JP6775730B2 - Reaction device and method for producing resin particles - Google Patents

Description

The present invention relates to a reactor and a method for producing resin particles.

The method of mounting the liquid crystal driving IC on the glass panel for liquid crystal display can be roughly divided into two types: COG (Chip on Glass) mounting and COF (Chip on Flex) mounting. In COG mounting, a liquid crystal IC is directly bonded to a glass panel using an anisotropic conductive material containing conductive particles. On the other hand, in COF mounting, a liquid crystal driving IC is bonded to a flexible tape having metal wiring, and they are bonded to a glass panel using an anisotropic conductive material containing conductive particles. The anisotropic conductive material referred to here means a material having conductivity in the pressurizing direction and maintaining insulating property in the non-pressurizing direction.

In recent years, along with the improvement of the display quality of the liquid crystal panel, the definition of the metal electrode arranged in the liquid crystal driving IC has been improved. At the same time as the pitch between adjacent electrodes is narrowed, it is necessary to increase the amount of conductive fine particles contained in the anisotropic conductive material in order to reduce the resistance at the time of connection and ensure the connection reliability. However, when the conductive particles contain coarse particles having a large particle diameter or have variations in particle diameter, there is a problem that it becomes difficult to secure the insulating property between the adjacent electrodes when the amount of the conductive particles is increased.

In order to cope with this, conductive particles having a more uniform particle size are required, and for that purpose, it is necessary to sharpen the particle size distribution of the resin particles, which are the cores of the conductive particles, at the target particle size.

Known methods for synthesizing resin particles include microemulsion polymerization, miniemulsion polymerization, emulsion polymerization, soap-free emulsion polymerization, dispersion polymerization, seed polymerization, suspension polymerization, etc., depending on the particle size of the particles to be synthesized.

However, since the resin particles obtained by suspension polymerization and emulsion polymerization are polydisperse, the particle size distribution becomes wide. Since it is necessary to classify the resin particles before use for the conductive particles, the productivity is inferior in the case of suspension polymerization and emulsion polymerization. On the other hand, it has been reported that monodisperse resin particles can be easily obtained when seed polymerization is used. For example, Patent Documents 1 to 3 disclose resin particles using polystyrene as seed particles.

Further, in Patent Document 4, seed particles made of (meth) acrylic acid ester containing an alkyl group having 6 or more carbon atoms are polymerized in a water-soluble emulsion containing a polymerizable monomer to obtain monodisperse particles. Is disclosed. Patent Document 5 describes a method for producing resin particles having a step of swelling seed particles obtained by emulsion polymerization of an ethylenically unsaturated monomer such as butyl acrylate with a polyfunctional acrylate monomer.

Japanese Unexamined Patent Publication No. 2005-327509 Japanese Patent No. 37392232 JP-A-2010-159328 Japanese Unexamined Patent Publication No. 2001-2716 Patent No. 4218848

However, the particles obtained by the prior art also show variations in particle size, and there is still room for improvement in further improving the insulating property between adjacent electrodes.

Therefore, an object of the present invention is to provide a reaction apparatus capable of producing resin particles having excellent monodispersity in particle size distribution and a method for producing resin particles.

The present invention provides the following reactors <1> to <8> and a method for producing resin particles of <9>.
<1> A reaction vessel in which the reaction solution is housed, a stirrer arranged in the reaction vessel, and a drive unit for stirring the reaction solution by rotating the stirrer around the rotation axis are provided for stirring. The body has a shape in which a discharge port and a suction port communicated with the discharge port via a communication path provided inside the base are provided on the surface of a convex-shaped substrate that is rotationally symmetric around the rotation axis. The suction port is located closer to the rotation axis than the discharge port and is provided on the bottom side of the container in the direction of the rotation axis, and the reaction vessel allows the flow of the reaction mixture to be stirred in the reaction vessel to flow through the reaction vessel. A reactor having a first wall surface that guides downward and closer to the axis of rotation.
<2> The reaction apparatus according to <1>, wherein the first wall surface reaches the lowest position of the reaction vessel while reducing the area of the region surrounded by the wall surface of the reaction vessel in the cross section perpendicular to the rotation axis.
<3> The reaction apparatus according to <1>, wherein the first wall surface reaches the lowest position of the reaction vessel while being reduced in diameter.
<4> The reaction vessel has a second wall surface located above the first wall surface, and the second wall surface is a direction in which the flow of the reaction solution agitated in the reaction vessel is located below the reaction vessel and away from the rotation axis. The reaction apparatus according to any one of <1> to <3>.
<5> The reaction apparatus according to any one of <1> to <4>, wherein the reaction vessel has a round bottom.
An introduction part that can introduce raw materials into the reaction vessel,
<7> The reaction apparatus according to <6>, wherein the minimum inner diameter of the communication passage is 100 times or more the average particle size of the seed particles in the seed polymerization.
<8> The reaction apparatus according to any one of <1> to <7>, wherein the introduction unit is configured to introduce the raw material to the wall surface side of the reaction vessel rather than the stirring body when viewed from the rotation axis.
<6> The reactor according to any one of <1> to <5>, which is used for seed polymerization.
<9> In a method for producing resin particles by performing a polymerization reaction while stirring an emulsion containing seed particles and a monomer in a reaction vessel, the emulsion is rotated around a rotation axis in the reaction vessel. The agitator has a shape in which a discharge port and a suction port communicated with the discharge port via a communication path provided inside the base are provided on the surface of the substrate which is rotationally symmetrical around the rotation axis. The suction port is located closer to the rotation axis than the discharge port and is provided on the bottom side of the container in the direction of the rotation axis, and the reaction vessel allows the flow of the reaction mixture to be agitated in the reaction vessel. A method having a first wall that guides below the reaction vessel and in a direction closer to the axis of rotation.

According to the present invention, it is possible to provide a reaction apparatus capable of producing resin particles having excellent monodispersity in particle size distribution and a method for producing resin particles.

It is a schematic cross-sectional view which shows the reaction apparatus which concerns on embodiment. It is a figure which shows the stirring body which concerns on embodiment. It is a figure which shows the stirring body which concerns on embodiment. It is a schematic cross-sectional view which shows the conductive particle which concerns on embodiment. It is a schematic cross-sectional view which shows the anisotropic conductive material which concerns on embodiment. It is a schematic cross-sectional view which shows the manufacturing method of the connection structure of the circuit member which concerns on embodiment.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings in some cases. However, the present invention is not limited to the following embodiments. In each drawing, the same or equivalent elements are given the same reference numerals, and duplicate description will be omitted. Further, in the present specification, "(meth) acrylic" means acrylic and the corresponding methacrylic, and "(meth) acrylate" means acrylate and the corresponding methacrylate, and "(meth) acryloyl". "" Means acryloyl and its corresponding methacryloyl.

FIG. 1 is a schematic cross-sectional view showing an example of the reaction device 1 according to the embodiment of the present invention. The reaction apparatus 1 is a drive unit that stirs the reaction solution by rotating the reaction vessel 3 in which the reaction solution is housed, the stirrer 13 arranged in the reaction vessel 3, and the stirrer around the rotation axis G. 18 and. The reaction apparatus 1 may have an introduction unit 5 into which a raw material can be introduced into the reaction vessel 3. The reaction vessel 3 may have a lid 4, and the introduction portion 5 may be provided so as to penetrate the lid 4. The lid 4 may have an opening 19, and the opening 19 may be further connected with additional introduction means, and is provided to replace the reaction solution with an inert gas or the like through the opening 19. It may have been. The raw material may be introduced directly from the opening 19 without providing the introduction portion 5. The drive unit 18 is not particularly limited as long as the stirring body 13 can be rotated around the rotation axis G, but a motor or the like can be mentioned. The stirring body 13 and the driving unit 18 may be connected to a shaft body 11 arranged along the rotating axis G so that the stirring body 13 can be rotated around the rotating axis G.

