JP4655487B2 - Adhesive composition, film-like adhesive and circuit connecting material using the same, circuit member connecting structure, and manufacturing method thereof - Google Patents

Description

  The present invention relates to an adhesive composition, a film adhesive and a circuit connecting material using the same, a circuit member connection structure, and a method for manufacturing the same.

  In the fields of the electric industry and the electronic industry, various adhesive materials are used for the purpose of bonding various members. In particular, in semiconductors and liquid crystal displays, higher density and higher definition are progressing, and adhesives applied to these applications are also required to have high adhesive strength, particularly excellent adhesive strength under high temperature and high humidity conditions. Yes.

In addition, the adherend to be bonded by an adhesive includes organic substrates such as printed wiring boards and polyimides, metals such as copper and aluminum, ITO (indium tin oxide), silicon nitride (SiN _x ), silicon dioxide. Substrates having various surface states such as (SiO ₂ ) are used. Therefore, the adhesive is preferably designed according to each adherend.

  Conventionally, thermosetting resins such as epoxy resins have been used as adhesives for semiconductor elements and liquid crystal display elements (see, for example, Patent Document 1). Such an adhesive is cured by heat treatment at 170 to 250 ° C. for 1 to 3 hours.

  In recent years, with the high integration of semiconductor elements and the high definition of liquid crystal display elements, the pitch between elements and wirings has been narrowed. Therefore, when heat treatment is performed at the above temperature, there is a possibility that the peripheral members may be adversely affected by heating during curing. Accordingly, in order to prevent adverse effects on the peripheral members, it is required to be cured at a relatively low temperature, and further, it is required to be cured in a short time (within 1 hour) in order to improve the throughput. Yes. In other words, an adhesive for “low temperature fast curing” is required.

  In order to meet such a requirement, Patent Document 2 discloses an anisotropic conductive adhesive containing a radical polymerizable resin, an organic peroxide, a thermoplastic elastomer, a phosphate ester, and an epoxy silane coupling agent as a resin composition. Is disclosed.

Japanese Patent Laid-Open No. 1-113480 JP 2000-44905 A

  However, the anisotropic conductive adhesive described in Patent Document 2 is capable of rapid curing at low temperatures, but has insufficient adhesive strength, particularly insufficient adhesive strength under high temperature and high humidity conditions. It was.

  The present invention has been made in view of the above-described problems of the prior art, and has an adhesive composition that has sufficient adhesive strength and is particularly excellent in adhesive strength under high-temperature and high-humidity conditions, and a film shape using the same It is an object of the present invention to provide an adhesive, a circuit connection material, a circuit member connection structure, and a manufacturing method thereof.

  In order to solve the above problems, the adhesive composition of the present invention comprises a radical polymerizable compound, a radical polymerization initiator, and a compound having a nitrogen-silicon bond (preferably a silazane compound). And

  The adhesive composition of the present invention is a so-called radical curable adhesive composition containing a radical polymerizable compound and a radical polymerization initiator. The adhesive composition of the present invention has sufficient adhesive strength by containing a compound having a nitrogen-silicon bond in the radical curable adhesive composition, particularly high temperature and high humidity (85 ° C., 85% RH). Excellent adhesive strength under conditions. In addition, the adhesive composition of the present invention exhibits high adhesive strength at least on an adherend composed of an inorganic material such as a metal at the surface, and can be cured at a low temperature. Thus, since the surface has high adhesive strength with respect to the adherend composed of an inorganic material, the adhesive composition of the present invention is suitable for circuit connection materials.

The reason why the adhesive composition of the present invention exhibits the above-mentioned effects is not clear, but the present inventors speculate as follows. That is, the adhesive composition of the present invention contains a compound having a nitrogen-silicon bond. Since such a nitrogen-silicon bond has a bonding mode similar to that of SiO ₂ or SiN _x , it is considered that the adhesive strength of the adhesive composition of the present invention is far superior to the adhesive strength of the conventional adhesive composition. Furthermore, in the adhesive composition of the present invention, it is considered that the compound having a nitrogen-silicon bond suppresses curing shrinkage at the time of curing, improves the adhesive strength, and exhibits sufficient adhesive strength.

  The film adhesive of this invention forms the adhesive composition of the said invention in a film form. According to this film adhesive, it is easy to handle, can be easily installed on the adherend, and can be easily connected.

  The circuit connection material of the present invention includes a first circuit member in which a first circuit electrode is formed on the main surface of the first circuit board, and a second circuit electrode on the main surface of the second circuit board. A circuit connection material for connecting the formed second circuit member in a state where the first circuit electrode and the second circuit electrode are arranged opposite to each other, wherein the adhesive composition of the present invention is It is characterized by containing. Since this circuit connecting material contains the adhesive composition of the present invention, it has high adhesive strength even for circuit members made of inorganic materials, and is suitable for bonding circuit members. is there.

The circuit member connection structure of the present invention includes a first circuit member in which a first circuit electrode is formed on the main surface of the first circuit board, and a second circuit on the main surface of the second circuit board. A second circuit member on which an electrode is formed; and a first circuit board and a second circuit electrode provided between the main surface of the first circuit board and the main surface of the second circuit board. A circuit connection member for connecting the first and second circuit members in a state of being opposed to each other, and a circuit member connection structure comprising:
A circuit connection member consists of hardened | cured material of the circuit connection material of this invention, and the 1st circuit electrode and the 2nd circuit electrode are electrically connected, It is characterized by the above-mentioned. In this circuit member connection structure, since the circuit connection member is made of a cured product of the circuit connection material of the present invention, the connection resistance is sufficiently reduced, and the reliability of the adhesive strength is excellent.

