Resin particle, and circuit board including insulation layer

Abstract

To provide a resin particle capable of exerting low thermal expansion property, and low dielectric property.SOLUTION: A resin particle includes: a resin particle body; a plurality of silica particles; and a plurality of polytetrafluoroethylene particles, where a plurality of the silica particles exist on a surface of, or inside of the resin particle body, a plurality of the polytetrafluoroethylene particles exist on a surface of, or inside of the resin particle body, the resin particle body is a polymer of a polymerizable constituent, and the polymerizable constituent includes a polymerizable compound having one or more ethylenic unsaturated group.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to resin particles containing polytetrafluoroethylene particles, and to a circuit board with an insulating layer using the resin particles. [Background technology]

[0002] Fluorine-based resins such as polytetrafluoroethylene (PTFE) are known to have excellent water repellency, chemical resistance, and low dielectric properties.

[0003] The following Patent Document 1 discloses a composite particle (C) containing a particle (F) containing a fluorine-containing polymer (A) and a polymer (B) having a monomer (b) as a constituent monomer. The composite particle (C) has a surface of the particle (F) covered with a coating layer containing the polymer (B), and has an impregnation layer in which the polymer (B) is impregnated from the surface of the particle (F) to the inside. Patent Document 1 lists vinyl resins, epoxy resins, polyurethane resins, and the like as examples of the polymer (B).

[0004] The following Patent Document 2 discloses composite particles containing a thermally fusible tetrafluoroethylene-based polymer and an inorganic substance. As a specific example of the composite particles, Patent Document 2 describes composite particles having a tetrafluoroethylene-based polymer as a core and the above-mentioned inorganic substance on the surface of the core. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2016-121352 A [Patent Document 2] WO2022 / 109252A1 Summary of the Invention [Problem to be solved by the invention]

[0006] In composite particles in which fluorine-containing particles are coated with urethane resin or the like as described in Patent Document 1, the excellent low dielectric properties of the fluorine-based resin may not be fully exhibited because the fluorine-based resin is coated with a polymer. Similarly, in coated particles in which a tetrafluoroethylene polymer is coated with an inorganic substance as described in Patent Document 2, the excellent low dielectric properties of the fluorine-based resin may not be fully exhibited.

[0007] Furthermore, conventional particles containing fluororesins have the problem of poor thermal expansion (low dimensional stability).

[0008] It is difficult for conventional resin particles to exhibit both low thermal expansion and low dielectric properties.

[0009] An object of the present invention is to provide resin particles capable of exhibiting low thermal expansion and low dielectric properties, and a circuit board with an insulating layer using the resin particles. [Means for solving the problem]

[0010] This specification discloses the following resin particles and circuit board with an insulating layer.

[0011] Item 1. A resin particle body, a plurality of silica particles, and a plurality of polytetrafluoroethylene particles, wherein the plurality of silica particles are present on the surface or inside of the resin particle body, and the plurality of polytetrafluoroethylene particles are present on the surface or inside of the resin particle body. a resin particle body being a polymer of a polymerizable component, the polymerizable component containing a polymerizable compound having one or more ethylenically unsaturated groups;

[0012] Item 2. The resin particles according to item 1, wherein the particle diameter of the resin particles is 0.5 μm or more.

[0013] Item 3. The resin particles according to item 1 or 2, wherein the silica particles have a particle diameter of 1.0 μm or less.

[0014] Item 4. The resin particles according to any one of Items 1 to 3, wherein a ratio of a particle size of the silica particles to a particle size of the resin particles is 0.001 or more and 0.5 or less.

[0015] Item 5. The resin particles according to any one of Items 1 to 4, wherein the content of the silica particles is 0.1% by weight or more and 20% by weight or less in 100% by weight of the resin particles.

[0016] Item 6. The resin particles according to any one of Items 1 to 5, wherein the content of the polytetrafluoroethylene particles is 0.1% by weight or more and 20% by weight or less in 100% by weight of the resin particles.

[0017] Item 7. The resin particles according to any one of Items 1 to 6, wherein the total content of the silica particles and the polytetrafluoroethylene particles is 25% by weight or less in 100% by weight of the resin particles.

[0018] Item 8. The resin particles according to any one of Items 1 to 7, wherein the polymerizable component contains a crosslinkable monomer.

[0019] Item 9. The resin particles according to item 8, wherein the crosslinkable monomer is divinylbenzene or a polymerizable compound having two or more (meth)acryloyl groups.

[0020] Item 10. The resin particles according to item 8 or 9, wherein the content of the crosslinkable monomer in 100% by weight of the polymerizable component is 10% by weight or more.

[0021] Item 11. The resin particles according to any one of Items 1 to 10, wherein the resin particles have a thermal expansion coefficient of less than 150 ppm / °C at 50°C to 150°C.

[0022] Item 12. The resin particles according to any one of Items 1 to 11, wherein the resin particles have a dielectric constant of 2.60 F / m or less and a dielectric loss tangent of 0.01 or less.

[0023] Item 13. In at least one of the plurality of silica particles, a part of the silica particle is present inside the resin particle body, and a part of the silica particle is present on the surface of the resin particle body. The resin particle according to any one of items 1 to 12.

[0024] Item 14. In at least one of the plurality of polytetrafluoroethylene particles, a portion of the polytetrafluoroethylene particle is present inside the resin particle body, and a portion of the polytetrafluoroethylene particle is present on the surface of the resin particle body. The resin particle according to any one of items 1 to 13.

[0025] Item 15. The number of the polytetrafluoroethylene particles present in a region from the surface of the resin particle body to 1 / 2 of the thickness toward the center is greater than the number of the polytetrafluoroethylene particles present in a region from the center of the resin particle body to the surface to 1 / 2 of the thickness.

[0026] Item 16. A circuit board with an insulating layer, comprising: a circuit board; and an insulating layer disposed on a surface of the circuit board, the insulating layer including the resin particles according to any one of items 1 to 15. Effect of the Invention

[0027] The resin particles according to the present invention include a resin particle body, a plurality of silica particles, and a plurality of polytetrafluoroethylene particles. In the resin particles according to the present invention, a plurality of the silica particles are present on the surface or inside of the resin particle body, and a plurality of the polytetrafluoroethylene particles are present on the surface or inside of the resin particle body. In the resin particles according to the present invention, the resin particle body is a polymer of a polymerizable component, and the polymerizable component contains a polymerizable compound having one or more ethylenically unsaturated groups. Since the resin particles according to the present invention have the above-mentioned configuration, they can exhibit low thermal expansion and low dielectric properties. [Brief description of the drawings]

[0028] [Figure 1] FIG. 1 is a cross-sectional view that illustrates a resin particle according to a first embodiment of the present invention. [Diagram 2] FIG. 2 is a cross-sectional view that illustrates a resin particle according to a second embodiment of the present invention. [Diagram 3] FIG. 3 is a cross-sectional view that illustrates a multilayer printed wiring board using the resin particles according to the first embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0029] The present invention will be described in detail below. In this specification, for example, "(meth)acryloxy" means one or both of "acryloxy" and "methacryloxy", and "(meth)acrylic" means one or both of "acrylic" and "methacrylic".

[0030] (Resin particles) The resin particles according to the present invention include a resin particle body, a plurality of silica particles, and a plurality of polytetrafluoroethylene particles. In the resin particles according to the present invention, a plurality of the silica particles are present on the surface or inside of the resin particle body, and a plurality of the polytetrafluoroethylene particles are present on the surface or inside of the resin particle body. In the resin particles according to the present invention, the resin particle body is a polymer of a polymerizable component, and the polymerizable component includes a polymerizable compound having one or more ethylenically unsaturated groups.

[0031] The resin particles according to the present invention have the above-mentioned configuration, and therefore can exhibit low thermal expansion and low dielectric properties. The resin particles according to the present invention can achieve both low thermal expansion and low dielectric properties. The resin particles according to the present invention are less susceptible to thermal expansion even when exposed to high temperatures, and can improve dimensional stability.

[0032] In addition, in composite particles in which fluorine-containing particles are coated with other resins or inorganic substances, the excellent water repellency and low dielectric properties of the fluorine-based resin may not be fully exhibited because the fluorine-based resin is coated with other resins or inorganic substances. In addition, in conventional composite particles, the composite particles may form unintended aggregates due to stimulation such as stirring, heating, or reaction during molding of the composite particles. As a result, the dispersibility of the composite particles in a solvent may not be sufficiently improved.

[0033] In contrast, the resin particles according to the present invention have the above-mentioned configuration, and therefore can improve dispersibility in a solvent. As a result, when the resin particles according to the present invention are dispersed in a solvent, the resin particles do not form unintended aggregates, and therefore inkjet ejection properties can be improved, and molding stability can be improved when molding a composition containing the resin particles. Furthermore, the resin particles according to the present invention do not require the addition of a large amount of a surfactant in order to disperse them in a solvent. Since the resin particles according to the present invention are not required, the environmental load can be reduced, the occurrence of bleed-out due to a surfactant can be suppressed, and peeling of the resin particles from a molded body of a composition containing the resin particles can be suppressed. Furthermore, since the resin particles according to the present invention have the above-mentioned configuration, they can have high water repellency and exhibit low dielectric properties.

[0034] In the resin particles of the present invention, multiple silica particles may be present on the surface (external) of the resin particle body, may be present inside the resin particle body, or may be present on the surface (external) and internally of the resin particle body.

[0035] In the resin particles, any one of the silica particles may be entirely present on the surface (exterior) of the resin particle body, or a part of any one of the silica particles may be present (exposed) on the surface (exterior) of the resin particle body. In the resin particles, any one of the silica particles may be entirely present inside the resin particle body, or a part of any one of the silica particles may be present inside the resin particle body.

