CN105900180B - The manufacturing method of conductive paste, connection structural bodies and connection structural bodies - Google Patents

The manufacturing method of conductive paste, connection structural bodies and connection structural bodies Download PDF

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Publication number
CN105900180B
CN105900180B CN201580004070.7A CN201580004070A CN105900180B CN 105900180 B CN105900180 B CN 105900180B CN 201580004070 A CN201580004070 A CN 201580004070A CN 105900180 B CN105900180 B CN 105900180B
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conductive paste
electrode
scolding tin
mentioned
object component
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CN105900180A (en
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久保田敬士
石泽英亮
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/14—Structural association of two or more printed circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/36—Assembling printed circuits with other printed circuits
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/11—Manufacturing methods
    • H01L2224/115—Manufacturing methods by chemical or physical modification of a pre-existing or pre-deposited material
    • H01L2224/1152—Self-assembly, e.g. self-agglomeration of the bump material in a fluid
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)
  • Combinations Of Printed Boards (AREA)
  • Non-Insulated Conductors (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Manufacturing Of Electrical Connectors (AREA)
  • Connections Effected By Soldering, Adhesion, Or Permanent Deformation (AREA)

Abstract

The present invention provides a kind of conductive paste, scolding tin particle can be efficiently configured on electrode, so as to improve interelectrode conducting reliability.The conductive paste of the present invention contains Thermocurable ingredient, fluxing agent and multiple scolding tin particles, viscosity of the conductive paste under the fluxing agent fusing point is more than 0.1Pas and 3Pas is hereinafter, the viscosity under the fusing point of the scolding tin particle is more than 0.1Pas and below 5Pas.

Description

The manufacturing method of conductive paste, connection structural bodies and connection structural bodies
Technical field
The present invention relates to a kind of conductive pastes containing scolding tin particle.Moreover, it relates to a kind of used above-mentioned lead The connection structural bodies of electric paste and the manufacturing method of connection structural bodies.
Background technology
The anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are well known.With regard to above-mentioned each For anisotropy conductive material, electroconductive particle is dispersed in adhesive resin.
In order to obtain various connection structural bodies, above-mentioned anisotropic conductive material has been used for such as flexible printing substrate Connection (COF (the Chipon of connection (FOG (Filmon Glass)), semiconductor chip and flexible printing substrate with glass substrate Film)), the connection (COG (Chipon Glass)) of semiconductor chip and glass substrate and flexible printing substrate and glass ring Connection (FOB (Filmon Board)) of oxygen substrate etc..
Above-mentioned anisotropic conductive material is being utilized to such as electricity of the electrode of flexible printing substrate and glass epoxy substrate When pole is electrically connected, the anisotropic conductive material containing electroconductive particle is configured on glass epoxy substrate.Then, lamination Flexible printing substrate, and heated and pressurizeed.Cure anisotropic conductive material as a result, by electroconductive particle to electricity Interpolar is electrically connected, so as to obtain connection structural bodies.
As an example of above-mentioned anisotropic conductive material, the following patent document 1 discloses a kind of splicing tape, Comprising the resin layer containing heat-curing resin, solder powder and curing agent, and above-mentioned solder powder and above-mentioned curing agent are present in It states in resin layer.The splicing tape is membranaceous rather than paste-like.
In addition, it is also disclosed in patent document 1 a kind of using the adhering method for having above-mentioned splicing tape.Specifically, under Side starts to carry out lamination to first substrate, splicing tape, second substrate, splicing tape and third substrate successively, so as to obtain laminated body. At this point, make the first electrode for being set to first substrate surface and the second electrode for being set to second substrate surface opposed.In addition, make It is set to the second electrode on second substrate surface and is set to the third electrode contraposition of third substrate surface.Moreover, with specified Temperature is heated and is bonded to laminated body.Connection structural bodies is obtained as a result,.
Existing technical literature
Patent document
Patent document 1:WO2008/023452A1
Invention content
The technical problems to be solved by the invention
Splicing tape described in patent document 1 is membranaceous rather than paste-like.Therefore, it is not easy solder powder being effectively configured In on electrode (line).For example, in splicing tape described in patent document 1, a part for solder powder, which is easily configurable at, does not form electricity The region (interval) of pole.The solder powder for being configured at the region for not forming electrode does not contribute to interelectrode conducting.
Even in addition, the anisotropic conductive paste containing solder powder, solder powder cannot be efficiently configured to electricity sometimes On pole (line).
The object of the present invention is to provide a kind of conductive pastes, and scolding tin particle can be efficiently configured on electrode, So as to improve interelectrode conducting reliability.The present invention also provides a kind of connection structural bodies for having used above-mentioned conductive paste And the manufacturing method of connection structural bodies.
For solving the technical solution of technical problem
Wide in range aspect according to the present invention, provides a kind of conductive paste, contains Thermocurable ingredient, fluxing agent and multiple Scolding tin particle, viscosity of the conductive paste under the fusing point of the fluxing agent is for more than 0.1Pas and 3Pas hereinafter, institute Viscosity of the conductive paste under the fusing point of the scolding tin particle is stated as more than 0.1Pas and below 4.8Pas.
In some particular aspects of the conductive paste of the present invention, the fusing point of the fluxing agent for 80 DEG C or more and 190 DEG C with Under, at other specific aspects, the fusing point of the fluxing agent is 100 DEG C or more and less than 190 DEG C.
In some particular aspects of the conductive paste of the present invention, 100 weight % of conductive paste, the content of the fluxing agent For more than 0.1 weight % and below 5 weight %.
In some particular aspects of the conductive paste of the present invention, the conductive paste does not contain filler or in electroconductive paste Contain the filler less than 0.25 weight % in 100 weight % of agent.
In some particular aspects of the conductive paste of the present invention, the scolding tin particle is surface-treated, and deposits carboxyl It is on the outer surface of the scolding tin particle.
In some particular aspects of the conductive paste of the present invention, the fusing point of the fluxing agent is than the fusing point of the scolding tin particle It is high.
Wide in range aspect according to the present invention, provides a kind of connection structural bodies, has：It has：
First connecting object component of the surface at least one first electrode, surface are at least one second electrode The second connecting object component, company that the first connecting object component and the second connecting object component link together Socket part, the connecting portion are formed using above-mentioned conductive paste, and the first electrode and the second electrode pass through the connection Solder sections in portion realize electrical connection.
Wide in range aspect according to the present invention provides a kind of manufacturing method of connection structural bodies, including：It is led using above-mentioned The conductive paste is configured on the surface of first connecting object component of the surface at least one first electrode in electric paste Process；On the surface opposite with the first connecting object component side of the conductive paste, configuration surface has at least one Second connecting object component of a second electrode, and make the first electrode and the opposed process of the second electrode；By described in Conductive paste is heated to more than the fusing point of the scolding tin particle and more than the solidification temperature of the Thermocurable ingredient, as a result, by The connection that the conductive paste formation links together the first connecting object component and the second connecting object component Portion, and the process being electrically connected by the solder sections in the connecting portion to the first electrode and the second electrode.
In some particular aspects of the manufacturing method of the connection structural bodies of the present invention, the second connecting object portion is configured described The process of part and the weight for being formed in the process of connecting portion, applying the second connecting object component to the conductive paste Amount, and without pressurization.
The second connecting object component is preferably resin film, flexible printing substrate, rigid-flexible combination substrate or flexble flat Cable.
The effect of invention
The conductive paste of the present invention contains Thermocurable ingredient, fluxing agent and multiple scolding tin particles, the conductive paste and exists Viscosity under the fusing point of above-mentioned fluxing agent is for more than 0.1Pas and 3Pas hereinafter, the conductive paste is in above-mentioned scolding tin particle Fusing point under viscosity for more than 0.1Pas and 4.8Pas hereinafter, therefore, in the case where being electrically connected between electrode, Scolding tin particle can be efficiently configured on electrode, so as to improve interelectrode conducting reliability.
Description of the drawings
Fig. 1 is to schematically show the connection structural bodies obtained using the conductive paste of an embodiment of the invention The front section view of biopsy cavity marker devices.
Fig. 2 (a)~Fig. 2 (c) is the conductive paste manufacture connection knot for illustrating using an embodiment of the invention The figure of each process of one example of the method for structure body.