The method for manufacturing a circuit member connection structure according to the present invention includes a first circuit member in which a first circuit electrode is formed on a main surface of a first circuit board, and a first circuit member on a main surface of a second circuit board. A first circuit electrode and a second circuit electrode provided between the second circuit member on which the second circuit electrode is formed and the main surface of the first circuit board and the main surface of the second circuit board; And a circuit connection member that connects the first and second circuit members in a state of facing each other, and a manufacturing method of a circuit member connection structure comprising:
The circuit connection material of the present invention is disposed between the main surface of the first circuit board and the main surface of the second circuit board, and the circuit connection material is heated and pressurized via the first and second circuit members. Then, a circuit member connection structure is manufactured by connecting the first circuit member and the second circuit member by curing. According to this method for manufacturing a circuit member connection structure, by using the circuit connection material of the present invention, low temperature rapid curing is possible, adverse effects on the circuit member are sufficiently suppressed, and throughput can be improved.

  The adhesive composition of the present invention has sufficient adhesive strength, and is particularly excellent in adhesive strength under conditions of high temperature and high humidity (85 ° C., 85% RH). In addition, the adhesive composition of the present invention exhibits high adhesive strength at least on an adherend composed of an inorganic material such as a metal at the surface, and can be cured at a low temperature.

  Moreover, the circuit connection material using the adhesive composition of the present invention is suitable for bonding circuit members (for example, semiconductor elements and liquid crystal display elements), and the circuit members produced using such circuit connection materials This connection structure has a sufficiently reduced connection resistance and is excellent in reliability of adhesive strength (particularly under high temperature and high humidity conditions). In addition, according to the method for manufacturing a circuit member connection structure using such a circuit connection material, low temperature rapid curing is possible, so that adverse effects on the circuit member are sufficiently suppressed, and throughput can be improved.

  Preferred embodiments of the present invention will be described below with reference to the accompanying drawings as the case may be. In addition, the same code | symbol shall be used for the same element and the overlapping description is abbreviate | omitted. In the following description, (meth) acrylate means acrylate or a corresponding methacrylate.

(Adhesive composition)
The adhesive composition of the present invention contains a radical polymerizable compound, a radical polymerization initiator, and a compound having a nitrogen-silicon bond.

  The radical polymerizable compound is a compound having a functional group that is polymerized by radicals. Examples of the radical polymerizable compound include a (meth) acrylate compound, a maleimide compound, a citraconimide compound, and a nadiimide compound. These may be used alone or in combination of two or more. Moreover, the radically polymerizable compound can be used in any state of a monomer or an oligomer, and a monomer and an oligomer may be mixed and used.

  (Meth) acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, etherene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and trimethylol. Propane tri (meth) acrylate, tetramethylene glycol tetra (meth) acrylate, 2-hydroxy-1,3-diaacryloxypropane, 2,2-bis [4- (acryloxymethoxy) phenyl] propane, 2,2- Bis [4- (acryloxyethoxy) phenyl] propane, dicyclopentenyl (meth) acrylate tricyclodecanyl (meth) acrylate, tris (acryloxyethyl) isocyanurate, urethane (meth) acrylate , And the like isocyanuric acid ethylene oxide-modified diacrylate. These may be used alone or in combination of two or more. A (meth) acrylic resin is obtained by radical polymerization of the (meth) acrylate compound.

  A maleimide compound is a compound having at least one maleimide group. As maleimide compounds, phenylmaleimide, 1-methyl-2,4-bismaleimidebenzene, N, N′-m-phenylenebismaleimide, N, N′-p-phenylenebismaleimide, N, N′-4,4 -Biphenylene bismaleimide, 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-diphenylmethane bismaleimide, N, N′-4,4-diphenylpropane bismaleimide, N, N′-4,4 -Diphenyl ether bismaleimide, N, N'-4,4-diphenylsulfone bismaleimide, 2,2-bis (4- (4-maleimidophenol) Xyl) phenyl) propane, 2,2-bis (3-s-butyl-3,4- (4-maleimidophenoxy) phenyl) propane, 1,1-bis (4- (4-maleimidophenoxy) phenyl) decane, 4,4'-cyclohexylidene-bis (1- (4-maleimidophenoxy) phenoxy) -2-cyclohexylbenzene, 2,2-bis (4- (4-maleimidophenoxy) phenyl) hexafluoropropane . These may be used alone or in combination of two or more.

  A citraconic imide compound is a compound having at least one citraconic imide group. Citraconimide compounds include phenyl citraconimide, 1-methyl-2,4-biscitraconimide benzene, N, N′-m-phenylene biscitraconimide, N, N′-p-phenylene biscitraconimide, N, N '-4,4-biphenylenebiscitraconimide, N, N'-4,4- (3,3-dimethylbiphenylene) biscitraconimide, N, N'-4,4- (3,3-dimethyldiphenylmethane) bis Citraconimide, N, N′-4,4- (3,3-diethyldiphenylmethane) biscitraconimide, N, N′-4,4-diphenylmethanebiscitraconimide, N, N′-4,4-diphenylpropanebis Citraconimide, N, N′-4,4-diphenyl ether biscitraconimide, N, N′-4,4- Phenylsulfone biscitraconimide, 2,2-bis (4- (4-citraconimidophenoxy) phenyl) propane, 2,2-bis (3-s-butyl-3,4- (4-citraconimidophenoxy) phenyl) Propane, 1,1-bis (4- (4-citraconimidophenoxy) phenyl) decane, 4,4′-cyclohexylidene-bis (1- (4-citraconimidophenoxy) phenoxy) -2-cyclohexylbenzene, 2 , 2-bis (4- (4-citraconimidophenoxy) phenyl) hexafluoropropane and the like. These may be used alone or in combination of two or more.

