CN204966070U - Conducting particles, insulating lining conducting particles, anisotropic electric conductivity bonding agent and connection structure body - Google Patents

Abstract

The utility model provides a conducting particles, insulating lining conducting particles, anisotropic electric conductivity bonding agent and connection structure body. A conducting particles (100a), its has resin particle (101) and configuration be in metal level (103) on resin particle (101) surface, metal level (103) contain palladium particle (105) and nickel shot (107) and have protruding (109) at the surface, and nickel shot (107) configuration is and lining palladium particle (105) between protruding (109) and resin particle (101).

Description

Conducting particles, insulation-coated electroconductive particles, anisotropic conductive adhesive and connection structural bodies

Technical field

The utility model relates to the manufacture method of conducting particles, insulation-coated electroconductive particles, anisotropic conductive adhesive, connection structural bodies and conducting particles.

Background technology

The mode that Glass for Liquid Crystal Display panel installs liquid crystal drive IC can be roughly divided into COG (Chip-on-Glass) and to install and COF (Chip-on-Flex) installs two kinds.In COG installs, the anisotropic conductive adhesive comprising conducting particles is used to be directly bonded on face glass by liquid crystal drive IC.On the other hand, in COF installs, liquid crystal drive IC is bonded on and has in the flexible tape of metal wiring, and use the anisotropic conductive adhesive comprising conducting particles they to be engaged on glass panels." anisotropy " mentioned here is conducting and keep the meaning of insulating properties on non-pressurised direction on compression aspect.

In the past, as conducting particles, surface is used to have the conducting particles of layer gold.The conducting particles that surface has layer gold is favourable in the low this point of resistance value.In addition, gold is difficult to oxidized, even if therefore when long-term preservation surface has the conducting particles of layer gold, resistance value also can be suppressed to uprise.

, the power consumption in order to the energy-saving of tackling in recent years and when suppressing liquid crystal drive, have studied the magnitude of current reducing and flow through IC.Therefore, the conducting particles that can realize than resistance value lower is in the past needed.In addition, in recent years due to the rise in price of noble metal, therefore require to use not reduce resistance value with the conducting particles of noble metal.

Such as, disclose in following patent documentation 1 and 2 and a kind ofly do not use noble metal and only use nickel to obtain the conducting particles of low-resistance value.Specifically, in patent documentation 1, describe following method: the selfdecomposition utilizing the nickel-plating liquid in chemically coated nickel method, Non-conductive particles is formed microspike and the nickel flashing of nickel simultaneously, thus be manufactured on the conducting particles that surface has conductivity projection.In addition, in patent documentation 2, describe following method: by the surface attachment at base material particulate as the conductive material of core material, and carry out chemical nickel plating further, thus be manufactured on the conducting particles that surface has conductivity projection.

Prior art document

Patent documentation

Patent documentation 1: Japan Patent No. 5184612 publication

Patent documentation 2: Japan Patent No. 4674096 publication

Utility model content

When using anisotropic conductive adhesive chip, be necessary to reduce the interelectrode conducting resistance connected and the insulation resistance fully improved between chip electrode.But, the connection structural bodies that collaboration has the anisotropic conductive adhesive of the conducting particles described in above-mentioned patent documentation 1 and 2 to obtain, although show sufficient insulating resistance value at the connection initial stage, but after carrying out the migration test of long-time conducting under hot and humid, insulating resistance value can reduce sometimes, has problem in insulating reliability.

The purpose of this utility model is to provide a kind of conducting particles and manufacture method thereof, and described conducting particles is as taking into account excellent conducting reliability and insulating reliability during the conducting particles be matched with in anisotropic conductive adhesive.In addition, the purpose of this utility model is to provide a kind of insulation-coated electroconductive particles, anisotropic conductive adhesive and the connection structural bodies that employ above-mentioned conducting particles.

In order to solve the problem, the present inventor etc. are studied the reason that above-mentioned insulating resistance value reduces, result obtains following opinion: if want the conductivity of the conducting particles improved described in above-mentioned patent documentation 1 and 2, then easily form the projection of abnormal size, the existence with the conducting particles of this abnormal precipitation portion (abnormal projection) can cause the reduction of insulating reliability.Namely, in the method described in patent documentation 1, be extremely difficult to the quantity of control projection, size and shape, if want to increase projection to reduce resistance value, then easily form the long projection (such as, length is more than the projection of 500nm) as abnormal precipitation portion.In addition, in the method described in patent documentation 2, in order to reduce resistance value and must at the core material of the surface attachment substantial amount of base material particulate, if but increase the adhesion amount of core material, then core material cohesion itself, the projection (such as, length is more than the projection of 500nm) that easy formation is long.

Based on such opinion, the present inventor etc. conduct in-depth research further, found that: by there is resin particle and being configured in this resin particle surface and in the conducting particles of the bossed metal level of outer surface tool, metal level is made to comprise palladium particle and nickel particles, nickel particles to be configured between projection and resin particle and coating palladium particle, thus excellent conducting reliability (low on-resistance (resistance value)) and insulating reliability when using this conducting particles in anisotropic conductive adhesive, can be taken into account, thus complete the utility model.

Conducting particles of the present utility model has resin particle and is configured in the metal level on this resin particle surface, above-mentioned metal level comprises palladium particle and nickel particles and has projection at outer surface, and above-mentioned nickel particles to be configured between above-mentioned projection and above-mentioned resin particle and coating above-mentioned palladium particle.

According to conducting particles of the present utility model, by having above-mentioned formation, the projection quantity, size and shape etc. of conducting particles can be controlled fully.Consequently, as taking into account excellent conducting reliability and insulating reliability during the conducting particles be matched with in anisotropic conductive adhesive.

Above-mentioned palladium particle can be configured between above-mentioned nickel particles and above-mentioned resin particle, also can be configured in above-mentioned resin particle side compared with above-mentioned nickel particles.

In conducting particles of the present utility model, above-mentioned metal level can comprise multiple above-mentioned nickel particles, above-mentioned nickel particles can and other above-mentioned nickel particles adjacent with this nickel particles be separated.In addition, in conducting particles of the present utility model, above-mentioned metal level can comprise multiple above-mentioned nickel particles, and above-mentioned multiple above-mentioned nickel particles can be configured on the direction vertical with the radial direction of conducting particles diffusedly.

In conducting particles of the present utility model, above-mentioned metal level can comprise multiple above-mentioned palladium particle, and above-mentioned multiple above-mentioned palladium particle can be configured on the direction vertical with the radial direction of conducting particles diffusedly.

In conducting particles of the present utility model, the length of above-mentioned palladium particle on the thickness direction of above-mentioned metal level is preferably greater than or equal to 4nm.

The present inventor etc. conduct in-depth research further, found that: by making the metal level being configured in resin particle surface have layer containing special component, thus as taking into account excellent conducting reliability and insulating reliability during the conducting particles be matched with in anisotropic conductive adhesive further to heavens.

In conducting particles of the present utility model, preferred above-mentioned metal level has the 1st layer containing at least one be selected from the group that is made up of nickel and copper, and above-mentioned 1st layer is configured in above-mentioned resin particle side compared with above-mentioned palladium particle.In this case, as taking into account excellent conducting reliability and insulating reliability during the conducting particles be matched with in anisotropic conductive adhesive further to heavens.

Conducting particles of the present utility model preferably meets the arbitrary formation in following (A1) ~ (A3).In this case, as taking into account excellent conducting reliability and insulating reliability during the conducting particles be matched with in anisotropic conductive adhesive further to heavens.

(A1) above-mentioned metal level has the 2nd layer containing nickel, compares the above-mentioned outer surface side being configured in above-mentioned metal level for above-mentioned 2nd layer with above-mentioned 1st layer with above-mentioned nickel particles.

(A2) above-mentioned metal level has the 3rd layer containing at least one be selected from the group that is made up of noble metal and cobalt, compares the above-mentioned outer surface side being configured in above-mentioned metal level for above-mentioned 3rd layer with above-mentioned 1st layer with above-mentioned nickel particles.

(A3) above-mentioned metal level has containing nickel the 2nd layer and containing at least one be selected from the group that is made up of noble metal and cobalt the 3rd layer, compare with above-mentioned 1st layer the above-mentioned outer surface side being configured in above-mentioned metal level with above-mentioned nickel particles for above-mentioned 3rd layer, above-mentioned 2nd layer is configured between above-mentioned 3rd layer and above-mentioned nickel particles.

In conducting particles of the present utility model, when the average thickness of above-mentioned metal level is designated as d, the interface of above-mentioned metal level and above-mentioned resin particle and the beeline of above-mentioned palladium particle are preferably greater than or equal to 0.1 × d.

In conducting particles of the present utility model, the interface of above-mentioned metal level and above-mentioned resin particle and the beeline of above-mentioned palladium particle are preferably greater than or equal to 10nm.

The present inventor etc. conduct in-depth research further, found that: during by possessing resin particle in manufacture and being configured in this resin particle surface and at outer surface, there is the conducting particles of the metal level of projection, use and separate out with the reduction of the chemical palladium plating solution of reducing agent the palladium particle formed and become nickel particles by comprising palladium ion as karyomorphism, thus can quantity, the size and shape of control projection to heavens, this conducting particles is matched with when using in anisotropic conductive adhesive and can takes into account excellent conducting reliability and insulating reliability.

The utility model provides a kind of manufacture method of conducting particles, it is have resin particle and be configured in this resin particle surface and have the manufacture method of the conducting particles of the metal level of projection at outer surface, has the core formation process forming palladium particle by comprising palladium ion and separating out with the reduction of the chemical palladium plating solution of reducing agent becomes nickel particles operation with using above-mentioned palladium particle as karyomorphism.

According to the manufacture method of conducting particles of the present utility model, by having above-mentioned formation, the quantity, size and shape etc. of conducting particles projection can be controlled fully.Consequently, the conducting particles that the manufacture method by conducting particles of the present utility model obtains is matched with when using in anisotropic conductive adhesive and can takes into account excellent conducting reliability and insulating reliability.

In the manufacture method of conducting particles of the present utility model, above-mentioned palladium particle can be configured between above-mentioned nickel particles and above-mentioned resin particle, also can be configured in above-mentioned resin particle side compared with above-mentioned nickel particles.

The manufacture method of conducting particles of the present utility model has further and on above-mentioned resin particle, forms the operation of the 1st layer containing at least one be selected from the group that is made up of nickel and copper by chemical plating, in above-mentioned core formation process, preferably on above-mentioned 1st layer, form above-mentioned palladium particle.In this case, can quantity, the size and shape of control projection to heavens further, the conducting particles obtained is matched with when using in anisotropic conductive adhesive and can takes into account excellent conducting reliability and insulating reliability further to heavens.

The manufacture method of conducting particles of the present utility model preferably meets the arbitrary formation in following (B1) ~ (B3).In this case, by making metal level, there is at least one party in layers 2 and 3, can quantity, the size and shape of control projection to heavens further, the conducting particles obtained is matched with when using in anisotropic conductive adhesive and can takes into account excellent conducting reliability and insulating reliability further to heavens.

(B1) have further and in above-mentioned nickel particles, form the operation of the 2nd layer containing nickel by chemical plating.

(B2) there is the operation of the 3rd layer further that to be formed in above-mentioned nickel particles containing at least one be selected from the group that is made up of noble metal and cobalt.

(B3) there is the operation of the 3rd layer further that formed the operation of the 2nd layer containing nickel by chemical plating and formed on above-mentioned 2nd layer containing at least one be selected from the group that is made up of noble metal and cobalt in above-mentioned nickel particles.

The utility model provide a kind of there is conducting particles of the present utility model or obtained by the manufacture method of conducting particles of the present utility model conducting particles and the insulating properties at least partially of above-mentioned outer surface of above-mentioned metal level of this conducting particles coating be coated to the insulation-coated electroconductive particles in portion.Insulation-coated electroconductive particles of the present utility model is as taking into account excellent conducting reliability and insulating reliability during the conducting particles be matched with in anisotropic conductive adhesive.

1st execution mode of anisotropic conductive adhesive of the present utility model contains conducting particles of the present utility model or the conducting particles that obtained by the manufacture method of conducting particles of the present utility model and bonding agent.According to the anisotropic conductive adhesive of the 1st execution mode, by containing above-mentioned conducting particles, the connection structural bodies of conducting reliability and insulating reliability excellence can be obtained when being connected to each other by circuit electrode.

2nd execution mode of anisotropic conductive adhesive of the present utility model contains insulation-coated electroconductive particles of the present utility model and bonding agent.According to the anisotropic conductive adhesive of the 2nd execution mode, by containing insulation-coated electroconductive particles of the present utility model, the connection structural bodies of conducting reliability and insulating reliability excellence can be obtained when being connected to each other by circuit electrode.

The anisotropic conductive adhesive of the 1st execution mode and the anisotropic conductive adhesive of the 2nd execution mode can be membranaceous respectively.

1st execution mode of connection structural bodies of the present utility model is: be configured in the mode that above-mentioned 1st circuit electrode is relative with above-mentioned 2nd circuit electrode with the 2nd circuit member with the 2nd circuit electrode by the 1st circuit member with the 1st circuit electrode, make anisotropic conductive adhesive of the present utility model between above-mentioned 1st circuit member and above-mentioned 2nd circuit member, carry out heating and pressurizeing, thus above-mentioned 1st circuit electrode is electrically connected with above-mentioned 2nd circuit electrode.

2nd execution mode of connection structural bodies of the present utility model is: possess the 1st circuit member with the 1st circuit electrode, 2nd circuit member with the 2nd circuit electrode and the connecting portion be configured between above-mentioned 1st circuit member and above-mentioned 2nd circuit member, under the state that above-mentioned connecting portion is configured in an opposing fashion at above-mentioned 1st circuit electrode and above-mentioned 2nd circuit electrode, above-mentioned 1st circuit member and above-mentioned 2nd circuit member are connected to each other, at conducting particles of the present utility model, or under the state of the conducting particles distortion obtained by the manufacture method of conducting particles of the present utility model, above-mentioned 1st circuit electrode is electrically connected by above-mentioned conducting particles with above-mentioned 2nd circuit electrode.

3rd execution mode of connection structural bodies of the present utility model is: possess the 1st circuit member with the 1st circuit electrode, there is the 2nd circuit member of the 2nd circuit electrode, and the connecting portion be configured between above-mentioned 1st circuit member and above-mentioned 2nd circuit member, under the state that above-mentioned connecting portion is configured in an opposing fashion at above-mentioned 1st circuit electrode and above-mentioned 2nd circuit electrode, above-mentioned 1st circuit member and above-mentioned 2nd circuit member are connected to each other, under the state that insulation-coated electroconductive particles of the present utility model is out of shape, above-mentioned 1st circuit electrode is electrically connected by above-mentioned conducting particles with above-mentioned 2nd circuit electrode.

According to the utility model, can provide a kind of conducting particles and manufacture method thereof, described conducting particles is as taking into account excellent conducting reliability and insulating reliability during the conducting particles be matched with in anisotropic conductive adhesive.In addition, according to the utility model, a kind of insulation-coated electroconductive particles, anisotropic conductive adhesive and the connection structural bodies that employ above-mentioned conducting particles can be provided.

Accompanying drawing explanation

Fig. 1 is the schematic section of the 1st execution mode representing conducting particles of the present utility model.

Fig. 2 is the schematic section of the 2nd execution mode representing conducting particles of the present utility model.

Fig. 3 is the schematic section of the 3rd execution mode representing conducting particles of the present utility model.

Fig. 4 (a) and Fig. 4 (b) is the figure for illustration of the Ni-Cu layer in an execution mode of conducting particles of the present utility model.

Fig. 5 is the schematic diagram of an execution mode for illustration of conducting particles of the present utility model.

Fig. 6 is the schematic diagram of an execution mode for illustration of conducting particles of the present utility model.

Fig. 7 is the schematic diagram of an execution mode for illustration of conducting particles of the present utility model.

Fig. 8 is the schematic section of the execution mode representing insulation-coated electroconductive particles of the present utility model.

Fig. 9 is the schematic section of the execution mode representing connection structural bodies of the present utility model.

Figure 10 (a) ~ Figure 10 (c) is the schematic section of an example of manufacture method for illustration of the connection structural bodies shown in Fig. 9.

Figure 11 is the SEM image observing the particle obtained by the operation c in the conducting particles making of embodiment 1.

Figure 12 (a) and Figure 12 (b) is the SEM image observing the particle surface obtained by the operation c in the conducting particles making of embodiment 1.

Figure 13 (a) ~ Figure 13 (d) is the drawing of the STEM picture observing the conducting particles cross section obtained by embodiment 1 and nickel, phosphorus and the palladium obtained by EDX.

Figure 14 (a) and Figure 14 (b) are the figure obtaining the method for the length of palladium particle for illustration of the drawing of the palladium obtained by EDX by Figure 13 (d).

Figure 15 is the SEM image observing the particle obtained by the operation d in the conducting particles making of embodiment 1.

Figure 16 (a) and Figure 16 (b) is the SEM image observing the particle surface obtained by the operation d in the conducting particles making of embodiment 1.

Figure 17 (a) and Figure 17 (b) obtains for illustration of the STEM picture by Figure 13 (a) figure that chemical nickel plating separates out the method for the length of core.

Figure 18 (a) and Figure 18 (b) is the schematic diagram for illustration of finishing processing.

Figure 19 is the schematic diagram for illustration of the method making the cut film that TEM measures.

Figure 20 is the SEM image observing the conducting particles obtained in embodiment 1.

Figure 21 (a) and Figure 21 (b) is the figure for illustration of being obtained the method for projection length by the STEM picture observing the conducting particles cross section obtained in embodiment 1.

Figure 22 (a) and Figure 22 (b) is the schematic diagram for illustration of abnormal precipitation portion.

Symbol description

100a, 100b, 100c, 100d, 400: conducting particles; 101: resin particle; 103: metal level; 103a: coating (the 1st layer); 103b: coating (the 2nd layer); 103c, 103d: coating (the 3rd layer); 103e: coating; 105: palladium particle; 107: nickel particles; 109: projection; 200: insulation-coated electroconductive particles; 210: insulating properties particle (insulating properties is coated to portion); 300: connection structural bodies; 310,320: circuit member; 311,321: circuit substrate; 311a, 321a: interarea; 312,322: circuit electrode; 330: connecting portion; 330a: anisotropic conductive adhesive; 332: the solidfied material of bonding agent; 332a: bonding agent; 401: abnormal precipitation portion; 402: the length in abnormal precipitation portion; A, B: direction; C1: the Central Line of the metal level on metal layer thickness direction; D1: the length of palladium particle; D2: beeline; D3: diameter; D4: the length of projection; D5: the length of nickel particles; D: the average thickness of metal level; H1: the face of the average thickness of metal level; P1: part 1; P2: part 2; P3: the 3 part; S1: the surface of palladium particle; S2: interface; T1: summit.

Embodiment

Below execution mode of the present utility model is described in detail.

< conducting particles >

The conducting particles of present embodiment is described.

Fig. 1 is the schematic section of the conducting particles representing the 1st execution mode.Conducting particles 100a shown in Fig. 1 has the resin particle 101 forming conductive particle daughter nucleus and the metal level 103 being configured in resin particle 101 surface.Metal level 103 comprises the palladium particle 105 containing palladium and the nickel particles 107 containing nickel.Palladium particle 105 is configured in resin particle 101 side compared with nickel particles 107, on the thickness direction being configured in metal level 103 between nickel particles 107 and resin particle 101.Metal level 103 has projection 109 at the outer surface of metal level 103.

Metal level 103 has coating (the 1st layer) 103a and coating (the 2nd layer) 103b according to from resin particle 101 order from the close-by examples to those far off.Coating 103a is configured in resin particle 101 side compared with palladium particle 105, is configured between palladium particle 105 and resin particle 101.Coating 103b compares with coating 103a the outer surface side being configured in metal level 103 with nickel particles 107, form the outer surface (outer surface of conducting particles 100a) of metal level 103.Palladium particle 105 and nickel particles 107 are configured between coating 103a and coating 103b.Nickel particles 107 is coated to palladium particle 105.Palladium particle 105 and nickel particles 107 form a part for resin particle 101 and metal level 103 upper process 109.

Fig. 2 is the schematic section of the conducting particles representing the 2nd execution mode.Conducting particles 100b shown in Fig. 2, replaces having the formation same with conducting particles 100a except this point of coating 103b except metal level 103 has coating (the 3rd layer) 103c.

The metal level 103 of conducting particles 100b has coating 103a and coating 103c according to from resin particle 101 order from the close-by examples to those far off.Coating 103c compares with coating 103a the outer surface side being configured in metal level 103 with nickel particles 107, form the outer surface (outer surface of conducting particles 100b) of metal level 103.Palladium particle 105 and nickel particles 107 are configured between coating 103a and coating 103c.

Fig. 3 is the schematic section of the conducting particles representing the 3rd execution mode.Conducting particles 100c shown in Fig. 3 has the formation same with conducting particles 100a except metal level 103 has this point of coating (the 3rd layer) 103d further.

The metal level 103 of conducting particles 100c has coating 103a, coating 103b and coating 103d according to from resin particle 101 order from the close-by examples to those far off.Coating 103b is configured between coating 103d and nickel particles 107.In addition, coating 103b to be configured in the region that coating 103a is not coated to by nickel particles 107 between coating 103a and coating 103d.Coating 103d compares with coating 103a, nickel particles 107 and coating 103b the outer surface side being configured in metal level 103, forms the outer surface (outer surface of conducting particles 100c) of metal level 103.Palladium particle 105 and nickel particles 107 are configured between coating 103a and coating 103b.

Material as resin particle 101 is not particularly limited, and include, for example polymethyl methacrylate, polymethyl acrylate etc. (methyl) acrylic resin; The vistanex such as polyethylene, polypropylene; Polyisobutylene resin; Polybutadiene.As resin particle 101, such as, also can use crosslinked (methyl) acrylic particles, crosslinked polystyrene particle etc.The material of resin particle can be used alone one or combination more than two kinds uses.

Resin particle 101 is preferably spherical.The average grain diameter of resin particle 101 preferably greater than or equal to 1 μm, more preferably greater than or equal 2 μm.Be above-mentioned scope by making the average grain diameter of resin particle 101, carry out under the state being configured with anisotropic conductive adhesive between electrode heating and pressurizeing, when electrode being electrically connected to each other by conducting particles, fully can guarantee the deflection of each conducting particles, thus can stably reduce contact resistance value.The average grain diameter of resin particle 101 is preferably less than or equal to 10 μm, is more preferably less than or equals 5 μm.By making the average grain diameter of resin particle 101 be above-mentioned scope, the deviation of particle diameter can be suppressed to become large, thus contact resistance value can be suppressed to produce deviation.As the average grain diameter of resin particle 101, the mean value that the particle size determination that the observation by employing scanning electron microscopy (hereinafter referred to " SEM ") can be adopted to carry out arbitrary 300 resin particles obtains.

