JP6107175B2 - Circuit connection material, circuit member connection structure, and method of manufacturing circuit member connection structure - Google Patents

Description

  The present invention relates to a circuit connection material, a connection structure for circuit members, and a method for manufacturing a connection structure for circuit members.

  Various adhesive materials are used for fixing electronic components and making circuit connections in the fields of semiconductors, liquid crystal displays, and the like.

  For example, circuit connection is more used for the connection between the liquid crystal display and the tape carrier package (TCP), the connection between the flexible printed circuit (FPC) and the TCP, and the connection between the FPC and the printed wiring board. In order to perform reliably, the anisotropic conductive adhesive which disperse | distributed electroconductive particle in the adhesive agent is used (for example, refer patent documents 1-4). Further, even when a semiconductor silicon chip is mounted on a substrate, a so-called chip-on-glass (COG) in which the semiconductor silicon chip is directly mounted on the substrate is used instead of the conventional wire bond. However, anisotropic conductive adhesive is applied.

  As such an anisotropic conductive adhesive, for example, Patent Document 5 discloses a radical polymerizable resin (A), an organic peroxide (B), a thermoplastic elastomer (C), and a predetermined phosphate ester (D). In the anisotropic conductive adhesive containing conductive particles in the adhesive resin composition comprising a predetermined epoxysilane coupling agent (E), a specific urethane acrylate is used as the radical polymerizable resin. A two-way conductive adhesive is described. Further, for example, Patent Document 6 describes an anisotropic conductive adhesive that has an insulating adhesive, conductive particles, and a silane coupling agent and that is conductive in the thickness direction and not conductive in the surface direction. Has been.

JP 59-120436 A JP-A-60-191228 JP-A-1-251787 JP-A-7-90237 Japanese Patent No. 3503740 JP-A-62-62874

  By the way, in recent years, in the field of precision electronic equipment, circuit flexibility has progressed, and a circuit member (for example, a circuit electrode in which a semiconductor silicon chip is formed on a plastic substrate such as polyimide (PI) or polyethylene terephthalate (PET)) Chip-on-plastic (COP) mounting which is directly mounted on a flexible circuit board or the like has begun to be performed. However, the circuit connection materials and the connection conditions used in conventional COG mounting have problems such as short circuit on the flexible circuit board, deformation of the plastic board during thermocompression bonding, lack of adhesive strength to the plastic board, and the like. It was. In order to solve these problems, connection at low temperature (for example, 100 to 160 ° C.), low pressure (for example, 10 to 30 MPa per bump area on the chip), and short time (for example, within 10 seconds), in other words, Thus, there is a need for a circuit connecting material that can be cured at low temperature and low pressure.

  While conventional adhesives for circuit connection using epoxy resin systems can achieve high adhesive strength, it is necessary to use a latent curing agent with high activity for low-temperature rapid curing, and storage stability It was difficult to achieve both. Further, in order to achieve connection at low pressure, it is essential that the resin composition has sufficient fluidity. However, conventional adhesives for circuit connection using epoxy resin systems lack fluidity. It was.

  In addition, as an adhesive material for COP mounting, for example, as disclosed in Patent Document 5 and Patent Document 6, when a material utilizing radical polymerization of an unsaturated compound is applied, although low temperature rapid curing is possible, the resin composition of The fluidity is still insufficient, and connection at a low pressure (for example, 10 to 30 MPa per bump area on the chip) has been extremely difficult.

  The present invention has been made in view of the above-described problems of the prior art, and provides a circuit connection material that can provide a sufficiently low connection resistance even when connected at a low pressure when used to connect circuit members. For the purpose. Another object of the present invention is to provide a circuit member connection structure using the circuit connection material, and a method for manufacturing the circuit member connection structure.

  The present inventors have found that a circuit connecting material containing an acrylic resin having a specific weight average molecular weight as a thermoplastic resin is particularly excellent for electrically connecting a circuit member and an IC chip, The present invention has been completed.

  That is, the present invention provides a first circuit member having a first circuit electrode formed on a substrate and a second circuit member having a second circuit electrode formed on a second substrate. A circuit connection material for adhering one circuit electrode and the second circuit electrode so as to be electrically connected, comprising a thermoplastic resin, a radical polymerizable compound, and a radical polymerization initiator And the circuit connection material whose said thermoplastic resin contains an acrylic resin and whose weight average molecular weight of the said acrylic resin is 1000-5000 is provided.

  The circuit connection material according to the present invention has a sufficiently low connection resistance even when a circuit member and an IC chip are connected at a low pressure, for example, a good connection resistance even after an acceleration test at 85 ° C. and 85% RH. As shown, the connection reliability is excellent. The circuit connecting material according to the present invention exhibits an excellent effect even when one of the circuit members is made of plastic or glass.

  When the weight average molecular weight of the acrylic resin is 1000 to 5000, the circuit connecting material according to the present invention can have both high fluidity and stable connection reliability.

  The acrylic resin preferably has a glass transition temperature of less than 70 ° C. The circuit connection material containing such an acrylic resin has sufficient fluidity to obtain a stable connection resistance even when connected at a low pressure.

  Further, the acrylic resin is preferably a non-functional type having no polar or reactive functional group such as hydroxyl group, carboxyl group, and glycidyl group in the side chain. The circuit connection material containing such an acrylic resin has sufficient fluidity to obtain a stable connection resistance even when connected at a low pressure.

［一般式（１）中、Ｌ^１、Ｌ^２及びＬ^３は、それぞれ独立に、アルコキシ陰イオン、β−ジケトンの共役陰イオン又はβ−ケトエステルの共役陰イオンを示す。Ｌ^１、Ｌ^２及びＬ^３は、同一であっても良く、異なっていてもよい。］ The circuit connection material according to the present invention may further contain an aluminum complex represented by the following general formula (1).

[In General Formula (1), L ¹ , L ² and L ³ each independently represent an alkoxy anion, a conjugated anion of β-diketone, or a conjugated anion of β-ketoester. L ¹ , L ² and L ³ may be the same or different. ]

  By containing the aluminum complex, a further sufficient adhesive strength can be obtained.

  The circuit connection material according to the present invention may further contain a silane coupling agent.

  The silane coupling agent preferably contains at least one alkoxysilyl group and a radical polymerizable double bond in the molecule. Thereby, adhesive force further improves.

  The circuit connection material according to the present invention may further contain conductive particles. By containing conductive particles, the connection reliability between the electrodes to be connected (between circuit electrodes and the like) can be increased, and the connection resistance can be reduced.

  The present invention is formed on one side of a conductive adhesive layer containing a thermoplastic resin, a radical polymerizable compound, a radical polymerization initiator, an aluminum complex, a silane coupling agent, and conductive particles, and a conductive adhesive layer. And a circuit connection material comprising at least an insulating adhesive layer containing a thermoplastic resin, a radical polymerizable compound, a radical polymerization initiator, an aluminum complex, and a silane coupling agent and not containing the conductive particles. To do.

  When a circuit connection material including such a conductive adhesive layer and an insulating adhesive layer is used, handling becomes easy, so that the connection work can be performed more simply.