  A nadiimide compound is a compound having at least one nadiimide group. Examples of the nadiimide compound include phenyl nadiimide, 1-methyl-2,4-bisnadiimidebenzene, N, N′-m-phenylenebisnadiimide, N, N′-p-phenylenebisnadiimide, N, N′-4, 4-biphenylenebisnadiimide, N, N′-4,4- (3,3-dimethylbiphenylene) bisnadiimide, N, N′-4,4- (3,3-dimethyldiphenylmethane) bisnadiimide, N, N′-4 , 4- (3,3-diethyldiphenylmethane) bisnadiimide, N, N′-4,4-diphenylmethanebisnadiimide, N, N′-4,4-diphenylpropanebisnadiimide, N, N′-4,4-diphenyl ether Bisnadiimide, N, N′-4,4-diphenylsulfone bisnadiimide, 2,2-bis (4- (4-nadiimidophenol) Xyl) phenyl) propane, 2,2-bis (3-s-butyl-3,4- (4-nadiimidophenoxy) phenyl) propane, 1,1-bis (4- (4-nadiimidophenoxy) phenyl) Decane, 4,4′-cyclohexylidene-bis (1- (4-nadiimidophenoxy) phenoxy) -2-cyclohexylbenzene, 2,2-bis (4- (4-nadiimidophenoxy) phenyl) hexafluoropropane Etc. These may be used alone or in combination of two or more.

［上記式中、ｎは１〜３の整数を示す。］ Furthermore, as the radical polymerizable compound, a radical polymerizable compound having a phosphate ester structure may be used, and a radical polymerizable compound having a phosphate ester structure represented by the following formula (I) is preferable.

[In the above formula, n represents an integer of 1 to 3. ]

  A radically polymerizable compound having a phosphate structure is preferable because it can improve the adhesive force of the adhesive composition to an inorganic substance such as a metal. The amount of the radical polymerizable compound having a phosphate ester structure is preferably from 0.1 to 30 parts by weight, more preferably from 0.5 to 10 parts by weight, based on 100 parts by weight of the solid content of the adhesive composition. 0.5-5 mass parts is the most preferable. The radically polymerizable compound having a phosphoric ester structure is obtained as a reaction product of phosphoric anhydride and 2-hydroxyethyl (meth) acrylate. Specific examples include mono (2-methacryloyloxyethyl) acid phosphate, di (2-methacryloyloxyethyl) acid phosphate (phosphate ester dimethacrylate), and the like. These may be used alone or in combination of two or more.

  As the radical polymerizable compound, it is preferable to use a combination of a (meth) acrylate compound and a radical polymerizable compound having a phosphate ester structure. In the case of such a combination, the adhesive strength of the adhesive composition is further improved as compared with the case where each of the (meth) acrylate compound and the radical polymerizable compound having a phosphate ester structure is used alone.

  The radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by light irradiation and / or heating. As such a radical polymerization initiator, a compound that generates a radical upon irradiation with light of 150 to 750 nm and / or heating at 80 to 200 ° C. is preferable, and specifically, a peroxide, an azo compound, or the like is preferable. These are appropriately selected in consideration of the intended connection temperature, connection time, storage stability, and the like.

  As the peroxide, an organic peroxide is preferable from the viewpoint of high reactivity and storage stability. Organic peroxide having a half-life of 10 hours at a temperature of 40 ° C or higher and a half-life of 1 minute at a temperature of 180 ° C or lower. Organic peroxides having a half-life of 10 hours at a temperature of 50 ° C. or more and a half-life of 1 minute at a temperature of 170 ° C. or less are particularly preferred. When the connection time is 10 seconds or less, the blending amount of the radical polymerization initiator for obtaining a sufficient reaction rate is preferably 0.5 to 20% by mass based on the total solid content of the adhesive composition. 1 to 15% by mass is particularly preferable.

  Specific examples of the organic peroxide include diacyl peroxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, hydroperoxide, silyl peroxide, and the like. Among them, peroxyesters, dialkyl peroxides, hydroperoxides, and silyl peroxides have a chlorine ion or organic acid concentration of 5000 ppm or less in the initiator, and less organic acids are generated after thermal decomposition. Since corrosion of an electrode can be suppressed, it is particularly preferable.

  Diacyl peroxide includes isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide, benzoyl Examples include peroxytoluene and benzoyl peroxide.

  Examples of peroxydicarbonate include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxymethoxyperoxydicarbonate, di ( 2-ethylhexyl peroxy) dicarbonate, dimethoxybutyl peroxydicarbonate, di (3-methyl-3-methoxybutylperoxy) dicarbonate and the like.

  Peroxyesters include cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxynoedecanoate, and t-hexyl. Peroxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2- Ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate Nate, t-butylperoxyisobutyrate, 1,1-bis (t-butylperoxy) cyclohexane, -Hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanonate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoyl par Oxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, t-butylperoxyacetate, and the like.

  Peroxyketals include 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t- Butyl peroxy) -3,3,5-trimethylcyclohexane, 1,1- (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) decane and the like.

  Dialkyl peroxides include α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and t-butyl. Cumyl peroxide and the like.

  Examples of the hydroperoxide include diisopropylbenzene hydroperoxide and cumene hydroperoxide.

  Examples of silyl peroxides include t-butyltrimethylsilyl peroxide, bis (t-butyl) dimethylsilyl peroxide, t-butyltrivinylsilyl peroxide, bis (t-butyl) divinylsilyl peroxide, and tris (t-butyl). Examples thereof include vinylsilyl peroxide, t-butyltriallylsilyl peroxide, bis (t-butyl) diallylsilyl peroxide, and tris (t-butyl) allylsilyl peroxide.