[0036] In the resin particles, all of the silica particles may be present on the surface (external) of the resin particle body, or a part (at least one) of the silica particles may be present on the surface (external) of the resin particle body. In the resin particles, all of the silica particles may be present on the surface (external) of the resin particle body, or at least one of the silica particles may be present on the surface (external) of the resin particle body. In the resin particles, all of the silica particles may be present inside the resin particle body, or a part (at least one) of the silica particles may be present inside the resin particle body. In the resin particles, all of the silica particles may be present inside the resin particle body, or at least one of the silica particles may be present inside the resin particle body.

[0037] In the resin particles, the silica particles may be present on the surface (external) of the resin particle body, the silica particles may be present on the surface (external) and in the resin particle body (a part of which is present outside the resin particle body), and the silica particles may be present inside the resin particle body. From the viewpoint of further enhancing water repellency, it is preferable that in at least one of the silica particles, a part of the silica particles is present inside the resin particle body, and a part of the silica particles is present (exposed) on the surface (external) of the resin particle body. From the viewpoint of more effectively exerting low thermal expansion, it is preferable that in a part (at least one) of the silica particles, a part of the silica particles is present inside the resin particle body, and a part of the silica particles is present (exposed) on the surface (external) of the resin particle body. In the resin particles, it is preferable that the silica particles are present only on the surface (external) of the resin particle body, the silica particles are present on the surface and in the resin particle body (a part of which is present outside the resin particle body), and the silica particles are present only inside the resin particle body. In these cases, the low thermal expansion property can be exhibited more effectively.

[0038] In the resin particles of the present invention, multiple polytetrafluoroethylene particles may be present on the surface (external) of the resin particle body, may be present inside the resin particle body, or may be present on the surface (external) and internally of the resin particle body.

[0039] In the resin particles, any one of the polytetrafluoroethylene particles may be present entirely on the surface (outside) of the resin particle body, or a part of any one of the polytetrafluoroethylene particles may be present (exposed) on the surface (outside) of the resin particle body. In the resin particles, any one of the polytetrafluoroethylene particles may be present entirely inside the resin particle body, or a part of any one of the polytetrafluoroethylene particles may be present inside the resin particle body.

[0040] In the resin particles, all of the polytetrafluoroethylene particles may be present on the surface (external) of the resin particle body, and a part (at least one) of the polytetrafluoroethylene particles may be present on the surface (external) of the resin particle body. In the resin particles, all of the polytetrafluoroethylene particles may be present on the surface (external) of the resin particle body, and at least one of the polytetrafluoroethylene particles may be present on the surface (external) of the resin particle body. In the resin particles, all of the polytetrafluoroethylene particles may be present inside the resin particle body, and a part (at least one) of the polytetrafluoroethylene particles may be present inside the resin particle body. In the resin particles, all of the polytetrafluoroethylene particles may be present inside the resin particle body, and at least one of the polytetrafluoroethylene particles may be present inside the resin particle body.

[0041] In the resin particles, the polytetrafluoroethylene particles may be present on the surface (outside) of the resin particle body, the polytetrafluoroethylene particles may be present on the surface (outside) and inside the resin particle body (a part of the polytetrafluoroethylene particles may be present outside the resin particle body), and the polytetrafluoroethylene particles may be present inside the resin particle body. From the viewpoint of further enhancing water repellency, it is preferable that in at least one of the multiple polytetrafluoroethylene particles, a part of the polytetrafluoroethylene particles is present inside the resin particle body, and a part of the polytetrafluoroethylene particles is present (exposed) on the surface (outside) of the resin particle body. From the viewpoint of further enhancing water repellency, it is preferable that in some (at least one) of the polytetrafluoroethylene particles, a part of the polytetrafluoroethylene particles is present inside the resin particle body, and a part of the polytetrafluoroethylene particles is present (exposed) on the surface (outside) of the resin particle body. In the resin particles, it is preferable that the polytetrafluoroethylene particles exist only on the surface (outside) of the resin particle body, the polytetrafluoroethylene particles exist on the surface and inside of the resin particle body (part exists outside the resin particle body), and the polytetrafluoroethylene particles exist only inside the resin particle body. In these cases, the water repellency can be further improved and the low dielectric property can be more effectively exhibited.

[0042] The present invention will now be described in detail with reference to the drawings.

[0043] FIG. 1 is a cross-sectional view that illustrates a resin particle according to a first embodiment of the present invention.

[0044] The resin particle 1 shown in Fig. 1 includes a resin particle body 2, a plurality of silica particles 3, and a plurality of polytetrafluoroethylene particles 4. The silica particles 3 are indicated by oblique hatching extending from the upper left to the lower right in Fig. 1. The polytetrafluoroethylene particles 4 are indicated by oblique hatching extending from the upper right to the lower left in Fig. 1.

[0045] In the resin particle 1, all of the silica particles 3 are present on the surface (outside) and inside of the resin particle body 2. In the resin particle 1, a portion of all of the silica particles 3 is present inside the resin particle body 2, and a portion of the silica particles 3 is present on the surface (outside) of the resin particle body 2.

[0046] In the resin particle 1, all of the polytetrafluoroethylene particles 4 are present on the surface (outside) and inside of the resin particle body 2. In the resin particle 1, a portion of all of the polytetrafluoroethylene particles 4 is present inside the resin particle body 2, and a portion of the polytetrafluoroethylene particles 4 is present on the surface (outside) of the resin particle body 2.

[0047] FIG. 2 is a cross-sectional view that illustrates a resin particle according to a second embodiment of the present invention.

[0048] Resin particle 1A shown in Fig. 2 includes a resin particle body 2, a plurality of silica particles 3A, and polytetrafluoroethylene particles 4A. Silica particles 3A are indicated by oblique hatching extending from the upper left to the lower right in Fig. 2. Polytetrafluoroethylene particles 4A are indicated by oblique hatching extending from the upper right to the lower left in Fig. 2.

[0049] In the resin particle 1A, at least one of the multiple silica particles 3A is present inside the resin particle body 2. In the resin particle 1A, a part (at least one) of the silica particles 3A is present inside the resin particle body 2. In the resin particle 1A, multiple silica particles 3A are dispersed in the resin particle body 2. In the resin particle 1A, multiple silica particles 3A are present on the surface (exterior) and interior of the resin particle body 2. In the resin particle 1A, a part (at least one) of the silica particles 3A is present on the surface (exterior) and interior of the resin particle body 2. In the resin particle 1A, in at least one of the multiple silica particles 3A, a part of the silica particle 3A is present inside the resin particle body 2, and a part of the silica particle 3A is present on the surface (exterior) of the resin particle body 2.

[0050] In the resin particle 1A, at least one of the multiple polytetrafluoroethylene particles 4A is present inside the resin particle body 2. In the resin particle 1A, a portion (at least one) of the polytetrafluoroethylene particles 4A is present inside the resin particle body 2. In the resin particle 1A, multiple polytetrafluoroethylene particles 4A are dispersed in the resin particle body 2. In the resin particle 1A, multiple polytetrafluoroethylene particles 4A are present on the surface (outside) and inside the resin particle body 2. In the resin particle 1A, a portion (at least one) of the polytetrafluoroethylene particles 4A is present on the surface (outside) and inside the resin particle body 2. In the resin particle 1A, in at least one of the multiple polytetrafluoroethylene particles 4A, a portion of the polytetrafluoroethylene particle 4A is present inside the resin particle body 2, and a portion of the polytetrafluoroethylene particle 4A is present on the surface (outside) of the resin particle body 2.

[0051] In the resin particle 1A, there are silica particles 3A present entirely inside the resin particle body 2, and silica particles 3A present partially on the surface (external) of the resin particle body 2. In the resin particle 1A, there are polytetrafluoroethylene particles 4A present entirely inside the resin particle body 2, and polytetrafluoroethylene particles 4A present partially on the surface (external) of the resin particle body 2.

[0052] The thermal expansion coefficient of the resin particles at 50°C to 150°C is preferably less than 150 ppm / °C, more preferably 120 ppm / °C or less, even more preferably 100 ppm / °C or less, even more preferably 90 ppm / °C or less, even more preferably 80 ppm / °C or less, particularly preferably 70 ppm / °C or less, particularly preferably 60 ppm / °C or less, and most preferably 50 ppm / °C or less. When the thermal expansion coefficient is equal to or less than the upper limit (or less than the upper limit), low thermal expansion is more effectively exhibited, and the dimensional change when the resin particles are exposed to high temperatures can be reduced. Therefore, for example, when the resin particles are used in an insulating layer, etc., even if the insulating layer is exposed to high temperatures, peeling and cracking can be suppressed. The thermal expansion coefficient of the resin particles at 50°C to 150°C may be 0 ppm / °C or more.

[0053] The thermal expansion coefficient of the resin particles at 50°C to 150°C can be measured, for example, as follows. Using a thermomechanical analyzer (TMA), the resin particles are held at 50°C for 5 minutes, and then heated from 50°C to 160°C at a heating rate of 5°C / min. The linear expansion coefficient from 50°C to 150°C is calculated. For example, a thermomechanical analyzer (TMA) such as " "TMA450" etc. are used.

[0054] The dielectric constant of the resin particles is preferably 2.60 F / m or less, more preferably 2.50 F / m or less, and even more preferably 2.40 F / m or less. When the dielectric constant of the resin particles is the upper limit or less, the low dielectric property can be more effectively exhibited. The lower limit of the dielectric constant of the resin particles is not particularly limited. The dielectric constant of the resin particles may be 1.80 F / m or more, or 1.90 F / m or more.