The circuit connecting material is a glass substrate, a plastic substrate formed from a thermoplastic resin such as polyethylene terephthalate, polycarbonate, polyimide, etc., gold plating as a circuit electrode, ITO (indium tinoxide), SiN _x (silicon nitride). It is particularly excellent for electrically connecting a circuit member on which a coating such as SiO _x (silicon dioxide) is formed and an IC chip or the like. Therefore, for example, it is suitably used for chip mounting such as chip-on-glass mounting or chip-on-plastic mounting.

  In the present invention, the first circuit member having the first circuit electrode formed on the substrate, the second circuit member having the second circuit electrode formed on the second substrate, the first and first A circuit connection member provided between the two circuit members and connecting the first circuit member and the second circuit member in a state where the first circuit electrode and the second circuit electrode are arranged to face each other. Provided is a circuit member connection structure in which the circuit connection member is made of a cured product of a circuit connection material, and the first circuit electrode and the second circuit electrode are electrically connected.

  According to the circuit member connection structure of the present invention, since the circuit connection material is used, the first circuit member and the second circuit member are bonded with high adhesive force, and the connection resistance between the circuit members is low. It is maintained. Therefore, the circuit member connection structure according to the present invention is excellent in connection reliability.

  In the present invention, the circuit is also provided between the first circuit member having the first circuit electrode formed on the substrate and the second circuit member having the second circuit electrode formed on the second substrate. The connecting material is disposed, the first circuit member and the second circuit member are heated and pressurized to cure the circuit connecting material, and the first circuit member and the second circuit member are connected and the first circuit is connected. Provided is a circuit member connection structure manufacturing method for electrically connecting an electrode and a second circuit electrode.

  According to this method for manufacturing a circuit member connection structure, since the circuit connection material is used, when one of the circuit members is formed of a glass substrate or a plastic substrate, the circuit member is particularly connected at a low pressure. A connection structure of circuit members bonded to each other with a sufficiently low connection resistance and a sufficient adhesive force can be obtained.

  According to the circuit connection material of the present invention, when one of the circuit members is used for connection of a circuit member composed of a glass substrate or a plastic substrate, the connection resistance is sufficiently low even when the connection is made at a particularly low pressure, A circuit member having high connection reliability can be obtained.

  Furthermore, the circuit connection material of the present invention is suitable for bonding a circuit member composed of a glass substrate or a plastic substrate and another circuit member (for example, a semiconductor element, a liquid crystal display element, etc.), and a connection resistance and connection. Excellent reliability. In particular, according to the method for manufacturing a circuit member connection structure using this circuit connection material, low temperature and low pressure rapid curing is possible, and thus adverse effects on the circuit member are sufficiently suppressed.

It is a schematic cross section which shows embodiment of a circuit connection material. It is a schematic cross section which shows embodiment of the connection structure of a circuit member. It is a schematic cross section which shows embodiment of the connection structure of a circuit member. (A)-(c) is a series of process drawings which manufacture the connection structure of the circuit member of FIG. (A)-(c) is a series of process drawings which manufacture the connection structure of the circuit member of FIG.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same or equivalent elements are denoted by the same reference numerals, and redundant description is omitted. In the present specification, “(meth) acrylic acid” means acrylic acid and methacrylic acid corresponding thereto, and the same applies to other similar expressions such as (meth) acrylate.

Moreover, in this specification, a weight average molecular weight (Mw) means the value measured using the analytical curve by a standard polystyrene from a gel permeation chromatograph (GPC) according to the conditions shown below.
(Measurement condition)
Device: GPC-8020 manufactured by Tosoh Corporation
Detector: RI-8020 manufactured by Tosoh Corporation
Column: Gelpack GL-A-160-S + GL-A150 manufactured by Hitachi Chemical Co., Ltd.
Sample concentration: 120 mg / 3 mL
Solvent: Tetrahydrofuran Injection volume: 60 μL
Pressure: 30 kgf / cm ²
Flow rate: 1.00 mL / min

Moreover, in this specification, a glass transition temperature (Tg) means the value measured by differential scanning calorimetry (DSC) according to the conditions shown below.
(Measurement condition)
Device: DSC7 manufactured by PerkinElmer
Sample weight: 0.01g
Measurement atmosphere: Under nitrogen atmosphere (flow rate: 50 ml / min)
Temperature range: -80 to 200 ° C
Temperature increase rate: 10 ° C / min
Determination method: The straight line before and after the inflection point of the obtained endothermic curve is extended, and the temperature at which the endothermic curve intersects with a half line between the two extended lines is defined as the glass transition temperature.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of a circuit connecting material. The circuit connection material 1 includes a first circuit member having a first circuit electrode formed on a substrate and a second circuit member having a second circuit electrode formed on a second substrate. A circuit connection material for adhering one circuit electrode and the second circuit electrode so as to be electrically connected, comprising a thermoplastic resin, a radical polymerizable compound, and a radical polymerization initiator And the said thermoplastic resin contains an acrylic resin, and the weight average molecular weight of the said acrylic resin is prescribed | regulated by 1000-5000.

(Thermoplastic resin)
Thermoplastic resins are in a liquid state with high viscosity when heated and are deformed freely by external force. When cooled, the external force is removed to become hard while maintaining its shape, and this process can be repeated (polymer). Say.

(acrylic resin)
In the circuit connection material according to the present embodiment, an acrylic resin defined by a specific weight molecular weight is included as one component of the thermoplastic resin. That is, by including an acrylic resin having a weight average molecular weight of 1000 to 5000 as one component of the thermoplastic resin, the circuit connection material according to the present embodiment can have both high fluidity and connection reliability.

  In addition, although the weight average molecular weight of the said acrylic resin is prescribed | regulated by 1000-5000 from a viewpoint of coexistence of fluidity | liquidity and connection reliability, 1200-4000 is also considered when improving the film formation property of a circuit connection material. More preferred is 1500 to 3000.

  The glass transition temperature (Tg) of the acrylic resin is preferably less than 70 ° C., more preferably less than 30 ° C., and still more preferably less than 0 ° C. from the viewpoint of sufficiently improving the fluidity of the circuit connecting material. Although the minimum of the glass transition temperature (Tg) of an acrylic resin is not specifically limited, For example, it can be -80 degreeC or more.

  Furthermore, the acrylic resin is preferably “non-functional type” having no polar or reactive functional group such as hydroxyl group, carboxyl group, and glycidyl group in the side chain. By including the “non-functional type” acrylic resin, the interaction with other components is suppressed, and as a result, the fluidity of the circuit connecting material can be further improved.

  The content of the acrylic resin in the circuit connecting material is preferably 1% by mass or more and 15% by mass or less, based on the total mass of the thermoplastic resin and the radical polymerizable compound, from the viewpoint of achieving both fluidity and connection reliability. The content is more preferably no less than 12% by mass and no greater than 12% by mass, and still more preferably no less than 4% by mass and no greater than 10% by mass.

  In addition, the acrylic resin which concerns on this embodiment can use the commercial item which has the said characteristic, and may use the synthetic product obtained using well-known synthesis methods, such as radical polymerization.

  The acrylic resin according to this embodiment includes, for example, any one or more of acrylic monomers and oligomers having crosslinkability, other acrylic monomers, and monomers copolymerizable with the acrylic monomers, a radical polymerization initiator, , Can be obtained by radical polymerization.

