KR101242235B1 - Insulating-particle-adhered electrically conductive particle, process for producing insulating-particle-adhered electrically conductive particle, anisotropic conductive material, and connected structure - Google Patents

Abstract

This invention provides the electroconductive particle with insulating particle which is hard to generate | occur | produce a rust in a conductive layer, can maintain high electroconductivity over a long period, and can raise conduction reliability, when used for the connection between electrodes. The electroconductive particle 1 with insulating particle which concerns on this invention is equipped with the electroconductive particle main body 2 with insulating particle, and the film 3 which coat | covers the surface of the electroconductive particle main body 2 with insulating particle. The electroconductive particle main body 2 with insulating particle has the electroconductive particle 11 which has the conductive layer 13 at least on the surface, and the insulating particle 15 adhering to the surface of the electroconductive particle 11. The film 3 is formed of a compound having an alkyl group having 6 to 22 carbon atoms.

Description

FIELD OF THE INVENTION Production of conductive particles with insulating particles, manufacturing method of conductive particles with insulating particles, anisotropic conductive materials and bonded structures }

This invention relates to the anisotropic conductive material and bonded structure using the electroconductive particle with insulating particle which can be used for the electrical connection between electrodes, the said electroconductive particle with insulating particle, and the said electroconductive particle with insulating particle, for example. .

Anisotropic conductive materials, such as an anisotropic conductive paste and an anisotropic conductive film, are widely known. In these anisotropic conductive materials, electroconductive particle is disperse | distributed in binder resin.

The said anisotropic electrically-conductive material is used for the connection of an IC chip and a flexible printed circuit board, and the connection of an IC chip and a circuit board which has an ITO electrode. For example, after placing an anisotropic conductive material between the electrode of an IC chip and the electrode of a circuit board, these electrodes can be electrically connected by heating and pressurizing.

As an example of the said electroconductive particle, following patent document 1 is fixed to the surface of the electroconductive particle and the said electroconductive particle, and the electroconductive particle with insulating particle which has the insulating particle which has fixing property is disclosed. The said insulating particle has a hard particle and the polymer resin layer which coat | covers the surface of the said hard particle. In this case, in order to fix the insulating particles on the surface of the conductive particles, a physical / mechanical hybridization method is used as the immobilization method.

Patent Document 2 below discloses conductive particles having a polar group on at least part of the surface and at least a portion of the surface of the conductive particles, and conductive particles with insulating particles having an insulating material containing insulating particles. The said insulating material contains the said polar group and the polymer electrolyte which can adsorb | suck specifically, and the inorganic oxide particle | grains which can adsorb | suck with the said polymer electrolyte. This inorganic oxide particle is an insulating particle.

Japanese Patent Publication No. 2007-537570 Japanese Patent Publication No. 2008-120990

In the conventional electroconductive particle with insulating particle as described in patent document 1, 2, the at least one area | region of a conductive layer is exposed. Therefore, rust is likely to occur on the surface of the conductive layer due to the corrosive gas in the atmosphere or the corrosive substance in the anisotropic conductive material. For this reason, high conductivity may not be sufficiently maintained over a long period of time. Moreover, when connecting between electrodes using the electroconductive particle with insulating particle which rust generate | occur | produced in the conductive layer, between electrodes may not electrically connect reliably, or the connection resistance between electrodes may become high.

Moreover, in the electroconductive particle with insulating particle of a conventional, insulating particle tends to detach | desorb from the surface of electroconductive particle. For example, when disperse | distributing electroconductive particle with insulating particle in binder resin, insulating particle may detach easily from the surface of electroconductive particle.

In particular, as described in Patent Literature 1, when the physical / mechanical hybridization method is used to fix the insulating particles on the surface of the conductive particles, the insulating particles tend to detach from the surface of the conductive particles.

In addition, when the physical / mechanical hybridization method is used, the polymer resin layer of the insulating particles is also attached to a portion other than the portion to which the insulating particles are attached on the surface of the conductive particles, and there is also a problem that the conductivity is easily damaged after the connection between the electrodes. .

An object of the present invention is to prevent rust from occurring in the conductive layer and to maintain high conductivity over a long period of time, and therefore, conductive particles with insulating particles and conductive particles with insulating particles, which can increase conduction reliability when used for connection between electrodes. The manufacturing method of this, and the anisotropic electrically-conductive material and bonded structure which used the said electroconductive particle with insulating particle are provided.

The limited object of this invention is the anisotropic conductive material and bonded structure which used the electroconductive particle with insulating particle which is hard to detach | desorb insulating particle from the surface of electroconductive particle, and the manufacturing method of the said electroconductive particle with insulating particle, and the said electroconductive particle with insulating particle, and a bonded structure. To provide.

According to the broad aspect of this invention, the electroconductive particle body with insulating particle which has electroconductive particle which has an electroconductive layer at least on the surface, and the insulating particle adhere | attached on the surface of the said electroconductive particle, and coats the surface of the electroconductive particle body with insulating particle Electroconductive particle with insulating particle provided with the film which the said film is formed by the compound which has the C6-C22 alkyl group is provided.

In certain specific aspects of the electroconductive particle with insulating particle which concerns on this invention, the said insulating particle contains an inorganic particle.

In another specific aspect of the electroconductive particle with insulating particle which concerns on this invention, the said compound which has a C6-C22 alkyl group consists of phosphate ester or its salt, phosphite ester or its salt, alkoxysilane, alkylthiol, and dialkyl disulfide At least one selected from the group.

In another specific aspect of the electroconductive particle with insulating particle which concerns on this invention, the said insulating particle has an insulating particle main body and the layer which covers at least one part area | region of the surface of the said insulating particle main body, and is formed of a high molecular compound.

In another specific situation of the electroconductive particle with insulating particle which concerns on this invention, the said polymeric compound is not affixed to parts other than the part to which the said insulating particle is affixed on the surface of the said electroconductive particle.

In another specific aspect of the electroconductive particle with insulating particle which concerns on this invention, the said high molecular compound has at least 1 sort (s) of reactive functional group chosen from the group which consists of a (meth) acryloyl group, a glycidyl group, and a vinyl group.

In another specific situation of the electroconductive particle with insulating particle which concerns on this invention, the said insulating particle is not affixed on the surface of the said electroconductive particle by the hybridization method.

In another specific aspect of the electroconductive particle with insulating particle which concerns on this invention, after processing the electroconductive particle with insulating particle with 5 weight% citric acid aqueous solution, and peeling the said film, after obtaining the process liquid containing the peeled film, the said process liquid The filtrate obtained by filtrating contains 50-10000 ppm of elemental phosphorus or silicon.

In another specific aspect of the electroconductive particle with insulating particle which concerns on this invention, after processing the electroconductive particle with insulating particle with 5 weight% citric acid aqueous solution, and peeling the said film, after obtaining the process liquid containing the peeled film, the said process liquid The filtrate obtained by filtrating contains 50-10000 ppm of phosphorus elements.

Moreover, according to the wide situation of this invention, the electroconductive particle main body with insulating particle which has electroconductive particle which has an electroconductive layer at least on the surface, and the insulating particle adhere | attached on the surface of the said electroconductive particle, and the surface of the electroconductive particle main body with insulating particle A filtrate obtained by filtering the treatment liquid after the treatment liquid including the peeled film was obtained by treating the conductive particles with insulating particles with a coating film attached to the conductive particles with an insulating particle in a 5% by weight aqueous solution of citric acid and peeling the coating film. It contains 50-10000 ppm of this phosphorus element or a silicon element. In this case, after treating the electroconductive particle with insulating particle with 5 weight% citric acid aqueous solution, and peeling the said film, the process liquid containing the peeled film was obtained, and the filtrate obtained by filtering the said process liquid is 50 elemental phosphorus. It is preferable to include from 10000 ppm.

The connection structure which concerns on this invention is equipped with the 1st connection object member, the 2nd connection object member, and the connection part which connects the said 1st, 2nd connection object member, The insulating particle which said connection part was comprised according to this invention. It is formed of adherent conductive particles or is formed of an anisotropic conductive material containing conductive particles with insulating particles and a binder resin.

Moreover, according to the wide situation of this invention, a C6-C22 alkyl group is formed on the surface of the electroconductive particle which has an electroconductive layer on the surface at least, and the electroconductive particle main body with insulating particle which has the insulating particle adhered to the surface of the said electroconductive particle. The manufacturing method of the electroconductive particle with insulating particle is provided which forms a film so that the surface of the said electroconductive particle main body with insulating particle may be coat | covered using the compound which has.

In a specific aspect of the manufacturing method of the electroconductive particle with insulating particle which concerns on this invention, the said electroconductive particle main body with insulating particle has a hydroxyl group in the at least one part area | region of a surface, to the hydroxyl group of the surface of the electroconductive particle main body with insulating particle, The film | membrane is formed so that the compound which has a C6-C22 alkyl group which has a hydroxyl group may react, and coats the surface of the said electroconductive particle main body with insulating particle.

The anisotropic conductive material which concerns on this invention contains the electroconductive particle with insulating particle and binder resin comprised by this invention, or the electroconductive particle with insulating particle and binder resin obtained by the manufacturing method of the electroconductive particle with insulating particle which concerns on this invention. It includes. It is preferable that the anisotropic electrically-conductive material which concerns on this invention is an anisotropic electrically conductive paste.

In the electroconductive particle with insulating particle which concerns on this invention, since the surface of the electroconductive particle main body with insulating particle is coat | covered with the film, and the said film is formed of the compound which has a C6-C22 alkyl group, rust generate | occur | produces in a conductive layer. it's difficult.

In the manufacturing method of the electroconductive particle with insulating particle which concerns on this invention, a film is coat | covered so that the surface of the electroconductive particle body with insulating particle may be coat | covered using the compound which has a C6-C22 alkyl group on the surface of the electroconductive particle body with insulating particle. Since it forms, the electroconductive particle with insulating particle which is hard to produce rust in a conductive layer can be obtained.

Therefore, when connecting between electrodes using the electroconductive particle with insulating particle which concerns on this invention, or using electroconductive particle with insulating particle obtained by the manufacturing method of the electroconductive particle with insulating particle which concerns on this invention, conduction reliability between electrodes is carried out. Can increase.

Moreover, the electroconductive particle with insulating particle which concerns on this invention adhere | attaches the film on the surface of the electroconductive particle body with insulating particle, and also peeled off by processing the said electroconductive particle with insulating particle with 5 weight% citric acid aqueous solution, and peeling the said film. After obtaining the process liquid containing a film, even if the filtrate obtained by filtering the process liquid contains 50-10000 ppm of elemental phosphorus or silicon, it is difficult to cause rust in the conductive layer. Therefore, when connecting between electrodes using the electroconductive particle with insulating particle which concerns on this invention, the conduction | electrical_connection reliability between electrodes can be improved.

