WO2006126305A1 - Modified polyurethane resin and adhesive composition using the same, method for connecting circuit member and connection structure of circuit member - Google Patents

Modified polyurethane resin and adhesive composition using the same, method for connecting circuit member and connection structure of circuit member Download PDF

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Publication number
WO2006126305A1
WO2006126305A1 PCT/JP2006/301356 JP2006301356W WO2006126305A1 WO 2006126305 A1 WO2006126305 A1 WO 2006126305A1 JP 2006301356 W JP2006301356 W JP 2006301356W WO 2006126305 A1 WO2006126305 A1 WO 2006126305A1
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WO
WIPO (PCT)
Prior art keywords
circuit
circuit member
adhesive composition
adhesive
modified polyurethane
Prior art date
Application number
PCT/JP2006/301356
Other languages
French (fr)
Japanese (ja)
Inventor
Minoru Sugiura
Emi Katayama
Shigeki Katogi
Original Assignee
Hitachi Chemical Company, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Company, Ltd. filed Critical Hitachi Chemical Company, Ltd.
Priority to JP2007517724A priority Critical patent/JP4743204B2/en
Priority to KR1020077030234A priority patent/KR100934802B1/en
Priority to CN2006800178120A priority patent/CN101180335B/en
Publication of WO2006126305A1 publication Critical patent/WO2006126305A1/en

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    • 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
    • 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
    • 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
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    • H01—ELECTRIC ELEMENTS
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    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
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Definitions

  • the present invention relates to a modified polyurethane resin, and an adhesive composition using the modified polyurethane resin
  • the sealing material is a composite material composed of an epoxy resin, a curing agent, various additives, an inorganic filler, etc., and a cresol novolac type epoxy resin is often used as the epoxy resin.
  • cresol novolac-type epoxy resin does not satisfy the required characteristics in terms of low water absorption and low elastic modulus, making it difficult to support surface mounting. For this reason, many new high-performance epoxy resins have been proposed and put to practical use.
  • a conductive adhesive for die bonding As a conductive adhesive for die bonding, a silver paste in which silver powder is kneaded with epoxy resin is often used. However, as the method for mounting a semiconductor element on a wiring board shifts to a surface mounting method, there is a need for a conductive adhesive for die bonding that has improved solder reflow resistance over silver paste. In order to meet this requirement, improvements have been made to the void, peel strength, water absorption, elastic modulus, etc. of the adhesive layer for die bonding after curing.
  • flip chip mounting in which an IC chip is directly mounted on a printed circuit board or a flexible wiring board, has been attracting attention as a new mounting method corresponding to low cost and high definition.
  • a flip chip mounting method a method for solder connection by providing solder bumps on the terminals of an IC chip and a method for electrical connection through a conductive adhesive are known.
  • stress based on the difference in thermal expansion coefficient between the IC chip and the substrate is generated at the connection interface, resulting in a decrease in connection reliability. There is a problem of doing.
  • circuit connection material for circuit connection used for connection with CP, connection between FPC and TCP, or connection between FPC and printed wiring board
  • anisotropic material in which conductive particles are dispersed in the adhesive
  • conductive adhesive is used. In these applications, higher density and higher definition are required and adhesives are required to have high adhesive strength and reliability.
  • connection conditions of circuit adhesives using conventional epoxy resin systems have problems such as wiring dropping, peeling, and misalignment. Furthermore, in order to improve productivity efficiency, there is a strong demand for shortening the connection time to 10 seconds or less, and it is indispensable that the adhesive has a low temperature fast curing property.
  • Patent Document 1 Japanese Patent No. 3279708
  • an object of the present invention is to provide a modified polyurethane resin that can provide a sufficiently strong adhesive force even between materials having different linear expansion coefficients when used in an adhesive.
  • the present invention is a modified polyurethane resin containing a molecular chain represented by the following general formula (I).
  • X is a divalent organic group having an aromatic ring or an aliphatic ring
  • Y is a divalent organic group having a molecular weight of 100 to: LOO 00
  • Z is a 4 r valence having 4 or more carbon atoms (ie, , Divalent to tetravalent) organic group
  • R is a reactive group
  • r is an integer of 0 to 2
  • n and m are each independently 1 to: an integer of LOO
  • a plurality of X in the same molecule , Y, ⁇ and R may be the same or different. However, at least one R exists in the molecular chain.
  • the modified polyurethane resin of the present invention includes a molecular chain having the specific structure described above, and thus exhibits sufficiently strong adhesive force even between materials having different linear expansion coefficients when used in an adhesive. It became a thing.
  • the polyurethane resin of the present invention has a divalent group (a) represented by the following general formula ( ⁇ ) in which the moiety represented by —Z (R) — in the general formula (I) is represented by the following formula (I):
  • the divalent group (b) represented by the general formula ( ⁇ ) or the divalent group (c) represented by the following general formula (IV) is preferable. This particularly improves the adhesive strength when used in an adhesive.
  • A represents a tetravalent organic group containing 4 or more carbon atoms, and R represents a reactive group.
  • the proportion of (a) is 10 to 90 mol%
  • the proportion of (b) is O to 90 mol%
  • (c) Is preferably O to 90 mol%.
  • R is preferably a group having a (meth) acrylate group.
  • the adhesive composition of the present invention contains the modified polyurethane resin of the present invention. This adhesive composition exhibits a sufficiently large adhesive force even between materials having different linear expansion coefficients.
  • the adhesive composition of the present invention preferably further contains a curable resin. This can improve adhesion reliability.
  • the curable resin is a resin that cures by a radical reaction
  • the adhesive composition contains a curing agent that generates free radicals by light irradiation or heating. This makes it possible to connect at a lower temperature and in a shorter time, and the adhesive strength is further improved.
  • the adhesive composition of the present invention preferably further contains conductive particles. As a result, the electrical connection reliability when used as a circuit connection material is further improved.
  • the circuit member connection method of the present invention includes a first circuit member having a first circuit electrode formed on the first substrate and the main surface thereof, a second circuit board, and the main surface thereof. Formed on The first circuit electrode and the second circuit electrode are electrically connected by bonding the second circuit member having the second circuit electrode with the adhesive composition of the present invention. It is.
  • the circuit member connection structure of the present invention includes a first circuit member having a first circuit electrode and a first circuit electrode formed on the first substrate, a second substrate, and a main surface thereof.
  • a second circuit member having a second circuit electrode formed thereon, and the first circuit member and the second circuit electrode are electrically connected to each other.
  • the second circuit member is bonded with the above-described adhesive composition of the present invention.
  • connection structure the circuit members are connected with a sufficiently strong adhesive force, and the connection reliability is high.
  • the adhesive composition using the modified urethane resin of the present invention has excellent adhesive strength and is suitable for an adhesive for circuit connection or semiconductor mounting.
  • the adhesive composition using the modified urethane resin of the present invention is also excellent in low temperature fast curing.
  • Fig. 1 is a cross-sectional view showing an embodiment of a film adhesive using the adhesive composition according to the present invention.
  • FIG. 2 is a cross-sectional view showing an embodiment of a circuit member connection structure according to the present invention.
  • the modified polyurethane resin of the present invention is a polymer compound containing a molecular chain represented by the above general formula (I).
  • X is a divalent organic group having an aromatic ring or an aliphatic ring
  • Y Is a divalent organic group having a molecular weight of 100 to 10,000
  • Z is a 4-r valent organic group having 4 or more carbon atoms (that is, a 4 r valent organic group containing 4 or more carbons)
  • R is a reaction R is an integer of 0 to 2
  • n and m are 1 to: an integer of LOO.
  • the divalent organic group containing an aromatic ring or an aliphatic ring represented by X in the general formula (I) preferably has an aromatic ring or an aliphatic ring.
  • Suitable X is, for example, the following chemical formula:
  • diisocyanate residues derived from diisocyanates used in the synthesis of modified polyurethane resins are generally diisocyanate residues derived from diisocyanates used in the synthesis of modified polyurethane resins.
  • a plurality of X in formula (I) may be the same or different.
  • the modified polyurethane resin may be obtained using one or a combination of two or more diisocyanates as a raw material.
  • Y in the general formula (I) has a molecular weight of 100 to 10,000, preferably 500 to 5,000.
  • the adhesive strength of the adhesive composition containing the modified polyurethane resin is not always sufficient.
  • the molecular weight of Y is less than 100, the modulus of elasticity increases and stress increases, so the solubility tends to decrease, and if it exceeds 10,000, the cohesive force and film strength decrease, There is a tendency to cause a decrease in adhesive strength due to cohesive failure.