The agitator 13 has a discharge port 15 and a suction port 16 on the surface. The agitator 13 has a shape in which a discharge port and a suction port communicated with the discharge port via a communication passage 14 provided inside the base 12 are provided on the surface of the base 12 which is rotationally symmetric around the rotation axis G. To have. The suction port 16 is provided at a position closer to the rotation axis G than the discharge port 15. When the stirrer is rotated in the reaction solution, centrifugal force is applied to the reaction solution inside the communication passage 14. At this time, since the discharge port 15 is provided at a position farther from the rotation axis G than the suction port 16, the centrifugal force applied to the reaction solution at the discharge port 15 is larger than the centrifugal force at the suction port 16. Therefore, a flow occurs in which the reaction liquid is sucked from the suction port 16 and the reaction liquid is discharged from the discharge port 15. In the reactor 1 of the present embodiment, the reaction solution is agitated by generating a flow in this way.

In a reactor using a conventional impeller stirrer, it is difficult to generate vertical convection, and the reaction caused by the collision between the blade and the object to be agitated tends to cause uneven stirring in the reaction solution during the reaction. On the other hand, in the reaction device 1 of the present embodiment, as described above, since the reaction liquid is discharged radially from the discharge port 15 by centrifugal force, the flow of the reaction liquid colliding with the wall surface of the reaction vessel 3 diffuses vertically upward and downward. Therefore, a circulating flow occurs not only in the horizontal direction but also in the vertical direction. Further, since the agitator 13 has the above-mentioned shape, recoil due to collision with the agitated object is unlikely to occur, and the reaction solution smoothly flows around the agitator 13, so that the generated flow is less likely to be disturbed. Therefore, it is easy to uniformly stir the entire reaction solution. As a result, the reactor 1 of the present embodiment can be suitably used for both homogeneous and heterogeneous liquid phase reactions. In particular, when resin particles are produced by microemulsion polymerization, mini-emulsion polymerization, emulsion polymerization, soap-free emulsion polymerization, dispersion polymerization, seed polymerization, suspension polymerization, etc., the CV value of the particle size of the resin particles produced is reduced. (That is, the particle size distribution of the resin particles can be made more monodisperse), and above all, when the resin particles are produced by seed polymerization, the CV value of the particle size of the resin particles can be further reduced.

The present inventors consider that the reason why resin particles having excellent monodispersity in particle size distribution can be produced by using the reaction device 1 is as follows. First, since the conventional reaction device uses an impeller stirrer, in addition to causing uneven stirring as described above during the reaction, the particles in the process of the reaction collide with the blades, and the particles in the process of the reaction collide with each other. The particles are united and adhered to the blades, and a shearing force is applied to the particles during the reaction due to the stirring operation. As a result, the particles in the middle of the reaction do not become single particles but aggregate and adhere to the blades as aggregates, resulting in a decrease in yield. Further, the particles in the process of reaction are crushed or united by the shearing force, so that the particle size distribution of the obtained resin particles is widened. On the other hand, in the reaction device 1 of the present embodiment, the stirring body 13 has a discharge port on the surface of the convex-shaped base 12 which is rotationally symmetric around the rotation axis G, and a communication passage 14 provided inside the discharge port and the base 12. Since it has a shape provided with a suction port communicated with the particles, it is possible to stir the particles during the reaction without applying a shearing force.

A shape in which the stirring body 13 is provided with a discharge port and a suction port communicated with the discharge port via a communication passage provided inside the base 12 on the surface of a convex base 12 having a rotational symmetry around the rotation axis G. have. The material of the substrate 12 is not particularly limited, and examples thereof include metal, ceramic, silicon, and wood, and metal is particularly preferable in consideration of durability and ease of processing. As the metal, stainless steel is particularly preferable from the viewpoint of solvent resistance, detergency, durability, heat resistance and the like. On the other hand, when the reaction solution has reactivity with a metal, a fluororesin is preferable as the material of the substrate 12. As the fluororesin, PTFE, PFA, FEP, PC, TFE, PVDF and the like are preferably used. In the direction perpendicular to the rotation axis G, the ratio of the width of the substrate 12 to the width of the reaction vessel 3 is preferably in the range of 1/10 to 4/5, more preferably 1/5 to 7/10, and 1 The range of / 3 to 3/5 is particularly preferable. The width of the reaction vessel refers to the largest width in the direction perpendicular to the rotation axis G, and the width of the substrate 12 refers to the largest width in the direction perpendicular to the rotation axis G. If the ratio is 1/10 or more, convection of the reaction solution is not sufficiently performed. On the other hand, if it is 4/5 or less, the distance from the inner wall of the reaction vessel cannot be sufficiently secured, so that the reaction vessel or the substrate 12 may be damaged.

The shape of the base 12 is not particularly limited as long as it is a convex shape rotationally symmetric around the rotation axis G, but it is preferable that the cross-sectional shape perpendicular to the rotation axis G is a regular n-sided shape or a circle. n may be 6 or more, and may be 8 or more. Here, the convex shape means a shape in which all points on a line segment connecting arbitrary two different points inside or on the surface of the base 12 are points inside or on the surface of the base 12. Specific shapes of the base 12 include a regular polyhedron, a truncated polyhedron, a regular n prism, a regular n pyramid, a sphere, an ellipsoid, a partial sphere or a partial ellipsoid obtained by cutting a part of the sphere or ellipsoid from a plane. Can be mentioned.
The agitator 13 can be produced by forming the discharge port, the suction port, and the communication passage by providing a through hole in the substrate 12 with a drill.

The suction port 16 is provided at a position closer to the rotation axis G than the discharge port 15. Further, the suction port 16 is provided on the bottom side of the stirring body 13. Here, the distance between the rotation axis G and the suction port 16 is the distance between the point on the edge of the suction port 16 that is closest to the rotation axis G and the rotation axis G. The same applies to the distance between the rotation axis G and the discharge port 15. The directions of the discharge port and the suction port are not particularly limited, but considering that the reaction solution enters from the inlet and exits from the outlet, it is preferable that the reaction solutions face different directions. The directions of the discharge port and the suction port are appropriately adjusted so that convection and stirring can be sufficiently performed. Specifically, the angle θ ₁ formed by the straight line parallel to the center line of the communication path on the surface connecting both ends of the suction port 16 with a straight line in the direction perpendicular to the rotation axis G and the vertically downward direction of the rotation axis G is suction. From the viewpoint of reducing the centrifugal force applied to the reaction solution at the mouth 16, the temperature is preferably 10 ° or less, more preferably 1 ° or less, still more preferably 0 °. 90 ° is more preferable. The angle θ ₂ formed by the straight line parallel to the center line of the communication path on the surface connecting both ends of the discharge port 15 with a straight line in the direction perpendicular to the rotation axis G and the vertically downward direction of the rotation axis G is the reaction liquid at the discharge port 15. From the viewpoint of increasing the centrifugal force applied to the water, the temperature is preferably 75 to 105 °, more preferably 90 °. Further, the absolute value of θ _2- θ ₁ is preferably 1 to 179 °, more preferably 10 to 160 °, further preferably 45 to 135 °, and most preferably 75 to 105 °.

