KR102391136B1 - Resin particles, conductive particles, conductive materials, adhesives, bonded structures, and liquid crystal display elements - Google Patents

Abstract

Provided is a resin particle capable of effectively suppressing the occurrence of springback and effectively suppressing the occurrence of floating or peeling. The resin particle according to the present invention is a polymer of a first polymerizable compound having one polymerizable functional group and a cyclic organic group and a second polymerizable compound having two or more polymerizable functional groups and a cyclic organic group, When the weight ratio of the content of the structure derived from the first polymerizable compound to the content of the structure derived from the second polymerizable compound is 7 or more, and the resin particles are heated at 150° C. for 1000 hours, the particles of the resin particles after heating The ratio of the diameter to the particle diameter of the resin particles before heating is 0.9 or less.

Description

Resin particles, conductive particles, conductive materials, adhesives, bonded structures, and liquid crystal display elements

The present invention relates to resin particles formed of resin. Moreover, this invention relates to the electroconductive particle which used the said resin particle, an electrically-conductive material, an adhesive agent, a bonded structure, and a liquid crystal display element.

Anisotropic electrically-conductive materials, such as an anisotropic electrically-conductive paste and an anisotropic electrically-conductive film, are known widely. In the said anisotropic electrically-conductive material, electroconductive particle is disperse|distributed in the binder.

The said anisotropic electrically-conductive material electrically connects between electrodes of various connection object members, such as a flexible printed circuit board (FPC), a glass substrate, a glass epoxy board|substrate, and a semiconductor chip, and is used in order to obtain a bonded structure. Moreover, as said electroconductive particle, the electroconductive particle which has a resin particle and the electroconductive part arrange|positioned on the surface of this resin particle may be used.

In addition, liquid crystal is arrange|positioned between two glass substrates, and the liquid crystal display element is comprised. In this liquid crystal display element, in order to keep the space|interval (gap) of two glass substrates uniform and constant, a spacer is used as a gap control material. As the spacer, resin particles are generally used.

As an example of the said electroconductive particle, in following patent document 1, the electroconductive particle which has a polymer particle and the conductive layer which has coat|covered the surface of this polymer particle is disclosed. The said polymer particle, the polyfunctional (meth)acrylate of at least 1 sort(s) of a bifunctional (meth)acrylate monomer, a trifunctional (meth)acrylate monomer, and a tetrafunctional (meth)acrylate monomer, and a monofunctional It is obtained by copolymerizing the copolymerization component containing the (meth)acrylate monomer of. The bifunctional (meth)acrylate monomer is 1,10-decanediol di(meth)acrylate. When the polyfunctional (meth)acrylate includes the bifunctional (meth)acrylate monomer, the copolymerization component is, with respect to 100 parts by weight of the bifunctional (meth)acrylate monomer, the monofunctional The (meth)acrylate monomer is contained in a range of 10 parts by weight to 400 parts by weight. When the polyfunctional (meth)acrylate includes the tetrafunctional (meth)acrylate monomer, the copolymerization component includes the tetrafunctional (meth)acrylate monomer and the monofunctional (meth)acrylate 80 weight% or less of the said monofunctional (meth)acrylate monomer is contained in 100 weight% of total of monomers. The compression set recovery rate of the said polymer particle is 70 % or more. The volume expansion coefficient of the said polymer particle is 1.3 or less.

In addition, as an example of the resin particle used for the said electroconductive particle or the said spacer, the following Patent Document 2 discloses a highly resilient resin particle composed of a cross-linked (meth)acrylic acid ester-based resin. The average particle diameter of the high-restorability resin particles is 1 µm to 100 µm. The recovery rate of the high recovery resin particles is 22% or more. The 30% compressive strength of the high-resilience resin particles is 1.5 kgf/mm ² to 5.0 kgf/mm ² .

WO2010/013668A1 WO2016/039357A1

When the conventional resin particle is used as electroconductive particle or a spacer, the effect|action which the compressed resin particle tries to return to an original shape may function, and the phenomenon called a springback may generate|occur|produce. When a springback generate|occur|produces in the resin particle used as electroconductive particle, the contact area of electroconductive particle and an electrode may fall, and conduction|electrical_connection reliability may fall. Moreover, when a springback generate|occur|produces in the resin particle used as a spacer, a spacer and the member for liquid crystal display elements etc. may not fully contact and the gap control effect may not fully be acquired.

Moreover, the electrically conductive material containing electroconductive particle and a binder, and the adhesive agent containing a spacer and a binder may be exposed to a heating environment at the time of use, and the binder may cure and shrink. Conventional resin particles do not sufficiently shrink upon heating, and may not be able to follow the curing shrinkage of the binder. As a result, between an electrically-conductive material and an electrode, or between an adhesive agent and a member for liquid crystal display elements, etc. WHEREIN: A float or peeling may generate|occur|produce.

An object of the present invention is to provide a resin particle capable of effectively suppressing the occurrence of springback and effectively suppressing the occurrence of floating or peeling. Moreover, the objective of this invention is providing the electroconductive particle which used the said resin particle, an electrically-conductive material, an adhesive agent, a bonded structure, and a liquid crystal display element.

According to a broad aspect of the present invention, it is a polymer of a first polymerizable compound having one polymerizable functional group and having a cyclic organic group, and a second polymerizable compound having two or more polymerizable functional groups and having a cyclic organic group, When the weight ratio of the content of the structure derived from the first polymerizable compound to the content of the structure derived from the second polymerizable compound is 7 or more, and the resin particles are heated at 150° C. for 1000 hours, the particles of the resin particles after heating A resin particle is provided, wherein the ratio of the diameter to the particle diameter of the resin particle before heating is 0.9 or less.

On the specific situation with the resin particle which concerns on this invention, the compression recovery factor at the time of carrying out compression deformation 60% is 10 % or less.

On the specific situation with the resin particle which concerns on this invention, a 10% K value is 3000 N/mm< ² > or less.

On the specific situation with the resin particle which concerns on this invention, 30% K-value is 1500 N/mm< ² > or less.

In a specific situation of the resin particles according to the present invention, when the resin particles are heated at 150° C. for 1000 hours, the ratio of the 30% K value of the resin particles after heating to the 30% K value of the resin particles before heating is 0.8 or more and 1.5 or less am.

On the specific situation with the resin particle which concerns on this invention, the cyclic organic group in the said 1st polymeric compound and the cyclic organic group in the said 2nd polymeric compound are a hydrocarbon group, respectively.

On the specific situation with the resin particle which concerns on this invention, the cyclic organic group in the said 1st polymeric compound is a phenylene group, a cyclohexyl group, or an isobornyl group.

On the specific situation with the resin particle which concerns on this invention, the cyclic organic group in the said 2nd polymeric compound is a phenylene group, a cyclohexyl group, or an isobornyl group.

On the specific situation with the resin particle which concerns on this invention, the said resin particle contains an acid phosphate compound.

On the specific situation with the resin particle which concerns on this invention, the said resin particle is used as a spacer, or an electroconductive part is formed on the surface, and it is used in order to obtain the electroconductive particle which has the said electroconductive part.

According to the broad situation of this invention, electroconductive particle provided with the resin particle mentioned above and the electroconductive part arrange|positioned on the surface of the said resin particle is provided.

According to the broad situation of this invention, it contains electroconductive particle and a binder, The said electroconductive particle is equipped with the resin particle mentioned above, and the electroconductive part arrange|positioned on the surface of the said resin particle, the electrically-conductive material is provided.

According to a broad aspect of the present invention, there is provided an adhesive comprising the above-described resin particles and a binder.

According to a broad aspect of the present invention, a first connection object member having a first electrode on its surface, a second connection object member having a second electrode on its surface, and the first connection object member and the second connection object member are provided. There is provided a bonded structure comprising a connecting portion to be connected, wherein the material of the connecting portion contains the above-described resin particles, and the first electrode and the second electrode are electrically connected by the connecting portion.

According to a broad aspect of the present invention, a first liquid crystal display element member, a second liquid crystal display element member, and a spacer disposed between the first liquid crystal display element member and the second liquid crystal display element member are provided. and wherein the spacer is the above-mentioned resin particle, a liquid crystal display element is provided.

The resin particle which concerns on this invention is a polymer of the 1st polymeric compound which has one polymerizable functional group and has a cyclic organic group, and the 2nd polymeric compound which has two or more polymerizable functional groups and has a cyclic organic group. In the resin particle which concerns on this invention, the weight ratio with respect to content of the structure derived from the said 2nd polymeric compound of content of the structure derived from a said 1st polymeric compound is 7 or more. In the resin particle which concerns on this invention, when a resin particle is heated at 150 degreeC for 1000 hours, ratio with respect to the particle diameter of the resin particle before heating of the particle diameter of the resin particle after heating is 0.9 or less. In the resin particle which concerns on this invention, since the said structure is provided, generation|occurrence|production of a springback can be suppressed effectively, and generation|occurrence|production of a float or peeling can be suppressed effectively.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows the electroconductive particle which concerns on 1st Embodiment of this invention.
It is sectional drawing which shows the electroconductive particle which concerns on 2nd Embodiment of this invention.
It is sectional drawing which shows the electroconductive particle which concerns on 3rd Embodiment of this invention.
It is sectional drawing which shows an example of the bonded structure using the electroconductive particle which concerns on 1st Embodiment of this invention.
5 : is sectional drawing which shows an example of the bonded structure using the resin particle which concerns on this invention.
6 : is sectional drawing which shows an example of the liquid crystal display element which used the resin particle which concerns on this invention as spacers for liquid crystal display elements.

