WO2013154203A1 - Matériau de connexion de circuit, structure de connexion et leur procédé de fabrication - Google Patents

Matériau de connexion de circuit, structure de connexion et leur procédé de fabrication Download PDF

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Publication number
WO2013154203A1
WO2013154203A1 PCT/JP2013/061216 JP2013061216W WO2013154203A1 WO 2013154203 A1 WO2013154203 A1 WO 2013154203A1 JP 2013061216 W JP2013061216 W JP 2013061216W WO 2013154203 A1 WO2013154203 A1 WO 2013154203A1
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Prior art keywords
circuit
connection
substrate
electrode
circuit member
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PCT/JP2013/061216
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English (en)
Japanese (ja)
Inventor
孝 中澤
竹村　賢三
Original Assignee
日立化成株式会社
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Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to KR1020147024584A priority Critical patent/KR102044574B1/ko
Priority to CN201380008376.0A priority patent/CN104093799B/zh
Priority to JP2014510223A priority patent/JP6107816B2/ja
Publication of WO2013154203A1 publication Critical patent/WO2013154203A1/fr

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0221—Insulating particles having an electrically conductive coating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/36—Assembling printed circuits with other printed circuits
    • H05K3/361—Assembling flexible printed circuits with other printed circuits

Definitions

  • the present invention relates to a circuit connection material that is interposed between circuit electrodes facing each other, pressurizes the circuit electrodes facing each other, and electrically connects the electrodes in the pressing direction, and a connection structure using the circuit connection material And a manufacturing method thereof.
  • thermosetting resin using an epoxy resin having high adhesiveness and high reliability As a circuit connection material for a semiconductor element or a liquid crystal display element, a thermosetting resin using an epoxy resin having high adhesiveness and high reliability is known (for example, see Patent Document 1).
  • a curing agent such as an epoxy resin, a phenol resin having reactivity with the epoxy resin, and a latent curing agent that accelerates the reaction between the epoxy resin and the curing agent are generally used.
  • the latent curing agent is an important factor for determining the curing temperature and the curing rate, and various compounds are used from the viewpoint of storage stability at room temperature and curing rate during heating.
  • (meth) acrylate derivative a radical curable adhesive using an acrylate derivative and / or a methacrylate derivative (hereinafter collectively referred to as “(meth) acrylate derivative”) and a peroxide as a radical polymerization initiator has attracted attention.
  • Radical curing can be cured in a short time because radicals that are reactive species are rich in reactivity (see, for example, Patent Documents 2 and 3).
  • circuit connection materials have been studied as alternative members of connectors from the viewpoint that the modules can be thinned. Since the connection pitch of circuit members in such a small module is coarser than the connection pitch (for example, 0.4 mm or less) of circuit members to which circuit connection materials have been conventionally applied, circuit connection materials have characteristics different from conventional ones. Required.
  • a circuit connection material used as an alternative member for a connector is required to have a higher adhesive force because the length of the connection portion is shorter than that of conventional fields (for semiconductor element use, liquid crystal display element use, etc.).
  • an adhesive force of 6 N / cm or more is usually required, but an adhesive force of 12 N / cm or more is required as an alternative member for a connector. There is a case.
  • connection with rough pitch for example, connection pitch of 0.5 mm or more
  • connection pitch for example, connection pitch of 0.5 mm or more
  • the adhesive force tends to decrease even when the same circuit connection material is used as compared with the connection with fine pitch. This is presumably because the adhesive force in the shearing direction generated at the interface between the electrode wall and the circuit connecting material decreases as the number of electrodes per unit length decreases.
  • the present invention provides a circuit connection material that can obtain a sufficiently high adhesive force even in rough pitch connection and has excellent connection reliability, a connection structure using the circuit connection material, and a method of manufacturing the same. Objective.
  • the present inventors have expressed a specific chain transfer agent in a specific amount, thereby exhibiting high adhesive force even in rough pitch connection, and good connection reliability.
  • the present inventors have found that the circuit connection material shown can be obtained and have completed the present invention.
