KR102546837B1 - High-strength Bid, Conductive Particles using the same - Google Patents

Abstract

The present invention is a high-strength bead, wherein the strain (%) deformed when an external force is applied to the bead is X, and the compressive strength when the strain is X is Y, and the strain is in the range of 0 <X≤40, the When the compressive strength when Y is minimum is Y1 and the strain rate at Y1 is X1, X1 is X1≤20, and 0.8 < Y1 / Y (X = 5).

Description

High-strength Bid, Conductive Particles using the same}

The present invention relates to a high-strength bead, conductive particles using the same, a conductive material, and a connection structure.

Conductive particles can be largely divided into generally circular metal powders or high-strength beads with conductive metal on the outside. Since the metal powder has an irregular particle shape and does not have a precise spherical shape, the size distribution is wide, so it is used where the electrode wiring width is large and the electrode surface is uneven, such as a PCB.

The form with conductive metal outside the high-strength bead has a regular and almost spherical particle shape, so the size distribution is very narrow, so it is used where the wire width of the electrode is small and the unevenness is low, such as a display. Since it is easy to control the particle size distribution and physical properties of the high-strength beads, polymer or inorganic beads or organic/inorganic hybrid particles are generally used.

The physical properties of the conductive particles must be optimized for the applied electrode material. Due to the optimization of display performance and advantages in the manufacturing process, recently, high-performance displays such as OLED often use electrodes with native oxide films such as Al and Ti. In such an electrode, the electrical resistance is lowered and connection reliability is increased only when the outer conductive layer of the conductive particles penetrates the oxide layer on the surface of the electrode and makes contact with the metal inside. In order to express the characteristics of these conductive particles, it is very important to control the physical properties of the beads.

Conductive particles are generally mixed with hardeners, adhesives, and resin binders to form dispersed anisotropic conductive materials such as anisotropic conductive film, anisotropic conductive adhesive, and anisotropic conductive paste. Paste), Anisotropic Conductive Ink, and Anisotropic Conductive Sheet.

Anisotropic conductive materials include FOG (Film on Glass; flexible substrate - glass substrate), COF (Chip on Film; semiconductor chip - flexible substrate), COG (Chip on Glass; semiconductor chip - glass substrate), FOB (Film on Board; flexible Substrate - glass epoxy substrate), etc. are used.

Assuming that a semiconductor chip and a flexible substrate are bonded, for example, the anisotropic conductive material is placed on the flexible substrate, the semiconductor chips are laminated, and the anisotropic conductive material is cured in a pressurized/heated state so that the conductive particles are bonded to the electrodes of the substrate. A connection structure electrically connecting electrodes of the semiconductor chip may be implemented.

Specifically, the anisotropic conductive material can be used as a method of connecting a display semiconductor chip and a glass substrate constituting a circuit, or a μ-LED, mini-LED and a circuit board.

When used in the anisotropic conductive material, the conductive particles are used in combination with a curing agent, adhesive, resin binder, etc., and when formed into a connection structure after pressurization/heating, the anisotropic conductive material is cured/attached to maintain electrical connection between upper and lower electrodes. do.

In terms of energy efficiency of electronic devices in maintaining electrical connection between electrodes, it is advantageous to have low initial connection resistance and low resistance increase after high temperature and high humidity evaluation, for example, 85℃/85% reliability evaluation. That is, the low initial resistance and low resistance after reliability evaluation is the most important point for the performance of the conductive particles used in the anisotropic conductive material.

In order to improve such performance, a method using the strength and recovery rate of conductive particles has been proposed, but conventional methods use only a part of the physical properties of conductive particles, and thus have limitations in explaining the effective connection resistance of anisotropic conductive materials. In particular, when there is an oxide film on the electrode, there is a limit to lowering the resistance by penetrating the oxide film.

This is because only the compressive strength according to the amount of deformation of the conductive particles is considered, and the change in compressive strength according to the amount of deformation of the bead, which affects deformation and strength, is not considered, so that the high-strength bead is highly deformed and cannot effectively penetrate the oxide film.

Therefore, it is possible to obtain conductive particles, anisotropic conductive materials, and connection structures with low connection resistance and low resistance increase after reliability evaluation only by controlling the physical properties of the high-strength beads.

Japanese Patent Registration No. 6049461

Embodiments of the present invention have been made to solve the above problems, and a technical problem to be achieved by the embodiments of the present invention is to provide a high-strength bead that supports conductive particles to easily penetrate and connect to an oxide film of an electrode. .

In addition, it is to provide a high-strength bead, conductive particle, anisotropic conductive material, and connection structure having excellent reliability due to low increase in resistance even under high temperature/high humidity.

A first aspect of the present invention is a high-strength bead, wherein the strain (%) deformed when an external force is applied to the bead is X, and the compressive strength when the strain is X is Y, and the strain is 0 <X≤40 In the range of, when the compressive strength when Y is minimum is Y1, the strain at Y1 is X1, and the compressive strength when X is 5% is Y (X = 5), X1 is X1 ≤20, and Y1/Y(X=5)>0.8.

At this time, it is preferable that the beads are not destroyed in the range of 0<X≤40.

At this time, the beads are preferably polymers obtained by using monomers such as urethane-based, styrene-based, acrylate-based, benzene-based, epoxy-based, amine-based, imide-based, modified monomers thereof, or mixed monomers of the monomers do.

In addition, the bead is preferably an organic/inorganic hybrid.

In addition, the organic/inorganic hybrid preferably has any one structure from the group consisting of a core-shell structure, a compound structure, and a composite structure.

In addition, it is preferable that a hydrophilic organic layer is further provided on the beads.

In addition, the organic layer is preferably formed by radical polymerization of a functional group having a carbon double bond provided at the surface terminal of the bead body and an organic monomer.

In addition, the organic layer is preferably provided with a thickness of 0.05㎛ to 0.2㎛.

Another aspect of the present invention provides a conductive particle comprising the above-described bead and a conductive layer provided on the surface of the bead.

At this time, the conductive layer is preferably made of one or two or more alloys selected from the group consisting of Ni, Sn, Ag, Cu, Pd, Zn, W, P, B, and Au.

In addition, it is preferable to further include an insulating layer or insulating particles on the surface of the conductive layer.

In addition, it is preferable that the outermost surface of the conductive layer is treated with a hydrophobic rust inhibitor.

Another aspect of the present invention provides an anisotropic conductive material containing conductive particles using the beads described above.

Another aspect of the present invention provides a connection structure including conductive particles using the aforementioned beads.

The high-strength beads according to the embodiments of the present invention are designed to control the compressive strength and strain rate of the high-strength beads according to the external force as external force is applied, so that the oxide film of the electrode can be more easily pierced than conventional high-strength particles there is

Conductive particles according to embodiments of the present invention can manufacture an anisotropic conductive material and a connection structure having a low initial connection resistance and a low increase in resistance after a high temperature/high humidity reliability test.

