Method for manufacturing printed matter and system for manufacturing printed matter

Abstract

The present invention relates to a printed matter manufacturing method and a printed matter manufacturing system. The printed matter manufacturing method of the present invention has the following steps: a color image forming step; a pressure phase change particle imparting step; a bonding step; and a pressure bonding step. The pressure phase change particle contains a styrene resin containing styrene and other vinyl monomers in the polymerization component and a (meth)acrylate resin containing at least two (meth)acrylates in the polymerization component, the mass ratio of the (meth)acrylate in the entire polymerization component of the (meth)acrylate resin being 90 mass% or more; the pressure phase change particle has at least two glass transition temperatures, and the difference between the lowest glass transition temperature and the highest glass transition temperature among the glass transition temperatures exhibited by the pressure phase change particle is 30°C or more.

Description

Technical Field

[0001] This invention relates to a method for manufacturing printed matter and a system for manufacturing printed matter. Background Technology

[0002] Japanese Patent Application Publication No. 2004-181910 discloses a type of press-fit concealed printed matter, which is a press-fit concealed printed matter (press-fit concealed printed matter) made of postcard paper. The press-fit concealed printed matter has 1 to 4 paper portions connected by bending lines. Public information is printed on the surface of the 1st and 4th paper portions, and concealed information is printed on the surface of the 2nd and 3rd paper portions. It is formed by M-folding. The characteristic feature is that the surface of the 2nd and 3rd paper portions is peelably bonded to each other by a weak adhesive layer, the back of the 1st and 2nd paper portions is non-peelably bonded to each other by a strong adhesive layer, and the back of the 3rd and 4th paper portions is non-peelably bonded to each other by a strong adhesive layer.

[0003] Japanese Patent Application Publication No. 02-265796 discloses a thin magnetic card postal packaging body, characterized in that a thin magnetic card is placed in a predetermined position other than the stamp affixing field, postal code field, and recipient name field on a quadrilateral paper the size of a postcard, which has a stamp affixing field, a postal code field, and a recipient name field. The packaging is sealed with a cover sheet, which is formed of an opaque sheet covering the front of the thin magnetic card and has a seam hole for removing the thin magnetic card.

[0004] Japanese Patent Application Publication No. 05-004477 discloses a folding postcard characterized in that, before and after printing, a specially adjusted pressure-sensitive adhesive is applied to the periphery and interior of a continuous or sheet-like computer-linked printout from an impact printer or laser printer, respectively, and the paper is folded in half and then pressed together, thereby sealing the periphery and interior and making it easy to open. Summary of the Invention

[0005] As a method for manufacturing printed matter, one can cite a method (hereinafter also referred to as "specific method") that involves the following steps: forming a color image on a recording medium using pigments; imparting pressure phase change particles to the recording medium; bonding the color image and pressure phase change particles to the recording medium; and folding and pressing the recording medium with the bonded color image and pressure phase change particles, or overlapping the recording medium with the bonded color image and pressure phase change particles with other recording media and then pressing them together.

[0006] In the press-printed material obtained using the specific method described above, it is required that the outer peripheral edge of the printed material is not easily peeled off even when subjected to impacts, for example.

[0007] The technical problem to be solved by the present invention is to provide a method and system for manufacturing printed matter, which can produce press-fit printed matter in which peeling of the outer peripheral edge is suppressed compared to cases where the image area ratio of the color image of the recording medium at the outer peripheral edge is greater than 20% in the above-described specific method.

[0008] According to a first aspect of the present invention, a method for manufacturing printed matter is provided, comprising the following steps:

[0009] In the color image forming step, a color image with an image area ratio of 20% or less at the outer peripheral edge of the recording medium is formed on the recording medium using a pigment.

[0010] The pressure phase change particle imparting step imparts pressure phase change particles to the region of the recording medium, including the outer peripheral edge.

[0011] The bonding step involves bonding the aforementioned color image and the aforementioned pressure-phase-change particles to the aforementioned recording medium; and

[0012] The pressing step involves folding the recording medium with the aforementioned color image and pressure phase change particles adhered to it and then pressing it, or overlapping the recording medium with the aforementioned color image and pressure phase change particles adhered to it with other recording media and then pressing it.

[0013] The aforementioned pressure-modified phase-change particles comprise styrene-based resins and (meth)acrylate-based resins. 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. The (meth)acrylates account for more than 90% by mass of the total polymerization composition of the (meth)acrylate-based resin.

[0014] The aforementioned pressure phase change particles have at least two glass transition temperatures, and the difference between the lowest and highest glass transition temperatures exhibited by the aforementioned pressure phase change particles is more than 30°C.

[0015] According to the second aspect of the present invention, the image area ratio of the aforementioned color image is 10% or less.

[0016] According to the third aspect of the present invention, the image area ratio of the aforementioned color image is 2% or more.

[0017] According to the fourth aspect of the present invention, the above-mentioned color image forming step is a step of forming a pattern image of a color image on the outer peripheral edge of the above-mentioned recording medium.

[0018] According to the fifth aspect of the present invention, the above-mentioned pattern image is a dotted pattern image.

[0019] According to the sixth aspect of the present invention, the above-mentioned pattern image is a yellow image.

[0020] According to the seventh aspect of the present invention, the mass percentage of styrene in the total polymeric component of the styrene-based resin of the above-mentioned pressure phase change particles is in the range of 60% to 95% by mass.

[0021] According to the eighth aspect of the present invention, the mass ratio of the two (meth)acrylates included as polymerizing components in the (meth)acrylate resin of the pressure phase change particles is in the range of 80:20 to 20:80.

[0022] According to the ninth aspect of the present invention, among the at least two types of (meth)acrylates included as polymerizing components in the (meth)acrylate resin of the above-mentioned pressure phase change particles, the two (meth)acrylates with the highest mass proportion are (meth)acrylate alkyl esters, and the difference in the number of carbon atoms of the alkyl groups of the two (meth)acrylate alkyl esters is in the range of 1 to 4.

[0023] According to the 10th aspect of the present invention, the other vinyl monomers included as polymerization components in the above-mentioned styrene-based resin include (meth)acrylates.

[0024] According to the 11th aspect of the present invention, the other vinyl monomers included as polymerizing components in the above-mentioned styrene-based resin are selected from n-butyl acrylate and 2-ethylhexyl acrylate.

[0025] According to the 12th aspect of the present invention, the above-mentioned styrene-based resin and the above-mentioned (meth)acrylate-based resin contain the same (meth)acrylate as a polymerization component.

[0026] According to the 13th embodiment of the present invention, the above-mentioned (meth)acrylate resin contains 2-ethylhexyl acrylate and n-butyl acrylate as polymerization components.

[0027] According to the 14th aspect of the present invention, in the pressure phase change particles, the content of the styrene-based resin is greater than the content of the (meth)acrylate-based resin.

[0028] According to the 15th aspect of the present invention, the pressure phase change particles have a marine phase comprising the styrene-based resin and an island phase comprising the (meth)acrylate-based resin dispersed in the marine phase.

[0029] According to the 16th aspect of the present invention, the average diameter of the island phase is in the range of 200 nm to 500 nm.

[0030] According to the 17th aspect of the present invention, the pressure phase change particles have a core and a shell, the core containing the styrene-based resin and the (meth)acrylate-based resin, and the shell covering the core.

[0031] According to the 18th aspect of the present invention, the shell layer contains the aforementioned styrene-based resin.

[0032] According to the 19th aspect of the present invention, the temperature at which the above-mentioned pressure phase change particles exhibit a viscosity of 10000 Pa·s at a pressure of 4 MPa is below 90°C.

[0033] According to a 20th aspect of the present invention, a printing manufacturing system is provided, comprising:

[0034] The color image forming unit uses pigment to form a color image on the recording medium in which the image area ratio of the outer peripheral edge of the recording medium is 20% or less;

[0035] The pressure phase change particle delivery section stores pressure phase change particles and delivers the pressure phase change particles to the region of the recording medium including the outer peripheral edge.

[0036] The adhesive portion bonds the aforementioned color image and the aforementioned pressure-phase change particles to the aforementioned recording medium; and

[0037] The crimping section is used to crimp the recording medium, which has the aforementioned color image and pressure phase change particles adhered to it, after folding it; or it is used to crimp the recording medium, which has the aforementioned color image and pressure phase change particles adhered to it, after overlapping it with other recording media.

[0038] The aforementioned pressure-modified phase-change particles comprise styrene-based resins and (meth)acrylate-based resins. 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. The (meth)acrylates account for more than 90% by mass of the total polymerization composition of the (meth)acrylate-based resin.

[0039] The aforementioned pressure phase change particles have at least two glass transition temperatures, and the difference between the lowest and highest glass transition temperatures exhibited by the aforementioned pressure phase change particles is more than 30°C.

[0040] Invention Effects

[0041] According to the above-mentioned first or 13, a method for manufacturing printed matter is provided, which can produce a press-fit printed matter in which peeling of the outer peripheral edge is suppressed compared to the case where the image area ratio of the color image at the outer peripheral edge of the recording medium in the above-mentioned specific method is greater than 20%.

[0042] According to the second embodiment above, a method for manufacturing printed matter is provided, which can produce a press-fit printed matter in which peeling of the outer peripheral edge is suppressed compared to cases where the image area ratio of the color image at the outer peripheral edge of the recording medium is greater than 10%.

[0043] According to the above-mentioned third, fourth or fifth scheme, a method for manufacturing printed matter is provided, which can produce a press-pressed printed matter that suppresses damage during peeling after storage under high temperature and high humidity, compared with the case where the image area ratio of the color image at the outer peripheral edge of the recording medium is less than 2%.

[0044] According to the sixth embodiment above, a method for manufacturing printed matter is provided, which can produce overprinted printed matter in which the pattern image is not easily noticeable compared to the case where the pattern image of the color image at the outer periphery edge of the recording medium is a black image.

[0045] According to the seventh embodiment above, a method for manufacturing printed matter is provided, which, compared with the case where the mass proportion of styrene in the total polymer component of styrene-based resin is greater than 95% by mass, can easily produce press-pressed printed matter with suppressed peeling at the outer peripheral edges.

[0046] According to the eighth embodiment above, a method for manufacturing printed matter is provided, which, compared to cases where the mass ratio of the two (meth)acrylates, which constitute the most abundant mass proportion of at least two (meth)acrylates in a (meth)acrylate resin as a polymerizing component, is outside the range of 80:20 to 20:80, can easily produce a press-pressed printed matter in which peeling at the outer peripheral edge is further suppressed.

[0047] According to the ninth embodiment above, a method for manufacturing printed matter is provided, which, compared to the case where the difference in the number of carbon atoms of the alkyl groups of the two (meth)acrylate alkyl esters is 5 or more, can easily produce a press-pressed printed matter in which peeling at the outer peripheral edge is further suppressed.

[0048] According to the above-mentioned schemes 10, 11 or 12, a method for manufacturing printed matter is provided, which, compared with the case where polystyrene-containing particles are used as pressure phase change particles instead of styrene-based resin, can easily produce press-pressed printed matter in which peeling at the outer peripheral edge is suppressed.

[0049] According to the 14th embodiment above, a method for manufacturing printed matter is provided, which, compared with the case where the content of styrene-based resin is less than the content of (meth)acrylate-based resin, can produce a press-pressed printed matter in which peeling at the outer peripheral edge is maintained.

[0050] According to the aforementioned 15th embodiment, a method for manufacturing printed matter is provided, which, compared to the case where the pressure phase change particles do not have the aforementioned island structure, can easily produce press-pressed printed matter in which peeling at the outer peripheral edge is further suppressed.

[0051] According to the 16th embodiment above, a method for manufacturing printed matter is provided, which can easily produce press-pressed printed matter in which peeling at the outer peripheral edge is suppressed compared to cases where the average diameter of the island phase is greater than 500 nm.

[0052] According to the aforementioned 17th embodiment, a method for manufacturing printed matter is provided, which, compared to the case where the core contains only styrene-based resin or only (meth)acrylate-based resin, can easily produce press-pressed printed matter in which peeling at the outer peripheral edge is suppressed.

[0053] According to the above-mentioned 18th embodiment, a method for manufacturing printed matter is provided, which, compared with the case where the shell does not contain styrene-based resin but contains other resins, can easily produce a press-pressed printed matter in which peeling at the outer peripheral edge is suppressed.

[0054] According to the aforementioned 19th embodiment, a method for manufacturing printed matter is provided, which, compared to the case where pressure phase change particles exhibit a viscosity of 10000 Pa·s at a pressure of 4 MPa at a temperature greater than 90°C, can easily produce press-pressed printed matter with suppressed peeling at the outer peripheral edges.

[0055] According to the aforementioned 20th embodiment, a printing manufacturing system is provided that can produce a press-pressed printed matter in which peeling at the outer periphery is suppressed, compared to cases where the image area ratio of the color image at the outer periphery edge of the recording medium is greater than 20%. Attached Figure Description

[0056] Figure 1 This is a schematic diagram illustrating an example of a recording medium according to this embodiment.

[0057] Figure 2 This is a schematic diagram illustrating another example of the recording medium of this embodiment.

[0058] Figure 3 This is a schematic diagram illustrating an example of a printing manufacturing system according to this embodiment.

[0059] Figure 4 This is a schematic diagram illustrating another example of the printing manufacturing system of this embodiment. Detailed Implementation

[0060] The embodiments of the present invention will now be described. These descriptions and examples are for illustrative purposes only and do not limit the scope of the embodiments.

[0061] In this specification, the upper or lower limit of a numerical range described in stages can be replaced with the upper or lower limit of other numerical ranges described in other stages. Furthermore, the upper or lower limit of a numerical range described in this specification can be replaced with the values ​​shown in the embodiments.

[0062] The term "step" in this specification includes not only independent steps, but also steps that achieve the desired purpose, even if they cannot be clearly distinguished from other steps.

[0063] When describing embodiments in this specification with reference to the accompanying drawings, the configuration of these embodiments is not limited to the configuration shown in the drawings. Furthermore, the sizes of the components in each figure are schematic, and the relative sizes of the components are not limited thereto.

[0064] Each component in this specification may contain two or more corresponding substances. When referring to the amount of each component in the composition of this specification, if there are two or more corresponding substances in the composition, it refers to the total amount of the two or more substances present in the composition, unless otherwise stated.

[0065] The particles corresponding to each component in this specification may contain two or more types. In the case of the presence of two or more particles corresponding to each component in the composition, unless otherwise stated, the particle size of each component refers to the value for a mixture of the two or more particles present in the composition.

[0066] The term "(meth)acrylic acid" in this specification means either "acrylic acid" or "methacrylic acid".

[0067] In this specification, "peel strength" is an indicator of the degree to which the opposing surfaces of the recording medium can peel off from each other, and it has essentially the same meaning as "adhesion," which indicates the degree of adhesion. It should be noted that, in the following text, when simply referred to as "peel strength," it refers to the peel strength between the opposing surfaces of the recording medium; conversely, when simply referred to as "adhesion," it refers to the adhesion between the opposing surfaces of the recording medium.

[0068] [Methods and systems for manufacturing printed materials]

[0069] The method for manufacturing printed matter according to this embodiment includes the following steps: a color image forming step, in which a color image is formed on the recording medium using an ink such that the image area ratio of the color image at the outer peripheral edge of the recording medium is 20% or less; a pressure phase change particle imparting step (hereinafter also referred to as the "imparting step"), in which pressure phase change particles are imparted to the recording medium in a region including at least the outer peripheral edge; an adhesive bonding step, in which the color image and the pressure phase change particles are bonded to the recording medium; and a pressing step, in which the recording medium with the bonded color image and the pressure phase change particles is folded and then pressed, or the recording medium with the bonded color image and the pressure phase change particles is overlapped with other recording media and then pressed.

[0070] Furthermore, the aforementioned pressure phase change particles comprise styrene-based resins and (meth)acrylate-based resins. The styrene-based resins contain styrene and other vinyl monomers in their polymerization components, and the (meth)acrylate-based resins contain at least two types of (meth)acrylates in their polymerization components. The (meth)acrylates account for more than 90% by mass of the total polymerization components of the (meth)acrylate-based resins.

[0071] In addition, the aforementioned pressure phase change particles have at least two glass transition temperatures, and the difference between the lowest and highest glass transition temperatures exhibited by the aforementioned pressure phase change particles is more than 30°C.

[0072] Here, "the outer peripheral edge of the recording medium" refers to the edge along the periphery of the recording surface of the recording medium, specifically, the area at a distance of 0 mm to 5 mm from the periphery.

[0073] Furthermore, "image area ratio" refers to the proportion of the area forming a color image within the outer periphery of the recording medium, calculated as follows. Specifically, it is obtained by calculating the area of ​​the color image formed in a 5mm × 5mm region (hereinafter referred to as the "measurement area") at any 8 locations within the outer periphery of the recording medium, calculating the proportion of the color image area relative to the entire measurement area, and averaging these values. The resulting average value is the image area ratio. It should be noted that the area of ​​the color image is measured, for example, using an image density meter (X-rite, model X-rite938).

[0074] It should be noted that the term "color image" is not particularly limited as long as it contains pigments. For example, an image with an average transmittance of less than 90% for light in the visible region (400nm to 700nm) can be cited. Preferably, the average transmittance of the aforementioned light in a color image is less than 50%, more preferably less than 10%. The aforementioned average transmittance was measured using a spectrophotometer V700 (manufactured by Nippon Spectrophotometer Co., Ltd.).

[0075] In addition, the aforementioned "pressure phase change particles" are particles that undergo a phase change due to pressure, specifically referring to particles that satisfy the following formula 1.

[0076] Equation 1…10℃≦T1-T2

[0077] In Equation 1, T1 is the temperature at which the viscosity reaches 10,000 Pa·s under a pressure of 1 MPa, and T2 is the temperature at which the viscosity reaches 10,000 Pa·s under a pressure of 10 MPa. The methods for determining temperatures T1 and T2 are described below.

[0078] In the following text, the pressure phase change particles will also be referred to as "specific particles": the pressure phase change particles comprise a styrene-based resin and a (meth)acrylate-based resin, 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 more than 90% by mass of the total polymer composition of the (meth)acrylate-based resin, and the pressure phase change particles have at least two glass transition temperatures, wherein the difference between the lowest and highest glass transition temperatures exhibited by the pressure phase change particles is more than 30°C.

[0079] Additionally, the following printed matter is referred to as "overpressed printed matter," which is a printed matter formed by folding a recording medium and pressing its opposing surfaces together, or a printed matter formed by overlapping two or more recording media and pressing their opposing surfaces together.

[0080] In addition, a recording medium to which specific particles are applied to a region including at least the outer edge is called a "post-application recording medium".