  Examples of the acrylic monomer and oligomer having crosslinkability include polytetramethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and dimethylol. Di (meth) acrylic acid ester derivatives such as tricyclodecane diacrylate, 2-hydroxy-1-acryloxy-3-methacryloxypropane di (meth) acrylate, polyethylene glycol di (meth) such as ethylene glycol di (meth) acrylate Acrylate, polypropylene glycol di (meth) acrylate such as propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 2,2-bi 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propanedi (meth) acrylate such as [4- (methacryloethoxy) phenyl] propanedi (meth) acrylate, 2,2-hydrogenated bis [4- ( Acryloxypolyethoxy) phenyl] propanedi (meth) acrylate, 2,2-bis [4- (acryloxyethoxypolypropoxy) phenyl] propanedi (meth) acrylate, and the like, and any of these can be used preferably. It is preferable that the side chain does not have a polar or reactive functional group such as a hydroxyl group, a carboxyl group, or a glycidyl group.

  Examples of other acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate-2-ethylhexyl, stearyl (meth) acrylate, ethylene glycol (Meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, (meth) acrylate derivatives such as cyclohexyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylmethanetri ( (Meth) acrylate, tetramethylolpropane tetra (meth) acrylate, diallyl phthalate and its isomers, triallyl isocyanurate and its derivatives, pentaerythritol tri (meth) acrylate, pentaerythris Examples include tall tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate, both of which can be suitably used, but polar or reactive such as hydroxyl group, carboxyl group and glycidyl group at the side chain and terminal. It preferably has no functional group.

  Examples of monomers that can be copolymerized with acrylic monomers include styrene derivatives such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, chloromethylsterene, vinyl chloride, vinyl acetate, vinyl propionate, and the like. Vinyl esters, unsaturated nitriles such as acrylonitrile, and conjugated dienes such as butadiene and isoprene, all of which can be suitably used, such as hydroxyl groups, carboxyl groups, and glycidyl groups at the side chain and terminal. It is preferable not to have a polar or reactive functional group.

(Thermoplastic resin other than acrylic resin)
The circuit connection material according to the present embodiment may contain a thermoplastic resin other than the acrylic resin. Examples of the thermoplastic resin other than the acrylic resin include phenoxy resin, polyurethane resin, polyester urethane resin, butyral resin (for example, polyvinyl butyral resin), polyimide resin, polyamide resin, and a copolymer having a structural unit of vinyl acetate (acetic acid). Vinyl copolymer, such as ethylene-vinyl acetate copolymer). These can be used individually by 1 type or in mixture of 2 or more types. The thermoplastic resin may contain a siloxane bond or a fluorine substituent. These are preferably in a state in which the resins to be mixed are completely compatible with each other, or in a state in which microphase separation occurs and becomes cloudy.

  Further, the glass transition temperature (Tg) of the thermoplastic resin other than the acrylic resin is preferably −30 ° C. or higher and 190 ° C. or lower, and −25 ° C. or higher and 170 ° C. or higher, from the viewpoint of achieving both the fluidity of the circuit connecting material and the connection reliability. More preferably, it is -20 ° C or higher and 150 ° C or lower.

  In addition, when the circuit connection material is used in the form of a film, the larger the Mw of the thermoplastic resin, the easier it is to obtain a good film formability and the influence on the fluidity as a film-like circuit connection material. The melt viscosity can be set in a wide range.

The Mw of the thermoplastic resin other than the acrylic resin according to this embodiment is preferably 5000 or more, more preferably 7000 or more, and still more preferably 10,000 or more. When the Mw of the thermoplastic resin is 5000 or more, good film formability is easily obtained.
The Mw of the thermoplastic resin other than the acrylic resin according to this embodiment is preferably 150,000 or less, more preferably 100,000 or less, and further preferably 80000 or less. When the Mw of the thermoplastic resin is 150,000 or less, good compatibility with other components is easily obtained.

  The amount of the thermoplastic resin other than the acrylic resin according to the present embodiment in the circuit connection material is preferably 5% by mass or more, more preferably 15% by mass or more based on the total mass of the thermoplastic resin and the radical polymerizable compound. preferable. When the blending amount of the thermoplastic resin is 5% by mass or more, when the circuit connection material is formed into a film and used, good film formability is easily obtained. Further, the blending amount of the thermoplastic resin other than the acrylic resin is preferably 80% by mass or less, more preferably 70% by mass or less, based on the total mass of the components other than the conductive particles in the circuit connecting material. When the blending amount of the thermoplastic resin is 80% by mass or less, good fluidity of the adhesive composition is easily obtained.

(Radically polymerizable compound)
The radical polymerizable compound is a substance having a functional group that is polymerized by radicals. Examples of the radical polymerizable compound include (meth) acrylate compounds, maleimide compounds, styrene derivatives, and the like. These can be used individually by 1 type or in mixture of 2 or more types. 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.

  Examples of (meth) acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, tetramethylene glycol di (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) acrylic Over DOO, and isocyanuric acid ethylene oxide-modified diacrylate. These can be used individually by 1 type or in mixture of 2 or more types.

  The maleimide compound is, for example, a compound having at least one maleimide group. Examples of the maleimide compound include 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-male Dophenoxy) 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, etc. It is done. You may use these individually by 1 type or in mixture of 2 or more types.

  A styrene derivative is a compound in which a hydrogen atom in the α-position or aromatic ring of styrene is substituted with a substituent.

  Further, the blending amount of the radical polymerizable compound is preferably 10 to 95% by mass, more preferably 30 to 80% by mass, and 40 to 60% by mass based on the total mass of the thermoplastic resin and the radical polymerizable compound. Further preferred. By setting to the said compounding quantity, there exists a tendency for the circuit connection material which has sufficient heat resistance after hardening and has favorable film formation property to be obtained.

(Radical polymerization initiator)
Examples of the radical polymerization initiator include peroxide compounds and azo compounds that decompose by heating to generate free radicals. These are appropriately selected depending on the intended connection temperature, connection time, storage stability, etc. From the viewpoint of reactivity and storage stability, the 10-hour half-life temperature is 40 ° C. or more and the 1-minute half-life temperature is 180 ° C. An organic peroxide or an azo compound having a temperature of 10 ° C. or less is preferable, and an organic peroxide or an azo compound having a 10-hour half-life temperature of 60 ° C. or more and a 1-minute half-life temperature of 170 ° C. or less is more preferable.

  When the connection time is 10 seconds or less, the blending amount of the radical polymerization initiator is 0.1 when the total mass of the thermoplastic resin and the radical polymerizable compound is 100 parts by mass in order to obtain a sufficient reaction rate. It is preferable to set it as -30 mass parts, and it is more preferable to set it as 0.5-20 mass parts. When the blending amount of the radical polymerization initiator is 0.1 parts by mass or more, it is easy to obtain a circuit connection material having good adhesive strength and low connection resistance while maintaining a sufficient reaction rate. On the other hand, when the blending amount of the radical polymerization initiator is 30 parts by mass or less, it is easy to suppress a decrease in fluidity of the circuit connection material, an increase in connection resistance, and a decrease in storage stability.

  Specific examples of the radical polymerization initiator include diacyl peroxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, hydroperoxide, silyl peroxide, and the like. Moreover, in order to suppress the corrosion of the connection terminal of a circuit member, it is preferable that the chlorine ion and organic acid which are contained in a radical polymerization initiator are 5000 ppm or less. Among these, a peroxy ester, a peroxy ketal, a dialkyl peroxide, a hydroperoxide, or a silyl peroxide is preferable, and a peroxy ester or a peroxy ketal with high reactivity is more preferable. These can be used individually by 1 type or in mixture of 2 or more types.

