WO2012014562A1 - Adhesive composition, connection structure, connection structure manufacturing method and application of adhesive composition - Google Patents

Adhesive composition, connection structure, connection structure manufacturing method and application of adhesive composition Download PDF

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Publication number
WO2012014562A1
WO2012014562A1 PCT/JP2011/062417 JP2011062417W WO2012014562A1 WO 2012014562 A1 WO2012014562 A1 WO 2012014562A1 JP 2011062417 W JP2011062417 W JP 2011062417W WO 2012014562 A1 WO2012014562 A1 WO 2012014562A1
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Prior art keywords
group
circuit member
adhesive composition
acrylate
urethane
Prior art date
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PCT/JP2011/062417
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French (fr)
Japanese (ja)
Inventor
伊澤　弘行
加藤木　茂樹
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日立化成工業株式会社
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Application filed by 日立化成工業株式会社 filed Critical 日立化成工業株式会社
Priority to CN2011800010169A priority Critical patent/CN102449096A/en
Priority to KR1020137006450A priority patent/KR20130042017A/en
Priority to KR1020117018211A priority patent/KR101296486B1/en
Priority to JP2011525055A priority patent/JP5855459B2/en
Publication of WO2012014562A1 publication Critical patent/WO2012014562A1/en

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    • C—CHEMISTRY; METALLURGY
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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    • H01L24/91—Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L24/80 - H01L24/90
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    • 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
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    • 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
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/14—Structural association of two or more printed circuits
    • H05K1/141—One or more single auxiliary printed circuits mounted on a main printed circuit, e.g. modules, adapters
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    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10613—Details of electrical connections of non-printed components, e.g. special leads
    • H05K2201/10954—Other details of electrical connections
    • H05K2201/10977—Encapsulated connections

Definitions

  • the present embodiment relates to an adhesive composition, a connection structure, a manufacturing method of the connection structure, and an application of the adhesive composition.
  • adherends used for adhesion include printed wiring boards, organic substrates such as polyimide, polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), metals such as copper and aluminum, Substrates having various surface states such as ITO (complex oxide of indium and tin), SiN, SiO 2 and the like are used, and molecular design in accordance with each adherend is required.
  • organic substrates such as polyimide, polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), metals such as copper and aluminum
  • Substrates having various surface states such as ITO (complex oxide of indium and tin), SiN, SiO 2 and the like are used, and molecular design in accordance with each adherend is required.
  • thermosetting resin using an epoxy resin having high adhesiveness and high reliability has been used (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 thermal latent catalyst for promoting the reaction between the epoxy resin and the curing agent are generally used.
  • a thermal latent catalyst is a substance that does not react at a storage temperature such as room temperature and exhibits high reactivity upon heating, and is an important factor that determines the curing temperature and the curing rate.
  • Various compounds have been used from the viewpoints of storage stability at room temperature and curing rate during heating.
  • the desired adhesion was obtained by curing at a temperature of 170 to 250 ° C. for 1 to 3 hours.
  • semiconductor elements, liquid crystal display elements and wirings may be formed on organic substrates with low heat resistance such as PET, PC, PEN, etc., but the organic substrate and peripheral members are heated by curing. Since there is a possibility of adverse effects, adhesion at lower temperature curing is required. In order to achieve low-temperature rapid curing with the above-described epoxy resin or the like, it is necessary to use a thermal latent catalyst with low activation energy, but it is difficult to combine storage stability near room temperature.
  • a radical curable adhesive using a radical polymerizable compound such as an acrylate derivative or a methacrylate derivative in combination with a peroxide which is a radical polymerization initiator has attracted attention.
  • Radical curing can be cured for a short time because radicals that are reactive species are rich in reactivity (see, for example, Patent Document 2).
  • the radical curing adhesive has a large curing shrinkage when heated, it is inferior in adhesive strength as compared with the case of using an epoxy resin.
  • urethane acrylate is applied to provide flexibility and improve the adhesive strength (see, for example, Patent Document 3).
  • the present invention can obtain excellent adhesive strength even under low temperature curing conditions for organic base materials such as polyethylene terephthalate, polycarbonate, polyethylene naphthalate, etc., and a long-term reliability test (high temperature and high humidity test).
  • Adhesive composition that can maintain stable performance (adhesive strength and connection resistance) afterwards, circuit member connection structure using the same, connection structure manufacturing method, and application of adhesive composition The purpose is to provide.
  • the present invention connects a first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface.
  • the first circuit member and / or the second circuit member is composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or lower, and the adhesive composition is Urethane (meth) acrylate containing (a) thermoplastic resin, (b) radical polymerizable compound and (c) radical polymerization initiator, and (b) radical polymerizable compound having a critical surface tension of 25 to 40 mN / m An adhesive composition is provided.
  • the adhesive composition includes a thermoplastic polymer having a Tg of 200 ° C. or less by containing (b) a radical polymerizable compound containing urethane (meth) acrylate having a critical surface tension of 25 to 40 mN / m.
  • a thermoplastic polymer having a Tg of 200 ° C. or less by containing (b) a radical polymerizable compound containing urethane (meth) acrylate having a critical surface tension of 25 to 40 mN / m.
  • a material for example, PET, PC, PEN, etc.
  • the urethane (meth) acrylate contained in the radically polymerizable compound (b) is preferably represented by the following general formula (A).
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group
  • R 3 represents a group derived from a ring-opening compound of ethylene group, propylene group or ⁇ -caprolactone, or the following general formula:
  • R 4 represents a group represented by the following general formula (B)
  • R 5 represents a saturated aliphatic group or a saturated alicyclic group
  • a represents 1 to 40 Indicates an integer.
  • R 6 and R 7 each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms, b represents an integer of 1 to 10, and c represents an integer of 1 to 25. Indicates. In the formula, R 6 s , R 7 s , b s, and c s may be the same or different.
  • the urethane (meth) acrylate contained in the radical polymerizable compound has a structure represented by the above general formula (A), whereby the cohesive energy density is improved, and the adhesive composition and Tg are 200.
  • the urethane (meth) acrylate contained in the radical polymerizable compound has a structure represented by the general formula (A), so that an appropriate flexibility is imparted to the adhesive composition. Adhesive strength between circuit members composed of a base material containing a thermoplastic resin such as PC and PEN is improved, and excellent connection reliability can be obtained.
  • the present invention also provides an adhesive composition for connecting a first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface.
  • the first circuit member and / or the second circuit member is composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less, and the adhesive composition is (a) a thermoplastic resin. , (B) a radically polymerizable compound and (c) a radical polymerization initiator, and (b) a radically polymerizable compound containing a urethane (meth) acrylate represented by the following general formula (A) I will provide a.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group
  • R 3 represents a group derived from a ring-opening compound of ethylene group, propylene group or ⁇ -caprolactone, or the following general formula:
  • R 4 represents a group represented by the following general formula (B)
  • R 5 represents a saturated aliphatic group or a saturated alicyclic group
  • a represents 1 to 40 Indicates an integer.
  • R 6 and R 7 each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms
  • b represents an integer of 1 to 10
  • c represents an integer of 1 to 25. Indicates.
  • R 6 s , R 7 s , b s, and c s may be the same or different.
  • This adhesive composition has a structure in which the urethane (meth) acrylate contained in the radically polymerizable compound (b) is represented by the general formula (A), whereby the cohesive energy density is improved, and the adhesive composition
  • a base material containing a thermoplastic resin having a Tg of 200 ° C. or lower for example, PET, PC, PEN, etc.
  • the base material contains a thermoplastic resin such as PET, PC, PEN, etc.
  • the adhesive strength between circuit members is improved, and excellent connection reliability can be obtained.
  • the urethane (meth) acrylate contained in the radical polymerizable compound has a structure represented by the general formula (A), so that an appropriate flexibility is imparted to the adhesive composition.
  • Adhesive strength between circuit members composed of a base material containing a thermoplastic resin such as PC and PEN is improved, and excellent connection reliability can be obtained. Furthermore, stable performance can be maintained even after a long-term reliability test.
  • the urethane (meth) acrylate is preferably obtained using an aliphatic polyester diol. Since the urethane (meth) acrylate is obtained using an aliphatic polyester diol, the flexibility of the adhesive composition is improved, and it is composed of a base material containing a thermoplastic resin such as PET, PC, or PEN. The adhesive strength between circuit members can be improved, and excellent connection reliability can be obtained.
  • the weight average molecular weight of urethane (meth) acrylate is 8000 or more and less than 25,000.
  • the adhesive strength with an organic base material such as PET, PC, PEN or the like is further improved, and excellent connection reliability can be obtained.
  • the radically polymerizable compound (b) is a vinyl compound having a phosphate group and one or more radically polymerizable compounds other than the vinyl compound having a phosphate group. It is preferable to contain. (B) Since the radically polymerizable compound has such a configuration, the adhesive strength with a base material made of a metal is further improved.
  • the thermoplastic resin contains at least one selected from the group consisting of phenoxy resin, polyurethane resin, polyester urethane resin, butyral resin, acrylic resin, and polyimide resin. It is preferable to do.
  • the thermoplastic resin contains at least one selected from the group consisting of phenoxy resin, polyurethane resin, polyester urethane resin, butyral resin, acrylic resin, and polyimide resin. It is preferable to do.
  • the heat resistance and adhesiveness of the adhesive composition are further improved.
  • the adhesive composition of the present invention preferably further contains (d) conductive particles.
  • (D) By containing conductive particles, it is possible to impart good conductivity or anisotropic conductivity to the adhesive composition. Therefore, it is preferably used for bonding applications between circuit members having connection terminals. It becomes possible. Moreover, the connection resistance of the circuit member electrically connected via the said adhesive composition can be reduced more fully.
  • this invention is a circuit member provided with the 1st circuit member which has a 1st connection terminal on a main surface, the 2nd circuit member which has a 2nd connection terminal on a main surface, and a connection member
  • the first circuit member and the second circuit member are arranged via the connection member made of the adhesive composition so that the first connection terminal and the second connection terminal face each other.
  • the first connection terminal and the second connection terminal are electrically connected, and the first circuit member and / or the second circuit member has a glass transition temperature of 200 ° C. or less.
  • a circuit member connection structure composed of a base material containing a resin.
  • the first circuit member and / or the second circuit member is a circuit member composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or lower, so that wetting with the adhesive composition As a result, the adhesive strength is further improved and excellent connection reliability can be obtained.
  • the thermoplastic resin having a glass transition temperature of 200 ° C. or lower is preferably at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate.
  • a circuit member composed of a base material containing polyethylene terephthalate or the like wettability with the adhesive composition is improved, adhesive strength is further improved, and excellent connection reliability can be obtained.
  • one circuit member of the first circuit member or the second circuit member is at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. It is comprised from the base material to contain, and the other circuit member is comprised from the base material which contains at least 1 sort (s) chosen from the group which consists of a polyimide resin and a polyethylene terephthalate among 1st circuit members or 2nd circuit members. It is preferable.
  • the first circuit member and the second circuit member are composed of the above-described base materials, so that the wettability and adhesive strength with the adhesive composition are further improved, and an excellent connection is achieved. Reliability can be obtained.
  • the present invention provides a first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface through the adhesive composition.
  • the manufacturing method of the connection structure of a circuit member provided with these is provided. According to this manufacturing method, the connection structure of the circuit member which has the outstanding connection reliability can be obtained by connecting the 1st circuit member and the 2nd circuit member with the said adhesive composition.
  • the present invention also includes (a) a thermoplastic resin, (b) a radical polymerizable compound, and (c) a radical polymerization initiator, and (b) the radical polymerizable compound has a critical surface tension of 25 to 40 mN / m.
  • a first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface of the adhesive composition containing urethane (meth) acrylate having As an adhesive composition for connecting the first circuit member and the second circuit member, wherein at least one circuit member is composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less.
  • the adhesive composition containing (b) a radical polymerizable compound containing urethane (meth) acrylate having a critical surface tension of 25 to 40 mN / m is a base material containing a thermoplastic resin having a Tg of 200 ° C. or less (for example, PET, PC, PEN, etc.) are improved in wettability and can be bonded by low-temperature curing. Therefore, it is suitable for application as an adhesive composition for connecting circuit members.
  • urethane (meth) acrylate is a urethane (meth) acrylate represented by the following general formula (A).
  • the urethane (meth) acrylate has a structure represented by the following general formula (A)
  • the adhesive strength between the circuit members is improved, and excellent connection reliability can be obtained.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group
  • R 3 represents a group derived from a ring-opening compound of ethylene group, propylene group or ⁇ -caprolactone, or the following general formula:
  • R 4 represents a group represented by the following general formula (B)
  • R 5 represents a saturated aliphatic group or a saturated alicyclic group
  • a represents 1 to 40 Indicates an integer.
  • R 6 and R 7 each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms
  • b represents an integer of 1 to 10
  • c represents an integer of 1 to 25. Indicates.
  • R 6 s , R 7 s , b s, and c s may be the same or different.
  • the present invention also includes (a) a thermoplastic resin, (b) a radical polymerizable compound, and (c) a radical polymerization initiator, and (b) the radical polymerizable compound is represented by the following general formula (A).
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group
  • R 3 represents a group derived from a ring-opening compound of ethylene group, propylene group or ⁇ -caprolactone, or the following general formula:
  • R 4 represents a group represented by the following general formula (B)
  • R 5 represents a saturated aliphatic group or a saturated alicyclic group
  • a represents 1 to 40 Indicates an integer.
  • R 6 and R 7 each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms, b represents an integer of 1 to 10, and c represents an integer of 1 to 25. Indicates. In the formula, R 6 s , R 7 s , b s, and c s may be the same or different.
  • the urethane (meth) acrylate is preferably obtained using an aliphatic polyester diol. Since the urethane (meth) acrylate is obtained using an aliphatic polyester diol, the flexibility of the adhesive composition is improved, and it is composed of a base material containing a thermoplastic resin such as PET, PC, or PEN. The adhesive strength between circuit members can be improved, and excellent connection reliability can be obtained.
  • the weight average molecular weight of urethane (meth) acrylate is preferably 8000 or more and less than 25000.
  • the adhesive strength with an organic base material such as PET, PC, PEN or the like is further improved, and excellent connection reliability can be obtained.
  • the (b) radical polymerizable compound contains at least one vinyl compound having a phosphate group and one or more radical polymerizable compounds other than the vinyl compound having a phosphate group.
  • the radically polymerizable compound has such a configuration, the adhesive strength with a base material made of a metal is further improved.
  • thermoplastic resin preferably contains at least one selected from the group consisting of phenoxy resin, polyurethane resin, polyester urethane resin, butyral resin, acrylic resin and polyimide resin.
  • thermoplastic resin By containing such a resin as a thermoplastic resin, heat resistance and adhesiveness are further improved.
  • the adhesive composition further contains (d) conductive particles.
  • conductive particles By containing conductive particles, it is possible to impart good conductivity or anisotropic conductivity to the adhesive composition, and more sufficiently reduce the connection resistance of electrically connected circuit members. can do.
  • an excellent adhesive strength can be obtained even under low temperature curing conditions on an organic substrate such as polyethylene terephthalate, polycarbonate, and polyethylene naphthalate, and a long-term reliability test (high temperature and high humidity) can be achieved.
  • Adhesive composition capable of maintaining stable performance (adhesive strength and connection resistance) even after test), circuit member connection structure using the same, circuit member connection structure manufacturing method, and adhesive composition Application of things can be provided.
  • (meth) acrylic acid means acrylic acid or methacrylic acid corresponding thereto
  • (meth) acrylate means acrylate or methacrylate corresponding thereto
  • (meth) acryloyl group means acryloyl. Means a group or a methacryloyl group.
  • Glass transition temperature (Tg) in the present embodiment refers to a film-like organic base material using a viscoelasticity analyzer “RSA-3” (trade name) manufactured by TA Instruments, Inc. The value of tan ⁇ peak temperature in the vicinity of Tg, measured under the conditions of 5 ° C./min, frequency 10 Hz, measurement temperature ⁇ 150 to 300 ° C.
  • weight average molecular weight and “number average molecular weight” refer to values measured using a standard polystyrene calibration curve from a gel permeation chromatograph (GPC) according to the conditions shown in Table 1.
  • the adhesive composition of the present embodiment is for connecting a first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface.
  • An adhesive composition wherein the first circuit member and / or the second circuit member is composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less, and the adhesive composition comprises (a A) a thermoplastic resin, (b) a radically polymerizable compound and (c) a radical polymerization initiator, and (b) the radically polymerizable compound contains a urethane (meth) acrylate having a critical surface tension of 25 to 40 mN / m.
  • An adhesive composition is for connecting a first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface.
  • thermoplastic resin (a) contained in the adhesive composition of the present embodiment becomes a liquid state having a high viscosity by heating and is freely deformed by external force, and is hardened while maintaining its shape when cooled and removed. That is, it refers to a resin (polymer) having the property of repeating this process. In addition, a resin (polymer) having a reactive functional group having the above properties is also included.
  • Tg of the thermoplastic resin is preferably 0 to 190 ° C, more preferably 20 to 170 ° C.
  • thermoplastic resin polyimide resin, polyamide resin, phenoxy resin, (meth) acrylic resin, urethane resin, polyester urethane resin, polyvinyl butyral resin, or the like can be used. These can be used alone or in admixture of two or more. Further, these thermoplastic resins may contain a siloxane bond or a fluorine substituent. These can be suitably used as long as the resins to be mixed are completely compatible with each other or microphase separation occurs and becomes cloudy.
  • the weight average molecular weight of the thermoplastic resin is preferably 5000 to 150,000, more preferably 10,000 to 80,000. If this value is less than 5000, good film formability tends to be difficult to obtain, and if it exceeds 150,000, good compatibility with other components tends to be difficult to obtain.
  • the content of the thermoplastic resin (a) is preferably 5 to 80% by mass, and preferably 15 to 70% by mass based on the total amount of the adhesive composition. More preferred. When this content is less than 5% by mass, particularly when the adhesive composition is used in the form of a film, good film formability tends to be difficult to obtain, and when it exceeds 80% by mass, good adhesion is obtained. The fluidity of the agent composition tends to be difficult to obtain.
  • the (b) radical polymerizable compound contained in the adhesive composition of the present embodiment refers to a compound that generates radical polymerization by the action of a radical polymerization initiator, but by applying activation energy such as light and heat. It may be a compound that itself generates a radical.
  • a compound having a functional group that is polymerized by an active radical such as a vinyl group, a (meth) acryloyl group, an allyl group, or a maleimide group can be preferably used.
  • radical polymerizable compound examples include epoxy (meth) acrylate oligomers, urethane (meth) acrylate oligomers, polyether (meth) acrylate oligomers, polyester (meth) acrylate oligomers, trimethylolpropane tri ( (Meth) acrylate, polyethylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, isocyanuric acid modified bifunctional (meth) acrylate, isocyanuric acid modified trifunctional (meth) acrylate, bisphenoxyeta (Meth) acrylic acid is added to the glycidyl group of bisphenol fluorene gly
  • R 8 and R 9 each independently represent a hydrogen atom or a methyl group, and d and e each independently represent an integer of 1 to 8. ]
  • R 10 and R 11 each independently represent a hydrogen atom or a methyl group, and f and g each independently represents an integer of 0 to 8. ]
  • the radically polymerizable compound (b) is a solid state having no fluidity such as waxy, waxy, crystalline, glassy or powdery when left alone at 30 ° C.
  • the (b) radical polymerizable compound include N, N′-methylenebisacrylamide, diacetone acrylamide, N-methylolacrylamide, N-phenylmethacrylamide, 2-acrylamido-2-methylpropanesulfonic acid.
  • Tris (2-acryloyloxyethyl) isocyanurate N-phenylmaleimide, N- (o-methylphenyl) maleimide, N- (m-methylphenyl) maleimide, N- (p-methylphenyl) -maleimide, N- (O-methoxyphenyl) maleimide, N- (m-methoxyphenyl) maleimide, N- (p-methoxyphenyl) -maleimide, N-methylmaleimide, N-ethylmaleimide, N-octylmaleimide, 4,4'-diphenylmethane Bismaleimide, m-fe Renbismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, N-methacryloxymaleimide, N-acryloxymaleimide 1,6-bismaleimide- (2,2,2,
  • R 12 and R 13 each independently represent a hydrogen atom or a methyl group, and i represents an integer of 15 to 30. ]
  • R 14 and R 15 each independently represent a hydrogen atom or a methyl group, and j represents an integer of 15 to 30. ]
  • R 16 represents a hydrogen atom or a methyl group.
  • R 17 represents a hydrogen atom or a methyl group, and k represents an integer of 1 to 10.
  • R 18 represents a hydrogen atom or an organic group represented by the following general formula (i) or (ii), and l represents an integer of 1 to 10. ]
  • R 19 represents a hydrogen atom or an organic group represented by the following general formula (iii) or (iv), and m represents an integer of 1 to 10. ]
  • R 20 represents a hydrogen atom or a methyl group.
  • R 21 represents a hydrogen atom or a methyl group.
  • the (b) radical polymerizable compound can be used in combination.
  • the combined use of the phosphoric acid group-containing vinyl compound makes it possible to improve the adhesion of the adhesive composition to the metal substrate.
  • the combined use of the N-vinyl compound can improve the crosslinking rate of the adhesive composition.
  • the phosphate group-containing vinyl compound is not particularly limited as long as it is a compound having a phosphate group and a vinyl group, but compounds represented by the following general formulas (O) to (Q) are preferable.
  • R 22 represents a (meth) acryloyloxy group
  • R 23 represents a hydrogen atom or a methyl group
  • n and o each independently represents an integer of 1 to 8.
  • R 22 s , R 23 s , n s, and o s may be the same or different.
  • R 24 represents a (meth) acryloyloxy group, and p and q each independently represents an integer of 1 to 8.
  • R 24 s , p s, and q s may be the same or different.
  • R 25 represents a (meth) acryloyloxy group
  • R 26 represents a hydrogen atom or a methyl group
  • r and s each independently represent an integer of 1 to 8.
  • R 26 and r may be the same or different.
  • the phosphoric acid group-containing vinyl compound examples include acid phosphooxyethyl methacrylate, acid phosphooxyethyl acrylate, acid phosphooxypropyl methacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, acid phosphooxypolyoxypropylene glycol monomethacrylate, Examples include 2,2′-di (meth) acryloyloxydiethyl phosphate, EO-modified phosphate dimethacrylate, phosphate-modified epoxy acrylate, and vinyl phosphate.
  • the blending amount of the phosphoric acid group-containing vinyl compound is, independently of the blending amount of the (b) radical polymerizable compound other than the phosphoric acid group-containing vinyl compound, (a) with respect to 100 parts by mass of the thermoplastic resin. It is preferably from ⁇ 300 parts by weight, more preferably from 1 to 200 parts by weight, even more preferably from 1 to 50 parts by weight, and particularly preferably from 1 to 15 parts by weight. If the amount of the phosphoric acid group-containing vinyl compound is less than 0.2 parts by mass, high adhesive strength tends to be difficult to obtain, and if it exceeds 300 parts by mass, the physical properties of the cured adhesive composition are likely to deteriorate. , Tend to be difficult to ensure reliability.
  • N-vinyl compounds include N-vinylimidazole, N-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, 4,4′-vinylidenebis (N, N -Dimethylaniline), N-vinylacetamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and the like.
  • the amount of the radically polymerizable compound (b) excluding the compound corresponding to the above-mentioned phosphate group-containing vinyl compound is preferably 50 to 250 parts by mass with respect to 100 parts by mass of the (a) thermoplastic resin. 60 to 150 parts by mass is more preferable. If the blending amount is less than 50 parts by mass, sufficient heat resistance tends to be difficult to obtain after curing, and if it exceeds 250 parts by mass, good film formability is obtained when used as a film. It tends to be difficult.
  • the adhesive composition of the present embodiment includes (b) a urethane (meth) acrylate having a critical surface tension of 25 to 40 mN / m as a radical polymerizable compound, and a urethane (meth) represented by the following general formula (A):
  • Urethane (meth) acrylate satisfying one or both conditions of acrylate is contained as an essential component.
  • fills the said conditions is used more suitably.
  • the urethane (meth) acrylate represented by the following general formula (A) can be obtained by a condensation reaction of an aliphatic diisocyanate and a polyester diol.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group
  • R 3 represents a group derived from a ring-opening compound of ethylene group, propylene group or ⁇ -caprolactone, or the following general formula:
  • R 4 represents a group represented by the following general formula (B)
  • R 5 represents a saturated aliphatic group or a saturated alicyclic group
  • a represents 1 to 40 Indicates an integer.
  • R 6 and R 7 each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms, b represents an integer of 1 to 10, and c represents an integer of 1 to 25. Indicates. In the formula, R 6 s , R 7 s , b s, and c s may be the same or different.
  • the aliphatic diisocyanate constituting the urethane (meth) acrylate is tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, 2, 2,4-trimethylhexamethylene-1,6-diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated trimethyl It is selected from xylylene diisocyanate and the like.
  • polyester diol constituting the urethane (meth) acrylate for example, an aliphatic polyester diol or an aromatic polyester diol can be used, and an aliphatic polyester diol is preferably used.
  • Aliphatic polyester diols are ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,2-pentane.
  • the weight average molecular weight of the said urethane (meth) acrylate is in the range of 8000 or more and less than 25000 from a viewpoint of the adhesive strength improvement with respect to base materials, such as PET, PC, and PEN. It can be freely adjusted and used suitably. If the weight average molecular weight of the urethane (meth) acrylate is within the above range, both flexibility and cohesive force can be obtained, and the adhesive strength with organic base materials such as PET, PC, and PEN is improved and excellent. Connection reliability can be obtained. Moreover, from the viewpoint of obtaining such effects more sufficiently, the weight average molecular weight of the urethane (meth) acrylate is more preferably 10,000 or more and less than 25,000. In addition, when this weight average molecular weight is less than 8000, there exists a tendency for sufficient flexibility not to be acquired, and when it is 25000 or more, there exists a tendency for the fluidity
  • the critical surface tension of the urethane (meth) acrylate is preferably 25 to 40 mN / m, and more preferably 25 to 35 mN / m.
  • the critical surface tension of urethane (meth) acrylate is 25 to 40 mN / m, it becomes close to the critical surface tension of the adherends PET, PC and PEN, and the wettability is improved, thereby improving the adhesive strength. Excellent connection reliability can be obtained.
  • this critical surface tension is less than 25 mN / m or more than 40 mN / m, the wettability with respect to PET, PC, PEN and the like may be deteriorated and the compatibility may deteriorate.
  • the critical surface tension of the urethane (meth) acrylate is related to the urethane bond equivalent and can be adjusted by changing the number average molecular weight of the diol. For example, when the number average molecular weight of the diol is increased, the urethane bond equivalent decreases, and the critical surface tension tends to decrease.
  • the blending amount of the urethane (meth) acrylate is preferably 5 to 95% by mass, more preferably 10 to 80% by mass based on the total amount of the adhesive composition.
  • the blending amount is less than 5% by mass, the heat resistance tends to decrease, and when it exceeds 95% by mass, the film formability tends to decrease when used as a film.
  • the radical polymerization initiator contained in the adhesive composition of the present embodiment conventionally known organic peroxides, azo compounds, and the like are compounds that generate radicals by applying external energy. Can be used.
  • the radical polymerization initiator is preferably an organic peroxide having a one-minute half-life temperature of 90 to 175 ° C. and a molecular weight of 180 to 1,000 from the viewpoints of stability, reactivity, and compatibility. When the 1-minute half-life temperature is within this range, the storage stability is excellent, the radical polymerizability is sufficiently high, and the composition can be cured in a short time.