[0081] In the printing method of this embodiment, in the specific method described above, by making the image area ratio of the color image at the outer peripheral edge of the recording medium 20% or less and using specific particles as pressure phase change particles, compared with the case where the image area ratio of the color image at the outer peripheral edge of the recording medium is greater than 20%, a press-fit printed product with suppressed peeling at the outer peripheral edge can be obtained. The reason for this is not yet certain, but it is speculated as follows.

[0082] When the image area ratio of the color image at the outer peripheral edge of the recording medium is greater than 20%, for example, when an impact is applied to the periphery of the resulting laminated print, unintentional peeling may occur from the end of the lamination surface. This peeling is believed to mostly originate at the location where the color image is formed at the outer peripheral edge of the recording medium. The reason for this is uncertain, but it is speculated that the adhesion of the recording medium to each other is reduced in the area where the color image is formed compared to areas where no color image is formed, due to the pressure bonding of phase-change particles between the recording media. This reduction in adhesion is considered particularly significant when the color image contains resin (i.e., when a color image is formed using a resin-containing pigment). Furthermore, it is believed that if the image area ratio of the color image at the outer peripheral edge is greater than 20%, the aforementioned reduction in adhesion easily leads to peeling at the outer peripheral edge of the laminated print.

[0083] In contrast, in this embodiment, it is speculated that since the image area ratio of the color image at the outer peripheral edge of the recording medium is less than 20%, the area of ​​reduced adhesion is reduced, thereby suppressing peeling at the outer peripheral edge of the press-printed material.

[0084] Furthermore, in the printing method of this embodiment, in the specific method described above, by making the image area ratio of the color image at the outer peripheral edge of the recording medium 20% or less and using specific particles as pressure phase change particles, compared to the case where particles containing a styrene-based resin and a (meth)acrylate-based resin, and the (meth)acrylate-based resin is a homopolymer of (meth)acrylate, are used without using specific particles, it is possible to produce a press-pressed printed product with suppressed peeling at the outer peripheral edge. The reason for this is not yet certain, but it is speculated as follows.

[0085] It is generally believed that due to the low compatibility between styrene-based resins and (meth)acrylate-based resins, the two resins are contained in the particles in a phase-separated state. It is also believed that if the particles are pressurized, the (meth)acrylate-based resin, with its lower glass transition temperature, will first flow, and this flow will then affect the styrene-based resin, causing both resins to flow as well. Furthermore, it is believed that when the two resins in the particles flow under pressure and then cure under reduced pressure to form a resin layer, the low compatibility will again lead to phase separation.

[0086] It is speculated that in (meth)acrylate-based resins containing at least two types of (meth)acrylates in their polymer composition, by ensuring that at least two types of ester groups are bonded to the main chain, the molecular ordering in the solid state is lower compared to (meth)acrylate homopolymers, thus making them more prone to fluidization under pressure. Furthermore, it is speculated that when the mass percentage of (meth)acrylates in the overall polymer composition of the (meth)acrylate-based resin is 90% or more, the high density of at least two ester groups further reduces the molecular ordering in the solid state, making them even more prone to fluidization under pressure. Therefore, it is speculated that compared to particles of (meth)acrylate homopolymers, the aforementioned specific particles are more prone to fluidization under pressure, i.e., more prone to phase transition due to pressure.

[0087] Furthermore, it can be inferred that methacrylate-based resins containing at least two types of (meth)acrylates in their polymer composition, where the (meth)acrylates constitute 90% or more of the total polymer composition, exhibit very low molecular alignment during re-curing. Therefore, the phase separation from the styrene-based resin is minimal. It is speculated that the smaller the phase separation between the styrene-based and (meth)acrylate-based resins, the higher the uniformity of the bonding surface relative to the adhered material, resulting in superior adhesion produced by compression bonding. Therefore, it can be inferred that the aforementioned specific particles exhibit superior adhesion produced by compression bonding compared to particles of homopolymers of (meth)acrylate-based resins.

[0088] Therefore, it can be inferred that in the method for manufacturing printed matter according to this embodiment, which uses specific particles with excellent adhesion generated by crimping, compared with the case where particles containing a homopolymer of styrene-based resin and (meth)acrylate-based resin, and the (meth)acrylate-based resin is a (meth)acrylate, are used instead of specific particles, crimped printed matter with suppressed peeling at the outer peripheral edge can be manufactured.

[0089] The method for manufacturing printed matter according to this embodiment is carried out using the printing matter manufacturing system of this embodiment shown below.

[0090] The printing manufacturing system of this embodiment includes: a color image forming unit that forms a color image on the recording medium using pigments in such a way that the image area ratio of the color image on the outer peripheral edge of the recording medium is 20% or less; a pressure phase change particle imparting unit that stores specific particles and imparts the specific particles to the recording medium in a region including at least the outer peripheral edge; an adhesive unit that adheres the color image and the specific particles to the recording medium; and a pressing unit that folds and presses the recording medium (i.e., the post-imparting recording medium) to which the color image and the specific particles are adhered, or overlaps and presses the recording medium (i.e., the post-imparting recording medium) to which the color image and the specific particles are adhered, with other recording media (i.e., recording media other than the post-imparting recording medium).

[0091] The steps of the printing method of this embodiment and the mechanisms of the printing system of this embodiment will be described below.

[0092] <Color Image Formation Steps and Color Image Formation Unit>

[0093] In the color image forming step, the color image is formed on the recording medium using a pigment such that the image area ratio of the color image at the outer peripheral edge of the recording medium is 20% or less.

[0094] Figure 1 An example of a recording medium used in the manufacture of overprinted printed matter is shown. Figure 1 The recording surface 50A of the recording medium 50 shown has an outer peripheral edge portion 54 along the periphery 52. ​​The outer peripheral edge portion 54 is a region at a distance D from the periphery 52 of at most 5 mm. In the color image forming step, a color image is formed on the recording surface 50A of the recording medium 50 in such a way that the image area ratio of at least the outer peripheral edge portion 54 is 20% or less.

[0095] The image area ratio of the color image at the outer peripheral edge of the recording medium is 20% or less, and from the perspective of suppressing peeling at the outer peripheral edge of the overprinted material, it is preferably 10% or less, more preferably 7% or less.

[0096] On the other hand, from the perspective of suppressing damage during peeling after storing the press-printed material under high temperature and high humidity, the image area ratio of the color image at the outer peripheral edge of the recording medium is preferably 2% or more, more preferably 3% or more, and even more preferably 4% or more.

[0097] That is, from the perspective of both suppressing peeling at the outer periphery of the press-printed material and suppressing damage during peeling after storing the press-printed material under high temperature and high humidity, the image area ratio of the color image at the outer periphery of the recording medium is preferably 2% to 20%, more preferably 3% to 10%, and even more preferably 4% to 7%.

[0098] The reason why overprinted prints that can be preserved under high temperature and high humidity conditions by making the image area ratio of the color image at the outer peripheral edge of the recording medium 2% or more is uncertain, but it is speculated as follows.

[0099] In press-pressed printed materials, the ends of the pressed surfaces are easily subjected to localized pressure during the pressing process. Therefore, storage under high temperature and humidity conditions can cause a time-dependent increase in localized adhesive strength. Consequently, if peeling occurs at the press-press point, breakage is likely to occur. In contrast, by ensuring that the image area ratio of the color image at the outer periphery of the recording medium is 2% or more, it is presumably possible to suppress the time-dependent increase in adhesive strength in the area forming the color image at the outer periphery, thereby suppressing breakage during peeling.

[0100] There are no particular limitations on the method of making the image area ratio of the color image at the outer peripheral edge of the recording medium 2% or more. For example, a method of forming a color pattern image at the outer peripheral edge of the recording medium can be cited. The pattern image is an image formed by periodically repeating a specific image.

[0101] Specific examples of patterned images include linear patterned images, dotted patterned images, and combinations thereof. Examples of linear patterned images include grid-like patterns and seam-like patterns. Furthermore, the shape of each dot in a dotted patterned image is not particularly limited; it can be geometric shapes such as circles, ellipses, polygons, and stars, or it can be a non-geometric shape.

[0102] When the pattern image is a dotted pattern image, there is no particular limit to the number of dotted images in a 5mm×5mm range; for example, a range of more than 10 and less than 200 dots can be given.

[0103] It should be noted that there are no particular restrictions on the color of the pattern image, but from the perspective of making the pattern image less eye-catching, a yellow pattern image is preferred.

[0104] Figure 2 The image shows an example of a color image recording medium in which a dotted pattern image is formed at the outer periphery. Figure 2In the recording medium 60 shown, a pattern image 66, which serves as a color image, is formed on the outer peripheral edge 64 of the recording surface 60A. The pattern image 66 is a dotted pattern image, with each dot having a circular shape. By forming the pattern image 66 on the outer peripheral edge 64 during the color image formation step, and by ensuring that the image area ratio of the color image on the outer peripheral edge 64 is 2% or more, a press-printed product that is resistant to breakage during peeling after storage under high temperature and high humidity conditions can be obtained.

[0105] Figure 2 In the recording medium 60 shown, the pattern image 66 is formed only at the outer peripheral edge 64, but it is not limited to this. The pattern image 66 can also be formed in the area other than the outer peripheral edge 64, or the pattern image 66 can be formed on the entire recording surface 60A.

[0106] In the color image formation step, there are no particular limitations on the form (image area ratio, shape, color, etc.) of the color image formed in the area outside the outer peripheral edge of the recording surface of the recording medium.

[0107] It should be noted that, in the area outside the outer peripheral edge of the recording surface of the recording medium, from the perspective of suppressing peeling of the outer peripheral edge of the press-printed material, the image area ratio of the color image in the area (hereinafter also referred to as "quasi-peripheral edge") at a distance greater than 5 mm and less than 10 mm from the periphery is preferably 20% or less, more preferably 10% or less, and even more preferably 7% or less.

[0108] There is no particular limitation on the color image forming unit that forms a color image on the recording medium. For example, an apparatus that forms a colored ink image as a color image on the recording medium by inkjet printing using colored ink as a pigment, or an apparatus that forms a colored toner image as a color image on the recording medium by electrophotography using an electrostatic image developer containing a colored toner as a pigment, etc.

[0109] A color image forming unit using inkjet technology may include a liquid printhead that ejects liquid as ink.

[0110] The color image forming unit using inkjet technology can be either a direct ejection method where the liquid nozzle directly ejects liquid onto the recording medium, or an intermediate transfer method where the liquid nozzle ejects liquid onto an intermediate transfer body and transfers the liquid ejected onto the intermediate transfer body to the recording medium.

[0111] A color image forming unit using electrophotography includes, for example: a photoreceptor; a charging mechanism for charging the surface of the photoreceptor; an electrostatic image forming mechanism for forming an electrostatic image on the charged surface of the photoreceptor; a developing mechanism for storing an electrostatic image developer containing a color toner and developing the electrostatic image formed on the surface of the photoreceptor into a color toner image using the electrostatic image developer; and a transfer mechanism for transferring the color toner image formed on the surface of the photoreceptor to the surface of a recording medium.

[0112] The color image forming unit using electrophotography can be a direct method that forms a color image directly onto a recording medium; or it can be an intermediate transfer method that forms a color image on the surface of an intermediate transfer body and transfers the color image formed on the surface of the intermediate transfer body to the surface of the recording medium; it can be equipped with a cleaning unit that cleans the surface of the photoreceptor after color image transfer and before charging, or it can be equipped with a de-energizing mechanism that removes static electricity by irradiating the surface of the photoreceptor with de-energizing light after color image transfer and before charging.

[0113] It should be noted that when the color image forming unit of the electrophotographic method is an intermediate transfer device, the transfer mechanism includes, for example: an intermediate transfer body that transfers a colored toner image to a surface; a primary transfer mechanism that transfers a colored toner image formed on the surface of a photoreceptor to the surface of the intermediate transfer body in one step; and a secondary transfer mechanism that 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.

[0114] Specifically, the steps for forming a color image on a recording medium can include, for example: forming a colored ink image on a recording medium by inkjet printing using colored ink as a pigment; forming a colored toner image on a recording medium by electrophotography using an electrostatic image developer containing a colored toner as a pigment; and so on.

[0115] The color image formation steps using inkjet technology include, for example, a liquid ejection step that ejects a liquid as ink.

[0116] The color image formation step using inkjet technology can be either a direct ejection method, in which liquid is ejected directly onto the recording medium, or an intermediate transfer method, in which liquid is ejected onto an intermediate transfer medium and then transferred onto the recording medium.

[0117] The color image forming steps using electrophotography include, for example, the following steps: a charging step, charging the surface of a photoreceptor; an electrostatic image forming step, forming an electrostatic image on the charged surface of the photoreceptor; a developing step, developing the electrostatic image formed on the surface of the photoreceptor into a colored toner image using an electrostatic image developer containing a colored toner; and a transfer step, transferring the colored toner image formed on the surface of the photoreceptor to the surface of a recording medium.

[0118] Recording media used in the color image formation process include, for example, paper, coated paper made by coating the surface of paper with resin, cloth, non-woven fabric, resin film, resin sheet, etc.

[0119] The recording medium forms an image on one or both sides through a color image forming step.

[0120] <Pressure phase change particle application steps and pressure phase change particle application section>

[0121] In the application step, specific particles are applied to a region of the recording medium, including at least the outer peripheral edge, at the pressure phase change particle application section (hereinafter also referred to as the "application section"). It should be noted that details regarding the specific particles are described below.

[0122] There are no particular restrictions on the specific particle imparting mechanism of the imparting part, as long as it is a mechanism that can impart specific particles to the target imparting position on the surface of the recording medium with the target imparting amount.

[0123] Specifically, as a mechanism for imparting specific particles, it includes methods such as blowing specific particles, coating specific particles, and electrophotography using specific particles as colorants.

[0124] (Assigning a position to a specific particle)

[0125] Specific particles are applied to at least one surface of the recording medium, to a region of the recording surface of the recording medium that includes at least the outer peripheral edge.

[0126] The location of a specific particle can be the entire surface of the recording medium or a portion thereof.

[0127] Furthermore, the location assigned to a specific particle on the recording medium can be either a region on the recording surface of the recording medium where no image is formed (i.e., a non-image area), or a region where an image is formed (i.e., an image area) or a non-image area.

[0128] As described below, the specific particles are preferably transparent.

[0129] When specific particles are applied to the image section of a recording medium, the visibility of the image section is good by making the specific particles transparent.

[0130] In this embodiment, "transparency" means that the area to which the specific particles are applied has an average transmittance of 10% or more for light in the visible light region (400 nm to 700 nm), preferably 50% or more, more preferably 80% or more, and even more preferably 90% or more.

[0131] The average transmittance mentioned above was measured using a V700 spectrophotometer (manufactured by Japan Spectrophotometer Co., Ltd.).

[0132] (The state assigned to a specific particle)

[0133] As a state of specific particles, it can be a state that retains the shape of the particles, or a state in which specific particles are aggregated to form a layer. From the perspective of obtaining sufficient peel strength (or adhesion generated by compression), it is preferable to form a layer.

[0134] A layer formed by specific particles can be a continuous layer or a discontinuous layer.

[0135] The preferred amount of specific particles, from the perspective of obtaining sufficient adhesion generated by compression, is 0.5 g / m. 2 Above 8.0g / m 2 The following, or more preferably, is 1.0 g / m 2 Above 6.0g / m 2 The following, and more preferably, is 1.5 g / m 2 Above 5.0g / m 2 the following.

[0136] (Assignment of specific particles)

[0137] Regarding the application of specific particles, as mentioned above, there are no particular restrictions as long as the target application location can be applied with specific particles. Specifically, this can be achieved using methods such as blowing specific particles, coating specific particles, or electrophotographic methods using specific particles as toners. Specific particles can be applied by falling directly onto the recording medium or by roller coating. There are no particular limitations on the method of applying specific particles, as long as the recording medium can be applied.

[0138] As an example of a part that imparts specific particles to a recording medium, as mentioned above, examples include a part for a blowing method that imparts specific particles, a part for a coating method that applies specific particles, and a part for an electrophotographic method that uses specific particles as a toning agent.

[0139] The imparting steps based on the blowing method include, for example, the step of preparing a dispersion containing specific particles; the step of blowing the dispersion onto a recording medium; and the step of drying the dispersion blown onto the recording medium.

[0140] In addition, the delivery unit based on the blowing method includes, for example, a blowing mechanism for blowing a dispersion containing specific particles onto a recording medium, and a drying mechanism for drying the dispersion blown onto the recording medium.

[0141] As a blowing mechanism, an atomizer can be cited as an example. As a drying mechanism, a hot air supply device, a near-infrared heater, or a laser irradiation device can be cited as an example.

[0142] The application steps based on the coating method may include, for example, a step of coating specific particles onto the recording medium. In this coating method, a coating liquid in which the specific particles are dispersed can be used. The application steps based on a coating method using a coating liquid may include, for example, a step of preparing a coating liquid in which the specific particles are dispersed; a step of applying the coating liquid onto the recording medium; and a step of drying the coating liquid applied to the recording medium.

[0143] Furthermore, the application unit based on the coating method may include, for example, a coating mechanism for coating specific particles onto the recording medium. The application unit based on a coating method using a coating liquid may include, for example, a coating mechanism for coating the coating liquid onto the recording medium, and a drying mechanism for drying the coating liquid coated onto the recording medium.

[0144] As a coating mechanism, a roller can be used, for example.

[0145] The electrophotographic method includes, for example, a charging step for charging the surface of an image holder; an electrostatic image forming step for forming an electrostatic image on the charged surface of the image holder; a developing step for developing the electrostatic image formed on the surface of the image holder into a specific particle area using an electrostatic image developer containing specific particles; and a transfer step for transferring the specific particle area formed on the surface of the image holder to the surface of a recording medium.

[0146] Additionally, the electrophotographic-based imparting unit may include, for example: an image holder; a charging mechanism for charging the surface of the image holder; an electrostatic image forming mechanism for forming an electrostatic image on the charged surface of the image holder; a developing mechanism for storing an electrostatic image developer containing specific particles and developing the electrostatic image formed on the surface of the image holder into a specific particle area using the electrostatic image developer; and a transfer mechanism for transferring the specific particle area formed on the surface of the image holder to the surface of the recording medium.

[0147] In the electrophotographic feeding section, the portion including the developing mechanism can be a cartridge structure (so-called a processing cartridge) that is loaded and unloaded in the particle feeding device. As a processing cartridge, for example, it is suitable to use a processing cartridge that has a developing mechanism that stores an electrostatic image developer containing specific particles, and the processing cartridge is loaded and unloaded in the particle feeding device.

[0148] Both the electrophotographic method and the electrophotographic unit can use the electrophotographic image forming method and the image forming apparatus, and can use the known steps and mechanisms employed in the electrophotographic image forming method and the image forming apparatus.