Examples of the cross-sectional shape perpendicular to the center line of the communication passage include a circle and a polygon, but a circle is preferable from the viewpoint that no external force is applied to the fine particle precursors such as seed particles and monomer oil droplets. The inner wall may have irregularities or a smooth surface, but a smooth surface is preferable in consideration of the fact that the fine particle precursor flows in the communication passage. The minimum inner diameter (diameter) of the communication passage is not particularly limited as long as it is sufficiently larger than the fine particle precursor, but is preferably 90 times or more. When the minimum inner diameter is 90 times or more, it is possible to prevent the fine particle precursor from being clogged in the communication passage.

The stirring body 13 is not particularly limited as long as it has one or more pairs of discharge ports and suction ports, but it is preferable to have two pairs, and more preferably three pairs or four pairs. By having 3 pairs or 4 pairs, a sufficient amount of reaction solution can be passed through the communication passage. That is, the reaction solution in the reaction vessel can be sufficiently stirred evenly. When there are a plurality of passages, the stirring body 13 preferably has a shape that is rotationally symmetric with respect to the rotation axis G, including the passages.

2 and 3 are diagrams showing an example of the agitator of the present embodiment, respectively. FIG. 2A is a front view of a stirring body formed by providing three pairs of discharge ports 15 and suction ports 16 on a partially spherical substrate 12. The three pairs of discharge ports 15 and suction ports 16 are communicated with each other via a communication passage 14. 2 (b) and 2 (c) are a plan view of the agitated body of FIG. 2 (a) viewed from the shaft body side and a bottom view of the stirrer body of FIG. FIG. 3 is a diagram showing a stirring body 33 in which a pair of discharge ports 35 and a suction port 36 are provided on a cylindrical substrate 12, and the discharge port 35 and the suction port 36 are communicated with each other by a communication passage 34. .. When the shape of the substrate 12 is a cylinder or a regular n-side prism, if the shaft body 31 and the suction port 36 are concentric, the suction direction is always constant, so that the reaction solution can be agitated more uniformly.

The communication passage may communicate with a pair of discharge ports and suction ports, but may communicate with a plurality of discharge ports and a plurality of suction ports. The shape of the suction port and the discharge port is not particularly limited, but may be circular, for example.

The material of the reaction vessel 3 is not particularly limited, and examples thereof include glass, metal, wood, plastic, and ceramic. Needless to say, the container material is selected according to the conditions for driving the reaction carried out in the reaction vessel. .. For example, when the reaction is carried out by heat, it is preferable to use a glass or metal container, and when the reaction is carried out by light, it is preferable to use a transparent glass or plastic container. The shapes of the container surface and the inner wall are not particularly limited, but it is preferable that the surface is a smooth surface because the flow in the container is not disturbed and uniform stirring is possible. Further, in the case of producing resin particles, since an extra external force is not applied to the fine particle precursor, coalescence due to collision can be reduced. The material of the lid 4 is not particularly limited, and the materials listed as the material of the reaction vessel 3 can be used.

The reaction vessel 3 has a first wall surface 3a that guides the flow of the reaction solution agitated in the reaction vessel 3 below the reaction vessel and in a direction approaching the rotation axis G. Here, since the reaction vessel used in the conventional reaction apparatus is composed of a side surface parallel to the rotation axis G and a flat bottom, the wall surface of the reaction vessel brings the reaction solution below the reaction vessel and approaches the rotation axis G. It cannot be guided in the direction, and as a result, a region where the flow of the reaction solution is weak is formed in the reaction vessel, and the entire lower side of the stirrer of the reaction vessel cannot be agitated smoothly. On the other hand, since the reaction vessel 3 of the present embodiment has the above-mentioned first wall surface, the reaction liquid discharged from the discharge port 15 when the stirring body 13 is rotated is a stirring body along the first wall surface 3a. It is guided in the direction directly below 13. The flow of the reaction solution guided in the direction directly below the stirring body 13 is sucked up by the suction port 16 provided on the bottom side of the stirring body 13, so that the reaction solution does not stagnate in the reaction vessel and smoothly. A circulating flow can be created. As described above, the reaction device 1 of the present embodiment can agitate the reaction solution more smoothly than the conventional reaction device, so that when the resin particles are produced, the CV value of the particle size of the resin particles is reduced. can do. Further, in the conventional reactor, as described above, a region having a weak flow is formed, so that solid matter such as resin particles in the process of synthesis is precipitated by gravity and is deposited on the bottom of the reaction vessel. In particular, when seed polymerization is carried out with a conventional reactor, the seed particles are deposited on the bottom of the reaction vessel and aggregated, which causes a decrease in yield and an increase in the CV value of the obtained resin particles. On the other hand, in the reaction apparatus 1 of the present embodiment, the solid matter dispersed in the reaction solution rides on the flow guided below the reaction vessel and in the direction approaching the rotation axis G, and is guided in the direction directly below the stirring body 13. Since it is sucked up from the suction port 16 of the stirrer 13, it is possible to prevent the solid matter from being deposited on the bottom of the reaction vessel. Therefore, the reactor 1 of the present embodiment can be suitably used for producing resin particles, and is particularly suitable for seed polymerization.

The first wall surface 3a preferably reaches the lowest position of the reaction vessel 3 while reducing the area of the region surrounded by the wall surface of the reaction vessel 3 in the cross section perpendicular to the rotation axis G, and reacts while being reduced in diameter. It is more preferable to reach the bottom position of the container 3. Here, the reduced diameter means that the shape of the region surrounded by the wall surface of the reaction vessel 3 in the vertical cross section is substantially circular, and the diameter of the circle is the direction of the lowest position of the reaction vessel 3 along the rotation axis G. It means that it becomes smaller as it goes toward. Specific shapes of the reaction vessel 3 include, for example, a round bottom and an eggplant type.

Further, the reaction vessel 3 may have a second wall surface 3b located above the first wall surface 3a. The second wall surface 3b guides the flow of the reaction solution agitated in the reaction vessel in a direction below the reaction vessel and away from the rotation axis G. By having the second wall surface, the flow of the reaction solution can be guided more smoothly below the reaction vessel and in the direction approaching the rotation axis G.

In the reaction apparatus 1 of the present embodiment, the reaction is carried out in the reaction solution by introducing the raw materials necessary for carrying out the desired liquid phase reaction from the introduction unit 5. Such a raw material may be, for example, a part of a reactant in a target liquid phase reaction such as a monomer, an oligomer, or a fine particle precursor such as seed particles used in seed polymerization. These may be introduced in the form of solutions or dispersions. When the monomer is introduced as a monomer oil droplet emulsified by ultrasonic waves or the like, the diameter of the monomer oil droplet is particularly preferably 10 nm to 10 μm. When the diameter of the monomer oil droplets is 10 nm to 10 μm, coalescence of the oil droplets is unlikely to occur, and the particle size of the produced resin particles is unlikely to vary. The average particle size of the seed particles is particularly preferably 20 nm to 50 μm. When the average particle size of the seed particles is 20 nm to 50 μm or more, the average particle size of the seed particles after swelling can be easily made uniform. The solvent contained in the reaction solution can be freely selected depending on the case, such as water, an organic solvent, and a mixture of water and an organic solvent. The ratio of the mixture is also arbitrary.