  • radical polymerization initiator examples include 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2 -Ethylhexyl) peroxydicarbonate, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, dilauroyl peroxide, 1-cyclohexyl-1-methylethylperoxynoe Decanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexa Noate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t Hex
  • These compounds may be used alone or in combination of two or more compounds.
  • the (c) radical polymerization initiator a compound that generates radicals upon irradiation with light of 150 to 750 nm can be used.
  • Such compounds include, for example, Photoinitiation, Photopolymerization, and Photocuring, J. MoI. -P. ⁇ -acetaminophenone derivatives and phosphine oxide derivatives described in Fouassier, Hanser Publishers (1995, p17 to p35) are more preferred because of their high sensitivity to light irradiation.
  • These compounds may be used alone or in combination with the above organic peroxides or azo compounds.
  • the blending amount of the (c) radical polymerization initiator is preferably 0.1 to 500 parts by weight, more preferably 1 to 300 parts by weight, and more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the (a) thermoplastic resin. More preferred is 10 to 30 parts by mass.
  • the blending amount of the radical polymerization initiator is less than 0.1 parts by mass, the adhesive composition tends to be hard to be cured sufficiently, and when it exceeds 500 parts by mass, the storage stability tends to deteriorate.
  • the conductive particles (d) contained in the adhesive composition of the present embodiment may be particles having conductivity on the whole or on the surface, but when used for connecting circuit members having connection terminals, The average particle size is preferably smaller than the distance between the connection terminals.
  • the conductive particles include metal particles such as Au, Ag, Ni, Cu, and solder, and carbon. Further, non-conductive glass, ceramic, plastic or the like may be used as a core, and the core may be coated with the metal, metal particles, or carbon.
  • the conductive particles are made of plastic as a core and the core is coated with the above metal, metal particles or carbon, or hot-melt metal particles, they are deformable by heating and pressurization, so that they are in contact with the electrode at the time of connection. This is preferable because the area is increased and the reliability is improved.
  • the fine particles obtained by coating the surface of the conductive particles (d) with a polymer resin or the like suppress a short circuit due to contact between the particles when the blending amount of the conductive particles is increased. Since insulation can be improved, it may be used alone or in admixture with (d) conductive particles.
  • the average particle diameter of the conductive particles is preferably 1 to 18 ⁇ m from the viewpoint of dispersibility and conductivity.
  • the adhesive composition can be suitably used as an anisotropic conductive adhesive.
  • the amount of the conductive particles used is not particularly limited, but is preferably 0.1 to 30% by volume, preferably 0.1 to 10% by volume based on the total volume of the adhesive composition. Is more preferable. If this value is less than 0.1% by volume, the conductivity tends to be low, and if it exceeds 30% by volume, a short circuit tends to occur.
  • volume% is determined based on the volume of each component before 23 degreeC hardening, the volume of each component can be converted into a volume from a weight using specific gravity. In addition, do not dissolve or swell the component in a graduated cylinder, etc., and put the component in a suitable solvent (water, alcohol, etc.) that wets the component well. It can also be determined as a volume.
  • a stabilizer can be added to the adhesive composition of the present embodiment in order to control the curing rate and to provide storage stability.
  • known compounds can be used without particular limitation, but quinone derivatives such as benzoquinone and hydroquinone; phenol derivatives such as 4-methoxyphenol and 4-t-butylcatechol; , 6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and the like; hindered amine derivatives such as tetramethylpiperidyl methacrylate;
  • the blending amount of the stabilizer is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the adhesive composition.
  • the blending amount is less than 0.01 parts by mass, it becomes difficult to control the curing rate and storage stability, and when it exceeds 30 parts by mass, the compatibility with other components tends to be adversely affected.
  • adhesion aids such as coupling agents represented by alkoxysilane derivatives and silazane derivatives, adhesion improvers, and leveling agents may be appropriately added to the adhesive composition of the present embodiment.
  • the compound represented by the following general formula (R) is preferable as the coupling agent, and two or more compounds may be mixed and used in addition to the compound used alone.
  • R 27 , R 28 and R 29 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkoxycarbonyl group having 1 to 5 carbon atoms.
  • R 30 represents (meth) acryloyl group, vinyl group, isocyanate group, imidazole group, mercapto group, amino group, methylamino group, dimethylamino group, benzylamino group, phenylamino group, cyclohexylamino group , A morpholino group, a piperazino group, a ureido group or a glycidyl group, and t represents an integer of 1 to 10. ]
  • a rubber component may be used in combination for the purpose of stress relaxation and adhesion improvement.
  • the rubber component refers to a component that exhibits rubber elasticity (JIS K6200) as it is or a component that exhibits rubber elasticity by reaction.
  • the rubber component may be solid or liquid at room temperature (25 ° C.), but is preferably liquid from the viewpoint of improving fluidity.
  • a compound having a polybutadiene skeleton is preferable.
  • the rubber component may have a cyano group, a carboxyl group, a hydroxyl group, a (meth) acryloyl group, or a morpholine group.
  • a rubber component containing a cyano group or a carboxyl group, which is a highly polar group, in the side chain or terminal is preferable.
  • a rubber component containing a cyano group or a carboxyl group, which is a highly polar group, in the side chain or terminal is preferable.
  • thermoplasticity even if it has a polybutadiene skeleton, if it exhibits thermoplasticity, it is classified as (a) a thermoplastic resin, and if it exhibits radical polymerizability, it is classified as (b) a radically polymerizable compound.
  • Specific rubber components include polyisoprene, polybutadiene, carboxyl-terminated polybutadiene, hydroxyl-terminated polybutadiene, 1,2-polybutadiene, carboxyl-terminated 1,2-polybutadiene, hydroxyl-terminated 1,2-polybutadiene, acrylic rubber, styrene- Butadiene rubber, hydroxyl-terminated styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylonitrile-butadiene rubber containing carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group at the polymer end, carboxylated nitrile rubber, hydroxyl-terminated poly (oxypropylene) ), Alkoxysilyl group-terminated poly (oxypropylene), poly (oxytetramethylene) glycol, polyolefin glycol, and the like.
  • the rubber component having a high polar group and being liquid at room temperature specifically includes a liquid acrylonitrile-butadiene rubber, a carboxyl group, a hydroxyl group, a (meth) acryloyl group or a morpholine group at the polymer end.
  • a liquid acrylonitrile-butadiene rubber specifically includes a carboxyl group, a hydroxyl group, a (meth) acryloyl group or a morpholine group at the polymer end.
  • examples thereof include liquid acrylonitrile-butadiene rubber and liquid carboxylated nitrile rubber.
  • the content of acrylonitrile, which is a polar group is preferably 10 to 60% by mass.
  • These compounds may be used alone or in combination of two or more compounds.
  • organic fine particles may be added to the adhesive composition of the present embodiment for the purpose of stress relaxation and adhesion improvement.
  • the average particle size of the organic fine particles is preferably 0.05 to 1.0 ⁇ m.
  • organic fine particles consist of the above-mentioned rubber component it classifies into a rubber component instead of organic fine particles, and when organic fine particles consist of the above-mentioned (a) thermoplastic resin, it is not organic fine particle (a) thermoplastic resin. Classify into:
  • organic fine particles include polyisoprene, polybutadiene, carboxyl-terminated polybutadiene, hydroxyl-terminated polybutadiene, 1,2-polybutadiene, carboxyl-terminated 1,2-polybutadiene, acrylic rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, Acrylonitrile-butadiene rubber, carboxylated nitrile rubber, hydroxyl-terminated poly (oxypropylene), alkoxysilyl-terminated poly (oxypropylene), poly (oxypropylene) containing carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group at the polymer end Tetramethylene) glycol, polyolefin glycol (meth) acrylic acid alkyl-butadiene-styrene copolymer, (meth) acrylic acid alkyl-silicone copolymer or Recone (meth) - include organic
  • organic fine particles may be used alone or in combination of two or more compounds.
  • the adhesive composition of this embodiment can be used in the form of a paste when it is liquid at room temperature. In the case of a solid at room temperature, it may be used by heating, or may be pasted using a solvent.
  • Solvents that can be used are preferably those that are not reactive with the adhesive composition and additives and that exhibit sufficient solubility, and those having a boiling point of 50 to 150 ° C. at normal pressure. When the boiling point is less than 50 ° C., it tends to volatilize when left at room temperature, and it tends to be difficult to use in an open system. On the other hand, if the boiling point exceeds 150 ° C., it is difficult to volatilize the solvent, and the reliability after adhesion tends to be adversely affected.
  • the adhesive composition of the present embodiment can be used in the form of a film.
  • a solution in which a solvent or the like is added to the adhesive composition as necessary is applied onto a peelable substrate such as a fluororesin film, a polyethylene terephthalate film or a release paper, or a substrate such as a nonwoven fabric is impregnated with the above solution. It can be placed on a peelable substrate and used as a film after removing the solvent and the like. Use in the form of a film is more convenient from the viewpoint of handleability.
  • the adhesive composition of the present embodiment can be bonded by using both heating and pressing.
  • the heating temperature is preferably 100 to 200 ° C.
  • the pressure is preferably in a range that does not damage the adherend, and generally 0.1 to 10 MPa. These heating and pressurization are preferably performed in the range of 0.5 seconds to 120 seconds, and can be bonded by heating at 120 to 190 ° C., 3 MPa, and 10 seconds.
  • the adhesive composition of the present embodiment can be used as an adhesive for different types of adherends having different thermal expansion coefficients. Specifically, it is used as a semiconductor element adhesive material typified by anisotropic conductive adhesive, silver paste, silver film, etc., circuit connection material, CSP elastomer, CSP underfill material, LOC tape, etc. Can do.
  • the adhesive composition of the present embodiment is for connecting a first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface.
  • said 1st circuit member and / or said 2nd circuit member are comprised from the base material containing the thermoplastic resin whose glass transition temperature is 200 degrees C or less.
  • a thermoplastic resin whose glass transition temperature is 200 degrees C or less For example, a polyethylene terephthalate, a polycarbonate, a polyethylene naphthalate, etc. are mentioned.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of a circuit member connection structure using the adhesive composition of the present embodiment.
  • FIG. 2 is a schematic cross-sectional view showing the first circuit member, the second circuit member, and the adhesive composition before producing the circuit member connection structure shown in FIG. 1.
  • a circuit member connection structure 100 shown in FIG. 1 includes a first circuit member 30 having a first connection terminal 32 on a main surface 31 a of a first circuit board 31, and a main surface of a second circuit board 41.
  • the main surface 31a of the first circuit board 31 so that the second circuit member 40 having the second connection terminal 42 on 41a and the first connection terminal 32 and the second connection terminal 42 face each other.
  • 10C of connection members which connect the main surface 41a of the 2nd circuit board 41.
  • the first connection terminal 32 and the second connection terminal 42 are electrically connected by being in contact with each other.
  • 10C of connection members consist of hardened
  • the circuit member connection structure 100 shown in FIG. 1 can be manufactured, for example, as follows.
  • the first circuit member 30, the second circuit member 40, and the adhesive composition 10 formed into a film shape are prepared.
  • the adhesive composition 10 is placed on the main surface 41a of the second circuit member 40 on which the second connection terminals 42 are formed, and the first connection terminals are further formed on the adhesive composition 10.
  • the first circuit member 30 is placed so that 32 faces the second connection terminal 42.
  • the adhesive composition 10 is cured while being heated through the first circuit member 30 and the second circuit member 40, and simultaneously pressurized in a direction perpendicular to the main surfaces 31a and 41a.
  • a connection member 10C is formed between the second circuit members 30 and 40 to obtain the circuit member connection structure 100 of FIG.
  • FIG. 3 is a schematic cross-sectional view showing an embodiment of a circuit member connection structure using the adhesive composition of this embodiment containing (d) conductive particles.
  • FIG. 4 is a schematic cross-sectional view showing the first circuit member, the second circuit member, and the adhesive composition (containing conductive particles) before producing the circuit member connection structure shown in FIG. 3.
  • a circuit member connection structure 200 shown in FIG. 3 includes a first circuit member 30 having a first connection terminal 32 on a main surface 31 a of a first circuit board 31, and a main surface of a second circuit board 41.
  • the main surface 31a of the first circuit board 31 so that the second circuit member 40 having the second connection terminal 42 on 41a and the first connection terminal 32 and the second connection terminal 42 face each other.
  • the connecting member 20C is a cured product of the adhesive composition 20 in which the conductive particles 22 are dispersed in the component 21 other than the conductive particles of the adhesive composition (that is, the components other than the conductive particles of the adhesive composition).
  • the conductive particles 22 are dispersed in the cured product 21C), and the conductive particles 22 are in contact with both connection terminals between the first connection terminal 32 and the second connection terminal 42 facing each other. Both connection terminals are electrically connected through the conductive particles 22.
  • the circuit member connection structure 200 shown in FIG. 3 includes, for example, as shown in FIG. 4, a first circuit member 30, a second circuit member 40, and an adhesive composition 20 formed into a film shape,
  • the circuit member connection structure 100 can be manufactured by the same method as described above.
  • At least one of the first circuit member 30 and the second circuit member 40 is composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less. That is, at least one of the first circuit board 31 and the second circuit board 41 contains a thermoplastic resin having a glass transition temperature of 200 ° C. or lower.
  • the thermoplastic resin having a glass transition temperature of 200 ° C. or lower is preferably at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate.
  • One of the first circuit member 30 and the second circuit member 40 may be composed of a base material that does not contain at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate.
  • a base material for forming such a circuit member a base material made of an inorganic material such as a semiconductor, glass or ceramic, a base material made of an organic material such as polyimide, a base material combining an inorganic material such as glass / epoxy and an organic material, etc. Can be used.
  • connection terminal 32 and the second connection terminal 42 is composed of at least one selected from the group consisting of ITO and IZO.
  • ITO and IZO are suitable as connection terminals because they are easily etched and have excellent pattern processability. And the corrosion of the connection terminal comprised by ITO and / or IZO can fully be suppressed by using the adhesive composition of this embodiment.
  • connection terminal 32 and the second connection terminal 42 may be made of a material other than ITO and IZO.
  • a connection terminal made of a metal such as copper, silver, aluminum, gold, palladium, nickel, or an alloy thereof can be used.
  • connection member does not need to be completely cured (the highest degree of curing that can be achieved under predetermined curing conditions) and is in a partially cured state as long as the above characteristics are produced. May be.
  • ⁇ Thermoplastic resin> 40 parts by mass of phenoxy resin (manufactured by Toto Kasei Co., Ltd., YP-50 (trade name)) was dissolved in 60 parts by mass of methyl ethyl ketone to obtain a solution having a solid content of 40% by mass.
  • polyester urethane resin Preparation of polyester urethane resin
  • UR-1400 trade name
  • a 1: 1 mixed solvent solution of methyl ethyl ketone and toluene having a resin content of 30% by mass was used.
  • urethane acrylate (L-1600S)
  • L-1600S urethane acrylate having a weight average molecular weight of 15000 and a critical surface tension of 15 mN / m (manufactured by Mitsui Polyurethane Co., Ltd., L-1600S (trade name)) was prepared.
  • L-1600S uses an ether diol and does not satisfy the general formula (A).
  • the reaction was terminated to obtain urethane acrylate.
  • the urethane acrylate (PE-UA1) obtained had a critical surface tension of 30 mN / m and a weight average molecular weight of 15,300.
  • PE-UA1 uses a polyester diol and satisfies the above general formula (A).
  • Polycaprolactone diol (aliphatic polyester diol, trade name: Plaxel 220EB, Daicel Chemical Industries, Ltd.) having a number average molecular weight of 2000 in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser equipped with a calcium chloride drying tube, and a nitrogen gas introduction tube Co., Ltd.) 2000 parts by mass (1.00 mol) and dibutyltin dilaurate (Aldrich Co., Ltd.) 5.53 parts by mass were added.
  • the mixture After sufficiently introducing nitrogen gas, the mixture is heated to 70 to 75 ° C., and 666 parts by mass (3.00 mol) of isophorone diisocyanate (aliphatic diisocyanate, manufactured by Aldrich Co., Ltd.) is uniformly added dropwise over 3 hours to be reacted. It was. The reaction was continued for about 10 hours after the completion of the dropwise addition. To this, 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Aldrich) and 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Aldrich) were further reacted for 10 hours.
  • isophorone diisocyanate aliphatic diisocyanate, manufactured by Aldrich Co., Ltd.
  • the reaction was terminated to obtain urethane acrylate.
  • the urethane acrylate (PE-UA2) obtained had a critical surface tension of 25 mN / m and a weight average molecular weight of 13,500.
  • PE-UA2 uses a polyester diol and satisfies the above general formula (A).
  • the mixture After sufficiently introducing nitrogen gas, the mixture is heated to 70 to 75 ° C., and 666 parts by mass (3.00 mol) of isophorone diisocyanate (aliphatic diisocyanate, manufactured by Aldrich Co., Ltd.) is uniformly added dropwise over 3 hours to be reacted. It was. The reaction was continued for about 15 hours after the completion of the dropwise addition. To this, 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Aldrich) and 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Aldrich) were further reacted for 10 hours.
  • isophorone diisocyanate aliphatic diisocyanate, manufactured by Aldrich Co., Ltd.
  • PE-UA5 The resulting urethane acrylate (PE-UA5) had a critical surface tension of 21 mN / m and a weight average molecular weight of 30000. PE-UA5 uses polycarbonate diol and does not satisfy the general formula (A).
  • Isocyanuric acid-modified bifunctional acrylate (manufactured by Toagosei Co., Ltd., M-215 (trade name)) was prepared.
  • Dibenzoyl peroxide (trade name: Nyper BW, manufactured by NOF Corporation) was prepared as a radical polymerization initiator.
  • a nickel layer having a thickness of 0.2 ⁇ m is provided on the surface of particles having polystyrene as a core, and a gold layer having a thickness of 0.02 ⁇ m is provided outside the nickel layer, and conductive particles having an average particle diameter of 10 ⁇ m and a specific gravity of 2.5. Was made.
  • Examples 1 to 10 and Comparative Examples 1 to 5 As shown in Table 2 in terms of solid mass ratio, a thermoplastic resin, a radical polymerizable compound, and a radical polymerization initiator were blended, and 1.5% by volume of conductive particles were blended and dispersed to obtain an adhesive composition.
  • the obtained adhesive composition was applied on a fluororesin film having a thickness of 80 ⁇ m using a coating apparatus, and a film-like adhesive composition having an adhesive layer thickness of 20 ⁇ m was dried by hot air at 70 ° C. for 10 minutes. Obtained.
  • a flexible circuit board having the film-like adhesive compositions of Examples 1 to 10 and Comparative Examples 1 to 5 having 80 copper circuits having a line width of 150 ⁇ m, a pitch of 300 ⁇ m, and a thickness of 8 ⁇ m on a polyimide film (Tg 350 ° C.). And a PET substrate (thickness 0.1 mm) on which a thin layer of 5 ⁇ m thick Ag paste was formed.
  • the film-like adhesive compositions of Examples 1 to 10 and Comparative Examples 1 to 5 were prepared by using FPC having 80 copper circuits having a line width of 150 ⁇ m, a pitch of 300 ⁇ m, and a thickness of 18 ⁇ m on a polyimide film, and PET (thickness 0. 1 mm) It was interposed between a substrate on which an Ag paste circuit having a line width of 150 ⁇ m, a pitch of 300 ⁇ m, and a thickness of 10 ⁇ m was formed on a film. These were each connected by heating and pressing at 150 ° C. and 2 MPa for 10 seconds using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.) to produce a connection body.
  • FPC having 80 copper circuits having a line width of 150 ⁇ m, a pitch of 300 ⁇ m, and a thickness of 18 ⁇ m on a polyimide film, and PET (thickness 0. 1 mm) It was interposed between a substrate on which an Ag
  • the resistance value between adjacent circuits of these connected bodies was measured with a multimeter immediately after bonding and after being kept in a high-temperature and high-humidity bath at 85 ° C. and 85% RH for 240 hours (after the test). The resistance value was shown as an average of 37 resistances between adjacent circuits.
  • connection strength of each connection body was measured by a 90-degree peeling method according to JIS-Z0237 and evaluated.
  • Tensilon UTM-4 peeleling speed 50 mm / min, 25 ° C.
  • the results of measurement of the connection resistance and adhesive strength of the film adhesive composition performed as described above are shown in Table 3 below.
  • the adhesive compositions of Examples 1 to 7 were about 1.2 ⁇ or less immediately after bonding at a heating temperature of 150 ° C. and after being kept in a high-temperature and high-humidity bath at 85 ° C. and 85% RH for 240 hours (after the test). And good adhesive strength of 600 N / m or more.
  • the adhesive compositions of Comparative Examples 1 and 3 show good connection resistance immediately after bonding and after being held in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 240 hours (after the test). The adhesive strength was low. Further, the adhesive compositions of Comparative Examples 2, 4, and 5 have high connection resistance immediately after connection and after being held in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 240 hours (after the test), and the adhesive strength was also implemented Lower than Examples 1-7.
  • the adhesive compositions of Examples 8 to 10 had good connections of about 1.2 ⁇ or less immediately after bonding and after being held in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 240 hours (after the test). Resistance was exhibited and the adhesive strength was superior to Comparative Examples 1 and 3.
  • the film-like adhesive compositions of Examples 3, 4 and 7 and Comparative Examples 3 and 4 are flexible circuit boards (FPC) having 80 copper circuits having a line width of 150 ⁇ m, a pitch of 300 ⁇ m and a thickness of 8 ⁇ m on a polyimide film.
  • FPC flexible circuit boards
  • a PET film thinness 0.1 mm, Tg 120 ° C.
  • a PC film thinness 0.1 mm, Tg 150 ° C.
  • a PEN film thickness 0.1 mm, Tg 160 ° C.
  • the adhesive compositions used in Examples 11 to 13 were heated at 150 ° C. for any substrate immediately after bonding and after being kept in a high-temperature and high-humidity bath at 85 ° C. and 85% RH for 240 hours. In (after test), good adhesive strength of 600 N / m or more was exhibited. On the other hand, the adhesive composition used in Comparative Examples 6 and 7 has low adhesive strength immediately after bonding and after being kept in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 240 hours (after the test). became.
  • the film-like adhesive compositions of Examples 3, 4, 6 and 7 and Comparative Examples 1 and 3 are flexible circuits having 500 copper circuits having a line width of 25 ⁇ m, a pitch of 50 ⁇ m and a thickness of 8 ⁇ m on a polyimide film. It was interposed between a plate (FPC) and glass (thickness 1.1 mm, surface resistance 20 ⁇ / ⁇ ) on which a thin layer of 0.2 ⁇ m ITO was formed. Using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.), this was heated and pressurized at 150 ° C.
  • connection body was measured with a multimeter immediately after bonding and after being held in a high-temperature and high-humidity bath at 85 ° C. and 85% RH for 240 hours (after the test). The resistance value was shown as an average of 37 resistances between adjacent circuits.
  • connection body was measured by a 90-degree peeling method according to JIS-Z0237 and evaluated.
  • Tensilon UTM-4 peeleling speed 50 mm / min, 25 ° C.
  • Table 5 shows the results of the measurement of the connection resistance and the adhesive strength of the film adhesive composition performed as described above.
  • the adhesive composition of the comparative example was inferior in connection resistance and adhesive strength.
  • Table 5 when the adherend is a glass with ITO, in all of Reference Examples 1 to 6 including the case where the adhesive composition of the comparative example was used, immediately after bonding and at 85 ° C., 85 ° C. It was confirmed that a good connection resistance of 2.5 ⁇ or less and a good adhesive strength of 680 N / m or more can be obtained after being kept in a high-temperature, high-humidity tank of% RH for 240 hours (after the test).
  • Adhesive composition 10C, 20C ... Connection member, 21 ... Adhesive composition which does not contain electroconductive particle, 22 ... Conductive particle, 21C ... Hardened

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Abstract

Disclosed is an adhesive composition for connecting a first circuit member having first connection terminals on the primary surface, and a second circuit member having second connection terminals on the primary surface, wherein the first and/or the second circuit members are configured from a substrate containing a thermoplastic resin with a glass transition temperature of 200C or less. The disclosed adhesive composition contains (a) a thermoplastic resin, (b) a radical-polymerizable compound, and (c) a radical polymerization initiator, wherein (b) the radical-polymerizable compound contains urethane (meth)acrylate having a critical surface tension of 25-40 mN/m.

Description

接着剤組成物、接続構造体、接続構造体の製造方法及び接着剤組成物の応用Adhesive composition, connection structure, method for producing connection structure, and application of adhesive composition
　本実施形態は、接着剤組成物、接続構造体、接続構造体の製造方法及び接着剤組成物の応用に関する。 The present embodiment relates to an adhesive composition, a connection structure, a manufacturing method of the connection structure, and an application of the adhesive composition.
　半導体素子及び液晶表示素子において、素子中の種々の部材を結合させる目的で従来から種々の接着剤が使用されている。接着剤に対する要求は、接着性をはじめとして、耐熱性、高温高湿状態における信頼性等多岐に渡る。また、接着に使用される被着体は、プリント配線板やポリイミド、ポリエチレンテレフタレート（ＰＥＴ）、ポリカーボネート（ＰＣ）、ポリエチレンナフタレート（ＰＥＮ）等の有機基材をはじめ、銅、アルミニウム等の金属やＩＴＯ（インジウムとスズの複合酸化物）、ＳｉＮ、ＳｉＯ２等の多種多様な表面状態を有する基材が用いられ、各被着体にあわせた分子設計が必要である。 In the semiconductor element and the liquid crystal display element, various adhesives are conventionally used for the purpose of bonding various members in the element. The demand for adhesives is diverse, including adhesiveness, heat resistance, and reliability in high temperature and high humidity conditions. In addition, adherends used for adhesion include printed wiring boards, organic substrates such as polyimide, polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), metals such as copper and aluminum, Substrates having various surface states such as ITO (complex oxide of indium and tin), SiN, SiO 2 and the like are used, and molecular design in accordance with each adherend is required.
　従来から、上記半導体素子や液晶表示素子用の接着剤としては、高接着性でかつ高信頼性を示すエポキシ樹脂を用いた熱硬化性樹脂が用いられてきた（例えば、特許文献１参照）。樹脂の構成成分としては、エポキシ樹脂、エポキシ樹脂と反応性を有するフェノール樹脂等の硬化剤、エポキシ樹脂と硬化剤の反応を促進する熱潜在性触媒が一般に用いられている。熱潜在性触媒は、室温等の貯蔵温度では反応せず、加熱の際に高い反応性を示す物質であって、硬化温度及び硬化速度を決定する重要な因子となっており、接着剤の室温での貯蔵安定性と加熱時の硬化速度の観点から種々の化合物が用いられてきた。実際の工程での硬化条件は、１７０～２５０℃の温度で１～３時間硬化することにより、所望の接着を得ていた。 Conventionally, as an adhesive for the semiconductor element and the liquid crystal display element, a thermosetting resin using an epoxy resin having high adhesiveness and high reliability has been used (for example, see Patent Document 1). As a constituent component of the resin, a curing agent such as an epoxy resin, a phenol resin having reactivity with the epoxy resin, and a thermal latent catalyst for promoting the reaction between the epoxy resin and the curing agent are generally used. A thermal latent catalyst is a substance that does not react at a storage temperature such as room temperature and exhibits high reactivity upon heating, and is an important factor that determines the curing temperature and the curing rate. Various compounds have been used from the viewpoints of storage stability at room temperature and curing rate during heating. As the curing conditions in the actual process, the desired adhesion was obtained by curing at a temperature of 170 to 250 ° C. for 1 to 3 hours.