[0149] Furthermore, the electrophotographic method and the application unit can employ an intermediate transfer method. In the intermediate transfer method, for example, specific granular regions formed on the surface of the image holder are temporarily transferred to the surface of an intermediate transfer body, and then finally transferred from the surface of the intermediate transfer body to the surface of the recording medium.

[0150] Furthermore, the electrophotographic method and the electrophotographic part may include, for example, a step and mechanism for cleaning the surface of the image holder, and a device having a de-electrostatic mechanism for irradiating the surface of the image holder with de-electrostatic light to remove static electricity, as well as other mechanisms and steps not mentioned above.

[0151] When using a recording medium on which an image is formed, specific grain can be pre-applied to the recording medium on which the image is formed, or the image forming step and the grain application step can be performed continuously on the recording medium.

[0152] As a method for performing the image forming step and the assignment step consecutively, examples include performing the assignment step after the image forming step using an inkjet recording method, and performing the image forming step and the assignment step using an electrophotographic method. Specifically, for example, a method can be used to form a composite image on the surface of a recording medium using an image forming pigment (preferably colored ink) from the image forming step and specific particles from the assignment step.

[0153] <Adhesion Steps and Adhesion Parts>

[0154] In the bonding step, for example, the color image formed on the recording medium and the specific particles imparted to the recording medium are heated at the bonding section.

[0155] There are no particular limitations on the mechanism for heating color images and specific particles (hereinafter also referred to as "particle heating mechanism"), as long as it is a mechanism capable of heating color images formed on the recording medium and specific particles applied to the recording medium.

[0156] As a mechanism for heating color images and specific particles (particle heating mechanism), it can be either a contact method or a non-contact method.

[0157] Contact-type particle heating mechanisms can include methods that heat components such as rollers, belts, and pads, and then bring these heated components into contact with a color image and specific particles.

[0158] Examples of non-contact particle heating mechanisms include: methods that heat a recording medium with a color image and specific particles by means of a heater, oven, or other heated area; methods that heat the color image and specific particles by means of illumination light from a halogen lamp, xenon lamp, or the like; and so on.

[0159] In terms of being able to heat specific particles and suppress the movement and detachment of specific particles, the bonding step preferably uses a particle heating mechanism with a contact method.

[0160] That is, the particle heating mechanism is preferably a contact-type particle heating mechanism.

[0161] (Heating of specific particles using contact method)

[0162] When heating a color image and specific particles using a contact method, the set temperature of the component that brings the color image and specific particles into contact (also called the contact component) is only required to be a temperature that can plasticize the specific particles. From the perspective of heating efficiency of the specific particles, for example, it is preferably 120°C to 250°C, more preferably 130°C to 200°C, and even more preferably 150°C to 180°C.

[0163] Here, the set temperature of the contact component refers to the target value of the surface temperature of the contact component that is in contact with the color image and specific particles.

[0164] As a contact component, there are no particular limitations as long as it is a component with a surface that can be heated to the aforementioned set temperature; for example, rollers, belts, pads, etc. can be cited.

[0165] The bonding step is preferably a step of heating and pressurizing the color image and specific particles.

[0166] By heating and pressurizing a color image and specific particles, smoothness can be imparted to the surface of specific particles (e.g., the surface of a specific particle layer).

[0167] The pressure applied to the color image and specific particles during the bonding step can be exemplified by the pressure applied by a fixing mechanism using electrophotography.

[0168] Examples of mechanisms (also known as heating and pressurizing components) that heat and pressurize color images and specific particles can be cited below.

[0169] That is, examples include: heated and pressurized roller pairs, which are two roller pairs in contact, with heat applied by at least one of the rollers, through which a recording medium with a color image and specific grain is inserted, applying heat and pressure; heated and pressurized components, which are components in contact between rollers and belts, with heat applied by at least one of the rollers and belts, through which a recording medium with a color image and specific grain is inserted, applying heat and pressure; heated and pressurized belt pairs, which are two belt pairs in contact, with heat applied by at least one of the belts, through which a recording medium with a color image and specific grain is inserted, applying heat and pressure; and so on.

[0170] <Crimping Steps and Crimping Section>

[0171] In the pressing step, a laminate is formed by folding the specific particles between a recording medium with a color image and specific particles bonded together (i.e., a post-recording medium), or a laminate formed by overlapping the specific particles between a post-recording medium with a color image and specific particles bonded together and other recording media, is pressed along the thickness direction.

[0172] The folding shape of the recording medium after application can be, for example, a fold in half, a third fold, a fourth fold, or a folding shape where only a portion of the recording medium is folded. It should be noted that, at this time, at least a portion of at least one of the two opposing surfaces of the recording medium after application is configured with heated specific particles through an adhesive bonding step.

[0173] The overlapping configuration of the post-converted recording medium with other recording media can take the following forms: one other recording medium is overlapped on the post-converted recording medium; one other recording medium is overlapped at multiple locations on the post-converted recording medium; and so on. Here, the other recording medium can be a recording medium with an image pre-formed on one or both sides, a recording medium without an image, or a pre-made laminated print. It should be noted that at this time, at least a portion of at least one of the two opposing sides of the post-converted recording medium and the other recording medium is configured with heated specific particles through an adhesive bonding step.

[0174] There are no particular restrictions on the mechanism for pressurizing the laminate (laminate pressurizing mechanism), as long as it is a mechanism that can pressurize the laminate along the thickness direction. It can be a mechanism that inserts the laminate through and between separate roller pairs, or a mechanism that uses a press or the like to pressurize the laminate.

[0175] The preferred step of the pressing step is to insert the laminate through the rollers separated by a gap C and press the laminate along the thickness direction.

[0176] That is, the laminate pressing mechanism is preferably a mechanism that inserts the laminate through between roller pairs separated by a distance C and presses the laminate along the thickness direction.

[0177] Here, the spacing C can be appropriately determined based on the thickness of the laminate being pressurized, from the perspective of obtaining the target peel strength (or the adhesion generated by the press), for example, preferably 0.01 mm or more and 0.40 mm or less, more preferably 0.05 mm or more and 0.30 mm or less, and even more preferably 0.10 mm or more and 0.25 mm or less.

[0178] (Conditions for pressurization)

[0179] The pressure applied in the thickness direction of the laminate (hereinafter also referred to as "crushing pressure") is preferably 48 MPa or more and 120 MPa or less, more preferably 60 MPa or more and 110 MPa or less, and even more preferably 80 MPa or more and 100 MPa or less, measured by the maximum pressure gauge.

[0180] By applying a crimping pressure of 48 MPa or higher, sufficient adhesion generated by crimping can be easily obtained. Furthermore, by applying a crimping pressure of 120 MPa or lower, damage and deformation of the recording medium during pressurization can be easily suppressed.

[0181] The crimping pressure was measured using a commercially available pressure measuring membrane. Specifically, a suitable pressure measuring membrane is the Prescale pressure measuring film manufactured by Fuji Film Co., Ltd. It should be noted that the maximum pressure mentioned above represents the maximum pressure change during the period when pressure is applied to the laminate using a laminate pressurization mechanism.

[0182] Commercially available devices can be used as pressurization mechanisms for laminates. Specifically, examples include PRESSLE LEADA, PRESSLE CORE, and PRESSLE Bee manufactured by ToppanForms Co., Ltd., and PS-500H, PS-500, EX-4100WI, EX-4100W, EX-4100 / 4150, and PS-100 manufactured by DUPLO SEIKO Co., Ltd.

[0183] The crimping process can be performed without heating or with heating.

[0184] That is, the lamination pressurization mechanism may not have a heating mechanism and pressurize the lamination without heating, or it may have a heating mechanism and pressurize the lamination while heating.

[0185] In the method for manufacturing printed matter according to this embodiment, in addition to the color image forming step, the imparting step, the bonding step, and the pressing step described above, other steps may also be included.

[0186] Other steps include trimming the lamination to the target size after the bonding step with a recording medium or after the pressing step.

[0187] <An Example of a Manufacturing System and Manufacturing Method>

[0188] The following is an example of a printing manufacturing system according to this embodiment, and the printing manufacturing method according to this embodiment will be explained, but this embodiment is not limited thereto.

[0189] Figure 3 This is a schematic configuration diagram illustrating an example of a printing manufacturing system according to this embodiment. Figure 3 The printed matter manufacturing system shown includes: a printing unit 500, which uniformly forms a color image on a recording medium using an inkjet method and applies specific grains; and a pressing unit 200, disposed downstream of the printing unit 500. Arrows indicate the direction of transport of the recording medium.

[0190] In the printing unit 500, as an example of a color image forming unit, an inkjet recording head 520 is provided that sprays ink droplets onto a recording medium P to form a color image.

[0191] A particle application device 518 is disposed downstream of the recording medium P as viewed from the inkjet recording head 520 in the transport direction (arrow direction in the figure) to impart specific particles 516 to the surface of the recording medium P. The particle application device 518 is an example of an application section that imparts specific particles to the recording medium by coating.

[0192] In addition, the printing mechanism 500 includes: a recording medium storage section (not shown) for storing a recording medium P; a conveying section (not shown) for conveying the recording medium P stored in the recording medium storage section; an adhesive device 564 for adhering ink droplets and specific particles 516 applied to the recording medium P to the recording medium P; and a recording medium discharge section (not shown) for discharging the recording medium P with ink droplets and specific particles 516 adhered by the adhesive device 564.

[0193] The bonding device 564 includes: a heating roller 564A with a built-in heating source; and a pressure roller 564B disposed opposite to the heating roller 564A.

[0194] The particle supplying device 518 is a device for supplying specific particles 516 to the surface of the recording medium P, thereby forming a specific particle region 516A on the surface of the recording medium P.

[0195] In the particle feeding device 518, a supply roller 518A is provided in the part opposite to the recording medium P, and specific particles 516 are fed to the corresponding coating area.

[0196] In the particle feeding device 518, specific particles 516 are supplied to the feed roller 518A (conductive roller), and the amount of specific particles 516 supplied to the recording medium P (i.e., the layer thickness of the specific particle region 516A supplied to the recording medium P in a layered manner) is adjusted.

[0197] The inkjet recording head 520 comprises an inkjet recording head 520Y that ejects yellow ink droplets from a nozzle, an inkjet recording head 520M that ejects magenta ink droplets from a nozzle, an inkjet recording head 520C that ejects cyan ink droplets from a nozzle, and an inkjet recording head 520K that ejects black ink droplets from a nozzle. These inkjet recording heads 520 are driven by piezoelectric, thermal, or other methods.

[0198] The inkjet recording head 520 can be a recording head that ejects droplets onto the recording medium P to record an image while maintaining a recording amplitude greater than or equal to the recording area and without moving in a direction intersecting the transport direction of the recording medium P. Alternatively, it can be a recording head that ejects droplets onto the recording medium P while moving in a direction intersecting the transport direction of the recording medium P to record an image.

[0199] Furthermore, regarding the ink ejected by the inkjet recorder 520, both water-based and oil-based inks can be used; from an environmental perspective, water-based inks are more suitable. In addition to recording materials such as pigments, water-based inks may also contain ink solvents (such as water and water-soluble organic solvents). Additionally, other additives may be included as needed.

[0200] In the printing unit 500, firstly, the recording medium P is conveyed from the recording medium storage unit to the inkjet recording head 520 via the transport unit. At this time, the inkjet recording head 520 applies ink droplets of various colors to the recording medium P to form a color image. Next, the recording medium P with the formed color image is conveyed to the grain application device 518 via the transport unit. At this time, the grain application device 518 applies specific grains 516 to the recording medium P to form a specific grain area 516A.

[0201] The recording medium P, on which the color image and specific grain region 516A are formed, is then conveyed to the bonding device 564 (an example of a bonding section). The pressure applied to the recording medium P by the bonding device 564 can be a low pressure lower than the pressure applied to the recording medium P by the pressure device 230, specifically, preferably 0.2 MPa or more and 1 MPa or less. The surface temperature of the recording medium P when heated by the heating roller 564A of the bonding device 564 is preferably 150°C or more and 220°C or less, more preferably 155°C or more and 210°C or less, and even more preferably 160°C or more and 200°C or less.

[0202] As described above, the recording medium P is passed through the printing mechanism 500, thereby becoming a post-recording medium P1 that forms a color image and is given specific grain.

[0203] Next, the recording medium P1 is transferred toward the crimping mechanism 200.

[0204] In the printing manufacturing system of this embodiment, the printing mechanism 500 and the pressing mechanism 200 can be close together or separated.

[0205] When the printing mechanism 500 is separated from the pressing mechanism 200, the printing mechanism 500 and the pressing mechanism 200 can be connected, for example, by a transport mechanism (e.g., a belt conveyor) that transports the recording medium P1 after it is applied.

[0206] The crimping mechanism 200 includes a folding device 220 and a pressing device 230, and is a mechanism for crimping the applied recording medium P1 after folding it.

[0207] The folding device 220 folds the recording medium P1 after it has been applied by the device, thus creating a folded recording medium, namely a laminate P2.

[0208] It should be noted that in the folded recording medium (i.e., the laminate), at least a portion of at least one of the two opposing surfaces of the recording medium is provided with specific particles imparted by the printing mechanism 500.

[0209] The crimping mechanism 200 may also have an overlapping device that overlaps the applied recording medium with other recording media instead of the folding device 220.

[0210] In the recording medium obtained by the overlay device, i.e., the laminate, at least a portion of at least one of the two opposing surfaces of the recording medium and other recording media after application is provided with specific particles applied by the printing mechanism 500.

[0211] The laminate P2, which leaves the folding device 220 (or overlapping device), is conveyed toward the pressurizing device 230.

[0212] The pressurizing device 230 includes, for example, a pair of pressurizing components (i.e., pressurizing rollers 231 and 232). The pressurizing rollers 231 and 232 are spaced apart by a gap C, and pressure is applied along the thickness direction of the laminate P2 by passing the laminate P2 between the rollers. The pair of pressurizing components in the pressurizing device 230 is not limited to a combination of pressurizing rollers, but can also be a combination of pressurizing rollers and a pressurizing belt, or a combination of pressurizing belts.

[0213] The pressurizing device 230 may or may not have a heating source (e.g., a halogen heater) for heating the laminate P2. When the pressurizing device 230 has a heating source, the surface temperature of the laminate P2 after being heated by the heating source is preferably 30°C to 120°C, more preferably 40°C to 100°C, and even more preferably 50°C to 90°C. It should be noted that when the pressurizing device 230 does not have a heating source, it is possible that the temperature inside the pressurizing device 230 may reach or exceed the ambient temperature due to heat dissipation from the motor or other components included in the pressurizing device 230.

[0214] When pressure is applied to the laminate P2 passing through the pressurizing device 230, the folded surfaces are bonded together by fluidized specific particles to produce a press-printed material P3.

[0215] In the produced press-printed material P3, the opposing surfaces are partially or completely bonded together.

[0216] The completed press-printed material P3 is removed from the pressurizing device 230.

[0217] The first method of press-printed P3 is press-printed by bonding folded recording media with specific particles on opposite sides.

[0218] The press-printed material P3 is manufactured using a printing manufacturing system equipped with a folding device 220.

[0219] The second type of overprinted print P3 is an overprinted print made by bonding two or more overlapping recording media together with specific particles on opposite surfaces.

[0220] The overprinted print P3 is manufactured using an overprinted print manufacturing system equipped with an overprinting device.

[0221] The printing manufacturing system of this embodiment is not limited to a device that continuously conveys the laminate P2 from the folding device 220 (or overlapping device) to the pressurizing device 230.

[0222] The printing manufacturing system of this embodiment can also be an apparatus in the following manner: storing the laminate P2 that has left the folding device 220 (or overlapping device), and after the storage amount of the laminate P2 reaches a preset amount, transferring the laminate P2 to the pressurizing device 230.

[0223] In the printing manufacturing system of this embodiment, the folding device 220 (or overlapping device) and the pressurizing device 230 can be close together or separated. When the folding device 220 (or overlapping device) and the pressurizing device 230 are separated, the folding device 220 (or overlapping device) and the pressurizing device 230 are connected, for example, through a conveying mechanism (e.g., a belt conveyor) that conveys the laminate P2.

[0224] Furthermore, the printing manufacturing system of this embodiment may include a cutting mechanism for pre-cutting the recording medium to a preset size. The cutting mechanism may be, for example, the following: a cutting mechanism disposed between the printing mechanism 300 and the pressing mechanism 200 that cuts off areas that are part of the applied recording medium P1 and do not have specific particles; a cutting mechanism disposed between the folding device 220 and the pressing device 230 that cuts off areas that are part of the laminate P2 and do not have specific particles; a cutting mechanism disposed downstream of the pressing mechanism 200 that cuts off areas that are part of the pressed printed material P3 and are not bonded by specific particles; and so on.

[0225] It should be noted that a portion of an area containing specific particles can also be cut off using a cutting mechanism.

[0226] The printing system of this embodiment is not limited to a single-page device. The printing system of this embodiment can also be a device that forms a strip-shaped press-fit printed product by performing a configuration step and an assignment step on a strip-shaped recording medium, and then cuts the strip-shaped press-fit printed product to a preset size.

[0227] Figure 4 This is a schematic configuration diagram illustrating an example of a printing manufacturing system according to this embodiment. Figure 4 The printed matter manufacturing system shown includes: a printing mechanism 300, which uniformly forms a color image on a recording medium and imparts specific grain; and a pressing mechanism 200, which is disposed downstream of the printing mechanism 300.

[0228] The printing mechanism 300 is a five-drum series printing mechanism with intermediate transfer printing.

[0229] The printing unit 300 includes: a unit 10T for imparting specific particles (T); and units 10Y, 10M, 10C, and 10K for forming images of yellow (Y), magenta (M), cyan (C), and black (K). Unit 10T is a particle-imparting mechanism (i.e., an imparting section) that imparts specific particles to a recording medium P using a developer containing specific particles. Units 10Y, 10M, 10C, and 10K are mechanisms for forming colored images (i.e., color images) on the recording medium P using a developer containing color toners. Units 10T, 10Y, 10M, 10C, and 10K employ electrophotography.

[0230] Units 10T, 10Y, 10M, 10C, and 10K are arranged side-by-side at horizontal intervals. Units 10T, 10Y, 10M, 10C, and 10K can be processing boxes that are loaded and unloaded in the printing unit 300.

[0231] Below units 10T, 10Y, 10M, 10C, and 10K, an intermediate transfer belt (an example of an intermediate transfer body) 20 extends through each unit. The intermediate transfer belt 20 is wound around a drive roller 22, a support roller 23, and a counter roller 24 that are in contact with the inner surface of the intermediate transfer belt 20, causing it to move in a direction from unit 10T toward unit 10K. An intermediate transfer body cleaning device 21 is provided on the image holding side of the intermediate transfer belt 20, opposite to the drive roller 22.