Hereinafter, the present invention will be described in detail.

(resin particles)

The resin particle which concerns on this invention is a polymer of the 1st polymeric compound which has one polymerizable functional group and has a cyclic organic group, and the 2nd polymeric compound which has two or more polymerizable functional groups and has a cyclic organic group. In the resin particle according to the present invention, the weight ratio (WM/WD) of the content (WM) of the structure derived from the first polymerizable compound to the content (WD) of the structure derived from the second polymerizable compound is 7 More than that. In the resin particles according to the present invention, when the resin particles are heated at 150° C. for 1000 hours, the ratio of the particle diameter of the resin particles after heating to the particle diameter of the resin particles before heating (the particle diameter of the resin particles after heating / the resin before heating) The particle diameter of the particles) is 0.9 or less.

In this invention, since the said structure is provided, generation|occurrence|production of a springback can be suppressed effectively, and generation|occurrence|production of a float or peeling can be suppressed effectively.

In the resin particles according to the present invention, since the above structure is provided, the compression recovery rate is relatively low, the action of the compressed resin particles to return to their original shape is relatively difficult to act, and springback is unlikely to occur. For example, when the resin particle which concerns on this invention is used as electroconductive particle, the fall of the contact area of electroconductive particle and an electrode can be prevented effectively, and the conduction|electrical_connection reliability between electrodes can be improved effectively. Moreover, when the resin particle which concerns on this invention is used as a spacer, a spacer can fully be made to contact the member for liquid crystal display elements, etc., and a gap can be further precisely controlled.

In addition, the electrically conductive material containing electroconductive particle and a binder, and the adhesive agent containing a spacer and a binder may be exposed to a heating environment at the time of use, and the binder may cure and shrink by heating. In the resin particle which concerns on this invention, since the said structure is provided, the resin particle shrink|contracts comparatively easily by heating. Since the particle diameter of the resin particle after heating becomes smaller than the particle diameter of the resin particle before heating suitably, a resin particle can track also cure shrinkage of a binder. As a result, between an electrically-conductive material and an electrode, or between an adhesive agent and the member for liquid crystal display elements, etc. WHEREIN: Generation|occurrence|production of a float or peeling can be suppressed effectively.

In the resin particle according to the present invention, the weight ratio (WM/WD) of the content (WM) of the structure derived from the first polymerizable compound to the content (WD) of the structure derived from the second polymerizable compound is 7 More than that. From the viewpoint of more effectively suppressing the occurrence of springback, and from the viewpoint of more effectively suppressing the occurrence of lifting or peeling, the weight ratio (WM/WD) is preferably 9 or more, more preferably 13 or more, and preferably is 20 or less, more preferably 17 or less.

The following methods are mentioned as a method of calculating|requiring content (WM) of the structure derived from a said 1st polymeric compound, and content (WD) of a structure derived from a said 2nd polymeric compound. From the blending amount of the first and second polymerizable compounds used to obtain the polymer, and the residual amount of the first and second polymerizable compounds after polymerization, the amounts of the first and second polymerizable compounds are determined, and the first and second polymerized compounds are obtained. , computed from the amount of the second polymerizable compound.

Moreover, the following method is mentioned as a method of calculating|requiring content (WM) of the structure derived from a said 1st polymeric compound, and content (WD) of a structure derived from a said 2nd polymeric compound from a resin particle. The amount of the functional group in each resin particle of the 1st, 2nd polymeric compound used when obtaining a polymer, and the functional group in each resin particle of the 1st, 2nd polymeric compound used when obtaining a polymer react It is calculated from the quantity of one qi.

In the resin particles according to the present invention, when the resin particles are heated at 150° C. for 1000 hours, the ratio of the particle diameter of the resin particles after heating to the particle diameter of the resin particles before heating (the particle diameter of the resin particles after heating / the resin before heating) The particle diameter of the particles) is 0.9 or less. From the viewpoint of more effectively suppressing the occurrence of floating or peeling, the ratio (particle diameter of the resin particles after heating/particle diameter of the resin particles before heating) is preferably 0.4 or more, more preferably 0.6 or more, and preferably is 0.85 or less, more preferably 0.8 or less.

The particle diameter of the said resin particle (the particle diameter of the resin particle before the said heating) can be set suitably according to a use. The particle diameter 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, still more preferably 150 µm or less, still more preferably is 100 μm or less, particularly preferably 50 μm or less. When the particle diameter of the said resin particle is more than the said lower limit and below the said upper limit, generation|occurrence|production of springback can be suppressed still more effectively, and generation|occurrence|production of a float or peeling can be suppressed further more effectively. If the particle diameter of the said resin particle is 0.5 micrometer or more and 500 micrometers or less, the said resin particle can be used suitably for the use of electroconductive particle. If the particle diameter of the said resin particle is 0.5 micrometer or more and 500 micrometer or less, the said resin particle can be used suitably for the use of a spacer.

The particle diameter of the resin particles (the particle diameter of the resin particles before heating and the particle diameter of the resin particles after heating) indicates the diameter when the resin particles are spherical, and the maximum diameter when the resin particles are not spherical.

It is preferable that it is an average particle diameter, and, as for the particle diameter (the particle diameter of the resin particle before heating, and the particle diameter of the resin particle after heating) of the said resin particle, it is more preferable that it is a number average particle diameter. The particle diameter of the said resin particle is calculated|required using a particle size distribution measuring apparatus etc. For example, the particle size distribution measuring apparatus using principles, such as laser-scattered light, a change in electrical resistance value, and image analysis after imaging, can be used. Specifically, as a method for measuring the particle diameter of the resin particles, for example, using a particle size distribution analyzer (“Multisizer 4” manufactured by Beckman Coulter), the particle diameter of about 100000 resin particles is measured, and the average value is calculated. and the like. It is preferable to calculate|require the particle diameter of a resin particle by observing 50 arbitrary resin particles with an electron microscope or an optical microscope, and calculating an average value. Electroconductive particle WHEREIN: When measuring the particle diameter of the said resin particle, it can measure as follows, for example.

It is added and disperse|distributed to "technobit 4000" by a Kulzer company so that content of electroconductive particle may be set to 30 weight%, and embedding resin for electroconductive particle test|inspection is produced. The cross section of electroconductive particle is cut out using the ion milling apparatus ("IM4000" by Hitachi High-Technologies company) so that center vicinity of the electroconductive particle disperse|distributed in embedding resin for a test|inspection may pass. And using a field emission scanning electron microscope (FE-SEM), the image magnification is set to 25000 times, 50 electroconductive particles are selected at random, and the resin particle of each electroconductive particle is observed. The particle diameter of the resin particle in each electroconductive particle is measured, these are arithmetic average, and let it be the particle diameter of a resin particle.

From the viewpoint of more effectively suppressing the occurrence of springback, and from the viewpoint of more effectively suppressing the occurrence of float or peeling, the coefficient of variation (CV value) of the particle diameter of the resin particles is preferably 0.5% or more, more preferably is 1% or more, preferably 10% or less, and more preferably 7% or less. If the coefficient of variation of the particle diameter of the said resin particle is more than the said minimum and below the said upper limit, the said resin particle can be used suitably for the use of a spacer and electroconductive particle. However, less than 0.5 % may be sufficient as the variation coefficient of the particle diameter of the said resin particle.

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

CV value (%) = (ρ/Dn) × 100

ρ: standard deviation of the particle diameter of the resin particles

Dn: average value of particle diameters of resin particles

The shape of the said resin particle is not specifically limited. A spherical shape may be sufficient as the shape of the said resin particle, and shapes other than spherical shapes, such as a flat shape, may be sufficient as it.

The 10% K value of the resin particles is preferably 1000 N/mm ² or more, more preferably 1500 N/mm ² or more, preferably 3000 N/mm ² or less, more preferably 2750 N/mm ² or less, still more preferably is 2500N/mm ² or less. When the 10% K value of the resin particles is equal to or higher than the lower limit and equal to or lower than the upper limit, the occurrence of springback can be suppressed more effectively, and the occurrence of floating or peeling can be suppressed even more effectively.

30% K value of the resin particles is preferably 300 N/mm ² or more, more preferably 500 N/mm ² or more, preferably 1500 N/mm ² or less, more preferably 1200 N/mm ² or less, still more preferably is 1000N/mm ² or less. Generation|occurrence|production of springback can be suppressed still more effectively that the 30% K value of the said resin particle is more than the said lower limit and below the said upper limit, and generation|occurrence|production of a float or peeling can be suppressed further more effectively.

When the resin particles are heated at 150° C. for 1000 hours, the ratio of the 30% K value of the resin particles after heating to the 30% K value of the resin particles before heating (30% K value of the resin particles after heating / of the resin particles before heating 30% K value) becomes like this. Preferably it is 0.8 or more, More preferably, it is 1.15 or more, More preferably, it is 1.2 or more. When the resin particles are heated at 150° C. for 1000 hours, the ratio of the 30% K value of the resin particles after heating to the 30% K value of the resin particles before heating (30% K value of the resin particles after heating / of the resin particles before heating 30% K value) becomes like this. Preferably it is 1.5 or less, More preferably, it is 1.45 or less, More preferably, it is 1.4 or less. When the ratio (30% K value of the resin particles after heating / 30% K value of the resin particles before heating) is equal to or higher than the lower limit and equal to or lower than the upper limit, the occurrence of springback can be further effectively suppressed, and no lifting or peeling generation can be more effectively suppressed.

The 10% K-value and the 30% K-value (the compressive elastic modulus when the resin particle is compressed 10% and the compressive elastic modulus when compressed 30%) of the said resin particle can be measured as follows.