　しかしながら、最近、ＰＥＴ、ＰＣ、ＰＥＮ等の耐熱性の低い有機基材上に半導体素子や液晶表示素子及び配線が形成される場合があるが、硬化時の加熱によって、有機基材及び周辺部材に悪影響を及ぼす恐れがあるため、より低温硬化での接着が要求されている。上述したエポキシ樹脂等にて低温速硬化を達成するには、活性化エネルギーの低い熱潜在性触媒を使用する必要があるが、室温付近での貯蔵安定性を兼備することは困難であった。 However, recently, semiconductor elements, liquid crystal display elements and wirings may be formed on organic substrates with low heat resistance such as PET, PC, PEN, etc., but the organic substrate and peripheral members are heated by curing. Since there is a possibility of adverse effects, adhesion at lower temperature curing is required. In order to achieve low-temperature rapid curing with the above-described epoxy resin or the like, it is necessary to use a thermal latent catalyst with low activation energy, but it is difficult to combine storage stability near room temperature.
　このような中、アクリレート誘導体やメタアクリレート誘導体等のラジカル重合性化合物とラジカル重合開始剤である過酸化物を併用した、ラジカル硬化型接着剤が注目されている。ラジカル硬化は、反応活性種であるラジカルが反応性に富むため、短時間硬化が可能である（例えば、特許文献２参照）。しかしながら、ラジカル硬化系の接着剤は、加熱時の硬化収縮が大きいために、エポキシ樹脂を用いた場合と比較して、接着強度に劣る。こうした接着強度の低下については、ウレタンアクリレートを適用することで、可とう性を付与し、接着強度を改善させる方法が提案されている（例えば、特許文献３参照）。また、被着体がＩＴＯ、ＳｉＮ、ＳｉＯ２等である無機基材に対しては、シランカップリング剤等の接着助剤を加えることによって、接着強度を改善する方法が提案されている（例えば、特許文献４参照）。 Under such circumstances, a radical curable adhesive using a radical polymerizable compound such as an acrylate derivative or a methacrylate derivative in combination with a peroxide which is a radical polymerization initiator has attracted attention. Radical curing can be cured for a short time because radicals that are reactive species are rich in reactivity (see, for example, Patent Document 2). However, since the radical curing adhesive has a large curing shrinkage when heated, it is inferior in adhesive strength as compared with the case of using an epoxy resin. Regarding such a decrease in adhesive strength, a method has been proposed in which urethane acrylate is applied to provide flexibility and improve the adhesive strength (see, for example, Patent Document 3). Further, a method for improving the adhesive strength by adding an adhesion assistant such as a silane coupling agent to an inorganic base material whose adherend is ITO, SiN, SiO 2 or the like has been proposed (for example, , See Patent Document 4).
特開平１－１１３４８０号公報Japanese Patent Laid-Open No. 1-113480 国際公開第９８／４４０６７号パンフレットInternational Publication No. 98/44067 Pamphlet 特許第３５０３７４０号公報Japanese Patent No. 3503740 特開昭６２－６２８７４号公報JP 62-62874 A
　しかしながら、熱可塑性樹脂であるＰＥＴ、ＰＣ、ＰＥＮ等の有機基材は、直鎖状であり、また、ベンゼン環による分子間の相互作用によって、結晶部分を形成しやすいため、接着剤組成物やシランカップリング剤との共有結合の形成は極めて困難である。そのため、上述の特許文献４に記載の方法では、十分な接着強度が得られない。また、ＰＥＴ、ＰＣ、ＰＥＮ等の表面は平滑であるため、物理的な投錨効果（アンカー効果）による接着効果が小さい。そのため、被着体に対する濡れ性や十分な可とう性が得られる接着剤組成物を適用する必要があるが、上述の特許文献３に記載の方法では、被着体に対する十分な濡れ性や可とう性が得られない。 However, organic substrates such as PET, PC, and PEN that are thermoplastic resins are straight-chain, and are easy to form crystal parts due to intermolecular interaction by benzene rings. Formation of a covalent bond with a silane coupling agent is extremely difficult. Therefore, the method described in Patent Document 4 described above cannot provide sufficient adhesive strength. Moreover, since the surface of PET, PC, PEN or the like is smooth, the adhesion effect due to the physical anchoring effect (anchor effect) is small. Therefore, it is necessary to apply an adhesive composition that provides wettability to the adherend and sufficient flexibility. However, in the method described in Patent Document 3 described above, sufficient wettability and flexibility to the adherend are required. The flexibility is not obtained.
　そこで、本発明は、ポリエチレンテレフタレート、ポリカーボネート、ポリエチレンナフタレート等の有機基材に対して、低温の硬化条件においても優れた接着強度を得ることができ、長時間の信頼性試験（高温高湿試験）後においても安定した性能（接着強度や接続抵抗）を維持することができる接着剤組成物、それを用いた回路部材の接続構造体、接続構造体の製造方法及び接着剤組成物の応用を提供することを目的とする。 Therefore, the present invention can obtain excellent adhesive strength even under low temperature curing conditions for organic base materials such as polyethylene terephthalate, polycarbonate, polyethylene naphthalate, etc., and a long-term reliability test (high temperature and high humidity test). ) Adhesive composition that can maintain stable performance (adhesive strength and connection resistance) afterwards, circuit member connection structure using the same, connection structure manufacturing method, and application of adhesive composition The purpose is to provide.
　上記目的を達成するために、本発明は、主面上に第一の接続端子を有する第一の回路部材と、主面上に第二の接続端子を有する第二の回路部材とを接続するための接着剤組成物であって、第一の回路部材及び／又は第二の回路部材は、ガラス転移温度が２００℃以下の熱可塑性樹脂を含む基材から構成され、接着剤組成物は、（ａ）熱可塑性樹脂、（ｂ）ラジカル重合性化合物及び（ｃ）ラジカル重合開始剤を含有し、（ｂ）ラジカル重合性化合物が２５～４０ｍＮ／ｍの臨界表面張力を有するウレタン（メタ）アクリレートを含む、接着剤組成物を提供する。 To achieve the above object, the present invention connects a first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface. The first circuit member and / or the second circuit member is composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or lower, and the adhesive composition is Urethane (meth) acrylate containing (a) thermoplastic resin, (b) radical polymerizable compound and (c) radical polymerization initiator, and (b) radical polymerizable compound having a critical surface tension of 25 to 40 mN / m An adhesive composition is provided.
　上記接着剤組成物は、２５～４０ｍＮ／ｍの臨界表面張力を有するウレタン（メタ）アクリレートを含む（ｂ）ラジカル重合性化合物を含有することによって、Ｔｇが２００℃以下の熱可塑性樹脂を含む基材（例えばＰＥＴ、ＰＣ、ＰＥＮ等）との濡れ性が向上し、低温硬化での接着が可能となり、回路部材間の接着強度を向上させることができる。また、長時間の信頼性試験後にも安定した性能を維持することができる。 The adhesive composition includes a thermoplastic polymer having a Tg of 200 ° C. or less by containing (b) a radical polymerizable compound containing urethane (meth) acrylate having a critical surface tension of 25 to 40 mN / m. The wettability with a material (for example, PET, PC, PEN, etc.) is improved, adhesion at low temperature is possible, and the adhesive strength between circuit members can be improved. In addition, stable performance can be maintained even after a long-term reliability test.
　また、本発明の接着剤組成物において、（ｂ）ラジカル重合性化合物に含まれるウレタン（メタ）アクリレートは下記一般式（Ａ）で表されるものであることが好ましい。
Figure JPOXMLDOC01-appb-C000009
 ［式（Ａ）中、Ｒ１及びＲ２はそれぞれ独立に水素原子またはメチル基を示し、Ｒ３はエチレン基、プロピレン基、ε－カプロラクトンの開環化合物から誘導される基、または下記一般式（Ｂ）で表される基を示し、Ｒ４は下記一般式（Ｂ）で表される基を示し、Ｒ５は飽和脂肪族基または飽和脂環式基を示し、ａは１～４０の整数を示す。］
Figure JPOXMLDOC01-appb-C000010
 ［式（Ｂ）中、Ｒ６及びＲ７はそれぞれ独立に炭素数２～１２の直鎖又は分岐鎖のアルキレン基を示し、ｂは１～１０の整数を示し、ｃは１～２５の整数を示す。なお、式中、Ｒ６同士、Ｒ７同士、ｂ同士及びｃ同士はそれぞれ同一でも異なってもよい。］ In the adhesive composition of the present invention, the urethane (meth) acrylate contained in the radically polymerizable compound (b) is preferably represented by the following general formula (A).
Figure JPOXMLDOC01-appb-C000009
 [In the formula (A), R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and R 3 represents a group derived from a ring-opening compound of ethylene group, propylene group or ε-caprolactone, or the following general formula: Represents a group represented by (B), R 4 represents a group represented by the following general formula (B), R 5 represents a saturated aliphatic group or a saturated alicyclic group, and a represents 1 to 40 Indicates an integer. ]
Figure JPOXMLDOC01-appb-C000010
 [In the formula (B), R 6 and R 7 each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms, b represents an integer of 1 to 10, and c represents an integer of 1 to 25. Indicates. In the formula, R 6 s , R 7 s , b s, and c s may be the same or different. ]
　臨界表面張力と凝集エネルギー密度の間には、比例関係があるため、凝集エネルギー密度の高い官能基を導入することで、臨界表面張力が向上すると考えられる。そのため、（ｂ）ラジカル重合性化合物に含まれるウレタン（メタ）アクリレートが上記一般式（Ａ）で表される構造であることによって、凝集エネルギー密度が向上して、接着剤組成物とＴｇが２００℃以下の熱可塑性樹脂を含む基材（例えばＰＥＴ、ＰＣ、ＰＥＮ等）との濡れ性が向上し、ＰＥＴやＰＣ、ＰＥＮ等の熱可塑性樹脂を含む基材から構成される回路部材間の接着強度が向上し、優れた接続信頼性を得ることができる。また、（ｂ）ラジカル重合性化合物に含まれるウレタン（メタ）アクリレートが上記一般式（Ａ）で表される構造であることによって、接着剤組成物に適度な可とう性が付与され、ＰＥＴやＰＣ、ＰＥＮ等の熱可塑性樹脂を含む基材から構成される回路部材間の接着強度が向上し、優れた接続信頼性を得ることができる。 Since there is a proportional relationship between the critical surface tension and the cohesive energy density, it is considered that the critical surface tension is improved by introducing a functional group having a high cohesive energy density. Therefore, (b) the urethane (meth) acrylate contained in the radical polymerizable compound has a structure represented by the above general formula (A), whereby the cohesive energy density is improved, and the adhesive composition and Tg are 200. Adhesion between circuit members composed of a substrate containing a thermoplastic resin such as PET, PC, PEN, etc., with improved wettability with a substrate containing a thermoplastic resin at a temperature of ℃ or less (for example, PET, PC, PEN, etc.) Strength is improved and excellent connection reliability can be obtained. In addition, (b) the urethane (meth) acrylate contained in the radical polymerizable compound has a structure represented by the general formula (A), so that an appropriate flexibility is imparted to the adhesive composition. Adhesive strength between circuit members composed of a base material containing a thermoplastic resin such as PC and PEN is improved, and excellent connection reliability can be obtained.
　また、本発明は、主面上に第一の接続端子を有する第一の回路部材と、主面上に第二の接続端子を有する第二の回路部材とを接続するための接着剤組成物であって、第一の回路部材及び／又は第二の回路部材は、ガラス転移温度が２００℃以下の熱可塑性樹脂を含む基材から構成され、接着剤組成物は、（ａ）熱可塑性樹脂、（ｂ）ラジカル重合性化合物及び（ｃ）ラジカル重合開始剤を含有し、（ｂ）ラジカル重合性化合物が下記一般式（Ａ）で表されるウレタン（メタ）アクリレートを含む、接着剤組成物を提供する。
Figure JPOXMLDOC01-appb-C000011
 ［式（Ａ）中、Ｒ１及びＲ２はそれぞれ独立に水素原子またはメチル基を示し、Ｒ３はエチレン基、プロピレン基、ε－カプロラクトンの開環化合物から誘導される基、または下記一般式（Ｂ）で表される基を示し、Ｒ４は下記一般式（Ｂ）で表される基を示し、Ｒ５は飽和脂肪族基または飽和脂環式基を示し、ａは１～４０の整数を示す。］
Figure JPOXMLDOC01-appb-C000012
 ［式（Ｂ）中、Ｒ６及びＲ７はそれぞれ独立に炭素数２～１２の直鎖又は分岐鎖のアルキレン基を示し、ｂは１～１０の整数を示し、ｃは１～２５の整数を示す。なお、式中、Ｒ６同士、Ｒ７同士、ｂ同士及びｃ同士はそれぞれ同一でも異なってもよい。］ The present invention also provides an adhesive composition for connecting a first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface. The first circuit member and / or the second circuit member is composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less, and the adhesive composition is (a) a thermoplastic resin. , (B) a radically polymerizable compound and (c) a radical polymerization initiator, and (b) a radically polymerizable compound containing a urethane (meth) acrylate represented by the following general formula (A) I will provide a.
Figure JPOXMLDOC01-appb-C000011
 [In the formula (A), R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and R 3 represents a group derived from a ring-opening compound of ethylene group, propylene group or ε-caprolactone, or the following general formula: Represents a group represented by (B), R 4 represents a group represented by the following general formula (B), R 5 represents a saturated aliphatic group or a saturated alicyclic group, and a represents 1 to 40 Indicates an integer. ]
Figure JPOXMLDOC01-appb-C000012
 [In the formula (B), R 6 and R 7 each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms, b represents an integer of 1 to 10, and c represents an integer of 1 to 25. Indicates. In the formula, R 6 s , R 7 s , b s, and c s may be the same or different. ]
　本接着剤組成物は、（ｂ）ラジカル重合性化合物に含まれるウレタン（メタ）アクリレートが上記一般式（Ａ）で表される構造であることによって、凝集エネルギー密度が向上して、接着剤組成物とＴｇが２００℃以下の熱可塑性樹脂を含む基材（例えばＰＥＴ、ＰＣ、ＰＥＮ等）との濡れ性が向上し、ＰＥＴやＰＣ、ＰＥＮ等の熱可塑性樹脂を含む基材から構成される回路部材間の接着強度が向上し、優れた接続信頼性を得ることができる。また、（ｂ）ラジカル重合性化合物に含まれるウレタン（メタ）アクリレートが上記一般式（Ａ）で表される構造であることによって、接着剤組成物に適度な可とう性が付与され、ＰＥＴやＰＣ、ＰＥＮ等の熱可塑性樹脂を含む基材から構成される回路部材間の接着強度が向上し、優れた接続信頼性を得ることができる。さらに、長時間の信頼性試験後にも安定した性能を維持することができる。 This adhesive composition has a structure in which the urethane (meth) acrylate contained in the radically polymerizable compound (b) is represented by the general formula (A), whereby the cohesive energy density is improved, and the adhesive composition The wettability between the product and a base material containing a thermoplastic resin having a Tg of 200 ° C. or lower (for example, PET, PC, PEN, etc.) is improved, and the base material contains a thermoplastic resin such as PET, PC, PEN, etc. The adhesive strength between circuit members is improved, and excellent connection reliability can be obtained. In addition, (b) the urethane (meth) acrylate contained in the radical polymerizable compound has a structure represented by the general formula (A), so that an appropriate flexibility is imparted to the adhesive composition. Adhesive strength between circuit members composed of a base material containing a thermoplastic resin such as PC and PEN is improved, and excellent connection reliability can be obtained. Furthermore, stable performance can be maintained even after a long-term reliability test.
　本発明の接着剤組成物において、ウレタン（メタ）アクリレートは脂肪族ポリエステルジオールを用いて得たものであることが好ましい。ウレタン（メタ）アクリレートが脂肪族ポリエステルジオールを用いて得たものであることで、接着剤組成物の可とう性が向上し、ＰＥＴやＰＣ、ＰＥＮ等の熱可塑性樹脂を含む基材から構成される回路部材間の接着強度が向上し、優れた接続信頼性を得ることができる。 In the adhesive composition of the present invention, the urethane (meth) acrylate is preferably obtained using an aliphatic polyester diol. Since the urethane (meth) acrylate is obtained using an aliphatic polyester diol, the flexibility of the adhesive composition is improved, and it is composed of a base material containing a thermoplastic resin such as PET, PC, or PEN. The adhesive strength between circuit members can be improved, and excellent connection reliability can be obtained.
　また、本発明の接着剤組成物においては、ウレタン（メタ）アクリレートの重量平均分子量が８０００以上２５０００未満であることが好ましい。ウレタン（メタ）アクリレートの重量平均分子量が上記範囲内であることによって、ＰＥＴ、ＰＣ、ＰＥＮ等の有機基材との接着強度がより向上し、優れた接続信頼性を得ることができる。 In the adhesive composition of the present invention, it is preferable that the weight average molecular weight of urethane (meth) acrylate is 8000 or more and less than 25,000. When the weight average molecular weight of the urethane (meth) acrylate is within the above range, the adhesive strength with an organic base material such as PET, PC, PEN or the like is further improved, and excellent connection reliability can be obtained.
　また、本発明の接着剤組成物においては、（ｂ）ラジカル重合性化合物が、リン酸基を有するビニル化合物と、リン酸基を有するビニル化合物以外のラジカル重合性化合物と、をそれぞれ１種以上含有することが好ましい。（ｂ）ラジカル重合性化合物がこのような構成を備えることにより、特に金属からなる基材との接着強度がより向上する。 In the adhesive composition of the present invention, the radically polymerizable compound (b) is a vinyl compound having a phosphate group and one or more radically polymerizable compounds other than the vinyl compound having a phosphate group. It is preferable to contain. (B) Since the radically polymerizable compound has such a configuration, the adhesive strength with a base material made of a metal is further improved.
　また、本発明の接着剤組成物においては、（ａ）熱可塑性樹脂としては、フェノキシ樹脂、ポリウレタン樹脂、ポリエステルウレタン樹脂、ブチラール樹脂、アクリル樹脂及びポリイミド樹脂からなる群より選ばれる少なくとも１種を含有することが好ましい。（ａ）熱可塑性樹脂として、このような樹脂を含有することにより、接着剤組成物の耐熱性、接着性がより向上する。 In the adhesive composition of the present invention, (a) the thermoplastic resin contains at least one selected from the group consisting of phenoxy resin, polyurethane resin, polyester urethane resin, butyral resin, acrylic resin, and polyimide resin. It is preferable to do. (A) By containing such a resin as a thermoplastic resin, the heat resistance and adhesiveness of the adhesive composition are further improved.
　また、本発明の接着剤組成物においては、さらに（ｄ）導電性粒子を含有することも好ましい。（ｄ）導電性粒子を含有することにより、接着剤組成物に良好な導電性又は異方導電性を付与することができるため、接続端子を有する回路部材同士の接着用途等により好適に使用することが可能となる。また、上記接着剤組成物を介して電気的に接続した回路部材の接続抵抗をより十分に低減することができる。 The adhesive composition of the present invention preferably further contains (d) conductive particles. (D) By containing conductive particles, it is possible to impart good conductivity or anisotropic conductivity to the adhesive composition. Therefore, it is preferably used for bonding applications between circuit members having connection terminals. It becomes possible. Moreover, the connection resistance of the circuit member electrically connected via the said adhesive composition can be reduced more fully.
　また、本発明は、主面上に第一の接続端子を有する第一の回路部材と、主面上に第二の接続端子を有する第二の回路部材と、接続部材と、を備える回路部材の接続構造体であって、第一の接続端子及び第二の接続端子が対向するように、第一の回路部材及び第二の回路部材が上記接着剤組成物からなる接続部材を介して配置されるとともに、第一の接続端子及び第二の接続端子が電気的に接続されており、第一の回路部材及び／又は前記第二の回路部材は、ガラス転移温度が２００℃以下の熱可塑性樹脂を含有する基材から構成されている、回路部材の接続構造体を提供する。 Moreover, this invention is a circuit member provided with the 1st circuit member which has a 1st connection terminal on a main surface, the 2nd circuit member which has a 2nd connection terminal on a main surface, and a connection member The first circuit member and the second circuit member are arranged via the connection member made of the adhesive composition so that the first connection terminal and the second connection terminal face each other. In addition, the first connection terminal and the second connection terminal are electrically connected, and the first circuit member and / or the second circuit member has a glass transition temperature of 200 ° C. or less. Provided is a circuit member connection structure composed of a base material containing a resin.
　第一の回路部材及び／又は第二の回路部材が、ガラス転移温度が２００℃以下の熱可塑性樹脂を含有する基材から構成されている回路部材であることによって、接着剤組成物との濡れ性が向上して接着強度がより向上し、優れた接続信頼性を得ることができる。 The first circuit member and / or the second circuit member is a circuit member composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or lower, so that wetting with the adhesive composition As a result, the adhesive strength is further improved and excellent connection reliability can be obtained.
　上記ガラス転移温度が２００℃以下の熱可塑性樹脂は、ポリエチレンテレフタレート、ポリカーボネート及びポリエチレンナフタレートからなる群より選ばれる少なくとも１種であることが好ましい。ポリエチレンテレフタレート等を含有する基材から構成されている回路部材であることによって、接着剤組成物との濡れ性が向上して接着強度がより向上し、優れた接続信頼性を得ることができる。 The thermoplastic resin having a glass transition temperature of 200 ° C. or lower is preferably at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. By being a circuit member composed of a base material containing polyethylene terephthalate or the like, wettability with the adhesive composition is improved, adhesive strength is further improved, and excellent connection reliability can be obtained.
　また、本発明の回路部材の接続構造体において、第一の回路部材又は第二の回路部材のうち一方の回路部材が、ポリエチレンテレフタレート、ポリカーボネート及びポリエチレンナフタレートからなる群より選ばれる少なくとも１種を含有する基材から構成され、第一の回路部材又は第二の回路部材のうちもう一方の回路部材が、ポリイミド樹脂及びポリエチレンテレフタレートからなる群より選ばれる少なくとも１種を含有する基材から構成されることが好ましい。本接続構造体は、第一の回路部材と第二の回路部材が上記のような基材で構成されることによって、接着剤組成物との濡れ性及び接着強度がより向上し、優れた接続信頼性を得ることができる。 In the circuit member connection structure of the present invention, one circuit member of the first circuit member or the second circuit member is at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. It is comprised from the base material to contain, and the other circuit member is comprised from the base material which contains at least 1 sort (s) chosen from the group which consists of a polyimide resin and a polyethylene terephthalate among 1st circuit members or 2nd circuit members. It is preferable. In this connection structure, the first circuit member and the second circuit member are composed of the above-described base materials, so that the wettability and adhesive strength with the adhesive composition are further improved, and an excellent connection is achieved. Reliability can be obtained.
　本発明は、主面上に第一の接続端子を有する第一の回路部材と、主面上に第二の接続端子を有する第二の回路部材とを、上記接着剤組成物を介して第一の接続端子及び第二の接続端子が対向するように、配置する工程と、接着剤組成物を加熱し、硬化させて、第一の回路部材と第二の回路部材とを接続する工程と、を備える、回路部材の接続構造体の製造方法を提供する。本製造方法によれば、第一の回路部材と第二の回路部材を上記接着剤組成物で接続することによって、優れた接続信頼性を有する回路部材の接続構造体を得ることができる。 The present invention provides a first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface through the adhesive composition. A step of disposing the first connection terminal and the second connection terminal so as to face each other, a step of heating and curing the adhesive composition, and connecting the first circuit member and the second circuit member; The manufacturing method of the connection structure of a circuit member provided with these is provided. According to this manufacturing method, the connection structure of the circuit member which has the outstanding connection reliability can be obtained by connecting the 1st circuit member and the 2nd circuit member with the said adhesive composition.
　また、本発明は、（ａ）熱可塑性樹脂、（ｂ）ラジカル重合性化合物及び（ｃ）ラジカル重合開始剤を含有し、（ｂ）ラジカル重合性化合物が２５～４０ｍＮ／ｍの臨界表面張力を有するウレタン（メタ）アクリレートを含む、接着剤組成物の、主面上に第一の接続端子を有する第一の回路部材と、主面上に第二の接続端子を有する第二の回路部材であって、少なくとも一方の回路部材がガラス転移温度２００℃以下の熱可塑性樹脂を含む基材から構成された、第一の回路部材及び第二の回路部材を接続するための接着剤組成物としての応用を提供する。２５～４０ｍＮ／ｍの臨界表面張力を有するウレタン（メタ）アクリレートを含む（ｂ）ラジカル重合性化合物を含有する本接着剤組成物は、Ｔｇが２００℃以下の熱可塑性樹脂を含む基材（例えばＰＥＴ、ＰＣ、ＰＥＮ等）との濡れ性が向上し、低温硬化での接着が可能となるため、回路部材を接続するための接着剤組成物としての応用に好適である。 The present invention also includes (a) a thermoplastic resin, (b) a radical polymerizable compound, and (c) a radical polymerization initiator, and (b) the radical polymerizable compound has a critical surface tension of 25 to 40 mN / m. A first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface of the adhesive composition containing urethane (meth) acrylate having As an adhesive composition for connecting the first circuit member and the second circuit member, wherein at least one circuit member is composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less. Provide application. The adhesive composition containing (b) a radical polymerizable compound containing urethane (meth) acrylate having a critical surface tension of 25 to 40 mN / m is a base material containing a thermoplastic resin having a Tg of 200 ° C. or less (for example, PET, PC, PEN, etc.) are improved in wettability and can be bonded by low-temperature curing. Therefore, it is suitable for application as an adhesive composition for connecting circuit members.
　上記応用においては、ウレタン（メタ）アクリレートが下記一般式（Ａ）で表されるウレタン（メタ）アクリレートであることが好ましい。ウレタン（メタ）アクリレートが下記一般式（Ａ）で表される構造であることによって、回路部材間の接着強度が向上し、優れた接続信頼性を得ることができる。
Figure JPOXMLDOC01-appb-C000013
 ［式（Ａ）中、Ｒ１及びＲ２はそれぞれ独立に水素原子またはメチル基を示し、Ｒ３はエチレン基、プロピレン基、ε－カプロラクトンの開環化合物から誘導される基、または下記一般式（Ｂ）で表される基を示し、Ｒ４は下記一般式（Ｂ）で表される基を示し、Ｒ５は飽和脂肪族基または飽和脂環式基を示し、ａは１～４０の整数を示す。］
Figure JPOXMLDOC01-appb-C000014
 ［式（Ｂ）中、Ｒ６及びＲ７はそれぞれ独立に炭素数２～１２の直鎖又は分岐鎖のアルキレン基を示し、ｂは１～１０の整数を示し、ｃは１～２５の整数を示す。なお、式中、Ｒ６同士、Ｒ７同士、ｂ同士及びｃ同士はそれぞれ同一でも異なってもよい。］ In the said application, it is preferable that urethane (meth) acrylate is a urethane (meth) acrylate represented by the following general formula (A). When the urethane (meth) acrylate has a structure represented by the following general formula (A), the adhesive strength between the circuit members is improved, and excellent connection reliability can be obtained.