  • the present invention provides a first circuit member in which a first circuit electrode is formed on a main surface of a first substrate, and a second circuit member in which a second circuit electrode is formed on a main surface of a second substrate.
  • a circuit connection material for connecting the first circuit electrode and the second circuit electrode in a state of facing each other comprising a radical polymerization initiator, a radical polymerizable substance, and a thiol And a thiol compound in which the number of hydrogen atoms bonded to the carbon atom to which the thiol group is bonded is 1 or 0, and the content of the thiol compound is 100 parts by mass of the radical polymerizable substance
  • a circuit connecting material having 7 to 17 parts by mass is provided.
  • Such a circuit connecting material can provide a sufficiently high adhesive force even in rough pitch connection. Further, a circuit connection material used as an alternative member of a connector is required to have a good connection reliability for a connection structure connected using the circuit connection material. According to the circuit connection material according to the present invention, a sufficiently high adhesive force in a rough pitch connection and good connection reliability can be achieved at the same time. Furthermore, according to the circuit connecting material according to the present invention, since the thiol compound functions as a chain transfer agent, the curing speed is high, the low temperature and short time connection can be realized, and the adhesion to an inorganic material such as a metal is improved. It is possible to effectively obtain an effect such as.
  • the thiol compound preferably has a molecular weight of 400 or more.
  • Such a circuit connection material has a higher adhesive force in connection with rough pitch, and more excellent connection reliability.
  • the first circuit member (or the second circuit member) is 0.5 mm or more on the main surface of the first substrate (or the second substrate). It is preferable to have a region where the first circuit electrode (or the second substrate) is formed at a connection pitch. Since the circuit connection material of the present invention can obtain a sufficiently high adhesive force even in rough pitch connection, it can be suitably used for the connection of circuit members as described above.
  • the present invention also includes a first circuit member having a first circuit electrode formed on the main surface of the first substrate, and a second circuit electrode formed on the main surface of the second substrate.
  • a second circuit member disposed so that the second circuit electrode and the first circuit electrode face each other; and provided between the first circuit member and the second circuit member,
  • An adhesive layer that electrically connects the one circuit member and the second circuit member, and the adhesive layer connects the circuit connection material between the first circuit member and the second circuit member.
  • a connection structure formed by being interposed and heated and pressed.
  • connection structure uses the circuit connection material according to the present invention, the first circuit member and the second circuit member are bonded with high adhesive force. Further, the first circuit member and the second circuit member are connected with good connection reliability. Therefore, the connection structure according to the present invention is excellent in durability, heat resistance, and moisture resistance.
  • the present invention further includes a first circuit member having a first circuit electrode formed on a main surface of a first substrate, and a second circuit member having a second circuit electrode formed on a main surface of a second substrate.
  • the circuit member and the circuit connection material are heated and pressurized in a state where the first circuit electrode and the second circuit electrode are arranged to face each other with the circuit connection material interposed therebetween.
  • a method for manufacturing a connection structure is provided, which includes a step of electrically connecting the first circuit electrode and the second circuit electrode. According to such a manufacturing method, the connection structure according to the present invention can be easily obtained.
  • a sufficiently high adhesive force can be obtained even in rough pitch connection, and a circuit connection material excellent in connection reliability, a connection structure using the circuit connection material, and a method of manufacturing the same are provided. .
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of a connection structure according to the present invention.
  • the circuit connection material includes a radical polymerization initiator, a radical polymerizable substance, a thiol having a thiol group, and the number of hydrogen atoms bonded to the carbon atom to which the thiol group is bonded is 1 or 0. And a compound.
  • the content of the thiol compound is 7 to 17 parts by mass with respect to 100 parts by mass of the radical polymerizable substance.
  • the circuit connection material according to the present embodiment includes a first circuit member in which a first circuit electrode is formed on the main surface of the first substrate, and a second circuit electrode on the main surface of the second substrate. It can be suitably used as 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 to face each other.