  • the divalent organic group having a molecular weight of 100 to 10,000 represented by Y in the general formula (I) is preferably a polyalkylene glycol group.
  • Examples of the polyalkylene glycol group include the following formula:
  • R 4 represents an organic group having 1 to 10 carbon atoms.
  • Y is generally a diol residue derived from a diol used for the synthesis of modified polyurethane resin.
  • a plurality of Y in formula (I) may be the same or different.
  • the modified polyurethane resin may be obtained using a diol that is a combination of one or more types as a raw material.
  • the average molecular weight of the diol is preferably 100 to 10,000, more preferably 500 to 5,000.
  • the Z (R) — moiety in the general formula (I) is a divalent group (a) represented by the above general formula ( ⁇ ) and a divalent group represented by the following general formula ( ⁇ ). Or a divalent group (c) represented by the following general formula (IV).
  • A is a tetravalent organic group having 4 or more carbon atoms (that is, a tetravalent organic group containing 4 or more carbon atoms), and R is a reactive group.
  • the proportion of (a) is 10 to 90 mol%
  • the proportion of (b) is 0 to 90 mol%
  • Examples of the tetravalent organic group having 4 or more carbon atoms represented by A in the general formulas ( ⁇ ), (III), and (IV) include, for example, the following chemical formula: [0036] [Chemical 4]
  • A is a tetracarboxylic anhydride residue derived from a tetracarboxylic anhydride generally used for the synthesis of modified polyurethane resin.
  • a plurality of A in formula (I) may be the same or different. In other words, these may be obtained using one or more types of tetracarboxylic anhydrides as raw materials.
  • R in the general formulas (I), (III) and (IV) is a reactive group.
  • the group having reactivity is a group having a functional group that can react with a curing agent or the like to form a crosslinked structure.
  • this functional group include a radically polymerizable unsaturated group, an epoxy group, and a cyanate ester group.
  • a radically polymerizable unsaturated group is preferable.
  • R is one or more (meta) keys
  • a group having a tallylate group is preferable.
  • R is represented by, for example, the following general formula (V).
  • the (meth) acrylate group means a meta acrylate group or an acrylate group.
  • R 1 represents a divalent organic group having 1 to 50 carbon atoms
  • R 2 represents a hydrogen atom or a methyl group.
  • n and m must be integers of 1 to 100, and more preferably 1 to 50.
  • n or m exceeds 100, the adhesive strength of the adhesive composition containing the modified polyurethane resin is not necessarily sufficient.
  • n or m exceeds 100, the molecular weight becomes too large, so that the viscosity increases and the solubility and fluidity tend to decrease.
  • the modified polyurethane resin is obtained, for example, by polycondensation of the following (A) and (B).
  • the mixture of (A) is obtained by reacting, for example, tetracarboxylic dianhydride and (meth) acrylate having a predetermined amount of hydroxyl group in a solvent at 70 ° C to 100 ° C for 1 hour to 10 hours. Can be obtained.
  • a tertiary amine or the like can be used as a catalyst in some cases.
  • a polymerization inhibitor such as phenols may be used for the purpose of suppressing polymerization of (meth) acrylate.
  • the isocyanate-terminated urethane oligomer of (B) can be obtained, for example, by reacting an excess of diisocyanate and diol at 70 ° C to 160 ° C for 1 hour to 10 hours in a solvent. In this reaction, a catalyst used for general urethane synthesis may be used in some cases.
  • the composition ratio of diisocyanate and diol constituting the urethane oligomer is preferably 0.1 to 1. Omol of the diol component with respect to 1. Omol of diisocyanate.
  • the composition ratio of the polyurethane oligomer constituting the modified polyurethane resin and the structure represented by Z (R) — in the general formula (I) is 0.1-2 Omol to 1. Omol polyurethane oligomer. preferable.
  • a modified polyurethane resin solution can be obtained by mixing (A) and (B) and reacting at 70 ° C to 100 ° C for 1 to 10 hours, optionally using a catalyst.
  • the terminal of the modified polyurethane resin can be modified by adding further monohydric alcohol, oxime, amine, isocyanate, acid anhydride or the like to the solution and continuing the reaction.
  • the solvent used in the polycondensation reaction between (A) and (B) may be the same as or different from the solvent used in the synthesis of (A) or (B), but the solvent in which the modified polyurethane resin is dissolved. It is preferable to use a high molecular weight modified polyurethane resin.
  • the modified polyurethane resin can be taken out by a reprecipitation method with water or the like, if necessary.
  • modified polyurethane resin of the present invention is used, for example, as an adhesive for circuit connection or the like, in which a semiconductor element is mounted in a display system such as a semiconductor or a liquid crystal display. Can do.
  • the modified polyurethane resin of the present invention is adhesive even when used alone as an adhesive. However, it is preferably used in the state of an adhesive composition in which a curable resin (three-dimensional crosslinkable resin) and its curing agent are combined. This provides higher connection reliability.
  • the curable resin may be a resin that forms a three-dimensional crosslinked structure by curing! ⁇ .
  • the curable resin include epoxy resin, cyanate ester resin, imide-based resin, and atallate, metatalylate and maleimide resin which are resin (radically polymerizable substance) cured by radical polymerization. Compound etc. are mentioned.
  • curable resin are usually used together with the curing agent.
  • hardeners such as known imidazole, hydrazide, boron trifluoride-amine complex, sulfo-um salt, aminimide, polyamine salt, dicyandiamide and the like are used as hardeners. Or a mixture thereof is used.
  • epoxy resin various epoxy compounds having two or more glycidyl groups in one molecule are used.
  • epoxy resins include bisphenol A, F, S, and AD isotropic bisphenol type epoxy resins, phenol novolac and talesol novolac force induced epoxy novolac type resins, and naphthalene skeletons.
  • naphthalene type epoxy resin glycidylamine type epoxy resin, glycidyl ether type epoxy resin, biphenyl type epoxy resin, and alicyclic epoxy resin other than the above. These may be used alone or in combination.
  • Epoxy resin generally contains impurity ions such as alkali metal ions, alkaline earth metal ions, and halogen ions.
  • impurity ions such as alkali metal ions, alkaline earth metal ions, and halogen ions.
  • concentration of these impurities especially chlorine ions or hydrolyzable chlorine
  • cyanate ester resin examples include bis (4-cyanatophenol) ethane, 2,2bis (4—cyanatophenol) propane, 2,2bis (3,5 dimethyl-4-cyanatophenol) methane, 2, 2 Bis (4 cyanatophenol) —1, 1, 1, 3, 3, 3 Hexafluoropronone ⁇ a, a '-bis (4-cyanatophenol) m Diisopropylbenzene, phenol ⁇ Cyanate esterification products of dicyclopentagen polymers and their prepolymers One is mentioned. These may be used alone or in combination. Of these, 2,2-bis (4-cyanatophenyl) propane and 2,2-bis (3,5-dimethyl-4-cyanatophenyl) are preferred because the dielectric properties of the cured product are particularly good. .
  • metal-based reaction catalysts for example, metal catalysts such as manganese, iron, cobalt, nickel, copper, and zinc are used.
  • metal catalysts such as manganese, iron, cobalt, nickel, copper, and zinc are used.
  • organometallic complexes such as 2-ethylhexanoate and naphthenate and organometallic complexes such as acetylacetone complex are used as curing agents.
  • the compounding amount of the metal-based reaction catalyst is preferably 1 to 3000 ppm with respect to the cyanate ester resin. 1 to: More preferably LOOOppm and 2 to 300 ppm. More preferred ⁇ . If the compounding amount of the metal-based reaction catalyst is less than 1 ppm, the reactivity and curability tend to be insufficient, and if it exceeds 3000 ppm, the reaction tends to be difficult to control or the curing tends to be too fast.
  • the resin cured by radical polymerization is composed of a compound having a functional group that is polymerized by radical reaction (radical polymerizable compound).
  • radical polymerizable compound examples include (meth) acrylate resin, maleimide resin, citraconimide resin, nadiimide resin, and a mixture of two or more of these.
  • the radical polymerizable compound can be used in either a monomer or oligomer state, and a monomer and an oligomer may be mixed and used.
  • (Meth) acrylic resin is a resin containing one or two or more (meth) atalytoy compound as a monomer, and forms a crosslinked structure by radical polymerization.
