JP2020097739A - Resin particles, conductive particles, conductive material and connection structure - Google Patents

Abstract

To provide resin particles which can effectively suppress aggregation and can effectively suppress occurrences of plating cracking and plating peeling.SOLUTION: Resin particles are polymers of a polymerizable compound, and have a compression recovery rate of 5% or more and 30% or less and a compression elastic modulus when being compressed by 30% of 500 N/mmor more and 2,000 N/mmor less, and a ratio of a volume or resin particles in 1 wt.% of an acetone dispersion of the resin particles to a volume of the resin particles of 1 wt.% of a water dispersion of the resin particles of 1.10 or less.SELECTED DRAWING: Figure 1

Description

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

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 the binder.

The anisotropic conductive material is used to electrically connect electrodes of various members to be connected such as a flexible printed circuit (FPC), a glass substrate, a glass epoxy substrate, and a semiconductor chip to obtain a connection structure. ing. In addition, as the conductive particles, conductive particles having resin particles and conductive portions arranged on the surface of the resin particles may be used.

Further, the liquid crystal display element is configured by disposing liquid crystal between two glass substrates. In the liquid crystal display device, a spacer is used as a gap control material in order to keep the gap (gap) between the two glass substrates uniform and constant. Resin particles are generally used as the spacer.

As an example of the conductive particles, Patent Document 1 below discloses conductive silicone rubber particles in which a precious metal coating layer is formed on the surface of the silicone rubber particles by a physical vapor deposition method. The average particle diameter of the silicone rubber particles is 0.1 μm to 100 μm. In the above conductive silicone rubber particles, the content of the noble metal coating layer is 10% by weight to 80% by weight based on 100% by weight of the entire noble metal coated silicone rubber particles after the vapor deposition treatment.

Patent Document 2 below discloses a conductive resin filler having a conductive metal coating layer on the surface of a polymer mainly composed of styrene. The polymer is spherical with an average particle size of 1 μm to 50 μm. The average layer thickness of the conductive metal coating layer is 200Å or more.

JP, 2004-238588, A JP-A-60-012603

In recent years, when electrically connecting electrodes using a conductive material containing conductive particles or a connecting material, even if the pressure is relatively low, the electrodes are securely connected electrically and the connection resistance is low. Is desired. For example, in a method of manufacturing a liquid crystal display device, when a flexible substrate is mounted by the FOG method, an anisotropic conductive material is arranged on a glass substrate, the flexible substrates are laminated, and thermocompression bonding is performed. 2. Description of the Related Art In recent years, liquid crystal panels are becoming narrower and glass substrates are becoming thinner. In this case, if thermocompression bonding is performed at a high pressure and a high temperature during mounting of the flexible substrate, distortion may occur in the mounting of the flexible substrate and display unevenness may occur. Therefore, when mounting the flexible substrate in the FOG method, it is desirable to perform thermocompression bonding with a relatively low pressure. In addition to the FOG method, it may be required to make the pressure and temperature during thermocompression bonding relatively low.

When the conventional resin particles are used as the conductive particles, the connection resistance may increase if the electrodes are electrically connected at a relatively low pressure. The cause of this is that plating cracks and plating peeling occur when the conductive particles are produced. With conventional resin particles, the resin particles may swell due to the solvent used during plating. When the plating layer (conductive layer) is formed on the swollen resin particles, the swollen resin particles contract during the drying after plating to cause plating cracking or plating peeling. Further, regarding the conductive particles having a plating layer (conductive layer) formed on the surface of the resin particles, the resin particles may swell with the solvent used for the purpose of dispersing the conductive particles. Swelling of the resin particles in the conductive particles causes plating cracks and plating peeling.

Further, in the conventional resin particles, the resin particles may aggregate during plating, and it may be difficult to perform the plating well. As a result, the particle diameter of the conductive particles may vary, or the thickness of the conductive layer in the conductive particles may vary, so that the conductive particles do not uniformly contact the electrodes and the connection resistance may increase.

Further, when conventional resin particles are used as a spacer used in a liquid crystal display element or the like, it is difficult to maintain a good dispersion state, and the resin particles may aggregate. Further, since the resin particles are hard, the area of contact with the liquid crystal display element member is small, and the resin particles may move within the liquid crystal display element. As a result, the particle diameter of the spacers may vary, the spacers may not evenly contact the liquid crystal display element member, etc., and a sufficient gap control effect may not be obtained, or display defects may occur.

An object of the present invention is to provide resin particles capable of effectively suppressing agglomeration and effectively suppressing the occurrence of plating cracks and plating peeling. Moreover, the objective of this invention is providing the electroconductive particle, electroconductive material, and connection structure which used the said resin particle.

According to a broad aspect of the present invention, the polymer is a polymer of a polymerizable compound, the compression recovery rate is 5% or more and 30% or less, and the compression elastic modulus when compressed by 30% is 500 N/mm ² or more and 2000 N/ mm ² or less, and the ratio of the volume of the resin particles in the 1 wt% acetone dispersion of the resin particles to the volume of the resin particles in the 1 wt% aqueous dispersion of the resin particles is 1.10 or less. Particles are provided.

In a specific aspect of the resin particles according to the present invention, the compression elastic modulus upon compression of 50%, is 800 N / mm ² or more 4000 N / mm ² or less.

In a particular aspect of the resin particles according to the present invention, the polymerizable compound constituting the polymer includes a crosslinkable compound and a non-crosslinkable compound, and the crosslinkable compound has an alkylene having 6 or more carbon atoms. It has a group or a cyclic structure having 6 or more carbon atoms.

In one specific aspect of the resin particles according to the present invention, the non-crosslinkable compound has an alkyl group having 4 or more carbon atoms or a cyclic structure having 6 or more carbon atoms.

In one specific aspect of the resin particles according to the present invention, the cyclic structure is a saturated aliphatic ring having no double bond.

In one specific aspect of the resin particles according to the present invention, the content of the structure derived from the crosslinkable compound in 100% by weight of the polymer is 10% by weight or more and less than 80% by weight.

In one particular aspect of the resin particles according to the present invention, the ratio of the volume of resin particles in a 1 wt% acetone dispersion of resin particles to the volume of resin particles in a 1 wt% aqueous dispersion of resin particles is 1 It is 0.03 or less.

In one specific aspect of the resin particles according to the present invention, the resin particles are used as spacers or used to obtain conductive particles having a conductive portion formed on the surface and having the conductive portion.

According to a broad aspect of the present invention, there is provided a conductive particle including the above-mentioned resin particle and a conductive portion arranged on the surface of the resin particle.

In a specific aspect of the conductive particles according to the present invention, the particle diameter of the conductive particles is 1 μm or more and 30 μm or less.

According to a broad aspect of the present invention, a conductive material comprising conductive particles and a binder, the conductive particles, the resin particles described above, and a conductive portion arranged on the surface of the resin particles, the conductive material. Provided.

According to a wide aspect of the present invention, a first connection target member having a first electrode on a surface, a second connection target member having a second electrode on a surface, and the first connection target member, A connecting portion connecting the second connection target member, the material of the connecting portion includes the resin particles described above, and the first electrode and the second electrode include the connecting portion. Provides a connection structure that is electrically connected by.

The resin particles according to the present invention are polymers of polymerizable compounds. The resin particles according to the present invention have a compression recovery rate of 5% or more and 30% or less. In the resin particles according to the present invention, the compression elastic modulus when compressed by 30% is 500 N/mm ² or more and 2000 N/mm ² or less. In the resin particles according to the present invention, the ratio of the volume of the resin particles in the 1 wt% acetone dispersion of the resin particles to the volume of the resin particles in the 1 wt% aqueous dispersion of the resin particles is 1.10 or less. .. Since the resin particle according to the present invention is provided with the above-mentioned constitution, it is possible to effectively suppress agglomeration, and it is possible to effectively suppress the occurrence of plating cracks and plating peeling.

FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention. FIG. 3 is a cross-sectional view showing conductive particles according to the third embodiment of the present invention. FIG. 4 is a cross-sectional view showing an example of a connection structure using conductive particles according to the first embodiment of the present invention. FIG. 5 is a sectional view showing an example of a connection structure using the resin particles according to the present invention. FIG. 6 is a sectional view showing an example of a liquid crystal display element using the resin particles according to the present invention as a spacer for a liquid crystal display element.

Hereinafter, the present invention will be described in detail.

(Resin particles)
The resin particles according to the present invention are polymers of polymerizable compounds. The resin particles according to the present invention have a compression recovery rate of 5% or more and 30% or less. In the resin particles according to the present invention, the compression elastic modulus when compressed by 30% is 500 N/mm ² or more and 2000 N/mm ² or less. In the resin particles according to the present invention, the ratio (swelling ratio) of the volume of the resin particles in the 1 wt% acetone dispersion of the resin particles to the volume of the resin particles in the 1 wt% aqueous dispersion of the resin particles is 1. It is 10 or less. The ratio of the volume of resin particles in a 1 wt% acetone dispersion of resin particles to the volume of resin particles in a 1 wt% aqueous dispersion of resin particles is specifically the following ratio. The resin particles are dispersed in acetone and stirred for 1 hour, and the resin particles having a volume of the resin particles in a 1% by weight acetone dispersion of the resin particles are dispersed in water and stirred for 1 hour. Ratio of the resin particles to the volume of the resin particles in a 1% by weight aqueous dispersion.