Fig. 3 is the front section view of the biopsy cavity marker devices for the variation for showing connection structural bodies.
Fig. 4 (a), Fig. 4 (b) and Fig. 4 (c) are to show to have used the conductive paste for being not included in embodiments of the present invention Connection structural bodies an example image, Fig. 4 (a) and Fig. 4 (b) are cross-sectional images, and Fig. 4 (c) is flat image.
Description of symbols
1st, 1X ... connection structural bodies
2 ... first connecting object components
2a ... first electrodes
3 ... second connecting object components
3a ... second electrodes
4th, 4X ... connecting portions
4A, 4XA ... solder sections
4B, 4XB ... solidfied material portion
11 ... conductive pastes
11A ... scolding tin particles
11B ... Thermocurable ingredients
Specific embodiment
Hereinafter, illustrate the details of the present invention.
The conductive paste of the present invention contains Thermocurable ingredient, fluxing agent and multiple scolding tin particles.With regard to the conduction of the present invention For paste, the viscosity under the fusing point of above-mentioned fluxing agent is more than 0.1Pas and below 3Pas.With regard to the conduction of the present invention For paste, the viscosity under the fusing point of above-mentioned scolding tin particle is more than 0.1Pas and below 4.8Pas.
For the conductive paste of the present invention, using above-mentioned composition, therefore, in situation about being electrically connected between electrode Under, multiple scolding tin particles are easily concentrated between electrode, and multiple scolding tin particles can be efficiently configured on electrode (line).Separately Outside, a part for multiple scolding tin particles is not easy to be configured at the region (interval) for not forming electrode, can largely reduce and be configured at not Form the amount of the scolding tin particle in the region of electrode.Therefore, it is possible to improve interelectrode conducting reliability.Furthermore, it is possible to it prevents not Electrical connection between the adjacent electrode on transverse direction that can be attached, and insulating reliability can be improved.It can obtain such effect Fruit is considered because in the oxide film thereon that scolding tin particle surface is removed with the fusing point of fluxing agent, the viscosity of conductive paste is appropriate, And in scolding tin pellet melting, the viscosity of conductive paste is appropriate.
The conductive paste of the present invention can be preferred for the manufacturing method of the connection structural bodies of the following present invention.
In the manufacturing method of the connection structural bodies of the present invention, connected using conductive paste, the first connecting object component and second Connect object Part.Conductive material used in the manufacturing method of the connection structural bodies of the present invention is conductive paste rather than conduction Film.Above-mentioned conductive paste contains Thermocurable ingredient, fluxing agent and multiple scolding tin particles.Above-mentioned first connecting object component is in table Face has at least one first electrode.Above-mentioned second connecting object component has at least one second electrode on surface.
The manufacturing method of the connection structural bodies of the present invention includes：This is configured on the surface of above-mentioned first connecting object component The process of the conductive paste of invention；On the surface opposite with above-mentioned first connecting object component side of above-mentioned conductive paste, match The second connecting object component is put, and makes above-mentioned first electrode and the opposed process of above-mentioned second electrode；Above-mentioned conductive paste is added More than heat to the fusing point of above-mentioned scolding tin particle and more than the solidification temperature of above-mentioned Thermocurable ingredient, as a result, by above-mentioned electroconductive paste Dosage form is into the connecting portion that above-mentioned first connecting object component and above-mentioned second connecting object component link together, and by upper State the process that the solder sections in connecting portion are electrically connected above-mentioned first electrode and above-mentioned second electrode.The connection knot of the present invention In the manufacturing method of structure body, preferably in the process that the process of above-mentioned second connecting object component is configured and forms above-mentioned connecting portion In, by the weight of above-mentioned second connecting object component be applied on above-mentioned conductive paste and without pressurization.The connection of the present invention In the manufacturing method of structure, preferably in the process that the process of above-mentioned second connecting object component is configured and forms above-mentioned connecting portion In, to moulding pressure of the above-mentioned conductive paste application more than the power of the weight of above-mentioned second connecting object component.
In the manufacturing method of the connection structural bodies of the present invention, using above-mentioned composition, therefore, multiple scolding tin particles easily collect In between the first electrode and the second electrode, multiple scolding tin particles can be efficiently configured on electrode (line).It is in addition, multiple A part for scolding tin particle is not easy to be configured at the region (interval) for not forming electrode, can largely reduce to be configured at and does not form electrode Region scolding tin particle amount.It is thus possible to improve the conducting reliability between first electrode and second electrode.It moreover, can To prevent the electrical connection between the adjacent electrode on the transverse direction that cannot be attached, so as to improve insulating reliability.
As described above, the inventors of the present invention have found：In order to which multiple scolding tin particles are efficiently configured on electrode, and largely subtract It is configured at the amount of the scolding tin particle in the region for not forming electrode less, needs using conductive paste, without the use of conductive film.
In addition, as the particle different from scolding tin particle, it is known to there is substrate particle and be configured at the substrate particle table The electroconductive particle of soldering-tin layer on face.Compared with using the situation of such electroconductive particle, in the feelings for using scolding tin particle Under condition, by the fusing point of above-mentioned fluxing agent and the fusing point of above-mentioned scolding tin particle in specific range, scolding tin particle is on the electrode The improvement effect of configuration precision becomes larger.
Also, the inventors of the present invention also found：If the process of above-mentioned second connecting object component is configured and is formed above-mentioned In the process of connecting portion, without pressurization, but apply the weight of above-mentioned second connecting object component to above-mentioned conductive paste, then Before connecting portion is formed, be configured at the region (interval) for not forming electrode scolding tin particle be easier to be collected in first electrode and Between second electrode, multiple scolding tin particles can be efficiently configured on electrode (line).In the present invention, combination uses following structures It is of great significance in pairs in order to obtain the effect of the present invention with higher level：Using conductive paste without the use of conduction Film；Apply the weight of above-mentioned second connecting object component to above-mentioned conductive paste and without pressurization.
In addition, in WO2008/023452A1, describing from along electrode surface promotion solder powder makes what it was effectively moved Viewpoint is set out, and can be pressurizeed, and describe from the sight that soldering tin is formed more reliably with specified pressure in bonding Point sets out, and moulding pressure is adjusted to such as more than 0MPa, preferably more than 1MPa, and splicing tape is intentionally applied even if also describing Pressure for 0MPa, can be by being configured at the dead weight of the component on splicing tape, the pressure specified to splicing tape application. In WO2008/023452A1, it can be 0MPa, but to assigning more than 0MPa's to describe the pressure intentionally applied to splicing tape It the situation of pressure and is set as the difference of effect of situation of 0MPa there is no record.
If it in addition, by the coating weight of conductive paste, can suitably be adjusted without the use of conductive film using conductive paste The thickness of whole connecting portion.On the other hand, there are the following problems in conductive film：For the thickness of variations or modifications connecting portion, it is necessary to The conductive film of thickness that the conductive film of preparation different-thickness or preparation are specified.
Hereinafter, being described with reference to the specific embodiment and embodiment of the present invention, carry out the clearly present invention.
First, Fig. 1 is illustrated with the front cross-sectional of schematically biopsy cavity marker devices using an embodiment of the invention The connection structural bodies that conductive paste obtains.
Connection structural bodies 1 shown in FIG. 1 has：First connecting object component 2, the second connecting object component 3 connect first Connect the connecting portion 4 that 2 and second connecting object component 3 of object Part links together.Connecting portion 4 by contain Thermocurable ingredient, The conductive paste of fluxing agent and multiple scolding tin particles is formed.For the conductive paste, the viscosity under above-mentioned fluxing agent fusing point And the viscosity under above-mentioned scolding tin particle fusing point is in a specific range.
The solder sections 4A and make Thermocurable ingredient hot that connecting portion 4 has multiple scolding tin particles aggregates and is welded to each other Cure the solidfied material portion 4B formed.
There are multiple first electrode 2a on the surface (upper surface) of first connecting object component 2.Second connecting object component 3 Surface (lower surface) on have multiple second electrode 3a.First electrode 2a and second electrode 3a are electrically connected by solder sections 4A It connects.Therefore, the first connecting object component 2 and the second connecting object component 3 are electrically connected by solder sections 4A.In addition, connection In portion 4, in region (the solidfied material portion 4B portion different from the solder sections 4A being collected between first electrode 2a and second electrode 3a Point) in, there is no scolding tin.In the region (solidfied material portion 4B part) different from solder sections 4A, there is no be detached from solder sections 4A Scolding tin.In addition, if it is a small amount of, then scolding tin can reside in and be collected in the weldering between first electrode 2a and second electrode 3a Regions (solidfied material portion 4B parts) different tin portion 4A.
