 nm, a glass transition temperature of 53°C, a weight average molecular weight of 33,000, and a number average molecular weight of 15,000, adjusted to a solids content of 30% by mass by adding deionized water.

[0455] <Preparation of Release Agent Dispersion>

[0456] (Preparation of release agent dispersion (1))

[0457] • Fe-Toro wax: 270 pieces

[0458] (Manufactured by Nippon Seiwa (Co., Ltd.), Product Name: FNP-0090, Melting Temperature = 90℃)

[0459] • Anionic surfactant: 1.0 part

[0460] (First Industrial Pharmaceuticals Co., Ltd. manufactures, and Neogen RK)

[0461] • Ion-exchanged water: 400 parts

[0462] The components were mixed and heated to 95°C, dispersed using a homogenizer (Ultraturrax T50 manufactured by IKA), and then dispersed for 360 minutes using a Manton Gaulin high-pressure homogenizer (Gaulin) to prepare a release agent dispersion (1) containing release agent particles with a volume average particle size of 0.23 μm (solid component concentration: 20% by mass).

[0463] <Preparation of Transparent Pressure-Responsive Mother Particles>

[0464] (Preparation of transparent pressure-responsive parent particle (A1))

[0465] • Core-grade resin particle dispersion (A1): 600 parts

[0466] • Release agent dispersion (1): 10 parts

[0467] Colloidal silica aqueous solution: 13 parts

[0468] (Nissan Chemical Co., Ltd. manufactures, Snowtex OS)

[0469] • Ion-exchanged water: 1000 parts

[0470] • Anionic surfactant: 1 part

[0471] (Manufactured by Dow Chemical (incorporated), Dowfax 2A1)

[0472] The components used as core-forming materials were placed into a 3-liter reaction vessel including a thermometer, pH meter, and stirrer. At a temperature of 25°C, 1.0% by mass nitric acid was added and the pH was adjusted to 3.0. Then, using a homogenizer (Ultraturrax T50 manufactured by IKA Ltd., Japan) at 5,000 rpm, 4 parts of the prepared 10% by mass aqueous solution of aluminum chloride were added and dispersed for 6 minutes.

[0473] Next, a stirrer and a mantle heater were installed in the reaction vessel. While thoroughly agitating the slurry, the stirrer speed was adjusted, and the temperature was increased at a rate of 0.2°C / min until 40°C was reached. Once above 40°C, the temperature was increased at a rate of 0.05°C / min. Particle size was measured every 10 minutes using a Multisizer II (pore size: 50 μm, Coulter). When the volume average particle size reached 7.5 μm, the temperature was maintained, and 115 parts of a shell-forming resin particle dispersion (B1) was added over 5 minutes. After maintaining this temperature for 30 minutes, the pH was adjusted to 6.0 using a 1% (w / w) sodium hydroxide aqueous solution. Subsequently, the pH was adjusted to 6.0 every 5°C, and the temperature was increased at a rate of 1°C / min until 90°C was reached, then maintained at 96°C. The shape and surface properties of the particles were observed using an optical microscope and a scanning electron microscope (field emission-scanning electron microscope, FE-SEM). After holding the particles at 96°C for 2.0 hours, the cohesion of the particles was confirmed. Therefore, the container was cooled to 30°C using cooling water for 5 minutes.

[0474] The cooled slurry was passed through a 30 μm nylon mesh to remove coarse particles. The pressure-responsive masterbatch slurry passing through the mesh was then filtered under reduced pressure using an aspirator. The remaining pressure-responsive masterbatch particles on the filter paper were ground as finely as possible by hand and added to 10 times the volume of ion-exchange water at 30°C, and stirred for 30 minutes. This was followed by another round of reduced-pressure filtration using an aspirator, with the remaining particles ground as finely as possible by hand and added to 10 times the volume of ion-exchange water at 30°C, stirred for 30 minutes, and then filtered again under reduced pressure using an aspirator. The conductivity of the filtrate was measured. This process was repeated until the conductivity of the filtrate reached below 10 μS / cm, at which point the pressure-responsive masterbatch particles were washed away. The cleaned pressure-responsive masterbatch particles were finely ground using a wet-dry granulator and then vacuum-dried in a desiccator at 25°C for 36 hours to obtain transparent pressure-responsive masterbatch particles (A1). The obtained transparent pressure-responsive masterbatch particles (A1) had a volume average particle size of 8.5 μm, a weight average molecular weight of 125,000, and a number average molecular weight of 17,000. Furthermore, the temperature T3 at which the transparent pressure-responsive masterbatch particles (A1) exhibited a viscosity of 10,000 Pa·s at 4 MPa was measured to be 69°C. The temperature difference (T1-T3) between T1 (exhibiting a viscosity of 10,000 Pa·s at 1 MPa) and T3 (exhibiting a viscosity of 10,000 Pa·s at 4 MPa) was 17°C.