1 is a fitted line graph of high-strength beads according to an embodiment of the present invention using mini-tab 17.

Prior to describing the present invention in detail below, it is understood that the terms used herein are intended to describe specific embodiments and are not intended to limit the scope of the present invention, which is limited only by the appended claims. shall. All technical and scientific terms used herein have the same meaning as commonly understood by a person of ordinary skill in the art unless otherwise specified.

Throughout this specification and claims, the terms "comprise", "comprise" and "comprising", unless stated otherwise, are meant to include a stated object, step or group of objects, and steps, and any other object However, it is not used in the sense of excluding a step or a group of objects or a group of steps.

On the other hand, various embodiments of the present invention can be combined with any other embodiments unless clearly indicated to the contrary. Any feature indicated as being particularly desirable or advantageous may be combined with any other features and characteristics indicated as being particularly desirable or advantageous.

<First aspect of the present invention>

According to a first aspect of the present invention, a high-strength bead and a manufacturing method thereof are provided.

In general, conductive particles are included in an anisotropic conductive material and heat-compressed. When compressed, the size of the conductive particles is transformed and protrusions penetrate the electrodes to electrically connect the electrodes. At this time, the distance between the electrodes varies depending on the size of the particles used, but is usually about 3 μm to 20 μm.

At this time, as the size of the beads inside the conductive particles is deformed, the compressive strength is also deformed, and usually shows a tendency to decrease and then increase again.

In the section where the initial compressive strength of the high-strength bead shows deformation, the area where the conductive particles initially contact is designed. It is desirable to design with the indicated interval. In other words, in order to penetrate the oxide film, the strength of the electrode or protrusion is important, but the role of the compressive strength according to the amount of deformation of the bead pushing the protrusion is also very important.

Therefore, in the present invention, with the deformation amount and compressive strength value of the manufactured beads, mini-tab 17 software (minitab company) is used to set the amount of deformation of the bead as the X-axis and the compressive strength according to the amount of bead deformation as the Y-axis. A fitted line graph was created using tab 17.

Here, Y is a cubic function of X, where X is the strain rate of the bead and Y is the compressive strength value according to the strain rate. In addition, the coefficient of the cubic term of X is negative, and the minimum inflection point and the maximum inflection point appear sequentially.

At this time, when the deformation range of X is set to 0 to 40, the significant inflection point is the minimum inflection point, and the maximum inflection point is meaningless. That is, the values of X at the minimum inflection point X1 and the compressive strength Y1 at X1 are significant values, and the values of X at the maximum inflection point X2 and the compressive strength Y2 at X2 are insignificant values.

The physical meaning of the minimum inflection point is the point where the compressive strength increases from decrease when an external force is applied to the bead, and it means the point where the compressive strength is minimum within the strain of 40% or less.

Therefore, considering the distance between electrodes where high-strength beads are used, conductive particles, and the size of protrusions, it is desirable to decrease the compressive strength before Y1 and increase the compressive strength after Y1. It is preferable to be designed to form in the section of.

This means that the initial compressive strength decreases when an external force is applied, and then converts to an increase again before the strain exceeds 20%, which has an important meaning in the design of high-strength beads.

In other words, in the range of more than 20%, it means that the projections of the conductive particles penetrate the oxide film of the electrode in a state where the conductive particles are excessively deformed. As the pressure decreases, the efficiency decreases by half.

On the other hand, if the compressive strength in the section showing the initial 5% deformation amount is significantly lower than the compressive strength in the section showing the initial 5% deformation amount, the deformation of the bead while the projection penetrates the electrode It becomes severe, and even if the strength of the protrusion is high, a phenomenon in which the protrusion cannot effectively penetrate the oxide film of the electrode occurs.

Therefore, it is preferable to design so that the compressive strength representing the lowest point compared to the compressive strength does not differ by more than 20% when the bead is initially deformed by 5%. That is, when X1 is the strain at Y1, it is preferable to satisfy 0.8 < Y1/Y (X = 5). Hereinafter, the value of Y when X is a is expressed as Y (X = a).

This means that the ratio of the minimum compressive strength Y1 to the compressive strength Y (X=5) at 5% strain is 0.8 or more.

That is, it means that the compressive strength at the lowest point compared to the compressive strength of Y (X=5) is 80% or more. nice to get in

Summarizing the above, the strain (%) deformed when an external force is applied to the bead is X, the compressive strength when the strain is X is Y, and the strain is in the range of 0 <X≤40, the Y is When the compressive strength at the minimum is Y1 and the strain at Y1 is X1, X1 is preferably designed so that X1≤20 and 0.8 < Y1/Y (X = 5).

In this case, the bead must be designed not to be destroyed in the range of 0<X≤40, and the value of Y when the X is 10 is Y (X=10) and the value of Y when the X is 20 When is set to Y (X = 20), it is preferable to satisfy the relationship of Y (X = 10) < Y (X = 20).

In addition, it is preferable to maintain the condition of Y(X=(10) < Y(X=20) < Y(X=30) < Y(X=40) in order to maintain high strength of the bead.

When the above-mentioned strength is satisfied, the material of the high-strength bead is not particularly limited. For example, general resin beads or organic/inorganic hybrid particles can be used.

Resin beads, for example, using monomers such as urethane-based, styrene-based, acrylate-based, benzene-based, epoxy-based, amine-based, imide-based monomers, modified monomers thereof, or mixed monomers of the above monomers, seed polymerization, A copolymer obtained by polymerization by a method such as dispersion polymerization, suspension polymerization, or emulsion polymerization can be used.

In addition, the organic/inorganic hybrid particles may be beads of a core-shell structure, a compound structure, or a composite structure containing both organic and inorganic materials. With a core-shell structure, when the core is organic, the shell is inorganic, and when the core is inorganic, the shell is organic. For organic materials, the above monomers or modified monomers or mixed monomers are used. For inorganic materials, oxides - SiO2, TiO2, Al2O3, ZrO2, etc., nitrides - AlN, Si3N4, TiN, BaN, etc., carbides - WC, TiC, SiC etc. are available. As a method of forming the shell, a chemical coating method, a Sol-Gel method, a spray coating method, a CVD (chemical vapor deposition method), a PVD (physical vapor deposition method), a plating method, or the like may be used. In addition, a form in which inorganic particles are dispersed in an organic matrix is possible, a form in which organic particles are dispersed in an inorganic matrix, and a form in which organic/inorganic particles are dispersed in a 50:50 ratio are also possible.

As an example, a polymer of monomers of two or more organo silanes may be used.

The organosilane polymer is preferably a polymer obtained by polymerizing two or more silanes essentially containing a monomer having at least one carbon double bond.

As the organosilane monomer having a carbon double bond, vinyltrimethoxysilane (VTMS), vinyltriethoxysilane, p-styryltrimethoxysilane, etc. may be used as a monomer having a vinyl group, and a monomer having an acryloyl group. As "3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acrylooxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacrylic Oxypropylmethyldiethoxysilane, 3-acrylooxypropyltriethoxysilane, 3-methacryloxyethoxypropyltrimethoxysilane and the like can be used.

