CN108604481A

CN108604481A - Insulation-coated electroconductive particles, anisotropic conductive adhesive and connection structural bodies

Info

Publication number: CN108604481A
Application number: CN201780010665.2A
Authority: CN
Inventors: 中川昌之; 赤井邦彦; 江尻芳则; 山崎将平; 渡边靖
Original assignee: Hitachi Chemical Co Ltd
Current assignee: Showa Denko Materials Co ltd
Priority date: 2016-02-10
Filing date: 2017-02-06
Publication date: 2018-09-28
Also published as: CN113345624A; WO2017138483A1; KR102649185B1; JPWO2017138483A1; TWI722109B; CN113345624B; JP6798509B2; TW201803960A; KR20180110019A

Abstract

Excellent insulating reliability can be provided offer in a kind of connection even if in fine circuit and the insulation-coated electroconductive particles of reliability are connected.Insulation-coated electroconductive particles (100a) have conducting particles (1) and are attached to multiple insulating particles (210) on the surface of conducting particles (1).The average grain diameter of conducting particles (1) is more than or equal to 1 μm and to be less than or equal to 10 μm.Insulating particle (210) includes the first insulating particle (210a) with the average grain diameter more than or equal to 200nm and less than or equal to 500nm and with more than or equal to 30nm and being less than or equal to the average grain diameter of 130nm and the second insulating particle (210b) for being made of silica.

Description

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

Technical field

The present invention relates to insulation-coated electroconductive particles, anisotropic conductive adhesive and connection structural bodies.

Background technology

Liquid crystal drive is installed on Glass for Liquid Crystal Display panel can be roughly divided into COG (Chip-on- with the mode of IC Glass, glass flip chip) it installs and both is installed with COF (Chip-on-Flex, membrane of flip chip).COG installation in, using containing There is the anisotropic conductive adhesive of conducting particles to be directly joined liquid crystal drive on glass panel with IC.On the other hand, In COF installations, liquid crystal drive IC is engaged on the flexible-belt with metal wiring, using each to different containing conducting particles They are engaged in glass panel by property conductive adhesive." anisotropy " described herein refers to being connected on compression aspect, And keep insulating properties on non-pressurised direction.

With the High precision of liquid crystal display in recent years, the metal coupling as the liquid crystal drive circuit electrode of IC is Thin space and leptoprosopy productization.Therefore, the conducting particles of anisotropic conductive adhesive flows out to adjacent circuit electrode Between and generate short circuit possibility.Especially the tendency is notable in COG installations.If conducting particles is flowed out to adjacent circuit electrode Between, then the conductive particle subnumber in the anisotropic conductive adhesive between metal coupling and glass panel is reduced.As a result, There is connection resistance between opposite circuit electrode to rise and causes the possibility of bad connection.If per unit area input be more than or Equal to 20,000/mm²Conducting particles, then such tendency is more notable.

As the method solved these problems, it is proposed that so that multiple insulating particles (seed) is attached to conducting particles (female Particle) surface and the method that forms compound particle.Such as proposed in patent document 1 and patent document 2 one kind make it is spherical Resin particle be attached to conducting particles surface method.Also disclose that one kind makes insulating particle deform in patent document 1 Method.It is proposed in patent document 3 and patent document 4 and a kind of being attached with hud typed resin particle on the surface of conducting particles Insulation-coated electroconductive particles.Propose that a kind of on the surface of conducting particles to be attached with hollow resin micro- in patent document 5 The compound particle of grain.

Even if proposing a kind of put into per unit area is greater than or equal to 70,000/mm²Conducting particles in the case of absolutely Edge reliability also excellent insulation-coated electroconductive particles.It proposes in patent document 6 a kind of in the attachment of the surface of conducting particles There are the first insulating particle and glass transition temperature less than the insulation-coated conductive particle of the second insulating particle of the first insulating particle Son.

Existing technical literature

Patent document

Patent document 1：No. 4773685 bulletins of Japanese Patent No.

Patent document 2：No. 3869785 bulletins of Japanese Patent No.

Patent document 3：No. 4686120 bulletins of Japanese Patent No.

Patent document 4：No. 4904353 bulletins of Japanese Patent No.

Patent document 5：No. 4391836 bulletins of Japanese Patent No.

Patent document 6：Japanese Unexamined Patent Publication 2014-17213 bulletins

Invention content

The subject that the invention solves

2,000 μm are less than for the area of metal coupling²It is stable in order to obtain for the connection of such fine circuit Reliability is connected, preferably increases the quantity of the conducting particles in anisotropic conductive adhesive.Based on such reason, also have When per unit area input be greater than or equal to 100,000/mm²Conducting particles.However, the connection for such fine circuit For, even if using the previous insulation-coated electroconductive particles described in Patent Documents 1 to 6, it is also difficult to obtain conducting reliability With the balance of insulating reliability, still there is room for improvement.

A kind of capable of being taken into account being designed to provide in the connection even if in fine circuit for an aspect of of the present present invention is excellent Insulating reliability and conducting reliability insulation-coated electroconductive particles.In addition, an aspect of of the present present invention is designed to provide A kind of anisotropic conductive adhesive and connection structural bodies having used above-mentioned insulation-coated electroconductive particles.

The method used for solving the problem

In order to solve the above problems, the reasons why the inventors of the present invention reduce above-mentioned insulating resistance value is studied.Special In method recorded in sharp document 1~5, it is known that the coating property for being coated on the insulating particle on conducting particles surface is low, even if every Unit area input is greater than or equal to 20,000/mm²Conducting particles in the case of, insulating resistance value is also easily reduced.In patent In document 6, the shortcomings that in order to make up Patent Documents 1 to 5, make the first insulating particle and glass transition temperature (Tg) less than the Second insulating particle of one insulating particle is attached to the surface of conducting particles.Even if as a result, per unit area input be more than or Equal to 70,000/mm²Conducting particles in the case of, also inhibit the reduction of insulating reliability.However it is known that in per unit face Product input is greater than or equal to 100,000/mm²Conducting particles in the case of, insulating reliability reduce.In patent document 6, The average grain diameter of one insulating particle is more than 200nm and is less than or equal to 500nm, and the average grain diameter of the second insulating particle is more than or waits In 50nm and it is less than or equal to 200nm.Herein, the Tg of the second insulating particle is down to 80~120 DEG C, so if will contain this absolutely The anisotropic conductive adhesive heating pressurization of edge coated electroconductive particles, then can melt and spread and disappear in resin.Therefore It is found that if the particle concentration of conducting particles improves, the part to disappear in the melting of the second insulating particle, adjacent conductive particle The metal surface of son is easy contact, therefore insulating reliability reduces.

The inventors of the present invention are further had made intensive studies based on such opinion, and as a result the inventors of the present invention, which are found that, makes With following insulation-coated electroconductive particles, the insulation-coated electroconductive particles by make to have more than or equal to 200nm and be less than or First insulating particle of the average grain diameter equal to 500nm and with being averaged more than or equal to 30nm and less than or equal to 130nm Grain size and the surface of conducting particles is attached to by the second insulating particle that silica forms and is formed.It will contain this as a result, When the anisotropic conductive adhesive heating pressurization of insulation-coated electroconductive particles, the second insulating particle for being made of silica It does not melt, prevents the metal surface of adjacent conducting particles from contacting.Thus, it is found that even if per unit area input be more than or Equal to 100,000/mm²Conducting particles in the case of, can also obtain excellent insulating reliability.In addition, it is found that due to second Insulating particle has the average grain diameter more than or equal to 30nm and less than or equal to 130nm, therefore connecting resistance will not be by this The obstruction of second insulating particle can obtain excellent conducting reliability in the connection in fine circuit.

Insulation-coated electroconductive particles involved by the form of the present invention have conducting particles and are attached to conductive particle sublist The average grain diameter of multiple insulating particles in face, conducting particles is greater than or equal to 1 μm and is less than or equal to 10 μm, and insulating particle includes The first insulating particle with the average grain diameter more than or equal to 200nm and less than or equal to 500nm and with being greater than or equal to 30nm and the second insulating particle for being less than or equal to the average grain diameter of 130nm and being made of silica.

The glass transition temperature of first insulating particle can be more than or equal to 100 DEG C and to be less than or equal to 200 DEG C.By This, temperature when heating pressurization according to the anisotropic conductive adhesive that will contain above-mentioned insulation-coated electroconductive particles is different, Sometimes the first insulating particle incomplete fusion.Therefore, the first insulating particle can give full play to function as insulation spacer.

Relative to the total surface area of conducting particles, the covering rate of the first insulating particle and the second insulating particle to conducting particles Can be 35~80%.Thereby, it is possible to obtain conducting reliability and the superior insulation-coated electroconductive particles of insulating reliability.

Conducting particles can have protrusion on its surface.In the conducting particles for making second insulating particle be attached to even surface In the case of, even if the average grain diameter of the second insulating particle is greater than or equal to 30nm and is less than or equal to 130nm, the second insulating particle The function as insulation spacer it is also high, therefore have the tendency that insulating reliability it is excellent but conducting reliability reduce.Therefore, lead to Crossing conducting particles has protrusion, can inhibit the reduction that reliability is connected.

It the surface of second insulating particle can also be coating by silicic acid anhydride agent.In order to make the first insulating particle and Two insulating particles adhere well to the surface of conducting particles, sometimes through cation property copolymer by the surface quilt of conducting particles It covers.At this point, by the second coating insulating particle of silicic acid anhydride agent compared with the second insulating particle without silicic acid anhydride It is easy to be negatively charged, conducting particles can be firmly adhered to by electrostatic.Therefore, as the function of insulation spacer height, energy Enough obtain the excellent insulation-coated electroconductive particles of insulating reliability.

The surface of second insulating particle can be selected from by the silicic acid anhydride agent of silazane system, siloxane-based silicic acid anhydride In the group of agent, the silicic acid anhydride agent of silane system and titanate esters system silicic acid anhydride agent composition.

Silicic acid anhydride agent can be selected from by hexa-methylene disilazane (HMDS), dimethyl silicone polymer (PDMS) and N, In the group of N- dimethylaminos trimethyl silane (DMATMS) composition.

The hydrophobization degree of the second insulating particle obtained by methanol titration can be greater than or equal to 30%.

Conducting particles can have nickeliferous the with the metal layer of resin particle and covering resin particle, metal layer One layer.In this case, when insulation-coated electroconductive particles are matched in anisotropic conductive adhesive, the anisotropy Conductive adhesive can take into account excellent conducting reliability and insulating reliability.

Metal layer can have the second layer being set on first layer, and the second layer can contain to be selected to be made of noble metal and cobalt Group in metal.It in this case, should when insulation-coated electroconductive particles are matched in anisotropic conductive adhesive Anisotropic conductive adhesive further can highly take into account excellent conducting reliability and insulating reliability.

Anisotropic conductive adhesive involved by another form of the present invention has above-mentioned insulation-coated electroconductive particles With the bonding agent for being dispersed with insulation-coated electroconductive particles.

According to the anisotropic conductive adhesive, the second insulating particle that the when of pressurizeing is made of silica is being heated not Melting, prevents the metal surface of adjacent conducting particles from contacting.Even if being greater than or equal to 100,000 in per unit area input as a result, A/mm²Conducting particles in the case of, can also obtain excellent insulating reliability.In addition, since the second insulating particle has Average grain diameter more than or equal to 30nm and less than or equal to 130nm, therefore connecting resistance will not be by second insulating particle Obstruction, excellent conducting reliability can be obtained in the connection in fine circuit.

In above-mentioned anisotropic conductive adhesive, bonding agent may be membranaceous.

Connection structural bodies involved by another form of the present invention has：The first circuit structure with the first circuit electrode Part, opposite with the first circuit member and second circuit component with second circuit electrode and by the first circuit member and the The above-mentioned anisotropic conductive adhesive of two circuit members bonding, the first circuit electrode and second circuit electrode are relative to each other, And it is electrically connected to each other by anisotropic conductive adhesive.

According to the connection structural bodies, by using above-mentioned anisotropic conductive adhesive by the first circuit member and second Circuit member is electrically connected to each other, and can take into account excellent conducting reliability and insulating reliability.

Connection structural bodies involved by another form of the present invention has：The first circuit structure with the first circuit electrode Part, it is opposite with the first circuit member and with second circuit electrode second circuit component and be configured at the first circuit member With the interconnecting piece between second circuit component, above-mentioned insulation-coated electroconductive particles, the first circuit electrode are dispersed in interconnecting piece It is relative to each other with second circuit electrode, and be electrically connected to each other by the insulation-coated electroconductive particles of deformation state.

According to the connection structural bodies, by using being scattered in the above-mentioned insulation-coated electroconductive particles of interconnecting piece by the first circuit Component and second circuit component are electrically connected to each other, and can take into account excellent conducting reliability and insulating reliability.

Invention effect

According to an aspect of the present invention, it can be taken into account being capable of providing in a kind of connection even if in fine circuit excellent The insulation-coated electroconductive particles of insulating reliability and conducting reliability.In addition, according to an aspect of the present invention, being capable of providing one kind The anisotropic conductive adhesive and connection structural bodies of above-mentioned insulation-coated electroconductive particles are used.

Description of the drawings

Fig. 1 is the schematic section for indicating the insulation-coated electroconductive particles involved by the 1st embodiment.

Fig. 2 is the schematic section for indicating the insulation-coated electroconductive particles involved by the 2nd embodiment.

Fig. 3 is the schematic section for indicating the insulation-coated electroconductive particles involved by the 3rd embodiment.

Fig. 4 is the schematic section for indicating the insulation-coated electroconductive particles involved by the 4th embodiment.

Fig. 5 is the schematic section for indicating the connection structural bodies involved by the 6th embodiment.

Fig. 6 is the schematic cross-section of an example of the manufacturing method for illustrating the connection structural bodies involved by the 6th embodiment Figure.

Fig. 7 is the SEM observed the particle of gained after the process d in the making of the conducting particles of embodiment 1 Image.

Fig. 8 is the SEM observed the particle of gained after the process d in the making of the conducting particles of embodiment 1 Image.

Fig. 9 is that the SEM observed the particle of gained in the process f in the making of the conducting particles of embodiment 1 schemes Picture.

Figure 10 is to observe the surface of the particle of gained in the process f in the making of the conducting particles of embodiment 1 SEM image.

Figure 11 is the schematic diagram for illustrating finishing processing.

Figure 12 is the schematic diagram of the method for the cut film for illustrating to make TEM measurement.

Figure 13 is the SEM image observed the insulation-coated electroconductive particles of gained in the process i of embodiment 1.

Figure 14 is the SEM image observed the insulation-coated electroconductive particles of gained in the process i of embodiment 1.

Figure 15 is the SEM image observed the insulation-coated electroconductive particles of gained in the process i of embodiment 7.

Figure 16 is the SEM image observed the insulation-coated electroconductive particles of gained in the process i of embodiment 7.

Figure 17 is the SEM image observed the surface of the insulation-coated electroconductive particles of gained in comparative example 1.

Specific implementation mode

Hereinafter, detaileding description of embodiments of the present invention while with reference to attached drawing.It should be noted that attached drawing In the same symbol is marked to same or equivalent part, and omit repeated explanation.In addition, up and down equal position relationships as long as no It illustrates, is just set as position relationship based on ... shown in the drawings.Further, the dimensional ratios of attached drawing are not limited to the ratio of diagram.

(the 1st embodiment)

Hereinafter, being illustrated to the insulation-coated electroconductive particles involved by the 1st embodiment.

<Insulation-coated electroconductive particles>

Fig. 1 is the schematic section for indicating the insulation-coated electroconductive particles involved by the 1st embodiment.It is shown in FIG. 1 exhausted Edge coated electroconductive particles 100a has：The resin particle 101 of the core of conducting particles 1 is constituted, the non-of resin particle 101 is attached to and leads Conductive inorganic particle 102, as covering resin particle 101 and the metal layer of non-conductive inorganic particulate 102 first layer 104, And it is attached to the insulating particle 210 of first layer 104.In the outer surface of first layer 104, forms reflection and be adhered to resin particle The protrusion 109 of the shape of 101 non-conductive inorganic particulate 102.Hereinafter, also will by resin particle 101 with it is non-conductive inorganic The particle that particle 102 is composed is known as compound particle 103, the grain being also composed of compound particle 103 and first layer 104 Son is known as conducting particles 1.First layer 104 is the conductive layer including at least metal.First layer 104 can be metal layer, can also For alloy-layer.Insulating particle 210 contains first with the average grain diameter more than or equal to 200nm and less than or equal to 500nm Insulating particle 210a and with more than or equal to 30nm and less than or equal to 130nm average grain diameter and be made of silica The second insulating particle 210b.

The average grain diameter of insulation-coated electroconductive particles 100a for example can be more than or equal to 1 μm, or be more than or Equal to 2 μm.The average grain diameter of insulation-coated electroconductive particles 100a for example can be less than or equal to 10 μm, or be less than or Equal to 5 μm.That is, the average grain diameter of insulation-coated electroconductive particles 100a is, for example, 1~10 μm.Pass through insulation-coated electroconductive particles The average grain diameter of 100a is in above range, to for example be led using the anisotropy containing insulation-coated electroconductive particles 100a Electrical bonding agent is come in the case of making connection structural bodies, electric conductivity is not easy the shape (height) of the electrode because of the connection structural bodies Deviation and change.The average grain diameter of insulation-coated electroconductive particles 100a can be set as the average value of gained in the following manner, I.e.：Arbitrary 300 insulation-coated conductions are carried out by using the observation of scanning electron microscope (hereinafter referred to as " SEM ") The particle size determination of particle.It is insulation-coated since insulation-coated electroconductive particles 100a has protrusion 109 and insulating particle 210 The grain size of conducting particles 100a be set as using in the image captured by SEM the circle external with insulation-coated electroconductive particles 100a it is straight Diameter.The average grain diameter of insulation-coated electroconductive particles 100a is measured in order to improve precision, can use the cities such as Coulter-counter The device sold.It in this case, can be accurately if carrying out the particle size determination of 50000 insulation-coated electroconductive particles Measure average grain diameter.Such as COULER MULTISIZER II (Beckman Kurt Co. Ltd. system, trade name) can be utilized 50000 insulation-coated electroconductive particles are measured, to measure the average grain diameter of insulation-coated electroconductive particles 100a.

The monodisperse rate of insulation-coated electroconductive particles 100a can be more than or equal to 96.0%, or be more than or wait In 98.0%.Monodisperse rate by insulation-coated electroconductive particles 100a is in above range, to can for example be tried in moisture absorption High insulating reliability is obtained after testing.50,000 conductions can be used for example in the monodisperse rate of insulation-coated electroconductive particles 100a Particle is measured by COULER MULTISIZER II (Beckman Kurt Co. Ltd. system, trade name).

Resin particle 101 is made of organic resin.As organic resin, can enumerate：Polymethyl methacrylate, polypropylene Sour methyl esters etc. (methyl) acrylic resin；The vistanexes such as polyethylene, polypropylene；Polyisobutylene resin；Polybutadiene Deng.As resin particle 101, crosslinking (methyl) acrylic particles, crosslinked polystyrene particle etc. can also be used organic tree Particle obtained by fat crosslinking.Resin particle can be made of a kind of of above-mentioned organic resin, can also be by the two of above-mentioned organic resin It plants combination of the above and constitutes.Organic resin is not limited to above-mentioned resin.

Resin particle 101 is spherical.The average grain diameter of resin particle 101 for example can be more than or equal to 1 μm and to be less than Or it is equal to 10 μm.The average grain diameter of resin particle 101 for example can be more than or equal to 1 μm, or be greater than or equal to 2 μ m.Average grain diameter by resin particle 101 is that can be sufficiently ensured the deflection of conducting particles 1 more than or equal to 1 μm.Resin particle The average grain diameter of son 101 for example can be less than or equal to 10 μm, or be less than or equal to 5 μm.Pass through resin particle 101 Average grain diameter be can inhibit the deviation of grain size less than or equal to 10 μm, and inhibit conducting particles 1 connection resistance value it is inclined Difference.The average grain diameter of resin particle 101 is set as the average value of gained in the following manner, i.e.,：Come by using the observation of SEM Carry out the particle size determination of arbitrary 300 resin particles.