  • Examples of (meth) atalytoy compounds include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, ethene glycol di (meth) acrylate, Diethylene glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, tetramethylene glycol tetra (meth) acrylate, 2-hydroxy-1,3-diacryloxypropane, 2, 2-bis (4- ( Atyloxymethoxy) phenol) propane, 2,2-bis (4- (ataryloxyethoxy) phenol) propane, dicyclopentayl (meth) acrylate, cyclodehydryl (meth) acryl
  • the amount of the radically polymerizable compound having a phosphate ester structure is preferably 0.1 to: LO parts by weight, more preferably 0.5 to 5 parts per 100 parts by weight of the adhesive composition. Parts by weight.
  • a radically polymerizable compound having a phosphate ester structure is obtained, for example, as a reaction product of phosphoric anhydride and 2-hydroxyethyl (meth) acrylate. Specific examples include mono (2-methacryloyloxychetyl) acid phosphate and di (2-methacryloyloxychetyl) acid phosphate. These can be used alone or in combination of two or more.
  • Maleimide resin is a curable resin that also has a compound power having at least one maleimide group in the molecule.
  • the citraconimide resin is a curable resin that also has a citraconimide compound strength having at least one citraconimide group in the molecule.
  • the citraconic imide compound include: ferulcitraconimide, 1-methyl 2,4 biscitraconimide benzene, N, N, -m phenylene biscitraconimide, N, N, 1 p phenylene biscitraconimide , N, N , 1,4-Biphenylene biscitraconimide, N, N, 1,4— (3,3-dimethylbiphenylene) biscitraconimide, N, N, 1,4,4— (3,3-dimethyldiphenol -Lumethane) biscitraconimide, N, N, 1,4,4- (3,3-jetyldiphenylmethane) biscitraconeimide, N, N, 1,4-4-diphenylmethane biscitraconimide, N
  • Nadiimide resin is a curable resin made of a nadiimide compound having at least one nadiimide group in the molecule.
  • nadiimide compounds include phenyl nadiimide, 1-methyl 2,4 bis nadiimide benzene, N, ⁇ '-m-phenol bis nadiimide, N, N, 1-p phenylene bis nadiimide, N, N, 1, 4, 4-biphenylene bisnadiimide, N, N, —4, 4— (3, 3-dimethylbiphenylene) bisnadiimide, N, N, —4, 4— (3, 3 — dimethyldiphenylmethane ) Bisnadiimide, N, N, 1,4,4— (3,3—Jetyldiphenol Ninolemethane) bisnadiimide, N, N, 1,4,4-Diphenolinenomethane bis
  • a polymerization initiator is used as a curing agent.
  • the polymerization initiator is not particularly limited as long as it is a compound that generates free radicals by heat or light. Examples of the polymerization initiator include peroxides and azo compounds.
  • the polymerization initiator is appropriately selected in consideration of the intended connection temperature, connection time, storage stability, etc. From the viewpoint of high reactivity and storage stability, the temperature of the half-life of 10 hours is 40 ° C or higher.
  • Half-life 10-hour temperature is 50 ° C or more and half-life 1-minute temperature is 170 ° C or less Acid acids are particularly preferred.
  • connection time 10 seconds
  • the blending amount of the hardener is preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight. .
  • organic peroxide used in the present invention include disilver oxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, and hyde-peroxide.
  • oxides and silyl peroxides These can be used by mixing two or more kinds as appropriate.
  • the concentration of chlorine ions and organic acids contained is 5000 ppm or less, and there are few organic acids generated after thermal decomposition! /, Therefore, peroxyesters, dialkyl peroxides, hydride peroxides and silyl peroxides. Is particularly preferred. Corrosion of the connection terminals of circuit members can be suppressed by reducing the amount of chlorine ions and organic acids.
  • disilver oxide examples include isobutyl peroxide, 2,4-dichlorobenzoic peroxide, 3, 5, 5-trimethylhexanoyl peroxide, otatanyl peroxide, lauroyl peroxide, stearoyl peroxide Succinic peroxide, benzoylperoxytoluene, benzoyl peroxide and the like.
  • Peroxydicarbonates include di-n-propinolever oxydicarbonate, diisopropyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, and di-2-ethoxymethoxy bar. Examples include oxydicarbonate, di (2-ethylhexyloxy) dicarbonate, dimethoxybutylbadium oxydicarbonate, di (3-methyl-3-methoxybutylbaxyxy) dicarbonate, and the like.
  • Peroxyesters include Tamil peroxyneodecanoate, 1, 1, 3, 3— Tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl 1-methylethylperoxynoedecanoate, tert-hexyloxyneodecanoate, tert-peroxybivalate, 1, 1, 3 , 3-Tetramethylbutylperoxy-2-ethylhexanate, 2,5-dimethyl-2,5-di (2-ethylhexylperoxy) hexane, 1-cyclohexyl, 1-methinoleethinolevoxy-2-ethylenole Hexanone, t-hexyloxy 2-ethyl hexanoate, t-butyl peroxy 2-ethyl hexanoate, t-butyl peroxyisobutyrate, 1, 1 bis (t-tylba monoyl) cyclohex
  • Peroxyketals include 1,1-bis (t-hexyloxy) -1,3,5 trimethylcyclohexane, 1,1-bis (thexyloxy) cyclohexane, 1, 1- Bis (t-butylperoxy) -3,3,5 trimethylcyclohexane, 1,1- (tert-butyloxy) cyclododecane, 2,2-bis (t-butylperoxy) decane and the like.
  • dialkyl peroxide examples include a, ⁇ , monobis (t-butylperoxy) diisopropyl pyrbenzene, dicumyl peroxide, 2,5 dimethyl-2,5 di (t-butyloxy) hexane, and t-butyltamperper.
  • examples include oxides.
  • Examples of the hydride-peroxide include diisopropylbenzene hydride-peroxide and cumene hydride-peroxide.
  • silyl peroxides include t-butyltrimethylsilyl peroxide, bis (t-butyl) dimethylsilyl peroxide, t-butyltributylsilyl peroxide, bis (tbutyl) dibulylsilyl peroxide, tris ( Examples thereof include t-butyl) butylsilyl peroxide, t-butyltriallylsilyl peroxide, bis (t-butyl) diallylsilyl peroxide, and tris (t-butyl) allylsilyl peroxide.
  • the concentration of chlorine ion or organic acid contained in the curing agent is preferably 5000 ppm or less. Furthermore, a curing agent with less organic acid generated after thermal decomposition is more preferable. In addition, since the stability of the adhesive composition (circuit connecting material) is improved, the curing agent preferably has a weight retention of 20% by weight or more after being left open at room temperature and normal pressure for 24 hours.
  • polymerization initiators can be used alone or in combination. You may mix and use a polymerization initiator, a decomposition accelerator, an inhibitor, etc.
  • Fillers and particles can be added to the adhesive composition for the purpose of improving fluidity, physical properties, or adding functions of conductivity, anisotropic conductivity, and thermal conductivity.
  • These fillers and particles include silica, antimony trioxide, gold, silver, copper, nickel, aluminum, stainless steel, carbon, and ceramic.
  • the above metal, non-conductive glass, ceramic, plastic or the like may be used as a core, and the core may be coated with the metal or carbon.
  • the amount of filler or particles used is not particularly limited, but is preferably 0.1 to 50% by volume with respect to 100% by volume of the total amount of the adhesive composition containing the modified polyurethane resin.
  • the adhesive composition particularly preferably contains conductive particles as a filler.
  • Preferred conductive particles include particles made of transition metals such as Ni, non-conductive glass, ceramics, plastics, etc., and the surface is covered with a coating layer made of a noble metal such as Au. There is what I did.
  • Such an adhesive composition using conductive particles having a precious metal coating layer when used as a circuit connection material, is deformed by heating and pressurization, thereby increasing the contact area with the circuit electrode. The connection reliability is particularly high.
  • the conductive particles include metal particles such as Au, Ag, Ni, Cu, and solder, and carbon particles.
  • the conductive particles preferably contain Au, Ag, or a platinum group metal, and more preferably contain Au.
  • the adhesive composition may contain various polymers for the purpose of improving the adhesive strength and the physical properties of the adhesive.
  • the polymer used is not particularly limited. Such polymers include bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol A ⁇ bisphenol F copolymer type phenoxy resin, polymethacrylates, polyacrylates, etc.
  • Rates polyimides, polyurethanes, polyesters, polybutyl petital, SBS and its epoxy modified products, SEBS and its modified products, and the like can be used. These can be used alone or in admixture of two or more. In addition, these polymers may contain siloxane bonds and fluorine substituents. These can be suitably used in the adhesive composition as long as they are completely compatible with each other or mixed with microphase separation and become cloudy.
