JP2015155532A - Base particle, conductive particle, conductive material and connection structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a base particle which can suppress complete destruction, scattering and springback of the base particle.

SOLUTION: With a base particle 11, a ratio of the compression modulus of the 10%-compressed base particle 11 to the compression modulus of the 30%-compressed base particle 11 is 1.5 or higher. In the compression displacement-compression load curve in a compression test of the base particle 11, there is no bent part in the range of up to 50% compression of the base particle 11, and there is a bent part between 50% compression and 80% compression.

COPYRIGHT: (C)2015,JPO&INPIT

Description

  The present invention relates to substrate particles having good compression deformation characteristics and compression fracture characteristics. The present invention also relates to a conductive particle, a conductive material, and a connection structure using the base particle.

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

  The anisotropic conductive material is used to electrically connect electrodes of various connection target members such as a flexible printed circuit (FPC), a glass substrate, a glass epoxy substrate, and a semiconductor chip to obtain a connection structure. ing. Moreover, as the conductive particles, conductive particles having base particles and a conductive layer disposed on the surface of the base particles may be used.

  As an example of the base particles used for the conductive particles, in Patent Document 1 below, before the main fracture behavior in which the entire polymer particles are broken in a compression test in which compression is performed at a load load rate of 0.2275 gf / sec. Disclosed is a polymer particle exhibiting a preliminary fracture behavior in which a part of the polymer particle is broken in advance. Patent Document 1 also discloses conductive particles having the polymer particles and a conductive metal layer.

  Patent Document 2 below discloses conductive particles having a base material formed of resin particles and at least one conductive metal layer formed on the surface of the base material. The average particle diameter of the resin particles is 1.0 μm to 2.5 μm. In a compression test in which the resin particles are compressed at a load load rate of 2.2 mN / sec, when a compression displacement curve indicating the relationship between the load and the displacement amount in the compression direction is obtained, the compression displacement curve indicates that the displacement amount is resin. There is no inflection point in the range of 55% or less of the diameter of the particles.

  In Patent Document 3 below, at least one of the inner layers is more flexible than the outermost layer, at least one of the two adjacent layers is chemically bonded, and the surface of the outermost layer is coated with metal. Multi-layered resin particles are disclosed.

  Patent Document 4 listed below includes inclined composite particles having two or more types of polyorganosiloxanes having different organic groups, the composition of which changes stepwise or continuously from the particle center toward the surface. It is disclosed.

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

  As an example of the conductive particles or the particles used for the liquid crystal display element spacer, the following Patent Document 5 describes hydrolysis of a polyfunctional silane compound having a polymerizable unsaturated group in the presence of a surfactant. And organic-inorganic composite particles (base particles) obtained by polycondensation are disclosed. In Patent Document 4, the polyfunctional silane compound is at least one radical polymerizable group-containing first silicon compound selected from a compound represented by a specific formula and derivatives thereof.

  Patent Document 6 below discloses core-shell particles in which the surface of hard particles is coated with a soft polymer layer. Preferable examples of the hard particles include metal particles such as nickel, inorganic particles such as glass fiber, alumina and silica, and resin cured particles such as cured benzoguanamine.

  Patent Document 7 below discloses insulating particles (base particles) having a core-shell structure including a shell layer on the outer periphery of the core. In Patent Document 7, when the core contains a vinyl polymer, the shell layer contains an amino resin, the core diameter is Dnm, and the shell layer thickness is dnm, 0.10 <d / D <2.0. is there.

JP 2012-36335 A JP2012-221952A JP 2002-33022 A JP 2010-235951 A JP 2000-204119 A Japanese Patent Laid-Open No. 7-140481 JP2013-62069A

  In the polymer particles described in Patent Document 1, in a compression test in which compression is performed by 50%, the polymer particles are discontinuously broken until 50% compression (see FIG. 1 of Patent Document 1). Patent Document 1 describes that the effect of the invention described in Patent Document 1 can be obtained with polymer particles exhibiting such properties. Further, in the resin particles of Patent Document 2, in a compression test in which the resin particles are compressed at a load load speed of 2.2 mN / sec, when a compression displacement curve indicating a relationship between a load and a displacement amount in a compression direction is obtained, The compression displacement curve does not have an inflection point in a range where the displacement amount is 55% or less of the diameter of the resin particles (see FIG. 2 of Patent Document 2).

  However, in the polymer particles described in Patent Document 1, the shell is easily broken during compression deformation. Further, in the resin particles described in Patent Document 2, there is a possibility that springback occurs at the time of high compression displacement. Further, the polymer particles or resin particles described in Patent Documents 1 and 2 are arranged between substrates as spacers for liquid crystal display elements, or a conductive layer is provided on the surface of the polymer particles or resin particles described in Patent Documents 1 and 2. When a conductive structure is obtained by electrically connecting the electrodes using the formed conductive particles, the connection reliability tends to be low. In addition, the display quality of the liquid crystal display element is likely to deteriorate, and the connection resistance between the electrodes in the connection structure tends to increase.

  In recent years, the distance between electrodes connected by conductive particles tends to be narrow and the electrode area tends to be small, and there is a demand for conductive particles that can be connected with even lower resistance.

  When conductive electrodes using conventional particles as described in Patent Documents 1 to 7 are used to electrically connect electrodes having a narrow interval, the substrate particles are completely destroyed at the time of connection between the electrodes. Or scattering, the connection resistance between the electrodes tends to be particularly high, and even when not completely destroyed, the connection resistance between the electrodes tends to increase due to the occurrence of springback. In addition, when the conventional particles as described in Patent Documents 1 to 7 are used as spacers for a liquid crystal display element and disposed between the substrates to obtain a liquid crystal display element, the particles are completely destroyed or scattered. Sometimes. For this reason, display quality may deteriorate in the obtained liquid crystal display element. In addition, when the particles are included in the peripheral sealing agent of the liquid crystal display element, the display quality may be deteriorated by the particles being completely destroyed or scattered.

  The objective of this invention is providing the base material particle which can suppress the complete destruction and scattering of base material particle, and can suppress a spring back. Another object of the present invention is to provide conductive particles, a conductive material, and a connection structure using the above-mentioned base material particles.

  A limited object of the present invention is to reduce the connection resistance when a conductive structure is obtained by electrically connecting electrodes using conductive particles having a conductive layer formed on the surface. On the other hand, when used as a spacer in a liquid crystal display element, it provides a base particle capable of enhancing the display quality of the liquid crystal display element, and conductive particles, a conductive material using the base particle, and It is to provide a connection structure.

  According to a wide aspect of the present invention, the ratio of the compression modulus when compressed by 10% to the compression modulus when compressed by 30% is 1.5 or more, and in the compression displacement-compression load curve in the compression test, Substrate particles are provided in which there is no bend before 50% compression and there is a bend between 50% compression and 80% compression.

  In a specific aspect of the base particle according to the present invention, the base particle is not a core-shell particle including a core and a shell disposed on the surface of the core, but in the base particle, the core and the shell There is no interface with.

  In a specific aspect of the base particle according to the present invention, the composition of the internal forming material and the composition of the surface portion forming material are different.

In a specific aspect of the base particles according to the present invention, the compression elastic modulus of when compressed 10% 1000 N / mm ² or more and 5000N / mm ² or less.

  In a specific aspect of the base particle according to the present invention, the ratio of the load value when compressed by 10% to the load value when compressed by 30% is 0.25 or more.

  In a specific aspect of the base material particle according to the present invention, the composition of the internal forming material is different from the composition of the surface portion forming material, and the surface portion forming material is an aromatic (di) vinyl compound or (meth) acrylic. It is at least one selected from the group consisting of a compound and a silane alkoxide.

  In a specific aspect of the substrate particle according to the present invention, the composition of the internal forming material and the composition of the surface portion forming material are different, and the internal forming material and the surface portion forming material are each aromatic (di) vinyl. It is at least one selected from the group consisting of a compound, a (meth) acryl compound and a silane alkoxide.

  In a specific aspect of the base particle according to the present invention, the internal forming material is a (meth) acrylic compound, and the surface portion forming material is at least one of an aromatic (di) vinyl compound and a silane alkoxide. is there.

  In a specific aspect of the base particle according to the present invention, an aromatic (di) vinyl polymer, a (meth) acrylic polymer, and an aromatic (di) vinyl- (meth) acrylic copolymer are not included in the center. Or at least one selected from the group consisting of aromatic (di) vinyl polymer, (meth) acrylic polymer and aromatic (di) vinyl- (meth) acrylic copolymer in less than 25%, The surface contains no polycondensate of silane alkoxide or less than 25% of polycondensate of silane alkoxide.

  The substrate particles according to the present invention are preferably used for obtaining conductive particles having a conductive layer formed on the surface thereof and having the conductive layer, or used as spacers for liquid crystal display elements. The base material particles according to the present invention are more preferably used for obtaining conductive particles having a conductive layer formed on the surface and having the conductive layer.

  According to a wide aspect of the present invention, there is provided a conductive particle comprising the above-described base particle and a conductive layer disposed on the surface of the base particle.

  On the specific situation with the electroconductive particle which concerns on this invention, the said electroconductive particle is further equipped with the insulating substance arrange | positioned on the outer surface of the said conductive layer.

  On the specific situation with the electroconductive particle which concerns on this invention, the said electroconductive particle has a processus | protrusion on the outer surface of the said conductive layer.

  According to a wide aspect of the present invention, the conductive particles include conductive particles and a binder resin, and the conductive particles include the base material particles described above and a conductive layer disposed on the surface of the base material particles. A conductive material is provided.