Metal level 103 such as comprises multiple palladium particle 105.Palladium particle 105 is separated from one another and configure along the surface (direction along vertical with the radial direction of conducting particles) of conducting particles.A palladium particle 105 and other palladium particle 105 adjacent with this palladium particle 105 are separated.Multiple palladium particle 105 configures diffusedly, such as, be configured in diffusedly on the direction vertical with the radial direction of conducting particles (thickness direction of metal level 103).A palladium particle 105 and other palladium particle 105 adjacent with this palladium particle 105 do not contact and configure independently.Palladium particle 105 has the side extending to bottom surface from top.Palladium particle 105 is such as the chemical palladium-plating formed by chemical palladium-plating separates out core (such as, comprising the reduction precipitate of the chemical palladium plating solution of palladium ion and reducing agent).

Metal level 103 such as comprises multiple nickel particles 107.Nickel particles 107 along conducting particles surface (direction along vertical with the radial direction of conducting particles) separated from one another configure.A nickel particles 107 and other nickel particles 107 adjacent with this nickel particles 107 are separated.Multiple nickel particles 107 configures diffusedly, such as, be configured in diffusedly on the direction vertical with the radial direction of conducting particles (thickness direction of metal level 103).A nickel particles 107 and other nickel particles 107 adjacent with this nickel particles 107 do not contact and configure independently.Nickel particles 107 has the side extending to bottom surface from top.Nickel particles 107 is such as the chemical nickel plating formed by chemical nickel plating separates out core (microspike).

Coating 103a contains at least one in the group being selected from and being made up of nickel and copper.Coating 103b contains nickel.Coating 103c, 103d contain at least one in the group being selected from and being made up of noble metal and cobalt, such as, containing at least one be selected from the group that is made up of palladium, rhodium, iridium, ruthenium, platinum, silver, gold and cobalt.

The average grain diameter of the conducting particles of present embodiment preferably greater than or equal to 1 μm, more preferably greater than or equal 2 μm.The average grain diameter of the conducting particles of present embodiment is preferably less than or equal to 10 μm, is more preferably less than or equals 5 μm.By making the average grain diameter of conducting particles be above-mentioned scope, when using the anisotropic conductive adhesive comprising conducting particles to make connection structural bodies, be not vulnerable to the impact of electrode height deviation.As the average grain diameter of the conducting particles of present embodiment, the mean value that the particle size determination by using the observation of SEM to carry out arbitrary 300 conducting particless obtains can be adopted.In addition, the conducting particles due to present embodiment has projection 109, and therefore the particle diameter of conducting particles is set to the diameter of a circle circumscribed with the conducting particles in SEM image.In addition, measuring average grain diameter accurately to carry further, can the commercial device such as Coulter-counter be used.In this case, if carry out the particle size determination of 50000 conducting particless, then can with high-precision measuring average grain diameter.The average grain diameter of conducting particles such as can use 50000 conducting particless, is measured by COULERMULTISZERII (Beckman Ku Erte Co., Ltd. system).

The single dispersing rate of the conducting particles of present embodiment preferably greater than or equal to 96.0%, more preferably greater than or equal 98.0%.By making the single dispersing rate of conducting particles be above-mentioned scope, even if when the spacing of wiring closet is narrow (when being such as 6 μm), also can easily obtain high insulating reliability after fuchsin(e)test.The single dispersing rate of conducting particles such as can use 50000 conducting particless, is measured by COULERMULTISZERII (Beckman Ku Erte Co., Ltd. system).

(the 1st layer: coating 103a)

Coating 103a contains at least one in the group being selected from and being made up of nickel and copper.Coating 103a can only containing the one in nickel and copper.Coating 103a such as can be formed by chemical nickel plating or electroless copper.

When coating 103a contains nickel as main component, nickel content in coating 103a with the total amount of coating 103a for benchmark is preferably greater than or equal to 83 quality %, more preferably greater than or equal 85 quality %, further preferably greater than or equal to 86 quality %.Nickel content in coating 103a is preferably less than or equal to 98 quality % with the total amount of coating 103a for benchmark, is more preferably less than or equals 93 quality %, being preferably less than or equal to 91 quality % further.By making content be above-mentioned scope, the form variations of the palladium particle 105 be formed on coating 103a can be suppressed further and can easily make palladium particle 105 distribute to high-density.Thereby, it is possible to suppress the form variations of the projection 109 of metal level 103 outer surface further, projection 109 can be formed to high-density.Further, the quantity by increasing projection also can obtain low on-resistance further.

Coating 103a containing nickel such as can be formed by chemical nickel plating.In this case, preferably palladium catalyst process is carried out to resin particle 101.Palladium catalyst process can be undertaken by known method.Its method is not particularly limited, and include, for example the catalyst processing method using and be called as the catalyst treatment fluid of base catalyst or acidic catalyst.

As the catalyst processing method using base catalyst, include, for example following methods.First, resin particle is immersed in comprises coordination and to have in the solution of the palladium ion of PA thus to make palladium ion be adsorbed on resin particle surface.After washing, the resin particles dispersion being adsorbed with palladium ion is carried out reduction treatment in the solution comprising the reducing agents such as inferior sodium phosphate, sodium borohydride, dimethylamine borane, hydrazine, formalin.Thus, the palladium ion being adsorbed on resin particle surface is reduced to Metal Palladium.

As the catalyst processing method using acidic catalyst, include, for example following methods.First, make resin particles dispersion in stannous chloride solution, after carrying out making tin ion be adsorbed on the sensitization process on resin particle surface, wash.Then, be dispersed in and comprise in the solution of palladium bichloride, carry out the activation processing caught by palladium ion on resin particle surface.After washing, be dispersed in the solution comprising the reducing agents such as inferior sodium phosphate, sodium borohydride, dimethylamine borane, hydrazine, formalin and carry out reduction treatment.Thus, the palladium ion being adsorbed on resin particle surface is reduced to Metal Palladium.

In these palladium catalyst processing methods, washing after being adsorbed on surface by making palladium ion, be dispersed in further in the solution comprising reducing agent and will be adsorbed on the palladium ion reduction on surface, thus the palladium that can form atomic level size separating out core.

Coating 103a preferably containing at least one be selected from the group that is made up of phosphorus and boron, more preferably containing phosphorus.Thereby, it is possible to improve the hardness of coating 103a, easily conducting resistance when compressing conducting particles can be kept reduced levels.

When forming coating 103a by chemical nickel plating, such as, by using the phosphorus-containing compounds such as inferior sodium phosphate as reducing agent, phosphorus eutectoid can be made, thus the coating 103a containing nickel-phosphor alloy can be formed.In addition, by using the boron-containing compounds such as dimethylamine borane, sodium borohydride, potassium borohydride as reducing agent, boron eutectoid can be made, thus the coating 103a containing nickel-boron alloy can be formed.The hardness of nickel-phosphor alloy is lower compared with nickel-boron alloy.Therefore, even if when conducting particles high compression being carried out crimping and connecting, break from the viewpoint of suppression coating 103a, also preferably coating 103a contains nickel-phosphor alloy.

When coating 103a contains copper as main component, copper content in coating 103a with the total amount of coating 103a for benchmark is preferably greater than or equal to 97 quality %, more preferably greater than or equal 98.5 quality %, further preferably greater than or equal to 99.5 quality %.By making content be above-mentioned scope, the form variations of the palladium particle 105 be formed on coating 103a can be suppressed further and can easily make palladium particle 105 distribute to high-density.Thereby, it is possible to suppress the form variations of the projection 109 of metal level 103 outer surface further, projection 109 can be formed to high-density.

Nickel content in coating 103a and the total of copper content with the total amount of coating 103a for benchmark is preferably greater than or equal to 84 quality %, more preferably greater than or equal 86 quality %, further preferably greater than or equal to 88 quality %.Nickel content in coating 103a and the aggregate upper of copper content are 100 quality %.Copper in preferred coating 103a has the concentration gradient along with uprising away from resin particle 101 surface relative to the elemental ratio (copper/nickel) of nickel.By such formation, even if also easily low on-resistance can be kept when conducting particles high compression being carried out crimping connection.Preferably this concentration gradient is continuous.

Constituent content in coating 103a such as can obtain as follows: after using ultrathin sectioning to cut out the cross section of conducting particles, use transmission electron microscope (hereinafter referred to as " TEM ") to observe with the multiplying power of 250,000 times, carry out constituent analysis by the incidental energy dispersion-type X-ray detector of TEM (hereinafter referred to as " EDX ") and obtain.

The thickness of coating 103a preferably greater than or equal to 20nm, more preferably greater than or equal 60nm.The thickness of coating 103a is preferably less than or equal to 200nm, is more preferably less than or equals 150nm, being preferably less than or equal to 100nm further.If the thickness of coating 103a is above-mentioned scope, even if then when conducting particles high compression being carried out crimping and connecting, also can easily suppress breaking of coating 103a.

Preferred coating 103a has the Ni-Cu layer containing nickel and copper.Fig. 4 (a) and Fig. 4 (b) is the figure for illustration of the Ni-Cu layer in the conducting particles of present embodiment, Fig. 4 (a) is the schematic section for illustration of Ni-Cu layer, and Fig. 4 (b) is the figure of the example representing nickel content in Ni-Cu layer and copper content.Conducting particles 100d shown in Fig. 4 (a) has resin particle 101 and is configured in the coating 103a on resin particle 101 surface, and coating 103a is the Ni-Cu layer containing nickel and copper.

In conducting particles 100d, the nickel content in coating 103a and the total of copper content with the total amount of coating 103a for benchmark is preferably greater than or equal to 97 quality %, more preferably greater than or equal 98.5 quality %, further preferably greater than or equal to 99.5 quality %.Nickel content in coating 103a and the aggregate upper of copper content are 100 quality %.Copper in preferred coating 103a has the concentration gradient along with uprising away from resin particle 101 surface relative to the elemental ratio (copper/nickel) of nickel.Preferably this concentration gradient is continuous.

Coating 103a, preferably as shown in Fig. 4 (b), comprises according to being laminated with from resin particle 101 order from the close-by examples to those far off containing nickel as (such as containing the nickel being more than or equal to 97 quality %) part 1 P1 of main component, containing comprising nickel and copper as the part 2 P2 of the alloy of main component with containing copper (such as containing the copper being more than or equal to 97 quality %) the 3rd structure of part P3 as main component.Thus, as easily taking into account excellent conducting reliability and insulating reliability during the conducting particles be matched with in anisotropic conductive adhesive.Part 1 P1, part 2 P2 and the 3rd part P3 form a part for the thickness direction of coating 103a respectively.Part 1 P1, part 2 P2 and the 3rd part P3 can be such as stratiform, can for the layer be configured with the almost all of coated with resin particle 101 or all modes.

The figure of Fig. 4 (b) represents nickel content and the copper content of the thickness direction of coating 103a.In the figure, the boundary line of part 1 P1 and part 2 P2 is the line drawn in the mode being the point of 97 quality % by Ni content (solid line).On the other hand, the boundary line of part 2 P2 and the 3rd part P3 is the line drawn in the mode being 97 quality % points by Cu content (dotted line).As shown in Fig. 4 (b), coating 103a have copper relative to nickel elemental ratio along with the part 2 P2 that uprises away from resin particle 101 surface.

Part 1 P1 contains nickel as main component.Nickel content in part 1 P1 with the total amount of part 1 P1 for benchmark is preferably greater than or equal to 97 quality %, more preferably greater than or equal 98.5 quality %, further preferably greater than or equal to 99.5 quality %.If nickel content is more than or equal to 97 quality %, then can keep the cementability of resin particle 101 and coating 103a well.Thus, even if when conducting particles 100d high compression being carried out crimping and connecting, also easily can suppress to compress rear resin particle 101 and peel off each other with coating 103a.In addition, if nickel content is more than or equal to 97 quality %, then easily can suppresses to compress the generation of rear metal and break.Further, if nickel content is more than or equal to 99 quality %, even if then when conducting particles 100d high compression being carried out crimping and connecting, also can suppress further to compress breaking of rear metal level 103.The upper limit of the nickel content in part 1 P1 is 100 quality %.

From the viewpoint of easily suppressing cohesion during plating, the thickness of preferred part 1 P1 is more than or equal to (2nm), more preferably greater than or equal (3nm), further preferably greater than or equal to (4nm).Even if from the viewpoint of also easily suppressing when conducting particles 100d high compression being carried out crimping and connecting to produce metal breakage in the part containing nickel, the thickness of preferred part 1 P1 is less than or equal to (20nm), be more preferably less than or equal (15nm), be preferably less than or equal to further (10nm).

Part 2 P2 contains and comprises nickel and the copper alloy as main component.Nickel content in part 2 P2 and the total of copper content with the total amount of part 2 P2 for benchmark is preferably greater than or equal to 97 quality %, more preferably greater than or equal 98.5 quality %, further preferably greater than or equal to 99.5 quality %.If the total of nickel content and copper content is more than or equal to 97 quality %, even if then when conducting particles 100d high compression being carried out crimping and connecting, also can suppress further to compress breaking of rear metal level 103.The aggregate upper of nickel content and copper content is 100 quality %.

Nickel content in part 2 P2 for benchmark can be less than or equal to 97 quality %, can be less than 97 quality % with the total amount of part 2 P2.Nickel content in part 2 P2 can be more than or equal to 3 quality %, can more than 3 quality %.Copper content in part 2 P2 for benchmark can be less than or equal to 97 quality %, can be less than 97 quality % with the total amount of part 2 P2.Copper content in part 2 P2 can be more than or equal to 3 quality %, can more than 3 quality %.

From the viewpoint of easily suppressing cohesion during plating, the thickness of part 2 P2 preferably greater than or equal to (2nm).Even if from the viewpoint of also easily suppressing when conducting particles 100d high compression being carried out crimping and connecting to produce metal breakage in the part containing nickel, the thickness of part 2 P2 is preferably less than or equal to (50nm), be more preferably less than or equal (40nm), be preferably less than or equal to further (20nm).

3rd part P3 contains copper as main component.Copper content in 3rd part P3 with the total amount of the 3rd part P3 for benchmark is preferably greater than or equal to 97 quality %, more preferably greater than or equal 98.5 quality %, further preferably greater than or equal to 99.5 quality %.If copper content is more than or equal to 97 quality %, even if then when conducting particles 100d high compression being carried out crimping and connecting, also can suppress further to compress breaking of rear metal level 103.The upper limit of the copper content in the 3rd part P3 is 100 quality %.

From the viewpoint of obtaining sufficient conductivity, the thickness of the 3rd part P3 preferably greater than or equal to (10nm), more preferably greater than or equal (20nm), further preferably greater than or equal to (30nm).From the viewpoint of easily suppressing cohesion during plating, the thickness of the 3rd part P3 is preferably less than or equal to (200nm), be more preferably less than or equal (150nm), be preferably less than or equal to further (100nm).

Part 1 P1, part 2 P2 and the 3rd part P3 all preferably use the chemical plating fluid comprising nickel, copper and formaldehyde to be formed, and more preferably build in the chemical plating fluid of bath at one and are formed successively.Forming part 1 P1, part 2 P2 and the 3rd part P3 successively by building in bath at one, adaptation each other can be kept well.

As for making part 1 P1 continuously by identical chemical plating fluid, the composition of the chemical plating fluid of part 2 P2 and the 3rd part P3, such as preferably by water-soluble mantoquitas (hereinafter referred to as " (a) composition ") such as (a) copper sulphate, b the water soluble nickel salt such as () nickelous sulfate are (hereinafter referred to as " (b) composition "), the reducing agents (hereinafter referred to as " (c) composition ") such as (c) formaldehyde, (d) Rochelle salt, the complexing agents such as EDTA (hereinafter referred to as " (d) composition "), (e) composition that is obtained by mixing of the pH adjusting agent (hereinafter referred to as " (e) composition ") such as alkaline hydrated oxide.

In order to form coating 103a by chemical plating on resin particle 101 surface, such as, can give palladium catalyst on resin particle 101 surface, carry out chemical plating afterwards, thus form plating tunicle.As the concrete grammar being formed part 1 P1, part 2 P2 and the 3rd part P3 by chemical plating, such as can build what (a) composition, (b) composition, (c) composition, (d) composition and (e) composition are obtained by mixing the resin particle adding in body lotion and impart palladium catalyst, thus form part 1 P1 and part 2 P2, supplement the replenisher (a) composition, (c) composition, (d) composition and (e) composition are obtained by mixing afterwards, thus form the 3rd part P3.

As the concentration of building (a) composition in body lotion that (a) composition, (b) composition, (c) composition, (d) composition and (e) composition are obtained by mixing, preferably greater than or equal to 0.0005mol/L, more preferably greater than or equal 0.001mol/L, further preferably greater than or equal to 0.005mol/L.If (a) concentration of composition is more than or equal to 0.0005mol/L, then easily can be formed uniformly part 2 P2 or the 3rd part P3.As the concentration of above-mentioned (a) composition built in body lotion, be preferably less than or equal to 0.05mol/L, be more preferably less than or equal 0.03mol/L, being preferably less than or equal to 0.02mol/L further.If (a) concentration of composition is less than or equal to 0.05mol/L, then can suppress the hyperactivity of liquid by suppressing the excessive concentration of copper, therefore, it is possible to easily suppress particle to aggregate with one another.

As the concentration of building (b) composition in body lotion that (a) composition, (b) composition, (c) composition, (d) composition and (e) composition are obtained by mixing, preferably greater than or equal to 0.0005mol/L, more preferably greater than or equal 0.001mol/L, further preferably greater than or equal to 0.005mol/L.If (b) concentration of composition is more than or equal to 0.0005mol/L, then the easy plated nickel flashing of the palladium catalyst on resin particle 101 surface covers, local on palladium catalyst can be suppressed to produce the position of separating out copper, can easily suppress particle to aggregate with one another, and easily can suppress the position producing non-precipitating metal in the part on resin particle 101 surface.As the concentration of above-mentioned (b) composition built in body lotion, be preferably less than or equal to 0.05mol/L, be more preferably less than or equal 0.03mol/L, being preferably less than or equal to 0.02mol/L further.If (b) concentration of composition is less than or equal to 0.05mol/L, then can suppress the hyperactivity of liquid by suppressing the excessive concentration of nickel, therefore, it is possible to easily suppress particle to aggregate with one another.

By comprising (a) composition and (b) composition in chemical plating fluid simultaneously, part 1 P1 and part 2 P2 can be made continuously by identical chemical plating fluid.As its reason, think as follows.That is, by using the reducing agents such as formaldehyde, because nickel is more preferably separated out than copper on the palladium catalyst of resin surface, therefore forming part 1 P1, forming part 2 P2 in the outside of part 1 P1 afterwards.The copper of part 2 P2 has the tendency uprised along with the grown in thickness of part 2 P2 relative to the content ratio of nickel.Think: preferential precipitating nickel on palladium catalyst, when palladium catalyst is coated to by nickel afterwards, the precipitation of copper also occurs immediately, therefore starts to be formed containing comprising nickel and the copper layer (part 2 P2) as the alloy of main component.And think, along with the thickness of plating tunicle is thickening, the impact of palladium catalyst weakens, therefore become to take as the leading factor than the precipitation of copper with the precipitated phase of nickel, as a result, along the thickness direction in plating tunicle from resin particle 101 side, the content ratio of copper uprises.

Form the situation of part 1 P1 on resin particle 101 surface, with compared with the surperficial situation directly forming copper plate of resin particle 101, resin particle 101 cohesion each other can be suppressed.As its reason, think as follows.Think: the precipitation process from copper ion to copper of electroless copper is the reaction that the valence mumber of copper carries out with Cu (divalent) → Cu (1 valency) → Cu (0 valency) changing, and generates 1 valency copper ion of the instability as reaction intermediate.By making this 1 valency copper ion produce disproportionated reaction, such as, produce Cu (0 valency) etc. in the plating solution and make the stability of liquid become very low.On the other hand, the precipitation process from nickel ion to nickel of chemical nickel plating is the reaction that the valence mumber of nickel carries out with Ni (divalent) → Ni (0 valency) changing, without 1 valency nickel ion of instability as the process of reaction intermediate.Therefore, if the electroless copper compared on palladium catalyst surface and chemical nickel plating, then chemical bronze plating liquid one side's deficient in stability and react fierce, therefore easily starts side by side to produce particle cohesion each other with reaction.Think on the other hand, chemical nickel plating stability described above is high, can suppress particle cohesion each other and form plating tunicle.

To use containing nickel and copper and the total of nickel content and copper content is more than or equal to the situation of the coating 103a of 97 quality %, though with compared with the not nickeliferous situation of the copper being more than or equal to 97 quality %, be difficult to produce pin hole.As its reason, the suppositions such as the present inventor be due to: though when not nickeliferous containing the copper being more than or equal to 97 quality %, plating tunicle formed time particle aggregate with one another.That is, at the initial stage particle coacervation of plating, when particle is separated from one another afterwards, even if therefore make plating tunicle grow afterwards, this position also by plating, can not can form pin hole not by plating the stage in the early stage for the position of cohesion.

Then, the reaction of the 3rd part P3 on the reaction of the part 2 P2 on the reaction of the electroless copper on the palladium catalyst surface on comparative studies resin particle 101 surface, part 1 P1, part 2 P2 and the growth of the 3rd part P3.

In the reaction of the electroless copper on the palladium catalyst surface on resin particle 101 surface, owing to easily carrying out the oxidation reaction of the reducing agents such as formaldehyde on the surface at palladium catalyst, the reaction of electroless copper is easily carried out and destabilization, and therefore particle easily condenses each other.On the other hand, in the reaction of the part 2 P2 on part 1 P1, part 1 P1 becomes the surface of self-catalysis agent, and reducing agent is oxidized.In the reaction of the 3rd part P3 on part 2 P2 surface, part 2 P2 becomes the surface of self-catalysis agent, and reducing agent is oxidized.In the growth of the 3rd part P3, copper itself becomes the surface of self-catalysis agent, and the growth of copper occurs.Relatively in part 1 P1, part 2 P2 and the 3rd part P3 oxidation reaction of the reducing agent such as formaldehyde and the oxidation reaction at the palladium catalyst reducing agent such as formaldehyde on the surface on the surface, in the oxidation reaction of part 1 P1, part 2 P2 and the 3rd part P3 reducing agent such as formaldehyde on the surface, with palladium catalyst on the surface compared with more difficultly to carry out.Therefore, in the electroless copper on palladium catalyst surface, particle easily condenses each other, even if but nickel and the alloy tunicle of copper or the growth of copper tunicle occur, particle cohesion each other is also difficult to occur.

