KR20210010447A - Substrate particle, conductive particle, conductive material and connection structure - Google Patents

Abstract

When the electrodes are electrically connected to each other using conductive particles having a conductive layer formed on the surface of the adherend, the adhesion and impact resistance with the conductive layer can be effectively improved, and the connection resistance is increased. It provides a substrate particle that can be effectively lowered and can effectively increase connection reliability. The substrate particle according to the present invention is a substrate particle used as a spacer, or a conductive layer is formed on a surface thereof, and a substrate particle used to obtain a conductive particle having the conductive layer, the BET specific surface area is 5 m ² /g or more, and the particle The CV value of the diameter is 10% or less.

Description

Substrate particle, conductive particle, conductive material and connection structure

The present invention relates to substrate particles having good compression properties. Further, the present invention relates to a conductive particle, a conductive material, and a connection structure using the substrate particle.

Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known. In the anisotropic conductive material, conductive particles are dispersed in a binder resin.

The anisotropic conductive material is used to electrically connect electrodes of various members to be connected, such as a flexible printed circuit board (FPC), a glass substrate, a glass epoxy substrate, and a semiconductor chip, to obtain a connection structure. Moreover, as said electroconductive particle, electroconductive particle which has a substrate particle and a conductive layer arrange|positioned on the surface of the said substrate particle may be used.

As an example of the substrate particle, in the following Patent Document 1, the specific surface area is 2.0 m ² /g, the amount of the eluted component relative to toluene is 1% to 5%, and the coefficient of variation (CV value) of the particle diameter is 15% or less. , Deformed monodisperse particles having an average particle diameter of 0.8 μm to 50 μm are disclosed. In the heterogeneous monodisperse particles, a polymer component derived from a monomer having two or more ethylenically unsaturated groups in 100% by mass of the total of the polymer component derived from an acrylic monomer and a polymer component derived from a monomer having two or more ethylenically unsaturated groups. The content of is 18% by mass to 89% by mass. In Examples of the following Patent Document 1, it is described that the specific surface area of the heterogeneous monodisperse particles is 2.0 m ² /g to 2.6 m ² /g.

In the following Patent Document 2, porous resin particles composed of a polymer of a monomer mixture are disclosed. In the porous resin particles, in 100% by weight of the monomer mixture, mono(meth)acrylic acid esters containing ethylenically unsaturated groups only in (meth)acrylic acid residues, and at least one of ether groups and ester groups and hydroxyl groups in alcohol residues The content of the monomer is 3% by weight to 40% by weight. In the porous resin particles, the content of the other monofunctional vinyl-based monomer having one ethylenically unsaturated group in 100% by weight of the monomer mixture is 10% by weight to 69% by weight. In the porous resin particles, the content of the polyfunctional vinyl-based monomer having two or more ethylenically unsaturated groups in 100% by weight of the monomer mixture is 30% by weight to 70% by weight. To the embodiment of Patent Document 2, the specific surface area of the porous resin particle it is described that is 4.9m ² / g to about 184.0m ² / g. In the following Patent Document 2, nothing is described about the compressive modulus of the porous resin particles. In the following Patent Document 2, none of the use of porous resin particles as spacers or for obtaining electroconductive particles is described.

Moreover, the liquid crystal display element is comprised by arrange|positioning a liquid crystal between two glass substrates. In the liquid crystal display device, in order to keep the gap (gap) between two glass substrates uniform and constant, a spacer is used as a gap control material. As the spacer, substrate particles are generally used.

As an example of the spacer, the following Patent Document 3 discloses a spacer for a liquid crystal display element having an uneven shape over the entire surface. In Examples of the following Patent Document 3, it is described that the BET specific surface area of the spacer for a liquid crystal display element is 1.24 m ² /g or 1.33 m ² /g.

Japanese Patent Publication No. 2010-168464 WO2013/114653A1 Japanese Patent Publication No. 2004-145128

In recent years, when electrically connecting between electrodes using a conductive material or a connecting material containing electroconductive particles, it is desired to electrically connect the electrodes reliably even at a relatively low pressure to lower the connection resistance. For example, in the manufacturing method of a liquid crystal display device, at the time of mounting a flexible substrate in the FOG method, an anisotropic conductive material is disposed on a glass substrate, a flexible substrate is laminated, and thermocompression bonding is performed. In recent years, narrowing of the frame width of a liquid crystal panel and thinning of the glass substrate have progressed. In this case, when thermal compression bonding is performed at a high pressure and high temperature at the time of mounting the flexible substrate, deformation occurs in the mounting of the flexible substrate, and display unevenness may occur. Therefore, it is preferable to perform thermocompression bonding at a relatively low pressure when mounting a flexible substrate in the FOG method. In addition to the FOG method, there is a requirement to relatively lower the pressure and temperature during thermocompression bonding.

In the conventional substrate particle, the following 1st problem exists.

In the case of using conventional substrate particles as conductive particles, connection resistance may increase if the electrodes are electrically connected at a relatively low pressure. The cause of this is that the conductive particles do not sufficiently contact the electrode (adherent), or the adhesion between the substrate particles and the conductive layer disposed on the surface of the substrate particles is low, and the conductive layer is peeled off. In addition, in the case of forming a connection portion that electrically connects the electrodes using conventional conductive particles, when an impact such as dropping is applied to the connection portion, the connection may be made by peeling off the conductive layer disposed on the surface of the substrate particle. Resistance sometimes increases.

In addition, in the conventional electroconductive particle, the particle diameter of electroconductive particle may fluctuate, and the electroconductive particle may not make uniform contact with an electrode (adherence), and connection resistance may become high.

In addition, when conventional substrate particles are used as spacers used in a liquid crystal display device or the like, a member for a liquid crystal display device or the like (adherence) may be sucked. In the conventional spacer, the particle diameter of the spacer may fluctuate, and the spacer may not evenly contact the member for a liquid crystal display element or the like (adherence), and a sufficient gap control effect may not be obtained.

With respect to the above first problem, an object of the present invention is to provide a substrate particle that can be brought into uniform contact with an adherend. In addition, with respect to the first problem, the object of the present invention is to effectively increase adhesion and impact resistance with the conductive layer when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface. It is to provide a substrate particle capable of effectively lowering connection resistance and effectively increasing connection reliability. Further, an object of the present invention is to provide a conductive particle, a conductive material, and a connection structure using the substrate particle.

Moreover, in the conventional substrate particle, there exists the following 2nd subject.

In the case of using conventional substrate particles as conductive particles, connection resistance may increase if the electrodes are electrically connected at a relatively low pressure. The cause of this is that the conductive particles are not in sufficient contact with the electrode (the adherend), so that the indentation, which is a concave portion formed by pressing the conductive particles, is difficult to form, or the conductive layer and the surface oxide film of the electrode cannot be sufficiently penetrated. have. In addition, in the conventional electroconductive particle, the adhesion between the substrate particle and the conductive layer disposed on the surface of the substrate particle is low, the conductive layer may be peeled off, and the connection resistance may increase.

In addition, in the conventional electroconductive particle, a flaw different from the above indentation is formed on the electrode (to-be-adhered body), and connection resistance may increase.

In addition, when conventional substrate particles are used as spacers used in a liquid crystal display device or the like, a member for a liquid crystal display device or the like (adherence) may be sucked. In the conventional spacer, there are cases where a sufficient gap control effect cannot be obtained.

Regarding the second problem, the object of the present invention is to effectively suppress the occurrence of scratches on an adherend, and when electrically connecting between electrodes using conductive particles having a conductive layer formed on the surface, the conductive layer It is to provide a substrate particle capable of effectively increasing the adhesion to and effectively lowering the connection resistance, and effectively increasing the connection reliability. Further, an object of the present invention is to provide a conductive particle, a conductive material, and a connection structure using the substrate particle.

Moreover, in the conventional substrate particle, there is the following 3rd subject.

In the case of using conventional substrate particles as conductive particles, connection resistance may increase if the electrodes are electrically connected at a relatively low pressure. The cause of this is that the conductive particles are not in sufficient contact with the electrode (adherent), so that the indentation, which is a concave portion formed by pressing the conductive particles, is difficult to form, or the conductive layer and the surface oxide film of the electrode are not sufficiently penetrated. have. Further, scratches different from the above indentations are formed on the electrode (adhered body), and connection resistance may increase.

In addition, when conventional substrate particles are used as spacers used in a liquid crystal display device or the like, a member for a liquid crystal display device or the like (adherence) may be sucked. In the conventional spacer, there are cases where a sufficient gap control effect cannot be obtained.

Regarding the third problem, the object of the present invention is to effectively suppress the occurrence of scratches on an adherend, and when electrically connecting between electrodes using conductive particles having a conductive layer formed on the surface, connection resistance It is to provide a substrate particle capable of effectively lowering the value and effectively increasing the connection reliability. Further, an object of the present invention is to provide a conductive particle, a conductive material, and a connection structure using the substrate particle.

Moreover, in the conventional substrate particle, there is the following 4th problem.

In the case of using conventional substrate particles as conductive particles, connection resistance may increase if the electrodes are electrically connected at a relatively low pressure. The cause of this is that the conductive particles do not sufficiently contact the electrode (adherent), or the adhesion between the substrate particles and the conductive layer disposed on the surface of the substrate particles is low, and the conductive layer is peeled off. In addition, in the case of forming a connection portion that electrically connects the electrodes using conventional conductive particles, when an impact such as dropping is applied to the connection portion, the connection may be made by peeling off the conductive layer disposed on the surface of the substrate particle. Resistance sometimes increases.

In addition, in the conventional electroconductive particle, not only the pressure at the time of connection but also the hardness (material) of an electrode (adherence), the electroconductive particle does not fully contact an electrode (adherence), and connection resistance may become high. In addition, scratches may be formed on the surface of the electrode (to-be-adhered body) and the connection resistance may increase.

In addition, when conventional substrate particles are used as spacers used in a liquid crystal display device or the like, a member for a liquid crystal display device or the like (adherence) may be sucked. In a conventional spacer, there is a case where a sufficient gap control effect cannot be obtained without sufficiently contacting a member for a liquid crystal display element or the like (adherence).

Regarding the fourth problem, it is an object of the present invention to effectively suppress the occurrence of scratches on an adherend, and when electrically connecting between electrodes using conductive particles having a conductive layer formed on the surface, the conductive layer It is to provide a substrate particle capable of effectively increasing the adhesion to and effectively increasing the impact resistance, and effectively lowering the connection resistance. Further, an object of the present invention is to provide a conductive particle, a conductive material, and a connection structure using the substrate particle.

The present specification provides substrate particles (at least four types of substrate particles) capable of solving the first problem, the second problem, the third problem, and the fourth problem, respectively.

According to a broad aspect of the present invention, it is a substrate particle used as a spacer or a conductive layer is formed on the surface to obtain the conductive particles having the conductive layer, and the BET specific surface area is 5 m ² /g or more, A substrate particle having a CV value of 10% or less of the particle diameter is provided.

In a particular aspect of the base particles of the present invention, the compression modulus of 10% when compressed at least 1N / mm ² 3500N / mm ² or less.

In a particular aspect of the base particles of the present invention, the compression elastic modulus at 30% compression hayeoteul least 1N / mm ² 3000N / mm ² or less.

In a specific aspect of the substrate particles according to the present invention, the compression recovery rate is 5% or more and 60% or less.

According to the broad aspect of the invention, the BET specific surface area of 300m ² / g more than 600m ² / g is less than a, the compression elastic modulus when compressed 10% 100N / mm ² more than 3000N / mm ² or less, base particles are provided.

In a particular aspect of the base particles of the present invention, the compression modulus is 100N / mm ² more than 2500N / mm ² or less at the time of 30% compression hayeoteul.

In a specific aspect of the substrate particles according to the present invention, the compression recovery rate is 5% or more and 60% or less.

In certain aspects of the substrate particles according to the present invention, the CV value of the particle diameter is 10% or less.

In a specific aspect of the substrate particle according to the present invention, the substrate particle is used as a spacer, or is used to obtain a conductive particle having the conductive layer by forming a conductive layer on the surface thereof.

According to the broad aspect of the invention, the BET specific surface area of 5m ² / g more than 300m ² / g is less than a, the compression modulus of the time 30% hayeoteul compression 100N / mm ² more than 3000N / mm ² or less, base particles are provided.

In a particular aspect of the base particles of the present invention, the compression modulus is 100N / mm ² more than 3500N / mm ² or less at the time when compressed 10%.

In a specific aspect of the substrate particles according to the present invention, the compression recovery rate is 5% or more and 60% or less.

In certain aspects of the substrate particles according to the present invention, the CV value of the particle diameter is 10% or less.

In a specific aspect of the substrate particle according to the present invention, the substrate particle is used as a spacer, or is used to obtain a conductive particle having the conductive layer by forming a conductive layer on the surface thereof.

According to a broad aspect of the present invention, the BET specific surface area is 600 m ² /g or more, the compressive elastic modulus when compressed by 10% is 1200 N/mm ² or less, and the compressive elastic modulus when compressed by 30% is 1200 N/mm ² or less. And the base particles having a compression recovery rate of 5% or more are provided.

In certain aspects of the substrate particles according to the present invention, the CV value of the particle diameter is 10% or less.

In a specific aspect of the substrate particle according to the present invention, the substrate particle is used as a spacer, or is used to obtain a conductive particle having the conductive layer by forming a conductive layer on the surface thereof.

In a specific aspect of the substrate particles according to the present invention, the density is 1 g/cm ³ or more and 1.4 g/cm ³ or less.

In certain aspects of the substrate particles according to the present invention, the total pore volume is 0.01 cm ³ /g or more and 3 cm ³ /g or less.

In certain aspects of the substrate particles according to the present invention, the average pore diameter is 10 nm or less.

In certain aspects of the substrate particles according to the present invention, the average particle diameter is 0.1 µm or more and 100 µm or less.

According to a broad aspect of the present invention, electroconductive particles are provided that include the above-described substrate particles and a conductive layer disposed on the surface of the substrate particles.

In a specific aspect of the conductive particles according to the present invention, an insulating material disposed on the outer surface of the conductive layer is further provided.

In a specific aspect of the electroconductive particle according to the present invention, a protrusion is provided on the outer surface of the electroconductive layer.

According to a broad aspect of the present invention, there is provided a conductive material comprising electroconductive particles and a binder resin, wherein the electroconductive particles include the aforementioned substrate particles and a conductive layer disposed on the surface of the substrate particles.

According to a broad aspect of the present invention, a first connection object member having a first electrode on its surface, a second connection object member having a second electrode on its surface, the first connection object member and the second connection object member are provided. A connecting portion to be connected is provided, the connecting portion is formed of conductive particles, or is formed of a conductive material containing the conductive particles and a binder resin, and the conductive particles are the aforementioned substrate particles and the substrate particles. There is provided a connection structure comprising a conductive layer disposed on the surface of the cell, wherein the first electrode and the second electrode are electrically connected by the conductive particles.

The substrate particle according to the present invention is used as a spacer, or a conductive layer is formed on the surface, and is used to obtain conductive particles having the conductive layer. In the substrate particle according to the present invention, the BET specific surface area is 5 m ² /g or more. In the substrate particle according to the present invention, the CV value of the particle diameter is 10% or less. In the substrate particle according to the present invention, since the above configuration is provided, it can be uniformly brought into contact with an adherend, and when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface, the conductive layer It is possible to effectively increase adhesion and impact resistance to and to effectively lower the connection resistance, and to increase connection reliability effectively.

In the substrate particle according to the present invention, the BET specific surface area is 300 m ² /g or more and less than 600 m ² /g. The base particles according to the present invention, the compression modulus is 100N / mm ² more than 3000N / mm ² or less at the time when compressed 10%. In the substrate particle according to the present invention, since the above configuration is provided, it is possible to effectively suppress the occurrence of scratches on the adherend, and when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface, The adhesion to the conductive layer can be effectively increased, the connection resistance can be effectively reduced, and the connection reliability can be effectively increased.

In the substrate particle according to the present invention, the BET specific surface area is 5 m ² /g or more and less than 300 m ² /g. The base particles according to the present invention, the compression modulus is 100N / mm ² more than 3000N / mm ² or less at the time of 30% compression hayeoteul. In the substrate particle according to the present invention, since the above configuration is provided, it is possible to effectively suppress the occurrence of scratches on the adherend, and when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface, Connection resistance can be effectively lowered, and connection reliability can be effectively increased.

In the substrate particle according to the present invention, the BET specific surface area is 600 m ² /g or more. In the substrate particles according to the present invention, the compressive elastic modulus when compressed by 10% is 1200 N/mm ² or less. In the substrate particles according to the present invention, the compressive elastic modulus when compressed by 30% is 1200 N/mm ² or less. In the substrate particle according to the present invention, the compression recovery rate is 5% or more. In the substrate particle according to the present invention, since the above configuration is provided, it is possible to effectively suppress the occurrence of scratches on the adherend, and when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface, The adhesion to the conductive layer can be effectively increased, the impact resistance can be effectively increased, and the connection resistance can be effectively reduced.