  According to a wide aspect of the present invention, a first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, the first connection target member, and the A connection portion connecting the second connection target member, and the connection portion is formed of conductive particles or formed of a conductive material including the conductive particles and a binder resin. The conductive particles include the base material particles described above and a conductive layer disposed on the surface of the base material particles, and the first electrode and the second electrode are electrically connected by the conductive particles. A connection structure is provided which is connected in a connected manner.

  The base material particle according to the present invention has a ratio of the compression elastic modulus when compressed by 10% to the compressive elastic modulus when compressed by 30% is 1.5 or more, and in the compression displacement-compression load curve in the compression test, There is no bending part until 50% compression, and there is a bending part between 50% compression and 80% compression, so that the base particles are completely destroyed and scattered, and spring back Can be suppressed.

FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention. FIG. 3 is a cross-sectional view showing conductive particles according to the third embodiment of the present invention. FIG. 4 is a front cross-sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention. FIG. 5 is a cross-sectional view schematically showing a liquid crystal display element using base particles according to an embodiment of the present invention as a spacer for a liquid crystal display element. FIG. 6 is a two-dimensional graph showing a compression displacement (X-axis) -compression load (Y-axis) curve in a compression test of substrate particles according to an embodiment of the present invention.

  Hereinafter, the present invention will be described in detail.

(Base particle)
In the base material particle according to the present invention, the ratio (10% K value / 30% K value) of the compression elastic modulus when the base material particle is compressed by 10% to the compressive elastic modulus when the base material particle is compressed by 30%. 1.5 or more.

  In the base particle according to the present invention, the ratio (10% K value / 30%) of the compression elastic modulus (10% K value) when compressed to 10% to the compression elastic modulus (30% K value) when compressed by 30% K value) is 1.5 or more. The ratio (10% K value / 30% K value) is preferably 1.55 or more, more preferably 1.6 or more, still more preferably 1.63 or more, and particularly preferably 2.0 or more. When the ratio (10% K value / 30% K value) is not less than the above lower limit, the contact area between the electrode and the conductive particles is sufficiently large, the connection resistance between the electrodes is effectively reduced, and the electrode The connection reliability between them becomes even higher. The ratio (10% K value / 30% K value) is preferably 5.0 or less.

  Moreover, in the base material particle which concerns on this invention, in the compression displacement-compression load curve in the compression test which compresses this base material particle 50%, a bending part does not exist before the said base material particle compresses 50%. .

  “No bent portion” means that no particle breakage occurs until 50% compression at a load rate of 0.3 mN / second, or particle breakage until 50% compression. That occurs but discontinuous failure does not occur. In the present invention, “no bent portion” below 50% compression deformation may mean that no particle breakage occurs until 50% compression, and until 50% compression. It may mean that particle breakage occurs but no discontinuous breakage occurs. Whether or not there is a bent portion below 50% compressive deformation is determined by a slight load difference in the two-dimensional graph showing the relationship between the compression displacement (X axis) and the compressive load (Y axis) in 50% compressive deformation. A case where the compression displacement is discontinuously changed is determined as a reference, and a case where the compression displacement difference is 0.1 μm or less within the range of the load value of 0.05 mN is evaluated as “there is no bending portion”.

  In the base particle according to the present invention, a bent portion exists in a compression displacement (X axis) -compression load (Y axis) curve in a compression test compressing from 50% to 80%. By destroying part of the particles within the compression range, the spring back of the base particles can be suppressed, the connection resistance between the electrodes is effectively reduced, and the connection reliability between the electrodes is further increased. . The fracture displacement rate at which a part of the substrate particles breaks (the bent portion exists) is preferably 55% or more, more preferably 60% or more, preferably 75% or less, more preferably 70% or less.

  In the present invention, “bending portion exists” between 50% compression and 80% compression means that between 50% compression and 80% compression at a load load speed of 0.3 mN / sec. Means that a part of the base particles is broken or that the base particles are completely broken. In the present invention, whether or not a bent portion exists between 50% compression and 80% compression is determined by the partial breakage of the base material particles between 50% compression and 80% compression. Or may mean that complete destruction of the substrate particles has occurred between 50% compression and 80% compression. Whether or not there is a bent portion in a region larger than 50% compressive deformation depends on a slight load difference in a two-dimensional graph showing the relationship between compressive deformation (X axis) and load value (Y axis). Judgment is based on the point where the compression displacement continuously changes, and the case where the difference in compression displacement exceeds 0.03 μm within the range of the load value of 0.2 mN is evaluated as “existing bent portion”.

  In the base particle according to the embodiment of the present invention, for example, a two-dimensional graph showing a compression displacement (X axis) -compression load (Y axis) curve in the compression test shown in FIG. 6 is obtained.

  The presence / absence of the bent portion and the fracture displacement rate can be measured as follows.

  Using a micro-compression tester, the substrate particles are compressed under the conditions of a smooth indenter end face of a cylinder (diameter 100 μm, made of diamond) at 25 ° C., a compression rate of 0.3 mN / sec, and a maximum test load of 20 mN. The compression displacement (mm) is measured when partial destruction of the substrate particles is confirmed. The fracture displacement rate can be obtained from the following formula from the obtained measured value and the average particle diameter of the base material particles. As the micro compression tester, for example, “Fischer Scope H-100” manufactured by Fischer is used.

  Fracture displacement rate (%) = D / (2R) × 100

  D: The compression displacement at the bending start point when the compression displacement difference exceeds 0.1 μm within the compression load of 0.05 mN in the region of compression deformation of 50% or less, and the compression load in the region greater than 50% compression The smaller compression displacement (mm) of the compression displacement at the bending start point when the difference in compression displacement exceeds 0.03 μm within the range of 0.2 mN.

  R: radius of base particle (mm)

The compression elastic modulus (10% K value) when the base particles are compressed by 10% is preferably 500 N / mm ² or more, more preferably 1000 N / mm ² or more, still more preferably 1500 N / mm ² or more, and further preferably. the 2000N / mm ² or more, preferably 6000 N / mm ² or less, more preferably 5000N / mm ² or less, even more preferably 4000 N / mm ^2, more preferably not more than 3000N / mm ^2.

The compression elastic modulus (30% K value) when the substrate particles are compressed by 30% is preferably 300 N / mm ² or more, more preferably 500 N / mm ² or more, still more preferably 700 N / mm ² or more, and further preferably. it is 1000 N / mm ² or more, preferably 3500 N / mm ² or less, more preferably 3000N / mm ^2, more preferably not more than 2000N / mm ^2.

  Further, the ratio (10% load value / 30% load value) of the load value when the base material particle is compressed by 10% to the load value when the base material particle is compressed by 30% is 0.25 or more and 50 It is preferable that the bent portion does not exist until% compression, and the bent portion exists between 50% compression and 80% compression. In this case, complete destruction and scattering of the base particles can be further suppressed, and spring back can be further suppressed. In particular, in the base particle according to the present invention until it is compressed by 50%, even if the base particle is strongly compressed, the complete destruction and scattering of the base particle can be suppressed and spring back can be suppressed. And the contact area between the substrate particles or the conductive particles and the contact object can be increased.

  In addition, as a result of suppressing the complete destruction and scattering of the base particles, using the conductive particles provided with the base particles according to the present invention, the connection structure in which the electrodes are connected is connected under a high load. However, the original function of the base material particles can be sufficiently exhibited without the base material particles being destroyed and scattered and without being spring-backed. Moreover, since the complete destruction and scattering of the base particles are suppressed and the spring back is suppressed, the connection resistance between the electrodes in the connection structure can be effectively reduced.

  Further, when the liquid crystal display element is obtained by arranging the base particle according to the present invention as a spacer for a liquid crystal display element to obtain a liquid crystal display element, even if the arrangement is performed with a high load, the surface portion of the base particle However, the original function of the substrate particles can be sufficiently exhibited without being broken or scattered. Moreover, since the destruction and scattering of the surface portion of the substrate particles are suppressed, the display quality in the liquid crystal display element can be improved. In addition, the spacer for the liquid crystal display element and the substrate can be satisfactorily brought into contact with each other, and variations in the interval between the substrates can be made difficult to occur. Also by this, the display quality of the liquid crystal display element can be improved.

  From the viewpoint of further suppressing the breakage and scattering of the base particles, the ratio (10% load value / 30% load value) is preferably 0.20 or more, more preferably 0.25 or more, and still more preferably 0.00. 30 or more, preferably 0.60 or less. From the viewpoint of further suppressing the destruction and scattering of the surface portion of the substrate particles, the load value (10% load value) when the substrate particles are compressed by 10% is preferably 0.08 mN or more, more preferably 0.8. 10 mN or more, more preferably 0.20 mN or more, particularly preferably 0.25 mN or more, preferably 0.70 mN or less, more preferably 0.50 mN or less, still more preferably 0.44 mN or less.

  The compression elastic modulus (10% K value and 30% K value) and the load value (10% load value and 30% load value) of the substrate particles can be measured as follows.

  Using a micro-compression tester, the substrate particles are compressed under the conditions of a smooth indenter end face of a cylinder (diameter 100 μm, made of diamond) at 25 ° C., a compression rate of 0.3 mN / sec, and a maximum test load of 20 mN. The load value (N) and compression displacement (mm) at this time are measured. From the measured value obtained, the compression elastic modulus can be obtained by the following formula. As the micro compression tester, for example, “Fischer Scope H-100” manufactured by Fischer is used.