Using a micro compression tester, one resin particle is compressed on the end face of a smooth indenter of a cylinder (100 µm in diameter, made of diamond) at 25°C under the conditions of a compression rate of 0.3 mN/sec and a maximum test load of 20 mN. At this time, the load value (N) and the compression displacement (mm) are measured. From the obtained measured value, a 10% K value or 30% K value in 25 degreeC can be calculated|required by a following formula. As said micro compression tester, the Shimadzu Corporation make "micro compression tester MCT-W200", the Fischer company "Fischer Scope H-100", etc. are used, for example. The 10% K value or 30% K value of the resin particles is preferably calculated by arithmetic average of the 10% K value or 30% K value of 50 arbitrarily selected resin particles.

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

F: The load value (N) when the resin particle is compressively deformed by 10% or the load value (N) when the resin particle is compressively deformed by 30%

S: Compressive displacement (mm) when the resin particles are compressively deformed by 10% or compressive displacement (mm) when compressed by 30%

R: radius of resin particles (mm)

The said K value shows the hardness of a resin particle universally and quantitatively. By using the said K value, the hardness of a resin particle can be expressed quantitatively and uniquely.

From the viewpoint of more effectively suppressing the occurrence of springback, and from the viewpoint of more effectively suppressing the occurrence of float or peeling, the compression recovery rate when the resin particles are subjected to compression deformation by 60% is preferably 2% or more, more preferably It is 4 % or more, Preferably it is 10 % or less, More preferably, it is 9.5 % or less, More preferably, it is 9 % or less.

The compression recovery factor at the time of carrying out compression deformation of the said resin particle 60% can be measured as follows.

The resin particles are spread on the sample stage. For one sprayed resin particle, using a micro compression tester, at the end face of the smooth indenter of a cylinder (100 μm in diameter, made of diamond), at 25° C. A load (reverse load value) is applied. Then, unloading is performed to the load value for origin (0.40 mN). The load-compression displacement during this is measured, and the compression recovery factor at the time of carrying out 60% compression deformation at 25 degreeC can be calculated|required from the following formula. In addition, the load speed shall be 0.33 mN/sec. As said micro compression tester, the Shimadzu Corporation make "micro compression tester MCT-W200", the Fischer company "Fischer Scope H-100", etc. are used, for example.

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

L1: Compressive displacement from the origin load value to the reversal load value when a load is applied

L2: unloading displacement from the reversal load value when the load is released to the origin load value

The use of the said resin particle is not specifically limited. The said resin particle is used suitably for various uses. It is preferable that the said resin particle is used as a spacer, or in order to obtain electroconductive particle which has an electroconductive part. The said electroconductive particle WHEREIN: The said electroconductive part is formed on the surface of the said resin particle. It is preferable that the said resin particle is used as a spacer. It is preferable that the said resin particle is used in order to obtain the electroconductive particle which has an electroconductive part. Examples of the method of using the spacer include a spacer for liquid crystal display elements, a spacer for gap control, a spacer for stress relaxation, and the like. The gap control spacer may be used for controlling the gap of a laminated chip to ensure standoff height and flatness, and controlling the gap of an optical component to secure the smoothness of the glass surface and the thickness of the adhesive layer. The spacer for stress relaxation can be used for stress relaxation of a sensor chip or the like, stress relaxation of a connection portion connecting two connection target members, and the like.

It is preferable that the said resin particle is used as a spacer for liquid crystal display elements, and it is preferable that it is used for the peripheral sealing compound for liquid crystal display elements. The said peripheral sealing compound for liquid crystal display elements WHEREIN: It is preferable that the said resin particle functions as a spacer. Since the resin particles have good compressive deformation properties, when the resin particles are used as a spacer and disposed between substrates, or when a conductive part is formed on the surface and used as conductive particles to electrically connect between electrodes, a spacer or conductive material is used. Particles are efficiently disposed between substrates or between electrodes. Moreover, in the said resin particle, since the generation|occurrence|production of flaws, such as a member for liquid crystal display elements, can be suppressed, the liquid crystal display element which used the said spacer for liquid crystal display elements, and the bonded structure which used the said electroconductive particle WHEREIN: Connection and poor display. This becomes difficult to occur.

The resin particles are also suitably used as inorganic fillers, toner additives, shock absorbers, or vibration absorbers. For example, as an alternative to rubber or spring, the resin particles may be used.

(Other detailed description of resin particles)

The resin particle which concerns on this invention is a polymer of the 1st polymeric compound which has one polymerizable functional group and has a cyclic organic group, and the 2nd polymeric compound which has two or more polymerizable functional groups and has a cyclic organic group. It is preferable to obtain the said resin particle by superposing|polymerizing a said 1st polymeric compound and a said 2nd polymeric compound.

From the viewpoint of more effectively suppressing the occurrence of springback, and from the viewpoint of more effectively suppressing the occurrence of float or peeling, in the resin particle, it is preferable that the central portion of the resin particle and the surface portion of the resin particle are composed of the same polymer. Do. The compounding ratio of the polymeric compound in the center part of the said resin particle and the compounding ratio of the polymeric compound in the surface part of the said resin particle may be same or different. The composition ratio of the structural component in the center part of the said resin particle and the structural ratio of the structural component in the surface part of the said resin particle may be same or different.

In the said resin particle, it is preferable that the center part of a resin particle is formed with the center part forming material, and it is preferable that the surface part of the resin particle is formed with the surface part forming material. From the viewpoint of more effectively suppressing the occurrence of springback, and from the viewpoint of more effectively suppressing the occurrence of float or peeling, in the resin particle, it is preferable that the component of the core forming material and the component of the surface portion forming material be the same. . In the said resin particle, the component ratio of the said center part forming material and the component ratio of the said surface part forming material may be same or different. Moreover, in the said resin particle, it is preferable that the area|region containing both the said center part forming material and the said surface part forming material exist exists. In the resin particle, it is preferable that the resin particle has a region in the center that contains the center portion forming material and does not contain the surface portion forming material or contains less than 25% of the surface portion forming material. In the resin particles, it is preferable that the surface portion of the resin particles have a region that contains the material for forming the surface portion and does not contain the material for forming the center portion or contains less than 25% of the material for forming the center portion in the surface portion.

It is preferable that the said resin particle is not a core-shell particle provided with a core and the shell arrange|positioned on the surface of this core, and it is preferable that it does not have the interface between a core and a shell in a resin particle. It is preferable not to have an interface in the resin particle, and, as for the said resin particle, it is more preferable that it does not have the interface with which different surfaces are in contact. It is preferable that the said resin particle does not have a discontinuous part in which a surface exists, and it is preferable that it does not have a discontinuous part in which a structure surface exists.

In the resin particle which concerns on this invention, the said 1st polymeric compound has one polymerizable functional group (1st polymerizable functional group). It does not specifically limit as said polymerizable functional group (1st polymerizable functional group), For example, a vinyl group, an acryloyl group, a methacryloyl group, etc. are mentioned. Examples of the first polymerizable compound include styrene, phenyl methacrylate, phenyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, isobornyl methacrylate, and isobornyl acrylate. As for the said 1st polymeric compound, only 1 type may be used and 2 or more types may be used together.

In the resin particle which concerns on this invention, the said 2nd polymeric compound has two or more polymerizable functional groups (2nd polymerizable functional group). It does not specifically limit as said polymerizable functional group (2nd polymerizable functional group), For example, a vinyl group, an acryloyl group, a methacryloyl group, etc. are mentioned. Examples of the second polymerizable compound include divinylbenzene, divinylnaphthalene, divinylcyclohexane, and trivinylcyclohexane. As for the said 2nd polymeric compound, only 1 type may be used and 2 or more types may be used together.

Preferably the said resin particle is 7 or more, More preferably, 9 or more by weight ratio (weight of 1st polymeric compound/weight of 2nd polymeric compound) of said 1st polymeric compound and said 2nd polymeric compound. , more preferably 13 or more, preferably 20 or less, more preferably 18.5 or less, still more preferably 17 or less. The resin particles are preferably obtained by polymerization of the first polymerizable compound and the second polymerizable compound in a weight ratio of 7 or more, more preferably obtained by polymerization of 9 or more, and further obtained by polymerization of 13 or more desirable. The resin particles are preferably obtained by polymerization of the first polymerizable compound and the second polymerizable compound in a weight ratio of 20 or less, more preferably obtained by polymerization of 18.5 or less, and further obtained by polymerization of 17 or less. desirable. The resin particles are obtained by polymerizing the first polymerizable compound and the second polymerizable compound in a weight ratio within the above-described preferred range, so that the occurrence of springback can be more effectively suppressed, and the occurrence of float or peeling can be reduced. It can be suppressed more effectively.

It is preferable that the resin particle which concerns on this invention contains 2 or more types of cyclic organic groups. In the resin particle which concerns on this invention, the said 1st polymeric compound has a cyclic organic group (1st cyclic organic group). The said 1st polymeric compound has one or more cyclic organic groups. In the resin particle which concerns on this invention, the said 2nd polymeric compound has a cyclic organic group (2nd cyclic organic group). The said 2nd polymeric compound has one or more cyclic organic groups. In the resin particle which concerns on this invention, even if the cyclic organic group (1st cyclic organic group) in the said 1st polymeric compound and the cyclic organic group (2nd cyclic organic group) in the said 2nd polymeric compound are the same, and may be different. It is preferable that the cyclic organic group (1st cyclic organic group) in the said 1st polymeric compound differ from the cyclic organic group (2nd cyclic organic group) in the said 2nd polymeric compound.