  These radical polymerization initiators can be used singly or in combination of two or more, and may be used by mixing a decomposition accelerator, an inhibitor and the like.

  In addition, those obtained by coating these radical polymerization initiators with a polyurethane-based or polyester-based polymeric substance to form a microcapsule are preferable because the pot life is extended.

  When the adhesive composition is used as a circuit connecting material, the concentration of chlorine ions and organic acids contained in the radical polymerization initiator is 5000 ppm or less in order to suppress corrosion of circuit electrodes of circuit members. It is preferable. Furthermore, a radical polymerization initiator that generates less organic acid after thermal decomposition is more preferable. Moreover, since the stability after hardening of adhesive composition improves, it is preferable to have a mass retention of 20 mass% or more after leaving open for 24 hours at room temperature and normal pressure.

  As the compound having a nitrogen-silicon bond in the molecule, a known compound can be used without particular limitation. The compound having a nitrogen-silicon bond in the molecule is preferably at least one selected from the group consisting of a silazane compound, silylamine, and aminosilane. Of these, silazane compounds are particularly preferred.

As a silazane compound, any of a polymer, an oligomer, and a monomer may be sufficient.
Specific examples of the silazane compound include hexamethyldisilazane, 1,1,3,3-tetramethyl-1,3-divinyldisilazane, tetramethyl-1,3-diphenyldisilazane, 1,1,1. , 3,3,3-hexamethyldisilazane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, heptamethyldisilazane, octamethylcyclotetrasilazane, 1,1,3,3-tetra Methyldisilazane, allyldimethyl (diisopropylamino) silane, trimethylsilylaniline, 1,3-bis (chloromethyl) tetramethyldisilazane, bis (diethylamino) dimethylsilane, bis (dimethylamino) diethylsilane, bis (dimethylamino) dimethyl Silane, bis (dimethylaminodimethylsilyl) ethane, bis (dimethylamino) Diphenylsilane, bis (dimethylamino) methylsilane, bis (dimethylamino) vinylethylsilane, bis (dimethylamino) vinylmethylsilane, bis (ethylamino) dimethylsilane, bis (N-methylbenzamido) ethoxymethylsilane, 1,3 -Bis (3,3,3-trifluoropropyl) tetramethyldisilazane, N-6,9-bis (trimethylsilyl) adenine, N, N'-bis (trimethylsilyl) -1,4-butanediamine, bis (trimethylsilyl) ) Cytosine, N, O-bis (trimethylsilyl) hydroxylamine, n-butyldimethyl (dimethylamino) silane, chloromethylsilatrane, m-chlorophenoxysilatrane, 3-cyanopropyl (diisopropyl) dimethylaminosilane, 3-cyanopropyl Tylcyclosilazane, di-n-butyltetramethyldisilazane, (diethylamino) trimethylsilane, (diisopropylamino) trimethylsilane, (N, N-dimethylamino) dimethylsilane, (N, N-dimethylamino) dimethylchlorosilane, dimethyl Aminomethylethoxysilane, (N, N-dimethylamino) triethylsilane, (N, N-dimethylamino) trimethylsilane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyl-1,1 , 3,3-tetramethyldisilazane, 1,3-dipropyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisilazane, , 1,3,3,5,5-hexamethylcyclotrisilazane, 1,2,3,4,5,6- Oxamethylcyclotrisilazane, hydroxyethoxysilatrane, methacrylamidetrimethylsilane, methacryloxypropylsilatrane, methylsilatrane, methyl-N-trimethylsilylcarbamate, N-methyl-N-trimethylsilyltrifluoroacetamide, nonamethyltrisilazane, n -Octadecyldiisobutyl (dimethylamino) silane, n-octadecyldimethyl (dimethylamino) silane, n-octyldimethyl (dimethylamino) silane, phenylbis (dimethylamino) chlorosilane, phenylmethylbis (dimethylamino) silane, 1,3, 5,7-tetraethyl-2,4,6,8-tetramethylcyclotetrasilazane, tetrakis (diethylamino) silane, tetrakis (dimethylamino) silane, 2,2 , 5,5-tetramethyl-2,5-disila-1-azacyclopentane, 1,1,3,3-tetraphenyldimethyldisilazane, 1,3,5,7-tetravinyl-1,3,5 , 7-tetramethylcyclotetrasilazane, 1,2,3-triethyl-2,4,6-trimethylcyclotrisilazane, tri-n-hexylsilylamine, N- (trimethylsilyl) acetamide, m-trimethylsilylaminophenylacetylene, N- (trimethylsilyl) morpholine, 3-trimethylsilyl-2-oxazolidinone, 1-trimethylsilylpyrrole, 1-trimethylsilyl-1,2,4-triazole, tris (cyclohexylamino) methylsilane, tris (dimethylamino) chlorosilane, tris (dimethylamino) ) Ethylsilane, Tris (Dime Ruamino) methylsilane, tris (dimethylamino) phenylsilane, tris (dimethylamino) silane, 1,3,5-trivinyl-1,3,5-trimethylcyclotrisilazane, (N-vinylformamido) trimethylsilane, vinylsilatrane 1-trimethylsilylpyrrolidone, poly (1,1-dimethylsilazane), poly (1,2-dimethylsilazane) and the like. You may use these individually by 1 type or in mixture of 2 or more types.

  Examples of silylamine include N, N-diethyl-1,1,1-trimethylsilylamine, N, N-diisopropyltrimethylsilylamine, N, O-bis (trimethylsilyl) acetamide, N-6,9-bis (trimethylsilyl) adenine, bis (Trimethylsilyl) cytosine, N, O-bis (trimethylsilyl) hydroxylamine and the like can be mentioned. These may be used alone or in combination of two or more.