In addition, as organosilane monomers having no carbon double bond, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldivinylsilane, methyltrivinylsilane, tetravinylsilane , tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4 -Epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like can be used.

As the number of silane monomers having carbon double bonds increases, it is advantageous to form an organic layer, which will be described later, and it is possible to form a polymer only with silane monomers having carbon double bonds. Silanes may also be included. Accordingly, it is preferable to include 120 parts by weight or less of the silane monomer having no carbon double bond, more preferably 110 parts by weight or less, based on 100 parts by weight of the silane monomer having a carbon double bond.

On the other hand, when all of the above-mentioned beads are composed of polymers of silane monomers having carbon double bonds, it is preferable to include a silane monomer having a vinyl group and a silane monomer having an acryloyl group, but many double bonds remain on the surface of the synthesized particles. This is because it is easy to form a hydrophilic organic layer through radical polymerization of double bonds by adding an organic monomer to the surface.

When the above-mentioned beads are all composed of polymers of silane monomers having carbon double bonds, the silane monomer having a vinyl group and the silane monomer having an acryloyl group are based on 100 parts by weight of the silane monomer having a vinyl group, and the silane monomer having an acryloyl group is It is preferable to include 70 parts by weight to 125 parts by weight.

Meanwhile, an organic layer may be further provided on the high-strength beads. The organic layer is formed using an organic monomer that binds to carbon having a double bond at the end of the bead surface, and the organic layer has hydrophilicity. The formed organic layer not only serves to ensure that the synthesized beads do not agglomerate after drying and have good dispersibility when dispersed in water, but also facilitates plating.

The organic monomer that can be used at this time is a Vinyl-based having a hydrophilic group, and the hydrophilic group includes an acryl group, an amine group, and the like.

For example, the vinyl type having the acrylic group is ethylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 3-butylene di (meth) acrylate, triethylene glycol (meth) ) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane (meth) acrylate, pentaerythritol tetra (meth) acrylate, etc., and vinyl having the amine group As the system, arylamine, N-vinyl-2-propen-1-amine, 3-buten-1-amine and the like can be used.

At this time, the thickness of the organic layer is preferably provided with a height of 0.05 μm to 0.2 μm. If it exceeds the above range, there is a problem in that the compressive strength is lowered and a large amount of small particles is generated, and if it is less than the above range, it is difficult to form an organic layer, aggregation between beads occurs, and there is a problem that sufficient hydrophilicity cannot be exhibited.

In addition, inorganic nanoparticles may be further included in the high-strength beads. As the inorganic nanoparticles, oxides including SiO 2 , TiO 2 , Al 2 O 3 , and ZrO 2 , nitrides including AlN, Si 3 N 4 , TiN, and BaN, and carbides including WC, TiC, and SiC may be used. The added inorganic nanoparticles can be dispersed into the beads during the process of synthesizing the beads to synthesize reinforced high-strength beads.

The size of the high-strength beads is not particularly limited, but is preferably 6 μm or less, more preferably 1.5 μm to 5 μm, and still more preferably 2.5 μm to 4.5 μm, considering the shape and surface roughness of a general electrode.

This is because the use of an anisotropic conductive material manufactured using conductive particles is limited by the electrode spacing. The size of the above-described beads is the same even when an organic layer is included or inorganic nanoparticles are further included.

The method for manufacturing high-strength beads described above includes a polymerization step, a classification step, and a heat treatment step.

The polymerization step is a step of polymerizing heterogeneous organosilane monomers, wherein the silane having no carbon double bond is 120 parts by weight or less, more preferably 110 parts by weight or less, based on 100 parts by weight of the silane monomer having a carbon double bond. It is preferable to include

The classification step is a step of classifying the polymerized beads according to their size in the polymerization step, but in the case of uniform polymerization or for applications where the size of the particles is not uniform, the classification step can be omitted.

The heat treatment step is a step of drying the beads and heat treatment to express desired physical properties.

In the case of forming an organic layer on beads, an organic layer forming step of forming an organic layer on the beads by injecting an organic monomer after the above-described polymerization step is further included.

<Second aspect of the present invention>

According to a second aspect of the present invention, conductive particles and a manufacturing method thereof are provided. The conductive particles include a bead of the first side described above and a conductive layer provided on the surface of the bead.

In addition, the conductive layer on the surface of the conductive particles may or may not have projections selectively provided depending on the use.

The conductive particle is a conductive particle included between electrodes to electrically connect the electrodes, and at least one of the electrodes has an oxide film on the surface.

The conductive layer is composed of a first element constituting a base and at least one second element or second elements selected from the group consisting of P, B, Cu, Au, Ag, W, Mo, Pd, Co, and Pt. It can be made of an alloy made of

For example, the conductive layer of the conductive particle may be composed of one or more elements such as P, B, Cu, Au, Ag, W, Mo, Pd, Co, and Pt on a Ni base. At this time, the conductive layer is composed of one layer, but inside, the concentration of each element except Ni is changed. At this time, the conductive layer preferably has a polycrystalline structure. As another example, an alloy of copper-zinc, copper-tin, or copper-zinc-tin is also possible.

The thickness of the conductive layer of conductive particles is not particularly limited. 50 to 500 nm is preferable depending on the electrode used and the driving principle. For example, 50 to 200 nm is preferable for voltage-driven electronic products, and 100 to 500 nm is preferable for current-driven electronic products. More preferably, it is 80 to 150 nm when driven by voltage and 120 to 400 nm when driven by current. This is because connection resistance deteriorates when the thickness of the conductive layer is less than 50 nm during voltage driving, and when it is more than 200 nm, performance and price of the product become unfavorable. This is because the resistance is high at less than 120nm when driving current, and loss due to heat generation is large, and the product performance and price are disadvantageous at more than 500nm.

When the conductive layer is provided with a protrusion, the shape of the protrusion is not particularly limited, and may be spherical, elliptical, or a shape in which several particles gather to form a cluster.

The size and shape of the protrusion is not particularly limited, and the size is preferably 50 to 500 nm. If the size of the protrusion is too small or too large, the effect of breaking the metal oxide layer and the binder resin is weakened, so the size of the protrusion is preferably 100 to 300 nm considering the spacing of the electrodes mainly used. The protrusion size of the manufactured conductive particles can be obtained as follows using the highest point concentric circle (DH) and the lowest point concentric circle (DL) of the outermost FE-SEM image. protrusion size = (DH-DL)/2.

The conductive layer of the conductive particles according to the embodiment of the present invention is formed as one layer, and the method of forming is not particularly limited, but a catalytic material is applied to the surface of the bead, and the conductive layer and the protrusion are formed through electroless plating. It is desirable to do At this time, as described above, the conductive layer includes at least two or more elements among Ni, P, B, Cu, Au, Ag, W, Mo, Pd, Co, and Pt, and the concentration gradient of the elements in the layer is It is preferable to apply in multiple stages while changing the concentration of elements during electroless plating in order to form a single layer.