[0475] Furthermore, the cross-section of the transparent pressure-responsive parent particle (A1) was observed using scanning electron microscopy (SEM), revealing an island structure. The transparent pressure-responsive parent particle (A1) possesses a core with an island phase and a shell without an island phase. The island phase comprises a styrene-based resin, and the island phase comprises a (meth)acrylate-based resin. The average diameter of the island phase was determined using the aforementioned measurement method. The average diameter of the island phase is shown in Table 2.

[0476] (Creation of transparent pressure-responsive parent particles (A2) to transparent pressure-responsive parent particles (A6))

[0477] The core resin particle dispersion shown in Table 2 was used instead of the core resin particle dispersion (A1). Otherwise, transparent pressure responsive master particles (A2) to transparent pressure responsive master particles (A6) were prepared using the same method as the transparent pressure responsive master particles (A1).

[0478] The results obtained by measuring the weight-average molecular weight, number-average molecular weight, temperature T3, temperature difference (T1-T3), and average diameter of the island phase in transparent pressure-responsive parent particles (A2) to transparent pressure-responsive parent particles (A6) are shown in Table 2.

[0479] [Table 2]

[0480]

[0481] <Creation of Added Transparent Pressure-Responsive Particles>

[0482] (The creation of externally added transparent pressure-responsive particles (A1))

[0483] 1.3 parts of hydrophobic silica (manufactured by Aerosil Co., Ltd., Japan, RY50, average primary particle size 40 nm) were added to 100 parts of the obtained transparent pressure-responsive parent particles (A1), and the mixture was ground at 13,000 rpm for 30 seconds using a sample mill. The mixture was then sieved using a vibrating sieve with a mesh size of 45 μm to prepare the externally added transparent pressure-responsive particles (A1). The obtained externally added transparent pressure-responsive particles (A1) had a volume average particle size of 8.6 μm.

[0484] The results obtained by using the method described above to determine the sulfur content and water absorption rate in the added transparent pressure-responsive particles (A1) are shown in Table 3.

[0485] In addition, the temperature T1 and temperature T2 in the externally added transparent pressure-responsive particles (A1) were determined using the method described above, and the results satisfied Equation 1 "10℃≦T1-T2".

[0486] On postcard paper V424 manufactured by Fuji Xerox (stock), the amount applied to the entire image-forming surface of the postcard is 6 g / m². 2 Pressure-responsive particles (A1) are dispersed in a manner that allows them to pass through a roller-type fixing machine, which acts as a fixing device, to fix the pressure-responsive particles to the image-forming surface of the postcard, forming a layer of pressure-responsive particles. Using a PRESSLE multiII sealer manufactured by Toppan Forms, the postcard with the layer of pressure-responsive particles on the image-forming surface is folded in half with the image-forming surface facing inwards. Pressure is applied to the folded postcard, and a pressure of 90 MPa is used to bond the inner image-forming surfaces together.

[0487] Under the aforementioned apparatus and conditions, ten postcards were continuously produced, folded in half with the image-forming surface facing inward and joined together, forming overprinted materials. The presence or absence of deformation and the pressure responsiveness and interlayer peeling properties of the overprinted materials after being placed at 28°C and 85% humidity for one week were evaluated. No deformation was observed. Furthermore, the peeling properties were also good.

[0488] (Creation of Added Transparent Pressure-Responsive Particles (A2) ~ Added Transparent Pressure-Responsive Particles (A6))

[0489] The transparent pressure-responsive parent particles shown in Table 3 were used instead of the transparent pressure-responsive parent particles (A1). Otherwise, the externally added transparent pressure-responsive particles (A2) to (A6) were prepared using the same method as the externally added transparent pressure-responsive particles (A1).