From a viewpoint of suppressing the generation|occurrence|production of springback more effectively, and a viewpoint of suppressing the generation|occurrence|production of float or peeling further effectively, the cyclic organic group (first cyclic organic group) and the said 2nd polymerization in said 1st polymeric compound It is preferable that each cyclic organic group (2nd cyclic organic group) in a sexual compound is a hydrocarbon group.

Examples of the hydrocarbon group include a phenyl group, a phenylene group, a naphthyl group, a naphthylene group, a cyclopropyl group, a cyclohexyl group, an isobornyl group, and a dicyclopentanyl group.

From the viewpoint of more effectively suppressing the occurrence of springback, and from the viewpoint of more effectively suppressing the occurrence of float or peeling, the resin particle according to the present invention is a cyclic organic group of two or more of a phenylene group, a cyclohexyl group, or an isobornyl group. It is preferable to have a group.

From the viewpoint of more effectively suppressing the occurrence of springback, and from the viewpoint of more effectively suppressing the occurrence of float or peeling, the cyclic organic group (first cyclic organic group) in the first polymerizable compound is a phenylene group; It is preferable that it is a cyclohexyl group or an isobornyl group.

From the viewpoint of more effectively suppressing the occurrence of springback, and from the viewpoint of more effectively suppressing the occurrence of float or peeling, the cyclic organic group (second cyclic organic group) in the second polymerizable compound is a phenylene group; It is preferable that it is a cyclohexyl group or an isobornyl group.

When the said resin particle is used as electroconductive particle, it is preferable that the said resin particle contains an acid phosphate compound from a viewpoint of improving the adhesiveness of a resin particle and plating still more effectively. It is preferable that the said resin particle has a phosphoric acid structure derived from an acid phosphate compound on the surface. When the said resin particle has the said phosphoric acid structure on the surface, adhesiveness with plating can be improved still more effectively. Moreover, when the said resin particle has the said phosphoric acid structure on the surface, even if the said resin particle shrinks by heating, plating crack can be suppressed still more effectively. For example, in conductive particles produced by electroless plating of resin particles containing an acid phosphate compound and a conductive material containing a binder, even if heated at the time of connection between electrodes or the conductive material is exposed to a heating environment, The plating crack can be suppressed more effectively, and the connection reliability between electrodes can be improved still more effectively. When the said resin particle is used in order to obtain electroconductive particle, it is preferable that the said resin particle contains an acid phosphate compound. When the said resin particle is used in order to obtain electroconductive particle, it is preferable that the said resin particle has a phosphoric acid structure derived from an acid phosphate compound on the surface. It is preferable that the said acid phosphate compound is an acidic phosphoric acid ester compound.

Examples of the acid phosphate compound include ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, isotridecyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, 2- Hydroxyethyl methacrylic acid phosphate, dibutyl acid phosphate, bis(2-ethylhexyl) acid phosphate, etc. are mentioned. As for the said acid phosphate compound, only 1 type may be used and 2 or more types may be used together.

From the viewpoint of further effectively enhancing the adhesion between the resin particles and the plating, the content of the acid phosphate compound in 100% by weight of the resin particles is preferably 1% by weight or more, more preferably 5% by weight or more, preferably It is 20 weight% or less, More preferably, it is 15 weight% or less.

(conductive particles)

The electroconductive particle which concerns on this invention is equipped with the resin particle mentioned above, and the electroconductive part arrange|positioned on the surface of this resin particle.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows the electroconductive particle which concerns on 1st Embodiment of this invention.

The electroconductive particle 1 shown in FIG. 1 has the resin particle 11 and the electroconductive part 2 arrange|positioned on the surface of the resin particle 11. As shown in FIG. The conductive part 2 is in contact with the surface of the resin particle 11 . The conductive part 2 has covered the surface of the resin particle 11 . The electroconductive particle 1 is the covering particle|grain by which the surface of the resin particle 11 was coat|covered with the electroconductive part 2 . In the electroconductive particle 1, the electroconductive part 2 is a single-layer electroconductive part (conductive layer).

It is sectional drawing which shows the electroconductive particle which concerns on 2nd Embodiment of this invention.

The electroconductive particle 21 shown in FIG. 2 has the resin particle 11 and the electroconductive part 22 arrange|positioned on the surface of the resin particle 11. As shown in FIG. The electroconductive part 22 has the 1st electroconductive part 22A on the side of the resin particle 11 in the whole, and the 2nd electroconductive part 22B on the opposite side to the resin particle 11 side.

From the electroconductive particle 1 shown in FIG. 1, and the electroconductive particle 21 shown in FIG. 2, only the electroconductive part 22 differs. That is, in the electroconductive particle 1, the 1st electroconductive part 22A and the 2nd electroconductive part 22B of a two-layer structure are formed in the electroconductive particle 21, whereas the electroconductive part of a one-layer structure is formed. has been 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 disposed on the surface of the resin particle 11 . The first conductive portion 22A is disposed between the resin particle 11 and the second conductive portion 22B. The first conductive portion 22A is in contact with the resin particle 11 . The second conductive portion 22B is in contact with the first conductive portion 22A. The first conductive part 22A is disposed on the surface of the resin particle 11 , and the second conductive part 22B is disposed on the surface of the first conductive part 22A.

It is sectional drawing which shows the electroconductive particle which concerns on 3rd Embodiment of this invention.

The electroconductive particle 31 shown in FIG. 3 has the resin particle 11, the electroconductive part 32, the some core substance 33, and the some insulating substance 34. The conductive portion 32 is disposed on the surface of the resin particle 11 . The plurality of core substances 33 are arranged on the surface of the resin particles 11 . The electroconductive part 32 is arrange|positioned on the surface of the resin particle 11 so that the resin particle 11 and the some core substance 33 may be covered. In the electroconductive particle 31, the electroconductive part 32 is a single-layer electroconductive part (conductive layer).

The electroconductive particle 31 has the some processus|protrusion 31a on the outer surface. In the electroconductive particle 31, the electroconductive part 32 has the some protrusion 32a on the outer surface. The plurality of core substances 33 raise the outer surface of the conductive portion 32 . The protrusions 31a and 32a are formed because the outer surface of the conductive portion 32 is raised by the plurality of core substances 33 . The plurality of core materials 33 are embedded in the conductive portion 32 . Inside the projections 31a and 32a, a core material 33 is disposed. In the electroconductive particle 31, the some core substance 33 is used in order to form the projections 31a and 32a. In the said electroconductive particle, in order to form the said processus|protrusion, it is not necessary to use several said core substance. The said electroconductive particle does not need to be equipped with the some said core substance.

The electroconductive particle 31 has the insulating substance 34 arrange|positioned on the outer surface of the electroconductive part 32. As shown in FIG. At least a part of the region of the outer surface of the conductive portion 32 is covered with the insulating material 34 . The insulating material 34 is made of an insulating material, and is an insulating particle. Thus, the electroconductive particle which concerns on this invention may have the insulating substance arrange|positioned on the outer surface of an electroconductive part. However, the said electroconductive particle does not necessarily need to have an insulating substance. The said electroconductive particle does not need to be equipped with the some insulating substance.

Challenge:

The metal for forming the said electroconductive part is not specifically 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, tungsten. , molybdenum, and alloys thereof. Examples of the metal include tin-doped indium oxide (ITO) and solder. Since the connection resistance between electrodes can be made further lower, the alloy containing a tin, nickel, palladium, copper, or gold|metal|money is preferable, and nickel or palladium is preferable.

Moreover, since conduction|electrical_connection reliability can be improved effectively, it is preferable that the said electroconductive part and the outer surface part of the said electroconductive part contain nickel. Content of nickel in 100 weight% of electroconductive parts containing nickel becomes like this. Preferably it is 10 weight% or more, More preferably, it is 50 weight% or more, More preferably, it is 60 weight% or more, More preferably, it is 70 weight% or more. , particularly preferably 90% by weight or more. 97 weight% or more may be sufficient as content of nickel in 100 weight% of the electroconductive parts containing the said nickel, 97.5 weight% or more may be sufficient, and 98 weight% or more may be sufficient as it.

Moreover, a hydroxyl group exists on the surface of an electroconductive part by oxidation in many cases. Generally, a hydroxyl group exists on the surface of the electroconductive part formed with nickel by oxidation. An insulating material can be disposed on the surface of the conductive portion having such a hydroxyl group (the surface of the conductive particles) through a chemical bond.

Like the electroconductive particles 1 and 31, the said electroconductive part may be formed by one layer. Like the electroconductive particle 21, the electroconductive part may be formed of several layers. That is, the conductive part 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, more preferably a gold layer. When the outermost layer is these preferable electroconductive parts, the connection resistance between electrodes can be made low still more effectively. Moreover, when the outermost layer is a gold|metal layer, corrosion resistance can be improved still more effectively.

The method of forming the said electroconductive part on the surface of the said resin particle is not specifically limited. As a method of forming the conductive part, for example, a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and coating a metal powder or a paste containing a metal powder and a binder on the surface of the resin particles. method and the like. Since formation of an electroconductive part is simple, the method by electroless plating is preferable. As a method by the said physical vapor deposition, methods, such as vacuum vapor deposition, ion plating, and ion sputtering, are mentioned.