1 is a cross-sectional view showing conductive particles according to a first embodiment of the present invention.
2 is a cross-sectional view showing conductive particles according to a second embodiment of the present invention.
3 is a cross-sectional view showing conductive particles according to a third embodiment of the present invention.
4 is a cross-sectional view showing an example of a connection structure using electroconductive particles according to the first embodiment of the present invention.
5 is a cross-sectional view showing an example of a liquid crystal display device in which the substrate particles according to the present invention are used as a spacer for a liquid crystal display device.

Hereinafter, the details of the present invention will be described.

(Substrate particle)

In the present invention, the following substrate particles 1 to 4 are disclosed.

Substrate particle 1:

The substrate particle according to the present invention is used as a spacer, or a conductive layer is formed on the surface, and is used to obtain conductive particles having the conductive layer. In the substrate particle according to the present invention, the BET specific surface area is 5 m ² /g or more. In the substrate particle according to the present invention, the CV value of the particle diameter is 10% or less.

In the substrate particle according to the present invention, since the above configuration is provided, it can be uniformly brought into contact with an adherend, and when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface, the conductive layer It is possible to effectively increase adhesion and impact resistance to and to effectively lower the connection resistance, and to increase connection reliability effectively.

In the substrate particle according to the present invention, since it has an appropriate BET specific surface area, when forming the conductive layer on the surface of the substrate particle, the conductive layer enters the fine pores of the surface of the substrate particle, and the adhesion between the substrate particle and the conductive layer is effective. It can be increased, and peeling of the conductive layer can be effectively prevented. In addition, in the case of forming a connection portion that electrically connects the electrodes using conductive particles having a conductive layer formed on the surface of the substrate particle according to the present invention, even if an impact by dropping or the like is applied to the connection portion, the conductive layer Peeling is effectively prevented, and connection resistance between electrodes can be effectively lowered. With the electroconductive particle using the base material particle of this invention, impact resistance can be improved effectively. Further, in the substrate particle according to the present invention, the CV value of the particle diameter is relatively small, the fluctuation of the particle diameter of the electroconductive particle can be effectively suppressed, and the electroconductive particle can be brought into uniform contact with the electrode. As a result, the connection resistance between the electrodes can be effectively lowered, and the connection reliability between the electrodes can be effectively increased. For example, even if the connection structure electrically connected between electrodes by electroconductive particles is left for a long time under high temperature and high humidity conditions, the connection resistance is more difficult to increase and conduction failure is more difficult to occur.

In addition, when the substrate particle according to the present invention is used as a spacer for a liquid crystal display element, it is possible to effectively suppress the occurrence of scratches on the member for a liquid crystal display element. Further, in the substrate particle according to the present invention, the CV value of the particle diameter is relatively small, the fluctuation of the particle diameter of the spacer can be effectively suppressed, and the spacer can be uniformly brought into contact with a member for a liquid crystal display element or the like. For this reason, a sufficient gap control effect can be obtained. As a result, the display quality of the liquid crystal display element can be further improved.

The substrate particle according to the present invention is used as a spacer, or a conductive layer is formed on the surface, and is used to obtain conductive particles having the conductive layer. The substrate particle according to the present invention may be used as a spacer. The substrate particle according to the present invention has a conductive layer formed on its surface, and may be used to obtain conductive particles having the conductive layer. It is preferable that the base material particle of this invention is a base material particle for spacers. It is preferable that the base material particle of this invention is a base material particle for electroconductive particle.

In the substrate particle according to the present invention, the BET specific surface area is 5 m ² /g or more. The BET specific surface area of the substrate particles is preferably 8 m ² /g or more, more preferably 12 m ² /g or more, preferably 1200 m ² /g or less, more preferably 1000 m ² /g or less, even more preferably Is not more than 700m ² /g. If the BET specific surface area is greater than or equal to the lower limit and less than or equal to the upper limit, when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface, the adhesion and impact resistance with the conductive layer are further effectively improved. This can be achieved, the connection resistance can be further effectively lowered, and the connection reliability can be further increased more effectively.

The BET specific surface area can be measured from the adsorption isotherm of nitrogen based on the BET method. Examples of the device for measuring the BET specific surface area include "NOVA4200e" manufactured by Cantachrom Instruments. In addition, the conditions at the time of measurement are preferably sample amount: 0.5 g, out gas type: nitrogen, out gas temperature: 28°C, out gas time: 3 hours, and bath temperature: 273 K (0° C.).

The density of the substrate particles is preferably 1 g/cm ³ or more, more preferably 1.1 g/cm ³ or more, preferably 1.4 g/cm ³ or less, more preferably 1.3 g/cm ³ or less. If the density is greater than or equal to the lower limit and less than or equal to the upper limit, when electrically connecting between electrodes using conductive particles having a conductive layer formed on the surface, the connection resistance can be further effectively lowered, and the connection reliability is further increased. You can increase it more effectively.

The density of the substrate particles can be measured using a specific gravity combination density measuring device. Examples of the specific gravity combined method density measuring device include "Accupyc 1330" manufactured by Shimadzu Corporation. In addition, the conditions at the time of measurement are preferably sample amount: 1 g and measurement temperature: 28°C.

The total pore volume of the substrate particles is preferably 0.01 cm ³ /g or more, more preferably 0.05 cm ³ /g or more, preferably ³ cm ³ /g or less, more preferably 1.5 cm ³ /g or less . When the total pore volume is greater than or equal to the lower limit and less than or equal to the upper limit, when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface, the adhesion and impact resistance with the conductive layer are further effectively improved. This can be achieved, the connection resistance can be further effectively lowered, and the connection reliability can be further increased more effectively.

The total pore volume can be measured from the adsorption isotherm of nitrogen in accordance with the BJH method. Examples of the device for measuring the total pore volume include "NOVA4200e" manufactured by Cantachrom Instruments.

The average pore diameter of the substrate particles is preferably 10 nm or less, more preferably 5 nm or less. The lower limit of the average pore diameter of the substrate particles is not particularly limited. The average pore diameter of the substrate particles may be 1 nm or more. If the average pore diameter is greater than or equal to the lower limit and less than or equal to the upper limit, when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface, the adhesion and impact resistance to the conductive layer are further effectively improved. This can be achieved, the connection resistance can be further effectively lowered, and the connection reliability can be further increased more effectively.

The average pore diameter can be measured from the adsorption isotherm of nitrogen in accordance with the BJH method. As the measuring device for the average pore diameter, "NOVA4200e" by Cantachrom Instruments Inc. is mentioned.

The substrate particles satisfying the preferred ranges of the BET specific surface area, the total pore volume, and the average pore diameter can be obtained, for example, by a method for producing a substrate particle comprising the following steps. A step of preparing a polymerizable monomer solution by mixing a polymerizable monomer and an organic solvent that does not react with the polymerizable monomer. A step of obtaining an emulsion by adding the polymerizable monomer solution and an anionic dispersion stabilizer to a polar solvent and emulsifying it. A step of dividing the emulsion into several times and absorbing the monomer into the seed particles to obtain a suspension containing the seed particles swollen with the monomer. A step of polymerizing the polymerizable monomer to obtain substrate particles. As said polymerizable monomer, a monofunctional monomer, a polyfunctional monomer, etc. are mentioned, for example. The organic solvent that does not react with the polymerizable monomer is not particularly limited as long as it is not compatible with a polar solvent such as water, which is a polymerization medium. Examples of the organic solvent include cyclohexane, toluene, xylene, ethyl acetate, butyl acetate, allyl acetate, propyl acetate, chloroform, methylcyclohexane, and methyl ethyl ketone. The amount of the organic solvent added is preferably 1 to 215 parts by weight, more preferably 5 to 210 parts by weight, based on 100 parts by weight of the polymerizable monomer component. If the amount of the organic solvent to be added is within the preferred range, the BET specific surface area can be controlled to a further suitable range, and fine pores are easily obtained inside the particles. In particular, in the case of a combination in which the SP value of the polymerizable monomer is 8.0 to 10.0 and the SP value of the organic solvent is 8.0 to 11.0, the BET specific surface area, the total pore volume, and the average pore diameter are more effectively suited to the range. Can be controlled by

Compression modulus (10% K value) when compressing the base particles 10%, preferably more than 1N / mm ² or more, and more preferably at least 100N / mm ^2, preferably 3500N / mm ² or less, Preferably it is 3000 N/mm ² or less. If the 10% K value is greater than or equal to the lower limit and less than or equal to the upper limit, the connection resistance can be lowered even more effectively when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface, and the connection Reliability can be improved even more effectively.

Compression modulus (30% K value) when compressing the base particles 30%, preferably more than 1N / mm ² or more, and more preferably at least 100N / mm ^2, preferably 3000N / mm ² or less, It is preferably 2800 N/mm ² or less. If the 30% K value is more than the lower limit and less than the upper limit, when electrically connecting between electrodes using conductive particles having a conductive layer formed on the surface, the connection resistance can be further effectively lowered, and further connection Reliability can be improved even more effectively.

The compressive elastic modulus (10% K value and 30% K value) in the substrate particle can be measured as follows.

Using a micro-compression tester, one substrate particle is compressed under the conditions of 25°C, a compression speed of 0.3 mN/sec, and a maximum test load of 20 mN, on an end surface of a smooth indenter of a circumference (diameter 50 μm, made of diamond). The load value (N) and compression displacement (mm) at this time are measured. From the obtained measured values, the compressive elastic modulus (10% K value and 30% K value) can be determined by the following equation. As the micro-compression tester, for example, "Fischer Scope H-100" manufactured by Fischer is used. The compressive elastic modulus (10% K value and 30% K value) of the substrate particles is calculated by arithmetic average of the compressive elastic modulus (10% K value and 30% K value) of 50 randomly selected substrate particles. desirable.

10% K value or 30% K value (N/mm ² )=(3/2 ^1/2 )·F·S ^-3/2 ·R ^-1/2

F: Load value (N) when the base particles are compressed by 10% or 30%

S: Compression displacement (mm) when the substrate particles are compressed by 10% or 30%

R: radius of the substrate particle (mm)

The compressive modulus is a universal and quantitative representation of the hardness of the substrate particles. By using the compression modulus, the hardness of the substrate particles can be quantitatively and uniquely expressed.

The compression recovery rate of the substrate particles is preferably 5% or more, more preferably 7% or more, preferably 60% or less, and more preferably 50% or less. If the compression recovery rate is more than the lower limit and less than the upper limit, when electrically connecting between electrodes using conductive particles having a conductive layer formed on the surface, the connection resistance can be further effectively lowered, and connection reliability is further improved. It can be increased more effectively.

The compression recovery rate of the substrate particles can be measured as follows.

The substrate particles are sprayed on the sample stage. For one sprayed substrate particle, using a micro-compression tester, the substrate particle will be compressed by 30% at the end face of the smooth indenter of the circumference (diameter 50 μm, made of diamond), in the direction of the center of the substrate particle at 25°C. The load (reverse load value) is applied until. After that, unloading is performed up to the original load value (0.40mN). The load-compression displacement in the meantime is measured, and the compression recovery rate can be calculated|required from the following formula. In addition, the load speed is set to 0.33 mN/sec. As the micro-compression tester, for example, "Fischer Scope H-100" manufactured by Fischer is used.

Compression recovery rate (%)=[L2/L1]×100

L1: Compression displacement from the origin load value at the time of applying the load to the reverse load value

L2: Unloading displacement from the reverse load value when the load is released to the origin load value

The substrate particle is used as a spacer, or a conductive layer is formed on a surface thereof, and is used to obtain conductive particles having the conductive layer. In the electroconductive particle, the electroconductive layer is formed on the surface of the substrate particle. It is preferable that the said substrate particle is formed with a conductive layer on the surface, and is used to obtain the electroconductive particle which has the said electroconductive layer. It is preferable that the substrate particles are used as spacers. As a method of using the spacer, a spacer for a liquid crystal display device, a spacer for gap control, a spacer for stress relaxation, and the like can be mentioned. The gap control spacer may be used for gap control of a laminated chip to ensure standoff height and flatness, and gap control of an optical component to ensure smoothness of a glass surface and a thickness of an adhesive layer. The stress relaxation spacer can be used for stress relaxation of a sensor chip or the like and stress relaxation of a connection portion connecting two members to be connected.

The substrate particle is preferably used as a spacer for a liquid crystal display device, and is preferably used for a peripheral sealant for a liquid crystal display device. In the peripheral sealing agent for a liquid crystal display device, it is preferable that the substrate particle functions as a spacer. Since the substrate particles have good compressive deformation properties, when the substrate particles are used as spacers and disposed between substrates, or a conductive layer is formed on the surface and used as conductive particles to electrically connect the electrodes, a spacer or The conductive particles are efficiently disposed between substrates or between electrodes. In addition, since the substrate particles can be uniformly brought into contact with a member for a liquid crystal display element, etc., in the liquid crystal display element using the spacer for the liquid crystal display element and the connection structure using the conductive particles, poor connection and display failure occur. It becomes difficult.

In the substrate particle according to the present invention, the CV value (coefficient of variation) of the particle diameter of the substrate particle is 10% or less. The CV value is preferably 7% or less, more preferably 5% or less. If the CV value is less than or equal to the above upper limit, the substrate particles can be brought into contact with the adherend more evenly, and the substrate particles can be used more suitably for the use of conductive particles and spacers. In addition, the CV value can be adjusted by classification of the substrate particles.

The CV value is expressed by the following equation.

CV value (%) = (ρ/Dn) × 100

ρ: standard deviation of the particle diameter of the substrate particle

Dn: the average value of the particle diameter of the substrate particles

Substrate particle 2:

In the substrate particle according to the present invention, the BET specific surface area is 300 m ² /g or more and less than 600 m ² /g. The base particles according to the present invention, the compression modulus is 100N / mm ² more than 3000N / mm ² or less at the time when compressed 10%.

In the substrate particle according to the present invention, since the above configuration is provided, it is possible to effectively suppress the occurrence of scratches on the adherend, and when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface, The adhesion to the conductive layer can be effectively increased, the connection resistance can be effectively reduced, and the connection reliability can be effectively increased.

In the substrate particle according to the present invention, the compressive elastic modulus (10% K value) when compressed by 10% is relatively high, and the hardness at the initial stage of compression is relatively high. For this reason, when electrically connecting between electrodes using conductive particles having a conductive layer formed on the surface of the substrate particles, the conductive layer or the surface oxide film of the electrode is sufficiently penetrated by the hardness of the substrate particles expressed at the initial stage of compression. I can make it. In addition, the substrate particles according to the present invention have an appropriate BET specific surface area, and in a step (mid-compression period) compressed to some extent, the hardness of the substrate particles is liable to be relatively lowered. For this reason, it can prevent that a flaw is formed in an electrode. In addition, since the substrate particle according to the present invention has an appropriate BET specific surface area, when forming the conductive layer on the surface of the substrate particle, the conductive layer enters the fine pores of the surface of the substrate particle, and the adhesion between the substrate particle and the conductive layer Can be effectively increased, and peeling of the conductive layer can be effectively prevented. As a result, the connection resistance between the electrodes can be effectively lowered, and the connection reliability between the electrodes can be effectively increased. For example, even if the connection structure electrically connected between electrodes by electroconductive particles is left for a long time under high temperature and high humidity conditions, the connection resistance is more difficult to increase and conduction failure is more difficult to occur.

In addition, when the substrate particle according to the present invention is used as a spacer for a liquid crystal display element, it is possible to effectively suppress the occurrence of scratches on the member for a liquid crystal display element, etc., and a sufficient gap control effect can be obtained. As a result, the display quality of the liquid crystal display element can be further improved.

In the substrate particle according to the present invention, the BET specific surface area is 300 m ² /g or more and less than 600 m ² /g. The BET specific surface area of the substrate particles is preferably 320 m ² /g or more, more preferably 340 m ² /g or more, preferably 580 m ² /g or less, more preferably 560 m ² /g or less. When the BET specific surface area is greater than or equal to the lower limit and less than or equal to the upper limit, the occurrence of scratches on the adherend can be more effectively suppressed. In addition, when the BET specific surface area is more than the lower limit and less than the upper limit, when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface, the adhesion with the conductive layer can be further effectively improved. In addition, the connection resistance can be further effectively lowered, and the connection reliability can be further effectively increased.

The BET specific surface area can be measured from the adsorption isotherm of nitrogen based on the BET method. Examples of the device for measuring the BET specific surface area include "NOVA4200e" manufactured by Cantachrom Instruments. In addition, the conditions at the time of measurement are preferably sample amount: 0.5 g, out gas type: nitrogen, out gas temperature: 28°C, out gas time: 3 hours, and bath temperature: 273 K (0° C.).

The density of the substrate particles is preferably 1 g/cm ³ or more, more preferably 1.1 g/cm ³ or more, preferably 1.4 g/cm ³ or less, more preferably 1.3 g/cm ³ or less. When the density is greater than or equal to the lower limit and less than or equal to the upper limit, it is possible to more effectively suppress the occurrence of scratches on the adherend. In addition, when the density is greater than or equal to the lower limit and less than the upper limit, connection resistance can be further effectively lowered and connection reliability when electrically connected between electrodes using conductive particles having a conductive layer formed on the surface thereof. Can be increased more effectively.

The density of the substrate particles can be measured using a specific gravity combination density measuring device. Examples of the specific gravity combined method density measuring device include "Accupyc 1330" manufactured by Shimadzu Corporation. In addition, the conditions at the time of measurement are preferably sample amount: 1 g and measurement temperature: 28°C.