  • the circuit connection material according to the present embodiment can obtain a sufficiently high adhesive force in rough pitch connection. Moreover, according to the circuit connection material which concerns on this embodiment, even when it uses for the connection of rough pitch, the connection structure which has favorable connection reliability is obtained. Therefore, the circuit connection material according to the present embodiment can be particularly suitably used for connection of circuit members having a rough pitch (connection pitch of 0.5 mm or more).
  • the radical polymerization initiator is a compound that generates free radicals, and can also be called a free radical generator.
  • a compound that decomposes by heating such as a peroxide compound or an azo compound, to generate a free radical is suitable.
  • the radical polymerization initiator is appropriately selected depending on the intended connection temperature, connection time, and the like.
  • the content of the radical polymerization initiator in the circuit connecting material is preferably 0.05 to 10% by mass, and more preferably 0.1 to 5% by mass.
  • radical polymerization initiator examples include diacyl peroxides, peroxydicarbonates, peroxyesters, peroxyketals, dialkyl peroxides, hydroperoxides and the like.
  • Diacyl peroxides include 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide, benzoyl peroxide And benzoyl peroxide.
  • Peroxydicarbonates include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethoxymethoxyperoxydicarbonate, di- (2-Ethylhexylperoxy) dicarbonate, dimethoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutylperoxy) dicarbonate and the like.
  • Peroxyesters include 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxynoedecanoate, t-hexylperoxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy Isobutyrate, 1,1-bis (t-butylperoxy) cyclohexane, t-hexylperoxyisopropy
  • Peroxyketals include 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t -Butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) decane and the like.
  • Dialkyl peroxides include ⁇ , ⁇ '-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t- Examples thereof include butyl cumyl peroxide.
  • hydroperoxides examples include diisopropylbenzene hydroperoxide and cumene hydroperoxide.
  • radical polymerization initiators can be used alone or in combination, and may be used in combination with a decomposition accelerator, an inhibitor and the like.
  • those obtained by coating these radical polymerization initiators with a polyurethane-based or polyester-based polymer substance and making them into microcapsules are preferable because the storage stability is extended.
  • the radical polymerizable substance is a compound having a radical polymerizable functional group.
  • a vinyl group, an acryloyl group, a methacryloyl group, or the like is preferable. Of these, compounds having an acryloyl group and / or a methacryloyl group are more preferred.
  • a compound described later can be used in either a monomer or oligomer state, and the monomer and oligomer can be used in combination.
  • radical polymerizable substance examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, 2-hydroxy-1,3-di ( (Meth) acryloxypropane, 2,2-bis [4-((meth) acryloxymethoxy) phenyl] propane, 2,2-bis [4-((meth) acryloxypolyethoxy) phenyl] propane, dicyclopentenyl (Meth) acrylate, tricyclodecanyl (meth) acrylate, tris ((meth) acryloyloxyethyl) isocyanurate, urethane (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, isocyanuric acid EO (ethylene oxy) De) modified diacrylate, 2-methacryloyl
  • the radical polymerizable substance preferably has at least one partial structure selected from the group consisting of a dicyclopentane skeleton, a tricyclodecane skeleton, and a triazine ring.
  • the radical polymerizable substance includes polystyrene, polyethylene, polyvinyl butyral, polyvinyl formal, polyimide, polyamide, polyester, polyvinyl chloride, polyphenylene oxide, urea resin, melamine resin, phenol resin, xylene resin, epoxy resin, polyisocyanate resin.
  • a polymer such as phenoxy resin can also be used.
  • the polymer used as the radical polymerizable substance has at least one radical polymerizable functional group in the molecule.
  • a polymer as a radical polymerizable substance because it is easy to handle and excellent in stress relaxation during curing, and is more preferable when the polymer has a functional group such as a hydroxyl group because adhesion is improved. What modified each polymer with the radically polymerizable functional group is more preferable.
  • the weight average molecular weight of these polymers is preferably 1.0 ⁇ 10 4 or more, and more preferably 1.0 ⁇ 10 4 or more and 1.0 ⁇ 10 6 or less from the viewpoint of mixing properties.
  • the weight average molecular weight defined in the present application refers to a value measured using a standard polystyrene calibration curve by gel permeation chromatography (GPC) according to the following conditions.