As shown in Figure 1, in connection structural bodies 1, after multiple scolding tin pellet meltings, the fusant wetting electrode of scolding tin particle Cure after surface and diffusion, so as to form solder sections 4A.Therefore, solder sections 4A and first electrode 2a and solder sections 4A and The connection area of second electrode 3a becomes larger.That is, by using scolding tin particle, the outer surface with using electric conductivity is nickel, gold or copper The situation of electroconductive particle of metals is waited to compare, solder sections 4A and first electrode 2a's and solder sections 4A and second electrode 3a Contact area becomes larger.Therefore, the conducting reliability in connection structural bodies 1 and connection reliability improve.In addition, institute in conductive paste The fluxing agent contained would generally gradually inactivate due to heating.
In addition, in connection structural bodies 1 shown in FIG. 1, solder sections 4A be entirely located in first electrode 2a and second electrode 3a it Between opposed region.In the connection structural bodies 1X of variation shown in Fig. 3, only connecting portion 4X and connection structural bodies 1 shown in FIG. 1 It is different.Connecting portion 4X has solder sections 4XA and solidfied material portion 4XB.Can be as connection structural bodies 1X, a large amount of solder sections 4XA Positioned at the opposed region of first electrode 2a and second electrode 3a, a part of solder sections 4XA is electric from first electrode 2a and second Expose to side in region opposed pole 3a.The solder sections that the region opposed from first electrode 2a and second electrode 3a is exposed to side 4XA is a part of solder sections 4XA, is not the scolding tin for being detached from solder sections 4XA.In addition, in present embodiment, it is possible to reduce be detached from The amount of the scolding tin of solder sections, but the scolding tin for being detached from solder sections can reside in solidfied material portion.
If reducing the usage amount of scolding tin particle, it is easy to get connection structural bodies 1.If increase the use of scolding tin particle Amount, then be easy to get connection structural bodies 1X.
Then, using the conductive paste of an embodiment of the invention, illustrate to manufacture the one of the method for connection structural bodies 1 A example.
First, prepare the first connecting object component 2 on surface (upper surface) with first electrode 2a.Then, such as Fig. 2 (a) shown in, on the surface of the first connecting object component 2 configuration containing Thermocurable ingredient 11B, multiple scolding tin particle 11A and The conductive paste 11 (the first step) of fluxing agent.It is configured on the surface equipped with first electrode 2a of the first connecting object component 2 Conductive paste 11.After conductive paste 11 is configured, scolding tin particle 11A is configured on first electrode 2a (line) and is not formed first electrode The two regions on the region (interval) of 2a.
It as the configuration method of conductive paste 11, is not particularly limited, the coating using dispenser, screen printing can be enumerated Brush and the spraying that passes through ink discharge device etc..
In addition, prepare the second connecting object component 3 on surface (lower surface) with second electrode 3a.Then, such as Fig. 2 (b) shown in, in the conductive paste 11 on the surface of the first connecting object component 2, in conductive paste 11 and the first connecting object The second connecting object component 3 (the second step) is configured on the surface of 2 side opposite side of component.On the surface of conductive paste 11, The second connecting object component 3 is initially configured from second electrode 3a sides.At this point, make first electrode 2a and second electrode 3a opposed.
Then, conductive paste 11 is heated to more than the fusing point of scolding tin particle 11A and the curing temperature of Thermocurable ingredient 11B More than degree (the third step).That is, conductive paste 11 is heated to fusing point than scolding tin particle 11A and Thermocurable ingredient 11B It is more than the lower temperature in solidification temperature.In the heating, it is present in the scolding tin particle 11A in the region for not forming electrode Gather between one electrode 2a and second electrode 3a (self-coagulation effect).In present embodiment, using conductive paste without the use of leading Electrolemma, therefore, scolding tin particle 11A effectively gather between first electrode 2a and second electrode 3a.In addition, scolding tin particle 11A It melts and is welded to each other.In addition, Thermocurable ingredient 11B carries out heat cure.Electroconductive paste should be utilized as a result, as shown in Fig. 2 (c) Agent 11 forms the connecting portion 4 that the first connecting object component 2 and the second connecting object component 3 link together.Utilize electroconductive paste Agent 11 forms connecting portion 4, is welded to form solder sections 4A by multiple scolding tin particle 11A, passes through Thermocurable ingredient 11B It carries out heat cure and forms solidfied material portion 4B.Since scolding tin particle 11A is rapidly moved, never positioned at first electrode The mobile beginning of scolding tin particle 11A between 2a and second electrode 3a is moved to first electrode 2a and second to scolding tin particle 11A Terminate between electrode 3a, constant temperature can not be kept.
For present embodiment, in above-mentioned the second step and above-mentioned the third step, without pressurization.Present embodiment In, to the weight of the second connecting object component 3 of application of conductive paste 11.Therefore, when forming connecting portion 4, scolding tin particle 11A exists Effectively gather between first electrode 2a and second electrode 3a.In addition, if in above-mentioned the second step and above-mentioned the third step At least one process in pressurize, then effect between first electrode and second electrode is collected in scolding tin particle and is carried out The tendency of obstruction increases.The situation is found by the inventors of the present invention.
As described above, it can obtain connection structural bodies 1 shown in FIG. 1.In addition, above-mentioned the second step and above-mentioned the third step can To be carried out continuously.Furthermore it is possible to after above-mentioned the second step is carried out, so as to get the first connecting object component 2, conductive paste 11 Heating part is transferred to the laminated body of the second connecting object component 3, carries out above-mentioned the third step.It, can in order to carry out above-mentioned heating Above-mentioned laminated body to be configured on heating element, above-mentioned laminated body can also be configured in the space heated.
As long as more than the fusing point of the heating temperature scolding tin particle in above-mentioned the third step and the curing of Thermocurable ingredient It more than temperature, is just not particularly limited.Above-mentioned heating temperature is preferably 130 DEG C or more, more preferably 160 DEG C or more, preferably 450 DEG C hereinafter, more preferably 250 DEG C hereinafter, further preferably less than 200 DEG C.
In addition, as long as above-mentioned first connecting object component has at least one first electrode.Above-mentioned first connection pair As component preferably has multiple first electrodes.As long as above-mentioned second connecting object component has at least one second electrode. Above-mentioned second connecting object component preferably has multiple second electrodes.
Above-mentioned first connecting object component and the second connecting object component are not particularly limited.As the above-mentioned first connection pair As component and the second connecting object component, specifically, can enumerate：The electronic units such as semiconductor chip, capacitor and diode, And resin film, printed base plate, flexible printing substrate, flexble flat's cable, rigid-flexible combination substrate, glass epoxy substrate and glass Electronic units such as the circuit boards such as substrate etc..Above-mentioned first to connect object Part and the second connecting object component be preferably the ministry of electronics industry Part.
At least one of above-mentioned first connecting object component and above-mentioned second connecting object component connecting object component are excellent It is selected as resin film, flexible printing substrate, flexble flat's cable or rigid-flexible combination substrate.Above-mentioned second connecting object component is preferably Resin film, flexible printing substrate, flexble flat's cable or rigid-flexible combination substrate.Resin film, flexible printing substrate, flexble flat's line Cable and rigid-flexible combination substrate have flexibility height, than the property of relatively lightweight.Conductive film is being used for connecting object as described above In the case of the connection of component, there is scolding tin particle to be difficult to be collected in the tendency on electrode.In contrast, due to the use of this hair Therefore bright conductive paste, even if using resin film, flexible printing substrate, flexble flat's cable or rigid-flexible combination substrate, also may be used Scolding tin particle is effectively collected on electrode, and it can fully improve interelectrode conducting reliability.Use resin film, In the case of flexible printing substrate, flexble flat's cable or rigid-flexible combination substrate, with having used his connection such as semiconductor chip The situation of object Part is compared, and can more effectively obtain carrying due to the interelectrode conducting reliability that is generated without pressurization High effect.