  • the molecular weight of the polymer is not particularly limited, but in general, the average molecular weight is preferably 5000 to 150,000, more preferably 10,000 to 80,000.
  • the amount used is preferably 20 to 320 parts by weight per 100 parts by weight of the adhesive composition containing the modified polyurethane resin. When the amount used is less than 20 parts by weight or more than 320 parts by weight, fluidity and adhesiveness tend to be lowered.
  • a softening agent, an accelerator, an anti-aging agent, a coloring agent, a flame retardant, and a cutting agent may be appropriately added to the adhesive composition.
  • the adhesive composition can be used in a paste state when it is liquid at room temperature. In the case of a solid at room temperature, it may be used in a liquid form by heating, or may be pasted using a solvent. Solvents that can be used are not particularly limited as long as they are not reactive with the adhesive composition and additives and exhibit sufficient solubility, but have a boiling point of 50 to 150 ° C at normal pressure. Those are preferred. If the boiling point is 50 ° C or less, there is a risk of volatilization if left at room temperature, limiting the use in open systems. If the boiling point is 150 ° C or higher, it may be difficult to evaporate the solvent, which may adversely affect the reliability after bonding.
  • the adhesive composition can be formed into a film and used as a film adhesive.
  • FIG. 1 shows an embodiment of a film adhesive using the adhesive composition according to the present invention. It is sectional drawing.
  • the conductive particles 5 are dispersed in the resin layer 3 made of other components in the adhesive composition.
  • the film-like adhesive 1 is, for example, a solution obtained by adding a solvent or the like to the adhesive composition as necessary on a peelable substrate such as a fluorine resin film, a polyethylene terephthalate film, or a release paper. There is! Is obtained by impregnating a base material such as a non-woven fabric with a solution and placing it on a peelable base material and removing the solvent. Use of the adhesive composition in the form of a film is more convenient from the viewpoint of handleability.
  • the adhesive composition can be suitably used as an adhesive for bonding different types of adherends having different thermal expansion coefficients.
  • Specific examples include circuit connection materials used for bonding and electrically connecting circuit members having circuit electrodes, CSP elastomers, CSP underfill materials, LOC tapes, and die bond adhesives. It can be used as a semiconductor element adhesive.
  • Circuit connection materials typified by silver paste, silver film and anisotropic conductive adhesive connect, for example, chip components such as semiconductor chips, resistor chips, capacitor chips, and circuit members such as printed boards. Used for.
  • FIG. 2 is a cross-sectional view showing an embodiment of a circuit member connection structure according to the present invention.
  • a circuit member connection structure 101 shown in FIG. 2 includes a first circuit member 10 having a first substrate 11 and a first circuit electrode 13 formed on the main surface thereof via an adhesive layer 12; And a second circuit member 20 having a second circuit electrode 23 and a second circuit electrode 23 formed on the main surface thereof. Then, the first circuit member 10 and the second circuit member 20 are bonded with the film adhesive 1 so that the first circuit electrode 13 and the second circuit electrode 23 are electrically connected.
  • the circuit connecting member la which is a cured product formed by curing the film adhesive 1, is formed so as to fill the space between the opposing surfaces of the first circuit member 10 and the second circuit member 20.
  • the first circuit electrode 13 and the second circuit electrode 23 face each other and are electrically connected.
  • the circuit connecting member la is composed of an insulating layer 3a derived from the resin layer 3 and conductive particles 5 dispersed therein.
  • the first circuit electrode 13 and the second circuit electrode 23 It is electrically connected through!
  • the first substrate 11 is a resin film containing at least one resin selected from the group consisting of polyester terephthalate, polyethersulfone, epoxy resin, acrylic resin, and polyimide resin.
  • the circuit electrode 13 is formed of a material having conductivity sufficient to function as an electrode (preferably at least one selected from the group consisting of gold, silver, tin, platinum group metals, and indium tin oxide). ing. A plurality of circuit electrodes 13 are bonded onto the main surface of the first substrate 11 via the adhesive layer 12.
  • the adhesive layer 12 is formed of a commonly used adhesive or the like for circuit members such as flexible wiring boards.
  • the second substrate 21 is a glass substrate, and a plurality of second circuit electrodes 23 are formed on the main surface of the second substrate 21.
  • the circuit member connection structure 101 includes, for example, the first circuit member 10, the film-like adhesive 1 and the second circuit member 20, and the first circuit electrode 13 and the second circuit member 20.
  • the first and second circuit electrodes 13 and 23 are electrically connected to each other by heating and pressurizing the laminate laminated in this order so that the circuit electrode 23 and the circuit electrode 23 are opposed to each other.
  • the circuit member 10 and the second circuit member 20 are bonded to each other.
  • the circuit-connecting material 1 is temporarily bonded by heating and pressurizing the film-like adhesive 1 formed on the support film on the second circuit member 20. After the support film is peeled off, the first circuit member 10 can be placed while aligning the circuit electrodes to prepare a laminate.
  • the circuit member connection structure according to the present invention is not limited to the above embodiment.
  • the first circuit electrode 13 may be directly formed on the main surface of the first substrate without an adhesive layer interposed therebetween.
  • Oxydiphthalic dianhydride (1. Omol), 2 hydroxyethyl methacrylate (0.2 mol), triethylamine (0. Olmol) and hydroquinone (0. Olmol) in ⁇ -butyrolatatone at 80 ° The mixture was stirred at C for 5 hours to obtain a mixed solution of oxydiphthalic dianhydride in which 2 hydroxyxetyl metatalylate was added to a part of oxydiphthalic dianhydride.
  • diphenylmethane 1,4,4,1 diisocyanate (1. Omol) diphenylmethane 1,2,4, -diisocyanate (1. Omol) and polytetramethylene glycol having an average molecular weight of 2000 (0.8 mol) was reacted in 1-methyl-2-pyrrolidone under nitrogen atmosphere at 100 ° C for 2 hours, and the above oxydiphthalic dianhydride mixture was added thereto, and further at 80 ° C for 5 hours. Reacted. Further, benzyl alcohol was added and stirred at 80 ° C. for 2 hours to complete the reaction. The solution after the reaction was placed in vigorously stirred water.
  • a modified polyurethane resin PU-2 containing a molecular chain in which the part of Z (R) — is a divalent group represented by the following chemical formula (IIa), (Ilia) or (IVa) was obtained.
  • PU-1 is dissolved in methyl ethyl ketone at a solid concentration of 40% by mass, and 1, 1-bis (t-hexyloxy) -1,3,5-trimethylcyclohexane (perhexane T MH) is used as a curing agent.
  • perhexane T MH 1, 1-bis (t-hexyloxy) -1,3,5-trimethylcyclohexane
  • T MH 1, 1-bis (t-hexyloxy) -1,3,5-trimethylcyclohexane
  • the conductive element has an average particle size of 5 m and a specific gravity of 2 m, with a 0.2 m thick nickel layer on the surface of polystyrene core particles and a 0.02 m thick gold layer outside the nickel layer. I used 5 items.
  • the conductive particle-dispersed solution is applied to an 80-m thick fluororesin film using a coating device, and dried with hot air at 70 ° C for 10 minutes.
  • the adhesive layer has a thickness of 20 m. A directionally conductive adhesive (film adhesive) was obtained.
  • a thin layer of ITO (ITO) is formed as an electrode, and the circuit member is heated and pressed using a thermocompression bonding device (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.) over a width of 2 mm.
  • the connection body which is the connection structure of a circuit member was produced.
  • the FPC used was formed by depositing 500 copper circuits with a line width of 50 ⁇ m, a pitch of 100 ⁇ m, and a thickness of 10 ⁇ m on a polyimide film with a thickness of 40 ⁇ m. Heating and pressurization were performed at 170 ° C and 3 MPa for 20 seconds.
  • a film-like adhesive was prepared in the same manner as in Example 1 except that PU-2 was used instead of PU-1, and a connection body was prepared in the same manner as in Example 1 using this film. It was measured.
  • the adhesive strength of the connector was measured in the same manner as in Example 1 except that urethane acrylate (UA-511, manufactured by Shin-Nakamura Engineering Co., Ltd.) was used instead of PU-1.
  • urethane acrylate U-511, manufactured by Shin-Nakamura Engineering Co., Ltd.

Abstract

A modified polyurethane resin comprising a molecular chain represented by the following general formula (I) and an adhesive composition comprising the same. [Chemical Formula 1] (I) (In the formula, X represents a divalent organic group containing an aromatic ring or an aliphatic ring; Y represents a divalent organic group with a molecular weight between 100 and 10000; Z represents a (4-r)-valent organic group having 4 or more carbon atoms; R represents a reactive group; r represents an integer of 0 to 2; and n and m each independently represents an integer of 1 to 100. A plurality of X, Y, Z, and R in the same molecule may be the same or different, respectively. However, at least one R is present in the molecular chain.)