Figure JPOXMLDOC01-appb-C000013
 [In the formula (A), R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and R 3 represents a group derived from a ring-opening compound of ethylene group, propylene group or ε-caprolactone, or the following general formula: Represents a group represented by (B), R 4 represents a group represented by the following general formula (B), R 5 represents a saturated aliphatic group or a saturated alicyclic group, and a represents 1 to 40 Indicates an integer. ]
Figure JPOXMLDOC01-appb-C000014
 [In the formula (B), R 6 and R 7 each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms, b represents an integer of 1 to 10, and c represents an integer of 1 to 25. Indicates. In the formula, R 6 s , R 7 s , b s, and c s may be the same or different. ]
　また、本発明は、（ａ）熱可塑性樹脂、（ｂ）ラジカル重合性化合物及び（ｃ）ラジカル重合開始剤を含有し、（ｂ）ラジカル重合性化合物が下記一般式（Ａ）で表されるウレタン（メタ）アクリレートを含む、接着剤組成物の、主面上に第一の接続端子を有する第一の回路部材と、主面上に第二の接続端子を有する第二の回路部材であって、少なくとも一方の回路部材がガラス転移温度２００℃以下の熱可塑性樹脂を含む基材から構成された、第一の回路部材及び第二の回路部材を接続するための接着剤組成物としての応用を提供する。ウレタン（メタ）アクリレートが下記一般式（Ａ）で表される構造であることによって、回路部材間の接着強度が向上し、優れた接続信頼性を得ることができる。
Figure JPOXMLDOC01-appb-C000015
 ［式（Ａ）中、Ｒ１及びＲ２はそれぞれ独立に水素原子またはメチル基を示し、Ｒ３はエチレン基、プロピレン基、ε－カプロラクトンの開環化合物から誘導される基、または下記一般式（Ｂ）で表される基を示し、Ｒ４は下記一般式（Ｂ）で表される基を示し、Ｒ５は飽和脂肪族基または飽和脂環式基を示し、ａは１～４０の整数を示す。］
Figure JPOXMLDOC01-appb-C000016
 ［式（Ｂ）中、Ｒ６及びＲ７はそれぞれ独立に炭素数２～１２の直鎖又は分岐鎖のアルキレン基を示し、ｂは１～１０の整数を示し、ｃは１～２５の整数を示す。なお、式中、Ｒ６同士、Ｒ７同士、ｂ同士及びｃ同士はそれぞれ同一でも異なってもよい。］ The present invention also includes (a) a thermoplastic resin, (b) a radical polymerizable compound, and (c) a radical polymerization initiator, and (b) the radical polymerizable compound is represented by the following general formula (A). A first circuit member having a first connection terminal on a main surface of an adhesive composition containing urethane (meth) acrylate, and a second circuit member having a second connection terminal on the main surface. And an application as an adhesive composition for connecting the first circuit member and the second circuit member, wherein at least one circuit member is composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or lower. I will provide a. When the urethane (meth) acrylate has a structure represented by the following general formula (A), the adhesive strength between the circuit members is improved, and excellent connection reliability can be obtained.
Figure JPOXMLDOC01-appb-C000015
 [In the formula (A), R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and R 3 represents a group derived from a ring-opening compound of ethylene group, propylene group or ε-caprolactone, or the following general formula: Represents a group represented by (B), R 4 represents a group represented by the following general formula (B), R 5 represents a saturated aliphatic group or a saturated alicyclic group, and a represents 1 to 40 Indicates an integer. ]
Figure JPOXMLDOC01-appb-C000016
 [In the formula (B), R 6 and R 7 each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms, b represents an integer of 1 to 10, and c represents an integer of 1 to 25. Indicates. In the formula, R 6 s , R 7 s , b s, and c s may be the same or different. ]
　上記応用においては、ウレタン（メタ）アクリレートは脂肪族ポリエステルジオールを用いて得たものであることが好ましい。ウレタン（メタ）アクリレートが脂肪族ポリエステルジオールを用いて得たものであることで、接着剤組成物の可とう性が向上し、ＰＥＴやＰＣ、ＰＥＮ等の熱可塑性樹脂を含む基材から構成される回路部材間の接着強度が向上し、優れた接続信頼性を得ることができる。 In the above application, the urethane (meth) acrylate is preferably obtained using an aliphatic polyester diol. Since the urethane (meth) acrylate is obtained using an aliphatic polyester diol, the flexibility of the adhesive composition is improved, and it is composed of a base material containing a thermoplastic resin such as PET, PC, or PEN. The adhesive strength between circuit members can be improved, and excellent connection reliability can be obtained.
　上記応用においては、ウレタン（メタ）アクリレートの重量平均分子量が８０００以上２５０００未満であることが好ましい。ウレタン（メタ）アクリレートの重量平均分子量が上記範囲内であることによって、ＰＥＴ、ＰＣ、ＰＥＮ等の有機基材との接着強度がより向上し、優れた接続信頼性を得ることができる。 In the above application, the weight average molecular weight of urethane (meth) acrylate is preferably 8000 or more and less than 25000. When the weight average molecular weight of the urethane (meth) acrylate is within the above range, the adhesive strength with an organic base material such as PET, PC, PEN or the like is further improved, and excellent connection reliability can be obtained.
　上記応用においては、（ｂ）ラジカル重合性化合物が、リン酸基を有するビニル化合物と、リン酸基を有するビニル化合物以外のラジカル重合性化合物と、をそれぞれ１種以上含有することが好ましい。（ｂ）ラジカル重合性化合物がこのような構成を備えることにより、特に金属からなる基材との接着強度がより向上する。 In the above application, it is preferable that the (b) radical polymerizable compound contains at least one vinyl compound having a phosphate group and one or more radical polymerizable compounds other than the vinyl compound having a phosphate group. (B) Since the radically polymerizable compound has such a configuration, the adhesive strength with a base material made of a metal is further improved.
　上記応用においては、（ａ）熱可塑性樹脂としては、フェノキシ樹脂、ポリウレタン樹脂、ポリエステルウレタン樹脂、ブチラール樹脂、アクリル樹脂及びポリイミド樹脂からなる群より選ばれる少なくとも１種を含有することが好ましい。（ａ）熱可塑性樹脂として、このような樹脂を含有することにより、耐熱性、接着性がより向上する。 In the above application, (a) the thermoplastic resin preferably contains at least one selected from the group consisting of phenoxy resin, polyurethane resin, polyester urethane resin, butyral resin, acrylic resin and polyimide resin. (A) By containing such a resin as a thermoplastic resin, heat resistance and adhesiveness are further improved.
　上記応用においては、接着剤組成物が（ｄ）導電性粒子をさらに含有することが好ましい。（ｄ）導電性粒子を含有することにより、接着剤組成物に良好な導電性又は異方導電性を付与することができ、また、電気的に接続した回路部材の接続抵抗をより十分に低減することができる。 In the above application, it is preferable that the adhesive composition further contains (d) conductive particles. (D) By containing conductive particles, it is possible to impart good conductivity or anisotropic conductivity to the adhesive composition, and more sufficiently reduce the connection resistance of electrically connected circuit members. can do.
　本発明によれば、ポリエチレンテレフタレート、ポリカーボネート、ポリエチレンナフタレート等の有機基材に対して、低温の硬化条件においても、優れた接着強度を得ることができ、長時間の信頼性試験（高温高湿試験）後においても安定した性能（接着強度や接続抵抗）を維持することができる接着剤組成物、それを用いた回路部材の接続構造体、回路部材の接続構造体の製造方法及び接着剤組成物の応用を提供することができる。 According to the present invention, an excellent adhesive strength can be obtained even under low temperature curing conditions on an organic substrate such as polyethylene terephthalate, polycarbonate, and polyethylene naphthalate, and a long-term reliability test (high temperature and high humidity) can be achieved. Adhesive composition capable of maintaining stable performance (adhesive strength and connection resistance) even after test), circuit member connection structure using the same, circuit member connection structure manufacturing method, and adhesive composition Application of things can be provided.
本実施形態の接着剤組成物を用いた、回路部材の接続構造体の一実施形態を示す模式断面図である。It is a schematic cross section which shows one Embodiment of the connection structure of a circuit member using the adhesive composition of this embodiment. 図１に示す回路部材の接続構造体を作製する前の、第一の回路部材、第二の回路部材及び接着剤組成物を示す模式断面図である。It is a schematic cross section which shows the 1st circuit member, the 2nd circuit member, and adhesive composition before producing the connection structure of the circuit member shown in FIG. 本実施形態の接着剤組成物（導電性粒子含有）を用いた、回路部材の接続構造体の一実施形態を示す模式断面図である。It is a schematic cross section which shows one Embodiment of the connection structure of a circuit member using the adhesive composition (electroconductive particle containing) of this embodiment. 図３に示す回路部材の接続構造体を作製する前の、第一の回路部材、第二の回路部材及び接着剤組成物（導電性粒子含有）を示す模式断面図である。It is a schematic cross section which shows the 1st circuit member, the 2nd circuit member, and adhesive composition (electroconductive particle containing) before producing the connection structure of the circuit member shown in FIG.
　以下、場合により図面を参照しつつ、本発明の好適な実施形態について詳細に説明する。なお、図面中、同一又は相当部分には同一符号を付し、重複する説明は省略する。また、本実施形態において、（メタ）アクリル酸とはアクリル酸又はそれに対応するメタクリル酸を示し、（メタ）アクリレートとはアクリレート又はそれに対応するメタアクリレートを意味し、（メタ）アクリロイル基とはアクリロイル基又はメタアクリロイル基を意味する。 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 corresponding parts are denoted by the same reference numerals, and redundant description is omitted. In this embodiment, (meth) acrylic acid means acrylic acid or methacrylic acid corresponding thereto, (meth) acrylate means acrylate or methacrylate corresponding thereto, and (meth) acryloyl group means acryloyl. Means a group or a methacryloyl group.
　本実施形態における「ガラス転移温度（Ｔｇ）」とは、フィルム状の有機基材をティー・エイ・インスツルメント社製粘弾性アナライザー「ＲＳＡ－３」（商品名）を用いて、昇温速度５℃／ｍｉｎ、周波数１０Ｈｚ、測定温度－１５０～３００℃の条件で測定した、Ｔｇ付近のｔａｎδピーク温度の値をいう。 “Glass transition temperature (Tg)” in the present embodiment refers to a film-like organic base material using a viscoelasticity analyzer “RSA-3” (trade name) manufactured by TA Instruments, Inc. The value of tan δ peak temperature in the vicinity of Tg, measured under the conditions of 5 ° C./min, frequency 10 Hz, measurement temperature −150 to 300 ° C.
　また、本実施形態における「臨界表面張力（γｃ）」とは、フィルム状にしたウレタン（メタ）アクリレートに純水、ぬれ張力試験用混合溶液Ｎｏ．５０、６０（和光純薬工業（株）製）をそれぞれ２３℃で１μｌ滴下した直後のウレタン（メタ）アクリレート表面とのなす角（接触角θ）を実測し、各液体の表面張力をｘ軸に、ＣＯＳθをｙ軸にプロットしたときに、３点を通る直線がＹ＝１となるときの表面張力をいう。なお、上記純水、Ｎｏ．５０、６０の測定で得られた３点を通る直線がＹ＝１のとき、Ｘが負の値になった場合については、純水、ぬれ張力試験用混合溶液Ｎｏ．６０、１－ブロモナフタレン（和光純薬工業（株）製）を用いて上記と同様の測定を行い、得られた３点を通る直線がＹ＝１となるときの表面張力の値を用いることもできる。 In addition, “critical surface tension (γ c )” in the present embodiment is a film-like urethane (meth) acrylate mixed with pure water and a wet tension test mixed solution No. 50 and 60 (manufactured by Wako Pure Chemical Industries, Ltd.) were each measured at the angle (contact angle θ) formed with the urethane (meth) acrylate surface immediately after dropping 1 μl at 23 ° C., and the surface tension of each liquid was measured on the x-axis. The surface tension when the straight line passing through the three points becomes Y = 1 when COSθ is plotted on the y-axis. In addition, the pure water, No. When the straight line passing through the three points obtained by the measurements of 50 and 60 is Y = 1, X is a negative value. 60, 1-Bromonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) is used for the same measurement as above, and the value of the surface tension when the obtained straight line passing through the three points is Y = 1 is used. You can also.
　また、本実施形態において、「重量平均分子量」及び「数平均分子量」とは、表１に示す条件に従って、ゲル浸透クロマトグラフ（ＧＰＣ）より標準ポリスチレンによる検量線を用いて測定した値をいう。 In the present embodiment, “weight average molecular weight” and “number average molecular weight” refer to values measured using a standard polystyrene calibration curve from a gel permeation chromatograph (GPC) according to the conditions shown in Table 1.
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
　本実施形態の接着剤組成物は、主面上に第一の接続端子を有する第一の回路部材と、主面上に第二の接続端子を有する第二の回路部材とを接続するための接着剤組成物であって、第一の回路部材及び／又は第二の回路部材は、ガラス転移温度が２００℃以下の熱可塑性樹脂を含む基材から構成され、接着剤組成物は、（ａ）熱可塑性樹脂、（ｂ）ラジカル重合性化合物及び（ｃ）ラジカル重合開始剤を含有し、（ｂ）ラジカル重合性化合物が２５～４０ｍＮ／ｍの臨界表面張力を有するウレタン（メタ）アクリレートを含む、接着剤組成物である。 The adhesive composition of the present embodiment is for connecting a first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface. An adhesive composition, wherein the first circuit member and / or the second circuit member is composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less, and the adhesive composition comprises (a A) a thermoplastic resin, (b) a radically polymerizable compound and (c) a radical polymerization initiator, and (b) the radically polymerizable compound contains a urethane (meth) acrylate having a critical surface tension of 25 to 40 mN / m. An adhesive composition.
　本実施形態の接着剤組成物に含有される（ａ）熱可塑性樹脂は、加熱により粘度の高い液状状態になって外力により自由に変形し、冷却し外力を取り除くとその形状を保ったままで硬くなり、この過程を繰り返して行える性質を持つ樹脂（高分子）をいう。また、上記の性質を有する反応性官能基を有する樹脂（高分子）も含む。（ａ）熱可塑性樹脂のＴｇは、０～１９０℃が好ましく、２０～１７０℃がより好ましい。 The thermoplastic resin (a) contained in the adhesive composition of the present embodiment becomes a liquid state having a high viscosity by heating and is freely deformed by external force, and is hardened while maintaining its shape when cooled and removed. That is, it refers to a resin (polymer) having the property of repeating this process. In addition, a resin (polymer) having a reactive functional group having the above properties is also included. (A) Tg of the thermoplastic resin is preferably 0 to 190 ° C, more preferably 20 to 170 ° C.
　このような熱可塑性樹脂としては、ポリイミド樹脂、ポリアミド樹脂、フェノキシ樹脂、（メタ）アクリル樹脂、ウレタン樹脂、ポリエステルウレタン樹脂、ポリビニルブチラール樹脂等を用いることができる。これらは単独あるいは２種類以上を混合して用いることができる。さらに、これら熱可塑性樹脂中にはシロキサン結合やフッ素置換基が含まれていてもよい。これらは、混合する樹脂同士が完全に相溶するか、もしくはミクロ相分離が生じて白濁する状態であれば好適に用いることができる。 As such a thermoplastic resin, polyimide resin, polyamide resin, phenoxy resin, (meth) acrylic resin, urethane resin, polyester urethane resin, polyvinyl butyral resin, or the like can be used. These can be used alone or in admixture of two or more. Further, these thermoplastic resins may contain a siloxane bond or a fluorine substituent. These can be suitably used as long as the resins to be mixed are completely compatible with each other or microphase separation occurs and becomes cloudy.
　接着剤組成物をフィルム状にして利用する場合、上記熱可塑性樹脂の分子量が大きいほど、良好なフィルム形成性が容易に得られ、またフィルム状接着剤組成物としての流動性に影響する溶融粘度を広範囲に設定できる。（ａ）熱可塑性樹脂の重量平均分子量としては５０００～１５００００が好ましく、１００００～８００００がより好ましい。この値が、５０００未満であると良好なフィルム形成性が得られにくい傾向があり、１５００００を超えると他の成分との良好な相溶性が得られにくい傾向がある。 When the adhesive composition is used in the form of a film, the higher the molecular weight of the thermoplastic resin, the easier it is to obtain good film formability, and the melt viscosity that affects the fluidity of the film-like adhesive composition. Can be set in a wide range. (A) The weight average molecular weight of the thermoplastic resin is preferably 5000 to 150,000, more preferably 10,000 to 80,000. If this value is less than 5000, good film formability tends to be difficult to obtain, and if it exceeds 150,000, good compatibility with other components tends to be difficult to obtain.
　本実施形態の接着剤組成物において、（ａ）熱可塑性樹脂の含有量は、接着剤組成物全量を基準として、５～８０質量％であることが好ましく、１５～７０質量％であることがより好ましい。この含有量が５質量％未満であると、接着剤組成物をフィルム状にして利用する場合に特に、良好なフィルム形成性が得られにくい傾向があり、８０質量％を超えると、良好な接着剤組成物の流動性が得られにくい傾向がある。 In the adhesive composition of the present embodiment, the content of the thermoplastic resin (a) is preferably 5 to 80% by mass, and preferably 15 to 70% by mass based on the total amount of the adhesive composition. More preferred. When this content is less than 5% by mass, particularly when the adhesive composition is used in the form of a film, good film formability tends to be difficult to obtain, and when it exceeds 80% by mass, good adhesion is obtained. The fluidity of the agent composition tends to be difficult to obtain.
　本実施形態の接着剤組成物に含有される（ｂ）ラジカル重合性化合物は、ラジカル重合開始剤の作用でラジカル重合を生じる化合物をいうが、光や熱等の活性化エネルギーを付与することでそれ自体ラジカルを生じる化合物であってもよい。（ｂ）ラジカル重合性化合物としては、例えば、ビニル基、（メタ）アクリロイル基、アリル基、マレイミド基等の活性ラジカルによって重合する官能基を有する化合物を好適に使用可能である。 The (b) radical polymerizable compound contained in the adhesive composition of the present embodiment refers to a compound that generates radical polymerization by the action of a radical polymerization initiator, but by applying activation energy such as light and heat. It may be a compound that itself generates a radical. (B) As the radically polymerizable compound, for example, a compound having a functional group that is polymerized by an active radical such as a vinyl group, a (meth) acryloyl group, an allyl group, or a maleimide group can be preferably used.
　（ｂ）ラジカル重合性化合物として具体的には、エポキシ（メタ）アクリレートオリゴマー、ウレタン（メタ）アクリレートオリゴマー、ポリエーテル（メタ）アクリレートオリゴマー、ポリエステル（メタ）アクリレートオリゴマー等のオリゴマー、トリメチロールプロパントリ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリアルキレングリコールジ（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニロキシエチル（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、イソシアヌル酸変性２官能（メタ）アクリレート、イソシアヌル酸変性３官能（メタ）アクリレート、ビスフェノキシエタノールフルオレンアクリレート、ビスフェノールフルオレンジグリシジルエーテルのグリシジル基に（メタ）アクリル酸を付加させたエポキシ（メタ）アクリレート、ビスフェノキシエタノールフルオレンアクリレート、ビスフェノールフルオレンジグリシジルエーテルのグリシジル基に（メタ）アクリル酸を付加させたエポキシ（メタ）アクリレート、ビスフェノールフルオレンジグリシジルエーテルのグリシジル基にエチレングリコールやプロピレングリコールを付加させた化合物に（メタ）アクリロイルオキシ基を導入した化合物、下記一般式（Ｃ）及び（Ｄ）で示される化合物等が挙げられる。 (B) Specific examples of the radical polymerizable compound include epoxy (meth) acrylate oligomers, urethane (meth) acrylate oligomers, polyether (meth) acrylate oligomers, polyester (meth) acrylate oligomers, trimethylolpropane tri ( (Meth) acrylate, polyethylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, isocyanuric acid modified bifunctional (meth) acrylate, isocyanuric acid modified trifunctional (meth) acrylate, bisphenoxyeta (Meth) acrylic acid is added to the glycidyl group of bisphenol fluorene glycidyl ether, epoxy (meth) acrylate obtained by adding (meth) acrylic acid to the glycidyl group of allyl fluorene acrylate and bisphenol fluorenediglycidyl ether A compound in which ethylene glycol or propylene glycol is added to a glycidyl group of epoxy (meth) acrylate, bisphenol fluorenediglycidyl ether, and (meth) acryloyloxy group introduced into the compound, and the following general formulas (C) and (D) And the like.
Figure JPOXMLDOC01-appb-C000018
 ［式（Ｃ）中、Ｒ８及びＲ９はそれぞれ独立に水素原子またはメチル基を示し、ｄ及びｅはそれぞれ独立に１～８の整数を示す。］
Figure JPOXMLDOC01-appb-C000018
 [In the formula (C), R 8 and R 9 each independently represent a hydrogen atom or a methyl group, and d and e each independently represent an integer of 1 to 8. ]
Figure JPOXMLDOC01-appb-C000019
 ［式（Ｄ）中、Ｒ１０及びＲ１１はそれぞれ独立に水素原子またはメチル基を示し、ｆ及びｇはそれぞれ独立に０～８の整数を示す。］
Figure JPOXMLDOC01-appb-C000019
 [In the formula (D), R 10 and R 11 each independently represent a hydrogen atom or a methyl group, and f and g each independently represents an integer of 0 to 8. ]
　また、（ｂ）ラジカル重合性化合物としては、単独で３０℃に静置した場合にワックス状、ろう状、結晶状、ガラス状、粉状等の流動性が無く固体状態を示すものであっても、特に制限することなく使用することができる。このような（ｂ）ラジカル重合性化合物として具体的には、Ｎ，Ｎ’－メチレンビスアクリルアミド、ダイアセトンアクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－フェニルメタクリルアミド、２－アクリルアミド－２－メチルプロパンスルホン酸、トリス（２－アクリロイルオキシエチル）イソシアヌレート、Ｎ－フェニルマレイミド、Ｎ－（ｏ－メチルフェニル）マレイミド、Ｎ－（ｍ－メチルフェニル）マレイミド、Ｎ－（ｐ－メチルフェニル）－マレイミド、Ｎ－（ｏ－メトキシフェニル）マレイミド、Ｎ－（ｍ－メトキシフェニル）マレイミド、Ｎ－（ｐ－メトキシフェニル）－マレイミド、Ｎ－メチルマレイミド、Ｎ－エチルマレイミド、Ｎ－オクチルマレイミド、４，４’－ジフェニルメタンビスマレイミド、ｍ－フェニレンビスマレイミド、３，３’－ジメチル－５，５’－ジエチル－４，４’－ジフェニルメタンビスマレイミド、４－メチル－１，３－フェニレンビスマレイミド、Ｎ－メタクリロキシマレイミド、Ｎ－アクリロキシマレイミド、１，６－ビスマレイミド－（２，２，４－トリメチル）ヘキサン、Ｎ－メタクリロイルオキシコハク酸イミド、Ｎ－アクリロイルオキシコハク酸イミド、２－ナフチルメタクリレート、２－ナフチルアクリレート、ペンタエリスリトールテトラアクリレート、ジビニルエチレン尿素、ジビニルプロピレン尿素、２－ポリスチリルエチルメタクリレート、Ｎ－フェニル－Ｎ’－（３－メタクリロイルオキシ－２－ヒドロキシプロピル）－ｐ－フェニレンジアミン、Ｎ－フェニル－Ｎ’－（３－アクリロイルオキシ－２－ヒドロキシプロピル）－ｐ－フェニレンジアミン、テトラメチルピペリジルメタクリレート、テトラメチルピペリジルアクリレート、ペンタメチルピペリジルメタクリレート、ペンタメチルピペリジルアクリレート、オクタデシルアクリレート、Ｎ－ｔ－ブチルアクリルアミド、ジアセトンアクリルアミド、Ｎ－（ヒドロシキメチル）アクリルアミド、下記一般式（Ｅ）～（Ｎ）で示される化合物等が挙げられる。 The radically polymerizable compound (b) is a solid state having no fluidity such as waxy, waxy, crystalline, glassy or powdery when left alone at 30 ° C. However, it can be used without any particular limitation. Specific examples of the (b) radical polymerizable compound include N, N′-methylenebisacrylamide, diacetone acrylamide, N-methylolacrylamide, N-phenylmethacrylamide, 2-acrylamido-2-methylpropanesulfonic acid. , Tris (2-acryloyloxyethyl) isocyanurate, N-phenylmaleimide, N- (o-methylphenyl) maleimide, N- (m-methylphenyl) maleimide, N- (p-methylphenyl) -maleimide, N- (O-methoxyphenyl) maleimide, N- (m-methoxyphenyl) maleimide, N- (p-methoxyphenyl) -maleimide, N-methylmaleimide, N-ethylmaleimide, N-octylmaleimide, 4,4'-diphenylmethane Bismaleimide, m-fe Renbismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, N-methacryloxymaleimide, N-acryloxymaleimide 1,6-bismaleimide- (2,2,4-trimethyl) hexane, N-methacryloyloxysuccinimide, N-acryloyloxysuccinimide, 2-naphthyl methacrylate, 2-naphthyl acrylate, pentaerythritol tetraacrylate, Divinylethyleneurea, divinylpropyleneurea, 2-polystyrylethyl methacrylate, N-phenyl-N '-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, N-phenyl-N'-(3-acryloyl) Oxy 2-hydroxypropyl) -p-phenylenediamine, tetramethylpiperidyl methacrylate, tetramethylpiperidyl acrylate, pentamethylpiperidyl methacrylate, pentamethylpiperidyl acrylate, octadecyl acrylate, Nt-butylacrylamide, diacetone acrylamide, N- (hydroxy) And methyl) acrylamide and compounds represented by the following general formulas (E) to (N).
Figure JPOXMLDOC01-appb-C000020
 ［式（Ｅ）中、ｈは１～１０の整数を示す。］
Figure JPOXMLDOC01-appb-C000020
 [In the formula (E), h represents an integer of 1 to 10. ]
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
 ［式（Ｇ）中、Ｒ１２及びＲ１３はそれぞれ独立に水素原子またはメチル基を示し、ｉは１５～３０の整数を示す。］
Figure JPOXMLDOC01-appb-C000022
 [In Formula (G), R 12 and R 13 each independently represent a hydrogen atom or a methyl group, and i represents an integer of 15 to 30. ]
Figure JPOXMLDOC01-appb-C000023
 ［式（Ｈ）中、Ｒ１４及びＲ１５はそれぞれ独立に水素原子またはメチル基を示し、ｊは１５～３０の整数を示す。］
Figure JPOXMLDOC01-appb-C000023
 [In the formula (H), R 14 and R 15 each independently represent a hydrogen atom or a methyl group, and j represents an integer of 15 to 30. ]
Figure JPOXMLDOC01-appb-C000024
 ［式（Ｉ）中、Ｒ１６は水素原子またはメチル基を示す。］
Figure JPOXMLDOC01-appb-C000024
 [In the formula (I), R 16 represents a hydrogen atom or a methyl group. ]
Figure JPOXMLDOC01-appb-C000025
 ［式（Ｊ）中、Ｒ１７は水素原子またはメチル基を示し、ｋは１～１０の整数を示す。］
Figure JPOXMLDOC01-appb-C000025
 [In the formula (J), R 17 represents a hydrogen atom or a methyl group, and k represents an integer of 1 to 10. ]
Figure JPOXMLDOC01-appb-C000026
 ［式（Ｋ）中、Ｒ１８は水素原子または下記一般式（ｉ）もしくは（ｉｉ）で示される有機基を示し、ｌは１～１０の整数を示す。］
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000026
 [In the formula (K), R 18 represents a hydrogen atom or an organic group represented by the following general formula (i) or (ii), and l represents an integer of 1 to 10. ]
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
 ［式（Ｌ）中、Ｒ１９は水素原子または下記一般式（ｉｉｉ）もしくは（ｉｖ）で示される有機基を示し、ｍは１～１０の整数を示す。］
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000029
 [In the formula (L), R 19 represents a hydrogen atom or an organic group represented by the following general formula (iii) or (iv), and m represents an integer of 1 to 10. ]
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
 ［式（Ｍ）中、Ｒ２０は水素原子またはメチル基を示す。］
Figure JPOXMLDOC01-appb-C000032
 [In the formula (M), R 20 represents a hydrogen atom or a methyl group. ]
Figure JPOXMLDOC01-appb-C000033
 ［式（Ｎ）中、Ｒ２１は水素原子またはメチル基を示す。］
Figure JPOXMLDOC01-appb-C000033
 [In formula (N), R 21 represents a hydrogen atom or a methyl group. ]
　また、（ｂ）ラジカル重合性化合物に属する化合物である、リン酸基含有ビニル化合物や、Ｎ－ビニル化合物及びＮ，Ｎ－ジアルキルビニル化合物からなる群より選ばれるＮ－ビニル系化合物を、これら以外の（ｂ）ラジカル重合性化合物と併用することができる。リン酸基含有ビニル化合物の併用により、接着剤組成物の金属基材への接着性を向上させることが可能になる。また、Ｎ－ビニル系化合物の併用により、接着剤組成物の橋かけ率を向上させることができる。 In addition, (b) a phosphate group-containing vinyl compound which is a compound belonging to the radical polymerizable compound, or an N-vinyl compound selected from the group consisting of an N-vinyl compound and an N, N-dialkylvinyl compound, The (b) radical polymerizable compound can be used in combination. The combined use of the phosphoric acid group-containing vinyl compound makes it possible to improve the adhesion of the adhesive composition to the metal substrate. In addition, the combined use of the N-vinyl compound can improve the crosslinking rate of the adhesive composition.