The specific configuration of the introduction unit 5 is not particularly limited, and examples thereof include a funnel, a rubber hose, a silicon tube, a polytetrafluoroethylene tube, a plastic pipe, a metal pipe, and a microtube pump. It is preferable that the introduction unit 5 is configured to introduce the raw material to the wall surface side of the reaction vessel 3 rather than the stirring body 13 when viewed from the rotation axis G. When the raw material is introduced at such a position, the raw material can be quickly placed on the convection generated by the rotation of the stirring body 13, so that the reaction in the reaction solution can be carried out more uniformly. As a specific shape of such an introduction section 5, the introduction port for introducing the raw material from the introduction section 5 into the reaction vessel 3 faces the wall surface side of the reaction vessel 3 rather than the stirring body 13 when viewed from the rotation axis G. Is preferable.

The reactor 1 of the present embodiment is suitable for producing resin particles. The average particle size of the produced resin particles is preferably 100 μm or less, more preferably 65 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less. The average particle size of the resin particles is preferably 1 μm or more, more preferably 1.5 μm or more, still more preferably 1.75 μm or more, from the viewpoint of preventing aggregation of the resin particles. Further, methods for synthesizing fine particles having high monodispersity include emulsion polymerization, soap-free emulsion polymerization, seed polymerization and the like, but seed polymerization is most preferable because it is easy to synthesize monodisperse fine particles.

The CV value of the particle size (diameter) of the resin particles is preferably 15% or less. If the CV value exceeds 15%, the performance of the resin particles in various applications tends to deteriorate. For example, the connection reliability may decrease when the resin particles are used for the conductive particles constituting the anisotropic conductive material, or the quantitativeness may decrease when the resin particles are used for the biopsy element. From the same viewpoint, the CV value of the particle size of the resin particles is more preferably 10% or less, still more preferably 5% or less, still more preferably 4% or less. In the present specification, the CV value (coefficient of variation) of the particle size means the ratio of the standard deviation of the particle size to the average value of the particle size expressed as a percentage.

The average particle size of the resin particles and the CV value of the particle size can be obtained by the following measurement method.
1) The particles are dispersed in water using an ultrasonic disperser to prepare a dispersion liquid containing 1% by mass of particles.
2) Using a wet flow type particle size / shape analyzer (manufactured by Sysmex Co., Ltd.), the images of about 100,000 particles in the dispersion are analyzed, and the average particle size and the CV of the particle size are calculated.

<Seed polymerization>
The method for producing resin particles of the present embodiment is a method for producing resin particles by performing a polymerization reaction while stirring an emulsion containing seed particles and a monomer in the reaction vessel, around the rotation axis G in the reaction vessel. The emulsion is agitated by rotating the stirrer, and the stirrer has a discharge port and a communication passage provided inside the discharge port and the base 12 on the surface of the base 12 which is rotationally symmetric around the rotation axis G. It has a shape provided with a suction port communicated through the container, and the suction port is located closer to the rotation axis G than the discharge port and is provided on the bottom side of the container in the direction of the rotation axis G, and reacts. The vessel has a first wall that guides the flow of emulsion stirred in the reaction vessel below the reaction vessel and in a direction closer to the rotation axis G.

The emulsion may contain a monomer of a polymer and an aqueous medium constituting the target resin particles. Further, the emulsion may contain a surfactant or a dispersant shown separately.

The reaction time can be changed depending on the type of seed particles or the monomer, but as an example, when considering the swelling of the seed particles with the monomer in the seed polymerization, it is preferably in the range of 0.1 to 72 hours, and is 0. . More preferably in the range of 2 to 48 hours, most preferably in the range of 0.5 to 30 hours. When the reaction time is 0.1 hours or more, poor formation of resin particles can be suppressed, and when the reaction time is 72 hours or less, aggregation and coalescence of the formed particles tend to be suppressed.

In seed polymerization, fine particles can be stably obtained by using temperature. For example, a polymerization reaction can be mentioned. The temperature at which the polymerization is carried out can be changed depending on the type of the reactive monomer, but is preferably in the range of 30 to 200 ° C, more preferably in the range of 30 to 175 ° C, and in the range of 30 to 150 ° C. Is most preferable. If it is lower than 30 ° C, the polymerization of the reactive monomer may not proceed sufficiently, and if it is 200 ° C or higher, the solvent used for the reaction may evaporate and a sufficient amount of solvent may not be secured. ..

<Seed particles>
The seed particles may be particles obtained by polymerizing either a monomer having an active hydrogen group or a (meth) acrylic acid ester, or particles obtained by copolymerizing these monomers. The seed particles may be particles obtained by copolymerizing the above-mentioned monomer having an active hydrogen group and (meth) acrylic acid ester with another monomer copolymerizable with these monomers.

The seed particles can be synthesized by a known method such as an emulsion polymerization method, a soap-free emulsion polymerization method, or a dispersion polymerization method.

By introducing an active hydrogen group into the seed particles, the interaction between the seed particles and the polymer synthesized from the monomer containing the di (meth) acrylate compound after the seed polymerization is increased, so that the resin particles are made of resin particles. , It is preferable because it has an excellent compression recovery rate even when heated.

Examples of the active hydrogen group include a hydroxyl group, a carboxyl group and an amide group.

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, silicic acid, itaconic acid, maleic acid, and fumaric acid, itaconic acid monoalkyl esters such as monobutyl itaconic acid, and maleic acid. Examples thereof include maleic acid monoalkyl esters such as monobutyl, vinyl group-containing aromatic carboxylic acids such as vinyl benzoic acid, and salts thereof.

Examples of the hydroxyl group-containing monomer include 4- (hydroxymethyl) cyclohexylmethyl (hydroxymethyl) cyclohexylmethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4 -Hydroxyhydroxybutyl (meth) acrylate and other hydroxyl group-containing (meth) acrylic monomers; (poly) ethylene glycol mono (meth) acrylate, (poly) propylene glycol mono (meth) acrylate and other (poly) alkylene glycol (meth) acrylic Examples thereof include hydroxyalkyl vinyl ether-based monomers such as hydroxyethyl vinyl ether and hydroxybutyl vinyl ether; and hydroxyl group-containing allyl monomers such as allyl alcohol and 2-hydroxyethyl allyl ether.

Examples of the amide group-containing monomer include (meth) acrylamide, α-ethyl (meth) acrylamide, N-methyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, and N, N-dimethyl. (Meta) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethyl-p-styrene sulfamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, Examples thereof include N, N-dimethylaminopropyl (meth) acrylamide and N, N-diethylaminopropyl (meth) acrylamide.

These monomers having an active hydrogen group can be used alone or in combination of two or more.

As the monomer having an active hydrogen group, a monomer capable of imparting an active hydrogen group can also be used. Examples of the monomer to which an active hydrogen group can be added include a monomer having a glycidyl group, an epoxy group or an isocyanate group.

From the viewpoint of efficiently absorbing the (meth) acrylate compound into the seed particles, the copolymerization ratio of the monomer having an active hydrogen group in the copolymer is 50% by mass or less based on the total amount of the monomers constituting the seed particles. It is preferable, it is more preferably 45% by mass or less, and further preferably 40% by mass or less. The lower limit of the copolymerization ratio of the monomer having an active hydrogen group is preferably 0.1% by mass or more, and more preferably 0.3% by mass or more.