Optionally, a noble metal layer such as gold, silver, platinum, or palladium may be included on the conductive layer of the conductive particles. This is because the noble metal layer can increase the conductivity of the conductive particles and obtain an anti-oxidation effect. The method of forming the noble metal layer is not particularly limited, and conventionally known techniques such as general sputtering, plating, and deposition can be used.

Optionally, an insulating layer may be provided on the outermost part of the conductive particle according to the embodiment of the present invention. As the miniaturization and integration of electronic products increase, the pitch of electrodes becomes smaller, and when there is no insulation particle on the outermost part, a phenomenon of electrical conduction with adjacent electrodes occurs.

Methods of forming the insulating layer include a method of chemically attaching insulating particles to the outermost portion of the conductive particles using a functional group, a method of dissolving an insulating solution in a solvent, and then coating by spraying or immersion.

In addition, it is preferable to apply anti-rust treatment to the conductive layer of the conductive particles of the present invention. Because the anti-corrosion treatment increases the contact angle with water to increase reliability in a high-humidity environment, and has the effect of reducing the performance degradation of the connection member by dissolving impurities in water. Therefore, it is preferable to use a hydrophobic rust inhibitor including phosphoric acid esters or salts thereof, alkoxysilanes containing silanes, alkylthiols containing thiols, dialkyl disulfide containing sulfides, and the like. After dissolving the rust inhibitor in a solvent, methods such as immersion and spraying may be used.

The method for manufacturing conductive particles according to the second aspect of the present invention includes a high-strength bead manufacturing step (S1), a catalyst treatment step (S2), a conductive layer forming step (S3), a rust prevention step (S4), and an insulation treatment step (S5). It may include, where the rust prevention step (S4), the insulation treatment step (S5) may be optionally included.

The bead manufacturing step is a step of preparing beads by polymerizing and crosslinking silane-based monomers, and is a step of preparing beads for high strength as described in the first aspect. That is, when an organic layer is formed after polymerization of silane-based monomers, organic monomers are introduced and cross-linked to synthesize silane-based polymer beads having an organic layer on the bead surface. The synthesized beads are sorted, dried, and heat-treated to obtain beads. At this time, the heat treatment temperature may be 200 to 700 degrees, preferably 350 to 650 degrees, 350 to 600 degrees.

The catalyst treatment step is a step of cleaning the surface of the prepared beads and attaching an electroless plating catalyst to the surface of the beads to activate them. The plating catalyst used at this time may be replaced with one attached with very small catalyst particles having catalytic properties, as long as the same effect can be provided.

Specifically, in the catalyst treatment step, the beads are pretreated using various methods known for sensitizing the electroless plating catalyst after treatment with a surfactant, and then the sensitized beads are put into a solution containing a precursor of the electroless metal plating catalyst, Perform activation processing.

The activated beads are put into a solution containing a strong acid and stirred at room temperature to perform an accelerated treatment to obtain catalyst-treated beads for electroless plating.

Next, the conductive layer forming step (S3) includes a bead dispersion step (S3a) and a protruding conductive layer forming step (S3b) in which the concentration gradient increases.

In the bead dispersing step (S3a), beads are added to and dispersed in the nickel-base alloy plating solution.

The nickel base alloy plating solution is prepared by sequentially dissolving the precursor of the nickel alloy element, complexing agent, lactic acid, stabilizer, and surfactant, and after confirming that the solution is completely dissolved, a pH adjusting agent that determines the quality of the plating layer is added to adjust the pH of the desired solution. manufacture At this time, the pH is adjusted to pH 5.5 to 6.5 using NaOH, ammonia water, or sulfuric acid to improve the adhesion and dispersibility of the beads and the conductive layer in the initial Ni reduction reaction in the conductive layer formation step (S3b) described later. It is desirable to be able to When the pH is less than 5.5, for example, below pH 4, the adhesion and dispersibility are good, but the reactivity is too low, so there is a possibility that some particles may be unplated. This may result in poor adhesion and dispersibility.

In the prepared plating solution, catalyst-treated high-strength beads are added, and dispersion treatment is performed using an ultrasonic homogenizer.

Subsequently, a treatment (S3b) of forming a conductive layer is performed on the high-strength beads in the dispersion-treated solution.

For example, the dispersed plating solution is prepared by dividingly introducing a solution containing a precursor of at least one element selected from the group consisting of P, B, Cu, Au, Ag, W, Mo, Pd, Co, and Pt. can do.

As another example, in the bead dispersing step (S2a), one or more precursors selected from P and B are added to the nickel-base alloy plating solution, and Cu and Au are added to the dispersing plating solution in the protruding conductive layer forming step (S2b). , Ag, W, Mo, Pd, Co, and Pt, an alloy element including a precursor of one or more selected elements may be separately introduced to form a conductive layer having protrusions.

At this time, the alloying element to be dividedly added may be divided and introduced 2 to 5 times at intervals of 10 to 30 minutes, and may be divided and introduced 2 to 4 times at intervals of 15 to 25 minutes.

In addition, it is more preferable to provide temperature rise conditions because it is possible to form desired projections without excessive abnormal precipitation in the projection formation mechanism.

The selectively performed anticorrosive step (S4) may be performed by introducing conductive particles into the anticorrosive solution, but is not limited thereto.

As the rust preventive solution, a hydrophobic rust preventive including phosphoric acid ester-based or its salt-based, silane-containing alkoxysilane-based, thiol-containing alkylthiol, sulfide-containing dialkyl disulfide, or the like may be used. As the hydrophobic rust preventive, electroless nickel rust preventives including product name SG-1 sold by MSC may be used.

An insulation treatment process (S5) may be performed on the prepared conductive particles. The insulation method is not particularly limited. Insulation particles may be applied to the surface of the conductive particles for dusting, or an organic layer may be formed on the surface of the conductive particles.

As a conductive particle included between electrodes and electrically connecting the electrodes in this way, at least one of the electrodes has an oxide film on a surface, and the conductive particle includes a bead and a protrusion provided on the surface of the bead. It is possible to manufacture conductive particles including a conductive layer with

<Third aspect of the present invention>

According to a third aspect of the present invention, an anisotropic conductive material is provided. The anisotropic conductive material may be prepared by dispersing the conductive particles of the second aspect described above in a binder resin.

Anisotropic conductive materials include, for example, anisotropic conductive pastes, anisotropic conductive films, and anisotropic conductive sheets.

The resin binder is not particularly limited. Examples thereof include vinyl resins such as styrene, acrylic, and vinyl acetate, thermoplastic resins such as polyolefins and polyamides, and curable resins such as urethanes and epoxies. These resins may be used alone or in combination of two or more.