As the electrode for being set to above-mentioned connecting object component, can enumerate：Gold electrode, nickel electrode, tin electrode, aluminium electrode, The metal electrodes such as copper electrode, silver electrode, molybdenum electrode, SUS electrodes and tungsten electrode.It is flexible printing base in above-mentioned connecting object component In the case of plate or flexble flat's cable, above-mentioned electrode is preferably gold electrode, nickel electrode, tin electrode, silver electrode or copper electrode. In the case that above-mentioned connecting object component is glass substrate, above-mentioned electrode is preferably aluminium electrode, copper electrode, molybdenum electrode, silver electrode Or tungsten electrode.Can be the electrode only formed by aluminium, or in gold in addition, in the case where above-mentioned electrode is aluminium electrode The electrode for belonging to the surface superimposed layer aluminium layer of oxide skin(coating) and being formed.As the material of above-mentioned metal oxide layer, doping can be enumerated There are the indium oxide of trivalent metallic element and the zinc oxide doped with trivalent metallic element etc..As the metallic element of above-mentioned trivalent, can arrange Lift Sn, Al and Ga etc..
The distance D1 of above-mentioned first electrode and the above-mentioned connecting portion on the opposed position of above-mentioned second electrode be preferably 5 μm with On, more preferably 20 μm or more, preferably 50 μm are hereinafter, more preferably less than 75 μm.Above-mentioned distance D1 is more than above-mentioned lower limit When, the further connection reliability for improving connecting portion and connecting object component.When above-mentioned distance D1 is below the above-mentioned upper limit, During the formation of connecting portion, scolding tin particle is easier to be collected on electrode, further improves interelectrode conducting reliability.
In order to which scolding tin particle is further efficiently configured on electrode, the viscosities il 1 at 25 DEG C of above-mentioned conductive paste Preferably more than 10Pas, more preferably more than 50Pas, further preferably more than 100Pas, preferably 800Pas Hereinafter, more preferably 600Pas is hereinafter, further preferably below 500Pas.
Above-mentioned viscosity can suitably be adjusted according to the type and use level of gradation composition.In addition, by the use of filler, it can So that viscosity is higher.But filler hinders the movement of scolding tin particle sometimes, it is therefore preferable that the content of filler is few.
In order to which scolding tin particle is further efficiently configured on electrode, above-mentioned conductive paste is under the fusing point of fluxing agent Viscosities il 2 be more than 0.1Pas and below 3Pas.From the sight being further efficiently configured to scolding tin particle on electrode Point sets out, and above-mentioned viscosities il 2 is preferably more than 0.15Pas, more preferably more than 0.2Pas, and preferably 2Pas is hereinafter, more Preferably below 1Pas.
In order to which scolding tin particle is further efficiently configured on electrode, above-mentioned conductive paste is in the fusing point of scolding tin particle Under viscosities il 3 be more than 0.1Pas and below 4.8Pas.It is further efficiently configured on electrode from by scolding tin particle From the perspective of, above-mentioned viscosities il 3 be preferably more than 0.15Pas, more preferably more than 0.2Pas, preferably 3Pas with Under, more preferably below 1Pas.
From the viewpoint of scolding tin particle further is efficiently configured on electrode, above-mentioned viscosities il 1 and above-mentioned viscosity The ratio (1/ η 2 of η) of η 2 is preferably more than 15, and more preferably more than 50, preferably 3000 are hereinafter, more preferably less than 2500.
From the viewpoint of scolding tin particle further is efficiently configured on electrode, above-mentioned viscosities il 1 and above-mentioned viscosity The ratio (1/ η 3 of η) of η 3 is preferably more than 10, and more preferably more than 40, preferably 2500 are hereinafter, more preferably less than 2000.
From the viewpoint of scolding tin particle further is efficiently configured on electrode, above-mentioned viscosities il 2 and above-mentioned viscosity The ratio (2/ η 3 of η) of η 3 is preferably more than 0.1, and more preferably more than 0.3, preferably 10 are hereinafter, more preferably less than 1.
Above-mentioned viscosity can be used such as E types viscosimeter (Toki Sangyo Co., Ltd.'s manufacture), at 25 DEG C and 5rpm Under the conditions of be measured.
Above-mentioned conductive paste contains Thermocurable ingredient, fluxing agent and multiple scolding tin particles.Above-mentioned Thermocurable ingredient is excellent Choosing contains the curability compound (Thermocurable compound) and thermal curing agents that can be cured by heating.
Hereinafter, illustrate other details of the present invention.
(scolding tin particle)
Above-mentioned scolding tin particle has scolding tin on the outer surface of electric conductivity.The central part and electric conductivity of above-mentioned scolding tin particle Outer surface formed by scolding tin.From the viewpoint of further being efficiently configured on electrode by scolding tin, preferably to above-mentioned Scolding tin particle, which carries out surface treatment, to be made it there are carboxyls in outer surface.Above-mentioned scolding tin particle is preferably being surface-treated and is making it After outer surface is there are carboxyl, it is matched in conductive paste.
Above-mentioned scolding tin is preferably the metal (low-melting-point metal) that fusing point is less than 450 DEG C.Above-mentioned scolding tin particle is preferably molten Point is less than 450 DEG C of metallic (low-melting-point metal particle).Above-mentioned low-melting-point metal particle is contains low-melting-point metal Particle.The low-melting-point metal represents the metal that fusing point is less than 450 DEG C.The fusing point of low-melting-point metal is preferably 300 DEG C hereinafter, more Preferably less than 160 DEG C.In addition, above-mentioned scolding tin particle contains tin.In above-mentioned scolding tin particle in contained 100 weight % of metal, The content of tin is preferably more than 30 weight % more preferably more than 40 weight %, further preferably more than 70 weight %, especially Preferably more than 90 weight %.When the content of tin in above-mentioned scolding tin particle is more than above-mentioned lower limit, the company of solder sections and electrode Reliability is connect further to improve.
In addition, the content of above-mentioned tin can utilize (the strain formula meeting of high-frequency inductive coupling plasma body emission spectrophotometer Manufactured by the making of society's hole field " ICP-AES ") or fluorescent x-ray analyzer (Shimadzu Scisakusho Ltd manufacture " EDX- 800HS ") etc. be measured.
By using above-mentioned scolding tin particle, scolding tin melting and and electrode welding, so as to which solder sections make to be connected between electrode.Example Such as, solder sections and electrode easily carry out face contact rather than point contact, and therefore, connection resistance reduces.In addition, pass through scolding tin grain The use of son, the weld strength between solder sections and electrode increase, as a result, are further not likely to produce the stripping of solder sections and electrode From so as to effectively improve conducting reliability and connection reliability.
The low-melting-point metal for forming above-mentioned scolding tin particle is not particularly limited.The low-melting-point metal is preferably tin or contains The alloy of tin.The alloy can be enumerated：Tin-silver alloy, tin-copper alloy, tin-silver-copper alloy, tin-bismuth alloy electroplating, tin-zinc alloy, Sn-In alloy etc..Wherein, since the wetability to electrode is excellent, above-mentioned low-melting-point metal is more preferably tin, Xi-silver and closes Gold, tin-silver-copper alloy, tin-bismuth alloy electroplating, Sn-In alloy are preferably.Tin-bismuth alloy electroplating, Sn-In alloy.
Above-mentioned scolding tin particle is preferably based on JIS Z3001：Term is welded, liquidus curve is less than 450 DEG C of filling metal. As the composition of above-mentioned scolding tin particle, it can be mentioned, for example the metal compositions containing zinc, gold, silver, lead, copper, tin, bismuth, indium etc..Its In, preferably low melting point and lead-free tin-indium system (117 DEG C of eutectics) or Sn-Bi system (139 DEG C of eutectics).That is, it is preferred that above-mentioned weldering Tin particle does not contain lead, preferably comprises tin and indium or containing tin and bismuth.
In order to further improve the weld strength of above-mentioned solder sections and electrode, above-mentioned scolding tin particle can include nickel, copper, The metals such as antimony, aluminium, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, bismuth, manganese, chromium, molybdenum, palladium.In addition, improve solder sections from further From the perspective of the bond strength of electrode, above-mentioned scolding tin particle preferably comprises nickel, copper, antimony, aluminium or zinc.It is improved from further From the perspective of solder sections and the weld strength of electrode, in 100 weight % of scolding tin particle, for improve bond strength these The content of metal is preferably more than 0.0001 weight % preferably below 1 weight %.