The total pore volume of the substrate particles is preferably 0.01 cm ³ /g or more, more preferably 0.05 cm ³ /g or more, preferably ³ cm ³ /g or less, more preferably 1.5 cm ³ /g or less . When the total pore volume is more than the lower limit and less than or equal to the upper limit, it is possible to more effectively suppress the occurrence of scratches on the adherend. In addition, when the total pore volume is greater than or equal to the lower limit and less than or equal to the upper limit, when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface, the adhesion with the conductive layer can be improved more effectively. In addition, the connection resistance can be further effectively lowered, and the connection reliability can be further effectively increased.

The total pore volume can be measured from the adsorption isotherm of nitrogen in accordance with the BJH method. Examples of the device for measuring the total pore volume include "NOVA4200e" manufactured by Cantachrom Instruments.

The average pore diameter of the substrate particles is preferably 10 nm or less, more preferably 5 nm or less. The lower limit of the average pore diameter of the substrate particles is not particularly limited. The average pore diameter of the substrate particles may be 1 nm or more. When the average pore diameter is greater than or equal to the lower limit and less than or equal to the upper limit, the occurrence of scratches on the adherend can be more effectively suppressed. In addition, when the average pore diameter is greater than or equal to the lower limit and less than or equal to the upper limit, when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface, the adhesion with the conductive layer can be further effectively improved. In addition, the connection resistance can be further effectively lowered, and the connection reliability can be further effectively increased.

The average pore diameter can be measured from the adsorption isotherm of nitrogen in accordance with the BJH method. As the measuring device for the average pore diameter, "NOVA4200e" by Cantachrom Instruments Inc. is mentioned.

The substrate particles satisfying the preferred ranges of the BET specific surface area, the total pore volume, and the average pore diameter can be obtained, for example, by a method for producing a substrate particle comprising the following steps. A step of preparing a polymerizable monomer solution by mixing a polymerizable monomer and an organic solvent that does not react with the polymerizable monomer. A step of obtaining an emulsion by adding the polymerizable monomer solution and an anionic dispersion stabilizer to a polar solvent and emulsifying it. A step of dividing the emulsion into several times and absorbing the monomer into the seed particles to obtain a suspension containing the seed particles swollen with the monomer. A step of polymerizing the polymerizable monomer to obtain substrate particles. As said polymerizable monomer, a monofunctional monomer, a polyfunctional monomer, etc. are mentioned, for example. The organic solvent that does not react with the polymerizable monomer is not particularly limited as long as it is not compatible with a polar solvent such as water, which is a polymerization medium. Examples of the organic solvent include cyclohexane, toluene, xylene, ethyl acetate, butyl acetate, allyl acetate, propyl acetate, chloroform, methylcyclohexane, and methyl ethyl ketone. The amount of the organic solvent added is preferably 55 parts by weight to 100 parts by weight, more preferably 60 parts by weight to 95 parts by weight, based on 100 parts by weight of the polymerizable monomer component. If the amount of the organic solvent to be added is within the preferred range, the BET specific surface area can be controlled to a further suitable range, and fine pores are easily obtained inside the particles. In particular, in the case of a combination in which the SP value of the polymerizable monomer is 8.0 to 10.0 and the SP value of the organic solvent is 8.0 to 11.0, the BET specific surface area, the total pore volume, and the average pore diameter are more effectively suited to the range. Can be controlled by

The base particles according to the present invention, the compression modulus (10% K value) when compressed 10% was 100N / mm ² it is at least 3000N / mm ² or less. 10% K value of the base particles is preferably 120N / mm ^2, more preferably at least 140N / mm ^2, preferably 2800N / mm ^2, more preferably at most 2600N / mm ² or less. When the 10% K value is greater than or equal to the lower limit and less than or equal to the upper limit, it is possible to more effectively suppress the occurrence of scratches on the adherend. In addition, when the 10% K value is more than the lower limit and less than the upper limit, when electrically connecting between electrodes using conductive particles having a conductive layer formed on the surface, the connection resistance can be further effectively lowered, Moreover, connection reliability can be improved more effectively.

The compressive elastic modulus (30% K value) when the substrate particles are compressed by 30% is preferably 100 N/mm ² or more, more preferably 120 N/mm ² or more, preferably 2500 N/mm ² or less, more It is preferably 2300 N/mm ² or less. When the 30% K value is equal to or greater than the lower limit and equal to or less than the upper limit, it is possible to more effectively suppress the occurrence of scratches on the adherend. In addition, when the 30% K value is more than the lower limit and less than the upper limit, when electrically connecting between electrodes using conductive particles having a conductive layer formed on the surface, the connection resistance can be further effectively lowered, Moreover, connection reliability can be improved more effectively.

The compressive elastic modulus (10% K value and 30% K value) in the substrate particle can be measured as follows.

Using a micro-compression tester, one substrate particle is compressed under the conditions of 25°C, a compression speed of 0.3 mN/sec, and a maximum test load of 20 mN, on an end surface of a smooth indenter of a circumference (diameter 50 μm, made of diamond). The load value (N) and compression displacement (mm) at this time are measured. From the obtained measured values, the compressive elastic modulus (10% K value and 30% K value) can be determined by the following equation. As the micro-compression tester, for example, "Fischer Scope H-100" manufactured by Fischer is used. The compressive elastic modulus (10% K value and 30% K value) of the substrate particles is calculated by arithmetic average of the compressive elastic modulus (10% K value and 30% K value) of 50 randomly selected substrate particles. desirable.

10% K value or 30% K value (N/mm ² )=(3/2 ^1/2 )·F·S ^-3/2 ·R ^-1/2

F: Load value (N) when the base particles are compressed by 10% or 30%

S: Compression displacement (mm) when the substrate particles are compressed by 10% or 30%

R: radius of the substrate particle (mm)

The compressive modulus is a universal and quantitative representation of the hardness of the substrate particles. By using the compression modulus, the hardness of the substrate particles can be quantitatively and uniquely expressed.

The compression recovery rate of the substrate particles is preferably 5% or more, more preferably 7% or more, preferably 60% or less, and more preferably 50% or less. When the compression recovery rate of the substrate particles is equal to or greater than the lower limit and equal to or less than the upper limit, the occurrence of scratches on the adherend can be further effectively suppressed. In addition, when the compression recovery rate is greater than or equal to the lower limit and less than or equal to the upper limit, the connection resistance can be further effectively lowered when the electrode is electrically connected using conductive particles having a conductive layer formed on the surface thereof. Reliability can be improved even more effectively.

The compression recovery rate of the substrate particles can be measured as follows.

The substrate particles are sprayed on the sample stage. For one sprayed substrate particle, using a micro-compression tester, the substrate particle will be compressed by 30% at the end face of the smooth indenter of the circumference (diameter 50 μm, made of diamond), in the direction of the center of the substrate particle at 25°C. The load (reverse load value) is applied until. After that, unloading is performed up to the original load value (0.40mN). The load-compression displacement in the meantime is measured, and the compression recovery rate can be calculated|required from the following formula. In addition, the load speed is set to 0.33 mN/sec. As the micro-compression tester, for example, "Fischer Scope H-100" manufactured by Fischer is used.

Compression recovery rate (%)=[L2/L1]×100

L1: Compression displacement from the origin load value at the time of applying the load to the reverse load value

L2: Unloading displacement from the reverse load value when the load is released to the origin load value

The use of the substrate particles is not particularly limited. The substrate particles can be suitably used for various uses. The substrate particle is used as a spacer, or a conductive layer is formed on a surface thereof, and is used to obtain conductive particles having the conductive layer. In the electroconductive particle, the electroconductive layer is formed on the surface of the substrate particle. It is preferable that the said substrate particle is formed with a conductive layer on the surface, and is used to obtain the electroconductive particle which has the said electroconductive layer. It is preferable that the substrate particles are used as spacers. As a method of using the spacer, a spacer for a liquid crystal display device, a spacer for gap control, a spacer for stress relaxation, and the like can be mentioned. The gap control spacer may be used for gap control of a laminated chip to ensure standoff height and flatness, and gap control of an optical component to ensure smoothness of a glass surface and a thickness of an adhesive layer. The stress relaxation spacer can be used for stress relaxation of a sensor chip or the like and stress relaxation of a connection portion connecting two members to be connected.

The substrate particle is preferably used as a spacer for a liquid crystal display device, and is preferably used for a peripheral sealant for a liquid crystal display device. In the peripheral sealing agent for a liquid crystal display device, it is preferable that the substrate particle functions as a spacer. Since the substrate particles have good compressive deformation properties, when the substrate particles are used as spacers and disposed between substrates, or a conductive layer is formed on the surface and used as conductive particles to electrically connect the electrodes, a spacer or The conductive particles are efficiently disposed between substrates or between electrodes. In addition, since the substrate particles can suppress the occurrence of scratches on the members for liquid crystal display elements, etc., in the liquid crystal display element using the spacer for the liquid crystal display element and the connection structure using the conductive particles, poor connection and display It becomes difficult to occur.

Further, the substrate particles are suitably used also as inorganic fillers, additives for toners, shock absorbers or vibration absorbers. For example, as a substitute for rubber or spring, the above substrate particles can be used.

In the substrate particles according to the present invention, the coefficient of variation (CV value) of the particle diameter of the substrate particles is preferably 10% or less, more preferably 7% or less, and still more preferably 5% or less. When the CV value is less than or equal to the above upper limit, the substrate particles can be used more suitably for the use of conductive particles and spacers. In addition, the CV value can be adjusted by classification of the substrate particles.

The CV value is expressed by the following equation.

CV value (%) = (ρ/Dn) × 100

ρ: standard deviation of the particle diameter of the substrate particle

Dn: the average value of the particle diameter of the substrate particles

Substrate particle 3:

In the substrate particle according to the present invention, the BET specific surface area is 5 m ² /g or more and less than 300 m ² /g. The base particles according to the present invention, the 30% compression the compression modulus (30% K value) when the 100N / mm ² is at least 3000N / mm ² or less.

In the substrate particle according to the present invention, since the above configuration is provided, it is possible to effectively suppress the occurrence of scratches on the adherend, and when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface, Connection resistance can be effectively lowered, and connection reliability can be effectively increased.

The substrate particle according to the present invention has a suitable BET specific surface area. In addition, in the substrate particles according to the present invention, even in the compressed stage (mid-compression period) to some extent, the hardness is less likely to decrease, and the hardness of the substrate particles is relatively maintained. For this reason, when electrically connecting between electrodes using conductive particles having a conductive layer formed on the surface of the substrate particles, the conductive layer or the surface oxide film of the electrode is sufficiently penetrated by the hardness of the substrate particles expressed at the initial stage of compression. I can make it. Further, by the hardness of the substrate particles that are retained even in the middle of compression, an indentation, which is a concave portion formed by pressing the conductive particles, can be formed. For this reason, the connection resistance between electrodes can be effectively reduced, and the connection reliability between electrodes can be improved effectively. For example, even if the connection structure electrically connected between electrodes by electroconductive particles is left for a long time under high temperature and high humidity conditions, the connection resistance is more difficult to increase and conduction failure is more difficult to occur. In addition, the indentation is not included in a scratch that is unintentionally formed on the electrode.

In addition, when the substrate particle according to the present invention is used as a spacer for a liquid crystal display element, it is possible to effectively suppress the occurrence of scratches on the member for a liquid crystal display element, and a sufficient gap control effect. As a result, the display quality of the liquid crystal display element can be further improved.

In the substrate particle according to the present invention, the BET specific surface area is 5 m ² /g or more and less than 300 m ² /g. The BET specific surface area of the substrate particles is preferably 8 m ² /g or more, more preferably 12 m ² /g or more, preferably 290 m ² /g or less, more preferably 280 m ² /g or less. When the BET specific surface area is greater than or equal to the lower limit and less than or equal to the upper limit, the occurrence of scratches on the adherend can be more effectively suppressed. In addition, when the BET specific surface area is greater than or equal to the lower limit and less than or equal to the upper limit, when electrically connecting between electrodes using conductive particles having a conductive layer formed on the surface, the connection resistance can be further effectively lowered, and further Connection reliability can be improved more effectively.

The BET specific surface area can be measured from the adsorption isotherm of nitrogen based on the BET method. Examples of the device for measuring the BET specific surface area include "NOVA4200e" manufactured by Cantachrom Instruments. In addition, the conditions at the time of measurement are preferably sample amount: 0.5 g, out gas type: nitrogen, out gas temperature: 28°C, out gas time: 3 hours, and bath temperature: 273 K (0° C.).

The density of the substrate particles is preferably 1 g/cm ³ or more, more preferably 1.1 g/cm ³ or more, preferably 1.4 g/cm ³ or less, more preferably 1.3 g/cm ³ or less. When the density is greater than or equal to the lower limit and less than or equal to the upper limit, it is possible to more effectively suppress the occurrence of scratches on the adherend. In addition, when the density is greater than or equal to the lower limit and less than the upper limit, connection resistance can be further effectively lowered and connection reliability when electrically connected between electrodes using conductive particles having a conductive layer formed on the surface thereof. Can be increased more effectively.

The density of the substrate particles can be measured using a specific gravity combination density measuring device. Examples of the specific gravity combined method density measuring device include "Accupyc 1330" manufactured by Shimadzu Corporation. In addition, the conditions at the time of measurement are preferably sample amount: 1 g and measurement temperature: 28°C.

The total pore volume of the substrate particles is preferably 0.01 cm ³ /g or more, more preferably 0.05 cm ³ /g or more, preferably ³ cm ³ /g or less, more preferably 1.5 cm ³ /g or less . When the total pore volume is more than the lower limit and less than or equal to the upper limit, it is possible to more effectively suppress the occurrence of scratches on the adherend. In addition, when the total pore volume is more than the lower limit and less than the upper limit, when electrically connecting between electrodes using conductive particles having a conductive layer formed on the surface, the connection resistance can be further effectively lowered, and further Connection reliability can be improved more effectively.

The total pore volume can be measured from the adsorption isotherm of nitrogen in accordance with the BJH method. Examples of the device for measuring the total pore volume include "NOVA4200e" manufactured by Cantachrom Instruments.

The average pore diameter of the substrate particles is preferably 10 nm or less, more preferably 5 nm or less. The lower limit of the average pore diameter of the substrate particles is not particularly limited. The average pore diameter of the substrate particles may be 1 nm or more. When the average pore diameter is greater than or equal to the lower limit and less than or equal to the upper limit, the occurrence of scratches on the adherend can be more effectively suppressed. In addition, when the average pore diameter is more than the lower limit and less than the upper limit, when electrically connecting between electrodes using conductive particles having a conductive layer formed on the surface, the connection resistance can be further effectively lowered, and further Connection reliability can be improved more effectively.

The average pore diameter can be measured from the adsorption isotherm of nitrogen in accordance with the BJH method. As the measuring device for the average pore diameter, "NOVA4200e" by Cantachrom Instruments Inc. is mentioned.

The substrate particles satisfying the preferred ranges of the BET specific surface area, the total pore volume, and the average pore diameter can be obtained, for example, by a method for producing a substrate particle comprising the following steps. A step of preparing a polymerizable monomer solution by mixing a polymerizable monomer and an organic solvent that does not react with the polymerizable monomer. A step of obtaining an emulsion by adding the polymerizable monomer solution and an anionic dispersion stabilizer to a polar solvent and emulsifying it. A step of dividing the emulsion into several times and absorbing the monomer into the seed particles to obtain a suspension containing the seed particles swollen with the monomer. A step of polymerizing the polymerizable monomer to obtain substrate particles. As said polymerizable monomer, a monofunctional monomer, a polyfunctional monomer, etc. are mentioned, for example. The organic solvent that does not react with the polymerizable monomer is not particularly limited as long as it is not compatible with a polar solvent such as water, which is a polymerization medium. Examples of the organic solvent include cyclohexane, toluene, xylene, ethyl acetate, butyl acetate, allyl acetate, propyl acetate, chloroform, methylcyclohexane, and methyl ethyl ketone. The amount of the organic solvent added is preferably 1 to 50 parts by weight, and more preferably 5 to 45 parts by weight, based on 100 parts by weight of the polymerizable monomer component. If the amount of the organic solvent to be added is within the preferred range, the BET specific surface area can be controlled to a further suitable range, and fine pores are easily obtained inside the particles. In particular, in the case of a combination in which the SP value of the polymerizable monomer is 8.0 to 10.0 and the SP value of the organic solvent is 8.0 to 11.0, the BET specific surface area, the total pore volume, and the average pore diameter are more effectively suited to the range. Can be controlled by

The base particles according to the present invention, the 30% compression the compression modulus (30% K value) when the 100N / mm ² is at least 3000N / mm ² or less. 30% K value of the base particles is preferably 150N / mm ^2, more preferably at least 200N / mm ^2, preferably 2800N / mm ^2, more preferably at most 2500N / mm ² or less. When the 30% K value is equal to or greater than the lower limit and equal to or less than the upper limit, it is possible to more effectively suppress the occurrence of scratches on the adherend. In addition, when the 30% K value is more than the lower limit and less than the upper limit, when electrically connecting between electrodes using conductive particles having a conductive layer formed on the surface, the connection resistance can be further effectively lowered, Moreover, connection reliability can be improved more effectively.