10% K value or 30% K value (N / mm ² ) = (3/2 ^1/2 ) · F · S ⁻³ / ² · R ^−1/2
F: Load value (N) when the base particle is 10% or 30% compressively deformed
S: Compression displacement (mm) when the substrate particles are 10% or 30% compressively deformed
R: radius of base particle (mm)

  The compression elastic modulus represents the hardness of the base particle universally and quantitatively. By using the compression elastic modulus, the hardness of the base particle can be expressed quantitatively and uniquely.

  The compression recovery rate of the substrate particles is preferably 15% or more, more preferably 20% or more, and further preferably 25% or more. When the compression recovery rate is equal to or higher than the lower limit, the conductive particles are easily followed and deformed corresponding to the variation in the distance between the electrodes. For this reason, it becomes difficult to produce the connection failure between electrodes. The compression recovery rate of the substrate particles is preferably less than 100%.

  The compression recovery rate can be measured as follows.

  Spread base particles on the sample stage. With respect to one dispersed base material particle, using a micro-compression tester, the base material particle is 30% in the center direction of the base material particle at 25 ° C. on the end face of a cylindrical (diameter 100 μm, made of diamond). Apply a load (reverse load value) until compressive deformation. Thereafter, unloading is performed up to the origin load value (0.40 mN). The load-compression displacement during this period is measured, and the compression recovery rate can be obtained from the following equation. The load speed is 0.33 mN / sec. As the micro compression tester, for example, “Fischer Scope H-100” manufactured by Fischer is used.

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

  The use of the substrate particles is not particularly limited. The said base particle is used suitably for various uses. The substrate particles are preferably used for obtaining conductive particles having a conductive layer formed on the surface and having the conductive layer, or used as spacers for liquid crystal display elements. The base particles according to the present invention are preferably used for obtaining conductive particles having a conductive layer formed on the surface and having the conductive layer. The substrate particles are preferably used as spacers for liquid crystal display elements, and are preferably used as peripheral sealing agents for liquid crystal display elements. In the peripheral sealing agent for a liquid crystal display element, the substrate particles preferably function as spacers. Since the base material particles have good compressive deformation characteristics and compression fracture characteristics, the base material particles are used as spacers for liquid crystal display elements and disposed between the substrates, or a conductive layer is formed on the surface to form conductive particles. When the electrodes are electrically connected to each other, the spacer for liquid crystal display element or the conductive particles is efficiently arranged between the substrates or between the electrodes. Furthermore, in the base material particles, since the destruction and scattering of the surface portion of the base material particles can be suppressed, connection failure in the liquid crystal display element using the liquid crystal display element spacer and the connection structure using the conductive particles. And display defects are less likely to occur.

  Furthermore, the substrate particles are also suitably used as an inorganic filler, a toner additive, a shock absorber or a vibration absorber. For example, the base material particles can be used as a substitute for rubber or a spring.

  The substrate particles satisfy the above ratio (10% K value / 30% K value) so as to have good compression deformation characteristics and good compression fracture characteristics without discontinuous fracture. Therefore, the structure of the base material particle | grains demonstrated below is employable.

  The base particle is preferably not a core-shell particle including a core and a shell disposed on the surface of the core, and it is preferable that an interface between the core and the shell does not exist in the base particle. The base particles preferably have no interface in the base particles, and more preferably have no interface where different surfaces are in contact with each other. The substrate particles preferably do not have a discontinuous portion where a surface exists, and preferably do not have a discontinuous portion where a structural surface exists.

  From the viewpoint of easily achieving good compression deformation characteristics and compression fracture characteristics, it is preferable that the composition of the internal forming material and the composition of the surface portion forming material are different in the base material particles. In the base particle, the inside is preferably formed using the internal forming material, and the surface portion is preferably formed using the surface forming material. Moreover, in the said base particle, it is preferable that the area | region containing both the said internal formation material and the said surface part formation material exists. In the base particle, the base particle preferably has a region including the inner forming material and not including the surface portion forming material or including the surface portion forming material in less than 25% at the center.

  In the said base material particle, it is preferable that the base material particle has the area | region which contains the said surface part formation material and does not contain the said internal formation material, or contains the said internal formation material in less than 25%. It is preferable that the whole base material particle does not have a single composition. The internal forming material is a material forming a region including the center of the base particle, and is preferably different from the material forming the surface. The surface portion forming material is a material forming a region including the surface of the base particle, and is preferably different from the material forming the center of the base particle.

  It is preferable that the surface portion forming material is included in a distance portion (position indicated by a broken line r1 shown in FIG. 1) having a thickness of 1/10 from the surface of the base material particle to the inside. In this case, the surface portion forming material is generally different from the surface treatment agent that surface-treats the particles. For example, when the particles are surface-treated with a silane coupling agent or the like, the thickness of the surface treatment substance is not so thick.

  From the viewpoint of easily achieving good compression deformation characteristics and compression fracture characteristics, the composition of the internal forming material and the composition of the surface portion forming material are different, and the surface portion forming material is aromatic (di) vinyl. It is preferably at least one selected from the group consisting of a compound, a (meth) acryl compound and a silane alkoxide. The aromatic (di) vinyl compound may be an aromatic vinyl compound or an aromatic divinyl compound. From the viewpoint of easily achieving good compressive deformation characteristics and compression fracture characteristics, the composition of the inner forming material and the composition of the surface portion forming material are different, and the inner forming material and the surface portion forming material are different from each other. It is preferably at least one selected from the group consisting of group (di) vinyl compounds, (meth) acrylic compounds and silane alkoxides. In this case, it is preferable that the internal forming material is a (meth) acrylic compound and the surface portion forming material is at least one of an aromatic (di) vinyl compound and a silane alkoxide.

  From the viewpoint of easily achieving good compressive deformation characteristics and compression fracture characteristics, the internal forming material is preferably a (meth) acrylic compound, the internal forming material is a (meth) acrylic compound, and surface portion formation is performed. More preferably, the material is a silane alkoxide.

  The center of the base particle does not contain aromatic (di) vinyl polymer, (meth) acrylic polymer and aromatic (di) vinyl- (meth) acrylic copolymer, or aromatic (di) vinyl heavy It is preferable that at least one selected from the group consisting of a coalescence, (meth) acrylic polymer and aromatic (di) vinyl- (meth) acrylic copolymer is contained in less than 25% (in the case of two or more types) Calculate the total content). It is preferable that the surface of the base material particle does not contain a polycondensate of silane alkoxide or contains a polycondensate of silane alkoxide in less than 25% (in the case of two or more types, the total content is calculated). It is preferable that the area | region (area | region R1 shown in FIG. 1) of thickness 1/10 toward the inner side from the surface of the said base particle is formed of the surface part formation material, and an aromatic (di) vinyl polymer, ( More preferably, it is formed of at least one selected from the group consisting of a (meth) acrylic polymer and an aromatic (di) vinyl- (meth) acrylic copolymer.

  The base particle preferably has a region where the composition of the base particle forming material changes continuously or stepwise from the center of the base particle toward the surface, and the composition of the base particle forming material is continuous. It is more preferable to have the area | region which is changing automatically. It is preferable that the base particle has a region where the content of each component in the composition is inclined from the center toward the surface.

  When the base particle uses a polycondensate of silane alkoxide, the base particle preferably has a region in which the content of carbon atoms continuously changes from the center of the base particle toward the surface. The base particles preferably have a region where the content of silicon atoms continuously changes from the center of the base particles toward the surface. When the carbon atom content increases, the flexibility of the base particle part having a large carbon atom content tends to increase, and the 10% K value decreases, and the above ratio (10% K value / 30% K value). ) Tends to approach 1.0. When the silicon atom content increases, the flexibility of the base particle portion having a large silicon atom content tends to be low, the 30% K value increases, and the above ratio (10% K value / 30% K value). ) Tends to approach 1.0.

  The content of silicon atoms at the center of the substrate particles is preferably 10% by weight or less, more preferably 5% by weight or less. The center of the substrate particles may not contain silicon atoms. It is preferable that the center of the base particle does not contain a silicon atom. The content of carbon atoms contained in the center of the base particle is preferably 50% by weight or more, more preferably 60% by weight or more, and still more preferably 65% by weight or more. The lower the silicon atom content at the center of the base particle and the greater the carbon atom content at the center of the base particle, the more flexible the base particle is derived from the composition at the center of the base particle. It gets even higher.

  The content of silicon atoms contained in the surface of the base particle and the surface portion forming material of the base particle is preferably 50% by weight or more, more preferably 54% by weight or more, still more preferably 56% by weight or more, particularly preferably. 60% by weight or more. Each of the surface of the base particle and the surface portion forming material of the base particle may not contain carbon atoms.

  The particle diameter of the substrate particles is preferably 0.5 μm or more, more preferably 1 μm or more, preferably 500 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, particularly preferably 20 μm or less, and most preferably 10 μm or less. It is. When the particle size of the substrate is not less than the above lower limit and not more than the above upper limit, it is easy for the above ratio (10% K value / 30% K value) to show a suitable value. And it becomes possible to use suitably for the use of a liquid crystal display element. For example, when the particle diameter of the base particle is not less than the above lower limit and not more than the above upper limit, the surface portion of the base particle is further prevented from being broken and scattered, and the electrodes are connected using the conductive particles. In this case, the contact area between the conductive particles and the electrode becomes sufficiently large, and the aggregated conductive particles are hardly formed when the conductive layer is formed. Further, the distance between the electrodes connected via the conductive particles does not become too large, and the conductive layer is difficult to peel from the surface of the base material particles.