Sometimes to 101 coating cation property copolymer of resin particle as surface treatment.As the cation property copolymer, The high-molecular compound of the functional group with positively chargeable as polyamine etc. can usually be enumerated.Cation property copolymer is for example It can be selected from by polyamine, polyimides, polyamide, diallyl dimethyl ammoniumchloride, polyvinylamine, polyvinylpyridine, gather In the group of vinyl imidazole and polyvinylpyrrolidone composition.From charge density height, with negative electrical charge surface and material Binding force it is strong from the viewpoint of, preferably polyimides, more preferably polyethyleneimine.Cation property copolymer is preferably soluble in The mixed solution of water or water and organic solvent.The molecular weight of cation property copolymer is according to used cation property copolymer Type and change, for example, 500~200000 degree.

By adjusting the type and molecular weight of cation property copolymer, non-conductive inorganic particulate 102 can be controlled to tree The covering rate of fat granule 101.Specifically, passing through the coating tree of the high cation property copolymer of the charge density such as polyethyleneimine In the case of fat granule 101, there is covering rate (the 102 coated with resin grain of non-conductive inorganic particulate of non-conductive inorganic particulate 102 Son 101 ratio) improve tendency.On the other hand, passing through the low cation property copolymer coated with resin particle of charge density In the case of 101, have the tendency that the covering rate of non-conductive inorganic particulate 102 reduces.In addition, in point of cation property copolymer In the case that son amount is big, have the tendency that the covering rate of non-conductive inorganic particulate 102 improves, in the molecule of cation property copolymer Measure it is small in the case of, have the tendency that non-conductive inorganic particulate 102 covering rate reduce.

Cation property copolymer can also be substantially free of alkali metal (Li, Na, K, Rb, Cs) ion, alkaline-earth metal (Ca, Sr, Ba, Ra) ion and halide ion (fluorine ion, chlorion, bromide ion, iodide ion).In this case, quilt can be inhibited It is covered with the electromigration and corrosion of the resin particle 101 of cation property copolymer.

By resin particle 101 of the cation property copolymer before coating surface have selected from hydroxyl, carboxyl, alkoxy, Functional group in glycidyl and alkoxy carbonyl.Cation property copolymer is easily adsorbed at the table of resin particle 101 as a result, Face.

<Non-conductive inorganic particulate>

Non-conductive inorganic particulate 102 is the particle of the core as protrusion 109, such as is adhered to resin by electrostatic force Particle 101.The shape of non-conductive inorganic particulate 102 is not particularly limited, and is ellipsoid, sphere, hemisphere, generally oblong Body, substantially sphere, substantially hemisphere etc..Wherein, preferably ellipsoid or sphere.

The material for forming non-conductive inorganic particulate 102 can be harder than forming the material of first layer 104.Conductive particle as a result, Son is easy to pierce through electrode etc., and electric conductivity improves.That is, idea is：Not conducting particles is made integrally to be hardened, but makes conducting particles A part is hardened.For example, the Mohs' hardness for forming the material of non-conductive inorganic particulate 102 is more than the gold for forming first layer 104 The Mohs' hardness of category.Specifically, the Mohs' hardness for forming the material of non-conductive inorganic particulate 102 is greater than or equal to 5.And And it forms the Mohs' hardness of the material of non-conductive inorganic particulate 102 and forms the difference of the Mohs' hardness of the metal of first layer 104 1.0 can be greater than or equal to.In the case where first layer 104 contains various metals, the Mohs of non-conductive inorganic particulate 102 is hard Degree can also be higher than the Mohs' hardness of all metals.As concrete example, the material for forming non-conductive inorganic particulate 102 can be selected from By silica (silica (SiO₂), Mohs' hardness 6~7), zirconium oxide (Mohs' hardness 8~9), aluminium oxide (Mohs' hardness 9) and in the group of diamond (Mohs' hardness 10) composition.For example, can be formed according on the surface of non-conductive inorganic particulate 102 The mode of hydroxyl (- OH) is coated with silicic acid anhydride agent.The silicic acid anhydride agent can with real to the second insulating particle 210b Silicic acid anhydride agent used in the silicic acid anhydride applied is identical (details is aftermentioned).The value of above-mentioned Mohs' hardness is with reference to " change Learn voluminous dictionary " (Kyoritsu Publishing Co., Ltd. distribution).Silicon dioxide granule can be used for example as non-conductive inorganic particulate 102.The grain size of silicon dioxide granule is preferably through control.

The average grain diameter of non-conductive inorganic particulate 102 is, for example, the average grain of 25nm~120nm or resin particle 101 1/120~1/10 degree of diameter.The average grain diameter of non-conductive inorganic particulate 102 may be 30nm~100nm, or 35nm~80nm.If the average grain diameter of non-conductive inorganic particulate 102 is greater than or equal to 25nm, the protrusion of first layer 104 109 easily become appropriate size, have the tendency that low resistance.If the average grain diameter of non-conductive inorganic particulate 102 is less than Or be equal to 120nm, then aftermentioned electroless nickel plating process, electroless nickel plating preceding processing etc. in the non-conductive inorganic particulate 102 is not easily to fall off.The quantity of protrusion 109 becomes abundant as a result, has the tendency that easy low resistance.Moreover, first layer 104 Coating metal becomes metallic foreign body on the substance made of the non-conductive inorganic particulate 102 by falling off agglomerates.Sometimes the gold Belong to foreign matter be attached to resin particle 101 again and the long protrusion that is formed as exception precipitation portion (such as length is more than 500nm's Protrusion).In this case, the main reason for becoming the insulating reliability of insulation-coated electroconductive particles 100a sometimes reduces.Into one The main reason for step, above-mentioned metallic foreign body itself becomes insulating reliability reduction sometimes.It is therefore preferable that inhibiting non-conductive inorganic Particle 102 falls off from resin particle 101.The grain size of non-conductive inorganic particulate 102 is for example by using the specific surface area of BET method Scaling method or low-angle scattering of X-rays method measure.

Non-conductive inorganic particulate 102 to the bonding of resin particle 101 can use organic solvent or water with it is water-soluble The mixed solution of organic solvent carries out.As the water-soluble organic solvent that can be used, can enumerate methanol, ethyl alcohol, propyl alcohol, Acetone, dimethylformamide, acetonitrile etc..By by the coating non-conductive inorganic particulate 102 of silicic acid anhydride agent, by cationic Polymer coated with resin particle 101, to which non-conductive inorganic particulate 102 can also be by electrostatic force with resin particle 101 Engagement.

The metal layer of coating compound particle 103 can be single layer structure, or with multiple layers of stepped construction. In the case that the metal layer of 1st embodiment is the first layer 104 of single layer structure, the first layer 104 or coating.As First layer 104 can be to contain conduction of the nickel as principal component from the viewpoint of cost, conducting reliability and corrosion resistance Layer.If it is considered that the flatness for being set to the electrode on glass in recent years can also be according to it then in order to improve conducting reliability There is the mode of protrusion 109 first layer 104 is arranged on surface.

The thickness of first layer 104 is, for example, 40nm~200nm.If the thickness of first layer 104 is in above range, i.e., Make compressed in conducting particles 1, can also inhibit the rupture of first layer 104.In addition, can be incited somebody to action by first layer 104 The surface of compound particle 103 is fully coating.Thereby, it is possible to make non-conductive inorganic particulate 102 be bonded to resin particle 101, And inhibit falling off for non-conductive inorganic particulate 102.As a result, it is possible to the conducting particles 1 to gained to be formed to high-density one by one The protrusion 109 of excellent in shape.The thickness of first layer 104 may be more than or equal to 60nm.The thickness of first layer 104 can be Less than or equal to 150nm, or be less than or equal to 120nm.First layer 104 can be single layer structure, or stacking Structure.In present embodiment, first layer 104 has double-layer structure.

The thickness of first layer 104 is by use the photo captured by the transmission electron microscope (hereinafter referred to as " TEM ") It calculates.As concrete example, the conductive particle is cut out in a manner of by the immediate vicinity of conducting particles 1 first with ultrathin sectioning The section of son 1.Then, cut out section is observed with 250,000 times of multiplying power using TEM and obtains image.It then, can be by basis The sectional area of the first layer 104 of the image estimation of gained and calculate the thickness of first layer 104.At this point, being difficult to differentiate between first layer 104, in the case of resin particle 101 and non-conductive inorganic particulate 102, pass through the incidental energy dispersion-type X-ray inspections of TEM It surveys device (hereinafter referred to as " EDX ") and carries out constituent analysis.First layer 104, resin particle 101 and non-conductive are clearly distinguished as a result, Inorganic particulate 102 only calculates the thickness of first layer 104.The thickness of first layer 104 is set as being averaged for the thickness of 10 conducting particles Value.

First layer 104 can also contain other than the metal using nickel as principal component selected from the group being made of phosphorus and boron At least one of.Thereby, it is possible to improve the hardness of nickeliferous first layer 104, when easily conducting particles 1 can be compressed Conducting resistance remain low-level.First layer 104 can also contain the metal of the eutectoid together with phosphorus or boron.104 institute of first layer The metal contained is, for example, cobalt, copper, zinc, iron, manganese, chromium, vanadium, molybdenum, palladium, tin, tungsten and rhenium.First layer 104 is by containing nickel and upper Metal is stated, the hardness of first layer 104 can be improved.Even if compressed in insulation-coated electroconductive particles 100a as a result, Also the part (protrusion 109) for being formed in 102 top of non-conductive inorganic particulate can be inhibited to be subject to crushing.Above-mentioned metal can also contain There is the tungsten with high rigidity.As the constituent material of first layer 104, such as the preferably combination of nickel (Ni) and phosphorus (P), nickel (Ni) The combination of combination, nickel (Ni) and tungsten (W) and boron (B) with boron (B) and the combination of nickel (Ni) and palladium (Pd).

In the case of forming first layer 104, sodium hypophosphite can be used for example by aftermentioned electroless nickel plating Equal phosphorus-containing compounds are as reducing agent.In this case, phosphorus eutectoid can be made, the first layer containing nickel-phosphor alloy can be formed 104.As reducing agent, the boron-containing compounds such as dimethyamine borane, sodium borohydride, potassium borohydride can also be used.In the situation Under, boron eutectoid can be made, the first layer 104 containing nickel-boron alloy can be formed.The hardness of nickel-boron alloy is closed higher than nickel-phosphor Gold.Therefore, in the case where using boron-containing compound as reducing agent, even if compressed in insulation-coated electroconductive particles 100a In the case of, it can also inhibit the protrusion 109 for being formed in 102 top of non-conductive inorganic particulate to be subject to crushing.

First layer 104 can also have the concentration (content) of nickel raised dense with the surface far from compound particle 103 Spend gradient.By such composition, even if can be kept if insulation-coated electroconductive particles 100a is compressed low Conducting resistance.The concentration gradient can be continuous, can not also be continuous.Concentration gradient in nickel is discontinuous, Ke Yi Multiple layers that the content of the surface setting nickel of compound particle 103 is different are used as first layer 104.In this case, it is set to separate The concentration of the nickel of the layer of 103 side of compound particle increases.

The content of nickel in first layer 104 increases on the thickness direction of first layer 104 with close to surface.First layer The content of nickel in the layer of 104 surface side is, for example, 99 mass of mass %~97 %.The thickness of the layer of above-mentioned surface side is for example For 5~60nm.The thickness of this layer can be 10~50nm, or 15~40nm.It is big in the thickness of the layer of above-mentioned surface side In or equal in the case of 5nm, having the tendency that the connection resistance value reduction of first layer 104.On the other hand, in the layer of surface side In the case that thickness is less than or equal to 60nm, have the tendency that the monodisperse rate of conducting particles 1 further increases.Therefore, first The content of nickel in the layer of the surface side of layer 104 be 99 mass of mass %~97 % and the thickness of the layer of above-mentioned surface side be 5~ It in the case of 60nm, is easy to make the more low resistance of first layer 104, is easy to further suppress 1 mutual cohesion of conducting particles, from And obtain high insulating reliability.

Can also be on the thickness direction of first layer 104, the content that nickel is formed in 103 side of compound particle is less than or equal to 97 The layer of quality %.The nickel content of the layer of 103 side of compound particle can be less than or equal to 95 mass %, might be less that or be equal to 94 mass %.The thickness of the layer of 103 side of compound particle can be greater than or equal to 20nm, can also be greater than or equal to 40nm, also may be used To be greater than or equal to 50nm.Especially if 103 side of compound particle of first layer 104 be greater than or equal to 20nm formation be less than or Equal to the layer of 94 mass %, then conducting particles 1 is not easily susceptible to magnetic influence each other, has the inhibition conducting particles 1 mutual solidifying Poly- tendency.

The content of element species and the element in first layer 104 for example can cut out conductive particle by using ultrathin sectioning Behind the section of son, measured by the incidental EDX of TEM carry out constituent analysis.

In present embodiment, first layer 104 is formed by electroless nickel plating.In this case, electroless nickel plating solution contains There is water-soluble nickel compound.Electroless nickel plating solution can also further contain selected from by stabilizer (such as bismuth nitrate), complexing agent, At least one of the group of reducing agent, pH adjusting agent and surfactant composition compound.

As water-soluble nickel compound, can use：The water solubility nickel inorganic salts such as nickel sulfate, nickel chloride, ortho phosphorous acid nickel； Water solubility nickel organic salt such as nickel acetate, malic acid nickel etc..Water-soluble nickel compound, which can be used alone, one kind or is applied in combination two kinds More than.

The concentration of water-soluble nickel compound in electroless nickel plating solution is preferably 0.001~1mol/L, and more preferably 0.01 ~0.3mol/L.By the precipitation speed that in a concentration of above range of water-soluble nickel compound, can fully obtain plating envelope Degree, and the viscosity of plating solution can be inhibited to become excessively high to improve the uniformity of nickel precipitation.

It is specific enumerable as long as being functioned as complexing agent as complexing agent：Ethylenediamine tetra-acetic acid；Ethylenediamine The sodium salt (such as 1- sodium salts, 2- sodium salts, 3- sodium salts and 4- sodium salts) of tetraacethyl；Ethylenediamine triacetic acid；Nitro tetraacethyl, its alkali Salt；Glycuronic acid (glyconic acid), tartaric acid, gluconate (gluconate), citric acid, gluconic acid (gluconic Acid), the alkali salt (such as sodium salt) of succinic acid, pyrophosphoric acid, Glycolic acid, lactic acid, malic acid, malonic acid, these acid；Triethanolamine Gluconic acid (γ)-lactone etc..Complexing agent can also use material other than the above.A kind of complexing agent or combination that can be used alone makes With two or more.

The concentration of complexing agent in electroless nickel plating solution is preferably generally 0.001~2mol/L, more preferably 0.002~ 1mol/L.By the way that in a concentration of above range of complexing agent, the precipitation and plating solution of the nickel hydroxide in plating solution can be inhibited Decomposition and obtain the sufficient speed of separating out of plating envelope, and the viscosity of plating solution can be inhibited to become excessively high to improve The uniformity that nickel is precipitated.The concentration of complexing agent can also be different according to type.

As reducing agent, well known reducing agent used in electroless nickel plating solution can be used.As reducing agent, can arrange It lifts：Sodium hypophosphite, ortho phosphorous acid potassium grade phosphorons acid compound；The boron hydrogen such as sodium borohydride, potassium borohydride, dimethyamine borane Compound；Hydrazine etc..

The concentration of reducing agent in electroless nickel plating solution is preferably generally 0.001~1mol/L, more preferably 0.002~ 0.5mol/L.If in a concentration of above range of reducing agent, can fully obtain the reduction speed of the nickel ion in plating solution Degree, and inhibit the decomposition of plating solution.It, can also be different according to the type of reducing agent about the concentration of reducing agent.

As pH adjusting agent, it can be mentioned, for example the pH adjusting agents of acid pH adjusting agent and alkalinity.As acid pH tune Agent is saved, can be enumerated：Hydrochloric acid；Sulfuric acid；Nitric acid；Phosphoric acid；Acetic acid；Formic acid；Copper chloride；The iron compounds such as ferric sulfate；Alkali metal chlorination Object；Ammonium persulfate；Aqueous solution containing more than one these compounds；Chromic acid, chromic acid-sulfuric acid, chromic acid-hydrofluoric acid, dichromic acid, The aqueous solution etc. containing Cr VI of the acidity such as dichromic acid-fluoboric acid.As the pH adjusting agent of alkalinity, can enumerate：Sodium hydroxide, The hydroxide of the alkali metal such as potassium hydroxide, sodium carbonate；The hydroxide of alkaline-earth metal；Ethylenediamine, methylamine, 2- ethylaminoethanols etc. Compound containing amino；Solution etc. containing more than one these compounds.

As surfactant, cationic surfactant, anion surfactant, amophoteric surface active can be used Agent, nonionic surfactant, these surfactants mixture etc..

By above-mentioned electroless nickel plating come in the case of forming first layer 104, can also be pre- to compound particle 103 advanced The processing of row palladium catalystization is used as pre-treatment.Palladium catalystization processing can be carried out using well known method.Such as it can pass through Used the catalyst processing method for the catalyst treatment fluid for being referred to as alkaline kind of liquid (seeder) or acid kind of liquid come into The above-mentioned pre-treatment of row.

On the surface (the specifically surface of first layer 104) of conducting particles 1, it is formed with the non-conductive inorganic particulate of reflection The protrusion 109 of 102 shape.Protrusion 109 comprising non-conductive inorganic particulate 102 and first layer 104 (such as is included into composition The protrusion 109 of the first layer 104 of the outer surface of conducting particles 1) diameter (outer diameter) is classified as less than the first protrusion of 100nm, straight Second protrusion and diameter of the diameter more than or equal to 100nm and less than 200nm are greater than or equal to 200nm and are less than or equal to 350nm Third protrusion.In this case, the ratio of the first protrusion in total bump count can be less than 80%, second in total bump count The ratio of protrusion can be 20~80%, and the ratio of the third protrusion in total bump count can be less than or equal to 10%.Total protrusion The ratio of the first protrusion in number might be less that 60%, the ratio of the second protrusion in total bump count may be 40~ 70%, the ratio of the third protrusion in total bump count might be less that or be equal to 5%.The first protrusion~third in total bump count The ratio of protrusion is insulation-coated electroconductive particles 100a in above range as being matched with anisotropic conductive adhesive In insulation-coated electroconductive particles when, can more highly take into account excellent conducting reliability and insulating reliability.It is so-called " total prominent Play number ", refer to the total number of protrusion existing in the concentric circles of 1/2 diameter of the diameter with conducting particles.

The area of the protrusion 109 of conducting particles 1 refers to the diameter with conducting particles 1 in the frontal plane of projection of conducting particles 1 1/2 diameter concentric circles in the area of protrusion 109 (separated by the recess portion between adjacent protrusion 109 each prominent Play the area of 109 profile).The diameter (outer diameter) of protrusion 109 refers to having conductive particle in the frontal plane of projection for conducting particles 1 Existing protrusion 109 is calculated in the concentric circles of 1/2 diameter of the diameter of son 1, is had identical as the area of the protrusion 109 Area positive diameter of a circle.Specifically, to being parsed with the image obtained by 30,000 times of observation conducting particles 1 as SEM, The profile for delimiting protrusion 109, so as to find out the area of each protrusion.

Protrusion 109 can also be included in 1/ of the diameter with conducting particles in the frontal plane of projection of conducting particles as described below In the concentric circles of 2 diameters.Number of projection in the concentric circles for example can be more than or equal to 50, or be more than or Equal to 70, or be greater than or equal to 90.Number of projection in the concentric circles for example can be less than or equal to 250 It is a, or to be less than or equal to 220, or to be less than or equal to 200.Number of projection in the concentric circles is In the case of in above range, the electrode is crimped each other between opposite electrode making insulation-coated electroconductive particles 100a When connection, substantially low conducting resistance can be readily available.

The area ratio (covering rate) of protrusion 109 for example can be more than or equal to 60%, or be greater than or equal to 80%, or be greater than or equal to 90%.If the covering rate of protrusion 109 is greater than or equal to 60%, even if will be conductive In the case that particle 1 is placed under high humidity, conducting resistance is not easy to increase.About the area ratio (covering rate) of protrusion 109, can incite somebody to action The gross area of the concentric circles of 1/2 diameter of the diameter with conducting particles 1, will as denominator in the frontal plane of projection of conducting particles 1 The summation of the area of protrusion 109 in the concentric circles of 1/2 diameter of the diameter with conducting particles 1 is as molecule, with except calculation Percentage indicates.