[0490] The results obtained by measuring the volume average particle size, sulfur content, and water absorption rate of the externally added transparent pressure-responsive particles (A2) to (A6) using the method described above are shown in Table 3.

[0491] In addition, the temperature T1 and temperature T2 of the externally added transparent pressure-responsive particles (A2) to (A6) were determined using the method described above. The results showed that any externally added transparent pressure-responsive particle satisfied Equation 1, "10℃≦T1-T2".

[0492] [Table 3]

[0493] <Developing the Developer>

[0494] (Preparation of developer (A1))

[0495] Developer (A1) was prepared by mixing 8 parts of externally added transparent pressure-responsive particles (A1) with 100 parts of the carrier (1) described below using a V-type stirrer.

[0496] (Making of carrier (1))

[0497] Ferrite particles (volume average particle size: 36 μm): 100 parts

[0498] Toluene: 14 parts

[0499] • Styrene-methyl methacrylate copolymer: 2 parts

[0500] (Component ratio: 90 / 10, Mw = 80000)

[0501] • Carbon black (R330: manufactured by Cabot): 0.2 parts

[0502] First, the components other than the ferrite particles are stirred for 10 minutes using a mixer to prepare a dispersed coating liquid. Second, the coating liquid and ferrite particles are placed in a vacuum degassing kneader and stirred at 60°C for 30 minutes. Then, the mixture is heated while being depressurized and degassed to dry it, thereby obtaining the carrier.

[0503] (Preparation of developer (A2) to developer (A6))

[0504] The externally added transparent pressure-responsive particles (A1) shown in Table 4 were used instead of the externally added transparent pressure-responsive particles (A1). Otherwise, the developer (A2) to developer (A6) were prepared using the same method as the developer (A1).

[0505] <Evaluation>

[0506] The obtained developer (i.e., developer (A1) to developer (A6)) is supplied to the fifth developer of the Fuji Xerox (Co., Ltd.) Color1000 Press modified machine, which is pre-filled with colored electrostatic image developers of cyan, magenta, yellow and black in the first to fourth developer units.

[0507] The recording paper (OK Prince Dowling Paper, manufactured by Prince Paper (Co., Ltd., water absorption rate: 1.5% by mass) was set, and the loading of transparent pressure-responsive particles was set to 3 g / m³. 2 This forms an image (area density 30%) that combines text and photographic images, and is applied at a temperature of 170℃ and a pressure of 4.0 kg / cm². 2 The process involves fixing transparent pressure-responsive particles and fixing the colored image. As a sequence for arranging the pressure-responsive particle images, the transparent pressure-responsive particle images are arranged on top of the colored image.

[0508] Recording paper, with transparent pressure-responsive particles fixed and colored images fixed, is bent with the image forming surfaces overlapping, and then pressed using a PRESSLE LEADA (Toppan Forms) press-sealing machine to produce a press-printed material. Furthermore, the pressing temperature is 20°C and the pressure is 90 MPa.

[0509] The evaluation assessed the presence or absence of deformation and the peeling properties between pressure-responsive particle layers of the press-printed material after it had been placed at 28°C and 85% humidity for one week. The presence or absence of deformation was evaluated visually. The peeling properties between pressure-responsive particle layers were evaluated by cutting the press-printed material along its long side to create a 15mm wide rectangular sample, peeling it, and visually confirming whether the colored image had transferred to the opposing surface. The evaluation results for the presence or absence of deformation (“Deformation” in the table) and the peeling properties (“Transfer to the opposing surface” in the table) are shown in Table 4.

[0510] [Table 4]

[0511] Based on the above results, it can be seen that, compared with the comparative example, the deformation after crimping can be suppressed in the embodiment.

[0512] Furthermore, it is known that, compared to Comparative Example A1, the transfer to the phase-facing surface in the embodiments can be suppressed, and the peelability is good. The transfer to the phase-facing surface that occurred in Comparative Example A1 is thought to be due to the high water absorption of the transparent pressure-responsive particles, which improves adhesion.