  The particle diameter of the base particle means a diameter when the base particle is a true sphere, and when the base particle is a shape other than a true sphere, it is assumed to be a true sphere corresponding to its volume. This means the diameter when Moreover, the particle size of a base material particle means the average particle diameter which measured the base material particle with the arbitrary particle size measuring apparatuses. For example, a particle size distribution measuring machine using principles such as laser light scattering, electrical resistance value change, and image analysis after imaging can be used.

  The thickness of the region including the surface portion forming material is preferably 50 nm or more, more preferably 75 nm or more, still more preferably 125 nm or more, preferably 500 nm or less, more preferably 300 nm or less. When the thickness of the region including the surface portion forming material is not less than the above lower limit and not more than the above upper limit, complete destruction and scattering of the base particles are further suppressed, and further, 10% K value and 30% K value are more preferable. Thus, the base particles can be suitably used for the use of conductive particles and spacers for liquid crystal display elements. The thickness of the region containing the surface portion forming material is an average thickness per base particle. The thickness of the region including the surface portion forming material can be controlled by controlling the sol-gel method.

  The aspect ratio of the substrate particles is preferably 2 or less, more preferably 1.5 or less, and still more preferably 1.2 or less. The aspect ratio indicates a major axis / minor axis.

  From the viewpoint of effectively reducing the connection resistance in the connection structure, effectively improving the display quality in the liquid crystal display element, and effectively increasing the impact resistance in the connection structure and the liquid crystal display element, Is preferably formed of an organic compound. Since the inside of the base particle is formed of an organic compound, complete destruction and scattering of the base particle can be suppressed.

  From the viewpoint of effectively reducing the connection resistance in the connection structure, effectively improving the display quality in the liquid crystal display element, and effectively increasing the impact resistance in the connection structure and the liquid crystal display element, the surface of the base material particle Is preferably formed by hydrolysis and polycondensation of an alkoxysilane compound. In this case, the destruction and scattering of the surface portion of the base particle are further suppressed.

  When the internal forming material of the base particles is an organic compound, the ratio (10% K value / 30% K value) and the compression recovery rate can easily satisfy the above-described values.

  Examples of the organic compound that can be used as the internal forming material include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polypropylene, polyisobutylene, and polybutadiene; polymethyl methacrylate, polymethyl acrylate, and the like. Acrylic resin; polyalkylene terephthalate, polysulfone, polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, one or two kinds of polymerizable monomers having ethylenically unsaturated groups Polymers obtained by polymerization as described above, silane alkoxide polymers having an organic functional group, polycondensates and the like are used. Especially, as above-mentioned, it is preferable that the said internal formation material is a (meth) acrylic polymer. When the internal forming material is a (meth) acrylic polymer, it is easy to design and synthesize substrate particles having physical properties at the time of compression suitable for a conductive material.

  When the internal forming material is a (meth) acrylic compound, examples of the (meth) acrylic compound include a non-crosslinkable monomer and a crosslinkable monomer.

  Examples of the non-crosslinkable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate. , Alkyl (meth) acrylates such as cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxy Examples include oxygen atom-containing (meth) acrylate monomers such as ethylene (meth) acrylate and glycidyl (meth) acrylate. Among these, cyclohexyl (meth) acrylate or isobornyl (meth) acrylate is preferable from the viewpoint of improving brittleness in the polymer particles. As for the said non-crosslinkable monomer, only 1 type may be used and 2 or more types may be used together.

  Examples of the crosslinkable monomer include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Examples thereof include polyfunctional (meth) acrylate monomers such as acrylate, (poly) tetramethylene glycol di (meth) acrylate, and 1,4-butanediol di (meth) acrylate. Especially, as above-mentioned, tetramethylol methane tetra (meth) acrylate or tetramethylol methane tri (meth) acrylate is preferable. As for the said crosslinkable monomer, only 1 type may be used and 2 or more types may be used together.

  The (meth) acrylic polymer can be obtained by polymerizing the monomer by a known method. Examples of this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerizing by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.

  Examples of compounds that can be used as the surface portion forming material include aromatic (di) vinyl compounds having an aromatic group such as divinylbenzene, and silane compounds having an alkoxy group. Especially, as for the said surface part formation material etc., it is preferable that the said surface part formation material which is preferably divinylbenzene or silane alkoxide may be used 1 type, and 2 or more types may be used together.

  The silane alkoxide is not particularly limited. The silane alkoxide preferably has a vinyl group because it can be polymerized with an organic compound which is an internal forming material. Examples of the silane alkoxide having a vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxy. Examples thereof include propylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

  As a method of forming the base material particles using the surface portion forming material, for example, the surface portion forming material is dissolved in the internal forming material, and the phase separation is performed by utilizing the reaction rate or the SP value difference. Method, first swell the internal forming material with the radical polymerization initiator using non-crosslinked seed particles, and then swell the surface forming material with the radical polymerization initiator having a different active temperature to polymerize in two stages Method, and after first swelling the internal forming material together with the radical polymerization initiator using the non-crosslinked seed particles, the surface forming material is swollen later, and the surface forming material is formed by the sol-gel method at the interface with water. And the like, and then polymerizing by radical polymerization.

  From the viewpoint of effectively reducing the connection resistance in the connection structure, effectively improving the display quality in the liquid crystal display element, and effectively suppressing the connection failure in the connection structure and the display defect in the liquid crystal display element, The particles are polymerized in two stages by first swelling the internal forming material together with the radical polymerization initiator using non-crosslinked seed particles and then swelling the surface forming material together with the radical polymerization initiator having a different activation temperature. Alternatively, first swell the internal forming material together with the radical polymerization initiator using non-crosslinked seed particles, then swell the surface forming material later, and form the surface portion by the sol-gel method at the interface with water It is preferably obtained by subjecting the materials to polycondensation followed by polymerization by radical polymerization.

  Specific examples of the sol-gel method include tetraethoxysilane in a dispersion liquid containing an internal part formed of an internal forming material, a solvent such as water, alcohol, and ketone, a surfactant, and an acidic or basic catalyst. For example, a method of performing an interfacial sol reaction in the presence of silane alkoxides such as

(Conductive particles)
The said electroconductive particle is equipped with the base material particle mentioned above and the conductive layer arrange | positioned on the surface of this base material particle.

  In FIG. 1, the electroconductive particle which concerns on the 1st Embodiment of this invention is shown with sectional drawing.

  The electroconductive particle 1 shown in FIG. 1 has the base material particle 11 and the electroconductive layer 2 arrange | positioned on the surface of the base material particle 11. FIG. The conductive layer 2 covers the surface of the base particle 11. The conductive particle 1 is a coated particle in which the surface of the base particle 11 is coated with the conductive layer 2.

  In FIG. 2, the electroconductive particle which concerns on the 2nd Embodiment of this invention is shown with sectional drawing.

  The conductive particle 21 shown in FIG. 2 has the base particle 11 and the conductive layer 22 arranged on the surface of the base particle 11. The conductive layer 22 includes a first conductive layer 22A that is an inner layer and a second conductive layer 22B that is an outer layer. The first conductive layer 22 </ b> A is disposed on the surface of the base particle 11. A second conductive layer 22B is disposed on the surface of the first conductive layer 22A.

  In FIG. 3, the electroconductive particle which concerns on the 3rd Embodiment of this invention is shown with sectional drawing.

  The conductive particles 31 shown in FIG. 3 include base material particles 11, a conductive layer 32, a plurality of core substances 33, and a plurality of insulating substances 34.

  The conductive layer 32 is disposed on the surface of the base particle 11. The conductive particles 31 have a plurality of protrusions 31a on the conductive surface. The conductive layer 32 has a plurality of protrusions 32a on the outer surface. Thus, the conductive particles may have protrusions on the conductive surface of the conductive particles, or may have protrusions on the outer surface of the conductive layer. A plurality of core substances 33 are arranged on the surface of the base particle 11. The plurality of core materials 33 are embedded in the conductive layer 32. The core substance 33 is disposed inside the protrusions 31a and 32a. The conductive layer 32 covers a plurality of core materials 33. The outer surface of the conductive layer 32 is raised by the plurality of core materials 33, and protrusions 31a and 32a are formed.

  The conductive particles 31 have an insulating material 34 disposed on the outer surface of the conductive layer 32. At least a part of the outer surface of the conductive layer 32 is covered with an insulating material 34. The insulating substance 34 is made of an insulating material and is an insulating particle. Thus, the said electroconductive particle may have the insulating substance arrange | positioned on the outer surface of a conductive layer.

  The metal for forming the conductive layer is not particularly limited. Examples of the metal include gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon, and tungsten. , Molybdenum, and alloys thereof. Examples of the metal include tin-doped indium oxide (ITO) and solder. Especially, since the connection resistance between electrodes can be made still lower, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is preferable.

  Like the conductive particles 1 and 31, the conductive layer may be formed of a single layer. Like the conductive particles 21, the conductive layer may be formed of a plurality of layers. That is, the conductive layer may have a stacked structure of two or more layers. When the conductive layer is formed of a plurality of layers, the outermost layer is preferably a gold layer, a nickel layer, a palladium layer, a copper layer, or an alloy layer containing tin and silver, and is a gold layer. Is more preferable. When the outermost layer is these preferred conductive layers, the connection resistance between the electrodes is further reduced. Moreover, when the outermost layer is a gold layer, the corrosion resistance is further enhanced.