As the method for forming protrusion 109 on the surface of conducting particles 1 (the specifically surface of first layer 104), can arrange Citing such as the method being precipitated extremely using plating and the method using core material.In view of shape for lugs, preferably Using the method for using core material.Core material conductive material such as can be nickel, carbon, palladium, gold, or plastics, titanium dioxide The non-conductive materials such as silicon, titanium oxide.If core material uses non-magnetic material, have in the stage of coating insulating particle 210 Magnetic cohesion is not generated, is easy the tendency for making insulating particle 210 be attached to conducting particles 1.Therefore, used as ferromagnetism material In the case that the nickel of material is as core material, core material can also further contain the non-magnetic materials such as phosphorus.In the 1st embodiment, make For the forming method of protrusion 109, using by non-conductive inorganic particulate 102 as the method for core material.Thereby, it is possible to control projections 109 size can form the protrusion 109 with excellent in shape, therefore can take into account insulating reliability and conducting reliability.Separately Outside, by using non-conductive inorganic particulate 102, even if can inhibit if in the case where substantially compressing conducting particles 1 The first layer 104 for being formed in the composition protrusion 109 on the top of non-conductive inorganic particulate 102 is subject to crushing.Thus, for example even if In the case of using silica as insulating particle 210, also it can inhibit first in the case where crimping is connected to electrode etc. The avalanche of layer 104, obtains low conducting resistance.

As described above, insulating particle 210 contains with the average grain more than or equal to 200nm and less than or equal to 500nm First insulating particle 210a of diameter and with more than or equal to 30nm and less than or equal to 130nm average grain diameter and by two Second insulating particle 210b of silica composition.

(the first insulating particle)

The average grain diameter of first insulating particle 210a is greater than or equal to 200nm and is less than or equal to 500nm.In the first insulation In the case that the average grain diameter of particle 210a is greater than or equal to 200nm, the first insulating particle 210a is filled as insulation spacer Divide and function, superior insulating reliability can be obtained.If the average grain diameter of the first insulating particle 210a is less than or waits In 500nm, then the first insulating particle 210a can be made to be easily attached to conducting particles 1.

The shape of first insulating particle 210a is not particularly limited, and is ellipsoid, sphere, hemisphere, generally oblong body, big Cause sphere, substantially hemisphere etc..In these shapes, preferably ellipsoid or sphere.

The deviation (hereinafter also referred to CV) of the grain size of first insulating particle 210a for example can be less than or equal to 10%, Can be less than or equal to 3%.In the case where CV is less than or equal to 10%, conducting reliability can be improved and insulation is reliable Property.So-called CV in this specification refers to the standard deviation of grain size expressed as a percentage relative to the ratio between average grain diameter.

In the case where conducting particles 1 has protrusion 109, from being easy that the first insulating particle 210a is made to be attached to conducting particles From the viewpoint of 1, it is generally desirable to which the average grain diameter of the first insulating particle 210a is more than the diameter of protrusion 109.

First insulating particle 210a is, for example, the particle being made of organic high molecular compound.As organic polymer chemical combination Object, it is however preferred to have the compound of thermal softening.As organic high molecular compound, can specifically use：Polyethylene, ethylene- Vinyl acetate copolymer, ethylene-(methyl) acrylic copolymer, ethylene-(methyl) acrylate copolymer, polyester, polyamides Amine, polyurethane, polystyrene, styrene diethylene benzene copoly mer, styreneisobutylene copolymer, styrene-butadiene Copolymer, styrene-(methyl) acrylic copolymer, ethylene-propylene copolymer, (methyl) acrylic ester rubber, styrene- Ethylene-butene copolymer, phenoxy resin, solid epoxy resin etc..Organic high molecular compound can be used alone a kind of or combine Using two or more.

It, can also be by the copolymer of the monomer containing silicon and acrylic acid from the viewpoint of taking into account flexibility and solvent resistance Equal organic-inorganics mixed type particle is used as the first insulating particle 210a.

As the manufacturing method of the first insulating particle 210a, it can be mentioned, for example emulsifier-free emulsion polymerizations.

In order to improve reliability, the first insulating particle 210a may be the copolymer using following monomer composition, on It states monomer composition and contains the alkoxy silane with double bond between carbon.As the alkoxy silane, can enumerate：3- methacryls Oxygroup hydroxypropyl methyl dimethoxysilane, 3- methacryloxypropyl trimethoxy silanes, 3- methacryloxies third Ylmethyl diethoxy silane, 3- methacryloxypropyls, 3- acryloxypropyl trimethoxies Silane etc..Wherein, it is preferable to use 3- methacryloxypropyl trimethoxy silanes.Relative to monomer composition total amount, tool It is preferably 0.5 mole of %~5 mole % to have the content of the alkoxy silane of double bond between carbon.

Radical polymerization initiator used, can enumerate when as the first insulating particle 210a of manufacture：Benzoyl peroxide, T-butyl perbenzoate, potassium peroxydisulfate, 1,1- azos bis- (hexamethylene -1- formonitrile HCNs), 2,2- azodiisobutyronitriles etc..Free radical polymerization Initiator is not limited to this.

If carrying out emulsifier-free emulsion polymerization using hydrophilic monomer, the first insulating particle can be more stably synthesized The control of 210a, grain size also become easier to.As the concrete example of hydrophilic monomer, sodium styrene sulfonate, methyl can be enumerated Acrylic acid, Sodium methacrylate etc..

Relative to monomer composition total amount, the content of hydrophilic monomer is preferably 0.1 mole of %~30 mole %.

The glass transition temperature (hereinafter also referred to Tg) of first insulating particle 210a can by the concentration of crosslinking agent or The ingredients such as alkyl acrylate are added to adjust.By adding crosslinking agent, have the tendency that the Tg of the first insulating particle 210a rises. In addition, the ratio by improving the ingredient with low Tg such as alkyl acrylate, can reduce the Tg of the first insulating particle 210a. The Tg of first insulating particle 210a is, for example, 100 DEG C~200 DEG C.In the present embodiment, using differential scanning calorimetry (DSC) (DSC, Such as Perkinelmer Inc.'s system, trade name " DSC-7 "), it is in sample size 10mg, 5 DEG C/min of heating rate, measurement atmosphere The glass transition temperature of each particle comprising the first insulating particle 210a is measured under conditions of air.

Crosslinking agent makes the Tg of the first insulating particle 210a rise, and makes the solvent resistance of the first insulating particle 210a and resistance to It is hot also to improve.As the concrete example of crosslinking agent, divinylbenzene, diacrylate etc. can be enumerated.From the sight of synthesis easiness Point considers, such as relative to all monomers of the first insulating particle 210a, the content of crosslinking agent is 0 mole of %~10 mole %. If further considering characteristic, the content of crosslinking agent may be 1 mole of %~5 mole %.

The method of emulsifier-free emulsion polymerization is well known to those skilled in the art.Such as by the monomer, water and polymerization of synthesis Initiator is added into flask, in a nitrogen atmosphere on one side with 100~500min^-1The mixing speed of (100~500rpm) carries out Stirring carries out above-mentioned emulsion polymerization on one side.Such as the water relative to solvent, the content of all monomers is 1 matter of mass %~20 Measure %.

The polymerization temperature of emulsifier-free emulsion polymerization is, for example, 40 DEG C~90 DEG C, and polymerization time is 2 hours~15 hours.It is appropriate Polymerization temperature and time can properly select.

(the second insulating particle)

The average grain diameter of second insulating particle 210b is greater than or equal to 30nm and is less than or equal to 130nm.Second insulation grain The average grain diameter of sub- 210b can also be more than 25nm, might be less that or be equal to 100nm.In being averaged for the second insulating particle 210b In the case that grain size is greater than or equal to 30nm, the second insulating particle 210b is fully functioned as insulation spacer, can Obtain superior insulating reliability.In the case where the average grain diameter of the second insulating particle 210b is less than or equal to 130nm, energy The second insulating particle 210b is enough set to be easily attached to conducting particles 1.

The shape of second insulating particle 210b is not particularly limited, for example, ellipsoid, sphere, hemisphere, generally oblong Body, substantially sphere, substantially hemisphere etc..Wherein, preferably ellipsoid or sphere.

The deviation (hereinafter also referred to CV) of the grain size of second insulating particle 210b for example can be less than or equal to 10%, Can be less than or equal to 3%.In the case where the CV of the second insulating particle 210b is less than or equal to 10%, conducting can be improved Reliability and insulating reliability.

Silica (SiO can also be used₂) particle is as the second insulating particle 210b.The grain size of silicon dioxide granule is excellent Choosing have passed through control.It as the type of silicon dioxide granule, is not particularly limited, colloidal silicon dioxide, gas phase dioxy can be enumerated SiClx, sol-gal process silica etc..Silicon dioxide granule can be used alone, and can also be used in mixed way two or more.Make For silicon dioxide granule, commercially available product can be used, composite can also be used.

As the manufacturing method of colloidal silicon dioxide, well known method can be enumerated.It is specific enumerable：" sol-gel method The hydrolysis using alkoxy silane described in page 154~156 of science " (making flower Ji husband to write, the distribution of AGNE Cheng Feng societies) Method；The mixture by methyl silicate or methyl silicate and methanol described in Japanese Unexamined Patent Publication 11-60232 bulletins is added dropwise to Including the in the mixed solvent of water, methanol and ammonia or ammonia and ammonium salt, the method for making methyl silicate be reacted with water；Japanese Unexamined Patent Publication Base catalyst after alkyl silicic acids salt hydrolysis, will be added using acid catalyst and being added described in 2001-48520 bulletins Heat carries out the polymerization of silicic acid and makes the method for particle growth；Described in Japanese Unexamined Patent Publication 2007-153732 bulletins in alkoxy The method etc. of particular kind of hydrolyst is used when the hydrolysis of silane with specific amount.Alternatively, can also enumerate by right Sodium metasilicate carries out ion exchange and the method that is manufactured.As the commercially available product of colloidal silicon dioxide water-dispersed, can enumerate： Snowtex, Snowtex UP (being Nissan Chemical Ind Ltd's system, trade name), the serial (Japan of Quartron PL Learn Industrial Co., Ltd's system, trade name) etc..

As the manufacturing method of aerosil, can enumerate：Using silicon tetrachloride is gasified and makes it in oxyhydrogen flame The known method of the gas phase reaction of burning.Further, aqueous dispersions can be made using well known method in aerosil.As The method that aqueous dispersions are made, it can be mentioned, for example Japanese Unexamined Patent Publication 2004-43298 bulletins, Japanese Unexamined Patent Publication 2003-176123 public affairs Method described in report, Japanese Unexamined Patent Publication 2002-309239 bulletins etc..It is examined from the viewpoint of the insulating reliability of aerosil Consider, preferably a concentration of of the alkali metal ion in aqueous dispersions and alkaline-earth metal ions is less than or equal to 100ppm.Gas phase dioxy The Mohs' hardness of SiClx can be more than or equal to 5, or be greater than or equal to 6.

The method that insulating particle 210 is attached to conducting particles 1 is set to be not particularly limited.Such as can enumerate make carry functional group Insulating particle 210 be attached to the method etc. of the conducting particles 1 with functional group.In this case, insulating particle 210 preferably exists Outer surface has hydroxyl, silanol group, the good functional group of carboxyl isoreactivity.

It can also be formed with the functional groups such as hydroxyl, carboxyl, alkoxy, alkoxy carbonyl on the surface of conducting particles 1.Pass through The surface of conducting particles 1 has these functional groups, so as to by the functional group on the functional group and the surface of insulating particle 210 by Form the firm keys such as covalent bond, the hydrogen bond based on dehydrating condensation.

For the conducting particles 1 of the 1st embodiment, the first layer 104 for containing nickel as principal component becomes surface. In this case, by using with forming the silanol group of firm key or the compound of hydroxyl or nitrogen compound with nickel, to It is imported on the surface of first layer 104 and selects one or more of free hydroxyl, the group of carboxyl, alkoxy and alkoxy carbonyl composition official It can roll into a ball and be preferred.Specifically usable carboxyl benzotriazole etc..

As the method handled the surface of first layer 104 with above compound, it is not particularly limited.Example can be enumerated It is organic molten that thioacetic acid, carboxyl benzotriazole compound are such as scattered in methanol, ethyl alcohol etc. with the concentration of 10~100mmol/L In agent, the method that makes conducting particles 1 be dispersed therein.

When pH is neutral region, surface has in the group for selecting free hydroxyl, carboxyl, alkoxy and alkoxy carbonyl composition The surface potential (boundary reaches current potential) of at least one conducting particles 1 is usually negative.The surface of insulating particle 210 with hydroxyl Current potential is also usually negative.It is negative to make the insulating particle 210 that surface potential is negative fully be attached to surface potential Conducting particles 1 surface, polyelectrolyte layers can also be set among the particles.Thereby, it is possible to effectively make absolutely Edge particle 210 is attached to conducting particles 1.

Further, by the way that polyelectrolyte layers are arranged, it is evenly affixed to conduction while 210 zero defect of insulating particle can be made The surface of particle 1.Insulating particle 210 is set to be attached to insulation-coated electroconductive particles made of conducting particles 1 by using such 100a, even if also ensuring that insulating reliability to be divided into thin space between circuit electrode, on the other hand, the electricity being electrically connected Interpolar connection resistance is low, and conducting reliability is good.

It is attached to functional group by polyelectrolyte as the above-mentioned insulating particle 210 with functional group is made The method on the surface of conducting particles 1, is not particularly limited.As make insulating particle 210 be attached to conducting particles 1 surface side Method, it can be mentioned, for example by polyelectrolyte and 210 alternately stacked method of insulating particle.

First, carrying out (1) makes to have the conducting particles 1 of functional group to be scattered in the solution containing polyelectrolyte, makes The process that polyelectrolyte is adsorbed in at least part on the surface of the conducting particles 1 with functional group and is rinsed.It connects It, carrying out (2) makes the conducting particles 1 for being adsorbed with polyelectrolyte be scattered in the solution containing insulating particle 210, makes insulation At least part that particle 210 is attached to the surface for the conducting particles 1 with functional group for being adsorbed with polyelectrolyte is gone forward side by side The process that row rinses.By these processes, the insulation quilt for being laminated polyelectrolyte and insulating particle 210 can be manufactured Cover conducting particles 100a., the sequence of (1) (1) process and (2) process can be the sequence of (1), (2), or (2).(1)、 (2) process can also alternate repetition progress.

Above-mentioned (1) is repeated, the method for (2) process is referred to as alternately laminated method (Layer-by-Layer assembly).Alternately laminated method is the method (solid film for forming organic film delivered in 1992 by G.Decher etc. (Thin Solid Films), 210/211, p831 (1992)).In this method, base material alternating impregnating is gathered in positively charged In the aqueous solution of polymer electrolyte (polycation) and negatively charged polymer dielectric (polyanion).As a result, by quiet Electric attraction and the group for being adsorbed in the polycation on base material and polyanion is laminated, to obtain composite membrane (alternately laminated film).

In alternately laminated method, by electrostatic attraction, the charge for being formed in the material on base material is opposite with the band in solution electric The material of lotus attracts each other, to carry out film growth.Therefore, if absorption carries out, charge neutralizes, and does not occur into one The absorption of step.Therefore, as long as reaching a certain saturation point, then film thickness will not further increase.Lvov etc. reports following methods, I.e.：Alternately laminated method is applied to particle, using each particle dispersion liquid of silica, titanium oxide and cerium oxide, using alternately Layered manner by the polyelectrolyte layers with the charge opposite with the surface charge of particle it is folded (Langmuir, Vol.13, (1997)p6195-6203).If opposite with its by the insulating particle that will carry negative surface charge using this method Alternately laminated, the energy such as the diallyl dimethyl ammoniumchloride (PDDA) as polycation of charge, polyethyleneimine (PEI) It is enough formed by insulating particle and polyelectrolyte it is alternately laminated made of particle laminate film.

It can also be soaked after will there is the conducting particles 1 of functional group to be impregnated in the solution containing polyelectrolyte Before stain is in the dispersion liquid containing insulating particle 210, by the flushing of only solvent to containing extra polyelectrolyte Solution is rinsed.The conducting particles 1 for being adsorbed with polyelectrolyte can also be impregnated in point containing insulating particle 210 After in dispersion liquid, the dispersion liquid containing extra insulating particle 210 is rinsed also by the flushing of only solution.

As solution used in such flushing, water, alcohol, acetone, their mixed solvent etc. can be enumerated, but do not limit In this.

Polyelectrolyte can be adsorbed with the above-mentioned functional group for being directed into 1 surface of conducting particles.The polyelectrolyte It is adsorbed on above-mentioned functional group for example, by electrostatic.As the polyelectrolyte, can be used for example：It is electric in aqueous solution From, and the macromolecule (polyanion or polycation) with electrically charged functional group in main chain or side chain.As it is poly- it is cloudy from Sub (anionic polymer), can usually enumerate sulfonic acid, sulfuric acid, carboxylic acid etc. has the compound of functional group that can be negatively charged. In the case where the surface potential of conducting particles 1 and/or insulating particle 210 is negative, polycation can also be used as high Polymeric electrolyte.As polycation (cation property copolymer), can usually polyamine class etc. be used to have like that can be positively charged The substance of the functional group of lotus, such as containing selected from by polyethyleneimine (PEI), polyallylamine hydrochloride (PAH), polydiene third At least one in the group that base alkyl dimethyl ammonium chloride (PDDA), polyvinylpyridine (PVP), polylysine and polyacrylamide form Kind or more copolymer etc..From charge density height, with the binding force on surface and material with negative electrical charge it is strong from the viewpoint of, it is excellent Choosing uses polyethyleneimine.The polyelectrolyte can also be with the above-mentioned cation of the surface treatment for resin particle 101 Property polymer phase is same.

In polyelectrolyte, in order to avoid electromigration and corrosion, be preferably substantially free of alkali metal (Li, Na, K, Rb, Cs) ion, alkaline-earth metal (Ca, Sr, Ba, Ra) ion and halide ion (fluorine ion, chlorion, bromide ion, iodide ion).

Polyelectrolyte dissolves in water-soluble organic solvent, alcohol etc..Weight-average molecular as polyelectrolyte Amount, can not lump together because of the type of used polyelectrolyte.The weight average molecular weight of polyelectrolyte for example may be used Think 1,000~200,000, or 10,000~200,000, or 20,000~100,000.In macromolecule electricity In the case that the weight average molecular weight of solution matter is 1,000~200,000, it can obtain sufficient insulation-coated electroconductive particles 100a's Dispersibility.Even if the average grain diameter of insulation-coated electroconductive particles 100a can prevent insulation-coated conduction if being less than or equal to 3 μm The mutual cohesions of particle 100a.

Solution containing polyelectrolyte is the in the mixed solvent that polyelectrolyte is dissolved in water and organic solvent Made of solution.As the water-soluble organic solvent that can be used, methanol, ethyl alcohol, propyl alcohol, acetone, dimethyl methyl can be enumerated Amide, acetonitrile etc..

The concentration of polyelectrolyte in solution for example can be 0.01 mass of mass %~10 %, or 0.03 The mass of quality %~3 %, or 0.1 mass of mass %~1 %.If polyelectrolyte in solution is a concentration of The 0.01 mass % of mass %~10 can then improve cementability of the insulating particle 210 to conducting particles 1.Polyelectrolyte is molten The pH of liquid is not particularly limited.

By adjusting the type, weight average molecular weight or concentration of polyelectrolyte, insulating particle 210 can be controlled to conduction The covering rate of particle 1.

Such as using the high polyelectrolyte of the charge density such as PEI, there is the covering rate of insulating particle 210 The tendency of raising.Using the low polyelectrolyte of the charge density such as PDDA, there is the covering rate of insulating particle 210 The tendency of reduction.In the case where the weight average molecular weight of polyelectrolyte is big, there is inclining for the covering rate raising of insulating particle 210 To.In the case where the weight average molecular weight of polyelectrolyte is small, have the tendency that the covering rate of insulating particle 210 reduces.It is inciting somebody to action In the case that polyelectrolyte in solution is set as high concentration, have the tendency that the covering rate of insulating particle 210 improves.Will be molten In the case that polyelectrolyte in liquid is set as low concentration, have the tendency that the covering rate of insulating particle 210 reduces.Macromolecule electricity Type, weight average molecular weight and the concentration of solution matter can be selected suitably.

If on the surface of conducting particles 1 there is such as weight average molecular weight to be greater than or equal to 1,000 polymer, then can Promote the dispersion of the conducting particles 1.Therefore, even if reducing and magnetic the case where agglomerating increase with the grain size of conducting particles 1 Under, it can also inhibit the cohesion of the conducting particles 1, insulating particle 210 can be made to be easily attached to conducting particles 1.