1: is sectional drawing which shows the electroconductive particle with insulating particle which concerns on 1st Embodiment of this invention.
It is sectional drawing which shows the electroconductive particle with insulating particle which concerns on 2nd Embodiment of this invention.
It is sectional drawing which shows the electroconductive particle with insulating particle which concerns on 3rd Embodiment of this invention.
It is sectional drawing which shows the electroconductive particle with insulating particle which concerns on 4th Embodiment of this invention.
FIG. 5: is front sectional drawing which shows typically the bonded structure using the electroconductive particle with insulating particle shown in FIG.
It is sectional drawing which shows the conventional electroconductive particle with insulating particle using the hybridization method.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is clarified by describing specific embodiment and Example of this invention, referring drawings.

(Conductive particle body with insulating particle)

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

The electroconductive particle 1 with insulating particle shown in FIG. 1 is equipped with the electroconductive particle main body 2 with insulating particle, and the film 3 which coat | covers the surface of the electroconductive particle main body 2 with insulating particle. The film 3 is attached to the surface of the electroconductive particle main body 2 with insulating particle. The film 3 covers the whole surface of the electroconductive particle main body 2 with insulating particle.

The electroconductive particle main body 2 with insulating particle is equipped with the electroconductive particle 11 and the some insulating particle 15 adhering to the surface of the electroconductive particle 11. The insulating particle 15 is formed of the material which has insulation.

The film 3 covers the surface of the electroconductive particle 11 and the surface of the insulating particle 15. The part of the film 3 covering the surface of the electroconductive particle 11 and the part of the film 3 covering the surface of the insulating particle 15 are continuous.

The electroconductive particle 11 has the substrate particle 12 and the conductive layer 13 provided on the surface of the substrate particle 12. The conductive layer 13 has covered the surface of the substrate particle 12. The electroconductive particle 11 is a coating particle by which the surface of the substrate particle 12 was coat | covered with the conductive layer 13. The electroconductive particle 11 has the conductive layer 13 on the surface.

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

The electroconductive particle 21 with insulating particle shown in FIG. 2 is equipped with the electroconductive particle main body 22 with insulating particle, and the film 23 which coat | covers the surface of the electroconductive particle main body 22 with insulating particle. The film 23 is adhered to the surface of the electroconductive particle main body 22 with insulating particle.

The electroconductive particle main body 22 with insulating particle is equipped with the electroconductive particle 31 and the some insulating particle 15 adhering to the surface of the electroconductive particle 31.

The film 23 covers the surface of the electroconductive particle 31 and the surface of the insulating particle 15. The coating 23 portion covering the surface of the electroconductive particle 31 and the coating 23 portion covering the surface of the insulating particle 15 are continuous.

The electroconductive particle 31 has the substrate particle 12 and the conductive layer 32 provided on the surface of the substrate particle 12. The electroconductive particle 31 has the some core substance 33 on the surface of the substrate particle 12. The conductive layer 32 coats the substrate particle 12 and the core substance 33. By covering the core material 33 with the conductive layer 32, the conductive particles 31 have a plurality of protrusions 34 on the surface thereof. The surface of the conductive layer 32 is raised by the core substance 33, and the some processus | protrusion 34 is formed.

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

The electroconductive particle 41 with insulating particle shown in FIG. 3 is equipped with the electroconductive particle main body 42 with insulating particle, and the film 3 which coat | covers the surface of the electroconductive particle main body 42 with insulating particle.

The electroconductive particle main body 42 with insulating particle is equipped with the electroconductive particle 11 and the some insulating particle 45 adhering to the surface of the electroconductive particle 11. That is, except that insulating particles differ, the electroconductive particle 41 with insulating particle is comprised similarly to the electroconductive particle 1 with insulating particle, and the electroconductive particle main body 42 with insulating particle is electroconductive particle with insulating particle. It is comprised similarly to the main body 2. As shown in FIG.

The insulating particle 45 has the insulating particle main body 45a and the layer 45b which covers the surface of the insulating particle main body 45a, and is formed of the high molecular compound. By presence of the layer 45b, the adhesiveness of the insulating particle 45 with respect to the electroconductive particle 11 can be heightened suitably.

The layer 45b has covered the whole surface of the insulating particle main body 45a. Therefore, the layer 45b is arrange | positioned between the electroconductive particle 11 and the insulating particle main body 45a. The layer 45b may exist so as to cover at least a portion of the surface of the insulating particle body, and may not cover the entire surface of the insulating particle body. It is preferable that the layer 45b is arrange | positioned between electroconductive particle and an insulating particle main body.

4, the electroconductive particle with insulating particle which concerns on 4th Embodiment of this invention is shown by sectional drawing.

The electroconductive particle 61 with insulating particle shown in FIG. 4 is equipped with the insulating particle main body 62 and the film 23 which coat | covers the surface of the electroconductive particle main body 62 with insulating particle. The film 23 is attached to the surface of the electroconductive particle main body 62 with insulating particle.

The electroconductive particle main body 62 with insulating particle is equipped with the electroconductive particle 71 and the some insulating particle 15 adhering to the surface of the electroconductive particle 71.

The electroconductive particle 71 has the substrate particle 12 and the conductive layer 76 provided on the surface of the substrate particle 12. The conductive layer 76 has a 1st conductive layer 76a provided on the surface of the substrate particle 12, and the 2nd conductive layer 76b provided on the surface of the 1st conductive layer 76a. The electroconductive particle 71 has the some core substance 33 on the surface of the 1st conductive layer 76a. The second conductive layer 76b covers the first conductive layer 76a and the core material 33. The substrate particle 12 and the core substance 33 are arrange | positioned at intervals. The first conductive layer 76a is present between the substrate particle 12 and the core substance 33. Since the 2nd conductive layer 76b coat | covers the core substance 33, the electroconductive particle 71 has the some processus | protrusion 77 on the surface. The surface of the conductive layer 76 and the second conductive layer 76b is raised by the core material 33, and a plurality of protrusions 77 are formed.

The coating films 3 and 23 cover the surfaces of the conductive particle bodies 2, 22, 42 and 62 with insulating particles, and the coating films 3 and 23 have 6 to 6 carbon atoms. It is preferable that it is formed of the compound which has 22 alkyl groups. As a result, rust is less likely to occur in the conductive layers 13, 32, and 76 in the conductive particles 1, 21, 41, and 61 with insulating particles. The coatings 3 and 23 give an antirust effect. Therefore, the electroconductivity of the electroconductive particle in the electroconductive particle with insulating particle becomes high, and high electroconductivity can be maintained over a long period of time. Therefore, when connecting between electrodes using the electroconductive particle (1), (21), (41), (61) with insulating particle, conduction | electrical_connection reliability can be improved.

Moreover, the peeled coating film 3, by peeling the coating films 3 and 23 by treating the conductive particles 1, 21, 41, and 61 with insulating particles with a 5% by weight aqueous citric acid solution. After obtaining the processing liquid containing (23), it is preferable that the filtrate obtained by filtering the said processing liquid contains 50-10000 ppm of elemental phosphorus or silicon. As a result, rust is less likely to occur in the conductive layers 13, 32, and 76 in the conductive particles 1, 21, 41, and 61 with insulating particles. Therefore, the electroconductivity of the electroconductive particle in the electroconductive particle with insulating particle becomes high, and high electroconductivity can be maintained over a long period of time. Therefore, when connecting between electrodes using the electroconductive particle (1), (21), (41), (61) with insulating particle, conduction | electrical_connection reliability can be improved.

In addition, from the viewpoint of making rust less likely to occur in the conductive layer, the conductive particles (1), (21), (41), and (61) with insulating particles are treated with a 5 wt% aqueous citric acid solution to form a coating (3), (23 It is preferable that the filtrate obtained by filtering the said process liquid after obtaining the process liquid containing the peeled film | membrane (3) and (23) by peeling ()) contains 50-10000 ppm of phosphorus element. From the viewpoint of making rust less likely to occur in the conductive layer, the conductive particles (1), (21), (41) and (61) with insulating particles are treated with 5 wt% aqueous citric acid solution to form the coatings (3) and (23). It is preferable that the filtrate obtained by filtering the said process liquid, after obtaining the process liquid containing the peeled film | membrane 3 and 23 by peeling contains 50-10000 ppm of elemental silicon. The content of the silicon element or the phosphorus element in the filtrate is more preferably 100 ppm or more, still more preferably 5000 ppm or less, particularly preferably 1000 ppm or less.

Content of the said phosphorus element and a silicon element can be measured using an ICP emission spectrometer. As a commercial item of an ICP luminescence analyzer, "ULTIMA2" by Horiba Seisakusho Co., etc. is mentioned.

In the case of the electroconductive particle (1), (21), (41), (61) with insulating particle which has the coating (3) and (23), content of the said phosphorus element and the said silicon element is normally a coating (3), Determined by (23). That is, content of the said phosphorus element and the said silicon element shows the ratio of the phosphorus element and the silicon element in the coating (3), (23).

The coatings 3 and 23 are preferably attached to the surfaces of the conductive particle bodies 2, 22, 42, and 62 with insulating particles. In electroconductive particle (1), (21), (41), (61) with insulating particle, the coating (3), (23) is the electroconductive particle main body (2), (22), (42), (with insulating particle It is preferable to cover the whole surface of 62).

In addition, the coating films 3 and 23 do not necessarily cover the entire surface of the conductive particle bodies 2, 22, 42, and 62 with insulating particles. The coatings 3 and 23 cover at least a portion of the surface of the conductive layers 13, 32, and 76, thereby conducting at the portion where the coatings 3, 23 are formed. Rust of the layers 23, 32, and 76 can be suppressed.

In addition, due to the presence of the coatings 3 and 23, the conductive particles 1, 21, 41, and 61 with insulating particles are used for the conductive particles 11, 31, and 71. The insulating particles 15 and 45 are difficult to detach from the surface. For example, when adding the electroconductive particle (1), (21), (41), (61) with insulating particle in binder resin, and knead | mixing, from the surface of electroconductive particle (11), (31), (71) The insulating particles 15 and 45 are hard to detach. Moreover, when the some electroconductive particle (1), (21), (41), (61) with some insulating particle contacts, the surface of electroconductive particle (11), (31), (71) by the impact at the time of a contact. The insulating particles 15 and 45 are hardly detached from the resin. Therefore, when electroconductive particle (1), (21), (41), (61) with insulating particle is used for the connection between electrodes, it is insulating particle between adjacent electroconductive particle (11), (31), (71). Since 15 and 45 exist, it is difficult to electrically connect between adjacent electrodes which should not be connected.