  • the thiol compound is a compound having a thiol group and having 0 or 1 hydrogen atoms bonded to the carbon atom to which the thiol group is bonded.
  • thiol compounds include aromatic thiols and secondary thiol compounds.
  • An aromatic thiol is a compound having a thiol group bonded to an aromatic ring, and examples of the aromatic thiol include allylbenzene thiol sulfonate, benzene thiol, o-ethoxybenzene thiol, p-ethoxybenzene thiol, 2-benzimidazole thiol, o-Mercaptobenzoic acid, o-mercaptobenzoic acid methyl ester, 2-benzothiazolethiol, mercaptobenzoxazole, naphthalenethiol, toluenethiol, thiobisbenzenethiol, p-methoxy-toluenethiol and the like.
  • the secondary thiol compound is a compound having a secondary thiol group.
  • Examples of the secondary thiol compound include secondary butanethiol, 2,3-butanedithiol, hexa-5-ene-3-thiol, and secondary dodecane.
  • Secondary thiol compounds have higher reactivity as chain transfer agents than alcohols, and are practically superior.
  • the content of the thiol compound in the circuit connecting material is preferably 7 to 17 parts by mass and more preferably 9 to 12 parts by mass with respect to 100 parts by mass of the radical polymerizable substance. If the content of the radical polymerizable substance is small, it is difficult to obtain the effect of high adhesive strength in rough pitch connection, and if the content of the radical polymerizable substance is large, the crosslinking density is lowered, and the resistance of the circuit connecting material is reliable. It tends to get worse.
  • the molecular weight of the thiol compound is preferably 90 or more, more preferably 150 or more, and further preferably 400 or more.
  • the molecular weight of the thiol compound is preferably 5000 or less, more preferably 2000 or less, and further preferably 1000 or less.
  • the molecular weight is less than 90, the boiling point of the compound reaches the boiling point due to heating at the time of connection, and the compound tends to evaporate, so that a sufficient amount of thiol compound cannot contribute to the reaction.
  • the molecular weight is larger than 5000, the resin exclusion property tends to deteriorate and the connection resistance tends to increase.
  • the molecular weight of the thiol compound is 400 or more.
  • the molecular weight is less than 400, when blending materials or handling products, the odor is strong and the workability and handling tend to decrease.
  • the molecular weight is 400 or more, the odor is suppressed and there is no problem in workability and handling.
  • the thiol equivalent of the thiol compound is preferably 50 or more and 500 or less, and more preferably 120 or more and 400 or less.
  • the thiol equivalent is less than 50, the crosslinking density is lowered, and the resistance reliability in the circuit connecting material tends to be lowered.
  • the thiol equivalent is 500 or less, the adhesive force tends to be further improved.
  • the circuit connection material according to the present embodiment may be composed only of a radical polymerization initiator, a radical polymerizable substance, and a thiol compound, but may further contain the following components as necessary. .
  • the circuit connection material according to the present embodiment can further contain a compound having one or more aminoxyl structures in the molecule.
  • the circuit connecting material contains a compound having an aminoxyl structure, the storage stability of the circuit connecting material can be further improved.
  • the circuit connection material according to the present embodiment can further contain a thermoplastic resin.
  • a thermoplastic resin polyvinyl butyral resin, polyvinyl formal resin, polyamide resin, polyester resin, phenol resin, epoxy resin, phenoxy resin, polystyrene resin, xylene resin, polyurethane resin, polyester urethane resin and the like can be used.
  • the weight average molecular weight of these thermoplastic resins is preferably from the viewpoint of film formability is 1.0 ⁇ 10 4 or more, mixing the viewpoint from 1.0 ⁇ 10 4 or more 1.0 ⁇ 10 than 6 More preferably.
  • the weight average molecular weight of the thermoplastic resin is measured in the same manner as the polymerization average molecular weight of the polymer that can be contained in the radical polymerizable substance.
  • thermoplastic resin a hydroxyl group-containing resin (for example, phenoxy resin) having a Tg (glass transition temperature) of 40 ° C. or higher and a weight average molecular weight of 1.0 ⁇ 10 4 or higher can be preferably used.