As the reducing agent of chemical plating fluid, such as, can use the reducing agents such as formaldehyde, inferior sodium phosphate, sodium borohydride, dimethylamine borane, hydrazine, most preferably be used alone formaldehyde.When use inferior sodium phosphate, sodium borohydride, dimethylamine borane etc., easily make phosphorus or boron eutectoid, therefore preferably adjust concentration, be more than or equal to 97 quality % to be adjusted to by the nickel content in part 1 P1.By using formaldehyde as reducing agent, easily the nickel content formed in part 1 P1 is more than or equal to the plating tunicle of 99 quality %.When using the reducing agent such as inferior sodium phosphate, sodium borohydride, dimethylamine borane, hydrazine, preferably at least a kind in these materials is used with formaldehyde.

As the complexing agent of chemical plating fluid, such as, the amino acid such as glycine can be used; The amine such as ethylenediamine, alkylamine; The copper such as EDTA, pyrophosphoric acid complexing agent; Citric acid, tartaric acid, glycolic acid, malic acid, lactic acid, gluconic acid.

Washing after electroless copper terminates preferably is carried out at short notice efficiently.Washing time shorter on copper surface more difficult formation oxide film thereon, therefore have the tendency of the plating be beneficial to below.

(palladium particle)

Fig. 5, Fig. 6 and Fig. 7 are the schematic diagrames of the part in the cross section represented when to be cut off the conducting particles of present embodiment by the face of conducting particles immediate vicinity.In fig. 5 and fig., in order to size and the location of palladium particle are easily described, show the section near by the summit of adjacent 2 projections and palladium particle centre.In the figure 7, in order to palladium particle being easily described and being configured in size and the location of the nickel particles (chemical nickel plating precipitation core) on palladium particle, show the section near by the summit of adjacent 2 projections and palladium particle centre.

Length (highly) D1 of palladium particle 105 on the thickness direction of metal level 103 preferably greater than or equal to 4nm, more preferably greater than or equal 6nm, further preferably greater than or equal to 8nm.There is by making metal level 103 comprise the palladium particle 105 of above-mentioned extent length, easily can form the projection 109 of abundant length at the outer surface of metal level 103.Easily configure palladium particle 105 diffusedly calmly and the easy viewpoint consideration forming the projection 109 of abundant length at the outer surface of metal level 103, the length D1 of palladium particle 105 is preferably less than or equal to 35nm, is more preferably less than or equals 25nm.

In order to obtain the length D1 of palladium particle 105, first to cut out the cross section of conducting particles by the mode of conducting particles immediate vicinity by ultrathin sectioning, focused ion beam processing method, cryoultramicrotome processing method etc. and to make the sample of cut film shape.Then, use TEM with the sliced sample of the multiplying power viewing film of 250,000 times, obtain D1 by the drawing of the palladium obtained by the incidental EDX of TEM.

In the present embodiment, when conducting particles is cut off with the face passing through this conducting particles immediate vicinity, the average length (average height) of the palladium particle 105 confirmed by said method is preferably greater than or equal to 4nm, more preferably greater than or equal 6nm, further preferably greater than or equal to 12nm.There is by making metal level 103 comprise the palladium particle 105 of above-mentioned extent length, easily can form the projection 109 of abundant length at the outer surface of metal level 103.Easily configure palladium particle 105 diffusedly calmly and the easy viewpoint consideration forming the projection 109 of abundant length at the outer surface of metal level 103, the average length of palladium particle 105 is preferably less than or equal to 35nm, be more preferably less than or equal 25nm, being preferably less than or equal to 20nm further.The average length of palladium particle 105 can calculate with the mean value formation of 10 palladium particles.

Metal level 103 preferably comprises: when the average thickness of metal level 103 is set to d, is more than or equal to the palladium particle 105 of 0.1 × d to resin particle 101 and the beeline at metal level 103 interface.That is, the surperficial S1 of resin particle 101 side of the palladium particle 105 shown in preferred Fig. 5 and the beeline D2 of the interface S2 of resin particle 101 and metal level 103 is more than or equal to 0.1 × d.The dotted line H1 of Fig. 5 and the distance of interface S2 represent the average thickness of metal level 103.

In metal level 103, the layer (such as coating 103a) of 0.1 × d is more than or equal to by there is thickness between palladium particle 105 and resin particle 101, the length D1 of easy adjustment palladium particle 105 on the thickness direction of metal level 103, such as, can be more than or equal to the palladium particle 105 of 4nm by the length D1 be easily formed on the thickness direction of metal level 103.Namely, be more than or equal to the layer (such as coating 103a) of 0.1 × d by there is thickness, thus make reducing agent be adsorbed on this layer, the oxidation reaction of reducing agent (that is, the reduction reaction of palladium ion) carry out continuously, therefore easily make palladium particle 105 grow.As a result, the easily length D1 of adjustment palladium particle 105 on the thickness direction of metal level 103, the palladium particle 105 that such as can easily make the length D1 on the thickness direction of metal level 103 be more than or equal to 4nm grows.Further, as shown in Figure 7, by making nickel particles 107 grow on such palladium particle 105, can easily obtain taking into account excellent conducting reliability and the projection 109 of insulating reliability.

Sometimes be difficult to directly form the palladium particle 105 with (being such as more than or equal to 4nm) length D1 necessarily on resin particle 101 surface.Palladium particle 105 is such as separated out by the chemical palladium plating solution reduction comprising palladium ion and reducing agent and is formed, even if but such as want directly to form the palladium particle with (being such as more than or equal to 4nm) length D1 necessarily on resin particle 101 surface, also there is the situation that reducing agent is difficult to be adsorbed on resin particle 101 surface.In this case, the oxidation reaction of reducing agent is not carried out, thus is difficult to make palladium particle become large.Think that the size of precipitation core of the palladium obtained in this situation is atomic level, even if forming nickel particles 107 on such precipitation core is also level and smooth tunicle.Therefore, the bossed shape of tool cannot be formed, thus existence is difficult to the situation obtaining low on-resistance.

The size of projection is controlled for size to a certain degree reduces the deviation of the shape for lugs between conducting particles thus stably obtain low on-resistance between conducting particles simultaneously from the viewpoint of on the whole surface of a conducting particles, beeline D2 more preferably greater than or equal 0.2 × d, further preferably greater than or equal to 0.4 × d.From the viewpoint of taking into account excellent conducting reliability and insulating reliability further to heavens, beeline D2 is preferably less than or equal to 0.7 × d, is more preferably less than or equals 0.4 × d.

Beeline D2 such as can draw according to palladium and obtain, and described palladium is drawn to utilize and obtained by the EDX in the cross section of conducting particles immediate vicinity.For the interface S2 of metal level 103 and resin particle 101, can be confirmed by the drawing obtained by EDX (such as, when being formed with coating 103a, the drawing of nickel or copper).

Metal level 103 preferably comprises the palladium particle 105 that beeline D2 is following ranges.When being configured with coating (such as coating 103a) between palladium particle 105 and resin particle 101, if this coating is the continuous film of free of pinholes etc., resin particle 101 is by the completely coating state of coating (such as coating 103a), then by forming the palladium particle 105 of (being such as more than or equal to 4nm) length D1 necessarily on the whole at conducting particles, easily form the nickel particles 107 on palladium particle 105 on the whole at conducting particles, therefore, it is possible to obtain low conducting resistance further.From such reason, beeline D2 preferably greater than or equal to 10nm, more preferably greater than or equal 20nm, further preferably greater than or equal to 40nm.

The metal level 103 diameter D3 preferably comprised on the direction vertical with the thickness direction of metal level 103 is the palladium particle 105 of following ranges.The diameter D3 of preferred palladium particle 105 is more than or equal to 5nm, more preferably greater than or equal 7nm, further preferably greater than or equal to 20nm.The diameter D3 of preferred palladium particle 105 is less than or equal to 100nm, is more preferably less than or equals 80nm, being preferably less than or equal to 60nm further.If the diameter D3 of palladium particle 105 is above-mentioned scope, then easily can form fully large projection 109 at the outer surface of metal level 103 with sufficient density.

In palladium particle 105, the particle ratio that preferred diameter (external diameter) is less than 20nm is less than 50% relative to total population, diameter is more than or equal to 20nm and the particle ratio being less than 60nm is 50 ~ 100% relative to total population, the particle ratio that diameter is more than or equal to 60nm is less than or equal to 50% relative to total population, more preferably the particle ratio that diameter is less than 20nm is less than 20% relative to total population, diameter is more than or equal to 20nm and the particle ratio being less than 60nm is 70 ~ 100% relative to total population, the particle ratio that diameter is more than or equal to 60nm is less than or equal to 20% relative to total population.The diameter of palladium particle 105 is distributed as the conducting particles of above-mentioned scope, as taking into account excellent conducting reliability and insulating reliability during the conducting particles be matched with in anisotropic conductive adhesive further to heavens.

So-called " diameter of palladium particle ", refers on the frontal plane of projection of determination object particle (palladium particle is coated to last stage particle by nickel particles), has the positive diameter of a circle of the same area with the area of palladium particle.Specifically, can obtain as follows: according to the SEM image obtained with 150,000 times of Observe and measure object particles by SEM, inferred the profile of palladium particle by image analysis, calculate the area of each palladium particle, obtained the diameter of palladium particle by this area." total population " about the palladium particle ratio with specified diameter refers in the total with the palladium particle existed in the concentric circles of 1/2 diameter of determination object particle diameter.

Diameter D3 is more than or equal to 20nm and the ratio being less than the palladium particle 105 of 60nm is preferably more than or equal to 50% relative to the sum of palladium particle 105 (such as length is more than or equal to the palladium particle 105 of 4nm), more preferably greater than or equal 60%, further preferably greater than or equal to 70%.

The length D1 of palladium particle 105 relative to the ratio (D1/D3) of the diameter D3 of palladium particle 105 preferably greater than or equal to 0.1, more preferably greater than or equal 0.2, further preferably greater than or equal to 0.3.If comprise the palladium particle 105 that above-mentioned ratio is above-mentioned scope in metal level 103, then easily can control the shape for lugs formed at metal level 103 outer surface.

Palladium particle 105 preferably is contained in from the central authorities (central authorities of average thickness d) of the metal level 103 thickness direction of metal level 103 to average thickness d ± 45% within scope in.In the cross section of the conducting particles shown in Fig. 6, dotted line C1 represents the Central Line of the metal level 103 on the thickness direction of metal level 103, apart from the distance of each d/2 of dotted line C1 on the thickness direction that the face (dotted line H1) of the average thickness of metal level 103 and the surface (interface S2) of resin particle are positioned at metal level 103.After palladium particle 105 is formed nickel particles 107, from the form variations suppressing projection, the viewpoint taking into account excellent conducting reliability and insulating reliability further is to heavens considered, on the thickness direction that preferred palladium particle 105 is present in metal level 103 apart from dotted line C1 be in the scope of ± 0.45 × d, more preferably being present in apart from dotted line C1 is in the scope of ± 0.3 × d, and being preferably present in distance dotted line C1 is further in the scope of ± 0.2 × d.

On the frontal plane of projection of the SEM of determination object particle (palladium particle 105 is coated to last stage particle by nickel particles 107), the quantity of the palladium particle 105 that conducting particles has in the concentric circles of 1/2 diameter with determination object particle diameter preferably greater than or equal to 20, more preferably greater than or equal 60, further preferably greater than or equal to 100.If the quantity of palladium particle 105 is above-mentioned scope, then easily can form the projection 109 of quantity sufficient at the outer surface of metal level 103.Thus, when making conducting particles between relative electrode and electrode being crimped connection each other, low on-resistance can be obtained further.

Form the projection 109 of quantity sufficient from the outer surface at metal level 103, the viewpoint reducing conducting resistance when connecting further is considered, preferred palladium particle 105 is configured on the direction vertical with the radial direction of conducting particles diffusedly.More preferably palladium particle 105 does not contact each other and is configured in diffusedly on the direction vertical with the radial direction of conducting particles.The quantity of the palladium particle 105 contacted with each other preferably is less than or equal to 15 in a conducting particles, is more preferably less than or equals 7, more preferably 0 (namely palladium particle 105 does not contact each other and whole palladium particles 105 is configured diffusedly).

The thickness direction that metal level 103 preferably is contained in metal level 103 is configured in the palladium particle 105 between projection 109 and resin particle 101.In addition, metal level 103 preferably comprises the palladium particle 105 being connected to form and passing through at the most short lines at the summit of the projection 109 of metal level 103 outer surface and the interface of metal level 103 and resin particle 101.In the cross section of the conducting particles shown in Fig. 6, straight line L1 is the most short lines connecting the summit T1 of the projection 109 and interface S2 of resin particle 101 and metal level 103.Metal level 103 shown in Fig. 6 comprises the palladium particle 105 that straight line L1 passes through.Like this, the projection 109 of metal level 103 is preferably formed in the position corresponding to palladium particle 105.

Comprise the palladium particle 105 that above-mentioned straight line L1 passes through in metal level 103, such as can cut off conducting particles with the section of the summit T1 by conducting particles immediate vicinity and projection 109, the drawing of the palladium obtained by the EDX by this section confirms.

The area ratio (covering rate) of the palladium particle 105 that coating 103a is coated to preferably greater than or equal to 1%, more preferably greater than or equal 3%, further preferably greater than or equal to 5%.Aforementioned proportion is preferably less than or equal to 70%, is more preferably less than or equals 50%, being preferably less than or equal to 30% further.If above-mentioned covering rate is above-mentioned scope, then easily can form good shape for lugs at the outer surface of metal level 103.Thus, low conducting resistance is obtained further when electrode being crimped each other connection enabling conducting particles between relative electrode.

The shape of palladium particle 105 is not particularly limited, and is preferably ellipsoid, spheroid, hemisphere, sub-elliptical body, approximate spheres, approximate hemisphere etc.Hemisphere or approximate hemisphere is preferably in these shapes.

Palladium particle 105 such as can be made by the chemical palladium plating solution comprising palladium ion and reducing agent its reduce separate out and formed.

As the supply source of chemical palladium plating solution palladium used, be not particularly limited, include, for example the palladium compounds such as palladium bichloride, palladium bichloride sodium, ammonium palladic chloride, palladium sulfate, palladium nitrate, acid chloride, palladium oxide.Specifically, acid chlorization palladium " PdCl can be used ₂/ HCl ", nitric acid four ammino palladium " Pd (NH ₃) ₄(NO ₃) ₂", dinitro two ammino palladium " Pd (NH ₃) ₂(NO ₂) ₂", dicyano two ammino palladium " Pd (CN) ₂(NH ₃) ₂", dichloro four ammino palladium " Pd (NH ₃) ₄cl ₂", sulfamic acid palladium " Pd (NH ₂sO ₃) ₂", sulfuric acid two ammino palladium " Pd (NH ₃) ₂sO ₄", oxalic acid four ammino palladium " Pd (NH ₃) ₄c ₂o ₄", palladium sulfate " PdSO ₄" etc.

As the reducing agent that chemical palladium plating solution is used, be not particularly limited, suppress the form variations of particle further, preferable formic acid compound (such as sodium formate) from the viewpoint of the palladium content fully improved in the palladium particle 105 that obtains.

Palladium particle 105 can contain phosphorus.Thereby, it is possible to improve the hardness of palladium particle 105, conducting resistance when can easily be compressed by conducting particles keeps reduced levels.Such palladium particle 105 can use the such as phosphorus-containing compound such as ortho phosphorous acid, phosphorous acid; Boron-containing compound obtains as chemical palladium plating solution reducing agent used.By using such reducing agent, the palladium particle 105 containing Pd-P alloys or palladium-boron alloy can be obtained.In this case, preferably adjusting the temperature etc. of the concentration of reducing agent, pH, plating solution, is the scope expected to make the palladium content in palladium particle 105.

In chemical palladium plating solution, complexing agent, buffer etc. can be added as required.As complexing agent, include, for example ethylenediamine and tartaric acid.Kind for buffer etc. is not particularly limited.

Palladium content in palladium particle 105 with the total amount of palladium particle 105 for benchmark is preferably greater than or equal to 94 quality %, more preferably greater than or equal 97 quality %, further preferably greater than or equal to 99 quality %.If the palladium content in palladium particle 105 is above-mentioned scope, then the size and number of the projection 109 that the outer surface at metal level 103 can be formed is adjusted to better scope.Thus, when electrode being crimped each other connection making conducting particles between relative electrode, low on-resistance can be obtained further.The upper limit of the palladium content in palladium particle 105 is 100 quality %.

Constituent content in palladium particle 105 such as can obtain as follows: after using ultrathin sectioning to cut out the cross section of conducting particles, uses TEM to observe with the multiplying power of 250,000 times, carries out constituent analysis and obtain by the incidental EDX of TEM.

When being separated out formation palladium particle 105 by above-mentioned reduction, the palladium content preferably obtained according to the constituent analysis carried out through EDX in the chemical palladium-plating tunicle by using the method for copper-clad laminated board described later to obtain is that the mode of above-mentioned scope sets the condition of reducing and separating out.

(nickel particles)

As shown in Figure 7, in the conducting particles of present embodiment, form projection 109 by nickel particles 107 and coating (being configured in the layer in the nickel particles 107 of the metal level 103) 103e be configured in nickel particles 107.Nickel particles 107 can be formed by chemical nickel plating.

Nickel content in nickel particles 107 with the total amount of nickel particles 107 for benchmark is preferably greater than or equal to 92 quality %, more preferably greater than or equal 93 quality %, further preferably greater than or equal to 94 quality %, be particularly preferably more than or equal to 95 quality %.Nickel content is preferably less than or equal to 99 quality % with the total amount of nickel particles 107 for benchmark, is more preferably less than or equals 98.5 quality %.If nickel content is above-mentioned scope, then, when forming nickel particles 107, easily can suppresses the cohesion of nickel particles 107, easily can prevent the formation in abnormal precipitation portion.Thus, when as the conducting particles be matched with in anisotropic conductive adhesive, can easily obtain taking into account excellent conducting reliability and the conducting particles of insulating reliability.

The content of the element in nickel particles 107 such as can obtain as follows: after using ultrathin sectioning to cut out the cross section of conducting particles, uses TEM to observe with the multiplying power of 250,000 times, carries out constituent analysis and obtain by the incidental EDX of TEM.

Nickel particles 107 on the thickness direction of metal level 103 and the total average thickness of coating 103e preferably greater than or equal to 10nm, more preferably greater than or equal 20nm, further preferably greater than or equal to 40nm.The total average thickness of nickel particles 107 and coating 103e is preferably less than or equal to 200nm, is more preferably less than or equals 160nm, being preferably less than or equal to 130nm further.If the aggregate thickness of nickel particles 107 and coating 103e is above-mentioned scope, then easily can form the projection 109 of excellent in shape, even and if also not easily produce breaking of metal level 103 when crimping and connecting by when conducting particles high compression.

The total average thickness of nickel particles 107 and coating 103e can calculate as follows: use ultrathin sectioning to be cut out the cross section of conducting particles by the mode of conducting particles immediate vicinity, TEM is used to carry out observing with the multiplying power of 250,000 times and after obtaining image, estimated the sectional area of nickel particles 107 and coating 103e by the image obtained, calculated by this sectional area.At this moment, when be difficult to difference coating 103a and nickel particles 107 and coating 103e, can by the constituent analysis undertaken by EDX, distinguish coating 103a and nickel particles 107 and coating 103e clearly, thus calculate the total average thickness of only nickel particles 107 and coating 103e.The thickness average value of nickel particles 107 and coating 103e can calculate with the mean value formation of 10 conducting particless.

Form the projection 109 of quantity sufficient from the outer surface at metal level 103, the viewpoint reducing conducting resistance when connecting further is considered, preferred nickel particles 107 is configured on the direction vertical with the radial direction of conducting particles diffusedly.More preferably nickel particles 107 does not contact each other and is configured in diffusedly on the direction vertical with the radial direction of conducting particles.The quantity of the nickel particles 107 contacted with each other preferably is less than or equal to 15 in a conducting particles, is more preferably less than or equals 7, further preferably 0 (i.e. nickel particles 107 do not contact each other and whole nickel particles 107 configures diffusedly).

When forming continuous film when making nickel particles 107 further growth, because the formative of projection is abundant, therefore, it is possible to obtain good conducting resistance, but particle easily condenses each other, cause single dispersing rate to reduce, therefore have the tendency that insulating reliability easily reduces.Therefore, make nickel particles 107 not contact each other and configure diffusedly more easily to obtain high insulating reliability, therefore nickel particles 107 preferably configures diffusedly.

The average length (average height) of nickel particles 107 on the thickness direction of metal level 103 preferably greater than or equal to 10nm, more preferably greater than or equal 20nm, further preferably greater than or equal to 30nm.The average length of nickel particles 107 is preferably less than or equal to 100nm, is more preferably less than or equals 90nm, being preferably less than or equal to 80nm further.If the average length of nickel particles 107 is above-mentioned scope, then when as the conducting particles be matched with in anisotropic conductive adhesive, can easily obtain taking into account excellent conducting reliability and the conducting particles of insulating reliability.

So-called " length of nickel particles ", referring to the D5 shown in Fig. 7, is the distance (highly) of straight line (connecting the straight line of the Gu Yugu of nickel particles both sides) to the summit of the nickel particles 107 vertical direction at the two ends of the radial direction from the cardinal extremity connecting nickel particles 107.The mean value of the length D5 of nickel particles 107 can calculate with the mean value formation of 10 nickel particles.

In nickel particles 107, the particle ratio that preferred length is less than 30nm is less than 80% relative to total population, length is more than or equal to 30nm and the particle ratio being less than 100nm is 20 ~ 80% relative to total population, the particle ratio that length is more than or equal to 100nm is less than or equal to 5% relative to total population, more preferably the particle ratio that length is less than 30nm is less than 60% relative to total population, length is more than or equal to 30nm and the particle ratio being less than 100nm is 40 ~ 70% relative to total population, the particle ratio that length is more than or equal to 100nm is less than or equal to 2% relative to total population.The distribution of lengths of particle is the conducting particles of above-mentioned scope, as taking into account excellent conducting reliability and insulating reliability during the conducting particles be matched with in anisotropic conductive adhesive further to heavens.

