KR20140019380A - Circuit connection material, circuit member connection structure, and circuit member connection structure manufacturing method - Google Patents

Abstract

The present invention is a circuit connection material for electrically connecting opposing circuit electrodes, and contains an adhesive composition and conductive particles, the conductive particles comprising a nucleus body containing a metal or nickel of Vickers hardness of 300 to 1000 and the nucleus body. The present invention relates to a circuit connecting material having bulky particles having an outermost layer containing a noble metal to be coated, having an average particle diameter of 5 to 20 µm, and having irregularities formed on the surface of the conductive particles.

Description

CIRCUIT CONNECTION MATERIAL, CIRCUIT MEMBER CONNECTION STRUCTURE, AND CIRCUIT MEMBER CONNECTION STRUCTURE MANUFACTURING METHOD}

The present invention relates to a circuit connection material, a connection structure of a circuit member, and a manufacturing method of the connection structure of a circuit member.

As an adhesive for semiconductor elements and liquid crystal display elements, thermosetting resins, such as an epoxy resin which is excellent in adhesiveness and show high reliability, are used (for example, refer patent document 1). As the constituent components of the adhesive, a curing agent such as an epoxy resin, a phenol resin having reactivity with the epoxy resin, and a heat latent catalyst for promoting the reaction between the epoxy resin and the curing agent are generally used. The heat latent catalyst is an important factor in determining the curing temperature and curing rate of the adhesive, and various compounds are used in terms of storage stability at room temperature and curing rate upon heating.

In recent years, attention has been paid to radical curable adhesives composed of radical polymerizable compounds such as acrylate derivatives and methacrylate derivatives, and peroxides which are radical polymerization initiators. The radical curable adhesive was able to cure in a short time while being low temperature (for example, refer patent documents 2 to 4).

Japanese Patent Laid-Open No. 1-13480 Japanese Patent Laid-Open No. 2002-203427 International Publication No. 98/044067 Japanese Patent Laid-Open No. 2005-314696

These adhesives are prevalent in the fields of flat panel displays (hereinafter referred to as "FPD"), such as liquid crystal panels, and are printed wiring boards (hereinafter referred to as "PWB") and tapes. It is beginning to be used for connection with a Carrier Package (hereinafter referred to as "TCP") or Chip On Flex (hereinafter referred to as "COF"). Circuit connection materials are used for the connection between the flexible printed wiring boards (hereinafter referred to as "FPC" in the case of FPD) and PWB in the field of FPD, and the circuit is generally gold-plated. On the other hand, in PWB in which components such as chips and capacitors are mounted, mounting by solder is the mainstream. In order to obtain favorable solderability, the process which forms the resin film containing an imidazole compound as a surface treatment of a circuit is tried. In addition, since the cost can be reduced to a large motherboard etc. without using gold, it is organic by processing with the solution containing organic resins, such as an imidazole compound ("OSP process" hereafter)). It is common to form a film (hereinafter, referred to as "OSP film" in some cases). The use of the said circuit connection material is also examined also in the mounting of the OSP process circuit board.

In addition, from the flow of high-density mounting, the circuit board structure has a mainstream multilayer structure, and via holes, through holes, and the like are provided in the vicinity of the connection part to cool the heat during the connection. . For this reason, sufficient time is needed to provide heat quantity to a connection part, and a short time connection is calculated | required from the point of a productive efficiency improvement.

The fast curing radical curable adhesive used for the connection of FPC and PWB in the field of FPD can be cured in a short time, but when applied to OSP-treated substrates, connection resistance is increased compared to that applied to gold-plated substrates. Tends to be easy.

In addition, the epoxy resin-based anion-curing adhesive, which has been conventionally used universally for applications that do not require fast curing connections, exhibits good adhesion to OSP treated substrates, but after passing through a reflow furnace for soldering, The connection resistance tends to rise.

Accordingly, the present invention provides a circuit connection material that can be cured in a short time and provides sufficiently high connection reliability when applied to an OSP treated substrate, a connection structure of a circuit member and a method of manufacturing the connection structure of a circuit member using the same. It aims to do it.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the said subject, when the said hardening-type adhesive agent is used, the raise of connection resistance is that OSP film | membrane is non-conductive, and OSP film | membrane of a circuit board becomes hard by passing through a reflow furnace for soldering. The finding that this is a factor came to complete the following invention.

That is, this invention is a circuit connection material for electrically connecting opposed circuit electrodes, and contains an adhesive composition and electroconductive particle, and an electroconductive particle contains the nucleus body which contains the metal of Vickers hardness of 300-1000, and the surface of the said nucleus body. Provided is a circuit connecting material which is a massive particle having an average particle diameter of 5 to 20 µm having an outermost layer containing a noble metal to be coated, and having irregularities formed on the surface of the conductive particles.

The present invention is also a circuit connecting material for electrically connecting opposing circuit electrodes, and contains an adhesive composition and conductive particles, the conductive particles comprising a nucleus containing nickel and a noble metal covering the surface of the nucleus. It provides the circuit connection material which is the bulk particle which has an average particle diameter of 5-20 micrometers which has an outermost surface layer, and the unevenness | corrugation is formed in the surface of electroconductive particle.

The circuit connection material of this invention can harden | cure in short time by containing the above-mentioned conductive particle with an adhesive composition, and can exhibit favorable connection reliability also about the OSP process board | substrate.

It is preferable that the difference of the height in unevenness | corrugation in the electrically conductive particle in the circuit connection material of this invention is 70 nm-2 micrometers. If the difference in height in the unevenness is within the above range, it is easy to penetrate the OSP film of the circuit electrode, and the rise of the connection resistance can be easily suppressed.

From the viewpoint of enabling hardening in a shorter time, in the circuit connection material of the present invention, it is preferable that the adhesive composition contains a radical polymerizable material and a curing agent that generates free radicals by heating.

Moreover, when the adhesive composition in the circuit connection material of this invention contains an epoxy resin and a latent hardening | curing agent, the connection reliability of the connection structure of a circuit member can be improved further.

Moreover, in the circuit connection material of this invention, it is preferable that at least 1 of the opposing circuit electrodes has a film containing an imidazole compound. The circuit connection material of this invention can contain the electrically conductive particle mentioned above with adhesive composition, and even if a circuit electrode has a film containing an imidazole compound, it becomes possible to obtain favorable connection property with a short connection time.

According to the present invention, a first circuit member having a first circuit electrode formed on a main surface of a first circuit board, a second circuit electrode formed on a main surface of a second circuit board, and a second circuit electrode disposed to face the first circuit electrode. It is provided between the 2nd circuit member arrange | positioned and the 1st circuit board and the 2nd circuit board, and the circuit connection part which connects a 1st circuit member and a 2nd circuit member so that a 1st and a 2nd circuit electrode is electrically connected is provided. It is a connection structure of one circuit member, and a circuit connection part provides the connection structure of the circuit member which is a hardened | cured material of the film-form circuit connection material of the said invention.

In the connection structure of the circuit member of this invention, it is preferable that at least one of a 1st and said 2nd circuit electrode has a film containing an imidazole compound.

