WO2018070208A1 - 接続構造体、回路接続部材及び接着剤組成物 - Google Patents

接続構造体、回路接続部材及び接着剤組成物 Download PDF

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Publication number
WO2018070208A1
WO2018070208A1 PCT/JP2017/034153 JP2017034153W WO2018070208A1 WO 2018070208 A1 WO2018070208 A1 WO 2018070208A1 JP 2017034153 W JP2017034153 W JP 2017034153W WO 2018070208 A1 WO2018070208 A1 WO 2018070208A1
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WIPO (PCT)
Prior art keywords
circuit
adhesive composition
mass
meth
temperature
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PCT/JP2017/034153
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English (en)
French (fr)
Japanese (ja)
Inventor
智樹 森尻
雅英 久米
田中　勝
潤 竹田津
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日立化成株式会社
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Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to KR1020227025671A priority Critical patent/KR20220107095A/ko
Priority to KR1020247002315A priority patent/KR20240014613A/ko
Priority to JP2018544726A priority patent/JP7006610B2/ja
Priority to KR1020197012839A priority patent/KR102467385B1/ko
Priority to CN201780062709.6A priority patent/CN109804508B/zh
Publication of WO2018070208A1 publication Critical patent/WO2018070208A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a connection structure, a circuit connection member, and an adhesive composition.
  • the circuit member includes, for example, a printed wiring board, an organic base material such as polyimide, or a metal having various surface states such as metal such as titanium, copper, and aluminum, ITO, IZO, IGZO, SiN, and SiO 2. Therefore, the material used for the adhesive needs to be molecularly designed according to the circuit member.
  • non-crystalline (amorphous) ITO films, organic insulating films, and the like in circuit members has been increasing for the purpose of simplifying the manufacturing process of semiconductor elements and display elements and lowering the temperature.
  • These film surfaces are often disadvantageous for adhesion from the physical viewpoint that surface irregularities are small, or from the chemical viewpoint that surface wettability is low.
  • a covalent bond, hydrogen bond, van der Waals force is provided between the circuit connecting member and the circuit member surface.
  • an additive such as a coupling agent that causes an interaction such as a hydrophobic interaction due to is added to the adhesive.
  • a silane coupling agent, a coupling agent having a phosphate group, a carboxyl group, or the like is used as the coupling agent.
  • an epoxysilane, acryloyl group, vinyl group, or other organic functional group is present in the resin constituting the circuit connecting member, and an alkoxysilane structure or phosphorous that causes an interaction between the circuit member surface and the circuit connecting member.
  • a coupling agent having an acid group or the like is used, the circuit member and the circuit connecting member can be bonded more firmly (see Patent Documents 1 to 3).
  • the interaction between the circuit connecting member and the circuit member is effective depending on the type of the circuit member in a high temperature and high humidity environment.
  • the circuit connecting member is peeled off from the circuit member.
  • this invention provides the connection structure which can suppress that a circuit connection member peels from a circuit member also in a high temperature, high humidity environment, and the circuit connection member and adhesive composition which are used for this connection structure. For the purpose.
  • a connection structure that satisfies the condition of dL (t) / dt ⁇ 0 at at least one temperature t of ⁇ 120 ° C.
  • a circuit connecting member that satisfies a condition of (t) / dt ⁇ 0.
  • the average linear thermal expansion coefficient at 30 ° C. to 120 ° C. of the circuit connecting member is preferably 500 ppm / ° C. or less.
  • the average linear thermal expansion coefficient at 30 ° C. to 120 ° C. of the cured product is preferably 500 ppm / ° C. or less.
  • connection structure which can suppress that a circuit connection member peels from a circuit member also in a high temperature, high humidity environment, and the circuit connection member and adhesive composition which are used for this connection structure are provided. be able to.
  • connection structure It is a schematic cross section showing one embodiment of a connection structure. It is a graph which shows an example of the relationship between temperature and the amount of linear thermal expansion.
  • (Meth) acrylic acid means acrylic acid or methacrylic acid, and the same applies to other similar expressions such as (meth) acrylate.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of a connection structure.
  • the connection structure 1 includes a first circuit member 2, a second circuit member 3, and a circuit connection provided between the first circuit member 2 and the second circuit member 3. And a member 4.
  • the first circuit member 2 includes a first substrate 5 and a first circuit electrode 6 provided on the main surface of the first substrate 5.
  • the second circuit member 3 includes a second substrate 7 and a second circuit electrode 8 provided on the main surface of the second substrate 7.