  Examples of the diacyl peroxide include isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic Peroxide, benzoyl peroxytoluene, benzoyl peroxide, etc. are mentioned.

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

  Examples of peroxyesters include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, and 1-cyclohexyl-1-methylethylperoxyneodecanoate. , T-hexylperoxyneodecanoate, 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, t-butylperoxyisobutyrate, 1,1-bis (t-butylperoxy) cyclohe Sun, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m- Toluoyl peroxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, t-butylperoxyacetate and the like.

  Examples of peroxyketals include 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) decane Etc.

  Examples of the dialkyl peroxide include α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, Examples include t-butyl cumyl peroxide.

  Examples of the hydroperoxide include diisopropylbenzene hydroperoxide and cumene hydroperoxide.

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

  These radical polymerization initiators that generate free radicals upon heating may further 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.

  The circuit connection material according to the present embodiment may further contain an aluminum complex.

  An aluminum complex is a molecule in which a ligand composed of an organic group is bonded to aluminum. The ligand may be a monodentate ligand having a coordination site only in one place, or a multidentate ligand having a coordination site in two or more places. The bond between aluminum and the ligand may be either a hydrogen bond or a coordinate bond. As an organic group, the group comprised from a carbon atom, a hydrogen atom, and an oxygen atom is mentioned, for example, These may further contain the sulfur atom, the nitrogen atom, etc.

［一般式（２）中、Ｌ^１、Ｌ^２及びＬ^３は、それぞれ独立に、アルコキシ陰イオン、β−ジケトンの共役陰イオン又はβ−ケトエステルの共役陰イオンを示す。Ｌ^１、Ｌ^２及びＬ^３は、同一であってもよく、異なっていてもよい。］ The aluminum complex is preferably represented by the following general formula (2).

[In General Formula (2), L ¹ , L ² and L ³ each independently represent an alkoxy anion, a conjugated anion of β-diketone or a conjugated anion of β-ketoester. L ¹ , L ² and L ³ may be the same or different. ]

Specific examples of the aluminum complex represented by the general formula (2) include, for example, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum monoacetyl Examples include acetonate bis (oleyl acetoacetate), diisopropoxy aluminum ethyl acetoacetate, diisopropoxy aluminum alkyl acetoacetate, and the like.
These can be used individually by 1 type or in mixture of 2 or more types.

  The compounding amount of the aluminum complex in the circuit connecting material is not particularly limited. For example, when the total mass of the thermoplastic resin and the radical polymerizable compound is 100 parts by mass, the amount is 0.1 to 20 parts by mass. be able to. Moreover, it is preferable to set it as 0.5-15 mass parts from a viewpoint of hardened | cured material property, and it is more preferable to set it as 1-10 mass parts.

  The circuit connection material according to the present embodiment may further contain a silane coupling agent.

  A silane coupling agent is a compound having an alkoxysilyl group (Si-OR) in its molecule. Although it does not restrict | limit especially as a silane coupling agent, For example, using the compound represented by the following general formula (6)-(8) which has at least 1 alkoxysilyl group (Si-OR) in a molecule | numerator. Can do.

X—R ²¹ —Si (OR ²² ) ₃ (6)
X—R ²¹ —SiR ²³ (OR ²² ) ₂ (7)
X—R ²¹ —Si (R ²³ ) ₂ —OR ²² (8)
[In the formulas (6) to (8), R ²¹ represents an alkylene group having 1 to 6 carbon atoms, and R ²² and R ²³ are each independently a linear or branched group having 1 to 12 carbon atoms. An alkyl group, a cycloalkyl group, a phenyl group or a substituted phenyl group is represented, and X represents a ureido group, a 3,4-epoxycyclohexyl group, a glycidyloxy group, an isocyanate group, a vinyl group, a methacryloyl group, an acryloyl group or a mercapto group. ]

  In addition, it is preferable as X in Formula (6)-(8) to contain group which has radically polymerizable double bonds, such as a (meth) acryloyl group. Thereby, adhesive force further improves.

Specific examples of the silane coupling agent include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. , 3-acryloxypropyltrimethoxysilane and the like.
These can be used individually by 1 type or in mixture of 2 or more types.

  The content of the silane coupling agent in the circuit connecting material is not particularly limited. For example, when the total mass of the thermoplastic resin and the radical polymerizable compound is 100 parts by mass, the content is 0.1 to 30 parts by mass. It can be. Moreover, it is preferable to set it as 1-20 mass parts from a viewpoint of adhesive force, and it is more preferable to set it as 2-10 mass parts.

  The circuit connection material according to the present embodiment may further include conductive particles.

  Examples of the conductive particles include metal particles such as Au, Ag, Ni, Cu, and solder, and conductive materials such as carbon. In order to obtain sufficient storage stability, the surface layer is preferably a noble metal such as Au or Ag, and more preferably Au. Further, the surface of a transition metal such as Ni or Cu may be formed with a noble metal such as Au or Ag. Moreover, what formed the coating layer with the said electroconductive substance on the surface, such as nonelectroconductive glass, a ceramic, a plastics, can also be used, and the coating layer formed with the noble metals is preferable also in this case.

  When conductive particles such as non-conductive plastics coated with a conductive material or hot-melt metal particles are used, these conductive particles are deformed by heating and pressurization. Is preferable because it tends to absorb variations in electrode thickness in the circuit member.

  The thickness of the noble metal coating layer is preferably 10 nm or more from the viewpoint of obtaining good resistance. However, when a noble metal layer is provided on a transition metal such as Ni or Cu, free radicals are generated due to redox action caused by defects in the noble metal layer, etc., and the storage stability tends to be lowered. Therefore, from the viewpoint of preventing this, the thickness of the coating layer is preferably 30 nm or more. In addition, although the upper limit of the thickness of a coating layer is not restrict | limited in particular, Since the effect acquired is saturated, it is preferable to set it as 1 micrometer or less.

  The average particle diameter of the conductive particles can be determined by SEM observation. The average particle size of the conductive particles is preferably 1 to 18 μm from the viewpoint of good dispersibility and conductivity. The blending amount of the conductive particles is preferably 0.1 to 60 parts by volume with respect to 100 parts by volume of the components other than the conductive particles in the circuit connecting material, and can be appropriately adjusted in accordance with the application within this range. preferable. In addition, it is more preferable that the blending amount is 0.1 to 30 parts by volume from the viewpoint of preventing short circuit of an adjacent circuit due to the presence of excessive conductive particles.

(Stabilizer)
In order to further improve the control of the curing rate and the storage stability, a stabilizer can be added to the circuit connecting material according to the present embodiment. As such a stabilizer, known compounds can be used without particular limitation. For example, quinone derivatives such as benzoquinone and hydroquinone, phenol derivatives such as 4-methoxyphenol and 4-t-butylcatechol, 2 Aminoxyl derivatives such as 1,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and hindered amine derivatives such as tetramethylpiperidyl methacrylate. It is done. A stabilizer can be used individually by 1 type or in mixture of 2 or more types.

  The blending amount of the stabilizer is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and more preferably 0.02% by mass or more based on the total mass of components other than the conductive particles in the circuit connecting material. Is more preferable. When the blending amount is 0.005% by mass or more, the curing rate tends to be controlled and the storage stability tends to be improved. The blending amount of the stabilizer is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less based on the total mass of components other than the conductive particles in the circuit connecting material. There exists a tendency for it to be easily compatible with another component as the said compounding quantity is 10 mass% or less.