In the connection structure of the circuit member using the conventional short-time hardening type circuit connection material, when a circuit electrode has an OSP film | membrane, it exists in the tendency which it is difficult to improve connectivity with a short time connection. On the other hand, in the connection structure of the circuit member of this invention, since a circuit connection part is a hardened | cured material of the circuit connection material of the said invention, favorable connection property can be obtained even with shorter connection time. In addition, since the circuit structure surface of the circuit member of the present invention is formed of a film made of a material containing an imidazole compound, the circuit electrode is protected from oxidation, and good solderability can be obtained. Moreover, the connection structure of this invention has sufficiently high adhesive strength and connection reliability by connecting circuit members with the circuit connection material of the said invention.

The present invention provides a first circuit member having a first circuit electrode formed on a main surface of a first circuit board, and a second circuit member having a second circuit electrode formed on a main surface of a second circuit board. Disposed so as to face each other, the whole is heated and pressurized in a state where the film-like circuit connection material is interposed between the first and second circuit electrodes that are disposed to face each other, and the first and second circuit electrodes are electrically connected. The manufacturing method of the connection structure of a circuit member provided with the process of connecting a 1st circuit member and a 2nd circuit member is provided. The manufacturing method of the connection structure of the circuit member of this invention has favorable connection property even with shorter connection time by heating and pressurizing the circuit connection material of the said invention between a 1st circuit electrode and a 2nd circuit electrode. The connection structure of a circuit member can be obtained.

The present invention is an adhesive containing an adhesive composition and conductive particles, wherein the conductive particles have a nucleus body containing a Vickers hardness of 300 to 1000 and an outermost layer containing a precious metal covering the surface of the nucleus. It is a mass particle of 20 micrometers, and relates to the use as a circuit connection material for electrically connecting the opposing circuit electrodes of an adhesive in which the unevenness | corrugation is formed in the surface of electroconductive particle.

Moreover, this invention is an adhesive agent containing an adhesive composition and electroconductive particle, Comprising: The electroconductive particle has an average particle diameter of 5-20 micrometers which has a nucleus body containing nickel and the outermost layer containing the noble metal which coat | covers the surface of the said nucleus body. It is a mass particle and relates to the use as a circuit connection material for electrically connecting the opposing circuit electrodes of an adhesive in which the unevenness | corrugation is formed in the surface of electroconductive particle.

The present invention is an adhesive containing an adhesive composition and conductive particles, wherein the conductive particles have a nucleus body containing a Vickers hardness of 300 to 1000 and an outermost layer containing a precious metal covering the surface of the nucleus. It is the mass particle of 20 micrometers, and relates to the use for manufacture of the circuit connection material for electrically connecting the opposing circuit electrodes of an adhesive agent in which the unevenness | corrugation is formed in the surface of electroconductive particle.

Moreover, this invention is an adhesive agent containing an adhesive composition and electroconductive particle, Comprising: The electroconductive particle has an average particle diameter of 5-20 micrometers which has a nucleus body containing nickel and the outermost layer containing the noble metal which coat | covers the surface of the said nucleus body. It is a mass particle and relates to the use for manufacture of the circuit connection material for electrically connecting the opposing circuit electrodes of an adhesive agent in which the unevenness | corrugation is formed in the surface of electroconductive particle.

According to the present invention, it is possible to provide a circuit connection material, a circuit structure connection structure, and a circuit structure connection method that can be cured in a short time and provide high connection reliability when applied to an OSP-treated substrate. .

1 is a cross-sectional view showing an embodiment of a circuit connecting material.
2 is an SEM image showing an example of the appearance of the conductive particles.
3 is an SEM image showing an example of an enlarged surface of conductive particles.
4 is a cross-sectional view showing an embodiment of the connection structure.
FIG. 5 is a cross-sectional view showing an embodiment of the connection structure. FIG.

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described in detail, referring drawings as needed. However, this invention is not limited to the following embodiment. In addition, the same code | symbol is attached | subjected to the same element in drawing, and the overlapping description is abbreviate | omitted. In addition, the positional relationship of up, down, left, right, etc. shall be based on the positional relationship shown in drawing unless there is particular notice. In addition, the dimensional ratios in the drawings are not limited to the illustrated ratios.

The circuit connection material which concerns on this embodiment is an adhesive agent used in order to electrically connect circuit electrodes. 1 is a cross-sectional view showing an embodiment of a circuit connection material. As shown in FIG. 1, the circuit connection material 1 is comprised from the resin layer 3 and the some electrically-conductive particle 8 dispersed in the resin layer 3, and has a film-like shape.

Hereinafter, each component material of the circuit connection material 1 is demonstrated.

(Conductive particles)

The electroconductive particle 8 is a bulk particle which has the nucleus body containing the metal of Vickers hardness 300-1000, and the outermost layer containing the noble metal which coat | covers the said nucleus body, and the some unevenness | corrugation is formed in the surface of electroconductive particle. . Moreover, the electrically-conductive particle 8 is a massive particle which has the nucleus body containing nickel and the outermost layer containing the noble metal which coat | covers the said nucleus body, and the some unevenness | corrugation is formed in the surface of electroconductive particle. The unevenness | corrugation of the surface of electroconductive particle is derived from the unevenness | corrugation of the nuclide surface mentioned later here.

FIG. 2 is an SEM image showing an example of the appearance of the conductive particles, and FIG. 3 is an SEM image showing an example of the surface on which the conductive particles are enlarged. As shown in FIG.2 and FIG.3, the electroconductive particle of this embodiment is not a spherical mass but a bulk particle, The unevenness | corrugation is formed in the surface. Such conductive particles 8 easily penetrate the non-conductive OSP film of the circuit electrode and easily suppress an increase in connection resistance. Therefore, the connection structure of the circuit member excellent in connection reliability can be produced using the circuit connection material 1 containing the said electroconductive particle 8.

The nucleus of the conductive particles 8 is at least selected from transition metals such as nickel, chromium, molybdenum, manganese, cobalt, iron, manganese, vanadium, titanium, platinum, iridium, osmium, tungsten, tantalum, niobium, zirconium and palladium. It is preferable that it is comprised with 1 type of metal, and it is more preferable that it is comprised with nickel.

The Vickers hardness of the metal which comprises a nuclide is 300-1000, It is more preferable that it is 400-800, It is further more preferable that it is 500-700. If the Vickers hardness of the nucleus body is less than 300, the conductive particles 8 tend to be deformed, and the exclusion property of the OSP film on the electrode tends to be lowered. It becomes difficult to secure a sufficient contact area to provide.

The nucleus body has irregularities on its surface. As the nucleus body has irregularities on the surface, irregularities can be formed on the surface of the conductive particles. The method of forming irregularities on the surface of the nucleus is not particularly limited. For example, when the nucleus is nickel, nickel ore is reacted with carbon monoxide at room temperature by carbonyl to form a nickel carbonyl complex, and further 100 Carbon monoxide can be detach | desorbed by heating at more than C, and nickel which the unevenness | corrugation was formed in the surface can be obtained.

It is preferable that the difference of the height in the unevenness | corrugation formed in the surface of the electroconductive particle 8 is 70 nm-2 micrometers, It is more preferable that it is 90 nm-1.5 micrometers, It is further more preferable that it is 120 nm-1 micrometer. If the difference in height in the unevenness is 70 nm or more, the circuit electrode having the OSP film tends to be eroded, and the connection resistance after the reliability test tends to be suppressed. Moreover, when the difference in height in unevenness | corrugation is less than 2 micrometers, it is difficult for an adhesive composition to remain in the root part of the convex part in unevenness | corrugation, and also there exists a tendency for the connection resistance after a reliability test to be suppressed.