Description

明 細 書  Specification
変性ポリウレタン樹脂及びこれを用いた接着剤組成物、並びに回路部材 の接続方法及び回路部材の接続構造  Modified polyurethane resin, adhesive composition using the same, circuit member connection method, and circuit member connection structure
技術分野  Technical field
[0001] 本発明は変性ポリウレタン榭脂、この変性ポリウレタン榭脂を用いた接着剤組成物 [0001] The present invention relates to a modified polyurethane resin, and an adhesive composition using the modified polyurethane resin
、並びに回路部材の接続方法及び回路部材の接続構造に関する。 And a circuit member connection method and a circuit member connection structure.
背景技術  Background art
[0002] 現在、半導体分野ではエポキシ榭脂などの有機材料が多く使われて 、る。封止材 の分野では、封止システムの 90%以上が榭脂封止システムに置き換わっている。封 止材はエポキシ榭脂、硬化剤、各種添加剤、無機充填剤などによって構成される複 合材料であり、エポキシ榭脂としてはクレゾ一ルノボラック型エポキシ榭脂が多く使用 されている。しかし、クレゾ一ルノボラック型エポキシ榭脂は低吸水率、低弾性率とい つた特性において要求特性を満足していないため、表面実装方式への対応が困難 である。そのため、これに代わる新規高性能エポキシ榭脂が多く提案され実用化に 至っている。  [0002] Currently, many organic materials such as epoxy resin are used in the semiconductor field. In the field of encapsulants, over 90% of encapsulating systems have been replaced with resin encapsulating systems. The sealing material is a composite material composed of an epoxy resin, a curing agent, various additives, an inorganic filler, etc., and a cresol novolac type epoxy resin is often used as the epoxy resin. However, cresol novolac-type epoxy resin does not satisfy the required characteristics in terms of low water absorption and low elastic modulus, making it difficult to support surface mounting. For this reason, many new high-performance epoxy resins have been proposed and put to practical use.
[0003] また、ダイボンディング用導電性接着剤として、エポキシ榭脂に銀粉を混練した銀 ペーストが多く使用されている。しかし、半導体素子の配線基板への装着方法が表 面実装法に移行するに従い、銀ペーストよりも更に耐はんだリフロー性を向上したダ ィボンディング用導電性接着剤が求められている。この要求に対応するために、硬化 後のダイボンディング用接着剤層のボイド、ピール強度、吸水率、弾性率等の改善が なされている。  [0003] As a conductive adhesive for die bonding, a silver paste in which silver powder is kneaded with epoxy resin is often used. However, as the method for mounting a semiconductor element on a wiring board shifts to a surface mounting method, there is a need for a conductive adhesive for die bonding that has improved solder reflow resistance over silver paste. In order to meet this requirement, improvements have been made to the void, peel strength, water absorption, elastic modulus, etc. of the adhesive layer for die bonding after curing.
[0004] 半導体実装分野では、低コスト化及び高精細化に対応した新し 、実装形態として I Cチップを直接プリント基板やフレキシブル配線板に搭載するフリップチップ実装が 注目されている。フリップチップ実装方式としては、 ICチップの端子にはんだバンプ を設けてはんだ接続を行う方式や、導電性接着剤を介して電気的接続を行う方式が 知られている。これらの方式では、半導体装置が各種環境に曝されたときに、 ICチッ プと基板の熱膨張係数差に基づくストレスが接続界面で発生して接続信頼性が低下 するという問題がある。このため、接続界面のストレスを緩和する目的でエポキシ榭脂 系のアンダフィル材をチップ z基板の間隙に注入する方式が検討されて 、る。しかし 、このアンダフィル注入の方式は、プロセスを煩雑化し、生産性、コストの面で不利に なるという問題がある。このような問題を解決すべく最近では異方導電性と封止機能 を有する異方導電性接着剤を用いたフリップチップ実装が、プロセス簡易性と 、う観 点から注目されている。 [0004] In the field of semiconductor mounting, flip chip mounting, in which an IC chip is directly mounted on a printed circuit board or a flexible wiring board, has been attracting attention as a new mounting method corresponding to low cost and high definition. As a flip chip mounting method, a method for solder connection by providing solder bumps on the terminals of an IC chip and a method for electrical connection through a conductive adhesive are known. In these methods, when the semiconductor device is exposed to various environments, stress based on the difference in thermal expansion coefficient between the IC chip and the substrate is generated at the connection interface, resulting in a decrease in connection reliability. There is a problem of doing. For this reason, a method of injecting an epoxy resin-based underfill material into the gap between the chip z substrate for the purpose of alleviating the stress at the connection interface is being studied. However, this underfill injection method has a problem that it complicates the process and is disadvantageous in terms of productivity and cost. In order to solve such problems, flip chip mounting using an anisotropic conductive adhesive having anisotropic conductivity and sealing function has recently attracted attention from the viewpoint of process simplicity.
[0005] 一方、近年、半導体や液晶ディスプレイなどの分野では、電子部品を固定したり、 回路接続を行うために各種の接着剤が使用されている。特に、液晶ディスプレイと τ [0005] On the other hand, in recent years, various adhesives are used in the fields of semiconductors, liquid crystal displays, and the like to fix electronic components and make circuit connections. In particular, LCDs and τ
CPとの接続、 FPCと TCPとの接続、又は FPCとプリント配線板との接続に用いる回 路接続用の接着剤（回路接続材料)としては、接着剤中に導電粒子を分散させた異 方導電性接着剤が使用されている。これらの用途では、ますます高密度化、高精細 化がすすみ、接着剤が高い接着力や信頼性を有することが求められている。 As an adhesive (circuit connection material) for circuit connection used for connection with CP, connection between FPC and TCP, or connection between FPC and printed wiring board, an anisotropic material in which conductive particles are dispersed in the adhesive A conductive adhesive is used. In these applications, higher density and higher definition are required and adhesives are required to have high adhesive strength and reliability.
[0006] また、これら精密電子機器の分野では、回路の高密度化が進んでおり、電極幅及 び電極間隔が極めて狭くなつている。そのため、従来のエポキシ榭脂系を用いた回 路接続用接着剤の接続条件では、配線の脱落、はく離、位置ずれが生じるなどの問 題点がある。更に、生産性効率向上のために接続時間を 10秒以下とする短縮化が 強く求められてきており、接着剤は低温速硬化性を有することが必要不可欠となって いる。 [0006] Further, in the field of these precision electronic devices, the density of circuits has been increased, and the electrode width and the electrode interval have become extremely narrow. For this reason, the connection conditions of circuit adhesives using conventional epoxy resin systems have problems such as wiring dropping, peeling, and misalignment. Furthermore, in order to improve productivity efficiency, there is a strong demand for shortening the connection time to 10 seconds or less, and it is indispensable that the adhesive has a low temperature fast curing property.
[0007] さらに、最近では、半導体シリコンチップを基板に実装する場合でも、従来のワイヤ 一ボンドではなぐ半導体シリコンチップをフェイスダウンで基板に実装する 、わゆる フリップチップ実装が行われており、ここでも異方導電性接着剤の適用が開始されて いる。このフリップチップ実装に用いる接着剤として、例えば、ポリウレタン系接着剤が 知られている（特許文献 1)。  Furthermore, recently, even when a semiconductor silicon chip is mounted on a substrate, a so-called flip chip mounting is performed in which a semiconductor silicon chip that is not a conventional wire-one bond is mounted face-down on a substrate. However, the application of anisotropic conductive adhesive has started. As an adhesive used for this flip chip mounting, for example, a polyurethane adhesive is known (Patent Document 1).
特許文献 1：特許第 3279708号  Patent Document 1: Japanese Patent No. 3279708
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0008] し力しながら、従来のポリウレタン系接着剤では部分的な硬化反応しか起こらず、特 に線膨張係数の異なる材料を接着する場合に接着力が全般的に劣るいう問題があ つた。 [0008] However, the conventional polyurethane-based adhesives have only a partial curing reaction, and there is a problem that the adhesive force is generally inferior when bonding materials having different linear expansion coefficients. I got it.
[0009] そこで、本発明は、接着剤に用いられたときに線膨張係数の異なる材料間でも十分 に強い接着力が得られる変性ポリウレタン榭脂を提供することを目的とする。  [0009] Accordingly, an object of the present invention is to provide a modified polyurethane resin that can provide a sufficiently strong adhesive force even between materials having different linear expansion coefficients when used in an adhesive.