(Other ingredients)
The circuit connection material according to the present embodiment may further contain a filler, a softening agent, an anti-aging agent, a flame retardant, a pigment, a thixotropic agent, a phenol resin, a melamine resin, isocyanates, and the like.

(One form of circuit connection material)
The circuit connection material according to the present embodiment can be used by being formed into a film shape, and may have a multilayer structure (not shown) composed of two or more layers. For example, a two-layer film type circuit connecting material includes a conductive adhesive layer containing conductive particles, and an insulating insulating adhesive layer formed on one side of the conductive adhesive layer, and conductive adhesive Both the agent layer and the insulating adhesive layer contain a thermoplastic resin, a radical polymerizable compound, a radical polymerization initiator, an aluminum complex, and a silane coupling agent. The thermoplastic resin, radical polymerizable compound, radical polymerization initiator, aluminum complex, and silane coupling agent contained in the conductive adhesive layer and the insulating adhesive layer may be the same or different. Good. In addition, the acrylic resin prescribed | regulated by this invention should just be contained in at least one layer, and is not specifically limited.

  When the circuit connection material according to the present embodiment is a film having a multilayer structure, for example, after each layer is manufactured separately, the multilayer film type circuit connection material can be manufactured by bonding the layers. For example, in the case of a two-layer film circuit connection material comprising a conductive adhesive layer containing conductive particles and an insulating insulating adhesive layer formed on one side of the conductive adhesive layer, The composition of the adhesive layer component dissolved in a solvent is applied onto a support (PET (polyethylene terephthalate) film, etc.) using a coating device, and dried with hot air for a predetermined time at a temperature at which the composition does not cure. By doing so, a conductive adhesive layer can be produced. Similarly, an insulating adhesive layer can be produced. Next, a two-layer film type circuit connection material can be produced by bonding the conductive adhesive layer and the insulating adhesive layer using, for example, a hot roll laminator. Moreover, the thickness of a conductive adhesive layer can be 1-10 micrometers, for example, and the thickness of an insulating adhesive layer can be 5-40 micrometers, for example, 2 layer film type circuit connection The thickness of the whole material can be 6-50 micrometers, for example.

(Circuit member connection structure)
FIG. 2 is a schematic cross-sectional view showing an embodiment of a circuit member connection structure. As shown in FIG. 2, the circuit member connection structure of the present embodiment includes a first circuit member 20 composed of a substrate 21 and a second circuit member 30 composed of a substrate 31 facing each other. A circuit connection member 10 is provided between the first circuit member 20 and the second circuit member 30 to connect them.

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

The first circuit member 20 is not particularly limited as long as an electrode that requires electrical connection is formed, for example. Specifically, a circuit member composed of a substrate on which electrodes are formed of ITO used in a liquid crystal display can be used. This substrate is formed of, for example, plastics such as polyimide (PI) resin, polyethylene terephthalate (PET) resin, polycarbonate (PC) resin, methacrylic resin, and cyclic olefin resin in addition to glass. In this embodiment, at least a part of the surface is formed of a material made of a metal such as gold, copper, or aluminum or an inorganic material such as ITO (indium tinoxide), silicon nitride (SiN _x ), or silicon dioxide (SiO ₂ ). Circuit members having a wide variety of surface states can be used.

  On the other hand, the second circuit member 30 includes a substrate (second substrate) 31 and a circuit electrode (second circuit electrode) 32 formed on the main surface 31 a of the substrate 31. In addition, an insulating layer (not shown) may be formed on the main surface 31a of the substrate 31 in some cases. The second circuit member 30 is not particularly limited as long as an electrode that requires electrical connection is formed. Specific examples include an IC chip. The second substrate may be a plastic substrate.

  The circuit connecting member 10 contains an insulating material 11 and conductive particles 7. The electroconductive particle 7 is arrange | positioned not only between the circuit electrode 22 and the circuit electrode 32 which oppose but between the main surface 21a and the main surface 31a. In the circuit member connection structure, the circuit electrode 22 and the circuit electrode 32 are electrically connected via the conductive particles 7.

  In the 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 electrode 22 and the circuit electrode 32 is sufficiently reduced. Therefore, the flow of current between the circuit electrode 22 and the circuit electrode 32 can be made smooth, and the functions of the circuit can be fully exhibited.

  FIG. 3 is a schematic cross-sectional view showing another embodiment of the circuit member connection structure. The circuit member connection structure shown in FIG. 3 is the same as the circuit member connection structure according to the above-described embodiment, except that the circuit connection member 10 does not contain the conductive particles 7. In the circuit member connection structure shown in FIG. 3, the circuit electrode 22 and the circuit electrode 32 are electrically connected without interposing conductive particles.

  As will be described later, since the circuit connecting member 10 is made of a cured product of the circuit connecting material, the first circuit member 20 made of the substrate 21 and the second circuit member 30 made of the substrate 31 are used. The circuit connection member 10 has a sufficiently high adhesive strength. In addition, stable adhesive strength can be obtained even in a high temperature and high humidity environment. Moreover, 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 electrode 22 and the circuit electrode 32 is sufficiently prevented, and the long-term reliability of the electrical characteristics between the circuit electrode 22 and the circuit electrode 32 can be sufficiently enhanced.

  Moreover, the circuit connection member 10 may be comprised with the hardened | cured material of the circuit connection material of the above-mentioned multilayer film structure. For example, it has at least a conductive adhesive layer containing conductive particles and an insulating insulating adhesive layer formed on one side of the conductive adhesive layer, and the conductive adhesive layer and the insulating adhesive Any of the layers may be composed of a cured product of a circuit connection material including at least a thermoplastic resin, a radical polymerizable compound, a radical polymerization initiator, an aluminum complex, and a silane coupling agent. In this case, the height of at least one of the first circuit electrode 22 and the second circuit electrode 32 is 3.0 μm or less, and the conductive adhesive layer in the circuit connection material 1 has a height of It is preferable to arrange on the circuit electrode side which is 3.0 μm or less.

(Method for manufacturing circuit member connection structure)
Next, the manufacturing method of the connection structure of the circuit member mentioned above is demonstrated. 4 and 5 are a series of process diagrams for manufacturing a circuit member connection structure.

  First, the first circuit member 20 and the circuit connection material 40 described above are prepared (see FIGS. 4A and 5A). The circuit connecting material 40 may contain the component 5 other than the conductive particles and the conductive particle 7 or may contain only the component 5 other than the conductive particles.

  The thickness of the circuit connection material 40 is preferably 10 to 50 μm. If the thickness of the circuit connection material 40 is less than 10 μm, the adhesive composition tends to be insufficiently filled between the circuit electrode 22 and the circuit electrode 32. On the other hand, when the thickness exceeds 50 μm, the circuit connection material between the circuit electrode 22 and the circuit electrode 32 cannot be sufficiently removed, and there is a tendency that it is difficult to ensure conduction between the circuit electrode 22 and the circuit electrode 32.