[0055] The dielectric loss tangent of the resin particles is preferably 0.01 or less, more preferably 0.005 or less, and even more preferably 0.001 or less. When the dielectric loss tangent of the resin particles is the upper limit or less, the low dielectric property can be more effectively exhibited. The lower limit of the dielectric loss tangent of the resin particles is not particularly limited. The dielectric loss tangent of the resin particles may be 0.0001 or more, or 0.0005 or more.

[0056] The dielectric constant and dielectric loss tangent of the resin particles can be measured, for example, as follows: A quartz tube is filled with resin particles and placed in a powder measurement resonator. The dielectric constant and dielectric loss tangent of the resin particles at 1 GHz are measured using a dielectric constant measuring device (manufactured by AET).

[0057] The 10% K value of the resin particles at 25° C. is preferably 100 N / mm 2 More preferably, 500N / mm 2 More preferably, 1000N / mm 2 or more, preferably 20000N / mm 2 Less than or equal to 15000N / mm 2 Less than 10000N / mm 2 Below 8000N / mm 2 When the 10% K value at 25° C. of the resin particles is equal to or higher than the above lower limit and equal to or lower than the above upper limit, interfacial peeling between the silica particles and the resin particle bodies can be suppressed.

[0058] The 10% K value of the resin particles at 25°C can be measured as follows. Using a microcompression tester, the resin particles are compressed with a smooth indenter end face of a cylinder (diameter 50 μm, made of diamond) at 25°C under the condition of applying a maximum test load of 20 mN for 60 seconds. The load value (N) and compression displacement (mm) at this time are measured. From the obtained measured values, the 10% K value of the resin particles at 25°C can be calculated by the following formula. As the microcompression tester, for example, Fischer Scope H-100 manufactured by Fischer Co., Ltd. can be used.

[0059] 10% K value (N / mm2 )=(3 / 2 1 / 2 )·F·S -3 / 2 ·R -1 / 2 F: Load value (N) when resin particles are compressed and deformed by 10% S: Compressive displacement (mm) when the resin particles are compressed and deformed by 10% R: Radius of resin particle (mm)

[0060] From the viewpoint of suppressing crushing of the resin particles when molding a composition containing the resin particles, the compression recovery rate of the resin particles at 25° C. is preferably 10% or more, more preferably 20% or more, and even more preferably 30% or more, and is preferably 95% or less, more preferably 90% or less, and even more preferably 80% or less. The compression recovery rate of the resin particles at 25° C. may be 70% or less.

[0061] The compression recovery rate of the resin particles at 25° C. can be measured as follows.

[0062] Resin particles are scattered on a sample stage. A micro-compression tester is used to apply a load to each scattered resin particle with the smooth end face of a cylindrical indenter (diameter 50 μm, made of diamond) at 25°C in the direction of the center of the resin particle under conditions of an origin load value of 1.0 mN and a reverse load value of 10 mN, and the recovery behavior after the load is removed is analyzed to derive the compression recovery rate. The load-compression displacement during this period is measured, and the compression recovery rate can be calculated from the following formula. The loading speed is The compression strength is set to 0.33 mN / sec. As the microcompression tester, for example, "Fischerscope H-100" manufactured by Fischer Co., Ltd., or the like can be used.

[0063] Compression recovery rate (%) = [L2 / L1] x 100 L1: Compressive displacement from the load value for the origin to the load value for the reverse load when applying a load L2: Unloading displacement from the reverse load value when releasing the load to the load value for the origin

[0064] From the viewpoint of further enhancing the dispersibility of the resin particles in the solvent, the particle diameter of the resin particles is preferably 0.5 μm or more, more preferably 1.0 μm or more, even more preferably 3.0 μm or more, particularly preferably 5.0 μm or more, and is preferably 100 μm or less, more preferably 50 μm or less, even more preferably 30 μm or less, particularly preferably 20 μm or less.

[0065] The particle size of the resin particles means the diameter when the resin particles are spherical, and when the resin particles are other than spherical, means the diameter when the resin particles are assumed to be a true sphere of equivalent volume.

[0066] The particle diameter of the resin particles is preferably an average particle diameter, and more preferably a number average particle diameter. The particle diameter of the resin particles can be measured by any particle size distribution measuring device. For example, it can be measured by using a particle size distribution measuring device using the principles of laser light scattering, electrical resistance value change, image analysis after imaging, etc. More specifically, as a method for measuring the particle diameter of the resin particles, a method of measuring the particle diameter of about 100,000 resin particles using a particle size distribution measuring device (Beckman Coulter's "Multisizer4") and calculating the average value can be mentioned.

[0067] From the viewpoint of further increasing the dispersibility of the resin particles in the solvent, the coefficient of variation (CV value) of the particle diameter of the resin particles is preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less. The lower limit of the coefficient of variation (CV value) of the particle diameter of the resin particles is not particularly limited. The coefficient of variation (CV value) of the particle diameter of the resin particles may be 0% or more, or 1% or more.

[0068] The coefficient of variation (CV value) of the particle size of the resin particles can be measured as follows.

[0069] CV value (%) of the particle diameter of the resin particles = (ρ / Dn) x 100 ρ: Standard deviation of the particle size of the resin particles Dn: average particle size of the resin particles

[0070] The shape of the resin particles is not particularly limited. The shape of the resin particles may be spherical, may be a shape other than spherical, or may be flat. From the viewpoint of further increasing the dispersibility of the resin particles in the solvent, the shape of the resin particles is preferably spherical.

[0071] From the viewpoint of further increasing the dispersibility of the resin particles in the solvent, the aspect ratio of the resin particles is preferably 1.5 or less, more preferably 1.3 or less, and even more preferably 1.1 or less. The lower limit of the aspect ratio of the resin particles is not particularly limited. The aspect ratio of the resin particles may be 1.0 or more, or may be 1.1 or more. From the viewpoint of further increasing the dispersibility of the resin particles in the solvent, the aspect ratio of the resin particles is most preferably 1.0.

[0072] The aspect ratio is the long diameter / short diameter. The aspect ratio is determined by observing 10 random resin particles using an electron microscope or an optical microscope, with the maximum diameter and the minimum diameter taken as the long diameter and the short diameter, respectively. It is preferable to obtain the diameter by calculating the average value of the major axis / minor axis of each of the spherical resin particles.

[0073] From the viewpoint of preventing the resin particles from settling in the solvent and further increasing the dispersibility of the resin particles in the solvent, the specific gravity of the resin particles is preferably 1.6 or less, more preferably 1.5 or less, even more preferably 1.4 or less, and particularly preferably 1.3 or less.

[0074] The resin particles are preferably used by dispersing them in a solvent. The resin particles are preferably used as a composition by dispersing them in a solvent. The solvent for dispersing the resin particles may be aqueous or oil-based. Examples of the solvent for dispersing the resin particles include silicone, water, mineral oil, polyether derivatives; alcohols such as methanol, ethanol, isopropanol, and fluorine-containing alcohol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and cyclic ether; esters such as acetate esters, pyruvate esters, 2-hydroxyisobutyric acid, and lactate esters; amides such as dimethylformamide; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as octane and decane; and resins. Examples of the resin include rubber, vinyl resin, acrylic resin, urethane resin, melamine resin, polyester resin, polyol resin, engineering plastic, silicone resin, fluorine resin, and epoxy resin. When the resin particles are dispersed in a solvent and used in a liquid state, the solvent is preferably silicone, water, mineral oil, polyether derivative, or the like. The composition in which the resin particles are dispersed in these solvents is particularly suitable for use as a lubricant, a non-adhesive agent, etc. When the resin particles are dispersed in a solvent and then the solvent is vaporized for use, the solvent is preferably an alcohol such as methanol, ethanol, isopropanol, or a fluorine-containing alcohol; a ketone such as acetone or methyl ethyl ketone; an ether such as tetrahydrofuran, diethyl ether, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, or a cyclic ether; an ester such as acetate, pyruvate, 2-hydroxyisobutyric acid, or lactate; an amide such as dimethylformamide; an aromatic hydrocarbon such as toluene or xylene; an aliphatic hydrocarbon such as octane or decane; or water. The composition in which the resin particles are dispersed in these solvents is particularly suitable for use as an ink, a coating agent, a paint, or a photoconductor.The composition in which the resin particles are dispersed in the resin is particularly suitable for use as a coating agent, paint, non-tackifier, anti-drip agent, and the like.

[0075] The composition containing the resin particles and the solvent may be applied by using an inkjet device, may be applied by screen printing, or may be applied by a dispensing method. In general, conventional composite particles containing fluorine-based resins tend to settle when dispersed in a solvent, so it may be difficult to improve the inkjet ejection properties. On the other hand, the resin particles have the above-mentioned configuration, so that the inkjet ejection properties can be improved when the resin particles are dispersed in a solvent.

[0076] From the viewpoint of further enhancing the dispersibility of the resin particles in the solvent, the specific gravity of the solvent in which the resin particles are dispersed is preferably 0.5 or more, more preferably 0.7 or more, even more preferably 0.8 or more, and is preferably 1.5 or less, more preferably 1.3 or less, even more preferably 1.1 or less.

[0077] From the viewpoint of further enhancing the dispersibility of the resin particles in a solvent, the resin particles are preferably used in a state dispersed in toluene or an epoxy resin.

[0078] Each component of the resin particles will be described in detail below.