[0513] [Example B]

[0514] <Preparation of dispersions containing styrene-based resin particles>

[0515] [Preparation of styrene-based resin particle dispersion (St1)]

[0516] Styrene: 390 portions

[0517] • n-Butyl acrylate: 100 parts

[0518] Acrylic acid: 10 parts

[0519] • Dodecanethiol: 7.5 parts

[0520] The materials are mixed and dissolved to prepare a monomer solution.

[0521] Eight parts of anionic surfactant (manufactured by Dow Chemical, Dowfax 2A1) were dissolved in 205 parts of ion-exchanged water, and the monomer solution was added to disperse and emulsify the solution to obtain an emulsion.

[0522] 2.2 parts of anionic surfactant (manufactured by Dow Chemical, Dowfax 2A1) were dissolved in 462 parts of deionized water and placed into a polymerization flask including a stirrer, thermometer, reflux cooling tube and nitrogen inlet tube. The mixture was heated to 73°C while stirring and maintained thereon.

[0523] Dissolve 3 parts of ammonium persulfate in 21 parts of ion-exchanged water, and add the solution dropwise to the polymerization flask over 15 minutes using a metering pump. Then, add the emulsion dropwise over 160 minutes using a metering pump.

[0524] Then, while stirring slowly and continuously, the polymerization flask was kept at 75°C for 3 hours before being brought back to room temperature.

[0525] Thus, a styrene-based resin particle dispersion (St1) containing styrene-based resin particles was obtained, with a volume average particle size (D50v) of 174 nm, a weight average molecular weight of 49 kJ as determined by GPC (ultraviolet (UV) detection), a glass transition temperature of 54 °C, and a solid content of 42%.

[0526] The styrene-based resin particle dispersion (St1) was dried and the styrene-based resin particles were removed. The thermal behavior in the temperature range of -100℃ to 100℃ was analyzed using a differential scanning calorimeter (Shimadzu Corporation, DSC-60A). A glass transition temperature was observed. The glass transition temperatures are shown in Table 5.

[0527] [Preparation of styrene-based resin particle dispersions (St2) to styrene-based resin particle dispersions (St13)]

[0528] Similar to the preparation of styrene-based resin particle dispersion (St1), styrene-based resin particle dispersions (St2) to (St13) were prepared by changing the monomers as described in Table 5.

[0529] In Table 5, the monomers are listed with the following abbreviations.

[0530] Styrene: St, n-Butyl acrylate: BA, 2-Ethylhexyl acrylate: 2EHA, Ethyl acrylate: EA, 4-Hydroxybutyl acrylate: 4HBA, Acrylic acid: AA, Methacrylic acid: MAA, 2-Carboxyethyl acrylate: CEA

[0531] [Table 5]

[0532]

[0533] <Preparation of dispersions containing composite resin particles>

[0534] [Preparation of composite resin particle dispersion (M1)]

[0535] • Styrene-based resin particle dispersion (St1): 1190 parts (500 parts solids)

[0536] ·Ethylhexyl acrylate: 250 parts

[0537] • n-Butyl acrylate: 250 parts

[0538] • Ion-exchanged water: 982 samples

[0539] The material was placed in a polymerization flask, stirred at 25°C for 1 hour, and then heated to 70°C.

[0540] Dissolve 2.5 parts of ammonium persulfate in 75 parts of ion-exchanged water and add the solution dropwise to the polymerization flask over 60 minutes using a metering pump.

[0541] Then, while stirring slowly and continuously, the polymerization flask was kept at 70°C for 3 hours before being brought back to room temperature.

[0542] Thus, 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 as determined by GPC (UV detection), and a solid content of 32% was obtained.

[0543] The composite resin particle dispersion (M1) was dried and the composite resin particles were removed. The thermal behavior in the temperature range of -150°C to 100°C was analyzed using a differential scanning calorimeter (Shimadzu Corporation, DSC-60A). Two glass transition temperatures were observed. The glass transition temperatures are shown in Table 6.

[0544] [Preparation of composite resin particle dispersions (M2) to (M21) and composite resin particle dispersions (cM1) to (cM3)]

[0545] Similar to the preparation of the composite resin particle dispersion (M1), the styrene-based resin particle dispersion (St1) is changed as described in Table 6, or the polymerization composition of the (meth)acrylate-based resin is changed as described in Table 6, thereby preparing composite resin particle dispersions (M2) to (M21) and composite resin particle dispersions (cM1) to (cM3).