  Next, the circuit connection material 40 is placed on the surface of the first circuit member 20 on which the circuit electrode 22 is formed. When the circuit connection material 40 is attached on a support (not shown), the circuit connection material 40 side is directed to the first circuit member 20 so that the circuit connection material 40 is placed on the first circuit member 20. Put it on. At this time, since the circuit connection material 40 is in the form of a film, it is easy to handle, and the circuit connection material 40 can be easily interposed between the first circuit member 20 and the second circuit member 30. Connection work between the first circuit member 20 and the second circuit member 30 can be easily performed.

  Then, the circuit connection material 40 is pressurized in the directions of arrows A and B in FIGS. 4A and 5A to temporarily connect the circuit connection material 40 to the first circuit member 20 (FIG. 4B). And FIG. 5 (b)). At this time, you may pressurize, heating. However, the heating temperature is lower than the temperature at which the radical polymerization initiator in the circuit connecting material 40 generates radicals.

  Subsequently, as shown in FIG. 4C and FIG. 5C, the second circuit member 30 is set so that the second circuit electrode 32 faces the first circuit member 20 (that is, the first circuit member 20 The circuit electrode 22 and the second circuit electrode 32 are placed on the circuit connection material 40). In addition, when the 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 circuit connection material 40. FIG.

  Then, while heating the circuit connection material 40, pressure is applied through the first circuit member 20 and the second circuit member 30 in the directions of arrows A and B in FIGS. 4C and 5C. 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 circuit connection material 40 is cured and the main connection is performed, so that a circuit member connection structure as shown in FIGS. 2 and 3 is obtained.

  The heating temperature is, for example, 90 to 200 ° C., the pressurizing pressure is, for example, 5 to 80 MPa, and the connection time is, for example, 1 second to 10 minutes. These conditions are appropriately selected depending on the adhesive composition and the circuit member, and may be post-cured as necessary. For example, as in this embodiment, when using a radical polymerizable compound and a radical polymerization initiator, the heating temperature is set to 100 to 160 ° C., the pressurizing pressure is set to 10 to 30 MPa, and the connection time is set to 10 seconds or less. It can also be cured at low temperature and low pressure.

  According to the manufacture of the circuit member connection structure, the connection resistance between the circuit electrode 22 and the circuit electrode 32 can be sufficiently reduced in the circuit member connection structure obtained.

  In addition, by heating the circuit connecting material 40, the component 5 other than the conductive particles is cured and becomes the insulating substance 11 in a state where the distance between the circuit electrode 22 and the circuit electrode 32 is sufficiently small. The member 20 and the second circuit member 30 are firmly connected via the circuit connection member 10. That is, in the obtained circuit member connection structure, since the circuit connection member 10 is composed of a cured product of the circuit connection material containing the adhesive composition, the first circuit member 20 or the second circuit member is formed. The adhesive strength of the circuit connecting member 10 to the circuit member 30 is sufficiently high, and particularly the adhesive strength is sufficiently high under high temperature and high humidity conditions. Moreover, in the circuit member connection structure, a sufficiently high adhesive strength is maintained for a long period of time. Therefore, the obtained connection structure of the circuit members is sufficiently prevented from changing with time in the distance between the circuit electrode 22 and the circuit electrode 32, and is excellent in long-term reliability of the electrical characteristics between the circuit electrode 22 and the circuit electrode 32.

  In the above embodiment, the circuit connection material 40 includes at least a radical polymerization initiator that generates radicals by heating. Instead of this radical polymerization initiator, radicals are generated only by light irradiation. A radical polymerization initiator may be used. In this case, when the circuit connection material 40 is cured, light irradiation may be performed instead of heating. In addition, a radical polymerization initiator that generates radicals by ultrasonic waves, electromagnetic waves, or the like may be used as necessary. Moreover, you may use an epoxy resin and a latent hardener as a sclerosing | hardenable component.

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

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

(Synthesis Example 1: Synthesis of acrylic resin AR-1)
A flask equipped with a stirrer, a thermometer, a cooler, and a dropping funnel was charged with 1 kg of isopropyl alcohol (hereinafter, IPA) and heated to 70 ° C. Separately, 335 g of nonanediol diacrylate (manufactured by Sigma-Aldrich), 210 g of n-butyl acrylate (manufactured by Sigma-Aldrich), 4 g of azobisisobutyronitrile (hereinafter referred to as AIBN, manufactured by Sigma-Aldrich), and 400 g of IPA A mixed solution was prepared, and polymerization was carried out by continuously dropping into the flask over 5 hours from the dropping funnel. After completion of the dropwise addition, 4 g of AIBN was further added and aged at 80 ° C. for 4 hours.
After completion of the polymerization, volatile components such as unreacted monomers and solvents were removed from the reaction solution under reduced pressure to obtain liquid AR-1. The weight average molecular weight of AR-1 was 1600, and the glass transition temperature was -70 ° C.

(Synthesis Example 2: Synthesis of acrylic resin AR-2)
A flask equipped with a stirrer, thermometer, cooler and dropping funnel was charged with 1 kg of IPA and heated to 70 ° C. Separately, a mixed solution consisting of 420 g of dicyclopentenyloxyethyl methacrylate (manufactured by Sigma-Aldrich), 210 g of n-butyl acrylate (manufactured by Sigma-Aldrich), 4 g of AIBN, and 400 g of IPA was prepared. Polymerization was carried out by continuously dropping into the inside. After completion of the dropwise addition, 4 g of AIBN was further added and aged at 80 ° C. for 4 hours.
After completion of the polymerization, volatile components such as unreacted monomers and solvents were removed from the reaction solution under reduced pressure to obtain liquid AR-2. AR-2 had a weight average molecular weight of 1700 and a glass transition temperature of -51 ° C.

(Synthesis Example 3: Synthesis of acrylic resin AR-3)
A flask equipped with a stirrer, thermometer, cooler and dropping funnel was charged with 1 kg of IPA and heated to 70 ° C. Separately, a mixed solution consisting of 800 g of n-butyl acrylate (manufactured by Sigma-Aldrich), 4 g of AIBN, and 400 g of IPA was prepared, and polymerization was carried out by continuously dropping into the flask over 5 hours from the dropping funnel. After completion of the dropwise addition, 4 g of AIBN was further added and aged at 80 ° C. for 4 hours.
After completion of the polymerization, volatile components such as unreacted monomers and solvents were removed from the reaction solution under reduced pressure to obtain liquid AR-3. AR-3 had a weight average molecular weight of 1800 and a glass transition temperature of -70 ° C.

(Synthesis Example 4: Synthesis of urethane acrylate UA-1)
Polycaprolactone diol (aliphatic polyester diol, trade name: Plaxel 220EB, Daicel) having a number average molecular weight of 2000 in a reaction vessel equipped with a stirrer, thermometer, reflux condenser equipped with a calcium chloride drying tube, and nitrogen gas introduction tube Chemical Industry Co., Ltd.) 2000 parts by mass (1.00 mol) and dibutyltin dilaurate (Sigma Aldrich) 5.53 parts by mass were added. After sufficiently introducing nitrogen gas, the mixture was heated to 70 to 75 ° C., and 688 parts by mass (3.10 mol) of isophorone diisocyanate (aliphatic isocyanate, Sigma-Aldrich) was added dropwise uniformly over 3 hours. Reacted. The reaction was continued for about 10 hours after the completion of the dropping. To this, 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Sigma-Aldrich) and 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Sigma-Aldrich) were added, and the reaction was further continued for 10 hours. It was confirmed by measurement that the isocyanate had disappeared, and the reaction was terminated to obtain urethane acrylate (UA-1). The obtained urethane acrylate had a weight average molecular weight of 10,000. The obtained UA-1 was dissolved in methyl ethyl ketone so as to have a solid content of 40% by mass.