課題を解決するための手段  Means for solving the problem
[0010] 本発明は、下記一般式 (I)で表される分子鎖を含む変性ポリウレタン榭脂である。  The present invention is a modified polyurethane resin containing a molecular chain represented by the following general formula (I).
[0011] [化 1] [0011] [Chemical 1]
Figure imgf000005_0001
Figure imgf000005_0001
[0012] 式中、 Xは芳香族環又は脂肪族環を有する 2価の有機基、 Yは分子量 100〜： LOO 00の 2価の有機基、 Zは炭素数 4以上の 4 r価（すなわち、 2〜4価）の有機基、 Rは 反応性を有する基、 rは 0〜2の整数、 n及び mはそれぞれ独立に 1〜： LOOの整数、を 示し、同一分子中の複数の X、 Y、 Ζ及び Rはそれぞれ同一でも異なっていてもよい。 ただし、分子鎖中には少なくとも 1個の Rが存在する。  [0012] In the formula, X is a divalent organic group having an aromatic ring or an aliphatic ring, Y is a divalent organic group having a molecular weight of 100 to: LOO 00, and Z is a 4 r valence having 4 or more carbon atoms (ie, , Divalent to tetravalent) organic group, R is a reactive group, r is an integer of 0 to 2, n and m are each independently 1 to: an integer of LOO, and a plurality of X in the same molecule , Y, Ζ and R may be the same or different. However, at least one R exists in the molecular chain.
[0013] 本発明の変性ポリウレタン榭脂は、上記特定構造の分子鎖を含んでいることにより 、接着剤に用いられたときに線膨張係数の異なる材料間でも十分に強い接着力を発 現するものとなった。  [0013] The modified polyurethane resin of the present invention includes a molecular chain having the specific structure described above, and thus exhibits sufficiently strong adhesive force even between materials having different linear expansion coefficients when used in an adhesive. It became a thing.
[0014] 本発明のポリウレタン榭脂は、一般式 (I)中の— Z (R)—で表される部分が、下記 一般式 (Π)で表される 2価の基 (a)、下記一般式 (ΠΙ)で表される 2価の基 (b)又は下 記一般式 (IV)で表される 2価の基 (c)であることが好ましい。これにより、接着剤に用 いられたときの接着力が特に向上する。  [0014] The polyurethane resin of the present invention has a divalent group (a) represented by the following general formula (Π) in which the moiety represented by —Z (R) — in the general formula (I) is represented by the following formula (I): The divalent group (b) represented by the general formula (ΠΙ) or the divalent group (c) represented by the following general formula (IV) is preferable. This particularly improves the adhesive strength when used in an adhesive.
[0015] [化 2]
Figure imgf000006_0001
[0015] [Chemical 2]
Figure imgf000006_0001
V 式 (Π)、（ΠΙ)及び (IV)中、 Aは 4個以上の炭素を含む 4価の有機基、 Rは反応性を 有する基、を示す。  V In formulas (Π), (ΠΙ) and (IV), A represents a tetravalent organic group containing 4 or more carbon atoms, and R represents a reactive group.
[0016] この場合、上記 (a)、（b)及び (c)の合計量を基準として、（a)の割合が 10〜90mol %、（b)の割合が O〜90mol%、（c)の割合が O〜90mol%であることが好ましい。こ れにより、接着剤に用いられたときの接着力が更により一層向上する。  [0016] In this case, based on the total amount of (a), (b) and (c) above, the proportion of (a) is 10 to 90 mol%, the proportion of (b) is O to 90 mol%, (c) Is preferably O to 90 mol%. Thereby, the adhesive force when used for the adhesive is further improved.
[0017] Rは (メタ)アタリレート基を有する基であることが好ましい。これにより、接着剤組成 物を低温、短時間で硬化することが可能となる。  [0017] R is preferably a group having a (meth) acrylate group. As a result, the adhesive composition can be cured at a low temperature in a short time.
[0018] 本発明の接着剤組成物は、上記本発明の変性ポリウレタン榭脂を含有する。この 接着剤組成物は、線膨張係数の異なる材料間でも十分に大きな接着力を発現する。  [0018] The adhesive composition of the present invention contains the modified polyurethane resin of the present invention. This adhesive composition exhibits a sufficiently large adhesive force even between materials having different linear expansion coefficients.
[0019] 本発明の接着剤組成物は、硬化性榭脂を更に含有することが好ましい。これにより 接着信頼性を向上できる。  [0019] The adhesive composition of the present invention preferably further contains a curable resin. This can improve adhesion reliability.
[0020] 上記硬化性榭脂がラジカル反応により硬化する榭脂であり、接着剤組成物が光照 射又は加熱により遊離ラジカルを発生する硬化剤を含有して ヽることが好ま ヽ。こ れにより、より低温短時間で接続可能となり、接着力も更に向上する。  [0020] Preferably, the curable resin is a resin that cures by a radical reaction, and the adhesive composition contains a curing agent that generates free radicals by light irradiation or heating. This makes it possible to connect at a lower temperature and in a shorter time, and the adhesive strength is further improved.
[0021] 本発明の接着剤組成物は、導電粒子を更に含有することが好ましい。これにより、 回路接続材料として用いられたときの電気的な接続信頼性がより優れるものとなる。  [0021] The adhesive composition of the present invention preferably further contains conductive particles. As a result, the electrical connection reliability when used as a circuit connection material is further improved.
[0022] 本発明の回路部材の接続方法は、第一の基板及びこれの主面上に形成された第 一の回路電極を有する第一の回路部材と、第二の基板及びこれの主面上に形成さ れた第二の回路電極を有する第二の回路部材とを上記本発明の接着剤組成物で接 着することにより、第一の回路電極と第二の回路電極とを電気的に接続するものであ る。 [0022] The circuit member connection method of the present invention includes a first circuit member having a first circuit electrode formed on the first substrate and the main surface thereof, a second circuit board, and the main surface thereof. Formed on The first circuit electrode and the second circuit electrode are electrically connected by bonding the second circuit member having the second circuit electrode with the adhesive composition of the present invention. It is.
[0023] この方法によれば、十分に強!、接着力で回路部材が接続された回路部材の接続 構造が得られる。  [0023] According to this method, it is possible to obtain a circuit member connection structure in which the circuit members are sufficiently strong and connected with an adhesive force.
[0024] 本発明の回路部材の接続構造は、第一の基板及びこれの主面上に形成された第 一の回路電極を有する第一の回路部材と、第二の基板及びこれの主面上に形成さ れた第二の回路電極を有する第二の回路部材と、を備え、第一の回路電極と第二の 回路電極とが電気的に接続されるように第一の回路部材と第二の回路部材とが上記 本発明の接着剤組成物で接着されて ヽるものである。  [0024] The circuit member connection structure of the present invention includes a first circuit member having a first circuit electrode and a first circuit electrode formed on the first substrate, a second substrate, and a main surface thereof. A second circuit member having a second circuit electrode formed thereon, and the first circuit member and the second circuit electrode are electrically connected to each other. The second circuit member is bonded with the above-described adhesive composition of the present invention.
[0025] この接続構造においては、回路部材同士が十分に強い接着力で接続されており、 接続信頼性が高い。  In this connection structure, the circuit members are connected with a sufficiently strong adhesive force, and the connection reliability is high.
発明の効果  The invention's effect
[0026] 本発明の変性ウレタン榭脂を用いた接着剤組成物は接着力に優れ回路接続又は 半導体実装用接着剤に好適である。また、本発明の変性ウレタン榭脂を用いた接着 剤組成物は低温速硬化性にも優れる。  [0026] The adhesive composition using the modified urethane resin of the present invention has excellent adhesive strength and is suitable for an adhesive for circuit connection or semiconductor mounting. In addition, the adhesive composition using the modified urethane resin of the present invention is also excellent in low temperature fast curing.
図面の簡単な説明  Brief Description of Drawings
[0027] [図 1]本発明に係る接着剤組成物を用いたフィルム状接着剤の一実施形態を示す断 面図である。  [0027] Fig. 1 is a cross-sectional view showing an embodiment of a film adhesive using the adhesive composition according to the present invention.
[図 2]本発明に係る回路部材の接続構造の一実施形態を示す断面図である。  FIG. 2 is a cross-sectional view showing an embodiment of a circuit member connection structure according to the present invention.