When the seed particles have (meth) acrylic acid ester as a monomer unit, they are easily compatible with the di (meth) acrylate compound, so that the fracture strength tends to be improved as compared with the case where polystyrene is used as the seed particles. Therefore, it is preferable.

Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and acrylic. Dodecyl acrylate, lauryl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, Examples thereof include (meth) acrylic acid esters having linear or branched alkyl groups such as hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate and stearyl methacrylate. These (meth) acrylic acid esters can be used alone or in combination of two or more. Among them, when a (meth) acrylic acid ester having a linear alkyl group is used, the compatibility with the di (meth) acrylate compound becomes good.

The weight average molecular weight (Mw) of the seed particles is determined from the viewpoint of improving the absorption capacity of the monomer of the seed particle or preventing the phase separation from the monomer to be absorbed to reduce the mechanical strength in the production of the resin particle. It is preferably 50,000 or less, and more preferably 30,000 or less. Further, from the viewpoint of making the particle size more uniform, the lower limit of Mw of the seed particles is preferably 3000 or more, and more preferably 5000 or more. The Mw defined in the present specification is a value measured by a gel permeation chromatography (GPC) using a calibration curve made of standard polystyrene.

The average particle size of the seed particles can be adjusted according to the design particle size of the obtained resin particles. The average particle size of the seed particles is preferably 0.1 to 30 μm, more preferably 0.1 to 25 μm, still more preferably 0.1 to 20 μm.

The CV value, which is the coefficient of variation of the particle size (diameter) of the seed particles, is preferably 10% or less, more preferably 7% or less, and 5% or less from the viewpoint of further improving the uniformity of the obtained resin particles. Is even more preferable.

The average particle size and the CV value of the particle size of the seed particles can be calculated by observing 100 target seed particles with a scanning electron microscope (SEM) and measuring the particle size, and microtrack particle size analysis. It is also possible to calculate from the particle size measured using a particle size measuring device such as a meter (manufactured by Nikkiso Co., Ltd.).

From the viewpoint of fully working the interaction between the seed particles and the polymer synthesized from the monomer, the particle size of the finally obtained resin particles is adjusted to be 3 to 100 times the average particle size of the seed particles. It is preferable that the amount is 3 to 70 times, more preferably 4 to 60 times, and further preferably 4 to 60 times. By increasing the interaction between the seed particles and the polymer synthesized from the monomer containing the di (meth) acrylate compound which may be contained in the emulsion described later, the compression characteristics of the resin particles are further improved. Can be done.

When the copolymerization ratio of the monomer having an active hydrogen group in the copolymer is 40% by mass or less, the monomer can be efficiently absorbed by the seed particles when the seed particles are added to the emulsion.

When the weight average molecular weight of the seed particles is 3000 to 50,000, it becomes easy to absorb the monomer when the seed particles are swollen in the emulsion.

<Manufacturing method of resin particles>
The resin particles are obtained by swelling the seed particles in an emulsion containing a monomer and then seed-polymerizing the monomer. The seed polymerization method can be carried out with reference to a known method. The general method of the seed polymerization method will be described below, but the method is not limited to this method.

First, seed particles are added to an emulsion containing a monomer and an aqueous medium. The seed particles may be added directly to the emulsion, or may be added in the form of the seed particles dispersed in an aqueous dispersion.

The emulsion can be prepared by a known method. For example, an emulsion can be obtained by adding a monomer to an aqueous medium and dispersing it in the aqueous medium with a fine emulsifier such as a homogenizer, an ultrasonic processor, or a nanomizer. The emulsion may contain a polymerization initiator, if necessary. The polymerization initiator may be mixed with the monomer in advance and then dispersed in an aqueous medium, or the polymerization initiator and the monomer may be separately dispersed in an aqueous medium and mixed. When the diameter of the monomer droplets in the obtained emulsion is smaller than the average particle size of the seed particles, the monomer can be easily absorbed by the seed particles efficiently.

After adding the seed particles to the emulsion, the seed particles are swollen to absorb the monomer. This absorption can usually be carried out by stirring the emulsion after adding the seed particles at room temperature for 1 to 24 hours. Further, the absorption of the monomer can be promoted by heating the emulsion to about 30 to 50 ° C. The amount of seed particles added can be appropriately adjusted according to the desired particle size, and is not particularly limited. However, from the viewpoint of facilitating uniform expansion of seed particles, the total amount of monomers in the emulsion is 100 parts by mass. The amount is preferably 0.0001 to 10 parts by mass, and preferably 0.0003 to 8 parts by mass.

Seed particles swell upon absorption of the monomer. When the mixing ratio of the monomer to the seed particles is small, the increase in the particle size of the resin particles produced by the seed polymerization of the monomer is small, and the productivity of the resin particles tends to decrease. On the other hand, if the mixing ratio of the monomers is large, the monomers are not absorbed by the seed particles, and the monomers are independently suspended and polymerized in the aqueous medium, and particles having a particle size other than the target particle size may be generated. The end of monomer absorption can be determined by observing the seed particles with an optical microscope and confirming the expansion of the particle size.

The emulsion according to this embodiment preferably contains a di (meth) acrylate compound as a monomer. The di (meth) acrylate compound is not particularly limited as long as it is a bifunctional monomer having two (meth) acryloyl groups, and for example, an alkanediol di (meth) acrylate can be included.

From the viewpoint of facilitating both low elasticity and compression recovery of the resin particles, the alkanediol di (meth) acrylate preferably contains a di (meth) acrylate compound represented by the following formula (1). The content of the di (meth) acrylate compound represented by the formula (1) is preferably 80 mol% or more, more preferably 85 mol% or more, and 90 mol% or more, based on the total amount of the monomers. Is even more preferable.

式中、Ｒ^１及びＲ^２はそれぞれ独立に水素原子又はメチル基を示し、Ｌ^１は炭素数４〜１２のアルキレン基を示し、該アルキレン基は、直鎖状でも分岐状でも環状でもよい。

In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, L ¹ represents an alkylene group having 4 to 12 carbon atoms, and the alkylene group may be linear, branched or cyclic.

Examples of the di (meth) acrylate compound represented by the formula (1) include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,5-pentanediol di. (Meta) acrylate, 1,6-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 3-methyl-1,5-pentane Alkanediol di (meth) acrylates such as diol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate can be mentioned. Be done.

As the monomer, other polyfunctional monomer and / or monofunctional monomer can be used in combination with the di (meth) acrylate compound.

Examples of the polyfunctional monomer include divinyl compounds such as divinylbenzene, divinylbiphenyl, and divinylnaphthalene; (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, and (poly) tetramethylene glycol. (Poly) alkylene glycol-based di (meth) acrylates such as di (meth) acrylates; trimethyl propanetri (meth) acrylates, tetramethylol methanetri (meth) acrylates, tetramethylol propanetetra (meth) acrylates, pentaerythritol tris ( Trifunctional or higher (meth) acrylates such as meta) acrylates, 1,1,1-trishydroxymethylethanetri (meth) acrylates, 1,1,1-trishydroxymethylpropanetri (meth) acrylates; ethoxylated bisphenol A Di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, 1,1,1-trishydroxymethylethanedi (meth) acrylate, cyclohexane ethoxylated Di (meth) acrylates such as dimethanol di (meth) acrylate; diallyl phthalate and its isomers; triallyl isocyanurate and its derivatives. Among these monomers, NK ester manufactured by Shin Nakamura Chemical Industry Co., Ltd. (A-TMPT-6P0, A-TMPT-3E0, A-TMM-3LMN, A-GLY series, A-9300, AD-TMP, AD-TMP -4CL, ATM-4E, A-DPH) and the like are commercially available. These polyfunctional monomers may be used alone or in combination of two or more.