[0079] <Resin particle body> The resin particle has a resin particle body. The resin particle and the resin particle body contain a resin. In the resin particle, the resin particle body is a polymer of a polymerizable component. The polymerizable component contains a polymerizable compound having one or more ethylenically unsaturated groups. The polymerizable component preferably contains a polymerizable compound having two or more ethylenically unsaturated groups. The resin particle body preferably contains a polymer of a polymerizable compound having one or more ethylenically unsaturated groups. The resin particle body preferably contains a polymer of a polymerizable compound having two or more ethylenically unsaturated groups.

[0080] Examples of the polymerizable compound (monomer) having one or more ethylenically unsaturated groups include a polymerizable compound having one ethylenically unsaturated group and a polymerizable compound having two or more ethylenically unsaturated groups. The polymerizable compound having two or more ethylenically unsaturated groups may have 100 or less ethylenically unsaturated groups, or may have 10 or less ethylenically unsaturated groups. The polymerizable compound having one or more ethylenically unsaturated groups may be used alone or in combination of two or more. The polymerizable compound having one or more ethylenically unsaturated groups may be used alone or in combination of two or more. The polymerizable compound having two or more ethylenically unsaturated groups may be used alone or in combination of two or more.

[0081] The polymerizable compound (monomer) having one or more ethylenically unsaturated groups includes a non-crosslinkable monomer and a crosslinkable monomer. The polymerizable compound (monomer) having one or more ethylenically unsaturated groups may be a polymerizable compound having one or more maleimide groups.

[0082] Examples of the non-crosslinkable monomer include styrene-based monomers such as styrene and α-methylstyrene; carboxyl group-containing monomers such as (meth)acrylic acid, maleic acid, and maleic anhydride; alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, and polyoxyethylene (meth)acrylate. nitrile-containing monomers such as (meth)acrylonitrile; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether; acid vinyl esters such as vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate; unsaturated hydrocarbons such as ethylene, propylene, isoprene, butadiene; halogen-containing monomers such as trifluoromethyl (meth)acrylate, pentafluoroethyl (meth)acrylate, (perfluorohexyl)ethyl (meth)acrylate, vinyl chloride, vinyl fluoride, chlorostyrene; and polymerizable compounds having one maleimide group.

[0083] Examples of the crosslinkable monomer include tetramethylolmethane tetra(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerol tri(meth)acrylate, glycerol di(meth)acrylate, (poly Examples of the polymerizable compound include polyfunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, (poly)tetramethylene glycol di(meth)acrylate, and 1,4-butanediol di(meth)acrylate; silane-containing monomers such as triallyl (iso)cyanurate, triallyl trimellitate, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, γ-(meth)acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, and vinyltrimethoxysilane; and polymerizable compounds having two or more maleimide groups. The polymerizable compound having two or more maleimide groups may be a polymerizable compound having two maleimide groups or a bismaleimide compound. The polymerizable compound having two or more maleimide groups may have 100 or less maleimide groups, or may have 10 or less maleimide groups.

[0084] From the viewpoint of more effectively exerting the effects of the present invention, particularly from the viewpoint of more effectively exerting low dielectric properties, the polymerizable compound (polymerizable component) having an ethylenically unsaturated group preferably contains a polymerizable compound having one or more maleimide groups. From the viewpoint of more effectively exerting the effects of the present invention, particularly from the viewpoint of more effectively exerting low dielectric properties, the polymerizable compound (polymerizable component) having an ethylenically unsaturated group preferably contains a polymerizable compound having two or more maleimide groups, and more preferably contains a bismaleimide compound.

[0085] From the viewpoint of more effectively exerting the solvent resistance and chemical resistance, the polymerizable component preferably contains a crosslinkable monomer. From the viewpoint of more effectively exerting the solvent resistance and chemical resistance, the crosslinkable monomer preferably contains divinylbenzene or a polymerizable compound having two or more (meth)acryloyl groups.

[0086] The resin particle body can be obtained by polymerizing the polymerizable compound having one or more ethylenically unsaturated groups by a known method, such as a suspension polymerization method in the presence of a radical polymerization initiator, or a method in which a polymerizable compound is swelled and polymerized together with a radical polymerization initiator using non-crosslinked seed particles.

[0087] The particle diameter of the resin particle body is preferably 0.5 μm or more, more preferably 1.0 μm or more, even more preferably 3.0 μm or more, particularly preferably 5.0 μm or more, and is preferably 100 μm or less, more preferably 50 μm or less, even more preferably 30 μm or less, particularly preferably 20 μm or less. When the particle diameter of the resin particle body is the above lower limit or more and the above upper limit or less, the dispersibility of the resin particles in a solvent and the water repellency can be further improved.

[0088] The particle diameter of the resin particle body means the diameter when the resin particle body is a perfect sphere, and when the resin particle body has a shape other than a perfect sphere, means the diameter when the resin particle body is assumed to be a perfect sphere of equivalent volume.

[0089] The particle diameter of the resin particle body is preferably an average particle diameter, and more preferably a number average particle diameter. The particle diameter of the resin particle body can be measured by any particle size distribution measuring device. For example, it can be measured by using a particle size distribution measuring device using the principles of laser light scattering, electrical resistance value change, image analysis after imaging, etc. More specifically, as a method for measuring the particle diameter of the resin particle body, a method of measuring the particle diameter of about 100,000 resin particle bodies using a particle size distribution measuring device (Beckman Coulter's "Multisizer4") and calculating the average particle diameter, etc., can be mentioned.

[0090] From the viewpoint of further increasing the dispersibility of the resin particles in a solvent, the coefficient of variation (CV value) of the particle diameter of the resin particle body is preferably 30% or less, more preferably 20% or less, and even more preferably The coefficient of variation (CV value) of the particle diameter of the resin particle body is not particularly limited, and the coefficient of variation (CV value) of the particle diameter of the resin particle body may be 0% or more, or 1% or more.

[0091] The coefficient of variation (CV value) of the particle diameter of the resin particle body can be measured as follows.

[0092] CV value (%) of the particle diameter of the resin particle body = (ρ / Dn) x 100 ρ: Standard deviation of the particle diameter of the resin particle body Dn: Average particle diameter of the resin particles

[0093] The shape of the resin particle body is not particularly limited, and may be spherical or a shape other than spherical, such as flat.

[0094] In 100% by weight of the resin particles, the content of the resin particle body is preferably 70% by weight or more, more preferably 80% by weight or more, even more preferably 90% by weight or more, particularly preferably 95% by weight or more, and is preferably 99.9% by weight or less, more preferably 99% by weight or less, and even more preferably 98% by weight or less. When the content of the resin particle body is equal to or more than the lower limit and equal to or less than the upper limit, the dispersibility of the resin particles in a solvent can be further improved.

[0095] In 100% by weight of the polymerizable component, the content of the polymerizable compound having one or more ethylenically unsaturated groups is preferably 80% by weight or more, more preferably 85% by weight or more, even more preferably 90% by weight or more, and particularly preferably 95% by weight or more. When the content of the polymerizable compound having one or more ethylenically unsaturated groups is the lower limit or more, the solvent resistance and chemical resistance can be improved. The upper limit of the content of the polymerizable compound having one or more ethylenically unsaturated groups is not particularly limited. In 100% by weight of the polymerizable component, the content of the polymerizable compound having one or more ethylenically unsaturated groups may be 100% by weight (total amount) or less than 100% by weight.

[0096] In 100% by weight of the polymerizable component, the content of the polymerizable compound having two or more ethylenically unsaturated groups is preferably 80% by weight or more, more preferably 85% by weight or more, even more preferably 90% by weight or more, and particularly preferably 95% by weight or more. When the content of the polymerizable compound having two or more ethylenically unsaturated groups is the lower limit or more, the solvent resistance and chemical resistance can be improved. The upper limit of the content of the polymerizable compound having two or more ethylenically unsaturated groups is not particularly limited. In 100% by weight of the polymerizable component, the content of the polymerizable compound having two or more ethylenically unsaturated groups may be 100% (total amount) or less than 100%.

[0097] In 100% by weight of the polymerizable component, the content of the polymerizable compound having one or more maleimide groups is preferably 1% by weight or more, more preferably 5% by weight or more, even more preferably 10% by weight or more, even more preferably 20% by weight or more, particularly preferably 30% by weight or more, and most preferably 50% by weight or more. When the content of the polymerizable compound having one or more maleimide groups is equal to or more than the lower limit, low dielectric properties can be more effectively exhibited. The upper limit of the content of the polymerizable compound having one or more maleimide groups is not particularly limited. In 100% by weight of the polymerizable component, the content of the polymerizable compound having one or more maleimide groups may be 100% by weight (total amount) or less than 100% by weight.

[0098] In 100% by weight of the polymerizable component, the content of the polymerizable compound having two or more maleimide groups is preferably 1% by weight or more, more preferably 5% by weight or more, even more preferably 10% by weight or more, still more preferably 20% by weight or more, particularly preferably 30% by weight or more, and most preferably 10% by weight or more. It is preferably 50% by weight or more. When the content of the polymerizable compound having two or more maleimide groups is the above lower limit or more, low dielectric properties can be more effectively exhibited. The upper limit of the content of the polymerizable compound having two or more maleimide groups is not particularly limited. In 100% by weight of the polymerizable component, the content of the polymerizable compound having two or more maleimide groups may be 100% by weight (total amount) or less than 100% by weight.