  The method for forming the conductive layer on the surface of the substrate particles is not particularly limited. As a method for forming the conductive layer, for example, a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and a method of coating the surface of base particles with metal powder or a paste containing metal powder and a binder Etc. Especially, since formation of a conductive layer is simple, the method by electroless plating is preferable. Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering.

  The particle diameter of the conductive particles is preferably 0.5 μm or more, more preferably 1 μm or more, preferably 520 μm or less, more preferably 500 μm or less, still more preferably 100 μm or less, still more preferably 50 μm or less, and particularly preferably 20 μm. It is as follows. When the particle size of the conductive particles is not less than the above lower limit and not more than the above upper limit, the contact area between the conductive particles and the electrode is sufficiently large when the electrodes are connected using the conductive particles, and the conductive layer When forming the conductive particles, it becomes difficult to form aggregated conductive particles. Further, the distance between the electrodes connected via the conductive particles does not become too large, and the conductive layer is difficult to peel from the surface of the base material particles. Further, when the particle size of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conductive particles can be suitably used for the use of the conductive material.

  The particle diameter of the conductive particles means a diameter when the conductive particles are spherical, and when the conductive particles have a shape other than a true spherical shape, it is assumed that the conductive particles have a true sphere corresponding to the volume. Means the diameter.

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

  When the conductive layer is formed of a plurality of layers, the thickness of the outermost conductive layer is preferably 0.001 μm or more, more preferably 0.01 μm or more, preferably 0.5 μm or less, more preferably 0. .1 μm or less. When the thickness of the outermost conductive layer is not less than the above lower limit and not more than the above upper limit, the coating with the outermost conductive layer becomes uniform, the corrosion resistance becomes sufficiently high, and the connection resistance between the electrodes is further increased. Lower. Further, when the outermost layer is a gold layer, the thinner the gold layer, the lower the cost.

  The thickness of the conductive layer can be measured by observing the cross section of the conductive particles using, for example, a transmission electron microscope (TEM).

  The conductive particles may have protrusions on the conductive surface. The conductive particles may have protrusions on the outer surface of the conductive layer. It is preferable that there are a plurality of the protrusions. An oxide film is often formed on the surface of the conductive layer and the surface of the electrode connected by the conductive particles. When conductive particles having protrusions are used, the oxide film is effectively eliminated by the protrusions by placing the conductive particles between the electrodes and pressing them. For this reason, an electrode and the conductive layer of electroconductive particle can be contacted still more reliably, and the connection resistance between electrodes can be made low. Furthermore, when the conductive particles are provided with an insulating material on the surface, or when the conductive particles are dispersed in a binder resin and used as a conductive material, the conductive particles and the electrodes are separated by protrusions of the conductive particles. Insulating substances or binder resins in between can be effectively eliminated. For this reason, the conduction | electrical_connection reliability between electrodes can be improved.

  As a method of forming protrusions on the surface of the conductive particles, a method of forming a conductive layer by electroless plating after attaching a core substance to the surface of the base particles, and electroless plating on the surface of the base particles Examples include a method of forming a conductive layer by, attaching a core substance, and further forming a conductive layer by electroless plating. In addition, the core material may not be used to form the protrusion.

  The conductive particles may include an insulating substance disposed on the outer surface of the conductive layer. In this case, when the conductive particles are used for connection between the electrodes, a short circuit between adjacent electrodes can be prevented. Specifically, when a plurality of conductive particles are in contact with each other, an insulating material is present between the plurality of electrodes, so that it is possible to prevent a short circuit between electrodes adjacent in the lateral direction instead of between the upper and lower electrodes. In addition, the insulating substance between the conductive layer of an electroconductive particle and an electrode can be easily excluded by pressurizing electroconductive particle with two electrodes in the case of the connection between electrodes. When the conductive particles have protrusions on the surface of the conductive layer, the insulating substance between the conductive layer of the conductive particles and the electrode can be more easily eliminated. The insulating substance is preferably an insulating resin layer or insulating particles, and more preferably insulating particles. The insulating particles are preferably insulating resin particles.

(Conductive material)
The conductive material includes the conductive particles described above and a binder resin. The conductive particles are preferably dispersed in a binder resin and used as a conductive material. The conductive material is preferably an anisotropic conductive material. The conductive material is preferably used for electrical connection of electrodes. The conductive material is preferably a circuit connection material.

  The binder resin is not particularly limited. As the binder resin, a known insulating resin is used. Examples of the binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. As for the said binder resin, only 1 type may be used and 2 or more types may be used together.

  Examples of the vinyl resin include vinyl acetate resin, acrylic resin, and styrene resin. Examples of the thermoplastic resin include polyolefin resins, ethylene-vinyl acetate copolymers, and polyamide resins. Examples of the curable resin include an epoxy resin, a urethane resin, a polyimide resin, and an unsaturated polyester resin. The curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin. The curable resin may be used in combination with a curing agent. Examples of the thermoplastic block copolymer include 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. -Hydrogenated product of a styrene block copolymer. Examples of the elastomer include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.

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

  The method for dispersing the conductive particles in the binder resin is not particularly limited, and a conventionally known dispersion method can be used. Examples of a method for dispersing the conductive particles in the binder resin include a method in which the conductive particles are added to the binder resin and then kneaded and dispersed with a planetary mixer or the like. The conductive particles are dispersed in water. Alternatively, after uniformly dispersing in an organic solvent using a homogenizer or the like, it is added to the binder resin and kneaded with a planetary mixer or the like, and the binder resin is diluted with water or an organic solvent. Then, the method of adding the said electroconductive particle, kneading with a planetary mixer etc. and disperse | distributing is mentioned.

  The conductive material can be used as a conductive paste and a conductive film. When the conductive material according to the present invention is a conductive film, a film that does not include conductive particles may be laminated on a conductive film that includes conductive particles. The conductive paste is preferably an anisotropic conductive paste. The conductive film is preferably an anisotropic conductive film.

  In 100% by weight of the conductive material, the content of the binder resin is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, preferably 99.% or more. It is 99 weight% or less, More preferably, it is 99.9 weight% or less. When the content of the binder resin is not less than the above lower limit and not more than the above upper limit, the conductive particles are efficiently arranged between the electrodes, and the connection reliability of the connection target member connected by the conductive material is further increased.

  In 100% by weight of the conductive material, the content of the conductive particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 80% by weight or less, more preferably 60% by weight or less, More preferably, it is 40% by weight or less, further preferably 20% by weight or less, and particularly preferably 10% by weight or less. When the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conduction reliability between the electrodes is further enhanced.

(Connection structure and liquid crystal display element)
A connection structure can be obtained by connecting the connection target members using the conductive particles described above or using a conductive material including the conductive particles described above and a binder resin.

  The connection structure includes a first connection target member, a second connection target member, and a connection portion connecting the first connection target member and the second connection target member, and the connection portion. Is preferably formed of the above-described conductive particles, or a connection structure formed of a conductive material containing the above-described conductive particles and a binder resin. When the conductive particles are used alone, the connection part itself is the conductive particles. That is, the first and second connection target members are connected by the conductive particles. The conductive material used for obtaining the connection structure is preferably an anisotropic conductive material.

  The first connection target member preferably has a first electrode on the surface. The second connection target member preferably has a second electrode on the surface. It is preferable that the first electrode and the second electrode are electrically connected by the conductive particles.

  FIG. 4 is a front sectional view schematically showing a connection structure using the conductive particles 1 shown in FIG.

  The connection structure 51 shown in FIG. 4 is a connection that connects the first connection target member 52, the second connection target member 53, and the first connection target member 52 and the second connection target member 53. Part 54. The connection part 54 is formed of a conductive material containing the conductive particles 1 and a binder resin. In FIG. 4, the conductive particles 1 are schematically shown for convenience of illustration. Instead of the conductive particles 1, other conductive particles such as the conductive particles 21 and 31 may be used.

  The first connection target member 52 has a plurality of first electrodes 52a on the surface (upper surface). The second connection target member 53 has a plurality of second electrodes 53a on the surface (lower surface). The first electrode 52 a and the second electrode 53 a are electrically connected by one or a plurality of conductive particles 1. Therefore, the first and second connection target members 52 and 53 are electrically connected by the conductive particles 1.

The manufacturing method of the connection structure is not particularly limited. As an example of a method of manufacturing a connection structure, a method of placing the conductive material between a first connection target member and a second connection target member to obtain a laminate, and then heating and pressurizing the laminate Etc. The pressure of the pressurization is about 9.8 × 10 ^{4 to} 4.9 × 10 ⁶ Pa. The temperature of the said heating is about 120-220 degreeC. The pressure of the pressurization for connecting the electrode of the flexible printed board, the electrode arranged on the resin film, and the electrode of the touch panel is about 9.8 × 10 ^{4 to} 1.0 × 10 ⁶ Pa.

  Specific examples of the connection target member include electronic components such as semiconductor chips, capacitors, and diodes, and electronic components such as printed boards, flexible printed boards, glass epoxy boards, and glass boards. The conductive material is preferably a conductive material for connecting electronic components. The conductive paste is a paste-like conductive material, and is preferably applied on the connection target member in a paste-like state.

  The conductive particles and the conductive material are also suitably used for touch panels. Therefore, the connection target member is preferably a flexible substrate or a connection target member in which electrodes are arranged on the surface of the resin film. The connection target member is preferably a flexible substrate, and is preferably a connection target member in which an electrode is disposed on the surface of the resin film. When the flexible substrate is a flexible printed substrate or the like, the flexible substrate generally has electrodes on the surface.