Similarly, on the surface of insulating particle 210, there may also be the polymerizations that such as weight average molecular weight is 500~10,000 Object or oligomer.The weight average molecular weight of the polymer or oligomer can be 1,000~4,000.The polymer or oligomer are excellent It is selected as the silicone oligomer with functional group of weight average molecular weight 1,000~4,000.As functional group, preferably with above-mentioned height The functional group of polymeric electrolyte reaction.As the functional group, it can be mentioned, for example glycidyl, carboxyl or isocyanate group, In preferably glycidyl.Thereby, it is possible to keep the dispersibility of insulating particle 210 better, while by making polymer or low Functional group on polymers and the functional group reactions on conducting particles 1 can expect the more firm of conducting particles 1 and insulating particle 210 Consolidation is closed.

In this way, by making the particle with chemically reactive polymer be bonded to each other, in the past no jail can be obtained Consolidation is closed.The major diameter of the path and insulating particle 210 of conducting particles 1 can especially be coped with.

If by the first insulating particle 210a compared with the second insulating particle 210b, by silica form second absolutely Edge particle 210b has the tendency that being easy to fall off from conducting particles 1.Even if using with glycidyl, carboxyl or isocyanates The polymer or oligomer of base can be used in the case that the second insulating particle 210b is also easy to fall off through silicic acid anhydride agent By the coating method in the surface of the second insulating particle 210b.The surface of second insulating particle 210b is more hydrophobic, by titanium dioxide The surface potential (boundary reaches current potential) of second insulating particle 210b of silicon composition more increases to negative side.Therefore, the second insulating particle The potential difference of 210b and the conducting particles 1 handled by polyelectrolyte increase, therefore second insulating particle 210b is firmly adhered to conducting particles 1 by electrostatic force.

As the silicic acid anhydride agent of coating second insulating particle 210b, (1) the silazane system that can enumerate following record dredges Hydration process agent, (2) siloxane-based silicic acid anhydride agent, the silicic acid anhydride agent of (3) silane system, at (4) titanate esters system hydrophobization Manage agent etc..From the viewpoint of reactivity, preferably (1) silazane system silicic acid anhydride agent.Silicic acid anhydride agent can also contain Selected from least one of the group being made of above-mentioned (1)~(4).

(1) silazane system silicic acid anhydride agent

As the silicic acid anhydride agent of silazane system, the silicic acid anhydride agent of organosilazanes system can be enumerated.As organic silazane Methane series silicic acid anhydride agent, can enumerate：Hexamethyldisilazane, trimethyldisilazane, tetramethyl-disilazane, pregnancy basic ring Three silazane, heptamethyldisilazane, diphenyltetramethyldisilazane, divinyl tetramethyl-disilazane etc..Organosilicon The silicic acid anhydride agent of azane system may be compound other than the above.

(2) siloxane-based silicic acid anhydride agent

As siloxane-based silicic acid anhydride agent, can enumerate：Dimethyl silicone polymer, methyl hydrogen disiloxane, diformazan Base disiloxane, hexamethyldisiloxane, 1,3- divinyl tetramethyl disiloxanes, two silica of 1,3- diphenyltetramethyls Alkane, methyl hydrogen polysiloxanes, dimethyl polysiloxane, amino modified siloxanes etc..Siloxane-based silicic acid anhydride agent also may be used Think compound other than the above.

(3) silane system silicic acid anhydride agent

As the silicic acid anhydride agent of silane system, can enumerate：N, N- dimethylamino trimethyl silane, trimethyl methoxy silicon Alkane, trimethylethoxysilane, trimethyl npropoxysilane, pheiiyldimetliyl methoxy silane, chloropropyl dimethyl methyl oxygroup Silane, dimethyldimethoxysil,ne, methyltrimethoxysilane, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxy-silicane Alkane, four butoxy silanes, ethyl trimethoxy silane, dimethyl diethoxysilane, propyl-triethoxysilicane, normal-butyl three Methoxy silane, n-hexyl trimethoxy silane, n-octytriethoxysilane, n-octyl methyldiethoxysilane, positive ten Eight alkyl trimethoxysilanes, phenyltrimethoxysila,e, phenyl methyl dimethoxysilane, phenethyl trimethoxy silane, Dodecyltrimethoxysilane, n-octadecane ethyl triethoxy silicane alkane, phenyltrimethoxysila,e, diphenyl dimethoxy silicon Alkane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl three (β methoxy ethoxies) silane, γ-methyl Acryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-(methacryloxies third Base) methyl dimethoxysilane, γ-methacryloxypropyl methyl diethoxysilane, γ-methacryloxy third Ethyl triethoxy silicane alkane, β-(3,4- epoxycyclohexyls) ethyl trimethoxy silane, γ-glycidoxypropyl trimethoxy Silane, γ-glycidoxypropyl diethoxy silane, γ-glycidoxypropyl triethoxysilane, N- β (amino-ethyl) γ-(aminopropyl) methyl dimethoxysilane, N- β (amino-ethyl) γ-(aminopropyl) trimethoxy silicon Alkane, N- β (amino-ethyl) γ-(aminopropyl) triethoxysilane, gamma-amino propyl trimethoxy silicane, gamma-amino propyl Triethoxysilane, N- phenyl-gamma-amino propyl trimethoxy silicane, γ mercaptopropyitrimethoxy silane, 3- isocyanic acids Ester propyl-triethoxysilicane, trifluoro propyl trimethoxy silane, 17-trifluoro propyl trimethoxy silanes, positive decyl front three Oxysilane, dimethoxy diethoxy silane, bis- (triethoxysilyl) ethane, six ethyoxyl disiloxane etc..

(4) titanate esters system silicic acid anhydride agent

As the silicic acid anhydride agent of titanate esters system, can enumerate：KRTTS、KR46B、KR55、KR41B、KR38S、KR138S、 KR238S, 338X, KR44, KR9SA (being Ajinimoto Fine Techno Co. Inc.'s system, trade name) etc..

In above-mentioned silicic acid anhydride agent, preferably hexa-methylene disilazane, dimethyl silicone polymer and N, N- dimethylaminos Base trimethyl silane.Therefore, silicic acid anhydride agent can also contain selected from by hexa-methylene disilazane, dimethyl silicone polymer And at least one of the group of N, N- dimethylamino trimethyl silane composition.Get over hydrophobic in the surface of second insulating particle 210b Change, the boundary of the second insulating particle 210b more increases to negative side up to current potential.Therefore, the second insulating particle 210b and pass through macromolecule The potential difference for the conducting particles 1 that electrolyte is handled increases.Therefore, conducting particles 1 and the second insulating particle 210b passes through Electrostatic force and be bonded securely.

The coating treatment on the surface of the second insulating particle of silicic acid anhydride agent pair 210b can in water, organic solvent, contain water With carry out in the liquid phases such as the mixed solution of organic solvent or in the gas phase.It, can as the water-soluble organic solvent that can be used Enumerate methanol, ethyl alcohol, propyl alcohol, acetone, dimethylformamide, acetonitrile etc..As the second insulating particle 210b, it is possible to use in advance The silica handled by silicic acid anhydride agent.

It is coated with the hydrophobization degree of the second insulating particle 210b of silicic acid anhydride agent obtained by methanol titration for example 30% can be greater than or equal to, 50% can also be greater than or equal to, 60% can also be greater than or equal to.Second insulating particle 210b Hydrophobization degree it is higher, the boundary of the second insulating particle 210b more becomes more negative value up to current potential.Therefore, the second insulating particle 210b It can be bonded securely with the conducting particles 1 handled by polyelectrolyte by electrostatic force.

So-called methanol titration, for use methanol measure powder hydrophobization degree method.For example, making 0.2g wait for first The powder for measuring hydrophobization degree floats on the water surface of 50ml.Then, in water while being gently mixed water and little by little add Add methanol.Methanol is for example added dropwise using buret.Then methanol at the time of, in the powder on the water surface all sinking to water makes Dosage is measured.Then, percentage of the methanol volume relative to total volume of water and methanol is calculated, the value conduct is calculated The hydrophobization degree of powder.

Relative to the total surface area of conducting particles 1, the covering rate of the first insulating particle 210a in insulating particle 210 is for example It is 20~50%.If the covering rate of the first insulating particle 210a is greater than or equal to 20%, more good insulation can be obtained Reliability.On the other hand, if covering rate is less than or equal to 50%, superior conducting reliability can be obtained.

By with the second insulating particle 210b by not by the surface of conducting particles 1 coating the first insulating particle 210a extremely Few part covering, can obtain more good insulating reliability.Relative to the total surface area of conducting particles 1, the first insulation grain Sub- 210a and the second insulating particle 210b to the covering rate of conducting particles 1 such as can be more than or equal to 35% and be less than or In 80%, or be greater than or equal to 40% and be less than or equal to 80%, or more than or equal to 50% and be less than or Equal to 80%, or be greater than or equal to 60% and be less than or equal to 80%.If the covering rate is greater than or equal to 35%, Insulating reliability can be improved.On the other hand, if the covering rate is less than or equal to 80%, insulation grain can efficiently be utilized Son 210 is coating by conducting particles 1.

The covering rate of insulating particle 210 refer to insulation-coated electroconductive particles 100a frontal plane of projection in have and insulation-coated lead The ratio of the surface area of insulating particle 210 in the concentric circles of 1/2 diameter of the diameter of charged particle 100a.Specifically, to logical It crosses SEM to be parsed with the image that 30,000 times of observations are formed with obtained by the insulation-coated electroconductive particles 100a of insulating particle 210, calculate Go out ratio of the insulating particle 210 shared by the surface of insulation-coated electroconductive particles 100a.

The insulation-coated electroconductive particles 100a involved by the 1st embodiment from the description above, in the table of conducting particles 1 Face be attached with more than or equal to 200nm and less than or equal to 500nm average grain diameter the first insulating particle 210a and With more than or equal to 30nm and the average grain diameter less than or equal to 130nm and the second insulating particle for being made of silica 210b.As a result, for example when pressurization will be heated containing the anisotropic conductive adhesive of insulation-coated electroconductive particles 100a, the Two insulating particle 210b are not melted, and prevent the metal surface of adjacent conducting particles 1 from contacting.Therefore, even if by per unit face Product is greater than or equal to 100,000/mm²Insulation-coated electroconductive particles 100a put into the feelings to anisotropic conductive adhesive Under condition, excellent insulating reliability can be also obtained.In addition, the second insulating particle 210b has more than or equal to 30nm and is less than Or the average grain diameter equal to 130nm, therefore connect the obstruction that resistance is not easily susceptible to second insulating particle 210b.Therefore, in electricity In the connection of the liner small fine circuit of area of pole, even if in the case that the number of the particle captured between electrode is few Excellent conducting reliability can be obtained.

The glass transition temperature of first insulating particle 210a can be more than or equal to 100 DEG C and to be less than or equal to 200 ℃.As a result, according to the temperature that will be heated containing the anisotropic conductive adhesive of insulation-coated electroconductive particles 100a when pressurizeing Difference, sometimes the first insulating particle 210a incomplete fusions.Therefore, the first insulating particle 210a can as insulation spacer and Fully function.

Relative to the total surface area of conducting particles 1, the first insulating particle 210a and the second insulating particle 210b are to conductive particle The covering rate of son 1 can be 35~80%.It is superior insulation-coated thereby, it is possible to obtain conducting reliability and insulating reliability Conducting particles 100a.In general, having insulating reliability in the case of the covering rate height of insulating particle in insulation-coated electroconductive particles The tendency for getting higher and being connected less reliable has conducting reliability to get higher and absolutely in the case where the covering rate of insulating particle is low The tendency of edge less reliable.But as the 1st embodiment, the mutually different first insulation grain of average grain diameter is being used In the case of sub- 210a and the second insulating particle 210b, good conducting reliability can be kept improving covering rate, it can Obtain the insulation-coated electroconductive particles 100a for having taken into account excellent insulating reliability with reliability being connected.

Conducting particles 1 has protrusion 109 on its surface.In the conductive particle for making the second insulating particle 210b be attached to even surface In the case of son, even if the average grain diameter of the second insulating particle 210b is greater than or equal to 30nm and is less than or equal to 130nm, second Insulating particle 210b is also high as the function of insulation spacer, therefore has insulating reliability excellent but inclining for reliability reduction is connected To.Therefore, there is protrusion 109 by conducting particles 1, the reduction that reliability is connected can be inhibited.

It the surface of second insulating particle 210b can also be coating by silicic acid anhydride agent.In order to make the first insulating particle 210a The surface that conducting particles 1 is adhered well to the second insulating particle 210b, sometimes through polyelectrolyte, (cationic is poly- Close object) surface of conducting particles 1 is coating.At this point, by the second coating insulating particle 210b of silicic acid anhydride agent and without dredging Second insulating particle 210b of hydration process is negatively charged compared to being easy, and can be firmly adhered to conducting particles 1 by electrostatic. Therefore, as the function of insulation spacer height, the excellent insulation-coated electroconductive particles of insulating reliability can be obtained.

The surface of second insulating particle 210b can be selected from by the silicic acid anhydride agent of silazane system, siloxane-based hydrophobization In the group for managing agent, the silicic acid anhydride agent of silane system and titanate esters system silicic acid anhydride agent composition.

The hydrophobization degree of the second insulating particle 210b obtained by methanol titration can be greater than or equal to 30%.

Conducting particles 1 can also be with the metal layer of resin particle 101 and covering resin particle 101, and metal layer can also With nickeliferous first layer 104.In this case, it glues insulation-coated electroconductive particles 100a is matched with anisotropic conductive When connecing in agent, which can take into account excellent conducting reliability and insulating reliability.

From the viewpoint of being easy to control lamination amount, insulating particle 210 can also be only coating by one layer.

Can also be by implementing heat drying to insulation-coated electroconductive particles 100a, and make insulating particle 210 and conductive particle The combination of son 1 further enhances.The reasons why enhancing as binding force, it can be mentioned, for example the carboxyls for being directed into 1 surface of conducting particles Equal functional groups enhance with the chemical bond for being directed into the functional groups such as the hydroxyl on 210 surface of insulating particle.The temperature of heat drying is for example It is set as 60~100 DEG C.If temperature is greater than or equal to 60 DEG C, insulating particle 210 is not easy to remove from conducting particles 1, if Less than or equal to 100 DEG C, then conducting particles 1 is unlikely to deform.The time of heat drying is for example set as 10 minutes~180 minutes.Such as The time of fruit heat drying be greater than or equal to 10 minutes, then insulating particle 210 be not easily stripped, if it is less than or be equal to 180 minutes, Then conducting particles 1 is unlikely to deform.

Insulation-coated electroconductive particles 100a can also be carried out at surface by silicone oligomer, octadecylamine etc. Reason.Thereby, it is possible to improve the insulating reliability of insulation-coated electroconductive particles 100a.Further, by as needed using condensation Agent can also further increase the insulating reliability of insulation-coated electroconductive particles 100a.

(the 2nd embodiment)

Hereinafter, being illustrated to the insulation-coated electroconductive particles involved by the 2nd embodiment.In saying for the 2nd embodiment In bright, the record repeated with the 1st embodiment is omitted, and records the part different from the 1st embodiment.I.e., it is possible in technology In upper possible range, the record of the 1st embodiment is suitably used in the 2nd embodiment.

Fig. 2 is the schematic section for indicating the insulation-coated electroconductive particles involved by the 2nd embodiment.It is shown in Fig. 2 exhausted Edge coated electroconductive particles 100b other than with 105 this point of the second layer on first layer 104, have with shown in Fig. 1 The identical compositions of insulation-coated electroconductive particles 100a.That is, the covering resin particle 101 of insulation-coated electroconductive particles 100b and non- The metal layer of Conductive inorganic particle 102 includes first layer 104 and the second layer 105.The second layer 105 can be metal layer, also may be used Think alloy-layer.

The conductive layer that the second layer 105 is arranged for coating first layer 104.The thickness of the second layer 105 be, for example, 5nm~ 100nm.The thickness of the second layer 105 can be more than or equal to 5nm, or be greater than or equal to 10nm.The thickness of the second layer 105 Degree may be to be less than or equal to 30nm.In the case where the thickness of the second layer 105 is in above range, the second layer is being formed The thickness of the second layer 105 can be made uniform in the case of 105, thus, it is possible to prevent the member contained by first layer 104 well Plain (such as nickel) is to the diffusion into the surface with 105 opposite side of the second layer.

The thickness of the second layer 105 is calculated using by the photo captured by TEM.As concrete example, first with ultra-thin Microtomy cuts out cutting for insulation-coated electroconductive particles 100b in a manner of by the immediate vicinity of insulation-coated electroconductive particles 100b Face.Then, cut out section is observed with 250,000 times of multiplying power using TEM and obtains image.It then, can be by the figure according to gained The thickness of the second layer 105 is calculated as the sectional area of the second layer 105 of estimation.At this point, being difficult to differentiate between the second layer 105, first In the case of layer 104, resin particle 101 and non-conductive inorganic particulate 102, ingredient point is carried out by the incidental EDX of TEM Analysis.The second layer 105, first layer 104, resin particle 101 and non-conductive inorganic particulate 102 are clearly distinguished as a result, only calculate the Two layer 105 of thickness.The thickness of the second layer 105 is set as the average value of the thickness of 10 conducting particles.

The second layer 105 contains selected from least one of the group being made of noble metal and cobalt.Noble metal be palladium, rhodium, iridium, Ruthenium, platinum, silver or gold.In the case where the second layer 105 is containing gold, leading for the surface of insulation-coated electroconductive particles 100b can be reduced Be powered resistance, improves the conductive characteristic of insulation-coated electroconductive particles 100b.In this case, the second layer 105 is as nickeliferous first Layer 104 anti oxidation layer and function.Therefore, the second layer 105 is formed on first layer 104.The second layer 105 when containing gold Thickness may be less than or equal to 30nm.In this case, the conducting resistance on the surface of insulation-coated electroconductive particles 100b Reducing effect and manufacturing cost balancing good.However, the thickness of the second layer 105 when containing gold can also be more than 30nm.

The second layer 105 selected from least one of the group being made of palladium, rhodium, iridium, ruthenium and platinum preferably by constituting.In the situation Under, the surface oxidation of insulation-coated electroconductive particles 100b can be inhibited, and the insulation for improving insulation-coated electroconductive particles 100b can By property.The second layer 105 selected from least one of the group being made of palladium, rhodium, iridium and ruthenium more preferably by constituting.In this case, It is formed on non-conductive inorganic particulate 102 even if can inhibit if in the case where compressing insulation-coated electroconductive particles 100b It is subject to crushing as the first layer 104 of protrusion 109, and the resistance of compressed insulation-coated electroconductive particles 100b is inhibited to increase.The It for example after forming first layer 104 by the fourth step of the 1st embodiment, is formed in by electroless plating for two layer 105 On the compound particle 103 covered by the first layer 104.

Containing palladium in the second layer 105, which can for example be formed by electroless plating palladium.Without electricity Solution plating palladium using without using reducing agent displaced type and using reducing agent reduced form it is any.As such no electricity Solution plating palladium liquid, displaced type can enumerate MCA (Co., Ltd.'s World Metal systems, trade name) etc..Reduced form can enumerate APP, and (stone is former Chemical Co., Ltd. system, trade name) etc..It is few from generated hole in the case where displaced type compares with reduced form, hold From the viewpoint of easily ensuring coating area, preferably reduced form.

Containing palladium in the second layer 105, on the basis of the total amount of the second layer 105, palladium in the second layer 105 contains The lower limit of amount can be more than or equal to 90 mass %, or be greater than or equal to 93 mass %, or be more than or wait In 94 mass %.On the basis of the total amount of the second layer 105, the upper limit of the content of the palladium in the second layer 105 can be to be less than or wait In 99 mass %, or be less than or equal to 98 mass %.The content of palladium in the second layer 105 is the feelings in above range Under condition, the hardness of the second layer 105 improves.Therefore, even if can inhibit if in the case where compressing insulation-coated electroconductive particles 100b Protrusion 109 is subject to crushing.

In order to adjust the content (such as in order to be adjusted to 93~99 mass %) of the palladium in the second layer 105, as electroless Reducing agent used in palladium liquid is plated, is not particularly limited, can use：Ortho phosphorous acid, phosphorous acid, these sour alkali salts etc. are phosphorous Compound；Boron-containing compound etc..In this case, the second layer 105 of gained contains Pd-P alloys or palladium-boron alloy.Therefore, It is preferred that adjusting the concentration of reducing agent, the temperature of pH, plating solution in such a way that the palladium content in the second layer 105 becomes desired range Degree etc..

In the case where the second layer 105 contains rhodium, which can for example be formed by electroless rhodanizing.As The supply source of rhodium used in electroless rhodanizing liquid, it can be mentioned, for example hydroxide ammino rhodium, nitric acid ammino rhodium, acetic acid ammino rhodium, Sulfuric acid ammino rhodium, sulfurous acid ammino rhodium, bromination ammino rhodium and ammino rhodium compound.