In nickel particles 107, the particle ratio that diameter (external diameter) is more than or equal to 100nm is preferably more than or equal to 25% relative to total population, more preferably greater than or equal 35%.The particle ratio that diameter is more than or equal to 100nm is preferably less than or equal to 90%, is more preferably less than or equals 70%.Above-mentioned particle ratio is the conducting particles of above-mentioned scope, as taking into account excellent conducting reliability and insulating reliability during the conducting particles be matched with in anisotropic conductive adhesive further to heavens.

In nickel particles 107, the particle ratio that preferred diameter (external diameter) is less than 100nm is less than 80% relative to total population, diameter is more than or equal to 100nm and the particle ratio being less than 200nm is 20 ~ 80% relative to total population, the particle ratio that diameter is more than or equal to 200nm is less than or equal to 10% relative to total population, more preferably the particle ratio that diameter is less than 100nm is less than 60% relative to total population, diameter is more than or equal to 100nm and the particle ratio being less than 200nm is 40 ~ 70% relative to total population, the particle ratio that diameter is more than or equal to 200nm is less than or equal to 5% relative to total population.The diameter of nickel particles 107 is distributed as the conducting particles of above-mentioned scope, when as the conducting particles be matched with in anisotropic conductive adhesive, can take into account excellent conducting reliability and insulating reliability further to heavens.

So-called " diameter of nickel particles " refers to: on the frontal plane of projection of determination object particle (nickel particles is coated to last stage particle by coating), have the positive diameter of a circle of the same area with the area of nickel particles.Specifically, according to the SEM image obtained with 100,000 times of Observe and measure object particles by SEM, the profile of nickel particles can be inferred by image analysis, calculates the area of each nickel particles, obtained the diameter of nickel particles by this area." total population " refers in the total with the nickel particles existed in the concentric circles of 1/2 diameter of determination object particle diameter.

On the frontal plane of projection of determination object particle (nickel particles 107 is coated to last stage particle by coating), in the concentric circles of 1/2 diameter with determination object particle diameter, described in being preferably as follows, comprise nickel particles 107.The quantity of nickel particles 107 preferably greater than or equal to 50, more preferably greater than or equal 70, further preferably greater than or equal to 90.The quantity of nickel particles 107 is preferably less than or equal to 200, is more preferably less than or equals 170, being preferably less than or equal to 150 further.When the quantity of nickel particles 107 is above-mentioned scope, when electrode being crimped each other connection making conducting particles between relative electrode, can easily obtain fully low conducting resistance.

Nickel particles 107 is preferably containing at least one be selected from the group that is made up of phosphorus and boron.Thereby, it is possible to improve the hardness of the coating (such as coating 103b) formed in nickel particles 107, easily conducting resistance when compressing conducting particles can be kept reduced levels.Nickel particles 107 also can contain the metal of eutectoid together with phosphorus and/or boron.As metal, include, for example cobalt, copper, zinc, iron, manganese, chromium, vanadium, molybdenum, palladium, tin, tungsten and rhenium.By making nickel particles 107 containing these metals, the hardness of nickel particles 107 can be improved, even if when conducting particles high compression being carried out projection 109 also can being suppressed to be crushed crimping connects, obtain low conducting resistance further.The tungsten that preferred hardness is high in above-mentioned metal.In this case, the nickel content in nickel particles 107 with the total amount of nickel particles 107 for benchmark is preferably greater than or equal to 85 quality %.

When forming nickel particles 107 by chemical nickel plating, such as, by using the phosphorus-containing compounds such as inferior sodium phosphate as reducing agent, phosphorus eutectoid can be made, thus the nickel particles 107 containing nickel-phosphor alloy can be formed.In addition, such as, by using the boron-containing compounds such as dimethylamine borane, sodium borohydride, potassium borohydride as reducing agent, boron eutectoid can be made, thus the nickel particles 107 containing nickel-boron alloy can be formed.The hardness of nickel-boron alloy is higher compared with nickel-phosphor alloy.Therefore, even if also suppress projection 109 to be crushed from when conducting particles high compression being carried out crimping connection, the viewpoint obtaining low on-resistance is further considered, nickel particles 107 can contain nickel-boron alloy.Detailed content about chemical nickel plating is aftermentioned.

(the 2nd layer: coating 103b)

Coating 103b contains nickel.In conducting particles 100a (Fig. 1), coating 103b forms the outermost layer of projection 109.Such coating 103b can be formed by chemical nickel plating.Such as, by implementing chemical nickel plating on coating 103a and nickel particles 107, thus can be formed in the coating 103b that outer surface (with the face of resin particle 101 side opposite side) has projection 109.In addition, also can be formed equally with the coating 103b in the intermediate layer between coating 103d for forming coating 103a in conducting particles 100c (Fig. 3).

Nickel content in coating 103b with the total amount of coating 103b for benchmark is preferably greater than or equal to 88 quality %, more preferably greater than or equal 90 quality %, further preferably greater than or equal to 93 quality %, be particularly preferably more than or equal to 96 quality %.Nickel content in coating 103b is preferably less than or equal to 99 quality %, is more preferably less than or equals 98.5 quality %.If nickel content is above-mentioned scope, then easily can suppresses the cohesion of nickel particles 107 when forming coating 103b by chemical nickel plating, easily can prevent the formation in abnormal precipitation portion.Thereby, it is possible to easily obtain at the conducting particles as the conducting reliability and insulating reliability that can take into account excellence during the conducting particles be matched with in anisotropic conductive adhesive.

Constituent content in coating 103b such as can obtain as follows: after using ultrathin sectioning to cut out the cross section of conducting particles, uses TEM to observe with the multiplying power of 250,000 times, carries out constituent analysis and obtain by the incidental EDX of TEM.

The thickness (average thickness) of coating 103b preferably greater than or equal to 5nm, more preferably greater than or equal 10nm, further preferably greater than or equal to 15nm.The thickness (average thickness) of coating 103b is preferably less than or equal to 150nm, is more preferably less than or equals 120nm, being preferably less than or equal to 100nm further.If the thickness of coating 103b is above-mentioned scope, then easily can form the projection 109 of excellent in shape, even and if produce breaking of metal level 103 when crimping and connecting by also can easily suppress when conducting particles high compression.

The average thickness of coating 103b can calculate as follows: to use ultrathin sectioning to cut out the cross section of conducting particles by the mode of conducting particles immediate vicinity, TEM is used to carry out observing with the multiplying power of 250,000 times and after obtaining image, estimated the sectional area of coating 103e (Fig. 7) by the image obtained, calculated by this sectional area.At this moment, when being difficult to difference coating 103a, nickel particles 107 and coating 103e, by the constituent analysis undertaken by EDX, distinguish coating 103a, nickel particles 107 and coating 103e clearly, thus the average thickness of only coating 103e can be calculated.The average thickness of coating 103b can calculate with the mean value formation of 10 conducting particless.

The average length comprising the projection 109 of nickel particles 107 and coating 103b preferably greater than or equal to 10nm, more preferably greater than or equal 20nm, further preferably greater than or equal to 30nm.The average length of above-mentioned projection 109 is preferably less than or equal to 120nm, is more preferably less than or equals 100nm, being preferably less than or equal to 80nm further.If the average length of projection 109 is above-mentioned scope, then can easily obtain at the conducting particles as the conducting reliability and insulating reliability that can take into account excellence during the conducting particles be matched with in anisotropic conductive adhesive.

" length of projection " refers to the D4 shown in Fig. 6, for from connecting the straight line (connecting the straight line of Gu Yugu of projection both sides) at two ends of radial direction of cardinal extremity of projection 109 to the distance (highly) on the summit of the projection 109 in vertical direction.About the mean value of the length D4 of projection 109, when obtaining the length D4 of 10 place's projections for 1 conducting particles, can calculate with the mean value formation of the length D4 of 100 place's projections of 10 conducting particless.

In the projection 109 comprising nickel particles 107 and coating 103b, the projection ratio that preferred length is less than 30nm is less than 80% relative to total bump count, length is more than or equal to 30nm and the projection ratio being less than 120nm is 20 ~ 80% relative to total bump count, the projection ratio that length is more than or equal to 120nm is less than or equal to 5% relative to total bump count, more preferably the projection ratio that length is less than 30nm is less than 60% relative to total bump count, length is more than or equal to 30nm and the projection ratio being less than 120nm is 40 ~ 70% relative to total bump count, the projection ratio that length is more than or equal to 120nm is less than or equal to 2% relative to total bump count.The distribution of lengths of projection is the conducting particles of above-mentioned scope, when as the conducting particles be matched with in anisotropic conductive adhesive, can take into account excellent conducting reliability and insulating reliability further to heavens." total bump count " about projection length refers to: such as 100 place's projections of 10 conducting particless when obtaining the length of 10 place's projections for 1 conducting particles.

Comprise the projection 109 of nickel particles 107 and coating 103b, the projection ratio that preferred diameter (external diameter) is less than 100nm is less than 80% relative to total bump count, diameter is more than or equal to 100nm and the projection ratio being less than 200nm is 20 ~ 80% relative to total bump count, the projection ratio that diameter is more than or equal to 200nm is less than or equal to 10% relative to total bump count, more preferably the projection ratio that diameter is less than 100nm is less than 60% relative to total bump count, diameter is more than or equal to 100nm and the projection ratio being less than 200nm is 40 ~ 70% relative to total bump count, the projection ratio that diameter is more than or equal to 200nm is less than or equal to 5% relative to total bump count.The diameter of projection is distributed as the conducting particles of above-mentioned scope, as taking into account excellent conducting reliability and insulating reliability during the conducting particles be matched with in anisotropic conductive adhesive further to heavens.

" diameter of projection " refers to have on the frontal plane of projection of conducting particles and area (contour area of the projection split by the paddy between projection) the positive diameter of a circle of the same area of projection.Specifically, according to the SEM image using SEM to observe conducting particles obtain with 30,000 times, the profile of projection can be inferred by image analysis, obtains the area of each projection.About " total bump count " of protrusion diameter, refer in the total with the projection existed in the concentric circles of 1/2 diameter of conducting particles diameter.

Comprise the projection of nickel particles 107 and coating 103b, the frontal plane of projection being included in conducting particles described in being preferably as follows has in the concentric circles of 1/2 diameter of conducting particles diameter.The quantity of projection preferably greater than or equal to 50, more preferably greater than or equal 70, further preferably greater than or equal to 90.The quantity of projection is preferably less than or equal to 200, is more preferably less than or equals 170, being preferably less than or equal to 150 further.When the quantity of projection is above-mentioned scope, when electrode being crimped each other connection making conducting particles between relative electrode, can easily obtain fully low conducting resistance.

Comprise the area ratio (covering rate) of the projection 109 (such as comprising the projection 109 of the coating 103b forming conducting particles outer surface) of nickel particles 107 and coating 103b preferably greater than or equal to 60%, more preferably greater than or equal 80%, further preferably greater than or equal to 90%.If covering rate is above-mentioned scope, though then under conducting particles is placed in high humidity when, conducting resistance be also difficult to increase.

Coating 103b is preferably containing at least one be selected from the group that is made up of phosphorus and boron.Thereby, it is possible to improve the hardness of coating 103b, easily the conducting resistance of having carried out conducting particles when compressing can be kept reduced levels.Coating 103b also can contain the metal of eutectoid together with phosphorus and/or boron.As metal, include, for example cobalt, copper, zinc, iron, manganese, chromium, vanadium, molybdenum, palladium, tin, tungsten and rhenium.By making coating 103b contain these metals, the hardness of coating 103b can be improved, even if when conducting particles high compression being carried out projection 109 also can being suppressed to be crushed crimping connects, obtain low conducting resistance further.The tungsten that preferred hardness is high in above-mentioned metal.In this case, the nickel content in coating 103b with the total amount of coating 103b for benchmark is preferably greater than or equal to 85 quality %.As the constituent material of coating 103b, the combination of the such as preferably combination of nickel (Ni) and phosphorus (P), nickel (Ni) and boron (B), nickel (Ni), tungsten (W) and the combination of boron (B) and the combination of nickel (Ni) and palladium (Pd).

When forming coating 103b by chemical nickel plating, such as, by using the phosphorus-containing compounds such as inferior sodium phosphate as reducing agent, phosphorus eutectoid can be made, thus the coating 103b containing nickel-phosphor alloy can be formed.In addition, such as, by using the boron-containing compounds such as dimethylamine borane, sodium borohydride, potassium borohydride as reducing agent, boron eutectoid can be made, thus the coating 103b containing nickel-boron alloy can be formed.The hardness of nickel-boron alloy is higher compared with nickel-phosphor alloy.Therefore, even if also suppress projection 109 to be crushed from when conducting particles high compression being carried out crimping connection, the viewpoint obtaining low on-resistance is further considered, coating 103b can contain nickel-boron alloy.Detailed content about chemical nickel plating is aftermentioned.

In the present embodiment, preferred coating 103a contains nickel, and coating 103b contains nickel, more preferably coating 103a contains nickel-phosphor alloy, coating 103b contains nickel-phosphor alloy or nickel-boron alloy, and preferably coating 103a contains nickel-phosphor alloy further, and coating 103b contains nickel-phosphor alloy.According to this combination, even if when conducting particles high compression being carried out crimping and connecting, projection 109 also can be suppressed to be crushed and to suppress breaking of metal level 103, stably can obtain low on-resistance further.

In the present embodiment, preferred coating 103a contains nickel-phosphor alloy, and nickel particles 107 is containing nickel-phosphor alloy or nickel-boron alloy, and coating 103b contains nickel-phosphor alloy or nickel-boron alloy.According to this combination, even if when conducting particles high compression being carried out crimping and connecting, projection 109 also can be suppressed to be crushed and to suppress breaking of metal level 103, stably can obtain low on-resistance further.

(chemical nickel plating)

In the present embodiment, coating 103a, nickel particles 107 and coating 103b are formed preferably by chemical nickel plating.Chemical nickel-plating liquid can comprise water-soluble nickel compound, preferably comprises at least one compound in the group being selected from and being made up of stabilizer (such as bismuth nitrate), complexing agent, reducing agent, pH adjusting agent and surfactant further.

As water-soluble nickel compound, such as, can use the water-soluble nickel inorganic salts such as nickelous sulfate, nickel chloride, ortho phosphorous acid nickel; The water-soluble nickel organic salts such as nickel acetate, malic acid nickel.Water-soluble nickel compound can be used alone one or combination more than two kinds uses.

The concentration of the water-soluble nickel compound in chemical nickel-plating liquid is preferably 0.001 ~ 1mol/L, is more preferably 0.01 ~ 0.3mol/L.By making the concentration of water-soluble nickel compound be above-mentioned scope, the speed of separating out of plating tunicle can be obtained fully, simultaneously the viscosity of plating solution can be suppressed too high and improving the uniformity that nickel separates out.

As complexing agent, as long as the material worked as complexing agent, include, for example ethylenediamine tetra-acetic acid; The sodium salt (such as 1-, 2-, 3-and 4-sodium salt) of ethylenediamine tetra-acetic acid; Ethylenediamine triacetic acid; Nitro tetraacethyl and alkali salt thereof; Glycolic acid, tartaric acid, gluconate, citric acid, gluconic acid, butanedioic acid, pyrophosphoric acid, glycolic, lactic acid, malic acid, malonic acid and their alkali salt (such as sodium salt); Triethanolamine gluconic acid (γ)-lactone, but be not limited to these materials.Complexing agent can be used alone one or combination more than two kinds uses.

Complexing agent concentration in chemical nickel-plating liquid is different according to the kind of complexing agent, is not particularly limited, but is usually preferably 0.001 ~ 2mol/L, is more preferably 0.002 ~ 1mol/L.By making the concentration of complexing agent be above-mentioned scope, the nickel hydroxide precipitate in plating solution and plating solution can be suppressed to decompose and obtain the abundant speed of separating out of plating tunicle, the viscosity of plating solution can be suppressed too high simultaneously and improve the uniformity that nickel separates out.

As reducing agent, the known reducing agent used in chemical nickel-plating liquid can be used in.As reducing agent, include, for example inferior sodium phosphate, ortho phosphorous acid potassium grade phosphorons acid compound; The hydroborons such as sodium borohydride, potassium borohydride, dimethylamine borane; Hydrazine class.

About the reductant concentration in chemical nickel-plating liquid, different according to the kind of reducing agent, be not particularly limited, but be usually preferably 0.001 ~ 1mol/L, be more preferably 0.002 ~ 0.5mol/L.If the concentration of reducing agent is above-mentioned scope, then can obtain the reduction rate of the nickel ion in plating solution fully and the decomposition of suppression plating solution.

As pH adjusting agent, include, for example acid pH adjusting agent and alkaline pH adjusting agent.As acid pH adjusting agent, include, for example hydrochloric acid; Sulfuric acid; Nitric acid; Phosphoric acid; Acetic acid; Formic acid; Copper chloride; The iron compounds such as ferric sulfate; Alkali metal chloride; Ammonium persulfate; Comprise the aqueous solution of more than a kind in these materials; The aqueous solution comprising 6 valency chromium that chromic acid, chromic acid-sulfuric acid, chromic acid-fluoric acid, dichromic acid, dichromic acid-fluoboric acid etc. are acid.As the pH adjusting agent of alkalescence, the alkali-metal hydroxide such as NaOH, potassium hydroxide, sodium carbonate can be enumerated; The hydroxide of alkaline-earth metal; Ethylenediamine, methyl amine, 2-ethylaminoethanol etc. are containing amino compound; Comprise the solution of more than a kind in these materials.

As surfactant, such as, can use the mixture of cationic surfactant, anion surfactant, amphoteric surfactant, non-ionic surface active agent or these materials.

(the 3rd layer: coating 103c, 103d)

Coating 103c, 103d contain at least one in the group being selected from and being made up of noble metal and cobalt.In conducting particles 100b (Fig. 2), metal level 103 has coating 103c on coating 103a and nickel particles 107.In conducting particles 100c (Fig. 3), metal level 103 has coating 103d on coating 103b.Coating 103c, 103d such as can be formed by chemical plating.

When the outermost layer of conducting particles contains nickel, nickel melts out and moves in the bonding agent of anisotropic conductive adhesive, thus when interelectrode distance is narrow, insulating reliability likely reduces.To this, as coating 103c, metal contained by 103d, high and the oxidation on conducting particles surface can be suppressed from the effect of the protection tunicle as nickel, the viewpoint obtaining good insulating reliability is further considered, be preferably selected from least one in the group be made up of palladium, rhodium, iridium, ruthenium, platinum, silver, gold and cobalt, be more preferably selected from least one in the group be made up of palladium, rhodium, iridium, ruthenium and platinum.From obtaining good insulating reliability further and hardness is high, even if projection 109 also can be suppressed to be crushed when conducting particles high compression being carried out crimping connection, the viewpoint obtaining low on-resistance is further considered, is preferably selected from least one in the group be made up of palladium, rhodium, iridium and ruthenium further.

Coating 103c containing noble metal or cobalt, 103d can work as the anti oxidation layer of nickel.Therefore, coating 103c, 103d are preferably configured in coating 103a and nickel particles 107 as shown in Figure 2, or are configured in as shown in Figure 3 on coating 103b.

The thickness of coating 103c, 103d preferably greater than or equal to 5nm, more preferably greater than or equal 10nm.The thickness of coating 103c, 103d is preferably less than or equal to 100nm, is more preferably less than or equals 30nm.If coating 103c, the thickness of 103d is above-mentioned scope, then forming coating 103c by plating etc., can improve the uniformity of layer when 103d, effectively can work as the layer preventing the nickel of nickel particles 107 grade to the diffusion into the surface with coating 103c, 103d opposite side.

When coating 103c, 103d contain gold, the conducting resistance on conducting particles surface can be reduced, improve the characteristic of conducting particles further.Coating 103c when containing gold, the thickness of 103d, from the viewpoint of the reduction effect of the conducting resistance on conducting particles surface and the balancing good of manufacturing cost, be preferably less than or equal to 30nm, even if but characteristically also no problem more than 30nm.

Coating 103c, the average thickness of 103d can calculate as follows: use ultrathin sectioning to be cut out the cross section of conducting particles by the mode of conducting particles immediate vicinity, TEM is used to carry out observing with the multiplying power of 250,000 times and after obtaining image, estimated the sectional area of coating 103e (Fig. 7) by the image obtained, calculated by this sectional area.At this moment, when being difficult to difference coating 103a, nickel particles 107 and coating 103e, by the constituent analysis undertaken by EDX, coating 103a, nickel particles 107 and coating 103e can be distinguished clearly, thus calculate the average thickness of only coating 103e.Even if when coating 103e has coating 103b and coating 103d, as long as coating 103b and coating 103d is distinguished by such method.The mean value of the thickness of coating 103c, 103d can calculate with the mean value formation of 10 conducting particless.

The average length comprising the projection 109 of nickel particles 107 and coating 103c, 103d preferably greater than or equal to 10nm, more preferably greater than or equal 20nm, further preferably greater than or equal to 30nm.The average length of preferred above-mentioned projection 109 is less than or equal to 120nm, is more preferably less than or equals 100nm, being preferably less than or equal to 80nm further.If the average length of projection 109 is above-mentioned scope, then can easily obtain at the conducting particles as the conducting reliability and insulating reliability that can take into account excellence during the conducting particles be matched with in anisotropic conductive adhesive.The definition of " length of projection " is same with the projection comprising coating 103b.

Comprising nickel particles 107 and coating 103c, in the projection 109 of 103d, the projection ratio that preferred length is less than 30nm is less than 80% relative to total bump count, length is more than or equal to 30nm and the projection ratio being less than 120nm is 20 ~ 80% relative to total bump count, the projection ratio that length is more than or equal to 120nm is less than or equal to 5% relative to total bump count, more preferably the projection ratio that length is less than 30nm is less than 60% relative to total bump count, length is more than or equal to 30nm and the projection ratio being less than 120nm is 40 ~ 70% relative to total bump count, the projection ratio that length is more than or equal to 120nm is less than or equal to 2% relative to total bump count.The distribution of lengths of projection is the conducting particles of above-mentioned scope, as taking into account excellent conducting reliability and insulating reliability during the conducting particles be matched with in anisotropic conductive adhesive further to heavens.