  • the first and second circuit members 2 and 3 may be the same as or different from each other, and may be a chip component such as a semiconductor chip, a resistor chip, or a capacitor chip, or a substrate such as a printed circuit board.
  • the first and second substrates 5 and 7 may be formed of an inorganic material such as a semiconductor, glass or ceramic, an organic material such as polyimide or polycarbonate, or a composite material such as glass / epoxy.
  • the first and second circuit electrodes 6 and 8 may be made of gold, silver, tin, ruthenium, rhodium, palladium, osmium, iridium, platinum, crystalline or amorphous indium tin oxide (ITO), or the like. .
  • circuit electrodes 6 and 8 are usually provided on the substrates 5 and 7 of these circuit members 2 and 3 (in some cases, one may be provided).
  • the first and second circuit members 2 and 3 are arranged such that at least a pair of the first circuit electrode 6 and the second circuit electrode 8 face each other.
  • the circuit connection member 4 contains a cured product 9 of an adhesive component and conductive particles 10 dispersed in the cured product 9 of the adhesive component. By interposing the conductive particles 10 in the circuit connecting member 4 between the first circuit electrode 6 and the second circuit electrode 8 facing each other, the first circuit electrode 6 and the second circuit electrode 8 are arranged. Are electrically connected to each other.
  • the circuit connecting member 4 has a linear thermal expansion amount at a temperature t ° C. of the circuit connecting member 4 of L (t) ⁇ m from the viewpoint of suppressing the peeling of the circuit connecting member 4 from the circuit members 2 and 3 and the circuit electrodes 6 and 8.
  • the amount of linear thermal expansion here means the amount of linear thermal expansion in the length direction of the sample.
  • the condition of dL (t) / dt ⁇ 0 is satisfied, preferably dL (t) /dt ⁇ 0.01, more preferably dL (t) /dt ⁇ 0.1, still more preferably Satisfies the condition of dL (t) /dt ⁇ 0.5.
  • the average linear thermal expansion coefficient at 30 ° C. to 120 ° C. of the circuit connecting member 4 is preferably 500 ppm / ° C. or less from the viewpoint of suppressing peeling of the circuit connecting member 4 from the circuit members 2 and 3 and the circuit electrodes 6 and 8. More preferably, it is 250 ppm / ° C. or less, and further preferably 150 ppm / ° C. or less.
  • the coefficient of linear thermal expansion (ppm / ° C.) of the circuit connecting member 4 is defined as the amount of linear thermal expansion ( ⁇ m) at a length of 1 m of the circuit connecting member 4 per 1 ° C. of temperature rise.
  • the cured product 9 and the conductive particles 10 of the adhesive component constituting the circuit connection member 4 are selected so that the circuit connection member 4 has the above-described characteristics.
  • the circuit connection member 4 is obtained, for example, by curing an adhesive composition containing an adhesive component and conductive particles 10. From the viewpoint of suppressing the peeling of the circuit connecting member 4 from the circuit members 2 and 3 and the circuit electrodes 6 and 8, the adhesive composition preferably has a linear thermal expansion amount at a temperature t of a cured product of the adhesive composition.
  • the cured product of the adhesive composition is, for example, a cured product obtained by molding the adhesive composition into a film adhesive having a thickness of 100 ⁇ 20 ⁇ m and heating the film adhesive at 180 ° C. for 1 hour. It may be.
  • the amount of linear thermal expansion here means the amount of linear thermal expansion in the length direction of the sample.
  • the linear thermal expansion amount l (t) of the cured product of the adhesive composition is a viewpoint that suppresses peeling of the cured product of the adhesive composition (circuit connection member 4) from the circuit members 2 and 3 and the circuit electrodes 6 and 8.
  • the average coefficient of linear thermal expansion at 30 ° C. to 120 ° C. of the cured product of the adhesive composition is that the cured product of the adhesive composition (circuit connection member 4) is peeled off from the circuit members 2 and 3 and the circuit electrodes 6 and 8. From the viewpoint of suppression, it is preferably 500 ppm / ° C. or less, more preferably 250 ppm / ° C. or less, and still more preferably 150 ppm / ° C. or less.
  • the linear thermal expansion coefficient (ppm / ° C.) of the cured product of the adhesive composition is defined as the amount of linear thermal expansion ( ⁇ m) at a length of 1 m of the cured product of the adhesive composition per 1 ° C. temperature increase.
  • the change amount of l (t) [unit: ⁇ m / 10 mm] is converted into the linear thermal expansion amount ( ⁇ m) at a length of 1 m of the cured product of the adhesive composition, and the average value per 1 ° C. temperature rise from the converted value. (That is, according to the following equation).