Since the resin particle according to the present invention is provided with the above-mentioned constitution, it is possible to effectively suppress agglomeration, and it is possible to effectively suppress the occurrence of plating cracks and plating peeling.

Further, in the present invention, it is possible to effectively suppress the swelling of the resin particles due to the solvent used during plating, and it is possible to effectively suppress the occurrence of plating cracks and plating peeling. Further, with respect to the conductive particles having a plating layer (conductive layer) formed on the surface of the resin particles, it is possible to effectively suppress the swelling of the resin particles by the solvent used for the purpose of dispersing the conductive particles. It is possible to effectively suppress the occurrence of plating cracks and plating peeling. As a result, by using conductive particles having a conductive layer formed on the surface of the resin particles according to the present invention, when electrically connecting the electrodes, even if thermocompression bonding is performed at a relatively low pressure, The connection resistance can be sufficiently reduced.

Further, in the resin particles according to the present invention, aggregation of resin particles can be effectively suppressed. As a result, when the resin particles according to the present invention are used as the conductive particles, the particle diameter of the conductive particles and the thickness of the conductive layer in the conductive particles can be made uniform, and the conductive particles are evenly distributed on the electrode. The contact resistance can be lowered. Further, when the resin particles according to the present invention are used as a spacer used in a liquid crystal display device or the like, the dispersed state can be kept good, the particle diameter of the spacer can be made uniform, and the spacer can be used for liquid crystal display. It is possible to make uniform contact with the element member and the like, and there is no movement of the spacer in the liquid crystal display member, and a sufficient gap control effect can be obtained.

The resin particles according to the present invention have a compression recovery rate of 5% or more and 30% or less. The compression recovery rate is preferably 7.5% or more, more preferably 10% or more, preferably 25% or less, more preferably 20% or less. When the compression recovery rate is equal to or higher than the lower limit and equal to or lower than the upper limit, it is possible to more effectively suppress the occurrence of plating cracks and peeling, and it is possible to control the gap with higher accuracy.

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

Disperse the resin particles on the sample table. For one dispersed resin particle, 30% of the resin particle is compressed and deformed in the center direction of the resin particle at 25° C. at the end face of a smooth indenter of a cylinder (diameter 100 μm, made of diamond) using a micro compression tester. Load (reverse load value) up to. After that, unloading is performed up to the load value for origin (0.40 mN). The load-compressive displacement during this period is measured, and the compression recovery rate can be obtained from the following formula. The load speed is 0.33 mN/sec. As the micro compression tester, for example, "Fisherscope H-100" manufactured by Fisher Co., Ltd. is used.

Compression recovery rate (%)=[L2/L1]×100
L1: Compressive displacement from load value for origin to reverse load value when load is applied L2: Unload displacement from reverse load value to load value for origin when releasing load

In the resin particles according to the present invention, the compression elastic modulus (30% K value) when compressed by 30% is 500 N/mm ² or more and 2000 N/mm ² or less. The 30% K value is preferably 650 N / mm ² or more, more preferably 800 N / mm ² or more, preferably 1800 N / mm ² or less, and more preferably not more than 1500 N / mm ^2. When the 30% K value is equal to or higher than the lower limit and equal to or lower than the upper limit, it is possible to more effectively suppress the occurrence of plating cracks and plating peeling, and it is possible to control the gap with higher accuracy.

In the above resin particles, the compression elastic modulus of when compressed 50% (50% K value) is preferably 800 N / mm ² or more, more preferably 1000 N / mm ² or more, more preferably 1200 N / mm ² or more, preferably 4000 N / mm ² or less, more preferably 3500 N / mm ^2, more preferably not more than 3000N / mm ^2. When the 50% K value is equal to or higher than the lower limit and equal to or lower than the upper limit, it is possible to more effectively suppress the occurrence of plating cracks and peeling, and it is possible to control the gap with higher accuracy.

The compression elastic modulus (30% K value and 50% K value) of the resin particles can be measured as follows.

Using a micro compression tester, one resin particle is compressed under the conditions of 25° C., a compression rate of 0.3 mN/sec, and a maximum test load of 20 mN on a smooth indenter end face of a cylinder (diameter 100 μm, made of diamond). At this time, the load value (N) and the compression displacement (mm) are measured. From the obtained measured values, the above compression elastic modulus (30% K value and 50% K value) can be calculated by the following formula. As the micro compression tester, for example, "Fisherscope H-100" manufactured by Fisher Co., Ltd. is used. The compression elastic modulus (30% K value and 50% K value) of the resin particles is the arithmetic mean of the compression elastic moduli (30% K value and 50% K value) of 50 resin particles selected arbitrarily. By doing so, it is preferable to calculate.

30% K value or 50% K value (N/mm ² )=(3/2 ^1/2 )·F·S ⁻³ / ² ·R ^−1/2
F: Load value (N) when the resin particles are compressed and deformed by 30% or 50%
S: Compressive displacement (mm) when the resin particles are compressed and deformed by 30% or 50%
R: Radius of resin particles (mm)

The compression elastic modulus universally and quantitatively represents the hardness of the resin particles. By using the above compression elastic modulus, the hardness of the resin particles can be quantitatively and uniquely expressed.

In the resin particles according to the present invention, the ratio (swelling ratio) of the volume of the resin particles in the 1 wt% acetone dispersion of the resin particles to the volume of the resin particles in the 1 wt% aqueous dispersion of the resin particles is 1. It is 10 or less. The swelling ratio is preferably 1.00 or more, preferably 1.08 or less, more preferably 1.05 or less, still more preferably 1.03 or less. When the swelling ratio is equal to or higher than the lower limit and equal to or lower than the upper limit, agglomeration can be suppressed more effectively, and the occurrence of plating cracks and plating peeling can be suppressed even more effectively.

The swelling ratio is an index of the resistance of the resin particles to the solvent. The closer the swelling ratio is to 1, the higher the solvent resistance of the resin particles is. As the solvent resistance of the resin particles is higher, aggregation can be suppressed more effectively, and the occurrence of plating cracks and plating peeling can be suppressed even more effectively.

The swelling ratio can be measured as follows.

1 g of resin particles is immersed in 100 g of methanol at 25° C. for 20 hours. Then, the resin particles are taken out and vacuum dried at 40° C. for 12 hours. The dried resin particles are dispersed in water to a concentration of 1% by weight and stirred for 1 hour to prepare a 1% by weight aqueous dispersion of resin particles. Immediately after the completion of stirring, the particle size of the resin particles is measured using a precision particle size distribution measuring device (“Multisizer 3” manufactured by Beckman Coulter, Inc.). Further, the dried resin particles are dispersed in acetone to have a concentration of 1% by weight and stirred for 1 hour to prepare a 1% by weight acetone dispersion liquid of the resin particles. Immediately after the completion of stirring, the particle size of the resin particles is measured using a precision particle size distribution measuring device (“Multisizer 3” manufactured by Beckman Coulter, Inc.). The swelling ratio can be calculated by the following formula (1).

Swelling ratio=[particle size of resin particles in acetone dispersion (μm)/particle size of resin particles in water dispersion (μm)] ³ ... Formula (1) (swelling ratio=[in acetone dispersion Volume of resin particles (μm ³ )/Volume of resin particles in aqueous dispersion (μm ³ )] Equation (1), volume=4/3×π×radius ^{3 of} resin particles ³ )

The use of the resin particles is not particularly limited. The resin particles are suitably used for various purposes. The resin particles are preferably used as spacers or for obtaining conductive particles having a conductive portion. In the conductive particle, the conductive portion is formed on the surface of the resin particle. The resin particles are preferably used as spacers. The resin particles are preferably used to obtain conductive particles having a conductive portion. Examples of the method of using the spacer include a liquid crystal display element spacer, a gap control spacer, and a stress relaxation spacer. The gap control spacer is used for gap control of a laminated chip for ensuring standoff height and flatness, and gap control of optical components for ensuring smoothness of a glass surface and thickness of an adhesive layer. Can be used. The stress relaxation spacer can be used for stress relaxation of a sensor chip or the like, stress relaxation of a connecting portion connecting two connection target members, and the like.

The resin particles are preferably used as a spacer for a liquid crystal display element, and are preferably used as a peripheral sealant for a liquid crystal display element. In the peripheral sealant for a liquid crystal display element, it is preferable that the resin particles function as a spacer. Since the resin particles have good compressive deformation characteristics, the resin particles are used as spacers to be arranged between substrates, or a conductive portion is formed on the surface to be used as conductive particles to electrically connect electrodes. The spacers or the conductive particles are effectively arranged between the substrates or the electrodes when the electrodes are turned on. Furthermore, since the resin particles can suppress the aggregation and movement of the spacer, in the liquid crystal display element using the spacer for the liquid crystal display element and the connection structure using the conductive particles, the connection failure and the display failure can occur. Is less likely to occur.

Further, the above resin particles are also suitably used as an inorganic filler, a toner additive, a shock absorber or a vibration absorber. For example, the above resin particles can be used as a substitute for rubber or spring.

(Other details of resin particles)
The resin particles are a polymer of a polymerizable compound. From the viewpoint of more effectively suppressing agglomeration, and from the viewpoint of more effectively suppressing the occurrence of plating cracks and plating peeling, in the above resin particles, the central portion of the resin particles and the surface portion of the resin particles are the same. It is preferable to be composed of the above-mentioned polymerizable compound. The compounding ratio of the polymerizable compound in the central part of the resin particles and the compounding ratio of the polymerizable compound in the surface parts of the resin particles may be the same or different. The composition ratio of the constituent components in the central portion of the resin particles and the constituent ratio of the constituent components in the surface portions of the resin particles may be the same or different.