For the purpose of polymerization or curing, a radical initiator such as BPO (Benzoyl peroxide), a photoinitiator such as TPO (Timethylbenzoyl phenylphosphinate), an epoxy latent curing agent such as HX3941HP, etc. may be used alone or in combination.

In addition, other materials may be added to the anisotropic conductive material binder resin within a range that does not impede achievement of the object of the present invention. For example, colorants, softeners, heat stabilizers, light stabilizers, antioxidants, inorganic particles and the like.

The manufacturing method of the anisotropic conductive material is not particularly limited. For example, it can be used as an anisotropic conductive paste by uniformly dispersing conductive particles in a resin binder, or it can be used as an anisotropic film by thinly spreading on release paper.

<Fourth aspect of the present invention>

According to a fourth aspect of the present invention, a connection structure is provided. The connection structure connects the circuit board by using the conductive particles on the second side or the anisotropic conductive material on the third side.

For example, the connection between the display semiconductor chip of a smart phone and a glass substrate constituting a circuit or the connection structure of the present invention does not cause malfunction of the circuit due to poor connection of the circuit or rapid increase in resistance.

Hereinafter, the present invention will be described in more detail through specific and various examples, but this is to aid understanding of the present invention and the technical spirit of the present invention is not limited thereto.

Example

Example 1

1) Bead manufacturing

A diluted base aqueous solution (a) was prepared by adding 1.2 g of 3% ammonia water to 200 g of deionized water, and a monomer mixture solution (b) was prepared by mixing 10 g of MTMS and 10 g of MPTMS. While stirring the base aqueous solution (a) at low speed, the monomer mixture solution (b) was added and reacted overnight at room temperature to synthesize a bead intermediate.

In order to separate the bead intermediate and the solution that did not participate in the reaction, the bead intermediate was naturally precipitated to remove the supernatant, and then 95% ethanol was added to remove small particles by centrifugation at least 10 times.

The bead intermediate from which the small particles were removed was dried in a convection oven at 70° C. for 18 hr or more, and heat-treated in a vacuum oven at 250° C. for 3 hr to prepare beads.

For the average diameter of the prepared beads, the mode value of the particles was used using a Particle Size Analyzer (BECKMAN MULTISIZER TM3), and the number of beads measured at this time was 75,000. The average diameter of the beads was 2.84 μm.

2) Formation of outer conductive layer of beads

① Catalyst treatment process

30 g of the prepared beads were put in a solution of 800 g of deionized water and 1 g of surfactant Triton X100, and treated in an ultrasonic bath for 1 hr to remove excess unreacted monomer and oil components present in the beads. At the end of the washing and degreasing process, a washing process was performed three times using 40° C. deionized water.

The beads after the washing process were put into a solution of 600 g of deionized water, 2 g of hydrofluoric acid (HF), and 15 g of zalic acid, treated in an ultrasonic bath for 20 minutes to etch the beads, and washed with water three times.

A Pd catalyst treatment was performed on the beads after the etching process was completed. After dissolving 150 g of stannous chloride and 300 g of 35-37% hydrochloric acid in 600 g of deionized water, the washed and degreased beads were added, immersed and stirred for 30 minutes at 30 ° C. to sensitize, and then washed with water three times.

The sensitized beads were put into 1 g of palladium chloride and 200 g of 35-37% hydrochloric acid in 600 g of deionized water and activated at 40 ° C for 1 hour. After the activation treatment, the water washing process was performed three times.

The activated beads were added to a solution of 100 g of 35-37% hydrochloric acid and 600 g of deionized water and stirred at room temperature for 10 minutes to accelerate treatment. After the accelerated treatment, water washing was performed three times to obtain catalyst-treated beads for electroless plating.

② Plating process

In a 5L reactor, 3500 g of deionized water contains 300 g of nickel sulfate as Ni salt, 5 g of sodium acetate as a complexing agent, 2 g of lactic acid, 0.001 g of Pb-acetate as a stabilizer, 0.001 g of sodium thiosulfate, 1 g of PEG-1200 as a surfactant, 1.5 g of PEG-400 as a stabilizer, 0.02 g of Triton X100 was sequentially dissolved to prepare a plating solution (a). The catalyst-treated beads were added to the prepared solution (a) and dispersed for 10 minutes using an ultrasonic homogenizer. After dispersion treatment, the pH of the solution was adjusted to 5.7 using ammonia water - Solution (b)

Solution (c) was prepared by dissolving 500 g of deionized water, 380 g of sodium hypophosphite as a reducing agent, and 0.0001 g of sodium thiosulfate as a stabilizer in a 1 L beaker.

While maintaining the temperature of the 5L reactor (solution (b)) at 65° C., solution (c) was added at an amount of 10 g per minute using a metering pump, and the temperature of the reactor was heated and maintained to reach 75° C. in 30 minutes.

After the addition of the solution (c) was completed, the mixture was maintained for 30 minutes to obtain Ni-plated conductive particles. The protrusion size of the manufactured conductive particles can be obtained as follows using the highest point concentric circle (DH) and the lowest point concentric circle (DL) of the outermost FE-SEM image.

Asperity size = (DH-DL)/2

The protrusion size of the prepared conductive particles was 130 nm.

Example 2

A diluted base aqueous solution (a) was prepared by adding 1.3 g of 3% ammonia water to 200 g of deionized water, and a monomer mixture solution (b) was prepared by mixing 10 g of VTMS and 10 g of MPTMS. While stirring the base aqueous solution (a) at low speed, the monomer mixture solution (b) was added and reacted overnight at room temperature to synthesize a bead intermediate.

Thereafter, 2 g of PVP (Polyvinylpyrrolidone) was dissolved in 10 g of deionized water and added to the reaction vessel, and after the temperature was raised to 75 ° C, an aqueous solution of 0.2 g of KPS dissolved in 5 g of deionized water was added and reacted for 10 hr.

After removing the supernatant by naturally settling the reaction solution, 95% ethanol was added to remove small particles by centrifugation at least 10 times.

The particles from which the small particles were removed were dried in a convection oven at 70° C. for 18 hr or more, and heat-treated in a vacuum oven at 250° C. for 3 hr to prepare beads. The average diameter of the beads was 2.49 μm. The formation of the outer conductive layer of the bead was performed in the same manner as in Example 1. The size of the protrusion after plating was 108 nm.

Example 3

1) Bead manufacturing

A diluted base aqueous solution (a) was prepared by adding 1.2 g of 3% ammonia water to 200 g of deionized water, and a monomer mixture solution (b) was prepared by mixing 10 g of VTMS and 10 g of MPTMS. While stirring the base aqueous solution (a) at low speed, the monomer mixture solution (b) was added and reacted overnight at room temperature to synthesize a bead intermediate. The particle average of the intermediate was 2.62 μm.