  • ⁇ l (t 30 ° C.) ⁇ ⁇ 100 / (120-30)
  • the adhesive composition having such characteristics includes, for example, two or more kinds of resin components having different glass transition points (Tg), a component that easily causes phase separation, a component that has a skeleton easily oriented, a negative line Contains a filler component having a thermal expansion coefficient.
  • Tg glass transition points
  • combinations of components that easily cause phase separation include combinations of components that have a large difference in molecular weight, combinations of components that have a large difference in polarity, and the like.
  • the combinations of components that are likely to cause phase separation include a combination of an acrylic resin and an epoxy resin, a combination of a urethane resin and a phenoxy resin, a combination of an acrylic rubber and a phenoxy resin, and a combination of an acrylic rubber and an epoxy resin.
  • the component having an easily oriented skeleton examples include a component containing an alkyl chain and a component containing a phenyl group.
  • the cured product (circuit connection member 4) of the resulting adhesive composition reduces minute voids due to temperature rise, reorients molecular chains, and filler components.
  • the present inventors consider that the shrinkage (volume phenomenon) accompanying the temperature rise occurs due to the rearrangement of.
  • the adhesive composition is preferably (a) a thermoplastic resin (hereinafter also referred to as “(a) component”) and (b) a radical polymerizable compound (hereinafter also referred to as “(b) component”). ) And (c) a radical polymerization initiator (hereinafter also referred to as “component (c)”).
  • the component (a) is not particularly limited, and for example, one or two selected from polyimide resin, polyamide resin, phenoxy resin, poly (meth) acrylic resin, polyester resin, polyurethane resin, polyester urethane resin and polyvinyl butyral resin. More than one type of resin may be mentioned.
  • the adhesive composition preferably contains two or more of the above thermoplastic resins, more preferably, from the viewpoint of easily obtaining a cured product (circuit connection member 4) of the adhesive composition having a desired amount of linear thermal expansion.
  • a thermoplastic resin having different Tg's.
  • Suitable resin combinations include, for example, a combination of phenoxy resin and poly (meth) acrylic resin, a combination of phenoxy resin and polyester resin, a combination of phenoxy resin and polyester urethane resin, and a combination of phenoxy resin and polyimide resin. Combinations are mentioned.
  • the ratio of the content of the thermoplastic resin having a higher Tg and the thermoplastic resin having a lower Tg is preferably 90/10 to 10/90, more preferably 90/10 to 20 from the viewpoint of easily obtaining a cured product (circuit connection member 4) of the adhesive composition having a desired amount of linear thermal expansion. / 80, more preferably 90/10 to 30/70.
  • the adhesive composition contains three or more thermoplastic resins having different Tg, the adhesive composition is preferably the above-mentioned thermoplastic resin having the highest Tg and the thermoplastic resin having the lowest Tg. It contains so that ratio of content may become said ratio.
  • the weight average molecular weight of the thermoplastic resin is preferably 5000 or more, more preferably 10,000 or more, and preferably 400,000 or less, more preferably 200000 or less, and further preferably 150,000 or less.
  • the weight average molecular weight of the thermoplastic resin is 5000 or more, the adhesive force of the adhesive composition tends to be improved.
  • the weight average molecular weight of the thermoplastic resin is 400000 or less, the compatibility with other components is excellent, and the fluidity of the adhesive tends to be improved.
  • the weight average molecular weight in this invention means the weight average molecular weight (standard polystyrene conversion value) measured by GPC (gel permeation chromatography).
  • the adhesive composition may contain a rubber component as a thermoplastic resin from the viewpoint of stress relaxation and further improvement in adhesiveness.
  • the rubber component include silicone rubber, acrylic rubber, polyisoprene rubber, polybutadiene rubber, carboxyl group-terminated polybutadiene rubber, hydroxyl group-terminated polybutadiene rubber, 1,2-polybutadiene rubber, carboxyl group-terminated 1,2-polybutadiene rubber, hydroxyl group-terminated 1 , 2-polybutadiene rubber, styrene-butadiene rubber, hydroxyl-terminated styrene-butadiene rubber, acrylonitrile-butadiene rubber, carboxylated nitrile rubber, hydroxyl-terminated poly (oxypropylene) rubber, alkoxysilyl-terminated poly (oxypropylene) rubber, poly ( Oxytetramethylene) glycol rubber, polyolefin glycol rubber, and poly- ⁇ -caprolactone rubber.