As reducing agent used in electroless rhodanizing liquid, it can be mentioned, for example hydrazine, sodium hypophosphite, boric acid dimethyl amine, Boric acid diethylamide and sodium borohydride.As reducing agent, preferably hydrazine.Can also be added in electroless rhodanizing liquid stabilizer or Complexing agent (ammonium hydroxide, hydroxyl amine salt, dichloride hydrazine etc.).

From the viewpoint of obtaining sufficient plating speed, the temperature (bath temperature) of electroless rhodanizing liquid can be to be more than or wait In 40 DEG C, or be greater than or equal to 50 DEG C.From the viewpoint of stably keeping electroless rhodanizing liquid, the temperature of plating solution Can be less than or equal to 90 DEG C, or be less than or equal to 80 DEG C.

In the case where the second layer 105 contains iridium, which can for example be formed by electroless plating iridium.As The supply source of iridium used in electroless plating iridium liquid, it can be mentioned, 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 two Potassium, hexaiodo iridium tripotassium, three sulfuric acid, two iridium and double sulfuric acid iridium.

As reducing agent used in electroless plating iridium liquid, it can be mentioned, for example hydrazine, sodium hypophosphite, boric acid dimethyl amine, Boric acid diethylamide and sodium borohydride.As reducing agent, preferably hydrazine.Can also be added in electroless plating iridium liquid stabilizer or Complexing agent.

As stabilizer or complexing agent, can add in the group that the salt by monocarboxylic acid, dicarboxylic acids and these acid forms At least one.As the concrete example of monocarboxylic acid, formic acid, acetic acid, propionic acid, butyric acid, lactic acid etc. can be enumerated.Tool as dicarboxylic acids Body example can enumerate oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, malic acid etc..As above-mentioned Salt, it can be mentioned, for example sodium, potassium, lithiums etc., and counter ion counterionsl gegenions to be used as to be bonded to compound made of above-mentioned carboxylic acid.Stabilizer or complexing agent The one kind that can be used alone is applied in combination two or more.

From the viewpoint of the corrosion for inhibiting plating object and obtaining sufficient plating speed, electroless plating iridium liquid PH can be more than or equal to 1, or be greater than or equal to 2.From the viewpoint of the obstruction that easy inhibition plating reacts, nothing The pH of electrolysis plating iridium liquid can be less than or equal to 6, or be less than or equal to 5.

From the viewpoint of obtaining sufficient plating speed, the temperature (bath temperature) of electroless plating iridium liquid can be to be more than or wait In 40 DEG C, or be greater than or equal to 50 DEG C.From the viewpoint of stably keeping electroless plating iridium liquid, electroless plating iridium liquid Temperature (bath temperature) can be less than or equal to 90 DEG C, or be less than or equal to 80 DEG C.

In the case where the second layer 105 contains ruthenium, which can for example be formed by electroless plating ruthenium.As Electroless plating ruthenium liquid, can be used for example commercially available plating solution, can use electroless ruthenium Ru (Okuno Chemical Industries Co., Ltd. System, trade name).

In the case where the second layer 105 contains platinum, which can for example be formed by electroless platinum plating.As The supply source of platinum used in electroless platinum plating solution, it can be mentioned, for example Pt (NH₃)₄(NO₃)₂、Pt(NH₃)₄(OH)₂、PtCl₂ (NH₃)₂、Pt(NH₃)₂(OH)₂、(NH₄)₂PtCl₆、(NH₄)₂PtCl₄、Pt(NH₃)₂Cl₄、H₂PtCl₆And PtCl₂。

As reducing agent used in electroless platinum plating solution, it can be mentioned, for example hydrazine, sodium hypophosphite, boric acid dimethyl amine, Boric acid diethylamide and sodium borohydride.As reducing agent, preferably hydrazine.Can also be added in electroless platinum plating solution stabilizer or Complexing agent (chlorination hydroxylamine, dichloride hydrazine, ammonium hydroxide, EDTA etc.).

From the viewpoint of obtaining sufficient plating speed, the temperature (bath temperature) of electroless platinum plating solution can be to be more than or wait In 40 DEG C, or be greater than or equal to 50 DEG C.From the viewpoint of stably keeping electroless platinum plating solution, electroless platinum plating solution Temperature (bath temperature) can be less than or equal to 90 DEG C, or be less than or equal to 80 DEG C.

When carrying out platinum plating using electroless platinum plating solution, as long as the pH of electroless platinum plating solution is for example 8~12.If PH is more than or equal to 8, then platinum is easy fully to be precipitated.If pH is less than or equal to 12, can readily insure that good Operating environment.

In the case where the second layer 105 is containing silver, which can for example be formed by electroless silver plating.As Silver-colored supply source, is not particularly limited as long as dissolving in plating solution used in electroless silver plating liquid.It can be used for example：Nitre Sour silver, silver oxide, silver sulfate, silver chlorate, silver sulfite, silver carbonate, silver acetate, actol, sulfosuccinic acid are silver-colored, sulfonic acid is silver-colored, Sulfamic acid silver and silver oxalate.Water-soluble silver compound, which can be used alone, one kind or to be applied in combination two or more.

As reducing agent used in electroless silver plating liquid, as long as having the water-soluble silver chemical combination in electroless silver plating liquid Object is reduced into the ability of metallic silver and is just not particularly limited for water-soluble compound.It can be used for example：Hydrazine derivate, first Aldehyde compound, hydroxyl amine, carbohydrate, Rochelle salt (Rochelle salt), hydroboron, hypophosphite, DMAB and anti- Bad hematic acid.Reducing agent, which can be used alone, one kind or to be applied in combination two or more.

Stabilizer or complexing agent can also be added in electroless silver plating liquid.As stabilizer or complexing agent, such as can be with It uses：Sulphite, succinimide, hydantoin derivatives, ethylenediamine and ethylenediamine tetra-acetic acid (EDTA).Stabilizer or network Mixture, which can be used alone, one kind or to be applied in combination two or more.

In electroless silver plating liquid, other than mentioned component, can also add well known surfactant, pH adjusting agent, The additives such as buffer, smooth agent, stress moderator.

About electroless silver plating liquid, as liquid temperature, as long as 0~80 DEG C of range.If electroless silver plating liquid Temperature is more than or equal to 0 DEG C, then silver-colored speed of separating out is sufficiently fast, can shorten for obtain scheduled silver-colored amount of precipitation when Between.If the temperature of electroless silver plating liquid is less than or equal to 80 DEG C, reducing agent caused by being reacted by selfdecomposition can be inhibited The stability of loss and electroless silver plating liquid reduces.If being set as 10~60 DEG C of degree, electroless silver plating liquid can be made Stability is further good.

The pH of electroless silver plating liquid (such as reduced form electroless silver plating liquid) is, for example, 1~14.PH by plating solution is 6 ~13 degree can make the stability of plating solution further good.PH as plating solution is adjusted, usually in the feelings for reducing pH Under condition, (such as made using silver sulfate using the acid with the anion part of the same race with the anion part of water soluble silver salt It is sulfuric acid in the case of for water soluble silver salt, is nitric acid in the case where using silver nitrate as water soluble silver salt).Improving nothing In the case of the pH for being electrolysed silver plating liquid, alkali metal hydroxide, ammonia etc. are used.

<Gold>

In the case where the second layer 105 is containing gold, which can for example be formed by electroless gold plating.As Electroless gold plating solution can use displaced type gold plating liquid (such as Hitachi Chemical Co., Ltd.'s system, trade name " HGS-100 "), go back Prototype gold plating liquid (such as Hitachi Chemical Co., Ltd.'s system, trade name " HGS-2000 ") etc..By displaced type compared with reduced form It is few from hole compared in the case of, it is easy to ensure that, it is preferable to use reduced form from the viewpoint of coating area.

In the case where the second layer 105 contains cobalt, which can for example be formed by electroless cobalt plating.As The supply source of cobalt used in electroless cobalt plating liquid, it can be mentioned, for example cobaltous sulfate, cobalt chloride, cobalt nitrate, cobalt acetate, cobalt carbonates.

As reducing agent used in electroless cobalt plating liquid, can be used for example：It is sodium hypophosphite, ammonium hypophosphite, secondary The hypophosphites such as phosphorous acid nickel and ortho phosphorous acid.Stabilizer or complexing agent (fat can also be added in electroless cobalt plating liquid Aliphatic carboxylic acid etc.).Stabilizer or complexing agent, which can be used alone, one kind or to be applied in combination two or more.

From the viewpoint of obtaining sufficient plating speed, the temperature (bath temperature) of electroless cobalt plating liquid can be to be more than or wait In 40 DEG C, or be greater than or equal to 50 DEG C.From the viewpoint of stably keeping electroless cobalt plating liquid, electroless cobalt plating liquid Temperature (bath temperature) can be less than or equal to 90 DEG C, or be less than or equal to 80 DEG C.

In the case that conducting particles 1 involved by 2nd embodiment has gold or palladium surface, can also use has and gold Or palladium forms the compound of any of sulfydryl, thioether group, disulfide base of coordinate bond, makes to select free hydroxyl, carboxyl, alcoxyl More than one functional group in the group of base and alkoxy carbonyl composition is attached to the surface of the second layer 105.Example as compound Son can use thioacetic acid, 2 mercapto ethanol, methyl thioglycolate, mercapto succinic acid, thioglycerol or cysteine etc..

Insulation-coated electroconductive particles 100b involved by 2nd embodiment described above is also played and the 1st embodiment Same function and effect.In addition, in the 1st embodiment, first layer 104 is outermost as insulation-coated electroconductive particles 100a's Layer.Insulation-coated electroconductive particles 100a is for example when being scattered in anisotropic conductive adhesive, sometimes in first layer 104 Contained nickel is dissolved out into bonding agent and is migrated.Sometimes lead to anisotropic conductive adhesive because of the nickel of the migration Insulating reliability reduce.In contrast, the metal layer of the 2nd embodiment has the second layer 105 being located on first layer 104, The second layer 105 contains the metal in the group being made of noble metal and cobalt.In this case, insulation-coated electroconductive particles 100b Outermost layer become the second layer 105.It, can since the second layer 105 has the function of preventing nickel from dissolving out from first layer 104 Inhibit the generation of the migration of the nickel.Moreover, because the second layer 105 is less oxidizable, therefore insulation-coated electroconductive particles 100b Electric conductivity be not easily deteriorated.There is the second layer 105 by insulation-coated electroconductive particles 100b, it being capable of highly control projection 109 quantity, size and shape.

(the 3rd embodiment)

Hereinafter, being illustrated to the insulation-coated electroconductive particles involved by the 3rd embodiment.In saying for the 3rd embodiment In bright, the record repeated with the 1st embodiment and the 2nd embodiment is omitted, and is recorded and the 1st embodiment and the 2nd embodiment party The different part of formula.That is, in the range of can also being technically possible, the 1st embodiment is suitably used in the 3rd embodiment With the record of the 2nd embodiment.

Fig. 3 is the schematic section for indicating the insulation-coated electroconductive particles involved by the 3rd embodiment.It is shown in Fig. 3 exhausted Edge coated electroconductive particles 100c has resin particle 101, palladium particle 106 containing palladium, the nickel particles 107 containing nickel, Yi Jizuo For set on the first layer 108 of the metal layer on 101 surface of resin particle.Palladium particle 106 is configured at compared with nickel particles 107 more by tree The side of fat granule 101, and covered by nickel particles 107.In the outer surface of first layer 108, formation reflects 106 He of palladium particle The protrusion 109 of the shape of nickel particles 107.First layer 108 includes the first coating 108a and the second coating 108b.It can from above Know, insulation-coated electroconductive particles 100c is different from the insulation-coated electroconductive particles 100a of the 1st embodiment, does not have non-conductive Inorganic particulate 102.

Multiple palladium particles 106 for example along the surface of the first coating 108a of first layer 108 (along with conducting particles 1 The vertical direction of radial direction) configure with being separated by.Multiple palladium particles 106 for example with the radial direction of conducting particles (first layer 108 Thickness direction) diffusedly configure on vertical direction.Therefore, a palladium particle 106 with and a palladium particle 106 it is adjacent The non-contiguously separate configurations of another palladium particle 106.Multiple palladium particles 106 respectively have the side for extending from top to bottom surface.It is more A palladium particle 106 is, for example, to be formed by electroless plating palladium by electroless plating palladium core is precipitated (containing palladium ion and reducing agent The reduction precipitate of electroless plating palladium liquid).

Multiple nickel particles 107 are separated by along the surface of conducting particles 1 and are configured.Multiple nickel particles 107 for example with The radial direction of conducting particles 1 diffusedly configures on vertical direction.Therefore, a nickel particles 107 with and 107 phase of nickel particles Adjacent another nickel particles 107 non-contiguously separate configurations.Multiple nickel particles 107 have the side for extending from top to bottom surface.It is more A nickel particles 107 are, for example, to be formed by electroless nickel plating by electroless nickel plating core (microspike) is precipitated.Multiple nickel particles 107 are formed with palladium particle 106 for core.Therefore, each palladium particle 106 can also be covered by corresponding nickel particles 107.

(the first coating)

First coating 108a can also contain for example other than the metal using nickel as principal component selected from by phosphorus and boron At least one of group of composition.In this case, the first coating 108a preferably comprises phosphorus.Thereby, it is possible to improve the first quilt The hardness of coating 108a, conducting resistance when can easily be compressed conducting particles 1 remain low-level.

It, can also be with the first of the 1st embodiment in the case where forming the first coating 108a by electroless nickel plating Layer 104 is identically formed.Such as the first coating 108a containing nickel-phosphor alloy or nickel-boron alloy can also be formed.From inhibition From the viewpoint of first coating 108a ruptures, the first coating 108a preferably comprises nickel-phosphor alloy.

On the basis of the total amount of the first coating 108a, the nickel content in the first coating 108a for example can be more than or Equal to 84 mass %, or be greater than or equal to 86 mass %, or be greater than or equal to 88 mass %.First coating Constituent content in 108a can measure in the same manner as the first layer 104 of the 1st embodiment.

The thickness of first coating 108a for example can be more than or equal to 20nm, or be greater than or equal to 60nm. The thickness of first coating 108a for example can be less than or equal to 200nm, or it is less than or equal to 150nm, it can also To be less than or equal to 100nm.If the thickness of the first coating 108a is in above range, the first quilt can be easily suppressed Coating 108a ruptures.

(the second coating)

Second coating 108b preferably comprises nickel.As shown in figure 3, the second coating 108b constitutes the outermost layer of protrusion 109. Such second coating 108b can for example be formed by electroless nickel plating.Such as by the first coating 108a and Nickel particle Implement electroless nickel plating on son 107, can be formed in outer surface has the second coating 108b of protrusion 109.

On the basis of the total amount of the second coating 108b, the nickel content in the second coating 108b for example can be more than or Equal to 88 mass %, or be greater than or equal to 90 mass %, or be greater than or equal to 93 mass %, or big In or equal to 96 mass %.Nickel content in second coating 108b for example can be less than or equal to 99 mass %, can also To be less than or equal to 98.5 mass %.In the case where the nickel content of the second coating 108b is in above range, passing through nothing Electrolytic ni plating can easily suppress the cohesion of nickel particles 107 when forming the second coating 108b, can be easily prevented from different The formation in normal precipitation portion.It can be easily achieved in as a result, insulation-coated in anisotropic conductive adhesive as being matched with The insulation-coated electroconductive particles 100c of excellent conducting reliability and insulating reliability can be taken into account when conducting particles.Second is coating Constituent content in layer 108b can measure in the same manner as the first layer 104 of the 1st embodiment and the first coating 108a.

The thickness (average thickness) of second coating 108b for example can be more than or equal to 5nm, or be more than or Equal to 10nm, or be greater than or equal to 15nm.The thickness (average thickness) of second coating 108b for example can be less than Or it is equal to 150nm, or be less than or equal to 120nm, or be less than or equal to 100nm.If the second coating The thickness of 108b is then to be able to easily form the protrusion 109 of excellent in shape, and even if in conducting particles 1 in above range In the case of substantially compressing, it can also easily suppress first layer 108 and rupture.

Second coating 108b also contains selected from being made of phosphorus and boron preferably other than the metal using nickel as principal component At least one of group.Thereby, it is possible to improve the hardness of the second coating 108b, easily conducting particles 1 can be pressed Conducting resistance when contracting remains low-level.Second coating 108b can also contain the metal of the eutectoid together with phosphorus or boron.The Metal contained by two coating 108b is, for example, cobalt, copper, zinc, iron, manganese, chromium, vanadium, molybdenum, palladium, tin, tungsten and rhenium.Second coating 108b can improve the hardness of the second coating 108b by containing nickel and above-mentioned metal.Even if as a result, in insulation-coated conduction In the case of particle 100c is compressed, also protrusion 109 can be inhibited to be subject to crushing.Above-mentioned metal can also include with high rigidity Tungsten.In this case, on the basis of the total amount of coating 103b, the nickel content in the second coating 108b is, for example, to be more than or wait In 85 mass %.As the constituent material of the second coating 108b, such as the preferably combination of nickel (Ni) and phosphorus (P), nickel (Ni) The combination of combination, nickel (Ni) and tungsten (W) and boron (B) with boron (B) and the combination of nickel (Ni) and palladium (Pd).

It, can also be same as the first coating 108a in the case where forming the second coating 108b by electroless nickel plating Ground is formed.Such as the first coating 108a containing nickel-phosphor alloy or nickel-boron alloy can also be formed.The hardness of nickel-boron alloy Higher than nickel-phosphor alloy.Therefore, protrusion 109 is inhibited to be subject to crushing in the case where substantially compressing conducting particles 1, from obtaining From the viewpoint of obtaining lower conducting resistance, preferably the second coating 108b contains nickel-boron alloy.

Insulation-coated electroconductive particles 100c involved by 3rd embodiment described above is also played and the 1st embodiment Same function and effect.In 3rd embodiment, preferably the first coating 108a contains nickel-phosphor alloy, and the second coating 108b contains There are nickel-phosphor alloy or nickel-boron alloy.According to the combination, even if can press down if in the case where substantially compressing conducting particles 1 Protrusion 109 processed is subject to crushing, and inhibits the rupture of first layer 108, can more stably obtain low conducting resistance.In the first quilt Coating 108a contains nickel-phosphor alloy, in the case that the second coating 108b contains nickel-phosphor alloy, inhibits prominent simultaneously because highly Rise 109 damage by pressure with the rupture of first layer 108 and it is preferred that.

In 3rd embodiment, more preferable nickel particles 107 contain nickel-phosphor alloy or nickel-boron alloy, the first coating 108a Containing nickel-phosphor alloy, the second coating 108b contains nickel-phosphor alloy or nickel-boron alloy.According to the combination, even if will be conductive In the case that particle 1 substantially compresses, it can also further suppress protrusion 109 and be subject to crushing, and it is broken to further suppress first layer 108 It splits, can more stably obtain low conducting resistance.

(the 4th embodiment)

Hereinafter, being illustrated to the insulation-coated electroconductive particles involved by the 4th embodiment.The explanation of 4th embodiment In, the record repeated with the embodiment of the 1st embodiment~the 3rd is omitted, and record and the embodiment of the 1st embodiment~the 3rd Different parts.That is, in the range of can also being technically possible, suitably used in the 4th embodiment the 1st embodiment~ The record of 3rd embodiment.

Fig. 4 is the schematic section for indicating the insulation-coated electroconductive particles involved by the 4th embodiment.It is shown in Fig. 4 exhausted In edge coated electroconductive particles 100d, metal layer further has the second layer 105 other than first layer 108, other than this point, It is similarly constituted with the insulation-coated electroconductive particles 100c with the 3rd embodiment.

Insulation-coated electroconductive particles 100d involved by 4th embodiment described above is also played and the 3rd embodiment Same function and effect.In addition, in the 4th embodiment, in a same manner as in the second embodiment, the second layer 105, which becomes insulation-coated, leads The outermost layer of charged particle 100d.Therefore, it is possible to inhibit the nickel in first layer 108 migration generation.In addition, insulation-coated conduction The electric conductivity of particle 100d is not easily deteriorated.Moreover, there is the second layer 105, Neng Gougao by insulation-coated electroconductive particles 100d Quantity, the size and shape of degree ground control projection 109.