Hereinafter, the detail of the coating 3, 23 and the detail of the electroconductive particle main body 2, 22, 42, 62 with insulating particle are demonstrated.

[film]

In order to make it difficult to generate rust in the conductive layer, the coating is preferably formed of a compound having an alkyl group having 6 to 22 carbon atoms (hereinafter also referred to as compound A). When carbon number of the said alkyl group is less than 6, rust will generate | occur | produce easily on the surface of a conductive layer. When carbon number of the said alkyl group exceeds 22, the electroconductivity of the electroconductive particle with insulating particle will become low. From a viewpoint of further improving the electroconductivity of the electroconductive particle with insulating particle, it is preferable that carbon number of the said alkyl group in the said compound A is 16 or less. The alkyl group may have a straight chain structure or may have a branched structure. It is preferable that the said alkyl group has a linear structure.

The compound A is not particularly limited as long as it has an alkyl group having 6 to 22 carbon atoms. The said compound A is a phosphate ester or its salt which has a C6-C22 alkyl group, the phosphite ester or its salt which has a C6-C22 alkyl group, the alkoxysilane which has a C6-C22 alkyl group, a C6-C22 alkyl group It is preferable that it is at least 1 sort (s) chosen from the group which consists of an alkylthiol which has and a dialkyl disulfide which has a C6-C22 alkyl group. That is, it is preferable that the compound A which has the said C6-C22 alkyl group is at least 1 sort (s) chosen from the group which consists of phosphate ester or its salt, phosphite ester or its salt, alkoxysilane, alkylthiol, and dialkyl disulfide. By the use of these preferred compounds A, rust can be made less likely to occur in the conductive layer. In view of making rust less likely to occur, the compound A is preferably at least one selected from the group consisting of the phosphate ester or salts thereof, phosphite ester or salts and alkoxysilanes, and the phosphate ester or salts thereof and phosphite esters or It is more preferable that it is at least 1 sort (s) of its salt. Only 1 type may be used for the said compound A, and 2 or more types may be used together.

It is preferable that the said compound A has the reactive functional group which can react with electroconductive particle. It is preferable that the said compound A has the reactive functional group which can react with insulating particle. It is preferable that the film chemically couples with the electroconductive particle main body with insulating particle. It is preferable that the film chemically couple | bonds with electroconductive particle. It is preferable that the film chemically couples with insulating particle. As for a film, it is more preferable to chemically couple | bond with electroconductive particle and insulating particle. Due to the presence of the reactive functional group and by the chemical bonding, peeling of the film becomes less likely to occur. As a result, rust is less likely to occur in the conductive layer, and insulating particles are less likely to be detached from the surface of the conductive particles unintentionally.

Examples of the phosphate ester or salt thereof having an alkyl group having 6 to 22 carbon atoms include hexyl phosphate ester, phosphate heptyl ester, phosphate monooctyl ester, phosphate monoyl ester, phosphate monodecyl ester, phosphate monoundecyl ester, and phosphate monophosphate. Dodecyl ester, monotridecyl phosphate, mono tetradecyl phosphate, monopentadecyl phosphate, monopenta phosphate monomonophosphate, monosodium salt phosphate, monoheptyl phosphate monosodium salt, monooctyl phosphate monosodium salt, monophosphate monophosphate Monosodium salt, monodecyl ester monosodium salt, monodecyl ester monosodium salt, monosodium phosphate monosodium salt, monotridecyl estermonophosphate monosodium salt, monotetradecyl ester monophosphate monosodium salt and monophosphate monophosphate Pentadecyl ester monosodium salt etc. are mentioned. . The potassium salt of the said phosphate ester can also be used.

As a phosphite ester or its salt which has the said C6-C22 alkyl group, For example, phosphite hexyl ester, phosphite heptyl ester, phosphite monooctyl ester, phosphite monomonyl ester, phosphite monodecyl ester, phosphite monoundecyl ester, Phosphoric acid monododecyl ester, phosphorous acid monotridecyl ester, phosphorous acid monotetradecyl ester, phosphorous acid monopentadecyl ester, phosphorous acid monohexyl ester monosodium salt, phosphorous acid monoheptyl ester monosodium salt, phosphorous acid monooctyl ester monosodium salt, phosphorous acid Monomonoyl ester monosodium salt, monodecyl ester monosodium salt, phosphorous acid monodecyl ester monosodium salt, monododecyl ester monosodium salt, phosphorous acid monotridecyl ester monosodium salt, phosphorous acid monotetradecyl ester monosodium salt Salts and phosphites Pentadecyl ester monosodium salt etc. are mentioned. The potassium salt of the said phosphite ester can also be used.

Examples of the alkoxysilane having an alkyl group having 6 to 22 carbon atoms include hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane and octyltriethoxy. Silane, nonyltrimethoxysilane, nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane, undecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltree Ethoxysilane, tridecyl trimethoxysilane, tridecyl triethoxysilane, tetradecyl trimethoxysilane, tetradecyl triethoxysilane, pentadecyl trimethoxysilane, pentadecyl triethoxysilane, etc. are mentioned. .

Examples of the alkylthiol having an alkyl group having 6 to 22 carbon atoms include hexyl thiol, heptyl thiol, octyl thiol, nonyl thiol, decyl thiol, undecyl thiol, dodecyl thiol, tridecyl thiol, tetradecyl thiol, and pentadecyl thiol. And hexadecyl thiol etc. are mentioned. It is preferable that the said alkylthiol has a thiol group in the terminal of an alkyl chain.

Examples of the dialkyl disulfide having an alkyl group having 6 to 22 carbon atoms include dihexyl disulfide, diheptyl disulfide, dioctyl disulfide, dinonyl disulfide, didecyl disulfide, didecyl disulfide, and dido. Decyl disulfide, ditridecyl disulfide, ditetradecyl disulfide, dipentadecyl disulfide, dihexadecyl disulfide, and the like.

[Conductive Particle Body with Insulating Particles]

The said electroconductive particle may have a conductive layer at least on the surface. Electroconductive particle may be electroconductive particle which has a substrate particle and a conductive layer provided on the surface of a substrate particle, and the metal particle whose whole is a conductive layer may be sufficient as it. Especially, the electroconductive particle which has a substrate particle and the conductive layer provided on the surface of a substrate particle is preferable from a viewpoint of reducing cost or improving the flexibility of electroconductive particle and raising the conduction reliability between electrodes.

Examples of the substrate particles include resin particles, inorganic particles, organic inorganic hybrid particles, metal particles, and the like.

It is preferable that the said substrate particle is a resin particle formed with resin. When connecting between electrodes using electroconductive particle with insulating particle, after arrange | positioning electroconductive particle with insulating particle between electrodes, the electroconductive particle with insulating particle is compressed by crimping | bonding. If a substrate particle is a resin particle, electroconductive particle will be easy to deform | transform at the time of the said crimp, and the contact area of electroconductive particle and an electrode can be enlarged. Therefore, the conduction | electrical_connection reliability between electrodes can be improved.

As the resin for forming the resin particles, for example, polyolefin resin, acrylic resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, Polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamideimide, polyether ether ketone, polyether sulfone and the like. Since the hardness of a substrate particle can be easily controlled to a preferable range, it is preferable that resin for forming the said resin particle is a polymer which superposed | polymerized the 1 type (s) or 2 or more types of the polymerizable monomer which has an ethylenically unsaturated group.

As an inorganic substance for forming the said inorganic particle, silica, carbon black, etc. are mentioned. As said organic inorganic hybrid particle, the organic-inorganic hybrid particle formed with the crosslinked alkoxysilyl polymer and acrylic resin etc. are mentioned, for example.

When the said substrate particle is a metal particle, silver, copper, nickel, silicon, gold, titanium, etc. are mentioned as a metal for forming the said metal particle.

The metal for forming the said conductive layer is not specifically limited. In addition, when electroconductive particle is a metal particle whose whole is a conductive layer, the metal for forming the said metal particle is not specifically limited. Examples of the metal include gold, silver, palladium, copper, platinum, palladium, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, and silicon. And these alloys. Moreover, as said metal, tin dope indium oxide (ITO), a solder, etc. are mentioned. Among them, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is preferable because the connection resistance between the electrodes can be further lowered.

As the rust easily occurs in the metal constituting the conductive layer, the coating effect by the coating is remarkably obtained. In the conductive layer formed of nickel, copper, or tin, rust tends to occur relatively on the surface of the conductive layer. By coating the surface of such a conductive layer with a film, it is possible to effectively suppress the occurrence of rust on the surface of the conductive layer. Since the coating effect by the said film is acquired effectively, the said conductive layer may contain nickel, copper, or tin.

In addition, hydroxyl groups are often present on the surface of the conductive layer by oxidation. Generally, hydroxyl groups exist on the surface of the conductive layer formed of nickel by oxidation. The conductive layer having such a hydroxyl group chemically bonds with the film.

The said conductive layer is formed by one layer. The conductive layer may be formed of a plurality of layers. That is, the conductive layer may have a laminated structure of two or more layers. In the case where the conductive layer is formed of a plurality of layers, the outermost layer is preferably a gold layer, a nickel layer, a palladium layer, a copper layer, or an alloy layer containing tin and silver, and more preferably a gold layer. When outermost layer is these preferable conductive layers, the connection resistance between electrodes can be further lowered. Moreover, when outermost layer is a gold layer, corrosion resistance can further be improved.

The method of forming a conductive layer on the surface of the said substrate particle is not specifically limited. As a method for forming the conductive layer, for example, a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and a paste containing a metal powder or a metal powder and a binder on the surface of the substrate particle The method etc. are mentioned. Especially, since formation of a conductive layer is easy, the method by electroless plating is preferable. As said method by physical vapor deposition, methods, such as vacuum deposition, ion plating, and ion sputtering, are mentioned.

It is preferable that the average particle diameter of the said electroconductive particle exists in the range of 0.5-100 micrometers. The average particle diameter of electroconductive particle becomes like this. More preferably, it is 1 micrometer or more, More preferably, it is 20 micrometers or less. When the average particle diameter of electroconductive particle is more than the said minimum and below the said upper limit, when connecting between electrodes using electroconductive particle with insulating particle, the contact area of electroconductive particle and an electrode can be enlarged enough, and when forming a conductive layer, Aggregated electroconductive particle becomes difficult to form. Moreover, the space | interval between the electrodes connected through electroconductive particle does not become large too much, and a conductive layer becomes difficult to peel from the surface of a substrate particle.