  • the rubber component preferably has a cyano group or a carboxyl group, which is a highly polar group, as a side chain group or a terminal group from the viewpoint of further improving adhesiveness.
  • These rubber components can be used singly or in combination of two or more.
  • the rubber component may be in the form of particles.
  • the average particle size of the rubber particles is preferably not more than twice the average particle size of the conductive particles 10, for example, 0.01 ⁇ m to 100 ⁇ m.
  • the storage elastic modulus of the rubber particles at room temperature (25 ° C.) is preferably 1 ⁇ 2 or less of the storage elastic modulus of the conductive particles 10 and the adhesive composition at room temperature, for example, 0.1 MPa to 100 MPa.
  • the rubber particles are preferably three-dimensionally crosslinked rubber particles from the viewpoint of excellent solvent resistance and being easily dispersed in the adhesive composition.
  • the content of the component (a) is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and further preferably 35 parts by mass or more with respect to 100 parts by mass of the total amount of the components (a) and (b). Moreover, it is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and still more preferably 65 parts by mass or less.
  • the adhesive force is further improved, and the film forming property of the adhesive composition tends to be improved.
  • the adhesive is used. There is a tendency for the fluidity of the to improve.
  • the component (b) is not particularly limited, and may be, for example, a compound (monomer) described below, an oligomer of the compound, or may contain both.
  • the component (b) is preferably a polyfunctional (meth) acrylate compound having two or more (meth) acryloyloxy groups.
  • Such (meth) acrylate compounds include epoxy (meth) acrylate, urethane (meth) acrylate, polyether (meth) acrylate, polyester (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) ) Polyalkylene glycol di (meth) acrylate such as acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Examples include isocyanuric acid-modified bifunctional (meth) acrylate and isocyanuric acid-modified trifunctional (meth) acrylate.
  • epoxy (meth) acrylate obtained by adding (meth) acrylic acid to two glycidyl groups of bisphenol fluorenediglycidyl ether, ethylene glycol and / or two glycidyl groups of bisphenol fluorenediglycidyl ether
  • examples thereof include compounds in which a (meth) acryloyloxy group is introduced into a compound to which propylene glycol has been added.
  • urethane (meth) acrylate is preferably used from the viewpoint of obtaining better adhesiveness by having a urethane bond. These compounds are used alone or in combination of two or more.
  • the adhesive composition may contain a monofunctional (meth) acrylate compound as the component (b) from the viewpoint of controlling fluidity.
  • monofunctional (meth) acrylate compounds include pentaerythritol (meth) acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl (meth).
  • the adhesive composition may contain a compound having a radical polymerizable functional group such as an allyl group, a maleimide group, and a vinyl group as the component (b) from the viewpoint of improving the crosslinking rate.
  • a compound having a radical polymerizable functional group such as an allyl group, a maleimide group, and a vinyl group as the component (b) from the viewpoint of improving the crosslinking rate.
  • examples of such compounds include N-vinylimidazole, N-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, 4,4′-vinylidenebis (N, N-dimethylaniline), Examples include N-vinylacetamide, N, N-dimethylacrylamide, N-isopropylacrylamide and N, N-diethylacrylamide.
  • the adhesive composition preferably contains a radically polymerizable compound having a phosphate ester structure as the component (b) for the purpose of improving the adhesive strength.
  • the radically polymerizable compound having a phosphate ester structure may be, for example, a compound represented by the following formula (1), (2) or (3).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a (meth) acryloyloxy group
  • a and b each independently represents an integer of 1 to 8.
  • a plurality of R 1 , R 2 , a and b in the same molecule may be the same or different from each other.
  • R 3 represents a (meth) acryloyloxy group
  • c and d each independently represents an integer of 1 to 8.
  • a plurality of R 3 , c and d in the same molecule may be the same or different from each other.
  • R 4 represents a hydrogen atom or a methyl group
  • R 5 represents a (meth) acryloyloxy group
  • e and f each independently represents an integer of 1 to 8.
  • a plurality of R 4 , R 4 , e and f in the same molecule may be the same as or different from each other.
  • radical polymerizable compound having a phosphate ester structure examples include acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate, and acid phosphooxypoly Oxypropylene glycol mono (meth) acrylate, 2,2'-di (meth) acryloyloxydiethyl phosphate, EO (ethylene oxide) modified di (meth) acrylate, phosphoric acid modified epoxy (meth) acrylate and vinyl phosphate Is mentioned.
  • the content of the component (b) in the adhesive composition is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and still more preferably with respect to 100 parts by mass of the total amount of the components (a) and (b). Is 35 parts by mass or more, preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and still more preferably 65 parts by mass or less.