  • the hydroxyl group-containing resin may be modified with an epoxy group-containing elastomer or a radical polymerizable functional group. Those modified with a radically polymerizable functional group are preferred because the heat resistance is improved.
  • the phenoxy resin can be obtained by reacting a bifunctional phenol and epihalohydrin to a high molecular weight or by polyaddition reaction of a bifunctional epoxy resin and a bifunctional phenol.
  • thermoplastic resin It is also preferable to use a polyester urethane resin as the thermoplastic resin.
  • a polyester urethane resin By containing a polyester urethane resin, the adhesive force in rough pitch connection tends to be further improved.
  • circuit connection material includes fillers, softeners, accelerators, anti-aging agents, colorants, flame retardants, thixotropic agents, coupling agents, phenol resins, melamine resins, isocyanates, and the like. Can also be contained.
  • a compound having at least one of a vinyl group, an acrylic group, an amino group, an epoxy group, or an isocyanate group is preferable from the viewpoint of improving adhesiveness.
  • a filler since an improvement in connection reliability and the like can be obtained.
  • the filler those having a maximum diameter smaller than the particle diameter of the conductive particles described later can be used.
  • the filler content is preferably in the range of 5 to 60% by volume based on the total volume of the circuit connecting material. If it is 60% by volume or more, the effect of improving the reliability is saturated.
  • the circuit connection material according to the present embodiment can obtain a connection by direct contact of circuit electrodes facing each other at the time of connection without containing conductive particles, but is more stable when further containing conductive particles. Connection can be obtained.
  • the conductive particles include metal particles such as Au, Ag, Ni, Cu, and solder, and carbon.
  • the surface of a transition metal such as Ni may be coated with a noble metal such as Au.
  • the surface layer is preferably made of Au, Ag, or a platinum group noble metal, and more preferably Au, rather than transition metals such as Ni and Cu.
  • a conductive layer was formed on the surface of the non-conductive particles by a method such as coating the surface of the non-conductive particles such as glass, ceramic, plastic, etc. with the above-mentioned conductive material, and the outermost layer was composed of noble metals. In the case of particles or hot-melt metal particles, since they are deformable by heating and pressing, the contact area with the electrode is increased at the time of connection, and the reliability is improved.
  • the blending amount of the conductive particles is appropriately set depending on the application, but is usually in the range of 0.1 to 30 parts by volume with respect to 100 parts by volume of the resin component in the circuit connecting material. In order to prevent an adjacent circuit from being short-circuited by excessive conductive particles, the amount is more preferably 0.1 to 10 parts by volume.
  • circuit connection material is divided into two or more layers and separated into a layer containing a curing agent and a layer containing conductive particles, an improvement in pot life can be obtained.
  • circuit connecting material according to the present embodiment may appropriately contain a polymerization inhibitor such as hydroquinone or methyl ether hydroquinone as necessary.
  • connection structure and the manufacturing method thereof according to this embodiment will be described.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of a connection structure.
  • a connection structure 1 shown in FIG. 1 includes a first circuit member 20 having a first circuit board 21 and a first circuit electrode (first connection terminal) 22 formed on a main surface 21a thereof, A second circuit member 30 having a second circuit board 31 and a second circuit electrode (second connection terminal) 32 formed on the main surface 31a thereof; the first circuit member 20; An adhesive layer 10 is provided between the circuit member 30 and the circuit member 30 to bond them together.
  • the second circuit member 30 is disposed to face the first circuit member 20 so that the second circuit electrode 32 faces the first circuit electrode 22.
  • the adhesive layer 10 is formed by interposing the circuit connecting material between the first circuit member 20 and the second circuit member 30 and pressing in that state.
  • the adhesive layer 10 is formed using a circuit connecting material containing conductive particles is shown.
  • the adhesive layer 10 is dispersed in the insulating layer 11 and the insulating layer 11. It is comprised from the electroconductive particle 7 which is carrying out.
  • the insulating layer 11 is a cured body that is derived from components other than the conductive particles in the adhesive and is formed by radical polymerization of a radical polymerizable substance.