符号の説明  Explanation of symbols
[0028] 1· ··フィルム状接着剤、 la…回路接続部材、 3…榭脂層、 3a…絶縁層、 5…導電粒 子、 10…第一の回路部材、 11…第一の基板、 13…第一の回路電極、 20· ··第二の 回路部材、 21· ··第二の基板、 23…第二の回路電極、 101…回路部材の接続構造。 発明を実施するための最良の形態  [0028] 1 ... Film adhesive, la ... circuit connecting member, 3 ... resin layer, 3a ... insulating layer, 5 ... conductive particles, 10 ... first circuit member, 11 ... first substrate, 13 ... 1st circuit electrode, 20 ... 2nd circuit member, 21 ... 2nd board | substrate, 23 ... 2nd circuit electrode, 101 ... Connection structure of circuit member. BEST MODE FOR CARRYING OUT THE INVENTION
[0029] 本発明の変性ポリウレタン榭脂は、上記一般式 (I)で表される分子鎖を含む高分子 化合物である。一般式 (I)中、 Xは芳香族環又は脂肪族環を有する 2価の有機基、 Y は分子量 100〜10000の 2価の有機基、 Zは炭素数 4以上の 4— r価の有機基（すな わち、 4個以上の炭素を含む 4 r価の有機基）、 Rは反応性を有する基、 rは 0〜2の 整数、 n及び mは 1〜： LOOの整数を示す。 [0029] The modified polyurethane resin of the present invention is a polymer compound containing a molecular chain represented by the above general formula (I). In general formula (I), X is a divalent organic group having an aromatic ring or an aliphatic ring, Y Is a divalent organic group having a molecular weight of 100 to 10,000, Z is a 4-r valent organic group having 4 or more carbon atoms (that is, a 4 r valent organic group containing 4 or more carbons), and R is a reaction R is an integer of 0 to 2, n and m are 1 to: an integer of LOO.
[0030] 一般式 (I)中の Xで表される芳香族環又は脂肪族環を含む 2価の有機基としては、 芳香族環又は脂肪族環を有することが好ましい。好適な Xとしては、例えば、下記化 学式： [0030] The divalent organic group containing an aromatic ring or an aliphatic ring represented by X in the general formula (I) preferably has an aromatic ring or an aliphatic ring. Suitable X is, for example, the following chemical formula:
[0031] [化 3] [0031] [Chemical 3]
Figure imgf000008_0001
で表される 2価の有機基が挙げられる。これらは、一般に、変性ポリウレタン榭脂の合 成に用いられるジイソシァネートに由来するジイソシァネート残基である。式 (I)中の 複数の Xは同一でも異なっていてもよい。言い換えると、変性ポリウレタン榭脂は 1種 類又は 2種類以上を組み合わせたジイソシァネートを原料として用いて得られるもの であってもよい。
Figure imgf000008_0001
And a divalent organic group represented by These are generally diisocyanate residues derived from diisocyanates used in the synthesis of modified polyurethane resins. A plurality of X in formula (I) may be the same or different. In other words, the modified polyurethane resin may be obtained using one or a combination of two or more diisocyanates as a raw material.
[0032] 一般式（I)中の Yは分子量が 100〜10000であり、 500〜5000であること力 S好まし い。 Yの分子量が 100未満であるか又は 10000を超えると、変性ポリウレタン榭脂を 含有する接着剤組成物の接着力が必ずしも十分でなくなる。また、 Yの分子量が 10 0未満であると弾性率が高くなり、応力が増カロしてしまうため、溶解性が低下する傾向 にあり、 10000を超えると凝集力及びフィルム強度の低下を引き起こし、凝集破壊に よる接着力の低下を招き易くなる傾向にある。  [0032] Y in the general formula (I) has a molecular weight of 100 to 10,000, preferably 500 to 5,000. When the molecular weight of Y is less than 100 or exceeds 10,000, the adhesive strength of the adhesive composition containing the modified polyurethane resin is not always sufficient. Also, if the molecular weight of Y is less than 100, the modulus of elasticity increases and stress increases, so the solubility tends to decrease, and if it exceeds 10,000, the cohesive force and film strength decrease, There is a tendency to cause a decrease in adhesive strength due to cohesive failure.
[0033] 一般式 (I)中の Yで表される分子量 100〜10000の 2価の有機基としては、ポリアル キレングリコール基が好ましい。ポリアルキレングリコール基としては、例えば、下記ィ匕 学式：  [0033] The divalent organic group having a molecular weight of 100 to 10,000 represented by Y in the general formula (I) is preferably a polyalkylene glycol group. Examples of the polyalkylene glycol group include the following formula:
-CH -CH -CH -CH 一 0—、  -CH -CH -CH -CH one 0—
2 2 2 2  2 2 2 2
-CH -CH(CH )- 0-、 -CH 一 CH - O—、 -CH -CH (CH)-0-, -CH one CH-O-,
2 2  twenty two
-CH 一 CH - CH - CH - O—、  -CH 1 CH-CH-CH-O-,
2 2 2 2  2 2 2 2
- (CH - CH(CH )-0) - (CH - CH - O) - (ただし、 a/b=9〜l/l〜9mol%の共重合体) -(CH-CH (CH) -0)-(CH-CH-O)-(where a / b = 9 to l / l to 9 mol% copolymer)
2 3 a 2 2 b 2 3 a 2 2 b
- co- _(CH ) - CO- Ό- -(CH ) - 0-、 -co- _ (CH)-CO- Ό--(CH)-0-,
2 4 2 2  2 4 2 2
- co- -(CH ) - CO- Ό- -(CH )—〇— (CH )—〇—、  -co--(CH)-CO- Ό--(CH) —〇— (CH) —〇—,
2 4 2 2 2 2  2 4 2 2 2 2
- co- -(CH ) - CO- Ό- -CH -CH(CH )—〇一、  -co--(CH)-CO- Ό- -CH -CH (CH) —
2 4 2 3  2 4 2 3
- co- -(CH ) - CO- Ό- -(CH ) - 0-、  -co--(CH)-CO- Ό--(CH)-0-,
2 4 2 4  2 4 2 4
- co- -(CH ) - CO- Ό- -(CH ) - 0-、  -co--(CH)-CO- Ό--(CH)-0-,
2 4 2 6  2 4 2 6
- co- -(CH ) - CO- Ό- -CH 一 C(CH ) 一 CH -〇—、  -co--(CH)-CO- Ό- -CH 1 C (CH) 1 CH -〇-
2 4 2 3 2 2  2 4 2 3 2 2
- co- -(CH ) - CO- Ό- -(CH ) - 0-、  -co--(CH)-CO- Ό--(CH)-0-,
2 8 2 6  2 8 2 6
一 co- -(CH ) — 0—、  One co--(CH) — 0—,
一 C〇—〇— (CH ) 一〇—、及び  One C〇-〇- (CH) Ten-
2 6  2 6
-R4-(Si(CH ) -0)-R4- (ただし、 R4は炭素数 1〜10の有機基を示す。 ) -R 4 - (Si (CH) -0) -R 4 - ( provided that, R 4 represents an organic group having 1 to 10 carbon atoms.)
3 2  3 2
等の繰り返し単位を有するものが挙げられる。 Yは、一般に、変性ポリウレタン榭脂の 合成に用いられるジオールに由来するジオール残基である。式 (I)中の複数の Yは 同一でも異なっていてもよい。言い換えると、変性ポリウレタン榭脂は 1種類又は 2種 類以上を組み合わせたジオールを原料として用いて得られるものであってもよ 、。こ の場合、ジオールの平均分子量は 100〜10000であることが好ましぐ 500〜5000 であればより好ましい。  Those having a repeating unit such as Y is generally a diol residue derived from a diol used for the synthesis of modified polyurethane resin. A plurality of Y in formula (I) may be the same or different. In other words, the modified polyurethane resin may be obtained using a diol that is a combination of one or more types as a raw material. In this case, the average molecular weight of the diol is preferably 100 to 10,000, more preferably 500 to 5,000.