The average grain diameter of above-mentioned scolding tin particle is preferably 0.5 μm or more, more preferably 1 μm or more, further preferably 3 μm More than, particularly preferably 5 μm or more, preferably 100 μm hereinafter, more preferably 40 μm hereinafter, still more preferably for 30 μm with Under, further preferably 20 μm hereinafter, particularly preferably 15 μm hereinafter, most preferably less than 10 μm.Above-mentioned scolding tin particle is put down When equal grain size is more than above-mentioned lower limit and below the above-mentioned upper limit, scolding tin particle can be further efficiently configured to electrode On.The average grain diameter of above-mentioned scolding tin particle is particularly preferably 3 μm or more and less than 30 μm.
" average grain diameter " of above-mentioned scolding tin particle represents number average bead diameter.The average grain diameter of scolding tin particle is for example by using electronics Microscope or the arbitrary 50 scolding tin particles of optical microphotograph sem observation simultaneously calculate average value and acquire.
In above-mentioned 100 weight % of conductive paste, the content of above-mentioned scolding tin particle is preferably more than 1 weight % more preferably 2 More than weight %, further preferably more than 10 weight %, particularly preferably more than 20 weight %, most preferably 30 weight % with On, preferably 80 weight % hereinafter, more preferably 60 weight % hereinafter, further preferably below 50 weight %.Above-mentioned scolding tin When the content of particle is more than above-mentioned lower limit and below the above-mentioned upper limit, scolding tin particle can be further efficiently configured to electricity On extremely, between scolding tin particle largely easily is configured at electrode, conducting reliability further improves.Conducting is improved from further From the perspective of reliability, the content of preferably above-mentioned scolding tin particle is more.
(by heating curable compound：Thermocurable ingredient)
As above-mentioned Thermocurable compound, can enumerate：Oxetane compound, epoxide, episulfide Close object, (methyl) acyclic compound, oxybenzene compound, amino-compound, unsaturated polyester compound, urethanes, Polysiloxane compound and polyimide compound etc..Wherein, it is further good from the curability and viscosity for making conductive paste It gets well, from the perspective of further raising connection reliability, preferably epoxide.
In conductive paste, above-mentioned Thermocurable compound is preferably disperseed with particle shape.
In above-mentioned 100 weight % of conductive paste, the content of above-mentioned Thermocurable compound is preferably more than 20 weight %, more Preferably more than 40 weight %, further preferably more than 50 weight %, preferably 99 weight % are hereinafter, more preferably 98 weights % is measured hereinafter, further preferably 90 weight % are hereinafter, particularly preferably below 80 weight %.Impact resistance is improved from further From the perspective of property, the content of preferably above-mentioned Thermocurable ingredient is more.
(thermal curing agents：Thermocurable ingredient)
Above-mentioned thermal curing agents make above-mentioned Thermocurable compound heat cure.As above-mentioned thermal curing agents, can enumerate：Imidazoles is consolidated Agent, amine hardener, phenol cured agent, Polymercaptan curing agent, acid anhydrides, hot cationic initiator and hot radical producing agent etc.. Above-mentioned thermal curing agents can be used alone, and can also be applied in combination two or more.
Wherein, conductive paste can be made further rapidly to cure at low temperature, it is therefore preferable that imidazole curing agent, poly- Polythiol hardener or amine hardener.In addition, to being mixed by heating curable curability compound and above-mentioned thermal curing agents During conjunction, storage stability improves, it is therefore preferable that the curing agent of latency.The curing agent of latency is preferably that latency imidazoles is consolidated Agent, latency Polymercaptan curing agent or latency amine hardener.In addition, above-mentioned thermal curing agents can utilize polyurethane resin or The polymer substances such as polyester resin are coated.
It as above-mentioned imidazole curing agent, is not particularly limited, can enumerate：2-methylimidazole, 2-ethyl-4-methylimidazole, 1- cyano ethyl -2- phenylimidazoles, 1- cyano ethyl -2- phenylimidazole trimellitic acids salt, 2,4- diamino -6- [2 '-methyl Imidazole radicals-(1 ')]-ethyl-s-triazine and 2,4- diamino -6- [2 '-methylimidazolyl-(1 ')]-ethyl-s-triazine isocyanide urea Sour addition product etc..
It as above-mentioned polythiol curing agent, is not particularly limited, can enumerate：Trimethylolpropane tris -3-thiopropionate, Pentaerythrite four (3- mercaptobutylates), six -3-thiopropionate of four -3-thiopropionate of pentaerythrite and dipentaerythritol Deng.
The solubility parameter of above-mentioned Polymercaptan curing agent is preferably more than 9.5, and preferably less than 12.Above-mentioned solubility parameter It is calculated by Fedors methods.For example, the solubility parameter of trimethylolpropane tris -3-thiopropionate is 9.6, dipentaerythritol The solubility parameter of six -3-thiopropionate is 11.4.
It as above-mentioned amine hardener, is not particularly limited, can enumerate：Hexamethylene diamine, eight methylene diamines, ten methylenes Bis- four spiral shell [5.5] hendecanes of (3- aminopropyls) -2,4,8,10- of base diamines, 3,9-, bis- (4- aminocyclohexyls) methane, Phenylenediamine and diamino diphenyl sulfone etc..
As above-mentioned hot cation curing agent, can enumerate iodine cationoid curing agent, oxygen cationoid curing agent and Sulfonium cationoid curing agent etc..As above-mentioned iodine cationoid curing agent, bis- (4- tert-butyl-phenyls) iodine hexafluoros can be enumerated Phosphate etc..As above-mentioned oxygen cationoid curing agent, trimethyl oxygen tetrafluoroborate etc. can be enumerated.As above-mentioned sulfonium class Cation curing agent can enumerate three-p-methylphenyl sulfonium hexafluorophosphate etc..
It as above-mentioned hot radical producing agent, is not particularly limited, azo-compound and organic peroxide etc. can be enumerated. As above-mentioned azo-compound, azobis isobutyronitrile (AIBN) etc. can be enumerated.As above-mentioned organic peroxide, it can enumerate two- Tert-butyl peroxide and methyl-ethyl-ketone peroxide etc..
The reaction start temperature of above-mentioned thermal curing agents is preferably 50 DEG C or more, more preferably 70 DEG C or more, further preferably Be 80 DEG C or more, preferably 250 DEG C hereinafter, more preferably 200 DEG C hereinafter, further preferably 150 DEG C hereinafter, particularly preferably Less than 140 DEG C.When the reaction start temperature of above-mentioned thermal curing agents is more than above-mentioned lower limit and below the above-mentioned upper limit, and by scolding tin grain Son is further efficiently configured on electrode.The reaction start temperature of above-mentioned thermal curing agents is 80 DEG C or more, particularly preferably Less than 140 DEG C.
From the viewpoint of further being efficiently configured on electrode by scolding tin, the reaction of above-mentioned thermal curing agents starts temperature The fusing point spent preferably than the scolding tin in above-mentioned scolding tin particle is low, more preferably low 5 DEG C or more, further preferably low 10 DEG C or more.
The reaction start temperature of above-mentioned thermal curing agents refers to the temperature that the exothermal peak in DSC is begun to ramp up.
The content of above-mentioned thermal curing agents is not particularly limited.It is above-mentioned relative to above-mentioned 100 parts by weight of Thermocurable compound The content of thermal curing agents is preferably more than 0.01 parts by weight, and more than more preferably 1 parts by weight, preferably 200 parts by weight are hereinafter, more Preferably 100 parts by weight are hereinafter, below further preferably 75 parts by weight.When the content of thermal curing agents is more than above-mentioned lower limit, Easily cure sufficiently conductive paste.When the content of thermal curing agents is below the above-mentioned upper limit, it is not used for after hardening cured Remaining thermal curing agents are not easy to remain, and further improve the heat resistance of solidfied material.