[0099] When the polymerizable component contains the crosslinkable monomer, the content of the crosslinkable monomer in 100% by weight of the polymerizable component is preferably more than 0% by weight, more preferably 1% by weight or more, even more preferably 5% by weight or more, even more preferably 10% by weight or more, even more preferably 20% by weight or more, particularly preferably 30% by weight or more, and most preferably 50% by weight or more. When the content of the crosslinkable monomer is equal to or more than the lower limit (or exceeds the lower limit), low thermal expansion can be more effectively exhibited. The upper limit of the content of the crosslinkable monomer is not particularly limited. In 100% by weight of the polymerizable component, the content of the crosslinkable monomer may be 99% by weight or less, 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, or 50% by weight or less.

[0100] <Silica particles> The resin particles include a plurality of silica particles.

[0101] In silica particles in which a part of the silica particles is present on the surface (outside) of the resin particle body, the volume of the part present on the surface (outside) of the resin particle body in 100 volume% of the silica particles is preferably 10 volume% or more, more preferably 20 volume% or more, and even more preferably 30 volume% or more. In 100 volume% of the silica particles, the volume of the part present on the surface (outside) of the resin particle body is preferably 99 volume% or less, more preferably 90 volume% or less, and even more preferably 80 volume% or less. When the volume of the part present on the surface (outside) of the resin particle body is the above lower limit or more and the above upper limit or less, low thermal expansion can be more effectively exhibited.

[0102] From the viewpoint of more effectively exerting low thermal expansion, the number of silica particles present on the surface (outside) of the resin particle body in the total number of silica particles 100% is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more. When a single silica particle is observed, if the whole or part of the silica particle is present (exposed) on the surface (outside) of the resin particle body, the silica particle is judged to correspond to the silica particle present on the surface (outside) of the resin particle body. When a single silica particle is observed, if at least a part of the silica particle is present (exposed) on the surface (outside) of the resin particle body, the silica particle is judged to correspond to the silica particle present on the surface (outside) of the resin particle body. When a single silica particle is observed, if the whole of the silica particle is not present on the surface (outside) of the resin particle body, the silica particle is judged not to correspond to the silica particle present on the surface (outside) of the resin particle body.

[0103] In the resin particles, the silica particles may be dispersed on the surface (outside) of the resin particle body, or may be unevenly distributed. From the viewpoint of more effectively exerting low thermal expansion, it is preferable that the silica particles are dispersed on the surface (outside) of the resin particle body.

[0104] The particle diameter of the silica particles is preferably 10 nm or more, more preferably 20 nm or more, even more preferably 100 nm or more, and is preferably 1.0 μm or less, more preferably less than 1.0 μm, even more preferably 500 nm or less, particularly preferably 400 nm or less, and most preferably 350 nm or less. When the particle diameter of the silica particles is the above lower limit or more and the above upper limit or less (or less than the above upper limit), it is possible to suppress the silica particles from aggregating together on the surface or inside of the resin particle body. In addition, when the particle diameter of the silica particles is the above upper limit or less (or less than the above upper limit), it is possible to more effectively exhibit low thermal expansion. From the viewpoint of more effectively exhibiting low thermal expansion, it is particularly preferable that the particle diameter of the silica particles is 1.0 μm or less.

[0105] The particle diameter of the silica particles is preferably equal to or smaller than the particle diameter of the resin particles, and more preferably smaller than the particle diameter of the resin particles. The ratio of the particle diameter of the silica particles to the particle diameter of the resin particles is described as the ratio (particle diameter of silica particles / particle diameter of resin particles). The ratio (particle diameter of silica particles / particle diameter of resin particles) is preferably 0.001 or more, more preferably 0.01 or more, even more preferably 0.03 or more, and preferably 0.5 or less, more preferably 0.3 or less, even more preferably 0.1 or less, and particularly preferably 0.06 or less. When the ratio (particle diameter of silica particles / particle diameter of resin particles) is equal to or greater than the lower limit and equal to or less than the upper limit, the silica particles can be prevented from aggregating together on the surface or inside of the resin particle body.

[0106] The particle size of the silica particles means the diameter when the silica particles are spherical, and means the diameter when the silica particles are other than spherical, assuming that the silica particles are a true sphere with a volume equivalent thereto.

[0107] The particle size of the silica particles is preferably an average particle size, and more preferably a number average particle size. The particle size of the silica particles can be measured by any particle size distribution measuring device. For example, the particle size can be measured by a particle size distribution measuring device using the principles of laser light scattering, electrical resistance change, image analysis after imaging, etc. More specifically, the particle size of the silica particles can be measured by a particle size distribution measuring device ("LS13" manufactured by Beckman Coulter, Inc.). 320") to measure the particle diameter of the silica particles and calculate the average value. The particle diameter of the silica particles can also be measured by observing the cross section of the resin particle.

[0108] From the viewpoint of further enhancing the dispersibility of the resin particles in the solvent, the coefficient of variation (CV value) of the particle size of the silica particles is preferably 1% or more, and preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less.

[0109] The coefficient of variation (CV value) of the particle size of the silica particles can be measured as follows.

[0110] CV value (%) of the particle size of the above silica particles = (ρ / Dn) × 100 ρ: Standard deviation of the particle size of the silica particles Dn: average particle size of the silica particles

[0111] The shape of the silica particles is not particularly limited. The shape of the silica particles may be spherical or may be a shape other than spherical, such as flat.

[0112] From the viewpoint of more effectively exerting low thermal expansion, it is preferable that the number of the silica particles present in the region (R2) from the surface of the resin particle body to the center to 1 / 2 the thickness is greater than the number of the silica particles present in the region (R1) from the center of the resin particle body to the surface to 1 / 2 the thickness. From the viewpoint of more effectively exerting low thermal expansion, it is preferable that the number of the silica particles present on the surface of the resin particle body is greater than the number of the silica particles present inside the resin particle body.

[0113] The number of the silica particles present in the region (R1) and the region (R2) can be measured, for example, as follows.

[0114] The resin particles are added to an epoxy resin so that the content of the resin particles is 30% by weight, and dispersed to prepare a resin body for embedding resin particles for inspection. A cross section of the resin particles is cut out using a CP (Crosssection Polisher) (JEOL Ltd., "IB-09010CP") so as to pass through the vicinity of the center of the resin particles dispersed in the resin body for embedding resin particles for inspection. Then, using a FIB-SEM (FEI Ltd., "Helios Nanolab 650"), 10 resin particles are randomly selected under conditions of 10 kV and 200 pA, and the silica particles of each resin particle are observed. In the cross section of the resin particle, the number of the silica particles present in the region (R2) from the surface of the resin particle body to the center to 1 / 2 the thickness, and the number of the silica particles present in the region (R1) from the center of the resin particle body to the surface to 1 / 2 the thickness are counted, and the average is calculated.

[0115] The ratio of the number of the silica particles present in the region (R2) to the number of the silica particles present in the region (R1) is the ratio (number of silica particles present in the region (R2) / number of silica particles present in the region (R1)). The ratio (number of silica particles present in the region (R2) / number of silica particles present in the region (R1)) is preferably 1.0 or more, more preferably 2.0 or more, even more preferably 3.0 or more, and particularly preferably 4.0 or more. When the ratio (number of silica particles present in the region (R2) / number of silica particles present in the region (R1)) is equal to or more than the lower limit, the water repellency can be further increased and the dielectric tangent can be further reduced. The ratio (number of silica particles present in the region (R2) / number of silica particles present in the region (R1)) may be 100 or less, or may be 10 or less.

[0116] In 100% by weight of the resin particles, the content of the silica particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, even more preferably 1.0% by weight or more, and particularly preferably 3.0% by weight or more. In 100% by weight of the resin particles, the content of the silica particles is preferably 35% by weight or less, more preferably 30% by weight or less, even more preferably 20% by weight or less, particularly preferably 15% by weight or less, and most preferably 10% by weight or less. When the content of the silica particles is the lower limit or more and the upper limit or less, low thermal expansion can be more effectively exhibited. When the content of the silica particles is the upper limit or less, the dispersibility of the resin particles in the solvent can be further improved.

[0117] The content of the silica particles is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, even more preferably 1.0 parts by weight or more, and particularly preferably 3.0 parts by weight or more, relative to 100 parts by weight of the resin particle body. The content of the silica particles is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, even more preferably 15 parts by weight or less, and particularly preferably 10 parts by weight or less, relative to 100 parts by weight of the resin particle body. When the content of the silica particles is the lower limit or more, low thermal expansion can be more effectively exhibited. When the content of the silica particles is the upper limit or less, the dispersibility of the resin particles in the solvent can be further improved.

[0118] <Polytetrafluoroethylene particles> The resin particles include a plurality of polytetrafluoroethylene particles (PTFE particles).

[0119] In polytetrafluoroethylene particles in which a part of the polytetrafluoroethylene particles is present on the surface (outside) of the resin particle body, the volume of the part present on the surface (outside) of the resin particle body in 100% by volume of the polytetrafluoroethylene particles is preferably 10% by volume or more, more preferably 20% by volume or more, and even more preferably 30% by volume or more. In 100% by volume of the polytetrafluoroethylene particles, the volume of the part present on the surface (outside) of the resin particle body is preferably 99% by volume or less, more preferably 90% by volume or less, and even more preferably 80% by volume or less. When the volume of the part present on the surface (outside) of the resin particle body is the above lower limit or more and the above upper limit or less, the dispersibility of the resin particles in the solvent can be further improved and the water repellency can be further improved.