"Average particle diameter" of the said electroconductive particle shows a number average particle diameter. The average particle diameter of electroconductive particle is calculated | required by observing 50 arbitrary electroconductive particles with an electron microscope or an optical microscope, and calculating an average value.

It is preferable that the thickness of the said conductive layer exists in the range of 0.005-1 micrometer. The thickness of the conductive layer is more preferably 0.01 µm or more, and more preferably 0.3 µm or less. If the thickness of a conductive layer is more than the said minimum and below the said upper limit, sufficient electroconductivity can be obtained, and electroconductive particle can fully be deformed at the time of connection between electrodes, without electroconductive particle becoming too hard.

In the case where the conductive layer is formed of a plurality of layers, the thickness of the conductive layer of the outermost layer is particularly preferably in the range of 0.001 to 0.5 µm when the outermost layer is a gold layer. The minimum with more preferable thickness of the conductive layer of the said outermost layer is 0.01 micrometer, and a more preferable upper limit is 0.1 micrometer. When the thickness of the conductive layer of the outermost layer is more than the lower limit and less than the upper limit, the coating by the conductive layer of the outermost layer can be uniform, the corrosion resistance can be sufficiently increased, and the connection resistance between the electrodes can be sufficiently lowered. . In addition, the thinner the thickness of the gold layer when the outermost layer is the gold layer, the lower the cost.

The thickness of the said conductive layer can be measured by observing the cross section of electroconductive particle or electroconductive particle with insulating particle, for example using a transmission electron microscope (TEM).

It is preferable that electroconductive particle has a processus | protrusion on the surface of a conductive layer, and it is preferable that the said processus | protrusion is plural. The oxide film is formed in the surface of the electrode connected by the electroconductive particle with insulating particle in many cases. When the electroconductive particle with insulating particle which has a processus | protrusion on the surface of a conductive layer is used, the said oxide film can be effectively excluded by protrusion by arrange | positioning and crimping | bonding electroconductive particle between electrodes. Therefore, the electrode and the conductive layer can be contacted more reliably, and the connection resistance between the electrodes can be lowered. In addition, at the time of connection between electrodes, the insulating particle between electroconductive particle and an electrode can be effectively excluded by protrusion of electroconductive particle. Therefore, the conduction | electrical_connection reliability between electrodes can be improved.

As a method of forming a protrusion on the surface of electroconductive particle, after attaching a core substance to the surface of a substrate particle, the method of forming a conductive layer by electroless plating, and the electroconductive layer by electroless plating on the surface of a substrate particle are carried out. After forming, a method of attaching the core material and further forming a conductive layer by electroless plating may be mentioned.

As a method for attaching the core material to the surface of the substrate particles, for example, a conductive material that becomes a core material is added to the dispersion of the substrate particles, and the core material is integrated on the surface of the substrate particles by, for example, van der Waals forces. The method of making it adhere | attach, and the method of attaching the core material to the surface of a substrate particle by the mechanical action by rotation of a container etc. are added, and the conductive substance used as a core material to the container which put the substrate particle is mentioned. Especially, since it is easy to control the quantity of the core substance to adhere, the method of accumulating and attaching a core substance to the surface of the substrate particle in a dispersion liquid is preferable.

The said electroconductive particle may have a 1st conductive layer on the surface of a substrate particle, and may have a 2nd conductive layer on the said 1st conductive layer. In this case, the core material may be attached to the surface of the first conductive layer. It is preferable that the core substance is covered with the second conductive layer. It is preferable that the thickness of the said 1st conductive layer exists in the range of 0.05-0.5 micrometer. Electroconductive particle forms a 1st conductive layer on the surface of a substrate particle, and then adheres a core material on the surface of the said 1st conductive layer, and then a 2nd conductive layer on the surface of a 1st conductive layer and a core material It is preferable that it is obtained by forming.

As an electroconductive substance which comprises the said core substance, electroconductive nonmetals, such as a metal, an oxide of a metal, graphite, an electroconductive polymer, etc. are mentioned, for example. Polyacetylene etc. are mentioned as a conductive polymer. Especially, since electroconductivity can be improved, a metal is preferable.

Examples of the metal include metals such as gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, and cadmium, and tin-lead. And alloys composed of two or more metals such as alloys, tin-copper alloys, tin-silver alloys, and tin-lead-silver alloys. Especially, nickel, copper, silver, or gold is preferable. The metal constituting the core material may be the same as or different from the metal constituting the conductive layer.

The shape of the said core substance is not specifically limited. The shape of the core material is preferably in the form of a lump. Examples of the core substance include particulate lumps, aggregated lumps in which a plurality of microparticles are aggregated, and irregular lumps.

The said insulating particle is particle | grains which have insulation. The insulating particles are smaller than the conductive particles. When connecting between electrodes using the electroconductive particle with insulating particle, the short circuit between adjacent electrodes can be prevented by insulating particle. Specifically, when the conductive particles with a plurality of insulating particles come in contact with each other, the insulating particles exist between the conductive particles in the conductive particles with the plurality of insulating particles. You can prevent it. Moreover, at the time of the connection between electrodes, the insulating particle between a conductive layer and an electrode can be easily excluded by pressurizing the electroconductive particle with insulating particle with two electrodes. When protrusions are provided on the surface of the conductive particles, insulating particles between the conductive layer and the electrode can be more easily removed.

As a material which comprises the said insulating particle, insulating resin, an insulating inorganic substance, etc. are mentioned. As said insulating resin, the said resin quoted as resin for forming the resin particle which can be used as a substrate particle is mentioned. As said insulating inorganic substance, the said inorganic substance mentioned as an inorganic substance for forming the inorganic particle which can be used as a substrate particle is mentioned.

As a specific example of insulating resin which is a material of the said insulating particle, polyolefin, a (meth) acrylate polymer, a (meth) acrylate copolymer, a block polymer, a thermoplastic resin, the crosslinked material of a thermoplastic resin, a thermosetting resin, a water-soluble resin, etc. are mentioned. Can be.

Examples of the polyolefins include polyethylene, ethylene-vinyl acetate copolymers, and ethylene-acrylic acid ester copolymers. As said (meth) acrylate polymer, polymethyl (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate, etc. are mentioned. Examples of the block polymers include polystyrene, styrene-acrylic acid ester copolymers, SB-type styrene-butadiene block copolymers and SBS-type styrene-butadiene block copolymers, and hydrogenated products thereof. As said thermoplastic resin, a vinyl polymer, a vinyl copolymer, etc. are mentioned. As said thermosetting resin, an epoxy resin, a phenol resin, a melamine resin, etc. are mentioned. As said water-soluble resin, polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, methyl cellulose, etc. are mentioned. Especially, water-soluble resin is preferable and polyvinyl alcohol is more preferable.

From the viewpoint of further increasing the detachment property of the insulating particles during thermocompression bonding, the insulating particles preferably contain inorganic particles, and are preferably silica particles. In the case where the insulating particles do not have a layer formed on the surface of the polymer compound, the insulating particles are preferably inorganic particles, and preferably silica particles. When using the insulating particle whose surface of the insulating particle main body was covered by the layer formed with the said polymeric compound, it is preferable that an insulating particle main body is an inorganic particle, and it is preferable that it is a silica particle. Examples of the inorganic particles include white sand particles, hydroxyapatite particles, magnesia particles, zirconium oxide particles, silica particles, and the like. From the viewpoint of further improving the detachment property of the insulating particles during thermocompression bonding, the insulating particles preferably contain silica particles, and the inorganic particles are preferably silica particles. Examples of the silica particles include pulverized silica and spherical silica, and spherical silica is preferably used. Moreover, it is preferable that a silica particle has functional groups which can chemically bond, such as a carboxyl group and a hydroxyl group, on the surface, and it is more preferable to have a hydroxyl group. Inorganic particles are relatively hard, in particular silica particles are relatively hard. When the electroconductive particle main body with insulating particle which has such hard insulating particle is used, when insulating the electroconductive particle main body with insulating particle and binder resin, hard insulating particle tends to detach | desorb from the surface of electroconductive particle. However, when the electroconductive particle with insulating particle which concerns on this invention is used, even if hard insulating particle is used, detachment of hard insulating particle by a film at the time of the said kneading can be suppressed. The layer formed of the said high molecular compound plays a role as a flexible layer, for example.

It is preferable that it is a compound which has the reactive functional group which can superpose | polymerize as a compound which becomes the said high molecular compound by the high molecular compound, superposition | polymerization, etc. in the layer formed with the said high molecular compound. It is preferable that the said reactive functional group which can superpose | polymerize is an unsaturated double bond. For example, the compound (compound which becomes a high molecular compound) which has an unsaturated double bond on the surface of an insulating particle main body may be polymerized, and the high molecular compound and the reactive functional group of the surface of an insulating particle main body may also be made to react. As a compound which becomes the said high molecular compound or the said high molecular compound, the compound which has a (meth) acryloyl group, the compound which has an epoxy group, the compound which has a vinyl group, etc. are mentioned. From the viewpoint of suppressing the detachment of the insulating particles from the surface of the conductive particles when dispersing the conductive particles with insulating particles or the like, the polymer compound or the compound which becomes the polymer compound is composed of a (meth) acryloyl group, glycidyl group and vinyl group. It is preferred to have at least one reactive functional group selected from the group. Especially, it is preferable that the said high molecular compound or the compound used as the said high molecular compound has a (meth) acryloyl group from a viewpoint which further suppresses detachment of insulating particle.

As a specific example of the compound which has the said (meth) acryloyl group, methacrylic acid, hydroxyethyl acrylate, dimethacrylate ethylene glycol, etc. are mentioned.

As a specific example of the said epoxy compound, bisphenol-A epoxy resin, resorcinol glycidyl ether, etc. are mentioned.

Styrene, vinyl acetate, etc. are mentioned as a specific example of the compound which has the said vinyl group.

It is preferable that the weight average molecular weight of the said high molecular compound is 1000 or more. Although the upper limit of the weight average molecular weight of the said high molecular compound is not specifically limited, It is preferable that the weight average molecular weight of the said high molecular compound is 20000 or less. The said weight average molecular weight shows the value in polystyrene conversion measured by the gel permeation chromatography (GPC).

The method of forming the layer formed with the said high molecular compound on the surface of insulating particle is not specifically limited. It is preferable to form a layer formed of a high molecular compound using a high molecular compound or a compound that becomes a high molecular compound so as to cover at least a portion of the surface of the insulating particle main body to obtain insulating particles. As an example of the formation method of the layer formed with the said high molecular compound, the method of superposing | polymerizing the compound which has a reactive double bond and a hydroxyl group on the surface of an insulating particle main body to the insulating particle body which has reactive functional groups, such as a vinyl group, on the surface, etc. Can be mentioned. However, methods other than this formation method can also be used.