(fluxing agent)
Above-mentioned conductive paste contains fluxing agent.By the use of fluxing agent, scolding tin further can be effectively configured In on electrode.The fluxing agent is not particularly limited.As fluxing agent, the fluxing agent commonly used in scolding tin welding etc. can be used. As above-mentioned fluxing agent, it can be mentioned, for example：Zinc chloride, the mixture of zinc chloride and inorganic halides, zinc chloride and inorganic acid Mixture, fuse salt, phosphoric acid, the derivative of phosphoric acid, organohalogen compounds, hydrazine, organic acid and rosin etc..Above-mentioned fluxing agent can be single Solely using one kind, can also be applied in combination two or more
As above-mentioned fuse salt, ammonium chloride etc. can be enumerated.As above-mentioned organic acid, lactic acid, citric acid, tristearin can be enumerated Acid, glutamic acid and glutaric acid etc..As above-mentioned rosin, activation rosin and deactivation rosin etc. can be enumerated.Above-mentioned fluxing agent Preferably there is organic acid, the rosin of more than two carboxyls.Above-mentioned fluxing agent can be with the organic of more than two carboxyls Acid, or rosin.By the use of the organic acid with more than two carboxyls, rosin, between further raising electrode Conducting reliability.
Above-mentioned rosin is the rosin using rosin acid as principal component.Fluxing agent is preferably rosin, more preferably rosin acid. By the use of the preferred fluxing agent, interelectrode conducting reliability is further improved.
The active temperature (fusing point) of above-mentioned fluxing agent is preferably 50 DEG C or more, more preferably 70 DEG C or more, further preferably It is 80 DEG C or more, particularly preferably 100 DEG C or more, preferably 200 DEG C hereinafter, more preferably 190 DEG C hereinafter, still more preferably For 160 DEG C hereinafter, further preferably 150 DEG C hereinafter, be still more preferably less than 140 DEG C.The activity temperature of above-mentioned fluxing agent When spending for more than above-mentioned lower limit and below the above-mentioned upper limit, fluxing agent effect is further effectively played, and by scolding tin particle more Effectively further it is configured on electrode.As a result, interelectrode connection resistance is lower, connection reliability also improves.It is above-mentioned fluxing The active temperature (fusing point) of agent is 80 DEG C or more, and preferably 190 DEG C hereinafter, more preferably 100 DEG C or more, less than 190 DEG C.It is above-mentioned The active temperature of fluxing agent is particularly preferably 80 DEG C or more, 140 DEG C hereinafter, more preferably 100 DEG C or more, less than 140 DEG C.
It is 80 DEG C or more as fusing point, less than 190 DEG C of above-mentioned fluxing agent, can enumerates：Succinic acid (186 DEG C of fusing point), penta The dicarboxylic acids such as diacid (96 DEG C of fusing point), adipic acid (152 DEG C of fusing point), pimelic acid (104 DEG C of fusing point), suberic acid (142 DEG C of fusing point), Benzoic acid (122 DEG C of fusing point), malic acid (130 DEG C of fusing point) etc..
In addition, the boiling point of above-mentioned fluxing agent is preferably less than 200 DEG C.
From the viewpoint of further being efficiently configured on electrode by scolding tin, the fusing point of preferably above-mentioned fluxing agent is than upper The fusing point for stating the scolding tin in scolding tin particle is high, more preferably high 5 DEG C or more, further preferably high 10 DEG C or more.
From the viewpoint of further being efficiently configured on electrode by scolding tin, the fusing point of preferably above-mentioned fluxing agent is than upper The reaction start temperature for stating thermal curing agents is high, more preferably high 5 DEG C or more, further preferably high 10 DEG C or more.
Above-mentioned fluxing agent can be scattered in conductive paste, can also be attached on the surface of scolding tin particle.
It is higher than the fusing point of scolding tin by the fusing point of fluxing agent, scolding tin particle can be made effectively to be aggregated in electrode section.This Be because：In the case of assigning heat in welding, by the electrode formed on connecting object component and the connection pair of electrode perimeter When being compared as the part of component, the thermal conductivity of the connecting object component part of the thermal conductivity ratio electrode perimeter of electrode section The quick heating of height, as a result, electrode section.In the stage of the fusing point more than scolding tin particle, the inside dissolving of scolding tin particle, but shape Do not reach the fusing point (active temperature) of fluxing agent into the oxide film thereon in surface, therefore, be not removed.In this state, The temperature of electrode section first reaches the fusing point (active temperature) of fluxing agent, therefore, the surface of the scolding tin particle on arrival electrode Oxide film thereon is preferentially removed, and scolding tin particle can be soaked on the surface of electrode and spreading.Thus, it is possible to have scolding tin particle The aggegation of effect ground is on electrode.
Above-mentioned fluxing agent releases the fluxing agent of cation preferably by heating.By releasing cation according to heating Fluxing agent use, scolding tin particle can be further efficiently configured on electrode.
As the fluxing agent that cation is released above by heating, above-mentioned hot cation curing agent can be enumerated.
In above-mentioned 100 weight % of conductive paste, the content of above-mentioned fluxing agent is preferably more than 0.5 weight % preferably 30 Weight % is hereinafter, more preferably below 25 weight %.Above-mentioned conductive paste can not contain fluxing agent.The content of fluxing agent is upper When stating more than lower limit and below the above-mentioned upper limit, further it is not easy to form oxide film thereon, also, can on the surface of scolding tin and electrode Further to remove effectively the oxide film thereon on the surface for being formed in scolding tin and electrode.
(filler)
Filler can be added in above-mentioned conductive paste.Filler can be organic filler, or inorganic filler.But It is that filler hinders the movement of scolding tin particle sometimes, it is therefore preferable that the content of filler is less.
It is preferred that above-mentioned conductive paste does not contain filler or contains in above-mentioned 100 weight % of conductive paste less than 5 weight % Filler.In above-mentioned 100 weight % of conductive paste, the content of above-mentioned filler is preferably more than 0 weight % (not containing), preferably 5 weight % hereinafter, more preferably 2 weight % hereinafter, further preferably 1 weight % hereinafter, still more preferably be less than 0.25 Weight %, particularly preferably below 0.1 weight %.The content of above-mentioned filler is more than above-mentioned lower limit and below the above-mentioned upper limit or low When the above-mentioned upper limit, scolding tin particle is further efficiently configured on electrode.Particularly preferred above-mentioned conductive paste does not contain Filler contains the filler for being less than 0.25 weight % in above-mentioned 100 weight % of conductive paste, and most preferably above-mentioned conductive paste is not Contain filler.If the content of filler is less than 0.25 weight %, the mobile obstruction of scolding tin particle caused by filler is fully small, If filler content be 0.1 weight % hereinafter, if scolding tin particle caused by filler mobile obstruction very little.
(other ingredients)
Above-mentioned conductive paste can contain such as filler, incremental agent, softening agent, plasticizer, polymerization catalyzed as needed Agent, curing catalysts, colorant, antioxidant, heat stabilizer, light stabilizer, ultra-violet absorber, lubricant, antistatic agent And the various additives such as fire retardant.
Hereinafter, enumerating embodiment and comparative example, the present invention is specifically described.The present invention is not limited to following reality Apply example.
Polymer A：
The synthesis of the reactant (polymer A) of Bisphenol F and 1,6-HD glycidol ether and bisphenol f type epoxy resin：
By Bisphenol F (with weight ratio meter 2:3:1 contains 4,4 '-methylene bis-phenol, 2,4 '-methylene bis-phenol and 2,2 '-methylene Base bis-phenol) (Dainippon Ink Chemicals manufactures for 72 parts by weight, 70 parts by weight of 1,6-HD glycidol ether and bisphenol f type epoxy resin " EPICLON EXA-830CRP ") 30 parts by weight be added to three-necked flask in, dissolved under nitrogen flowing, at 150 DEG C.Its Afterwards, four-normal-butyl bromination sulfonium 0.1 parts by weight of the addition as hydroxyl and the addition reaction catalyst of epoxy group, under nitrogen flowing, Polyaddition reaction is carried out with 150 DEG C 6 hours, thus obtains reactant (polymer A).
By NMR, confirmation has carried out polyaddition reaction, further acknowledges that reactant (polymer A) has to come on main chain The structure list formed from hydroxyl and the epoxy group of 1,6-HD glycidol ether and the bisphenol f type epoxy resin bonding of Bisphenol F Member, and there is epoxy group in two ends.
It is 10000 using the weight average molecular weight of reactant (polymer A) that GPC is obtained, number-average molecular weight 3500.