  • the content of the component (b) is 20 parts by mass or more, the heat resistance of the cured adhesive composition (circuit connection member 4) tends to be improved, and when it is 80 parts by mass or less, high temperature and high humidity. It exists in the tendency which can further suppress peeling of the circuit connection member 4 in an environment.
  • the content of the radical polymerizable compound having a phosphate ester structure is the amount of the component (a) and the component (b).
  • it is 0.1 mass part or more with respect to a total amount of 100 mass parts, More preferably, it is 0.5 mass part or more, Preferably it is 15 mass parts or less, More preferably, it is 10 mass parts or less.
  • the content of the radical polymerizable compound having a phosphate ester structure is 0.1 parts by mass or more, the adhesive strength of the adhesive composition tends to be further increased, and if it is 15 parts by mass or less, the adhesive composition The physical properties of the cured product (circuit connection member 4) are not easily lowered, and the reliability tends to be improved.
  • the component (c) can be arbitrarily selected from compounds such as peroxides and azo compounds.
  • a peroxide having a 1 minute half-life temperature of 90 ° C. to 175 ° C. and a molecular weight of 180 to 1000 is preferably used from the viewpoint of excellent stability, reactivity, and compatibility.
  • 1 minute half-life temperature means a temperature at which the half-life of the peroxide is 1 minute.
  • Half-life refers to the time it takes for the concentration of a compound to decrease to half of its initial value at a given temperature.
  • radical polymerization initiator examples include 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, and di (2-ethylhexyl) peroxydicarbonate.
  • the radical polymerization initiator preferably has a chlorine ion or organic acid content of 5000 ppm or less, and has a small amount of organic acid generated after decomposition. Is more preferably used. From the viewpoint of improving the stability of the adhesive composition, a radical polymerization initiator having a mass retention of 20% by mass or more after being left in the atmosphere at room temperature (25 ° C.) and atmospheric pressure for 24 hours is preferably used. It is done.
  • the content of the component (c) in the adhesive composition is preferably 1 part by mass or more, more preferably 2.5 parts by mass or more with respect to 100 parts by mass of the total amount of the components (a) and (b). Yes, and preferably 15 parts by mass or less, more preferably 10 parts by mass or less.
  • the adhesive composition is preferably (a) a thermoplastic resin, (d) an epoxy resin (hereinafter also referred to as “component (d)”), and (e) a curing agent (hereinafter referred to as “a”). , Also referred to as “component (e)”).
  • component (a) in the present embodiment is the same component as the component (a) described in the above embodiment.
  • Epoxy resin is a resin having at least one epoxy group in the molecule.
  • Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, fat Examples thereof include cyclic epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, and aliphatic chain epoxy resins.
  • the epoxy resin may be a halogenated epoxy resin obtained by halogenating the above epoxy resin, or may be a hydrogenated epoxy resin obtained by hydrogenating the above epoxy resin. These epoxy resins, halogenated epoxy resins and hydrogenated epoxy resins are used singly or in combination of two or more.
  • the content of the component (d) in the adhesive composition is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably with respect to 100 parts by mass of the total amount of the components (a) and (d). Is 30 parts by mass or more, preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and still more preferably 70 parts by mass or less.
  • the content of the component (d) is 10 parts by mass or more, better adhesiveness tends to be obtained, and when it is 90 parts by mass or less, there is little stickiness and workability tends to be good.
  • the curing agent (also referred to as “epoxy polymerization initiator” or “latent curing agent”) may be (d) a curing agent capable of curing the epoxy resin.
  • the curing agent include an anion polymerizable catalyst type curing agent, a cationic polymerizable catalyst type curing agent, and a polyaddition type curing agent. These are used singly or in combination of two or more.
  • the curing agent is preferably an anion-polymerizable or cation-polymerizable catalyst-type curing agent from the viewpoint of being excellent in rapid curability and not requiring chemical equivalent consideration.
  • anionic polymerizable or cationic polymerizable catalytic curing agent examples include imidazole curing agent, hydrazide curing agent, boron trifluoride-amine complex, onium salt such as sulfonium salt, diazonium salt, amine imide, diaminomaleonitrile, melamine And derivatives thereof, polyamine salts, dicyandiamide and the like, and these modified products can also be used.
  • the epoxy resin is cured by heating at a temperature of about 160 ° C. to 200 ° C. for several tens of seconds to several hours. To do. For this reason, the pot life of the adhesive composition can be made relatively long.