The average particle diameter of the electroconductive particle 8 is 5-20 micrometers, It is preferable that it is 8-20 micrometers, It is more preferable that it is 8-15 micrometers. If the average particle diameter is less than 5 µm, the curing of the resin layer 3 proceeds before the conductive particles 8 and the electrode contact each other. If the average particle diameter exceeds 20 µm, the radius of curvature of the conductive particles 8 is large. The exclusion of the film is lowered, making it difficult to obtain electrical conduction in any case. In addition, the average particle diameter of the electrically-conductive particle prescribed | regulated by this application is a measured value obtained by observing electrically conductive particle | grains (n number of 50 pieces) by a SEM image, for example, it can calculate it by averaging the longest particle size part and the shortest particle size part. Can be.

The outermost layer of the conductive particles 8 contains a noble metal, and is preferably composed of at least one metal selected from precious metals such as gold, silver, platinum, palladium, rhodium, iridium, ruthenium, osmium, gold or It is more preferable to consist of platinum, and it is still more preferable to consist of gold. By making up the outermost layer of the electroconductive particle 8 with these metals, the pot life of the circuit connection material 1 can be made long enough.

It is preferable that it is 0.03-0.4 micrometer, and, as for the thickness of the outermost layer of the electroconductive particle 8, it is more preferable that it is 0.08-0.2 micrometer. If the thickness of the outermost layer is 0.03 µm or more, the conductivity of the conductive particles 8 is maintained and the connection resistance tends to be suppressed. If the thickness of the outermost layer is within 0.4 µm, the cost of forming the outermost layer in the nucleus is suppressed and thus it is inexpensive. This tends to be excellent. In addition, although the nucleus body is preferably covered with the outermost layer containing the precious metal on its entire surface, a part of the nucleus, for example, irregularities on the surface of the nuclide, may be exposed from the outermost layer within the scope not departing from the effect of the present invention. .

Although the compounding quantity in the circuit connection material 1 of the electrically-conductive particle 8 is suitably set by a use, Usually, the adhesive composition (that is, of the resin layer 3 other than the electrically-conductive particle 8 in the circuit connection material 1) is used. Part) in the range of 0.1 to 30 parts by volume with respect to 100 parts by volume. Moreover, it is more preferable that the compounding quantity of the electroconductive particle 8 is 0.1-10 volume parts from a viewpoint of preventing the short circuit of the adjacent circuit electrodes on the same circuit board.

(Adhesive composition)

The adhesive composition which forms the resin layer 3 can contain the hardening | curing agent which generate | occur | produces free radicals, and a radically polymerizable substance. In other words, the circuit connection material 1 can contain the adhesive composition containing the hardening | curing agent which generates a free radical, and a radically polymerizable substance, and the electrically-conductive particle 8. When the circuit connection material 1 is heated, a crosslinked structure is formed in the adhesive composition by polymerization of the radically polymerizable substance, and a cured product of the circuit connection material 1 is formed. In this case, the circuit connection material 1 functions as a radical hardening type adhesive agent.

The curing agent for generating free radicals used in the circuit connection material (1) decomposes by heating such as a peroxide compound, an azo compound, and generates free radicals, depending on the desired connection temperature, connection time, and available time. Appropriately selected. 0.05-10 mass% is preferable based on the total mass of the circuit connection material 1, and 0.1-5 mass% (0.05-10 mass parts is preferable for the total mass of the circuit connection material 1 as 100 mass parts), , 0.1 to 5 parts by mass) is more preferable. Specifically, the curing agent for generating free radicals may be selected from diacyl peroxide, peroxydicarbonate, peroxy ester, peroxy ketal, dialkyl peroxide, hydroperoxide and the like. Moreover, in order to suppress corrosion of the connection terminal of a circuit member, it is preferable to select from peroxy ester, dialkyl peroxide, and hydroperoxide, and it is more preferable to select from peroxy ester from which high reactivity is obtained.

As the diacyl peroxides, for example, 2,4-dichlorobenzoyl peroxide, 3,5,5, -trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinct Nickel peroxide, benzoyl peroxy toluene, and benzoyl peroxide are mentioned.

As peroxy dicarbonate, di-n-propyl peroxy dicarbonate, diisopropyl peroxy dicarbonate, bis (4-t- butylcyclohexyl) peroxy dicarbonate, di-, for example 2-ethoxymethoxyperoxydicarbonate, di (2-ethylhexylperoxy) dicarbonate, dimethoxybutylperoxydicarbonate and di (3-methyl-3-methoxybutylperoxy) dicarbonate Can be mentioned.

As peroxy esters, it is 1,1,3,3,-tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxy nodecanoate, t-hexyl fur, for example. Oxyneodecanoate, t-butylperoxy pivalate, 1,1,3,3, -tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2- Ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexano Nate, t-butylperoxy isobutyrate, 1,1-bis (t-butylperoxy) cyclohexane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethyl Hexanonate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate and t-butyl perox It may be mentioned acetate.

As peroxy ketals, it is 1,1-bis (t-hexyl peroxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexyl peroxy) cyclohexane, 1, 1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- (t-butylperoxy) cyclododecane and 2,2-bis- (t-butylperoxy) decane Can be mentioned.

Examples of the dialkyl peroxides include α, α 'bis (t-butylperoxy) diisopropylbenzene, dicumylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy ) Hexane and t-butyl cumyl peroxide.

As hydroperoxides, diisopropyl benzene hydroperoxide and cumene hydroperoxide are mentioned, for example.

The hardening | curing agent which generate | occur | produces these free radicals can be used individually or in mixture, and can also be used in combination with a decomposition accelerator, an inhibitor, etc. Moreover, it is preferable to coat these hardening | curing agents with the polyurethane-type, polyester-type high molecular substance, etc., and to microencapsulate, since the pot life is extended.

The radically polymerizable substance used for the circuit connection material (1) is a substance which has a functional group to superpose | polymerize with a radical, and an acrylate, a methacrylate, a maleimide compound, a citraconimide resin, a nadiimide resin, etc. are mentioned. have. As for the compounding quantity of a radically polymerizable substance, 20-50 mass parts is preferable, and, as for the total mass of the circuit connection material 1, 100-40 mass parts is more preferable. A radically polymerizable substance can be used also in any of a monomer and an oligomer, and can also use a monomer and an oligomer together.

Examples of the acrylate (including the corresponding methacrylate, which are the same below) include methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, ethylene glycol diacrylate, and diethylene glycol di. Acrylate, trimethylolpropanetriacrylate, tetramethylolmethanetetraacrylate, 2-hydroxy-1,3-diacryloxypropane, 2,2-bis [4- (acryloxymethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, dicyclopentenyl acrylate, tricyclodecanyl acrylate, tris (acryloyloxyethyl) isocyanurate and urethane acrylate Can be mentioned. These can be used individually or in combination of 2 or more types, You can also use polymerization inhibitors, such as hydroquinone and methyl ether hydroquinones suitably as needed. Moreover, when it has a dicyclopentenyl group and / or a tricyclo decanyl group, and / or a triazine ring, since heat resistance improves, it is preferable.