　リン酸基含有ビニル化合物としては、リン酸基及びビニル基を有する化合物であれば特に制限はないが、下記一般式（Ｏ）～（Ｑ）で示される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000034
 ［式（Ｏ）中、Ｒ２２は（メタ）アクリロイルオキシ基を示し、Ｒ２３は水素原子またはメチル基を示し、ｎ及びｏはそれぞれ独立に１～８の整数を示す。なお、式中、Ｒ２２同士、Ｒ２３同士、ｎ同士及びｏ同士はそれぞれ同一でも異なってもよい。］ The phosphate group-containing vinyl compound is not particularly limited as long as it is a compound having a phosphate group and a vinyl group, but compounds represented by the following general formulas (O) to (Q) are preferable.
Figure JPOXMLDOC01-appb-C000034
 [In the formula (O), R 22 represents a (meth) acryloyloxy group, R 23 represents a hydrogen atom or a methyl group, and n and o each independently represents an integer of 1 to 8. In the formula, R 22 s , R 23 s , n s, and o s may be the same or different. ]
Figure JPOXMLDOC01-appb-C000035
 ［式（Ｐ）中、Ｒ２４は（メタ）アクリロイルオキシ基を示し、ｐ及びｑはそれぞれ独立に１～８の整数を示す。なお、式中、Ｒ２４同士、ｐ同士及びｑ同士はそれぞれ同一でも異なってもよい。］
Figure JPOXMLDOC01-appb-C000035
 [In the formula (P), R 24 represents a (meth) acryloyloxy group, and p and q each independently represents an integer of 1 to 8. In the formula, R 24 s , p s, and q s may be the same or different. ]
Figure JPOXMLDOC01-appb-C000036
 ［式（Ｑ）中、Ｒ２５は（メタ）アクリロイルオキシ基を示し、Ｒ２６は水素原子又はメチル基を示し、ｒ及びｓはそれぞれ独立に１～８の整数を示す。なお、式中、Ｒ２６同士及びｒ同士はそれぞれ同一でも異なってもよい。］
Figure JPOXMLDOC01-appb-C000036
 [In Formula (Q), R 25 represents a (meth) acryloyloxy group, R 26 represents a hydrogen atom or a methyl group, and r and s each independently represent an integer of 1 to 8. In the formulae, R 26 and r may be the same or different. ]
　リン酸基含有ビニル化合物として具体的には、アシッドホスホオキシエチルメタクリレート、アシッドホスホオキシエチルアクリレート、アシッドホスホオキシプロピルメタクリレート、アシッドホスホオキシポリオキシエチレングリコールモノメタクリレート、アシッドホスホオキシポリオキシプロピレングリコールモノメタクリレート、２，２’－ジ（メタ）アクリロイロキシジエチルホスフェート、ＥＯ変性リン酸ジメタクリレート、リン酸変性エポキシアクリレート、リン酸ビニル等が挙げられる。 Specific examples of the phosphoric acid group-containing vinyl compound include acid phosphooxyethyl methacrylate, acid phosphooxyethyl acrylate, acid phosphooxypropyl methacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, acid phosphooxypolyoxypropylene glycol monomethacrylate, Examples include 2,2′-di (meth) acryloyloxydiethyl phosphate, EO-modified phosphate dimethacrylate, phosphate-modified epoxy acrylate, and vinyl phosphate.
　リン酸基含有ビニル化合物の配合量は、リン酸基含有ビニル化合物以外の（ｂ）ラジカル重合性化合物の配合量とは独立に、（ａ）熱可塑性樹脂１００質量部に対して、０．２～３００質量部とするのが好ましく、１～２００質量部とするのがより好ましく、１～５０質量部とするのがさらに好ましく、１～１５質量部とするのが特に好ましい。リン酸基含有ビニル化合物の配合量を０．２質量部未満とすると、高い接着強度が得られにくくなる傾向があり、３００質量部を越えると硬化後の接着剤組成物の物性が低下しやすく、信頼性を確保しにくくなる傾向がある。 The blending amount of the phosphoric acid group-containing vinyl compound is, independently of the blending amount of the (b) radical polymerizable compound other than the phosphoric acid group-containing vinyl compound, (a) with respect to 100 parts by mass of the thermoplastic resin. It is preferably from ˜300 parts by weight, more preferably from 1 to 200 parts by weight, even more preferably from 1 to 50 parts by weight, and particularly preferably from 1 to 15 parts by weight. If the amount of the phosphoric acid group-containing vinyl compound is less than 0.2 parts by mass, high adhesive strength tends to be difficult to obtain, and if it exceeds 300 parts by mass, the physical properties of the cured adhesive composition are likely to deteriorate. , Tend to be difficult to ensure reliability.
　一方、Ｎ－ビニル系化合物として、具体的には、Ｎ－ビニルイミダゾール、Ｎ－ビニルピリジン、Ｎ－ビニルピロリドン、Ｎ－ビニルホルムアミド、Ｎ－ビニルカプロラクタム、４，４’－ビニリデンビス（Ｎ，Ｎ－ジメチルアニリン）、Ｎ－ビニルアセトアミド、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジエチルアクリルアミド等が挙げられる。 On the other hand, specific examples of N-vinyl compounds include N-vinylimidazole, N-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, 4,4′-vinylidenebis (N, N -Dimethylaniline), N-vinylacetamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and the like.
　上述したリン酸基含有ビニル化合物に該当する化合物を除いた（ｂ）ラジカル重合性化合物の配合量は、（ａ）熱可塑性樹脂１００質量部に対して、５０～２５０質量部であることが好ましく、６０～１５０質量部であることがより好ましい。上記配合量が５０質量部未満であると、硬化後に充分な耐熱性が得られにくい傾向があり、また、２５０質量部を越えると、フィルムとして使用する場合に、良好なフィルム形成性が得られにくい傾向がある。 The amount of the radically polymerizable compound (b) excluding the compound corresponding to the above-mentioned phosphate group-containing vinyl compound is preferably 50 to 250 parts by mass with respect to 100 parts by mass of the (a) thermoplastic resin. 60 to 150 parts by mass is more preferable. If the blending amount is less than 50 parts by mass, sufficient heat resistance tends to be difficult to obtain after curing, and if it exceeds 250 parts by mass, good film formability is obtained when used as a film. It tends to be difficult.
　本実施形態の接着剤組成物は、（ｂ）ラジカル重合性化合物として臨界表面張力が２５～４０ｍＮ／ｍであるウレタン（メタ）アクリレート、及び下記一般式（Ａ）で表されるウレタン（メタ）アクリレートの一方又は両方の条件を満たすウレタン（メタ）アクリレートを必須成分として含有する。このうち、本実施形態においては、上記条件を満たすウレタンアクリレートがより好適に用いられる。ここで、下記一般式（Ａ）で表されるウレタン（メタ）アクリレートは、脂肪族系ジイソシアネート及びポリエステルジオールの縮合反応により得ることができる。
Figure JPOXMLDOC01-appb-C000037
 ［式（Ａ）中、Ｒ１及びＲ２はそれぞれ独立に水素原子またはメチル基を示し、Ｒ３はエチレン基、プロピレン基、ε－カプロラクトンの開環化合物から誘導される基、または下記一般式（Ｂ）で表される基を示し、Ｒ４は下記一般式（Ｂ）で表される基を示し、Ｒ５は飽和脂肪族基または飽和脂環式基を示し、ａは１～４０の整数を示す。］ The adhesive composition of the present embodiment includes (b) a urethane (meth) acrylate having a critical surface tension of 25 to 40 mN / m as a radical polymerizable compound, and a urethane (meth) represented by the following general formula (A): Urethane (meth) acrylate satisfying one or both conditions of acrylate is contained as an essential component. Among these, in this embodiment, the urethane acrylate which satisfy | fills the said conditions is used more suitably. Here, the urethane (meth) acrylate represented by the following general formula (A) can be obtained by a condensation reaction of an aliphatic diisocyanate and a polyester diol.
Figure JPOXMLDOC01-appb-C000037
 [In the formula (A), R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and R 3 represents a group derived from a ring-opening compound of ethylene group, propylene group or ε-caprolactone, or the following general formula: Represents a group represented by (B), R 4 represents a group represented by the following general formula (B), R 5 represents a saturated aliphatic group or a saturated alicyclic group, and a represents 1 to 40 Indicates an integer. ]
Figure JPOXMLDOC01-appb-C000038
 ［式（Ｂ）中、Ｒ６及びＲ７はそれぞれ独立に炭素数２～１２の直鎖又は分岐鎖のアルキレン基を示し、ｂは１～１０の整数を示し、ｃは１～２５の整数を示す。なお、式中、Ｒ６同士、Ｒ７同士、ｂ同士及びｃ同士はそれぞれ同一でも異なってもよい。］
Figure JPOXMLDOC01-appb-C000038
 [In the formula (B), R 6 and R 7 each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms, b represents an integer of 1 to 10, and c represents an integer of 1 to 25. Indicates. In the formula, R 6 s , R 7 s , b s, and c s may be the same or different. ]
　上記ウレタン（メタ）アクリレートを構成する脂肪族系ジイソシアネートは、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、リジンジイソシアネート、２－メチルペンタン－１，５－ジイソシアネート、３－メチルペンタン－１，５－ジイソシアネート、２，２，４－トリメチルヘキサメチレン－１，６－ジイソシアネート、２，４，４－トリメチルヘキサメチレン－１，６－ジイソシアネート、イソホロンジイソシアネート、シクロヘキシルジイソシアネート、水素添加キシリレンジイソシアネート、水素添加ジフェニルメタンジイソシアネート、水素添加トリメチルキシリレンジイソシアネート等から選択される。 The aliphatic diisocyanate constituting the urethane (meth) acrylate is tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, 2, 2,4-trimethylhexamethylene-1,6-diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated trimethyl It is selected from xylylene diisocyanate and the like.
　また、上記ウレタン（メタ）アクリレートを構成するポリエステルジオールとしては、例えば脂肪族系ポリエステルジオールや芳香族系ポリエステルジオールを用いることができ、脂肪族系ポリエステルジオールを用いることが好ましい。脂肪族系ポリエステルジオールは、エチレングリコール、プロピレングリコール、１,２－プロパンジオール、１,３－プロパンジオール、１,３－ブタンジオール、１,４－ブタンジオール、ネオペンチルグリコール、１、２－ペンタンジオール、１、４－ペンタンジオール、１、５－ペンタンジオール、２，４－ペンタンジオール、２－メチル－２，４－ペンタンジオール、２、４－ジメチル－２，４－ペンタンジオール、２、２，４－トリメチル－１，３－ペンタンジオール、１，２－ヘキサンジオール、１，５－ヘキサンジオール、１，６－ヘキサンジオール、２，５－ヘキサンジオール、２－エチル－１，３－ヘキサンジオール、２、５－ジメチル－２，５－ヘキサンジオール、１，２－オクタンジオール、１，８－オクタンジオール、１，７－ヘプタンジオール、１，９－ノナンジオール、１，２－デカンジオール、１，１０－デカンジオール、１，１２－デカンジオール、ドデカンジオール、ピナコール、１,４－ブチンジオール、トリエチレングリコール、ジエチレングリコール、ジプロピレングリコール、シクロヘキサンジメタノール等の飽和の低分子グリコール類、少なくとも１種類以上の上記グリコール類とホスゲンとの反応によって得られるポリカーボネートジオール類、少なくとも１種類以上の上記グリコール類を開始剤としてエチレンオキサイド、プロピレンオキサイド、エピクロルヒドリン等のモノマーの１種又はそれ以上を公知の方法により付加重合することによって得られるポリエーテルジオールなどのジオール類と、アジピン酸、３－メチルアジピン酸、２，２，５，５－テトラメチルアジピン酸、マレイン酸、フマル酸、コハク酸、２，２－ジメチルコハク酸、２－エチル－２－メチルコハク酸、２，３－ジメチルコハク酸、しゅう酸、マロン酸、メチルマロン酸、エチルマロン酸、ブチルマロン酸、ジメチルマロン酸、グルタル酸、２－メチルグルタル酸、３－メチルグルタル酸、２，２－ジメチルグルタル酸、３，３－ジメチルグルタル酸、２，４－ジメチルグルタル酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等の二塩基酸もしくはこれらに対応する酸無水物を脱水縮合させて得られる脂肪族系ポリエステルジオール類や、ε－カプロラクトン等の環状エステル化合物を開環重合して得られる脂肪族系ポリエステル系ジオール類から選択される。上記ジオール類及びジカルボン酸から得られるポリエステルジオール類は単独で用いる他に、２種以上のポリエステルジオール類を混合して用いてもよい。 Further, as the polyester diol constituting the urethane (meth) acrylate, for example, an aliphatic polyester diol or an aromatic polyester diol can be used, and an aliphatic polyester diol is preferably used. Aliphatic polyester diols are ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,2-pentane. Diol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2,2 , 4-Trimethyl-1,3-pentanediol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2-ethyl-1,3-hexanediol 2,5-dimethyl-2,5-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,7-heptanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,12-decanediol, dodecanediol, pinacol, 1,4-butynediol, triethylene glycol Saturated low molecular glycols such as diethylene glycol, dipropylene glycol and cyclohexanedimethanol, polycarbonate diols obtained by the reaction of at least one kind of the above glycols with phosgene, and at least one kind of the above glycols as an initiator Diols such as polyether diol obtained by addition polymerization of one or more monomers such as ethylene oxide, propylene oxide, epichlorohydrin and the like by a known method, and adipic acid, 3-methyladipine Acid, 2,2,5,5-tetramethyladipic acid, maleic acid, fumaric acid, succinic acid, 2,2-dimethylsuccinic acid, 2-ethyl-2-methylsuccinic acid, 2,3-dimethylsuccinic acid, oxalic acid Acid, malonic acid, methylmalonic acid, ethylmalonic acid, butylmalonic acid, dimethylmalonic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid Aliphatic polyester diols obtained by dehydration condensation of dibasic acids such as acid, 2,4-dimethylglutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or the like, or acid anhydrides corresponding thereto, and ε -Selected from aliphatic polyester-based diols obtained by ring-opening polymerization of cyclic ester compounds such as caprolactone. The polyester diols obtained from the diols and dicarboxylic acids may be used alone or in combination of two or more polyester diols.
　また、本実施形態の接着剤組成物においては、ＰＥＴ、ＰＣ、ＰＥＮ等の基材に対する接着強度向上の観点から、上記ウレタン（メタ）アクリレートの重量平均分子量は、８０００以上２５０００未満の範囲内で自由に調整し、好適に使用することができる。上記ウレタン（メタ）アクリレートの重量平均分子量が上記範囲内であれば、柔軟性と凝集力の双方を得ることができ、ＰＥＴ、ＰＣ、ＰＥＮ等の有機基材との接着強度が向上し、優れた接続信頼性を得ることができる。また、かかる効果をより十分に得る観点から、上記ウレタン（メタ）アクリレートの重量平均分子量は、１００００以上２５０００未満であることがより好ましい。なお、この重量平均分子量が８０００未満の場合、十分な可とう性が得られない傾向があり、２５０００以上であると、接着剤組成物の流動性が低下する傾向がある。 Moreover, in the adhesive composition of this embodiment, the weight average molecular weight of the said urethane (meth) acrylate is in the range of 8000 or more and less than 25000 from a viewpoint of the adhesive strength improvement with respect to base materials, such as PET, PC, and PEN. It can be freely adjusted and used suitably. If the weight average molecular weight of the urethane (meth) acrylate is within the above range, both flexibility and cohesive force can be obtained, and the adhesive strength with organic base materials such as PET, PC, and PEN is improved and excellent. Connection reliability can be obtained. Moreover, from the viewpoint of obtaining such effects more sufficiently, the weight average molecular weight of the urethane (meth) acrylate is more preferably 10,000 or more and less than 25,000. In addition, when this weight average molecular weight is less than 8000, there exists a tendency for sufficient flexibility not to be acquired, and when it is 25000 or more, there exists a tendency for the fluidity | liquidity of an adhesive composition to fall.
　上記ウレタン（メタ）アクリレートの臨界表面張力は、２５～４０ｍＮ／ｍであることが好ましく、２５～３５ｍＮ／ｍであることがより好ましい。ウレタン（メタ）アクリレートの臨界表面張力が２５～４０ｍＮ／ｍである場合、被着体であるＰＥＴ、ＰＣ、ＰＥＮの臨界表面張力と近くなり、濡れ性が向上することで、接着強度が向上し、優れた接続信頼性を得ることができる。また、この臨界表面張力が２５ｍＮ／ｍ未満又は４０ｍＮ／ｍを超えるとＰＥＴ、ＰＣ、ＰＥＮ等に対する濡れ性の低下や相容性が悪化する恐れがある。上記ウレタン（メタ）アクリレートの臨界表面張力は、ウレタン結合当量に関係し、ジオールの数平均分子量を変化させることで調整できると考えられる。例えば、ジオールの数平均分子量を大きくするとウレタン結合当量が減り、臨界表面張力が低下する傾向にある。 The critical surface tension of the urethane (meth) acrylate is preferably 25 to 40 mN / m, and more preferably 25 to 35 mN / m. When the critical surface tension of urethane (meth) acrylate is 25 to 40 mN / m, it becomes close to the critical surface tension of the adherends PET, PC and PEN, and the wettability is improved, thereby improving the adhesive strength. Excellent connection reliability can be obtained. Moreover, when this critical surface tension is less than 25 mN / m or more than 40 mN / m, the wettability with respect to PET, PC, PEN and the like may be deteriorated and the compatibility may deteriorate. It is considered that the critical surface tension of the urethane (meth) acrylate is related to the urethane bond equivalent and can be adjusted by changing the number average molecular weight of the diol. For example, when the number average molecular weight of the diol is increased, the urethane bond equivalent decreases, and the critical surface tension tends to decrease.
　また、上記ウレタン（メタ）アクリレートの配合量は、接着剤組成物全量を基準として、５～９５質量％であることが好ましく、１０～８０質量％であることがより好ましい。配合量が５質量％未満の場合、耐熱性が低下しやすい傾向があり、９５質量％を超えるとフィルムとして使用する場合にフィルム形成性が低下しやすい傾向がある。 The blending amount of the urethane (meth) acrylate is preferably 5 to 95% by mass, more preferably 10 to 80% by mass based on the total amount of the adhesive composition. When the blending amount is less than 5% by mass, the heat resistance tends to decrease, and when it exceeds 95% by mass, the film formability tends to decrease when used as a film.
　本実施形態の接着剤組成物に含有される（ｃ）ラジカル重合開始剤としては、従来から知られている有機過酸化物やアゾ化合物等、外部からのエネルギーの付与によりラジカルを発生する化合物を用いることができる。（ｃ）ラジカル重合開始剤としては、安定性、反応性、相溶性の観点から、１分間半減期温度が９０～１７５℃で、かつ分子量が１８０～１，０００の有機過酸化物が好ましい。１分間半減期温度がこの範囲にあることで、貯蔵安定性に優れ、ラジカル重合性も充分に高く、短時間で硬化できる。 As the (c) radical polymerization initiator contained in the adhesive composition of the present embodiment, conventionally known organic peroxides, azo compounds, and the like are compounds that generate radicals by applying external energy. Can be used. (C) The radical polymerization initiator is preferably an organic peroxide having a one-minute half-life temperature of 90 to 175 ° C. and a molecular weight of 180 to 1,000 from the viewpoints of stability, reactivity, and compatibility. When the 1-minute half-life temperature is within this range, the storage stability is excellent, the radical polymerizability is sufficiently high, and the composition can be cured in a short time.
　（ｃ）ラジカル重合開始剤としては、具体的には、１，１，３，３－テトラメチルブチルパーオキシネオデカノエート、ジ（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート、ジ（２－エチルヘキシル）パーオキシジカーボネート、クミルパーオキシネオデカノエート、１，１，３，３－テトラメチルブチルパーオキシネオデカノエート、ジラウロイルパーオキサイド、１－シクロヘキシル－１－メチルエチルパーオキシノエデカノエート、ｔ－ヘキシルパーオキシネオデカノエート、ｔ－ブチルパーオキシネオデカノエート、ｔ－ブチルパーオキシピバレート、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート、２，５－ジメチル－２，５－ジ（２－エチルヘキサノイルパーオキシ）ヘキサン、ｔ－ヘキシルパーオキシ－２－エチルヘキサノエート、ｔ－ブチルパーオキシ－２－エチルヘキサノエート、ｔ－ブチルパーオキシネオヘプタノエート、ｔ－アミルパーオキシ－２－エチルヘキサノエート、ジ－ｔ－ブチルパーオキシヘキサヒドロテレフタレート、ｔ－アミルパーオキシ－３，５，５－トリメチルヘキサノエート、３－ヒドロキシ－１，１－ジメチルブチルパーオキシネオデカノエート、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート、ｔ－アミルパーオキシネオデカノエート、ｔ－アミルパーオキシ－２－エチルヘキサノエート、ジ（３－メチルベンゾイル）パーオキサイド、ジベンゾイルパーオキサイド、ジ（４－メチルベンゾイル）パーオキサイド、ｔ－ヘキシルパーオキシイソプロピルモノカーボネート、ｔ－ブチルパーオキシマレイン酸、ｔ－ブチルパーオキシ－３，５，５－トリメチルヘキサノエート、ｔ－ブチルパーオキシラウレート、２，５－ジメチル－２，５－ジ（３－メチルベンゾイルパーオキシ）ヘキサン、ｔ－ブチルパーオキシ－２－エチルヘキシルモノカーボネート、ｔ－ヘキシルパーオキシベンゾエート、２，５－ジメチル－２，５－ジ（ベンゾイルパーオキシ）ヘキサン、ｔ－ブチルパーオキシベンゾエート、ジブチルパーオキシトリメチルアジペート、ｔ－アミルパーオキシノルマルオクトエート、ｔ－アミルパーオキシイソノナノエート、ｔ－アミルパーオキシベンゾエート等の有機過酸化物；２，２’－アゾビス－２，４－ジメチルバレロニトリル、１，１’－アゾビス（１－アセトキシ－１－フェニルエタン）、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２－メチルブチロニトリル）、ジメチル－２，２’－アゾビスイソブチロニトリル、４，４’－アゾビス（４－シアノバレリン酸）、１，１’－アゾビス（１－シクロヘキサンカルボニトリル）等のアゾ化合物；等が挙げられる。 (C) Specific examples of the radical polymerization initiator include 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2 -Ethylhexyl) peroxydicarbonate, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, dilauroyl peroxide, 1-cyclohexyl-1-methylethylperoxynoe Decanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexa Noate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t Hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneoheptanoate, t-amylperoxy-2-ethylhexanoate, di-t -Butylperoxyhexahydroterephthalate, t-amylperoxy-3,5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, 1,1,3,3- Tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxyneodecanoate, t-amylperoxy-2-ethylhexanoate, di (3-methylbenzoyl) peroxide, dibenzoylperoxide , Di (4-methylbenzoyl) peroxide, t-hexylperoxyisopropyl Carbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (3- Methylbenzoylperoxy) hexane, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate , Organic peroxides such as dibutyl peroxytrimethyladipate, t-amyl peroxy normal octoate, t-amyl peroxy isononanoate, t-amyl peroxybenzoate; 2,2′-azobis-2,4-dimethyl Valeronitrile, 1,1'-azobis (1-acetoxy-1-fur Phenylethane), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyronitrile, 4,4′-azobis Azo compounds such as (4-cyanovaleric acid) and 1,1′-azobis (1-cyclohexanecarbonitrile);
　これらの化合物は、単独で用いる他に、２種以上の化合物を混合して用いてもよい。 These compounds may be used alone or in combination of two or more compounds.
　また、（ｃ）ラジカル重合開始剤としては、１５０～７５０ｎｍの光照射によってラジカルを発生する化合物を用いることができる。このような化合物としては、例えば、Ｐｈｏｔｏｉｎｉｔｉａｔｉｏｎ，Ｐｈｏｔｏｐｏｌｙｍｅｒｉｚａｔｉｏｎ，ａｎｄ　Ｐｈｏｔｏｃｕｒｉｎｇ，Ｊ．－Ｐ．　Ｆｏｕａｓｓｉｅｒ，Ｈａｎｓｅｒ　Ｐｕｂｌｉｓｈｅｒｓ（１９９５年、ｐ１７～ｐ３５）に記載されているα－アセトアミノフェノン誘導体やホスフィンオキサイド誘導体が光照射に対する感度が高いためより好ましい。 In addition, as the (c) radical polymerization initiator, a compound that generates radicals upon irradiation with light of 150 to 750 nm can be used. Such compounds include, for example, Photoinitiation, Photopolymerization, and Photocuring, J. MoI. -P. Α-acetaminophenone derivatives and phosphine oxide derivatives described in Fouassier, Hanser Publishers (1995, p17 to p35) are more preferred because of their high sensitivity to light irradiation.
　これらの化合物は、単独で用いる他に、上記有機過酸化物やアゾ化合物と混合して用いてもよい。 These compounds may be used alone or in combination with the above organic peroxides or azo compounds.
　上記（ｃ）ラジカル重合開始剤の配合量は、（ａ）熱可塑性樹脂１００質量部に対して０．１～５００質量部が好ましく、１～３００質量部がより好ましく、５～５０質量部がさらに好ましく、１０～３０質量部が特に好ましい。（ｃ）ラジカル重合開始剤の配合量が０．１質量部未満では、接着剤組成物が充分に硬化しにくくなる傾向があり、５００質量部を超えると貯蔵安定性が悪化する傾向にある。 The blending amount of the (c) radical polymerization initiator is preferably 0.1 to 500 parts by weight, more preferably 1 to 300 parts by weight, and more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the (a) thermoplastic resin. More preferred is 10 to 30 parts by mass. (C) When the blending amount of the radical polymerization initiator is less than 0.1 parts by mass, the adhesive composition tends to be hard to be cured sufficiently, and when it exceeds 500 parts by mass, the storage stability tends to deteriorate.