Examples of the monofunctional monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, 2,4-. Dimethylstyrene, pn-butylstyrene, pt-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecyl Styrene such as styrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene and derivatives thereof; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, acrylic acid Isobutyl, hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, dodecyl acrylate, lauryl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-methyl chloroacrylate, methyl methacrylate , Ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, etc. (meth) ) Acrylic acid ester; vinyl ester such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate; N-vinyl compound such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone; Fluorinated monomers such as vinyl oxide, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, trifluoroethyl acrylate, tetrafluoropropyl acrylate; conjugated diene such as butadiene and isoprene can be mentioned. These can be used alone or in combination of two or more.

Examples of the aqueous medium include water or a mixed medium of water and a water-soluble solvent (for example, a lower alcohol). The aqueous medium contains a surfactant. As the surfactant, any of anionic, cationic, nonionic and zwitterionic surfactants can be used.

Examples of the anionic surfactant include fatty acid oils such as sodium oleate and potassium castor oil, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, and alkylnaphthalene sulfonates. Dialkyl sulfosuccinates such as acid salts, alkane sulfonates, sodium dioctyl sulfosuccinate, alkernyl succinate (dipotassium salt), alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl phenyl ether sulfate Examples thereof include salts, polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate, polyoxyethylene alkyl sulfates, and triethanol dodecyl sulfate.

Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.

Examples of nonionic surfactants include hydrocarbon-based nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines, and amides. Examples thereof include polyethylene oxide adducts of silicon, polyether-modified silicon nonionic surfactants such as polypropylene oxide adducts, and fluorine nonionic surfactants such as perfluoroalkyl glycols.

Examples of the amphoteric ion-based surfactant include hydrocarbon surfactants such as lauryldimethylamine oxide, phosphate ester-based surfactants, and phosphite ester-based surfactants.

As the surfactant, one type may be used alone or two or more types may be used in combination. Among the above-mentioned surfactants, anionic surfactants are preferable from the viewpoint of dispersion stability during polymerization of the monomer.

Examples of the polymerization initiator added as needed include benzoyl peroxide, lauroyl peroxide, orthochlorobenzoyl peroxide, benzoyl orthomethoxy benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and t-butylper. Organic peroxides such as oxy-2-ethylhexanoate and di-t-butyl peroxide; 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexanecarbonitrile, 2,2' Examples thereof include azo compounds such as −azobis (2,4-dimethylvaleronitrile). The polymerization initiator may be used in the range of 0.1 to 7.0 parts by mass with respect to 100 parts by mass of the monomer.

Next, by polymerizing the monomer absorbed by the seed particles, monodisperse resin particles can be obtained.

The polymerization temperature can be appropriately selected depending on the type of the monomer and the polymerization initiator. The polymerization temperature is preferably 25 to 110 ° C, more preferably 50 to 100 ° C. The polymerization reaction is preferably carried out by raising the temperature after the seed particles are sufficiently swollen and the monomer and optionally the polymerization initiator are completely absorbed. After the seed polymerization is completed, if necessary, the aqueous medium is removed from the polymerization solution by centrifugation, washed with water and a solvent, and then dried to isolate the resin particles.

In the above polymerization step, in order to improve the dispersion stability of the seed particles, a dispersion stabilizer may be added to the emulsion, but in the method for producing resin particles of the present embodiment, shearing acting on the resin particles during polymerization Due to the low force, it is not necessary to use a dispersion stabilizer. When the dispersion stabilizer is not used, the step of removing the dispersion stabilizer from the produced resin particles can be omitted, which is preferable.

Examples of the dispersion stabilizer include polyvinyl alcohol, polycarboxylic acid, celluloses (hydroxyethyl cellulose, carboxymethyl cellulose, etc.) and polyvinylpyrrolidone, and an inorganic water-soluble polymer compound such as sodium tripolyphosphate can also be used in combination. .. Of these, polyvinyl alcohol or polyvinylpyrrolidone is preferable. The amount of the dispersion stabilizer added is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the monomer.

In order to suppress the generation of particles in which the monomer is independently emulsion-polymerized in water, water-soluble polymerization inhibitors such as nitrites, sulfites, hydroquinones, ascorbic acids, water-soluble B vitamins, citric acid, and polyphenols are used. You may use it.

<Conductive particles>
The conductive particles of the present embodiment have the above resin particles and a metal film formed on the surface of the resin particles. FIG. 4 is a schematic cross-sectional view showing the conductive particles according to the present embodiment. As shown in FIG. 4, the conductive particle 40 has a resin particle 41 and a metal film (metal layer) 42 covering the surface of the resin particle 41.

The metal constituting the metal layer 42 is not particularly limited, but for example, gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, etc. Examples thereof include cadmium, tin-lead alloys, tin-copper alloys, tin-silver alloys and tin-lead-silver alloys. Among them, the metal layer 2 preferably contains nickel, copper, gold or a tin-silver alloy.

The method of forming the metal layer 42 on the surface of the resin particles 41 is not particularly limited. Examples of the method for forming the metal layer 42 include an electroless plating method, an electroplating method, a physical vapor deposition method, and a method of applying a paste containing a metal powder to the surface of the resin particles 41. As the physical vapor deposition method, vacuum vapor deposition, ion plating or ion sputtering can be used. As a method for forming the metal layer 42, an electroless plating method is preferable.

The metal layer 42 may be a single layer or a plurality of metal layers in which two or more layers are laminated. From the viewpoint of reducing the connection resistance between the electrodes, the surface of the conductive particles 40 (the outermost layer of the metal layer 42) is preferably a gold layer, a palladium layer, or a tin-silver alloy layer.

The thickness of the metal layer 42 is preferably 0.02 to 1 μm, more preferably 0.02 to 0.5 μm. If the thickness of the metal layer 42 is 0.02 μm or more, good conductivity is likely to be exhibited, and if it is 1 μm or less, the conductive particles are easily deformed at the time of connection. The thickness of the metal layer 2 can be determined, for example, by observing the cross section of the conductive particles using a transmission electron microscope (TEM).

The average particle size of the conductive particles 40 is preferably 1.02 to 101 μm, more preferably 1.5 to 80 μm, and even more preferably 2 to 67 μm.

The CV value of the particle size of the conductive particles 40 is preferably 10% or less, more preferably 7% or less, and further preferably 5% or less. When the CV value of the conductive particles 40 is 10% or less, the electrical connection reliability can be further improved.

The average particle size and the CV value of the particle size of the conductive particles 40 can be measured by the same method as that of the resin particles 41.

<Glue conductive material>
The anisotropic conductive material of the present embodiment includes the above-mentioned conductive particles and a binder resin. FIG. 5 is a schematic cross-sectional view showing an anisotropic conductive material according to the present embodiment. The anisotropic conductive material 60 includes an insulating binder resin 50 and conductive particles 40 dispersed in the binder resin 50.

As the binder resin 50, a thermosetting resin composition containing a thermosetting resin, a curing agent, a film-forming polymer, or the like can be used.