As said maleimide compound, at least 2 or more maleimide groups are contained in a molecule | numerator, for example, 1-methyl- 2, 4-bismaleimide benzene, N, N'-m-phenylene bismaleimide, N, N'-p-phenylenebismaleimide, N, N'-m-toluylenebismaleimide, N, N'-4,4-biphenylenebismaleimide, N, N'-4,4- ( 3,3'-dimethylbiphenylene) bismaleimide, N, N'-4,4- (3,3'-dimethyldiphenylmethane) bismaleimide, N, N'-4,4- (3, 3'-diethyldiphenylmethane) bismaleimide, N, N'-4,4-diphenylmethanebismaleimide, N, N'-4,4-diphenylpropanebismaleimide, N, N'- 3,3'-diphenylsulfonebismaleimide, N, N'-4,4-diphenyletherbismaleimide, 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane, 2, 2-bis (3-s-butyl-4,8- (4-maleimidephenoxy) phenyl) propane, 1,1-bis (4- (4-maleimidephenoxy) phenyl) decane, 4,4 ' -Cyclohexylidene-bis (1- (4-maleimidephenoxy) -2-cyclohexylbenzene and 2 And 2-bis (4- (4-maleimidephenoxy) phenyl) hexafluoropropane, which may be used alone or in combination of two or more thereof.

The citraconimide resin is a polymerized citraconimide compound having at least one citraconimide group in a molecule, and examples of the citraconimide compound include phenylcitraconimide and 1-methyl. -2,4-biscitraconimide benzene, N, N'-m-phenylenebiscitraconimide, N, N'-p-phenylenebiscitraconimide, N, N'-4,4 Biphenylenebiscitraconimide, N, N'-4,4- (3,3-dimethylbiphenylene) biscitraconimide, N, N'-4,4- (3,3-dimethyl Diphenylmethane) biscitraconimide, N, N'-4,4- (3,3-diethyldiphenylmethane) biscitraconimide, N, N'-4,4-diphenylmethanebissheet Laconimide, N, N'-4,4-diphenylpropanebiscitraconimide, N, N'-4,4-diphenyletherbiscitraconimide, N, N'-4,4-di Phenyl sulfonbiscitraconimide, 2,2-bis (4- (4-citraconimidephenoxy) phenyl) propane, 2,2-bis (3-s-butyl-3,4- (4-sheet Laconimidephenoxy) phenyl) propane , 1,1-bis (4- (4-citraconimidephenoxy) phenyl) decane, 4,4'-cyclohexylidene-bis (1- (4-citraconimidephenoxy) phenoxy) 2-cyclohexyl benzene and 2, 2-bis (4- (4-citraconimide phenoxy) phenyl) hexafluoro propane are mentioned. These can be used individually or in combination of 2 or more types.

The said nadiimide resin superposed | polymerized the nadiimide compound which has at least 1 nadiimide group in a molecule | numerator, As a nadiimide compound, For example, phenyl naimide, 1-methyl- 2, 4- bis naimide benzene, N, N'-m-phenylenebisnamidimide, N, N'-p-phenylenebisnamidimide, N, N'-4,4-biphenylenebisnamidimide, N, N'-4,4 -(3,3-dimethylbiphenylene) bisnamidimide, N, N'-4,4- (3,3-dimethyldiphenylmethane) bisnamidimide, N, N'-4,4- (3, 3-diethyldiphenylmethane) bisnamidimide, N, N'-4,4-diphenylmethanebisnamidimide, N, N'-4,4-diphenylpropanebisnamidimide, N, N'-4 , 4-diphenyletherbisnamidimide, N, N'-4,4-diphenylsulfonbisnamidimide, 2,2-bis (4- (4-namidimidephenoxy) phenyl) propane, 2,2- Bis (3-s-butyl-3,4- (4-nadiimidphenoxy) phenyl) propane, 1,1-bis (4- (4-nadiimidphenoxy) phenyl) decane, 4,4'-cyclo Hexylidene-bis (1- (4-nadiiimi Phenoxy) phenoxy) -2-cyclohexylbenzene and 2,2-bis (4- (4-nadiyi mid-phenoxy) phenyl) hexafluoropropane. These can be used individually or in combination of 2 or more types.

The circuit connection material 1 may contain other components in addition to the hardening | curing agent and radically polymerizable substance which generate | occur | produce a free radical. For example, it may contain a thermoplastic resin and a thermosetting resin.

As thermoplastic resin, polyethylene resin, polyimide resin, polyvinyl chloride resin, polyphenylene oxide resin, polyvinyl butyral resin, polyvinyl formal resin, polyamide resin, polyester resin, phenoxy resin, polystyrene resin, xylene Resins, polyurethane resins and the like can be used.

As the thermoplastic resin, a hydroxyl group-containing resin having a Tg (glass transition temperature) of 40 ° C. or more and a molecular weight of 10000 or more can be preferably used, for example, a phenoxy resin can be preferably used. A phenoxy resin is obtained by making bifunctional phenols and epihalohydrin react until high molecular weight, or carrying out heavy addition reaction of a bifunctional epoxy resin and a bifunctional phenol.

Examples of the thermosetting resin include urea resin, melamine resin, phenol resin, xylene resin, epoxy resin, polyisocyanate resin and the like.

When it contains the said thermoplastic resin, since handling is also favorable and the stress relaxation at the time of hardening is excellent, it is preferable. Moreover, when the said thermoplastic resin and thermosetting resin have functional groups, such as a hydroxyl group, since adhesiveness improves, it is more preferable, and may be modified by epoxy group containing elastomer and radically polymerizable functional group. Modification with a radically polymerizable functional group is preferable because heat resistance is improved.

It is preferable that the weight average molecular weight of the said thermoplastic resin is 10000 or more from a viewpoint of film forming property, etc., However, when it becomes 1 million or more, there exists a tendency for mixing property to deteriorate. In addition, the weight average molecular weight prescribed | regulated by this application means the thing measured using the analytical curve by standard polystyrene by the gel permeation chromatography method (GPC) on the following conditions.

<GPC condition>

Equipment used: Hitachi L-6000 type (manufactured by Hitachi Seisakusho Co., Ltd.)

Column: Gel Pack GL-R420 + Gel Pack GL-R430 + Gel Pack GL-R440 (3 in total) (manufactured by Hitachi Kasei Kogyo Co., Ltd.)

Eluent: tetrahydrofuran

Measuring temperature: 40 ° C

Flow rate: 1.75 mL / min

Detector: L-3300RI (made by Hitachi Seisakusho Co., Ltd.)

Moreover, an adhesive composition (resin layer 3) may contain an epoxy resin and a latent hardener instead of the hardening | curing agent and radically polymerizable substance which generate | occur | produce a free radical. That is, the circuit connection material 1 can contain the adhesive composition and electroconductive particle 8 containing an epoxy resin and a latent hardening | curing agent. When the circuit connection material 1 is heated, a crosslinked structure is formed from an adhesive composition by hardening of an epoxy resin, and the hardened | cured material of the circuit connection material 1 is formed. In this case, the circuit connection material 1 functions as an epoxy hardening-type adhesive agent.

Examples of the epoxy resins include bisphenol-type epoxy resins, which are glycidyl ethers of bisphenols such as bisphenol A, F, and AD, and epoxy novolac resins derived from phenol novolac or cresol novolac. As another example, the naphthalene type | mold epoxy resin which has a naphthalene frame | skeleton, glycidyl amine type | mold epoxy resin, glycidyl ester type epoxy resin, an alicyclic epoxy resin, and a heterocyclic epoxy resin are mentioned. These are used individually or in mixture of 2 or more types.