(the 5th embodiment)

Hereinafter, being illustrated to the anisotropic conductive adhesive involved by the 5th embodiment.5th embodiment In explanation, the record repeated with the embodiment of the 1st embodiment~the 4th is omitted, and records and implements with the 1st embodiment~4th The different part of mode.That is, in the range of can also being technically possible, the 1st embodiment party is suitably used in the 5th embodiment The record of the embodiment of formula~the 4th.

Anisotropic conductive adhesive involved by 5th embodiment contains the insulation quilt involved by the 1st embodiment It covers conducting particles 100a and is dispersed with the bonding agent of insulation-coated electroconductive particles 100a.

As bonding agent, the mixture of heat reactivity resin and curing agent can be used for example.As bonding agent, can enumerate Such as the mixing of the mixture and free-radical polymerised compound and organic peroxide of epoxy resin and latent curing agent Object.

As bonding agent, paste or membranaceous bonding agent can be used.In order to which anisotropic conductive adhesive is molded To be membranaceous, can also coordinate in bonding agent phenoxy resin, polyester resin, polyamide, polyester resin, polyurethane resin, The thermoplastic resins such as (methyl) acrylic resin, polyester polyurethane resin.

Anisotropic conductive adhesive involved by 5th embodiment described above also in a same manner as in the first embodiment, Excellent insulating reliability can be obtained, and it is reliable to obtain in the connection in fine circuit excellent conducting Property.

As the insulation-coated electroconductive particles in the anisotropic conductive adhesive involved by the 5th embodiment, such as The insulation-coated electroconductive particles 100b involved by the 2nd embodiment etc. can be used to replace insulation-coated electroconductive particles 100a. In this case, anisotropic conductive adhesive can play the insulation-coated electroconductive particles 100b's involved by the 2nd embodiment Function and effect.Insulation-coated electroconductive particles 100c can also be used to replace insulation-coated electroconductive particles 100a.In this case, respectively Anisotropy conductive adhesive can play the function and effect of the insulation-coated electroconductive particles 100c involved by the 3rd embodiment. Insulation-coated electroconductive particles 100d can be used to replace insulation-coated electroconductive particles 100a.In this case, anisotropic conductive Property bonding agent can play the function and effect of the insulation-coated electroconductive particles 100d involved by the 3rd embodiment.

(the 6th embodiment)

Hereinafter, being illustrated to the connection structural bodies involved by the 6th embodiment.In the explanation of 6th embodiment, omit The record repeated with the embodiment of the 1st embodiment~the 5th, and record the portion different from the 1st embodiment~the 5th embodiment Point.That is, in the range of can also being technically possible, suitably the 1st embodiment~5th is used to implement in the 6th embodiment The record of mode.

Connection structural bodies involved by 6th embodiment is illustrated.Connection structural bodies involved by present embodiment Have：It the first circuit member with the first circuit electrode, the second circuit component with second circuit electrode and is configured at Between first circuit member and second circuit component and it is dispersed with the interconnecting pieces of insulation-coated electroconductive particles.Interconnecting piece is by first Circuit electrode and second circuit electrode configure in an opposing fashion in the state of by the first circuit member and second circuit component that This connection.First circuit electrode and second circuit electrode are electrically connected to each other by the insulation-coated electroconductive particles of deformation state.

Then, the connection structural bodies involved by the 6th embodiment is further illustrated on one side with reference to Fig. 5 on one side.Figure 5 be the schematic section for indicating the connection structural bodies involved by the 6th embodiment.Connection structural bodies 300 shown in fig. 5 has： First circuit member 310 relative to each other and second circuit component 320 and it is configured at the first circuit member 310 and the second electricity Interconnecting piece 330 between road component 320.As connection structural bodies 300, liquid crystal display, personal computer, mobile electricity can be enumerated The portable products such as words, smart mobile phone, tablet computer.

First circuit member 310 has circuit board (the first circuit board) 311 and is configured at the master of circuit board 311 Circuit electrode (the first circuit electrode) 312 on the 311a of face.Second circuit component 320 has circuit board (the first circuit board) 321 and the circuit electrode (second circuit electrode) 322 that is configured on the interarea 321a of circuit board 321.

As the concrete example of circuit member 310, one of 320, can enumerate：IC chip (semiconductor chip), resistor The chip parts such as chip, capacitor chip, driver IC；The package substrate etc. of hard type.These circuit members have circuit electricity Pole is generally configured with multiple circuit electrodes.It (is connect with said one circuit member as circuit member 310, the other of 320 Circuit member) concrete example, can enumerate：Flexible tape substrate, flexible printing patch panel, vapor deposition with metal wiring have indium tin Wiring substrates such as the glass substrate of oxide (ITO) etc..It, can such as by using membranaceous anisotropic conductive adhesive Effectively and with high connecting reliability these circuit members are connected to each other.Such as the 5th anisotropy involved by embodiment Conductive adhesive is suitable for having COG installation or COF installation of the chip part of multiple fine circuits electrodes on wiring substrate.

The insulation-coated conductive particle that interconnecting piece 330 has the solidfied material 332 of bonding agent and is scattered in the solidfied material 332 The membranaceous anisotropic conductive adhesive described in above-mentioned 5th embodiment can be used for example in sub- 100a.Connection structure In body 300, opposite circuit electrode 312 is electric by conducting particles 1 of insulation-coated electroconductive particles 100a with circuit electrode 322 Connection.More specifically, as shown in fig. 6, insulation-coated electroconductive particles 100a is deformed because of compression, and it is electrically connected to circuit electrode 312, both 322.On the other hand, in insulation-coated electroconductive particles 100a, on the direction intersected with compression direction, insulating particle 210 between conducting particles 1, so as to maintain the mutual insulating properties of insulation-coated electroconductive particles 100a.Therefore, it is possible to further Improve insulating reliability when thin space (such as 10 μm of horizontal spacing).

Connection structural bodies 300 obtains in the following manner, i.e.,：By with circuit electrode 312 the first circuit member 310 with Second circuit component 320 with circuit electrode 322 configures in such a way that circuit electrode 312 is opposite with circuit electrode 322, makes each Anisotropy conductive adhesive heats them and is added between the first circuit member 310 and second circuit component 320 It presses and circuit electrode 312 is made to be electrically connected with circuit electrode 322.First circuit member 310 and second circuit component 320 pass through bonding The solidfied material 332 of agent and be bonded.

The manufacturing method of connection structural bodies while with reference to Fig. 6 involved by pair the 6th embodiment illustrates.Fig. 6 For the schematic section of an example of the manufacturing method for illustrating connection structural bodies shown in fig. 5.In 6th embodiment, make each The heat cure of anisotropy conductive adhesive and manufacture connection structural bodies.

First, prepare the first circuit member 310 and anisotropic conductive adhesive 330a.In present embodiment, use Be shaped to it is membranaceous made of adhesive film (anisotropic conductive adhesive film) be used as anisotropic conductive adhesive 330a. Anisotropic conductive adhesive 330a contains insulation-coated electroconductive particles 100a and the bonding agent 332a of insulating properties.

Then, the interarea 311a that anisotropic conductive adhesive 330a is placed in the first circuit member 310 (is formed with The face of circuit electrode 312) on.Then, as shown in Fig. 6 (a), along direction A and direction B to anisotropic conductive adhesive 330a pressurizes.As a result, as shown in Fig. 6 (b), anisotropic conductive adhesive 330a is laminated in the first circuit member On 310.

Then, as shown in Fig. 6 (c), in such a way that circuit electrode 312 is opposite with circuit electrode 322, by second circuit component 320 are placed on anisotropic conductive adhesive 330a.Then, anisotropic conductive adhesive 330a is heated on one side, Entirety (the first circuit member 310 and second circuit component 320) is carried out along direction A shown in Fig. 6 (c) and direction B on one side Pressurization.

By heating, anisotropic conductive adhesive 330a is solidified to form interconnecting piece 330, to obtain shown in Fig. 5 Such connection structural bodies 300.Anisotropic conductive adhesive may be paste.

In connection structural bodies 300 involved by 6th embodiment described above, implement containing the 3rd in interconnecting piece 330 Insulation-coated electroconductive particles 100a involved by mode.According to above-mentioned connection structural bodies 300, insulation-coated conductive particle can be passed through Circuit electrode 312 is electrically connected by sub- 100a well with circuit electrode 322.Therefore, even if in circuit electrode 312 and circuit electrode 322 area is small, and the few situation of number of the insulation-coated electroconductive particles 100a captured between circuit electrode 312,322 Under, excellent conducting reliability can be also played for a long time.Moreover, there is insulating particle 210 by insulation-coated electroconductive particles 100a, To which the first layer 104 (referring to Fig.1) of the insulation-coated electroconductive particles 100a in interconnecting piece 330 is not easy to contact each other.Therefore, example Even if as being e.g., less than or equal to 10 μm in the mutual spacing of electrode in circuit electrode 312 (in circuit electrode 322) In the case of, the insulation-coated electroconductive particles 100a in interconnecting piece 330 is not easy to be connected each other, the insulation of connection structural bodies 300 Reliability also suitably improves.

More than, embodiments of the present invention are illustrated, but the present invention is not limited to the above embodiment.Example Such as, insulation-coated electroconductive particles 100a~100d has protrusion 109, but insulation-coated electroconductive particles 100a in the above embodiment ~100d can not also have protrusion 109.It can not also implement hydrophobization to the second insulating particle 210b in insulating particle 210 Processing.

Embodiment

Hereinafter, enumerating embodiment and comparative example is more particularly described present disclosure.It should be noted that this hair It is bright to be not limited to following embodiments.

[making of conducting particles]

(process a) cation property copolymers are coating to resin particle surface

By 3.0 μm of crosslinked polystyrene particle (Nippon Shokubai Co., Ltd's system, trade name of 6g average grain diameters " Soliostar ") it is added to 30 mass % aq. polyethyleneimines of 9g average molecular weight 70,000 (M.W. be 70,000) (and light Chun Yao Industrial Co., Ltd system) be dissolved in 300ml pure water obtained by aqueous solution, be stirred at room temperature 15 minutes.Then, pass through It has used the filtering of the molecular filter (Merck Millipore Corp. system) of 3 μm of Φ and has taken out resin particle.With 600g ultra-pure waters by membrane filtration Resin particle on device cleans 2 times, and unadsorbed polyethyleneimine is removed, and obtains the resin particle for being adsorbed with polyethyleneimine Son.

(process b) silicic acid anhydrides agent is to the coating of non-conductive surface of inorganic particles

Using the vapor phase method hydrophily spherical silicon dioxide powder of average grain diameter 60nm as non-conductive inorganic particulate.It will The 100g spherical silicon dioxide powders are contained in vibrational fluidized bed device (central chemical industry machine Co. Ltd. system, trade name " vibration stream Change bed apparatus VUA-15 types ") in.Then, spherical silicon dioxide is made to flow using the air recycled by sucktion fan on one side On one side spray 1.5g water and flow mixing 5 minutes.Then, spraying HMDS (hexa-methylene disilazane) (steps figure new high-tech material day This contract corporation, trade name " TSL-8802 ") 2.5g, flowing mixing 30 minutes.It is hydrophobic to obtained by as methanol titration The hydrophobization degree of property spherical silicon dioxide powder body is measured.Hydrophobization degree measures by the following method, non-conductive inorganic The hydrophobization degree of particle is 70%.

(electrostatic bonding process of the non-conductive inorganic particulates of process c) to resin particle surface

The resin particle that 6g is adsorbed with to polyethyleneimine is added in methanol, irradiates resonant frequency 28kHz, output on one side The ultrasonic wave of power 100W is stirred at room temperature 5 minutes on one side.Then, 0.15g has been carried out to spherical the two of hydrophobization using HMDS Silicon oxide powder is added in above-mentioned methanol, enters one while irradiating the ultrasonic wave of resonant frequency 28kHz, output power 100W Step is stirred at room temperature 5 minutes.Resin particle (the particle a) that non-conductive inorganic particulate is adsorbed with by electrostatic is obtained as a result,. The particle A that non-conductive inorganic particulate is adsorbed with by electrostatic is 6.15g.

(process d) palladium catalysts assign process

The pH that 6.15g particles A is added to 300mL is adjusted to 1.0 and (Hitachi is melted into containing 20 mass % palladium catalysts Co. Ltd. system, trade name " HS201 ") palladium catalyst liquid in.Then, resonant frequency 28kHz, output power are irradiated on one side The ultrasonic wave of 100W stirs 30 minutes at 30 DEG C on one side.Then, it is filtered using the molecular filter (Merck Millipore Corp. system) of 3 μm of Φ Afterwards, it is washed, to make palladium catalyst be adsorbed in the surface of particle A.Then, particle A is added to pH and is adjusted to 6.0 In 0.5 mass % dimethyamine borane liquid, exist 60 while irradiating the ultrasonic wave of resonant frequency 28kHz, output power 100W DEG C stirring 5 minutes, obtains 6.15g and is fixed with the particle B of palladium catalyst.Then, 6.15g is fixed with to the particle B of palladium catalyst After being impregnated in the distilled water of 20mL, ultrasonic wave dispersion is carried out to particle B, to obtain resin particle dispersion liquid.SEM will be passed through The table of (Hitachi Ltd.'s system, trade name " S-4800 ") to the resin particle for being adsorbed with spherical silicon dioxide powder The result that face is observed is shown in Fig. 7, Fig. 8.

(the formation of process e) first layers

The water for being heated up to 80 DEG C using 3000mL adds 3mL conducts by after the particle B dispersion liquids dilution of gained in process d The aqueous bismuth nitrate solution of the 1g/L of plating stabilizer.Then, it is added dropwise with 15mL/ minutes rate of addition in particle B dispersion liquids Following composition (the aqueous solutions containing following compositions of 240mL.Per the aqueous bismuth nitrate solution 1mL of 1L plating solution additions 1g/L.It is the same below Sample) first layer formation electroless nickel plating solution.After completion of dropwise addition, by after ten minutes, by the dispersion liquid added with plating solution Filtering.After washing with water filtrate, it is dried using 80 DEG C of vacuum drier.Particle C is consequently formed, particle C has (first be equivalent in the above embodiment is coating for the first layer of nickel-phosphor alloy envelope comprising 80nm film thickness shown in table 1-1 Layer).It is 12.15g as forming the particle C obtained by first layer.The composition of the electroless nickel plating solution of first layer formation is as follows.

Nickel sulfate ... ... ... 400g/L

Sodium hypophosphite ... ... 150g/L

Sodium citrate ... ... ... 120g/L

Aqueous bismuth nitrate solution (1g/L) ... 1mL/L

(the formation of the process f) second layers

After the particle C washings and filtering of gained in 12.15g processes e, it is made to be scattered in the water that 3000mL is heated up to 70 DEG C In.Aqueous bismuth nitrate solution 3mL of the addition as the 1g/L of plating stabilizer in the dispersion liquid.Then, with 15mL/ minutes drops The second layer formation electroless nickel plating solution of the following compositions of 60mL is added dropwise in acceleration.After completion of dropwise addition, by after ten minutes, will add Added with the dispersion liquid filtering of plating solution.After washing with water filtrate, it is dried using 80 DEG C of vacuum drier.It is consequently formed There is the second layer of the nickel-phosphor alloy envelope comprising 20nm film thickness shown in table 1-1 (to be equivalent to above-mentioned reality by particle D, particle D Apply the second coating in mode).It is 13.65g as forming the particle D obtained by the second layer.Second layer formation it is electroless The composition of nickel-plating liquid is as follows.

Nickel sulfate ... ... ... 400g/L

Sodium hypophosphite ... ... 150g/L

Sodium tartrate dihydrate ... 60g/L

Aqueous bismuth nitrate solution (1g/L) ... 1mL/L

Conducting particles is obtained by above process a~f.

[evaluation of conducting particles]

Conducting particles is evaluated based on following projects.It shows the result in table 1-1.

(evaluation of film thickness and ingredient)

By ultrathin sectioning section is cut out in the way of by the immediate vicinity of the conducting particles of gained.Use TEM (days This Electronics Co., Ltd system, trade name " JEM-2100F ") section observed with 250,000 times of multiplying power.Estimated according to the image of gained The sectional area for calculating first layer, the second layer and third layer, the film thickness of first layer, the second layer and third layer is calculated according to the section. In embodiment 1~16,19 and the Comparative Examples 1 to 5, do not form third layer, thus in these embodiments and comparative example only by first layer, The film thickness of the second layer is as measure object.When calculating the film thickness of each layer based on section, width is read by image analysis The sectional area of each layer in the section of 500nm calculates film of height when being converted into the rectangle of width 500nm as each layer It is thick.The average value of the film thickness calculated to 10 conducting particles is shown in table 1-1.At this point, being difficult to differentiate between first layer, the second layer In the case of third layer, by using the incidental EDX of TEM (Jeol Ltd.'s system, trade name " JED-2300 ") Constituent analysis clearly distinguish first layer, the second layer and third layer, to estimate sectional area, measure film thickness.It is drawn according to EDX Data calculate the constituent content (purity) in first layer, the second layer and third layer.Sample (conducting particles about cut film shape Cross-section samples) production method details, utilize the constituent content in the details and each layer of the drawing practice of EDX Calculation method details, it is aftermentioned.

(evaluation for being formed in the protrusion on conducting particles surface)

{ covering rate of protrusion }

Based on the SEM image observed obtained by conducting particles with 30,000 times as SEM, the protrusion on conducting particles surface is calculated Covering rate (ratio of area).Specifically, 1/2 of the diameter with conducting particles in the frontal plane of projection of conducting particles is straight In the concentric circles of diameter, projecting formation and flat part are distinguished by image analysis.Then, existing in concentric circles dash forward is calculated The area ratio for playing forming portion, using the ratio as the covering rate of protrusion.Fig. 9 is indicated through SEM to the particle D in embodiment 1 The result observed.

{ diameter and quantity of protrusion }

In the frontal plane of projection of conducting particles, calculates and deposited in the concentric circles of 1/2 diameter of the diameter with conducting particles Protrusion covering rate and with the number of projection of predetermined diameter.

Specifically, to being parsed with the image obtained by 100,000 times of observation conducting particles as SEM, the wheel of protrusion delimited It is wide.Then, the area (area of the profile of the protrusion separated by the recess portion between protrusion) for measuring protrusion, calculating has and the face Diameter (outer diameter) of the positive diameter of a circle of the identical area of product as protrusion.It is shown in Figure 10 through SEM to the grain in embodiment 1 The result that sub- D is observed.

Range based on diameter shown in table 1-1 classifies protrusion, finds out the protrusion quantity of each range.Figure 10 is with grain A part in the concentric circles of 1/2 diameter of the diameter of sub- D.

(production methods of the cross-section samples of conducting particles)

The details of the production method of the cross-section samples of conducting particles is illustrated.It is as follows using ultrathin sectioning The thickness with 60nm ± 20nm made for carrying out tem analysis and STEM/EDX analyses by the section of conducting particles Cross-section samples (hereinafter referred to as " cut film of TEM measurement ").

In order to steadily carry out filming processing, conducting particles is made to be scattered in foundry resin.Specifically, in bisphenol-A Mixture (RefineTec Co. Ltd. systems, the commodity of type liquid-state epoxy resin, butyl glycidyl ether and other epoxy resin Name " Epomount host agents 27-771 ") 1.0g diethylenetriamine (Refine Tec Co. Ltd. systems, trade name are mixed in 10g " Epomount curing agent 27-772 ").It is stirred using spatula, determines uniformly mix by visual observation.In the 3g mixtures After the dried conducting particles of middle addition 0.5g, it is stirred using spatula until becoming uniform.By the mixing containing conducting particles Object flows into the mold (D.S.K slope EM Co. Ltd. systems, trade name " organosilicon embedding plate II types ") of resin casting, 24 hours are stood under room temperature (room temperature).Confirm that foundry resin has solidified, obtains the resin moulding of conducting particles.

Using ultramicrotome (Leica Microsystems Co. Ltd. systems, trade name " EM-UC6 "), led by containing The resin moulding of charged particle makes the cut film of TEM measurement.When making the cut film of TEM measurement, make first The front end of resin moulding is carried out as shown in Figure 11 (a) with the glass system knife being fixed on the apparatus main body of ultramicrotome Finishing processing is until become the shape for the cut film that can cut out TEM measurement.

More specifically, as shown in Figure 11 (b), being become with the cross sectional shape of the front end of resin moulding has longitudinal 200 The mode of the substantially rectangular parallelepiped of~400 μm and laterally 100~200 μm of length carries out finishing processing.The transverse direction in section is grown Degree be set as 100~200 μm be in order to when cutting out the cut film of TEM measurement from resin moulding, reduce diamond tool with Generated friction between sample.It is easy to prevent gauffer and the bending of the cut film of TEM measurement as a result, is easy to make TEM The cut film of measurement.