Compression modulus (10% K value) when compressing the base material particles of 10% is preferably 100N / mm ^2, more preferably at least 150N / mm ^2, preferably 3500N / mm ² or less, more preferably It is less than 3000N/mm ² . When the 10% K value is greater than or equal to the lower limit and less than or equal to the upper limit, it is possible to more effectively suppress the occurrence of scratches on the adherend. In addition, when the 10% K value is more than the lower limit and less than the upper limit, when electrically connecting between electrodes using conductive particles having a conductive layer formed on the surface, the connection resistance can be further effectively lowered, Moreover, connection reliability can be improved more effectively.

The compressive elastic modulus (10% K value and 30% K value) in the substrate particle can be measured as follows.

Using a micro-compression tester, one substrate particle is compressed under the conditions of 25°C, a compression speed of 0.3 mN/sec, and a maximum test load of 20 mN, on an end surface of a smooth indenter of a circumference (diameter 50 μm, made of diamond). The load value (N) and compression displacement (mm) at this time are measured. From the obtained measured values, the compressive elastic modulus (10% K value and 30% K value) can be determined by the following equation. As the micro-compression tester, for example, "Fischer Scope H-100" manufactured by Fischer is used. The compressive elastic modulus (10% K value and 30% K value) of the substrate particles is calculated by arithmetic average of the compressive elastic modulus (10% K value and 30% K value) of 50 randomly selected substrate particles. desirable.

10% K value or 30% K value (N/mm ² )=(3/2 ^1/2 )·F·S ^-3/2 ·R ^-1/2

F: Load value (N) when the base particles are compressed by 10% or 30%

S: Compression displacement (mm) when the substrate particles are compressed by 10% or 30%

R: radius of the substrate particle (mm)

The compressive modulus is a universal and quantitative representation of the hardness of the substrate particles. By using the compression modulus, the hardness of the substrate particles can be quantitatively and uniquely expressed.

The compression recovery rate of the substrate particles is preferably 5% or more, more preferably 7% or more, preferably 60% or less, and more preferably 50% or less. When the compression recovery rate of the substrate particles is equal to or greater than the lower limit and equal to or less than the upper limit, the occurrence of scratches on the adherend can be further effectively suppressed. In addition, when the compression recovery rate is greater than or equal to the lower limit and less than or equal to the upper limit, the connection resistance can be further effectively lowered when the electrode is electrically connected using conductive particles having a conductive layer formed on the surface thereof. Reliability can be improved even more effectively.

The compression recovery rate of the substrate particles can be measured as follows.

The substrate particles are sprayed on the sample stage. For one sprayed substrate particle, using a micro-compression tester, the substrate particle will be compressed by 30% at the end face of the smooth indenter of the circumference (diameter 50 μm, made of diamond), in the direction of the center of the substrate particle at 25°C. The load (reverse load value) is applied until. After that, unloading is performed up to the original load value (0.40mN). The load-compression displacement in the meantime is measured, and the compression recovery rate can be calculated|required from the following formula. In addition, the load speed is set to 0.33 mN/sec. As the micro-compression tester, for example, "Fischer Scope H-100" manufactured by Fischer is used.

Compression recovery rate (%)=[L2/L1]×100

L1: Compression displacement from the origin load value at the time of applying the load to the reverse load value

L2: Unloading displacement from the reverse load value when the load is released to the origin load value

The use of the substrate particles is not particularly limited. The substrate particles can be suitably used for various uses. The substrate particle is used as a spacer, or a conductive layer is formed on a surface thereof, and is used to obtain conductive particles having the conductive layer. In the electroconductive particle, the electroconductive layer is formed on the surface of the substrate particle. It is preferable that the said substrate particle is formed with a conductive layer on the surface, and is used to obtain the electroconductive particle which has the said electroconductive layer. It is preferable that the substrate particles are used as spacers. As a method of using the spacer, a spacer for a liquid crystal display device, a spacer for gap control, a spacer for stress relaxation, and the like can be mentioned. The gap control spacer may be used for gap control of a laminated chip to ensure standoff height and flatness, and gap control of an optical component to ensure smoothness of a glass surface and a thickness of an adhesive layer. The stress relaxation spacer can be used for stress relaxation of a sensor chip or the like and stress relaxation of a connection portion connecting two members to be connected.

The substrate particle is preferably used as a spacer for a liquid crystal display device, and is preferably used for a peripheral sealant for a liquid crystal display device. In the peripheral sealing agent for a liquid crystal display device, it is preferable that the substrate particle functions as a spacer. Since the substrate particles have good compressive deformation properties, when the substrate particles are used as spacers and disposed between substrates, or a conductive layer is formed on the surface and used as conductive particles to electrically connect the electrodes, a spacer or The conductive particles are efficiently disposed between substrates or between electrodes. In addition, since the substrate particles can suppress the occurrence of scratches on the members for liquid crystal display elements, etc., in the liquid crystal display element using the spacer for the liquid crystal display element and the connection structure using the conductive particles, poor connection and display It becomes difficult to occur.

Further, the substrate particles are suitably used also as inorganic fillers, additives for toners, shock absorbers or vibration absorbers. For example, as a substitute for rubber or spring, the above substrate particles can be used.

In the substrate particles according to the present invention, the coefficient of variation (CV value) of the particle diameter of the substrate particles is preferably 10% or less, more preferably 7% or less, and still more preferably 5% or less. When the CV value is less than or equal to the above upper limit, the substrate particles can be used more suitably for the use of conductive particles and spacers. In addition, the CV value can be adjusted by classification of the substrate particles.

The CV value is expressed by the following equation.

CV value (%) = (ρ/Dn) × 100

ρ: standard deviation of the particle diameter of the substrate particle

Dn: the average value of the particle diameter of the substrate particles

Substrate particle 4:

In the substrate particle according to the present invention, the BET specific surface area is 600 m ² /g or more. In the substrate particles according to the present invention, the compressive elastic modulus when compressed by 10% is 1200 N/mm ² or less. In the substrate particles according to the present invention, the compressive elastic modulus when compressed by 30% is 1200 N/mm ² or less. In the substrate particle according to the present invention, the compression recovery rate is 5% or more.

In the substrate particle according to the present invention, since the above configuration is provided, it is possible to effectively suppress the occurrence of scratches on the adherend, and when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface, The adhesion to the conductive layer can be effectively increased, the impact resistance can be effectively increased, and the connection resistance can be effectively reduced.

In the substrate particle according to the present invention, the value of the BET specific surface area is relatively large, and it is easily deformed at a relatively low pressure and temperature. For this reason, in the case of electrically connecting between electrodes using conductive particles having a conductive layer formed on the surface of the substrate particles, even if the pressure or temperature during thermocompression bonding is relatively low, the conductive particles can be sufficiently brought into contact with the electrodes. In addition, it is possible to prevent the formation of scratches on the electrode. In addition, in the substrate particle according to the present invention, since the value of the BET specific surface area is relatively large, when forming the conductive layer on the surface of the substrate particle, the conductive layer enters the fine pores of the surface of the substrate particle, and the substrate particle and the conductive layer The adhesiveness of can be effectively improved, and peeling of the conductive layer can be effectively prevented. In addition, in the case of forming a connection portion that electrically connects the electrodes using conductive particles having a conductive layer formed on the surface of the substrate particle according to the present invention, even if an impact by dropping or the like is applied to the connection portion, the conductive layer Peeling is effectively prevented, and connection resistance between electrodes can be effectively lowered. In the electroconductive particle using the substrate particle according to the present invention, impact resistance can be effectively improved. Further, in the substrate particle according to the present invention, the compression recovery rate is relatively large and has good recovery properties. For this reason, even though the value of the BET specific surface area is relatively large, the substrate particles do not buckling, and are less likely to be destroyed, and the conductive particles can be sufficiently brought into contact with the electrode. As a result, the connection resistance between the electrodes can be effectively lowered, and the connection reliability between the electrodes can be effectively increased.

In addition, when the substrate particle according to the present invention is used as a spacer for a liquid crystal display element, it is possible to effectively suppress the occurrence of scratches on the member for a liquid crystal display element. Further, the liquid crystal display element member or the like can be sufficiently contacted, and a sufficient gap control effect can be obtained. As a result, the display quality of the liquid crystal display element can be further improved.

In the substrate particle according to the present invention, the BET specific surface area is 600 m ² /g or more. The BET specific surface area of the substrate particles is preferably 605 m ² /g or more, more preferably 610 m ² /g or more, preferably 1200 m ² /g or less, more preferably 1000 m ² /g or less. When the BET specific surface area is greater than or equal to the lower limit and less than or equal to the upper limit, the occurrence of scratches on the adherend can be more effectively suppressed. In addition, when the BET specific surface area is more than the lower limit and less than the upper limit, when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface, the adhesion with the conductive layer can be further effectively improved. In addition, the impact resistance can be increased more effectively, and the connection resistance can be further effectively lowered.

The BET specific surface area can be measured from the adsorption isotherm of nitrogen based on the BET method. Examples of the device for measuring the BET specific surface area include "NOVA4200e" manufactured by Cantachrom Instruments. In addition, the conditions at the time of measurement are preferably sample amount: 0.5 g, out gas type: nitrogen, out gas temperature: 28°C, out gas time: 3 hours, and bath temperature: 273 K (0° C.).

The density of the substrate particles is preferably 1 g/cm ³ or more, more preferably 1.1 g/cm ³ or more, preferably 1.4 g/cm ³ or less, more preferably 1.3 g/cm ³ or less. When the density is greater than or equal to the lower limit and less than or equal to the upper limit, it is possible to more effectively suppress the occurrence of scratches on the adherend. In addition, when the density is greater than or equal to the lower limit and less than the upper limit, connection resistance can be further effectively lowered and connection reliability when electrically connected between electrodes using conductive particles having a conductive layer formed on the surface thereof. Can be increased more effectively.

The density of the substrate particles can be measured using a specific gravity combination density measuring device. Examples of the specific gravity combined method density measuring device include "Accupyc 1330" manufactured by Shimadzu Corporation. In addition, the conditions at the time of measurement are preferably sample amount: 1 g and measurement temperature: 28°C.

The total pore volume of the substrate particles is preferably 0.01 cm ³ /g or more, more preferably 0.05 cm ³ /g or more, preferably ³ cm ³ /g or less, more preferably 1.5 cm ³ /g or less . When the total pore volume is more than the lower limit and less than or equal to the upper limit, it is possible to more effectively suppress the occurrence of scratches on the adherend. In addition, when the total pore volume is greater than or equal to the lower limit and less than or equal to the upper limit, when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface, the adhesion with the conductive layer can be improved more effectively. In addition, the impact resistance can be increased more effectively, and the connection resistance can be further effectively lowered.

The total pore volume can be measured from the adsorption isotherm of nitrogen in accordance with the BJH method. Examples of the device for measuring the total pore volume include "NOVA4200e" manufactured by Cantachrom Instruments.

The average pore diameter of the substrate particles is preferably 10 nm or less, more preferably 5 nm or less. The lower limit of the average pore diameter of the substrate particles is not particularly limited. The average pore diameter of the substrate particles may be 1 nm or more. When the average pore diameter is greater than or equal to the lower limit and less than or equal to the upper limit, the occurrence of scratches on the adherend can be more effectively suppressed. In addition, when the average pore diameter is greater than or equal to the lower limit and less than or equal to the upper limit, when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface, the adhesion with the conductive layer can be further effectively improved. In addition, the impact resistance can be increased more effectively, and the connection resistance can be further effectively lowered.

The average pore diameter can be measured from the adsorption isotherm of nitrogen in accordance with the BJH method. As the measuring device for the average pore diameter, "NOVA4200e" by Cantachrom Instruments Inc. is mentioned.

The substrate particles satisfying the preferred ranges of the BET specific surface area, the total pore volume, and the average pore diameter can be obtained, for example, by a method for producing a substrate particle comprising the following steps. A step of preparing a polymerizable monomer solution by mixing a polymerizable monomer and an organic solvent that does not react with the polymerizable monomer. A step of obtaining an emulsion by adding the polymerizable monomer solution and an anionic dispersion stabilizer to a polar solvent and emulsifying it. A step of dividing the emulsion into several times and absorbing the monomer into the seed particles to obtain a suspension containing the seed particles swollen with the monomer. A step of polymerizing the polymerizable monomer to obtain substrate particles. As said polymerizable monomer, a monofunctional monomer, a polyfunctional monomer, etc. are mentioned, for example. The organic solvent that does not react with the polymerizable monomer is not particularly limited as long as it is not compatible with a polar solvent such as water, which is a polymerization medium. Examples of the organic solvent include cyclohexane, toluene, xylene, ethyl acetate, butyl acetate, allyl acetate, propyl acetate, chloroform, methylcyclohexane, and methyl ethyl ketone. The amount of the organic solvent added is preferably 105 parts by weight to 215 parts by weight, more preferably 110 parts by weight to 210 parts by weight, based on 100 parts by weight of the polymerizable monomer component. If the amount of the organic solvent to be added is within the preferred range, the BET specific surface area can be controlled to a further suitable range, and fine pores are easily obtained inside the particles. In particular, in the case of a combination in which the SP value of the polymerizable monomer is 8.0 to 10.0 and the SP value of the organic solvent is 8.0 to 11.0, the BET specific surface area, the total pore volume, and the average pore diameter are more effectively suited to the range. Can be controlled by

In the substrate particles according to the present invention, the compressive elastic modulus when compressed by 10% is 1200 N/mm ² or less. 10% K value of the base particles is preferably from 5N / mm ^2, more preferably at least 10N / mm ^2, preferably 1100N / mm ^2, more preferably at most 1000N / mm ² or less. When the 10% K value is greater than or equal to the lower limit and less than or equal to the upper limit, it is possible to more effectively suppress the occurrence of scratches on the adherend. In addition, when the 10% K value is more than the lower limit and less than the upper limit, when electrically connecting between electrodes using conductive particles having a conductive layer formed on the surface, the connection resistance can be further effectively lowered, Moreover, connection reliability can be improved more effectively.

In the substrate particles according to the present invention, the compressive elastic modulus when compressed by 30% is 1200 N/mm ² or less. 30% K value of the base particles is preferably from 5N / mm ^2, more preferably at least 10N / mm ^2, preferably 1100N / mm ^2, more preferably at most 1000N / mm ² or less. When the 30% K value is equal to or greater than the lower limit and equal to or less than the upper limit, it is possible to more effectively suppress the occurrence of scratches on the adherend. In addition, when the 30% K value is more than the lower limit and less than the upper limit, when electrically connecting between electrodes using conductive particles having a conductive layer formed on the surface, the connection resistance can be further effectively lowered, Moreover, connection reliability can be improved more effectively.

The compressive elastic modulus (10% K value and 30% K value) in the substrate particle can be measured as follows.

Using a micro-compression tester, one substrate particle is compressed under the conditions of 25°C, a compression speed of 0.3 mN/sec, and a maximum test load of 20 mN, on an end surface of a smooth indenter of a circumference (diameter 50 μm, made of diamond). The load value (N) and compression displacement (mm) at this time are measured. From the obtained measured values, the compressive elastic modulus (10% K value and 30% K value) can be determined by the following equation. As the micro-compression tester, for example, "Fischer Scope H-100" manufactured by Fischer is used. The compressive elastic modulus (10% K value and 30% K value) of the substrate particles is calculated by arithmetic average of the compressive elastic modulus (10% K value and 30% K value) of 50 randomly selected substrate particles. desirable.

10% K value or 30% K value (N/mm ² )=(3/2 ^1/2 )·F·S ^-3/2 ·R ^-1/2

F: Load value (N) when the base particles are compressed by 10% or 30%

S: Compression displacement (mm) when the substrate particles are compressed by 10% or 30%

R: radius of the substrate particle (mm)

The compressive modulus is a universal and quantitative representation of the hardness of the substrate particles. By using the compression modulus, the hardness of the substrate particles can be quantitatively and uniquely expressed.

In the substrate particle according to the present invention, the compression recovery rate is 5% or more. The compression recovery rate of the substrate particles is preferably 10% or more, more preferably 15% or more, preferably 60% or less, and more preferably 50% or less. When the compression recovery rate of the substrate particles is equal to or greater than the lower limit and equal to or less than the upper limit, the occurrence of scratches on the adherend can be further effectively suppressed. In addition, when the 10% K value is more than the lower limit and less than the upper limit, when electrically connecting between electrodes using conductive particles having a conductive layer formed on the surface, the connection resistance can be further effectively lowered, Moreover, connection reliability can be improved more effectively.

The compression recovery rate of the substrate particles can be measured as follows.

The substrate particles are sprayed on the sample stage. For one sprayed substrate particle, using a micro-compression tester, the substrate particle will be compressed by 30% at the end face of the smooth indenter of the circumference (diameter 50 μm, made of diamond), in the direction of the center of the substrate particle at 25°C. The load (reverse load value) is applied until. After that, unloading is performed up to the original load value (0.40mN). The load-compression displacement in the meantime is measured, and the compression recovery rate can be calculated|required from the following formula. In addition, the load speed is set to 0.33 mN/sec. As the micro-compression tester, for example, "Fischer Scope H-100" manufactured by Fischer is used.