It is preferable that the said insulating particle main body and the said layer are chemically couple | bonded. This chemical bond includes a covalent bond, a hydrogen bond, an ionic bond, a coordination bond, and the like. Especially, a covalent bond is preferable and the chemical bond using a reactive functional group is preferable.

As a reactive functional group which forms the said chemical bond, for example, a vinyl group, a (meth) acryloyl group, a silane group, a silanol group, a carboxyl group, an amino group, an ammonium group, a nitro group, a hydroxyl group, a carbonyl group, a thiol group, a sulfonic acid group, a sulfonium group And a boric acid group, an oxazoline group, a pyrrolidone group, a phosphoric acid group and a nitrile group. Especially, a vinyl group and a (meth) acryloyl group are preferable.

It is preferable to use the insulating particle main body which has a reactive functional group on the surface as said insulating particle main body from a viewpoint which further suppresses detachment of insulating particle and further improves the insulation reliability in a bonded structure. It is preferable to use the insulating particle main body surface-treated using the compound which has a reactive functional group as said insulating particle main body from the viewpoint which further suppresses detachment of insulating particle and further improves the insulation reliability in a bonded structure. From the viewpoint of further suppressing the detachment of the insulating particles and further increasing the insulation reliability in the bonded structure, the insulating particle body using the insulating particle body having a reactive functional group on the surface, and a polymer compound or a compound that becomes the polymer compound It is preferable that the said insulating particle which the said insulating particle main body and the said layer chemically couple | bonds is obtained by chemically bonding the layer formed with the said high molecular compound to the reactive functional group of the surface of the.

As said reactive functional group which the said insulating particle main body has on the surface, a (meth) acryloyl group, glycidyl group, a hydroxyl group, a vinyl group, an amino group, etc. are mentioned. It is preferable that the said reactive functional group which the said insulating particle main body has on a surface is at least 1 sort (s) of reactive functional group chosen from the group which consists of a (meth) acryloyl group, glycidyl group, a hydroxyl group, a vinyl group, and an amino group.

As a compound (surface treatment material) for introducing the said reactive functional group into the surface of the said insulating particle main body, the compound which has a (meth) acryloyl group, the compound which has an epoxy group, the compound which has a vinyl group, etc. are mentioned.

As a compound (surface treatment material) for introducing the vinyl group which is the said reactive functional group into the surface of the said insulating particle main body, the silane compound which has a vinyl group, the titanium compound which has a vinyl group, the phosphoric acid compound which has a vinyl group, etc. are mentioned. It is preferable that the said surface treatment substance is a silane compound which has a vinyl group. Examples of the silane compound having a vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltriisopropoxysilane, and the like.

As a compound (surface treatment material) for introducing the (meth) acryloyl group which is the said reactive functional group into the surface of the said insulating particle main body, the silane compound which has a (meth) acryloyl group, and the titanium which has a (meth) acryloyl group A phosphoric acid compound etc. which have a compound and a (meth) acryloyl group are mentioned. It is also preferable that the said surface treatment substance is a silane compound which has a (meth) acryloyl group. As a silane compound which has the said (meth) acryloyl group, (meth) acryloxypropyl triethoxysilane, (meth) acryloxypropyl trimethoxysilane, (meth) acryloxypropyl tridimethoxysilane, etc. are mentioned. .

It is preferable that the said insulating particle is not formed by the friction by mixing using the said insulating particle main body and a high molecular compound or the compound used as the said high molecular compound. Moreover, it is preferable that the surface of the said insulating particle main body is not coat | covered using the hybridization method by the said layer. When insulating particle is formed using the friction by mixing and the hybridization method, a layer becomes easy to detach | desorb from the surface of an insulating particle main body. Moreover, the fragment of the layer formed at the time of kneading | mixing on the surface of insulating particle becomes easy to adhere. Therefore, there exists a tendency for the layer and the fragment of the layer which detached on the surface of the conductive layer of electroconductive particle with insulating particle to adhere, and the conduction | electrical_connection reliability in a bonded structure tends to fall. Therefore, from the viewpoint of further suppressing the detachment of the insulating particles and further increasing the insulation reliability and conduction reliability in the bonded structure, it is preferable that the insulating particles are not formed by friction by mixing, and it is preferable not to use the hybridization method. Do.

The amount of the polymer compound or the compound which becomes the polymer to 100 parts by weight of the insulating particle body when obtaining the insulating particles is preferably 30 parts by weight or more, more preferably 50 parts by weight or more, preferably 500 parts by weight. Or less, more preferably 300 parts by weight or less. If the usage-amount of the said high molecular compound is more than the said minimum and below the said upper limit, a favorable layer can be formed.

The following manufacturing conditions are mentioned as an example of the specific manufacturing conditions of the layer formed with the said high molecular compound.

First, in an amount of 100 to 500 parts by weight of a solvent such as water, 1 to 3 parts by weight of the insulating particle body having a reactive functional group on the surface, and 0.1 to 20 parts by weight of a compound having a reactive double bond and a hydroxyl group (preferably 0.1 to 1 parts by weight) , 0.01 to 5 parts by weight of the crosslinking agent (preferably 0.01 to 1 parts by weight), 0.1 to 5 parts by weight of the dispersant (preferably 0.1 to 3 parts by weight) and 0.1 to 5 parts by weight of the thermal polymerization initiator (preferably 0.1 to 3) Parts by weight) is added. Subsequently, the mixture is heated up to the reaction temperature or higher of the thermal polymerization initiator in an oil bath while stirring with a three-one motor to initiate polymerization, and the reaction is maintained by maintaining this state for 5 hours or more. Thereafter, the unreacted compound is removed using a centrifugal separator to obtain insulating particles whose surface of the insulating particle body is covered by the layer.

As a method of attaching insulating particle to the surface of the said electroconductive particle and the said conductive layer, a chemical method, a physical or mechanical method, etc. are mentioned. As said chemical method, an interfacial polymerization method, suspension polymerization method, emulsion polymerization method, etc. are mentioned, for example. Examples of the physical or mechanical methods include spray drying, hybridization, electrostatic deposition, spraying, dipping and vacuum deposition. However, in the hybridization method, since detachment of the insulating particles tends to occur, the method of adhering the insulating particles to the surfaces of the conductive particles and the conductive layer is preferably a method other than the hybridization method. Especially, since insulating particle is hard to detach | desorb, the method of making insulating particle adhere to the surface of a conductive layer via a chemical bond is preferable.

In the electroconductive particle with insulating particle which concerns on this invention, it is preferable that insulating particle does not adhere to the surface of electroconductive particle by the hybridization method.

In addition, as shown in FIG. 6, in the conventional electroconductive particle 101 with insulating particle which used the hybridization method, parts other than the part 102a to which the insulating particle 103 of the surface of electroconductive particle 102 are affixed ( The polymer compound 104 is also attached to 102b). This is because the compression shearing force is applied in the hybridization method, adhesion and detachment of the insulating particles occur repeatedly, and the insulating particles gradually adhere. The layer formed by the polymer compound of the insulating particles is peeled off by the compressive shearing force, and the peeled polymer compound is attached to a portion other than the part to which the insulating particles on the surface of the conductive particles are attached. The high molecular compound attached to parts other than the part to which the insulating particle on the surface of electroconductive particle adheres increases the volume resistivity of electroconductive particle, or reduces the connection resistance between electrodes. Moreover, even when the surface of the electroconductive particle 101 with insulating particle shown in FIG. 6 is coat | covered with a film, electroconductivity becomes low and connection resistance between electrodes falls easily.

The following method is mentioned as an example of the method which makes insulating particle adhere to the surface of the said electroconductive particle and the said conductive layer.

First, electroconductive particle is put into 3 L of solvents, such as water, and insulating particle is added gradually, stirring. After stirring sufficiently, electroconductive particle with insulating particle is isolate | separated, it is dried by a vacuum dryer etc., and electroconductive particle with insulating particle is obtained.

It is preferable that the said conductive layer has the reactive functional group which can react with insulating particle on the surface, and it is preferable to have the reactive functional group which can react with a film. It is preferable that insulating particle has a reactive functional group which can react with a conductive layer on the surface, and it is preferable to have a reactive functional group which can react with a film. It is preferable that the said film has the reactive functional group which can react with a conductive layer on the surface, and it is preferable to have a functional group which can react with insulating particle. By these reactive functional groups, insulating particles are unlikely to detach from the surface of the conductive particles unintentionally, and the film is difficult to peel off from the surface of the conductive particles and the surface of the insulating particles. In addition, the surface of the conductive layer can be sufficiently covered with a film, and the surface of the insulating particles can be sufficiently covered with a film.

As the reactive functional group, an appropriate group is selected in consideration of reactivity. As said reactive functional group, a hydroxyl group, a vinyl group, an amino group, etc. are mentioned. Since the reactivity is excellent, the reactive functional group is preferably a hydroxyl group. It is preferable that the said electroconductive particle main body with insulating particle has a hydroxyl group in at least one area | region of a surface. It is preferable that the said electroconductive particle has a hydroxyl group on the surface. It is preferable that the said insulating particle has a hydroxyl group on the surface. It is preferable that the said film has a hydroxyl group on the surface.

When there is a hydroxyl group on the surface of insulating particle and the surface of electroconductive particle, the adhesive force of insulating particle and electroconductive particle increases suitably by dehydration reaction.

As a compound which has the said hydroxyl group, P-OH group containing compound, Si-OH group containing compound, etc. are mentioned. As a compound which has a hydroxyl group for introducing a hydroxyl group into the surface of an insulating particle, a P-OH group containing compound, a Si-OH group containing compound, etc. are mentioned.

Specific examples of the P-OH group-containing compound include acid phosphooxyethyl methacrylate, acid phosphooxypropyl methacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate and acid phosphooxypolyoxypropylene glycol Monomethacrylate etc. are mentioned. Only 1 type may be used for the said P-OH group containing compound, and 2 or more types may be used together.

As a specific example of the said Si-OH group containing compound, vinyl trihydroxysilane, 3-methacryloxypropyl trihydroxysilane, etc. are mentioned. Only 1 type may be used for the said Si-OH group containing compound, and 2 or more types may be used together.

For example, the insulating particle which has a hydroxyl group on the surface can be obtained by the process using a silane coupling agent. As said silane coupling agent, hydroxy trimethoxysilane etc. are mentioned, for example.

(Method for producing conductive particles with insulating particles)

In the manufacturing method of the electroconductive particle with insulating particle which concerns on this invention, the surface of the said electroconductive particle main body with insulating particle is used using the compound (compound A) which has a C6-C22 alkyl group on the surface of the electroconductive particle body with insulating particle. A film is formed so that it may coat | cover.