[0232] Units 10T, 10Y, 10M, 10C, and 10K are equipped with developing apparatuses (an example of a developing mechanism) 4T, 4Y, 4M, 4C, and 4K, respectively. Specific particles, yellow toner, magenta toner, cyan toner, and black toner stored in cartridges 8T, 8Y, 8M, 8C, and 8K are supplied to the developing apparatuses 4T, 4Y, 4M, 4C, and 4K, respectively.

[0233] Units 10T, 10Y, 10M, 10C, and 10K have the same structure and operation, so unit 10T, which imparts specific particles to the recording medium, will be used as an example for explanation.

[0234] Unit 10T includes a photoreceptor (an example of an image holder) 1T. Around the photoreceptor 1T are arranged in sequence: a charging roller (an example of a charging mechanism) 2T, which charges the surface of the photoreceptor 1T; an exposure device (an example of an electrostatic image forming mechanism) 3T, which exposes the charged surface of the photoreceptor 1T using a laser line to form an electrostatic image; a developing device (an example of a developing mechanism) 4T, which supplies specific particles to the electrostatic image and develops the image to form a specific particle area; a primary transfer roller (an example of a primary transfer mechanism) 5T, which transfers the specific particle area formed by development onto an intermediate transfer belt 20; and a photoreceptor cleaning device (an example of a cleaning unit) 6T, which removes the specific 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.

[0235] The following example illustrates the operation of unit 10T in terms of imparting specific grain and forming a color image on the recording medium P.

[0236] First, the surface of the photoreceptor 1T is charged using the charging roller 2T. The exposure apparatus 3T then irradiates a laser line onto the surface of the charged photoreceptor 1T based on image data sent from a control unit (not shown). This forms an electrostatic image on the surface of the photoreceptor 1T, representing areas where specific particles are applied.

[0237] The electrostatic image formed on the photoreceptor 1T rotates to the developing position as the photoreceptor 1T rotates. Then, at the developing position, the electrostatic image on the photoreceptor 1T is developed by the developing apparatus 4T, forming a specific particle area.

[0238] The developing apparatus 4T stores a developer containing at least specific particles and a carrier. The specific particles are agitated together with the carrier inside the developing apparatus 4T, thereby generating triboelectric charge and being held on the developer rollers. The surface of the photoreceptor 1T passes through the developing apparatus 4T, thereby electrostatically attaching the specific particles to the electrostatic image on the surface of the photoreceptor 1T. The electrostatic image is developed using the specific particles, thus forming a specific particle region. The photoreceptor 1T, having formed the specific particle region, continues to operate, conveying the specific particle region formed on the photoreceptor 1T to a primary transfer position.

[0239] When a specific particle area on the photoreceptor 1T is conveyed to the primary transfer position, a transfer bias is applied to the primary transfer roller 5T. An electrostatic force from the photoreceptor 1T towards the primary transfer roller 5T acts on the specific particle area, transferring the specific particle area on the photoreceptor 1T onto the intermediate transfer belt 20. Specific particles remaining on the photoreceptor 1T are removed and recovered by the photoreceptor cleaning device 6T. The photoreceptor cleaning device 6T is, for example, a cleaning scraper, a cleaning brush, etc., preferably a cleaning brush.

[0240] In units 10Y, 10M, 10C, and 10K, the same operation as in unit 10T is performed using a developer containing toners. The intermediate transfer belt 20, which has been used to transfer a specific grainy area in unit 10T, is then passed sequentially through units 10Y, 10M, 10C, and 10K, thus transferring the toner images multiple times onto the intermediate transfer belt 20.

[0241] The intermediate transfer belt 20, which has undergone multiple transfers of specific grain regions and four toner images via units 10T, 10Y, 10M, 10C, and 10K, arrives at the secondary transfer section. This secondary transfer section consists of the intermediate transfer belt 20, an opposing roller 24 in contact with the inner surface of the intermediate transfer belt, and a secondary transfer roller 26 (an example of a secondary transfer mechanism) disposed on the image holding side of the intermediate transfer belt 20. Meanwhile, the recording medium P is fed to the gap between the secondary transfer roller 26 and the intermediate transfer belt 20 by a supply member, and a secondary transfer bias is applied to the opposing roller 24. At this time, electrostatic forces from the intermediate transfer belt 20 toward the recording medium P act on the specific grain regions and toner images, transferring the specific grain regions and toner images from the intermediate transfer belt 20 onto the recording medium P.

[0242] A recording medium P, on which a specific particle area and toner image are transferred, is conveyed to a heating device (an example of a particle heating mechanism) 28, which serves as an adhesive part. By heating with the heating device 28, the colored toner image is thermally fixed on the recording medium P, and the specific particle area is heated to promote the plasticization of the specific particles.

[0243] From the perspective of suppressing the shedding of specific particles from the recording medium P, improving the fixing properties of the colored toner on the recording medium P, and promoting the plasticization of specific particles, the heating device 28 is preferably a device that applies pressure while heating (also called a heating and pressurizing device).

[0244] When the heating device 28 is a heating and pressurizing device, it preferably includes a heating source such as a halogen heater, and includes a pair of rollers that contact and heat the specific particle area and toner image on the recording medium P. By passing the recording medium having the specific particle area and toner image between the rollers, the colored toner image is thermally fixed on the recording medium P, and the specific particle area is heated, promoting the plasticization of the specific particles.

[0245] By passing the recording medium P through the printing mechanism 300 as described above, it becomes a post-recording medium P4 with a color image formed and given specific grain.

[0246] Next, the recording medium P4 is transferred to the crimping mechanism 200.

[0247] In the printing manufacturing system of this embodiment, the printing mechanism 300 and the pressing mechanism 200 can be close together or separated.

[0248] When the printing mechanism 300 and the pressing mechanism 200 are separated, the printing mechanism 300 and the pressing mechanism 200 are connected, for example, through a transport mechanism (e.g., a belt conveyor) that transmits the recording medium P4.

[0249] Figure 4 The crimping mechanism 200 shown is Figure 3 The crimping mechanism 200 shown is also a mechanism that includes a folding device 220 and a pressing device 230, which folds the recording medium P4 and crimps the resulting laminate P5 to obtain a crimped printed product P6.

[0250] As Figure 4 The crimping mechanism 200 in the printing manufacturing system shown is used with Figure 3 The same crimping mechanism 200 is shown in the printing manufacturing system.

[0251] <Specific particles>

[0252] The specific particles in this embodiment contain at least master particles and, if necessary, additives.

[0253] That is, the master particles contained in the specific particles contain styrene-based resin and (meth)acrylate-based resin. The styrene-based resin contains styrene and other vinyl monomers in its polymerization composition. The (meth)acrylate-based resin contains at least two (meth)acrylates in its polymerization composition. The (meth)acrylates account for more than 90% by mass of the total polymerization composition of the (meth)acrylate-based resin. Furthermore, the master particles have at least two glass transition points, and the difference between the lowest and highest glass transition temperatures is more than 30°C. The particles are described below.

[0254] [Master Particles]

[0255] (Adhesive resin)

[0256] The masterbatch contains a styrene-based resin and a (meth)acrylate-based resin as the binding resin. The styrene-based resin contains styrene and other vinyl monomers in its polymerization component, and the (meth)acrylate-based resin contains at least two (meth)acrylates in its polymerization component. The (meth)acrylates account for more than 90% by mass of the total polymerization component of the (meth)acrylate-based resin.

[0257] In the following text, "styrene-based resins containing styrene and other vinyl monomers in the polymer composition" are also referred to as "specific styrene-based resins", and "(meth)acrylate resins containing at least two (meth)acrylates in the polymer composition, wherein the (meth)acrylates account for more than 90% by mass of the total polymer composition of the (meth)acrylate resin" are also referred to as "specific (meth)acrylate resins".

[0258] In the masterbatch, from the perspective of maintaining the adhesion generated by compression, it is preferable that the content of a specific styrene-based resin is greater than the content of a specific (meth)acrylate-based resin. The content of the specific styrene-based resin relative to the total content of the specific styrene-based resin and the specific (meth)acrylate-based resin is preferably 55% by mass or more and 80% by mass or less, more preferably 60% by mass or more and 75% by mass or less, and even more preferably 65% ​​by mass or more and 70% by mass or less.

[0259] -Specific styrene-based resins-

[0260] The master particles that make up the specific particles contain a specific styrene-based resin that includes styrene and other vinyl monomers in the polymer composition.

[0261] From the perspective of suppressing the flow of specific particles in an unpressurized state, the mass percentage of styrene in the total polymeric component of the specific 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.

[0262] From the perspective of forming specific particles that are prone to phase change due to pressure, the mass percentage of styrene in the total polymeric component of a specific styrene-based resin is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0263] That is, the mass percentage of styrene in the total polymer components of a specific styrene-based resin is preferably 60% by mass or more and 95% by mass or less.

[0264] Other vinyl monomers (hereinafter also referred to as other vinyl monomers) included in the polymerization components of a particular styrene-based resin, such as styrene monomers and acrylic monomers, can be listed as examples.

[0265] Other styrene monomers among vinyl monomers include, for example: 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, 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, 2,5-difluorostyrene; nitro-substituted styrene such as m-nitrostyrene, o-nitrostyrene, p-nitrostyrene; and so on.

[0266] These styrene monomers can be used individually or in combination of two or more.

[0267] As an acrylic monomer among other vinyl monomers, at least one acrylic monomer selected from the group consisting of (meth)acrylic acid and (meth)acrylates is preferred. Examples of (meth)acrylates include alkyl (meth)acrylates, carboxyl-substituted alkyl (meth)acrylates, hydroxyl-substituted alkyl (meth)acrylates, alkoxy-substituted alkyl (meth)acrylates, and di(meth)acrylates.

[0268] These acrylic monomers can be used alone or in combination of two or more.

[0269] 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.

[0270] Examples of carboxyl-substituted alkyl esters of (meth)acrylic acid include (meth)acrylic acid-2-carboxyethyl ester.

[0271] 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.

[0272] Examples of alkoxy-substituted alkyl esters of (meth)acrylate include 2-methoxyethyl (meth)acrylate.

[0273] Examples of di(meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, pentanediol di(meth)acrylate, hexanediol di(meth)acrylate, nonanediol di(meth)acrylate, and decanediol di(meth)acrylate.

[0274] Other examples of (meth)acrylates include 2-(diethylamino)ethyl (meth)acrylate, benzyl (meth)acrylate, and methoxy polyethylene glycol (meth)acrylate.

[0275] Other vinyl monomers included as polymer components of a specific styrene-based resin, in addition to styrene monomers and acrylic monomers, include, for example, (meth)acrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, and vinyl isopropenyl ketone; and olefins such as isoprene, butene, and butadiene.

[0276] From the perspective of forming specific particles that are prone to phase change due to pressure, other vinyl monomers included as polymer components preferably include (meth)acrylates, more preferably include (meth)acrylates, even more preferably include (meth)acrylates containing alkyl carbon atoms of alkyl groups of 2 to 10, and even more preferably include (meth)acrylates containing alkyl groups of 4 to 8.

[0277] In certain styrene-based resins, from the perspective of forming specific particles that are prone to phase change due to pressure, other vinyl monomers included as polymerizing components are particularly preferably at least one of n-butyl acrylate and 2-ethylhexyl acrylate.

[0278] From the perspective of forming specific particles that are prone to phase change due to pressure, the specific styrene-based resin and the specific (meth)acrylate-based resin described later preferably contain the same (meth)acrylate as a polymerization component.

[0279] From the perspective of suppressing the flow of specific particles under unpressurized conditions, the mass percentage of (meth)acrylate in the total polymer component of the specific 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 perspective of forming specific particles that are prone to phase change due to pressure, this mass percentage is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. As the (meth)acrylate here, alkyl (meth)acrylate is preferred, more preferably alkyl (meth)acrylate with 2 to 10 carbon atoms in the alkyl group, and even more preferably alkyl (meth)acrylate with 4 to 8 carbon atoms in the alkyl group.

[0280] The styrene-based resin particularly preferably contains at least one of n-butyl acrylate and 2-ethylhexyl acrylate as a polymerization component. Regarding the mass ratio of the total amount of n-butyl acrylate and 2-ethylhexyl acrylate in the total polymerization component of the styrene-based resin, from the viewpoint of suppressing the flow of specific particles under unpressurized conditions, this mass ratio 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 specific particles that are prone to phase change due to pressure, this mass ratio is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more.

[0281] Regarding the weight-average molecular weight of a specific styrene-based resin, from the perspective of suppressing the flow of specific particles under unpressurized conditions, it is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more. From the perspective of forming specific particles that are prone to phase change due to pressure, it is preferably 60,000 or less, more preferably 55,000 or less, and even more preferably 50,000 or less.

[0282] The weight-average molecular weight of the resin in this invention was determined by gel permeation chromatography (GPC). For the GPC-based molecular weight determination, a Tosoh HLC-8120 GPC was used as the GPC apparatus, a Tosoh TSKgel SuperHM-M (15cm) column was used as the column, and tetrahydrofuran was used as the solvent. The weight-average molecular weight of the resin was calculated using a molecular weight calibration curve prepared from monodisperse polystyrene standard samples.

[0283] Regarding the glass transition temperature of a specific styrene-based resin, from the perspective of suppressing the flow of specific particles under unpressurized conditions, it is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher. From the perspective of forming specific 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.

[0284] In this invention, the glass transition temperature of the resin is determined based on the differential scanning calorimetry (DSC) curve obtained by performing differential scanning calorimetry (DSC). More specifically, it is determined by extrapolating the glass transition onset temperature as described in the method for determining the glass transition temperature of JIS K7121:1987 "Method for determination of transition temperature of plastics".

[0285] The glass transition temperature of a resin is controlled by the type and ratio of polymerizing components. A higher density of soft units such as methylene, ethylene, and ethylene oxide in the main chain tends to result in a lower glass transition temperature; conversely, a higher density of rigid units such as aromatic rings and cyclohexane rings in the main chain tends to result in a higher glass transition temperature. Furthermore, a higher density of aliphatic groups in the side chains tends to result in a lower glass transition temperature.

[0286] In this embodiment, regarding the mass percentage of the specific styrene-based resin in the total master particles, from the perspective of suppressing the flow of the specific particles in an unpressurized state, this mass percentage 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 perspective of forming specific particles that are prone to phase change due to pressure, this mass percentage is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.

[0287] -Specific (meth)acrylate resins-

[0288] The master particles constituting the specific particles contain a (meth)acrylate resin, which contains at least two (meth)acrylates in its polymer composition, and the (meth)acrylates account for more than 90% by mass of the total polymer composition of the (meth)acrylate resin.

[0289] The mass percentage of (meth)acrylate in the total polymer component of (meth)acrylate resin is 90% by mass or more, more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 100% by mass.

[0290] Examples of (meth)acrylates include alkyl (meth)acrylates, carboxyl-substituted alkyl (meth)acrylates, hydroxyl-substituted alkyl (meth)acrylates, alkoxy-substituted alkyl (meth)acrylates, and di(meth)acrylates.

[0291] 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.

[0292] Examples of carboxyl-substituted alkyl esters of (meth)acrylic acid include (meth)acrylic acid-2-carboxyethyl ester.

[0293] 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.

[0294] Examples of alkoxy-substituted alkyl esters of (meth)acrylate include 2-methoxyethyl (meth)acrylate.

[0295] Examples of di(meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, pentanediol di(meth)acrylate, hexanediol di(meth)acrylate, nonanediol di(meth)acrylate, and decanediol di(meth)acrylate.

[0296] Other examples of (meth)acrylates include 2-(diethylamino)ethyl (meth)acrylate, benzyl (meth)acrylate, and methoxy polyethylene glycol (meth)acrylate.

[0297] (Meth)acrylates can be used alone or in combination with two or more types.

[0298] From the perspective of forming specific particles that are easy to undergo phase change due to pressure and have excellent adhesion when pressed, alkyl methacrylates are preferred as (meth)acrylates, alkyl methacrylates with 2 to 10 carbon atoms in the alkyl group are more preferred, alkyl methacrylates with 4 to 8 carbon atoms in the alkyl group are even more preferred, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.

[0299] As mentioned above, from the perspective of forming specific particles that are prone to phase change due to pressure, specific (meth)acrylate resins and specific styrene resins preferably contain the same type of (meth)acrylate as a polymerization component.

[0300] From the perspective of forming specific particles that are prone to phase change under pressure and have excellent adhesion due to compression, the mass percentage of (meth)acrylate alkyl esters in the total polymeric components of a specific (meth)acrylate resin is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 98% by mass or more, and even more preferably 100% by mass. As the (meth)acrylate alkyl ester here, it is preferable to have an alkyl acrylate with 2 to 10 carbon atoms, more preferably an alkyl acrylate with 4 to 8 carbon atoms.

[0301] In a specific (meth)acrylate resin, among at least two (meth)acrylates included as polymerizing components, the mass ratio of the two (meth)acrylates with the highest mass proportion is preferably 80:20 to 20:80, more preferably 70:30 to 30:70, and even more preferably 60:40 to 40:60, from the perspective of forming specific particles that are easy to undergo phase change due to pressure and have excellent adhesion when produced by compression.

[0302] In a specific meth)acrylate resin, among at least two meth)acrylates included as polymerizing components, the two meth)acrylates with the highest mass proportion are preferably alkyl meth)acrylates. As the alkyl meth)acrylates herein, alkyl meth)acrylates with an alkyl group having 2 to 10 carbon atoms are preferred, and alkyl meth)acrylates with an alkyl group having 4 to 8 carbon atoms are more preferred.

[0303] In a specific (meth)acrylate resin, when the two (meth)acrylates included as polymerizing components are alkyl (meth)acrylates with the highest mass proportion, from the viewpoint of forming specific particles that are easy to undergo phase change due to pressure and have excellent adhesion generated by compression, the difference in the number of carbon atoms of the alkyl groups of the two (meth)acrylates is preferably 1 to 4, more preferably 2 to 4, and even more preferably 3 or 4.

[0304] From the perspective of forming specific particles that readily undergo phase change under pressure and exhibit excellent adhesion resulting from compression bonding, the specific (meth)acrylate resin preferably includes n-butyl acrylate and 2-ethylhexyl acrylate as polymerization components. Particularly preferred are n-butyl acrylate and 2-ethylhexyl acrylate, which, by mass proportion, constitute the two (meth)acrylate components comprising at least two types of (meth)acrylates in the (meth)acrylate resin. The total mass proportion of n-butyl acrylate and 2-ethylhexyl acrylate in the overall polymerization components of the (meth)acrylate resin is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 98% by mass or more, and even more preferably 100% by mass.

[0305] Certain (meth)acrylate resins may contain vinyl monomers other than (meth)acrylates in their polymerization composition.

[0306] 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 can be used individually or in combination of two or more.