In the above resin particles, it is preferable that the central portion of the resin particle is formed of the central portion forming material and the surface portion of the resin particle is formed of the surface portion forming material. From the viewpoint of more effectively suppressing agglomeration, and from the viewpoint of more effectively suppressing the occurrence of plating cracks and plating peeling, in the resin particles, the components of the central part forming material and the surface part forming material are The components are preferably the same. In the resin particles, the component ratio of the central part forming material and the component ratio of the surface part forming material may be the same or different. In addition, it is preferable that the resin particles have a region including both the central portion forming material and the surface portion forming material. In the resin particles, it is preferable that the resin particles have a region in the central portion that includes the central portion forming material and does not include the surface portion forming material or contains the surface portion forming material in an amount of less than 25% by weight. In the resin particles, it is preferable that the resin particles have a region in the surface portion that includes the surface portion forming material and does not include the center portion forming material or contains the center portion forming material in an amount of less than 25% by weight.

It is preferable that the resin particles are not core-shell particles including a core and a shell arranged on the surface of the core, and it is preferable that the resin particles do not have an interface between the core and the shell. The resin particles preferably have no interface within the resin particles, and more preferably do not have an interface in which different surfaces are in contact with each other. The resin particles preferably do not have a discontinuous portion where the surface exists, and preferably do not have a discontinuous portion where the structured surface exists.

From the viewpoint of more effectively suppressing aggregation, and from the viewpoint of more effectively suppressing the occurrence of plating cracks and plating peeling, the polymerizable compound constituting the polymer is a crosslinkable compound and a non-crosslinkable compound. It is preferable to include a compound. From the viewpoint of more effectively suppressing aggregation and more effectively suppressing the occurrence of plating cracks and plating peeling, the crosslinkable compound has an alkylene group having 6 or more carbon atoms, or a carbon number of 6 or more. It preferably has a cyclic structure of 6 or more, and more preferably has a cyclic structure of 6 or more carbon atoms.

From the viewpoint of more effectively suppressing aggregation and more effectively suppressing the occurrence of plating cracks and plating peeling, the non-crosslinkable compound is an alkyl group having 4 or more carbon atoms, or a carbon number. Preferably has a cyclic structure of 6 or more, and more preferably has a cyclic structure of 6 or more carbon atoms.

The number of atoms forming the above-mentioned cyclic structure is preferably 6 or more from the viewpoint of more effectively suppressing aggregation and further effectively suppressing the occurrence of plating cracks and plating peeling. The atom forming the above cyclic structure is not particularly limited, and examples thereof include carbon, nitrogen, and oxygen. The cyclic structure may be formed of one type of atom or two or more types of atoms. From the viewpoint of more effectively suppressing agglomeration, and from the viewpoint of more effectively suppressing the occurrence of plating cracks and plating peeling, the atom forming the cyclic structure is preferably carbon. The cyclic structure is preferably formed only of carbon.

From the viewpoint of more effectively suppressing agglomeration and the effect of further effectively suppressing the occurrence of plating cracks and plating peeling, it is preferable that the cyclic structure does not have a double bond. The cyclic structure is preferably a saturated aliphatic ring having no double bond.

Examples of the crosslinkable compound include 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate. As for the said crosslinkable compound, only 1 type may be used and 2 or more types may be used together.

From the viewpoint of more effectively suppressing agglomeration and further effectively suppressing the occurrence of plating cracks and plating peeling, the crosslinkable compound is 1,6-hexanediol di(meth)acrylate or tris. It is preferably cyclodecane dimethanol di(meth)acrylate. From the viewpoint of more effectively suppressing aggregation and further effectively suppressing the occurrence of plating cracks and plating peeling, the crosslinkable compound is 1,6-hexanediol di(meth)acrylate. Is more preferable.

Examples of the non-crosslinkable compound include n-butyl(meth)acrylate, isobutyl(meth)acrylate, tert-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isodecyl(meth)acrylate, n-lauryl(meth). Examples thereof include acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate. As for the said non-crosslinkable compound, only 1 type may be used and 2 or more types may be used together.

From the viewpoint of further effectively suppressing aggregation and further effectively suppressing the occurrence of plating cracks and plating peeling, the non-crosslinkable compound is tert-butyl (meth)acrylate or isobornyl (meth). Acrylate is preferable, and isobornyl (meth)acrylate is more preferable.

The content (CC) of the structure derived from the crosslinkable compound in 100% by weight of the polymer is preferably 10% by weight or more, more preferably 20% by weight or more, and preferably less than 80% by weight, more preferably Is 70% by weight or less, more preferably 60% by weight or less, and particularly preferably 50% by weight or less. The content (CN) of the structure derived from the non-crosslinkable compound in 100% by weight of the polymer is preferably more than 20% by weight, more preferably 30% by weight or more, further preferably 40% by weight or more, particularly It is preferably 50% by weight or more, preferably 90% by weight or less, and more preferably 80% by weight or less. When the content (CC) of the structure derived from the crosslinkable compound and the content (CN) of the structure derived from the non-crosslinkable compound are not less than the lower limit and not more than the upper limit, aggregation is more effectively performed. It is possible to suppress, and it is possible to more effectively suppress the occurrence of plating cracks and plating peeling.

Examples of the method for obtaining the content (CC) of the structure derived from the crosslinkable compound and the content (CN) of the structure derived from the non-crosslinkable compound include the following methods. From the blending amount of the crosslinkable compound and the non-crosslinkable compound used in obtaining the polymer and the residual amount of the crosslinkable compound and the non-crosslinkable compound after the polymerization, the amount of the polymerized crosslinkable compound and the non-crosslinkable compound is obtained. , Calculated from the amount of polymerized crosslinkable compound and non-crosslinkable compound.

Further, as a method for obtaining the content (CC) of the structure derived from the crosslinkable compound and the content (CN) of the structure derived from the non-crosslinkable compound from the resin particles, the following methods can be mentioned. The amount of functional groups in the respective resin particles of the crosslinkable compound and the non-crosslinkable compound used in obtaining the polymer, and in the respective resin particles of the crosslinkable compound and the non-crosslinkable compound used in obtaining the polymer It is calculated from the amount of groups reacted with the functional group.

From the viewpoint of more effectively suppressing aggregation, and from the viewpoint of more effectively suppressing the occurrence of plating cracks and plating peeling, the resin particles and the polymer are the crosslinkable compound and the non-crosslinkable compound. Is preferably obtained by polymerizing and in a weight ratio of 5:95 to 80:20. The resin particles and the polymer are more preferably obtained by polymerizing the crosslinkable compound and the non-crosslinkable compound at a weight ratio of 10:90 to 70:30, and 20:80 to 60: It is more preferably obtained by polymerizing at 40, and particularly preferably obtained by polymerizing at 20:80 to 50:50. When the resin particles and the polymer satisfy the above-described preferred embodiments, aggregation can be suppressed more effectively, and the occurrence of plating cracks and plating peeling can be suppressed even more effectively. In this case, a crosslinkable compound (other crosslinkable compound) or a noncrosslinkable compound (other noncrosslinkable compound) other than the above crosslinkable compound and the above noncrosslinkable compound may be used.

The particle size of the resin particles can be appropriately set according to the application. The particle size of the resin particles is preferably 0.5 μm or more, more preferably 1 μm or more, preferably 500 μm or less, more preferably 300 μm or less, even more preferably 100 μm or less, further preferably 50 μm or less, particularly preferably It is 30 μm or less. When the particle size of the resin particles is equal to or more than the lower limit and equal to or less than the upper limit, agglomeration can be more effectively suppressed, and the occurrence of plating cracks and plating peeling can be more effectively suppressed. .. When the particle diameter of the resin particles is 0.5 μm or more and 500 μm or less, the resin particles can be suitably used for the purpose of conductive particles. When the particle size of the resin particles is 0.5 μm or more and 500 μm or less, the resin particles can be suitably used for the use of the spacer.

The particle size of the resin particles is preferably an average particle size, and more preferably a number average particle size. The particle diameter of the resin particles is, for example, by observing 50 arbitrary resin particles with an electron microscope or an optical microscope, calculating an average value of the particle diameters of the resin particles, and performing laser diffraction particle size distribution measurement. It is required by In observation with an electron microscope or an optical microscope, the particle size of each resin particle is determined as the particle size in terms of a circle equivalent diameter. In the observation with an electron microscope or an optical microscope, the average particle diameter of the circle equivalent diameter of any 50 resin particles is almost equal to the average particle diameter of the spherical equivalent diameter. In the laser diffraction particle size distribution measurement, the particle size of each resin particle is determined as the particle size in terms of a sphere equivalent diameter. The average particle diameter of the resin particles is preferably calculated by laser diffraction particle size distribution measurement.

In addition, in the case of measuring the particle size of the above resin particles in the conductive particles, it can be measured as follows, for example.

The conductive particles are added to "Technobit 4000" manufactured by Kulzer so that the content of the conductive particles is 30% by weight, and dispersed to prepare a conductive particle inspection embedded resin. A cross section of the conductive particles is cut out using an ion milling device (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the conductive particles dispersed in the inspection embedded resin. Then, using a field emission scanning electron microscope (FE-SEM), the image magnification is set to 25,000 times, 50 conductive particles are randomly selected, and the resin particles of each conductive particle are observed. .. The particle diameter of the resin particles in each conductive particle is measured, and they are arithmetically averaged to obtain the particle diameter of the resin particles.