[0120] From the viewpoint of further improving dispersibility, in the resin particles, the number of polytetrafluoroethylene particles present on the surface (outside) of the resin particle body is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more, out of the total number of the polytetrafluoroethylene particles (100%). Note that when one polytetrafluoroethylene particle is observed, when all or a part of the polytetrafluoroethylene particle is present (exposed) on the surface (outside) of the resin particle body, the polytetrafluoroethylene particle is judged to correspond to the polytetrafluoroethylene particle present on the surface (outside) of the resin particle body. When one polytetrafluoroethylene particle is observed, when at least a part of the polytetrafluoroethylene particle is present (exposed) on the surface (outside) of the resin particle body, the polytetrafluoroethylene particle is judged to correspond to the polytetrafluoroethylene particle present on the surface (outside) of the resin particle body. When a single polytetrafluoroethylene particle is observed and the entirety of the polytetrafluoroethylene particle is not present on the surface (exterior) of the resin particle body, the polytetrafluoroethylene particle is determined not to correspond to a polytetrafluoroethylene particle present on the surface (exterior) of the resin particle body.

[0121] In the resin particles, the polytetrafluoroethylene particles may be dispersed on the surface (outside) of the resin particle body, or may be unevenly distributed. From the viewpoint of further increasing the water repellency and more effectively exerting the low dielectric property, it is preferable that the polytetrafluoroethylene particles are dispersed on the surface (outside) of the resin particle body.

[0122] The particle size of the polytetrafluoroethylene particles is preferably 10 nm or more, more preferably 20 nm or more, even more preferably 100 nm or more, and is preferably 500 nm or less, more preferably 400 nm or less, even more preferably 350 nm or less. When the particle size of the polytetrafluoroethylene particles is the above lower limit or more and the above upper limit or less, the polytetrafluoroethylene particles can be prevented from aggregating together on the surface or inside of the resin particle body.

[0123] The particle diameter of the polytetrafluoroethylene particles is preferably equal to or smaller than the particle diameter of the resin particles, and more preferably smaller than the particle diameter of the resin particles. The ratio of the particle diameter of the polytetrafluoroethylene particles to the particle diameter of the resin particles is described as the ratio (particle diameter of polytetrafluoroethylene particles / particle diameter of resin particles). The ratio (particle diameter of polytetrafluoroethylene particles / particle diameter of resin particles) is preferably 0.001 or more, more preferably 0.01 or more, even more preferably 0.03 or more, and preferably 0.5 or less, more preferably 0.3 or less, even more preferably 0.1 or less, and particularly preferably 0.06 or less. When the ratio (particle diameter of polytetrafluoroethylene particles / particle diameter of resin particles) is equal to or greater than the lower limit and equal to or less than the upper limit, the polytetrafluoroethylene particles can be suppressed from coagulating with each other on the surface or inside of the resin particle body.

[0124] The particle size of the polytetrafluoroethylene particles means the diameter when the polytetrafluoroethylene particles are spherical, and when the polytetrafluoroethylene particles are other than spherical, means the diameter when the polytetrafluoroethylene particles are assumed to be a true sphere of equivalent volume.

[0125] The particle size of the polytetrafluoroethylene particles is preferably an average particle size, It is more preferable that the particle size is the number average particle size. The particle size of the polytetrafluoroethylene particles can be measured by any particle size distribution measuring device. For example, it can be measured by using a particle size distribution measuring device using the principles of laser light scattering, electrical resistance value change, image analysis after imaging, etc. More specifically, as a method for measuring the particle size of polytetrafluoroethylene particles, a method of measuring the particle size of polytetrafluoroethylene particles using a particle size distribution measuring device (manufactured by Beckman Coulter, Inc., "LS13 320") and calculating the average value can be mentioned. The particle size of the polytetrafluoroethylene particles can also be measured by observing the cross section of the resin particle.

[0126] From the viewpoint of further enhancing the dispersibility of the resin particles in the solvent, the coefficient of variation (CV value) of the particle size of the polytetrafluoroethylene particles is preferably 1% or more, and preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less.

[0127] The coefficient of variation (CV value) of the particle size of the polytetrafluoroethylene particles can be measured as follows.

[0128] CV value (%) of the particle size of the polytetrafluoroethylene particles = (ρ / Dn) x 100 ρ: Standard deviation of the particle size of the polytetrafluoroethylene particles Dn: average particle size of the polytetrafluoroethylene particles

[0129] The shape of the polytetrafluoroethylene particles is not particularly limited. The shape of the polytetrafluoroethylene particles may be spherical or may be a shape other than spherical, such as flat.

[0130] It is preferable that the number of the polytetrafluoroethylene particles present in the region (R2) from the surface of the resin particle body to 1 / 2 the thickness toward the center is greater than the number of the polytetrafluoroethylene particles present in the region (R1) from the center of the resin particle body to 1 / 2 the thickness toward the surface. In this case, the water repellency can be further improved and the low dielectric property can be more effectively exhibited. From the viewpoint of further improving the water repellency and more effectively exhibiting the low dielectric property, it is preferable that the number of the polytetrafluoroethylene particles present on the surface of the resin particle body is greater than the number of the polytetrafluoroethylene particles present inside the resin particle body.

[0131] The number of the polytetrafluoroethylene particles present in the region (R1) and the region (R2) can be measured, for example, as follows.

[0132] The resin particles are added to an epoxy resin so that the content of the resin particles is 30% by weight, and dispersed to prepare a resin body for embedding resin particles for inspection. A cross section of the resin particles is cut out using a CP (Crosssection Polisher) ("IB-09010CP" manufactured by JEOL Ltd.) so as to pass through the vicinity of the center of the resin particles dispersed in the resin body for embedding resin particles for inspection. Then, using a FIB-SEM ("Helios Nanolab 650" manufactured by FEI Ltd.), 10 resin particles are randomly selected under conditions of 10 kV and 200 pA, and the polytetrafluoroethylene particles of each resin particle are observed. In the cross section of the resin particle, the number of the polytetrafluoroethylene particles present in the region (R2) from the surface of the resin particle body to the center to 1 / 2 the thickness, and the number of the polytetrafluoroethylene particles present in the region (R1) from the center of the resin particle body to the surface to 1 / 2 the thickness are counted, and the average is calculated.

[0133] The ratio of the number of the polytetrafluoroethylene particles present in the region (R2) to the number of the polytetrafluoroethylene particles present in the region (R1) is defined as the ratio (number of the polytetrafluoroethylene particles present in the region (R2) / number of the polytetrafluoroethylene particles present in the region (R1)). The ratio (number of polytetrafluoroethylene particles present in region (R2) / number of polytetrafluoroethylene particles present in region (R1)) is preferably 1.0 or more, more preferably 2.0 or more, even more preferably 3.0 or more, and particularly preferably 4.0 or more. When the ratio (number of polytetrafluoroethylene particles present in region (R2) / number of polytetrafluoroethylene particles present in region (R1)) is equal to or more than the lower limit, the water repellency can be further increased and the dielectric tangent can be further reduced. The ratio (number of polytetrafluoroethylene particles present in region (R2) / number of polytetrafluoroethylene particles present in region (R1)) may be 100 or less, or may be 10 or less.

[0134] In 100% by weight of the resin particles, the content of the polytetrafluoroethylene particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, even more preferably 1.0% by weight or more, and particularly preferably 3.0% by weight or more. In 100% by weight of the resin particles, the content of the polytetrafluoroethylene particles is preferably 35% by weight or less, more preferably 30% by weight or less, even more preferably 20% by weight or less, particularly preferably 15% by weight or less, and most preferably 10% by weight or less. When the content of the polytetrafluoroethylene particles is above the lower limit and below the upper limit, the water repellency can be further increased and the low dielectric property can be more effectively exhibited. When the content of the polytetrafluoroethylene particles is below the upper limit, the dispersibility of the resin particles in the solvent can be further increased.

[0135] The content of the polytetrafluoroethylene particles is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, even more preferably 1.0 parts by weight or more, and particularly preferably 3.0 parts by weight or more, relative to 100 parts by weight of the resin particle body. The content of the polytetrafluoroethylene particles is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, even more preferably 15 parts by weight or less, and particularly preferably 10 parts by weight or less, relative to 100 parts by weight of the resin particle body. When the content of the polytetrafluoroethylene particles is above the lower limit, the water repellency can be further increased and the low dielectric property can be more effectively exhibited. When the content of the polytetrafluoroethylene particles is below the upper limit, the dispersibility of the resin particles in the solvent can be further increased.

[0136] In 100% by weight of the resin particles, the total content of the silica particles and the polytetrafluoroethylene particles is preferably 0.02% by weight or more, more preferably 0.1% by weight or more, even more preferably 1.0% by weight or more, and particularly preferably 3.0% by weight or more. In 100% by weight of the resin particles, the total content of the silica particles and the polytetrafluoroethylene particles is preferably 35% by weight or less, more preferably 30% by weight or less, even more preferably 25% by weight or less, even more preferably 20% by weight or less, particularly preferably 15% by weight or less, and most preferably 10% by weight or less. When the total content of the silica particles and the polytetrafluoroethylene particles is the lower limit or more and the upper limit or less, the low thermal expansion can be more effectively exhibited, the water repellency can be more effectively enhanced, and the low dielectric property can be more effectively exhibited. When the total content of the silica particles and the polytetrafluoroethylene particles is the upper limit or less, the dispersibility of the resin particles in the solvent can be more effectively enhanced.