　本実施形態の接着剤組成物に含有される（ｄ）導電性粒子は、その全体又は表面に導電性を有する粒子であればよいが、接続端子を有する回路部材の接続に使用する場合は、接続端子間距離より平均粒径が小さいことが好ましい。 The conductive particles (d) contained in the adhesive composition of the present embodiment may be particles having conductivity on the whole or on the surface, but when used for connecting circuit members having connection terminals, The average particle size is preferably smaller than the distance between the connection terminals.
　（ｄ）導電性粒子としては、Ａｕ、Ａｇ、Ｎｉ、Ｃｕ、はんだ等の金属粒子やカーボン等が挙げられる。また、非導電性のガラス、セラミック、プラスチック等を核とし、この核に上記金属、金属粒子やカーボンを被覆したものでもよい。（ｄ）導電性粒子が、プラスチックを核とし、この核に上記金属、金属粒子やカーボンを被覆したものや熱溶融金属粒子の場合、加熱加圧により変形性を有するので接続時に電極との接触面積が増加し信頼性が向上するので好ましい。 (D) Examples of the conductive particles include metal particles such as Au, Ag, Ni, Cu, and solder, and carbon. Further, non-conductive glass, ceramic, plastic or the like may be used as a core, and the core may be coated with the metal, metal particles, or carbon. (D) In the case where the conductive particles are made of plastic as a core and the core is coated with the above metal, metal particles or carbon, or hot-melt metal particles, they are deformable by heating and pressurization, so that they are in contact with the electrode at the time of connection. This is preferable because the area is increased and the reliability is improved.
　また、これらの（ｄ）導電性粒子の表面を、さらに高分子樹脂などで被覆した微粒子は、導電性粒子の配合量を増加した場合の粒子同士の接触による短絡を抑制し、電極回路間の絶縁性が向上できることから、適宜これを単独あるいは（ｄ）導電性粒子と混合して用いてもよい。 In addition, the fine particles obtained by coating the surface of the conductive particles (d) with a polymer resin or the like suppress a short circuit due to contact between the particles when the blending amount of the conductive particles is increased. Since insulation can be improved, it may be used alone or in admixture with (d) conductive particles.
　この（ｄ）導電性粒子の平均粒径は、分散性、導電性の点から１～１８μｍであることが好ましい。このような（ｄ）導電性粒子を含有する場合、接着剤組成物は異方導電性接着剤として、好適に用いることができる。 (D) The average particle diameter of the conductive particles is preferably 1 to 18 μm from the viewpoint of dispersibility and conductivity. When such (d) conductive particles are contained, the adhesive composition can be suitably used as an anisotropic conductive adhesive.
　（ｄ）導電性粒子の使用量は、特に制限は受けないが、接着剤組成物全体積に対して０．１～３０体積％とすることが好ましく、０．１～１０体積％とすることがより好ましい。この値が、０．１体積％未満であると導電性が低くなる傾向があり、３０体積％を超えると回路の短絡が生じやすくなる傾向がある。なお、体積％は２３℃の硬化前の各成分の体積をもとに決定されるが、各成分の体積は、比重を利用して重量から体積に換算することができる。また、メスシリンダー等にその成分を溶解したり膨潤させたりせず、その成分をよくぬらす適当な溶媒（水、アルコール等）を入れたものに、その成分を投入し増加した体積をその成分の体積として求めることもできる。 (D) The amount of the conductive particles used is not particularly limited, but is preferably 0.1 to 30% by volume, preferably 0.1 to 10% by volume based on the total volume of the adhesive composition. Is more preferable. If this value is less than 0.1% by volume, the conductivity tends to be low, and if it exceeds 30% by volume, a short circuit tends to occur. In addition, although volume% is determined based on the volume of each component before 23 degreeC hardening, the volume of each component can be converted into a volume from a weight using specific gravity. In addition, do not dissolve or swell the component in a graduated cylinder, etc., and put the component in a suitable solvent (water, alcohol, etc.) that wets the component well. It can also be determined as a volume.
　また、本実施形態の接着剤組成物には、硬化速度の制御や貯蔵安定性を付与するために、安定化剤を添加することできる。このような安定化剤としては、特に制限なく公知の化合物を使用することができるが、ベンゾキノンやハイドロキノン等のキノン誘導体；４－メトキシフェノールや４－ｔ－ブチルカテコール等のフェノール誘導体；２，２，６，６－テトラメチルピペリジン－１－オキシルや４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン－１－オキシル等のアミノキシル誘導体；テトラメチルピペリジルメタクリレート等のヒンダードアミン誘導体；等が好ましい。 Further, a stabilizer can be added to the adhesive composition of the present embodiment in order to control the curing rate and to provide storage stability. As such a stabilizer, known compounds can be used without particular limitation, but quinone derivatives such as benzoquinone and hydroquinone; phenol derivatives such as 4-methoxyphenol and 4-t-butylcatechol; , 6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and the like; hindered amine derivatives such as tetramethylpiperidyl methacrylate;
　安定化剤の配合量は、接着剤組成物１００質量部に対して、０．０１～３０質量部が好ましく、０．０５～１０質量部がより好ましい。配合量が０．０１質量部未満の場合、硬化速度の制御や貯蔵安定性が付与されにくくなり、３０質量部を越える場合には、他の成分との相溶性に悪影響を及ぼしやすくなる。 The blending amount of the stabilizer is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the adhesive composition. When the blending amount is less than 0.01 parts by mass, it becomes difficult to control the curing rate and storage stability, and when it exceeds 30 parts by mass, the compatibility with other components tends to be adversely affected.
　また、本実施形態の接着剤組成物には、アルコキシシラン誘導体やシラザン誘導体に代表されるカップリング剤、密着向上剤及びレベリング剤などの接着助剤を適宜添加してもよい。カップリング剤として具体的には、下記一般式（Ｒ）で示される化合物が好ましく、単独で用いる他に、２種以上の化合物を混合して用いてもよい。 In addition, adhesion aids such as coupling agents represented by alkoxysilane derivatives and silazane derivatives, adhesion improvers, and leveling agents may be appropriately added to the adhesive composition of the present embodiment. Specifically, the compound represented by the following general formula (R) is preferable as the coupling agent, and two or more compounds may be mixed and used in addition to the compound used alone.
Figure JPOXMLDOC01-appb-C000039
 ［式（Ｒ）中、Ｒ２７、Ｒ２８及びＲ２９はそれぞれ独立に、水素原子、炭素数１～５のアルキル基、炭素数１～５のアルコキシ基、炭素数１～５のアルコキシカルボニル基又はアリール基を示し、Ｒ３０は（メタ）アクリロイル基、ビニル基、イソシアナート基、イミダゾール基、メルカプト基、アミノ基、メチルアミノ基、ジメチルアミノ基、ベンジルアミノ基、フェニルアミノ基、シクロヘキシルアミノ基、モルホリノ基、ピペラジノ基、ウレイド基又はグリシジル基を示し、ｔは１～１０の整数を示す。］
Figure JPOXMLDOC01-appb-C000039
 [In the formula (R), R 27 , R 28 and R 29 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkoxycarbonyl group having 1 to 5 carbon atoms. Or R 30 represents (meth) acryloyl group, vinyl group, isocyanate group, imidazole group, mercapto group, amino group, methylamino group, dimethylamino group, benzylamino group, phenylamino group, cyclohexylamino group , A morpholino group, a piperazino group, a ureido group or a glycidyl group, and t represents an integer of 1 to 10. ]
　本実施形態の接着剤組成物は、応力緩和及び接着性向上を目的に、ゴム成分を併用してもよい。ゴム成分とは、そのままの状態でゴム弾性（ＪＩＳ　Ｋ６２００）を示す成分又は反応によりゴム弾性を示す成分をいう。ゴム成分は、室温（２５℃）で固形でも液状でもよいが、流動性向上の観点から液状であることが好ましい。ゴム成分としては、ポリブタジエン骨格を有する化合物が好ましい。ゴム成分は、シアノ基、カルボキシル基、水酸基、（メタ）アクリロイル基またはモルホリン基を有していてもよい。また、接着性向上の観点から、高極性基であるシアノ基、カルボキシル基を側鎖あるいは末端に含むゴム成分が好ましい。なお、ポリブタジエン骨格を有していても、熱可塑性を示す場合は（ａ）熱可塑性樹脂に分類し、ラジカル重合性を示す場合は（ｂ）ラジカル重合性化合物に分類する。 In the adhesive composition of the present embodiment, a rubber component may be used in combination for the purpose of stress relaxation and adhesion improvement. The rubber component refers to a component that exhibits rubber elasticity (JIS K6200) as it is or a component that exhibits rubber elasticity by reaction. The rubber component may be solid or liquid at room temperature (25 ° C.), but is preferably liquid from the viewpoint of improving fluidity. As the rubber component, a compound having a polybutadiene skeleton is preferable. The rubber component may have a cyano group, a carboxyl group, a hydroxyl group, a (meth) acryloyl group, or a morpholine group. From the viewpoint of improving adhesiveness, a rubber component containing a cyano group or a carboxyl group, which is a highly polar group, in the side chain or terminal is preferable. In addition, even if it has a polybutadiene skeleton, if it exhibits thermoplasticity, it is classified as (a) a thermoplastic resin, and if it exhibits radical polymerizability, it is classified as (b) a radically polymerizable compound.
　ゴム成分として具体的には、ポリイソプレン、ポリブタジエン、カルボキシル基末端ポリブタジエン、水酸基末端ポリブタジエン、１，２－ポリブタジエン、カルボキシル基末端１，２－ポリブタジエン、水酸基末端１，２－ポリブタジエン、アクリルゴム、スチレン－ブタジエンゴム、水酸基末端スチレン－ブタジエンゴム、アクリロニトリル－ブタジエンゴム、カルボキシル基、水酸基、（メタ）アクリロイル基またはモルホリン基をポリマ末端に含有するアクリロニトリル－ブタジエンゴム、カルボキシル化ニトリルゴム、水酸基末端ポリ（オキシプロピレン）、アルコキシシリル基末端ポリ（オキシプロピレン）、ポリ（オキシテトラメチレン）グリコール、ポリオレフィングリコール等が挙げられる。 Specific rubber components include polyisoprene, polybutadiene, carboxyl-terminated polybutadiene, hydroxyl-terminated polybutadiene, 1,2-polybutadiene, carboxyl-terminated 1,2-polybutadiene, hydroxyl-terminated 1,2-polybutadiene, acrylic rubber, styrene- Butadiene rubber, hydroxyl-terminated styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylonitrile-butadiene rubber containing carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group at the polymer end, carboxylated nitrile rubber, hydroxyl-terminated poly (oxypropylene) ), Alkoxysilyl group-terminated poly (oxypropylene), poly (oxytetramethylene) glycol, polyolefin glycol, and the like.
　また、上記高極性基を有し、室温で液状であるゴム成分としては、具体的には、液状アクリロニトリル－ブタジエンゴム、カルボキシル基、水酸基、（メタ）アクリロイル基またはモルホリン基をポリマ末端に含有する液状アクリロニトリル－ブタジエンゴム、液状カルボキシル化ニトリルゴム等が挙げられ、極性基であるアクリロニトリル含有量は１０～６０質量％が好ましい。 Further, the rubber component having a high polar group and being liquid at room temperature specifically includes a liquid acrylonitrile-butadiene rubber, a carboxyl group, a hydroxyl group, a (meth) acryloyl group or a morpholine group at the polymer end. Examples thereof include liquid acrylonitrile-butadiene rubber and liquid carboxylated nitrile rubber. The content of acrylonitrile, which is a polar group, is preferably 10 to 60% by mass.
　これらの化合物は単独で用いる他に、２種以上の化合物を混合して用いてもよい。 These compounds may be used alone or in combination of two or more compounds.
　また、本実施形態の接着剤組成物には、応力緩和及び接着性向上を目的に、有機微粒子を添加してもよい。有機微粒子の平均粒径は０．０５～１．０μｍが好ましい。なお、有機微粒子が上述のゴム成分からなる場合は、有機微粒子ではなくゴム成分に分類し、有機微粒子が上述の（ａ）熱可塑性樹脂からなる場合は、有機微粒子ではなく（ａ）熱可塑性樹脂に分類する。 In addition, organic fine particles may be added to the adhesive composition of the present embodiment for the purpose of stress relaxation and adhesion improvement. The average particle size of the organic fine particles is preferably 0.05 to 1.0 μm. In addition, when organic fine particles consist of the above-mentioned rubber component, it classifies into a rubber component instead of organic fine particles, and when organic fine particles consist of the above-mentioned (a) thermoplastic resin, it is not organic fine particle (a) thermoplastic resin. Classify into:
　有機微粒子として具体的には、ポリイソプレン、ポリブタジエン、カルボキシル基末端ポリブタジエン、水酸基末端ポリブタジエン、１，２－ポリブタジエン、カルボキシル基末端１，２－ポリブタジエン、アクリルゴム、スチレン－ブタジエンゴム、アクリロニトリル－ブタジエンゴム、カルボキシル基、水酸基、（メタ）アクリロイル基またはモルホリン基をポリマ末端に含有するアクリロニトリル－ブタジエンゴム、カルボキシル化ニトリルゴム、水酸基末端ポリ（オキシプロピレン）、アルコキシシリル基末端ポリ（オキシプロピレン）、ポリ（オキシテトラメチレン）グリコール、ポリオレフィングリコール（メタ）アクリル酸アルキル－ブタジエン－スチレン共重合体、（メタ）アクリル酸アルキル－シリコーン共重合体又はシリコーン（メタ）－アクリル共重合体若しくは複合体からなる有機微粒子が挙げられる。 Specific examples of organic fine particles include polyisoprene, polybutadiene, carboxyl-terminated polybutadiene, hydroxyl-terminated polybutadiene, 1,2-polybutadiene, carboxyl-terminated 1,2-polybutadiene, acrylic rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, Acrylonitrile-butadiene rubber, carboxylated nitrile rubber, hydroxyl-terminated poly (oxypropylene), alkoxysilyl-terminated poly (oxypropylene), poly (oxypropylene) containing carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group at the polymer end Tetramethylene) glycol, polyolefin glycol (meth) acrylic acid alkyl-butadiene-styrene copolymer, (meth) acrylic acid alkyl-silicone copolymer or Recone (meth) - include organic fine particles of acrylic copolymer or complex.
　これらの有機微粒子は単独で用いる他に、２種以上の化合物を併用して用いてもよい。 These organic fine particles may be used alone or in combination of two or more compounds.
　本実施形態の接着剤組成物は、常温で液状である場合にはペースト状で使用することができる。室温で固体の場合には、加熱して使用する他、溶媒を使用してペースト化してもよい。使用できる溶媒としては、接着剤組成物及び添加剤と反応性がなく、かつ十分な溶解性を示すものが好ましく、常圧での沸点が５０～１５０℃であるものが好ましい。沸点が５０℃未満の場合、室温で放置すると揮発する恐れが多くなり、開放系での使用が困難となる傾向にある。また、沸点が１５０℃を超えると、溶媒を揮発させることが困難で、接着後の信頼性に悪影響を及ぼすことが多くなる傾向にある。 The adhesive composition of this embodiment can be used in the form of a paste when it is liquid at room temperature. In the case of a solid at room temperature, it may be used by heating, or may be pasted using a solvent. Solvents that can be used are preferably those that are not reactive with the adhesive composition and additives and that exhibit sufficient solubility, and those having a boiling point of 50 to 150 ° C. at normal pressure. When the boiling point is less than 50 ° C., it tends to volatilize when left at room temperature, and it tends to be difficult to use in an open system. On the other hand, if the boiling point exceeds 150 ° C., it is difficult to volatilize the solvent, and the reliability after adhesion tends to be adversely affected.
　また、本実施形態の接着剤組成物は、フィルム状にして用いることもできる。接着剤組成物に必要により溶媒等を加えるなどした溶液を、フッ素樹脂フィルム、ポリエチレンテレフタレートフィルム、離型紙等の剥離性基材上に塗布し、あるいは不織布等の基材に上記溶液を含浸させて剥離性基材上に載置し、溶媒等を除去してフィルムとして使用することができる。フィルムの形状で使用すると取扱性等の点から一層便利である。 Also, the adhesive composition of the present embodiment can be used in the form of a film. A solution in which a solvent or the like is added to the adhesive composition as necessary is applied onto a peelable substrate such as a fluororesin film, a polyethylene terephthalate film or a release paper, or a substrate such as a nonwoven fabric is impregnated with the above solution. It can be placed on a peelable substrate and used as a film after removing the solvent and the like. Use in the form of a film is more convenient from the viewpoint of handleability.
　本実施形態の接着剤組成物は、加熱及び加圧を併用して接着させることができる。加熱温度は、１００～２００℃の温度が好ましい。圧力は、被着体に損傷を与えない範囲が好ましく、一般的には０．１～１０ＭＰａが好ましい。これらの加熱及び加圧は、０．５秒～１２０秒間の範囲で行うことが好ましく、１２０～１９０℃、３ＭＰａ、１０秒の加熱でも接着させることが可能である。 The adhesive composition of the present embodiment can be bonded by using both heating and pressing. The heating temperature is preferably 100 to 200 ° C. The pressure is preferably in a range that does not damage the adherend, and generally 0.1 to 10 MPa. These heating and pressurization are preferably performed in the range of 0.5 seconds to 120 seconds, and can be bonded by heating at 120 to 190 ° C., 3 MPa, and 10 seconds.
　本実施形態の接着剤組成物は、熱膨張係数の異なる異種の被着体の接着剤として使用することができる。具体的には、異方導電接着剤、銀ペースト、銀フィルム等に代表される回路接続材料、ＣＳＰ用エラストマー、ＣＳＰ用アンダーフィル材、ＬＯＣテープ等に代表される半導体素子接着材料として使用することができる。 The adhesive composition of the present embodiment can be used as an adhesive for different types of adherends having different thermal expansion coefficients. Specifically, it is used as a semiconductor element adhesive material typified by anisotropic conductive adhesive, silver paste, silver film, etc., circuit connection material, CSP elastomer, CSP underfill material, LOC tape, etc. Can do.
　本実施形態の接着剤組成物は、主面上に第一の接続端子を有する第一の回路部材と、主面上に第二の接続端子を有する第二の回路部材とを接続するための接着剤組成物として用いられる。ここで、上記第一の回路部材及び／又は上記第二の回路部材は、ガラス転移温度が２００℃以下の熱可塑性樹脂を含む基材から構成される。ガラス転移温度が２００℃以下の熱可塑性樹脂としては、特に限定されないが、例えば、ポリエチレンテレフタレート、ポリカーボネート及びポリエチレンナフタレート等が挙げられる。 The adhesive composition of the present embodiment is for connecting a first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface. Used as an adhesive composition. Here, said 1st circuit member and / or said 2nd circuit member are comprised from the base material containing the thermoplastic resin whose glass transition temperature is 200 degrees C or less. Although it does not specifically limit as a thermoplastic resin whose glass transition temperature is 200 degrees C or less, For example, a polyethylene terephthalate, a polycarbonate, a polyethylene naphthalate, etc. are mentioned.
　次に、上述した本実施形態の接着剤組成物を用いた回路部材の接続構造体について説明する。図１は、本実施形態の接着剤組成物を用いた、回路部材の接続構造体の一実施形態を示す模式断面図である。図２は、図１に示す回路部材の接続構造体を作製する前の、第一の回路部材、第二の回路部材及び接着剤組成物を示す模式断面図である。 Next, a circuit member connection structure using the above-described adhesive composition of the present embodiment will be described. FIG. 1 is a schematic cross-sectional view showing an embodiment of a circuit member connection structure using the adhesive composition of the present embodiment. FIG. 2 is a schematic cross-sectional view showing the first circuit member, the second circuit member, and the adhesive composition before producing the circuit member connection structure shown in FIG. 1.
　図１に示す回路部材の接続構造体１００は、第一の回路基板３１の主面３１ａ上に第一の接続端子３２を有する第一の回路部材３０と、第二の回路基板４１の主面４１ａ上に第二の接続端子４２を有する第二の回路部材４０と、第一の接続端子３２と第二の接続端子４２とが対向するように、第一の回路基板３１の主面３１ａと第二の回路基板４１の主面４１ａとを接続する接続部材１０Ｃと、を備える。第一の接続端子３２と第二の接続端子４２は、互いに接することにより電気的に接続されている。また、接続部材１０Ｃは、本実施形態の接着剤組成物１０の硬化物からなる。 A circuit member connection structure 100 shown in FIG. 1 includes a first circuit member 30 having a first connection terminal 32 on a main surface 31 a of a first circuit board 31, and a main surface of a second circuit board 41. The main surface 31a of the first circuit board 31 so that the second circuit member 40 having the second connection terminal 42 on 41a and the first connection terminal 32 and the second connection terminal 42 face each other. 10C of connection members which connect the main surface 41a of the 2nd circuit board 41. The first connection terminal 32 and the second connection terminal 42 are electrically connected by being in contact with each other. Moreover, 10C of connection members consist of hardened | cured material of the adhesive composition 10 of this embodiment.
　図１に示す回路部材の接続構造体１００は、例えば次のようにして製造することができる。 The circuit member connection structure 100 shown in FIG. 1 can be manufactured, for example, as follows.
　まず、図２に示すように、第一の回路部材３０、第二の回路部材４０及びフィルム状に成形した接着剤組成物１０を用意する。次に、接着剤組成物１０を、第二の回路部材４０における第二の接続端子４２が形成されている主面４１ａに載せ、さらに、接着剤組成物１０の上に、第一の接続端子３２が第二の接続端子４２と対向するように、第一の回路部材３０を載せる。続いて、第一の回路部材３０及び第二の回路部材４０を介して接着剤組成物１０を加熱しながらこれを硬化させ、同時に主面３１ａ、４１ａに垂直な方向に加圧し、第一及び第二の回路部材３０、４０の間に接続部材１０Ｃを形成させて、図１の回路部材の接続構造体１００を得る。 First, as shown in FIG. 2, the first circuit member 30, the second circuit member 40, and the adhesive composition 10 formed into a film shape are prepared. Next, the adhesive composition 10 is placed on the main surface 41a of the second circuit member 40 on which the second connection terminals 42 are formed, and the first connection terminals are further formed on the adhesive composition 10. The first circuit member 30 is placed so that 32 faces the second connection terminal 42. Subsequently, the adhesive composition 10 is cured while being heated through the first circuit member 30 and the second circuit member 40, and simultaneously pressurized in a direction perpendicular to the main surfaces 31a and 41a. A connection member 10C is formed between the second circuit members 30 and 40 to obtain the circuit member connection structure 100 of FIG.
　図３は、（ｄ）導電性粒子を含有する本実施形態の接着剤組成物を用いた、回路部材の接続構造体の一実施形態を示す模式断面図である。図４は、図３に示す回路部材の接続構造体を作製する前の、第一の回路部材、第二の回路部材及び接着剤組成物（導電性粒子含有）を示す模式断面図である。 FIG. 3 is a schematic cross-sectional view showing an embodiment of a circuit member connection structure using the adhesive composition of this embodiment containing (d) conductive particles. FIG. 4 is a schematic cross-sectional view showing the first circuit member, the second circuit member, and the adhesive composition (containing conductive particles) before producing the circuit member connection structure shown in FIG. 3.
　図３に示す回路部材の接続構造体２００は、第一の回路基板３１の主面３１ａ上に第一の接続端子３２を有する第一の回路部材３０と、第二の回路基板４１の主面４１ａ上に第二の接続端子４２を有する第二の回路部材４０と、第一の接続端子３２と第二の接続端子４２とが対向するように、第一の回路基板３１の主面３１ａと第二の回路基板４１の主面４１ａとを接続する接続部材２０Ｃと、を備える。なお、接続部材２０Ｃは、接着剤組成物の導電性粒子以外の成分２１中に導電性粒子２２が分散した接着剤組成物２０の硬化物（すなわち、接着剤組成物の導電性粒子以外の成分の硬化物２１Ｃ中に導電性粒子２２が分散したもの）であり、対向する第一の接続端子３２と第二の接続端子４２との間において、導電性粒子２２が両接続端子に接することにより、導電性粒子２２を介して両接続端子が電気的に接続されている。 A circuit member connection structure 200 shown in FIG. 3 includes a first circuit member 30 having a first connection terminal 32 on a main surface 31 a of a first circuit board 31, and a main surface of a second circuit board 41. The main surface 31a of the first circuit board 31 so that the second circuit member 40 having the second connection terminal 42 on 41a and the first connection terminal 32 and the second connection terminal 42 face each other. A connecting member 20C for connecting the main surface 41a of the second circuit board 41. The connecting member 20C is a cured product of the adhesive composition 20 in which the conductive particles 22 are dispersed in the component 21 other than the conductive particles of the adhesive composition (that is, the components other than the conductive particles of the adhesive composition). The conductive particles 22 are dispersed in the cured product 21C), and the conductive particles 22 are in contact with both connection terminals between the first connection terminal 32 and the second connection terminal 42 facing each other. Both connection terminals are electrically connected through the conductive particles 22.
　図３に示す回路部材の接続構造体２００は、例えば、図４に示すように、第一の回路部材３０、第二の回路部材４０及びフィルム状に成形した接着剤組成物２０を用意し、上記の回路部材の接続構造体１００を得るのと同様の方法により、製造することができる。 The circuit member connection structure 200 shown in FIG. 3 includes, for example, as shown in FIG. 4, a first circuit member 30, a second circuit member 40, and an adhesive composition 20 formed into a film shape, The circuit member connection structure 100 can be manufactured by the same method as described above.
　ここで、第一の回路部材３０及び第二の回路部材４０のうちの少なくとも一方は、ガラス転移温度が２００℃以下の熱可塑性樹脂を含有する基材から構成される。すなわち、第一の回路基板３１及び第二の回路基板４１のうちの少なくとも一方は、ガラス転移温度が２００℃以下の熱可塑性樹脂を含有する。ここで、ガラス転移温度が２００℃以下の熱可塑性樹脂としては、ポリエチレンテレフタレート、ポリカーボネート及びポリエチレンナフタレートからなる群より選ばれる少なくとも１種であることが好ましい。第一の回路部材３０及び第二の回路部材４０のうちの少なくとも一方が、ポリエチレンテレフタレート、ポリカーボネート及びポリエチレンナフタレートからなる群より選ばれる少なくとも１種を含有する基材から構成されている回路部材であると、接着剤組成物との濡れ性が向上して接着強度がより向上する。そのため、このような回路部材の接続構造体は、より優れた接続信頼性を得ることができる。 Here, at least one of the first circuit member 30 and the second circuit member 40 is composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less. That is, at least one of the first circuit board 31 and the second circuit board 41 contains a thermoplastic resin having a glass transition temperature of 200 ° C. or lower. Here, the thermoplastic resin having a glass transition temperature of 200 ° C. or lower is preferably at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. A circuit member in which at least one of the first circuit member 30 and the second circuit member 40 is composed of a base material containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. If it exists, the wettability with an adhesive composition will improve and adhesive strength will improve more. Therefore, such a connection structure of circuit members can obtain better connection reliability.
　なお、第一の回路部材３０及び第二の回路部材４０のうちの一方は、ポリエチレンテレフタレート、ポリカーボネート及びポリエチレンナフタレートからなる群より選ばれる少なくとも１種を含有しない基材から構成されていてもよい。そのような回路部材を形成する基材としては、半導体、ガラス、セラミック等の無機物からなる基材、ポリイミド等の有機物からなる基材、ガラス／エポキシ等の無機物と有機物とを組合せた基材などを用いることができる。 One of the first circuit member 30 and the second circuit member 40 may be composed of a base material that does not contain at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. . As a base material for forming such a circuit member, a base material made of an inorganic material such as a semiconductor, glass or ceramic, a base material made of an organic material such as polyimide, a base material combining an inorganic material such as glass / epoxy and an organic material, etc. Can be used.