The particle diameter of the said electroconductive particle becomes like this. Preferably it is 0.5 micrometer or more, More preferably, it is 1.0 micrometer or more, Preferably it is 500 micrometers or less, More preferably, it is 450 micrometers or less, More preferably, it is 100 micrometers or less, and still more Preferably it is 50 micrometers or less, Especially preferably, it is 20 micrometers or less. When the particle diameters of the said electroconductive particle are more than the said minimum and below the said upper limit and between electrodes are connected using electroconductive particle, the contact area of electroconductive particle and an electrode becomes large enough, and the electroconductive particle aggregated when forming an electroconductive part. becomes difficult to form. Moreover, the space|interval between the electrodes connected via electroconductive particle does not become large too much, and an electroconductive part becomes difficult to peel from the surface of a resin particle. Moreover, electroconductive particle can be used suitably for the use of an electrically-conductive material as the particle diameter of the said electroconductive particle is more than the said minimum and below the said upper limit.

The particle diameter of the said electroconductive particle shows a diameter, when electroconductive particle is a spherical shape, and shows a maximum diameter, when electroconductive particle is not a spherical shape.

It is preferable that it is an average particle diameter, and, as for the particle diameter of the said electroconductive particle, it is more preferable that it is a number average particle diameter. The particle diameter of the said electroconductive particle observes 50 arbitrary electroconductive particles with an electron microscope or an optical microscope, and calculates an average value, or calculates the average value of the measurement result by multiple times of laser diffraction type particle size distribution analyzers, for example. saved

The thickness of the said conductive part becomes like this. Preferably it is 0.005 micrometer or more, More preferably, it is 0.01 micrometer or more, Preferably it is 10 micrometers or less, More preferably, it is 1 micrometer or less, More preferably, it is 0.3 micrometer or less. Sufficient electroconductivity is acquired as the thickness of the said electroconductive part is more than the said minimum and below the said upper limit, and electroconductive particle does not become hard too much, but electroconductive particle fully deform|transforms at the time of the connection between electrodes.

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 0.1 µm or more. is below. When the thickness of the conductive portion of the outermost layer is greater than or equal to the lower limit and less than or equal to the upper limit, the coating by the conductive portion of the outermost layer becomes uniform, corrosion resistance becomes sufficiently high, and the connection resistance between electrodes becomes sufficiently low. In addition, when the outermost layer is a gold layer, the lower the thickness of the gold layer, the lower the cost.

The thickness of the said electroconductive part can be measured by observing the cross section of electroconductive particle using a transmission electron microscope (TEM), for example. About the thickness of the said electroconductive part, it is preferable to compute the average value of 5 thickness places of arbitrary electroconductive parts as the thickness of the electroconductive part of one electroconductive particle, and it is more preferable to calculate the average value of the thickness of the whole electroconductive part as the thickness of one electroconductive part. desirable. In the case of some electroconductive particle, the thickness of the said electroconductive part becomes like this. Preferably it computes and calculates|requires these average values with respect to 10 arbitrary electroconductive particles.

Core material:

It is preferable that the said electroconductive particle has several processus|protrusion on the outer surface of the said electroconductive part. When the said electroconductive particle has several processus|protrusion on the outer surface of the said electroconductive part, the conduction|electrical_connection reliability between electrodes can be improved further. An oxide film is formed in the surface of the electrode connected by the said electroconductive particle in many cases. Moreover, the oxide film is formed in the surface of the electroconductive part of the said electroconductive particle in many cases. By using the electroconductive particle which has the said processus|protrusion, after arrange|positioning electroconductive particle between electrodes, an oxide film is effectively excluded by a processus|protrusion by crimping|bonding. For this reason, an electrode and electroconductive particle can be made to contact still more reliably, and the connection resistance between electrodes can be made low still more effectively. In addition, when the conductive particles have an insulating material on the surface, or when the conductive particles are dispersed in a binder resin and used as a conductive material, the insulating material or binder resin between the conductive particles and the electrode is formed by the projections of the conductive particles. effectively excluded. For this reason, the conduction|electrical_connection reliability between electrodes can be improved still more effectively.

Since the core material is embedded in the conductive part, it is possible to easily form a plurality of protrusions on the outer surface of the conductive part. However, in order to form a processus|protrusion on the surface of the electroconductive part of electroconductive particle, it is not necessary to necessarily use a core substance.

As a method of forming the projections, a method of forming a conductive portion by electroless plating after attaching a core material to the surface of the resin particle, and a method of forming a conductive portion by electroless plating on the surface of the resin particle, followed by a core material and a method of forming an electroconductive part by further electroless plating, and the like. As another method of forming the projections, a method of forming a first conductive part on the surface of a resin particle, arranging a core material on the first conductive part, and then forming a second conductive part, and a method of forming a resin particle A method of adding a core material in a step in the middle of forming a conductive portion (such as a first conductive portion or a second conductive portion) on the surface may be mentioned. In addition, without using the core material to form the projections, after forming the conductive portion on the resin particles by electroless plating, plating is deposited on the projections on the surface of the conductive portion, and further conductive by electroless plating You may use the method of forming a part, etc.

As a method of disposing the core material on the surface of the resin particles, for example, a method in which a core material is added to a dispersion of resin particles, the core material is accumulated on the surface of the resin particles by van der Waals force, and a method of attaching it; And the method of adding a core substance to the container in which the resin particle was put, and making the core substance adhere to the surface of a resin particle by the mechanical action by rotation of a container, etc. are mentioned. Since it is easy to control the amount of the core substance to be adhered, a method in which the core substance is accumulated and adhered to the surface of the resin particles in the dispersion is preferred.

The material of the core material is not particularly limited. As a material of the said core substance, an electroconductive substance and a non-conductive substance are mentioned, for example. Examples of the conductive material include metals, metal oxides, conductive nonmetals such as graphite, and conductive polymers. Polyacetylene etc. are mentioned as said conductive polymer. Examples of the non-conductive material include silica, alumina, barium titanate, and zirconia. Since electroconductivity can be raised and connection resistance can be made low effectively, a metal is preferable. The core material is preferably a metal particle. As a metal which is a material of the said core substance, the metal illustrated as a metal for forming the said electroconductive part can be used suitably.

Insulating material:

It is preferable that the said electroconductive particle is equipped with the insulating substance arrange|positioned on the surface of the said electroconductive part. In this case, when electroconductive particle is used for the connection between electrodes, the short circuit between adjacent electrodes can be prevented further. Since an insulating substance exists between some electrodes when some electroconductive particle contacts specifically, the short circuit between the electrodes adjacent to the horizontal direction instead of between the upper and lower electrodes can be prevented. Moreover, at the time of the connection between electrodes, the insulating substance between the electroconductive part of electroconductive particle and an electrode can be excluded easily by pressurizing electroconductive particle with two electrodes. When the said electroconductive particle has a some processus|protrusion on the outer surface of an electroconductive part, the insulating substance between the electroconductive part of electroconductive particle, and an electrode can be excluded still more easily.

In view of the fact that the insulating material can be more easily removed during compression between electrodes, the insulating material is preferably an insulating particle.

Examples of the material of the insulating material include polyolefin compounds, (meth)acrylate polymers, (meth)acrylate copolymers, block polymers, thermoplastic resins, crosslinked products of thermoplastic resins, thermosetting resins, and water-soluble resins. As for the material of the said insulating substance, only 1 type may be used and 2 or more types may be used together.

Examples of the polyolefin compound include polyethylene, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid ester copolymer. As said (meth)acrylate polymer, polymethyl (meth)acrylate, polydodecyl (meth)acrylate, polystearyl (meth)acrylate, etc. are mentioned. Examples of the block polymer include polystyrene, styrene-acrylic acid ester copolymer, SB-type styrene-butadiene block copolymer and SBS-type styrene-butadiene block copolymer, and hydrogenated products thereof. As said thermoplastic resin, a vinyl polymer, a vinyl copolymer, etc. are mentioned. As said thermosetting resin, an epoxy resin, a phenol resin, a melamine resin, etc. are mentioned. Introduction of polyethylene glycol methacrylate, alkoxylated trimethylolpropane methacrylate, and alkoxylated pentaerythritol methacrylate is exemplified as crosslinking of the thermoplastic resin. Examples of the water-soluble resin include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, and methyl cellulose. Moreover, you may use a chain transfer agent for adjustment of polymerization degree. A thiol, carbon tetrachloride, etc. are mentioned as a chain transfer agent.

A chemical method, a physical or mechanical method, etc. are mentioned as a method of arrange|positioning an insulating material on the surface of the said electroconductive part. Examples of the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, an emulsion polymerization method, and the like. As said physical or mechanical method, the method by spray drying, hybridization, the electrostatic adhesion method, the spraying method, dipping, and vacuum vapor deposition, etc. are mentioned. Since it is difficult for the insulating material to be detached, a method of disposing the insulating material through a chemical bond on the surface of the conductive part is preferable.

The outer surface of the said conductive part and the surface of the insulating substance may be respectively coat|covered with the compound which has 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 chemically bonded indirectly by a compound having a reactive functional group. After the carboxyl group is introduced into the outer surface of the conductive part, the carboxyl group may be chemically bonded to the surface functional group of the insulating material through a polymer electrolyte such as polyethyleneimine.

(conductive material)

The electrically-conductive material which concerns on this invention contains the electroconductive particle mentioned above and a binder. It is preferable that the said electroconductive particle is disperse|distributed and used in a binder, It is preferable that it disperse|distributes in a binder and can use it as an electrically-conductive material. It is preferable that the said electrically-conductive material is an anisotropic electrically-conductive material. It is preferable that the said electrically-conductive material is used for the electrical connection between electrodes. It is preferable that the said electrically-conductive material is an electrically-conductive material for circuit connection.