[0307] When a particular (meth)acrylate resin contains vinyl monomers other than (meth)acrylates in its polymerization composition, acrylic acid and methacrylic acid are preferred as vinyl monomers other than (meth)acrylates, and acrylic acid is more preferred.

[0308] Regarding the weight-average molecular weight of the specific (meth)acrylate resin, from the perspective of suppressing the flow of specific particles under unpressurized conditions, it is preferably 100,000 or more, more preferably 120,000 or more, and even more preferably 150,000 or more. From the perspective of forming 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.

[0309] Regarding the glass transition temperature of a specific (meth)acrylate resin, from the perspective of forming particles that are prone to phase change due to pressure, it is preferably 10°C or less, more preferably 0°C or less, and even more preferably -10°C or less. From the perspective of suppressing the flow of specific 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.

[0310] Regarding the mass percentage of the specific (meth)acrylate resin in the total master particles of this embodiment, from the viewpoint of forming particles that are prone to phase change due to pressure, it is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 30% by mass or more. From the viewpoint of suppressing the flow of specific 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.

[0311] In this embodiment, the total amount of the specific styrene-based resin and the specific (meth)acrylate-based resin contained in the masterbatch is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 100% by mass relative to the total masterbatch.

[0312] The masterbatch may also contain, as needed, non-vinyl resins such as polystyrene, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, modified rosin, etc.

[0313] These resins can be used alone or in combination of two or more.

[0314] (Other ingredients)

[0315] The masterbatch can contain other ingredients as needed.

[0316] Other components include colorants (such as pigments and dyes), release agents (such as hydrocarbon waxes; natural waxes such as carnauba wax, rice bran wax, and candelilla wax; synthetic or mineral / petroleum-based waxes such as lignite wax; ester-based waxes such as fatty acid esters and lignite esters), and charge control agents.

[0317] Specific particles can contain colorants within a range that does not impair the visibility of the image.

[0318] From the perspective of improving the transparency of specific particles, the lower the content of colorant in the master particles, the better. Specifically, the content of colorant relative to the total master particles is preferably 1.0% by mass or less, more preferably 0.1% by mass or less, further preferably 0.01% by mass or less, and particularly preferably does not contain any colorant.

[0319] It should be noted that certain particles can be transparent.

[0320] In this embodiment, "transparency" means that the area to which the specific particles are applied has an average transmittance of 10% or more for light in the visible light region (400 nm to 700 nm), and the average transmittance is preferably 50% or more, more preferably 80% or more, and even more preferably 90% or more.

[0321] The average transmittance mentioned above was measured using a V700 spectrophotometer (manufactured by Japan Spectrophotometer Co., Ltd.).

[0322] (Structure of the parent particle)

[0323] The internal structure of the master particle is preferably an island structure.

[0324] As an island structure, a preferred island structure is one having a marine phase containing one of two or more binding resins and an island phase containing another resin dispersed within that marine phase. More specifically, from the perspective of ease of phase transformation under pressure, a preferred island structure is one having a marine phase containing a specific styrene-based resin and an island phase containing a specific (meth)acrylate-based resin dispersed within that marine phase. Details of the specific styrene-based resin contained in the marine phase and the (meth)acrylate-based resin contained in the island phase are as described above. It should be noted that an island phase not containing a (meth)acrylate-based resin may also be dispersed within the marine phase.

[0325] When the master particles have an island structure, the average diameter of the island phase is preferably 200 nm or more and 500 nm or less. When the average diameter of the island phase is less than 500 nm, the master particles are prone to phase transition due to pressure; when the average diameter of the island phase is 200 nm or more, the required mechanical strength of the master particles (e.g., the strength to resist deformation during stirring in a developer) is excellent. Based on these aspects, 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.

[0326] As a method to control the average diameter of the island phase in the island structure within the aforementioned range, examples include increasing or decreasing the amount of a specific (meth)acrylate resin relative to the amount of a specific styrene resin in the method for manufacturing master particles described later, and increasing or decreasing the time of maintaining the high temperature in the step of fusing / merging the aggregated resin particles.

[0327] The confirmation of island structure and the determination of the average diameter of island facies were carried out by the following methods.

[0328] Specific particles were embedded in epoxy resin, and sections were prepared using a diamond scalpel. The prepared sections were then stained with osmium tetroxide or ruthenium tetroxide in a desiccator. The stained sections were observed using a scanning electron microscope (SEM). The presence or absence of island structures was determined by the intensity of the osmium tetroxide or ruthenium tetroxide staining on the resin, thus confirming the presence of island structures. One hundred island phases were randomly selected from the SEM images, and the major axis of each island phase was measured. The average of the 100 major axes was taken as the mean diameter.

[0329] The parent particle can be a single-layer structure or a core / shell structure with a core and a shell covering the core. From the perspective of suppressing the flow of specific particles under unpressurized conditions, the parent particle is preferably a core / shell structure.

[0330] When the parent particles have a core / shell structure, from the perspective of ease with which a phase change can occur due to pressure, it is preferable that the core contains a specific styrene-based resin and a specific (meth)acrylate-based resin. Furthermore, from the perspective of suppressing the flow of specific particles in an unpressurized state, the shell layer preferably contains a specific styrene-based resin.

[0331] When the parent material has a core / shell structure, it is preferable that the core has a marine phase containing a specific styrene-based resin and an island phase containing a specific (meth)acrylate-based resin dispersed within the marine phase. The average diameter of the island phase is preferably within the range described above. Furthermore, in addition to the core having the above-described configuration, it is also preferable that the shell layer contains a specific styrene-based resin. In this case, the marine phase in the core and the shell layer form a continuous structure, and the parent material is prone to phase transition due to pressure.

[0332] Examples of resins included in the shell include: polystyrene; epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, modified rosin, and other non-vinyl resins; and so on.

[0333] These resins can be used alone or in combination of two or more.

[0334] Regarding the average thickness of the shell, from the perspective of suppressing the deformation of the parent particles, it is preferably 120 nm or more, more preferably 130 nm or more, and even more preferably 140 nm or more. From the perspective of the parent particles being 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.

[0335] The average thickness of the shell was determined by the following method.

[0336] The particles were embedded in epoxy resin, and sections were prepared using a diamond scalpel. The sections were then stained with osmium tetroxide or ruthenium tetroxide in a desiccator. The stained sections were observed using a scanning electron microscope (SEM). Ten cross-sections of the parent particle were randomly selected from the SEM images. For each parent particle, the thickness of the shell at 20 locations was measured, and the average value was calculated. The average value of the ten parent particles was taken as the average thickness.

[0337] Regarding the volume average particle size (D50v) of the masterbatch, from the perspective of ease of processing, it is preferably 4 μm or more, more preferably 5 μm or more, and even more preferably 6 μm or more. Furthermore, the volume average particle size of the masterbatch is preferably 15 μm or less, more preferably 12 μm or less, and even more preferably 10 μm or less.

[0338] The volume average particle size (D50v) of the masterbatch was determined using a Coulter Multisizer II (Beckman Coulter) with a pore size of 100 μm. Masterbatch particles of 0.5 mg to 50 mg 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 volume average particle size (D50v) was defined as the particle size at the cumulative 50% point of the particle size distribution measured from the smallest diameter side.

[0339] [Additives]

[0340] Examples of additives include inorganic particles. 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, and MgSO4.

[0341] The surface of inorganic particles used as additives can be hydrophobically treated. This 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 agents can be used alone or in combination. The amount of the hydrophobic agent is, for example, between 1 and 10 parts by mass relative to 100 parts by mass of the inorganic particles.

[0342] Other examples of additives include resin particles (such as polystyrene, polymethyl methacrylate, and melamine resin particles) and cleaning and activating agents (such as metal salts of higher fatty acids, such as zinc stearate, and particles of fluorine-based high molecular weight substances).

[0343] The amount of additive added relative to the masterbatch is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.01% by mass or more and 2.0% by mass or less.

[0344] [Specific particle characteristics]

[0345] The specific particles have at least two glass transition temperatures, one of which is presumed to be the glass transition temperature of one of two or more adhesive resins, and the other is presumed to be the glass transition temperature of another of two or more adhesive resins. As mentioned above, when the adhesive resin includes a specific styrene-based resin and a specific (meth)acrylate-based resin, one of the glass transition temperatures is presumed to be the glass transition temperature of the specific styrene-based resin, and the other is presumed to be the glass transition temperature of the specific (meth)acrylate-based resin.

[0346] A particular particle may also have more than three glass transition temperatures, but it is preferred that the number of glass transition temperatures is two. As a way to have two glass transition temperatures, there are the following ways: the resin contained in the particular particle is only a particular styrene-based resin and a particular (meth)acrylate-based resin; or the content of other resins that are not the particular styrene-based resin and the particular (meth)acrylate-based resin is small (for example, the content of other resins is less than 5% by mass relative to the total content of the particular particle).

[0347] The specific particles have at least two glass transition temperatures, with the difference between the lowest and highest glass transition temperatures being 30°C or more. From the perspective of the particles readily undergoing phase transitions due to pressure, the difference between the lowest and highest glass transition temperatures is more preferably 40°C or more, further preferably 50°C or more, and even more preferably 60°C or more. The upper limit of the difference between the lowest and highest glass transition temperatures is, for example, 140°C or less, 130°C or less, or 120°C or less.

[0348] From the perspective that particles are prone to phase transition due to pressure, the minimum glass transition temperature exhibited by the specific particles is preferably 10°C or less, more preferably 0°C or less, and even more preferably -10°C or less. From the perspective of suppressing the flow of specific particles in an unpressurized state, the glass transition temperature is preferably -90°C or more, more preferably -80°C or more, and even more preferably -70°C or more.

[0349] From the perspective of suppressing the flow of specific particles under unpressurized conditions, the highest glass transition temperature exhibited by the specific particles is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher. From the perspective of the particles being prone to phase change due to pressure, the glass transition temperature is preferably 70°C or lower, more preferably 65°C or lower, and even more preferably 60°C or lower.

[0350] In this invention, resin particles are compressed to form a plate-shaped sample, and differential scanning calorimetry (DSC) is performed. The glass transition temperature of a specific particle is determined from the obtained DSC curve. More specifically, it is determined by extrapolating the glass transition onset temperature as described in JIS K7121:1987 "Method for determination of transition temperature of plastics".

[0351] A specific particle is a particle that undergoes a phase change due to pressure, and it satisfies the following equation 1.

[0352] Equation 1…10℃≦T1-T2

[0353] In Equation 1, T1 is the temperature at which the viscosity reaches 10,000 Pa·s under a pressure of 1 MPa, and T2 is the temperature at which the viscosity reaches 10,000 Pa·s under a pressure of 10 MPa. The methods for determining T1 and T2 are described below.

[0354] From the perspective that particles are prone to phase change due to pressure, the temperature difference (T1-T2) is 10°C or more, preferably 15°C or more, and more preferably 20°C or more. From the perspective of suppressing the flow of specific particles in an unpressurized state, the temperature difference (T1-T2) is preferably 120°C or less, more preferably 100°C or less, and even more preferably 80°C or less.

[0355] The value of T1 is preferably below 140°C, more preferably below 130°C, further preferably below 120°C, and even more preferably below 115°C. The lower limit of temperature T1 is preferably above 80°C, more preferably above 85°C.

[0356] The value of 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.

[0357] As an indicator of how easily specific particles undergo a phase transition under pressure, the temperature difference (T1-T3) between the temperature T1, which exhibits a viscosity of 10000 Pa·s at a pressure of 1 MPa, and the temperature T3, which exhibits a viscosity of 10000 Pa·s at a pressure of 4 MPa, can be used. The temperature difference (T1-T3) is preferably 5°C or more. The temperature difference (T1-T2) is typically 25°C or less.

[0358] In specific particles, from the perspective of ease with which a phase change occurs due to pressure, the temperature difference (T1-T2) is preferably 5°C or more, and more preferably 10°C or more.

[0359] It should be noted that the upper limit of the temperature difference (T1-T3) is usually below 25℃.

[0360] For specific particles, from the perspective of achieving a temperature difference (T1-T3) of 5°C or more, the temperature T3 that exhibits a viscosity of 10000 Pa·s at 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.

[0361] The method for determining temperatures T1, T2, and T3 is as follows.

[0362] Specific particles are compressed to prepare granular samples. The granular samples are placed in a flow testing apparatus (Shimadzu CFT-500), and the applied pressure is fixed at 1 MPa. The viscosity relative to temperature is measured at 1 MPa. The resulting viscosity curve indicates that the viscosity reaches 10 at an applied pressure of 1 MPa. 4 Temperature T1 is determined at a pressure of 1 MPa to 10 MPa. Temperature T2 is determined using the same method as for temperature T1, except that the applied pressure is changed from 1 MPa to 4 MPa. Temperature T3 is determined using the same method as for temperature T1. The temperature difference (T1-T2) is calculated from temperatures T1 and T2. The temperature difference (T1-T3) is calculated from temperatures T1 and T3.

[0363] [Manufacturing method for specific particles]

[0364] Specific particles are obtained by adding additives to the master particles after they have been manufactured.

[0365] Masterbatch can be manufactured using any of the following methods: dry manufacturing (e.g., mixing and pulverizing) or wet manufacturing (e.g., agglomeration, suspension polymerization, dissolution suspension). There are no particular limitations on these methods; well-known methods can be used. Among these, agglomeration can be used to obtain masterbatch.

[0366] The following is an example of a method for manufacturing master particles by agglomeration and merging.

[0367] In the case of manufacturing master particles by agglomeration and merging, the master particles are manufactured, for example, through the following steps:

[0368] Steps for preparing a styrene-based resin particle dispersion containing styrene-based resin particles with a specific styrene-based resin (styrene-based resin particle dispersion preparation steps).

[0369] The step of polymerizing a specific (meth)acrylate resin in a styrene-based resin particle dispersion to form composite resin particles containing a specific styrene-based resin and a specific (meth)acrylate resin (composite resin particle formation step).

[0370] The step of agglomerating composite resin particles in a composite resin particle dispersion to form agglomerated particles (agglomerated particle formation step); and

[0371] The step of heating the dispersion of agglomerated particles to fuse / merge the agglomerated particles and form mother particles (fusion / merging step).

[0372] The details of each step are explained below.

[0373] The following description outlines a method for obtaining masterbatch free of release agent. Release agents and other additives may be used as needed.

[0374] When the master particles contain colorants and / or release agents, the composite resin particle dispersion is mixed with the colorant particle dispersion and / or release agent particle dispersion in the agglomerated particle forming step, so that the composite resin particles and colorants and / or release agents agglomerate to form agglomerated particles.

[0375] Colorant particle dispersions and release agent particle dispersions are respectively prepared, for example, by dispersing the colorant or release agent with a dispersion medium using a known disperser.

[0376] -Preparation steps for styrene-based resin particle dispersion-

[0377] In the preparation step of the styrene-based resin particle dispersion, a styrene-based resin particle dispersion containing styrene-based resin particles of a specific styrene-based resin is prepared.

[0378] Styrene-based resin particle dispersions are, for example, dispersions formed by dispersing styrene-based resin particles in a dispersion medium using a surfactant.

[0379] Examples of dispersion media include aqueous media such as water and alcohols. These dispersion media can be used individually or in combination of two or more.

[0380] 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. Among these, anionic surfactants are preferred. A surfactant can be used alone or in combination with two or more surfactants.

[0381] As a method for dispersing styrene-based resin particles in a dispersion medium, examples include mixing a specific styrene-based resin with a dispersion medium and then dispersing it by stirring using a rotary shear homogenizer, a ball mill with a media, a sand mill, a bead mill, or the like.

[0382] Another method for dispersing styrene-based resin particles in a dispersion medium is emulsion polymerization. Specifically, a specific styrene-based resin polymerization component is mixed with a chain transfer agent or polymerization initiator, and then further mixed with an aqueous medium containing a surfactant. The mixture is stirred to prepare an emulsion, in which the styrene-based resin is polymerized. In this case, dodecyl mercaptan is preferably used as the chain transfer agent.

[0383] 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.

[0384] 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., Horiba Manufacturing Co., Ltd. LA-700), and the particle size of the cumulative 50% point in the volume reference particle size distribution measured from the small diameter side is taken as the volume average particle size (D50v).

[0385] The content of styrene-based resin particles in the styrene-based resin particle dispersion is preferably 30% to 60% by mass, more preferably 40% to 50% by mass, relative to the total mass of the styrene-based resin particle dispersion.

[0386] -Composite resin particle formation steps-

[0387] In the composite resin particle formation step, a specific (meth)acrylate resin is polymerized in a styrene-based resin particle dispersion to form composite resin particles containing a specific styrene-based resin and a specific (meth)acrylate resin.

[0388] In the composite resin particle formation step, a styrene-based resin particle dispersion is mixed with a polymerizing component of a specific (meth)acrylate resin, and the specific (meth)acrylate resin is polymerized in the styrene-based resin particle dispersion to form composite resin particles containing the specific styrene-based resin and the specific (meth)acrylate resin.

[0389] The composite resin particles are preferably resin particles comprising a specific styrene-based resin and a specific (meth)acrylate-based resin in a microphase-separated state. These resin particles are manufactured, for example, by the method described below.

[0390] Add the polymerization component of a specific (meth)acrylate resin (containing a monomer group of at least two (meth)acrylates) to a styrene-based resin particle dispersion, and add an aqueous medium as needed. Then, while slowly stirring the dispersion, heat the dispersion to above the glass transition temperature of the specific styrene-based resin (e.g., a temperature 10°C to 30°C higher than the glass transition temperature of the specific styrene-based resin). Next, while maintaining the temperature, slowly add the aqueous medium containing the polymerization initiator dropwise, and continue stirring for an extended period of 1 hour to 15 hours. Ammonium persulfate is preferably used as the polymerization initiator at this time.

[0391] Although the detailed mechanism may not be clear, it is speculated that, using the above method, monomers and polymerization initiators are impregnated within styrene-based resin particles, and specific (meth)acrylates polymerize within the styrene-based resin particles. It is speculated that this yields composite resin particles containing specific (meth)acrylate resins within the styrene-based resin particles, with the specific styrene-based resins within the particles forming a microphase-separated state with the specific (meth)acrylate resins.

[0392] 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.

[0393] The content of composite resin particles in the composite resin particle dispersion is preferably 20% to 50% by mass and more preferably 30% to 40% by mass relative to the total mass of the composite resin particle dispersion.

[0394] -Steps in the formation of aggregated particles-

[0395] In the aggregated particle formation step, the composite resin particles in the composite resin particle dispersion containing the composite resin particles are aggregated to form aggregated particles.

[0396] Here, in the agglomerated particle formation step, the composite resin particles are agglomerated to form agglomerated particles with a diameter similar to that of the target master particle.