[0546] [Preparation of composite resin particle dispersions (M22) to (M27)]

[0547] Similar to the preparation of the composite resin particle dispersion (M1), composite resin particle dispersions (M22) to (M27) are prepared by adjusting the amounts of 2-ethylhexyl acrylate and n-butyl acrylate.

[0548] The monomers in Table 6 are listed with the following abbreviations.

[0549] Styrene: St, n-Butyl acrylate: BA, 2-Ethylhexyl acrylate: 2EHA, Ethyl acrylate: EA, 4-Hydroxybutyl acrylate: 4HBA, Acrylic acid: AA, Methacrylic acid: MAA, 2-Carboxyethyl acrylate: CEA, Hexyl acrylate: HA, Propylene acrylate: PA

[0550] [Table 6]

[0551]

[0552] <Preparation of Pressure-Responsive Particles>

[0553] [Preparation of pressure-responsive particles (1) and developer (1)]

[0554] • Composite resin particle dispersion (M1): 504 parts

[0555] • Ion-exchanged water: 710 parts

[0556] • Anionic surfactant (manufactured by Dow Chemical, Dowfax 2A1)

[0557] 1 copy

[0558] The material was placed in a reaction vessel equipped with a thermometer and a pH meter. At 25°C, a 1.0% nitric acid aqueous solution was added to adjust the pH to 3.0. Then, using a homogenizer (IKA, Ultraturrax T50) at 5000 rpm, 23 parts of a 2.0% aluminum sulfate aqueous solution were added simultaneously. Next, a stirrer and a jacketed heater were installed in the reaction vessel, and the temperature was increased to 40°C at a rate of 0.2°C / min. After exceeding 40°C, the temperature was increased at a rate of 0.05°C / min. Particle size was measured every 10 minutes using a Multisizer II (50 μm pore size, Beckman Coulter). When the volume average particle size reached 5.0 μm, the temperature was maintained, and 170 parts of a styrene-based resin particle dispersion (St1) were added over 5 minutes. After the initial addition, the mixture was kept at 50°C for 30 minutes. Then, a 1.0% sodium hydroxide aqueous solution was added to adjust the pH of the slurry to 6.0. Subsequently, the pH was adjusted to 6.0 every 5°C while simultaneously increasing the temperature to 90°C at a rate of 1°C / min, and this temperature was maintained at 90°C. The particle shape and surface properties were observed using an optical microscope and a field emission scanning electron microscope (FE-SEM). The results confirmed particle aggregation at the 10th hour, so the container was cooled to 30°C using cooling water for 5 minutes.

[0559] The cooled slurry was passed through a 15μm nylon mesh to remove coarse particles. The slurry passing through the mesh was then filtered under reduced pressure using a suction device. Any remaining solids on the filter paper were ground as finely as possible by hand and added to 10 times the volume of the solids in ion-exchanged water (30°C), and stirred for 30 minutes. Then, reduced pressure filtration was performed again using a suction device, and the remaining solids on the filter paper were ground as finely as possible by hand and added to 10 times the volume of the solids in ion-exchanged water (30°C), and stirred for 30 minutes. The filtrate was then filtered under reduced pressure again using a suction device, and the conductivity of the filtrate was measured. This process was repeated until the conductivity of the filtrate reached below 10 μS / cm, at which point the solids were washed away.

[0560] The cleaned solid components were finely ground using a wet-dry granulator and then vacuum dried in an oven at 25°C for 36 hours to obtain pressure-responsive parent particles (1). The volume average particle size of the pressure-responsive parent particles (1) was 8.0 μm.

[0561] 100 parts of pressure-responsive master particles (1) were mixed with 1.5 parts of hydrophobic silica (manufactured by Aerosil Co., Ltd., Japan, RY50) and mixed for 30 seconds at a rotation speed of 13,000 rpm using a sample mill. The mixture was then sieved using a vibrating screen with a mesh size of 45 μm to obtain the pressure-responsive particles (1).