  • the first circuit electrode 22 and the second circuit electrode 32 facing each other are electrically connected through the conductive particles 7.
  • the first circuit electrodes 22 and the second circuit electrodes 32 formed on the same circuit board are insulated from each other.
  • connection pitch of the first circuit electrode 22 and / or the second circuit electrode 32 may be 0.4 mm or more, and may be 0.45 mm or more.
  • the upper limit of the connection pitch of the first circuit electrode 22 and / or the second circuit electrode 32 is not particularly limited, but may be, for example, 1.0 mm or less, or 0.9 mm or less.
  • At least a part of the first circuit electrode 22 and / or the second circuit electrode 32 is a connection pitch (rough pitch) of 0.5 mm or more. (That is, the first circuit member 20 and / or the second circuit member 30 is formed with the first circuit electrode 22 and / or the second circuit electrode 32 at a connection pitch of 0.5 mm or more. It is preferred that the
  • the first circuit electrode 22 and the second circuit electrode 32 are, for example, partly or entirely formed so that L / S (Line / Space) is 4/6 to 9/1.
  • L / S may be 5/5 to 9/1. That is, the first circuit member 20 and / or the second circuit member 30 has the first circuit electrode 22 and / or the second circuit electrode 32 so that L / S is 4/6 to 9/1. It may have a formed region. Further, from the viewpoint of facilitating better conduction, the connection structure 1 has a sum of L / S of the first circuit electrode 22 and L / S of the second circuit electrode 32 of 5/5. It is preferable to have a region of 1/9.
  • Examples of the first circuit board 31 and the second circuit board 21 include chip parts such as semiconductor chips, resistor chips, and capacitor chips, and boards such as printed boards.
  • the circuit member is provided with a large number of connection terminals, but the number of connection terminals may be one in some cases.
  • a substrate made of an inorganic material such as a semiconductor, glass or ceramic, a plastic substrate, or a glass / epoxy substrate is used.
  • the plastic substrate include a polyimide film, a polycarbonate film, and a polyester film.
  • the first circuit electrode and the second circuit electrode are formed from a metal such as copper.
  • at least one surface of the first circuit electrode and the second circuit electrode is made of a metal selected from the group consisting of gold, silver, tin, and platinum.
  • the surface layer is selected from gold, silver, platinum group, or tin, and these may be used in combination.
  • one of the first circuit member 20 and the second circuit member 30 may be a liquid crystal display panel having a glass substrate or a plastic substrate as a circuit substrate and having connection terminals formed from ITO or the like.
  • one of the first circuit member 20 and the second circuit member 30 is a flexible printed wiring board (FPC), a tape carrier package (TCP) or a chip-on-film (COF) having a polyimide film as a circuit board, or It may be a semiconductor silicon chip having a semiconductor substrate as a circuit board.
  • FPC flexible printed wiring board
  • TCP tape carrier package
  • COF chip-on-film
  • the connection structure 1 includes, for example, the first circuit member 20, the film-like circuit connection material, and the second circuit member 30, in which the first connection terminal 22 and the second connection terminal 32 are relative to each other. In this state, they are formed by pressurizing or further heating.
  • the pressure is not particularly limited as long as it does not damage the adherend, but it is generally preferably 0.1 to 10 MPa.
  • the heating temperature is not particularly limited but is preferably 100 to 200 ° C. These pressurization and heating are preferably performed in the range of 0.5 to 100 seconds, and can be bonded by heating at 130 to 180 ° C., 3 MPa, and 10 seconds.
  • Example 1 Polyester urethane resin (UR-8200, manufactured by Toyobo Co., Ltd., 30% solution) as a thermoplastic resin is dissolved in methyl ethyl ketone by dissolving 40 parts by mass in terms of non-volatile content and polyurethane resin (T-6075N, manufactured by DIC Bayer Polymer Co., Ltd.). 10 parts by mass of the 15% by mass solution obtained in terms of non-volatile content, and 20% by mass solution obtained by dissolving ethylene-vinyl acetate copolymer (EV40W, Mitsui DuPont Polychemical Co., Ltd.) in toluene.