Comprise nickel particles 107 and coating 103c, the projection ratio that the preferred diameter (external diameter) of projection 109 of 103d is less than 100nm is less than 80% relative to total bump count, diameter is more than or equal to 100nm and the projection ratio being less than 200nm is 20 ~ 80% relative to total bump count, the projection ratio that diameter is more than or equal to 200nm is less than or equal to 10% relative to total bump count, more preferably the projection ratio that diameter is less than 100nm is less than 60% relative to total bump count, diameter is more than or equal to 100nm and the projection ratio being less than 200nm is 40 ~ 70% relative to total bump count, the projection ratio that diameter is more than or equal to 200nm is less than or equal to 5% relative to total bump count.The diameter of projection is distributed as the conducting particles of above-mentioned scope, as taking into account excellent conducting reliability and insulating reliability during the conducting particles be matched with in anisotropic conductive adhesive further to heavens.The definition of the diameter of projection 109 and assay method same with the projection comprising coating 103b.

Comprise the projection of nickel particles 107 and coating 103c, 103d, the frontal plane of projection being included in conducting particles described in being preferably as follows has in the concentric circles of 1/2 diameter of conducting particles diameter.The quantity of projection preferably greater than or equal to 50, more preferably greater than or equal 70, further preferably greater than or equal to 90.The quantity of projection is preferably less than or equal to 200, is more preferably less than or equals 170, being preferably less than or equal to 150 further.When the quantity of projection is above-mentioned scope, when electrode being crimped each other connection enabling conducting particles between relative electrode, easily obtain fully low conducting resistance.

Comprise nickel particles 107 and coating 103c, the projection 109 of 103d (such as comprises the coating 103c forming conducting particles outer surface, the projection 109 of 103d) area ratio (covering rate) preferably greater than or equal to 50%, more preferably greater than or equal 65%.If covering rate is above-mentioned scope, though then under conducting particles is placed in high humidity when conducting resistance be also difficult to increase.

{ palladium }

Coating 103c, 103d such as can be formed by plating palladium, preferably by the palladium layers that chemical palladium-plating is formed.Chemical palladium-plating can use not by any one in the displaced type of reducing agent and the reduced form of use reducing agent.As this chemical palladium plating solution, displaced type can enumerate MCA (Co., Ltd. WorldMetal system, trade name) etc.Reduced form can enumerate APP (Shi Yuan pharmaceutical industries Co., Ltd. system, trade name) etc.When relatively displaced type and reduced form, few from the viewpoint of space, easily guarantee coating area, preferred reduced form.

At coating 103c, when 103d contains palladium, coating 103c, palladium content in 103d is with coating 103c, the total amount of 103d be benchmark preferably greater than or equal to 90 quality %, more preferably greater than or equal 93 quality %, further preferably greater than or equal to 94 quality %.Coating 103c, the palladium content in 103d is that benchmark is preferably less than or equal to 99 quality % with the total amount of coating 103c, 103d, is more preferably less than or equals 98 quality %.If coating 103c, the palladium content in 103d is above-mentioned scope, then hardness is high, even if when conducting particles high compression being carried out projection 109 also can being suppressed to be crushed crimping connects, obtain low conducting resistance further.

In order to adjust coating 103c, palladium content (such as in order to be adjusted to 93 ~ 99 quality %) in 103d, be not particularly limited as the reducing agent used in chemical palladium plating solution, the phosphorus-containing compounds such as ortho phosphorous acid, phosphorous acid and their alkali salt can be used; Boron-containing compound.In this case, because the coating 103c obtained, 103d comprise Pd-P alloys or palladium-boron alloy, therefore preferably adjust the temperature etc. of the concentration of reducing agent, pH, plating solution, to make coating 103c, the palladium content in 103d is the scope expected.

{ rhodium }

Supply source as the rhodium used in chemical rhodanizing liquid is not particularly limited, and include, for example hydroxide ammino rhodium, nitric acid ammino rhodium, acetic acid ammino rhodium, sulfuric acid ammino rhodium, sulfurous acid ammino rhodium, ammino rhodium bromide and ammino rhodium compound.

As the reducing agent used in chemical rhodanizing liquid, include, for example hydrazine, inferior sodium phosphate, dimethylamine borate, boric acid diethylamine and sodium borohydride, preferred hydrazine.In plating bath, stabilizer or complexing agent (ammonium hydroxide, hydroxyl amine salt, dichloride hydrazine etc.) can be added, but non-essential.

From the viewpoint of obtaining sufficient plating speed, preferred bath temperature (bath temperature) is more than or equal to 40 DEG C, more preferably greater than or equal 50 DEG C.From the viewpoint of stably keeping chemical rhodanizing liquid, preferred bath temperature (bath temperature) is less than or equal to 90 DEG C, is more preferably less than or equals 80 DEG C.

{ iridium }

As the supply source of the iridium used in chemical plating iridium liquid, include, for example iridous chloride, iridic chloride, tribromide iridium, tetrabormated iridium, six iridium chloride tripotassiums, six iridium chloride dipotassiums, six iridium chloride trisodiums, six iridium chloride disodiums, hexabromo iridium tripotassium, hexabromo iridium dipotassium, hexaiodo iridium tripotassium, three sulfuric acid two iridium and two sulfuric acid iridium.

As the reducing agent used in chemical plating iridium liquid, include, for example hydrazine, inferior sodium phosphate, dimethylamine borate, boric acid diethylamine and sodium borohydride, preferred hydrazine.In plating bath, stabilizer or complexing agent can be added, but non-essential.

As stabilizer or complexing agent, at least one in the group being selected from and being made up of monocarboxylic acid, dicarboxylic acids and their salt can be added.As monocarboxylic object lesson, include, for example formic acid, acetic acid, propionic acid, butyric acid and lactic acid.As the object lesson of dicarboxylic acids, include, for example oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, fumaric acid, maleic acid and malic acid.As above-mentioned salt, include, for example sodium, potassium, lithium etc. with above-mentioned carboxylic acid with the compound be combined the form of ion.Stabilizer or complexing agent can be used alone one or combination more than two kinds uses.

From the viewpoint of suppressing the corrosion of plating object and obtaining sufficient plating speed, the pH of preferred chemical plating iridium liquid is more than or equal to 1, more preferably greater than or equal 2.From the viewpoint of easily suppressing plating reaction to be obstructed, the pH of preferred chemical plating iridium liquid is less than or equal to 6, is more preferably less than or equals 5.

From the viewpoint of obtaining sufficient plating speed, preferred bath temperature (bath temperature) is more than or equal to 40 DEG C, more preferably greater than or equal 50 DEG C.From the viewpoint of stably keeping chemical plating iridium liquid, preferred bath temperature (bath temperature) is less than or equal to 90 DEG C, is more preferably less than or equals 80 DEG C.

{ ruthenium }

As chemical plating ruthenium liquid, such as, can use commercially available liquid, chemical ruthenium Ru (Okuno Chemical Industries Co., Ltd.'s system, trade name) can be used.

{ platinum }

Supply source as the platinum used in chemically plating platinum liquid is not particularly limited, and include, for example Pt (NH ₃) ₄(NO ₃) ₂, Pt (NH ₃) ₄(OH) ₂, PtCl ₂(NH ₃) ₂, Pt (NH ₃) ₂(OH) ₂, (NH ₄) ₂ptCl ₆, (NH ₄) ₂ptCl ₄, Pt (NH ₃) ₂cl ₄, H ₂ptCl ₆, and PtCl ₂.

As the reducing agent used in chemically plating platinum liquid, hydrazine, inferior sodium phosphate, dimethylamine borate, boric acid diethylamine and sodium borohydride can be enumerated, preferred hydrazine in these materials.Stabilizer or complexing agent (chlorination hydroxylamine, dichloride hydrazine, ammonium hydroxide, EDTA etc.) can be added in plating bath.

From the viewpoint of obtaining sufficient plating speed, preferred bath temperature (bath temperature) is more than or equal to 40 DEG C, more preferably greater than or equal 50 DEG C.From the viewpoint of stably keeping chemically plating platinum liquid, preferred bath temperature (bath temperature) is less than or equal to 90 DEG C, is more preferably less than or equals 80 DEG C.

When using chemically plating platinum liquid to carry out platinum plating, the pH of preferred chemically plating platinum liquid is 8 ~ 12.If pH is more than or equal to 8, then platinum is easily made fully to separate out.If pH is less than or equal to 12, then easily guarantee good operating environment.

{ silver }

Supply source as the silver used in chemical plating liquid is not particularly limited, as long as the material dissolving in plating solution is just not particularly limited.Such as can use silver nitrate, silver oxide, silver sulfate, silver chlorate, silver sulfite, silver carbonate, silver acetate, actol, sulfosuccinic acid silver, sulfonic acid is silver-colored, sulfamic acid is silver-colored and silver oxalate.These water-soluble silver compounds can be used alone one or combination more than two kinds uses.

As the reducing agent used in chemical plating liquid, as long as be just not particularly limited for having the water soluble compound water-soluble silver compound in plating solution being reduced to the ability of argent.Such as can use hydrazine derivate, formaldehyde compounds, hydroxyl amine, carbohydrate, Rochelle salt, hydroboron, hypophosphite, DMAB and ascorbic acid.These reducing agents can be used alone one or combination more than two kinds uses.

Stabilizer or complexing agent can be added in chemical plating liquid, can add as required.Be not particularly limited as stabilizer or complexing agent, sulphite, succinimide, hydantoin derivatives, ethylenediamine, ethylenediamine tetra-acetic acid (EDTA) etc. can be used.Stabilizer or complexing agent can be used alone one or combination more than two kinds uses.

In chemical plating liquid except mentioned component, the additives such as known surfactant, pH adjusting agent, buffer, smooth agent, stress moderator can be mixed as required.

Chemical plating liquid can use with the liquid temperature of the scope of 0 ~ 80 DEG C.Particularly by using with 10 ~ 60 DEG C of degree, the stability of plating solution can be made better.If the temperature of plating solution is more than or equal to 0 DEG C, then silver-colored speed of separating out is fully fast, can shorten the time for obtaining the silver-colored amount of precipitation specified.If the temperature of plating solution is less than or equal to 80 DEG C, then can easily suppress because the reducing agent loss and the reduction of bath stability caused is reacted in selfdecomposition.

The pH of chemical plating liquid (such as reduced form chemical plating liquid) is such as 1 ~ 14.Particularly by making the pH of plating solution be 6 ~ 13 degree, the stability of plating solution can be made better.PH about plating solution adjusts, usually when reducing pH, use have the anionicsite of the same race with the anionicsite of water soluble silver salt acid (such as when uses silver sulfate as when water soluble silver salt for sulfuric acid, when use silver nitrate as when water soluble silver salt be nitric acid) carry out, when improving pH, alkali metal hydroxide, ammonia etc. is used to carry out.

{ gold }

Chemical gold plating liquid such as can use the displaced type gold plating liquids such as HGS-100 (Hitachi Chemical Co., Ltd.'s system, trade name); The reduced form gold plating liquids such as HGS-2000 (Hitachi Chemical Co., Ltd.'s system, trade name).When relatively displaced type and reduced form, few from the viewpoint of space, easily guarantee coating area, can reduced form be used.

{ cobalt }

Supply source as the cobalt used in electroless cobalt plating liquid is not particularly limited, and include, for example cobaltous sulfate, cobalt chloride, cobalt nitrate, cobalt acetate and cobalt carbonate.

As the reducing agent used in electroless cobalt plating liquid, hypophosphite, the ortho phosphorous acids such as such as preferred inferior sodium phosphate, ammonium hypophosphite, ortho phosphorous acid nickel.Stabilizer or complexing agent (aliphatic carboxylic acid etc.) can be added in plating bath, but non-essential.Stabilizer or complexing agent can be used alone one or combination more than two kinds uses.

From the viewpoint of obtaining sufficient plating speed, preferred bath temperature (bath temperature) is more than or equal to 40 DEG C, more preferably greater than or equal 50 DEG C.From the viewpoint of stably keeping electroless cobalt plating liquid, preferred bath temperature (bath temperature) is less than or equal to 90 DEG C, is more preferably less than or equals 80 DEG C.

The manufacture method > of < conducting particles

In the manufacture method of the conducting particles of present embodiment, manufacture and there is resin particle 101 and be configured in resin particle 101 surface and there is at outer surface the conducting particles of the metal level 103 of projection 109.The manufacture method of the conducting particles of present embodiment has the 1st core formation process and the 2nd core formation process.In the 1st core formation process, separated out by the reduction comprising the chemical palladium plating solution of palladium ion and reducing agent and form palladium particle 105.In the 2nd core formation process, the palladium particle 105 formed is used as core and forms nickel particles 107 in the 1st core formation process.

The manufacture method of the conducting particles of present embodiment preferably to have further by chemical plating the operation that on resin particle 101 (such as the surface of resin particle 101) forms coating (the 1st layer) 103a containing at least one be selected from the group that is made up of nickel and copper.In this case, in the 1st core formation process, preferably on coating 103a, (such as the surface of coating 103a) forms palladium particle 105.

The manufacture method of the conducting particles of present embodiment preferably meets the arbitrary formation in following (b1) ~ (b3).

(b1) be there is operation further that formed coating (the 2nd layer) 103b containing nickel by chemical plating in nickel particles 107.

(b2) there is the operation (such as forming the operation of the coating 103c containing at least one be selected from the group that is made up of palladium, rhodium, iridium, ruthenium, platinum, silver, gold and cobalt in nickel particles 107) of coating (the 3rd layer) 103c formed in nickel particles 107 containing at least one be selected from the group that is made up of noble metal and cobalt further.

(b3) have further and in nickel particles 107, form the operation of coating (the 2nd layer) 103b containing nickel by chemical plating and on coating 103b, form the operation (such as forming the operation of the coating 103d containing at least one be selected from the group that is made up of palladium, rhodium, iridium, ruthenium, platinum, silver, gold and cobalt on coating 103b) of coating (the 3rd layer) 103d containing at least one be selected from the group that is made up of noble metal and cobalt.

In above-mentioned (b1) and (b3), coating 103b is such as formed on nickel particles 107 surface.In above-mentioned (b1) and (b3), coating 103b such as except being formed in nickel particles 107, and also on the region be not coated to by nickel particles 107 of coating 103a, (surface in such as this region) is formed.In above-mentioned (b2), coating 103c is such as formed on nickel particles 107 surface.In above-mentioned (b2), coating 103c such as except being formed in nickel particles 107, and also on the region be not coated to by nickel particles 107 of coating 103a, (surface in such as this region) is formed.In above-mentioned (b3), coating 103d is such as formed on coating 103b surface.The nickel particles 107 formed in 2nd core formation process can be used as core and be formed by coating 103b, 103c.

According to the manufacture method meeting arbitrary formation in above-mentioned (b1) ~ (b3), coating 103b can be controlled to heavens, 103c, the quantity of the projection after 103d is formed, size and shape, can obtain taking into account excellent conducting reliability and the conducting particles of insulating reliability further to heavens.

Manufacture method for the conducting particles by present embodiment obtains the reason of above-mentioned conducting particles, and the present inventor etc. infer as follows.Think: the particle of the reduction of the chemical palladium plating solution comprised by comprising palladium ion and reducing agent being separated out the palladium particle 105 formed is immersed in the chemical nickel-plating liquid for the formation of nickel particles 107, then preferentially oxidized on palladium the particle 105 and ejected electron of the reducing agent contained by plating solution.Think thus, nickel is preferentially separated out on palladium particle 105, and nickel can be separated out with shape for lugs on palladium particle 105.Think thus, the little nickel particles of form variations 107 can be formed.Like this, the suppositions such as the present inventor: by arranging the time difference that nickel starts to separate out, thus the little nickel particles of form variations 107 can be formed, the little projection of form variations 109 can be formed.

In addition, be there is by the manufacture method of the conducting particles making present embodiment the operation being formed coating 103a by chemical plating on resin particle 101, thus can easily obtain at the conducting particles as the conducting reliability and insulating reliability that can take into account excellence during the conducting particles be matched with in anisotropic conductive adhesive.The reason the present inventor etc. obtaining such conducting particles is inferred as follows.Think: be immersed in the chemical nickel-plating liquid for the formation of nickel particles 107 by being included in the particle of palladium particle 105 that coating 103a is formed, then compared with on coating 103a, preferentially oxidized on palladium the particle 105 and ejected electron of the reducing agent contained by plating solution.Think thus, compared with on coating 103a, nickel is preferentially separated out on palladium particle 105, and nickel can be separated out with shape for lugs on palladium particle 105.Like this, the suppositions such as the present inventor: by arranging the time difference that nickel starts to separate out on coating 103a, thus easily can form the little nickel particles of form variations 107 on coating 103a, easily can form the little projection of form variations 109.

In above-mentioned palladium catalyst process in the past, nickel particles 107 cannot be formed.As its reason, think that palladium catalyst core is little.Namely think, the reduction treatment that palladium catalyst processing example utilizes as comprised (1) that the sensitization process of tin ion, (2) catch the activation processing of palladium ion in the solution comprising palladium chloride aqueous solution, (3) utilize reducing agent to make the palladium ion reduction being adsorbed on surface to separate out, but because these process only make the palladium ion reduction being adsorbed on surface, therefore palladium catalyst core is the size of atomic level.In the present embodiment, by utilizing reducing agent, the palladium ion in chemical palladium plating solution is separated out continuously, the palladium particle with abundant size (such as can be carried out the size of constituent analysis by EDX) can be obtained, thus by above-mentioned effect, the little nickel particles of form variations 107 can be formed.

About the resin particle 101, chemical palladium plating solution and the chemical nickel-plating liquid that use in the manufacture method of the conducting particles of present embodiment, material cited in the explanation of the conducting particles of present embodiment can be used in.In addition, in the manufacture method of the conducting particles of present embodiment, consider from the viewpoint of the uniformity improving coating 103a (such as, the coating 103a containing nickel), resin particle 101 has preferably carried out palladium catalyst process.At this moment palladium catalyst process can use process cited in the explanation of the conducting particles of present embodiment.

In the manufacture method of the conducting particles of present embodiment, the mode that palladium particle 105 is preferably more than or equal to 4nm with the length on the thickness direction (thickness direction of coating 103a) of metal level 103 is separated out.This length of palladium particle 105 can be adjusted by the nickel content (purity) changed in coating 103a.Such as, when coating 103a contains phosphorus, increase the content of phosphorus and the content that reduces nickel can make palladium particle 105 easily grow in a thickness direction.

Therefore, from the viewpoint of the length fully increasing palladium particle 105, the nickel content in coating 103a is preferably following ranges.That is, the nickel content in coating 103a with the total amount of coating 103a for benchmark is preferably greater than or equal to 83 quality %, more preferably greater than or equal 85 quality %, further preferably greater than or equal to 86 quality %.Nickel content in coating 103a is preferably less than or equal to 98 quality % with the total amount of coating 103a for benchmark, is more preferably less than or equals 93 quality %, being preferably less than or equal to 91 quality % further.In addition, owing to more making palladium high purity, the length of palladium particle 105 more can be made to become large, the palladium content therefore in palladium particle 105 preferably greater than or equal to 94 quality %, more preferably greater than or equal 97 quality %, further preferably greater than or equal to 99 quality %.

In the manufacture method of the conducting particles of present embodiment, palladium particle 105 is preferably separated out in the mode be dispersed on the direction vertical with the thickness direction of metal level 103 (thickness direction of coating 103a).The distribution of palladium particle 105 can be adjusted by the nickel content (purity) changed in coating 103a.When coating 103a contains phosphorus, in the same manner as palladium particle 105 growth in a thickness direction, increase the content of phosphorus and the content that reduces nickel can make palladium particle 105 easily distribute.Therefore, from the viewpoint of the form variations easily suppressing palladium particle 105, the nickel content in coating 103a is preferably following ranges.That is, the nickel content in coating 103a with the total amount of coating 103a for benchmark is preferably greater than or equal to 83 quality %, more preferably greater than or equal 85 quality %, further preferably greater than or equal to 86 quality %.Nickel content in coating 103a is preferably less than or equal to 98 quality % with the total amount of coating 103a for benchmark, is more preferably less than or equals 93 quality %, being preferably less than or equal to 91 quality % further.In addition, more make palladium high purity, more can suppress the form variations of palladium particle 105, the palladium content therefore in palladium particle 105 with the total amount of palladium particle 105 for benchmark is preferably greater than or equal to 94 quality %, more preferably greater than or equal 97 quality %, further preferably greater than or equal to 99 quality %.More make palladium high purity as mentioned above, the diameter of palladium particle 105 more can be made to become large, if the palladium content therefore in such as palladium particle 105 is in above-mentioned scope, then can reduce the palladium particle 105 that diameter is less than 20nm, can easily suppress diameter to be more than or equal to 20nm and be less than the form variations of the palladium particle 105 of 60nm.

The manufacture method of conducting particles according to the present embodiment, can obtain the conducting particles of present embodiment.In the manufacture method of the conducting particles of present embodiment, preferably carry out above-mentioned operation, to meet more than in the condition of the conducting particles of above-mentioned present embodiment.

< insulation-coated electroconductive particles >

The insulation-coated electroconductive particles of present embodiment is described.Fig. 8 is the schematic section of the insulation-coated electroconductive particles representing present embodiment.Insulation-coated electroconductive particles 200 shown in Fig. 8 has the insulating properties particle (insulating properties is coated to portion) 210 at least partially on metal level 103 surface of conducting particles 100a and coated electroconductive particles 100a.As the conducting particles in insulation-coated electroconductive particles, such as conducting particles 100b (Fig. 2) and conducting particles 100c (Fig. 3) etc. can be used to replace conducting particles 100a.

In recent years, the anisotropic conductive adhesive installed COG requires the insulating reliability under the thin space of 10 μm of levels.In order to improve insulating reliability further, preferably carry out insulation-coated to conducting particles.Insulation-coated electroconductive particles according to the present embodiment, can effectively realize this and require characteristic.

As the insulating properties particle 210 of coated electroconductive particles, organic high molecular compound particulate, inorganic oxide particle etc. can be enumerated.Wherein, more excellent from the viewpoint of insulating reliability, preferred inorganic oxide particle.When using organic high molecular compound particulate, easily conducting resistance can be reduced.

As organic high molecular compound, preferably there is the compound of thermal softening, such as be suitable for using polyethylene, vinyl-vinyl acetate copolymer, ethene-(methyl) acrylic copolymer, ethene-(methyl) acrylate copolymer, polyester, polyamide, polyurethane, polystyrene, styrene diethylene benzene copoly mer, styreneisobutylene copolymer, Styrene-Butadiene, styrene-(methyl) acrylic copolymer, ethylene-propylene copolymer, (methyl) acrylic ester rubber, styrene-ethylene-butadiene copolymer, phenoxy resin, and solid epoxy.Organic high molecular compound can be used alone one or combination more than two kinds uses.