The thermosetting resin is not particularly limited, but it is preferable to use an epoxy resin from the viewpoint of heat resistance. As the epoxy resin, various epoxy compounds having two or more glycidyl groups in the molecule can be used. For example, a bisphenol type epoxy resin, a novolac type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, and an alicyclic. Examples thereof include type epoxy resins, glycidyl amine compounds, glycidyl ether compounds and glycidyl ester compounds.

When a high-purity product in which impurity ions (Na ⁺ , Cl ^−, etc.), hydrolyzable chlorine, etc. are reduced to 300 ppm or less is used as the epoxy resin, it becomes easy to prevent electromigration.

The curing agent is not particularly limited, but a latent curing agent can be used. Potential curing agents include, for example, imidazole compounds, hydrazide compounds, boron trifluoride-amine complexes, sulfonium salts, amineimides, polyamine salts and dicyandiamides.

The film-forming polymer is not particularly limited as long as it can form an anisotropic conductive material in the form of a film. Examples of the film-forming polymer include thermoplastic resins such as phenoxy resin, polyester resin, and polyamide resin.

The binder resin 50 can be mixed with butadiene rubber, acrylic rubber, styrene-butadiene rubber, silicone rubber and the like in order to reduce the stress after adhesion or to improve the adhesiveness.

An inorganic filler can also be blended in the binder resin 50. As the inorganic filler, for example, a filler composed of silica, magnesia, bentonite, smectite, alumina or boron nitride can be used.

The binder resin 50 may be a photocurable resin composition containing a photopolymerization initiator such as a radical polymerizable resin and an organic peroxide instead of the thermosetting resin and the curing agent.

The anisotropic conductive material 60 can be produced, for example, as follows. First, a thermosetting resin composition containing an epoxy resin, acrylic rubber, a latent curing agent, and a film-forming polymer is dissolved or dispersed in an organic solvent, if necessary, and liquefied to prepare a binder resin 50. Next, the liquid anisotropic conductive material 60 is produced by dispersing the conductive particles 40 in the binder resin 50. As the organic solvent, a solvent capable of dissolving a resin component and having a boiling point at normal pressure of 50 to 150 ° C. is preferable.

The liquid anisotropic conductive material 60 can be used as it is for connecting the circuit members, but can be molded into a film and used. The film-shaped anisotropic conductive material 60 is formed by applying a liquid anisotropic conductive material 60 on a releasable film, removing an organic solvent at a temperature equal to or lower than the active temperature of a curing agent, and then peeling the film from the releasable film. Can be made. As the releasable film, a resin film such as a fluororesin film, a polyethylene terephthalate film, or a polyolefin film is preferably used. The anisotropic conductive material 60 is convenient in terms of handleability when used in the form of a film.

The thickness of the film-shaped anisotropic conductive material 60 is relatively determined in consideration of the average particle size of the conductive particles 40 and the characteristics of the anisotropic conductive material 60, but is preferably 1 to 100 μm. More preferably, it is ~ 50 μm. If the thickness of the anisotropic conductive material 60 is less than 1 μm, it is difficult to obtain sufficient adhesiveness, and if it exceeds 100 μm, a large amount of conductive particles 40 are required to obtain conductivity, which is not realistic.

<Connection structure>
The connection structure 48 of the circuit member according to the present embodiment includes the first circuit member in which the first circuit electrode 45 is formed on the main surface of the first circuit board 44, and the main of the second circuit board 46. A second circuit member having a second circuit electrode 47 formed on the surface thereof, and a connecting portion interposed between the first circuit member and the second circuit member are provided. The second circuit member is arranged so that the second circuit electrode faces the first circuit electrode, and the connecting portion contains the conductive particles according to the present embodiment.

FIG. 6 is a schematic cross-sectional view showing a method of manufacturing a connection structure of a circuit member using an anisotropic conductive material according to the present embodiment.

First, as shown in FIG. 6A, a first circuit board 44 on which the first circuit electrode 45 is formed and a second circuit board 46 on which the second circuit electrode 47 is formed are prepared. Then, the heteroelectric conductive material 60 is placed between them. At this time, the positions are adjusted so that the first circuit electrode 45 and the second circuit electrode 47 face each other. After that, the first circuit board 44 and the second circuit board 46 are laminated while being pressurized and heated in the direction in which the first circuit electrode 45 and the second circuit electrode 47 face each other. The connection structure 10 shown in b) is obtained. The connection structure 10 is electrically connected by a cured product of the anisotropic conductive material 60.

Examples of the first circuit board 44 and the second circuit board 46 include a glass substrate, a tape substrate such as polyimide, a bare chip such as a driver IC, and a rigid type package substrate.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples.

<Synthesis of seed particles>
(Synthesis Example 1)
70 g of methyl methacrylate (MMA), 2.1 g of octanethiol (OCT), 0.7 g of potassium persulfate (KPS) and 400 g of water were put together in a 500 mL three-necked flask and heated in a water bath at 70 ° C. While stirring with a stirrer for about 8 hours, seed particles (particle size: 700 nm) were formed.

<Examination of reaction vessel shape>
(Example 1)
A monomer in which 1.33 g of benzoyl peroxide is dissolved in 18 g of 1,4-butanediol diacrylate (BDDA) is mixed with 295 g of ion-exchanged water in which 3.0 g of triethanol dodecyl sulfate is dissolved, and treated with an ultrasonic homogenizer for 10 minutes. The emulsion was prepared.

Using a round-bottom flask as a container for synthesis, 5.0 g (0.9 g of seed particles) of the seed particle dispersion of Synthesis Example 1 was added to the emulsion and stirred at room temperature for 12 hours, and then the inner diameter of the communication passage was increased. Was polymerized at 80 ° C. for 8 hours using a stirrer of 200 μm to synthesize resin particles.

(Example 2)
Resin particles in the same manner as in Example 1 except that the amount of the seed particle dispersion liquid added in Synthesis Example 1 was changed to 0.6 g (seed particles 0.1 g) and a stirrer having an inner diameter of 400 μm was used. Was synthesized.

(Example 3)
Resin particles were synthesized in the same manner as in Example 2 except that a stirring body having an inner diameter of 1.0 mm was used.

(Example 4)
Resin particles were synthesized in the same manner as in Example 2 except that a stirrer having an inner diameter of 5.0 mm was used.

(Example 5)
Resin particles were synthesized in the same manner as in Example 2 except that a stirring body having an inner diameter of 10.0 mm was used.

(Example 6)
The same as in Example 1 except that the amount of the seed particle dispersion liquid added in Synthesis Example 1 was changed to 0.2 g (seed particles 0.03 g) and a stirrer having an inner diameter of 10.0 mm was used. Resin particles were synthesized.

(Example 7)
The same as in Example 1 except that the amount of the seed particle dispersion liquid added in Synthesis Example 1 was changed to 0.07 g (seed particles 0.01 g) and a stirrer having an inner diameter of 10.0 mm in the communication passage was used. Resin particles were synthesized.

(Example 8)
The amount of the seed particle dispersion liquid added in Synthesis Example 1 was changed to 0.04 g (seed particles 0.007 g), and the same as in Example 1 except that a stirrer having an inner diameter of 10.0 mm was used. Resin particles were synthesized.

(Example 9)
The resin particles were synthesized in the same manner as in Example 1 except that a stirrer having an inner diameter of 10.0 mm was used instead of the type flask forming the container for synthesis.