[0397] Regarding the steps for forming aggregated particles, specifically, for example, a coagulant is added to the composite resin particle dispersion, and the pH of the composite resin particle dispersion is adjusted to acidic (e.g., pH 2 or higher than pH 5). After adding a dispersing stabilizer as needed, the mixture is heated to a temperature close to the glass transition temperature of a specific styrene-based resin (specifically, for example, a temperature 30°C or higher to 10°C below the glass transition temperature of a specific styrene-based resin) to cause the composite resin particles to aggregate and form aggregated particles.

[0398] In the step of forming aggregated particles, a coagulant can be added to the composite resin particle dispersion at room temperature (e.g., 25°C) while stirring with a rotary shear homogenizer, the pH of the composite resin particle dispersion can be adjusted to acidic (e.g., pH 2 or higher than 5), and a dispersant stabilizer can be added as needed before heating.

[0399] Examples of flocculants include surfactants with polarity opposite to that of the surfactant contained in the composite resin particle dispersion, inorganic metal salts, and metal complexes with a polarity of two or higher. When metal complexes are used as flocculants, the amount of surfactant required is reduced, and the charging characteristics are improved.

[0400] Additives that form complexes or similar bonds with the metal ions of the flocculant can be used as needed. Chelating agents are suitable as such additives.

[0401] Examples of inorganic metal salts include calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate; inorganic metal salt polymers such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide; and so on.

[0402] Water-soluble chelating agents can be used as chelating agents. Examples of chelating agents include hydroxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid; aminocarboxylic acids such as iminodiacetic acid (IDA), nitrotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA); and so on.

[0403] 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.

[0404] -Merge / merge steps-

[0405] In the fusion / merging (fusion·unification) step, the dispersion of agglomerated particles containing agglomerated particles is heated to fuse / merge the agglomerated particles and form mother particles.

[0406] In the fusion / merging step, the dispersion of agglomerated particles containing the agglomerated particles is heated to, for example, above the glass transition temperature of a specific styrene-based resin (e.g., a temperature 10°C to 30°C higher than the glass transition temperature of a specific styrene-based resin) to fuse / merge the agglomerated particles and form master particles.

[0407] The master particles obtained through the above steps typically have an island structure, which consists of a marine phase containing a specific styrene-based resin and an island phase containing a specific (meth)acrylate-based resin dispersed within the marine phase. It is speculated that when the specific styrene-based resin and the specific (meth)acrylate-based resin in the composite resin particles are in a microphase-separated state, during the fusion / merging step, the specific styrene-based resin aggregates to form the marine phase, and the specific (meth)acrylate-based resin aggregates to form the island phase.

[0408] 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 the amount of at least two (meth)acrylates used in the composite resin particle formation step, or by increasing or decreasing the time maintained at high temperature in the fusion / merging step.

[0409] Core / shell structured master particles are manufactured, for example, through the following steps:

[0410] After obtaining the aggregated particle dispersion (hereinafter also referred to as the first aggregated particle dispersion containing the first aggregated particles) using the above-described aggregated particle forming step, the aggregated particle dispersion and the styrene-based resin particle dispersion are further mixed, and the aggregated particles are agglomerated in such a way that styrene-based resin particles are further attached to the surface of the aggregated particles to form the second aggregated particles (the second aggregated particle forming step); and

[0411] The step of heating the dispersion of the second aggregated particles containing the second aggregated particles to fuse / merge the second aggregated particles and form a core / shell structured parent particle (core / shell structure formation step).

[0412] The core / shell structured master particles obtained through the above steps have a shell containing a specific styrene-based resin.

[0413] 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.

[0414] After the fusion / merging step is completed, the mother particles formed in the solution are subjected to a known washing step, a solid-liquid separation step, and a drying step to obtain dried mother particles.

[0415] Regarding the cleaning process, from a rechargeability perspective, displacement cleaning using ion-exchange water can be fully implemented. Regarding the solid-liquid separation process, from a productivity perspective, methods such as vacuum filtration and pressure filtration can be implemented. Regarding the drying process, from a productivity perspective, methods such as freeze drying, airflow drying, fluidized bed drying, and vibrating fluidized bed drying can be implemented.

[0416] Then, for example, an additive is added to the obtained dry masterbatch and mixed to produce specific particles.

[0417] Mixing can be done using a V-type mixer, Henschel mixer, Loedige mixer, etc.

[0418] Furthermore, large particles can be removed by using vibrating screens, air screens, etc., as needed.

[0419] The specific particles can be applied directly or used as an electrostatic image developer. The aforementioned electrostatic image developers can be single-component developers containing only the specific particles, or two-component developers composed of a mixture of the specific particles and a carrier.

[0420] There are no particular limitations on the carrier, and known carriers can be cited. Examples of carriers include: a coated carrier in which resin is coated on the surface of a core material formed of magnetic powder; a magnetic powder dispersion carrier in which magnetic powder is dispersed and mixed in a matrix resin; a resin impregnating carrier in which resin is impregnated in porous magnetic powder; and so on. Magnetic powder dispersion carriers and resin impregnating carriers can also be carriers in which the constituent particles of the carrier are used as the core material and their surfaces are coated with resin.

[0421] Examples of magnetic powders include: magnetic metals such as iron, nickel, and cobalt; magnetic oxides such as ferrite and magnetite; and so on.

[0422] Examples of resins used for coating 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 comprising organosiloxane bonds, fluoropolymers, polyesters, polycarbonates, phenolic resins, and epoxy resins. The coating resin and matrix resin may contain other additives such as conductive particles. Examples of conductive particles include metals such as gold, silver, and copper, carbon black, titanium dioxide, zinc oxide, tin oxide, barium sulfate, aluminum borate, and potassium titanate.

[0423] When using resin to coat the surface of a core material, examples include coating methods that utilize a coating layer forming solution, where the resin to be coated and various additives (used as needed) are dissolved in a suitable solvent. There are no particular limitations on the solvent; it can be selected considering the type of resin used and its coating suitability.

[0424] Specific resin coating methods include: impregnation, in which the core material is impregnated in a coating layer forming solution; spraying, 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 suspended by flowing air; 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; and so on.

[0425] The mixing ratio (mass ratio) of specific particles and carrier in the two-component developer is preferably particles:carrier = 1:100 to 30:100, more preferably 3:100 to 20:100.

[0426] [Example]

[0427] The following examples illustrate the implementation of the invention in detail, but the implementation of the invention is not limited to these examples. In the following description, unless otherwise stated, "parts" and "%" are based on mass.

[0428] Example A

[0429] <Production of Specific Particles>

[0430] [Preparation of styrene-based resin particle dispersion (A1) and composite resin particle dispersion (A1)]

[0431] Styrene: 450 parts

[0432] • n-Butyl acrylate: 140 parts

[0433] Acrylic acid: 20 parts

[0434] • Dodecanthiol: 10 parts

[0435] The above components are mixed and dissolved to prepare a monomer solution.

[0436] Ten parts of anionic surfactant (DOWFAX2A1 manufactured by Dow Chemical Company) were dissolved in 250 parts of ion-exchanged water. The monomer solution was then added to the solution and dispersed and emulsified in a flask to obtain an emulsion.

[0437] One part of anionic surfactant (DOWFAX2A1 manufactured by Dow Chemical Company) was dissolved in 555 parts of ion-exchanged water and added to a polymerization flask equipped with a stirrer, thermometer, reflux cooling tube and nitrogen inlet tube. While injecting nitrogen and stirring slowly, the polymerization flask was heated to 75°C in a water bath and maintained.

[0438] Nine parts of ammonium persulfate were dissolved in 43 parts of ion-exchanged water and added dropwise to a polymerization flask over 20 minutes using a metering pump. Then, the emulsion was added dropwise over 200 minutes using a metering pump.

[0439] Subsequently, the polymerization flask was kept at 75°C for 3 hours while continuously stirring, and then returned to room temperature (25°C) to end the first stage of polymerization.

[0440] Thus, a styrene-based resin particle dispersion (A1) was obtained, which contained styrene-based resin particles with a volume average particle size (D50v) of 195 nm, a glass transition temperature of 53 °C, and a weight average molecular weight of 32,000 as determined by GPC (UV detection).

[0441] Next, the styrene-based resin particle dispersion (A1) cooled to room temperature (25°C) was added to a polymerization flask, and 240 parts of 2-ethylhexyl acrylate, 160 parts of n-butyl acrylate, and 1200 parts of deionized water were added to the flask. The mixture was then slowly stirred for 2 hours.

[0442] The temperature was then raised to 70°C with continuous stirring, and 4.5 parts of ammonium persulfate and 100 parts of deionized water were added dropwise over 20 minutes via a metering pump. The polymerization was then maintained with continuous stirring for 3 hours to complete the polymerization.

[0443] After the above steps, a composite resin particle dispersion (A1) with a volume average particle size (D50v) of 240 nm, a weight average molecular weight of 133,000 and a number average molecular weight of 18,000 as determined by GPC (UV detection), and solid content of 30% by mass was obtained by adding ion-exchanged water.

[0444] The obtained composite resin particle dispersion (A1) was dried, and a sample was prepared by embedding the dried composite resin particles in epoxy resin. The sample was then cut with a diamond scalpel to prepare cross-sectional sections of the composite resin particles. The cross-sections were then stained in ruthenium tetroxide vapor and observed using a transmission electron microscope for confirmation. Based on the cross-sectional observations, it was confirmed that the composite resin particles consist of multiple regions of low-Tg (meth)acrylate resin dispersed within a high-Tg styrene resin matrix.

[0445] Furthermore, when analyzing the glass transition temperature (Tg) behavior of dried composite resin particles using a differential scanning calorimeter (DSC) manufactured by Shimadzu Corporation, starting from -150°C, a glass transition caused by low-Tg (meth)acrylate resin was observed at -60°C. Additionally, a glass transition caused by high-Tg styrene resin was observed at 53°C (glass transition temperature difference: 113°C).

[0446] [Preparation of styrene-based resin particle dispersion (B1)]

[0447] Styrene: 450 parts

[0448] • n-Butyl acrylate: 135 parts

[0449] Acrylic acid: 12 parts

[0450] • Dodecanethiol: 9 parts

[0451] The above components are mixed and dissolved to prepare a monomer solution.

[0452] In addition, 10 parts of anionic surfactant (DOWFAX2A1 manufactured by Dow Chemical Company) were dissolved in 250 parts of ion-exchanged water, and the above monomer solution was added to a flask for dispersion and emulsification to obtain an emulsion.

[0453] One part of anionic surfactant (DOWFAX2A1 manufactured by Dow Chemical Company) was dissolved in 555 parts of ion-exchange water and added to a polymerization flask equipped with a stirrer, thermometer, reflux cooling tube and nitrogen inlet tube. While injecting nitrogen and stirring slowly, the polymerization flask was heated to 75°C in a water bath and maintained.

[0454] Nine parts of ammonium persulfate were dissolved in 43 parts of ion-exchanged water and added dropwise to a polymerization flask over 20 minutes using a metering pump. Then, the emulsion was added dropwise over 200 minutes using a metering pump.

[0455] Subsequently, the polymerization flask was kept at 75°C for 3 hours while continuously stirring, and then returned to room temperature (25°C) to end the first stage of polymerization.

[0456] Thus, a styrene-based resin particle dispersion (B1) was obtained, comprising styrene-based resin particles with a volume average particle size (D50v) of 190 nm, a glass transition temperature of 53 °C, a weight average molecular weight of 33,000, and a weight average molecular weight of 15,000 as determined by GPC (UV detection). The dispersion was adjusted to a solid content of 40% by mass by adding ion-exchanged water.

[0457] [Preparation of release agent dispersion (A1)]

[0458] Fischer-Tropsch wax: 270 pieces

[0459] (Made by Nippon Seiro Co., Ltd., trade name: FNP-0090, melting temperature = 90°C)

[0460] • Anionic surfactant: 1.0 part

[0461] (Made by Daiichi Kogyo Pharmaceutical Co., Ltd., NEOGEN RK)

[0462] • Ion-exchanged water: 400 parts

[0463] The above components were mixed, heated to 95°C, dispersed using a homogenizer (IKA, ULTRA-TURRAX T50), and then dispersed for 360 minutes using a Manton Gaulin high-pressure homogenizer (Gaulin) to prepare a release agent dispersion (A1) containing a release agent with a volume average particle size of 0.23 μm (solid component concentration: 20% by mass).

[0464] [Preparation of specific particles (A1) and developer (A1)]

[0465] • Composite resin particle dispersion (A1): 600 parts

[0466] • Release agent dispersion (A1): 8 parts

[0467] Colloidal silica aqueous solution: 13 parts

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

[0469] • Ion-exchanged water: 1000 parts

[0470] • Anionic surfactant: 1 part

[0471] (Made by Dow Chemical Co., Ltd., Dowfax2A1)

[0472] The above components were placed into a 3-liter reaction vessel equipped with a thermometer, pH meter and stirrer. 1.0% by mass nitric acid aqueous solution was added at 25°C to make the pH 3.0. Then, the mixture was dispersed at 5,000 rpm using a homogenizer (IKA Japan Co., Ltd., ULTRA-TURRAXTT50). Four parts of the prepared 10% by mass polyaluminum chloride aqueous solution were added and dispersed for 6 minutes.

[0473] A heating mantle was then installed in the reaction vessel, and the stirrer speed was adjusted to ensure thorough mixing of the slurry. The temperature was increased at a rate of 0.2°C / min until reaching 40°C, and at a rate of 0.05°C / min after exceeding 40°C. Particle size was measured every 10 minutes using a Multisizer II (pore size: 50 μm, manufactured by Coulter). Once the volume average particle size reached 7.5 μm, the temperature was maintained, and 115 parts of a styrene-based resin particle dispersion (B1) were added over 5 minutes. After addition, the mixture was maintained for 30 minutes, and then the pH of the slurry was adjusted to 6.0 using a 1.0% (w / w) sodium hydroxide aqueous solution. Subsequently, the pH was adjusted to 6.0 every 5°C, and the temperature was increased to 96°C at a rate of 1°C / min and maintained at 96°C. The particle shape and surface properties were observed using an optical microscope and a field emission scanning electron microscope (FE-SEM). The results showed that particle aggregation was confirmed at 2.0 hours. Therefore, the container was cooled to 30°C with cooling water for 5 minutes.

[0474] The cooled slurry was passed through a nylon mesh with a 30 μm opening to remove coarse particles. The slurry that had passed through the mesh was then filtered under reduced pressure using a suction device. The remaining solids on the filter paper were crushed 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 process was repeated under reduced pressure using a suction device, and the conductivity of the filtrate was measured. This operation was repeated until the conductivity of the filtrate reached below 10 μS / cm, at which point the solids were washed away.

[0475] The cleaned solid components were finely ground using a wet-dry granulator (pulverizer and granulator), and then vacuum dried in a dryer at 25°C for 36 hours to obtain master particles (A1). The obtained master particles (A1) had a volume average particle size of 8.1 μm, a weight average molecular weight of 126,000, and a number average molecular weight of 17,000.

[0476] Next, 1.5 parts of hydrophobic silica (manufactured by NIPPON AEROSIL Co., Ltd., RY50) were added to 100 parts of the obtained master particles (A1), and the mixture was mixed in a sample mill at a rotation speed of 13,000 rpm for 30 seconds. The mixture was then sieved using a vibrating sieve with a mesh size of 45 μm to prepare specific particles (A1). The volume average particle size of the obtained specific particles (A1) was 8.4 μm.

[0477] Using specific particles (A1) as samples, thermal behavior analysis was performed in the temperature range of -150°C to 100°C using a differential scanning calorimeter (Shimadzu DSC-60A). The results showed that glass transition temperatures were observed at -60°C and 53°C.

[0478] The temperatures T1 and T2 of a specific particle (A1) were determined using the above measurement method. The results showed that the specific particle (A1) satisfied Equation 1, "10℃≦T1-T2".

[0479] Cross-sections of a specific particle (A1) were observed using scanning electron microscopy (SEM), revealing an island structure. The particle (A1) possessed a core with an island phase and a shell without an island phase. The marine phase contained styrene-based resin, while the island phase contained (meth)acrylate-based resin. The average diameter of the island phase was determined using the aforementioned measurement method, yielding a result of 250 nm.

[0480] For a specific particle (A1), the temperature difference (T1-T3) was determined as an indicator of how easily the particle undergoes a phase change due to pressure. Specifically, temperature T1 and temperature T3 were measured using a flow testing instrument (Shimadzu CFT-500). The results showed that temperature T3 was 76°C and temperature difference (T1-T3) was 17°C.

[0481] An image with an image area ratio of 10% of the outer peripheral edge (i.e., the area at a distance of 0 mm to 5 mm from the periphery of the recording medium) is formed on one side of a recording medium (recording paper (OK Prince fiberless paper, manufactured by Oji Paper Co., Ltd.)) using an inkjet recording device. Next, specific particles (1) are applied at a dosage of 3 g / m². 2 The particles (1) are spread across the entire image-forming surface and passed through a roller-heated fixing machine, which serves as a fixing device. The specific particles (1) are heated and shaped onto the image-forming surface of the recording medium at 150°C to form a layer of specific particles. Using a PRESSLE multiII sealing machine manufactured by Toppan Forms Co., Ltd., the recording medium with the specific particle layer on the image-forming surface is folded in half with the image-forming surface facing inward. Pressure is applied to the folded recording medium to bond the inner image-forming surfaces together under a pressure of 90 MPa.

[0482] Recording media folded with the image forming surface facing inward under the above-mentioned apparatus and conditions, and with the image forming surfaces adhered to each other, showed no initial peeling, and also exhibited good peeling over time under high temperature and high humidity.

[0483] Eight parts of specific particles (A1) and 100 parts of the resin-coated carrier described below were placed into a V-type mixer and stirred for 20 minutes. Then, the mixture was sieved using a vibrating sieve with a mesh size of 212 μm to obtain the developer (A1).

[0484] 14 parts of toluene, 2 parts of styrene-methyl methacrylate copolymer (mass ratio: 80 / 20, weight average molecular weight: 70,000), and 0.6 parts of MZ500 (zinc oxide, titanium industry) were mixed and stirred for 10 minutes to prepare a coating layer forming solution with dispersed zinc oxide. Next, this coating layer forming solution and 100 parts of ferrite particles (volume average particle size: 38 μm) were loaded into a vacuum degassing kneader and stirred at 60°C for 30 minutes. Then, further heating and simultaneous depressurization were performed to degas the mixture and dry it, thereby producing a resin-coated carrier.

[0485] <Preparation of Toners and Developers for Color Image Formation>

[0486] [Crystall Polyester Resin Dispersion (A2)]

[0487] Add a monomeric component consisting of 100 mol% dimethyl sebacate and 100 mol% nonanediol, along with 0.3 parts dibutyltin oxide as a catalyst (relative to 100 parts of the monomeric component), to a heated and dried three-necked flask. Then, under reduced pressure, the air inside the container is made inert using nitrogen, and the mixture is stirred and refluxed at 180°C for 4 hours with mechanical stirring.