  Examples of the electrode provided on the connection target member include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a silver electrode, a molybdenum electrode, and a tungsten electrode. When the connection object member is a flexible substrate, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode. When the connection target member is a glass substrate, the electrode is preferably 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 with aluminum may be sufficient and the electrode by which the aluminum layer was laminated | stacked on the surface of the metal oxide layer may be sufficient. Examples of the material for the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al, and Ga.

  Moreover, the said base particle is used suitably as a spacer for liquid crystal display elements. That is, the base particle includes a pair of substrates constituting a liquid crystal cell, a liquid crystal sealed between the pair of substrates, and a liquid crystal display element spacer disposed between the pair of substrates. It is suitably used to obtain The spacer for a liquid crystal display element may be contained in a peripheral sealant.

  FIG. 5 is a cross-sectional view of a liquid crystal display element using substrate particles according to an embodiment of the present invention as a spacer for a liquid crystal display element.

A liquid crystal display element 81 shown in FIG. 5 has a pair of transparent glass substrates 82. The transparent glass substrate 82 has an insulating film (not shown) on the opposing surface. Examples of the material for the insulating film include SiO ₂ . A transparent electrode 83 is formed on the insulating film in the transparent glass substrate 82. Examples of the material of the transparent electrode 83 include ITO. The transparent electrode 83 can be formed by patterning, for example, by photolithography. An alignment film 84 is formed on the transparent electrode 83 on the surface of the transparent glass substrate 82. Examples of the material of the alignment film 84 include polyimide.

  A liquid crystal 85 is sealed between the pair of transparent glass substrates 82. A plurality of base material particles 11 are arranged between the pair of transparent glass substrates 82. The base particle 11 is used as a spacer for a liquid crystal display element. The space between the pair of transparent glass substrates 82 is regulated by the plurality of base material particles 11. A sealing agent 86 is disposed between the edges of the pair of transparent glass substrates 82. Outflow of the liquid crystal 85 to the outside is prevented by the sealing agent 86. The sealing agent 86 includes base material particles 11 </ b> A that differ from the base material particles 11 only in particle size.

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

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

Example 1
(1) Production of substrate particles Polystyrene particles having an average particle diameter of 0.85 μm were prepared as seed particles. 3.0 g of the polystyrene particles, 500 g of ion-exchanged water, and 120 g of a 5% by weight aqueous solution of polyvinyl alcohol were mixed and dispersed by ultrasonic waves, and then added to a separable flask and stirred uniformly.

  Further, as an internal forming material, 49 g of isobornyl acrylate as the organic compound A, 1.5 g of 2,2′-azobis (methyl isobutyrate) (“V-601” manufactured by Wako Pure Chemical Industries, Ltd.), and trilauryl sulfate An emulsion A was prepared by adding 3.0 g of ethanolamine and 40 g of ethanol to 400 g of ion-exchanged water.

  The emulsified liquid A is further added to the separable flask to which the polystyrene particles as seed particles are added, and the mixture is stirred for 4 hours. The seed particles absorb the organic compound A, and the internally formed material is swollen. A suspension containing was obtained.

  Next, 49 g of divinylbenzene (purity 96 wt%) as an organic compound B, 1.5 g of benzoyl peroxide (“NIPER BW” manufactured by NOF Corporation), and 3.0 g of lauryl sulfate triethanolamine as surface portion forming materials And 40 g of ethanol were added to 400 g of ion-exchanged water to prepare an emulsion B.

  The emulsion B was further added to the separable flask containing the suspension, and the mixture was stirred for 4 hours to absorb the organic compound B in the seed particles in which the internal forming material was swollen.

  Thereafter, 360 g of a 5% by weight aqueous solution of polyvinyl alcohol was added, heating was started, and the mixture was reacted at 75 ° C. for 5 hours and then at 85 ° C. for 6 hours to obtain base particles having an average particle size of 3.02 μm.

(2) Production of conductive particles The obtained base particles were washed and dried. Then, the nickel layer was formed in the surface of the obtained base material particle | grains by the electroless-plating method, and the electroconductive particle was produced. The nickel layer had a thickness of 0.1 μm.

(Example 2)
The amount of addition of isobornyl acrylate of organic compound A was changed from 49 g to 39.2 g as an internal forming material, and the amount of addition of divinylbenzene of organic compound B was changed from 49 g to 58.8 g as a surface portion forming material. Base material particles and conductive particles were produced in the same manner as in Example 1 except that the changes were made.

(Example 3)
Substrate particles and conductive particles were produced in the same manner as in Example 1 except that the organic compound A was changed from isobornyl acrylate to tetramethylolmethane dimethacrylate as an internal forming material.

Example 4
As in Example 1, except that the addition amount of divinylbenzene of organic compound B was changed from 49 g to 22 g as the surface portion forming material, and 22 g of vinyltrimethoxysilane was further added as the surface portion forming material. Thus, base particles and conductive particles were produced.

(Example 5)
Base material particles and conductive particles were produced in the same manner as in Example 4 except that vinyltrimethoxysilane was changed to vinyltriethoxysilane as the surface portion forming material.

(Example 6)
Substrate particles and conductive particles were produced in the same manner as in Example 4 except that vinyltrimethoxysilane was changed to 3-acryloxypropyltrimethoxysilane as the surface portion forming material.

(Example 7)
Base material particles and conductive particles were produced in the same manner as in Example 4 except that 15 ml of a 25% aqueous ammonia solution was added at the start of heating.

(Example 8)
In preparation of the base particles, polystyrene particles having an average particle size of 0.85 μm were prepared as seed particles. 1.1 g of the polystyrene particles, 98 g of ion-exchanged water, and 120 g of a 5% by weight aqueous solution of polyvinyl alcohol were mixed and dispersed by ultrasonic waves, and then added to a separable flask and stirred uniformly.

  Further, as an internal forming material, 69 g of isobornyl acrylate as organic compound A, 1.75 g of 2,2′-azobis (methyl isobutyrate) (“V-601” manufactured by Wako Pure Chemical Industries, Ltd.), and trilauryl sulfate Emulsion A was prepared by adding 3.7 g of ethanolamine and 48 g of ethanol to 480 g of ion-exchanged water.

  The emulsified liquid A is further added to the separable flask to which the polystyrene particles as seed particles are added, and the mixture is stirred for 4 hours. The seed particles absorb the organic compound A, and the internally formed material is swollen. A suspension containing was obtained.

  Next, as a surface portion forming material, 69 g of divinylbenzene (purity 96 wt%) as an organic compound B, 1.75 g of benzoyl peroxide (“NIPER BW” manufactured by NOF Corporation), 3.7 g of triethanolamine lauryl sulfate And 48 g of ethanol were added to 480 g of ion-exchanged water to prepare an emulsion B.

  The emulsion B was further added to the separable flask containing the suspension, and the mixture was stirred for 4 hours to absorb the organic compound B in the seed particles in which the internal forming material was swollen.

  Thereafter, 480 g of a 5% by weight aqueous solution of polyvinyl alcohol was added, heating was started, and the reaction was carried out at 75 ° C. for 5 hours and then at 85 ° C. for 6 hours to obtain base particles having an average particle size of 4.75 μm.

  Conductive particles were produced in the same manner as in Example 1 except that the obtained base particles were used.

Example 9
In preparation of the base particles, polystyrene particles having an average particle size of 0.85 μm were prepared as seed particles. 3.0 g of the polystyrene particles, 265 g of ion-exchanged water, and 60 g of a 5 wt% aqueous solution of polyvinyl alcohol were mixed and dispersed by ultrasonic waves, and then added to a separable flask and stirred uniformly.

  Further, as an internal forming material, 15 g of isobornyl acrylate as the organic compound A, 0.4 g of 2,2′-azobis (methyl isobutyrate) (“V-601” manufactured by Wako Pure Chemical Industries, Ltd.), and trilauryl sulfate Ethanolamine 0.8 g and ethanol 11 g were added to 105 g of ion-exchanged water to prepare an emulsion A.

  The emulsified liquid A is further added to the separable flask to which the polystyrene particles as seed particles are added, and the mixture is stirred for 4 hours. The seed particles absorb the organic compound A, and the internally formed material is swollen. A suspension containing was obtained.

  Next, 15 g of divinylbenzene (purity 96% by weight) as organic compound B, 0.4 g of benzoyl peroxide (“NIPER BW” manufactured by NOF Corporation), and 0.8 g of lauryl sulfate triethanolamine as surface portion forming materials And 11 g of ethanol were added to 105 g of ion-exchanged water to prepare an emulsion B.

  The emulsion B was further added to the separable flask containing the suspension, and the mixture was stirred for 4 hours to absorb the organic compound B in the seed particles in which the internal forming material was swollen.

  Thereafter, 105 g of a 5% by weight aqueous solution of polyvinyl alcohol was added, heating was started, and the mixture was reacted at 75 ° C. for 5 hours and then at 85 ° C. for 6 hours to obtain base particles having an average particle size of 2.42 μm.

  Conductive particles were produced in the same manner as in Example 1 except that the obtained base particles were used.

(Example 10)
The organic compound A was changed from 49 g of isobornyl acrylate to 34.3 g of tetramethylolmethane dimethacrylate and 14.7 g of isobornyl acrylate as the internal forming material, and the organic compound B was divinylbenzene as the surface forming material. Substrate particles and conductive particles were produced in the same manner as in Example 1 except that 49 g was changed to 19.6 g of tetramethylolmethane dimethacrylate, 24.5 g of benzyl acrylate, and 4.9 g of pentaerythritol tetraacrylate.