From the viewpoint of more effectively suppressing the occurrence of plating cracks and plating peeling and controlling the gap with higher accuracy, the coefficient of variation (CV value) of the particle diameter of the resin particles is preferably 10%. Or less, more preferably 7% or less. When the variation coefficient of the particle diameter of the resin particles is equal to or less than the upper limit, the resin particles can be suitably used for the spacer and the conductive particles.

The coefficient of variation (CV value) can be measured as follows.

CV value (%)=(ρ/Dn)×100
ρ: Standard deviation of particle size of resin particles Dn: Average value of particle size of resin particles

The shape of the resin particles is not particularly limited. The resin particles may have a spherical shape, a shape other than a spherical shape, or a flat shape.

(Conductive particles)
The conductive particle according to the present invention includes the above-mentioned resin particle and a conductive portion arranged on the surface of the resin particle.

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

The conductive particle 1 shown in FIG. 1 has a resin particle 11 and a conductive portion 2 arranged on the surface of the resin particle 11. The conductive portion 2 is in contact with the surface of the resin particle 11. The conductive portion 2 covers the surface of the resin particles 11. The conductive particle 1 is a coated particle in which the surface of the resin particle 11 is coated with the conductive portion 2. In the conductive particle 1, the conductive portion 2 is a single-layer conductive portion (conductive layer).

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

The conductive particle 21 shown in FIG. 2 has the resin particle 11 and the conductive portion 22 arranged on the surface of the resin particle 11. The conductive portion 22 as a whole has a first conductive portion 22A on the resin particle 11 side and a second conductive portion 22B on the side opposite to the resin particle 11 side.

The conductive particles 1 shown in FIG. 1 and the conductive particles 21 shown in FIG. 2 differ only in the conductive portion 22. That is, in the conductive particle 1, the conductive portion having a one-layer structure is formed, whereas in the conductive particle 21, the first conductive portion 22A and the second conductive portion 22B having a two-layer structure are formed. There is. The first conductive portion 22A and the second conductive portion 22B may be formed as different conductive portions or may be formed as the same conductive portion.

The first conductive portion 22A is arranged on the surface of the resin particle 11. The first conductive portion 22A is arranged between the resin particles 11 and the second conductive portion 22B. The first conductive portion 22A is in contact with the resin particles 11. The second conductive portion 22B is in contact with the first conductive portion 22A. The first conductive portion 22A is arranged on the surface of the resin particles 11, and the second conductive portion 22B is arranged on the surface of the first conductive portion 22A.

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

The conductive particle 31 shown in FIG. 3 includes the resin particle 11, a conductive portion 32, a plurality of core substances 33, and a plurality of insulating substances 34. The conductive portion 32 is arranged on the surface of the resin particles 11. The plurality of core substances 33 are arranged on the surface of the resin particles 11. The conductive portion 32 is arranged on the surface of the resin particles 11 so as to cover the resin particles 11 and the plurality of core substances 33. In the conductive particle 31, the conductive portion 32 is a single-layer conductive portion (conductive layer).

The conductive particle 31 has a plurality of protrusions 31a on the outer surface. In the conductive particle 31, the conductive portion 32 has a plurality of protrusions 32a on the outer surface. The plurality of core substances 33 raise the outer surface of the conductive portion 32. The protrusions 31 a and 32 a are formed by the outer surface of the conductive portion 32 being raised by the plurality of core substances 33. The plurality of core substances 33 are embedded in the conductive portion 32. The core substance 33 is arranged inside the protrusions 31 a and 32 a. The conductive particles 31 use a plurality of core substances 33 to form the protrusions 31 a and 32 a. The conductive particles do not need to use a plurality of core materials in order to form the protrusions. The conductive particles do not have to include a plurality of the core substances.

The conductive particles 31 have an insulating substance 34 disposed on the outer surface of the conductive portion 32. At least a part of the outer surface of the conductive portion 32 is covered with the insulating material 34. The insulating substance 34 is formed of a material having an insulating property and is an insulating particle. Thus, the conductive particles according to the present invention may have an insulating substance arranged on the outer surface of the conductive portion. However, the conductive particles do not necessarily have to have an insulating substance. The conductive particles do not have to include a plurality of insulating substances.

Conductive part:
The metal for forming the conductive portion is not particularly limited. Examples of the metal include gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon and tungsten. , Molybdenum and alloys thereof. Examples of the metal include tin-doped indium oxide (ITO) and solder. An alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is preferable, because the connection resistance between the electrodes can be further reduced.

Further, it is preferable that the conductive portion and the outer surface portion of the conductive portion contain nickel, because the conduction reliability can be effectively enhanced. The content of nickel in 100% by weight of the conductive portion containing nickel is preferably 10% by weight or more, more preferably 50% by weight or more, even more preferably 60% by weight or more, further preferably 70% by weight or more, particularly preferably Is 90% by weight or more. The content of nickel in 100% by weight of the conductive portion containing nickel may be 97% by weight or more, 97.5% by weight or more, or 98% by weight or more.

Incidentally, hydroxyl groups often exist on the surface of the conductive portion due to oxidation. Generally, hydroxyl groups are present on the surface of the conductive portion formed of nickel due to oxidation. An insulating substance can be arranged on the surface of the conductive portion having such a hydroxyl group (the surface of the conductive particles) through a chemical bond.

Like the conductive particles 1 and 31, the conductive portion may be formed of one layer. Like the conductive particles 21, the conductive portion may be formed of a plurality of layers. That is, the conductive portion may have a laminated structure of two or more layers. When the conductive part 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 is a gold layer. Is more preferable. When the outermost layer is these preferable conductive parts, the connection resistance between the electrodes can be lowered more effectively. Further, when the outermost layer is the gold layer, the corrosion resistance can be more effectively enhanced.

The method for forming the conductive portion on the surface of the resin particles is not particularly limited. Examples of the method of forming the conductive portion include a method of electroless plating, a method of electroplating, a method of physical vapor deposition, and a method of coating the surface of resin particles with a metal powder or a paste containing a metal powder and a binder. Etc. The method by electroless plating is preferable because the conductive portion is easily formed. Examples of the physical vapor deposition method include vacuum vapor deposition, ion plating, and ion sputtering.

The particle diameter of the conductive particles is preferably 0.5 μm or more, more preferably 1 μm or more, preferably 500 μm or less, more preferably 300 μm or less, still more preferably 100 μm or less, further preferably 50 μm or less, particularly preferably Is 30 μm or less. The particle size of the conductive particles is not less than the above lower limit and not more than the above upper limit, when connecting the electrodes using the conductive particles, the contact area between the conductive particles and the electrode becomes sufficiently large, and It becomes difficult for aggregated conductive particles to be formed when forming the conductive portion. In addition, the distance between the electrodes connected via the conductive particles does not become too large, and the conductive portion is less likely to peel off from the surface of the resin particles. Further, when the particle diameter of the conductive particles is not less than the lower limit and not more than the upper limit, the conductive particles can be suitably used for the purpose of the conductive material.

The particle size of the conductive particles is preferably an average particle size, and more preferably a number average particle size. The particle diameter of the conductive particles can be obtained, for example, by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope and calculating the average value of the particle diameter of each conductive particle. In observation with an electron microscope or an optical microscope, the particle size of each conductive particle is determined as the particle size in terms of a circle equivalent diameter. In observation with an electron microscope or an optical microscope, the average particle diameter of any 50 conductive particles in a circle-equivalent diameter is substantially equal to the average particle diameter in a sphere-equivalent diameter.

The thickness of the conductive portion 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, still more preferably 0.3 μm or less. When the thickness of the conductive portion is not less than the above lower limit and not more than the above upper limit, sufficient conductivity is obtained, and the conductive particles do not become too hard, and the conductive particles are sufficient when connecting between the electrodes. Deform.

When the conductive portion is formed of a plurality of layers, the thickness of the conductive portion of the outermost layer is preferably 0.001 μm or more, more preferably 0.01 μm or more, preferably 0.5 μm or less, more preferably Is 0.1 μm or less. When the thickness of the conductive portion of the outermost layer is not less than the lower limit and not more than the upper limit, the coating of the conductive portion of the outermost layer is uniform, the corrosion resistance is sufficiently high, and the connection resistance between the electrodes is sufficient. It becomes low. When the outermost layer is a gold layer, the thinner the gold layer, the lower the cost.

The thickness of the conductive part can be measured by observing the cross section of the conductive particle using, for example, a transmission electron microscope (TEM). As for the thickness of the conductive portion, it is preferable to calculate the average value of the thicknesses of 5 portions of the conductive portion as the thickness of the conductive portion of one conductive particle, and the average value of the thickness of the entire conductive portion is 1 It is more preferable to calculate it as the thickness of the conductive portion. In the case of a plurality of conductive particles, the thickness of the conductive portion is preferably obtained by calculating an average value of 10 arbitrary conductive particles.