As inorganic oxide, such as, preferably comprise the oxide of at least one element in the group being selected from and being made up of silicon, aluminium, zirconium, titanium, niobium, zinc, tin, cerium and magnesium.Inorganic oxide can be used alone one or combination more than two kinds uses.Preferred silicon dioxide in inorganic oxide, aqueous dispersion cataloid (SiO ₂) there is hydroxyl due to surface, therefore excellent with the associativity of conducting particles, easily make particle diameter consistent, and cheap, therefore suitable especially.As the commercially available product of this inorganic oxide particle, include, for example SNOWTEX, SNOWTEXUP (Nissan Chemical Ind Ltd's system, trade name) and QUOTRONPL series (Fukawa Chemical Industries Co., Ltd.'s system, trade name).

Inorganic oxide particle, when surface has hydroxyl, can use silane coupler etc. to be amino, carboxyl, epoxy radicals etc. by hydroxyl modification.But, when the average grain diameter of inorganic oxide particle is less than or equal to 500nm, be sometimes difficult to carry out modification.In this case, modification is not preferably carried out and coated electroconductive particles.

Usually, by having hydroxyl, can combine with hydroxyl, carboxyl, alkoxyl, alkoxy carbonyl etc.As combination, include, for example the covalent bond, hydrogen bond, coordinate bond etc. that are obtained by dehydrating condensation.

When the outer surface of conducting particles is made up of gold or palladium, be preferably used in molecule the compound with the sulfydryl, thioether group, disulfide base etc. that form coordinate bond with them, form the functional groups such as hydroxyl, carboxyl, alkoxyl, alkoxy carbonyl on surface.As above-claimed cpd, include, for example TGA, 2 mercapto ethanol, methyl thioglycolate, mercapto succinic acid, thioglycerol and cysteine.

Noble metal and the copper etc. such as gold, palladium are easily and thiol reactant.The base metals such as nickel are difficult to and thiol reactant.Therefore, the outermost layer of the outermost layer of conducting particles situation about being made up of noble metal or copper etc. and conducting particles compared with the situation that base metal is formed easily and thiol reactant.

Such as, be not particularly limited as the method at gold surface process above-claimed cpd, the above-claimed cpds such as TGA can be dispersed in the organic solvent such as methyl alcohol, ethanol with 10 ~ 100mmol/L degree, and make outermost layer be that golden conducting particles is dispersed in wherein.

The average grain diameter of insulating properties particle is preferably 20 ~ 500nm.The average grain diameter of insulating properties particle is such as measured by the specific area scaling method or low-angle scattering of X-rays method that use BET method.If average grain diameter is above-mentioned scope, then the insulating properties particle be such as adsorbed on conducting particles easily plays a role effectively as dielectric film, and the conductivity of the compression aspect connected easily becomes good.Such effect easily obtains as when insulating properties particle at use inorganic oxide particle.

From the viewpoint of easily reduce resistance, easily suppress resistance through time rise, the average grain diameter of insulating properties particle is preferably less than or equal to 1/10 relative to the average grain diameter of conducting particles, is more preferably less than or equals 1/15.From the viewpoint of obtaining better insulating reliability, the average grain diameter of insulating properties particle is preferably more than or equal to 1/20 relative to the average grain diameter of conducting particles.

Insulating properties particle is preferably the surface of the mode coated electroconductive particles of 20 ~ 70% with covering rate.From the viewpoint of the effect positively obtaining insulating properties and conductivity further, covering rate is more preferably 20 ~ 60%, and more preferably 25 ~ 60%, be particularly preferably 28 ~ 55%." covering rate " refers on the frontal plane of projection of insulation-coated electroconductive particles, has the ratio of the surface area of the insulating properties particle in the concentric circles of 1/2 diameter of insulation-coated electroconductive particles diameter.Specifically, according to the SEM image using SEM to observe insulation-coated electroconductive particles obtain with 30,000 times, the ratio of insulating properties particle shared by insulation-coated electroconductive particles surface is calculated by image analysis.

As the method by inorganic oxide particle coated electroconductive particles surface, preference is as the method for alternately laminated polyelectrolyte and inorganic oxide particle.More particularly, the stacked insulation-coated electroconductive particles having the insulating properties particle of polyelectrolyte and inorganic oxide particle coating in surface can be manufactured by following method, described method has following operation: conducting particles is dispersed in polymer electrolyte solution by (1), after making polyelectrolyte be adsorbed on the surface of conducting particles, carry out the operation of rinsing; (2) conducting particles is dispersed in the dispersion soln of inorganic oxide particle, after making inorganic particles be adsorbed on the surface of conducting particles, carries out the operation of rinsing.This method is called as alternately laminated method (Layer-by-Layerassembly).Alternately laminated method is the method (ThinSolidFilms, 210/211, P831 (1992)) that G.Decher equals the formation organic film delivered for 1992.According to the method, base material (substrate etc.) is alternately immersed in the aqueous solution of the polymer dielectric (polycation) with positive charge and the polymer dielectric (polyanion) with negative electrical charge, be adsorbed onto polycation on base material due to electrostatic attraction and polyanion group is carried out stacked, thus obtain composite membrane (alternately laminated film).Above-mentioned (1) operation and (2) operation can be the order of (1), (2), also can be the order of (2), (1), preferably repeatedly carry out alternately laminated repeatedly.

In alternately laminated method, due to electrostatic attraction, be formed in the material in the electric charge of the material on base material and solution with opposite charges and attract each other, thus carry out film growth, therefore to occur carrying out adsorbing in electric charge and time can not continue to adsorb.Therefore, if reach certain saturation point, then thickness can not continue to increase.Lvov etc. report and alternately laminated method are applied to particulate, use each particle dispersion liquid of silicon dioxide, titanium dioxide, cerium oxide etc., by alternately laminated method is stacked, there is the method (Langmuir with the polyelectrolyte of microparticle surfaces electric charge opposite charges, Vol.13, (1997) p6195-6203).If use the method, the silicon dioxide microparticle then having a negative surface charge by alternately laminated and as the diallyl dimethyl ammoniumchloride (PDDA) or polymine (PEI) etc. of polycation with its opposite charges, can form the particulate layer laminate film being alternately laminated with silicon dioxide microparticle and polyelectrolyte.

As polyelectrolyte, such as, can use and ionize in aqueous, there is at main chain or side chain the macromolecule of the functional group with electric charge.Specifically, preferably polycation is used.As polycation, the material as polyamine class etc. with functional group that can be positively charged can be used, such as polymine (PEI), PAH (PAH), diallyl dimethyl ammoniumchloride (PDDA), polyvinyl pyridine (PVP), polylysine, polyacrylamide or the monomer polymerization of more than a kind of these polymer will be obtained and the copolymer that obtains.Wherein, polymine because charge density is high, adhesion is strong, therefore preferably.

< anisotropic conductive adhesive and adhesive film >

The anisotropic conductive adhesive of present embodiment and adhesive film are described.The anisotropic conductive adhesive of the 1st execution mode contains the conducting particles of present embodiment or the conducting particles obtained by the manufacture method of the conducting particles of present embodiment and bonding agent.The anisotropic conductive adhesive of the 2nd execution mode contains insulation-coated electroconductive particles and the bonding agent of present embodiment.The adhesive film (anisotropic conductive adhesive film) of present embodiment is membranaceous anisotropic conductive adhesive, the anisotropic conductive adhesive of present embodiment is formed as membranaceous and forms.In anisotropic conductive adhesive and adhesive film, conducting particles or insulation-coated electroconductive particles are dispersed in bonding agent.

As bonding agent, such as, use the mixture of heat reactivity resin and curing agent.As bonding agent, include, for example the mixture of epoxy resin and potentiality curing agent and the mixture of free-radical polymerised compound and organic peroxide.

As bonding agent, use pasty state or membranaceous material.Membranaceous in order to be shaped to, in bonding agent, coordinate phenoxy resin, mylar, polyamide, mylar, polyurethane resin, thermoplastic resin such as (methyl) acrylic resin, polyester polyurethane resin etc. is effective.

< connection structural bodies >

The connection structural bodies of present embodiment is described.The connection structural bodies of present embodiment possesses: the 1st circuit member with the 1st circuit electrode, the 2nd circuit member with the 2nd circuit electrode and the connecting portion be configured between the 1st circuit member and the 2nd circuit member.1st circuit electrode and the 2nd circuit electrode are configured in an opposing fashion, are electrically connected to each other by conducting particles or insulation-coated electroconductive particles.Conducting particles or insulation-coated electroconductive particles, such as with the state of being out of shape because of compression between the 1st circuit electrode and the 2nd circuit electrode.Under the state that connecting portion is configured in an opposing fashion at the 1st circuit electrode and the 2nd circuit electrode, the 1st circuit member and the 2nd circuit member are connected to each other.Connecting portion is anisotropic conductive adhesive or its solidfied material of present embodiment.

The connection structural bodies of the 1st execution mode is formed as follows: be configured in the mode that the 1st circuit electrode is relative with the 2nd circuit electrode with the 2nd circuit member with the 2nd circuit electrode by the 1st circuit member with the 1st circuit electrode, make the anisotropic conductive adhesive of present embodiment between the 1st circuit member and the 2nd circuit member, these the 1st circuit members and the 2nd circuit member are heated and pressurize and be electrically connected with the 2nd circuit electrode by the 1st circuit electrode.Anisotropic conductive adhesive can be adhesive film.The connection structural bodies of the 2nd execution mode possesses: the 1st circuit member with the 1st circuit electrode, the 2nd circuit member with the 2nd circuit electrode and the connecting portion be configured between the 1st circuit member and the 2nd circuit member, 1st circuit member and the 2nd circuit member are connected to each other under the state that connecting portion is configured in an opposing fashion at the 1st circuit electrode and the 2nd circuit electrode, the conducting particles that the manufacture method of the 1st relative circuit electrode and the conducting particles of the 2nd circuit electrode by present embodiment or the conducting particles by present embodiment obtains is electrically connected.Conducting particles such as with distortion state between the 1st circuit electrode and the 2nd circuit electrode.The connection structural bodies of the 3rd execution mode possesses: the 1st circuit member with the 1st circuit electrode, the 2nd circuit member with the 2nd circuit electrode and the connecting portion be configured between the 1st circuit member and the 2nd circuit member, 1st circuit member and the 2nd circuit member are connected to each other by the state that connecting portion is configured in an opposing fashion at the 1st circuit electrode and the 2nd circuit electrode, and the 1st relative circuit electrode is electrically connected by the insulation-coated electroconductive particles of present embodiment with the 2nd circuit electrode.Insulation-coated electroconductive particles such as with distortion state between the 1st circuit electrode and the 2nd circuit electrode.

Then, reference Fig. 9 is while further illustrate connection structural bodies.Fig. 9 is the schematic section of the connection structural bodies representing present embodiment.Connection structural bodies 300 shown in Fig. 9 has the 1st relative circuit member 310 and the 2nd circuit member 320, is configured with the connecting portion 330 being connected them between circuit member 310 with circuit member 320.

The circuit electrode (the 1st circuit electrode) 312 that 1st circuit member 310 has circuit substrate (the 1st circuit substrate) 311 and is configured on the interarea 311a of circuit substrate 311.The circuit electrode (the 2nd circuit electrode) 322 that 2nd circuit member 320 has circuit substrate (the 2nd circuit substrate) 321 and is configured on the interarea 321a of circuit substrate 321.

As circuit member 310, the object lesson of a side in 320, include, for example the chip parts such as IC chip (semiconductor chip), resistive element chip, capacitor chip, drive IC; Rigid type base plate for packaging.These circuit members have circuit electrode, and usually have multiple circuit electrode.As circuit member 310, the object lesson of the opposing party in 320 (connecting the circuit member of the circuit member of one side), include, for example flexible tape substrate, flexible printing patch panel, the evaporation with metal wiring has the wiring substrates such as the glass substrate of indium tin oxide (ITO).According to membranaceous anisotropic conductive adhesive, can effectively and there is high connecting reliability these circuit members are connected to each other.The COG of chip part on wiring substrate that the anisotropic conductive adhesive of present embodiment is suitable for having multiple fine circuits electrode installs or COF installation.

The solidfied material 332 that connecting portion 330 has bonding agent and the insulation-coated electroconductive particles 200 be dispersed in wherein.In connection structural bodies 300, relative circuit electrode 312 is electrically connected by insulation-coated electroconductive particles 200 with circuit electrode 322.More particularly, as shown in Figure 9, the conducting particles 100a in insulation-coated electroconductive particles 200 is out of shape because of compression, with circuit electrode 312, is electrically connected both 322.On the other hand, laterally make insulating properties particle 210 between conducting particles 100a in diagram, thus maintain insulating properties.Therefore, by using the anisotropic conductive adhesive of present embodiment, the insulating reliability under thin space (such as the spacing of 10 μm of levels) can be improved further.Also can use according to purposes and do not replaced insulation-coated electroconductive particles by insulation-coated conducting particles (conducting particles of present embodiment).

Connection structural bodies 300 obtains as follows: be configured in the mode that circuit electrode 312 is relative with circuit electrode 322 with the circuit member 320 with circuit electrode 322 by the circuit member 310 with circuit electrode 312, make anisotropic conductive adhesive between circuit member 310 and circuit member 320, they are heated and pressurizes and circuit electrode 312 is electrically connected with circuit electrode 322.Circuit member 310 and circuit member 320 are undertaken bonding by the solidfied material 332 of bonding agent.

The manufacture method > of < connection structural bodies

While be described with reference to Figure 10 (a) ~ manufacture method of Figure 10 (c) to the connection structural bodies of present embodiment.Figure 10 (a) ~ Figure 10 (c) is the schematic section of an example of manufacture method for illustration of the connection structural bodies shown in Fig. 9.In the present embodiment, make anisotropic conductive adhesive hot curing and manufacture connection structural bodies.

First, circuit member 310 and anisotropic conductive adhesive (being be shaped to membranaceous adhesive film (anisotropic conductive adhesive film) in the present embodiment) 330a is prepared.Anisotropic conductive adhesive 330a contains the bonding agent 332a of insulation-coated electroconductive particles 200 and insulating properties.

Then, anisotropic conductive adhesive 330a is placed on the interarea 311a (being formed with the face of circuit electrode 312) of circuit member 310.Then, the direction A and direction B of Figure 10 (a) pressurize to anisotropic conductive adhesive 330a, anisotropic conductive adhesive 330a is layered in (Figure 10 (b)) on circuit member 310.

Then, as shown in Figure 10 (c), in the mode that circuit electrode 312 is relative with circuit electrode 322, circuit member 320 is placed on anisotropic conductive adhesive 330a.Then, anisotropic conductive adhesive 330a is heated, while pressurize to entirety on the direction A and direction B of Figure 10 (c).

Be solidified to form connecting portion 330 by anisotropic conductive adhesive 330a, obtain connection structural bodies 300 as shown in Figure 9.In addition, bonding agent 332a is solidified to form solidfied material 332.In addition, in the present embodiment, anisotropic conductive adhesive is membranaceous, but also can be pasty state.

As the connection structural bodies with above-mentioned syndeton, include, for example the portable product such as liquid crystal display, personal computer, mobile phone, smart mobile phone, hand-written panel.

Above execution mode of the present utility model is illustrated, but the utility model is not limited only to above-mentioned execution mode.

Embodiment

Below, embodiment is enumerated and comparative example is more specifically described content of the present utility model.In addition, the utility model is not limited to following embodiment.

< embodiment 1 >

[making of conducting particles]

(operation is pretreatment procedure a)

That the crosslinked polystyrene particle (Nippon Shokubai Co., Ltd's system, trade name " SOLIOSTAR ") of 2g average grain diameter 3.0 μm is added to 100mL contains 8 quality % as in the palladium catalyst liquid of the AtotechNEOGANT834 (Atotech Amada Co., Ltd. system, trade name) of palladium catalyst, stirs 30 minutes at 30 DEG C.Then, with film filter (Mi Libo Co., Ltd. system) filter after, carry out washing and obtaining resin particle.Afterwards, resin particle is added to and is adjusted in the 0.5 quality % dimethylamine borane liquid of pH6.0, obtain surface by the resin particle activated.Then, surface is immersed in by the resin particle of activity after in the distilled water of 20mL, carries out ultrasonic wave dispersion, thus obtain resin particle dispersion liquid.

The formation that (operation b) is the 1st layer

After diluting resin particle dispersion liquid obtained above with the water that 1000mL is heated to 80 DEG C, add the aqueous bismuth nitrate solution 1mL of 1g/L as plating stabilizer.Then, following for 80mL composition (is comprised the aqueous solution of following compositions.Every 1L plating solution adds the aqueous bismuth nitrate solution 1mL of 1g/L.Same below) the 1st layer of formation chemical nickel-plating liquid drip to the speed of dripping of 5mL/ minute in the dispersion liquid comprising 2g resin particle.Drip after terminating, after 10 minutes, the dispersion liquid being added with plating solution is filtered.After the cleaned screening of water, dry in the vacuum drier of 80 DEG C.Thus, the 1st layer that is made up of nickel-phosphor alloy tunicle of the 80nm thickness shown in formation table 1.By forming the 1st layer and the particle A obtained is 4g.

(the 1st layer of formation chemical nickel-plating liquid)

The formation of (operation c) palladium particle

Particle A 4g being formed with above-mentioned 1st layer is immersed in the chemical palladium plating solution of the following composition of 1L, obtains the particle B being formed with palladium particle (plating palladium separates out core) on the surface of this particle A.In addition, process with 10 minutes reaction time, temperature 60 C.

(chemical palladium plating solution)

(operation d) chemical nickel plating separates out the formation of core

The particle B that 4.05g is obtained by operation c, in washing with after filtering, is dispersed in 1000mL and is heated in the water of 70 DEG C.In this dispersion liquid, add the aqueous bismuth nitrate solution 1mL of 1g/L as plating stabilizer.Then, the chemical nickel plating of following for 25mL composition is separated out karyomorphism one-tenth plating solution to drip with the speed of dripping of 5mL/ minute.Drip after terminating, after 10 minutes, the dispersion liquid being added with plating solution is filtered.After the cleaned screening of water, dry in the vacuum drier of 80 DEG C.Thus, the chemical nickel plating be made up of nickel-phosphor alloy of the 56nm average length shown in formation table 1 separates out core.The particle C obtained by forming chemical nickel plating precipitation core is 5.0g.

(chemical nickel plating separates out karyomorphism one-tenth plating solution)

The formation that (operation e) is the 2nd layer

The particle C that 5.0g is obtained by operation d, in washing with after filtering, is dispersed in 1000mL and is heated in the water of 70 DEG C.In this dispersion liquid, add the aqueous bismuth nitrate solution 1mL of 1g/L as plating stabilizer.Then, the 2nd of following for 20mL composition the layer of formation chemical nickel-plating liquid is dripped with the speed of dripping of 5mL/ minute.Drip after terminating, after 10 minutes, the dispersion liquid being added with plating solution is filtered.After the cleaned screening of water, dry in the vacuum drier of 80 DEG C.Thus, the 2nd layer that is made up of nickel-phosphor alloy tunicle of the 20nm thickness shown in formation table 1.By forming the 2nd layer and the conducting particles obtained is 5.5g.

(the 2nd layer of formation chemical nickel-plating liquid)

By above operation a ~ e, obtain conducting particles.

[evaluation of conducting particles]

According to following project appraisal conducting particles.Show the result in table 1.

(evaluation of thickness and composition)

Ultrathin sectioning is used to cut out cross section in the mode of the conducting particles immediate vicinity by obtaining.Transmission electron microscope device (below referred to as " TEM device ", Jeol Ltd.'s system, trade name " JEM-2100F ") is used to observe with the multiplying power of 250,000 times.The 1st layer, the sectional area of layers 2 and 3 is estimated by the image obtained, by this sectional area calculate the 1st layer, the thickness of layers 2 and 3 (in embodiment 1, owing to not forming the 3rd layer, therefore only using the thickness of layers 1 and 2 as determination object).About the thickness calculating each layer according to sectional area, the sectional area of each layer on the cross section of being read width 500nm by image analysis, is calculated the thickness of height when being scaled the rectangle of width 500nm as each layer.The thickness mean value calculated 10 conducting particless has been shown in table 1.At this moment, when be difficult to difference the 1st layer, the 2nd layer, chemical nickel plating separate out core and the 3rd layer, by by energy dispersion-type X-ray detector (below referred to as " EDX detector ", Jeol Ltd.'s system, trade name " JED-2300 ") constituent analysis carried out, core and the 3rd layer are separated out in difference the 1st layer, the 2nd layer clearly, chemical nickel plating, thus estimation sectional area, measure thickness.In addition, calculate the 1st layer by EDX draw data, chemical nickel plating separates out core, constituent content (purity) in the 2nd layer and the 3rd layer.Detailed content about the calculation method of the constituent content in the detailed content of the manufacture method of the sample (cross-section samples of conducting particles) of cut film shape, the detailed content being obtained the method for drawing by EDX detector and each layer is aftermentioned.

(evaluation of palladium particle)

{ quantity of palladium particle and ratio }

On the frontal plane of projection of the particle B after defining palladium particle by above-mentioned operation c, calculate there is the palladium number of particles that exists in the concentric circles of 1/2 diameter of particle B diameter and there is the palladium particle ratio of specified diameter.

Specifically, the quantity of palladium particle is evaluated according to the SEM image using scanning electron microscopy (below referred to as " SEM device ", Hitachi Ltd.'s system) to obtain with 30,000 times of observation particle B.Figure 11 represents the SEM image defining the particle B after palladium particle observed and obtained by operation c.

As the palladium particle ratio with specified diameter, the frontal plane of projection of particle B is obtained respectively diameter be less than 20nm, be more than or equal to 20nm and the quantity of palladium particle being less than 60nm and being more than or equal to 60nm relative to the ratio of sum with the palladium particle existed in the concentric circles of 1/2 diameter of particle B diameter.About the diameter of palladium particle, as shown in Figure 12 (a) He Figure 12 (b), according to the SEM image discriminating observing particle B surface with 150,000 times.Measuring the area of each palladium particle, calculating having with this area positive diameter of a circle of the same area diameter as palladium particle.In addition, Figure 12 (a) and Figure 12 (b) is the part in the concentric circles of 1/2 diameter with particle B diameter.