The method of forming a film on the surface of the electroconductive particle main body with insulating particle using the said compound A is not specifically limited, The method of sticking the solution containing the said compound A to the surface of the electroconductive particle main body with insulating particle, etc. are mentioned. have.

It is preferable that the solvent in the solution containing the said compound A is water. The solvent in the solution containing the compound A may contain an organic solvent such as tetrahydrofuran and alcohols such as methanol, ethanol and propanol. After the said solution is made to adhere to the surface of the electroconductive particle body with insulating particle, a solvent is removed as needed.

Content of the said compound A in the solution containing the said compound A is adjusted suitably so that a desired film may be obtained. It is preferable that content of the said compound A exists in the range of 0.5-3 weight% in 100 weight% of solutions containing the said compound A.

For example, when the reactive functional group which can react with the said compound A exists in the surface of a conductive layer or the surface of insulating particle, the said reactive functional group and the said compound A are made to react, and the surface of the said conductive layer and the surface of insulating particle. Compound A may be chemically bonded to the compound.

The compound which has a hydroxyl group in the surface of the electroconductive particle main body with insulating particle, and has a C6-C22 alkyl group which has a hydroxyl group in the electroconductive particle main body with insulating particle in the at least one area | region of a surface (henceforth a compound A1). It is preferable to form a film so that it may react and coat | cover the surface of the electroconductive particle main body with insulating particle. Moreover, it is preferable to form a film so that electroconductive particle has a hydroxyl group on the surface, and the said compound A1 is made to react with the hydroxyl group on the surface of the said electroconductive particle to coat | cover the surface of the electroconductive particle main body with insulating particle. It is preferable that an insulating particle has a hydroxyl group on the surface, and a film is formed so that the said compound A1 may react with the hydroxyl group of the insulating particle surface, and coat | cover the surface of the electroconductive particle main body with insulating particle. Moreover, the surface of electroconductive particle and the surface of insulating particle have a hydroxyl group, respectively, and the said compound A1 is made to react with the hydroxyl group of the surface of electroconductive particle and the surface of insulating particle, and to form a film so that the surface of the electroconductive particle body with insulating particle may be coat | covered. It is preferable. By forming a film in these preferred embodiments, the surface of the conductive layer can be sufficiently covered by the film, and the surface of the insulating particles can be sufficiently covered by the film. Therefore, rust is less likely to occur in the conductive layer, the film is less likely to be peeled off, and the insulating particles are unlikely to detach unintentionally.

(Anisotropic Conductive Material)

The anisotropic electrically-conductive material which concerns on this invention contains the electroconductive particle with insulating particle of this invention, and binder resin, or contains the electroconductive particle with insulating particle and binder resin obtained by the manufacturing method of the electroconductive particle with insulating particle of this invention. .

When the said electroconductive particle with insulating particle is used, since the surface of insulating particle and electroconductive particle is coat | covered with a film, when an electroconductive particle with insulating particle is disperse | distributed in binder resin, an insulating particle detach | desorbs from the surface of electroconductive particle, etc. It's hard to be.

The binder resin is not particularly limited. Generally as said binder resin, insulating resin is used. As said binder resin, a vinyl resin, a thermoplastic resin, curable resin, a thermoplastic block copolymer, an elastomer, etc. are mentioned, for example. Only 1 type may be used for the said binder resin, and 2 or more types may be used together.

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

The anisotropic conductive material is, in addition to the conductive particles with insulating particles and the binder resin, for example, fillers, extenders, softeners, plasticizers, polymerization catalysts, curing catalysts, colorants, antioxidants, thermal stabilizers, light stabilizers, ultraviolet absorbers, lubricants And various additives such as an antistatic agent and a flame retardant.

The method of disperse | distributing the said electroconductive particle with insulating particle in the said binder resin can use a conventionally well-known dispersion method, and is not specifically limited. As a method of disperse | distributing electroconductive particle with insulating particle in binder resin, for example, after adding electroconductive particle with insulating particle in binder resin, it is knead | mixed and disperse | distributed by a planetary mixer etc., and electroconductive particle with insulating particle is water or After uniformly dispersing in an organic solvent using a homogeneous group or the like, adding it to a binder resin, kneading and dispersing it in a planetary mixer or the like, and diluting the binder resin with water or an organic solvent, and then attaching insulating particles. The electroconductive particle is added, the method of kneading | mixing and disperse | distributing with a planetary mixer etc. are mentioned.

The anisotropic conductive material which concerns on this invention can be used as an anisotropic conductive paste or an anisotropic conductive film. When the anisotropic conductive material which concerns on this invention is used as an anisotropic conductive film, the film which does not contain electroconductive particle may be laminated | stacked on the anisotropic conductive film containing the said electroconductive particle.

It is preferable that the anisotropic electrically-conductive material which concerns on this invention is an anisotropic electrically conductive paste. Anisotropic conductive pastes are excellent in handling and circuit chargeability. When obtaining an anisotropic conductive paste, comparatively large force is given to the electroconductive particle with insulating particle, However, detachment of insulating particle from the surface of electroconductive particle by the presence of the said film can be suppressed.

It is preferable that content of the said binder resin is in the range of 10-99.99 weight% in 100 weight% of said anisotropic conductive materials. Content of binder resin becomes like this. More preferably, it is 30 weight% or more, More preferably, it is 50 weight% or more, Especially preferably, it is 70 weight% or more, More preferably, it is 99.9 weight% or more. If content of binder resin is more than the said minimum and below the said upper limit, the electroconductive particle with insulating particle can be efficiently arrange | positioned between electrodes, and the conduction | electrical_connection reliability of the connection object member connected by the anisotropic conductive material can further be improved.

It is preferable that content of the said electroconductive particle with insulating particle exists in the range of 0.01-20 weight% in 100 weight% of said anisotropic conductive materials. Content of the said electroconductive particle with insulating particle becomes like this. More preferably, it is 0.1 weight% or more, More preferably, it is 20 weight% or less, Especially preferably, it is 15 weight% or less. When content of the electroconductive particle with insulating particle is more than the said minimum and below the said upper limit, the conduction | electrical_connection reliability between electrodes can be improved further.

(Connection structure)

A connection structure can be obtained by using the electroconductive particle with insulating particle of this invention, or connecting a connection object member using the anisotropic conductive material containing the said electroconductive particle with insulating particle and binder resin. Moreover, by connecting the connection object member using the electroconductive particle with insulating particle obtained by the manufacturing method of the electroconductive particle with insulating particle of this invention, or using the anisotropic conductive material containing the said electroconductive particle with insulating particle and binder resin. , You can get a connection structure.

The said bonded structure is equipped with the connection part which electrically connects the 1st connection object member, the 2nd connection object member, and the 1st, 2nd connection object member, The said connection part is formed of the said electroconductive particle with insulating particle. It is preferable that it is a connection structure formed of the anisotropic electrically-conductive material containing the said electroconductive particle with insulating particle, and binder resin. When electroconductive particle with insulating particle is used, connection part itself is formed of electroconductive particle with insulating particle. That is, the 1st, 2nd connection object member is electrically connected by the electroconductive particle in the electroconductive particle with insulating particle.

FIG. 5: is sectional drawing which shows typically the bonded structure using the electroconductive particle 1 with insulating particle shown in FIG.

The connection structure 51 shown in FIG. 5 connects the 1st connection object member 52, the 2nd connection object member 53, and the 1st, 2nd connection object member 52, 53 The connection part 54 is provided. The connection part 54 is formed of the anisotropic conductive material containing the electroconductive particle 1 with insulating particle, and binder resin. In FIG. 5, the electroconductive particle 1 with insulating particle is shown schematically for convenience of illustration. Instead of the electroconductive particle 1 with insulating particle, electroconductive particle 21, 41, 61 with insulating particle can also be used.

The first connection object member 52 has a plurality of electrodes 52b on the upper surface 52a. The second connection object member 53 has a plurality of electrodes 53b on the lower surface 53a. The electrode 52b and the electrode 53b are electrically connected by the electroconductive particle 1 with one or some insulating particle. Therefore, the 1st, 2nd connection object members 52 and 53 are electrically connected by the electroconductive particle 1 with insulating particle.

The manufacturing method of the said bonded structure is not specifically limited. As an example of the manufacturing method of a bonded structure, after the said anisotropic electrically-conductive material is arrange | positioned between a 1st connection object member and a 2nd connection object member, and obtaining a laminated body, the method of heating and pressurizing the laminated body, etc. are mentioned. have. The pressure of the pressurization is about 9.8 × 10 ⁴ to 4.9 × 10 ⁶ Pa. The temperature of the said heating is about 120-220 degreeC.

When heating and pressurizing the said laminated body, the insulating particle 15 which existed between the electroconductive particle 11 and the electrodes 52b, 53b can be excluded. For example, at the time of the said heating and pressurization, the insulating particle 15 which existed between the electroconductive particle 11 and the electrodes 52b, 53b melt | dissolves or deform | transforms, and the surface of the electroconductive particle 11 is partially Is exposed. In addition, since large force is provided at the time of the said heating and pressurization, some insulating particle 15 may peel from the surface of the electroconductive particle 11, and the surface of the electroconductive particle 11 may be partially exposed. When the part in which the surface of the electroconductive particle 11 was exposed contacts the electrodes 52b and 53b, the electrodes 52b and 53b can be electrically connected through the electroconductive particle 11.

Specifically as said connection object member, electronic components, such as a semiconductor chip, a capacitor | condenser, and a diode, and electronic components, such as a circuit board, such as a printed circuit board, a flexible printed circuit board, and a glass substrate, etc. are mentioned. It is preferable that the said anisotropic conductive material is a paste form, and is apply | coated on a connection object member in the state of a paste. It is preferable that the said electroconductive particle with insulating particle and an anisotropic conductive material are used for the connection of the connection object member which is an electronic component.

The electroconductive particle with insulating particle which concerns on this invention connects COG (glass on chip) which makes a glass substrate and a semiconductor chip a connection object member especially, or a glass substrate and a flexible printed circuit (FPC; Flexible Printed Circuit). It is preferably used for FOG (Film On Glass) serving as a target member. The electroconductive particle with insulating particle which concerns on this invention may be used for COG, and may be used for FOG. In the bonded structure which concerns on this invention, it is preferable that the said 1st, 2nd connection object member is a glass substrate and a semiconductor chip, or it is a glass substrate and a flexible printed circuit board. A glass substrate and a semiconductor chip may be sufficient as the said 1st, 2nd connection object member, and a glass substrate and a flexible printed circuit board may be sufficient as it.