Core substance:
The conductive particles preferably have a plurality of protrusions on the outer surface of the conductive portion. Since the conductive particles have a plurality of protrusions on the outer surface of the conductive portion, the reliability of conduction between the electrodes can be further enhanced. An oxide film is often formed on the surface of the electrode connected by the conductive particles. Furthermore, an oxide film is often formed on the surface of the conductive portion of the conductive particles. By using the conductive particles having the protrusions, the conductive particles are arranged between the electrodes and then pressure-bonded, whereby the oxide film is effectively removed by the protrusions. Therefore, the electrodes and the conductive particles can be more surely brought into contact with each other, and the connection resistance between the electrodes can be lowered more effectively. Furthermore, when the conductive particles have an insulating substance on the surface, or when the conductive particles are dispersed in a binder resin and used as a conductive material, the projections of the conductive particles cause the conductive particles and the electrodes to be separated from each other. Insulating material and binder resin between them are effectively eliminated. For this reason, the conduction reliability between the electrodes can be more effectively enhanced.

By embedding the core substance in the conductive portion, a plurality of protrusions can be easily formed on the outer surface of the conductive portion. However, the core substance does not necessarily have to be used in order to form the protrusion on the surface of the conductive portion of the conductive particle.

As a method of forming the protrusions, after attaching a core substance to the surface of the resin particles, a method of forming a conductive portion by electroless plating, and after forming a conductive portion by electroless plating on the surface of the resin particles, Examples include a method of attaching a core substance and further forming a conductive portion by electroless plating. As another method of forming the protrusions, a method of adding a core substance in the middle of forming a conductive portion (first conductive portion, second conductive portion, or the like) on the surface of resin particles can be mentioned. .. Further, in order to form a protrusion, without using the core substance, after forming a conductive portion on the resin particles by electroless plating, deposit plating in a protrusion shape on the surface of the conductive portion, further by electroless plating You may use the method of forming a conductive part, etc.

As a method of arranging the core substance on the surface of the resin particles, for example, a core substance is added to a dispersion liquid of the resin particles, the core substance is accumulated on the surface of the resin particles by Van der Waals force, and adhered. And a method in which a core substance is added to a container containing resin particles and the core substance is attached to the surface of the resin particles by a mechanical action such as rotation of the container. A method of accumulating and adhering the core substance on the surface of the resin particles in the dispersion liquid is preferable because it is easy to control the amount of the core substance to be adhered.

The material of the core substance is not particularly limited. Examples of the material of the core substance include a conductive substance and a non-conductive substance. Examples of the conductive substance include metals, metal oxides, conductive nonmetals such as graphite, and conductive polymers. Examples of the conductive polymer include polyacetylene. Examples of the non-conductive substance include silica, alumina, barium titanate and zirconia. A metal is preferable because it can increase the conductivity and can effectively lower the connection resistance. The core substance is preferably metal particles. As the metal that is the material of the core substance, the metals mentioned above as the metal for forming the conductive portion can be appropriately used.

Insulating material:
It is preferable that the conductive particles include an insulating substance disposed on the surface of the conductive portion. In this case, if conductive particles are used to connect the electrodes, a short circuit between adjacent electrodes can be further prevented. Specifically, when a plurality of conductive particles come into contact with each other, the insulating substance exists between the plurality of electrodes, so that a short circuit between adjacent electrodes in the lateral direction can be prevented, not between the upper and lower electrodes. In addition, when connecting the electrodes, the conductive particles are pressed by the two electrodes, so that the insulating material between the conductive portion of the conductive particles and the electrodes can be easily removed. When the conductive particle has a plurality of protrusions on the outer surface of the conductive portion, the insulating substance between the conductive portion of the conductive particle and the electrode can be more easily removed.

The insulating substance is preferably insulating particles because the insulating substance can be more easily removed during pressure bonding between the electrodes.

Examples of the material of the insulating substance include polyolefin compounds, (meth)acrylate polymers, (meth)acrylate copolymers, block polymers, thermoplastic resins, crosslinked products of thermoplastic resins, thermosetting resins and water-soluble resins. Are listed. As the material of the insulating material, only one kind may be used, or two or more kinds may be used in combination.

Examples of the polyolefin compound include polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer and the like. Examples of the (meth)acrylate polymer include polymethyl(meth)acrylate, polydodecyl(meth)acrylate, and polystearyl(meth)acrylate. Examples of the block polymer include polystyrene, styrene-acrylic acid ester copolymer, SB type styrene-butadiene block copolymer, SBS type styrene-butadiene block copolymer, and hydrogenated products thereof. Examples of the thermoplastic resin include vinyl polymers and vinyl copolymers. Examples of the thermosetting resin include epoxy resin, phenol resin and melamine resin. Examples of the crosslinking of the thermoplastic resin include introduction of polyethylene glycol methacrylate, alkoxylated trimethylolpropane methacrylate, alkoxylated pentaerythritol methacrylate, and the like. Examples of the water-soluble resin include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide and methyl cellulose. A chain transfer agent may be used to adjust the degree of polymerization. Examples of the chain transfer agent include thiol and carbon tetrachloride.

Examples of the method of disposing the insulating substance on the surface of the conductive portion include a chemical method and a physical or mechanical method. Examples of the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, and an emulsion polymerization method. Examples of the physical or mechanical method include spray drying, hybridization, electrostatic adhesion method, spraying method, dipping method and vacuum deposition method. Since it is difficult for the insulating substance to be released, it is preferable to dispose the insulating substance on the surface of the conductive portion through a chemical bond.

The outer surface of the conductive part and the surface of the insulating material may be coated with a compound having a reactive functional group. The outer surface of the conductive portion and the surface of the insulating substance may not be directly chemically bonded, or may be indirectly chemically bonded by a compound having a reactive functional group. After introducing a carboxyl group to the outer surface of the conductive portion, the carboxyl group may be chemically bonded to a functional group on the surface of the insulating substance via a polymer electrolyte such as polyethyleneimine.

(Conductive material)
The conductive material according to the present invention includes the conductive particles described above and a binder. The conductive particles include the resin particles described above and a conductive portion arranged on the surface of the resin particles. The conductive particles are preferably dispersed in a binder for use, and are preferably dispersed in the binder for use as a conductive material. The conductive material is preferably an anisotropic conductive material. The conductive material is preferably used for electrical connection between electrodes. The conductive material is preferably a conductive material for circuit connection.

The binder is not particularly limited. A known insulating resin is used as the binder. The binder preferably contains a thermoplastic component (thermoplastic compound) or a curable component, and more preferably contains a curable component. Examples of the curable component include a photocurable component and a thermosetting component. The photocurable component preferably contains a photocurable compound and a photopolymerization initiator. The thermosetting component preferably contains a thermosetting compound and a thermosetting agent.

Examples of the binder include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers and elastomers. The binder may be used alone or in combination of two or more.

Examples of the vinyl resin include vinyl acetate resin, acrylic resin and styrene resin. Examples of the thermoplastic resin include polyolefin resin, ethylene-vinyl acetate copolymer, and polyamide resin. Examples of the curable resin include epoxy resin, urethane resin, polyimide resin and unsaturated polyester resin. 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. Examples of the thermoplastic block copolymer include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, hydrogenated products of styrene-butadiene-styrene block copolymer, and styrene-isoprene. -A hydrogenated product of a styrene block copolymer and the like. Examples of the elastomer include styrene-butadiene copolymer rubber, acrylonitrile-styrene block copolymer rubber, and the like.

The conductive material may be, for example, a filler, a filler, a softening agent, a plasticizer, a polymerization catalyst, a curing catalyst, a coloring agent, an antioxidant, a heat stabilizer, a light stabilizer, in addition to the conductive particles and the binder. , An ultraviolet absorber, a lubricant, an antistatic agent, and a flame retardant may be added.

As a method for dispersing the conductive particles in the binder, a conventionally known dispersion method can be used and is not particularly limited. As a method of dispersing the conductive particles in the binder, after adding the conductive particles in the binder, a method of kneading and dispersing with a planetary mixer or the like, the conductive particles in water or an organic solvent In addition, a method in which it is uniformly dispersed using a homogenizer or the like, then added to the above binder, and kneaded and dispersed by a planetary mixer or the like can be mentioned. Further, as a method of dispersing the conductive particles in the binder, after diluting the binder with water or an organic solvent or the like, add the conductive particles, kneading with a planetary mixer or the like to disperse Are listed.

The conductive material can be used as a conductive paste, a conductive film, or the like. When the conductive material is a conductive film, a film containing no conductive particles may be laminated on a conductive film containing conductive particles. The conductive paste is preferably an anisotropic conductive paste. The conductive film is preferably an anisotropic conductive film.

The content of the binder in 100% by weight of the conductive material is preferably 10% by weight or more, more preferably 30% by weight or more, further preferably 50% by weight or more, particularly preferably 70% by weight or more, and preferably It is 99.99% by weight or less, more preferably 99.9% by weight or less. When the content of the binder is not less than the lower limit and not more than the upper limit, the conductive particles are efficiently arranged between the electrodes, and the connection reliability of the connection target member 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, more preferably 40% by weight or less, particularly preferably 20% by weight or less, and most preferably 10% by weight or less. When the content of the conductive particles is equal to or higher than the lower limit and equal to or lower than the upper limit, conduction reliability between the electrodes is further enhanced.

(Connection structure)
A connection structure can be obtained by connecting the members to be connected using the conductive particles or using a conductive material containing the conductive particles and a binder resin.

A connection structure according to the present invention includes a first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, and the first connection target member, And a connection part that connects the second connection target member. In the connection structure according to the present invention, the material of the connection portion includes the resin particles described above. The material of the connecting portion is preferably the above-mentioned conductive particles or the above-mentioned conductive material. It is preferable that the connection portion is a connection structure formed of the above-mentioned conductive particles or formed of the above-mentioned conductive material.