{ average length }

The average length of palladium particle on the thickness direction of metal level (average height) is obtained according to following steps.First, using ultrathin sectioning to cut out the cross section of the conducting particles obtained by above-mentioned operation e, in the sample of the cut film shape cut out, is maximum sample using particle diameter as with the sample cut out by the cross section of conducting particles immediate vicinity.For this sample, use TEM device, utilize the scanning transmission electron microscope pattern (STEM pattern) of one of the mode determination as TEM device, carry out observing (250,000 times) with accelerating voltage 200kV.Then, STEM pattern is utilized to carry out observation while find mensuration visual field, by the incidental EDX detector of TEM device, obtain the drawing (will STEM pattern be utilized like this to observe, the method for being undertaken by EDX detector analyzing be referred to as " STEM/EDX analysis ") of nickel, phosphorus and palladium below.The STEM picture (Figure 13 (a)) that Figure 13 (a) ~ Figure 13 (d) represents conducting particles cross section and the drawing (Figure 13 (b): nickel of nickel, phosphorus and palladium obtained by EDX, Figure 13 (c): phosphorus, Figure 13 (d): palladium).Then, the length of palladium particle on the thickness direction of metal level is obtained by the drawing of the palladium obtained.Figure 14 (a) and Figure 14 (b) are the figure obtaining the method for the length of palladium particle for illustration of the drawing of the palladium by Figure 13 (d).Obtain the length of 10 palladium particles, using the average length of their mean value as palladium particle.Detailed content about the calculation method of the average length of palladium particle is aftermentioned.

(chemical nickel plating separates out the evaluation of core)

{ chemical nickel plating separates out quantity and the ratio of core }

Become by above-mentioned operation D-shaped chemical nickel plating to separate out on the frontal plane of projection of the particle C after core, calculating there is the chemical nickel plating existed in the concentric circles of 1/2 diameter of particle C the diameter quantity separating out core and the chemical nickel plating with specified diameter separating out the ratio of core.

Specifically, the SEM image that the quantity that chemical nickel plating separates out core obtains with 30,000 times of observation particle C according to use SEM device is evaluated.Figure 15 represents the SEM image defining the particle C after chemical nickel plating precipitation core observed and obtained by operation d.

Separate out the ratio of core as the chemical nickel plating with specified diameter, the frontal plane of projection of particle C is obtained quantity that chemical nickel plating that diameter is less than 100nm and is more than or equal to 100nm separates out core respectively relative to the ratio there is the chemical nickel plating existed in the concentric circles of 1/2 diameter of particle C diameter separating out the sum of core.Separating out the diameter of core about chemical nickel plating, as shown in Figure 16 (a) He Figure 16 (b), differentiating by observing the surperficial SEM image obtained of particle C with 100,000 times.In Figure 16 (a) and Figure 16 (b), confirm the 1st layer and separate out core with the chemical nickel plating distributed diffusedly.

{ average length }

Obtain chemical nickel plating according to following steps and separate out the average length of core on the thickness direction of metal level (average height).The STEM picture (Figure 13 (a)) in the conducting particles cross section obtained in the evaluation by above-mentioned palladium particle is obtained chemical nickel plating and is separated out the length of core on the thickness direction of metal level.Figure 17 (a) and Figure 17 (b) obtains for illustration of the STEM picture by conducting particles cross section the figure that chemical nickel plating separates out the method for the length of core.Obtain the length that 10 chemical nickel platings separate out core, their mean value is separated out the average length of core as chemical nickel plating.

(manufacture method of the cross-section samples of conducting particles)

The manufacture method of the cross-section samples of conducting particles is described in detail.Use ultrathin sectioning makes the cross-section samples (hereinafter referred to " cut film that TEM measures ") with 60nm ± 20nm thickness for carrying out STEM/EDX analysis to the cross section of conducting particles as described below.

In order to stably carry out filming processing, conducting particles is dispersed in castable resin.Specifically, in mixture (RefineTech Co., Ltd. system, trade name " EPOMOUNT host the 27-771 ") 10g of bisphenol A-type liquid epoxy resin, butyl glycidyl ether and other epoxy resin, 1.0g Diethylenetriamine (RefineTech Co., Ltd. system, trade name " EPOMOUNT curing agent 27-772 ") is mixed.Use spatula to stir, confirm Homogeneous phase mixing by range estimation.Add the conducting particles of 0.5g drying in this mixture of 3g after, spatula is used to be stirred to evenly.The mixture comprising conducting particles is injected in the mould (D.S.K Tang Ban EM Co., Ltd. system, trade name " organosilicon embedding plate II type ") of resin casting mold, under normal temperature (room temperature), leaves standstill 24 hours.Confirm that castable resin solidifies, obtain the resin casting mold thing of conducting particles.

Use ultramicrotome (LeicaMicrosystems Co., Ltd. system, trade name " EM-UC6 "), made the cut film of TEM mensuration by the resin casting mold thing of conducting particles.When making the cut film that TEM measures, first, use the glass cutter (being made by the glass cutter manufactory of Xin EM Co., Ltd.) be fixed on the apparatus main body of ultramicrotome, as shown in Figure 18 (a), finishing processing is carried out to the top of resin casting mold thing, until become the shape that can cut out the cut film that TEM measures.

In more detail, finishing is processed into as shown in Figure 18 (b), and the cross sectional shape on the top of resin casting mold thing is the approximate rectangular-shaped of the length with long 200 ~ 400 μm and wide 100 ~ 200 μm.The length of cross section transverse direction is set to 100 ~ 200 μm, is to reduce the friction produced between diamond tool and sample when being cut out the cut film that TEM measures by resin casting mold thing.The fold of the cut film easily preventing TEM from measuring thus is with bending, and the making of the cut film that TEM is measured becomes easy.

Then, at the diamond tool (DIATONE Inc., trade name " CryoWet ", the wide 2.0mm of blade, knife edge angular 35 °) of predetermined portion fixed band ship shape dish (boat) of ultramicrotome apparatus main body.Then, fill up ship shape dish with ion exchange water, the angle that arranges of adjustment cutter also uses ion-exchange water-wet point of a knife.

Here, the adjustment that angle is set of Figure 19 tool setting is used to be described.Arrange in the adjustment of angle at cutter, the angle of above-below direction, the angle of left and right directions and clearance angle (clearanceangle) can be adjusted.So-called " angle adjustment of above-below direction ", as shown in figure 19, refers to the angle of the above-below direction adjusting specimen mounting according to the mode that specimen surface is parallel with the direct of travel of cutter.So-called " angle adjustment of left and right directions ", as shown in figure 19, refers to the angle of the left and right directions adjusting cutter according to the mode that the point of a knife of cutter is parallel with specimen surface.So-called " adjustment of clearance angle ", as shown in figure 19, refers to minimum angles formed by the face of sample side of the point of a knife of adjustment cutter and the direct of travel of cutter.Clearance angle is preferably 5 ~ 10 °.If clearance angle is above-mentioned scope, then can reduce the point of a knife of cutter and the friction of specimen surface, cutter friction sample surface after simultaneously preventing cutting out cut film from sample.

While confirm the light microscope be attached on ultramicrotome apparatus main body, while the distance of sample and diamond tool is furthered, with blade speed 0.3mm/ second, film cut out the set point that mode that thickness is 60nm ± 20nm sets slicing machine device, cut out cut film by resin casting mold thing.Then, cut film TEM being measured floats on the water surface of ion exchange water.From the copper mesh (Xin EM Co., Ltd. system, trade name " copper mesh of band microgrid ") that the upper surface pressing TEM of the cut film of the TEM mensuration of keeping afloat measures, the cut film that TEM is measured is adsorbed on copper mesh, makes TEM sample.In addition, the cut film measured due to the TEM obtained by slicing machine is consistent with the set point inaccuracy cutting out thickness of slicing machine, therefore obtains the set point that can obtain expecting thickness in advance.

(being obtained the method for drawing by EDX detector)

The method being obtained by EDX detector drawing is described in detail.The cut film measured by TEM is fixed on specimen mounting (Jeol Ltd.'s system, trade name " beryllium sample 2 axle tilting rack, EM-31640 ") together with copper mesh, is inserted into TEM device inner.After starting the electronbeam irradiation to sample with accelerating voltage 200kV, the irradiation system of electron ray is switched to STEM pattern.

By scanning as finder be inserted into STEM observe time position, after starting the software " JEOLSimpleImageViewer (Version1.3.5) " (Jeol Ltd.'s system) of STEM observation, observe the cut film that TEM measures.In the cross section of the conducting particles observed wherein, find the position being suitable for EDX and measuring, photograph.Here so-called " being suitable for the position measured ", refer to the position being cut off, can observing the cross section of metal level at the immediate vicinity of conducting particles, the position that cross section tilts and getting rid of outside determination object at the position that the position of departing from conducting particles immediate vicinity is cut-off.During photography, observing multiplying power is 250,000 times, and pixel count STEM being observed picture is set to longitudinally 512 points, laterally 512 points.If observed under this condition, then can obtain the observation picture of visual angle 600nm, if but device change, even if be then identical multiplying power sometimes, visual angle also changes, and therefore must be noted that.

When STEM/EDX analyzes, if the cut film measured the TEM of conducting particles irradiates electron ray, then cause the plastics nucleome of conducting particles and the contraction of castable resin and thermal expansion, in mensuration, sample can be out of shape or movement.Sample deformation in measuring to suppress such EDX and sample move, and measurement site are irradiated to the electron ray of 30 minutes ~ 1 hour degree in advance, analyze after confirming distortion and mobile end.

In order to carry out STEM/EDX analysis, EDX detector being moved to and locates, start the software " AnalysisStation " (Jeol Ltd.'s system) that EDX measures.When being drawn by EDX detector, due to sufficient resolution must be obtained when drawing, therefore use the focused light coil apparatus for making electron ray focus on target site.

When STEM/EDX analyzes, the some footpath of electron ray is adjusted in the scope of 0.5 ~ 1.0nm, is more than or equal to 10,000CPS to make the counting of the characteristic X-ray of detection (CPS:CountsPerSecond).After mensuration, measuring in the EDX spectrum simultaneously obtained with drawing, the height confirming the peak of the K α line from nickel is at least more than or equal to 5,000Counts.When data obtain, pixel count is set to longitudinally 256 points, laterally 256 points by visual angle identical during to observe with above-mentioned STEM.The accumulated time of every bit is set to 20 milliseconds, measures for 1 time with cumulative frequency.

In order to calculate the length of palladium particle, analyzing data according to the STEM/EDX obtained, making the Drawing image of palladium.In the Drawing image of this palladium, as shown in Figure 14 (a) He Figure 14 (b), by being the black and white existence part that decides palladium by the Drawing image obtained 2 value and there is not portion boundary line, the distance between this boundary line on the thickness direction of metal level is designated as the length of palladium particle.But, in determination data, comprising hash, implementing filter process to improve S/N ratio.Filter process is software " AnalysisStation " the incidental function that EDX measures, at each measuring point, can except the data of each measuring point, and also the data of multiple points that accumulation is adjacent with measuring point show.Thus, the S/N of Drawing image improves, therefore, it is possible to calculated the length of palladium particle by the Drawing image of palladium.In the present embodiment, utilize this filter process, except the data of each measuring point, accumulate the data of 8 points (upper and lower, left and right, upper left, lower-left, upper right, bottom right) adjacent with measuring point, after reducing the hash of Drawing image, calculate the length of palladium particle.

By the EDX draw data obtained, extracting the 1st layer as required, chemical nickel plating separates out core, the EDX spectrum of the 2nd layer, there is ratio in the element calculated in each several part.Wherein, when calculating quantitative values, the ratio of noble metal, nickel and phosphorus being added up to and is set to 100 quality %, calculating the quality % concentration of each element.

About element other than the above, because following reason ratio easily changes, except when therefore calculating quantitative values.About carbon, be adsorbed on the pollutant effects of specimen surface and cause sliding scale when the carbon support membrane that the net due to TEM mensuration uses or electronbeam irradiation.About oxygen, there is the possibility of increase due to air oxidation after making TEM sample until between measuring.Copper can measure the copper mesh used from TEM and detect.

(palladium content in palladium particle)

Sample for evaluation is made by using the following method of copper-clad laminated board.

" MCL-E-679F " (Hitachi Chemical Co., Ltd.'s system, trade name) as copper-clad laminated board is obtained substrate with the cut-out of the size of 1cm × 1cm.This substrate, is washed 1 minute after 1 minute in 50 DEG C of dippings in degreaser " Z-200 " (Co., Ltd. WorldMetal system, trade name).Then, flood after 1 minute in the ammonium persulfate solution of 100g/L, wash 1 minute.Then, flood after 1 minute in the sulfuric acid of 10 quality %, wash 1 minute.Then, wash 1 minute after 5 minutes in 25 DEG C of impregnation process in as " SA-100 " (Hitachi Chemical Co., Ltd.'s system, trade name) of plating activation processing liquid.Then, flood 4 minutes in 85 DEG C in as " TOPNICORONNAC " (Okuno Chemical Industries Co., Ltd.'s system, trade name) of chemical nickel-plating liquid, thus form the chemical nickel plating tunicle containing 11.5 quality % phosphorus with 0.7 μm of thickness on Copper Foil.Then, 1 minute is washed.Then, in the composition of above-mentioned (operation c) and the chemical palladium plating solution of liquid measure, flood 10 minutes at 60 DEG C, thus on chemical nickel plating tunicle, form the chemical palladium-plating tunicle of about 0.1 μm of thickness.Then, after being washed 1 minute, drying obtains sample for evaluation.

Then, the sample for evaluation obtained is buried in castable resin (material by 90 quality % epoxy resin 815 (japan epoxy resin Co., Ltd. system, trade name) and 10 quality % triethylene tetramines (Wako Pure Chemical Industries, Ltd.'s system, trade name) mix).After using ultrathin sectioning to cut out this cross section in the mode in the cross section can observing chemical palladium-plating tunicle, TEM device is used to observe with the multiplying power of 250,000 times.Then, for chemical palladium-plating tunicle, carry out constituent analysis by EDX detector, calculate palladium content, it can be used as the palladium content in palladium particle.Palladium content in the palladium particle obtained thus is 100 quality %.When palladium particle contains composition beyond palladium (composition beyond de-carbon and oxygen), the content of its composition also in the same manner as palladium by utilizing EDX detector to carry out constituent analysis to calculate to sample for evaluation.

(being formed in the evaluation of the projection on conducting particles surface)

{ covering rate of projection }

According to the SEM image using SEM device to observe conducting particles obtain with 30,000 times, calculate the covering rate (ratio of area) of the projection on conducting particles surface.Specifically, in the concentric circles of 1/2 diameter with conducting particles diameter, distinguish projecting formation and par by image analysis, calculate the area ratio of the projecting formation existed in concentric circles, using the covering rate of this ratio as projection.Figure 20 represents the result using SEM device to observe conducting particles.

{ the diameter distribution of projection }

On the frontal plane of projection of conducting particles, calculate having the projection quantity that exists in the concentric circles of 1/2 diameter of conducting particles diameter and the projection ratio with specified diameter.

Specifically, according to the SEM image using SEM device to observe conducting particles obtain with 30,000 times, the profile of projection is inferred by image analysis.Measuring the area (contour area of projection separated by the paddy between projection) of projection, calculating having with this area positive diameter of a circle of the same area diameter (external diameter) as projection.

As the projection ratio with specified diameter, on the frontal plane of projection of conducting particles, obtain respectively diameter be less than 100nm, be more than or equal to 100nm and the projection being less than 200nm and being more than or equal to 200nm relative to having quantity and the ratio of the projection sum existed in the concentric circles of 1/2 diameter of conducting particles diameter.

{ distribution of average length and projection length }

The measurement result of projection length D4 is as shown in Figure 6 obtained.Specifically, use ultrathin sectioning to be cut out the cross section of conducting particles by the mode of conducting particles immediate vicinity, carry out observable image according to use TEM device with the multiplying power of 250,000 times, obtain the length of projection.Figure 21 (a) and Figure 21 (b) is the figure for illustration of the method being obtained projection length by STEM picture.As shown in Figure 21 (a) He Figure 21 (b), the length of projection is measured to the distance on the projection summit in vertical direction as the straight line (connecting the straight line of the Gu Yugu of projection both sides) at the diametric two ends of the cardinal extremity from connection projection.The length of 10 place's projections is obtained for 1 conducting particles.Then, obtain the length of 10 conducting particless, 10 place's projections separately, calculate the length of total 100 place projection.Using the average length (average height) of the mean value of the length of 100 place's projections as projection.In addition, obtain projection length to be respectively less than 30nm, to be more than or equal to 30nm and to be less than 120nm and to be more than or equal to 120nm and to be less than quantity and the ratio of the projection of 500nm.

{ presence or absence in abnormal precipitation portion }

The method that length is schematically shown by Figure 22 (a) and Figure 22 (b) more than the presence or absence of the projection (abnormal precipitation portion) of 500nm differentiates.Specifically, SEM device is used to observe 1000 conducting particless 400 with 30,000 times, measure the distance from the straight line (connecting the straight line of the Gu Yugu of both sides, abnormal precipitation portion 401) at the diametric two ends of the cardinal extremity connecting abnormal precipitation portion 401 to the summit in the exception precipitation portion 401 vertical direction, thus obtain the length 402 in abnormal precipitation portion 401.Then, calculating has the conductive particle subnumber of length more than the exception precipitation portion of 500nm.

(mensuration of single dispersing rate)

0.05g conducting particles is dispersed in brine electrolysis, adds surfactant, carry out 5 minutes ultrasonic waves dispersion (ASONE Co., Ltd. US-4R, high frequency output: 160W, frequency of oscillation: 40kHz single-frequency).The dispersion liquid of conducting particles is injected in the sample cup for liquid of COULERMULTISZERII (Beckman Ku Erte Co., Ltd. system), single dispersing rate is measured to 50000 conducting particless.Single dispersing rate is calculated by following formula, judges the coherency of the particle in aqueous solvent according to this value according to following benchmark.

Single dispersing rate (%)={ firstpeak population (individual)/total population (individual) } × 100

[making of insulation-coated electroconductive particles]

Use ultra-pure water that the 30 quality % aqueous solution (Wako Pure Chemical Industries, Ltd.'s system) of the polymine of molecular weight 70000 are diluted to 0.3 quality %.200g is added in this 0.3 quality % aq. polyethyleneimine of 300mL by the conducting particles that method similar to the above obtains, stirring at normal temperature 15 minutes.By using the filtration of film filter (Mi Libo Co., Ltd. system) take out conducting particles, the conducting particles of taking-up to be joined in 200g ultra-pure water and in stirring at normal temperature 5 minutes.Further, by using the filtration of film filter (Mi Libo Co., Ltd. system) take out conducting particles, use 200g ultra-pure water that the conducting particles on film filter is cleaned 2 times, thus remove the polymine do not adsorbed.

Then, ultra-pure water dilution is used cataloid dispersion liquid, obtain 0.1 quality % silicon dioxide granule dispersion liquid.The conducting particles that 200g undertakies by above-mentioned polymine processing is added, stirring at normal temperature 15 minutes to it.By using the filtration of film filter (Mi Libo Co., Ltd. system) take out conducting particles, the conducting particles of taking-up to be joined in 200g ultra-pure water and in stirring at normal temperature 5 minutes.Further, by using film filter (Mi Libo Co., Ltd. system) filtration take out conducting particles.Then, use 200g ultra-pure water that the conducting particles on film filter is cleaned 2 times, remove the silicon dioxide granule do not adsorbed, obtain the insulation-coated electroconductive particles that adsorption has silicon dioxide granule.

The insulation-coated electroconductive particles surface SC6000 as silicone oligomer of molecular weight 3000 (Hitachi Chemical Co., Ltd.'s system, trade name) being attached to obtain, surface-hydrophobicized by insulation-coated electroconductive particles.To the insulation-coated electroconductive particles after hydrophobization according at 80 DEG C 30 minutes, at 120 DEG C the heating that sequentially passes through of 1 hour carry out drying, obtain the insulation-coated electroconductive particles of hydrophobization.By carrying out image analysis to SEM image, measure silicon dioxide granule to the average covering rate of conducting particles, result is about 28%.

[making of anisotropic conductive adhesive film and connection structural bodies]

By 100g phenoxy resin (Union Carbide Corporation's system, trade name " PKHC ") and the 75g acrylic rubber (copolymer of 40 mass parts butyl acrylates, 30 mass parts ethyl acrylates, 30 mass parts acrylonitrile, 3 mass parts glycidyl methacrylate, molecular weight: 850,000) be dissolved in 400g ethyl acetate, obtain solution.The liquid epoxy resin (epoxide equivalent 185, epoxy Co., Ltd. of Asahi Chemical Industry system, trade name " NOVACUREHX-3941 ") 300g being contained microcapsule-type potentiality curing agent adds in this solution, stirs, obtains adhesive solution.

Insulation-coated electroconductive particles obtained above is dispersed in this adhesive solution, and making with the total amount of adhesive solution as benchmark is 9 volume %, obtains dispersion liquid.Roll coater is used to be coated on by the dispersion liquid obtained on barrier film (polyethylene terephthalate film, thickness 40 μm through organosilicon process), by within 10 minutes, carrying out drying 90 DEG C of heating, thus on barrier film, make the anisotropic conductive adhesive film of thickness 25 μm.

Then, the anisotropic conductive adhesive film of use, i according to shown below) ~ iii) step carries out chip (1.7mm × 1.7mm, thickness: 0.5 μm) with golden projection (area: 30 μm × 90 μm, highly: 15 μm, number of lugs 362) and the connection of the glass substrate (thickness: 0.7mm) of band IZO circuit, obtains connection structural bodies.As golden projection, use spacing 6 μm, 3 kinds of projections of 8 μm, 10 μm.

I) with 80 DEG C, 0.98MPa (10kgf/cm ²) anisotropic conductive adhesive film (2mm × 19mm) is pasted onto on the glass substrate of band IZO circuit.

Ii) peel off barrier film, carry out the projection of chip and the location of the glass substrate of band IZO circuit.

Iii) 190 DEG C, 40gf/ projection, carry out heating and pressurizeing above chip under the condition of 10 seconds, formally connect.

[evaluation of connection structural bodies]

Carry out conducting resistance test and the insulation resistance test of obtained connection structural bodies as follows.

(conducting resistance test)

As the conducting resistance between chip electrode (projection)/IZO circuit, measure the value after the initial value of conducting resistance and moisture absorption heat resistant test (placing 100,300,500,1000,2000 hours under the condition of temperature 85 DEG C, humidity 85%).According to the joint area of about 40 μm × about 40 μm between chip electrode (projection)/IZO circuit, connect by the mode that 10 conducting particless connect.In addition, 20 samples are measured, calculates their mean value.By the mean value obtained according to following benchmark evaluation conducting resistance.Show the result in table 2.Be good to the average evaluation conducting resistance meeting following A or B benchmark in moisture absorption heat resistant test after 500 hours.