Thereafter, 2 g of PVP (Polyvinylpyrrolidone) was dissolved in 10 g of deionized water, added to the reaction vessel, and 1.0 g of organic monomer EGDMA (Ethylene glycol dimathacrylate) was added, and the temperature was raised to 75 ° C. added and reacted for 10 h.

After removing the supernatant by naturally settling the reaction solution, 95% ethanol was added to remove small particles by centrifugation at least 10 times.

The particles from which the small particles were removed were dried in a convection oven at 70° C. for 18 hr or more, and heat-treated in a vacuum oven at 250° C. for 3 hr to prepare beads. The average diameter of the intermediate was 2.62 μm, and the average diameter of the beads was 2.88 μm.

1) Formation of outer conductive layer of beads

① Catalyst treatment process

30 g of the prepared beads were put in a solution of 800 g of deionized water and 1 g of surfactant Triton X100, and treated in an ultrasonic bath for 1 hr to remove excess unreacted monomer and oil components present in the beads. At the end of the washing and degreasing process, a washing process was performed three times using 40° C. deionized water.

Beads were treated with a Pd catalyst. After dissolving 150 g of stannous chloride and 300 g of 35-37% hydrochloric acid in 600 g of deionized water, the washed and degreased beads were added, immersed and stirred for 30 minutes at 30 ° C, followed by sensitization treatment, followed by washing with water three times.

The sensitized beads were put into 1 g of palladium chloride and 200 g of 35-37% hydrochloric acid in 600 g of deionized water and activated at 40 ° C for 1 hour. After the activation treatment, the water washing process was performed three times.

The activated beads were added to a solution of 100 g of 35-37% hydrochloric acid and 600 g of deionized water and stirred at room temperature for 10 minutes to accelerate treatment. After the accelerated treatment, water washing was performed three times to obtain catalyst-treated beads for electroless plating.

② Plating process

In a 5L reactor, 3500 g of deionized water contains 300 g of nickel sulfate as a Ni salt, 5 g of sodium acetate as a complexing agent, 2 g of lactic acid, 0.001 g of Pb-acetate as a stabilizer, 0.001 g of sodium thiosulfate as a stabilizer, 1 g of PEG-1200 as a surfactant, 1.5 g of PRG-400 as a surfactant, 0.02 g of Triton X100 was sequentially dissolved to prepare a plating solution (a). The catalyst-treated beads were added to the prepared solution (a) and dispersed for 10 minutes using an ultrasonic homogenizer. After dispersion treatment, the pH of the solution was adjusted to 5.7 using ammonia water - Solution (b)

Solution (c) was prepared by dissolving 500 g of deionized water, 380 g of sodium hypophosphite as a reducing agent, and 0.0001 g of sodium thiosulfate as a stabilizer in a 1 L beaker.

While maintaining the temperature of the 5L reactor (solution (b)) at 65° C., solution (c) was added at an amount of 10 g per minute using a metering pump, and the temperature of the reactor was heated and maintained to reach 75° C. in 30 minutes.

After the addition of the solution (c) was completed, the mixture was maintained for 30 minutes to obtain Ni-plated conductive particles. The size of the protrusion after plating was 136 nm.

Example 4

In Example 3, the amount of ammonia water was changed to 1.3 g, and the organosilane monomer was changed to VTMS 8 g and MPTMS 12 g to prepare beads. The rest of the process was performed in the same manner as in Example 3. The average diameter of the intermediate was 2.59 μm, and the average diameter of the beads was 2.99 μm. The size of the protrusion after plating was 145 nm.

Example 5

In Example 3, the amount of ammonia water was changed to 1.4 g, and the organic monomer was changed to 2 g of TMPTA (Trimethylolpropane trimethacrylate) to prepare beads. The rest of the process was performed in the same manner as in Example 3. The average diameter of the intermediate was 2.15 μm, and the average diameter of the beads was 2.39 μm. The size of the protrusion after plating was 122 nm.

Example 6

In Example 3, beads were prepared by changing the amount of ammonia water to 1.5 g and changing the organic monomer to 2 g of HDDA (1,6-Hexanediol diacrylate). The rest of the process was performed in the same manner as in Example 3. The average diameter of the intermediate was 2.01 μm, and the average diameter of the beads was 2.29 μm. The size of the protrusion after plating was 105 nm.

Example 7

Beads were prepared by changing the heat treatment conditions in Example 6 to 3 hr in a nitrogen atmosphere and 350 ° C. The rest of the process was performed in the same manner as in Example 6. The average diameter of the intermediate was 2.01 μm, and the average diameter of the beads was 2.29 μm. The size of the protrusion after plating was 108 nm.

Example 8

Beads were prepared by changing the heat treatment conditions in Example 6 to 3 hr in a nitrogen atmosphere and 450 ° C. The rest of the process was performed in the same manner as in Example 6. The average diameter of the intermediate was 2.01 μm, and the average diameter of the beads was 2.29 μm. The size of the protrusion after plating was 104 nm.

Example 9

In Example 3, 1.5 g of silica nanoparticle (silica nanoparticle 30wt% in DI Water, Particle size = 5-15 nm) was mixed with a monomer mixture solution, and the rest of the process was prepared in the same manner as in Example 3. The average diameter of the intermediate was 2.65 μm, and the average diameter of the beads was 2.91 μm. The size of the protrusion after plating was 158 nm.

Example 10: Manufacturing of anisotropic conductive material

2 g of naphthalene-based epoxy resin HP4032D (manufactured by DIC, trade name), 20 g of phenoxy resin YP-50 (manufactured by Tohto Kasei, trade name), 25 g of acrylic epoxy resin VR-60 (manufactured by Showa Denko, trade name), HXA-3922HP (thermal curing agent) 22 g of Asahi Chemical Co., Ltd., trade name) and 5 g of epoxysilane coupling agent A-187 (manufactured by Momentive, trade name) were mixed well, and a mixture having a solid content of 50% was prepared using toluene as a solvent. The conductive particles prepared in Examples and Comparative Examples were added at a weight ratio of 10% and then mixed for 5 minutes under conditions of revolution of 400 rpm and rotation of 150 rpm using an orbital mixer to prepare an anisotropic conductive paste. A film having a thickness of 20 μm was formed on the release film using the above anisotropic conductive paste, and then dried in the air using a hot air drying furnace at 75° C. for 5 minutes to obtain a final anisotropic conductive film having a thickness of 12 μm.

Example 11: Manufacturing of connection structure

The electrodes used in the connection structure deposited ITO (Indium Tin Oxide) on a glass substrate to produce a glass substrate with a transparent electrode and an FPCB with an electrode width of 15㎛ and an electrode interval of 50㎛, and the pattern of the electrode was on the Au base Al was the final coating.

The anisotropic conductive film prepared in Experimental Example 1 was cut into a width of 3 mm, and using a bonding jig having a width of 1 mm and a length of 20 mm, pre-bonding was performed on a glass substrate with ITO at 0.2 MPa, 120 ° C, and 10 seconds. After placing the FPCB, bonding was performed at 60 MPa, 200 ° C for 20 seconds to produce a connection structure.