Compression recovery rate (%)=[L2/L1]×100

L1: Compression displacement from the origin load value at the time of applying the load to the reverse load value

L2: Unloading displacement from the reverse load value when the load is released to the origin load value

The use of the substrate particles is not particularly limited. The substrate particles can be suitably used for various uses. The substrate particle is used as a spacer, or a conductive layer is formed on a surface thereof, and is used to obtain conductive particles having the conductive layer. In the electroconductive particle, the electroconductive layer is formed on the surface of the substrate particle. It is preferable that the said substrate particle is formed with a conductive layer on the surface, and is used to obtain the electroconductive particle which has the said electroconductive layer. It is preferable that the substrate particles are used as spacers. As a method of using the spacer, a spacer for a liquid crystal display device, a spacer for gap control, a spacer for stress relaxation, and the like can be mentioned. The gap control spacer may be used for gap control of a laminated chip to ensure standoff height and flatness, and gap control of an optical component to ensure smoothness of a glass surface and a thickness of an adhesive layer. The stress relaxation spacer can be used for stress relaxation of a sensor chip or the like and stress relaxation of a connection portion connecting two members to be connected.

The substrate particle is preferably used as a spacer for a liquid crystal display device, and is preferably used for a peripheral sealant for a liquid crystal display device. In the peripheral sealing agent for a liquid crystal display device, it is preferable that the substrate particle functions as a spacer. Since the substrate particles have good compressive deformation properties and good compression fracture properties, the substrate particles are used as spacers to be disposed between substrates, or a conductive layer is formed on the surface and used as conductive particles to electrically connect the electrodes. In the case, spacers or conductive particles are efficiently disposed between substrates or between electrodes. In addition, since the substrate particles can suppress the occurrence of scratches on the members for liquid crystal display elements, etc., in the liquid crystal display element using the spacer for the liquid crystal display element and the connection structure using the conductive particles, poor connection and display It becomes difficult to occur.

Further, the substrate particles are suitably used also as inorganic fillers, additives for toners, shock absorbers or vibration absorbers. For example, as a substitute for rubber or spring, the above substrate particles can be used.

In the substrate particles according to the present invention, the coefficient of variation (CV value) of the particle diameter of the substrate particles is preferably 10% or less, more preferably 7% or less, and still more preferably 5% or less. When the CV value is less than or equal to the above upper limit, the substrate particles can be used more suitably for the use of conductive particles and spacers. In addition, the CV value can be adjusted by classification of the substrate particles.

The CV value is expressed by the following equation.

CV value (%) = (ρ/Dn) × 100

ρ: standard deviation of the particle diameter of the substrate particle

Dn: the average value of the particle diameter of the substrate particles

As a manufacturing method satisfying the preferable ranges of the 10% K value, 30% K value, and compression recovery rate of the above-described substrate particles (substrate particles 1 to 4), the above-described substrate particles (substrate particles 1 to 4) A method for producing a substrate particle having the following steps similar to the case where the BET specific surface area, the total pore volume, and the preferable range of the average pore diameter are satisfied is mentioned. A step of preparing a polymerizable monomer solution by mixing a polymerizable monomer and an organic solvent that does not react with the polymerizable monomer. A step of obtaining an emulsion by adding the polymerizable monomer solution and an anionic dispersion stabilizer to a polar solvent and emulsifying it. A step of dividing the emulsion into several times and absorbing the monomer into the seed particles to obtain a suspension containing the seed particles swollen with the monomer. A step of polymerizing the polymerizable monomer to obtain substrate particles. As said polymerizable monomer, a monofunctional monomer, a polyfunctional monomer, etc. are mentioned, for example. The organic solvent that does not react with the polymerizable monomer is not particularly limited as long as it is not compatible with a polar solvent such as water, which is a polymerization medium. Examples of the organic solvent include cyclohexane, toluene, xylene, ethyl acetate, butyl acetate, allyl acetate, propyl acetate, chloroform, methylcyclohexane, and methyl ethyl ketone. The amount of the organic solvent added is preferably 1 to 215 parts by weight, more preferably 5 to 210 parts by weight, based on 100 parts by weight of the polymerizable monomer component. In particular, in the case of a combination in which the SP value of the polymerizable monomer is 8.0 to 10.0 and the SP value of the organic solvent is 8.0 to 11.0, the 10% K value, the 30% K value, and the compression recovery rate are more effectively suited. Can be controlled by range.

Hereinafter, other details of the above-described substrate particles (substrate particles 1 to 4) will be described. In addition, in this specification, "(meth)acrylate" means one or both of "acrylate" and "methacrylate", and "(meth)acryl" is one of "acrylic" and "methacryl" Or mean both.

(Other details of the above-described substrate particles (substrate particles 1 to 4))

The material of the substrate particle is not particularly limited. The material of the substrate particle may be an organic material or an inorganic material.

Examples of the organic material include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; Acrylic resins such as polymethyl methacrylate and polymethyl acrylate; Polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester Resin, saturated polyester resin, polyethylene terephthalate, polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamideimide, polyetheretherketone, polyethersulfone, divinylbenzene polymer, and divinylbenzene copolymer, etc. Can be mentioned. Examples of the divinylbenzene copolymer and the like include divinylbenzene-styrene copolymer and divinylbenzene-(meth)acrylic acid ester copolymer. Since the compression properties of the substrate particles can be easily controlled within a suitable range, the material of the substrate particles is preferably a polymer obtained by polymerizing one or two or more polymerizable monomers having an ethylenically unsaturated group.

When the substrate particle is obtained by polymerizing a polymerizable monomer having an ethylenically unsaturated group, examples of the polymerizable monomer having an ethylenically unsaturated group include a non-crosslinkable monomer and a crosslinkable monomer.

As the non-crosslinkable monomer, examples of the vinyl compound include styrene monomers such as styrene, α-methylstyrene, and chlorostyrene; Vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether; Acid vinyl ester compounds such as vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stearate; Halogen-containing monomers such as vinyl chloride and vinyl fluoride; As (meth)acrylic compounds, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth) Alkyl (meth)acrylate compounds such as acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate; Oxygen atom-containing (meth)acrylate compounds such as 2-hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, polyoxyethylene (meth)acrylate, and glycidyl (meth)acrylate; Nitrile-containing monomers such as (meth)acrylonitrile; Halogen-containing (meth)acrylate compounds such as trifluoromethyl (meth)acrylate and pentafluoroethyl (meth)acrylate; Examples of the α-olefin compound include olefin compounds such as diisobutylene, isobutylene, linealene, ethylene, and propylene; As a conjugated diene compound, isoprene, butadiene, etc. are mentioned.

Examples of the crosslinkable monomer include vinyl monomers such as divinylbenzene, 1,4-divinyloxybutane, and divinyl sulfone as vinyl compounds; As (meth)acrylic compounds, tetramethylolmethane tetra(meth)acrylate, polytetramethylene glycol diacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethanedi(meth)acrylate, trimethylol Propane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerol tri(meth)acrylate, glycerol di(meth)acrylate, polyethylene glycol di( Polyfunctional (meth)acrylate compounds such as meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and 1,4-butanediol di(meth)acrylate; As an allyl compound, triallyl (iso) cyanurate, triallyl trimellitate, diallyl phthalate, diallyl acrylamide, diallyl ether; As a silane compound, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isopropyltrimethoxysilane, isobutyltrimethoxysilane Silane, cyclohexyl trimethoxysilane, n-hexyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di Silane alkoxy such as isopropyldimethoxysilane, trimethoxysilylstyrene, γ-(meth)acryloxypropyltrimethoxysilane, 1,3-divinyltetramethyldisiloxane, methylphenyldimethoxysilane, and diphenyldimethoxysilane De compounds; Vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, dimethoxyethylvinylsilane, diethoxymethylvinylsilane, diethoxyethylvinylsilane, ethylmethyldivinylsilane, methylvinyldimethoxysilane, ethyl Vinyldimethoxysilane, methylvinyldiethoxysilane, ethylvinyldiethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Polymerizable double bond-containing silane alkoxides such as methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; Cyclic siloxanes such as decamethylcyclopentasiloxane; Modified (reactive) silicone oils such as one-end modified silicone oil, both terminal silicone oil, and branched silicone oil; Carboxyl group-containing monomers, such as (meth)acrylic acid, maleic acid, and maleic anhydride, etc. are mentioned.

The substrate particle can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group. The polymerization method is not particularly limited, and known methods such as radical polymerization, ionic polymerization, polycondensation (condensation polymerization, condensation polymerization), addition condensation, living polymerization and living radical polymerization can be mentioned. In addition, as another polymerization method, suspension polymerization is mentioned in the presence of a radical polymerization initiator.

Examples of the inorganic material include silica, alumina, barium titanate, zirconia, carbon black, silicate glass, borosilicate glass, lead glass, soda lime glass, and alumina silicate glass.

The substrate particle may be formed of only the organic material, may be formed of only the inorganic material, or may be formed of both the organic material and the inorganic material. It is preferable that the substrate particles are formed of only an organic material. In this case, the compressive properties of the substrate particles can be easily controlled within a suitable range, and thus they can be used more suitably for the use of conductive particles and spacers.

The substrate particle may be an organic-inorganic hybrid particle. The said substrate particle may be a core shell particle. When the substrate particle is an organic-inorganic hybrid particle, examples of the inorganic material that is a material of the substrate particle include silica, alumina, barium titanate, zirconia, and carbon black. It is preferable that the inorganic material is not a metal. The substrate particles formed of the silica are not particularly limited, but substrate particles obtained by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups to form crosslinked polymer particles, followed by firing as necessary. have. Examples of the organic-inorganic hybrid particles include organic-inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.

The organic-inorganic hybrid particle is preferably a core-shell type organic-inorganic hybrid particle having a core and a shell disposed on the surface of the core. It is preferred that the core is an organic core. It is preferred that the shell is an inorganic shell. The substrate particle is preferably an organic-inorganic hybrid particle having an organic core and an inorganic shell disposed on the surface of the organic core.

Examples of the material for the organic core include the organic materials described above.

As the material of the inorganic shell, an inorganic material exemplified as the material of the substrate particle described above can be mentioned. It is preferable that the material of the inorganic shell is silica. It is preferable that the said inorganic shell is formed on the surface of the said core by making a metal alkoxide into a shell-like material by a sol-gel method, and then firing the shell-like material. It is preferable that the metal alkoxide is a silane alkoxide. It is preferable that the inorganic shell is formed of a silane alkoxide.

The average particle diameter of the substrate particles is preferably 0.1 μm or more, more preferably 1 μm or more, preferably 100 μm or less, and more preferably 80 μm or less. When the average particle diameter of the substrate particles is greater than or equal to the lower limit and less than or equal to the upper limit, the substrate particles can be used more suitably for use as conductive particles and spacers. From the viewpoint of using as a spacer, the average particle diameter of the substrate particles is preferably 1 µm or more and 80 µm or less. From the viewpoint of use as conductive particles, the average particle diameter of the substrate particles is preferably 1 µm or more and 20 µm or less.

The particle diameter of the substrate particle means the diameter when the substrate particle is in a spherical shape, and when the substrate particle has a shape other than a spherical shape, it means the diameter assuming that the particle size is a spherical sphere equivalent to the volume. The average particle diameter of the substrate particles is preferably a number average particle diameter. The average particle diameter of the substrate particles can be measured by an arbitrary particle size distribution measuring device. For example, the measurement can be performed using a particle size distribution measuring apparatus using principles such as laser light scattering, change in electric resistance value, and image analysis after imaging. More specifically, as a method of measuring the average particle diameter of the substrate particles, a particle size distribution measuring device (``Multisizer4'' manufactured by Beckman Coulter) is used to measure the particle diameter of about 100000 substrate particles, and the average particle diameter is measured. There is a method.

The aspect ratio of the substrate particles is preferably 2 or less, more preferably 1.5 or less, and still more preferably 1.2 or less. The aspect ratio represents a long diameter/short diameter. The aspect ratio is obtained by observing 10 arbitrary substrate particles with an electron microscope or an optical microscope, and calculating the average value of the long/short diameters of each substrate particle by denoting the maximum and minimum diameters as long and short diameters, respectively. It is desirable to seek.

(Conductive particles)

The electroconductive particle includes the above-described substrate particles (substrate particles 1 to 4) and a conductive layer disposed on the surface of the substrate particles.

1 is a cross-sectional view showing conductive particles according to a first embodiment of the present invention.

The electroconductive particle 1 shown in FIG. 1 has a substrate particle 11 and a conductive layer 2 disposed on the surface of the substrate particle 11. The conductive layer 2 covers the surface of the substrate particle 11. The electroconductive particle 1 is a coated particle in which the surface of the substrate particle 11 is covered with the electroconductive layer 2. The substrate particle 11 is preferably any of the substrate particles 1 to 4 described above.

2 is a cross-sectional view showing conductive particles according to a second embodiment of the present invention.

The electroconductive particle 21 shown in FIG. 2 has the base material particle 11 and the electroconductive layer 22 arrange|positioned on the surface of the base material particle 11. In the electroconductive particle 21 shown in FIG. 2, only the electroconductive layer 22 differs from the electroconductive particle 1 shown in FIG. The conductive layer 22 has a first conductive layer 22A as an inner layer and a second conductive layer 22B as an outer layer. The first conductive layer 22A is disposed on the surface of the substrate particle 11. On the surface of the first conductive layer 22A, the second conductive layer 22B is disposed.

3 is a cross-sectional view showing conductive particles according to a third embodiment of the present invention.

The electroconductive particle 31 shown in FIG. 3 has a base particle 11, a conductive layer 32, a plurality of core substances 33, and a plurality of insulating substances 34.

The conductive layer 32 is disposed on the surface of the substrate particle 11. The electroconductive particle 31 has a plurality of protrusions 31a on the electroconductive surface. The conductive layer 32 has a plurality of protrusions 32a on the outer surface. In this way, the electroconductive particle may have a protrusion on the conductive surface of the electroconductive particle, or may have a protrusion on the outer surface of the conductive layer. A plurality of core materials 33 are disposed on the surface of the substrate particle 11. A plurality of core materials 33 are embedded in the conductive layer 32. The core material 33 is disposed inside the protrusions 31a and 32a. The conductive layer 32 covers a plurality of core materials 33. The outer surface of the conductive layer 32 is raised by the plurality of core materials 33, and projections 31a and 32a are formed.

The conductive particles 31 have an insulating material 34 disposed on the outer surface of the conductive layer 32. At least a part of the outer surface of the conductive layer 32 is covered with an insulating material 34. The insulating material 34 is formed of an insulating material and is an insulating particle. In this way, the conductive particles may have an insulating material disposed on the outer surface of the conductive layer.

The metal for forming the conductive layer is not particularly limited. As the metals, gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon, tungsten, molybdenum and These alloys, etc. are mentioned. Moreover, as said metal, tin-doped indium oxide (ITO), solder, etc. are mentioned. From the viewpoint of further enhancing the connection reliability between electrodes, the metal is preferably an alloy containing tin, nickel, palladium, copper or gold, and preferably nickel or palladium.

Like the electroconductive particle 1, 31, the said electroconductive layer may be formed by one layer. Like the conductive particles 21, the conductive layer may be formed of a plurality of layers. That is, the conductive layer may have a laminated structure of two or more layers. When the conductive layer is formed of a plurality of layers, the outermost layer is preferably a gold layer, a nickel layer, a palladium layer, a copper layer, or an alloy layer containing tin and silver, and more preferably a gold layer. When the outermost layer is these preferable conductive layers, the connection reliability between electrodes can be further improved. In addition, when the outermost layer is a gold layer, the corrosion resistance can be further improved.

The method of forming the conductive layer on the surface of the substrate particle is not particularly limited. As a method of forming the conductive layer, a method of electroless plating, a method of electroplating, a method of physical vapor deposition, a method of coating a metal powder or a paste containing a metal powder and a binder on the surface of the substrate particles, etc. Can be mentioned. From the viewpoint of forming the conductive layer more easily, a method by electroless plating is preferable. Examples of the physical vapor deposition method include vacuum vapor deposition, ion plating, and ion sputtering.

The average particle diameter of the conductive particles is preferably 0.5 µm or more, more preferably 1.0 µm or more, preferably 500 µm or less, more preferably 450 µm or less, still more preferably 100 µm or less, even more preferably It is preferably 50 µm or less, particularly preferably 20 µm or less. If the average particle diameter of the electroconductive particle is greater than or equal to the lower limit and less than or equal to the upper limit, the contact area between the electroconductive particle and the electrode becomes sufficiently large when the electrode is connected using electroconductive particles, and the aggregated electroconductivity when forming the conductive layer. It becomes difficult to form particles. In addition, the gap between the electrodes connected via the electroconductive particle does not become too large, and the electroconductive layer becomes difficult to peel off from the surface of the substrate particle. Moreover, as long as the average particle diameter of the electroconductive particle is more than the said lower limit and less than the said upper limit, electroconductive particle can be used suitably for the use of a conductive material.

The particle diameter of the electroconductive particle means the diameter when the electroconductive particle is a spherical shape, and when the electroconductive particle has a shape other than the spherical shape, it means the diameter assuming that the electroconductive particle is a spherical equivalent of the volume.