When the conductive particles are used alone, the connecting portion itself is the conductive particles. That is, the first and second connection target members are connected by the conductive particles. The conductive material used to obtain the connection structure is preferably an anisotropic conductive material. In the connection structure according to the present invention, the first electrode and the second electrode are electrically connected by the connection portion.

FIG. 4 is a cross-sectional view showing an example of a connection structure using the conductive particles 1 shown in FIG.

The connection structure 41 shown in FIG. 4 is a connection that connects the first connection target member 42, the second connection target member 43, and the first connection target member 42 and the second connection target member 43. And a section 44. The connecting portion 44 is formed of a conductive material containing the conductive particles 1 and a binder. In FIG. 4, the conductive particles 1 are schematically illustrated for convenience of illustration. Instead of the conductive particles 1, other conductive particles such as the conductive particles 21 and 31 may be used.

The first connection target member 42 has a plurality of first electrodes 42a on the surface (upper surface). The second connection target 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. Therefore, the first and second connection target members 42 and 43 are electrically connected by the conductive particles 1.

FIG. 5 is a sectional view showing an example of a connection structure using the resin particles according to the present invention.

The connection structure 51 shown in FIG. 5 is a bond that bonds the first connection target member 52, the second connection target member 53, and the first connection target member 52 and the second connection target member 53. And layer 54.

The adhesive layer 54 includes the resin particles 11 described above. The resin particles 11 are not in contact with both the first and second connection target members 52 and 53. The resin particles 11 are used as spacers for stress relaxation.

The adhesive layer 54 includes gap control particles 61 and a thermosetting component 62. In the adhesive layer 54, the gap control particles 61 are in contact with both the first and second connection target members 52 and 53. The gap control particles 61 may be conductive particles or particles having no conductivity. The gap control particles may be the resin particles described above. The thermosetting component 62 includes a thermosetting compound and a thermosetting agent. The thermosetting component 62 is a cured product of a thermosetting compound. The thermosetting component 62 is formed by curing a thermosetting compound.

The first connection target member may have a first electrode on its surface. The second connection target member may have a second electrode on its surface.

The method for manufacturing the connection structure is not particularly limited. As an example of a method for manufacturing a connection structure, a method in which the conductive material is arranged between a first connection target member and a second connection target member to obtain a laminated body, and then the laminated body is heated and pressed Etc. The pressure of the pressurization is about 9.8×10 ⁴ Pa to 4.9×10 ⁶ Pa. The heating temperature is about 120°C to 220°C. The pressure applied to connect the electrodes of the flexible printed circuit board, the electrodes arranged on the resin film, and the electrodes of the touch panel is about 9.8×10 ⁴ Pa to 1.0×10 ⁶ Pa.

Specific examples of the connection target member include electronic components such as semiconductor chips, capacitors and diodes, and electronic components such as printed circuit boards, flexible printed circuit boards, glass epoxy substrates and circuit boards such as glass substrates. The connection target member is preferably an electronic component. At least one of the first connection target member and the second connection target member is preferably a semiconductor wafer or a semiconductor chip. The connection structure is preferably a semiconductor device.

The conductive material is preferably a conductive material for connecting electronic components. The conductive paste is a paste-like conductive material, and it is preferable that the conductive paste is applied to the connection target member in a paste-like state.

The conductive particles, the conductive material, and the adhesive are also suitable for use in a touch panel. Therefore, it is also preferable that the connection target member is a flexible substrate or a connection target member in which electrodes are arranged on the surface of the resin film. The connection target member is preferably a flexible substrate, and is preferably a connection target member in which electrodes are arranged on the surface of a resin film. When the flexible substrate is a flexible printed circuit board or the like, the flexible substrate generally has electrodes on its surface.

Examples of the electrodes provided on the connection target member include metal electrodes such as gold electrodes, nickel electrodes, tin electrodes, aluminum electrodes, silver electrodes, SUS electrodes, copper electrodes, molybdenum electrodes, and tungsten electrodes. When the member to be connected is a flexible printed board, the electrode is preferably a gold electrode, a nickel electrode, a tin 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. 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. Examples of the trivalent metal element include Sn, Al and Ga.

(Liquid crystal display element)
The resin particles can be suitably used as a spacer for a liquid crystal display element. The first connection target member may be a first liquid crystal display element member. The second connection target member may be a second liquid crystal display element member. The connection portion is such that the first liquid crystal display element member and the second liquid crystal display element member are in a state where the first liquid crystal display element member and the second liquid crystal display element member face each other. It may be a seal part that seals the outer periphery of the.

The resin particles can also be used as a peripheral sealant for liquid crystal display elements. The liquid crystal display device includes a first liquid crystal display device member, a second liquid crystal display device member, the first liquid crystal display device member, and the second liquid crystal display device member facing each other. , A seal portion that seals the outer peripheries of the first liquid crystal display element member and the second liquid crystal display element member. The liquid crystal display element includes liquid crystal disposed inside the seal portion and between the first liquid crystal display element member and the second liquid crystal display element member. In this liquid crystal display element, the liquid crystal dropping method is applied, and the seal portion is formed by thermosetting a sealing agent for the liquid crystal dropping method.

FIG. 6 is a sectional view showing an example of a liquid crystal display element using the resin particles according to the present invention as a spacer for a liquid crystal display element.

The liquid crystal display element 81 shown in FIG. 6 has a pair of transparent glass substrates 82. The transparent glass substrate 82 has an insulating film (not shown) on the opposite surface. Examples of the material of the insulating film include SiO _{2 and the} like. A transparent electrode 83 is formed on the insulating film of the transparent glass substrate 82. Examples of the material of the transparent electrode 83 include ITO. The transparent electrode 83 can be formed by patterning by photolithography, for example. An alignment film 84 is formed on the transparent electrode 83 on the surface of the transparent glass substrate 82. Examples of the material of the alignment film 84 include polyimide.

A liquid crystal 85 is sealed between the pair of transparent glass substrates 82. A plurality of resin particles 11 are arranged between the pair of transparent glass substrates 82. The resin particles 11 are used as spacers for liquid crystal display elements. The interval between the pair of transparent glass substrates 82 is regulated by the plurality of resin particles 11. A sealant 86 is arranged between the edges of the pair of transparent glass substrates 82. The sealant 86 prevents the liquid crystal 85 from flowing out. The sealant 86 contains resin particles 11A which differ from the resin particles 11 only in particle size.

In the above liquid crystal display element, the arrangement density of the spacers for liquid crystal display element per 1 mm ² is preferably 10 pieces/mm ² or more, and preferably 1000 pieces/mm ² or less. When the arrangement density is 10 cells/mm ² or more, the cell gap becomes more uniform. When the arrangement density is 1000 pieces/mm ² or less, the contrast of the liquid crystal display device is further improved.

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

(Example 1)
(1) Preparation of Resin Particles Polystyrene particles having an average particle diameter of 0.80 μm were prepared as seed particles. A mixture solution was prepared by mixing 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 aqueous solution of polyvinyl alcohol. After the above mixed solution was dispersed by ultrasonic waves, it was placed in a separable flask and stirred uniformly.

Further, 1,6-hexanediol dimethacrylate (“HD-N” manufactured by Shin Nakamura Chemical Co., Ltd.) as a crosslinkable compound, and tert-butyl methacrylate (“light ester TB” manufactured by Kyoeisha Chemical Co., Ltd.) as a non-crosslinkable compound. I prepared. 20 parts by weight of the crosslinkable compound and 80 parts by weight of the non-crosslinkable compound were mixed to obtain a mixture. To this mixture, 2 parts by weight of 2,2′-azobis(methyl isobutyrate) (“V-601” manufactured by Wako Pure Chemical Industries, Ltd.) and 2 parts by weight of benzoyl peroxide (“NIPER BW” manufactured by NOF CORPORATION) were added. And 8 parts by weight of triethanolamine lauryl sulfate, 100 parts by weight of ethanol, and 1000 parts by weight of ion-exchanged water were further added to prepare an emulsion.

The emulsion was further added to the mixed solution in the separable flask and stirred for 4 hours to allow the seed particles to absorb the monomer to obtain a suspension containing the swollen seed particles of the monomer.

Then, 490 parts by weight of a 5% by weight aqueous solution of polyvinyl alcohol was added, heating was started, and the reaction was carried out at 85° C. for 10 hours to obtain resin particles.

(2) Production of conductive particles The obtained resin particles were washed, classified, and dried. Then, a nickel layer was formed on the surface of the obtained resin particles by electroless plating to prepare conductive particles. The thickness of the nickel layer was 0.1 μm.

(3) Preparation of conductive material (anisotropic conductive paste) In order to prepare a conductive material (anisotropic conductive paste), the following materials were prepared.

(Material of conductive material (anisotropic conductive paste))
Thermosetting compound A: Epoxy compound ("EP-3300P" manufactured by Nagase Chemtex)
Thermosetting compound B: Epoxy compound ("EPICLON HP-4032D" manufactured by DIC)
Thermosetting compound C: Epoxy compound (“Epogosei PT” manufactured by Yokkaichi Gosei Co., polytetramethylene glycol diglycidyl ether)
Thermosetting agent: thermal cation generator (San-Aid "SI-60" manufactured by Sanshin Chemical Co., Ltd.)
Filler: silica (average particle size 0.25 μm)

A conductive material (anisotropic conductive paste) was produced as follows.