  As aminosilane, allylaminotrimethylsilane, allyldimethyl (diisopropylamino) silane, anilinotrimethylsilane, bis (diethylamino) dimethylsilane, bis (dimethylamino) diethylsilane, bis (dimethylamino) dimethylsilane, bis (dimethylamino) Examples include diphenylsilane, bis (dimethylamino) dimethylsilane, bis (dimethylamino) vinylethylsilane, bis (N-methylbenzamido) ethoxymethylsilane, and n-butyldimethyl (dimethylamino) silane. These may be used alone or in combination of two or more.

  Moreover, adhesive composition may contain radical polymerization inhibitors, such as hydroquinone and methyl ether hydroquinone, in the range which does not impair sclerosis | hardenability as needed.

  The adhesive composition may include a thermosetting resin other than the radical polymerizable compound. Examples of such a thermoplastic resin include an epoxy resin. Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, fat Examples thereof include cyclic epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, and aliphatic chain epoxy resins. These epoxy resins may be halogenated or hydrogenated. These epoxy resins may be used alone or in combination of two or more.

  Moreover, what is used as a hardening | curing agent of a normal epoxy resin can be used as a hardening | curing agent of the said epoxy resin. Specific examples include amines, phenols, acid anhydrides, imidazoles, dicyandiamide and the like. Furthermore, tertiary amines and organic phosphorus compounds that are usually used as curing accelerators may be used as appropriate.

  Further, as a method of reacting the epoxy resin, in addition to using the above curing agent, cationic polymerization may be performed using a sulfonium salt, an iodonium salt, or the like.

  The adhesive composition may contain a polymer compound in order to impart film formability, adhesiveness, and stress relaxation during curing. Examples of the polymer compound include polyvinyl butyral resin, polyvinyl formal resin, polyester resin, polyamide resin, polyimide resin, xylene resin, phenoxy resin, polyurethane resin, urea resin, and the like.

  These polymer compounds preferably have a molecular weight of 10,000 to 10,000,000. Further, these polymer compounds may be modified with radically polymerizable functional groups, and in this case, heat resistance is improved. Furthermore, these polymer compounds may contain a carboxyl group. The blending amount of the polymer compound in the adhesive composition is preferably 2 to 80% by mass, more preferably 5 to 70% by mass, and particularly preferably 10 to 60% by mass with respect to the total solid content in the adhesive composition. preferable. When the blending amount of the polymer compound is less than 2% by mass, stress relaxation and adhesive force tend to be insufficient. On the other hand, when it exceeds 80 mass%, it exists in the tendency for fluidity | liquidity to fall.

  You may add a filler, a softening agent, an accelerator, an anti-aging agent, a coloring agent, a flame retardant, and a coupling agent to an adhesive composition suitably.

  In the adhesive composition demonstrated above, it is preferable to contain 0.5-30 mass parts of radical polymerization initiators with respect to 100 mass parts of radically polymerizable compounds, and it is more preferable to contain 1.0-10 mass parts. preferable. When the content of the radical polymerization initiator is less than 0.5 parts by mass, the curing reaction does not proceed sufficiently and the curing tends to be insufficient. On the other hand, when it exceeds 30 mass parts, there exists a tendency for storage stability to fall.

  Moreover, it is preferable to contain 0.1-20 mass parts of compounds which have a nitrogen-silicon bond with respect to 100 mass parts of radically polymerizable compounds, and it is more preferable to contain 0.5-15 mass parts. It is most preferable to contain 5-10 mass parts. When the content of the compound having a nitrogen-silicon bond is less than 0.1 parts by mass, the adhesive force tends to decrease or the adhesive force cannot be improved. On the other hand, when it exceeds 20 mass parts, there exists a tendency for hardened | cured material property to worsen.

  The usage form of the adhesive composition is not particularly limited. For example, a solution in which each of the above components is dissolved and / or dispersed in an organic solvent such as toluene or ethyl acetate, or the solvent is removed from the solution to obtain a predetermined content. It can be used as a molded body (for example, a film-like adhesive described later) formed into a shape of 1.

  FIG. 1 is a cross-sectional view showing an embodiment of a film adhesive. The film adhesive 1 shown in FIG. 1 is formed by forming the above-described adhesive composition into a film. According to this film adhesive, it is easy to handle, can be easily installed on the adherend, and can be easily connected.

  In addition, the film adhesive 1 is good also as a multilayer structure (not shown) which consists of 2 or more types of layers from which Tg (glass transition temperature) when hardening adhesive composition differs 5 degreeC or more.

  The film adhesive 1 is, for example, a temperature at which an adhesive composition is dissolved in a solvent and applied on a support (PET (polyethylene terephthalate) film or the like) using a coating apparatus, and the adhesive composition is not cured. And can be produced by drying with hot air for a predetermined time. Moreover, it is preferable that the thickness of the film adhesive 1 is 10-50 micrometers.

(Circuit member connection structure)
FIG. 2 is a schematic cross-sectional view showing an embodiment of the circuit member connection structure of the present invention. As shown in FIG. 2, the circuit member connection structure of the present embodiment includes a first circuit member 20 and a second circuit member 30 that are opposed to each other. A circuit connection member 10 is provided between the circuit member 30 and the circuit member 30.

  The first circuit member 20 includes a circuit board (first circuit board) 21 and a circuit electrode (first circuit electrode) 22 formed on the main surface 21 a of the circuit board 21. Note that an insulating layer (not shown) may be formed on the main surface 21a of the circuit board 21 in some cases.

  On the other hand, the second circuit member 30 includes a circuit board (second circuit board) 31 and a circuit electrode (second circuit electrode) 32 formed on the main surface 31 a of the circuit board 31. In addition, an insulating layer (not shown) may be formed on the main surface 31a of the circuit board 31 according to circumstances.