Then, by the diamond tool with ship shape dish (boat), (DIATONE corporations, trade name " CryoWet ", knife is wide 2.0mm, 35 ° of nose angle degree) it is fixed on the predetermined position of ultramicrotome apparatus main body.Then, ship shape is filled up with ion exchange water Dish adjusts the setting angle of knife and soaks point of a knife with ion exchange water.

Herein, the adjustment of the setting angle of knife is illustrated using Figure 12.When adjusting the setting angle of knife, can adjust The angle of upper and lower directions, the angle of left and right directions and clearance angle.As shown in figure 12, so-called " angle of adjustment upper and lower directions " is Refer to the angle for the upper and lower directions that sample frame is adjusted in such a way that specimen surface is parallel with the direction of travel of knife.As shown in figure 12, institute Meaning " angle of adjustment left and right directions ", refers to the angle for the left and right directions that knife is adjusted in such a way that the point of a knife of knife is parallel with specimen surface Degree.As shown in figure 12, so-called " adjustment clearance angle ", refer to the sample side for the point of a knife for adjusting knife face and knife direction of travel institute at Minimum angles.Clearance angle is preferably 5~10 °.If clearance angle is above range, the point of a knife and sample table of knife can be reduced The friction in face, and prevent from sample cut out cut film after knife friction sample surface.

The incidental light microscope of ultramicrotome apparatus main body is confirmed on one side, makes sample and diamond on one side The distance of knife is close, by knife speed 0.3mm/ second, film cut out thickness as 60nm ± 20nm in a manner of set slicer and fill The setting value set cuts out cut film from resin moulding.Then, the cut film of TEM measurement is made to float on ion exchange On the water surface of water.Copper mesh (the band of TEM measurement is pressed from the upper surface of the cut film of the TEM measurement floated on the water surface The copper mesh of microgrid), so that the cut film of TEM measurement is adsorbed in copper mesh, TEM samples are made.It is obtained using slicer The cut film of TEM measurement is not accurately consistent with the setting value for cutting out thickness of slicer, therefore finds out and can obtain in advance Obtain the setting value of desired thickness.

(drawing practice for utilizing EDX)

The details of drawing practice using EDX is illustrated.By the cut film of TEM measurement together with copper mesh one It rises and is fixed on sample frame (Jeol Ltd.'s system, trade name " beryllium sample bi-axial tilt frame, EM-31640 "), be inserted into Inside TEM.Started after irradiating electron ray to sample with accelerating potential 200kV, the irradiation system of electron ray is switched to STEM patterns.

By scanning as observation device is inserted into position when STEM is observed, the software " JEOL of startup STEM observations Simple Image Viewer) (Version 1.3.5) " after (Jeol Ltd.'s system), observation TEM measurement it is thin Film is sliced.In the section of the conducting particles observed by wherein, search is suitable for the position that EDX is measured and is shot.Herein So-called " position for being suitable for measuring " refers to the portion that the section of metal layer can be observed in the immediate vicinity cut-out of conducting particles Position.By the inclined position in section and deviate conducting particles immediate vicinity position cut-out position from measure object It excludes.When shooting, observation multiplying power is 250,000 times, and the pixel number that STEM is observed to picture is set as longitudinal, lateral at 512 points at 512 points.If It observes under this condition, then can get the observation picture of visual angle 600nm, but if changing device, even if then sometimes for phase same multiplying Visual angle also changes, it is therefore necessary to pay attention to.

When STEM/EDX is analyzed, if the cut film to TEM measurement irradiates electron ray, the resin of conducting particles Particle and foundry resin can shrink and thermally expand, and sample can be deformed or be moved in the assay.In order to inhibit such EDX to survey Sample deformation in fixed and sample movement, irradiate 30 minutes~1 hour degree of electron ray to measurement site in advance, confirm deformation It is analyzed with after mobile calm down.

In order to carry out STEM/EDX analyses, so that EDX is moved to and locate, start the software " Analysis of EDX measurement Station " (Jeol Ltd.'s system).When using the drawing of EDX, need to obtain sufficient resolution ratio when drawing, Therefore using for making electron ray focus on the focusing iris apparatus of target site.

When STEM/EDX is analyzed, with the counting (CPS of detected characteristic X-ray：Counts Per Second, it is per second Count) become the mode for being greater than or equal to 10,000CPS, the point diameter of electron ray is adjusted in the range of 0.5~1.0nm.It surveys After fixed, at least becoming big with the height in the EDX spectrum that measurement obtains simultaneously of drawing, confirming the Alpha-ray peaks K from nickel In or equal to 5,000Counts.When obtaining data, pixel number is set as vertical by identical visual angle when being observed with above-mentioned STEM To 256 points, laterally 256 points.The accumulated time of every bit is set as 20 milliseconds, is measured for 1 time with cumulative frequency.

It extracts the EDX spectrum of first layer, the second layer and third layer as needed from the EDX draw datas of gained, calculates each Partial element exist than.In embodiment 1~16,19, the Comparative Examples 1 to 5, due to not forming third layer, only to first layer, The film thickness of the second layer extracts EDX spectrum, calculate each section element exist than.About embodiment 19, extraction plating palladium be precipitated core and Electroless nickel plating be precipitated core nickel EDX spectrum, calculate each section element exist than.It wherein, will be expensive when calculating quantitative values Total ratio of metal, nickel and phosphorus is set as 100 mass %, calculates the quality % concentration of each element.

About element other than the above, ratio is easy to change due to following reasons, thus when calculating quantitative values except.Carbon Net of the ratio due to TEM measurement used in carbon support membrane or when electronbeam irradiation be adsorbed in the impurity of specimen surface Influence and increase and decrease.The ratio of oxygen is likely due to that air oxidation occurs during after making TEM samples until measuring And increase.Copper can be measured from TEM and be detected in copper mesh used.

(measurement of monodisperse rate)

So that 0.05g conducting particles is scattered in electrolysis water, add surfactant, carries out 5 minutes ultrasonic waves and disperse (AS- One Co. Ltd. systems, trade name " US-4R ", output high frequency power：160W, frequency of oscillation：40kHz single-frequency).By conducting particles Dispersion liquid be injected into the sample cup for liquid of COULER MULTISIZER II (Beckman Kurt Co., Ltd. manufacture, trade name) In, measure the monodisperse rate of 50000 conducting particles.Monodisperse rate is calculated by following formula, based on its value according to following benchmark To judge the coherency of the particle in aqueous solvent.

Monodisperse rate (%)={ first peak (first peak) population (a)/total population (a) } × 100

(process g) [making of the first insulating particle]

Monomer is added to loaded in 500ml flasks according to the cooperation molar ratio of insulating particle No.1 shown in table 6 In 400g pure water.Coordinate in such a way that the total amount of all monomers becomes 10 mass % relative to pure water.After nitrogen displacement, exist on one side 70 DEG C of stirrings carry out heating for 6 hours on one side.Mixing speed is 300min^-1(300rpm).KBM-503 (SHIN-ETSU HANTOTAI's chemistry strains in table 6 Formula commercial firm system, trade name) it is 3- methacryloxypropyl trimethoxy silanes.

The average grain diameter of synthesized insulating particle is measured by parsed to the image captured by the SEM.It is tied Fruit is shown in Table 6.

Using DSC (Perkinelmer Inc.'s system, trade name " DSC-7 "), sample size be 10mg, heating rate be 5 DEG C/ Minute measures atmosphere to measure the Tg (glass transition temperature) of synthesized insulating particle under conditions of air.

(modulation of silicone oligomer)

In the glass flask for having agitating device, condenser and thermometer, add the 3- glycidoxypropyls of 118g Propyl trimethoxy silicane and solution made of the cooperation of 5.9g methanol.5g atlapulgites and 4.8g distilled water are further added, 75 DEG C of stirrings after a certain period of time, obtain the silicone oligomer of weight average molecular weight 1300.The silicone oligomer of gained has first Oxygroup or silanol group are as the functional end-group with hydroxyl reaction.Methanol is added in the silicone oligomer solution of gained, Modulate the treatment fluid that solid constituent is 20 mass %.

The weight average molecular weight of silicone oligomer is measured by using gel permeation chromatography (GPC) method, and uses mark The calibration curve of quasi- polystyrene is converted and is calculated.When measuring the weight average molecular weight of silicone oligomer, pump (strain is used Formula commercial firm Hitachi's system, trade name " L-6000 "), chromatographic column (GelpackGL-R420, Gelpack GL-R430, Gelpack GL-R440 (be above Hitachi Chemical Co., Ltd.'s system, trade name)), detector (Hitachi Co., Ltd System, trade name " L-3300 types RI ").Using tetrahydrofuran (THF) as eluent, measuring temperature is set as 40 DEG C, by flow It is set as being measured for 2.05mL/ minutes.

(process h) [making of the second insulating particle]

Using the vapor phase method hydrophily spherical silicon dioxide powder of average grain diameter 60nm as the second insulating particle.By 100g The spherical silicon dioxide powder is contained in vibrational fluidized bed device (central chemical industry machine Co. Ltd. system, trade name " vibrated fluidized bed Device VUA-15 types ") in.Then, on one side using the air recycled by sucktion fan make spherical silicon dioxide flow while Spraying 1.5g water and flow mixing 5 minutes.Then, spraying HMDS (hexa-methylene disilazane) (steps figure new high-tech material Japan to close Same corporation, trade name " TSL-8802 ") 2.5g, flowing mixing 30 minutes.Titanium dioxide silicon grain shown in table 7-1 is made as a result, Sub- No.3.It is measured as the hydrophobization degree of hydrophobicity spherical silicon dioxide powder body of the methanol titration to obtained by.It is hydrophobic Change degree measures by the following method, and the hydrophobization degree of the second insulating particle is 70%.The characteristic of second insulating particle is summarized and is shown In table 7-1 and table 7-2.

(hydrophobization degree (%))

The hydrophobization degree of second insulating particle measures by the following method.First, 50ml ion exchange waters, 0.2g are tried Sample (the second insulating particle) is added into beaker, buret is followed while being stirred using magnetic stirring apparatus, methanol is added dropwise. As the methanol concentration in beaker increases, powder gradually settles, in the methanol-water mixed solution when terminal that its total amount is precipitated Methanol hydrophobization degree (%) of the mass fraction as the second insulating particle.

(average grain diameter of the second insulating particle)

It is measured about the grain size of the second insulating particle to being parsed with the image obtained by 100,000 times of observations as SEM 500 respective areas of particle.Then, average grain of the diameter as the second insulating particle that particle is converted into bowlder is calculated Diameter.Average grain diameter the ratio between of the standard deviation of grain size relative to gained is calculated with percentage, is set as CV.

(boundary reaches the measurement of current potential)

The boundary of second insulating particle measures by the following method up to current potential.When measuring boundary up to current potential, Zetasizer is used ZS (Malvern Instruments corporations, trade name).It is used in such a way that the second insulating particle becomes about 0.02 mass % Methanol dilutes dispersion, measures boundary and reaches current potential.

(process i) [making of insulation-coated electroconductive particles]

8mmol thioacetic acid is set to be dissolved in 200ml methanol and modulate reaction solution.Then by conducting particles (in embodiment 1 For particle D) it is added in the above-mentioned reaction solutions of 10g, utilize the stirring wing of 31 motors (Three-One Motor) and diameter 45mm It is stirred at room temperature 2 hours.After being cleaned using methanol, it is filtered using 3 μm of the molecular filter (Merck Millipore Corp. system) in aperture, There is the conducting particles of carboxyl to obtain the surfaces 10g.

Then, with ultra-pure water by (and the Wako Pure Chemical Industries strain of 30% aq. polyethyleneimine of weight average molecular weight 70,000 Formula commercial firm system) dilution, obtain 0.3 mass % aq. polyethyleneimines.There is the conducting particles of carboxyl to add the above-mentioned surfaces 10g It adds in 0.3 mass % aq. polyethyleneimines, is stirred at room temperature 15 minutes.Then, (silent using the molecular filter in 3 μm of aperture Gram Millipore Corp.'s system) conducting particles is filtered, filtered conducting particles is added into 200g ultra-pure waters, is stirred at room temperature 5 minutes.The molecular filter (Merck Millipore Corp. system) for further using 3 μm of aperture filters conducting particles, in above-mentioned molecular filter On 2 cleanings are carried out with the ultra-pure water of 200g.By carrying out these operations, unadsorbed polyethyleneimine is removed, obtains table Face is by the coating conducting particles of amido polymer.

Then, it is handled using the first insulating particle of silicone oligomer pair, modulation surface, which has, contains glycidyl The methanol decentralized medium (the methanol decentralized medium of the first insulating particle) of first insulating particle of oligomer.

Then, modulation has methanol decentralized medium (the second insulating particle for the second insulating particle being made of silica Methanol decentralized medium).

Above-mentioned surface is impregnated in by the coating conducting particles of amido polymer in methanol, the first insulating particle is added dropwise Methanol decentralized medium.The covering rate of first insulating particle is adjusted by the dripping quantity of the methanol decentralized medium of the first insulating particle It is whole.Then, the methanol decentralized medium of the second insulating particle is added dropwise, to make the first insulating particle and the second insulating particle be attached to Conducting particles.The covering rate of second insulating particle is adjusted by the dripping quantity of the second insulating particle.By the first insulating particle and The respective covering rate of second insulating particle summarizes in shown in table 1-1.

Using condensing agent and octadecylamine to be attached with the conducting particles of the first insulating particle and the second insulating particle into Row surface treatment after, cleaned, to carry out the conducting particles surface hydrophobization.Then with 80 DEG C, 1 hour condition It is thermally dried, makes insulation-coated electroconductive particles.

(measurement of the covering rate of insulating particle)

In the frontal plane of projection of insulation-coated electroconductive particles, 1/ of the diameter with insulation-coated electroconductive particles is calculated respectively The covering rate of existing the first insulating particle and the second insulating particle in the concentric circles of 2 diameters.Specifically, with insulation In the concentric circles of 1/2 diameter of the diameter of coated electroconductive particles, the first insulating particle, the second insulation are distinguished by image analysis Particle and conducting particles calculate the ratio of the area of the first insulating particle existing in concentric circles and the second insulating particle respectively Example, using the ratio as the first insulating particle and the respective covering rate of the second insulating particle.Find out 200 insulation-coated conductive particles The average value of son.

Specifically, the covering rate of the first insulating particle and the second insulating particle is based on observing with 20,000 5 thousand times by SEM Image obtained by insulation-coated electroconductive particles is evaluated.Insulation-coated electroconductive particles are observed in figure 13 illustrates SEM image.In the case where being difficult to differentiate between the first insulating particle and the second insulating particle, can also be based on through SEM with 50,000 times Image obtained by observation insulation-coated electroconductive particles is evaluated.It is shown in FIG. 14 and insulation-coated electroconductive particles is observed SEM image.Figure 14 is the part in the concentric circles of 1/2 diameter of the diameter with insulation-coated electroconductive particles.

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

By 100g phenoxy resins (Union Carbide Corporation's system, trade name " PKHC "), 75g acrylic rubbers (40 mass parts Butyl acrylate, 30 mass parts ethyl acrylates, 30 mass parts acrylonitrile, 3 mass parts glycidyl methacrylate are total to Polymers, weight average molecular weight：Ten thousand) 85 are dissolved in 300g by ethyl acetate and toluene with mass ratio 1:In 1 solvent mixed, obtain Obtain solution.Liquid-state epoxy resin (Asahi Chemical Industry's epoxy strain that 300g contains microcapsule-type latent curing agent is added in the solution Formula commercial firm system, trade name " Novacure HX-3941 ", epoxide equivalent 185) and 400g liquid-state epoxy resins (oiling shell epoxy Co. Ltd. system, trade name " YL980 ") and be stirred.Addition is to the two of average grain diameter 14nm in the mixed solution of gained Silica carries out the silica slurry (Japanese Aerosil Co. Ltd. systems, trade name " R202 ") of solvent dispersion gained, to Modulate adhesive solution.Silica slurry with the content of silica solid ingredient relative to above-mentioned mixed solution solid at Point total amount is added as the mode of 5 mass %.

10g is added in beaker by ethyl acetate and toluene with mass ratio 1:1 decentralized medium mixed and insulation quilt Conducting particles is covered, ultrasonic wave dispersion is carried out, makes dispersion liquid.The condition of ultrasonic wave dispersion is frequency 38kHZ, energy 400W, is incited somebody to action Above-mentioned beaker is impregnated in stirring 1 minute in the ultrasonic bath (Zhu Shihui SNT societies system, trade name " US107 ") that volume is 20L.

Above-mentioned dispersion liquid is mixed into adhesive solution, solution is made.Using roll coater by the solution coating in diaphragm On (polyethylene terephthalate film handled through organosilicon, 40 μm of thickness).Then, make the diaphragm for being coated with solution 90 DEG C heat drying 10 minutes makes the adhesive film A of 10 μm of thickness on diaphragm.By changing containing for insulation-coated electroconductive particles Amount has 70,000/mm to make per unit area²Insulation-coated electroconductive particles adhesive film and per unit area With 100,000/mm²Insulation-coated electroconductive particles two kinds of adhesive film.

Adhesive solution is coated on the diaphragm (polyethylene terephthalate handled through organosilicon using roll coater Film, 40 μm of thickness) on after, in 90 DEG C of heat dryings 10 minutes, make the adhesive film B of 3 μm of thickness.

Further, adhesive solution is coated on diaphragm (the poly terephthalic acid second handled through organosilicon using roll coater Diol ester film, 40 μm of thickness) on after, dry 10 minutes at 90 DEG C, make the adhesive film C of 10 μm of thickness.

Then, each adhesive film is laminated with the sequence of adhesive film B, adhesive film A, adhesive film C, it includes three to make The anisotropic conductive adhesive film D of layer.

Then, using made anisotropic conductive adhesive film, according to i as shown below)~iii) the step of, into Row is respectively equipped with 362 golden convex block (1) (areas：About 30 about 40 μm of μ ms, height：15 μm), golden convex block (2) (area：About 40 μm × about 40 μm, height：15 μm) and golden convex block chip (1.7mm × 20mm, thickness：0.5 μm) and the glass base with IZO circuits Plate (thickness：Connection 0.7mm) obtains connection structural bodies.The gap of golden convex block (1), (2) is set as 8 μm.So-called gap, phase When in the mutual distance of golden convex block.

I) with 80 DEG C, 0.98MPa (10kgf/cm²) anisotropic conductive adhesive film (2mm × 24mm) is attached at band On the glass substrate of IZO circuits.

Ii) diaphragm is removed, carries out the contraposition of the convex block and the glass substrate with IZO circuits of chip.

Iii it) is heated and pressurizeed above chip with 190 DEG C, 40gf/ convex blocks, 10 seconds conditions, carries out chip and glass The bonding of glass substrate, and carry out the convex block of chip and being electrically connected for IZO circuits.

[evaluation of connection structural bodies]

The conducting resistance experiment of the following connection structural bodies for carrying out gained and insulation resistance test.

(conducting resistance experiment)

In the connection of chip electrode (convex block) and IZO circuits, the initial value and moisture absorption heat resistant test of conducting resistance are measured After (being placed 100 hours, 300 hours, 500 hours, 1000 hours, 2000 hours under conditions of 85 DEG C of temperature, humidity 85%) Value.In conducting resistance experiment, there is 70,000/mm using per unit area²Insulation-coated electroconductive particles adhesive film make For adhesive film A.Chip electrode (convex block) and the join domain of IZO circuits are set as about 40 μm of about 30 μ m and about 40 μ ms about 40 μm.In the join domain of about 40 μm of about 30 μ m, it is set to pass through 6 insulation-coated conductions with chip electrode and IZO circuits Particle (capturing insulation-coated electroconductive particles) connection.In the join domain of about 40 μm of about 40 μ m, it is set to chip electrode It is connect by 10 insulation-coated electroconductive particles with IZO circuits.It should be noted that being measured to 20 samples, it is calculated Average value.According to the average value of gained according to following benchmark evaluation conducting resistances, show the result in table 8-1.In convex block When number 6 in the case where moisture absorption heat resistant test meets following A benchmark after 500 hours, it is good to be evaluated as conducting resistance.