[0488] The mixture was then slowly heated to 230°C under reduced pressure and stirred for 2 hours until it became viscous. Afterward, it was air-cooled to stop the reaction, thus synthesizing a crystalline polyester resin (A2). Molecular weight determination (converted to polystyrene) of the obtained crystalline polyester resin (A2) using gel permeation chromatography revealed a weight-average molecular weight (Mw) of 15300, a number-average molecular weight (Mn) of 3800, and an acid value of 13.5 mg KOH / g.

[0489] In addition, the melting point (Tm) of the crystalline polyester resin (A2) was determined using a differential scanning calorimeter (DSC), and the results showed a clear endothermic peak at a temperature of 77.2 °C.

[0490] Next, using crystalline polyester resin (A2), a resin particle dispersion was prepared as follows.

[0491] • Crystalline polyester resin (A2): 90 parts

[0492] • Ionic surfactant (NEOGEN RK, Daiichi Kogyo Pharmaceutical): 1.8 parts

[0493] • Ion-exchanged water: 210 parts

[0494] The above components were mixed and heated to 100°C. After dispersion using a homogenizer (IKA Corporation, ULTRA-TURRAX T50), the mixture was heated to 110°C and dispersed for 1 hour using a pressure-jet Gaulin homogenizer to obtain a crystalline polyester resin dispersion (A2) with a volume average particle size of 210 nm and a solid content of 30% by mass.

[0495] [Amorphous polyester resin dispersion (A2)]

[0496] Bisphenol A propylene oxide adduct: 80 mol%

[0497] • Bisphenol A ethylene oxide 2-molar adduct: 20 mol%

[0498] ·Terephthalic acid: 60 mol%

[0499] Fumaric acid: 20 mol%

[0500] • Dodecenyl succinic anhydride: 20 mol%

[0501] The monomer components described above were added to a 5-liter flask equipped with a stirrer, nitrogen inlet pipe, temperature sensor, and distillation column. The temperature was raised to 190°C over 1 hour. After confirming that there were no fluctuations in the reaction system, 1.2 parts of dibutyltin oxide were added to every 100 parts of the monomer components. The generated water was further removed by distillation, and the temperature was raised to 240°C over 6 hours. A dehydration condensation reaction was carried out at 240°C for another 2 hours to obtain an amorphous polyester resin (A2) with a glass transition temperature of 63°C, an acid value of 10.5 mg KOH / g, a weight-average molecular weight of 17000, and a number-average molecular weight of 4200.

[0502] Next, using the obtained amorphous polyester resin (A2), a resin particle dispersion was prepared as follows.

[0503] • Amorphous polyester resin (A2): 100 parts

[0504] Ethyl acetate: 50 parts

[0505] Ethyl acetate was added to a 5-liter detachable flask, followed by the slow addition of the aforementioned resin components. The mixture was stirred using a three-in-one motor until completely dissolved, yielding an oil phase. Two parts of a 10% ammonia solution were then slowly added dropwise to this stirred oil phase using a dropper. Subsequently, 230 parts of deionized water were added dropwise at a rate of 10 ml / min to induce phase inversion emulsification. The mixture was then further depressurized using an evaporator while simultaneously removing the solvent, resulting in an amorphous polyester resin dispersion (A2). The amorphous polyester resin particles in this dispersion had a volume average particle size of 120 nm and a solids concentration of 30% by mass.

[0506] [Colorant Particle Dispersion (A1)]

[0507] • Carbon black (Cabot Corporation, Legal 330): 50 parts

[0508] • Anionic surfactant (manufactured by Nippon Oil Co., Ltd., New Rex R): 2 parts

[0509] • Ion-exchanged water: 198 samples

[0510] The above components were mixed and pre-dispersed for 10 minutes using a homogenizer (IKA Corporation, ULTRA-TURRAX). Then, the mixture was dispersed for 15 minutes using an Ultimaizer (face-to-face impact wet pulverizer, Sugino Machine) at a pressure of 245 MPa to obtain a colorant particle dispersion (A1) with a volume average particle size of 354 nm and a solid content of 20.0% by mass.

[0511] [Colorant Particle Dispersion (A2)]

[0512] • Blue pigment (phthalocyanine copper, CI pigment blue 15:3, manufactured by Dainippon Seika): 50 parts

[0513] • Ionic surfactant (NEOGEN RK, Daiichi Kogyo Pharmaceutical): 5 parts

[0514] • Ion-exchanged water: 195 parts

[0515] The above components were mixed and dispersed for 10 minutes using a homogenizer (IKA Corporation, ULTRA-TURRAX). Then, the mixture was dispersed for 15 minutes using an Ultimaizer (face-to-face wet pulverizer, Sugino Machine) at a pressure of 245 MPa to obtain a colorant particle dispersion (A2) with a volume average particle size of 462 nm and a solid content of 20.0% by mass.

[0516] [Colorant Particle Dispersion (A3)]

[0517] • Magenta pigment (CI Pigment Red 122): 80 parts

[0518] • Anionic surfactant (NEOGEN SC, Daiichi Kogyo Pharmaceutical): 8 parts

[0519] • Ion-exchanged water: 200 parts

[0520] The above components were mixed and dissolved, dispersed for 10 minutes using a homogenizer (ULTRA-TURRAX T50, manufactured by IKA), and then irradiated with ultrasonic waves at 28 kHz for 10 minutes using an ultrasonic disperser to obtain a colorant particle dispersion (A3) with a volume average particle size of 132 nm and a solid content of 29.0% by mass.

[0521] [Colorant Particle Dispersion (A4)]

[0522] • Yellow pigment (5g x 03, made by Clariant): 80 parts

[0523] • Anionic surfactant (NEOGEN SC, Daiichi Kogyo Pharmaceutical): 8 parts

[0524] • Ion-exchanged water: 200 parts

[0525] The above components were mixed and dissolved, dispersed for 10 minutes using a homogenizer (ULTRA-TURRAX T50, manufactured by IKA), and then irradiated with ultrasonic waves at 28 kHz for 20 minutes using an ultrasonic disperser to obtain a colorant particle dispersion (A4) with a volume average particle size of 108 nm and a solid content of 29.0% by mass.

[0526] [Release agent particulate dispersion (A2)]

[0527] • Olefin wax (melting point: 88℃): 90 parts

[0528] • Ionic surfactant (NEOGEN RK, Daiichi Kogyo Pharmaceutical): 1.8 parts

[0529] • Ion-exchanged water: 210 parts

[0530] The above components were mixed and heated to 100°C. After dispersion using a homogenizer (IKA Corporation, ULTRA-TURRAX T50), the mixture was heated to 110°C and dispersed for 1 hour using a pressure-spray type Gaulin homogenizer to obtain a release agent particle dispersion (A2) with a volume average particle size of 180 nm and a solid content of 30% by mass.

[0531] [Preparation of Black Toner Granules (A1)]

[0532] • Amorphous polyester resin dispersion (A2): 166 parts

[0533] • Crystalline polyester resin dispersion (A2): 50 parts

[0534] • Colorant particle dispersion (A1): 25 parts

[0535] • Release agent particle dispersion (A2): 40 parts

[0536] The above components were mixed and dispersed in a round stainless steel flask using a homogenizer (ULTRA-TURRAXT50). Next, 0.20 parts of polyaluminum chloride were added, and dispersion was continued using the ULTRA-TURRAX T50. The flask was stirred in an oil bath while simultaneously heated to 48°C. After maintaining this temperature at 48°C for 60 minutes, 60 parts of the amorphous polyester resin dispersion (A2) were added little by little. Then, the pH of the system was adjusted to 8.0 with a 0.5 mol / L sodium hydroxide aqueous solution. The stainless steel flask was then sealed, and the mixture was continuously stirred using a magnetic stir bar while simultaneously heated to 90°C and maintained for 3 hours.

[0537] After the reaction, the solution was cooled, filtered, and washed with ion-exchanged water. Solid-liquid separation was then performed using a Buchner funnel filtration system. The solution was further redispersed in 1 liter of ion-exchanged water at 40°C, and stirred and washed at 300 rpm for 15 minutes. This process was repeated five times until the filtrate reached a pH of 7.5 and a conductivity of 7.0 μS / cm. Solid-liquid separation was then performed using a Buchner funnel filtration system and No. 5A filter paper. Finally, the solution was vacuum dried for 12 hours to obtain black colorant particles (A1).

[0538] The particle size of the black colorant particles (A1) was determined using Multisizer II, and the results showed that the volume average particle size D50 was 6.4 μm and the volume particle size distribution index GSDv was 1.21.

[0539] [Making of Black Toning Agent (A1)]

[0540] 100 parts of black colorant particles (A1), 0.8 parts of decylsilane-treated hydrophobic titanium dioxide with an average particle size of 15 nm, and 1.3 parts of hydrophobic silica (NY50, manufactured by NIPPON AEROSIL) with an average particle size of 30 nm were mixed. The mixture was then mixed for 10 minutes at a circumferential speed of 32 m / s using a Henschel mixer. After mixing, coarse particles were removed using a sieve with a mesh size of 45 μm to obtain black colorant (A1).

[0541] [Preparation of developer (C1)]

[0542] Ferritic particles (volume average particle size: 50 μm, volume resistivity: 108 Ωcm): 100 parts

[0543] Toluene: 14 parts

[0544] • Perfluorooctyl ethyl acrylate / methyl methacrylate copolymer (copolymer ratio 40 / 60, Mw: 50,000): 1.6 parts

[0545] • Carbon black (VXC-72, manufactured by Cabot): 0.12 parts

[0546] • Cross-linked melamine resin particles (number average particle size: 0.3 μm): 0.3 parts

[0547] The components other than the ferrite particles in the above composition are mixed and dispersed for 10 minutes using a stirrer to prepare a coating forming solution. The coating forming solution and ferrite particles are placed in a vacuum degassing kneader and stirred at 60°C for 30 minutes. After depressurization, toluene is removed by distillation to form a resin coating on the surface of the ferrite particles, thus creating a carrier (A2).

[0548] 94 parts of carrier (A2) and 6 parts of black toning agent (A1) were mixed and stirred at 40 rpm for 20 minutes using a V-type mixer. The mixture was then sieved using a sieve with a mesh size of 177 μm to prepare developer (C1).

[0549] [Preparation of Cyan Toner Particles (A2), Cyan Toner (A2), and Developer (C2)]

[0550] In the preparation of black tone particles (A1), 20 parts of colorant particle dispersion (A2) were used to replace colorant particle dispersion (A1). Otherwise, cyan tone particles (A2) were prepared according to the same procedure as black tone particles (A1). The volume average particle size D50 of the obtained tone particles was 7.2 μm, and the volume particle size distribution index was 1.19.

[0551] A cyan toner (A2) is obtained in the same way as the black toner (A1), except that cyan toner particles (A2) are used instead of black toner particles (A1).

[0552] Except that a cyan toner (A2) is used instead of a black toner (A1), the developer (C2) is obtained in the same way as the developer (C1).

[0553] [Preparation of magenta toner particles (A3), magenta toner (A3), and developer (C3)]

[0554] In the preparation of black toner particles (A1), 25 parts of colorant particle dispersion (A3) were used to replace colorant particle dispersion (A1). Otherwise, magenta toner particles (A3) were obtained according to the preparation method of black toner particles (A1). The volume average particle size D50 of the obtained toner particles was 6.8 μm, and the volume particle size distribution index was 1.22.

[0555] Except that magenta toner particles (A3) are used instead of black toner particles (A1), magenta toner (A3) is obtained in the same way as black toner (A1).

[0556] The developer (C3) is obtained in the same way as the developer (C1), except that a magenta toner (A3) is used instead of a black toner (A1).

[0557] [Preparation of yellow tone particles (A4), yellow tone agent (A4), and developer (C4)]

[0558] In the preparation of black toner particles (A1), 25 parts of colorant particle dispersion (A4) were used to replace colorant particle dispersion (A1). Otherwise, yellow toner particles (A4) were obtained according to the preparation method of black toner particles (A1). The volume average particle size D50 of the obtained toner particles was 7.4 μm, and the volume particle size distribution index was 1.19.

[0559] A yellow toner (A4) is obtained in the same way as the black toner (A1), except that yellow toner particles (A4) are used instead of black toner particles (A1).

[0560] The developer (C4) is obtained in the same way as the developer (C1), except that a yellow toner (A4) is used instead of a black toner (A1).

[0561] <Production of Overprinted Printed Materials>

[0562] [Crimped Printed Matter (A1)]

[0563] A developer (A1) containing specific particles is supplied to the developer of the Color1000 Press modified machine manufactured by Fuji Xerox Corporation, which is filled with developer (C1) to (C4) for forming black, cyan, magenta and yellow color images.

[0564] Recording paper (OK Prince fiberless paper, manufactured by Oji Paper Co., Ltd.) is placed as the recording medium to form a mixed image containing text and photographic images as a color image (the image area ratio relative to the overall recording surface of the recording medium is 50%).

[0565] Further, a loading amount of 3g / m² is formed on the entire recording surface of the recording medium. 2 A solid image of a specific particle (A1) (i.e., a specific particle region), taken at a fixing temperature of 170℃ and a fixing pressure of 4.0 kg / cm². 2 Then fixation is performed. As the image arrangement order, the color image and specific grain areas are arranged sequentially, starting from the side closest to the recording paper.

[0566] Next, the fixed image is bent with the fixing surfaces overlapping, and then crimped using a modified PRESSELLEADA (Toppan Forms Co., Ltd.) crimping and sealing machine to produce crimped printed matter (A1).

[0567] Table 1 shows the image area ratio of the color image of the outer peripheral edge of the recording medium (i.e., the area at a distance of 0 mm to 5 mm from the periphery of the recording medium) and the image area ratio of the color image of the quasi-outer peripheral edge of the recording medium (i.e., the area at a distance of more than 5 mm and less than 10 mm from the periphery of the recording medium) in the obtained overprinted print (A1).

[0568] [Crimped Printed Matter (A2~(A5))]

[0569] In addition to forming a mixed image according to the values ​​shown in Table 1 for the image area ratio of the color image at the outer periphery of the recording medium and the image area ratio of the color image at the quasi-outer periphery of the recording medium, overprinted prints (A2) to (A5) are obtained in the same manner as overprinted prints (A1).

[0570] [Crimped Printed Matter (A6)]

[0571] As a color image, in addition to the mixed image, a dotted pattern image (yellow image) is also formed on the outer peripheral edge of the recording medium. Otherwise, the overprinted print (A6) is obtained in the same way as the overprinted print (A1). It should be noted that, regarding the above-mentioned dotted pattern image, the number of dotted images in the 5mm×5mm range is 100. The image area ratio of the color image on the outer peripheral edge of the recording medium and the image area ratio of the color image on the quasi-outer peripheral edge of the recording medium in the overprinted print (A6) are shown in Table 1.

[0572] [Crimped Printed Matter (A7)]

[0573] As a color image, in addition to the mixed image, a dotted pattern image (yellow image) is also formed on the entire recording surface of the recording medium. Otherwise, the overprinted print (A7) is obtained in the same way as the overprinted print (A1). It should be noted that, regarding the above-mentioned dotted pattern image, the number of dotted images in the 5mm×5mm range is 150. The image area ratio of the color image at the outer peripheral edge of the recording medium and the image area ratio of the color image at the quasi-outer peripheral edge of the recording medium in the overprinted print (A7) are shown in Table 1.

[0574] [Crimped Printed Matter (A8)]

[0575] As a color image, in addition to the mixed image, a dotted pattern image (yellow image) is also formed on the outer peripheral edge of the recording medium. Otherwise, the overprinted print (A8) is obtained in the same way as the overprinted print (A5). It should be noted that, regarding the above-mentioned dotted pattern image, the number of dotted images in the 5mm×5mm range is 20. The image area ratio of the color image on the outer peripheral edge of the recording medium and the image area ratio of the color image on the quasi-outer peripheral edge of the recording medium in the overprinted print (A8) are shown in Table 1.

[0576] <Evaluation>

[0577] [Initial divestiture evaluation]

[0578] Use scissors to cut along the edge (periphery of the recording medium) 5 mm away from the edge, and evaluate the adhesion of the obtained sample (outer peripheral edge). The evaluation criteria are as follows, and the results are shown in Table 1 (“Initial Delamination” in Table 1).

[0579] -Evaluation Criteria-

[0580] A: Seamless bonding

[0581] B: Gaps exist in some areas.

[0582] C: Peeling occurs simultaneously with cutting.

[0583] [Evaluation of peeling over time under high temperature and high humidity]

[0584] The obtained embossed printed materials were left to stand in a high temperature and high humidity environment (specifically, 28°C and 85% humidity) for 14 days before a peel test was conducted. The peel test was used to confirm whether damage occurred due to peeling the embossed surface of the printed materials, and the peel force (N) during peeling without damage. It should be noted that the peel force was measured using a tensile testing machine (Toyo Seiki Co., Ltd., model: SEM STROGRAPH V1-C) via a 90-degree peel method. Rectangular specimens were used as test samples, which were obtained by cutting perpendicularly along a direction parallel to the long side of the embossed printed materials, 15 mm from the end of the long side. The results are shown in Table 1 (Table 1: "Peeling over Time").

[0585] It should be noted that "-" in Table 1 indicates that no evaluation of time-dependent stripping was conducted due to initial stripping.

[0586] [Table 1]

[0587]

[0588] As can be seen from Table 1 above, compared with the comparative example, the embodiment suppressed the initial peeling of the outer peripheral edge of the press-printed material.

[0589] Example B

[0590] Preparation of dispersions containing styrene-based resin particles

[0591] [Preparation of styrene-based resin particle dispersion (St1)]

[0592] Styrene: 390 portions

[0593] • n-Butyl acrylate: 100 parts

[0594] Acrylic acid: 10 parts

[0595] • Dodecanthiol: 7.5 parts

[0596] The above materials are mixed and dissolved to prepare a monomer solution.

[0597] Eight parts of anionic surfactant (Dow Chemical Company, Dowfax 2A1) were dissolved in 205 parts of ion-exchanged water, and the above monomer solution was added for dispersion and emulsification to obtain an emulsion.

[0598] 2.2 parts of anionic surfactant (Dow Chemical Company, Dowfax 2A1) were dissolved in 462 parts of ion-exchanged water and added to a polymerization flask equipped with a stirrer, thermometer, reflux cooling tube and nitrogen inlet tube. The mixture was heated to 73°C with stirring and maintained.

[0599] Dissolve 3 parts of ammonium persulfate in 21 parts of ion-exchanged water and add it dropwise to the polymerization flask over 15 minutes using a metering pump. Then add the emulsion dropwise over 160 minutes using a metering pump.