　また、第一の接続端子３２及び第二の接続端子４２のうちの少なくとも一方は、ＩＴＯ及びＩＺＯからなる群より選ばれる少なくとも１種で構成されることが好ましい。ＩＴＯ及びＩＺＯは、エッチングが容易でパターン加工性に優れるため、接続端子として好適である。そして、本実施形態の接着剤組成物を用いることにより、ＩＴＯ及び／又はＩＺＯで構成された接続端子の腐食を充分に抑制することができる。 In addition, it is preferable that at least one of the first connection terminal 32 and the second connection terminal 42 is composed of at least one selected from the group consisting of ITO and IZO. ITO and IZO are suitable as connection terminals because they are easily etched and have excellent pattern processability. And the corrosion of the connection terminal comprised by ITO and / or IZO can fully be suppressed by using the adhesive composition of this embodiment.
　なお、第一の接続端子３２及び第二の接続端子４２のうちの一方又は両方は、ＩＴＯ及びＩＺＯ以外の材料で構成されていてもよい。そのような接続端子としては、銅、銀、アルミニウム、金、パラジウム、ニッケル及びこれらの合金等の金属からなる接続端子を用いることができる。 It should be noted that one or both of the first connection terminal 32 and the second connection terminal 42 may be made of a material other than ITO and IZO. As such a connection terminal, a connection terminal made of a metal such as copper, silver, aluminum, gold, palladium, nickel, or an alloy thereof can be used.
　なお、接続部材として用いられる本実施形態の接着剤組成物は、完全硬化（所定硬化条件で達成できる最高度の硬化）している必要はなく、上記特性を生じる限りにおいて部分硬化の状態であってもよい。 Note that the adhesive composition of the present embodiment used as a connection member does not need to be completely cured (the highest degree of curing that can be achieved under predetermined curing conditions) and is in a partially cured state as long as the above characteristics are produced. May be.
　以下に、本実施形態を実施例に基づいて具体的に説明するが、本実施形態はこれに限定されるものではない。 Hereinafter, although the present embodiment will be specifically described based on examples, the present embodiment is not limited thereto.
＜熱可塑性樹脂＞
（フェノキシ樹脂の調整）
　フェノキシ樹脂（東都化成株式会社製、ＹＰ－５０（商品名））４０質量部を、メチルエチルケトン６０質量部に溶解して、固形分４０質量％の溶液とした。 <Thermoplastic resin>
(Adjustment of phenoxy resin)
40 parts by mass of phenoxy resin (manufactured by Toto Kasei Co., Ltd., YP-50 (trade name)) was dissolved in 60 parts by mass of methyl ethyl ketone to obtain a solution having a solid content of 40% by mass.
（ポリエステルウレタン樹脂の準備）
　ポリエステルウレタン樹脂（東洋紡株式会社製、ＵＲ－１４００（商品名））は、樹脂分３０質量％のメチルエチルケトンとトルエンの１：１混合溶媒溶解品を用いた。 (Preparation of polyester urethane resin)
As the polyester urethane resin (Toyobo Co., Ltd., UR-1400 (trade name)), a 1: 1 mixed solvent solution of methyl ethyl ketone and toluene having a resin content of 30% by mass was used.
(ウレタン樹脂の合成)
　攪拌機、温度計、塩化カルシウム乾燥管を備えた還流冷却管、窒素ガス導入管を備えた反応容器に、重量平均分子量２０００のポリブチレンアジペートジオール４５０質量部、重量平均分子量２０００のポリオキシテトラメチレングリコール４５０質量部、及び、１，４－ブチレングリコール１００質量部をメチルエチルケトン４０００質量部中で均一に混合し、ジフェニルメタンジイソシアネート３９０質量部を加えて７０℃にて反応させて、重量平均分子量３５万のウレタン樹脂を得た。 (Synthesis of urethane resin)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser equipped with a calcium chloride drying tube, and a nitrogen gas introduction tube, 450 parts by weight of polybutylene adipate diol having a weight average molecular weight of 2000 and polyoxytetramethylene glycol having a weight average molecular weight of 2000 450 parts by mass and 100 parts by mass of 1,4-butylene glycol are uniformly mixed in 4000 parts by mass of methyl ethyl ketone, and 390 parts by mass of diphenylmethane diisocyanate is added and reacted at 70 ° C. to give a urethane having a weight average molecular weight of 350,000. A resin was obtained.
＜ラジカル重合性化合物＞
（ウレタンアクリレート（Ｌ－１６００Ｓ）の準備）
　重量平均分子量が１５０００、臨界表面張力が１５ｍＮ／ｍのウレタンアクリレート（三井ポリウレタン株式会社製、Ｌ－１６００Ｓ（商品名））を準備した。また、Ｌ－１６００Ｓはエーテル系ジオールを用いているものであり、上記一般式（Ａ）を満たさないものである。 <Radically polymerizable compound>
(Preparation of urethane acrylate (L-1600S))
A urethane acrylate having a weight average molecular weight of 15000 and a critical surface tension of 15 mN / m (manufactured by Mitsui Polyurethane Co., Ltd., L-1600S (trade name)) was prepared. L-1600S uses an ether diol and does not satisfy the general formula (A).
（ウレタンアクリレート（ＰＥ－ＵＡ１）の合成）
　攪拌機、温度計、塩化カルシウム乾燥管を備えた還流冷却管、窒素ガス導入管を備えた反応容器に、数平均分子量２０００のポリ（３－メチルペンタンアジペート）ジオール（脂肪族ポリエステルジオール、株式会社クラレ社製、クラポールＰ－２０１０（商品名））２０００質量部（１．００モル）、ジブチルスズジラウレート（Ａｌｄｒｉｃｈ株式会社製）５．５３質量部を投入した。充分に窒素ガスを導入した後、７０～７５℃に加熱し、ジシクロヘキシルメタン４，４’－ジイソシアナート（脂肪族ジイソシアネート、エボニックデグサ社製、ＶＥＳＴＡＮＡＴ　Ｈ１２ＤＭＩ（商品名））７８７質量部（３．００モル）を３時間で均一に滴下し、反応させた。滴下完了後約１０時間反応を継続した。これに２－ヒドロキシエチルアクリレート（Ａｌｄｒｉｃｈ株式会社製）２３８質量部（２．０５モル）、ハイドロキノンモノメチルエーテル（Ａｌｄｒｉｃｈ株式会社製）０．５３質量部を投入し、さらに１０時間反応させ、ＩＲ測定によりイソシアネートが消失したことを確認して反応を終了し、ウレタンアクリレートを得た。得られたウレタンアクリレート（ＰＥ－ＵＡ１）の臨界表面張力は３０ｍＮ／ｍ、重量平均分子量は１５３００であった。また、ＰＥ－ＵＡ１はポリエステルジオールを用いているものであり、上記一般式（Ａ）を満たすものである。 (Synthesis of urethane acrylate (PE-UA1))
Poly (3-methylpentaneadipate) diol (aliphatic polyester diol, Kuraray Co., Ltd.) having a number average molecular weight of 2000 was added to a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser equipped with a calcium chloride drying tube, and a nitrogen gas introduction tube. Kurapol P-2010 (trade name) 2000 parts by mass (1.00 mol) and dibutyltin dilaurate (Aldrich Co., Ltd.) 5.53 parts by mass were added. After sufficiently introducing nitrogen gas, the mixture was heated to 70 to 75 ° C., and dicyclohexylmethane 4,4′-diisocyanate (aliphatic diisocyanate, manufactured by Evonik Degussa, VESTANAT H 12 DMI (trade name)) 787 parts by mass ( 3.00 mol) was uniformly added dropwise over 3 hours to react. The reaction was continued for about 10 hours after the completion of the dropwise addition. To this, 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Aldrich) and 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Aldrich) were further reacted for 10 hours. After confirming that the isocyanate had disappeared, the reaction was terminated to obtain urethane acrylate. The urethane acrylate (PE-UA1) obtained had a critical surface tension of 30 mN / m and a weight average molecular weight of 15,300. PE-UA1 uses a polyester diol and satisfies the above general formula (A).
（ウレタンアクリレート（ＰＥ－ＵＡ２）の合成）
　攪拌機、温度計、塩化カルシウム乾燥管を備えた還流冷却管、窒素ガス導入管を備えた反応容器に、数平均分子量２０００のポリカプロラクトンジオール（脂肪族ポリエステルジオール、商品名：プラクセル２２０ＥＢ、ダイセル化学工業株式会社製）２０００質量部（１．００モル）、ジブチルスズジラウレート（Ａｌｄｒｉｃｈ株式会社製）５．５３質量部を投入した。充分に窒素ガスを導入した後、７０～７５℃に加熱し、イソフォロンジイソシアネート（脂肪族ジイソシアネート、Ａｌｄｒｉｃｈ株式会社製）６６６質量部（３．００モル）を３時間で均一に滴下し、反応させた。滴下完了後約１０時間反応を継続した。これに２－ヒドロキシエチルアクリレート（Ａｌｄｒｉｃｈ株式会社製）２３８質量部（２．０５モル）、ハイドロキノンモノメチルエーテル（Ａｌｄｒｉｃｈ株式会社製）０．５３質量部を投入し、さらに１０時間反応させ、ＩＲ測定によりイソシアネートが消失したことを確認して反応を終了し、ウレタンアクリレートを得た。得られたウレタンアクリレート（ＰＥ－ＵＡ２）の臨界表面張力は２５ｍＮ／ｍ、重量平均分子量は１３５００であった。また、ＰＥ－ＵＡ２はポリエステルジオールを用いているものであり、上記一般式（Ａ）を満たすものである。 (Synthesis of urethane acrylate (PE-UA2))
Polycaprolactone diol (aliphatic polyester diol, trade name: Plaxel 220EB, Daicel Chemical Industries, Ltd.) having a number average molecular weight of 2000 in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser equipped with a calcium chloride drying tube, and a nitrogen gas introduction tube Co., Ltd.) 2000 parts by mass (1.00 mol) and dibutyltin dilaurate (Aldrich Co., Ltd.) 5.53 parts by mass were added. After sufficiently introducing nitrogen gas, the mixture is heated to 70 to 75 ° C., and 666 parts by mass (3.00 mol) of isophorone diisocyanate (aliphatic diisocyanate, manufactured by Aldrich Co., Ltd.) is uniformly added dropwise over 3 hours to be reacted. It was. The reaction was continued for about 10 hours after the completion of the dropwise addition. To this, 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Aldrich) and 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Aldrich) were further reacted for 10 hours. After confirming that the isocyanate had disappeared, the reaction was terminated to obtain urethane acrylate. The urethane acrylate (PE-UA2) obtained had a critical surface tension of 25 mN / m and a weight average molecular weight of 13,500. PE-UA2 uses a polyester diol and satisfies the above general formula (A).
（ウレタンアクリレート（ＰＥ－ＵＡ３）の合成）
　攪拌機、温度計、塩化カルシウム乾燥管を備えた還流冷却管、窒素ガス導入管を備えた反応容器に、２－ヒドロキシエチルアクリレート（Ａｌｄｒｉｃｈ株式会社製）２３８質量部（２．０５モル）、ハイドロキノンモノメチルエーテル（Ａｌｄｒｉｃｈ株式会社製）０．５３質量部、数平均分子量１０００のポリカプロラクトンジオール（脂肪族ポリエステルジオール、商品名：プラクセル２１０Ｎ、ダイセル化学工業株式会社製）２０００質量部（２．００モル）、ジブチルスズジラウレート（Ａｌｄｒｉｃｈ株式会社製）５．５３質量部を投入した。充分に窒素ガスを導入した後、７０～７５℃に加熱し、イソフォロンジイソシアネート（脂肪族ジイソシアネート、Ａｌｄｒｉｃｈ株式会社製）６６６質量部（３．００モル）を３時間で均一に滴下し、反応させた。滴下完了後約１０時間反応を継続し、ＩＲ測定によりイソシアネートが消失したことを確認して反応を終了し、ウレタンアクリレートを得た。得られたウレタンアクリレート（ＰＥ－ＵＡ３）の臨界表面張力は２８ｍＮ／ｍ、重量平均分子量は１４５００であった。また、ＰＥ－ＵＡ３はポリエステルジオールを用いているものであり、上記一般式（Ａ）を満たすものである。 (Synthesis of urethane acrylate (PE-UA3))
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser equipped with a calcium chloride drying tube, and a nitrogen gas introduction tube, 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Aldrich), hydroquinone monomethyl 0.53 parts by mass of ether (manufactured by Aldrich), polycaprolactone diol having a number average molecular weight of 1000 (aliphatic polyester diol, trade name: Plaxel 210N, manufactured by Daicel Chemical Industries, Ltd.), 2000 parts by mass (2.00 mol), Dibutyltin dilaurate (Aldrich Co., Ltd.) 5.53 parts by mass was added. After sufficiently introducing nitrogen gas, the mixture is heated to 70 to 75 ° C., and 666 parts by mass (3.00 mol) of isophorone diisocyanate (aliphatic diisocyanate, manufactured by Aldrich Co., Ltd.) is uniformly added dropwise over 3 hours to be reacted. It was. The reaction was continued for about 10 hours after completion of the dropping, and the reaction was terminated after confirming that the isocyanate had disappeared by IR measurement, to obtain urethane acrylate. The obtained urethane acrylate (PE-UA3) had a critical surface tension of 28 mN / m and a weight average molecular weight of 14,500. PE-UA3 uses a polyester diol and satisfies the above general formula (A).
（ウレタンアクリレート（ＰＥ－ＵＡ４）の合成）
　攪拌機、温度計、塩化カルシウム乾燥管を備えた還流冷却管、窒素ガス導入管を備えた反応容器に、３－メチル－１，５－ペンタンジオール１６５０質量部（１４モル）とイソフタル酸１６６０質量部（１０モル）を仕込み、常圧下、充分に窒素ガスを導入した後、約１７０℃で生成する水を系外に留去しながらエステル化反応を行った。ポリエステルの酸価が０．３ｍｇＫＯＨ／ｇ以下になった時点で真空ポンプにより徐々に真空度を上げ、反応を完結させた。このようにして得られた芳香族ポリエステルジオール（ＥＤ－１）は数平均分子量２０００を有していた。 (Synthesis of urethane acrylate (PE-UA4))
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser equipped with a calcium chloride drying tube, and a nitrogen gas introduction tube, 1650 parts by mass (14 mol) of 3-methyl-1,5-pentanediol and 1660 parts by mass of isophthalic acid (10 mol) was charged, nitrogen gas was sufficiently introduced under normal pressure, and then the esterification reaction was carried out while distilling out the water produced at about 170 ° C. out of the system. When the acid value of the polyester became 0.3 mgKOH / g or less, the degree of vacuum was gradually increased by a vacuum pump to complete the reaction. The aromatic polyester diol (ED-1) thus obtained had a number average molecular weight of 2000.
　更に、攪拌機、温度計、塩化カルシウム乾燥管を備えた還流冷却管、窒素ガス導入管を備えた反応容器に、得られた芳香族ポリエステルジオール（ＥＤ－１）を２０００質量部（１．００モル）、ジブチルスズジラウレート（Ａｌｄｒｉｃｈ株式会社製）５．５３質量部を投入した。充分に窒素ガスを導入した後、７０～７５℃に加熱し、イソフォロンジイソシアネート（脂肪族ジイソシアネート、Ａｌｄｒｉｃｈ株式会社製）６６６質量部（３．００モル）を３時間で均一に滴下し、反応させた。滴下完了後、約１５時間反応を継続した。これに２－ヒドロキシエチルアクリレート（Ａｌｄｒｉｃｈ株式会社製）２３８質量部（２．０５モル）、ハイドロキノンモノメチルエーテル（Ａｌｄｒｉｃｈ株式会社製）０．５３質量部を投入し、さらに７時間反応させ、ＩＲ測定によりイソシアネートが消失したことを確認して反応を終了し、ウレタンアクリレートを得た。得られたウレタンアクリレート（ＰＥ－ＵＡ４）の臨界表面張力は４２ｍＮ／ｍ、重量平均分子量は１１５００であった。また、ＰＥ－ＵＡ４はポリエステルジオールを用いているものであり、上記一般式（Ａ）を満たすものである。 Further, 2000 parts by mass (1.00 mol) of the obtained aromatic polyester diol (ED-1) was added to a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser equipped with a calcium chloride drying tube, and a nitrogen gas introduction tube. ), 5.53 parts by mass of dibutyltin dilaurate (manufactured by Aldrich). After sufficiently introducing nitrogen gas, the mixture is heated to 70 to 75 ° C., and 666 parts by mass (3.00 mol) of isophorone diisocyanate (aliphatic diisocyanate, manufactured by Aldrich Co., Ltd.) is uniformly added dropwise over 3 hours to be reacted. It was. After completion of the dropwise addition, the reaction was continued for about 15 hours. To this, 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Aldrich) and 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Aldrich) were further reacted for 7 hours. After confirming that the isocyanate had disappeared, the reaction was terminated to obtain urethane acrylate. The resulting urethane acrylate (PE-UA4) had a critical surface tension of 42 mN / m and a weight average molecular weight of 11,500. PE-UA4 uses a polyester diol and satisfies the above general formula (A).
（ウレタンアクリレート（ＰＥ－ＵＡ５）の合成）
　攪拌機、温度計、塩化カルシウム乾燥管を備えた還流冷却管、窒素ガス導入管を備えた反応容器に、数平均分子量２０００のポリ（１，６－ヘキサンジオールカーボネート）ジオール（脂肪族ポリカーボネートジオール、旭化成ケミカルズ株式会社製、ＰＣＤＬ　Ｔ５６５２（商品名））４０００質量部（２．００モル）、ジブチルスズジラウレート（Ａｌｄｒｉｃｈ株式会社製）５．５３質量部を投入した。充分に窒素ガスを導入した後、７０～７５℃に加熱し、イソフォロンジイソシアネート（脂肪族ジイソシアネート、Ａｌｄｒｉｃｈ株式会社製）６６６質量部（３．００モル）を３時間で均一に滴下し、反応させた。滴下完了後約１５時間反応を継続した。これに２－ヒドロキシエチルアクリレート（Ａｌｄｒｉｃｈ株式会社製）２３８質量部（２．０５モル）、ハイドロキノンモノメチルエーテル（Ａｌｄｒｉｃｈ株式会社製）０．５３質量部を投入し、さらに１０時間反応させ、ＩＲ測定によりイソシアネートが消失したことを確認して反応を終了し、ウレタンアクリレートを得た。得られたウレタンアクリレート（ＰＥ－ＵＡ５）の臨界表面張力は２１ｍＮ／ｍ、重量平均分子量は３００００であった。また、ＰＥ－ＵＡ５はポリカーボネートジオールを用いているものであり、上記一般式（Ａ）を満たさないものである。 (Synthesis of urethane acrylate (PE-UA5))
A poly (1,6-hexanediol carbonate) diol (aliphatic polycarbonate diol, Asahi Kasei) with a number average molecular weight of 2000 was added to a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser equipped with a calcium chloride drying tube, and a nitrogen gas introduction tube. Chemicals Co., Ltd., PCDL T5652 (trade name) 4000 parts by mass (2.00 mol) and dibutyltin dilaurate (Aldrich Co., Ltd.) 5.53 parts by mass were added. After sufficiently introducing nitrogen gas, the mixture is heated to 70 to 75 ° C., and 666 parts by mass (3.00 mol) of isophorone diisocyanate (aliphatic diisocyanate, manufactured by Aldrich Co., Ltd.) is uniformly added dropwise over 3 hours to be reacted. It was. The reaction was continued for about 15 hours after the completion of the dropwise addition. To this, 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Aldrich) and 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Aldrich) were further reacted for 10 hours. After confirming that the isocyanate had disappeared, the reaction was terminated to obtain urethane acrylate. The resulting urethane acrylate (PE-UA5) had a critical surface tension of 21 mN / m and a weight average molecular weight of 30000. PE-UA5 uses polycarbonate diol and does not satisfy the general formula (A).
（イソシアヌル酸変性２官能アクリレート（Ｍ－２１５）の準備）
　イソシアヌル酸変性２官能アクリレート（東亞合成株式会社製、Ｍ－２１５（商品名）を準備した。 (Preparation of isocyanuric acid-modified bifunctional acrylate (M-215))
Isocyanuric acid-modified bifunctional acrylate (manufactured by Toagosei Co., Ltd., M-215 (trade name)) was prepared.
（リン酸基を有するビニル化合物（Ｐ－２Ｍ）の準備）
　２－（メタ）アクリロイロキシエチルホスフェート（商品名：ライトエステルＰ－２Ｍ、共栄社化学株式会社製）を準備した。 (Preparation of a vinyl compound having a phosphate group (P-2M))
2- (Meth) acryloyloxyethyl phosphate (trade name: Light Ester P-2M, manufactured by Kyoeisha Chemical Co., Ltd.) was prepared.
＜ラジカル重合開始剤＞
　ラジカル重合開始剤としてジベンゾイルパーオキサイド（商品名：ナイパーＢＷ、日油株式会社製）を準備した。 <Radical polymerization initiator>
Dibenzoyl peroxide (trade name: Nyper BW, manufactured by NOF Corporation) was prepared as a radical polymerization initiator.
＜導電性粒子＞
（導電性粒子の作製）
　ポリスチレンを核とする粒子の表面に、厚み０．２μｍのニッケル層を設け、このニッケル層の外側に、厚み０．０２μｍの金層を設け、平均粒径１０μｍ、比重２．５の導電性粒子を作製した。 <Conductive particles>
(Preparation of conductive particles)
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, and conductive particles having an average particle diameter of 10 μm and a specific gravity of 2.5. Was made.
［実施例１～１０及び比較例１～５］
　固形質量比で表２に示すように熱可塑性樹脂、ラジカル重合性化合物及びラジカル重合開始剤を配合し、さらに導電性粒子を１．５体積％配合分散させ、接着剤組成物を得た。得られた接着剤組成物を、塗工装置を用いて厚み８０μｍのフッ素樹脂フィルム上に塗布し、７０℃、１０分の熱風乾燥によって接着剤層の厚みが２０μｍのフィルム状接着剤組成物を得た。 [Examples 1 to 10 and Comparative Examples 1 to 5]
As shown in Table 2 in terms of solid mass ratio, a thermoplastic resin, a radical polymerizable compound, and a radical polymerization initiator were blended, and 1.5% by volume of conductive particles were blended and dispersed to obtain an adhesive composition. The obtained adhesive composition was applied on a fluororesin film having a thickness of 80 μm using a coating apparatus, and a film-like adhesive composition having an adhesive layer thickness of 20 μm was dried by hot air at 70 ° C. for 10 minutes. Obtained.
Figure JPOXMLDOC01-appb-T000040
Figure JPOXMLDOC01-appb-T000040
〔接続抵抗、接着強度の測定〕
　実施例１～１０及び比較例１～５のフィルム状接着剤組成物を、ポリイミドフィルム（Ｔｇ３５０℃）上にライン幅１５０μｍ、ピッチ３００μｍ、厚み８μｍの銅回路を８０本有するフレキシブル回路板（ＦＰＣ）と、厚み５μｍのＡｇペーストの薄層を形成したＰＥＴ基板（厚み０．１ｍｍ）との間に介在させた。また、実施例１～１０及び比較例１～５のフィルム状接着剤組成物を、ポリイミドフィルム上にライン幅１５０μｍ、ピッチ３００μｍ、厚み１８μｍの銅回路を８０本有するＦＰＣと、ＰＥＴ（厚み０．１ｍｍ）フィルム上にライン幅１５０μｍ、ピッチ３００μｍ、厚み１０μｍのＡｇペースト回路を形成した基板との間に介在させた。これらを、それぞれ熱圧着装置（加熱方式：コンスタントヒート型、東レエンジニアリング社製）を用いて、１５０℃、２ＭＰａで１０秒間加熱加圧して幅２ｍｍにわたり接続し、接続体を作製した。これらの接続体の隣接回路間の抵抗値を、接着直後と、８５℃、８５％ＲＨの高温高湿槽中に２４０時間保持した後（試験後）にマルチメータで測定した。抵抗値は隣接回路間の抵抗３７点の平均で示した。 [Measurement of connection resistance and adhesive strength]
A flexible circuit board (FPC) having the film-like adhesive compositions of Examples 1 to 10 and Comparative Examples 1 to 5 having 80 copper circuits having a line width of 150 μm, a pitch of 300 μm, and a thickness of 8 μm on a polyimide film (Tg 350 ° C.). And a PET substrate (thickness 0.1 mm) on which a thin layer of 5 μm thick Ag paste was formed. Further, the film-like adhesive compositions of Examples 1 to 10 and Comparative Examples 1 to 5 were prepared by using FPC having 80 copper circuits having a line width of 150 μm, a pitch of 300 μm, and a thickness of 18 μm on a polyimide film, and PET (thickness 0. 1 mm) It was interposed between a substrate on which an Ag paste circuit having a line width of 150 μm, a pitch of 300 μm, and a thickness of 10 μm was formed on a film. These were each connected by heating and pressing at 150 ° C. and 2 MPa for 10 seconds using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.) to produce a connection body. The resistance value between adjacent circuits of these connected bodies was measured with a multimeter immediately after bonding and after being kept in a high-temperature and high-humidity bath at 85 ° C. and 85% RH for 240 hours (after the test). The resistance value was shown as an average of 37 resistances between adjacent circuits.
　また、それぞれの接続体の接着強度をＪＩＳ－Ｚ０２３７に準じて９０度剥離法で測定し、評価した。ここで、接着強度の測定装置は東洋ボールドウィン株式会社製テンシロンＵＴＭ－４（剥離速度５０ｍｍ／ｍｉｎ、２５℃）を使用した。以上のようにして行ったフィルム状接着剤組成物の接続抵抗及び接着強度の測定の結果を下記表３に示した。 Further, the adhesive strength of each connection body was measured by a 90-degree peeling method according to JIS-Z0237 and evaluated. Here, Tensilon UTM-4 (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used as an adhesive strength measuring apparatus. The results of measurement of the connection resistance and adhesive strength of the film adhesive composition performed as described above are shown in Table 3 below.
Figure JPOXMLDOC01-appb-T000041
Figure JPOXMLDOC01-appb-T000041
　実施例１～７の接着剤組成物は、加熱温度１５０℃において、接着直後及び８５℃、８５％ＲＨの高温高湿槽中に２４０時間保持した後（試験後）で、約１．２Ω以下の良好な接続抵抗及び６００Ｎ／ｍ以上の良好な接着強度を示した。 The adhesive compositions of Examples 1 to 7 were about 1.2Ω or less immediately after bonding at a heating temperature of 150 ° C. and after being kept in a high-temperature and high-humidity bath at 85 ° C. and 85% RH for 240 hours (after the test). And good adhesive strength of 600 N / m or more.
　これらに対して、比較例１及び３の接着剤組成物は、接着直後及び８５℃、８５％ＲＨの高温高湿槽中に２４０時間保持した後（試験後）は良好な接続抵抗を示すものの、接着強度が低くなった。また、比較例２、４及び５の接着剤組成物は接続直後及び８５℃、８５％ＲＨの高温高湿槽中に２４０時間保持した後（試験後）の接続抵抗が高く、接着強度も実施例１～７と比較して低くなった。 On the other hand, the adhesive compositions of Comparative Examples 1 and 3 show good connection resistance immediately after bonding and after being held in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 240 hours (after the test). The adhesive strength was low. Further, the adhesive compositions of Comparative Examples 2, 4, and 5 have high connection resistance immediately after connection and after being held in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 240 hours (after the test), and the adhesive strength was also implemented Lower than Examples 1-7.