[chemical formula 1]
Polymer B：Two terminal epoxy groups rigid backbone phenoxy resins, Mitsubishi chemical Co., Ltd manufacture " YX6900BH45 ", weight average molecular weight 16000
Thermocurable compound 1：Resorcinol type ring the oxygen compound, " EX- of Nagase Chemtex Co., Ltd. manufacture 201 ", it cleans and uses after being crystallized at low temperature
Thermocurable compound 2：Bisphenol f type epoxy resin, Dainippon Ink Chemicals manufacture " EPICLONEXA-830CRP ", It cleans and uses after being crystallized at low temperature
Thermal curing agents 1：Pentaerythrite four (3- mercaptobutylates), " CURRANTS of Showa Denko K. K's manufacture MTPE1”
Latency epoxy thermosetting agent 1：" Fujicure 7000 " of T＆K TOKA Co., Ltd. manufacture
Fluxing agent 1：Adipic acid, Wako Pure Chemical Industries, Ltd.'s manufacture, 152 DEG C of fusing point (active temperature)
Fluxing agent 2：Succinic acid, Wako Pure Chemical Industries, Ltd.'s manufacture, 186 DEG C of fusing point (active temperature)
Fluxing agent 3：Rosin acid, Wako Pure Chemical Industries, Ltd.'s manufacture, 174 DEG C of fusing point (active temperature)
Scolding tin particle 1 (" DS10 " that SnBi scolding tin particle, 139 DEG C of fusing point, Co., Ltd. of Mitsui Metal Co., Ltd. manufacture) carries out 13 μm of the particle of following surface treatment, average grain diameter
The surface treatment of scolding tin particle：
Scolding tin particle 200g, adipic acid 40g and acetone 70g are weighed in three-necked flask, adds 0.3g Dibutyltin oxides The dehydrating condensation catalyst of the hydroxyl on the surface as scolding tin particle and the carboxyl of adipic acid reacts 4 hours at 60 DEG C.Its Afterwards, it is recycled by filtering scolding tin particle.
Weigh the scolding tin particle of recycling, adipic acid 50g, toluene 200g and p-methyl benzenesulfonic acid 0.3g in three-necked flask, one While being vacuumized and being flowed back, reacted 3 hours at 120 DEG C on one side.At this point, it is removed on one side using Dean-Stark extraction elements The water generated by dehydrating condensation, is reacted on one side.
Thereafter, scolding tin particle is recovered by filtration, is cleaned, dried with hexane.Thereafter, the scolding tin particle ball milling that will be obtained After machine crushes, sieve is selected to become the CV values specified.Obtained scolding tin particle is surface-treated, it is made to be deposited in outer surface In carboxyl.
Scolding tin particle 2 (SnBi scolding tin particle, 139 DEG C of fusing point, Co., Ltd. of Mitsui Metal Co., Ltd. manufacture " DS30 ") be and weldering Tin particle 1 has been carried out similarly the particle of surface treatment, 32 μm of average grain diameter
Electroconductive particle 1：The layers of copper of 1 μm of thickness is formed on the surface of resin particle, thickness is formed on the surface of the layers of copper Soldering-tin layer (the tin of 3 μm of degree:The weight % of bismuth=43:57 weight %) electroconductive particle
Phenoxy resin (" YP-50S " of Nippon Steel ＆ Sumitomo Metal Corporation's manufacture)
(Examples 1 to 4,6~9)
(1) making of anisotropic conductive paste
The ingredient shown in following tables 1 is coordinated with the use level shown in following tables 1, obtains anisotropic conductive Paste.In addition, obtained anisotropy, in conductive paste, Thermocurable compound is disperseed with particle shape.
The making of (2) first connection structural bodies (L/S=50 μm/50 μm)
Preparing upper surface has the glass ring oxygroup of copper electrode pattern (10 μm of copper electrode thickness) that L/S is 50 μm/50 μm Plate (FR-4 substrates) (the first connecting object component).In addition, prepare the copper electrode pattern that there is L/S to be 50 μm/50 μm for lower surface The flexible printing substrate (the second connecting object component) of (10 μm of copper electrode thickness).
The overlapping area of glass epoxy substrate and flexible substrate is set as 1.5cm × 4mm, and the number of electrodes of connection is set as 75 pairs.
Be coated on the upper surface of above-mentioned glass epoxy substrate the anisotropic conductive paste just prepared formed it is each to different Property electroconductive paste oxidant layer, and make its thickness become 50 μm.Then, it scratches the upper surface superimposed layer of anisotropic conductive paste layer is above-mentioned Property printed base plate simultaneously makes electrode opposite each other.At this point, without pressurization.Apply above-mentioned flexible print to anisotropic conductive paste layer The weight of brush substrate.Thereafter, carrying out heating on one side makes the temperature of anisotropic conductive paste layer become 190 DEG C, makes scolding tin on one side Melting, and anisotropic conductive paste layer is made to cure at 190 DEG C, obtain the first connection structural bodies.
The making of (3) second connection structural bodies (L/S=75 μm/75 μm)
Preparing upper surface has the glass ring oxygroup of copper electrode pattern (10 μm of copper electrode thickness) that L/S is 75 μm/75 μm Plate (FR-4 substrates) (the first connecting object component).In addition, prepare the copper electrode pattern that there is L/S to be 75 μm/75 μm for lower surface The flexible printing substrate (the second connecting object component) of (10 μm of copper electrode thickness).
In addition to the above-mentioned glass epoxy substrate and flexible printing substrate that use L/S different, with the first connection structural bodies Making similarly operates, and obtains the second connection structural bodies.
(4) making of the connection structural bodies (L/S=100 μm/100 μm) of third
Preparing upper surface has the glass epoxide of copper electrode pattern (10 μm of copper electrode thickness) that L/S is 100 μm/100 μm Substrate (FR-4 substrates) (the first connecting object component).In addition, prepare the copper electrode that there is L/S to be 100 μm/100 μm for lower surface The flexible printing substrate (the second connecting object component) of pattern (10 μm of copper electrode thickness).
In addition to the above-mentioned glass epoxy substrate and flexible printing substrate that use L/S different, with the first connection structural bodies Making similarly operates, and obtains the connection structural bodies of third.
(embodiment 5)
It is 100 μm/100 μm (the connection structural bodies use of third), 75 to prepare as electrode size (L)/electricity pole spacing (S) μm/75 μm (second connection structural bodies use), the semiconductor chip (thickness of the 5mm square of 50 μm/50 μm (the first connection structural bodies use) Degree 400 μm) and with the electrode opposed with its glass epoxy substrate (30 × 30mm of size, thickness 0.4mm).It is partly led except using It other than body chip and glass epoxy substrate, operates similarly to Example 1, obtains the first connection structural bodies, the second connection structure Body and third connection structural bodies.
(Comparative Examples 1 and 2,5)
(1) making of anisotropic conductive paste
Coordinate the ingredient shown in following tables 2 with the use level shown in following tables 2, obtain anisotropic conductive paste. It in addition to the anisotropic conductive paste used, operates similarly to Example 1, obtains the first connection structural bodies, second Connection structural bodies and third connection structural bodies.
(comparative example 3)
Phenoxy resin (" YP-50S " of Nippon Steel ＆ Sumitomo Metal Corporation's manufacture) 10 parts by weight is made to be dissolved in methyl second Base ketone (MEK), and solid constituent is made to obtain lysate for 50 weight %.With the use level shown in following tables 2 and above-mentioned dissolving The total amount of liquid, the ingredient of the removing phenoxy resin shown in following table 2 are coordinated, using planetary stirring machine with 2000rpm is stirred after five minutes, is coated on demoulding PET (polyethylene terephthalate) film using bar coater, and make drying Thickness afterwards becomes 30 μm.By being dried in vacuo at room temperature, MEK is removed, thus obtains anisotropic conductive film.
It in addition to anisotropic conductive film is used, operates similarly to Example 1, obtains the first connection structural bodies, second Connection structural bodies and third connection structural bodies.
(comparative example 4)
It is 100 μm/100 μm (the connection structural bodies use of third), 75 to prepare as electrode size (L)/electricity pole spacing (S) μm/75 μm (second connection structural bodies use), the semiconductor chip (thickness of the 5mm square of 50 μm/50 μm (the first connection structural bodies use) Degree 400 μm) and with the electrode opposed with its glass epoxy substrate (30 × 30mm of size thickness 0.4mm).Except use this half It other than conductor chip and glass epoxy substrate, is operated in the same manner as comparative example 1, obtains the first connection structural bodies, the second connection knot Structure body and third connection structural bodies.