The binder is not particularly limited. As the binder, a known insulating resin is used. It is preferable that a thermoplastic component (thermoplastic compound) or a sclerosing|hardenable component is included, and, as for the said binder, it is more preferable that a sclerosing|hardenable component is included. As said curable component, a photocurable component and a thermosetting component are mentioned. It is preferable that the said photocurable component contains a photocurable compound and a photoinitiator. It is preferable that the said thermosetting component contains a thermosetting compound and a thermosetting agent.

Examples of the binder include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers and elastomers. As for the said binder, only 1 type may be used and 2 or more types may be used together.

As said vinyl resin, a vinyl acetate resin, an acrylic resin, a styrene resin, etc. are mentioned, for example. As said thermoplastic resin, polyolefin resin, ethylene-vinyl acetate copolymer, polyamide resin, etc. are mentioned, for example. As said curable resin, an epoxy resin, a urethane resin, a polyimide resin, an unsaturated polyester resin, etc. are mentioned, for example. In addition, room temperature curable resin, thermosetting resin, photocurable resin, or moisture curable resin may be sufficient as the said curable resin. The said curable resin may be used together with a hardening|curing agent. Examples of the thermoplastic block copolymer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated product of a styrene-butadiene-styrene block copolymer, and a styrene-isoprene-styrene block copolymer. A hydrogenated substance etc. are mentioned. Examples of the elastomer include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.

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

A conventionally well-known dispersion method can be used for the method of disperse|distributing the said electroconductive particle in the said binder, and it is not specifically limited. As a method of dispersing the conductive particles in the binder, after adding the conductive particles in the binder, kneading and dispersing the conductive particles with a planetary mixer or the like, using a homogenizer or the like for the conductive particles in water or an organic solvent and uniformly dispersed therein, added to the binder, and kneaded with a planetary mixer or the like to disperse. In addition, as a method of dispersing the conductive particles in the binder, after diluting the binder with water or an organic solvent, the conductive particles are added, and kneading with a planetary mixer or the like to disperse. .

The said electrically-conductive material can be used as an electrically-conductive paste, an electrically-conductive film, etc. When the said electrically-conductive material is a conductive film, the film which does not contain electroconductive particle may be laminated|stacked on the conductive film containing electroconductive particle. It is preferable that the said electrically conductive paste is an anisotropic electrically conductive paste. It is preferable that the said conductive film is an anisotropic conductive film.

In 100 weight% of the said electrically-conductive material, content of the said binder becomes like this. Preferably it is 10 weight% or more, More preferably, it is 30 weight% or more, More preferably, it is 50 weight% or more, Especially preferably, it is 70 weight% or more. Preferably it is 99.99 weight% or less, More preferably, it is 99.9 weight% or less. Electroconductive particles are efficiently arrange|positioned between electrodes as content of the said binder is more than the said minimum and below the said upper limit, and the connection reliability of the connection object member connected with the electrically-conductive material becomes still higher.

In 100 weight% of the said electrically-conductive material, content of the said electroconductive particle becomes like this. Preferably it is 0.01 weight% or more, More preferably, it is 0.1 weight% or more, Preferably it is 80 weight% or less, More preferably, it is 60 weight% or less, further Preferably it is 40 wt% or less, particularly preferably 20 wt% or less, and most preferably 10 wt% or less. The conduction|electrical_connection reliability between electrodes becomes it still higher that content of the said electroconductive particle is more than the said minimum and below the said upper limit.

(glue)

The adhesive according to the present invention contains the above-mentioned resin particles and a binder. The resin particles are preferably dispersed in a binder and used, and are preferably dispersed in a binder and used as an adhesive. It is preferable that the said resin particle is used as a spacer in a binder. The said adhesive agent does not need to contain electroconductive particle.

The said adhesive agent is used in order to form the adhesive bond layer which adhere|attaches two connection object members. In addition, the adhesive is used for controlling the gap of the adhesive layer with high precision or for relieving the stress of the adhesive layer.

The binder is not particularly limited. As a specific example of the said binder, the binder etc. used for the electrically-conductive material mentioned above are mentioned. It is preferable that the said adhesive agent contains an epoxy resin as the said binder.

The content of the binder in 100% by weight of the adhesive is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, and preferably is 99.99% by weight or less, more preferably 99.9% by weight or less. When the content of the binder is greater than or equal to the lower limit and less than or equal to the upper limit, the adhesive force of the adhesive layer can be further effectively increased, and the resin particles can more effectively function as a spacer.

The content of the resin particles in 100% by weight of the adhesive 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, still more preferably preferably 40% by weight or less, particularly preferably 20% by weight or less, and most preferably 10% by weight or less. When content of the said resin particle is more than the said minimum and below the said upper limit, the said resin particle can exhibit the function as a spacer much more effectively.

(connection structure)

A bonded structure can be obtained by connecting a connection object member using the electrically-conductive material containing the said electroconductive particle and a binder using the said electroconductive particle.

The connection structure which concerns on this invention is a 1st connection object member which has a 1st electrode on the surface, A 2nd connection object member which has a 2nd electrode on the surface, The said 1st connection object member, and the said 2nd connection object member A connecting portion is provided. The material of the said connection part contains the resin particle mentioned above. It is preferable that the material of the said connection part is the electroconductive particle mentioned above, or it is the electroconductive material mentioned above. It is preferable that the said connection part is formed with the electroconductive particle mentioned above, or it is a bonded structure formed with the electrically-conductive material mentioned above.

When the said electroconductive particle is used independently, connection part itself is electroconductive particle. That is, the 1st, 2nd connection object member is connected by the said electroconductive particle. It is preferable that the said electrically-conductive material used in order to obtain the said bonded structure is an anisotropic electrically-conductive material. It is preferable that the said 1st electrode and the said 2nd electrode are electrically connected by the said connection part.

4 : is sectional drawing which shows an example of the bonded structure using the electroconductive particle 1 shown in FIG.

The connection structure 41 shown in FIG. 4 includes the 1st connection object member 42, the 2nd connection object member 43, the 1st connection object member 42, and the 2nd connection object member 43 A connecting portion 44 is provided. The connection part 44 is formed of the electrically-conductive material containing the electroconductive particle 1 and a binder. In FIG. 4, for convenience of illustration, the electroconductive particle 1 is shown schematically. Instead of the electroconductive particle 1, you may use other electroconductive particle, such as electroconductive particle 21 and 31.

The 1st connection object member 42 has the some 1st electrode 42a on the surface (upper surface). The 2nd connection object member 43 has the some 2nd electrode 43a on the surface (lower surface). The 1st electrode 42a and the 2nd electrode 43a are electrically connected by the 1 or some electroconductive particle 1 . Therefore, the 1st, 2nd connection object members 42 and 43 are electrically connected by the electroconductive particle 1 .

5 : is sectional drawing which shows an example of the bonded structure using the resin particle which concerns on this invention.

The connection structure 51 shown in FIG. 5 is the 1st connection object member 52, the 2nd connection object member 53, the 1st connection object member 52, and the 2nd connection object member 53 An adhesive layer 54 to be adhered is provided.

The adhesive layer 54 contains the resin particle 11 mentioned above. The resin particle 11 is not in contact with both the 1st, 2nd connection object members 52 and 53. The resin particles 11 are used as a spacer 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 object members 52 and 53 . The gap control particles 61 may be conductive particles or particles having no conductivity. The said gap control particle|grains may be the resin particle mentioned above. The thermosetting component 62 contains 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 hardening a thermosetting compound.

The said 1st connection object member may have a 1st electrode on the surface. The said 2nd connection object member may have a 2nd electrode on the surface.

The manufacturing method of the said bonded structure is not specifically limited. As an example of the manufacturing method of a bonded structure, after arrange|positioning the said electrically-conductive material between a 1st connection object member and a 2nd connection object member and obtaining a laminated body, the method of heating and pressurizing this laminated body, etc. are mentioned. The pressure at the time of pressurization is about 9.8×10 ⁴ Pa to 4.9×10 ⁶ Pa. The temperature at the time of the said heating is about 120 degreeC - 220 degreeC. The pressure at the time of the said press for connecting the electrode of a flexible printed circuit board, the electrode arrange|positioned on the resin film, and the electrode of a touch panel is about 9.8x10 ⁴ Pa - 1.0x10 ⁶ Pa.

Specific examples of the connection target member include electronic components such as semiconductor chips, capacitors and diodes, and electronic components such as circuit boards such as printed circuit boards, flexible printed circuit boards, glass epoxy boards and glass boards. It is preferable that the said connection object member is an electronic component. It is preferable that at least one of the said 1st connection object member and the said 2nd connection object member is a semiconductor wafer or a semiconductor chip. It is preferable that the said connection structure is a semiconductor device.

It is preferable that the said electrically-conductive material is an electrically-conductive material for connecting an electronic component. The said electrically conductive paste is a paste-form electrically conductive material, It is preferable to apply on the connection object member in a paste-form state.

The said electroconductive particle, the said electrically-conductive material, and the said adhesive agent are used suitably also for a touchscreen. Therefore, it is preferable that the said connection object member is also a flexible substrate or the connection object member in which the electrode was arrange|positioned on the resin film surface. It is preferable that the said connection object member is a flexible substrate, and it is preferable that it is a connection object member by which the electrode was arrange|positioned 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 an electrode on its surface.

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

(liquid crystal display element)

The said resin particle can be used suitably as spacers for liquid crystal display elements.

A liquid crystal display element according to the present invention comprises a first liquid crystal display element member, a second liquid crystal display element member, and a spacer disposed between the first liquid crystal display element member and the second liquid crystal display element member. be prepared The said spacer is the resin particle mentioned above.

The said liquid crystal display element seals the outer periphery of the said 1st liquid crystal display element member and the said 2nd liquid crystal display element member in the state which the said 1st liquid crystal display element member and the said 2nd liquid crystal display element member face each other You may be equipped with the sealing part which is doing.