(Method for producing conductive material (anisotropic conductive paste))
10 parts by weight of thermosetting compound A, 10 parts by weight of thermosetting compound B, 15 parts by weight of thermosetting compound C, 5 parts by weight of thermosetting agent, and 20 parts by weight of filler were blended to obtain a blend. Further, the conductive particles thus obtained were added so that the content in the compound 100% by weight was 10% by weight, and the mixture was stirred at 2000 rpm for 5 minutes using a planetary stirrer to obtain a conductive material (anisotropic material). Conductive conductive paste) was obtained.

(4) Fabrication of Connection Structure As a first connection target member, a glass substrate having an aluminum electrode pattern having L/S of 20 μm/20 μm on its upper surface was prepared. As the second connection target member, a semiconductor chip having a gold electrode pattern (gold electrode thickness 20 μm) having L/S of 20 μm/20 μm on the lower surface was prepared.

A conductive material (anisotropic conductive paste) immediately after fabrication was applied on the upper surface of the glass substrate to a thickness of 30 μm to form a conductive material (anisotropic conductive paste) layer. Next, the semiconductor chip was laminated on the upper surface of the conductive material (anisotropic conductive paste) layer so that the electrodes face each other. After that, while adjusting the temperature of the head so that the temperature of the conductive material (anisotropic conductive paste) layer becomes 170° C., the pressure heating head is placed on the upper surface of the semiconductor chip to set the conductive material (anisotropic conductive paste). The layer was cured under conditions of 170° C., 1 MPa, and 15 seconds to obtain a connection structure.

(Example 2)
In the same manner as in Example 1 except that the amount of the crosslinkable compound was changed to 50 parts by weight and the amount of the non-crosslinkable compound was changed to 50 parts by weight when producing the resin particles, The conductive particles, the conductive material, and the connection structure were obtained.

(Example 3)
When preparing the resin particles, the crosslinkable compound was changed to tricyclodecane dimethanol diacrylate (“Light acrylate DCP-A” manufactured by Kyoeisha Chemical Co., Ltd.), and the non-crosslinkable compound was isobornyl acrylate (Kyoeisha Chemical Co., Ltd.). "Light acrylate IB-XA"). Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 1 except for the above changes.

(Example 4)
When preparing the resin particles, the crosslinkable compound was changed to tricyclodecane dimethanol diacrylate (“Light acrylate DCP-A” manufactured by Kyoeisha Chemical Co., Ltd.), and the non-crosslinkable compound was isobornyl acrylate (Kyoeisha Chemical Co., Ltd.). "Light acrylate IB-XA"). The amount of the crosslinkable compound was changed to 50 parts by weight, and the amount of the non-crosslinkable compound was changed to 50 parts by weight. Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 1 except for the above changes.

(Example 5)
When preparing the resin particles, the crosslinkable compound was changed to tricyclodecane dimethanol diacrylate (Kyoeisha Chemical Co., Ltd. “Light acrylate DCP-A”), and the non-crosslinkable compound was styrene (Fuji Film Wako Pure Chemical Industries, Ltd.). "Styrene monomer"). Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 1 except for the above changes.

(Comparative Example 1)
When preparing the resin particles, the crosslinkable compound was changed to divinylbenzene (“DVB960” manufactured by NS Styrene Monomer Co., Ltd.) and the non-crosslinkable compound was changed to cyclohexyl methacrylate (“Light acrylate CH” manufactured by Kyoeisha Chemical Co., Ltd.). Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 1 except for the above changes.

(Comparative example 2)
When preparing the resin particles, the crosslinkable compound was changed to divinylbenzene (“DVB960” manufactured by NS Styrene Monomer Co., Ltd.) and the non-crosslinkable compound was changed to cyclohexyl methacrylate (“Light acrylate CH” manufactured by Kyoeisha Chemical Co., Ltd.). The amount of the crosslinkable compound was changed to 50 parts by weight, and the amount of the non-crosslinkable compound was changed to 50 parts by weight. Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 1 except for the above changes.

(Comparative example 3)
When preparing the resin particles, the crosslinkable compound was changed to divinylbenzene (“DVB960” manufactured by NS Styrene Monomer Co., Ltd.) and the non-crosslinkable compound was changed to cyclohexyl methacrylate (“Light acrylate CH” manufactured by Kyoeisha Chemical Co., Ltd.). The amount of the crosslinkable compound was changed to 80 parts by weight, and the amount of the non-crosslinkable compound was changed to 20 parts by weight. Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 1 except for the above changes.

(Comparative Example 4)
In the same manner as in Example 1 except that the amount of the crosslinkable compound was changed to 80 parts by weight and the amount of the noncrosslinkable compound was changed to 20 parts by weight when producing the resin particles, The conductive particles, the conductive material, and the connection structure were obtained.

(Comparative example 5)
When preparing the resin particles, the crosslinkable compound was changed to tricyclodecane dimethanol diacrylate (“Light acrylate DCP-A” manufactured by Kyoeisha Chemical Co., Ltd.), and the non-crosslinkable compound was isobornyl acrylate (Kyoeisha Chemical Co., Ltd.). "Light acrylate IB-XA"). The amount of the crosslinkable compound was changed to 80 parts by weight, and the amount of the non-crosslinkable compound was changed to 20 parts by weight. Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 1 except for the above changes.

(Comparative example 6)
When producing the resin particles, the crosslinkable compound was changed to divinylbenzene (“DVB960” manufactured by NS Styrene Monomer Co., Ltd.) and the non-crosslinkable compound was isobornyl acrylate (“Light acrylate IB-XA” manufactured by Kyoeisha Chemical Co., Ltd.). Changed to. Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 1 except for the above changes.

(Comparative Example 7)
When preparing the resin particles, the crosslinkable compound was changed to tricyclodecane dimethanol diacrylate (Kyoeisha Chemical Co., Ltd. “Light acrylate DCP-A”), and the non-crosslinkable compound was styrene (Fuji Film Wako Pure Chemical Industries, Ltd.). "Styrene monomer"). The amount of the crosslinkable compound was changed to 50 parts by weight, and the amount of the non-crosslinkable compound was changed to 50 parts by weight. Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 1 except for the above changes.

(Evaluation)
(1) Particle Diameter of Resin Particles and Conductive Particles The particle diameters of the obtained resin particles and conductive particles were measured using precision particle size distribution measurement (“Multisizer 3” manufactured by Beckman Coulter, Inc.).

(2) Compression recovery rate of resin particles The compression recovery rate of the obtained resin particles was measured by the above-described method using a micro compression tester (“Fisherscope H-100” manufactured by Fisher Co.).

(3) Compressive Elastic Modulus of Resin Particles The compressive elastic modulus (30% K value and 50% K value) of the obtained resin particles was measured by the above-described method using a micro compression tester (“Fischer Scope H-100” manufactured by Fisher Co.). ]) was used for the measurement.

(4) Physical properties of resin particles for low-voltage mounting method Based on the results of (2) compression recovery rate of resin particles and (3) compression elastic modulus of resin particles described above, the physical properties of resin particles for low-voltage mounting method are based on the following criteria. It was judged by. When the compression recovery rate exceeds 30%, the physical properties of the resin particles in the low pressure mounting method are considerably poor.

[Criteria for determining physical properties of resin particles for low-voltage mounting method]
◯: The compression recovery rate is 5% or more and 30% or less, the 30% K value is 500 N/mm ² or more and 2000 N/mm ² or less, and the 50% K value is 800 N/mm ² or more and 4000 N/. mm ² or less ○: is the compression recovery ratio is less than 5% to 30% and has a 30% K value is 500 N / mm ² or more 2000N / mm ² or less, and less than value 50% K is 800 N / mm ² Or exceeds 4000 N/mm ^2. △: Does not correspond to any of the criteria of ○○, ○ and × ×: Compression recovery rate exceeds 30%

(5) Swelling ratio of resin particles 1 g of resin particles was immersed in 100 g of methanol at 25° C. for 20 hours. Then, the resin particles were taken out and vacuum dried at 40° C. for 12 hours. The dried resin particles were dispersed in water to 1% by weight and stirred for 1 hour to prepare a 1% by weight aqueous dispersion of resin particles. Immediately after the completion of stirring, the particle size of the resin particles was measured using a precision particle size distribution measuring device ("Multisizer 3" manufactured by Beckman Coulter, Inc.). Further, the dried resin particles were dispersed in acetone to have a concentration of 1% by weight and stirred for 1 hour to prepare a 1% by weight acetone dispersion liquid of the resin particles. Immediately after the completion of stirring, the particle size of the resin particles was measured using a precision particle size distribution measuring device ("Multisizer 3" manufactured by Beckman Coulter, Inc.). The swelling ratio was calculated by the following formula (1).

Swelling ratio=[particle size of resin particles in acetone dispersion (μm)/particle size of resin particles in water dispersion (μm)] ³ ... Formula (1) (swelling ratio=[in acetone dispersion Volume of resin particles (μm ³ )/Volume of resin particles in aqueous dispersion (μm ³ )] Equation (1), volume=4/3×π×radius ³ )

(6) Cohesiveness of resin particles The cohesiveness of the resin particles was evaluated by measuring the sedimentation rate when the obtained resin particles were mixed with an organic solvent and allowed to stand. 2.5 g of the obtained resin particles and 25 mL of acetone were mixed to prepare a mixed solution, and the prepared mixed solution was ultrasonicated for 1 minute by an ultrasonic cleaner (“VS-1003” manufactured by AS ONE Co., Ltd.). Dispersed. Then, it was put in a 20 mL glass graduated cylinder and allowed to stand. The actual sedimentation rate was calculated by confirming the sedimentation of the resin particles every 60 minutes. The ratio of the theoretical settling velocity to the measured settling velocity ([theoretical settling velocity (m/h)/actual settling velocity value (m/h)]) was calculated and judged according to the following criteria.