Among the above epoxy resins, bisphenol-type epoxy resins are available in a wide range of grades having different molecular weights, and are preferable because they can arbitrarily set adhesiveness, reactivity, and the like. Among bisphenol type epoxy resins, bisphenol F type epoxy resins are particularly preferable. The viscosity of bisphenol F-type epoxy resin is low, and by using it in combination with a phenoxy resin, the fluidity | liquidity of the circuit connection material 1 can be set easily and extensively. Moreover, bisphenol F-type epoxy resin also has the advantage of being easy to provide favorable adhesiveness to the circuit connection material (1).

It is preferable to use an epoxy resin having an impurity ion (Na ⁺ , Cl ^−, etc.) concentration or a hydrolyzable chlorine of 300 ppm or less to prevent electromigration.

What is necessary is just to be able to harden an epoxy resin as a latent hardening | curing agent. In addition, the latent curing agent may be a compound which reacts with the epoxy resin and is introduced into the crosslinked structure, or may be a catalytic curing agent that promotes the curing reaction of the epoxy resin. It is also possible to use both together.

As a catalyst type hardening | curing agent, the anionic polymerization type latent hardening agent which accelerates | stimulates the anion polymerization of an epoxy resin, and the cationic polymerization type latent hardening agent which accelerates cation polymerization of an epoxy resin are mentioned, for example.

As an anionic polymerization type latent hardening | curing agent, an imidazole series, a hydrazide system, a boron trifluoride-amine complex, an amine imide, the salt of a polyamine, dicyandiamide, and these modified substances are mentioned, for example. The imidazole-based anionic polymerization type latent curing agent is formed by, for example, adding imidazole or a derivative thereof to the epoxy resin.

As a cationic polymerization type latent hardening | curing agent, the photosensitive onium salt (aromatic diazonium salt, aromatic sulfonium salt, etc. are mainly used) which hardens an epoxy resin by energy-beam irradiation, for example is preferable. In addition to the energy ray irradiation, there are aliphatic sulfonium salts that are activated by heating to cure the epoxy resin. This type of curing agent is preferable because it has the characteristics of fast curing.

The microencapsulation of these latent curing agents by coating a polymer material such as polyurethane or polyester, a metal thin film such as nickel or copper and an inorganic material such as calcium silicate is preferable because the pot life can be extended.

It is preferable that it is 30-60 mass parts with respect to 100 mass parts of epoxy resins, and, as for the compounding quantity of a latent hardening | curing agent, it is more preferable that it is 40-55 mass parts. When the compounding quantity of latent hardening | curing agent is 30 mass parts or more, the tightening force with respect to the to-be-adhered body by hardening shrinkage of the circuit connection material 1 will become difficult to fall. As a result, there exists a tendency for the contact of the electroconductive particle 8 and a circuit electrode to be maintained, and the connection resistance after a reliability test becomes easy to be suppressed. On the other hand, since the tightening force does not become too strong when it is within 60 mass parts of the compounding quantity of a latent hardening | curing agent, internal stress in the hardened | cured material of the circuit connection material 1 becomes large, and it tends to become easy to suppress the fall of adhesive strength. have.

When the circuit connection material 1 is an epoxy resin adhesive, it is preferable to contain a film formation material. When the film-forming material solidifies the liquid and forms the constituent composition in the form of a film, the film-forming material facilitates handling of the film, and imparts mechanical properties that are not easily torn, broken, or stuck to each other. Normal temperature and normal pressure) can be handled as a film.

Since the thermoplastic resin mentioned above can be used as a film forming material, and it is excellent in adhesiveness, compatibility, heat resistance, and mechanical strength, it is preferable to use a phenoxy resin.

Phenoxy resin is resin obtained by making it react until it polymerizes bifunctional phenols and epihalohydrin, or carrying out polyaddition of bifunctional epoxy resin and bifunctional phenols. The phenoxy resin can be obtained, for example, by reacting 1 mole of bifunctional phenols and 0.985 to 1.015 mole of epihalohydrin at a temperature of 40 to 120 ° C. in a nonreactive solvent in the presence of a catalyst such as an alkali metal hydroxide. have.

In addition, as the phenoxy resin, in view of the mechanical properties and thermal properties of the resin, the compounding equivalence ratio between the bifunctional epoxy resin and the bifunctional phenols is set to the epoxy group / phenol hydroxyl group = 1 / 0.9 to 1 / 1.1, Reaction solid content is 50 mass% or less in organic solvents, such as amide type, ether type, ketone type, lactone type, and alcohol type, whose boiling point is 120 degreeC or more in presence of catalyst, such as an alkali metal compound, an organophosphorus compound, and a cyclic amine compound, etc. It is preferable that it is obtained by heating at 50-200 degreeC on the conditions of, and carrying out heavy part reaction.

As the bifunctional epoxy resin, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, and bisphenol S type epoxy resins can be used. The bifunctional phenols have two phenolic hydroxyl groups, and examples thereof include bisphenol compounds such as hydroquinones, bisphenol A, bisphenol F, bisphenol AD, and bisphenol S.

The phenoxy resin may be modified with a radical polymerizable functional group. The phenoxy resin can be used individually by 1 type or in mixture of 2 or more types.

In addition, the circuit connection material 1 may contain a filler, a softener, an accelerator, an antiaging agent, a coloring agent, a flame retardant, a thixotropic agent, a coupling agent, an isocyanate, and the like. When the filler is contained, the connection reliability and the like can be improved, which is preferable. It can be used if the largest diameter of a filler is less than the particle diameter of the electroconductive particle 8, and the compounding quantity has a preferable range of 5 to 60 volume%. If it is 5 to 60 volume%, the effect of a reliability improvement will become easy to be maintained. As a coupling agent, a vinyl group, an acryl group, an amino group, an epoxy group, and an isocyanate group containing material are preferable at the point of an adhesive improvement. As needed, polymerization inhibitors, such as hydroquinone and methyl ether hydroquinones, can also be used suitably.

The circuit connection material of this embodiment is an adhesive agent used in order to electrically connect circuit electrodes as mentioned above.

That is, the adhesive agent of this embodiment is an adhesive agent containing an adhesive composition and electroconductive particle, and an electroconductive particle contains the nucleus body containing the metal of Vickers hardness 300-1000, and the outermost layer containing the noble metal which coat | covers the surface of the said nucleus body. It is a bulk particle which has an average particle diameter of 5-20 micrometers, and an unevenness | corrugation is formed in the surface of electroconductive particle. This adhesive agent can be used as a circuit connection material for electrically connecting opposed circuit electrodes. Moreover, it can use for manufacture of the circuit connection material for electrically connecting opposing circuit electrodes.

Moreover, the adhesive agent of this embodiment is an adhesive agent containing an adhesive composition and electroconductive particle, An electroconductive particle has an average particle diameter of 5 which has a nucleus body containing nickel and the outermost layer containing the noble metal which coat | covers the surface of the said nucleus body. It is a bulk particle of 20 micrometers, and the unevenness | corrugation is formed in the surface of an electroconductive particle. This adhesive agent can be used as a circuit connection material for electrically connecting opposed circuit electrodes. Moreover, it can use for manufacture of the circuit connection material for electrically connecting opposing circuit electrodes.