It is preferable that bumps are provided in the semiconductor chip used by COG which uses a glass substrate and a semiconductor chip as a connection object member. The bump size is preferably an electrode area of 1000 µm ² or more and 10000 µm ² or less. The electrode space in the semiconductor chip provided with the bumps (electrodes) is preferably 30 µm or less, more preferably 20 µm or less, even more preferably 10 µm or less. For such COG use, the electroconductive particle with insulating particle which concerns on this invention is used preferably. In FPC used by FOG which uses a glass substrate and a flexible printed circuit board as a connection object member, electrode space becomes like this. Preferably it is 30 micrometers or less, More preferably, it is 20 micrometers or less.

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

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. This invention is not limited only to a following example.

(Example 1)

Electroconductive particle (average particle diameter 3.01 micrometer, thickness of a conductive layer 0.2 micrometer) which has the metal layer in which the nickel plating layer is formed on the surface of the divinylbenzene resin particle was prepared.

Moreover, the surface of the silica particle (average particle diameter 200nm) produced using the sol-gel method was coat | covered with hydroxytriethoxysilane, and the insulating particle which has a hydroxyl group on the surface was obtained. This insulating particle was disperse | distributed to 30 mL of pure waters, and the dispersion liquid containing insulating particle was obtained.

250 mL of pure water, 50 mL of ethanol, and 15 weight part of said electroconductive particle were put into the 1 L separate flask, and it stirred enough, and obtained the liquid containing electroconductive particle. The dispersion liquid containing insulating particle was dripped over the liquid containing this electroconductive particle over 10 minutes, irradiating with ultrasonic waves. Then, it filtered and dried for 8 hours at 100 degreeC by the vacuum dryer, and obtained the electroconductive particle main body with insulating particle.

10 parts by weight of the conductive particle body with insulating particles and 0.5 parts by weight of monohexyl phosphate were added to a mixture of 25 g of pure water and 25 g of ethanol, and the mixture was stirred at 50 ° C. for 1 hour. Then, it filtered and dried for 8 hours at 100 degreeC with a vacuum dryer, and obtained electroconductive particle with insulating particle which has the film formed by the said monohexyl phosphate on the surface of the electroconductive particle body with insulating particle. The said coating coat | covered the surface of electroconductive particle and the surface of insulating particle. The coating part covering the surface of electroconductive particle and the coating part covering the surface of insulating particle were continuous.

(Example 2)

The same electroconductive particle (average particle diameter 3.01 micrometer, thickness 0.2 micrometer of a conductive layer) similar to Example 1 was prepared.

Moreover, the surface of the silica particle (average particle diameter 200nm) produced using the sol-gel method was coat | covered with vinyltriethoxysilane, and the insulating particle which has a vinyl group on the surface was obtained as an insulating particle main body.

Three parts by weight of the insulating particle body, 0.22 parts by weight of methacrylic acid, 0.05 parts by weight of ethylene glycol dimethacrylate, and 0.5 parts by weight of an initiator ("V-50" manufactured by Wako Pure Chemical Industries, Ltd.) in 200 mL of water The temperature was raised to 70 DEG C while sufficiently stirring with a one-motor, and maintained at 70 DEG C for 6 hours to polymerize the monomer.

Then, it cooled, solid-liquid separation was performed twice with the centrifugal separator, and the excess monomer was removed by washing | cleaning, and the insulating particle which covered the whole surface with the high molecular compound was obtained. Next, the obtained insulating particles were dispersed in 30 mL of pure water to obtain a dispersion of insulating particles.

250 mL of pure water, 50 mL of ethanol, and 15 weight part of said electroconductive particle were put into the 1 L separate flask, and it stirred enough, and obtained the liquid containing electroconductive particle. After disperse | distributing the dispersion liquid of the said insulating particle over 10 minutes, irradiating ultrasonic wave to the liquid containing this electroconductive particle, it heated up at 40 degreeC and stirred for 1 hour. Then, it filtered and dried for 8 hours at 100 degreeC with the vacuum dryer, and obtained the electroconductive particle main body with insulating particle.

Except having used the obtained electroconductive particle main body with insulating particle, it carried out similarly to Example 1, and obtained electroconductive particle with insulating particle. The said coating coat | covered the surface of electroconductive particle and the surface of insulating particle. The coating part covering the surface of electroconductive particle and the coating part covering the surface of insulating particle were continuous.

(Example 3)

10 g of resin particles were etched and washed with water. Next, palladium sulfate was added to the resin particles, and the palladium ions were adsorbed onto the resin particles. The resin particles with palladium were stirred for 3 minutes in 300 mL of ion-exchanged water, and dispersed to obtain a dispersion. Subsequently, 1 g of a metal nickel particle slurry ("2020SUS" by Mitsui Kinzo Co., Ltd., 200 nm of average particle diameters) was added to the said dispersion liquid over 3 minutes, and the resin particle with a core substance was obtained. The nickel layer was formed on the surface of the resin particle to which the core substance adhered by electroless nickel plating. Thus, the core material adhered to the surface of the resin particle, and the electroconductive particle by which the surface of the resin particle and the core material was coat | covered with the nickel layer was obtained. The average particle diameter of this electroconductive particle was 3.02 micrometers, and the thickness of the conductive layer was 0.2 micrometer. This electroconductive particle had protrusion on the surface.

Except having used obtained electroconductive particle, it carried out similarly to Example 1, and obtained electroconductive particle with insulating particle.

(Example 4)

Except having changed monohexyl phosphate into monooctyl ester of phosphate, it carried out similarly to Example 1, and obtained electroconductive particle with insulating particle.

(Example 5)

Except having changed monohexyl phosphate into monododecyl phosphate, it carried out similarly to Example 1, and obtained electroconductive particle with insulating particle.

(Example 6)

Except having changed the monohexyl phosphate ester into the monohexadecyl ester phosphate, it carried out similarly to Example 1, and obtained electroconductive particle with insulating particle.

(Example 7)

Except having changed the monohexyl phosphate ester into hexyl triethoxysilane, it carried out similarly to Example 1, and obtained electroconductive particle with insulating particle.

(Example 8)

Except having changed monohexyl phosphate into octyl triethoxysilane, it carried out similarly to Example 1, and obtained electroconductive particle with insulating particle.

(Example 9)

Except having changed the monohexyl phosphate ester into dodecyl triethoxysilane, it carried out similarly to Example 1, and obtained electroconductive particle with insulating particle.

(Example 10)

Fabrication of insulating particles:

The surface of the silica particle (average particle diameter 200nm) produced using the sol-gel method was coat | covered with vinyltriethoxysilane, and the insulating particle which has the vinyl group which is a reactive functional group on the surface was obtained as an insulating particle main body. Specifically, 10 parts by weight of silica particles were dispersed in 400 ml of a mixture of water and ethanol in a weight ratio of 1: 9 using a three-one motor to obtain a first dispersion. Subsequently, 0.1 part by weight of vinyltriethoxysilane was dispersed in 100 ml of a mixture of water and ethanol in a weight ratio of 1: 9 to obtain a second dispersion. Then, the said 2nd dispersion liquid was dripped at the said 1st dispersion liquid over 10 minutes, and the mixed liquid was obtained. After dripping, the obtained liquid mixture was stirred for 30 minutes. Thereafter, the mixed liquid was filtered, dried at 100 ° C. for 2 hours, and then filtered to obtain an insulating particle body.

In 200 mL of water, 1 part by weight of the insulating particle body, 2 parts by weight of methacrylic acid which is a compound to be a high molecular compound, 1 part by weight of ethylene glycol dimethacrylate as a compound to be a high molecular compound, and initiator 0.5 weight part of teacher-made "V-50"), and 1 weight part of polyoxyethylene lauryl ether ("Emulgen 106" by Kao Corporation) were mix | blended as an emulsifier, and it fully emulsified using the ultrasonic irradiation machine. Thereafter, the temperature was raised to 70 ° C. while sufficiently stirring with a three-one motor, and the monomer was polymerized by maintaining at 70 ° C. for 6 hours.

Then, it cooled, solid-liquid separation was performed twice with the centrifugal separator, and the excess monomer was removed by washing | cleaning, and the insulating particle which covered the whole surface with the high molecular compound was obtained. Subsequently, the obtained insulating particles were dispersed in 30 mL of pure water to obtain a dispersion containing the insulating particles. In the state of the dispersion of the insulating particles, the average particle diameter of the insulating particles coated with the polymer compound was 324 nm.

Preparation of conductive particles with insulating particles:

Electroconductive particle with insulating particle was obtained like Example 1 except having used the dispersion liquid containing the insulating particle obtained as a dispersion liquid containing insulating particle.

(Example 11)

The dispersion liquid containing insulating particle was obtained like Example 10 except having changed the compound used as a high molecular compound into 2.5 weight part of methacrylic acid and 1.2 weight part of divinylbenzene. In addition, in the state of the dispersion liquid of the said insulating particle, the average particle diameter of the insulating particle coat | covered with the high molecular compound was 335 nm.

Electroconductive particle with insulating particle was obtained like Example 1 except having used the dispersion liquid containing the insulating particle obtained as a dispersion liquid containing insulating particle.

(Example 12)

2.2 parts by weight of vinyl acetate, N, which were obtained by coating the surface of the silica particles with methacryloxypropyltriethoxysilane to obtain insulating particles having methacryloyl groups on the surface as the insulating particle body, and a compound to be a high molecular compound; Except having changed into 1.0 weight part of N-methylenebisacrylamide, it carried out similarly to Example 10, and obtained the dispersion liquid containing insulating particle.

Moreover, the insulating particle main body was obtained by the method similar to Example 10 except having used 10 weight part of silica particles and 0.1 weight part of methacryloxypropyl triethoxysilane when obtaining an insulating particle main body. In the state of the dispersion of the insulating particles, the average particle diameter of the insulating particles coated with the polymer compound was 326 nm.

Electroconductive particle with insulating particle was obtained like Example 1 except having used the dispersion liquid containing the insulating particle obtained as a dispersion liquid containing insulating particle.

(Example 13)

Electroconductive particle, electroconductive in which nickel powder (100 nm) is attached as a core substance to the surface of the divinylbenzene resin particle, and the nickel plating layer (conductive layer) is formed on the surface of the divinylbenzene particle with nickel powder. Conductive particles with insulating particles were obtained in the same manner as in Example 1 except that the particles (average particle diameter 3.03 µm and the thickness of the conductive layer 0.21 µm) were used.

(Example 14)

The dispersion liquid containing insulating particle was obtained like Example 10 except having changed the compound used as a high molecular compound into 0.4 weight part of methacrylic acid and 0.05 weight part of ethylene glycol dimethacrylate.