Comparative Example 1

A first solution was prepared by putting 750 g of PS (Poly Styrene) and 750 g of DVB in a 3L glass beaker, adding 5 g of BPO as an initiator, and treating the mixture in a 40 kHz ultrasonic bath for 10 minutes.

A second solution was prepared by dissolving 500 g of polyvinylpyrrolidone (PVP)-30K as a dispersion stabilizer and Solusol (Dioctyl sulfosuccinate sodium salt) as a surfactant in 4,000 g of deionized water in a 5L PP beaker.

The first solution and the second solution were put in a 50 L reactor, 41,000 g of deionized water was added, and ultrasonic homogeniser (20 kHz, 600 W) was treated for 90 minutes, and the temperature was raised to 85 ° C. while rotating the solution at 120 rpm. After the solution reached 85 ° C., the polymerization process was performed by maintaining for 16 hours.

Polymerized beads were obtained through filtration, washing, classification, and drying processes. The average diameter of the prepared beads was 3.80 μm.

The formation of the outer conductive layer of the bead was performed in the same manner as in Example 3. The size of the protrusion after plating was 165 nm.

Comparative Example 2

In a 3L glass beaker, 750 g of TMMT (Tetramethylol methane tetraacrylate), 50 g of HDEDA (1,6-Hexanediol ethoxylate diacrylate), and 550 g of DVB (Divinylbenzrne) were added, and 5 g of initiator BPO was added and treated in a 40 kHz ultrasonic bath for 10 minutes to prepare the first solution. . The rest of the process proceeded in the same manner as in Comparative Example 1 to prepare beads, and the size of the beads was 2.98 μm. The asperity size after plating was 134 nm

Comparative Example 3

In a 3L glass beaker, 750 g of TMPETA (Trimethylolpropane ethoxylate triacrylate), 40 g of HDEDA (1,6-Hexanediol ethoxylate diacrylate), and 750 g of DVB (Divinylbenzrne) were added, and 5 g of initiator BPO was added and treated in a 40 kHz ultrasonic bath for 10 minutes to prepare the first solution. . The rest of the process proceeded in the same manner as in Comparative Example 1 to prepare beads, and the size of the beads was 2.46 μm. The protrusion size after plating was 95 nm.

Comparative Example 4

In a 3L glass beaker, 750 g of TMMT (Tetramethylol methane tetraacrylate), 40 g of HDEDA (1,6-Hexanediol ethoxylate diacrylate), and 750 g of DVB (Divinylbenzrne) were put into a 3L glass beaker, and 5 g of initiator BPO was added and treated in a 40 kHz ultrasonic bath for 10 minutes to prepare the first solution. . The rest of the process proceeded in the same manner as in Comparative Example 1 to prepare beads, and the size of the beads was 2.98 μm. The asperity size after plating was 131 nm

Comparative Example 5:

In a 3L glass beaker, 750 g of EGDMA (Ethylene Glycol Dimethacrylate), 40 g of HDEDA (1,6-Hexanediol ethoxylate diacrylate), and 750 g of DVB (Divinylbenzrne) were put into a 3L glass beaker, and 5 g of initiator BPO was added and treated in a 40 kHz ultrasonic bath for 10 minutes to prepare the first solution. . The rest of the process proceeded in the same manner as in Comparative Example 1 to prepare beads, and the size of the beads was 3.01 μm. The protrusion size after plating was 135 nm.

Experimental example

Experimental Example 1: Compressive strength test

Compressive strength means the compressive strength value according to the amount of deformation of the particles while compressing the beads. That is, when compressing a bead, the relationship between the compressive force and the amount of deformation can be expressed by the following Equation 1).

[Equation 1]

Here, F is the load value in % compression strain (kg), S is the compression displacement in % compression strain (mm), E is the compressive strength of the bead (kgf/mm2), R is the radius of the bead (mm) and δ is the Poisson's ratio of the bead.

In Equation 1, if the K value, that is, the compressive strength according to the amount of deformation is defined, it can be written as Equation 2.

[Equation 2]

Here, K is the compressive strength according to the amount of bead deformation.

Therefore, by substituting Equation 2 into Equation 1, the compressive strength value according to the amount of bead deformation can be obtained as in Equation 3.

[Equation 3]

Therefore, the compression speed of the indenter is set to 0.33mN/sec by using a flat indenter with a side length of 50㎛ in the equipment of MCT (Micro Compress Tester, FISHERSCOPE HM2000), and the rising speed is 10 seconds. If it was measured under the condition of reaching 0.1 mN, the maximum force was measured under the condition that the deformation of the bead could be more than 40%.

At this time, the compressive strength according to the amount of deformation was calculated from Equation 3 using the compressive displacement of the beads of Examples 1 to 9 and Comparative Examples 1 to 5 obtained at this time and the force at that time. For the compressive strength value, the average value was used by measuring 5 particles, and the compressive strength according to the amount of deformation was calculated in increments of 5%, 10%, 15%, 20%, 25%, 30%, 35%, and 40%. are shown in Tables 1 to 2, respectively.

On the other hand, Figure 1 compresses the bead according to Example 3 of the present invention, the amount of bead deformation is the x-axis, and the compressive strength according to the amount of bead deformation determined by the above-described Equation 3 is the y-axis, mini-tab 17 It is a fitted line graph created using

Here, Y is a cubic function of X, where X is the strain rate of the bead and Y is the compressive strength value according to the strain rate. In addition, since the coefficient of the cubic term of X is negative, the minimum inflection point and the maximum inflection point appear sequentially. At this time, since the deformation range of X in this measurement is 0 to 40, the significant inflection point is the minimum inflection point, and the maximum inflection point is meaningless. X1, the value of X at the minimum inflection point, and Y1, the compressive strength at X1, are significant values, and X2, the value of X at the maximum inflection point, and compressive strength Y2 at X2 are insignificant values.

The physical meaning of the minimum inflection point is the point at which the compressive strength increases from the decrease when an external force is applied to the bead, and means the point at which the compressive strength is minimum within the deformation range.

Therefore, by using the beads of Examples 1 to 9 and Comparative Examples 1 to 5, the fitted line equation was first differentiated to calculate the compressive strength and X1, X2, Y1, Y2 values according to the amount of deformation, and Tables 3 to 4 showed up

According to this, the embodiments of the present invention show characteristics of X1<20 and 0.8<Y(X1)/Y(X=5), whereas comparative examples do not show such characteristics. At this time, Y (X = 5) is the compressive strength when X is 5.

On the other hand, the R2 value is a value that means that the fitted line formula is valid/non-existent, and a value greater than 80% indicates a significant value.

Experimental Example 2: Measurement of connection resistance

① Measurement of initial connection resistance

Resistance was measured using the electrodes of the FPCB of the above connection structure. Resistance was measured using ADCMT 6871E Digital Multimeter 2probe.