Next, the connection structure of the circuit member of this embodiment using the circuit connection material 1 is demonstrated. The circuit connection material 1 is preferable in order to form the connection structure in which the chip components, such as a semiconductor chip, a resistor chip, and a capacitor chip, and circuit members which have 1 or 2 or more circuit electrodes (connection terminals), such as a printed wiring board, are connected. Is used.

4 is a cross-sectional view showing an embodiment of a connection structure of a circuit member. The connection structure 100 of the circuit member shown in FIG. 4 includes the first circuit member 10 having the first circuit board 11 and the first circuit electrode 13 formed on the main surface thereof, and the second circuit board. 2nd circuit member 20 which has 21 and 2nd circuit electrode 23 formed on the main surface, and is arrange | positioned so that 2nd circuit electrode 23 and 1st circuit electrode 13 may oppose, and 1st The connection part 1a interposed between the circuit member 10 and the 2nd circuit member 20 is provided.

The connection part 1a is hardened | cured material formed by hardening | curing the circuit connection material 1, and contains the electroconductive particle 8. As shown in FIG. The connection part 1a adhere | attaches the 1st circuit member 10 and the 2nd circuit member 20 so that the opposing 1st circuit electrode 13 and the 2nd circuit electrode 23 may electrically connect. Opposing first circuit electrodes 13 and second circuit electrodes 23 are electrically connected via conductive particles 8. Moreover, even when the connection part 1a does not contain the electroconductive particle 8, the 1st circuit electrode 13 and the 2nd circuit electrode 23 can be electrically connected through the circuit connection material 1.

The first circuit board 11 is a resin film containing at least one resin selected from the group consisting of polyester terephthalate, polyether sulfone, epoxy resin, acrylic resin and polyimide resin. The first circuit electrode 13 is made of a material (preferably at least one selected from the group consisting of gold, silver, tin, platinum group metals, and indium-tin oxides) having a conductivity sufficient to function as an electrode. Formed.

The second circuit board 21 is a multilayer wiring board formed from an insulating substrate such as silicon, gallium arsenide, or the like of semiconductor chips, glass, ceramic, glass, epoxy composite, or plastic. The 2nd circuit electrode 23 has the conductor part 23a and the film 23b which forms the part which contact | connects the connection part 1a among the surfaces of the circuit electrode 23, and the film 23b is the electroconductive particle 8 It is preferable to penetrate and electrically connect with the unevenness | corrugation formed in the surface. The conductor portion 23a is at least one selected from the group consisting of a material (preferably gold, silver, tin, a platinum group metal, and an indium-tin oxide) having a conductivity sufficient for the circuit electrode 23 to function as an electrode. Species).

The film 23b is a film made of a material containing an organic resin, and preferably contains an organic resin such as an imidazole compound. The film 23b is formed by treating the second circuit board 21 with an organic solder preservative (OSP). OSP treatment is a method of processing a substrate, also referred to as a water-soluble preflux, and generally forms an OSP film by treating the substrate with a solution containing an imidazole compound. The film containing an imidazole compound is a film | membrane formed by mutually bonding the imidazole derivative and the complex produced | generated from the metal on the electrode surface. That is, the film containing an imidazole compound can be formed by OSP treatment of the board | substrate with a circuit electrode with the solution containing an imidazole compound. As the imidazole compound, a benzimidazole derivative is preferably used in terms of heat resistance. OSP treatment is commercially available as a commercially available product of Shikoku Kasei Co., Ltd. brand name Tarpace F2, F2 (LX) or Co., Ltd., Tosho G. Co., Ltd., or Ensonone Inc. Entek106A , 106A (X), or McSeal CL-5824S, CL-5018, CL-5018S can be used.

The circuit connection material which concerns on this embodiment can be used for the connection of the circuit member which has the film | membrane in which at least one of a 1st and 2nd circuit electrode contains the material containing organic resin. In addition, not only the 2nd circuit electrode 23 but the 1st circuit electrode 13 is a conductor part 13a, and a circuit electrode like sectional drawing which shows one Embodiment of the connection structure of the circuit member shown in FIG. It may have a film 13b which forms the part which contacts the connection part 1a among the surfaces of 13, and the film 13b of the 1st circuit electrode 13 also has an unevenness | corrugation formed in the surface of the electroconductive particle 8 It is preferable to penetrate and electrically connect. The film 13b is formed by the same method as the film 23b.

The manufacturing method of the connection structure of the circuit member of this embodiment is the 1st circuit member in which the 1st circuit electrode was formed on the main surface of the 1st circuit board, and the 2nd circuit member in which the 2nd circuit electrode was formed on the main surface of the 2nd circuit board. Is arranged so that the first circuit electrode and the second circuit electrode face each other, and the whole is heated and pressed in a state where the film-like circuit connection material of the present embodiment is interposed between the first circuit electrode and the second circuit electrode which face each other. And a step of connecting the first circuit member and the second circuit member so that the first and second circuit electrodes are electrically connected.

The connection structure 100 of the circuit member is, for example, the first circuit member 10, the film-like circuit connection material 1 described above, and the second circuit member 20 with the first circuit electrode 13. The first circuit member 10 is configured such that the first circuit electrode 13 and the second circuit electrode 23 are electrically connected by heating and pressurizing the laminated body stacked in this order so that the second circuit electrode 23 is opposed. And the manufacturing method of connecting the 2nd circuit member 20 to it.

In this manufacturing method, the circuit connection material 1 is temporarily bonded by heating and pressurizing in the state which bonded the film-form circuit connection material 1 formed on the support film on the 2nd circuit member 20, for example. After peeling a support film, the laminated body can be prepared by loading the 1st circuit member 10, arrange | positioning so that a circuit electrode may oppose. In order to prevent the influence on the connection by the volatile component which arises by the heating at the time of connection, it is preferable to heat-process a circuit member before a connection process previously.

The conditions for heating and pressurizing the laminate are appropriately adjusted in accordance with the curability of the composition, etc. in the circuit connection material, so that the circuit connection material is cured to obtain sufficient adhesive strength. Moreover, it can also be connected by light irradiation according to a composition in a circuit connection material.

The board | substrate which the circuit member which comprises a connection structure has may be a semiconductor chip, such as silicon and gallium arsenide, and insulating boards, such as glass, a ceramic, a glass, an epoxy composite, and plastics.

Example

Hereinafter, the content of the present invention will be described in more detail using examples. However, the present invention is not limited to these examples.