In addition, in the state of the dispersion liquid of the said insulating particle, the average particle diameter of the insulating particle coat | covered with the high molecular compound was 248 nm.

Electroconductive particle with insulating particle was obtained like Example 1 except having used the dispersion liquid containing the insulating particle obtained as a dispersion liquid containing insulating particle.

(Example 15)

Except having obtained the electroconductive particle main body with insulating particle using the hybridization method, it carried out similarly to Example 2, and obtained electroconductive particle with insulating particle.

(Comparative Example 1)

Electroconductive particle with insulating particle which is the electroconductive particle main body with insulating particle obtained in Example 1. That is, in Comparative Example 1, the following evaluation was performed by using the conductive particle body with insulating particles obtained in Example 1 as the conductive particles with insulating particles, without forming a film on the conductive particle body with insulating particles obtained in Example 1. It was done.

(Comparative Example 2)

Electroconductive particle with insulating particle which is the electroconductive particle main body with insulating particle obtained in Example 2. That is, in the comparative example 2, the following evaluation is performed using the electroconductive particle main body with insulating particle obtained in Example 2 as electroconductive particle with insulating particle, without forming a film in the electroconductive particle main body with insulating particle obtained in Example 2. It was done.

(Comparative Example 3)

Electroconductive particle with insulating particle was obtained like Example 1 except having changed monohexyl phosphate into monopentyl phosphate (5 carbon atoms of an alkyl group).

(Comparative Example 4)

Electroconductive particle with insulating particle was obtained like Example 1 except having changed monohexyl phosphate into monotricosyl phosphate (C23 of an alkyl group).

(evaluation)

(1) Evaluation of content of phosphorus element or silicon element in electroconductive particle with insulating particle

1 weight part of electroconductive particle with insulating particle of an Example and a comparative example was put into 100 weight part of 5 weight% citric acid aqueous solution (solution which melt | dissolved 5 weight% citric acid in 95 weight% of water), it was made into 40 degreeC, and stirred for 30 minutes, and a processing liquid After the obtained liquid, the process liquid was filtered through filter paper, and the filtrate was obtained. In the electroconductive particle with insulating particle of Examples 1-9, the film adhered to the surface of the electroconductive particle main body with insulating particle after peeling off with the citric acid aqueous solution.

The content of phosphorus element or silicon element in the obtained filtrate was measured using the ICP emission spectrometer ("ULTIMA2" manufactured by Horiba Seisakusho Co., Ltd.).

(2) Preparation of bonded structure

The electroconductive particle with insulating particle of an Example and a comparative example was added to Mitsui Chemical Co., Ltd. "struct bond bond XN-5A" so that content might be 10 weight%, and it disperse | distributed and obtained the anisotropic conductive paste.

The transparent glass substrate in which the ITO electrode pattern whose L / S is 30 micrometers / 30 micrometers was formed in the upper surface was prepared. In addition, a semiconductor chip having a copper electrode pattern having an L / S of 30 µm / 30 µm was formed on the lower surface thereof.

The anisotropic conductive paste obtained on the said transparent glass substrate was coated so that it might be set to 30 micrometers in thickness, and the anisotropic conductive paste layer was formed. Next, the semiconductor chip was laminated on the anisotropic conductive paste layer so as to face the electrodes. Thereafter, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer is 185 ° C, the pressure heating head is placed on the upper surface of the semiconductor chip, and the pressure of 1 MPa is applied to completely cure the anisotropic conductive paste layer at 185 ° C. A bonded structure was obtained.

(3) Conductivity evaluation (between upper and lower electrodes)

The connection resistance between the upper and lower electrodes of the obtained bonded structure was measured by the four terminal method, respectively. The average value of two connection resistances was computed. From the relationship of voltage = current x resistance, the connection resistance can be obtained by measuring the voltage when a constant current is passed. Although the average value of connection resistance is 2.0 ohms or less, and a high molecular compound is not attached to the part other than the part to which the insulating particle on the surface of electroconductive particle adheres, the average value of connection resistance is 2 ohms or less, but the surface of electroconductive particle "△" and the case where the average value of connection resistance exceeds 2 (ohm) for the case where the polymer compound is attached to parts other than the part to which the insulating particle of is attached are shown in Table 1 as follows. It was.

(4) Insulation evaluation (between electrodes adjacent in the horizontal direction)

In the obtained bonded structure, the presence or absence of leakage between adjacent electrodes was evaluated by measuring resistance with a tester. When the resistance exceeds 500 MΩ, it is determined that there is no leakage, and the result is set to "(circle)", and when the resistance is 500 MΩ or less, it is determined that there is leakage, and the result is set to "x", and it is shown in following Table 1.

(5) antirust evaluation

The bonded structure produced by the said insulation evaluation was left to stand on 85 degreeC and conditions of 85% of a relative humidity. After 100 hours from the start of standing, the connection resistance between the electrodes was measured by the four-terminal method in the same manner as above. In the case where the average value of the connection resistance (after leaving) is less than 150% compared to the average value of the connection resistance (before leaving) at the time of the conduction evaluation described above, the case where the average value of the connection resistance (after leaving) rises by 150% or more The results are shown in Table 1 below.

The results are shown in Table 1 below.

As shown in the said Table 1, in the rust prevention evaluation using the electroconductive particle with insulating particle of Comparative Examples 1 and 2, the resistance value rose 150% or more. This is because rust occurred on the surface of the conductive layer.

Moreover, in the electroconductive particle with insulating particle of Examples 1-14, it confirmed that a high molecular compound did not adhere to parts other than the part to which the insulating particle on the surface of electroconductive particle adheres. In addition, in Example 15, since the physical / mechanical hybridization method was used, there existed a point where the high molecular compound adhered to parts other than the part to which the insulating particle on the surface of electroconductive particle adheres. Thus, when a high molecular compound adheres to parts other than the part to which the insulating particle on the surface of electroconductive particle adheres, there exists a possibility that conduction | electrical_connection reliability may become low in some cases.

(6) Desorption of insulating particles

In addition, in the anisotropic conductive paste obtained by the insulation evaluation, it was observed whether insulating particles were detached from the surface of electroconductive particle.

As a result, in the anisotropic conductive paste using the electroconductive particle with insulating particle of Examples 1-15, the ratio of the insulating particle detached from the surface of electroconductive particle compared with the anisotropic conductive paste using the electroconductive particle with insulating particle of Comparative Examples 1 and 2 This was very little. In particular, in the anisotropic conductive paste using the electroconductive particle with insulating particle of Example 1, the ratio of the insulating particle detached from the surface of electroconductive particle was very small compared with the anisotropic conductive paste using the electroconductive particle with insulating particle of Comparative Example 1. Moreover, in the anisotropic conductive paste using the electroconductive particle with insulating particle of Example 2, the ratio of the insulating particle detached from the surface of electroconductive particle was very small compared with the anisotropic conductive paste using the electroconductive particle with insulating particle of Comparative Example 2. This is considered that in the electroconductive particle with insulating particle of Examples 1-15, since the film is formed, desorption of insulating particle was suppressed.

In addition, in the anisotropic conductive paste using the electroconductive particle with insulating particle of Example 2, compared with the anisotropic conductive paste using the electroconductive particle with insulating particle of Example 1, the ratio of the insulating particle detached from the surface of electroconductive particle was small. This is considered that in the insulating particle of Example 2, since the surface of the insulating particle was covered by the flexible layer formed of the polymer compound, the detachment of the insulating particle was suppressed.

One… Electroconductive particle with insulating particle
2… Electroconductive particle body with insulating particle
3 ... film
11 ... Conductive particles
12... Substrate particles
13 ... Conductive layer
15... Insulating particles
21 ... Electroconductive particle with insulating particle
22... Electroconductive particle body with insulating particle
23 ... film
31 ... Conductive particles
32 ... Conductive layer
33 ... Core material
34... spin
35 ... Insulating particles
41... Electroconductive particle with insulating particle
42 ... Electroconductive particle body with insulating particle
45... Insulating particles
45a... Insulating particle body
45b... layer
51 ... Connection structure
52 ... The first connection object member
52a ... Top surface
52b ... electrode
53 ... The second connection object member
53a ... if
53b ... electrode
54 ... Connection
61... Electroconductive particle with insulating particle
62 ... Electroconductive particle body with insulating particle
71 ... Conductive particles
76... Conductive layer
76a... First conductive layer
76b... Second conductive layer
77... spin

Claims (18)

Electroconductive particle main body with insulating particle which has electroconductive particle which has an electroconductive layer at least on the surface, and insulating particle | grains adhered to the surface of the said electroconductive particle via a chemical bond, and
It is provided with the film which coat | covers the surface of the said electroconductive particle main body with insulating particle,
The said film is formed of the compound which has a C6-C22 alkyl group,
The film has a film portion covering the surface of the conductive particles and a film portion covering the surface of the insulating particles,
Electroconductive particle with insulating particle which the coating part covering the surface of the said electroconductive particle, and the coating part covering the surface of the said insulating particle are continuous. Electroconductive particle with insulating particle of Claim 1 in which the said insulating particle contains an inorganic particle. 3. The compound according to claim 1, wherein the compound having an alkyl group having 6 to 22 carbon atoms is at least one selected from the group consisting of phosphate esters or salts thereof, phosphite esters or salts thereof, alkoxysilanes, alkylthiols and dialkyldisulfides. Electroconductive particle with insulating particle which is a seed. The electroconductive particle with insulating particle of Claim 1 or 2 which has the insulating particle main body and the layer which covers at least one area | region of the surface of the said insulating particle main body, and is formed of the high molecular compound. Electroconductive particle with insulating particle of Claim 4 in which the said polymeric compound is not affixed to parts other than the part to which the said insulating particle is affixed on the surface of the said electroconductive particle. Electroconductive particle with insulating particle of Claim 4 in which the said high molecular compound has at least 1 sort (s) of reactive functional group chosen from the group which consists of a (meth) acryloyl group, a glycidyl group, and a vinyl group. Electroconductive particle with insulating particle of Claim 1 or 2 in which the said insulating particle is not affixed on the surface of the said electroconductive particle by the hybridization method. The anisotropic conductive material containing the electroconductive particle with insulating particle of Claim 1, or 2, and binder resin. The anisotropic conductive material according to claim 8, which is an anisotropic conductive paste. It is provided with the 1st connection object member, the 2nd connection object member, and the connection part which connects the said 1st, 2nd connection object member,
The connection structure in which the said connection part is formed of the electroconductive particle with insulating particle of Claim 1 or 2, or is formed of the anisotropic conductive material containing the said electroconductive particle with insulating particle and binder resin. delete delete delete delete delete delete delete delete

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