It is preferable that the average particle diameter of the said electroconductive particle is a number average particle diameter. The average particle diameter of the electroconductive particle is determined by observing 50 arbitrary electroconductive particles with an electron microscope or an optical microscope, calculating an average value, or performing a laser diffraction particle size distribution measurement. In observation with an electron microscope or an optical microscope, the particle diameter of each electroconductive particle is calculated|required as the particle diameter in a circle equivalent diameter. In observation with an electron microscope or an optical microscope, the average particle diameter at the equivalent circle diameter of any 50 electroconductive particle becomes almost equal to the average particle diameter at the sphere equivalent diameter. In the laser diffraction type particle size distribution measurement, the particle diameter of each electroconductive particle is determined as the particle diameter in the equivalent sphere diameter. It is preferable to calculate the average particle diameter of the said electroconductive particle by laser diffraction type particle size distribution measurement.

The thickness of the conductive layer is preferably 0.005 µm or more, more preferably 0.01 µm or more, preferably 10 µm or less, more preferably 1 µm or less, and still more preferably 0.3 µm or less. The thickness of the conductive layer is the thickness of the entire conductive layer when the conductive layer is a multilayer. When the thickness of the conductive layer is greater than or equal to the lower limit and less than or equal to the upper limit, sufficient conductivity is obtained, and the conductive particles do not become too hard, and the conductive particles are sufficiently deformed at the time of connection between electrodes.

In the case where the conductive layer is formed of a plurality of layers, the thickness of the outermost conductive layer is preferably 0.001 μm or more, more preferably 0.01 μm or more, preferably 0.5 μm or less, more preferably It is 0.1 μm or less. When the thickness of the outermost conductive layer is greater than or equal to the lower limit and less than or equal to the upper limit, the covering by the outermost conductive layer becomes uniform, corrosion resistance is sufficiently high, and connection reliability between electrodes can be further improved. Further, when the outermost layer is a gold layer, the thinner the gold layer, the lower the cost.

The thickness of the conductive layer can be measured by observing the cross section of the conductive particles using, for example, a transmission electron microscope (TEM). With respect to the thickness of the conductive layer, it is preferable to calculate the average value of five thicknesses of an arbitrary conductive layer as the thickness of the conductive layer of one conductive particle, and the average value of the thickness of the entire conductive layer is the conductive layer of one conductive particle. It is more preferable to calculate it as the thickness of. The thickness of the conductive layer is preferably determined by calculating the average value of the thickness of the conductive layer of each conductive particle for 10 arbitrary conductive particles.

It is preferable that the said electroconductive particle has a protrusion on the outer surface of a conductive layer. It is preferable that the said electroconductive particle has a protrusion on the electroconductive surface. It is preferable that the protrusion is plural. An oxide film is often formed on the surface of the conductive layer and the surface of the electrode connected by the conductive particles. When conductive particles having protrusions are used, the oxide film is effectively removed by the protrusions by placing and pressing electroconductive particles between electrodes. For this reason, the electrode and the conductive layer of the electroconductive particle can be brought into contact more reliably, and the connection resistance between the electrodes can be further lowered. In addition, when the conductive particles have an insulating material on the surface, or when the conductive particles are dispersed in a binder resin and used as a conductive material, the protrusion of the conductive particles causes the insulating material or binder resin between the conductive particles and the electrode. Can be removed more effectively. For this reason, connection reliability between electrodes can be further improved.

As a method of forming protrusions on the surface of the conductive particles, a method of forming a conductive layer by electroless plating after attaching a core material to the surface of the base particles, and a conductive layer by electroless plating on the surface of the base particles After forming, a method of attaching a core material and further forming a conductive layer by electroless plating may be mentioned. In addition, since the protrusion is formed, the core material does not need to be used.

As a method of forming the projections, the following methods and the like are also mentioned. A method of adding a core material in a step during forming a conductive layer on the surface of a substrate particle by electroless plating. As a method of forming projections without using a core material by electroless plating, metal nuclei are generated by electroless plating to attach metal nuclei to the surface of substrate particles or conductive layer, and conduct by electroless plating. How to form a layer.

It is preferable that the conductive particles further include an insulating material disposed on the outer surface of the conductive layer. In this case, if electroconductive particles are used for connection between electrodes, a short circuit between adjacent electrodes can be prevented. Specifically, when a plurality of conductive particles are in contact, since an insulating material is present between the plurality of electrodes, it is possible to prevent a short circuit between electrodes adjacent to each other in the horizontal direction rather than between the upper and lower electrodes. Further, at the time of connection between the electrodes, by pressing the conductive particles with the two electrodes, the insulating material between the conductive layer of the conductive particles and the electrodes can be easily removed. When the conductive particles have protrusions on the surface of the conductive layer, the insulating material between the conductive layer of the conductive particles and the electrode can be more easily removed. The insulating material is preferably an insulating resin layer or insulating particles, more preferably insulating particles. It is preferable that the said insulating particle is an insulating resin particle.

The outer surface of the conductive layer and the surface of the insulating particles may be each covered with a compound having a reactive functional group. The outer surface of the conductive layer and the surface of the insulating particles do not need to be chemically bonded directly, but may be chemically bonded indirectly by a compound having a reactive functional group. After introducing a carboxyl group to the outer surface of the conductive layer, the carboxyl group may be chemically bonded to the surface functional group of the insulating particles through a polymer electrolyte such as polyethyleneimine.

(Conductive material)

The conductive material contains the above-described conductive particles and a binder resin. It is preferable that the said electroconductive particle is dispersed in a binder resin and used as a conductive material. It is preferable that the said conductive material is an anisotropic conductive material. The conductive material is suitably used for electrical connection of electrodes. It is preferable that the said conductive material is a circuit connection material.

The binder resin is not particularly limited. As the binder resin, a known insulating resin is used. It is preferable that the said binder resin contains a thermoplastic component (thermoplastic compound) or a curable component, and it is more preferable that it contains a curable component. As said curable component, a photocurable component and a thermosetting component are mentioned. It is preferable that the photocurable component contains a photocurable compound and a photopolymerization initiator. It is preferable that the thermosetting component includes a thermosetting compound and a thermosetting agent. Examples of the binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers and elastomers. Only 1 type may be used for the said binder resin, and 2 or more types may be used together.

As said vinyl resin, a vinyl acetate resin, an acrylic resin, a styrene resin, etc. are mentioned, for example. Examples of the thermoplastic resin include polyolefin resin, ethylene-vinyl acetate copolymer, and polyamide resin. As said curable resin, an epoxy resin, a urethane resin, a polyimide resin, an unsaturated polyester resin, etc. are mentioned, for example. Further, the curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin or a moisture curable resin. The curable resin may be used in combination with a curing agent. As the thermoplastic block copolymer, for example, a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated product of a styrene-butadiene-styrene block copolymer, and hydrogen of a styrene-isoprene-styrene block copolymer Additives, etc. are mentioned. As said elastomer, a styrene-butadiene copolymer rubber, an acrylonitrile-styrene block copolymer rubber, etc. are mentioned, for example.

In addition to the conductive particles and the binder resin, the conductive material is, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant. Various additives such as may be contained.

The method of dispersing the conductive particles in the binder resin may be a conventionally known dispersion method, and is not particularly limited. As a method of dispersing the conductive particles in the binder resin, for example, the following methods may be mentioned. After adding the electroconductive particle to the binder resin, kneading and dispersing with a planetary mixer or the like. A method in which the conductive particles are uniformly dispersed in water or an organic solvent using a homogenizer or the like, added to the binder resin, and kneaded in a planetary mixer to disperse. After diluting the binder resin with water or an organic solvent, the conductive particles are added and kneaded with a planetary mixer to disperse.

The viscosity (η25) of the conductive material at 25°C is preferably 30 Pa·s or more, more preferably 50 Pa·s or more, preferably 400 Pa·s or less, and more preferably 300 Pa·s or less. When the viscosity of the conductive material at 25° C. is equal to or greater than the lower limit and equal to or lower than the upper limit, the connection reliability between electrodes can be further effectively improved. The viscosity (η25) can be appropriately adjusted depending on the type and amount of the components to be blended.

The viscosity (η25) can be measured under conditions of 25°C and 5 rpm using, for example, an E-type viscometer ("TVE22L" manufactured by Toki Sangyo).

The conductive material can be used as a conductive paste and a conductive film. When the conductive material according to the present invention is a conductive film, a film not containing conductive particles may be laminated on a conductive film containing conductive particles. It is preferable that the said conductive paste is an anisotropic conductive paste. It is preferable that the said conductive film is an anisotropic conductive film.

In 100% by weight of the conductive material, the content of the binder resin is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, It is preferably 99.99% by weight or less, more preferably 99.9% by weight or less. When the content of the binder resin is greater than or equal to the lower limit and less than or equal to the upper limit, conductive particles are efficiently disposed between electrodes, and the connection reliability of the member to be connected connected by the conductive material is further increased.

In 100% by weight of the conductive material, the content of the conductive particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 80% by weight or less, more preferably 60% by weight or less, further It is more preferably 40% by weight or less, still more preferably 20% by weight or less, and particularly preferably 10% by weight or less. When the content of the conductive particles is more than the lower limit and less than the upper limit, the connection resistance between the electrodes can be further effectively lowered, and the connection reliability between the electrodes can be further effectively improved.

(Connection structure)

A connection structure can be obtained by connecting the member to be connected using the conductive particles described above or the conductive material containing the conductive particles and a binder resin described above.

The connection structure connects a first connection object member having a first electrode on its surface, a second connection object member having a second electrode on its surface, and the first connection object member and the second connection object member. It has a connection part. In the connection structure, it is preferable that the connection portion is formed of conductive particles or a conductive material containing the conductive particles and a binder resin. It is preferable that the said electroconductive particle comprises the above-mentioned base material particle, and the conductive layer arrange|positioned on the surface of the said base material particle. In the connection structure, it is preferable that the first electrode and the second electrode are electrically connected by the conductive particles.

When the said electroconductive particle is used individually, the connection part itself is electroconductive particle. That is, the first connection object member and the second connection object member are connected by the conductive particles. It is preferable that the conductive material used to obtain the connection structure is an anisotropic conductive material.

4 is a cross-sectional view showing an example of a connection structure using electroconductive particles according to the first embodiment of the present invention.

The connection structure 41 shown in FIG. 4 connects the first connection object member 42, the second connection object member 43, the first connection object member 42 and the second connection object member 43, and It is provided with a connecting portion 44. The connection portion 44 is formed of a conductive material containing the conductive particles 1 and a binder resin. In FIG. 4, for convenience of illustration, the conductive particles 1 are schematically shown. Instead of the electroconductive particle 1, you may use another electroconductive particle of the electroconductive particle 21, 31.

The first connection object member 42 has a plurality of first electrodes 42a on its surface (upper surface). The second connection object member 43 has a plurality of second electrodes 43a on the surface (lower surface). The first electrode 42a and the second electrode 43a are electrically connected by one or a plurality of conductive particles 1. Accordingly, the first and second connection object members 42 and 43 are electrically connected by the electroconductive particle 1.

The manufacturing method of the connection structure is not particularly limited. As an example of the manufacturing method of the connection structure, after disposing the said conductive material between a 1st connection object member and a 2nd connection object member, and obtaining a laminated body, the method of heating and pressing the laminated body etc. is mentioned. The pressure during the pressurization is preferably 40 MPa or more, more preferably 60 MPa or more, preferably 90 MPa or less, and more preferably 70 MPa or less. The temperature during the heating is preferably 80°C or higher, more preferably 100°C or higher, preferably 140°C or lower, and more preferably 120°C or lower.

The first connection object member and the second connection object member are not particularly limited. As the first connection target member and the second connection target member, specifically, semiconductor chips, semiconductor packages, LED chips, LED packages, electronic components such as capacitors and diodes, and resin films, printed circuit boards, flexible printed circuit boards, and flexible flats. Electronic components such as circuit boards such as cables, rigid flexible substrates, glass epoxy substrates, and glass substrates. It is preferable that the said 1st connection object member and 2nd connection object member are electronic components.

It is preferable that the said conductive material is a conductive material for connecting electronic components. The conductive paste is a paste-like conductive material, and is preferably applied on a member to be connected in a paste-like state.

The said electroconductive particle and said electroconductive material are used suitably also for a touch panel. Therefore, it is preferable that the connection object member is a flexible substrate or a connection object member in which an electrode is disposed on the surface of a resin film. It is preferable that the said connection object member is a flexible substrate, and it is preferable that it is a connection object member in which an electrode is arrange|positioned on the surface of a resin film. In the case where the flexible substrate is a flexible printed circuit board or the like, the flexible substrate generally has an electrode on its surface.

Metal electrodes, such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, a SUS electrode, and a tungsten electrode, are mentioned as an electrode provided in the said connection object member. When the connection object member is a flexible printed circuit board, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, a silver electrode, or a copper electrode. When the member to be connected is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode. Further, when the electrode is an aluminum electrode, it may be an electrode formed of only aluminum, or an electrode in which an aluminum layer is laminated on the surface of a metal oxide layer. Examples of the material for the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Sn, Al, Ga, etc. are mentioned as said trivalent metal element.

Further, the substrate particles can be suitably used as a spacer for a liquid crystal display device. The first member to be connected may be a member for a first liquid crystal display element. The second connection object member may be a second liquid crystal display element member. The connection portion seals an outer periphery of the first liquid crystal display element member and the second liquid crystal display element member in a state in which the first liquid crystal display element member and the second liquid crystal display element member face each other. You can also give it a seal.

The said substrate particle can also be used for the peripheral sealing agent for liquid crystal display elements. A liquid crystal display device includes a first member for a liquid crystal display device and a second member for a liquid crystal display device. The liquid crystal display element seals an outer periphery of the first liquid crystal display element member and the second liquid crystal display element member in a state in which the first liquid crystal display element member and the second liquid crystal display element member face each other, And a liquid crystal disposed between the first liquid crystal display element member and the second liquid crystal display element member on the inside of the seal portion. In this liquid crystal display element, a liquid crystal dropping method is applied, and the sealing portion is formed by thermosetting a sealing agent for a liquid crystal dropping method.

5 is a cross-sectional view showing an example of a liquid crystal display device in which the substrate particles according to the present invention are used as a spacer for a liquid crystal display device.

The liquid crystal display device 81 shown in FIG. 5 has a pair of transparent glass substrates 82. The transparent glass substrate 82 has an insulating film (not shown) on the opposite surface. As a material of the insulating film, SiO ₂ etc. are mentioned, for example. The transparent electrode 83 is formed on the insulating film in the transparent glass substrate 82. As a material of the transparent electrode 83, ITO etc. are mentioned. The transparent electrode 83 can be formed by patterning, for example, by photolithography. The alignment film 84 is formed on the transparent electrode 83 on the surface of the transparent glass substrate 82. As the material of the alignment film 84, polyimide or the like is exemplified.

A liquid crystal 85 is sealed between a pair of transparent glass substrates 82. Between the pair of transparent glass substrates 82, a plurality of substrate particles 11 are arranged. The substrate particles 11 are used as a spacer for a liquid crystal display device. The spacing between the pair of transparent glass substrates 82 is regulated by the plurality of substrate particles 11. A sealing agent 86 is disposed between the frame portions of the pair of transparent glass substrates 82. The sealing agent 86 prevents the liquid crystal 85 from leaking to the outside. The sealing agent 86 contains the substrate particles 11A different only from the substrate particles 11 in particle diameters.

In the liquid crystal display device, the arrangement density of spacers for liquid crystal display elements per 1 mm ² is preferably 10 pieces/mm ² or more, and preferably 1000 pieces/mm ² or less. If the batch density is 10 pieces/mm ² or more, the cell gap becomes even more uniform. When the said arrangement density is 1000 pieces/mm ² or less, the contrast of a liquid crystal display element becomes more favorable.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited only to the following examples.

(Evaluation of Test Examples (1), (2), (3) and (4))

The following evaluation was performed about the base material particle, electroconductive particle, and connection structure of Test Examples (1)-(4) mentioned later. In addition, since the manufacturing conditions of the connection structure are different between Test Examples (1), (2), (3) and (4), the connection between Test Examples (1), (2), (3) and (4) The evaluation results of the structure cannot be directly compared to each other.

(Evaluation 1) BET specific surface area of substrate particles

About the obtained base material particle|grains, the adsorption isotherm of nitrogen was measured using "NOVA4200e" by the Cantachrome Instruments company. From the measurement results, the specific surface area of the substrate particles was calculated according to the BET method.

(Evaluation 2) Total pore volume of substrate particles

About the obtained base material particle|grains, the adsorption isotherm of nitrogen was measured using "NOVA4200e" by the Cantachrome Instruments company. From the measurement results, the total pore volume of the substrate particles was calculated according to the BJH method.

(Evaluation 3) Average pore diameter of substrate particles

About the obtained base material particle|grains, the adsorption isotherm of nitrogen was measured using "NOVA4200e" by the Cantachrome Instruments company. From the measurement results, the average pore diameter of the substrate particles was calculated according to the BJH method.

(Evaluation 4) Compression modulus of substrate particles

With respect to the obtained substrate particles, the compression modulus (10% K value and 30% K value) was measured using a micro compression tester ("Fisher Scope H-100" manufactured by Fisher) by the method described above. From the measurement result, a 10% K value and a 30% K value were calculated.