The first and second circuit members 20 and 30 are not particularly limited as long as electrodes that require electrical connection are formed. Specific examples include glass or plastic substrates with electrodes formed of ITO or the like used for liquid crystal displays, printed wiring boards, ceramic wiring boards, flexible wiring boards, semiconductor silicon chips, and the like. Used in combination accordingly. As described above, in this embodiment, a material made of an organic substance such as a printed wiring board or polyimide, a metal such as copper or aluminum, ITO (indium tin oxide), silicon nitride (SiN _x ), silicon dioxide (SiO ₂ ). Circuit members having various surface states such as inorganic materials such as the above can be used.

  The circuit connecting member 10 contains an insulating material 11 and conductive particles 7. The conductive particles 7 are disposed not only between the circuit electrode 22 and the circuit electrode 32 facing each other but also between the principal surfaces 21a and 31a. In the circuit member connection structure, the circuit electrodes 22 and 32 are electrically connected via the conductive particles 7. That is, the conductive particles 7 are in direct contact with both the circuit electrodes 22 and 32.

  Here, the conductive particles 7 are not particularly limited as long as they have conductivity capable of obtaining electrical connection, but there are metal particles such as Au, Ag, Ni, Cu, Co, and solder, carbon, and the like. . In addition, non-conductive glass, ceramics, plastics, or the like coated with a conductive material such as the metal can be used. At this time, the thickness of the metal layer to be coated is preferably 10 nm or more in order to obtain sufficient conductivity.

  In this circuit member connection structure, the circuit electrode 22 and the circuit electrode 32 facing each other are electrically connected via the conductive particles 7 as described above. For this reason, the connection resistance between the circuit electrodes 22 and 32 is sufficiently reduced. Therefore, the flow of current between the circuit electrodes 22 and 32 can be made smooth, and the functions of the circuit can be fully exhibited. In addition, when the circuit connection member 10 does not contain the conductive particles 7, the circuit electrode 22 and the circuit electrode 32 are in direct contact with each other to be electrically connected.

  As described later, since the circuit connection member 10 is composed of a cured product of the circuit connection material containing the adhesive composition, the adhesion strength of the circuit connection member 10 to the circuit member 20 or 30 is sufficiently high, In particular, the adhesive strength is sufficiently increased under high temperature and high humidity conditions. In the circuit member connection structure, a sufficiently high adhesive strength is maintained for a long period of time. Therefore, the change with time of the distance between the circuit electrodes 22 and 32 is sufficiently prevented, and the long-term reliability of the electrical characteristics between the circuit electrodes 22 and 32 can be sufficiently increased.

(Method for manufacturing circuit member connection structure)
Next, a method for manufacturing the circuit member connection structure described above will be described.

  First, the first circuit member 20 and the film-like circuit connecting material 40 described above are prepared (see FIG. 3A). The film-like circuit connection material 40 is formed by forming a circuit connection material into a film shape. The circuit connection material contains an adhesive composition 5 and conductive particles 7. Here, the adhesive composition 5 includes the above-described radical polymerizable compound, a radical polymerization initiator that generates radicals by heating, and a compound having a nitrogen-silicon bond. Even when the circuit connecting material does not contain the conductive particles 7, the circuit connecting material can be used for anisotropic conductive bonding as an insulating adhesive, and is sometimes called NCP (Non-Conductive Paste). When the circuit connecting material contains the conductive particles 7, the circuit connecting material may be called ACP (Anisotropic Conductive Paste).

  Moreover, it is preferable that it is 0.1-30 volume% with respect to the whole quantity of a circuit connection material, and, as for content of the electrically-conductive particle 7 in a circuit connection material, it is more preferable that it is 1.0-20 volume%. When the content is less than 0.1% by volume, it tends to be difficult to obtain good conduction. On the other hand, if it exceeds 30% by volume, there is a possibility of causing a short circuit (short circuit) of the adjacent circuit.

  The thickness of the film-like circuit connecting material 40 is preferably 10 to 50 μm. If the thickness of the film-like circuit connecting material 40 is less than 10 μm, the circuit connecting material tends to be insufficiently filled between the circuit electrodes 22 and 32. On the other hand, when it exceeds 50 μm, the adhesive composition between the circuit electrodes 22 and 32 cannot be sufficiently removed, and it is difficult to ensure conduction between the circuit electrodes 22 and 32.

  Next, the film-like circuit connecting material 40 is placed on the surface of the first circuit member 20 on which the circuit electrodes 22 are formed. When the film-like circuit connecting material 40 is attached on a support (not shown), the film-like circuit connecting material 40 side is directed to the first circuit member 20 so that the first circuit is connected. Place on member 20. At this time, the film-like circuit connecting material 40 is film-like and easy to handle. For this reason, the film-like circuit connecting material 40 can be easily interposed between the first circuit member 20 and the second circuit member 30, and the first circuit member 20 and the second circuit member 30 Connection work can be performed easily.

  And the film-form circuit connection material 40 is pressurized to the arrow A and B direction of Fig.3 (a), and the film-form circuit connection material 40 is temporarily connected to the 1st circuit member 20 (refer FIG.3 (b)). . At this time, you may pressurize, heating. However, the heating temperature is a temperature at which the adhesive composition in the film-like circuit connecting material 40 is not cured, that is, a temperature lower than the temperature at which the radical polymerization initiator generates radicals.

  Subsequently, as shown in FIG. 3C, the second circuit member 30 is placed on the film-like circuit connection material 40 so that the second circuit electrode faces the first circuit member 20. In addition, when the film-form circuit connection material 40 has adhered on the support body (not shown), after peeling a support body, the 2nd circuit member 30 is mounted on the film-form circuit connection material 40. FIG.