  • UR-8200 manufactured by Toyobo Co., Ltd., 30% solution
  • T-6075N manufactured by DIC Bayer Polymer Co., Ltd.
  • the compounding amount of the compound having a secondary thiol group is 10.5 parts by mass with respect to 100 parts by mass of the radical polymerizable substance (herein, UA5500, DCP-A, M-215 and P-2M). It is.
  • Example 2 A circuit connection material was obtained in the same manner as in Example 1 except that the amount of thiol A (molecular weight 567.7) was 3 parts by mass.
  • the compounding amount of the compound having a secondary thiol group with respect to 100 parts by mass of the radical polymerizable substance here, UA5500, DCP-A, M-215 and P-2M
  • UA5500, DCP-A, M-215 and P-2M is 7.89 parts by mass. It is.
  • Example 3 A circuit connecting material was obtained in the same manner as in Example 1 except that the amount of thiol A (molecular weight 567.7) was 6 parts by mass.
  • the compounding amount of the compound having a secondary thiol group is 15.8 parts by mass with respect to 100 parts by mass of the radical polymerizable substance (here, UA5500, DCP-A, M-215 and P-2M). It is.
  • Example 4 The blending amount of polyester urethane resin (UR8240) is 34 parts by mass in terms of nonvolatile content, the blending amount of dicyclopentadiene diacrylate (DCP-A) is 8 parts by mass, isocyanuric acid EO modified diacrylate (manufactured by Toagosei Co., Ltd., A circuit connecting material was obtained in the same manner as in Example 1 except that the amount of M-215) was 8 parts by mass.
  • the compounding amount of the compound having a secondary thiol group with respect to 100 parts by mass of the radical polymerizable substance herein, UA5500, DCP-A, M-215 and P-2M is 9.09 parts by mass. It is.
  • Example 5 A circuit connecting material was obtained in the same manner as in Example 1 except that 3 parts by mass of thiol B (molecular weight: 544.77) was used instead of thiol A.
  • the compounding amount of the compound having a secondary thiol group with respect to 100 parts by mass of the radical polymerizable substance herein, UA5500, DCP-A, M-215 and P-2M is 7.89 parts by mass. It is.
  • Example 6 A circuit connecting material was obtained in the same manner as in Example 1 except that 6 parts by mass of thiol B (molecular weight: 544.77) was used instead of thiol A.
  • the compounding amount of the compound having a secondary thiol group is 15.8 parts by mass with respect to 100 parts by mass of the radical polymerizable substance (herein, UA5500, DCP-A, M-215 and P-2M). It is.
  • Comparative Example 1 A circuit connecting material was obtained in the same manner as in Example 1 except that the amount of thiol A (molecular weight 567.7) was 2 parts by mass.
  • the compounding amount of the compound having a secondary thiol group is 5.26 parts by mass with respect to 100 parts by mass of the radical polymerizable substance (herein, UA5500, DCP-A, M-215 and P-2M). It is.
  • Comparative Example 2 A circuit connection material was obtained in the same manner as in Example 1 except that the amount of thiol A (molecular weight 567.7) was 8 parts by mass.
  • the compounding amount of the compound having a secondary thiol group is 21.1 parts by mass with respect to 100 parts by mass of the radically polymerizable substance (here, UA5500, DCP-A, M-215 and P-2M). It is.
  • Comparative Example 3 A circuit connecting material was obtained in the same manner as in Example 4 except that the amount of thiol A (molecular weight 567.7) was 2 parts by mass.
  • the compounding amount of the compound having a secondary thiol group with respect to 100 parts by mass of the radical polymerizable substance herein, UA5500, DCP-A, M-215 and P-2M is 4.55 parts by mass. It is.
  • Comparative Example 5 A circuit connecting material was obtained in the same manner as in Example 4 except that 8 parts by mass of thiol B (molecular weight: 544.77) was used instead of thiol A.