(Evaluation 5) Compression recovery rate of base particles

The compression recovery rate of the obtained substrate particles was measured using a micro compression tester ("Fischer Scope H-100" manufactured by Fischer) by the method described above.

(Evaluation 6) CV value of the average particle diameter of the substrate particles and the particle diameter of the substrate particles

With respect to the obtained substrate particles, a particle size distribution measuring device ("Multisizer4" manufactured by Beckman Coulter) was used to measure the particle diameter of about 100,000 substrate particles, and the average particle diameter was calculated. In addition, from the particle diameter measurement results of the substrate particles, the CV value of the particle diameter of the substrate particles was calculated from the following equation.

CV value (%) = (ρ/Dn) × 100

ρ: standard deviation of the particle diameter of the substrate particle

Dn: the average value of the particle diameter of the substrate particles

(Evaluation 7) adhesion between the substrate particles and the conductive layer

The obtained electroconductive particle was pulverized using an automatic induction device ("AMM-140D" manufactured by Nitto Chemical Co., Ltd.) at 120 rpm, 7 rpm, and 30 minutes of treatment time. The electroconductive particle after the disintegration was photographed by using a scanning electron microscope ("Regulus8220" manufactured by Hitachi High-Technology Co., Ltd.), while moving the photographing location, and photographing five particle images of 3000 times. For 100 electroconductive particles in the obtained five images, it was confirmed whether or not the electroconductive layer disposed on the surface of the substrate particles had peeled off. The adhesion between the substrate particles and the conductive layer was determined based on the following criteria.

[Criteria for judging adhesion between substrate particles and conductive layer]

○○○: 0 conductive particles from which the conductive layer was peeled off

○○: More than 0 and 15 or less conductive particles from which the conductive layer was peeled off

○: More than 15 electroconductive particles from which the conductive layer was peeled off and not more than 30

△: More than 30 conductive particles from which the conductive layer was peeled off and not more than 50

X: More than 50 electroconductive particles from which the conductive layer was peeled off

(Evaluation 8) Connection reliability (between upper and lower electrodes)

The connection resistance between the upper and lower electrodes of the obtained 20 connection structures was measured by the four-terminal method, respectively. The average value of the connection resistance was calculated. Further, from the relationship between voltage = current x resistance, the connection resistance can be obtained by measuring the voltage when a constant current is passed. Connection reliability was determined based on the following criteria.

[Connection Reliability Criteria]

○○○: The average value of connection resistance is 1.5Ω or less

○○: The average value of the connection resistance exceeds 1.5 Ω and is 2.0 Ω or less

○: The average value of the connection resistance exceeds 2.0 Ω and is 5.0 Ω or less

△: The average value of the connection resistance exceeds 5.0 Ω and is 10 Ω or less

×: The average value of the connection resistance exceeds 10 Ω

(Evaluation 9) Impact resistance

The connection structure obtained in the evaluation of the (Evaluation 8) connection reliability was dropped from the position of 70 cm in height, and the impact resistance was evaluated by checking the connection resistance in the same manner as in the evaluation of (Evaluation 8). The impact resistance was determined based on the following criteria by the rate of increase of the resistance value from the average value of the connection resistance obtained in the evaluation of (Evaluation 8).

[Criteria for determining impact resistance]

○: The increase rate of the resistance value from the average value of the connection resistance is 30% or less

△: The increase rate of the resistance value from the average value of the connection resistance exceeds 30% and is 50% or less

X: The increase rate of the resistance value from the average value of the connection resistance exceeds 50%

(Evaluation 10) Connection reliability after high temperature and high humidity conditions

The 100 connection structures obtained in the above (Evaluation 8) connection reliability evaluation were left at 85°C and 85% RH for 100 hours. With respect to the 100 connection structures after standing, it was evaluated whether or not a conduction failure between the upper and lower electrodes occurred. Connection reliability after high temperature and high humidity conditions was determined by the following criteria.

[Criteria for judging connection reliability after high temperature and high humidity conditions]

○○: Out of 100 connection structures, the number of defective conduction is one or less.

○: Out of 100 connection structures, the number of occurrence of conduction failure is 2 to 5

△: Out of 100 connection structures, the number of defective conduction is 6 to 10

×: Out of 100 connection structures, the number of occurrence of conduction failure is 11 or more

(Test Example (1))

In Test Example (1), substrate particles 1 and the like were produced.

(Example (1)-1)

(1) Preparation of substrate particles

As seed particles, polystyrene particles having an average particle diameter of 0.69 µm were prepared. 3.9 parts by weight of the polystyrene particles, 500 parts by weight of ion-exchanged water, and 120 parts by weight of a 5% by weight polyvinyl alcohol aqueous solution were mixed to prepare a mixed solution. After dispersing the mixture by ultrasonic waves, it was put into a separable flask and stirred uniformly.

Next, 150 parts by weight of divinylbenzene (monomer component), 2 parts by weight of 2,2'-azobis (methyl isobutyrate) ("V-601" manufactured by Wako Pure Chemical Industries, Ltd.), and benzoyl peroxide (manufactured by Nichiyu Corporation) Niper BW") 2 parts by weight were mixed. Further, 9 parts by weight of lauryl sulfate triethanolamine, 30 parts by weight of toluene (solvent), and 1100 parts by weight of ion-exchanged water were added to prepare an emulsion.

To the mixed solution in a separable flask, the emulsion was added in several portions, stirred for 12 hours, and the monomer was absorbed into the seed particles to obtain a suspension containing the seed particles in which the monomer was swollen.

Then, 490 parts by weight of a 5% by weight polyvinyl alcohol aqueous solution was added, heating was started, and the reaction was carried out at 85°C for 9 hours to obtain base particles having a particle diameter of 3.24 μm.

(2) Preparation of conductive particles

After washing and drying the obtained substrate particles, 10 parts by weight of the substrate particles are dispersed in 100 parts by weight of an alkali solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser, and then the solution is filtered to remove the base particles. It was taken out. Subsequently, the substrate particles were added to 100 parts by weight of a 1% by weight solution of dimethylamine borane to activate the surface of the substrate particles. After sufficiently washing the surface-activated substrate particles with water, 500 parts by weight of distilled water was added and dispersed to obtain a dispersion. Subsequently, 1 g of a nickel particle slurry (average particle diameter of 100 nm) was added to the dispersion over 3 minutes to obtain a suspension containing the substrate particles to which the core material was attached.

Further, a nickel plating solution (pH 8.5) containing 0.35 mol/L of nickel sulfate, 1.38 mol/L of dimethylamine borane and 0.5 mol/L of sodium citrate was prepared.

While stirring the obtained suspension at 60° C., the nickel plating solution was gradually added dropwise to the suspension to perform electroless nickel plating. Thereafter, the suspension was filtered to remove particles, washed with water, and dried to form a nickel-boron conductive layer (thickness 0.15 µm) on the surface of the substrate particles, thereby obtaining conductive particles having a conductive portion on the surface.

(3) Preparation of insulating particles

After putting the following monomer composition into a 1000 mL separable flask equipped with a four-neck separable cover, stirring blade, three-way cock, cooling tube, and temperature probe, distilled water was added so that the solid content of the following monomer composition became 10% by weight, and stirred at 200 rpm. Then, polymerization was performed at 60°C for 24 hours in a nitrogen atmosphere. The monomer composition includes 360 mmol of methyl methacrylate, 45 mmol of glycidyl methacrylate, 20 mmol of parastyryldiethylphosphine, 13 mmol of dimethacrylate ethylene glycol, 0.5 mmol of polyvinylpyrrolidone and 2,2'-azobis{ 2-[N-(2-carboxyethyl)amidino]propane} 1 mmol. After completion of the reaction, it was freeze-dried to obtain insulating particles (particle diameter of 360 nm) having a phosphorus atom derived from parastyryldiethylphosphine on the surface.

(4) Preparation of conductive particles with insulating particles

The insulating particles obtained above were dispersed in distilled water under ultrasonic irradiation to obtain a 10% by weight aqueous dispersion of the insulating particles. 10 g of the obtained electroconductive particles were dispersed in 500 mL of distilled water, 1 g of a 10% by weight aqueous dispersion of insulating particles was added, followed by stirring at room temperature for 8 hours. After filtration with a 3 µm mesh filter, it was further washed with methanol and dried to obtain conductive particles with insulating particles.

(5) Preparation of conductive material (anisotropic conductive paste)

7 parts by weight of the obtained conductive particles, 25 parts by weight of a bisphenol A-type phenoxy resin, 4 parts by weight of a fluorene-type epoxy resin, 30 parts by weight of a phenol novolak-type epoxy resin, and SI-60L (manufactured by Sanshin Chemical Industries, Ltd.) Was blended, defoaming and stirring for 3 minutes to obtain a conductive material (anisotropic conductive paste).

(6) Fabrication of connection structure

A transparent glass substrate on which an IZO electrode pattern having an L/S of 10 µm/10 µm (a first electrode and a Vickers hardness of 100 Hv of metal on the electrode surface) was formed on the upper surface was prepared. Further, a semiconductor chip having an L/S of 10 μm/10 μm (second electrode, Vickers hardness of metal on the electrode surface of 50 Hv) formed on the lower surface thereof was prepared. The anisotropic conductive paste obtained on the transparent glass substrate was applied to a thickness of 30 µm to form an anisotropic conductive paste layer. Next, the semiconductor chips were stacked on the anisotropic conductive paste layer so that the electrodes face each other. Thereafter, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer becomes 100°C, a pressurized heating head is placed on the upper surface of the semiconductor chip, and a pressure of 78 MPa is applied to cure the anisotropic conductive paste layer at 100°C. Got it.

(Examples (1)-2 to (1)-32 and Comparative Examples (1)-1 to (1)-7)

In the same manner as in Example (1)-1, except that the types of monomer components used in the production of the substrate particles, the types of solvents, and their blending amounts were changed as shown in Tables 1 to 4 below, the substrate particles, conductive particles, and An anisotropic conductive film and a connection structure were obtained.

The details and results of the substrate particles and electroconductive particles in Test Example (1) are shown in Tables 1 to 4.

(Test Example 2)

In Test Example 2, substrate particles 2 and the like were produced.

(Example (2)-1)

(1) Preparation of substrate particles

As seed particles, polystyrene particles having an average particle diameter of 0.69 µm were prepared. 3.9 parts by weight of the polystyrene particles, 500 parts by weight of ion-exchanged water, and 120 parts by weight of a 5% by weight polyvinyl alcohol aqueous solution were mixed to prepare a mixed solution. After dispersing the mixture by ultrasonic waves, it was put into a separable flask and stirred uniformly.

Next, 150 parts by weight of divinylbenzene (monomer component), 2 parts by weight of 2,2'-azobis (methyl isobutyrate) ("V-601" manufactured by Wako Pure Chemical Industries, Ltd.), and benzoyl peroxide (manufactured by Nichiyu Corporation) Niper BW") 2 parts by weight were mixed. Further, 9 parts by weight of lauryl sulfate triethanolamine, 70 parts by weight of toluene (solvent), and 1100 parts by weight of ion-exchanged water were added to prepare an emulsion.

To the mixed solution in a separable flask, the emulsion was added in several portions, stirred for 12 hours, and the monomer was absorbed into the seed particles to obtain a suspension containing the seed particles in which the monomer was swollen.

Thereafter, 490 parts by weight of a 5% by weight polyvinyl alcohol aqueous solution was added, heating was started, and the reaction was carried out at 85°C for 9 hours to obtain substrate particles having a particle diameter of 3.69 µm.

(2) Preparation of conductive particles

After washing and drying the obtained substrate particles, 10 parts by weight of the substrate particles are dispersed in 100 parts by weight of an alkali solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser, and then the solution is filtered to remove the base particles. It was taken out. Subsequently, the substrate particles were added to 100 parts by weight of a 1% by weight solution of dimethylamine borane to activate the surface of the substrate particles. After sufficiently washing the surface-activated substrate particles with water, 500 parts by weight of distilled water was added and dispersed to obtain a dispersion. Subsequently, 1 g of a nickel particle slurry (average particle diameter of 100 nm) was added to the dispersion over 3 minutes to obtain a suspension containing the substrate particles to which the core material was attached.

Further, a nickel plating solution (pH 8.5) containing 0.35 mol/L of nickel sulfate, 1.38 mol/L of dimethylamine borane and 0.5 mol/L of sodium citrate was prepared.

While stirring the obtained suspension at 60° C., the nickel plating solution was gradually added dropwise to the suspension to perform electroless nickel plating. Thereafter, the suspension was filtered to remove particles, washed with water, and dried to form a nickel-boron conductive layer (thickness 0.15 µm) on the surface of the substrate particles, thereby obtaining conductive particles having a conductive portion on the surface.

(3) Preparation of insulating particles

After putting the following monomer composition into a 1000 mL separable flask equipped with a four-neck separable cover, stirring blade, three-way cock, cooling tube, and temperature probe, distilled water was added so that the solid content of the following monomer composition became 10% by weight, and stirred at 200 rpm. Then, polymerization was performed at 60°C for 24 hours in a nitrogen atmosphere. The monomer composition includes 360 mmol of methyl methacrylate, 45 mmol of glycidyl methacrylate, 20 mmol of parastyryldiethylphosphine, 13 mmol of dimethacrylate ethylene glycol, 0.5 mmol of polyvinylpyrrolidone and 2,2'-azobis{ 2-[N-(2-carboxyethyl)amidino]propane} 1 mmol. After completion of the reaction, it was freeze-dried to obtain insulating particles (particle diameter of 360 nm) having a phosphorus atom derived from parastyryldiethylphosphine on the surface.

(4) Preparation of conductive particles with insulating particles

The insulating particles obtained above were dispersed in distilled water under ultrasonic irradiation to obtain a 10% by weight aqueous dispersion of the insulating particles. 10 g of the obtained electroconductive particles were dispersed in 500 mL of distilled water, 1 g of a 10% by weight aqueous dispersion of insulating particles was added, followed by stirring at room temperature for 8 hours. After filtration with a 3 µm mesh filter, it was further washed with methanol and dried to obtain conductive particles with insulating particles.

(5) Preparation of conductive material (anisotropic conductive paste)

7 parts by weight of the obtained conductive particles, 25 parts by weight of a bisphenol A-type phenoxy resin, 4 parts by weight of a fluorene-type epoxy resin, 30 parts by weight of a phenol novolak-type epoxy resin, and SI-60L (manufactured by Sanshin Chemical Industries, Ltd.) Was blended, defoaming and stirring for 3 minutes to obtain a conductive material (anisotropic conductive paste).

(6) Fabrication of connection structure

A transparent glass substrate on which an IZO electrode pattern having an L/S of 10 µm/10 µm (a first electrode and a Vickers hardness of 100 Hv of metal on the electrode surface) was formed on the upper surface was prepared. Further, a semiconductor chip having an L/S of 10 μm/10 μm (second electrode, Vickers hardness of metal on the electrode surface of 50 Hv) formed on the lower surface thereof was prepared. The anisotropic conductive paste obtained on the transparent glass substrate was applied to a thickness of 30 µm to form an anisotropic conductive paste layer. Next, the semiconductor chips were stacked on the anisotropic conductive paste layer so that the electrodes face each other. Thereafter, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer becomes 100°C, a pressurized heating head is placed on the upper surface of the semiconductor chip, and a pressure of 70 MPa is applied to cure the anisotropic conductive paste layer at 100°C. Got it.

(Examples (2)-2 to (2)-17 and Comparative Examples (2)-1 to (2)-7)

In the same manner as in Example (2)-1, except that the type of the monomer component used in the production of the substrate particle, the type of the solvent, and the amount of the mixture were changed as shown in Tables 5 to 7 below, the substrate particle, the conductive particle, An anisotropic conductive film and a connection structure were obtained.

The details and results of the substrate particles and electroconductive particles in Test Example 2 are shown in Tables 5 to 7.

(Test Example 3)

In Test Example 3, substrate particles 3 and the like were produced.

(Example (3)-1)

(1) Preparation of substrate particles

As seed particles, polystyrene particles having an average particle diameter of 0.69 µm were prepared. 3.9 parts by weight of the polystyrene particles, 500 parts by weight of ion-exchanged water, and 120 parts by weight of a 5% by weight polyvinyl alcohol aqueous solution were mixed to prepare a mixed solution. After dispersing the mixture by ultrasonic waves, it was put into a separable flask and stirred uniformly.

Next, 150 parts by weight of divinylbenzene (monomer component), 2 parts by weight of 2,2'-azobis (methyl isobutyrate) ("V-601" manufactured by Wako Pure Chemical Industries, Ltd.), and benzoyl peroxide (manufactured by Nichiyu Corporation) Niper BW") 2 parts by weight were mixed. Further, 9 parts by weight of lauryl sulfate triethanolamine, 30 parts by weight of toluene (solvent), and 1100 parts by weight of ion-exchanged water were added to prepare an emulsion.

To the mixed solution in a separable flask, the emulsion was added in several portions, stirred for 12 hours, and the monomer was absorbed into the seed particles to obtain a suspension containing the seed particles in which the monomer was swollen.