The said resin particle can also be used for the peripheral sealing compound for liquid crystal display elements. The liquid crystal display element includes a first liquid crystal display element member, a second liquid crystal display element member, and the first liquid crystal display element in a state where the first liquid crystal display element member and the second liquid crystal display element member are opposed to each other. The sealing part which seals the outer periphery of the member for display elements and the said 2nd member for liquid crystal display elements is provided. A liquid crystal display element is equipped with the liquid crystal arrange|positioned between the said 1st member for liquid crystal display elements and the said 2nd member for liquid crystal display elements inside the said sealing part. In this liquid crystal display element, the liquid crystal dropping method is applied, and the said sealing part is formed by thermosetting the sealing compound for liquid crystal dropping methods.

6 : is sectional drawing which shows an example of the liquid crystal display element which used the resin particle which concerns on this invention as spacers for liquid crystal display elements.

The liquid crystal display element 81 illustrated in FIG. 6 has a pair of transparent glass substrates 82 . The transparent glass substrate 82 has an insulating film (not shown) on the surface which opposes. As a material _of an insulating film, SiO2 etc. are mentioned, for example. A transparent electrode 83 is formed on the insulating film in the transparent glass substrate 82 . As a material of the transparent electrode 83, ITO etc. are mentioned. The transparent electrode 83 can be formed by, for example, patterning by photolithography. An alignment film 84 is formed on the transparent electrode 83 on the surface of the transparent glass substrate 82 . As a material of the orientation film 84, polyimide etc. are mentioned.

A liquid crystal 85 is sealed between the pair of transparent glass substrates 82 . A plurality of resin particles 11 are disposed between the pair of transparent glass substrates 82 . The resin particle 11 is used as a spacer for liquid crystal display elements. The spacing between the pair of transparent glass substrates 82 is regulated by the plurality of resin particles 11 . A sealing compound 86 is disposed between the edge portions of the pair of transparent glass substrates 82 . The outflow to the outside of the liquid crystal 85 is prevented by the sealing compound 86. In the sealing compound 86, the resin particle 11 and the resin particle 11A from which only a particle diameter differs are contained.

In the said liquid crystal display element, the arrangement density of the spacers for liquid crystal display elements per 1 ^mm2 becomes like this. Preferably it is 10 pieces/ ^mm2 or more, Preferably it is 1000 pieces/ ^mm2 or less. When the batch density is 10 pieces/mm ² or more, the cell gap becomes even more uniform. Contrast of a liquid crystal display element becomes it more favorable that the said arrangement density is 1000 pieces/mm< ² > or less.

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

(Example 1)

(1) Preparation of resin particles

Polystyrene particles having an average particle diameter of 6.0 µm were prepared as seed particles. 5.0 parts by weight of the polystyrene particles, 900 parts by weight of ion-exchanged water, and 170 parts by weight of a 5% by weight aqueous solution of polyvinyl alcohol were mixed to prepare a liquid mixture. After the mixture was dispersed by ultrasonication, it was placed in a separable flask and stirred uniformly.

Moreover, cyclohexyl methacrylate is prepared as the 1st polymeric compound 1 which has one polymerizable functional group and has a cyclic organic group, and isoisomer as the 1st polymeric compound 2 which has one polymerizable functional group and has a cyclic organic group. Bornyl acrylate was prepared. Furthermore, divinylbenzene was prepared as a 2nd polymerizable compound which has two or more polymerizable functional groups and has a cyclic organic group.

Next, 9 parts by weight of polytetramethylene glycol diacrylate, 1 part by weight of divinylbenzene, 15 parts by weight of cyclohexyl methacrylate, and 75 parts by weight of isobornyl acrylate were mixed to obtain a mixture. To the obtained mixture, 6.0 parts by weight of benzoyl peroxide ("Niper BW" manufactured by Nichi Industries Co., Ltd.) was added, and 1000 parts by weight of ion-exchanged water was further added to prepare an emulsion.

The said emulsion liquid was further added to the said liquid mixture in a separable flask, and it stirred for 16 hours, the seed particle was made to absorb a monomer, and the suspension containing the seed particle by which the monomer swelled was obtained.

Then, 510 weight part of 5 weight% of polyvinyl alcohol aqueous solutions were added, heating was started, it was made to react at 85 degreeC for 10 hours, and the resin particle was obtained.

(2) Preparation of conductive particles

It dried after wash|cleaning the obtained resin particle and performing classification operation. Then, by the electroless-plating method, the nickel layer was formed in the surface of the obtained resin particle, and electroconductive particle was produced. In addition, the thickness of the nickel layer was 0.1 micrometer.

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

In order to produce an electrically-conductive material (anisotropic electrically-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 Corporation)

Thermosetting compound B: Epoxy compound ("EPICLON HP-4032D" manufactured by DIC)

Thermosetting compound C: Epoxy compound ("Epogose PT" manufactured by Yokkaichi Kosei Co., Ltd., polytetramethylene glycol diglycidyl ether)

Thermosetting agent: Thermal cation generator (Sun-Aid “SI-60” manufactured by Sanshin Chemical Co., Ltd.)

Filler: Silica (average particle diameter 0.25 µm)

An electrically-conductive material (anisotropic electrically-conductive paste) was produced as follows.

(Method for Producing Conductive Material (Anisotropic Conductive Paste))

10 parts by weight of the thermosetting compound A, 10 parts by weight of the thermosetting compound B, 15 parts by weight of the thermosetting compound C, 5 parts by weight of the thermosetting agent, and 20 parts by weight of the filler were blended to obtain a mixture. Furthermore, after adding the obtained electroconductive particle so that content in 100 weight% of compounds might be set to 10 weight%, the electrically-conductive material (anisotropic electrically-conductive paste) was obtained by stirring at 2000 rpm for 5 minutes using the planetary stirrer.

(4) Fabrication of the bonded structure

As a 1st connection object member, the glass substrate which has an aluminum electrode pattern whose L/S is 20 micrometers/20 micrometers on an upper surface was prepared. Moreover, as a 2nd connection object member, the semiconductor chip which has a gold electrode pattern (gold electrode thickness of 20 micrometers) of L/S of 20 micrometers/20 micrometers was prepared on the lower surface.

On the upper surface of the said glass substrate, the electrically-conductive material (anisotropic electrically-conductive paste) immediately after preparation was coated so that it might become 30 micrometers in thickness, and the electrically-conductive material (anisotropic electrically conductive paste) layer was formed. Next, the semiconductor chip was laminated on the upper surface of the conductive material (anisotropic conductive paste) layer so that the electrodes were opposed to each other. Then, while adjusting the temperature of the head so that the temperature of the conductive material (anisotropic conductive paste) layer is 170°C, a pressure heating head is placed on the upper surface of the semiconductor chip, and the conductive material (anisotropic conductive paste) layer is 170°C, 1.0 MPa And it hardened on the conditions for 15 second, and the bonded structure was obtained.

(Example 2)

When producing resin particles, 9 parts by weight of polytetramethylene glycol diacrylate is changed to 91 parts by weight of methyl methacrylate, and the compounding amount of cyclohexyl methacrylate is changed from 15 parts by weight to 5 parts by weight, and isobornyl acrylate The blending amount was changed from 75 parts by weight to 3 parts by weight. Except for the above-mentioned change, it carried out similarly to Example 1, and obtained electroconductive particle, an electrically-conductive material, and bonded structure.

(Example 3)

Conductive particles, conductive material and bonded structure were prepared in the same manner as in Example 1 except that 9 parts by weight of polytetramethylene glycol diacrylate was changed to 9 parts by weight of 2-methacryloyloxyethyl acid phosphate when producing resin particles. got it

(Example 4)

When producing resin particle, except having changed 5 weight part of cyclohexyl methacrylate into 5 weight part of phenoxyethylene glycol methacrylate, it carried out similarly to Example 2, and obtained electroconductive particle, an electrically-conductive material, and bonded structure.

(Example 5)

When producing a resin particle, except having changed 5 weight part of cyclohexyl methacrylate into 5 weight part of dicyclopentenyl acrylates, it carried out similarly to Example 2, and obtained electroconductive particle, an electrically-conductive material, and bonded structure.

(Example 6)

When producing the resin particle, except having changed 1 weight part of divinylbenzene into 1 weight part of tricyclodecane dimethanol diacrylates, it carried out similarly to Example 1, and obtained electroconductive particle, an electrically-conductive material, and bonded structure.

(Comparative Example 1)

Conductive particles in the same manner as in Example 1, except that the compounding amount of polytetramethylene glycol diacrylate was changed from 9 parts by weight to 10 parts by weight, and divinylbenzene was not mixed when producing the resin particles; An electrically-conductive material and bonded structure were obtained.

(Comparative Example 2)

When producing the resin particles, 9 parts by weight of polytetramethylene glycol diacrylate is changed to 94 parts by weight of methyl methacrylate, the compounding amount of cyclohexyl methacrylate is changed from 15 parts by weight to 5 parts by weight, and isobornyl acrylate is It was changed not to mix. Except for the above-mentioned change, it carried out similarly to Example 1, and obtained electroconductive particle, an electrically-conductive material, and bonded structure.

(Comparative Example 3)

When producing the resin particles, the compounding amount of polytetramethylene glycol diacrylate was changed from 9 parts by weight to 50 parts by weight, and the compounding amount of isobornyl acrylate was changed from 75 parts by weight to 34 parts by weight, except that It carried out similarly to Example 1, and obtained electroconductive particle, an electrically-conductive material, and bonded structure.