  • the compounding amount of the compound having a secondary thiol group with respect to 100 parts by mass of the radical polymerizable substance (referred to here as UA5500, DCP-A, M-215 and P-2M) is 18.2 parts by mass. It is.
  • Comparative Example 6 A circuit connection material was obtained in the same manner as in Example 1 except that 2 parts by mass of thiol B (molecular weight: 544.77) was used instead of thiol A.
  • the compounding amount of the compound having a secondary thiol group is 5.26 parts by mass with respect to 100 parts by mass of the radical polymerizable substance (herein, UA5500, DCP-A, M-215 and P-2M). It is.
  • Tables 1 and 2 show the compositions of the circuit connection materials of Examples and Comparative Examples.
  • connection structure connection between COF and PWB
  • a multilayer printed wiring board (PWB-TEG) was connected at 130 ° C.-2 MPa-10 seconds with a width of 2.0 mm.
  • connection resistance After connecting the circuits, the initial resistance value between adjacent circuits of the FPC-PWB including the connection part was measured with a multimeter, and then the connection structure was left in an environment of a temperature of 40 ° C. and a humidity of 60% for 5 days. The resistance value between adjacent circuits was measured with a multimeter. As the resistance value, an average value and a maximum value of 37 resistance values between adjacent circuits were measured. When the maximum rate of change was 3 times or less, A was taken as B, and when it was larger than 3 times, the connection reliability after the high temperature and high humidity test at 85 ° C. and 85% RH for 500 hours was evaluated. The smaller the rate of change of the maximum value, the better the connection reliability. The obtained results are shown in Tables 3 and 4.
  • tin-plated flexible circuit board COF-TEG
  • line width 100 ⁇ m, pitch 200 ⁇ m, thickness 35 ⁇ m copper circuit formed on the copper surface 0.1 ⁇ m thick gold plated glass epoxy
  • PWB-TEG multilayer printed wiring board
  • each of Examples 1 to 6 showed good adhesive strength, but increased resistance in connection reliability. Further, in the fine pitch, all of the comparative examples show good adhesive strength, and in Comparative Examples 1, 3, 4, and 6 in which the ratio of the secondary thiol to 100 parts by mass of the radical polymerizable substance is less than 7, stable connection reliability Sex was obtained.
  • SYMBOLS 1 Connection structure, 7 ... Electroconductive particle, 10 ... Adhesive layer, 11 ... Insulating layer, 20 ... 1st circuit member, 21 ... 1st circuit board, 22 ... 1st circuit electrode (1st connection Terminal), 30 ... second circuit member, 31 ... second circuit board, 32 ... second circuit electrode (second connection terminal).

Abstract

La présente invention concerne un matériau de connexion de circuit pour la connexion d'un premier élément de circuit qui comporte une première électrode de circuit formée en haut de la surface principale d'un premier substrat, et d'un second élément de circuit comportant une seconde électrode de circuit formée en haut de la surface principale d'un second substrat, dans un état où la première électrode de circuit et la seconde électrode de circuit sont disposées face à face. Le matériau de connexion de circuit comprend un initiateur de polymérisation radicalaire, un matériau polymère radicalaire et un mercaptan contenant un groupe thiol dans lequel le nombre d'atomes d'hydrogène qui se lieront aux atomes de carbone auxquels le groupe thiol s'est lié est 1 ou 0, et la teneur en mercaptan est de 7 à 17 parties pour 100 parties de matériau polymère radicalaire.
PCT/JP2013/061216 2012-04-13 2013-04-15 Matériau de connexion de circuit, structure de connexion et leur procédé de fabrication WO2013154203A1 (fr)

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KR1020147024584A KR102044574B1 (ko) 2012-04-13 2013-04-15 회로 접속 재료, 접속 구조체 및 그의 제조 방법
CN201380008376.0A CN104093799B (zh) 2012-04-13 2013-04-15 电路连接材料、连接结构体及其制造方法
JP2014510223A JP6107816B2 (ja) 2012-04-13 2013-04-15 回路接続材料、接続構造体及びその製造方法

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CN104093799A (zh) 2014-10-08
JPWO2013154203A1 (ja) 2015-12-21

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