[0137] The sum of the content of the silica particles and the content of the polytetrafluoroethylene particles is preferably 0.2 parts by weight or more, more preferably 0.5 parts by weight or more, even more preferably 1.0 parts by weight or more, and particularly preferably 3.0 parts by weight or more, relative to 100 parts by weight of the resin particle body. The sum of the content of the silica particles and the content of the polytetrafluoroethylene particles is preferably 30 parts by weight or less, more preferably 25 parts by weight or less, even more preferably 20 parts by weight or less, even more preferably 15 parts by weight or less, and particularly preferably 10 parts by weight or less, relative to 100 parts by weight of the resin particle body. When the sum of the content of the silica particles and the content of the polytetrafluoroethylene particles is above the lower limit, the low thermal expansion is more uniform. When the total content of the silica particles and the polytetrafluoroethylene particles is equal to or less than the upper limit, the dispersibility of the resin particles in a solvent can be further improved.

[0138] <Other ingredients> The resin particles and the resin particle bodies may contain other components as necessary. Examples of the other components include dispersants, preservatives, polymerization inhibitors, polymerization initiators, colorants, and surfactants. Only one type of the other components may be used, or two or more types may be used in combination.

[0139] The resin particles may or may not contain a surfactant, which may include anionic surfactants such as carboxylates, sulfonates, sulfates, and phosphates, cationic surfactants such as amine salts and ammonium salts, amphoteric surfactants, nonionic surfactants of ester and ether types, and fluorine-based surfactants such as per(poly)fluoroalkyls.

[0140] From the viewpoint of reducing the environmental load, it is preferable that the resin particles contain a surfactant in an amount of 1 wt% or less based on 100 wt% of the resin particles, or contain no surfactant. When the resin particles contain the surfactant, the content of the surfactant in 100 wt% of the resin particles is preferably 0.5 wt% or less, more preferably 0.1 wt% or less, and even more preferably 0.01 wt% or less. From the viewpoint of reducing the environmental load, it is more preferable that the resin particles do not contain a surfactant.

[0141] (Insulating layer circuit board) The resin particles are preferably used to obtain a circuit board with an insulating layer. An example of the circuit board with an insulating layer includes a circuit board and an insulating layer disposed on a surface of the circuit board, the insulating layer including the resin particles.

[0142] In the circuit board with an insulating layer, the insulating layer is preferably laminated on a surface of the circuit board on which the circuits are provided. In the circuit board with an insulating layer, a part of the insulating layer is preferably embedded between the circuits.

[0143] Specific examples of the circuit board with an insulating layer include a multilayer board and a multilayer printed wiring board.

[0144] An example of the multilayer board is a multilayer board including a circuit board and an insulating layer laminated on the circuit board. The insulating layer of the multilayer board includes the above-mentioned resin particles. The insulating layer is preferably laminated on the surface of the circuit board on which the circuit (metal layer) is provided. A part of the insulating layer is preferably embedded between the circuits. The multilayer board preferably further includes a copper plating layer laminated on the surface of the insulating layer.

[0145] Another example of the multilayer board is a multilayer board including a circuit board, an insulating layer laminated on a surface of the circuit board, and a copper foil laminated on a surface of the insulating layer opposite to the surface on which the circuit board is laminated.

[0146] Another example of the multilayer board is a multilayer board including a circuit board and a plurality of insulating layers laminated on a surface of the circuit board. At least one of the insulating layers arranged on the circuit board contains the resin particles. The multilayer board preferably further includes a circuit laminated on at least one surface of the insulating layer.

[0147] The multilayer printed wiring board includes, for example, a circuit board, a plurality of insulating layers disposed on a surface of the circuit board, and a metal layer disposed between the plurality of insulating layers, and at least one of the insulating layers contains the resin particles described above.

[0148] FIG. 3 is a cross-sectional view that illustrates a multilayer printed wiring board using the resin particles according to the first embodiment of the present invention.

[0149] In the multilayer printed wiring board 11 (circuit board with insulating layer) shown in FIG. 3, a plurality of insulating layers 13-16 are laminated on the upper surface 12a of the circuit board 12. A metal layer 17 is formed in a partial region of the upper surface 12a of the circuit board 12. Of the plurality of insulating layers 13-16, the insulating layers 13-15 other than the insulating layer 16 located on the outer surface opposite to the circuit board 12 side have a metal layer 17 formed in a partial region of the upper surface. The metal layer 17 is a circuit. The metal layer 17 is disposed between the circuit board 12 and the insulating layer 13, and between each of the laminated insulating layers 13-16. The lower metal layer 17 and the upper metal layer 17 are connected to each other by at least one of a via hole connection and a through hole connection not shown.

[0150] In the multilayer printed wiring board 11, the insulating layers 13-16 contain resin particles 1. In addition, in the multilayer printed wiring board 11, good insulation reliability is provided between the upper metal layer 17 and the lower metal layer 17 that are not connected by via hole connection and through hole connection (not shown). In this embodiment, all of the insulating layers 13-16 contain resin particles 1, but it is sufficient that at least one of the insulating layers 13-16 contains resin particles 1. In addition, resin particles such as resin particles 1A may be used instead of the resin particles 1. In FIG. 3, the resin particles 1 are shown in a simplified diagram.

[0151] The resin particles can also be used in copper-clad laminates. An example of the copper-clad laminate is a copper-clad laminate having a copper foil and an insulating layer laminated on one surface of the copper foil. The insulating layer of the copper-clad laminate contains the resin particles.

[0152] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0153] The following materials were prepared:

[0154] (Material of the resin particle body) Styrene ("Styrene Monomer" manufactured by NS Styrene Monomer Co., Ltd.) Divinylbenzene (NS Styrene Monomer "DVB960") Tetramethylolpropane trimethacrylate ("A-TMMT" manufactured by Shin-Nakamura Chemical Co., Ltd.) N-alkyl bismaleimide compound (Designer Molecules Inc. "BMI-689")

[0155] (Silica particles) Silica particles (1) ("ADMAFINE" manufactured by Admatechs Co., Ltd., average particle size 0.3 μm) Silica particles (2) ("ADMAFINE" manufactured by Admatechs Co., Ltd., average particle size 0.6 μm) Silica particles (3) ("ADMAFINE" manufactured by Admatechs Co., Ltd., average particle size 2 μm)

[0156] (Polytetrafluoroethylene particles) Polytetrafluoroethylene particles (Kitamura "KTL-500F", average particle size 0.3 μm)

[0157] Example 1 Preparation of resin particles: 50 parts by weight of divinylbenzene, 1 part by weight of silica particles (1), and 5 parts by weight of polytetrafluoroethylene particles were added to 44 parts by weight of styrene and stirred to obtain a monomer liquid in which silica particles and polytetrafluoroethylene particles were dispersed. Next, 1 part by weight of a radical polymerization initiator (tert-butyl-2-ethylperoxyhexanoate, NOF Corp.'s "Perbutyl O") was added to the obtained monomer liquid and stirred until it became uniform, to obtain a monomer mixture. 200 parts by weight of a 1.0% by weight aqueous solution in which polyvinyl alcohol having a molecular weight of about 2000 was dissolved in pure water was placed in a reaction vessel. The obtained monomer mixture was placed in this and stirred until the monomer droplets reached a predetermined particle size. Next, the mixture was heated at 90°C for 9 hours to carry out a polymerization reaction of the monomer droplets to obtain particles. The obtained particles were washed three times with hot water and acetone, respectively, and then classified to recover the resin particles. In the obtained resin particles, at least one silica particle has a part of the silica particle present inside the resin particle body and a part of the silica particle present (exposed) on the surface (exterior) of the resin particle body. In the obtained resin particles, at least one polytetrafluoroethylene particle has a part of the polytetrafluoroethylene particle present inside the resin particle body and a part of the polytetrafluoroethylene particle present (exposed) on the surface (exterior) of the resin particle body.

[0158] Film preparation: A composition was obtained by dispersing 10 parts by weight of the obtained resin particles in a mixture of 50 parts by weight of epoxy resin (bisphenol A type epoxy resin, "jER" manufactured by Mitsubishi Chemical Corporation), 50 parts by weight of glycidyl ether, and 1 part by weight of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) The obtained composition was applied to a substrate to a thickness of 100 μm and heated at 100° C. for 2 hours to obtain a film.

[0159] (Examples 2 to 11) Resin particles were produced in the same manner as in Example 1, except that the type and content (wt%) of the material of the resin particle body, the type and content (wt%) of the silica particles, and the type and content (wt%) of the polytetrafluoroethylene particles were set as shown in Tables 1 to 3. A film containing the resin particles was produced in the same manner as in Example 1, except that the obtained resin particles were used.

[0160] Comparative Example 1 Resin particles were produced in the same manner as in Example 1, except that the type and content (wt%) of the material of the resin particle body was changed as shown in Table 3 and that polytetrafluoroethylene particles were not used. A film containing resin particles was produced in the same manner as in Example 1, except that the obtained resin particles were used.

[0161] Comparative Example 2 Resin particles were produced in the same manner as in Example 1, except that the type and content (wt%) of the material of the resin particle body was changed as shown in Table 4, and that silica particles and polytetrafluoroethylene particles were not used. A film containing resin particles was produced in the same manner as in Example 1, except that the obtained resin particles were used.

[0162] Comparative Example 3 Silica particles (1) were prepared without using any material for the resin particle body. A film containing silica particles was produced in the same manner as in Example 1, except that the silica particles (1) were used instead of the resin particles.

[0163] Comparative Example 4 Polytetrafluoroethylene particles were prepared without using any resin particle body material. A film containing polytetrafluoroethylene particles was produced in the same manner as in Example 1, except that tetrafluoroethylene particles were used instead of the resin particles.

[0164] Comparative Example 5 Instead of using the material of the resin particle body, a mixed particle of silica particles (3) and polytetrafluoroethylene particles was used. A film containing the mixed particles was produced in the same manner as in Example 1, except that the obtained mixed particles were used instead of the resin particles.