[0562] The pressure-responsive particle (1) was used as the sample, and its thermal behavior in the temperature range of -150°C to 100°C was analyzed using a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-60A). Two glass transition temperatures were observed. The glass transition temperatures are shown in Table 7.

[0563] The temperature T1 and temperature T2 of the pressure-responsive particle (1) were determined using the aforementioned measurement method. The results showed that the pressure-responsive particle (1) satisfied Equation 1, “10℃≦T1-T2”.

[0564] The cross-section of the pressure-responsive particle (1) was observed using a scanning electron microscope (SEM), revealing an island structure. The pressure-responsive particle (1) has a core containing an island phase and a shell without an island phase. The marine phase contains a styrene-based resin, and the island phase contains a (meth)acrylate-based resin. The average diameter of the island phase was determined using the aforementioned measurement method. The average diameter of the island phase is shown in Table 7.

[0565] Ten parts of pressure-responsive particles (1) and 100 parts of the resin-coated carrier described below were placed in a V-type stirrer and stirred for 20 minutes. Then, the mixture was sieved using a vibrating sieve with a mesh size of 212 μm to obtain the developer (1).

[0566] • Mn-Mg-Sr ferrite particles (average particle size 40 μm): 100 parts

[0567] Toluene: 14 parts

[0568] • Polymethyl methacrylate: 2 parts

[0569] • Carbon black (VXC72: manufactured by Cabot): 0.12 parts

[0570] The materials, excluding ferrite particles, were mixed with glass beads (1 mm in diameter, in equal amounts to toluene) and stirred at 1200 rpm for 30 minutes using a sand mill manufactured by Kansai Paint Co., Ltd., to obtain a dispersion. The dispersion and ferrite particles were then placed in a vacuum degassing kneader and dried under reduced pressure while stirring, thereby obtaining a resin-coated carrier.

[0571] [Preparation of pressure-responsive particles (2) to pressure-responsive particles (27) and developer (2) to developer (27)]

[0572] Similar to the preparation of pressure-responsive particles (1), the composite resin particle dispersion and the styrene-based resin particle dispersion are changed as described in Table 7, thereby preparing pressure-responsive particles (2) to pressure-responsive particles (27) and developer (2) to developer (27).

[0573] The temperatures T1 and T2 of the pressure-responsive particles (2) to (27) were determined using the aforementioned measurement method. The results showed that the pressure-responsive particles (2) to (27) all satisfied Equation 1, “10℃≦T1-T2”.

[0574] [Preparation of pressure-responsive particles (c1) to pressure-responsive particles (c3) and developers (c1) to developers (c3) for comparison]

[0575] Similar to the preparation of pressure-responsive particles (1), the composite resin particle dispersion and the styrene-based resin particle dispersion are changed as described in Table 7, thereby preparing pressure-responsive particles (c1) to pressure-responsive particles (c3) and developers (c1) to developers (c3).

[0576] [Evaluation of pressure-responsive phase transitions]

[0577] The temperature difference (T1-T3) was determined as an indicator of how easily pressure-responsive particles undergo a phase transition under pressure. Each pressure-responsive particle was used as a sample, and temperatures T1 and T3 were measured using a flow testing instrument (Shimadzu CFT-500). The temperature difference (T1-T3) was then calculated. Table 7 shows the temperature difference (T1-T3).

[0578] [Evaluation of continuity]

[0579] As a manufacturing apparatus for printed materials, preparation Figure 3 The apparatus shown is a printing device that prepares a printed material, comprising: a printing unit that performs a series of five sequential transfers of pressure-responsive particles and colored images on a recording medium in accordance with the present embodiment; and a pressing unit having a bending device and a pressing device.

[0580] The pressure-responsive particles (or pressure-responsive particles for comparison), yellow pigment, magenta pigment, cyan pigment, and black pigment of this embodiment are placed in the five developing tubes of the printing unit, respectively. The yellow pigment, magenta pigment, cyan pigment, and black pigment are commercially available products manufactured by Fuji Xerox.

[0581] As the recording medium, we prepared postcard paper V424 manufactured by Fuji Xerox.

[0582] The image formed on the postcard paper is an image with an area density of 30%, consisting of a mixture of black text and a full-color photographic image, formed on one side of the postcard paper.