  • a photosensitive onium salt aromatic diazonium salt, aromatic sulfonium salt, etc. that cures an epoxy resin by energy ray irradiation is preferably used.
  • Examples of the cationic polymerizable catalyst-type curing agent that is activated by heating and cures the epoxy resin include aliphatic sulfonium salts. These anionic polymerizable or cationic polymerizable catalyst-type curing agents are preferably used in that they have fast curability.
  • polyaddition type curing agents examples include polyamines, polymercaptans, polyphenols, and acid anhydrides.
  • the content of the component (e) in the adhesive composition is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, with respect to 100 parts by mass of the total amount of the components (a) and (d). Moreover, Preferably it is 80 mass parts or less, More preferably, it is 70 mass parts or less.
  • the conductive particles 10 include metal particles such as Au, Ag, Ni, Cu, and solder, and conductive particles such as conductive carbon particles.
  • the conductive particle 10 is a coated conductive material comprising a core composed of particles of non-conductive glass, ceramic, plastic, etc., and a layer composed of the above metal, metal particles, conductive carbon particles, etc. covering the core. It may be a conductive particle.
  • the conductive particles 10 are coated conductive particles or metal particles that are melted by heat (heat-melted metal particles), the conductive particles 10 are deformed by heating and pressing at the time of circuit connection. Even if there is a variation in thickness, the contact area between the conductive particles 10 and the circuit electrodes 6 and 8 increases, and good reliability can be obtained.
  • the conductive particles 10 prevent a short circuit between the conductive particles 10, particularly when the blending amount of the conductive particles 10 is increased, and between the adjacent first circuit electrodes 6, 6 or the second circuit electrodes 8, Insulating coated conductive particles comprising the above-described conductive particles and an insulating coating layer formed of an insulating material such as a polymer resin, which covers the surfaces of the conductive particles, from the viewpoint of improving the insulation between the eight particles It may be.
  • These conductive particles, coated conductive particles, and insulating coated conductive particles are used singly or in combination of two or more.
  • the average particle diameter of the conductive particles 10 is preferably 1 ⁇ m to 50 ⁇ m from the viewpoint of excellent dispersibility and conductivity.
  • the content of the conductive particles is preferably 0.1% by volume or more, preferably 30% by volume or less, more preferably 10% by volume or less, based on the total amount of the adhesive composition. When the content is 0.1% by volume or more, the conductivity tends to be further improved, and when the content is 30% by volume or less, between the adjacent first circuit electrodes 6, 6 or the second circuit electrode 8, It exists in the tendency which can suppress the short circuit between 8.
  • the content of the conductive particles 10 is determined based on the volume of each component of the adhesive composition (before curing) at 23 ° C.
  • volume of each component for example, a value converted from weight to volume using specific gravity can be used.
  • a component that does not dissolve or swell the component in a graduated cylinder, etc., and that contains an appropriate solvent (water, alcohol, etc.) that wets the component well is added to the component to increase the volume. It can also be determined as a volume.
  • the adhesive composition is added to the component (a), the component (b), the component (c) and the conductive particles 10.
  • Other resins such as phenol resin, melamine resin, filler (filler), softener, curing accelerator, anti-aging agent, colorant, flame retardant, thixotropic agent, coupling agent, etc.
  • You may further contain a thickener, a leveling agent, a weather resistance improvement agent, an isocyanate compound, etc.
  • the filler is composed of silicon, calcium, zirconium, titanium, aluminum, carbon, bismuth, cobalt, copper, iron, indium, manganese, tin, yttrium, zinc or the like, a compound containing them, an organic compound, or the like. Particles.
  • the average particle diameter of the particles is preferably 1 ⁇ 2 or less of the average particle diameter of the conductive particles 10, for example, 0.005 ⁇ m to 25 ⁇ m.
  • the adhesive composition contains non-conductive particles (for example, the rubber particles)
  • the average particle size of the particles used as the filler is equal to or less than the average particle size of the non-conductive particles. Good.
  • the filler is preferably from the viewpoint of further improving electrical characteristics such as connection reliability between the circuit electrodes 6 and 8 by a cured product (circuit connection member 4) of the adhesive composition having a desired amount of linear thermal expansion.
  • the filler has a negative average linear thermal expansion coefficient at 30 ° C. to 120 ° C.
  • Examples of the filler having a negative average linear thermal expansion coefficient at 30 ° C. to 120 ° C. include particles composed of a zirconium-based compound.
  • the content of the filler is preferably 5 parts by mass or more and preferably 60 parts by mass or less with respect to 100 parts by mass of the adhesive composition.