　一方、実施例８～１０の接着剤組成物は、接着直後及び８５℃、８５％ＲＨの高温高湿槽中に２４０時間保持した後（試験後）で、約１．２Ω以下の良好な接続抵抗を示し、かつ、比較例１及び３に比べ接着強度に優れていた。 On the other hand, the adhesive compositions of Examples 8 to 10 had good connections of about 1.2Ω or less immediately after bonding and after being held in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 240 hours (after the test). Resistance was exhibited and the adhesive strength was superior to Comparative Examples 1 and 3.
［実施例１１～１３並びに比較例６及び７］
　また、実施例３、４及び７並びに比較例３及び４のフィルム状接着剤組成物を、ポリイミドフィルム上にライン幅１５０μｍ、ピッチ３００μｍ、厚み８μｍの銅回路を８０本有するフレキシブル回路板（ＦＰＣ）と、ＰＥＴフィルム（厚み０．１ｍｍ、Ｔｇ１２０℃）、ＰＣフィルム（厚み０．１ｍｍ、Ｔｇ１５０℃）及びＰＥＮフィルム（厚み０．１ｍｍ、Ｔｇ１６０℃）との間にそれぞれ介在させた。これらを、それぞれ熱圧着装置（加熱方式：コンスタントヒート型、東レエンジニアリング社製）を用いて、１５０℃、２ＭＰａで１０秒間加熱加圧して幅２ｍｍにわたり圧着し、接続体を作製した。 [Examples 11 to 13 and Comparative Examples 6 and 7]
Further, the film-like adhesive compositions of Examples 3, 4 and 7 and Comparative Examples 3 and 4 are flexible circuit boards (FPC) having 80 copper circuits having a line width of 150 μm, a pitch of 300 μm and a thickness of 8 μm on a polyimide film. And a PET film (thickness 0.1 mm, Tg 120 ° C.), a PC film (thickness 0.1 mm, Tg 150 ° C.) and a PEN film (thickness 0.1 mm, Tg 160 ° C.). These were each heat-pressed at 150 ° C. and 2 MPa for 10 seconds using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.), and pressure-bonded over a width of 2 mm to prepare a connected body.
　また、それぞれの接続体の接着強度は上記方法と同様に測定した。以上のようにして行ったフィルム状接着剤組成物の接着強度の測定結果を下記表４に示した。 Further, the adhesive strength of each connection body was measured in the same manner as described above. The measurement results of the adhesive strength of the film adhesive composition performed as described above are shown in Table 4 below.
Figure JPOXMLDOC01-appb-T000042
Figure JPOXMLDOC01-appb-T000042
　実施例１１～１３で用いられた接着剤組成物は、いずれの基材に対しても加熱温度１５０℃において、接着直後及び８５℃、８５％ＲＨの高温高湿槽中に２４０時間保持した後（試験後）で、６００Ｎ／ｍ以上の良好な接着強度を示した。これらに対して、比較例６及び７で用いられた接着剤組成物は、接着直後及び８５℃、８５％ＲＨの高温高湿槽中に２４０時間保持した後（試験後）は接着強度が低くなった。 The adhesive compositions used in Examples 11 to 13 were heated at 150 ° C. for any substrate immediately after bonding and after being kept in a high-temperature and high-humidity bath at 85 ° C. and 85% RH for 240 hours. In (after test), good adhesive strength of 600 N / m or more was exhibited. On the other hand, the adhesive composition used in Comparative Examples 6 and 7 has low adhesive strength immediately after bonding and after being kept in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 240 hours (after the test). became.
［参考例１～６］
　参考例として、実施例３、４、６及び７並びに比較例１及び３のフィルム状接着剤組成物を、ポリイミドフィルム上にライン幅２５μｍ、ピッチ５０μｍ、厚み８μｍの銅回路を５００本有するフレキシブル回路板（ＦＰＣ）と、０．２μｍのＩＴＯの薄層を形成したガラス（厚み１．１ｍｍ、表面抵抗２０Ω／□）との間に介在させた。これを、熱圧着装置（加熱方式：コンスタントヒート型、東レエンジニアリング社製）を用いて、１５０℃、２ＭＰａで１０秒間加熱加圧して幅２ｍｍにわたり接続し、接続体を作製した。この接続体の隣接回路間の抵抗値を、接着直後と、８５℃、８５％ＲＨの高温高湿槽中に２４０時間保持した後（試験後）にマルチメータで測定した。抵抗値は隣接回路間の抵抗３７点の平均で示した。 [Reference Examples 1 to 6]
As a reference example, the film-like adhesive compositions of Examples 3, 4, 6 and 7 and Comparative Examples 1 and 3 are flexible circuits having 500 copper circuits having a line width of 25 μm, a pitch of 50 μm and a thickness of 8 μm on a polyimide film. It was interposed between a plate (FPC) and glass (thickness 1.1 mm, surface resistance 20Ω / □) on which a thin layer of 0.2 μm ITO was formed. Using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.), this was heated and pressurized at 150 ° C. and 2 MPa for 10 seconds to be connected over a width of 2 mm to produce a connected body. The resistance value between adjacent circuits of this connection body was measured with a multimeter immediately after bonding and after being held in a high-temperature and high-humidity bath at 85 ° C. and 85% RH for 240 hours (after the test). The resistance value was shown as an average of 37 resistances between adjacent circuits.
　また、この接続体の接着強度をＪＩＳ－Ｚ０２３７に準じて９０度剥離法で測定し、評価した。ここで、接着強度の測定装置は東洋ボールドウィン株式会社製テンシロンＵＴＭ－４（剥離速度５０ｍｍ／ｍｉｎ、２５℃）を使用した。以上のようにして行ったフィルム状接着剤組成物の接続抵抗及び接着強度の測定の結果を下記表５に示した。 Further, the adhesive strength of this connection body was measured by a 90-degree peeling method according to JIS-Z0237 and evaluated. Here, Tensilon UTM-4 (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used as an adhesive strength measuring apparatus. Table 5 below shows the results of the measurement of the connection resistance and the adhesive strength of the film adhesive composition performed as described above.
Figure JPOXMLDOC01-appb-T000043
Figure JPOXMLDOC01-appb-T000043
　先に示したとおり、比較例の接着剤組成物は、被着体がＰＥＴフィルム、ＰＣフィルム及びＰＥＮフィルムの場合、接続抵抗や接着強度に劣っていた。しかし、表５に示したとおり、被着体がＩＴＯ付きガラスである場合は、比較例の接着剤組成物を用いた場合を含む参考例１～６の全てにおいて、接着直後及び８５℃、８５％ＲＨの高温高湿槽中に２４０時間保持した後（試験後）で、２．５Ω以下の良好な接続抵抗及び６８０Ｎ／ｍ以上の良好な接着強度を得られることが確認された。 As previously indicated, when the adherend was a PET film, a PC film and a PEN film, the adhesive composition of the comparative example was inferior in connection resistance and adhesive strength. However, as shown in Table 5, when the adherend is a glass with ITO, in all of Reference Examples 1 to 6 including the case where the adhesive composition of the comparative example was used, immediately after bonding and at 85 ° C., 85 ° C. It was confirmed that a good connection resistance of 2.5Ω or less and a good adhesive strength of 680 N / m or more can be obtained after being kept in a high-temperature, high-humidity tank of% RH for 240 hours (after the test).
　本実施形態によれば、ポリエチレンテレフタレート、ポリカーボネート、ポリエチレンナフタレート等の有機基材に対して、低温の硬化条件においても、優れた接着強度を得ることができ、長時間の信頼性試験（高温高湿試験）後においても安定した性能（接着強度や接続抵抗）を維持することができる接着剤組成物、それを用いた回路部材の接続構造体、接続構造体の製造方法及び接着剤組成物の応用を提供することができる。 According to this embodiment, it is possible to obtain excellent adhesive strength even under low-temperature curing conditions for organic base materials such as polyethylene terephthalate, polycarbonate, and polyethylene naphthalate, and a long-term reliability test (high temperature high Of an adhesive composition capable of maintaining stable performance (adhesion strength and connection resistance) even after a wet test), a connection structure for a circuit member using the same, a method for producing the connection structure, and an adhesive composition Application can be provided.
　１０、２０…接着剤組成物、１０Ｃ、２０Ｃ…接続部材、２１…導電性粒子を含まない接着剤組成物、２２…導電性粒子、２１Ｃ…導電性粒子を含まない接着剤組成物の硬化物、３０…第一の回路部材、３１…第一の回路基板、３１ａ…主面、３２…第一の接続端子、４０…第二の回路部材、４１…第二の回路基板、４１ａ…主面、４２…第二の接続端子、１００、２００…回路部材の接続構造体。 DESCRIPTION OF SYMBOLS 10,20 ... Adhesive composition, 10C, 20C ... Connection member, 21 ... Adhesive composition which does not contain electroconductive particle, 22 ... Conductive particle, 21C ... Hardened | cured material of adhesive composition which does not contain electroconductive particle 30 ... first circuit member, 31 ... first circuit board, 31a ... main surface, 32 ... first connection terminal, 40 ... second circuit member, 41 ... second circuit board, 41a ... main surface 42, second connection terminals, 100, 200, connection structure for circuit members.

Claims (20)

  1. 　主面上に第一の接続端子を有する第一の回路部材と、主面上に第二の接続端子を有する第二の回路部材とを接続するための接着剤組成物であって、
    　前記第一の回路部材及び／又は前記第二の回路部材は、ガラス転移温度が２００℃以下の熱可塑性樹脂を含む基材から構成され、
    　前記接着剤組成物は、（ａ）熱可塑性樹脂、（ｂ）ラジカル重合性化合物及び（ｃ）ラジカル重合開始剤を含有し、前記（ｂ）ラジカル重合性化合物が２５～４０ｍＮ／ｍの臨界表面張力を有するウレタン（メタ）アクリレートを含む、接着剤組成物。     An adhesive composition for connecting a first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface,
    Said 1st circuit member and / or said 2nd circuit member are comprised from the base material containing the thermoplastic resin whose glass transition temperature is 200 degrees C or less,
    The adhesive composition contains (a) a thermoplastic resin, (b) a radical polymerizable compound, and (c) a radical polymerization initiator, and the (b) radical polymerizable compound has a critical surface of 25 to 40 mN / m. An adhesive composition comprising urethane (meth) acrylate having tension.
  2. 　前記ウレタン（メタ）アクリレートが下記一般式（Ａ）で表されるウレタン（メタ）アクリレートである、請求項１記載の接着剤組成物。
    Figure JPOXMLDOC01-appb-C000001
     ［式（Ａ）中、Ｒ１及びＲ２はそれぞれ独立に水素原子またはメチル基を示し、Ｒ３はエチレン基、プロピレン基、ε－カプロラクトンの開環化合物から誘導される基、または下記一般式（Ｂ）で表される基を示し、Ｒ４は下記一般式（Ｂ）で表される基を示し、Ｒ５は飽和脂肪族基または飽和脂環式基を示し、ａは１～４０の整数を示す。］
    Figure JPOXMLDOC01-appb-C000002
     ［式（Ｂ）中、Ｒ６及びＲ７はそれぞれ独立に炭素数２～１２の直鎖又は分岐鎖のアルキレン基を示し、ｂは１～１０の整数を示し、ｃは１～２５の整数を示す。なお、式中、Ｒ６同士、Ｒ７同士、ｂ同士及びｃ同士はそれぞれ同一でも異なってもよい。］     The adhesive composition according to claim 1, wherein the urethane (meth) acrylate is a urethane (meth) acrylate represented by the following general formula (A).
    Figure JPOXMLDOC01-appb-C000001
     [In the formula (A), R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and R 3 represents a group derived from a ring-opening compound of ethylene group, propylene group or ε-caprolactone, or the following general formula: Represents a group represented by (B), R 4 represents a group represented by the following general formula (B), R 5 represents a saturated aliphatic group or a saturated alicyclic group, and a represents 1 to 40 Indicates an integer. ]
    Figure JPOXMLDOC01-appb-C000002
     [In the formula (B), R 6 and R 7 each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms, b represents an integer of 1 to 10, and c represents an integer of 1 to 25. Indicates. In the formula, R 6 s , R 7 s , b s, and c s may be the same or different. ]
  3. 　主面上に第一の接続端子を有する第一の回路部材と、主面上に第二の接続端子を有する第二の回路部材とを接続するための接着剤組成物であって、
    　前記第一の回路部材及び／又は前記第二の回路部材は、ガラス転移温度が２００℃以下の熱可塑性樹脂を含む基材から構成され、
    　前記接着剤組成物は、（ａ）熱可塑性樹脂、（ｂ）ラジカル重合性化合物及び（ｃ）ラジカル重合開始剤を含有し、前記（ｂ）ラジカル重合性化合物が下記一般式（Ａ）で表されるウレタン（メタ）アクリレートを含む、接着剤組成物。
    Figure JPOXMLDOC01-appb-C000003
     ［式（Ａ）中、Ｒ１及びＲ２はそれぞれ独立に水素原子またはメチル基を示し、Ｒ３はエチレン基、プロピレン基、ε－カプロラクトンの開環化合物から誘導される基、または下記一般式（Ｂ）で表される基を示し、Ｒ４は下記一般式（Ｂ）で表される基を示し、Ｒ５は飽和脂肪族基または飽和脂環式基を示し、ａは１～４０の整数を示す。］
    Figure JPOXMLDOC01-appb-C000004
     ［式（Ｂ）中、Ｒ６及びＲ７はそれぞれ独立に炭素数２～１２の直鎖又は分岐鎖のアルキレン基を示し、ｂは１～１０の整数を示し、ｃは１～２５の整数を示す。なお、式中、Ｒ６同士、Ｒ７同士、ｂ同士及びｃ同士はそれぞれ同一でも異なってもよい。］     An adhesive composition for connecting a first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface,
    Said 1st circuit member and / or said 2nd circuit member are comprised from the base material containing the thermoplastic resin whose glass transition temperature is 200 degrees C or less,
    The adhesive composition contains (a) a thermoplastic resin, (b) a radical polymerizable compound, and (c) a radical polymerization initiator, and the (b) radical polymerizable compound is represented by the following general formula (A). An adhesive composition comprising urethane (meth) acrylate.
    Figure JPOXMLDOC01-appb-C000003
     [In the formula (A), R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and R 3 represents a group derived from a ring-opening compound of ethylene group, propylene group or ε-caprolactone, or the following general formula: Represents a group represented by (B), R 4 represents a group represented by the following general formula (B), R 5 represents a saturated aliphatic group or a saturated alicyclic group, and a represents 1 to 40 Indicates an integer. ]
    Figure JPOXMLDOC01-appb-C000004
     [In the formula (B), R 6 and R 7 each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms, b represents an integer of 1 to 10, and c represents an integer of 1 to 25. Indicates. In the formula, R 6 s , R 7 s , b s, and c s may be the same or different. ]
  4. 　前記ウレタン（メタ）アクリレートが、脂肪族ポリエステルジオールを用いて得たものである、請求項１～３のいずれか一項に記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 3, wherein the urethane (meth) acrylate is obtained using an aliphatic polyester diol.
  5. 　前記ウレタン（メタ）アクリレートの重量平均分子量が８０００以上２５０００未満である、請求項１～４のいずれか一項に記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 4, wherein the urethane (meth) acrylate has a weight average molecular weight of 8000 or more and less than 25,000.
  6. 　前記（ｂ）ラジカル重合性化合物が、リン酸基を有するビニル化合物と、前記リン酸基を有するビニル化合物以外のラジカル重合性化合物と、をそれぞれ１種以上含有する、請求項１～５のいずれか一項に記載の接着剤組成物。 6. The method according to claim 1, wherein the radically polymerizable compound (b) contains at least one vinyl compound having a phosphate group and one or more radically polymerizable compounds other than the vinyl compound having a phosphate group. The adhesive composition according to claim 1.
  7. 　前記（ａ）熱可塑性樹脂が、フェノキシ樹脂、ポリウレタン樹脂、ポリエステルウレタン樹脂、ブチラール樹脂、アクリル樹脂及びポリイミド樹脂からなる群より選ばれる少なくとも１種を含有する、請求項１～６のいずれか一項に記載の接着剤組成物。 The thermoplastic resin (a) contains at least one selected from the group consisting of phenoxy resin, polyurethane resin, polyester urethane resin, butyral resin, acrylic resin and polyimide resin. The adhesive composition described in 1.
  8. 　（ｄ）導電性粒子をさらに含有する、請求項１～７のいずれか一項に記載の接着剤組成物。 (D) The adhesive composition according to any one of claims 1 to 7, further comprising conductive particles.
  9. 　主面上に第一の接続端子を有する第一の回路部材と、主面上に第二の接続端子を有する第二の回路部材と、接続部材と、を備える回路部材の接続構造体であって、
    　前記第一の接続端子及び前記第二の接続端子が対向するように、前記第一の回路部材及び前記第二の回路部材が請求項１～８のいずれか一項に記載の接着剤組成物からなる前記接続部材を介して配置されるとともに、前記第一の接続端子及び前記第二の接続端子が電気的に接続されており、
    　前記第一の回路部材及び／又は前記第二の回路部材は、ガラス転移温度が２００℃以下の熱可塑性樹脂を含有する基材から構成されている、回路部材の接続構造体。     A circuit member connection structure comprising: a first circuit member having a first connection terminal on a main surface; a second circuit member having a second connection terminal on a main surface; and a connection member. And
    The adhesive composition according to any one of claims 1 to 8, wherein the first circuit member and the second circuit member are arranged so that the first connection terminal and the second connection terminal face each other. And the first connection terminal and the second connection terminal are electrically connected with each other through the connection member.
    Said 1st circuit member and / or said 2nd circuit member are the connection structures of a circuit member comprised from the base material containing the thermoplastic resin whose glass transition temperature is 200 degrees C or less.
  10. 　前記ガラス転移温度が２００℃以下の熱可塑性樹脂は、ポリエチレンテレフタレート、ポリカーボネート及びポリエチレンナフタレートからなる群より選ばれる少なくとも１種である、請求項９記載の回路部材の接続構造体。 The circuit member connection structure according to claim 9, wherein the thermoplastic resin having a glass transition temperature of 200 ° C or lower is at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate.
  11. 　前記第一の回路部材又は前記第二の回路部材のうち一方の回路部材が、ポリエチレンテレフタレート、ポリカーボネート及びポリエチレンナフタレートからなる群より選ばれる少なくとも１種を含有する基材から構成され、
    　前記第一の回路部材又は第二の回路部材のうちもう一方の回路部材が、ポリイミド樹脂及びポリエチレンテレフタレートからなる群より選ばれる少なくとも１種を含有する基材から構成される、請求項９又は１０記載の回路部材の接続構造体。     One of the first circuit member or the second circuit member is composed of a base material containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate and polyethylene naphthalate,
    The other circuit member of the first circuit member or the second circuit member is composed of a base material containing at least one selected from the group consisting of polyimide resin and polyethylene terephthalate. The connection structure of the circuit member described.
  12. 　主面上に第一の接続端子を有する第一の回路部材と、主面上に第二の接続端子を有する第二の回路部材とを、請求項１～８のいずれか一項に記載の接着剤組成物を介して前記第一の接続端子及び前記第二の接続端子が対向するように、配置する工程と、
    　前記接着剤組成物を加熱し、硬化させて、前記第一の回路部材と前記第二の回路部材とを接続する工程と、
    を備える、回路部材の接続構造体の製造方法。     The first circuit member having a first connection terminal on the main surface and the second circuit member having a second connection terminal on the main surface are described in any one of claims 1 to 8. A step of arranging the first connection terminal and the second connection terminal to face each other through an adhesive composition;
    Heating and curing the adhesive composition to connect the first circuit member and the second circuit member;
    The manufacturing method of the connection structure of a circuit member provided with this.
  13. 　（ａ）熱可塑性樹脂、（ｂ）ラジカル重合性化合物及び（ｃ）ラジカル重合開始剤を含有し、前記（ｂ）ラジカル重合性化合物が２５～４０ｍＮ／ｍの臨界表面張力を有するウレタン（メタ）アクリレートを含む、接着剤組成物の、
    　主面上に第一の接続端子を有する第一の回路部材と、主面上に第二の接続端子を有する第二の回路部材であって、少なくとも一方の回路部材がガラス転移温度２００℃以下の熱可塑性樹脂を含む基材から構成された、前記第一の回路部材及び第二の回路部材を接続するための接着剤組成物の応用。     Urethane (meth) containing (a) a thermoplastic resin, (b) a radical polymerizable compound and (c) a radical polymerization initiator, wherein the (b) radical polymerizable compound has a critical surface tension of 25 to 40 mN / m An adhesive composition comprising an acrylate,
    A first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface, wherein at least one circuit member has a glass transition temperature of 200 ° C. or less. Application of the adhesive composition for connecting the first circuit member and the second circuit member, each of which is composed of a base material containing the thermoplastic resin.
  14. 　前記ウレタン（メタ）アクリレートが下記一般式（Ａ）で表されるウレタン（メタ）アクリレートである、請求項１３記載の応用。
    Figure JPOXMLDOC01-appb-C000005
     ［式（Ａ）中、Ｒ１及びＲ２はそれぞれ独立に水素原子またはメチル基を示し、Ｒ３はエチレン基、プロピレン基、ε－カプロラクトンの開環化合物から誘導される基、または下記一般式（Ｂ）で表される基を示し、Ｒ４は下記一般式（Ｂ）で表される基を示し、Ｒ５は飽和脂肪族基または飽和脂環式基を示し、ａは１～４０の整数を示す。］
    Figure JPOXMLDOC01-appb-C000006
     ［式（Ｂ）中、Ｒ６及びＲ７はそれぞれ独立に炭素数２～１２の直鎖又は分岐鎖のアルキレン基を示し、ｂは１～１０の整数を示し、ｃは１～２５の整数を示す。なお、式中、Ｒ６同士、Ｒ７同士、ｂ同士及びｃ同士はそれぞれ同一でも異なってもよい。］     The application according to claim 13, wherein the urethane (meth) acrylate is a urethane (meth) acrylate represented by the following general formula (A).
    Figure JPOXMLDOC01-appb-C000005
     [In the formula (A), R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and R 3 represents a group derived from a ring-opening compound of ethylene group, propylene group or ε-caprolactone, or the following general formula: Represents a group represented by (B), R 4 represents a group represented by the following general formula (B), R 5 represents a saturated aliphatic group or a saturated alicyclic group, and a represents 1 to 40 Indicates an integer. ]
    Figure JPOXMLDOC01-appb-C000006
     [In the formula (B), R 6 and R 7 each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms, b represents an integer of 1 to 10, and c represents an integer of 1 to 25. Indicates. In the formula, R 6 s , R 7 s , b s, and c s may be the same or different. ]
  15. 　（ａ）熱可塑性樹脂、（ｂ）ラジカル重合性化合物及び（ｃ）ラジカル重合開始剤を含有し、前記（ｂ）ラジカル重合性化合物が下記一般式（Ａ）で表されるウレタン（メタ）アクリレートを含む、接着剤組成物の、
    　主面上に第一の接続端子を有する第一の回路部材と、主面上に第二の接続端子を有する第二の回路部材であって、少なくとも一方の回路部材がガラス転移温度２００℃以下の熱可塑性樹脂を含む基材から構成された、前記第一の回路部材及び第二の回路部材を接続するための接着剤組成物の応用。
    Figure JPOXMLDOC01-appb-C000007
     ［式（Ａ）中、Ｒ１及びＲ２はそれぞれ独立に水素原子またはメチル基を示し、Ｒ３はエチレン基、プロピレン基、ε－カプロラクトンの開環化合物から誘導される基、または下記一般式（Ｂ）で表される基を示し、Ｒ４は下記一般式（Ｂ）で表される基を示し、Ｒ５は飽和脂肪族基または飽和脂環式基を示し、ａは１～４０の整数を示す。］
    Figure JPOXMLDOC01-appb-C000008
     ［式（Ｂ）中、Ｒ６及びＲ７はそれぞれ独立に炭素数２～１２の直鎖又は分岐鎖のアルキレン基を示し、ｂは１～１０の整数を示し、ｃは１～２５の整数を示す。なお、式中、Ｒ６同士、Ｒ７同士、ｂ同士及びｃ同士はそれぞれ同一でも異なってもよい。］     Urethane (meth) acrylate containing (a) thermoplastic resin, (b) radical polymerizable compound and (c) radical polymerization initiator, wherein (b) radical polymerizable compound is represented by the following general formula (A) An adhesive composition comprising
    A first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface, wherein at least one circuit member has a glass transition temperature of 200 ° C. or less. Application of the adhesive composition for connecting the first circuit member and the second circuit member, each of which is composed of a base material containing the thermoplastic resin.
    Figure JPOXMLDOC01-appb-C000007
     [In the formula (A), R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and R 3 represents a group derived from a ring-opening compound of ethylene group, propylene group or ε-caprolactone, or the following general formula: Represents a group represented by (B), R 4 represents a group represented by the following general formula (B), R 5 represents a saturated aliphatic group or a saturated alicyclic group, and a represents 1 to 40 Indicates an integer. ]
    Figure JPOXMLDOC01-appb-C000008
     [In the formula (B), R 6 and R 7 each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms, b represents an integer of 1 to 10, and c represents an integer of 1 to 25. Indicates. In the formula, R 6 s , R 7 s , b s, and c s may be the same or different. ]
  16. 　前記ウレタン（メタ）アクリレートが、脂肪族ポリエステルジオールを用いて得たものである、請求項１３～１５のいずれか一項に記載の応用。 The application according to any one of claims 13 to 15, wherein the urethane (meth) acrylate is obtained by using an aliphatic polyester diol.
  17. 　前記ウレタン（メタ）アクリレートの重量平均分子量が８０００以上２５０００未満である、請求項１３～１６のいずれか一項に記載の応用。 The application according to any one of claims 13 to 16, wherein the urethane (meth) acrylate has a weight average molecular weight of 8000 or more and less than 25,000.
  18. 　前記（ｂ）ラジカル重合性化合物が、リン酸基を有するビニル化合物と、前記リン酸基を有するビニル化合物以外のラジカル重合性化合物と、をそれぞれ１種以上含有する、請求項１３～１７のいずれか一項に記載の応用。 18. The method according to claim 13, wherein the radical polymerizable compound (b) contains at least one vinyl compound having a phosphate group and one or more radical polymerizable compounds other than the vinyl compound having a phosphate group. Application as described in one.
  19. 　前記（ａ）熱可塑性樹脂が、フェノキシ樹脂、ポリウレタン樹脂、ポリエステルウレタン樹脂、ブチラール樹脂、アクリル樹脂及びポリイミド樹脂からなる群より選ばれる少なくとも１種を含有する、請求項１３～１８のいずれか一項に記載の応用。 The thermoplastic resin (a) contains at least one selected from the group consisting of phenoxy resin, polyurethane resin, polyester urethane resin, butyral resin, acrylic resin and polyimide resin. Application as described in.
  20. 　前記接着剤組成物が（ｄ）導電性粒子をさらに含有する、請求項１３～１９のいずれか一項に記載の応用。 The application according to any one of claims 13 to 19, wherein the adhesive composition further contains (d) conductive particles.
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