[0583] In this embodiment, the amount of pressure-responsive particles (or pressure-responsive particles for comparison) imparted is set to 3 g / m² in the image-forming area of ​​the postcard paper's image-forming surface. 2 .

[0584] The bending device is designed to fold the postcard paper in half with the image forming surface as the inside.

[0585] The pressure of the pressurizing device is set to 90 MPa.

[0586] Under the aforementioned apparatus and conditions, ten postcards are continuously produced by folding them in half with the image-forming surfaces facing inwards and then joining the image-forming surfaces together.

[0587] The tenth postcard was cut along its long side to a width of 15mm to create a rectangular test piece, which was then subjected to a 90-degree peel test. The peeling speed for the 90-degree peel test was set to 20mm / min. After the start of the test, load (N) was collected at 0.4mm intervals from 10mm to 50mm, and the average value was calculated. The load (N) of the three test pieces was then averaged. The required peel load (N) was classified as follows. The results are shown in Table 7.

[0588] A: 0.8N or more

[0589] B: 0.6N or more but less than 0.8N

[0590] C: 0.4N or more but less than 0.6N

[0591] D: 0.2N or more but less than 0.4N

[0592] E: Less than 0.2N

[0593] [Table 7]

[0594]

Claims

1. A conveyance device comprising: a conveyance member that conveys a spread medium in which pressure-responsive particles are spread, the pressure-responsive particles containing at least a binding resin and having pressure phase transition properties, and a content of sulfur element with respect to the entire pressure-responsive particles is set to a range of 0.1 mass% or more and 0.5 mass% or less by a fluorescent X-ray measurement; and a removal member that removes the pressure-responsive particles remaining on the conveyance member in contact with the conveyance member, the pressure-responsive particles having the pressure phase transition properties are pressure-responsive particles that satisfy the following Formula 1: Formula 1 ••• 10°C ≦ T1 - T2 In Formula 1, T1 is a temperature at which a viscosity of 10,000 Pa-s is shown at a pressure of 1 MPa, and T2 is a temperature at which a viscosity of 10,000 Pa-s is shown at a pressure of 10 MPa, the pressure-responsive particles have at least two glass transition temperatures, and a difference between the lowest glass transition temperature and the highest glass transition temperature is 30°C or more, the binding resin contains a styrene resin containing styrene and other vinyl monomers in a polymerization component and a (meth)acrylate resin containing at least two (meth)acrylates in a polymerization component, a mass ratio of the (meth)acrylate in the entire polymerization component of the (meth)acrylate resin is 90 mass% or more, and a weight average molecular weight of the (meth)acrylate resin is 50,000 or more and 250,000 or less.

2. The conveyance device according to claim 1, wherein the removal member has: a support member; and an elastic member containing a base layer engaged with the support member and a contact layer having a greater hardness than the base layer and being in contact with a surface of the conveyance member. The elastic member has a type A durometer hardness of 77 or more and 85 or less at 23°C, a coefficient of resilience of 35% or more and 45% or less at 23°C, an angle of 7.0° or more and 15.5° or less with respect to the surface of the conveying member, and a pressing pressure of 0.6 gf / mm or more and 6.0 gf / mm or less with respect to the conveying member 2 and 6.0 gf / mm 2 or more and 6.0 gf / mm or less.

3. The conveyance device according to claim 1, wherein the removing member includes silicone rubber, the silicone rubber being set to 0.5 gf / mm or more for the pressing pressure of the conveyance member 2 0.5 gf / mm or more and 5 gf / mm or less 2 Hereinafter, the angle at which the silicone rubber contacts the surface of the conveyance member is set to 5° or more and 20° or less.

4. The conveyance device according to claim 1, wherein the removal member includes a silicone rubber, and a 100% modulus at 23°C of the silicone rubber is set to 4 MPa or more and 10 MPa or less.

5. The conveyance device according to claim 1, wherein the removal member has: a first removal portion that removes the pressure-responsive particles; and a second removal portion that removes an adherent adhering to a surface of the conveyance member, the second removal portion includes a squeegee made of metal.

6. An image forming apparatus comprising: the conveyance device according to any one of claims 1 to 5 that conveys a spread medium; and an image forming portion that forms an image using the pressure-responsive particles spread on the spread medium.

Images