(1) Preparation of the circuit connection material

(1-1) Preparation of each component which comprises an adhesive composition

"Perhexa 25O": 2,5-dimethyl-2,5-di (2-ethylhexanoyl) hexane (manufactured by Nippon Yushi, trade name)

"UN5500": urethane acrylate oligomer (made by Negami Kogyo, trade name)

"DCP-A": Dicyclopentadiene type diacrylate (Toagosei Co., Ltd. brand name)

"M-215": isocyanuric acid EO modified diacrylate (made by Toagosei, brand name)

"P-2M": 2-methacryloyloxyethyl acid phosphate (the Kyoeisha Chemical Co., Ltd. make, brand name)

"HX3941HP": Anionic polymerization type latent hardener-containing epoxy resin (35 mass% of imidazole microcapsule type hardeners, Asahi Kasei Chemicals make, brand name)

"UR-8200": Polyester urethane (Toyo Bonde Co., Ltd. brand name)

"EV40W": Ethylene-vinyl acetate copolymer (Mitsui DuPont Polychemical make, brand name)

"PKHC": Bisphenol A phenoxy resin (weight average molecular weight 45000, the Inchem Corporation make, brand name)

"Acrylic rubber A": Copolymer of butyl acrylate 40 mass parts-ethyl acrylate 30 mass parts-acrylonitrile 30 mass parts-glycidyl methacrylate 3 mass parts (weight average molecular weight about 850,000)

"SH6040": silane coupling agent (γ-glycidoxypropyltrimethoxysilane, manufactured by Toray Dow Corning, trade name)

(1-2) Preparation of Conductive Particles

A conductive particle having an average particle diameter of 10 µm was prepared as a "conductive particle A" having a nucleus body including Ni particles having a plurality of irregularities formed on the surface thereof, and an outermost layer made of gold formed by gold plating the nucleus body. As "conductive particle B", conductive particles having an average particle diameter of 10 µm having a nucleus body including Ni particles having a plurality of irregularities formed on the surface thereof, and an outermost layer made of gold formed by applying palladium plating to the nucleus body were prepared. Further, as "conductive particles C", conductive particles having an average particle diameter of 10 µm having a nucleus body containing spherical Ni particles and an outermost layer made of gold formed by gold plating the nucleus body were prepared. As "conductive particle D", conductive particles having an average particle diameter of 10 µm having a nucleus body containing spherical Ni particles and an outermost layer made of gold formed by gold plating the nucleus body were prepared. Moreover, as "conductive particle E", the electrically-conductive particle of 10 micrometers of average particle diameters which has only the nuclear body containing Ni particle in which the unevenness | corrugation was formed in the surface was prepared. As "conductive particle F", the electrically-conductive particle of 10 micrometers of average particle diameters which has only the nuclear body which is spherical Ni particle was prepared. Here, the nucleus body including Ni particles having a plurality of irregularities formed on the surface reacts nickel ore with carbon monoxide in a 25 ° C. environment to form a nickel carbonyl complex, heats the nickel carbonyl complex at 100 ° C., and desorbs carbon monoxide. (Carbonyl method).

(Example 1)

8 parts by mass of a 50% by mass hydrocarbon solvent solution of "perhexa 25O" (4 parts by mass in terms of non volatile matter), 60 parts by mass of 50% by mass of toluene solution of "UN5500" as a radical polymerizable material (30 parts by mass in terms of nonvolatile matter) ), 8 parts by mass of "DCP-A", 8 parts by mass of "M-215", 2 parts by mass of "P-2M", 30% by mass methylethylketone / toluene (= 50/50) solution of "UR-8200" 150 parts by mass (45 parts by mass in terms of non volatile matter) and 50 parts by mass (10 parts by mass in terms of non volatile matter) of 20 mass% toluene solution of "EV40W" are added, and 10 parts by mass of "conductive particles A" are further blended. It was. This mixed solution was apply | coated on PET film with an applicator, and the film-form circuit connection material whose thickness of a resin layer is 35 micrometers was obtained by 70 degreeC hot air drying for 10 minutes.

(Example 2)

A film-like circuit connection material was obtained in the same manner as in Example 1 except that 10 parts by mass of the conductive particles B were used as the conductive particles.

(Example 3)

Except having used 20 mass parts of electroconductive particle A as electroconductive particle, it carried out similarly to Example 1, and obtained the film-form circuit connection material.

(Example 4)

50 mass parts of "HX3941HP-SS", 37.5 mass parts of 40 mass% toluene / ethyl acetate (= 50/50) solution of "PKHC" (15 mass parts in terms of non volatile matter), and 10 mass% toluene of "acrylic rubber A" 350 parts by mass of the ethyl acetate (= 50/50) solution (35 parts by mass in terms of non-volatile content) and 2 parts by mass of "SH6040" were blended, and 10 parts by mass of "conductive particles A" were further blended. This mixed solution was apply | coated on PET film with an applicator, and the film-form circuit connection material whose thickness of a resin layer is 35 micrometers was obtained by 70 degreeC hot air drying for 10 minutes.

(Example 5)

A film-like circuit connection material was obtained in the same manner as in Example 4 except that 10 parts by mass of the conductive particles B were used as the conductive particles.

(Example 6)

A film-like circuit connection material was obtained in the same manner as in Example 4 except that 20 parts by mass of the conductive particles A were used as the conductive particles.

(Comparative Example 1)

A film-like circuit connection material was obtained in the same manner as in Example 1 except that 10 parts by mass of the conductive particles C were used as the conductive particles.

(Comparative Example 2)

A film-like circuit connection material was obtained in the same manner as in Example 1 except that 10 parts by mass of the conductive particles D were used as the conductive particles.

(Comparative Example 3)

Except having used 10 mass parts of electroconductive particle E as electroconductive particle, it carried out similarly to Example 1, and obtained the film-form circuit connection material.

(Comparative Example 4)

A film-like circuit connection material was obtained in the same manner as in Example 1 except that 10 parts by mass of the conductive particles F were used as the conductive particles.

(Comparative Example 5)

A film-like circuit connection material was obtained in the same manner as in Example 4 except that 10 parts by mass of the conductive particles C were used as the conductive particles.

(Comparative Example 6)

A film-like circuit connection material was obtained in the same manner as in Example 4 except that 10 parts by mass of the conductive particles D were used as the conductive particles.

(Comparative Example 7)

A film-like circuit connection material was obtained in the same manner as in Example 4 except that 10 parts by mass of the conductive particles E were used as the conductive particles.

(Comparative Example 8)

A film-form circuit connection material was obtained in the same manner as in Example 4 except that 10 parts by mass of the conductive particles F were used as the conductive particles.

The compositions of the circuit connection materials of Examples 1 to 6 and Comparative Examples 1 to 8 are shown in Tables 1 and 2 below in terms of mass (in terms of nonvolatile matter).

(2) Preparation of the connection structure of the circuit member

(2-1) Preparation of OSP Treated Printed Wiring Board (PWB)

A copper circuit electrode having a line width of 100 μm, a pitch of 400 μm, and a thickness of 35 μm was formed on a glass / epoxy multilayer printed wiring board (hereinafter referred to as “PWB”). Furthermore, OSP treatment was carried out on the surface of the copper circuit electrode of PWB using a benzimidazole compound (manufactured by Shikoku Kasei Co., Ltd., product name "Tap Ace") to form a coating film of a benzimidazole-based resin complex having a thickness of 0.10 to 0.32 µm. (Hereinafter referred to as "OSP-PWB").

(2-2) Preparation of OSP Treated Flexible Printed Wiring Board (FPC)

A flexible printed wiring board (hereinafter referred to as “FPC”) in which a copper circuit electrode having a line width of 100 μm, a pitch of 400 μm, and a thickness of 18 μm was directly formed on a polyimide film having a thickness of 25 μm was prepared. An OSP treatment was carried out in the same manner as the above OSP-PWB to form a coating film of a benzimidazole-based resin complex having a thickness of 0.10 to 0.32 µm (hereinafter referred to as "OSP-FPC").