The theoretical settling velocity was calculated using the Stokes equation. This is an equation used when it is assumed that a true spherical particle exists as a single particle. However, it is not considered because it does not include the term based on the slurry concentration.

Theory sedimentation rate ^{_{(m / h) = D p}} 2 (ρ p -ρ f) g / 18η
D _p : Particle diameter of resin particles (m)
ρ _p : Density of resin particles (kg/m ³ )
ρ _f : Density of acetone (kg/m ³ ): 784 kg/m ³
g: Gravity acceleration (m/s)
η: Viscosity of acetone (kg/m·s): 0.00032 kg/m·s

A dry automatic densitometer (“Acupic” manufactured by Shimadzu Corporation) was used for measuring the density of the resin particles. To measure the density of the resin particles, resin particles obtained by immersing 1 g of the resin particles in 100 g of methanol at 25° C. for 20 hours and then vacuum drying at 40° C. for 12 hours were used.

[Criteria for Resin Particle Cohesion]
◯: The ratio ([theoretical sedimentation rate (m/h)/measured sedimentation rate value (m/h)]) was less than 0.55 (no aggregates of resin particles were observed)
Δ: The ratio ([theoretical sedimentation rate (m/h)/measured sedimentation rate value (m/h)]) was 0.55 or more and less than 0.75 (a few aggregates of resin particles were observed) Be)
X: The value of the above ratio ([theoretical sedimentation rate (m/h)/measured sedimentation rate value (m/h)]) is 0.75 or more (aggregates in which resin particles are aggregated are recognized)

(7) Plated state 0.1 g of the obtained conductive particles was immersed in 10 g of ethanol at 25° C. for 20 hours. Then, the conductive particles were taken out and vacuum dried at 40° C. for 12 hours. The plating state of 10,000 dried conductive particles was observed with a scanning electron microscope. The presence or absence of plating cracks or plating peeling was evaluated. The plating state was judged according to the following criteria.

[Judgment criteria of plating state]
◯: The number of conductive particles in which plating cracking or plating peeling was confirmed was less than 20 ○: The number of conductive particles in which plating cracking or plating peeling was confirmed was 20 or more and less than 200 x: Plating cracking or plating The number of conductive particles confirmed to be peeled off is 200 or more

(8) Connection resistance The connection resistance between the opposing electrodes of the obtained connection structure was measured by the 4-terminal method. The connection resistance of the connection structure was judged according to the following criteria.

[Evaluation criteria for connection resistance]
○ ○: Connection resistance 3.0Ω or less ○: Connection resistance more than 3.0Ω and 4.0Ω or less △: Connection resistance more than 4.0Ω and 5.0Ω or less ×: Connection resistance more than 5.0Ω

(9) State of Spacer in Liquid Crystal Display Element In the same manner as (10) described later, the obtained resin particles are used as spacers (spacers for liquid crystal display element) so that the number is 100/mm ² in the liquid crystal display element. A liquid crystal display element was produced by dispersing. The range of 1000 mm ² was observed with an optical microscope, the number of aggregates in which 5 or more spacers in the liquid crystal display element were aggregated was measured, and the aggregation property was evaluated. The spacer cohesiveness was judged according to the following criteria.

Further, the range of 1000 mm ² was observed by an optical microscope and a polarization microscope, and an abnormal alignment portion generated by damaging the alignment film when the spacer moved was measured as a trace of movement of the spacer, and the number thereof was measured. The movement of the spacer was judged according to the following criteria.

[Spacer cohesiveness]
◯: The number of aggregates aggregated by the spacer is less than 2 Δ: The number of aggregates aggregated by the spacer is 2 or more and less than 5 ×: The number of aggregates aggregated by the spacer is 5 or more

[Move spacer]
◯: There are less than 1 (0) places with traces of spacer movement.
△: 1 or more and less than 3 places where spacers have traces moved ×: 3 or more places where spacers have traces of movement

Details and results of the resin particles and the conductive particles are shown in Tables 1 to 4 below.

(10) Example of use as spacer for liquid crystal display element Fabrication of STN type liquid crystal display element:
In a dispersion medium containing 70 parts by weight of isopropyl alcohol and 30 parts by weight of water, the solid content concentration of the spacers (resin particles) for liquid crystal display devices of Examples 1 to 5 was 2% by weight in 100% by weight of the resulting spacer dispersion liquid. To obtain a spacer dispersion liquid for liquid crystal display device.

After depositing a SiO ₂ film on one surface of a pair of transparent glass plates (length 50 mm, width 50 mm, thickness 0.4 mm) by a CVD method, an ITO film was formed on the entire surface of the SiO ₂ film by sputtering. A polyimide alignment film composition (SE3510, manufactured by Nissan Chemical Co., Ltd.) was applied to the obtained glass substrate with an ITO film by a spin coating method, and baked at 280° C. for 90 minutes to form a polyimide alignment film. After rubbing the alignment film, the one liquid crystal display device spacer was wet-dispersed on the alignment film side of one substrate so that 100 spacers per 1 mm ² . After forming a sealant around the other substrate, this substrate and the substrate on which the spacers were scattered were placed so as to face each other so that the rubbing direction was 90°, and both were bonded. Then, it was treated at 160° C. for 90 minutes to cure the sealant to obtain an empty cell (screen containing no liquid crystal). An STN type liquid crystal (manufactured by DIC) containing a chiral agent was injected into the obtained empty cell, and then the injection port was closed with a sealing agent, followed by heat treatment at 120° C. for 30 minutes to obtain an STN type liquid crystal display element. Obtained.

In the obtained liquid crystal display element, the spacing between the substrates was well regulated by the liquid crystal display element spacers (resin particles) of Examples 1 to 5. Further, the liquid crystal display element showed good display quality. Even when the resin particles of Examples 1 to 5 were used as the spacer for the liquid crystal display element as the spacer for the liquid crystal display element, the display quality of the obtained liquid crystal display element was good.

DESCRIPTION OF SYMBOLS 1... Conductive particle 2... Conductive part 11... Resin particle 11A... Resin particle 21... Conductive particle 22... Conductive part 22A... First conductive part 22B... Second conductive part 31... Conductive particle 31a... Protrusion 32... Conductive part 32a... Protrusion 33... Core substance 34... Insulating substance 41... Connection structure 42... First connection target member 42a... First electrode 43... Second connection target member 43a... Second electrode 44... Connection Part 51... Connection structure 52... First connection target member 53... Second connection target member 54... Adhesive layer 61... Gap control particle 62... Thermosetting component 81... Liquid crystal display element 82... Transparent glass substrate 83... Transparent Electrode 84... Alignment film 85... Liquid crystal 86... Sealing agent

Claims (12)

Is a polymer of a polymerizable compound,
The compression recovery rate is 5% or more and 30% or less,
The compression elastic modulus when compressed by 30% is 500 N/mm ² or more and 2000 N/mm ² or less,
The resin particles, wherein the ratio of the volume of the resin particles in the 1 wt% acetone dispersion of the resin particles to the volume of the resin particles in the 1 wt% aqueous dispersion of the resin particles is 1.10 or less. Compressive modulus upon compression 50%, is 800 N / mm ² or more 4000 N / mm ² or less, the resin particles of claim 1. The polymerizable compound constituting the polymer contains a crosslinkable compound and a non-crosslinkable compound,
The resin particle according to claim 1 or 2, wherein the crosslinkable compound has an alkylene group having 6 or more carbon atoms or a cyclic structure having 6 or more carbon atoms. The resin particle according to claim 3, wherein the non-crosslinkable compound has an alkyl group having 4 or more carbon atoms or a cyclic structure having 6 or more carbon atoms. The resin particle according to claim 3 or 4, wherein the cyclic structure is a saturated aliphatic ring having no double bond. The resin particles according to any one of claims 3 to 5, wherein the content of the structure derived from the crosslinkable compound in 100% by weight of the polymer is 10% by weight or more and less than 80% by weight. The resin particles, wherein the ratio of the volume of the resin particles in the 1 wt% acetone dispersion liquid to the volume of the resin particles in the 1 wt% water dispersion liquid of the resin particles is 1.03 or less. The resin particle according to any one of claims 1 to 7, which is used as a spacer or used for obtaining a conductive particle having a conductive portion formed on a surface thereof and having the conductive portion. Resin particles according to any one of claims 1 to 8,
Conductive particles disposed on the surface of the resin particles. The conductive particle according to claim 9, wherein the particle diameter of the conductive particle is 1 μm or more and 30 μm or less. Including conductive particles and a binder,
A conductive material, wherein the conductive particles include the resin particles according to any one of claims 1 to 8 and a conductive portion arranged on the surface of the resin particles. A first connection target member having a first electrode on its surface;
A second connection target member having a second electrode on the surface;
A first connection target member, and a connection portion that connects the second connection target member,
The material of the connection portion includes the resin particles according to any one of claims 1 to 8,
A connection structure in which the first electrode and the second electrode are electrically connected by the connection portion.

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