A: the mean value of conducting resistance is less than 2 Ω

B: the mean value of conducting resistance is more than or equal to 2 Ω and is less than 5 Ω

C: the mean value of conducting resistance is more than or equal to 5 Ω and is less than 10 Ω

D: the mean value of conducting resistance is more than or equal to 10 Ω and is less than 20 Ω

E: the mean value of conducting resistance is more than or equal to 20 Ω

(insulation resistance test)

As the insulation resistance between chip electrode, measure the initial value of insulation resistance and migration test (temperature 60 C, humidity 90%, execute 20V outward condition under place 100,300,1000,2000 hours) after value.20 samples are measured, calculates insulating resistance value in whole 20 samples and be more than or equal to 10 ⁹the ratio of the sample of Ω.Measure respectively to 3 kinds of spacing 6 μm, 8 μm, 10 μm carry out.By the ratio obtained according to following benchmark evaluation insulation resistance.Show the result in table 2.When spacing 8 μm, evaluating insulation resistance when moisture absorption heat resistant test meets following A or B benchmark after 1000 hours is good.

A: insulating resistance value is more than or equal to 10 ⁹the ratio of Ω is 100%

B: insulating resistance value is more than or equal to 10 ⁹the ratio of Ω is more than or equal to 90% and is less than 100%

C: insulating resistance value is more than or equal to 10 ⁹the ratio of Ω is more than or equal to 80% and is less than 90%

D: insulating resistance value is more than or equal to 10 ⁹the ratio of Ω is more than or equal to 50% and is less than 80%

E: insulating resistance value is more than or equal to 10 ⁹the ratio of Ω is less than 50%

< embodiment 2 >

In (the operation e) of embodiment 1, except the 2nd layer of formation chemical nickel-plating liquid is changed to except the plating solution of following composition, operate similarly to Example 1, carry out the making of conducting particles, insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies, and the evaluation of conducting particles and connection structural bodies.Show the result in table 1 and table 2.

(the 2nd layer of formation chemical nickel-plating liquid)

< embodiment 3 >

In (the operation e) of embodiment 1, except the 2nd layer of formation chemical nickel-plating liquid is changed to except the plating solution of following composition, operate similarly to Example 1, carry out the making of conducting particles, insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies, and the evaluation of conducting particles and connection structural bodies.Show the result in table 1 and table 2.

(the 2nd layer of formation chemical nickel-plating liquid)

< embodiment 4 >

In (the operation e) of embodiment 1, except the 2nd layer of formation chemical nickel-plating liquid is changed to except the plating solution of following composition, operate similarly to Example 1, carry out the making of conducting particles, insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies, and the evaluation of conducting particles and connection structural bodies.Show the result in table 1 and table 2.

(the 2nd layer of formation chemical nickel-plating liquid)

< embodiment 5 >

By 5.0g and embodiment 1 (operation a) ~ (operation d) the same particle C made is immersed in the chemical palladium plating solution of the following composition of 1L, forms the 3rd layer.In addition, process with 10 minutes reaction time, temperature 50 C.The average thickness of the 3rd layer is 10nm, and the palladium content in the 3rd layer is 100 quality %.Operate similarly to Example 1 except using this conducting particles, carry out the making of insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies, and the evaluation of conducting particles and connection structural bodies.Show the result in table 1 and table 2.

(chemical palladium plating solution)

< embodiment 6 >

By 5.0g and embodiment 1 (operation a) ~ (operation d) the same particle C made is immersed in the chemical palladium plating solution of the following composition of 1L, forms the 3rd layer.In addition, process with 10 minutes reaction time, temperature 50 C.The average thickness of the 3rd layer is 10nm, and the palladium content in the 3rd layer is almost 97 quality % (palladium: 97 quality %, phosphorus: 3 quality %).Operate similarly to Example 1 except using this conducting particles, carry out the making of insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies, and the evaluation of conducting particles and connection structural bodies.Show the result in table 1 and table 2.

(chemical palladium plating solution)

< embodiment 7 >

By 5.0g and embodiment 1 (operation a) ~ (operation d) the same particle C made is immersed in the chemical rhodanizing liquid of the following composition of 1L, forms the 3rd layer.In addition, process with 10 minutes reaction time, temperature 60 C.The average thickness of the 3rd layer is 10nm, rhodium content in the 3rd layer is almost 100 quality %.Operate similarly to Example 1 except using this conducting particles, carry out the making of insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies, and the evaluation of conducting particles and connection structural bodies.Show the result in table 1 and table 2.

(chemical rhodanizing liquid)

RH-1A (Okuno Chemical Industries Co., Ltd.'s system): 500mL/L

RH-1B (Okuno Chemical Industries Co., Ltd.'s system): 150mL/L

RH-1C (Okuno Chemical Industries Co., Ltd.'s system): 100mL/L

< embodiment 8 >

By 5.0g and embodiment 1 (operation a) ~ (operation d) the same particle C made is immersed in the chemical plating iridium liquid of the following composition of 1L, forms the 3rd layer.In addition, process with 20 minutes reaction time, temperature 70 C.The average thickness of the 3rd layer is 10nm, iridium content in the 3rd layer is almost 100 quality %.Operate similarly to Example 1 except using this conducting particles, carry out the making of insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies, and the evaluation of conducting particles and connection structural bodies.Show the result in table 3 and table 4.

(chemical plating iridium liquid)

Six iridium chloride trisodium 5g/L

22% titanium trichloride solution 40mL/L

pH3.5

< embodiment 9 >

By 5.0g and embodiment 1 (operation a) ~ (operation d) the same particle C made is immersed in the chemical plating ruthenium liquid of the following composition of 1L, forms the 3rd layer.In addition, process with 10 minutes reaction time, temperature 60 C.The average thickness of the 3rd layer is 10nm, and the ruthenium content in the 3rd layer is almost 100 quality %.Operate similarly to Example 1 except using this conducting particles, carry out the making of insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies, and the evaluation of conducting particles and connection structural bodies.Show the result in table 3 and table 4.

(chemical plating ruthenium liquid)

Ru-1 (Okuno Chemical Industries Co., Ltd.'s system): 500mL/L

Ru-2 (Okuno Chemical Industries Co., Ltd.'s system): 50mL/L

Ru-3 (Okuno Chemical Industries Co., Ltd.'s system): 50mL/L

< embodiment 10 >

By 5.0g and embodiment 1 (operation a) ~ (operation d) the same particle C made is immersed in the chemically plating platinum liquid of the following composition of 1L, forms the 3rd layer.In addition, process with 10 minutes reaction time, temperature 60 C.The average thickness of the 3rd layer is 10nm, and the platinum content in the 3rd layer is almost 100 quality %.Operate similarly to Example 1 except using this conducting particles, carry out the making of insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies, and the evaluation of conducting particles and connection structural bodies.Show the result in table 3 and table 4.

(chemically plating platinum liquid)

LECTROLESSPt100 basic liquid (Japanese electroplating engineering Co., Ltd. system): 500mL/L

LECTROLESSPt100 reducing solution (Japanese electroplating engineering Co., Ltd. system): 10mL/L

25% ammoniacal liquor (Wako Pure Chemical Industries, Ltd.'s system): 50mL/L

< embodiment 11 >

By 5.0g and embodiment 1 (operation a) ~ (operation d) the same particle C made is immersed in the chemical plating liquid of the following composition of 1L, forms the 3rd layer.In addition, process with 10 minutes reaction time, temperature 60 C.The average thickness of the 3rd layer is 10nm, and the silver content in the 3rd layer is almost 100 quality %.Operate similarly to Example 1 except using this conducting particles, carry out the making of insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies, and the evaluation of conducting particles and connection structural bodies.Show the result in table 3 and table 4.

(chemical plating liquid)

MUDENSILVER (system デ Application シ ル バ ー) SS-1 (Okuno Chemical Industries Co., Ltd.'s system): 50mL/L

MUDENSILVERSS-2 (Okuno Chemical Industries Co., Ltd.'s system): 500mL/L

MUDENSILVERSS-3 (Okuno Chemical Industries Co., Ltd.'s system): 5mL/L

< embodiment 12 >

Using 5.0g and embodiment 1 (operation a) ~ (operation d) the same particle C made floods 2 minutes in 85 DEG C in the solution of 1L as HGS-100 (Hitachi Chemical Co., Ltd., the trade name) 100mL/L of immersion gold plating liquid, further washing 2 minutes, forms the 3rd layer.In addition, process with 10 minutes reaction time, temperature 60 C.The average thickness of the 3rd layer is 10nm, and the gold content in the 3rd layer is almost 100 quality %.Operate similarly to Example 1 except using this conducting particles, carry out the making of insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies, and the evaluation of conducting particles and connection structural bodies.Show the result in table 3 and table 4.

< embodiment 13 >

The conducting particles made similarly to Example 3 by 5.5g is immersed in the chemical palladium plating solution of 1L and embodiment 5 same composition, forms the 3rd layer.In addition, process with 10 minutes reaction time, temperature 50 C.The average thickness of the 3rd layer is 10nm, and the palladium content in the 3rd layer is 100 quality %.Operate similarly to Example 1 except using this conducting particles, carry out the making of insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies, and the evaluation of conducting particles and connection structural bodies.Show the result in table 3 and table 4.

[table 1]

[table 2]

[table 3]

[table 4]

< comparative example 1 >

Carry out similarly to Example 1 (operation a) and (operation b), obtains 4g is formed with the 1st layer particle A on resin particle surface.

Carry out above-mentioned particle A washing and after filtering, stir the CLEANERCONDITIONER231 aqueous solution (ROHM AND HAAS Electronics Materials Co., Ltd system, concentration 40mL/L) of 200mL, on one side input 4g particle A wherein.While apply ultrasonic wave while stir 30 minutes at 60 DEG C, thus carry out the surface treatment of particle A.Then, filtering solution, after washing, makes 4g particle dispersion in water, obtains the slurry of 200mL the particle obtained.In this slurry, add 200mL (concentration 1.2g/L) the stannous chloride aqueous solution, stirring at normal temperature 5 minutes, carry out making tin ion to adsorb sensitization process on layer 1.

Then, filter slurry, after the particle obtained is washed, make 4g particle dispersion in water, obtain the slurry of 400mL.After slurry being heated to 60 DEG C, and stir slurry with ultrasonic wave, while add the palladium chloride aqueous solution 3mL of 19.5g/L.Maintain former state and stir 5 minutes, thus carry out making palladium ion seizure activation processing on layer 1.Afterwards, filter slurry, after the particle obtained is washed, carry out hot water cleaning further.Make the 4g particle dispersion obtained in water, obtain the slurry of 200mL.The mixed aqueous solution 20mL of the dimethylamine borane of 1g/L and the boric acid of 10g/L also with ultrasonic wave while stir this slurry, is added wherein in one side.The stirring on one side 2 minutes on one side and with ultrasonic wave at normal temperatures, carries out the reduction treatment of palladium ion.

Afterwards, carry out (operation d) similarly to Example 1, form the 2nd layer, obtain conducting particles.Operate similarly to Example 1 except using this conducting particles, carry out the making of insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies, and the evaluation of connection structural bodies.For the evaluation of conducting particles, carry out part evaluation similarly to Example 1.Show the result in table 5 and table 6.

< comparative example 2 >

By the crosslinked polystyrene particle (Inc. of Nippon Shokubai Co., Ltd, trade name " SOLIOSTAR ") of average grain diameter 3.0 μm as resin particle.While stir the CLEANERCONDITIONER231 aqueous solution (ROHM AND HAAS Electronics Materials Co., Ltd system, concentration 40mL/L) of 400mL, drop into 30g resin particle wherein.Then, the aqueous solution is heated to 60 DEG C, applies ultrasonic wave and stir 30 minutes, carry out surface modification and the dispersion treatment of resin particle.

Filter the above-mentioned aqueous solution, after 1 time is washed to the particle obtained, make 30g particle dispersion in water, obtain the slurry of 200mL.In this slurry, add 200mL (concentration 1.5g/L) the stannous chloride aqueous solution, stir 5 minutes at normal temperatures, carry out making tin ion be adsorbed on the sensitization process of particle surface.Then, filtering solution, washes 1 time to the particle obtained.Then, make 30g particle dispersion in water, after the slurry of modulation 400mL, be heated to 60 DEG C.Slurry is also stirred with ultrasonic wave in one side, adds the palladium chloride aqueous solution 2mL of 10g/L.Maintain former state and stir 5 minutes, thus carry out making palladium ion to catch activation processing at particle surface.Then, filtering solution, washes 1 time to the particle obtained.

Then, the chemical plating fluid that the aqueous solution that 3 liters are obtained by the inferior sodium phosphate of dissolving the sodium tartrate of 20g/L, the nickelous sulfate of 10g/L and 0.5g/L is formed is warming up to 60 DEG C, in this chemical plating fluid, drops into the above-mentioned particle of 10g.Stirred 5 minutes, confirmed that the foaming of hydrogen stops.

Afterwards, side by side use measuring pump to be added to continuously by the NaOH mixed aqueous solution of the nickel sulfate solution of 400mL200g/L and the inferior sodium phosphate of 400mL200g/L and 90g/L respectively to comprise in the plating solution of particle.Interpolation speed is all set to 3mL/ minute.Then, this solution is remained on 60 DEG C while stir after 5 minutes, filtering solution.After 3 times are cleaned to filtrate, dry in the vacuum drier of 100 DEG C, obtain the conducting particles with nickel-phosphor alloy tunicle.To the conducting particles obtained, use ultrathin sectioning to cut out cross section by the mode near particle centre, use TEM device to observe with the multiplying power of 250,000 times.According to the cross-sectional image obtained, calculate thickness by the mean value of sectional area, result average film thickness is 105nm.

Operate similarly to Example 1 except using above-mentioned conducting particles, carry out the making of insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies, and the evaluation of connection structural bodies.For the evaluation of conducting particles, carry out part evaluation similarly to Example 1.Show the result in table 5 and table 6.

< comparative example 3 >

By the crosslinked polystyrene particle (Inc. of Nippon Shokubai Co., Ltd, trade name " SOLIOSTAR ") of average grain diameter 3.0 μm as resin particle.While stir the CLEANERCONDITIONER231 aqueous solution (ROHM AND HAAS Electronics Materials Co., Ltd system, concentration 40mL/L) of 400mL, drop into 7g resin particle wherein.Then, the aqueous solution is heated to 60 DEG C, applies ultrasonic wave and stir 30 minutes, carry out surface modification and the dispersion treatment of resin particle.

Filter the above-mentioned aqueous solution, after 1 time is washed to the particle obtained, make 7g particle dispersion in pure water, obtain the slurry of 200mL.In this slurry, add 200mL (concentration 1.5g/L) the stannous chloride aqueous solution, stir 5 minutes at normal temperatures, carry out making tin ion be adsorbed on the sensitization process of particle surface.Then, filtering solution, washes 1 time to the particle obtained.Then, make 7g particle dispersion in water, the slurry of modulation 400mL, is heated to 60 DEG C.Slurry is also stirred with ultrasonic wave in one side, adds the palladium chloride aqueous solution 2mL of 10g/L.Maintain former state and stir 5 minutes, thus carry out making palladium ion to catch activation processing at particle surface.Then, filtering solution, washes 1 time to the particle obtained.

The 7g particle obtained is added in 300mL pure water, stirs and make it disperse in 3 minutes.Then, in this dispersion liquid, add the nickel particles (Mitsu Mining & Smelting Co., Ltd system, trade name " 2007SUS ", average grain diameter 50nm) of 2.25g as core material, obtain the particle being attached with core material.

Dilute above-mentioned dispersion liquid with 1200mL water further, add 4mL aqueous bismuth nitrate solution (concentration 1g/L) as plating stabilizer.Then, the mixed solution of the 450g/L nickelous sulfate of 120mL, 150g/L inferior sodium phosphate, 116g/L natrium citricum and 6mL plating stabilizer [aqueous bismuth nitrate solution (concentration 1g/L)] is added in this dispersion liquid by measuring pump with the interpolation speed of 81mL/ minute.Afterwards, stir until pH stablizes, confirm that the foaming of hydrogen stops.

Then, added the mixed solution of the 450g/L nickelous sulfate of 650mL, 150g/L inferior sodium phosphate, 116g/L natrium citricum and 35mL plating stabilizer (aqueous bismuth nitrate solution (concentration 1g/L)) by measuring pump with the interpolation speed of 27mL/ minute.Afterwards, stir until pH stablizes, confirm that the foaming of hydrogen stops.

Then, plating solution is filtered, by the cleaned screening of water.Afterwards, dry in the vacuum drier of 80 DEG C, obtain the conducting particles with nickel-phosphor alloy tunicle.To the conducting particles obtained, use ultrathin sectioning to cut out cross section by the mode near particle centre, use TEM device to observe with the multiplying power of 250,000 times.According to the cross-sectional image obtained, calculate thickness by the mean value of sectional area, result average film thickness is 101nm.

Operate similarly to Example 1 except using above-mentioned conducting particles, carry out the making of insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies and the evaluation of connection structural bodies.For the evaluation of conducting particles, carry out part evaluation similarly to Example 1.Show the result in table 5 and table 6.

In comparative example 1, implement palladium catalyst process and replace forming palladium particle and obtaining conducting particles.The conducting particles of comparative example 2 corresponds to the conducting particles of patent documentation 1.The conducting particles of comparative example 3 corresponds to the conducting particles of patent documentation 2.

[table 5]

[table 6]

Claims (20)

1. a conducting particles, is characterized in that, has resin particle and the metal level being configured in this resin particle surface,

Described metal level comprises palladium particle and nickel particles and has projection at outer surface,

Described nickel particles to be configured between described projection and described resin particle and coating described palladium particle.

2. conducting particles according to claim 1, is characterized in that, described palladium particle is configured between described nickel particles and described resin particle.

3. the conducting particles according to claims 1 or 2, is characterized in that, described palladium particle is configured in described resin particle side compared with described nickel particles.

4. the conducting particles according to claims 1 or 2, is characterized in that, described metal level comprises multiple described nickel particles,

Described in a described nickel particles and other adjacent with this nickel particles, nickel particles is separated.

5. the conducting particles according to claims 1 or 2, is characterized in that, described metal level comprises multiple described nickel particles,

Described multiple described nickel particles is configured on the direction vertical with the radial direction of conducting particles diffusedly.

6. the conducting particles according to claims 1 or 2, is characterized in that, described metal level comprises multiple described palladium particle,

Be configured on the direction vertical with the radial direction of conducting particles to described multiple described palladium particle diffusion.

7. the conducting particles according to claims 1 or 2, is characterized in that, the length of described palladium particle on the thickness direction of described metal level is more than or equal to 4nm.

8. the conducting particles according to claims 1 or 2, is characterized in that, described metal level has the 1st layer containing at least one be selected from the group that is made up of nickel and copper,

Described 1st layer is configured in described resin particle side compared with described palladium particle.

9. conducting particles according to claim 8, is characterized in that, described metal level has the 2nd layer containing nickel,

The described outer surface side being configured in described metal level is compared with described nickel particles for described 2nd layer with described 1st layer.

10. conducting particles according to claim 8, is characterized in that, described metal level has the 3rd layer containing at least one be selected from the group that is made up of noble metal and cobalt,

The described outer surface side being configured in described metal level is compared with described nickel particles for described 3rd layer with described 1st layer.

11. conducting particless according to claim 8, is characterized in that, described metal level has containing nickel the 2nd layer and containing at least one be selected from the group that is made up of noble metal and cobalt the 3rd layer,

The described outer surface side being configured in described metal level is compared with described nickel particles for described 3rd layer with described 1st layer,

Described 2nd layer is configured between described 3rd layer and described nickel particles.

12. conducting particless according to claims 1 or 2, it is characterized in that, when the average thickness of described metal level is designated as d, the interface of described metal level and described resin particle and the beeline of described palladium particle are more than or equal to 0.1 × d.

13. conducting particless according to claims 1 or 2, it is characterized in that, the interface of described metal level and described resin particle and the beeline of described palladium particle are more than or equal to 10nm.

14. 1 kinds of insulation-coated electroconductive particles, is characterized in that, the conducting particles had according to any one of claim 1 ~ 13 is coated to portion with the insulating properties at least partially of the described outer surface of the described metal level of this conducting particles coating.

15. 1 kinds of anisotropic conductive adhesives, is characterized in that, containing the conducting particles according to any one of claim 1 ~ 13 and bonding agent.

16. 1 kinds of anisotropic conductive adhesives, is characterized in that, containing insulation-coated electroconductive particles according to claim 14 and bonding agent.

17. anisotropic conductive adhesives according to claim 15 or 16, is characterized in that, for membranaceous.

18. 1 kinds of connection structural bodies, it is characterized in that, following formation: the 1st circuit member with the 1st circuit electrode is configured in the mode that described 1st circuit electrode is relative with described 2nd circuit electrode with the 2nd circuit member with the 2nd circuit electrode, make the anisotropic conductive adhesive according to any one of claim 15 ~ 17 between described 1st circuit member and described 2nd circuit member, and carry out heating and pressurizeing, thus described 1st circuit electrode is electrically connected with described 2nd circuit electrode.

19. 1 kinds of connection structural bodies, is characterized in that possessing: the 1st circuit member with the 1st circuit electrode, the 2nd circuit member with the 2nd circuit electrode and the connecting portion be configured between described 1st circuit member and described 2nd circuit member,

Under the state that described connecting portion is configured in an opposing fashion at described 1st circuit electrode and described 2nd circuit electrode, described 1st circuit member and described 2nd circuit member are connected to each other,

Under the state of the conducting particles distortion according to any one of claim 1 ~ 13, described 1st circuit electrode is electrically connected by described conducting particles with described 2nd circuit electrode.

20. 1 kinds of connection structural bodies, is characterized in that possessing: the 1st circuit member with the 1st circuit electrode, the 2nd circuit member with the 2nd circuit electrode and the connecting portion be configured between described 1st circuit member and described 2nd circuit member,

Under the state that described connecting portion is configured in an opposing fashion at described 1st circuit electrode and described 2nd circuit electrode, described 1st circuit member and described 2nd circuit member are connected to each other,

Under the state that insulation-coated electroconductive particles according to claim 14 is out of shape, described 1st circuit electrode is electrically connected by described conducting particles with described 2nd circuit electrode.