(Example 11)
The organic compound A was changed from 49 g of isobornyl acrylate to 42.8 g of divinylbenzene and 6.1 g of styrene as an internal forming material, and the organic compound B was changed from 49 g of divinylbenzene to divinylbenzene 42. The reaction conditions were changed to 8 g and 6.1 g of styrene, and the reaction conditions were changed from the conditions of the reaction at 75 ° C. for 5 hours and then at 85 ° C. for 6 hours. Base material particles and conductive particles were produced in the same manner as in Example 1 except that the conditions were changed to 6 hours at ° C.

(Example 12)
Substrate particles and conductive particles were produced in the same manner as in Example 1 except that the organic compound A was changed from isobornyl acrylate to cyclohexyl methacrylate as an internal forming material.

(Example 13)
(1) Palladium adhesion process The base material particle obtained in Example 1 was prepared. The obtained substrate particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash | cleaned. Substrate particles were added to a 0.5 wt% dimethylamine borane solution at pH 6 to obtain substrate particles to which palladium was attached.

(2) Core substance adhesion process The base material particle | grains to which palladium was adhered were stirred and dispersed for 3 minutes in 300 mL of ion-exchange water, and the dispersion liquid was obtained. Next, 1 g of metallic nickel particle slurry (average particle size 100 nm) was added to the dispersion over 3 minutes to obtain base particles to which the core material was adhered.

(3) Electroless nickel plating step In the same manner as in Example 1, a nickel layer was formed on the surface of the substrate particles to produce conductive particles. The nickel layer had a thickness of 0.1 μm.

(Example 14)
(1) Production of insulating particles A 1000 mL separable flask equipped with a four-neck separable cover, a stirring blade, a three-way cock, a condenser tube and a temperature probe was charged with 100 mmol methyl methacrylate and N, N, N-trimethyl. Ion-exchanged water containing a monomer composition containing 1 mmol of -N-2-methacryloyloxyethylammonium chloride and 1 mmol of 2,2'-azobis (2-amidinopropane) dihydrochloride so that the solid content is 5% by weight. Then, the mixture was stirred at 200 rpm and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, it was freeze-dried to obtain insulating particles having an ammonium group on the surface, an average particle size of 220 nm, and a CV value of 10%.

  The insulating particles were dispersed in ion exchange water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating particles.

  10 g of the conductive particles obtained in Example 1 were dispersed in 500 mL of ion exchange water, 4 g of an aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 6 hours. After filtration through a 3 μm mesh filter, the particles were further washed with methanol and dried to obtain conductive particles having insulating particles attached thereto.

  When observed with a scanning electron microscope (SEM), only one coating layer of insulating particles was formed on the surface of the conductive particles. The coverage of the insulating particles with respect to the area of 2.5 μm from the center of the conductive particles by image analysis (that is, the projected area of the particle diameter of the insulating particles) was calculated to be 30%.

(Example 15)
Using the substrate particles obtained in Example 1, without using nickel particle slurry, a nickel core material is generated by reaction in the plating bath, and electroless nickel plating is co-deposited together with the generated core material. Thus, conductive particles having a plurality of protrusions on the outer surface of the nickel layer were obtained.

(Example 16)
By using the conductive particles of Example 15 and attaching the insulating particles produced in Example 14 in the same manner as in Example 14, conductive particles having the insulating particles attached thereto were obtained.

(Comparative Example 1)
After mixing 48 g of polystyrene particles having an average particle size of 1.30 μm as seed particles, 100 g of ion-exchanged water, 342 g of methanol, and 6 g of a 5% by weight aqueous solution of polyvinylpyrrolidone and dispersing them by ultrasonic waves, The mixture was added and stirred uniformly to prepare a polystyrene particle suspension.

  Further, as organic compound A, 100 g of triethylene glycol dimethacrylate, 150 g of 2-ethylhexyl methacrylate, 3 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.) 12.5 g of a 20% aqueous solution of polyoxyethylene styrenated phenyl ether sulfate ammonium salt (Daiichi Kogyo Seiyaku Co., Ltd., “Hitenol (registered trademark) NF-08”) and 980 g of methanol with 250 g of ion-exchanged water To prepare an emulsion.

  The emulsified liquid was added to a separable flask to which a polystyrene suspension was added and stirred for 8 hours to allow the seed particles to absorb the organic compounds A and B.

  Thereafter, 60 g of a 10% by weight aqueous solution of polyvinyl alcohol and 250 g of ion-exchanged water were added and then reacted at 65 ° C. for 2 hours to obtain base particles having an average particle size of 2.85 μm. Using the obtained base material particles, conductive particles were produced in the same manner as in Example 1.

(Comparative Example 2)
Polystyrene particles having an average particle diameter of 0.85 μm were prepared as seed particles. 3.0 g of the polystyrene particles, 500 g of ion-exchanged water, and 120 g of a 5% by weight aqueous solution of polyvinyl alcohol were mixed and dispersed by ultrasonic waves, and then added to a separable flask and stirred uniformly.

  Further, 49 g of isobornyl acrylate as the organic compound A, 49 g of divinylbenzene (purity 96 wt%) as the organic compound B, 3.0 g of benzoyl peroxide (“NIPER BW” manufactured by NOF Corporation), and triethanol lauryl sulfate An emulsion was prepared by adding 6.0 g of amine and 80 g of ethanol to 800 g of ion-exchanged water.

  The emulsified liquid was added in two portions to a separable flask to which the polystyrene particles as seed particles were added, and the mixture was stirred for 8 hours to absorb the organic compounds A and B in the seed particles.

  Thereafter, 360 g of a 5 wt% aqueous solution of polyvinyl alcohol was added, and then reacted at 85 ° C. for 11 hours to obtain base particles having an average particle size of 3.33 μm. Using the obtained base material particles, conductive particles were produced in the same manner as in Example 1.

(Comparative Example 3)
Substrate particles and electroconductivity were the same as in Comparative Example 2 except that the addition amount of divinylbenzene of organic compound B was changed from 49 g to 22 g, and 22 g of vinyltrimethoxysilane was further added together with organic compounds A and B. Particles were prepared.

(Comparative Example 4)
Core production:
Polystyrene particles having an average particle diameter of 0.85 μm were prepared as seed particles. 3.0 g of the polystyrene particles, 500 g of ion-exchanged water, and 120 g of a 5% by weight aqueous solution of polyvinyl alcohol were mixed and dispersed by ultrasonic waves, and then added to a separable flask and stirred uniformly.

  Moreover, 34 g of isobornyl acrylate as the organic compound A, 34 g of divinylbenzene (purity 96% by weight) as the organic compound B, 1.4 g of benzoyl peroxide (“NIPER BW” manufactured by NOF Corporation), and triethanol lauryl sulfate An emulsion was prepared by adding 3.0 g of amine and 40 g of ethanol to 400 g of ion-exchanged water.

  The emulsified liquid was added in two portions to the separable flask to which the polystyrene particles as seed particles were added, and the mixture was stirred for 6 hours to absorb the organic compounds A and B in the seed particles. Thereafter, 196 g of a 5% by weight aqueous solution of polyvinyl alcohol was added and then reacted at 85 ° C. for 9 hours to obtain base particles having an average particle size of 2.75 μm.

Shell formation:
30 g of the obtained polymer particles (organic core), 6 g of hexadecyltrimethylammonium bromide as a surfactant, and 24 g of a 25 wt% aqueous ammonia solution were placed in 540 g of 2-propanol and 20 g of pure water and mixed. A dispersion of polymer particles was obtained. To this dispersion, 67 g of tetraethoxysilane and 360 g of 2-propanol were added, and a condensation reaction by a sol-gel reaction was performed. Tetraethoxysilane was deposited on the surface of the polymer particles to form a shell to obtain particles. The obtained particles were washed twice with hot water, twice with methanol, and dried to obtain core-shell particles (base material particles). The obtained core-shell particles had a particle size of 3.01 μm. From the core particle size and the core-shell particle size, the thickness of the shell was calculated to be 0.13 μm.

  Using the obtained base material particles, conductive particles were produced in the same manner as in Example 1.

(Evaluation)
(1) Average Particle Diameter of Base Particles About the obtained base particles, about 100,000 particles were measured using a particle size distribution measuring device (“Multisizer 4” manufactured by Beckman Coulter, Inc.). Deviation was measured.

(2) Compressive elastic modulus (10% K value and 30% K value) of substrate particles, and compression load value (10% load value and 30% load value)
By the above-mentioned method, the compression elastic modulus (10% K value and 30% K value) of the obtained base particles and the load value (10% load value and 30% load value) under the condition of 23 ° C. The measurement was performed using a micro compression tester (“Fischerscope H-100” manufactured by Fischer). 10% K value / 30% K value and 10% load value / 30% load value were determined.

(3) Compression recovery rate and fracture displacement rate of substrate particles, and presence / absence of bent portions in compression test of substrate particles In the compression test of substrate particles, the compression recovery rate and fracture displacement rate of the substrate particles The presence or absence of a bent portion was measured by the above-described method using a micro compression tester (“Fischer Scope H-100” manufactured by Fischer).

(4) Core-shell interface and particle internal composition ratio An ultra-thin slice sample of the obtained base particles was prepared and stained with osmium tetroxide. The dyed base material particles were observed with a transmission electron microscope. The internal composition ratio was evaluated from the ratio of the contrast at the center of the particle, the contrast at the half of the radius, and the contrast at the surface layer.