  And it heats through the 1st and 2nd circuit members 20 and 30 to the arrow A and B direction of FIG.3 (c), heating the film-form circuit connection material 40. FIG. The heating temperature at this time is a temperature at which the radical polymerization initiator can generate radicals. As a result, radicals are generated in the radical polymerization initiator, and polymerization of the radical polymerizable compound is started. In this way, the film-like circuit connecting material 40 is cured, and the main connection is performed, so that a circuit member connection structure as shown in FIG. 2 is obtained.

  The heating temperature is, for example, 90 to 200 ° C., and the connection time is, for example, 1 second to 10 minutes. These conditions are appropriately selected depending on the application to be used, the adhesive composition, and the circuit member, and may be post-cured as necessary. Thus, since the film-form circuit connection material 40 contains the adhesive composition of this invention, it can connect at low temperature rather than the circuit connection material containing an epoxy resin etc.

  When the circuit member connection structure is manufactured as described above, in the circuit member connection structure obtained, the conductive particles 7 can be brought into contact with both of the circuit electrodes 22 and 32 facing each other. The connection resistance between them can be sufficiently reduced.

  In addition, the adhesive composition 5 is cured by the heating of the film-like circuit connecting material 40 in a state where the distance between the circuit electrode 22 and the circuit electrode 32 is sufficiently small, so that the insulating circuit 11 is obtained. The member 20 and the second circuit member 30 are firmly connected via the circuit connection member 10. That is, in the circuit member connection structure obtained, the circuit connection member 10 is made of a cured product of the circuit connection material containing the adhesive composition, so that the circuit connection member 10 is connected to the circuit member 20 or 30. Adhesive strength is sufficiently high, and in particular, the adhesive strength is sufficiently high under high temperature and high humidity conditions. In the circuit member connection structure, a sufficiently high adhesive strength is maintained for a long period of time. Therefore, the obtained circuit member connection structure sufficiently prevents the time-dependent change in the distance between the circuit electrodes 22 and 32 and is excellent in the long-term reliability of the electrical characteristics between the circuit electrodes 22 and 32.

  In the above-described embodiment, the adhesive composition 5 includes at least a radical polymerization initiator that generates radicals upon heating. Instead of this radical polymerization initiator, radicals can be generated only by light irradiation. A generated radical polymerization initiator may be used. In this case, when the film-like circuit connecting material 40 is cured, light irradiation may be performed instead of heating. Moreover, in the said embodiment, although the connection structure of a circuit member is manufactured using the film-form circuit connection material 40, it may replace with the film-form circuit connection material 40, and may use a circuit connection material. Even in this case, if the circuit connection material is dissolved in a solvent and the solution is applied to either the first circuit member 20 or the second circuit member 30 and dried, the first and second circuit members 20 are used. , 30 can interpose a circuit connecting material.

  In addition, in the manufacturing method of the circuit member connection structure, in addition to the radical polymerization initiator that generates radicals by heating or light irradiation, a radical polymerization initiator that generates radicals by ultrasonic waves, electromagnetic waves, or the like is used as necessary. May be.

  Further, instead of the conductive particles 7, other conductive materials may be used. Examples of other conductive materials include particulate or short fiber carbon, metal wires such as Au-plated Ni wire, and the like.

  Hereinafter, the content of the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Example 1
50 g of phenoxy resin (trade name PKHC, manufactured by Union Carbide Co., Ltd., average molecular weight 45,000) in terms of mass ratio is toluene (boiling point 110.6 ° C., SP value 8.90) / ethyl acetate (boiling point 77.1 ° C., SP A value 9.10) = dissolved in a 50/50 mixed solvent to prepare a phenoxy resin solution having a solid content of 40% by mass.

  As the radical polymerizable compound, hydroxyethyl glycol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: 80MFA) and phosphate ester dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: P-2M) were prepared.

  As a silazane compound (compound having a nitrogen-silicon bond), 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasilazane (manufactured by Chisso Corporation) was prepared.

  As a radical polymerization initiator, di-2-ethylhexyl peroxydicarbonate (manufactured by NOF Corporation, trade name Parroyl OPP) was prepared.

  A nickel layer having a thickness of 0.2 μm was provided using nickel as a material on the surface of particles having polystyrene as a core, and a gold layer having a thickness of 0.04 μm was provided outside the nickel layer using gold as a material. In this way, conductive particles having an average particle diameter of 5 μm were produced.

  The prepared materials were blended in a solid content mass ratio as shown in Table 1, and 1.5% by volume of conductive particles were blended and dispersed. The obtained solution was applied to a fluororesin film having a thickness of 80 μm using a coating apparatus, and dried with hot air at 70 ° C. for 10 minutes to obtain a film-like circuit connection material having a thickness of 20 μm. The obtained film-like circuit connecting material showed sufficient flexibility at room temperature.

(Example 2)
A film-like circuit connection having a thickness of 20 μm was performed in the same manner as in Example 1 except that 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisilazane (manufactured by Chisso Corporation) was used as the silazane compound. Obtained material. The obtained film-like circuit connecting material showed sufficient flexibility at room temperature.

(Example 3)
A film-like circuit connection material having a thickness of 20 μm was obtained in the same manner as in Example 1 except that poly (1,2-dimethylsilazane) (manufactured by Chisso Corporation) was used as the silazane compound. The obtained film-like circuit connecting material showed sufficient flexibility at room temperature.

(Comparative Example 1)
A film-like circuit connecting material having a thickness of 20 μm was obtained in the same manner as in Example 1 except that no silazane compound was added. The obtained film-like circuit connecting material showed sufficient flexibility at room temperature.