Then, 490 parts by weight of a 5% by weight polyvinyl alcohol aqueous solution was added, heating was started, and the reaction was carried out at 85°C for 9 hours to obtain base particles having a particle diameter of 3.24 μm.

(2) Preparation of conductive particles

After washing and drying the obtained substrate particles, 10 parts by weight of the substrate particles are dispersed in 100 parts by weight of an alkali solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser, and then the solution is filtered to remove the base particles. It was taken out. Subsequently, the substrate particles were added to 100 parts by weight of a 1% by weight solution of dimethylamine borane to activate the surface of the substrate particles. After sufficiently washing the surface-activated substrate particles with water, 500 parts by weight of distilled water was added and dispersed to obtain a dispersion. Subsequently, 1 g of a nickel particle slurry (average particle diameter of 100 nm) was added to the dispersion over 3 minutes to obtain a suspension containing the substrate particles to which the core material was attached.

Further, a nickel plating solution (pH 8.5) containing 0.35 mol/L of nickel sulfate, 1.38 mol/L of dimethylamine borane and 0.5 mol/L of sodium citrate was prepared.

While stirring the obtained suspension at 60° C., the nickel plating solution was gradually added dropwise to the suspension to perform electroless nickel plating. Thereafter, the suspension was filtered to remove particles, washed with water, and dried to form a nickel-boron conductive layer (thickness 0.15 µm) on the surface of the substrate particles, thereby obtaining conductive particles having a conductive portion on the surface.

(3) Preparation of insulating particles

After putting the following monomer composition into a 1000 mL separable flask equipped with a four-neck separable cover, stirring blade, three-way cock, cooling tube, and temperature probe, distilled water was added so that the solid content of the following monomer composition became 10% by weight, and stirred at 200 rpm. Then, polymerization was performed at 60°C for 24 hours in a nitrogen atmosphere. The monomer composition includes 360 mmol of methyl methacrylate, 45 mmol of glycidyl methacrylate, 20 mmol of parastyryldiethylphosphine, 13 mmol of dimethacrylate ethylene glycol, 0.5 mmol of polyvinylpyrrolidone and 2,2'-azobis{ 2-[N-(2-carboxyethyl)amidino]propane} 1 mmol. After completion of the reaction, it was freeze-dried to obtain insulating particles (particle diameter of 360 nm) having a phosphorus atom derived from parastyryldiethylphosphine on the surface.

(4) Preparation of conductive particles with insulating particles

The insulating particles obtained above were dispersed in distilled water under ultrasonic irradiation to obtain a 10% by weight aqueous dispersion of the insulating particles. 10 g of the obtained electroconductive particles were dispersed in 500 mL of distilled water, 1 g of a 10% by weight aqueous dispersion of insulating particles was added, followed by stirring at room temperature for 8 hours. After filtration with a 3 µm mesh filter, it was further washed with methanol and dried to obtain conductive particles with insulating particles.

(5) Preparation of conductive material (anisotropic conductive paste)

7 parts by weight of the obtained conductive particles, 25 parts by weight of a bisphenol A-type phenoxy resin, 4 parts by weight of a fluorene-type epoxy resin, 30 parts by weight of a phenol novolak-type epoxy resin, and SI-60L (manufactured by Sanshin Chemical Industries, Ltd.) Was blended, defoaming and stirring for 3 minutes to obtain a conductive material (anisotropic conductive paste).

(6) Fabrication of connection structure

A transparent glass substrate on which an IZO electrode pattern having an L/S of 10 µm/10 µm (a first electrode and a Vickers hardness of 100 Hv of metal on the electrode surface) was formed on the upper surface was prepared. Further, a semiconductor chip having an L/S of 10 μm/10 μm (second electrode, Vickers hardness of metal on the electrode surface of 50 Hv) formed on the lower surface thereof was prepared. The anisotropic conductive paste obtained on the transparent glass substrate was applied to a thickness of 30 µm to form an anisotropic conductive paste layer. Next, the semiconductor chips were stacked on the anisotropic conductive paste layer so that the electrodes face each other. Thereafter, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer becomes 100°C, a pressurized heating head is placed on the upper surface of the semiconductor chip, and a pressure of 85 MPa is applied to cure the anisotropic conductive paste layer at 100°C. Got it.

(Examples (3)-2 to (3)-17 and Comparative Examples (3)-1 to (3)-6)

In the same manner as in Example (3)-1, except that the types of monomer components used in the production of the substrate particles, the types of solvents, and their blending amounts were changed as shown in Tables 8 to 10 below, the substrate particles, conductive particles, and An anisotropic conductive film and a connection structure were obtained.

The details and results of the substrate particles and electroconductive particles in Test Example 3 are shown in Tables 8 to 10.

(Test Example 4)

In Test Example 4, substrate particles 4 and the like were produced.

(Example (4)-1)

(1) Preparation of substrate particles

As seed particles, polystyrene particles having an average particle diameter of 0.69 µm were prepared. 3.9 parts by weight of the polystyrene particles, 500 parts by weight of ion-exchanged water, and 120 parts by weight of a 5% by weight polyvinyl alcohol aqueous solution were mixed to prepare a mixed solution. After dispersing the mixture by ultrasonic waves, it was put into a separable flask and stirred uniformly.

Next, 150 parts by weight of divinylbenzene (monomer component), 2 parts by weight of 2,2'-azobis (methyl isobutyrate) ("V-601" manufactured by Wako Pure Chemical Industries, Ltd.), and benzoyl peroxide (manufactured by Nichiyu Corporation) Niper BW") 2 parts by weight were mixed. Further, 9 parts by weight of lauryl sulfate triethanolamine, 180 parts by weight of toluene (solvent), and 1100 parts by weight of ion-exchanged water were added to prepare an emulsion.

To the mixed solution in a separable flask, the emulsion was added in several portions, stirred for 12 hours, and the monomer was absorbed into the seed particles to obtain a suspension containing the seed particles in which the monomer was swollen.

Thereafter, 490 parts by weight of a 5% by weight polyvinyl alcohol aqueous solution was added, heating was started, and the reaction was carried out at 85°C for 9 hours to obtain substrate particles having a particle diameter of 3.83 µm.

(2) Preparation of conductive particles

After washing and drying the obtained substrate particles, 10 parts by weight of the substrate particles are dispersed in 100 parts by weight of an alkali solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser, and then the solution is filtered to remove the base particles. It was taken out. Subsequently, the substrate particles were added to 100 parts by weight of a 1% by weight solution of dimethylamine borane to activate the surface of the substrate particles. After sufficiently washing the surface-activated substrate particles with water, 500 parts by weight of distilled water was added and dispersed to obtain a dispersion. Subsequently, 1 g of a nickel particle slurry (average particle diameter of 100 nm) was added to the dispersion over 3 minutes to obtain a suspension containing the substrate particles to which the core material was attached.

Further, a nickel plating solution (pH 8.5) containing 0.35 mol/L of nickel sulfate, 1.38 mol/L of dimethylamine borane and 0.5 mol/L of sodium citrate was prepared.

While stirring the obtained suspension at 60° C., the nickel plating solution was gradually added dropwise to the suspension to perform electroless nickel plating. Thereafter, the suspension was filtered to remove particles, washed with water, and dried to form a nickel-boron conductive layer (thickness 0.15 µm) on the surface of the substrate particles, thereby obtaining conductive particles having a conductive portion on the surface.

(3) Preparation of insulating particles

After putting the following monomer composition into a 1000 mL separable flask equipped with a four-neck separable cover, stirring blade, three-way cock, cooling tube, and temperature probe, distilled water was added so that the solid content of the following monomer composition became 10% by weight, and stirred at 200 rpm. Then, polymerization was performed at 60°C for 24 hours in a nitrogen atmosphere. The monomer composition includes 360 mmol of methyl methacrylate, 45 mmol of glycidyl methacrylate, 20 mmol of parastyryldiethylphosphine, 13 mmol of dimethacrylate ethylene glycol, 0.5 mmol of polyvinylpyrrolidone and 2,2'-azobis{ 2-[N-(2-carboxyethyl)amidino]propane} 1 mmol. After completion of the reaction, it was freeze-dried to obtain insulating particles (particle diameter of 360 nm) having a phosphorus atom derived from parastyryldiethylphosphine on the surface.

(4) Preparation of conductive particles with insulating particles

The insulating particles obtained above were dispersed in distilled water under ultrasonic irradiation to obtain a 10% by weight aqueous dispersion of the insulating particles. 10 g of the obtained electroconductive particles were dispersed in 500 mL of distilled water, 1 g of a 10% by weight aqueous dispersion of insulating particles was added, followed by stirring at room temperature for 8 hours. After filtration with a 3 µm mesh filter, it was further washed with methanol and dried to obtain conductive particles with insulating particles.

(5) Preparation of conductive material (anisotropic conductive paste)

7 parts by weight of the obtained conductive particles, 25 parts by weight of a bisphenol A-type phenoxy resin, 4 parts by weight of a fluorene-type epoxy resin, 30 parts by weight of a phenol novolak-type epoxy resin, and SI-60L (manufactured by Sanshin Chemical Industries, Ltd.) Was blended, defoaming and stirring for 3 minutes to obtain a conductive material (anisotropic conductive paste).

(6) Fabrication of connection structure

A transparent glass substrate on which an IZO electrode pattern having an L/S of 10 µm/10 µm (a first electrode and a Vickers hardness of 100 Hv of metal on the electrode surface) was formed on the upper surface was prepared. Further, a semiconductor chip having an L/S of 10 μm/10 μm (second electrode, Vickers hardness of metal on the electrode surface of 50 Hv) formed on the lower surface thereof was prepared. The anisotropic conductive paste obtained on the transparent glass substrate was applied to a thickness of 30 µm to form an anisotropic conductive paste layer. Next, the semiconductor chips were stacked on the anisotropic conductive paste layer so that the electrodes face each other. Thereafter, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer becomes 100°C, a pressurized heating head is placed on the upper surface of the semiconductor chip, and a pressure of 55 MPa is applied to cure the anisotropic conductive paste layer at 100°C. Got it.

(Examples (4)-2 to (4)-17 and Comparative Examples (4)-1 to (4)-7)

In the same manner as in Example (4)-1, except that the types of monomer components used in the production of the substrate particles, the types of solvents, and their blending amounts were changed as shown in Tables 11 to 13 below, the substrate particles, conductive particles, and An anisotropic conductive film and a connection structure were obtained.

The details and results of the substrate particles and electroconductive particles in Test Example 4 are shown in Tables 11 to 13.

(Other evaluations of Test Examples (1), (2), (3) and (4))

The following evaluation was performed on the substrate particles of the above-described Test Examples (1) to (4).

(Evaluation 11) Example of use as a spacer for a liquid crystal display element

Fabrication of STN type liquid crystal display element:

To a dispersion medium containing 70 parts by weight of isopropyl alcohol and 30 parts by weight of water, in 100% by weight of the obtained spacer dispersion, spacers for liquid crystal display elements (substrate particles) of Examples 1 to 32 were added so that the solid content concentration became 2% by weight, and stirred. Thus, a liquid crystal display device spacer dispersion was obtained.

After depositing a SiO ₂ film on one side of a pair of transparent glass plates (50 mm in length, 50 mm in width, 0.4 mm in thickness) by the CVD method, an ITO film was formed on the entire surface of the SiO ₂ film by sputtering. A polyimide alignment film composition (manufactured by Nissan Chemical Co., Ltd., SE3510) was applied to the obtained glass substrate with an ITO film by spin coating and fired at 280°C for 90 minutes to form a polyimide alignment film. After performing the rubbing treatment on the alignment film, the liquid crystal display element spacers were wet-spread on the alignment film side of one of the substrates to be 100 per 1 mm ² . After forming the sealing agent around the other substrate, the substrate and the substrate to which the spacer was sprayed were opposed to each other so that the rubbing direction was 90°, and both were bonded. Then, it processed at 160 degreeC for 90 minutes, and the sealing agent was hardened, and the empty cell (a screen which did not contain liquid crystal) was obtained. In the obtained empty cell, an STN type liquid crystal (manufactured by DIC) containing a chiral agent was injected, and the injection port was then covered with a sealing agent, and then heat-treated at 120°C for 30 minutes to obtain an STN type liquid crystal display element.

In the obtained liquid crystal display device, Examples (1)-1 to (1)-32, (2)-1 to (2)-17, (3)-1 to (3)-17 and (4)-1 to The space between the substrates was well regulated by the liquid crystal display element spacers of (4)-17. In addition, the liquid crystal display device exhibited good display quality. In addition, to the peripheral sealing agent of the liquid crystal display device, Examples (1)-1 to (1)-32, (2)-1 to (2)-17, (3)-1 to (3)-17 and ( Even when the substrate particles of 4)-1 to (4)-17 were used as a spacer for a liquid crystal display element, the display quality of the obtained liquid crystal display element was good.

One… Conductive particles
2… Conductive layer
11... Substrate particle
11A... Substrate particle
21... Conductive particles
22... Conductive layer
22A... First conductive layer
22B... Second conductive layer
31... Conductive particles
31a... spin
32... Conductive layer
32a... spin
33... Core material
34... Insulating material
41... Connection structure
42... First connection target member
42a... First electrode
43... Second connection target member
43a... Second electrode
44... Connection
81... Liquid crystal display element
82... Transparent glass substrate
83... Transparent electrode
84... Alignment film
85... LCD
86... Seal system

Claims (26)

It is a substrate particle used as a spacer or used to obtain conductive particles having the conductive layer by forming a conductive layer on the surface thereof,
BET specific surface area is 5m ² /g or more,
The substrate particle, wherein the CV value of the particle diameter is 10% or less. The method of claim 1 wherein the compression elastic modulus when compressed 10% 1N / mm ² more than 3500N / mm ² or less, the base material particles. Claim 1 or 2, wherein the base particles, the compression elastic modulus at 30% compression hayeoteul 1N / mm ^2, more than 3000N / mm ² or less in the. The substrate particle according to any one of claims 1 to 3, wherein the compression recovery rate is 5% or more and 60% or less. BET specific surface area is 300m ² /g or more and less than 600m ² /g,
The compression elastic modulus of the time of 10% compression hayeoteul 100N / mm ² more than 3000N / mm ² or less, the base material particles. The method of claim 5, wherein the compression elastic modulus at 30% compression hayeoteul 100N / mm ² more than 2500N / mm ² or less, the base material particles. The substrate particle according to claim 5 or 6, wherein the compression recovery rate is 5% or more and 60% or less. The substrate particle according to any one of claims 5 to 7, wherein the CV value of the particle diameter is 10% or less. The substrate particle according to any one of claims 5 to 8, which is used as a spacer or is used to obtain conductive particles having the conductive layer by forming a conductive layer on the surface thereof. BET specific surface area is 5m ² /g or more and less than 300m ² /g,
The compression elastic modulus at 30% compression hayeoteul 100N / mm ² more than 3000N / mm ² or less, the base material particles. The method of claim 10, wherein the compression elastic modulus when compressed 10% 100N / mm ² more than 3500N / mm ² or less, the base material particles. The substrate particle according to claim 10 or 11, wherein the compression recovery rate is 5% or more and 60% or less. The substrate particle according to any one of claims 10 to 12, wherein the CV value of the particle diameter is 10% or less. The substrate particle according to any one of claims 10 to 13, which is used as a spacer or used to obtain conductive particles having the conductive layer by forming a conductive layer on the surface thereof. BET specific surface area is 600m ² /g or more,
The compressive elastic modulus when compressed by 10% is 1200 N/mm ² or less,
The compressive elastic modulus when compressed by 30% is 1200 N/mm ² or less,
A substrate particle having a compression recovery rate of 5% or more. The substrate particle according to claim 15, wherein the CV value of the particle diameter is 10% or less. The substrate particle according to claim 15 or 16, which is used as a spacer or is used to obtain conductive particles having the conductive layer by forming a conductive layer on the surface thereof. The substrate particle according to any one of claims 1 to 17, wherein the density is 1 g/cm ³ or more and 1.4 g/cm ³ or less. The substrate particle according to any one of claims 1 to 18, wherein the total pore volume is 0.01 cm ³ /g or more and 3 cm ³ /g or less. The substrate particle according to any one of claims 1 to 19, wherein the average pore diameter is 10 nm or less. The substrate particle according to any one of claims 1 to 20, wherein the average particle diameter is 0.1 µm or more and 100 µm or less. The substrate particle according to any one of claims 1 to 21, and
A conductive particle comprising a conductive layer disposed on the surface of the substrate particle. The conductive particle according to claim 22, further comprising an insulating material disposed on the outer surface of the conductive layer. The electroconductive particle of Claim 22 or 23 which has a protrusion on the outer surface of the said electroconductive layer. Including conductive particles and a binder resin,
A conductive material, wherein the conductive particles include the substrate particles according to any one of claims 1 to 21, and a conductive layer disposed on the surface of the substrate particles. A first connection object member having a first electrode on its surface,
A second connection object member having a second electrode on its surface,
And a connection portion connecting the first connection object member and the second connection object member,
The connection portion is formed of conductive particles or a conductive material containing the conductive particles and a binder resin,
The said electroconductive particle comprises the base material particle of any one of Claims 1-21, and the conductive layer arrange|positioned on the surface of the said base material particle,
The connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles.

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