③ Reliability resistance measurement

Reliability resistance was measured after leaving it for 100 hours at 85°C/85% humidity conditions. Resistance was measured using ADCMT 6871E Digital Multimeter 2probe and is shown in Table 5. According to this, the embodiments of the present invention showing the characteristics of X1 <20 and Y1 / Y (X = 5) > 0.8 have good initial connection resistance and reliability characteristics, whereas the comparative examples show low initial connection resistance and reliability characteristics.

The criterion for initial connection resistance is as follows.

OOO: 2Ω or less

OO: More than 2Ω and less than 3Ω

O: More than 3Ω and less than 5Ω

X: Over 5Ω

The criterion for the increase in connection resistance after reliability at 85℃/85% for 100 hours is as follows:

OOO: Rise below 2Ω

OO: rise above 2Ω and below 4Ω

O: rise above 4Ω and below 6Ω

X: Rising above 6Ω

strain rate Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 5% 5,439 5,912 5,159 4,818 5,702 5,059 5,064 10% 5,070 5,177 4,681 4,413 5,245 4,643 4,716 15% 5,091 5,054 4,680 4,333 5,220 4,612 4,731 20% 5,324 5,196 4,943 4,472 5,439 4,795 4,974 25% 5,791 5,566 5,413 4,840 5,855 5,187 5,425 30% 6,441 6,123 6,037 5,413 6,426 5,760 6,057 35% 7,158 6,812 6,746 6,107 7,020 6,414 6,786 40% 7,804 7,469 7,315 6,782 7,479 7,010 7,491

strain rate Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 5% 7,581 6,829 3,469 4,127 4,489 4,590 4,779 10% 7,324 6,481 2,589 3,558 3,858 3,703 3,691 15% 7,467 6,551 1,993 3,052 3,420 3,186 3,004 20% 7,813 6,840 1,582 2,754 3,186 2,908 2,581 25% 8,335 7,287 1,327 2,647 3,183 2,850 2,398 30% 8,940 7,780 1,221 2,770 3,446 3,035 2,452 35% 9,508 8,165 1,239 3,138 4,014 3,497 2,749 40% 9,902 8,316 1,395 3,746 4,835 4,229 3,238

Cubic equation: Ax^3+Bx^2+Cx+D Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 A -95,651 -118,553 -124,123 -68,501 -123,635 -89,019 -80,559 B 99,713 123,634 119,053 84,138 114,705 94,647 90,158 C -20,629 -29,496 -24,719 -19,724 -23,947 -20,740 -18,910 D 6,237 7,069 6,107 5,609 6,627 5,871 5,794 X1 12.6% 15.3% 13.0% 14.2% 13.3% 13.5% 12.6% X2 56.9% 54.2% 50.9% 67.7% 48.6% 57.3% 62.0% Y1 5,029 5,026 4,633 4,309 5,180 4,577 4,682 Y2 9,161 8,525 8,001 9,564 7,889 8,315 9,527 Y1/5% 92.5% 85.0% 89.8% 89.4% 90.8% 90.5% 92.4% R2 99.9% 99.8% 99.9% 99.9% 99.9% 99.9% 100.0%

Cubic equation: Ax^3+Bx^2+Cx+D Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 A -132,419 -160,558 -32,184 34,925 29,659 -5,443 -33,599 B 111,398 125,125 54,318 17,702 29,249 54,818 73,385 C -19,310 -22,740 -24,486 -15,440 -17,571 -24,683 -31,272 D 8,283 7,672 4,550 4,862 5,292 5,669 6,150 X1 10.7% 11.7% 31.2% 25.0% 22.4% 23.3% 25.9% X2 45.4% 40.2% 81.3% -58.8% -88.1% 648.1% 119.7% Y1 7,330 6,467 1,220 2,654 3,157 2,825 2,389 Y2 10,086 8,321 3,251 12,961 23,193 666,497 16,239 Y1/5% 96.7% 94.7% 35.2% 64.3% 70.3% 61.5% 50.0% R2 100.0% 100.0% 100.0% 99.9% 100.0% 99.8% 99.9%

initial resistance 85/85 rise Example 1 OO OO Example 2 OOO OO Example 3 OOO OOO Example 4 OOO OO Example 5 OO OO Example 6 OO OO Example 7 OO OO Example 8 OOO OOO Example 9 OOO OOO Comparative Example 1 X X Comparative Example 2 O X Comparative Example 3 OO X Comparative Example 4 OO X Comparative Example 5 O X

The features, structures, effects, etc. illustrated in each of the above-described embodiments can be combined or modified with respect to other embodiments by those skilled in the art in the field to which the embodiments belong. Therefore, contents related to these combinations and variations should be construed as being included in the scope of the present invention.

Claims (14)

As a high-strength bead,
A hydrophilic organic layer is included on the polymer beads of at least two or more silane monomers,
The strain (%) deformed when an external force is applied to the bead is X, the compressive strength when the strain is X is Y, and the strain is in the range of 0 <X≤40, when Y is minimum When the compressive strength is Y1, the strain at Y1 is X1, and the compressive strength is Y (X = 5) when X is 5%, the X1 is X1 ≤ 20, and Y1 / Y (X = 5) High-strength organic/inorganic hybrid beads with >0.8. According to claim 1,
The beads are high-strength organic / inorganic hybrid beads that are not destroyed in the range of 0 <X≤40. According to claim 1,
The beads are high-strength organic / inorganic hybrid polymers obtained by using monomers such as urethane-based, styrene-based, acrylate-based, benzene-based, epoxy-based, amine-based, imide-based, modified monomers thereof, or mixed monomers of the monomers bead. delete delete delete According to claim 1,
The hydrophilic organic layer is a high-strength organic / inorganic hybrid bead in which a functional group having a carbon double bond provided at a surface terminal of the bead body and an organic monomer are formed by radical polymerization. According to claim 7,
The hydrophilic organic layer is provided with a thickness of 0.05㎛ to 0.2㎛ high-strength organic / inorganic hybrid beads. Conductive particles comprising the high-strength organic/inorganic hybrid beads of any one of claims 1 to 3 and 7 to 8 and a conductive layer provided on the surface of the high-strength organic/inorganic hybrid beads. According to claim 9,
Wherein the conductive layer is made of one or two or more alloys selected from the group consisting of Ni, Sn, Ag, Cu, Pd, Zn, W, P, B, and Au. According to claim 10,
Conductive particles further comprising an insulating layer or insulating particles on the surface of the conductive layer. According to claim 11,
Conductive particles that are rust-preventive treated by using a hydrophobic rust-preventive agent on the outermost surface of the conductive layer. An anisotropic conductive material containing conductive particles using the high-strength organic/inorganic hybrid beads of any one of claims 1 to 3 and 7 to 8. A connection structure comprising conductive particles using the high-strength organic/inorganic hybrid beads of any one of claims 1 to 3 and 7 to 8.

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