(Synthesis Example 5: Synthesis of polyester urethane resin PEU-1)
Digalbonic acid as terephthalic acid (Sigma-Aldrich), diol as propylene glycol (Sigma-Aldrich) and neopentyl glycol (Sigma-Aldrich), diisocyanate as 4,4'-diphenylmethane diisocyanate (Sigma-Aldrich) Made).
(Procedure 1: Synthesis of polyester polyol)
First, terephthalic acid / propylene glycol / neopentyl glycol is mixed to a mass ratio of 59/21/3, and a stainless steel with a heater equipped with a stirrer, thermometer, condenser, vacuum generator, and nitrogen gas introduction pipe It put into the autoclave made. Further, antimony trioxide was added as a catalyst in a ratio of 0.003 mol with respect to 100 mol of terephthalic acid, and choline hydroxide as a surfactant was added in a ratio of 4 mol with respect to 100 mol of terephthalic acid. Subsequently, it heated up to 250 degreeC over 2.5 hours under 0.35 MPa nitrogen pressure, and stirred at 250 degreeC for 1 hour. Thereafter, the pressure was reduced to 4.0 × 10 ⁻³ MPa / min to atmospheric pressure (0.1 MPa), and the mixture was stirred at 250 ° C. for 3 hours. After cooling to 25 ° C., a white precipitate was taken out, washed with water, and vacuum dried to obtain a polyester polyol.
(Procedure 2: Synthesis of polyester urethane PEU-1)
The polyester polyol obtained in Procedure 1 was sufficiently dried and then dissolved in toluene, and charged into a four-necked flask equipped with a stirrer, a dropping funnel, a reflux condenser, and a nitrogen gas inlet tube. Dibutyltin laurate was added as a catalyst at a ratio of 0.02 parts by mass with respect to 100 parts by mass of the polyester polyol. On the other hand, 4,4′-diphenylmethane diisocyanate was prepared to be 17 parts by mass with respect to 59 parts by mass of terephthalic acid, dissolved in toluene, and charged into the dropping funnel. After the inside of the reaction system was replaced with dry nitrogen, heating was started, and when refluxing started, half of the 4,4′-diphenylmethane diisocyanate solution in the dropping funnel was added all at once and stirred vigorously. The remaining half of the solution was added dropwise over 3 hours, and the mixture was further stirred for 1 hour after the addition. The precipitate obtained by cooling to 25 ° C. was dissolved in dimethylformamide, methanol equal to dimethylformamide was added, and the mixture was left overnight in a refrigerator (5 ° C.). After standing, the obtained precipitate was taken out and vacuum-dried to obtain PEU-1. The obtained polyester urethane resin had a weight average molecular weight of 45,000 and a glass transition temperature of 106 ° C. The obtained polyester urethane resin was dissolved in a 1: 1 solvent of methyl ethyl ketone and toluene so as to have a solid content of 32% by mass.

(YP-70: Preparation of phenoxy resin)
As a thermoplastic resin, a phenoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., trade name: YP-70) dissolved in methyl ethyl ketone so as to have a solid content of 40% by mass was prepared.
(M313: Preparation of urethane acrylate)
A polyfunctional urethane acrylate (manufactured by Toa Gosei Co., Ltd., trade name: M313) dissolved in methyl ethyl ketone so as to have a solid content of 80% by mass was prepared as a radical polymerizable compound.
(INI: Preparation of dilauroyl peroxide)
As a radical polymerization initiator, dilauroyl peroxide (manufactured by Wako Pure Chemical Industries, Ltd., symbol: INI) dissolved in toluene so as to have a solid content of 20% by mass was prepared.
(AC-1: Preparation of aluminum complex)
As an aluminum complex, bis (ethylacetoacetate) (2,4-pentanedionato) aluminum (made by Wako Pure Chemical Industries, Ltd., symbol: AC-1) dissolved in methyl ethyl ketone so as to have a solid content of 80% by mass is prepared. did.
(SC-1: Preparation of silane coupling agent)
As a silane coupling agent, 3-methacryloxypropyltrimethoxysilane (manufactured by Wako Pure Chemical Industries, Ltd., symbol: SC-1) was prepared.
(CP-1: Preparation of conductive particles)
Conductive particles having an average particle diameter of 3 μm and a specific gravity of 2.5, in which a nickel layer having a thickness of 0.2 μm is provided on the surface of particles having polystyrene as a core, and a gold layer having a thickness of 0.02 μm is provided outside the nickel layer. (Symbol: CP-1) was prepared and prepared.

(Production of circuit connection material)
Examples 1-10 which mix | blend each component with the compounding ratio shown in Table 1, apply | coat to a 40-micrometer-thick PET resin film using a coating apparatus, and are 20 micrometers in thickness by 70 degreeC and hot air drying for 5 minutes. And the circuit connection material of Comparative Examples 1 and 2 was obtained.

表１中、導電性粒子を除き、各数値は質量部（ただし、溶液に関しては固形分換算）を表す。導電性粒子の数値は、導電性粒子以外の各成分の合計１００体積部に対する体積部を表す。

In Table 1, except for the conductive particles, each numerical value represents part by mass (however, in terms of solution, solid content conversion). The numerical value of electroconductive particle represents the volume part with respect to a total of 100 volume parts of each component other than electroconductive particle.

(Evaluation of connection resistance)
The circuit connection materials of Examples 1 to 10 and Comparative Examples 1 and 2 are: (A) Glass substrate (outer dimensions 38 mm × 28 mm, thickness 0.5 mm, surface ITO (indium tinoxide) wiring pattern (pattern width 50 μm, pitch 50 μm) )), (B) polyimide (PI) substrate (external dimensions 38 mm × 28 mm, thickness 0.125 mm, surface having ITO wiring pattern (pattern width 50 μm, pitch 50 μm)), or (C) polyethylene terephthalate Transfer from a PET resin film in a size of 2 mm x 20 mm to a (PET) substrate (outer dimensions 38 mm x 28 mm, thickness 0.125 mm, with a gold (Au) wiring pattern on the surface (pattern width 50 µm, pitch 50 µm)) did. An IC chip (outside 1.7 mm × 17.2 mm, thickness 0.55 mm, bump size 50 μm × 50 μm, bump pitch 50 μm, bump height 15 μm) is 30 MPa (bumps) at 140 ° C. for 5 seconds. It was mounted by heating and pressing with a load of area conversion. The resistance value between adjacent circuits of the obtained connection structure (average value among 14 terminals measured) was measured using a multimeter. In addition, the above resistance value is immediately after connection (indicated as “before test” in Table 2) and after a high temperature and high humidity test (85 ° C., 85% RH) for 48 hours (in Table 2, “after test”). Measured).

  Immediately after the connection (before the high-temperature and high-humidity test), the resistance values when using the circuit connection materials of Examples 1 to 10 were sufficiently lower and better than those of Comparative Examples 1 and 2. In addition, after the high temperature and high humidity test, the resistance value is sufficiently lower than those of Comparative Examples 1 and 2, and the connection structure of the circuit member using the circuit connection material of Examples 1 to 10 has good connection reliability. showed that.