A：The average value of conducting resistance is less than 2 Ω

B：The average value of conducting resistance is greater than or equal to 2 Ω and is less than 5 Ω

C：The average value of conducting resistance is greater than or equal to 5 Ω and is less than 10 Ω

D：The average value of conducting resistance is greater than or equal to 10 Ω and is less than 20 Ω

E：The average value of conducting resistance is greater than or equal to 20 Ω

(insulation resistance test)

As the insulation resistance between chip electrode, measure insulation resistance initial value and migration test (temperature 60 C, Humidity 90%, apply 20V under conditions of place 100 hours, 300 hours, 1000 hours, 2000 hours) after value.In electric conduction In resistance experiment, there is 70,000/mm using per unit area²Insulation-coated electroconductive particles adhesive film and per unit face Product has 100,000/mm²Insulation-coated electroconductive particles adhesive film both as adhesive film A.For containing insulation Each film of coated electroconductive particles measures 20 samples respectively.Insulating resistance value in 20 samples of each film is calculated to be greater than or equal to 10⁹The ratio of the sample of Ω.According to the ratio of gained according to following benchmark evaluation insulation resistances.It shows the result in table 8-1.It closes In with 100,000/mm²Insulation-coated electroconductive particles adhesive film, under meeting after moisture absorption heat resistant test 100 hours It is good that the case where stating A benchmark is evaluated as insulation resistance.

A：Insulating resistance value is greater than or equal to 10⁹The ratio of Ω is 100%

B：Insulating resistance value is greater than or equal to 10⁹The ratio of Ω is more than or equal to 90% and to be less than 100%

C：Insulating resistance value is greater than or equal to 10⁹The ratio of Ω is more than or equal to 80% and to be less than 90%

D：Insulating resistance value is greater than or equal to 10⁹The ratio of Ω is more than or equal to 50% and to be less than 80%

E：Insulating resistance value is greater than or equal to 10⁹The ratio of Ω is less than 50%

The insulating particle of average grain diameter 239nm shown in table 6 is changed to instead of the first insulating particle of embodiment 1 (absolutely Edge particle No.2), it in addition to this, operates similarly with example 1, carries out conducting particles, insulation-coated electroconductive particles, respectively to different Property electric conductivity adhesive film and the making of connection structural bodies and the evaluation of insulation-coated electroconductive particles and connection structural bodies.By result In shown in table 1-1 and table 8-1.

The insulating particle of average grain diameter 402nm shown in table 6 is changed to instead of the first insulating particle of embodiment 1 (absolutely Edge particle No.3), it in addition to this, operates similarly with example 1, carries out conducting particles, insulation-coated electroconductive particles, respectively to different Property electric conductivity adhesive film and the making of connection structural bodies and the evaluation of insulation-coated electroconductive particles and connection structural bodies.By result In shown in table 1-1 and table 8-1.

It is changed to include the vapor phase method of average grain diameter 40nm shown in table 7-1 instead of the second insulating particle of embodiment 1 The insulating particle (silicon dioxide granule No.2) of hydrophily spherical silicon dioxide powder is grasped similarly to Example 1 in addition to this Make, carries out conducting particles, insulation-coated electroconductive particles, the making of anisotropic conductive adhesive film and connection structural bodies and absolutely The evaluation of edge coated electroconductive particles and connection structural bodies.It shows the result in table 1-1 and table 8-1.

It is changed to include the vapor phase method of average grain diameter 80nm shown in table 7-1 instead of the second insulating particle of embodiment 1 The insulating particle (silicon dioxide granule No.4) of hydrophily spherical silicon dioxide powder is grasped similarly to Example 1 in addition to this Make, carries out conducting particles, insulation-coated electroconductive particles, the making of anisotropic conductive adhesive film and connection structural bodies and absolutely The evaluation of edge coated electroconductive particles and connection structural bodies.It shows the result in table 1-2 and table 8-2.

The vapor phase method comprising average grain diameter 100nm for being changed to table 7-1 instead of the second insulating particle of embodiment 1 is hydrophilic The insulating particle (silicon dioxide granule No.5) of property spherical silicon dioxide powder operates similarly with example 1 in addition to this, Carry out the making and insulation of conducting particles, insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies The evaluation of coated electroconductive particles and connection structural bodies.It shows the result in table 1-2 and table 8-2.

It is changed to include the vapor phase method of average grain diameter 120nm shown in table 7-1 instead of the second insulating particle of embodiment 1 The insulating particle (silicon dioxide granule No.6) of hydrophily spherical silicon dioxide powder is grasped similarly to Example 1 in addition to this Make, carries out conducting particles, insulation-coated electroconductive particles, the making of anisotropic conductive adhesive film and connection structural bodies and absolutely The evaluation of edge coated electroconductive particles and connection structural bodies.It shows the result in table 1-2 and table 8-2.In Figure 15 and Figure 16, show SEM image observed by after coating insulation-coated electroconductive particles.Figure 16 is the 1/2 straight of the diameter with insulation-coated electroconductive particles A part in the concentric circles of diameter.

(in process i), the dripping quantity of the methanol decentralized medium of the first insulating particle is changed, to by the in embodiment 1 The covering rate of one insulating particle is changed to range shown in table 2-1, in addition to this, operates similarly with example 1, and carries out conductive Making and the insulation-coated conduction of particle, insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies The evaluation of particle and connection structural bodies.It shows the result in table 2-1, table 8-2 and table 8-3.

(in process i), the dripping quantity of the methanol decentralized medium of the second insulating particle is changed, to by the in embodiment 1 The covering rate of two insulating particles is changed to range shown in table 2-1 and table 2-2 and operates similarly with example 1 in addition to this, Carry out the making and insulation of conducting particles, insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies The evaluation of coated electroconductive particles and connection structural bodies.It shows the result in table 2-1, table 2-2 and table 9-1.

The second insulating particle of embodiment 1 is replaced using the colloidal silicon dioxide dispersion liquid of average grain diameter 40nm.It is specific and Speech, uses the second insulating particle (silicon dioxide granule No.8) of surface free hydrophobization shown in table 7-2.In addition to this, with Embodiment 1 similarly operates, and carries out conducting particles, insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection knot The evaluation of the making of structure body and insulation-coated electroconductive particles and connection structural bodies.It shows the result in table 2-2 and table 9-1.

The second insulating particle of embodiment 1 is replaced using the colloidal silicon dioxide dispersion liquid of average grain diameter 60nm.It is specific and Speech, uses the second insulating particle (silicon dioxide granule No.9) of surface free hydrophobization shown in table 7-2.In addition to this, with Embodiment 1 similarly operates, and carries out conducting particles, insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection knot The evaluation of the making of structure body and insulation-coated electroconductive particles and connection structural bodies.It shows the result in table 3-1 and table 9-2.

The second insulating particle of embodiment 1 is replaced using the colloidal silicon dioxide dispersion liquid of average grain diameter 80nm.It is specific and Speech, uses the second insulating particle (silicon dioxide granule No.10) of surface free hydrophobization shown in table 7-2.In addition to this, with Embodiment 1 similarly operates, and carries out conducting particles, insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection knot The evaluation of the making of structure body and insulation-coated electroconductive particles and connection structural bodies.It shows the result in table 3-1 and table 9-2.

(the second insulation grain of process h) of embodiment 1 is replaced using the colloidal silicon dioxide dispersion liquid of average grain diameter 100nm Son.Specifically, using the second insulating particle (silicon dioxide granule No.11) of surface free hydrophobization shown in table 7-2.It removes It other than this, operates similarly with example 1, carries out conducting particles, insulation-coated electroconductive particles, anisotropic conductive then film The evaluation of making and insulation-coated electroconductive particles and connection structural bodies with connection structural bodies.Show the result in table 3-1 and table In 9-2.

Particle Ds of the 13.65g as obtained by (the process a~f) of embodiment 1 is impregnated in the electroless plating of the following compositions of 3L Third layer (being equivalent to the second layer in the above embodiment) is formed in palladium liquid, to obtain conducting particles shown in table 3-1. It is handled under conditions of the reaction time is 10 minutes, temperature is 50 DEG C.The average thickness of third layer is 10nm, in third layer Palladium content be 100 mass %.It other than using the conducting particles, operates similarly with example 1, carries out insulation-coated lead Charged particle, the making of anisotropic conductive adhesive film and connection structural bodies and insulation-coated electroconductive particles and connection structural bodies Evaluation.It shows the result in table 3-1 and table 9-2.The composition of electroless plating palladium liquid is as follows.

Palladium bichloride ... ... 0.07g/L

EDETATE SODIUM ... 1g/L

Disodium citrate ... 1g/L

Sodium formate ... ... 0.2g/L

pH……………6

By particle Ds of the 13.65g as obtained by (the process a~f) of embodiment 1 at 85 DEG C in 3L immersion gold plating liquid (Hitachi At Co. Ltd. system, trade name " HGS-100 ") it impregnates 2 minutes in the solution of 100mL/L, further washing 2 minutes, form the Three layers.It is handled under conditions of the reaction time is 10 minutes, temperature is 60 DEG C.The average thickness of third layer is 10nm, the Gold content in three layers is almost 100 mass %.It other than using the conducting particles, operates similarly with example 1, carries out Insulation-coated electroconductive particles, the making of anisotropic conductive adhesive film and connection structural bodies and insulation-coated electroconductive particles and The evaluation of connection structural bodies.It shows the result in table 3-2 and table 9-3.

Conducting particles by following process j~n recorded in acquisition table 4 replaces 13.65g to pass through the (work of embodiment 1 Sequence a~f) obtained by particle D.It other than using the conducting particles, operates similarly with example 1, carries out insulation-coated lead Charged particle, the making of anisotropic conductive adhesive film and connection structural bodies and insulation-coated electroconductive particles and connection structural bodies Evaluation.It shows the result in table 4 and table 9-3.

[making of conducting particles]

(process j) pretreatment procedures

By 3.0 μm of crosslinked polystyrene particle (Nippon Shokubai Co., Ltd's system, trade name of 6g average grain diameters " Soliostar ") be added to 100mL contain 8 mass % palladium catalysts (Ato Tech Amada Co., Ltd.s system, trade name " Atotech Neoganth 834 ") palladium catalyst liquid in, stirred 30 minutes at 30 DEG C.Then, by using 3 μm of Φ Molecular filter (Merck Millipore Corp. system) filtering and take out resin particle.Then, the resin particle taken out is added to PH is adjusted in 6.0 0.5 mass % dimethyamine borane liquid, obtains the resin particle that surface is activated.Then, After the resin particle that surface is activated is impregnated in the distilled water of 60mL, ultrasonic wave dispersion is carried out, to be set Fat particle dispersion.

(the formation of process k) first layers

The water for being heated up to 80 DEG C using 3000mL adds conduct by after the resin particle dispersion liquid dilution of gained in process j The aqueous bismuth nitrate solution 3mL of the 1g/L of plating stabilizer.Then, in the dispersion liquid containing 6g resin particles, with 5mL/ minutes Rate of addition the first layer formation electroless nickel plating solution also used in 240mL embodiments 1 is added dropwise.After completion of dropwise addition, pass through After ten minutes, the dispersion liquid added with plating solution is filtered.After washing with water filtrate, carried out using 80 DEG C of vacuum driers It is dry.The first layer of the nickel-phosphor alloy envelope comprising 80nm film thickness shown in table 4 is consequently formed.As being formed obtained by first layer Particle E be 12g.

The formation of (process 1) palladium particle

The particle E (12g) for being formed with first layer is immersed in the electroless plating palladium liquid of the following compositions of 1L.Thus to obtain The particle F of palladium particle (core is precipitated in plating palladium) is formed on the surface of particle E.In 10 minutes reaction time, the item of temperature 60 C It is handled under part.The composition of the electroless plating palladium liquid of palladium particle formation is as follows.

Palladium bichloride ... 0.07g/L

Ethylenediamine ... 0.05g/L

Sodium formate ... 0.2g/L

Tartaric acid ... 0.11g/L

pH………7

(formation of core is precipitated in process m) electroless nickel platings

After particle F (12g) washings and filtering of gained in process 1, it is made to be scattered in the water that 3000mL is heated up to 70 DEG C In.Aqueous bismuth nitrate solution 3mL of the addition as the 1g/L of plating stabilizer in the dispersion liquid.Then, with 15mL/ minutes drops The precipitation karyomorphism of the following compositions of 60mL is added dropwise at electroless nickel plating solution in acceleration.After completion of dropwise addition, by after ten minutes, will add Added with the dispersion liquid filtering of plating solution.After washing with water filtrate, it is dried using 80 DEG C of vacuum drier.It is consequently formed Core is precipitated in the electroless nickel plating comprising nickel-phosphor alloy of 56nm average lengths.It is precipitated obtained by core as forming electroless nickel plating Particle G is 13.5g.Karyomorphism is precipitated at as follows with the composition of electroless nickel plating solution.

Nickel sulfate ... ... ... 400g/L

Sodium hypophosphite ... ... 150g/L

Sodium tartrate dihydrate ... 120g/L

Aqueous bismuth nitrate solution (1g/L) ... 1mL/L

(the formation of the process n) second layers

After particle G (13.5g) washings and filtering of gained in process m, so that it is scattered in 1000mL and be heated up to 70 DEG C In water.Aqueous bismuth nitrate solution 3mL of the addition as the 1g/L of plating stabilizer in the dispersion liquid.Then, with 15mL/ minutes The second layer formation electroless nickel plating solution of following compositions of 60mL is added dropwise in rate of addition.After completion of dropwise addition, by after ten minutes, By the dispersion liquid filtering added with plating solution.After washing with water filtrate, it is dried using 80 DEG C of vacuum drier.Thus Form the second layer of the nickel-phosphor alloy envelope comprising 20nm film thickness shown in table 4.It is as forming the particle H obtained by the second layer 15.0g.The composition of second layer formation electroless nickel plating solution is as follows.

Nickel sulfate ... ... ... ... 400g/L

Sodium hypophosphite ... ... ... 150g/L

Sodium tartrate dihydrate ... 120g/L

Aqueous bismuth nitrate solution (1g/L) ... 1mL/L

Conducting particles is obtained by above process j~n.

Using only embodiment 1 the first insulating particle without the use of embodiment 1 the second insulating particle, in addition to this, with Embodiment 1 similarly operates, and carries out conducting particles, insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection knot The evaluation of the making of structure body and insulation-coated electroconductive particles and connection structural bodies.It shows the result in table 5-1 and table 10-1. In Figure 17, the result observed the conducting particles after coating insulating particle by SEM devices is shown.

Using only embodiment 1 the second insulating particle without the use of embodiment 1 the first insulating particle, in addition to this, with Embodiment 1 similarly operates, and carries out conducting particles, insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection knot The evaluation of the making of structure body and insulation-coated electroconductive particles and connection structural bodies.It shows the result in table 5-1 and table 10-1.

Using average grain diameter 145nm shown in table 6 insulating particle (insulating particle No.4) as the first insulating particle, remove It other than this, operates similarly with example 1, carries out conducting particles, insulation-coated electroconductive particles, anisotropic conductive adhesive film The evaluation of making and insulation-coated electroconductive particles and connection structural bodies with connection structural bodies.Show the result in table 5-1 and table In 10-1.

Use the insulation grain for the vapor phase method hydrophily spherical silicon dioxide powder for shown in table 7-1 including average grain diameter 25nm Sub (silicon dioxide granule No.1) is operated similarly with example 1 in addition to this as the second insulating particle, carries out conductive particle Making and the insulation-coated conductive particle of son, insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies The evaluation of son and connection structural bodies.It shows the result in table 5-2 and table 10-2.

Use the exhausted of the vapor phase method hydrophily spherical silicon dioxide powder for shown in table 7-2 including average grain diameter 150nm Edge particle (silicon dioxide granule No.7) operates similarly with example 1 in addition to this as the second insulating particle, is led Charged particle, insulation-coated electroconductive particles, anisotropic conductive adhesive film and connection structural bodies making and insulation-coated lead The evaluation of charged particle and connection structural bodies.It shows the result in table 5-2 and table 10-2.

Using the insulating particle (insulating particle No.5) of average grain diameter 100nm shown in table 6 as the second insulating particle.It is flat The insulating particle of equal grain size 100nm uses the insulating particle handled using silicone oligomer.It is above-mentioned exhausted in addition to using It other than edge particle, operates similarly with example 1, it is viscous to carry out conducting particles, insulation-coated electroconductive particles, anisotropic conductive Connect the making of film and connection structural bodies and the evaluation of insulation-coated electroconductive particles and connection structural bodies.Show the result in table 5-2 In table 10-2.Comparative example 6 corresponds to the conducting particles of patent document 6.

[table 1-1]

[table 1-2]

[table 2-1]

[table 2-2]

[table 3-1]

[table 3-2]

[table 4]

[table 5-1]

[table 5-2]

[table 6]

[table 7-1]

[table 7-2]

[table 8-1]

[table 8-2]

[table 8-3]

[table 9-1]

[table 9-2]

[table 9-3]

[table 10-1]

[table 10-2]

Symbol description

1：Conducting particles；100a、100b、100c、100d：Insulation-coated electroconductive particles；101：Resin particle；102：It is non-to lead Conductive inorganic particle；103：Compound particle；104：First layer；105：The second layer；106：Palladium particle；107：Nickel particles；108：The One layer；108a：First coating；108b：Second coating；109：Protrusion；210：Insulating particle；210a：First insulating particle； 210b：Second insulating particle；300：Connection structural bodies；310：First circuit member；311、321：Circuit board；311a、321a： Interarea；312、322：Circuit electrode；320：Second circuit component；330：Interconnecting piece；330a：Anisotropic conductive adhesive； 332：Solidfied material；332a：Bonding agent.

Claims

1. a kind of insulation-coated electroconductive particles, have：

Conducting particles and

Multiple insulating particles on the surface of the conducting particles are attached to,

The average grain diameter of the conducting particles is greater than or equal to 1 μm and less than or equal to 10 μm,

The insulating particle includes：

The first insulating particle with the average grain diameter more than or equal to 200nm and less than or equal to 500nm；And

The the second insulation grain formed with the average grain diameter more than or equal to 30nm and less than or equal to 130nm and by silica Son.

2. the glass transition temperature of insulation-coated electroconductive particles according to claim 1, first insulating particle is More than or equal to 100 DEG C and it is less than or equal to 200 DEG C.

3. insulation-coated electroconductive particles according to claim 1 or 2, relative to the total surface area of the conducting particles, institute It is more than or equal to 35% and to be less than to the covering rate of the conducting particles to state the first insulating particle and second insulating particle Or it is equal to 80%.

4. insulation-coated electroconductive particles described in any one of claim 1 to 3, the conducting particles is on its surface With protrusion.

5. insulation-coated electroconductive particles according to any one of claims 1 to 4, the surface of second insulating particle by Silicic acid anhydride agent is coating.

6. insulation-coated electroconductive particles according to claim 5, the silicic acid anhydride agent is selected from hydrophobic by silazane system Change inorganic agent, siloxane-based silicic acid anhydride agent, the silicic acid anhydride agent of silane system and titanate esters system silicic acid anhydride agent composition In group.

7. insulation-coated electroconductive particles according to claim 6, the silicic acid anhydride agent is selected from by two silicon of hexa-methylene Azane, dimethyl silicone polymer and N, N- dimethylamino trimethyl silanes composition group in.

8. the insulation-coated electroconductive particles according to any one of claim 5~7, described obtained by methanol titration The hydrophobization degree of two insulating particles is greater than or equal to 30%.

9. according to insulation-coated electroconductive particles according to any one of claims 1 to 8, the conducting particles has resin particle With the metal layer for covering the resin particle,

The metal layer has nickeliferous first layer.

10. insulation-coated electroconductive particles according to claim 9, the metal layer has the be set on the first layer Two layers,

The second layer contains the metal in the group being made of noble metal and cobalt.

11. a kind of anisotropic conductive adhesive, has：

Insulation-coated electroconductive particles according to any one of claims 1 to 10 and

It is dispersed with the bonding agent of the insulation-coated electroconductive particles.

12. anisotropic conductive adhesive according to claim 11, the bonding agent is membranaceous.

13. a kind of connection structural bodies, has：

First circuit member has the first circuit electrode；

Second circuit component, it is opposite with first circuit member, and there is second circuit electrode；And

Anisotropic conductive adhesive described in claim 11 or 12, by first circuit member and the second circuit Component is bonded,

First circuit electrode and the second circuit electrode are relative to each other, and are bonded by the anisotropic conductive Agent and be electrically connected to each other.

14. a kind of connection structural bodies, has：

First circuit member has the first circuit electrode；

Interconnecting piece is configured between first circuit member and the second circuit component,

Insulation-coated electroconductive particles according to any one of claims 1 to 10 are dispersed in the interconnecting piece,

First circuit electrode and the second circuit electrode are relative to each other, and pass through the described insulation-coated of deformation state Conducting particles and be electrically connected to each other.