(Comparative Example 1)
Resin particles were synthesized in the same manner as in Example 1 except that the container to be synthesized was a cylinder type having a side surface parallel to the rotation axis and a bottom surface perpendicular to the rotation axis.

(Comparative Example 2)
Resin particles were synthesized in the same manner as in Example 1 except that a vertical disc turbine having six blades was used as the agitator instead of the agitator.

(Comparative Example 3)
Resin particles were synthesized in the same manner as in Example 1 except that a paddle turbine (blade angle 45 °) having four blades was used as the stirrer instead of the stirrer.

The particle size of the resin particles obtained in each Example and Comparative Example was measured with a wet flow type particle size / shape analyzer (manufactured by Sysmex Co., Ltd.), and the average particle size and the CV value of the particle size were calculated. The results are shown in Table 1.

From the results in Table 1, it was confirmed that the particles synthesized by the production method of the present invention were very monodisperse.

Preparation of Conductive Particles A nickel layer having a thickness of 0.2 μm is formed on the surfaces of the resin particles obtained in Examples 1 to 9 and Comparative Examples 1 to 3 by an electroless plating method, and the thickness is further outside the nickel layer. A 0.04 μm palladium layer was formed to prepare conductive particles 1 to 12, respectively.

[Manufacturing of anisotropic conductive materials]
Using the conductive particles 1 to 12, an anisotropic conductive material was produced as follows.

Phenoxy resin (manufactured by Union Carbide, trade name "PKHC") 5 parts by mass, acrylic rubber (copolymer of butyl acrylate, ethyl acrylate, acrylonitrile and glycidyl methacrylate, copolymerization ratio (mass) 40/30/30/3, Mw850,000) 18 parts by mass, epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "YL-983U") 15 parts by mass dissolved in 10 parts by mass of ethyl acetate, a cationic curing agent (Sanshin Chemical Industry Co., Ltd.) A thermosetting resin composition was prepared by adding 2 parts by mass (manufactured by the company, trade name "SI-60"). Next, 10 parts by mass of a silica filler (manufactured by Nippon Aerosil Co., Ltd., trade name "Aerosil R805") and 30 parts by mass of an ethyl acetate dispersion were added to the thermosetting resin composition and mixed, and then 20 parts by mass of conductive particles were added. And 10 parts by mass of ethyl acetate were added and subjected to ultrasonic dispersion to prepare a liquid heteroconductive material.

A liquid anisotropic conductive material is applied on a silicone-treated polyethylene terephthalate film (thickness 40 μm, hereinafter referred to as “PET film”) with a roll coater, and dried at 80 ° C. for 5 minutes to form a film having a thickness of 20 μm. An anisotropic conductive material was prepared.

[Preparation of connection structure]
Using the prepared film-like anisotropic conductive material, a tip with gold bumps (area: 30 μm × 90 μm, space 10 μm, height: 15 μm, number of bumps: 362) (1.7 mm × 17 mm, thickness: 0.5 mm) And a glass substrate with an AlNd film (manufactured by Geomatec, thickness: 0.7 mm) were thermocompression bonded as follows to prepare a connection structure.

The surface opposite to the surface on which the PET film of the film-like anisotropic conductive material cut to a predetermined size (2 mm × 19 mm) is provided is placed on the surface on which the AlNd film of the glass substrate with the AlNd film is formed. The film was attached at ° C., 0.98 MPa (10 kgf / cm ² ) for 5 seconds. Then, the PET film was peeled off, and heating and pressurization were performed under the conditions of 170 ° C., 70 MPa, and 5 seconds via an anisotropic conductive material to obtain a mounting sample (connection structure).

(Confirmation of indentation)
Using a liquid crystal panel inspection microscope (BH3-MJL, manufactured by Olympus Corporation), the state of indentations was observed from the glass substrate side by Nomarski differential interference contrast observation. The case where the outline can be clearly confirmed is good, and the other cases are unclear. In addition, 1000 indentations were counted, and the variation of indentations was evaluated with the number of indistinct indentations being 50 or more as B and less than 50 as A. The results are also shown in Table 1.

It was confirmed that the resin particles synthesized by the production method of the present embodiment have high monodispersity. Further, it was confirmed that a connecting structure with less indentation variation can be produced by using the conductive particles formed by using the resin particles.

1 ... Reaction device, 3 ... Reaction vessel, 3a ... First wall surface, 3b ... Second wall surface, 4 ... Lid, 5 ... Introduction part, 11, 31 ... Shaft, 12 ... Base, 13, 33 ... Stirrer, 14 , 34 ... consecutive passages, 15, 35 ... discharge port, 16, 36 ... suction port, 18 ... drive unit, 40 ... conductive particles, 41 ... resin particles, 42 ... metal layer, 50 ... binder resin, 60 ... anisotropic Conductive material, 44 ... first circuit board, 45 ... first circuit electrode, 46 ... second circuit board, 47 ... second circuit electrode, 48 ... connection structure, G ... rotating axis.

Claims (9)

A reaction vessel containing the reaction solution and
With the stirrer arranged in the reaction vessel,
A drive unit for stirring the reaction solution by rotating the stirrer around the rotation axis is provided.
The agitator has a shape in which a discharge port and a suction port communicated with the discharge port via a communication passage provided inside the base are provided on the surface of a rotationally symmetric convex substrate around the rotation axis. Have and
The suction port is located closer to the rotation axis than the discharge port and is provided on the bottom side of the container in the direction of the rotation axis.
The reaction vessel is a reaction apparatus having a first wall surface that guides the flow of the reaction solution agitated in the reaction vessel in a direction below the reaction vessel and in a direction approaching the rotation axis. The reaction apparatus according to claim 1, wherein the first wall surface reaches the lowest position of the reaction vessel while reducing the area of the region surrounded by the wall surface of the reaction vessel in the cross section perpendicular to the rotation axis. .. The reaction apparatus according to claim 1, wherein the first wall surface reaches the lowest position of the reaction vessel while being reduced in diameter. The reaction vessel has a second wall surface located above the first wall surface and has a second wall surface.
The reaction apparatus according to any one of claims 1 to 3, wherein the second wall surface guides the flow of the reaction solution to be stirred in the reaction vessel in a direction below the reaction vessel and away from the rotation axis. The reaction apparatus according to any one of claims 1 to 4, wherein the reaction vessel has a round bottom. The reaction apparatus according to any one of claims 1 to 5, further comprising an introduction unit capable of introducing a raw material into the reaction vessel. The reaction apparatus according to claim 6, wherein the introduction portion is configured to introduce the raw material to the wall surface side of the reaction vessel rather than the stirring body when viewed from the rotation axis. The reaction device according to any one of claims 1 to 7, which is used for seed polymerization. In a method for producing resin particles by carrying out a polymerization reaction while stirring an emulsion containing seed particles and a monomer in a reaction vessel.
The emulsion is agitated by rotating the stirrer around the axis of rotation in the reaction vessel.
The agitator has a shape in which a discharge port and a suction port communicated with the discharge port via a communication passage provided inside the base are provided on the surface of a substrate that is rotationally symmetric around the rotation axis. And
The suction port is located closer to the rotation axis than the discharge port and is provided on the bottom side of the container in the direction of the rotation axis.
The method, wherein the reaction vessel has a first wall surface that guides the flow of the emulsion to be agitated in the reaction vessel in a direction below the reaction vessel and closer to the rotation axis.

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