  • the content is 60 parts by mass or less, the effect of improving the connection reliability tends to be obtained more sufficiently, and when the content is 5 parts by mass or more, the effect of adding the filler tends to be sufficiently obtained.
  • the coupling agent may be, for example, a silane coupling agent.
  • a coupling agent such as a silane coupling agent
  • the adhesion of the adhesive composition can be further improved.
  • the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3- (meth) acryloxypropylmethyldimethoxy.
  • Silane 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, N-2- (aminoethyl) -3- Aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and condensates thereof And the like.
  • the content of the coupling agent is preferably 0.1 parts by mass or more, more preferably 0.25 parts by mass with respect to 100 parts by mass of the adhesive components (for example, components (a) to (e)) of the adhesive composition. Part or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less.
  • the content of the coupling agent is 0.1 parts by mass or more, the occurrence of peeling between the circuit member and the circuit connection member tends to be further suppressed, and the content of the coupling agent is 10 parts by mass or less.
  • the pot life of the adhesive composition tends to be long.
  • the adhesive composition When the adhesive composition is liquid at 15 to 25 ° C., for example, it can be used as a paste adhesive composition.
  • the adhesive composition When the adhesive composition is solid at room temperature (25 ° C.), it can be used as a paste adhesive composition by heating, or it can be dissolved in a solvent and used as a paste adhesive composition.
  • the solvent is not particularly limited as long as it is not reactive with the components contained in the adhesive composition and the components contained in the adhesive composition exhibit sufficient solubility, but has a boiling point of 50 at atmospheric pressure.
  • a solvent having a temperature of from 150 ° C. to 150 ° C. is preferably used.
  • the boiling point is 50 ° C. or higher, the solvent can be prevented from volatilizing at room temperature (25 ° C.), and use in an open system becomes easy.
  • the boiling point is 150 ° C. or lower, the solvent is easily volatilized after the adhesive composition is applied to the circuit members 2 and 3, and the reliability after bonding can be ensured.
  • the adhesive composition can also be used as a film adhesive.
  • the adhesive composition is, for example, a solution obtained by adding a solvent or the like to the adhesive composition, if necessary, on a peelable substrate such as a fluororesin film, a polyethylene terephthalate film, a release paper, or a substrate such as a nonwoven fabric.
  • the solution is impregnated with and placed on a peelable substrate, and then the solvent is removed to form a film.
  • the film adhesive is preferably used from the viewpoint of handleability and the like.
  • the adhesive composition is used as a semiconductor element adhesive material typified by anisotropic conductive adhesive, silver paste, circuit connection material typified by silver film, CSP elastomer, CSP underfill material, LOC tape, etc. be able to.
  • connection structure 1 for example, the first circuit member 2 and the second circuit member 3 are arranged so that the first circuit electrode 6 and the second circuit electrode 8 face each other, A film adhesive is interposed between the circuit member 2 and the second circuit member 3, and these are heated and pressurized to electrically connect the first circuit electrode 6 and the second circuit electrode 8 to each other. Can be obtained.
  • the heating temperature during heating is not particularly limited, but is preferably 50 ° C to 250 ° C.
  • the pressure at the time of pressurization is not particularly limited as long as it does not damage the adherend (circuit members 2 and 3), but is preferably 0.1 MPa to 10 MPa. Heating and pressurization are preferably performed for 0.5 seconds to 3 hours.
  • light irradiation may be performed simultaneously with heating and pressurization from the viewpoint of connection at a lower temperature and in a shorter time.
  • irradiation light having a wavelength range of 150 nm to 750 nm is preferably used.
  • Light irradiation for example, low pressure mercury lamp, medium pressure mercury lamps, high pressure mercury lamp, ultra-high pressure mercury lamp, using a xenon lamp or a metal halide lamp, may be carried out in dose of 0.1J / cm 2 ⁇ 10J / cm 2.
  • cured material (circuit connection member 4) of the adhesive composition which concerns on this embodiment is a case where it puts in a high-temperature, high-humidity environment compared with the hardened
  • the glass transition temperature (Tg) of the obtained polyurethane resin was ⁇ 20 ° C.
  • the glass transition temperature (Tg) was measured using a thermomechanical analyzer.
  • the weight average molecular weight of the obtained polyurethane resin was 320,000.
  • the weight average molecular weight is a standard polystyrene equivalent value measured by GPC (gel permeation chromatography).
  • GPC analysis conditions are shown in Table 1 below.
  • the reaction was continued for 15 hours, and it was confirmed that the NCO group content was 0.2% by mass or less using a potentiometric automatic titrator (product name AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.).