(Measurement of adhesive strength and connection resistance)
First, a flexible circuit board (FPC board) having 500 copper circuits having a line width of 50 μm, a pitch of 100 μm, and a thickness of 18 μm, and a 0.2 μm indium oxide on a glass substrate (thickness 1.1 mm, surface resistance 20Ω / □) An ITO substrate on which a thin layer of ITO was formed was prepared. The film-like circuit connecting materials of Examples 1 to 3 and Comparative Example 1 are disposed between the FPC substrate and the ITO substrate, and 160 ° C. using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.). Heating and pressing were performed at 3 MPa for 15 seconds. At this time, the FPC board and the ITO board were connected using a film-like circuit connection material having a width of 2 mm, and thus the circuit member connection structure (ITO / FPC connection structure) of Examples 1 to 3 and Comparative Example 1 was produced.

  The resistance value between adjacent circuits of the ITO / FPC connection structures of Examples 1 to 3 and Comparative Example 1 was immediately after bonding and after high temperature and high humidity treatment that was maintained in a high temperature and high humidity bath at 85 ° C. and 85% RH for 240 hours. Measured with a multimeter. The resistance value is shown as an average (x + 3σ) of 150 resistances between adjacent circuits. The obtained results are shown in Table 2.

  Further, the adhesive strengths of the ITO / FPC connection structures of Examples 1 to 3 and Comparative Example 1 were measured and evaluated by a 90-degree peeling method in accordance with JIS-Z0237. Here, Tensilon UTM-4 (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used as a measuring device for adhesive strength. The obtained results are shown in Table 2.

Next, a flexible circuit board (FPC board) having 500 copper circuits having a line width of 50 μm, a pitch of 100 μm, and a thickness of 18 μm, and a thin film of 0.5 μm silicon nitride (SiN _x ) on glass (thickness 0.7 mm). A SiN _x substrate having a layer formed thereon was prepared. The film-like circuit connecting materials of Examples 1 to 3 and Comparative Example 1 are arranged between the FPC substrate and the SiN _x substrate, and using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.). Heating and pressing were performed at 160 ° C. and 3 MPa for 15 seconds. The FPC board and the SiN _x board were connected using a film-like circuit connection material having a width of 2 mm, and the circuit member connection structure (SiN _x / FPC connection structure) of Examples 1 to 3 and Comparative Example 1 was produced.

The adhesive strengths of the SiN _x / FPC connection structures of Examples 1 to 3 and Comparative Example 1 were measured and evaluated using the apparatus and conditions described above by the 90-degree peeling method in accordance with JIS-Z0237. The obtained results are shown in Table 2.

It was confirmed that the film-like circuit connecting materials of Examples 1 to 3 exhibited good connection resistance and adhesive strength immediately after bonding and after high-temperature and high-humidity treatment. On the other hand, in Comparative Example 1 in which the adhesive composition did not contain a silazane compound, the connection resistance showed a high value, and in particular, there was no adhesion at all after the high-temperature and high-humidity treatment in the SiN _x / FPC connection structure. A connection structure having satisfactory performance was not obtained.

It is sectional drawing which shows one Embodiment of the film adhesive of this invention. It is a schematic sectional drawing which shows one Embodiment of the connection structure of the circuit member of this invention. (A)-(c) is a series of process drawings which connect a circuit member, respectively.

Claims (8)

Containing a radical polymerizable compound, a radical polymerization initiator, and a silazane compound ,
The adhesive composition which contains 0.5-20 mass parts of said silazane compounds with respect to 100 mass parts of said radically polymerizable compounds . The adhesive composition according to claim 1 , wherein the radical polymerization initiator generates radicals by light irradiation and / or heating. The adhesive composition according to claim 1 or 2 , comprising 0.5 to 30 parts by mass of the radical polymerization initiator with respect to 100 parts by mass of the radical polymerizable compound. A film adhesive comprising the adhesive composition according to any one of claims 1 to 3 formed into a film. A first circuit member having a first circuit electrode formed on the main surface of the first circuit board, and a second circuit member having a second circuit electrode formed on the main surface of the second circuit board And a circuit connection material for connecting the first circuit electrode and the second circuit electrode in a state of facing each other,
A circuit connection material comprising the adhesive composition according to any one of claims 1 to 3 . The circuit connection material according to claim 5 , further comprising conductive particles and 0.1 to 30% by volume of the conductive particles with respect to the total amount of the circuit connection material. A first circuit member having a first circuit electrode formed on the main surface of the first circuit board;
A second circuit member having a second circuit electrode formed on the main surface of the second circuit board;
The first circuit board is provided between the main surface of the first circuit board and the main surface of the second circuit board, and the first circuit electrode and the second circuit electrode are arranged to face each other. And a circuit connecting member for connecting the second circuit members,
A circuit member connection structure comprising:
The circuit connection member comprises a cured product of the circuit connection material according to claim 5 or 6 ,
The circuit member connection structure, wherein the first circuit electrode and the second circuit electrode are electrically connected. A first circuit member having a first circuit electrode formed on the main surface of the first circuit board;
A second circuit member having a second circuit electrode formed on the main surface of the second circuit board;
The first circuit board is provided between the main surface of the first circuit board and the main surface of the second circuit board, and the first circuit electrode and the second circuit electrode are arranged to face each other. And a circuit connecting member for connecting the second circuit members,
A circuit member connection structure manufacturing method comprising:
The circuit connection material according to claim 5 or 6 is disposed between a main surface of the first circuit board and a main surface of the second circuit board,
A circuit member connection structure by connecting the first circuit member and the second circuit member by heating and pressurizing and curing the circuit connection material through the first and second circuit members. The manufacturing method of the connection structure of the circuit member characterized by manufacturing this.

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