[0600] Next, while stirring slowly and continuously, the polymerization flask was kept at 75°C for 3 hours, and then returned to room temperature (25°C).

[0601] Thus, a styrene-based resin particle dispersion (St1) was obtained, comprising styrene-based resin particles, with a volume average particle size (D50v) of 174 nm, a weight average molecular weight of 49 kJ as determined by GPC (UV detection), a glass transition temperature of 54 °C, and a solid content of 42% by mass.

[0602] 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 DSC-60A). One glass transition temperature was observed. The glass transition temperatures are shown in Table 2.

[0603] [Preparation of styrene-based resin particle dispersions (St2) to (St13)]

[0604] As shown in Table 2, styrene-based resin particle dispersions (St2) to (St13) were prepared in the same manner as the preparation of styrene-based resin particle dispersion (St1).

[0605] The monomers in Table 2 are represented by the following abbreviations.

[0606] 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

[0607] [Table 2]

[0608]

[0609] Preparation of dispersions containing composite resin particles

[0610] [Preparation of composite resin particle dispersion (M1)]

[0611] • Styrene-based resin particle dispersion (St1): 1190 parts (500 parts solids)

[0612] · 2-Ethylhexyl acrylate: 250 parts

[0613] • n-Butyl acrylate: 250 parts

[0614] • Ion-exchanged water: 982 samples

[0615] The above materials were added to a polymerization flask, stirred at 25°C for 1 hour, and then heated to 70°C.

[0616] Dissolve 2.5 parts of ammonium persulfate in 75 parts of ion-exchanged water and add it dropwise to the polymerization flask over 60 minutes using a metering pump.

[0617] Next, while stirring slowly and continuously, the polymerization flask was kept at 70°C for 3 hours, and then returned to room temperature (25°C).

[0618] Thus, a composite resin particle dispersion (M1) was obtained, comprising composite resin particles, with 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% by mass.

[0619] The composite resin particle dispersion (M1) was dried, and the composite resin particles were removed. The thermal behavior of the particles was analyzed using a differential scanning calorimeter (Shimadzu DSC-60A) from -150°C to 100°C. Two glass transition temperatures were observed. The glass transition temperatures are shown in Table 3.

[0620] [Preparation of composite resin particle dispersions (M2)~(M21) and (cM1)~(cM3)]

[0621] As shown in Table 3, the styrene-based resin particle dispersion (St1) is modified, or the polymerization composition of the (meth)acrylate-based resin is modified as shown in Table 3, and composite resin particle dispersions (M2) to (M21) and (cM1) to (cM3) are prepared in the same manner as the preparation of composite resin particle dispersion (M1).

[0622] [Preparation of composite resin particle dispersions (M22) to (M27)]

[0623] Adjust the amounts of 2-ethylhexyl acrylate and n-butyl acrylate, and prepare composite resin particle dispersions (M22) to (M27) in the same manner as the preparation of composite resin particle dispersion (M1).

[0624] The monomers in Table 3 are represented by the following abbreviations.

[0625] 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

[0626] [Table 3]

[0627]

[0628] <Preparation of Specific Particles>

[0629] [Preparation of specific particles (1) and developer (1)]

[0630] • Composite resin particle dispersion (M1): 504 parts

[0631] • Ion-exchanged water: 710 parts

[0632] • Anionic surfactant (manufactured by Dow Chemical Company, Dowfax 2A1): 1 part

[0633] The above materials were added to a reaction vessel equipped with a thermometer and a pH meter. A 1.0% (w / w) aqueous nitric acid solution was added at 25°C to adjust the pH to 3.0. While dispersing using a homogenizer (IKA, ULTRA-TURRAX T50) at 5000 rpm, 23 parts of a 2.0% (w / w) aqueous aluminum sulfate solution were added. A stirrer and heating mantle were then installed in the reaction vessel. The temperature was increased at a rate of 0.2°C / min until reaching 40°C, and at a rate of 0.05°C / min after exceeding 40°C. Particle size was measured every 10 minutes using a Multisizer II (50 μm pore size, Beckman Coulter). Once 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 addition, the mixture was maintained at 50°C for 30 minutes, and then a 1.0% (w / w) aqueous sodium hydroxide solution was added to adjust the pH of the slurry to 6.0. The pH was then adjusted to 6.0 every 5°C, and the temperature was increased to 90°C at a rate of 1°C / min and maintained at 90°C. The particle shape and surface properties were observed using an optical microscope and a field emission scanning electron microscope (FE-SEM). Particle aggregation was confirmed at the 10th hour, so the container was cooled to 30°C with cooling water for 5 minutes.

[0634] The cooled slurry was passed through a 15μm mesh nylon screen to remove coarse particles. The slurry that had passed through the screen was then filtered under reduced pressure using a suction device. The remaining solids on the filter paper were crushed 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 slurry was then filtered again under reduced pressure using a suction device, and the remaining solids on the filter paper were crushed 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 slurry 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.

[0635] The cleaned solid components were finely ground using a wet-dry granulator (pulverizer and granulator) and then vacuum dried in an oven at 25°C for 36 hours to obtain master particles (1). The volume average particle size of master particles (1) was 8.0 μm.

[0636] 100 parts of master particles (1) were mixed with 1.5 parts of hydrophobic silica (manufactured by NIPPON AEROSIL Co., Ltd., 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 sieve with a mesh size of 45 μm to obtain specific particles (1).

[0637] Using a specific particle (1) as a sample, thermal behavior analysis was performed in the temperature range of -150°C to 100°C using a differential scanning calorimeter (Shimadzu DSC-60A). Two glass transition temperatures were observed. The glass transition temperatures are shown in Table 4.

[0638] The temperatures T1 and T2 of a specific particle (1) were determined using the above measurement method. The results showed that the specific particle (1) satisfied Equation 1, “10℃≦T1-T2”.

[0639] Cross-sections of a specific particle (1) were observed using a scanning electron microscope (SEM), revealing an island structure. The specific particle (1) had a core containing an island phase and a shell without an island phase. The marine phase contained styrene-based resin, and the island phase contained (meth)acrylate-based resin. The average diameter of the island phase was determined using the methods described above. The average diameter of the island phase is shown in Table 4.

[0640] Ten parts of specific particles (1) and 100 parts of the resin-coated carrier described below were loaded into a V-type mixer and stirred for 20 minutes. Then, the mixture was sieved using a vibrating screen with a mesh size of 212 μm to obtain developer (1).

[0641] • Mn-Mg-Sr ferrite particles (average particle size 40 μm): 100 parts

[0642] Toluene: 14 parts

[0643] • Polymethyl methacrylate: 2 parts

[0644] • Carbon black (VXC72: made from Cabot): 0.12 parts

[0645] The above 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. This dispersion and ferrite particles were then placed in a vacuum degassing kneader and dried under reduced pressure by stirring, thereby obtaining a resin-coated carrier.

[0646] [Preparation of specific particles (2) to (27) and developer (2) to (27)]

[0647] As shown in Table 4, the composite resin particle dispersion and the styrene-based resin particle dispersion were changed, and the specific particles (2) to (27) and the developer (2) to (27) were prepared in the same way as the specific particles (1).

[0648] The temperatures T1 and T2 of specific particles (2) to (27) were determined using the above measurement method. The results showed that all specific particles (2) to (27) satisfied Equation 1 "10℃≦T1-T2".

[0649] [Comparison of the preparation of particles (c1) to (c3) and developers (c1) to (c3)]

[0650] As shown in Table 4, by changing the composite resin particle dispersion and the styrene-based resin particle dispersion, particles (c1) to (c3) and developer (c1) to (c3) were prepared in the same way as the preparation of specific particles (1).

[0651] [Evaluation of pressure-responsive phase transitions]

[0652] The temperature difference (T1-T3) was determined as an indicator of how easily particles undergo a phase transition due to pressure. Using each particle as a sample, temperatures T1 and T3 were measured using a flow testing instrument (Shimadzu CFT-500), and the temperature difference (T1-T3) was calculated. Table 4 shows the temperature difference (T1-T3).

[0653] [Evaluation of Adhesion]

[0654] As a manufacturing device for printed materials, preparation Figure 4 The apparatus shown is for preparing a printed material manufacturing apparatus, which includes: a printing mechanism that uniformly forms a color image on a recording medium and imparts specific grains in a series of five drums with intermediate transfer; and a pressing mechanism having a folding device and a pressing device.

[0655] Specific particles (or comparative particles), yellow toner, magenta toner, cyan toner, and black toner are added to the five developers in the printing facility. The yellow toner, magenta toner, cyan toner, and black toner are commercially available products manufactured by Fuji Xerox.

[0656] As a recording medium, we prepared postcard paper V424 manufactured by Fuji Xerox.

[0657] The color image formed on postcard paper is an image with an area density of 30% that contains both black text and full-color photographic images, formed on one side of the postcard paper.

[0658] The amount of a specific particle (or a particle for comparison) imparted in the color image forming area of ​​the color image forming surface of the postcard paper is 3 g / m². 2 .

[0659] The folding device is a device for folding a postcard in half with the color image forming surface facing inwards.

[0660] The pressurization device is set to a pressure of 90 MPa.

[0661] Ten postcards were produced consecutively under the above-described apparatus and conditions, folded in half with the color image forming surfaces facing inwards and then glued together.

[0662] The 10th 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. Loads (N) were collected at 0.4mm intervals from 10mm to 50mm after the start of the measurement, and the average value was calculated. The loads (N) of the three test pieces were then averaged. The required peel loads (N) were categorized according to the following criteria. The results are shown in Table 4.

[0663] A: 0.8N or more

[0664] B: Above 0.6N and less than 0.8N

[0665] C: Above 0.4N, less than 0.6N

[0666] D: Above 0.2N and less than 0.4N

[0667] E: less than 0.2N

[0668] [Table 4]

[0669]

Claims

1. A method for manufacturing printed matter, comprising the following steps: The color image forming step involves using a pigment to form a color image on a recording medium in which the image area ratio of the outer peripheral edge of the recording medium is 20% or less. The pressure phase change particle imparting step imparts pressure phase change particles to the region of the recording medium, including the outer peripheral edge. The bonding step involves bonding the aforementioned color image and the aforementioned pressure-phase-change particles to the aforementioned recording medium; and The pressing step involves folding the recording medium with the aforementioned color image and pressure phase change particles adhered to it and then pressing it, or overlapping the recording medium with the aforementioned color image and pressure phase change particles adhered to it with other recording media and then pressing it. The aforementioned pressure-sensitive phase change particles comprise styrene-based resins and (meth)acrylate-based resins. The styrene-based resin contains styrene and other vinyl monomers in its polymerization component. The (meth)acrylate-based resin contains at least two types of (meth)acrylates in its polymerization component. The (meth)acrylates constitute at least 90% by mass of the total polymerization component of the (meth)acrylate-based resin. Among the at least two types of (meth)acrylates included as a polymerization component in the (meth)acrylate-based resin of the aforementioned pressure-sensitive phase change particles, the mass ratio of the two (meth)acrylates with the highest mass proportion is in the range of 80:20 to 20:

80. The aforementioned pressure phase change particles have at least two glass transition temperatures, and the difference between the lowest and highest glass transition temperatures exhibited by the aforementioned pressure phase change particles is more than 30°C.

2. A method for manufacturing printed matter, comprising the following steps: The color image forming step involves using a pigment to form a color image on a recording medium in which the image area ratio of the outer peripheral edge of the recording medium is 20% or less. The pressure phase change particle imparting step imparts pressure phase change particles to the region of the recording medium, including the outer peripheral edge. The bonding step involves bonding the aforementioned color image and the aforementioned pressure-phase-change particles to the aforementioned recording medium; and The pressing step involves folding the recording medium with the aforementioned color image and pressure phase change particles adhered to it and then pressing it, or overlapping the recording medium with the aforementioned color image and pressure phase change particles adhered to it with other recording media and then pressing it. The aforementioned pressure phase change particles comprise styrene-based resins and (meth)acrylate-based resins. The styrene-based resin contains styrene and other vinyl monomers in its polymerization component. The (meth)acrylate-based resin contains at least two types of (meth)acrylates in its polymerization component, with the (meth)acrylates accounting for at least 90% by mass of the total polymerization component. Among the at least two types of (meth)acrylates included as polymerization components in the (meth)acrylate-based resin of the aforementioned pressure phase change particles, the two (meth)acrylates with the highest mass proportion are alkyl (meth)acrylates, and the difference in the number of carbon atoms in the alkyl groups of these two alkyl (meth)acrylates is in the range of 1 to 4. The aforementioned pressure phase change particles have at least two glass transition temperatures, and the difference between the lowest and highest glass transition temperatures exhibited by the aforementioned pressure phase change particles is more than 30°C.

3. The method for manufacturing printed matter as described in claim 2, wherein, In the above-mentioned pressure phase change particle (meth)acrylate resin, the mass ratio of the two (meth)acrylates that are included as polymerizing components is in the range of 80:20 to 20:80, where the mass proportion of the two (meth)acrylates is the largest.

4. The method for manufacturing printed matter according to any one of claims 1 to 3, wherein, The area ratio of the aforementioned color images is less than 10%.

5. The method for manufacturing printed matter according to any one of claims 1 to 3, wherein, The image area ratio of the aforementioned color images is 2% or more.

6. The method for manufacturing printed matter according to any one of claims 1 to 3, wherein, The above-mentioned color image forming step is a step of forming a pattern image of a color image on the outer peripheral edge of the above-mentioned recording medium.

7. The method for manufacturing printed matter as described in claim 6, wherein, The above pattern image is a dotted pattern image.

8. The method for manufacturing printed matter as described in claim 6, wherein, The above pattern image is a yellow image.

9. The method for manufacturing printed matter according to any one of claims 1 to 3, wherein, The mass percentage of styrene in the total polymeric component of the styrene-based resin of the aforementioned pressure phase change particles ranges from 60% to 95% by mass.

10. The method for manufacturing printed matter according to any one of claims 1 to 3, wherein, The other vinyl monomers included as polymerizing components in the above-mentioned styrene-based resins include (meth)acrylates.

11. The method for manufacturing printed matter according to any one of claims 1 to 3, wherein, The other vinyl monomers included as polymerizing components in the above-mentioned styrene-based resins are selected from n-butyl acrylate and 2-ethylhexyl acrylate.

12. The method for manufacturing printed matter according to any one of claims 1 to 3, wherein, The above-mentioned styrene-based resin and the above-mentioned (meth)acrylate-based resin contain the same (meth)acrylate as a polymerization component.

13. The method for manufacturing printed matter according to any one of claims 1 to 3, wherein, The above-mentioned (meth)acrylate resins contain 2-ethylhexyl acrylate and n-butyl acrylate as polymerization components.

14. The method for manufacturing printed matter according to any one of claims 1 to 3, wherein, In the aforementioned pressure phase change particles, the content of the aforementioned styrene-based resin is greater than the content of the aforementioned (meth)acrylate-based resin.

15. The method for manufacturing printed matter according to any one of claims 1 to 3, wherein, The pressure phase change particles described above have a marine phase containing the styrene-based resin and an island phase containing the (meth)acrylate-based resin dispersed in the marine phase.

16. The method for manufacturing printed matter as described in claim 15, wherein, The average diameter of the aforementioned island phases ranges from 200 nm to 500 nm.

17. The method for manufacturing printed matter according to any one of claims 1 to 3, wherein, The aforementioned pressure phase change particles have a core and a shell, the core containing the aforementioned styrene-based resin and the aforementioned (meth)acrylate-based resin, and the shell covering the aforementioned core.

18. The method for manufacturing printed matter as described in claim 17, wherein, The aforementioned shell layer contains the aforementioned styrene-based resin.

19. The method for manufacturing printed matter according to any one of claims 1 to 3, wherein, The aforementioned pressure-phase change particles exhibit a viscosity of 10000 Pa·s at a pressure of 4 MPa at temperatures below 90 °C.

20. A system for manufacturing printed matter, comprising: The color image forming unit uses pigments to form a color image on a recording medium in which the image area ratio of the outer peripheral edge of the recording medium is 20% or less; The pressure phase change particle delivery section stores pressure phase change particles and delivers the pressure phase change particles to the region of the recording medium including the outer peripheral edge. The adhesive portion bonds the aforementioned color image and the aforementioned pressure-phase change particles to the aforementioned recording medium; and The crimping section is used to crimp the recording medium, which has the aforementioned color image and pressure phase change particles adhered to it, after folding it; or it is used to crimp the recording medium, which has the aforementioned color image and pressure phase change particles adhered to it, after overlapping it with other recording media. The aforementioned pressure-sensitive phase change particles comprise styrene-based resins and (meth)acrylate-based resins. The styrene-based resin contains styrene and other vinyl monomers in its polymerization component. The (meth)acrylate-based resin contains at least two types of (meth)acrylates in its polymerization component. The (meth)acrylates constitute at least 90% by mass of the total polymerization component of the (meth)acrylate-based resin. Among the at least two types of (meth)acrylates included as a polymerization component in the (meth)acrylate-based resin of the aforementioned pressure-sensitive phase change particles, the mass ratio of the two (meth)acrylates with the highest mass proportion is in the range of 80:20 to 20:

80. The aforementioned pressure phase change particles have at least two glass transition temperatures, and the difference between the lowest and highest glass transition temperatures exhibited by the aforementioned pressure phase change particles is more than 30°C.

21. A printing manufacturing system, comprising: The color image forming unit uses pigments to form a color image on a recording medium in which the image area ratio of the outer peripheral edge of the recording medium is 20% or less; The pressure phase change particle delivery section stores pressure phase change particles and delivers the pressure phase change particles to the region of the recording medium including the outer peripheral edge. The adhesive portion bonds the aforementioned color image and the aforementioned pressure-phase change particles to the aforementioned recording medium; and The crimping section is used to crimp the recording medium, which has the aforementioned color image and pressure phase change particles adhered to it, after folding it; or it is used to crimp the recording medium, which has the aforementioned color image and pressure phase change particles adhered to it, after overlapping it with other recording media. The aforementioned pressure phase change particles comprise styrene-based resins and (meth)acrylate-based resins. The styrene-based resin contains styrene and other vinyl monomers in its polymerization component. The (meth)acrylate-based resin contains at least two types of (meth)acrylates in its polymerization component, with the (meth)acrylates accounting for at least 90% by mass of the total polymerization component. Among the at least two types of (meth)acrylates included as polymerization components in the (meth)acrylate-based resin of the aforementioned pressure phase change particles, the two (meth)acrylates with the highest mass proportion are alkyl (meth)acrylates, and the difference in the number of carbon atoms in the alkyl groups of these two alkyl (meth)acrylates is in the range of 1 to 4. The aforementioned pressure phase change particles have at least two glass transition temperatures, and the difference between the lowest and highest glass transition temperatures exhibited by the aforementioned pressure phase change particles is more than 30°C.

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