(2-3) Connection of circuit electrodes (connection of PWM and FPC)

OSP-PWB and OSP-FPC were heat treated on a 250 ° C. hot plate for 30 seconds as a simulated pass through reflow before connecting. After affixing the adhesive surface of the above-mentioned film-form circuit connection material on OSP-PWB, PET film was peeled off after heating and pressurizing at 70 degreeC and 1 MPa for 2 second, and temporarily connecting. Next, after aligning so that the circuit electrode of OSP-FPC and the circuit electrode of OSP-PWB faced each other, about Example 1-3 and Comparative Examples 1-4, it heated and pressed at 160 degreeC and 4 MPa for 6 second. In addition, about Examples 4-6 and Comparative Examples 5-8, it heated at 170 degreeC and 4 MPa for 20 second. The width between the substrate of the FPC and the PWB was 2 mm.

(3) Evaluation of the connection structure of the circuit member

(3-1) Measurement of connection resistance

The resistance value between circuits containing the circuit connection part of the produced connection structure was measured by the 4-probe method using a digital multimeter. The measurement of the connection resistance was measured after the high temperature and high humidity process which hold | maintain for 1000 hours in 85 degreeC and 85% RH constant temperature and humidity tank immediately after connection, and after 1000 cycles of thermal shock test of -40 degreeC-+100 degreeC, respectively. It was judged that the connection resistance by the 4-probe method after the reliability test had a range of 100 mΩ or less. The results are shown in Table 3 below.

As shown in Table 3, it was confirmed that the circuit connection materials of Examples 1 to 6 had a small increase in connection resistance and excellent connection reliability in either of the high-temperature, high-humidity treatment and after the thermal shock test. On the other hand, the circuit connection material of the comparative examples 1-8 showed the connection resistance exceeding 100 m (ohm) in either after high temperature, high humidity process, and after a thermal shock test, and connection reliability was inferior.

[Industrial Availability]

According to the present invention, it is possible to provide a circuit connection material, a circuit structure connection structure, and a circuit structure connection method that can be cured in a short time and provide high connection reliability when applied to an OSP-treated substrate. .

One… Circuit connection material, 1a... 3,. Resin layer, 8... Conductive particles, 10 ... First circuit member, 11... First circuit board, 13... First circuit electrode, 20... Second circuit member, 21... Second circuit board, 23... Second circuit electrode, 23a... Conductor portion, 23b... Film, 100... Connection structure of the circuit member.

Claims (21)

It is a circuit connection material for electrically connecting opposed circuit electrodes,
Contains an adhesive composition and conductive particles,
The said electrically-conductive particle is a bulk particle which has an average particle diameter of 5-20 micrometers which has a nucleus body containing the metal of Vickers hardness 300-1000, and the outermost layer containing the precious metal which coat | covers the surface of the said nucleus body, The circuit connection material in which the unevenness | corrugation is formed in the surface of the said electroconductive particle. It is a circuit connection material for electrically connecting opposed circuit electrodes,
Contains an adhesive composition and conductive particles,
The conductive particles are bulk particles having an average particle diameter of 5 to 20 µm having a nucleus body containing nickel and an outermost layer containing a noble metal covering the surface of the nucleus, and irregularities are formed on the surface of the conductive particles. Circuit connection material. The circuit connection material of Claim 1 or 2 whose difference in height in the said unevenness | corrugation is 70 nm-2 micrometers. The circuit connection material of any one of Claims 1-3 in which the said adhesive composition contains a radically polymerizable substance and the hardening | curing agent which generate | occur | produces free radical by heating. The circuit connection material of any one of Claims 1-3 in which the said adhesive composition contains an epoxy resin and a latent hardening | curing agent. The circuit connection material according to any one of claims 1 to 5, wherein at least one of the opposing circuit electrodes has a coating containing an imidazole compound. A first circuit member having a first circuit electrode formed on a main surface of the first circuit board,
A second circuit member formed on a main surface of a second circuit board, the second circuit member disposed so that the second circuit electrode is disposed to face the first circuit electrode;
A circuit connecting portion provided between the first circuit board and the second circuit board and connecting the first circuit member and the second circuit member to electrically connect the first and second circuit electrodes.
Is a connection structure of a circuit member having a
The connection structure of the circuit member whose said circuit connection part is a hardened | cured material of the film-form circuit connection material of any one of Claims 1-6. The connection structure of Claim 7 in which at least one of the said 1st and said 2nd circuit electrode has a film containing an imidazole compound. The first circuit member having the first circuit electrode formed on the main surface of the first circuit board, and the second circuit member having the second circuit electrode formed on the main surface of the second circuit board, the first circuit electrode and the second circuit electrode Arranged so as to face each other, the whole is heated and pressurized in the state which interposed the film-form circuit connection material in any one of Claims 1-6 between the said 1st circuit electrode and the 2nd circuit electrode which were arrange | positioned, And a step of connecting the first circuit member and the second circuit member so that the first and the second circuit electrodes are electrically connected to each other. An adhesive containing an adhesive composition and conductive particles,
The said electrically-conductive particle is a mass particle of 5-20 micrometers of average particle diameters which has a nucleus body containing the metal of Vickers hardness 300-1000, and the outermost layer containing the noble metal which coat | covers the surface of the said nucleus body, Of adhesive with irregularities on the surface
Use as a circuit connection material for electrically connecting opposed circuit electrodes. An adhesive containing an adhesive composition and conductive particles,
The conductive particles are bulk particles having an average particle diameter of 5 to 20 µm having a nucleus body containing nickel and an outermost layer containing a noble metal covering the surface of the nucleus, and irregularities are formed on the surface of the conductive particles. Adhesive
Use as a circuit connection material for electrically connecting opposed circuit electrodes. Use according to claim 10 or 11, wherein the difference in height in the unevenness is 70 nm to 2 m. The use according to any one of claims 10 to 12, wherein the adhesive composition comprises a radically polymerizable material and a curing agent which generates free radicals by heating. The use according to any one of claims 10 to 12, wherein the adhesive composition comprises an epoxy resin and a latent curing agent. The use according to any one of claims 10 to 14, wherein at least one of the first and second circuit electrodes has a coating comprising an imidazole compound. An adhesive containing an adhesive composition and conductive particles,
The said electrically-conductive particle is a mass particle of 5-20 micrometers of average particle diameters which has a nucleus body containing the metal of Vickers hardness 300-1000, and the outermost layer containing the noble metal which coat | covers the surface of the said nucleus body, Of adhesive with irregularities on the surface
Use for the manufacture of a circuit connection material for electrically connecting opposed circuit electrodes. An adhesive containing an adhesive composition and conductive particles,
The conductive particles are bulk particles having an average particle diameter of 5 to 20 µm having a nucleus body containing nickel and an outermost layer containing a noble metal covering the surface of the nucleus, and irregularities are formed on the surface of the conductive particles. Adhesive
Use for the manufacture of a circuit connection material for electrically connecting opposed circuit electrodes. Use according to claim 16 or 17, wherein the difference in height in the unevenness is 70 nm to 2 m. The use according to any one of claims 16 to 18, wherein the adhesive composition comprises a radically polymerizable material and a curing agent which generates free radicals by heating. The use according to any of claims 16 to 18, wherein the adhesive composition comprises an epoxy resin and a latent curing agent. The use according to any one of claims 16 to 20, wherein at least one of the first and second circuit electrodes has a coating comprising an imidazole compound.

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