(5) Connection resistance Fabrication of connection structure:
10 parts by weight of bisphenol A type epoxy resin (“Epicoat 1009” manufactured by Mitsubishi Chemical Corporation), 40 parts by weight of acrylic rubber (weight average molecular weight of about 800,000), 200 parts by weight of methyl ethyl ketone, and a microcapsule type curing agent (Asahi Kasei E-material) 50 parts by weight of “HX3941HP” manufactured by S. Co., Ltd. and 2 parts by weight of silane coupling agent (“SH6040” manufactured by Toray Dow Corning Silicone Co., Ltd.) are added, and conductive particles are added to a content of 3% by weight. And dispersed to obtain a resin composition.

  The obtained resin composition was applied to a 50 μm-thick PET (polyethylene terephthalate) film whose one surface was released from the mold, and dried with hot air at 70 ° C. for 5 minutes to produce an anisotropic conductive film. The thickness of the obtained anisotropic conductive film was 12 μm.

  The obtained anisotropic conductive film was cut into a size of 5 mm × 5 mm. A glass substrate (width 3 cm, length 3 cm) provided with an aluminum electrode (height 0.2 μm, L / S = 20 μm / 20 μm) having a lead wire for resistance measurement on one side of the cut anisotropic conductive film. The aluminum electrode was affixed almost to the center of the aluminum electrode. Next, a two-layer flexible printed board (width 2 cm, length 1 cm) provided with the same aluminum electrode was aligned and pasted together so that the electrodes overlap each other. The laminated body of the glass substrate and the two-layer flexible printed circuit board was thermocompression bonded under pressure bonding conditions of 40 N, 180 ° C., and 15 seconds to obtain a connection structure.

Connection resistance measurement:
The connection resistance between the opposing electrodes of the obtained connection structure was measured by the 4-terminal method.

[Evaluation criteria for connection resistance]
◯: Connection resistance is 3.0Ω or less ○: Connection resistance exceeds 3.0Ω, 4.0Ω or less △: Connection resistance exceeds 4.0Ω, 5.0Ω or less ×: Connection resistance exceeds 5.0Ω

(6) Springback prevention property The connection structure obtained by the evaluation of the above (5) connection resistance was left at 85 ° C. and 85% (under high temperature and high humidity) for 100 hours. After leaving, the increase in connection resistance due to springback was evaluated. The connection resistance between the opposing electrodes of the connection structure after standing was measured by the four-terminal method. From the connection resistance of the connection structure after standing, the impact resistance of the connection structure was determined according to the following criteria. In addition, when the connection resistance was rising, it confirmed that the spring back had arisen largely.

[Evaluation criteria for impact resistance of connection structure]
○○: Less than 15% increase in connection resistance after leaving with respect to connection resistance before leaving ○: 15% or more, 30% increase in connection resistance after leaving with respect to connection resistance before leaving Less than △: The increase rate of the connection resistance after leaving untreated is 30% or more and less than 50% X: The increase rate of the connection resistance after leaving untreated is 50% that's all

  Details and results of the base particles are shown in Tables 1 and 2 below. In addition, in the evaluation of the above (5) connection resistance, it was confirmed that the worse the evaluation result, the more the damage and scattering of the surface portion of the base particle were observed.

(7) Example of use as spacer for liquid crystal display element Production of STN type liquid crystal display element:
In a dispersion medium containing 70 parts by weight of isopropyl alcohol and 30 parts by weight of water, the liquid crystal display element spacers (base material particles) before heating of Examples 1 to 12 in solid dispersion concentration in 100% by weight of the obtained spacer dispersion liquid. Was added so that it might become 2 weight%, and it stirred, and obtained the spacer dispersion liquid for liquid crystal display elements.

An SiO ₂ film was deposited on one surface of a pair of transparent glass plates (length 50 mm, width 50 mm, thickness 0.4 mm) 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 (SE3510, manufactured by Nissan Chemical Industries, Ltd.) was applied to the obtained glass substrate with an ITO film by spin coating, and baked at 280 ° C. for 90 minutes to form a polyimide alignment film. After the alignment film was rubbed, wet alignment was performed on the alignment film side of one substrate so that the number of spacers for liquid crystal display elements was 100 per 1 mm ² . After forming a sealant around the other substrate, this substrate and the substrate on which the spacers were spread were placed opposite to each other so that the rubbing direction was 90 °, and both were bonded together. Then, it processed at 160 degreeC for 90 minute (s), the sealing agent was hardened, and the empty cell (screen which does not contain a liquid crystal) was obtained. An STN type liquid crystal containing a chiral agent (made by DIC) was injected into the obtained empty cell, and then the injection port was closed with a sealant, followed by heat treatment at 120 ° C. for 30 minutes to produce an STN type liquid crystal display element. Obtained.

  In the obtained liquid crystal display element, the space | interval between board | substrates was favorably controlled by the spacer for liquid crystal display elements before the heating of Examples 1-12. Moreover, the liquid crystal display element showed favorable display quality. Moreover, as a result of leaving the liquid crystal display element using the spacer for liquid crystal display elements of Examples 1-12 at 75 degreeC for 168 hours, the springback was suppressed and the display quality of the liquid crystal display element was maintained favorable. . In addition, even when the base material particles of Examples 1 to 12 were used as the liquid crystal display element spacers in the peripheral sealant of the liquid crystal display elements, the display quality of the obtained liquid crystal display elements was good. In the evaluation of this liquid crystal display element, it was confirmed that the display quality was good because the surface portion of the base particles was prevented from being damaged and scattered.

DESCRIPTION OF SYMBOLS 1 ... Conductive particle 2 ... Conductive layer 11 ... Base material particle 11A ... Base material particle 21 ... Conductive particle 22 ... Conductive layer 22A ... 1st conductive layer 22B ... 2nd conductive layer 31 ... Conductive particle 31a ... Protrusion 32 ... Conductive layer 32a ... Projection 33 ... Core material 34 ... Insulating material 51 ... Connection structure 52 ... First connection object member 52a ... First electrode 53 ... Second connection object member 53a ... Second electrode 54 ... Connection part 81 ... Liquid crystal display element 82 ... Transparent glass substrate 83 ... Transparent electrode 84 ... Alignment film 85 ... Liquid crystal 86 ... Sealing agent

Claims (16)

The ratio of the compression modulus when compressed by 10% to the compression modulus when compressed by 30% is 1.5 or more,
In the compression displacement-compression load curve in the compression test, there is no bending portion until 50% compression, and there is a bending portion between 50% compression and 80% compression. particle. Rather than core-shell particles comprising a core and a shell disposed on the surface of the core,
The base particle according to claim 1, wherein an interface between the core and the shell does not exist in the base particle.   The base particle according to claim 1 or 2, wherein the composition of the internal forming material and the composition of the surface portion forming material are different. 10% compressed compressive elastic modulus of when the 1000 N / mm ² or more and 5000N / mm ² or less, the substrate particles according to any one of claims 1 to 3.   The base material particle according to any one of claims 1 to 4, wherein a ratio of a load value when compressed by 10% to a load value when compressed by 30% is 0.25 or more.   The composition of the internal forming material is different from the composition of the surface portion forming material, and the surface portion forming material is at least one selected from the group consisting of aromatic (di) vinyl compounds, (meth) acrylic compounds, and silane alkoxides. The base particle according to any one of claims 1 to 5, wherein   The composition of the internal forming material is different from the composition of the surface portion forming material, and the internal forming material and the surface portion forming material are each selected from the group consisting of an aromatic (di) vinyl compound, a (meth) acrylic compound, and a silane alkoxide. The base particle according to claim 6, which is at least one selected. The internal forming material is a (meth) acrylic compound,
The base particle according to any one of claims 1 to 7, wherein the surface portion forming material is at least one of an aromatic (di) vinyl compound and a silane alkoxide. It does not contain aromatic (di) vinyl polymer, (meth) acrylic polymer and aromatic (di) vinyl- (meth) acrylic copolymer in the center, or aromatic (di) vinyl polymer, (meta ) Containing at least one selected from the group consisting of acrylic polymers and aromatic (di) vinyl- (meth) acrylic copolymers in less than 25%;
The base particle according to any one of claims 1 to 8, wherein the surface does not contain a polycondensate of silane alkoxide or contains less than 25% of a polycondensate of silane alkoxide.   The base material of any one of Claims 1-9 by which a conductive layer is formed on the surface, and it is used in order to obtain the electroconductive particle which has the said conductive layer, or is used as a spacer for liquid crystal display elements. particle.   The base particle according to claim 10, wherein a conductive layer is formed on a surface and used to obtain conductive particles having the conductive layer. Base material particles according to any one of claims 1 to 11,
Electroconductive particle provided with the conductive layer arrange | positioned on the surface of the said base material particle.   The conductive particle according to claim 12, further comprising an insulating material disposed on an outer surface of the conductive layer.   The electroconductive particle of Claim 12 or 13 which has a processus | protrusion on the outer surface of the said electroconductive layer. Containing conductive particles and a binder resin,
A conductive material, wherein the conductive particles include the base particles according to claim 1 and a conductive layer disposed on a surface of the base particles. A first connection object member having a first electrode on its surface;
A second connection target member having a second electrode on its surface;
A connection portion connecting the first connection target member and the second connection target member;
The connecting portion is formed of conductive particles or formed of a conductive material containing the conductive particles and a binder resin;
The conductive particles comprise the substrate particles according to any one of claims 1 to 11 and a conductive layer disposed on the surface of the substrate particles,
A connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles.

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