(evaluation)
(1) viscosity
Under conditions of 25 DEG C and 5rpm, anisotropy is led using E types viscosimeter (Toki Sangyo Co., Ltd.'s manufacture) Viscosities il 1 of the electric paste at 25 DEG C is measured.In addition, using E types viscosimeter (Toki Sangyo Co., Ltd.'s system), fluxing The viscosities il 2 under the fusing point of the fluxing agent of anisotropic conductive paste is measured under conditions of the fusing point and 5rpm of agent.Separately Outside, using E types viscosimeter (Toki Sangyo Co., Ltd.'s manufacture), to each to different under conditions of the fusing point and 5rpm of scolding tin particle Viscosities il 3 under the scolding tin particle fusing point of property conductive paste is measured.Ratio (1/ η 2 of η), ratio are acquired by obtained measured value (1/ η 3 of η) and ratio (2/ η 3 of η).
(2) distance (interelectrode interval) of connecting portion
By carrying out cross-section to the first obtained connection structural bodies, the connection of the position of upper and lower electrode contraposition is evaluated The distance D1 (interelectrode interval) in portion.
(3) the configuration precision of the scolding tin on electrode
In the section of the first obtained connection structural bodies (section in direction shown in FIG. 1), the gross area of scolding tin is evaluated In 100%, it is detached from the area (%) for being configured at interelectrode solder sections and remaining on the scolding tin in solidfied material.In addition, calculate 5 Area in section is averaged.The configuration precision of the scolding tin on electrode is judged by following benchmark.
[determinating reference of the configuration precision of the electroconductive particle on electrode]
○○：In the gross area 100% of the scolding tin occurred in section, disengaging is configured at interelectrode solder sections and remains on The area of scolding tin (scolding tin particle) in solidfied material is more than 0% and less than 1%
○：In the gross area 100% of the scolding tin occurred in section, disengaging is configured at interelectrode solder sections and remains on solid The area of scolding tin (scolding tin particle) in compound is more than 1% and less than 10%
△：In the gross area 100% of the scolding tin occurred in section, disengaging is configured at interelectrode solder sections and remains on solid The area of scolding tin (scolding tin particle) in compound is more than 10% and less than 30%
×：In the gross area 100% of the scolding tin occurred in section, disengaging is configured at interelectrode solder sections and remains on solid The area of scolding tin (scolding tin particle) in compound is more than 30%
(4) interelectrode conducting reliability up and down
In obtained the first connection structural bodies, the second connection structural bodies and third connection structural bodies (n=15), respectively Upper and lower interelectrode connection resistance is measured using 4 terminal methods.Calculate the average value of connection resistance.In addition, according to electricity The relationship of pressure=electric current × resistance, voltage during by being flowed through to constant current are measured, can be in the hope of connecting resistance.Pass through Following benchmark judgement conducting reliabilities.
[determinating reference of conducting reliability]
○○：The average value for connecting resistance is 8.0 below Ω
○：The average value for connecting resistance is more than 8.0 Ω and 10.0 below Ω
△：The average value for connecting resistance is more than 10.0 Ω and 15.0 below Ω
×：The average value for connecting resistance is more than 15.0 Ω
(5) adjacent interelectrode insulating reliability
In the connection structural bodies (n=15) of obtained the first connection structural bodies, the second connection structural bodies and third, After being placed 100 hours in the atmosphere of 85 DEG C of temperature and humidity 85%, apply 5V between adjacent electrode, resistance is measured at 25 Value.Judge insulating reliability by following benchmark.
[determinating reference of insulating reliability]
○○：The average value for connecting resistance is 107More than Ω
○：The average value for connecting resistance is 106Ω is less than 107Ω
△：The average value for connecting resistance is 105Ω is less than 106Ω
×：The average value for connecting resistance is less than 105Ω
Show the result in following tables 1,2.
According to the difference and embodiment 5 of embodiment 1 and the result of comparative example 1 with the difference of the result of comparative example 4： In the case that second connecting object component is flexible printing substrate, with the situation phase that the second connecting object component is semiconductor chip Than by the use of the conductive paste of the present invention, further effectively obtaining the improvement effect of conducting reliability.
Not only flexible printing substrate, in the case where using resin film, flexble flat's cable and rigid-flexible combination substrate, also really Accreditation obtains same result.
Also, it shows to have used in Fig. 4 (a), Fig. 4 (b) and Fig. 4 (c) and is not included in leading for embodiments of the present invention One example of the connection structural bodies of electric paste.Fig. 4 (a) and Fig. 4 (b) is cross-sectional image, and Fig. 4 (c) is flat image.It understands： In Fig. 4 (a), Fig. 4 (b) and Fig. 4 (c), there are multiple disengagings beside solder sections to be configured at interelectrode solder sections and residual Stay the scolding tin (scolding tin particle) in solidfied material.In contrast, in the present invention, it can realize that there is no be detached to be configured between electrode Solder sections and remain on the scolding tin in solidfied material (scolding tin particle).

Claims (13)

1. a kind of conductive paste, containing Thermocurable ingredient, fluxing agent and multiple scolding tin particles,
Viscosity of the conductive paste under the fusing point of the fluxing agent for more than 0.1Pas and 3Pas hereinafter,
Viscosity of the conductive paste under the fusing point of the scolding tin particle is more than 0.1Pas and below 4.8Pas.
2. conductive paste as described in claim 1, wherein,
Viscosity of the conductive paste under the fusing point of the scolding tin particle is more than 0.1Pas and below 3Pas.
3. conductive paste as claimed in claim 1 or 2, wherein,
The fusing point of the fluxing agent is 80 DEG C or more and less than 190 DEG C.
4. conductive paste as claimed in claim 3, wherein,
The fusing point of the fluxing agent is 100 DEG C or more and less than 190 DEG C.
5. conductive paste as claimed in claim 1 or 2, wherein,
In 100 weight % of conductive paste, the content of the fluxing agent is more than 0.1 weight % and below 5 weight %.
6. conductive paste as claimed in claim 1 or 2 contains low without filler or in 100 weight % of conductive paste In the filler of 0.25 weight %.
7. conductive paste as claimed in claim 1 or 2, wherein,
The scolding tin particle is surface-treated, and carboxyl is made to be present on the outer surface of the scolding tin particle.
8. conductive paste as claimed in claim 1 or 2, wherein,
The fusing point of the fluxing agent is higher than the fusing point of the scolding tin particle.
9. a kind of connection structural bodies, has：
First connecting object component of the surface at least one first electrode,
Second connecting object component of the surface at least one second electrode,
The connecting portion that the first connecting object component and the second connecting object component are linked together,
The connecting portion is formed by conductive paste according to any one of claims 1 to 8,
The first electrode and the second electrode realize electrical connection by the solder sections in the connecting portion.
10. connection structural bodies as claimed in claim 9, wherein,
The second connecting object component is resin film, flexible printing substrate, rigid-flexible combination substrate or flexible flat cable.
11. a kind of manufacturing method of connection structural bodies, including：
Using the conductive paste described in any one of claim 1~8, have the first of at least one first electrode to connect on surface Connect the process that the conductive paste is configured on the surface of object Part；
On the surface opposite with the first connecting object component side of the conductive paste, configuration surface has at least one Second connecting object component of second electrode, and make the first electrode and the opposed process of the second electrode；
By the conductive paste be heated to more than the fusing point of the scolding tin particle and the solidification temperature of the Thermocurable ingredient with On, it is formed by the conductive paste be connected to the first connecting object component and the second connecting object component as a result, Connecting portion together, and the first electrode and the second electrode are electrically connected by the solder sections in the connecting portion Process.
12. the manufacturing method of connection structural bodies as claimed in claim 11, wherein,
In the process of the second connecting object component of the configuration and the process of the formation connecting portion, the conductive paste is applied Add the weight of the second connecting object component, and without pressurization.
13. the manufacturing method of the connection structural bodies as described in claim 11 or 12, wherein,
The second connecting object component is resin film, flexible printing substrate, rigid-flexible combination substrate or flexible flat cable.
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