(Production of circuit connection material: two-layer film type circuit connection material)
(Preparation of conductive adhesive layer)
In the blending ratio shown in Table 3, a thermoplastic resin, a radical polymerizable compound, a radical polymerization initiator, an aluminum complex, a silane coupling agent, and conductive particles are blended, and a coating apparatus is used for a PET resin film having a thickness of 40 μm. A conductive adhesive layer having a thickness of 6 μm was produced by hot air drying at 70 ° C. for 5 minutes.
(Preparation of insulating adhesive layer)
In a blending ratio shown in Table 4, a thermoplastic resin, a radical polymerizable compound, a radical polymerization initiator, an aluminum complex, and a silane coupling agent are blended and applied to a PET resin film having a thickness of 40 μm using a coating apparatus. An insulating adhesive layer having a thickness of 14 μm was produced by hot air drying at 70 ° C. for 5 minutes.
(Production of two-layer film type circuit connection material)
The said conductive adhesive layer and the said insulating adhesive layer were bonded together using the hot roll laminator, and the 2 layer film type circuit connection material shown in Examples 11-16 and Comparative Examples 3 and 4 was obtained.

表３、４中、導電性粒子を除き、各数値は質量部（ただし、溶液に関しては固形分換算）を表す。導電性粒子の数値は、導電性粒子以外の各成分の合計１００体積部に対する体積部を表す。

In Tables 3 and 4, with the exception of conductive particles, each numerical value represents part by mass (however, solid content conversion for the solution). The numerical value of electroconductive particle represents the volume part with respect to a total of 100 volume parts of each component other than electroconductive particle.

(Evaluation of connection resistance)
The two-layer film type circuit connecting materials of Examples 11 to 16 and Comparative Examples 3 and 4 were used as follows: (A) Glass substrate (outer dimensions 38 mm × 28 mm, thickness 0.5 mm, ITO (indium tinoxide) wiring pattern (pattern width) (B) polyimide (PI) substrate (outer dimensions 38 mm × 28 mm, thickness 0.125 mm, ITO wiring pattern on the surface (pattern width 50 μm, pitch 50 μm)), or ( C) Polyethylene terephthalate (PET) substrate (outer dimensions 38 mm × 28 mm, thickness 0.125 mm, having a gold (Au) wiring pattern on the surface (pattern width 50 μm, pitch 50 μm) in a size of 2 mm × 20 mm, Place the conductive adhesive layer in contact with each substrate and transfer it from the PET resin film. . An IC chip (outside 1.7 mm × 17.2 mm, thickness 0.55 mm, bump size 50 μm × 50 μm, bump pitch 50 μm, bump height 15 μm) is 30 MPa (bumps) at 140 ° C. for 5 seconds. It was mounted by heating and pressing with a load of area conversion. The resistance value between adjacent circuits of the obtained connection structure (average value among 14 terminals measured) was measured using a multimeter. In addition, the above resistance values are obtained immediately after connection (indicated as “before test” in Table 5) and after a high temperature and high humidity test (85 ° C., 85% RH) for 48 hours (in Table 5, “after test”). Measured).

  Immediately after connection (before the high-temperature and high-humidity test), the resistance values when using the circuit connection materials of Examples 11 to 16 were sufficiently low and good compared to Comparative Examples 3 and 4. Further, after the high temperature and high humidity test, the resistance value is sufficiently lower than those of Comparative Examples 3 and 4, and the connection structure of the circuit connection member using the circuit connection material of Examples 11 to 16 has good connection reliability. Showed sex.

DESCRIPTION OF SYMBOLS 1,40 ... Circuit connection material, 5 ... Component other than electroconductive particle, 7 ... Conductive particle, 10 ... Circuit connection member, 11 ... Insulative substance, 20 ... First circuit member, 21 ... Substrate (first Substrate), 21a ... main surface, 22 ... circuit electrode (first circuit electrode), 30 ... second circuit member, 31 ... substrate (second substrate), 31a ... main surface, 32 ... circuit electrode (second) Circuit electrode).

Claims (9)

A first circuit member having a first circuit electrode formed on a substrate; and a second circuit member having a second circuit electrode formed on a second substrate. A circuit connection material for adhering so as to be electrically connected to a second circuit electrode, comprising a thermoplastic resin, a radical polymerizable compound, and a radical polymerization initiator, the thermoplastic resin There comprises an acrylic resin, the weight average molecular weight of acrylic resin Ri der 1000-5000, the glass transition temperature of the acrylic resin is less than 30 ° C., the circuit connecting material. A first circuit member having a first circuit electrode formed on a substrate; and a second circuit member having a second circuit electrode formed on a second substrate. A circuit connection material for adhering so as to be electrically connected to a second circuit electrode, comprising a thermoplastic resin, a radical polymerizable compound, and a radical polymerization initiator, the thermoplastic resin Is a circuit connection material , comprising an acrylic resin , wherein the acrylic resin has a weight average molecular weight of 1000 to 5000, and the acrylic resin is a non-functional type . A first circuit member having a first circuit electrode formed on a substrate; and a second circuit member having a second circuit electrode formed on a second substrate. A circuit connection material for adhering so as to be electrically connected to a second circuit electrode, wherein a thermoplastic resin, a radical polymerizable compound, a radical polymerization initiator, and the following general formula (1) The circuit connection material which contains the aluminum complex represented , the said thermoplastic resin contains an acrylic resin, and the weight average molecular weight of the said acrylic resin is 1000-5000.

[In General Formula (1), L ¹ , L ² and L ³ each independently represent an alkoxy anion, a conjugated anion of β-diketone, or a conjugated anion of β-ketoester. L ¹ , L ² and L ³ may be the same or different. ] A first circuit member having a first circuit electrode formed on a substrate; and a second circuit member having a second circuit electrode formed on a second substrate. a second circuit electrode is a circuit connecting material for bonding so as to be electrically connected, containing a thermoplastic resin, a radically polymerizable compound, a radical polymerization initiator, and a silane coupling agent And the circuit connection material whose said thermoplastic resin contains an acrylic resin and whose weight average molecular weight of the said acrylic resin is 1000-5000. The circuit connecting material according to claim 4 , wherein the silane coupling agent has at least one alkoxysilyl group and a radical polymerizable double bond in the molecule. Conductive particles further comprising a circuit connecting material according to any one of claims 1-5. The circuit connection material according to any one of claims 1 to 6 , which is used for chip mounting. A first circuit member having a first circuit electrode formed on a first substrate;
A second circuit member having a second circuit electrode formed on the second substrate;
The first circuit member and the second circuit member are connected in a state where the first circuit electrode and the second circuit electrode are arranged to face each other, provided between the first and second circuit members. A circuit connecting member,
A circuit in which the circuit connection member is made of a cured product of the circuit connection material according to any one of claims 1 to 7 , and the first circuit electrode and the second circuit electrode are electrically connected to each other. Member connection structure. The first of the first circuit member and the claims 1-7 between the second circuit member having a second circuit electrode formed on a second substrate on which the first circuit electrode formed on a substrate The circuit connection material according to any one of the above is disposed, and the circuit connection material is heated and pressed to cure through the first circuit member and the second circuit member, and the first circuit member and A method for manufacturing a connection structure for a circuit member, wherein the second circuit member is connected and the first circuit electrode and the second circuit electrode are electrically connected.

Images