  • a potentiometric automatic titrator product name AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.
  • the weight average molecular weight of urethane acrylate was 8500.
  • the weight average molecular weight of urethane acrylate was measured similarly to the weight average molecular weight of the above-mentioned polyurethane resin.
  • A1 Phenoxy resin (product name: PKHC, manufactured by Union Carbide, weight average molecular weight 45000, Tg: 90 ° C., bisphenol A skeleton)
  • A2 Phenoxy resin (Product name: YD-6020, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., weight average molecular weight 5000, Tg: 70 ° C., bisphenol A / bisphenol F skeleton)
  • A3 Phenoxy resin (product name: FX-316, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., weight average molecular weight 50000, Tg: 70 ° C., bisphenol F skeleton)
  • A4 Phenoxy resin (product name: FX-293AT40, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Tg: 160 ° C., high heat resistant skeleton)
  • A5 Polyurethane resin synthesized as described above
  • A6 Polyester resin (Product name: PK
  • conductive particles having an average particle diameter of 5 ⁇ m and a specific gravity of 2.5 having a nickel layer having a thickness of 0.2 ⁇ m were prepared on the surface of polystyrene particles (nuclei).
  • This electroconductive particle was disperse
  • This coating solution was applied to a polyethylene terephthalate (PET) film having a thickness of 50 ⁇ m using a coating apparatus. The coating film was dried with hot air at 70 ° C. for 10 minutes to obtain a film adhesive having a thickness of 18 ⁇ m.
  • PET polyethylene terephthalate
  • connection structure A flexible circuit board (FPC) having about 2200 copper circuit electrodes having a line width of 75 ⁇ m, a pitch of 150 ⁇ m and a thickness of 18 ⁇ m, and a glass (SiO 2 ) substrate (product name: Preclin slide S7224, manufactured by Matsunami Glass Industrial Co., Ltd.), or Each said film adhesive was arrange
  • the connection was made by heating and pressurizing at 160 ° C.
  • thermocompression bonding apparatus heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.
  • the pressure at the time of pressurization was calculated by setting the pressure-bonding area to 0.495 cm 2 .
  • a connection structure was obtained in which the FPC and the glass substrate or the glass substrate with amorphous ITO were connected over a width of 1.5 mm by a cured product of the film adhesive.
  • connection appearance after the high-temperature and high-humidity test immediately after connection and after being left in a constant temperature and humidity chamber of 85 ° C. and 85% RH for 250 hours is observed using an optical microscope.
  • the peeling occurrence area of the substrate-resin interface in the space portion was measured.
  • the case where the peeling occurrence area in the entire space exceeded 30% was evaluated as “existing”, and the case where it was 30% or less was evaluated as “no” peeling.
  • the results are shown in Tables 2 and 3.
  • circuit connection members of Examples 1 to 7 can suppress the occurrence of peeling even under high temperature and high humidity conditions as compared with the circuit connection members of Comparative Examples 1 to 9.
  • SYMBOLS 1 Connection structure, 2 ... 1st circuit member, 3 ... 2nd circuit member, 4 ... Circuit connection member, 6 ... 1st circuit electrode, 8 ... 2nd circuit electrode, 10 ... Conductive particle

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
PCT/JP2017/034153 2016-10-11 2017-09-21 接続構造体、回路接続部材及び接着剤組成物 WO2018070208A1 (ja)

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JP2000500921A (ja) * 1995-11-06 2000-01-25 フォード モーター カンパニー フリップ・チップ組立体
JP2003017149A (ja) * 2001-06-29 2003-01-17 Matsushita Electric Ind Co Ltd 電気接続部材とそれを用いた電気部品
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JPH0323959A (ja) * 1989-06-22 1991-01-31 Mitsubishi Electric Corp Ｌｅｄアレイプリントヘッド
US5552092A (en) * 1994-05-31 1996-09-03 Corning Incorporated Waveguide coupler
JP2000500921A (ja) * 1995-11-06 2000-01-25 フォード モーター カンパニー フリップ・チップ組立体
JP2003017149A (ja) * 2001-06-29 2003-01-17 Matsushita Electric Ind Co Ltd 電気接続部材とそれを用いた電気部品
JP2007297597A (ja) * 2006-03-31 2007-11-15 E I Du Pont De Nemours & Co 有利な熱膨張特性を有するアラミド充填ポリイミド、およびこれに関連する方法
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TWI763551B (zh) 2022-05-01
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CN113555703A (zh) 2021-10-26
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