(Comparative Example 4)

When producing a resin particle, except having changed 15 weight part of cyclohexyl methacrylate into 15 weight part of phenoxyethylene glycol methacrylate, it carried out similarly to the comparative example 1, and obtained electroconductive particle, an electrically-conductive material, and bonded structure.

(evaluation)

(1) Content (WM) of a structure derived from a 1st polymeric compound, and content (WD) of a structure derived from a 2nd polymeric compound

The first and second resin particles obtained by obtaining the polymerized first and second polymerizable compounds from the blending amounts of the first and second polymerizable compounds used to obtain the polymer and the residual amounts of the first and second polymerizable compounds after polymerization Content (WM) of the structure derived from a polymeric compound, and content (WD) of the structure derived from a 2nd polymeric compound were computed. The weight ratio (WM/WD) of content (WM) of the structure derived from a 1st polymeric compound with respect to content (WD) of a structure derived from a 2nd polymeric compound was computed.

(2) particle diameter

The particle diameter (particle diameter before heating) of the obtained resin particles was determined by measuring the particle diameters of about 100000 resin particles using a particle size distribution analyzer (“Multisizer 4” manufactured by Beckman Coulter), and calculating an average value.

Next, the resin particle used for the measurement of a particle diameter was heated at 150 degreeC for 1000 hours. The particle diameter of the resin particle after heating for 1000 hours was measured by the method mentioned above. From the obtained measurement result, the ratio (particle diameter of the resin particle after heating/particle diameter of the resin particle before heating) with respect to the particle diameter of the resin particle before heating of the particle diameter of the resin particle after heating was computed.

(3) 10% K value and 30% K value

The 10% K value and 30% K value (30% K value before heating) of the obtained resin particles were measured by the method described above.

Next, the resin particle used for the measurement of the 30% K value was heated at 150 degreeC for 1000 hours. The 30% K value of the resin particle after heating for 1000 hours was measured by the method mentioned above. From the obtained measurement result, the ratio of the 30% K value after heating to the 30% K value before heating (30% K value after heating / 30% K value before heating) was calculated.

(4) Compression recovery rate when subjected to compression deformation by 60%

The compression recovery factor at the time of carrying out compression deformation of the obtained resin particle 60% was measured by the method mentioned above.

(5) Plating state

The obtained electroconductive particle was heated at 150 degreeC for 1000 hours. The plating state of 50 electroconductive particles after heating was observed with the scanning electron microscope. The presence or absence of plating unevenness, such as plating crack or plating peeling, was evaluated. The plating state was judged according to the following criteria.

[Criteria for judgment of plating state]

○○: less than 3 conductive particles in which plating nonuniformity was confirmed

(circle): 3 or more and less than 6 electroconductive particles by which plating nonuniformity was confirmed

x: 6 or more electroconductive particles by which plating nonuniformity was confirmed

(6) Connection strength

The connection strength in 260 degreeC of the obtained bonded structure was measured using the mount strength measuring apparatus. Connection strength was judged on the following reference|standard.

[Criteria for judgment of connection strength]

○○: shear strength of 150N/cm ² or more

○: shear strength of 100N/cm ² or more and less than 150N/cm ²

×: shear strength less than 100N/cm ²

(7) springback

With a scanning electron microscope, it was observed whether or not springback generate|occur|produced in the connection part of the obtained bonded structure. Springback was judged according to the following criteria.

[Spring Bag Judgment Criteria]

○: No springback occurred

×: Springback occurred

(8) Cooling/heating cycle characteristics (connection reliability)

1000 cycles of the cooling-heat cycle test which makes 1 cycle the process of heating the obtained bonded structure from -65 degreeC to 150 degreeC, and cooling to -65 degreeC was implemented. The presence or absence of generation|occurrence|production of a float or peeling in a connection part was observed with the ultrasonic flaw detection apparatus (SAT). The cooling/heating cycle characteristics (connection reliability) were determined on the basis of the following criteria.

[Criteria for determination of cooling/heating cycle characteristics (connection reliability)]

○: No floating or peeling at the connection part

x: There is a float or peeling in the connection part

The results are shown in Tables 1, 2 and 3 below.

(9) Examples of use as spacers for liquid crystal display elements

Preparation of STN type liquid crystal display element:

To a dispersion medium containing 70 parts by weight of isopropyl alcohol and 30 parts by weight of water, the spacer for liquid crystal display (resin particles) of Examples 1 to 6 in 100% by weight of the obtained spacer dispersion is added so that the solid content concentration is 2% by weight, It stirred and obtained the dispersion liquid of the spacer for liquid crystal display elements.

On one side of a pair of transparent glass plates (length 50 mm, width 50 mm, thickness 0.4 mm), a SiO ₂ film was deposited by a CVD method, and then an ITO film was formed on the entire surface of the SiO ₂ film by sputtering. A polyimide alignment film composition (the Nissan Chemical Company make, SE3510) was coated to the obtained glass substrate with an ITO film by the spin coating method, and the polyimide alignment film was formed by baking at 280 degreeC for 90 minutes. After rubbing an alignment film, it wet-sprayed so that it might become 100 spacers for liquid crystal display elements per 1 mm< ² > to the alignment film side of one board|substrate. After forming the sealing compound in the periphery of the other board|substrate, this board|substrate and the board|substrate which spread|dispersed the spacer were arrange|positioned so that a rubbing direction might become 90 degrees, and both were bonded together. Then, it processed at 160 degreeC for 90 minutes, the sealing compound was hardened, and the empty cell (screen in which a liquid crystal does not enter) was obtained. STN-type liquid crystal (manufactured by DIC) containing a chiral agent was injected into the obtained empty cell, the injection port was then blocked with a sealing agent, and then heat-treated at 120°C for 30 minutes to obtain an STN-type liquid crystal display element.

In the obtained liquid crystal display element, the space|interval between board|substrates was favorably regulated by the spacer (resin particle) for liquid crystal display elements of Examples 1-6. Moreover, the liquid crystal display element showed favorable display quality. Moreover, even when it used the resin particle of Examples 1-6 for the peripheral sealing compound of a liquid crystal display element as a spacer for liquid crystal display elements, the display quality of the obtained liquid crystal display element was favorable.

One… conductive particles
2… conductive part
11… resin particles
11A… resin particles
21… conductive particles
22… conductive part
22A… first conductive part
22B… 2nd conductive part
31… conductive particles
31a… spin
32… conductive part
32a… spin
33… core material
34… insulating material
41… connection structure
42… 1st connection target member
42a... first electrode
43… 2nd connection target member
43a… second electrode
44… junction
51… connection structure
52... 1st connection target member
53… 2nd connection target member
54… adhesive layer
61... Gap Control Particles
62... thermosetting ingredients
81… liquid crystal display
82… transparent glass substrate
83… transparent electrode
84… alignment film
85… liquid crystal
86… sealed

Claims (15)

A polymer of a first polymerizable compound having one polymerizable functional group and having a cyclic organic group, and a second polymerizable compound having two or more polymerizable functional groups and having a cyclic organic group,
The weight ratio of the content of the structure derived from the first polymerizable compound to the content of the structure derived from the second polymerizable compound is 7 or more,
The resin particle whose ratio with respect to the particle diameter of the resin particle before heating of the particle diameter of the resin particle after heating is 0.9 or less when a resin particle is heated at 150 degreeC for 1000 hours. The resin particle according to claim 1, wherein the compression recovery factor when subjected to 60% compression deformation is 10% or less. The resin particle according to claim 1 or 2, wherein the 10% K value is 3000 N/mm ² or less. The resin particle according to claim 1 or 2, wherein the 30% K value is 1500 N/mm ² or less. The resin according to claim 1 or 2, wherein when the resin particles are heated at 150° C. for 1000 hours, the ratio of the 30% K value of the resin particles after heating to the 30% K value of the resin particles before heating is 0.8 or more and 1.5 or less. particle. The resin particle according to claim 1 or 2, wherein the cyclic organic group in the first polymerizable compound and the cyclic organic group in the second polymerizable compound are each a hydrocarbon group. The resin particle according to claim 1 or 2, wherein the cyclic organic group in the first polymerizable compound is a phenylene group, a cyclohexyl group, or an isobornyl group. The resin particle according to claim 1 or 2, wherein the cyclic organic group in the second polymerizable compound is a phenylene group, a cyclohexyl group, or an isobornyl group. The resin particle according to claim 1 or 2, comprising an acid phosphate compound. The resin particle of Claim 1 or 2 which is used as a spacer, or an electroconductive part is formed on the surface, and is used for obtaining the electroconductive particle which has the said electroconductive part. The resin particles according to claim 1 or 2,
Electroconductive particle provided with the electroconductive part arrange|positioned on the surface of the said resin particle. Conductive particles and a binder,
The electrically-conductive material in which the said electroconductive particle is equipped with the resin particle of Claim 1 or 2, and the electroconductive part arrange|positioned on the surface of the said resin particle. The resin particles according to claim 1 or 2,
An adhesive comprising a binder. a first connection object member having a first electrode on its surface;
a second connection object member having a second electrode on its surface;
a connection portion connecting the first connection object member and the second connection object member;
The material of the said connection part contains the resin particle of Claim 1 or 2,
The connection structure in which the said 1st electrode and the said 2nd electrode are electrically connected by the said connection part. A member for a first liquid crystal display element;
a member for a second liquid crystal display element;
a spacer disposed between the first member for liquid crystal display elements and the second member for liquid crystal display elements;
The liquid crystal display element whose said spacer is the resin particle of Claim 1 or 2.

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