[0165] (evaluation) (1) Average particle size of resin particles, and average particle size of silica particles / average particle size of resin particles The average particle size of the obtained resin particles was measured by measuring the particle sizes of about 100,000 particles using a particle size distribution analyzer (Multisizer 4 manufactured by Beckman Coulter, Inc.). In addition, the ratio of the average particle size of the silica particles to the average particle size of the resin particles (average particle size of the silica particles / average particle size of the resin particles) was calculated.

[0166] (2) Ratio (number of polytetrafluoroethylene particles present in region (R2) / number of polytetrafluoroethylene particles present in region (R1)) For the obtained resin particles, the number of polytetrafluoroethylene particles present in the region (R2) from the surface of the resin particle body to the center to 1 / 2 the thickness in the cross section of the resin particle, and the number of polytetrafluoroethylene particles present in the region (R1) from the center of the resin particle body to the surface to 1 / 2 the thickness in the cross section of the resin particle were measured by the above-mentioned method. Then, the ratio (the number of polytetrafluoroethylene particles present in the region (R2) / the number of polytetrafluoroethylene particles present in the region (R1)) was calculated.

[0167] (3) Dielectric constant of resin particles (or other particles) The dielectric constant of the obtained resin particles was calculated at 1 GHz using a dielectric constant measuring device (manufactured by AET, using a powder measurement resonator). In Comparative Example 3, the dielectric constant of silica particles was evaluated instead of resin particles. In Comparative Example 4, the dielectric constant of polytetrafluoroethylene particles was evaluated instead of resin particles. In Comparative Example 5, the dielectric constant of a mixed particle of silica particles and polytetrafluoroethylene particles was evaluated instead of resin particles.

[0168] (4) Dielectric tangent of resin particles (or other particles) The dielectric loss tangent at 1 GHz of the obtained resin particles was calculated using a dielectric constant measuring device (manufactured by AET, using a powder measurement resonator). In Comparative Example 3, the dielectric loss tangent of silica particles was evaluated instead of the resin particles. In Comparative Example 4, the dielectric loss tangent of polytetrafluoroethylene particles was evaluated instead of the resin particles. In Comparative Example 5, the dielectric loss tangent of a mixed particle of silica particles and polytetrafluoroethylene particles was evaluated instead of the resin particles.

[0169] (5) Thermal expansion coefficient of resin particles (or other particles) The thermal expansion coefficient of the obtained resin particles at 50°C to 150°C was evaluated as follows. Using a thermomechanical analysis (TMA), the resin particles (or silica particles) were held at 50°C for 5 minutes, and then the resin particles (or silica particles) were heated from 50°C to 160°C at a temperature increase rate of 5°C / min. The linear expansion coefficient from 50°C to 150°C was calculated. For the thermomechanical analysis (TMA), a "TMA450" manufactured by TA Instruments was used. In Comparative Example 3, the thermal expansion coefficient of silica particles was evaluated instead of the resin particles. In Comparative Example 4, the thermal expansion coefficient of polytetrafluoroethylene particles was evaluated instead of the resin particles. In Comparative Example 5, the thermal expansion coefficient of a mixed particle of silica particles and polytetrafluoroethylene particles was evaluated instead of the resin particles.

[0170] (6) Dielectric constant of film The dielectric constant of the obtained film was calculated at 1 GHz using a dielectric constant measuring device (manufactured by AET, using a powder measurement resonator). The dielectric constant of the film was judged according to the following criteria.

[0171] [Criteria for determining the dielectric constant of films] ○○○: Dielectric constant is less than 2.50 F / m ○○: Dielectric constant is 2.50 F / m or more and less than 2.70 F / m ○: Dielectric constant is 2.70 F / m or more and less than 2.90 F / m ×: Dielectric constant is 2.90 F / m or more

[0172] (7) Dielectric tangent of film The dielectric loss tangent at 1 GHz of the obtained film was calculated using a dielectric constant measuring device (manufactured by AET, using a powder measurement resonator). The dielectric loss tangent of the film was evaluated according to the following criteria.

[0173] [Criteria for determining the dielectric tangent of film] ○○○: Dielectric tangent is less than 0.005 ○○: Dielectric tangent is 0.005 or more and less than 0.008 ○: Dielectric tangent is 0.008 or more and less than 0.01 ×: Dielectric tangent is 0.01 or more

[0174] (8) Thermal expansion coefficient of film The thermal expansion coefficient of the obtained film at 50°C to 150°C was evaluated as follows. Using a thermomechanical analyzer (TMA), the film was held at 50°C for 5 minutes, and then heated from 50°C to 160°C at a temperature increase rate of 5°C / min. The linear expansion coefficient from 50°C to 150°C was calculated. For the thermomechanical analyzer (TMA), a "TMA450" manufactured by TA Instruments was used. The film thermal expansion coefficient was judged according to the following criteria.

[0175] [Criteria for determining the thermal expansion coefficient of film] ○○○: Thermal expansion coefficient is less than 80 ppm / ℃ ○○: Thermal expansion coefficient is 80 ppm / ℃ or more and less than 110 ppm / ℃ ○: Thermal expansion coefficient is 110 ppm / ℃ or more and less than 150 ppm / ℃ ×: Thermal expansion coefficient is 150 ppm / ℃ or more

[0176] The composition of the resin particles (or the configuration of the silica particles, polytetrafluoroethylene particles, or mixed particles) and the results are shown in Tables 1 to 4 below.

[0177] [Table 1]

[0178] [Table 2]

[0179] [Table 3]

[0180] [Table 4]

[0181] As shown in Tables 3 and 4, the following results can be seen. Comparative Example 1, which is a resin particle that does not include polytetrafluoroethylene particles, was inferior in low dielectric properties. Comparative Example 2, which is a resin particle that does not include both silica particles and polytetrafluoroethylene particles, was inferior in both low dielectric properties and low thermal expansion properties. Comparative Example 3, which is a silica particle, was inferior in low dielectric properties. Comparative Example 4, which is a polytetrafluoroethylene particle, was inferior in low thermal expansion properties. Comparative Example 5, which is a mixed particle of silica particles and polytetrafluoroethylene particles, was inferior in low dielectric properties and low thermal expansion properties due to low dispersibility of the mixed particles in the film. [Explanation of symbols]

[0182] 1,1A…Resin particles 2…Resin particle body 3,3A…Silica particles 4, 4A…Polytetrafluoroethylene particles 11...Multilayer printed wiring board (circuit board with insulating layer) 12...Circuit board 12a…Top surface 13~16…Insulating layer 17...Metal layer

Claims

1. The present invention includes a resin particle body, a plurality of silica particles, and a plurality of polytetrafluoroethylene particles, A plurality of the silica particles are present on the surface or inside of the resin particle body, A plurality of the polytetrafluoroethylene particles are present on the surface or inside the resin particle body, the resin particle body is a polymer of a polymerizable component, The polymerizable component comprises a polymerizable compound having one or more ethylenically unsaturated groups.

2. The resin particles according to claim 1 , wherein the particle diameter of the resin particles is 0.5 μm or more.

3. The resin particles according to claim 1 or 2, wherein the silica particles have a particle diameter of 1.0 μm or less.

4. 4. The resin particles according to claim 1, wherein a ratio of a particle size of the silica particles to a particle size of the resin particles is 0.001 or more and 0.5 or less.

5. 5. The resin particles according to claim 1, wherein the content of the silica particles is 0.1% by weight or more and 20% by weight or less based on 100% by weight of the resin particles.

6. 6. The resin particles according to claim 1, wherein the content of the polytetrafluoroethylene particles is 0.1% by weight or more and 20% by weight or less based on 100% by weight of the resin particles.

7. 7. The resin particles according to claim 1, wherein the total content of the silica particles and the polytetrafluoroethylene particles is 25% by weight or less, based on 100% by weight of the resin particles.

8. The resin particle according to any one of claims 1 to 7, wherein the polymerizable component comprises a crosslinkable monomer.

9. The resin particle according to claim 8, wherein the crosslinkable monomer is divinylbenzene or a polymerizable compound having two or more (meth)acryloyl groups.

10. 10. The resin particle according to claim 8, wherein the content of the crosslinkable monomer is 10% by weight or more based on 100% by weight of the polymerizable component.

11. The resin particles according to any one of claims 1 to 10, wherein the resin particles have a thermal expansion coefficient of less than 150 ppm / °C at 50°C to 150°C.

12. The dielectric constant of the resin particles is 2.60 F / m or less, The resin particles according to any one of claims 1 to 11, wherein the resin particles have a dielectric loss tangent of 0.01 or less.

13. The resin particle according to any one of claims 1 to 12, wherein in at least one of the plurality of silica particles, a portion of the silica particle is present inside the resin particle body, and a portion of the silica particle is present on the surface of the resin particle body.

14. In at least one of the plurality of polytetrafluoroethylene particles, the poly The resin particle according to any one of claims 1 to 13, wherein a portion of the tetrafluoroethylene particle is present inside the resin particle body, and a portion of the polytetrafluoroethylene particle is present on the surface of the resin particle body.

15. The number of the polytetrafluoroethylene particles present in the region from the surface of the resin particle body toward the center to 1 / 2 of the thickness is greater than the number of the polytetrafluoroethylene particles present in the region from the center of the resin particle body toward the surface to 1 / 2 of the thickness.

16. A circuit board; an insulating layer disposed on a surface of the circuit board; A circuit board with an insulating layer, wherein the insulating layer contains the resin particles according to any one of claims 1 to 15.

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