[0034] 一般式 (I)中の Z (R)—の部分は、上記一般式 (Π)で表される 2価の基 (a)、下 記一般式 (ΠΙ)で表される 2価の基 (b)又は下記一般式 (IV)で表される 2価の基 (c) であることが好ましい。これらの式中、 Aは炭素数 4以上の 4価の有機基 (すなわち、 4 個以上の炭素を含む 4価の有機基)、 Rは反応性を有する基である。この場合、（a)、 (b)及び (c)の合計量を基準として、（a)の割合が 10〜90mol%、（b)の割合が 0〜 90mol%、（c)の割合力^〜 90mol%であることが好ましい。  [0034] The Z (R) — moiety in the general formula (I) is a divalent group (a) represented by the above general formula (Π) and a divalent group represented by the following general formula (ΠΙ). Or a divalent group (c) represented by the following general formula (IV). In these formulas, A is a tetravalent organic group having 4 or more carbon atoms (that is, a tetravalent organic group containing 4 or more carbon atoms), and R is a reactive group. In this case, based on the total amount of (a), (b) and (c), the proportion of (a) is 10 to 90 mol%, the proportion of (b) is 0 to 90 mol%, and the proportion power of (c) ^ It is preferably ~ 90 mol%.
[0035] 一般式 (Π)、 (III)、 (IV)中の Aで表される炭素数 4以上の 4価の有機基としては、 例えば、下記化学式： [0036] [化 4] [0035] Examples of the tetravalent organic group having 4 or more carbon atoms represented by A in the general formulas (、), (III), and (IV) include, for example, the following chemical formula: [0036] [Chemical 4]
Figure imgf000010_0001
で表される基が挙げられる。 Aは、一般に、変性ポリウレタン榭脂の合成に用いられる テトラカルボン酸無水物に由来するテトラカルボン酸無水物残基である。式 (I)中の 複数の Aは同一でも異なっていてもよい。言い換えると、これらは 1種類又は 2種類以 上のテトラカルボン酸無水物を原料として用いて得られるものであってもよ 、。
Figure imgf000010_0001
The group represented by these is mentioned. A is a tetracarboxylic anhydride residue derived from a tetracarboxylic anhydride generally used for the synthesis of modified polyurethane resin. A plurality of A in formula (I) may be the same or different. In other words, these may be obtained using one or more types of tetracarboxylic anhydrides as raw materials.
[0037] 一般式 (I)、 (III)及び (IV)中の Rは反応性を有する基である。反応性を有する基 は、硬化剤等と反応して架橋構造を形成し得る官能基を有する基である。この官能 基としてはラジカル重合性不飽和基、エポキシ基、シァネートエステル基等が挙げら れ、これらの中でもラジカル重合性不飽和基が好ましい。特に、 Rは 1以上の (メタ)ァ タリレート基を有する基であることが好ましい。この場合、 Rは、例えば下記一般式 (V )で表される。なお、（メタ）アタリレート基は、メタタリレート基又はアタリレート基を意味 する。 [0037] R in the general formulas (I), (III) and (IV) is a reactive group. The group having reactivity is a group having a functional group that can react with a curing agent or the like to form a crosslinked structure. Examples of this functional group include a radically polymerizable unsaturated group, an epoxy group, and a cyanate ester group. Among these, a radically polymerizable unsaturated group is preferable. In particular, R is one or more (meta) keys A group having a tallylate group is preferable. In this case, R is represented by, for example, the following general formula (V). Incidentally, the (meth) acrylate group means a meta acrylate group or an acrylate group.
[0038] [化 5]  [0038] [Chemical 5]
Figure imgf000011_0001
Figure imgf000011_0001
[0039] 式 (V)中、 R1は炭素数 1〜50の 2価の有機基を示し、 R2は水素原子又はメチル基 を示す。 In the formula (V), R 1 represents a divalent organic group having 1 to 50 carbon atoms, and R 2 represents a hydrogen atom or a methyl group.
[0040] 一般式（I)中の n及び mは 1〜100の整数である必要があり、 1〜50の整数であるこ とがより好ましい。 n又は mが 100を超えると、変性ポリウレタン榭脂を含有する接着剤 組成物の接着力が必ずしも十分でなくなる。また、 n又は mが 100を超えると分子量 が大きくなり過ぎるため粘度が増大し、溶解性の低下や流動性の低下を招く傾向に ある。  [0040] In the general formula (I), n and m must be integers of 1 to 100, and more preferably 1 to 50. When n or m exceeds 100, the adhesive strength of the adhesive composition containing the modified polyurethane resin is not necessarily sufficient. On the other hand, when n or m exceeds 100, the molecular weight becomes too large, so that the viscosity increases and the solubility and fluidity tend to decrease.
[0041] 変性ポリウレタン榭脂は、例えば、下記 (A)と (B)との重縮合により得られる。  [0041] The modified polyurethane resin is obtained, for example, by polycondensation of the following (A) and (B).
(A)：下記一般式 (VI)で表される化合物、下記一般式 (VII)で表される化合物及び 下記一般式 (VIII)で表される化合物の混合物  (A): a mixture of a compound represented by the following general formula (VI), a compound represented by the following general formula (VII), and a compound represented by the following general formula (VIII)
[0042] [化 6]  [0042] [Chemical 6]
Figure imgf000011_0002
Figure imgf000011_0002
R R V R R V
HOOC' 、COOH ( V I I I ) (B)：イソシァネート末端ウレタンオリゴマ HOOC ', COOH (VIII) (B): Isocyanate-terminated urethane oligomer
[0043] 上記 (A)の混合物は、例えば、テトラカルボン酸二無水物と所定量のヒドロキシル 基を有する (メタ)アタリレートとを溶媒中 70°C〜100°Cで 1時間から 10時間反応させ ることにより得られる。この反応においては、場合により、触媒として 3級アミン類等を 用いることができる。また、（メタ)アタリレートの重合を抑制する目的で、フエノール類 等の重合禁止剤を用いることもできる。 [0043] The mixture of (A) is obtained by reacting, for example, tetracarboxylic dianhydride and (meth) acrylate having a predetermined amount of hydroxyl group in a solvent at 70 ° C to 100 ° C for 1 hour to 10 hours. Can be obtained. In this reaction, a tertiary amine or the like can be used as a catalyst in some cases. In addition, a polymerization inhibitor such as phenols may be used for the purpose of suppressing polymerization of (meth) acrylate.
[0044] 上記 (B)のイソシァネート末端ウレタンオリゴマは、例えば、溶媒中、過剰のジィソシ ァネート及びジオールを 70°C〜160°Cで 1時間から 10時間反応させることにより得ら れる。この反応においては、場合により一般的なウレタン合成に使用される触媒を用 いることちでさる。  [0044] The isocyanate-terminated urethane oligomer of (B) can be obtained, for example, by reacting an excess of diisocyanate and diol at 70 ° C to 160 ° C for 1 hour to 10 hours in a solvent. In this reaction, a catalyst used for general urethane synthesis may be used in some cases.
[0045] ウレタンオリゴマを構成するジイソシァネートとジオールの組成比は、ジイソシネート 1. Omolに対して、ジオール成分 0. 1〜1. Omolが好ましい。変性ポリウレタン榭脂 を構成するポリウレタンオリゴマと一般式 (I)中で Z (R) —で表される構造物の組成 比は、ポリウレタンオリゴマ 1. Omolに対して、 0. 1〜2. Omolが好ましい。  [0045] The composition ratio of diisocyanate and diol constituting the urethane oligomer is preferably 0.1 to 1. Omol of the diol component with respect to 1. Omol of diisocyanate. The composition ratio of the polyurethane oligomer constituting the modified polyurethane resin and the structure represented by Z (R) — in the general formula (I) is 0.1-2 Omol to 1. Omol polyurethane oligomer. preferable.
[0046] 上記 (A)及び (B)を混合し、 70°C〜100°Cで 1時間から 10時間、場合により触媒 を用いて反応させることにより、変性ポリウレタン榭脂溶液を得ることができる。また、 場合により、更に 1価のアルコール、ォキシム、ァミン、イソシァネート、酸無水物等を 溶液に添加して更に反応を続け、変性ポリウレタン榭脂の末端を修飾することもでき る。  [0046] A modified polyurethane resin solution can be obtained by mixing (A) and (B) and reacting at 70 ° C to 100 ° C for 1 to 10 hours, optionally using a catalyst. . In some cases, the terminal of the modified polyurethane resin can be modified by adding further monohydric alcohol, oxime, amine, isocyanate, acid anhydride or the like to the solution and continuing the reaction.
[0047] (A)と (B)との重縮合反応に用いる溶媒は (A)又は (B)を合成する際の溶媒と同じ でも異なっていてもよいが、変性ポリウレタン榭脂が溶解する溶媒を用いることが、高 分子量化された変性ポリウレタン榭脂を得るためには好まし ヽ。  [0047] The solvent used in the polycondensation reaction between (A) and (B) may be the same as or different from the solvent used in the synthesis of (A) or (B), but the solvent in which the modified polyurethane resin is dissolved. It is preferable to use a high molecular weight modified polyurethane resin.
[0048] 得られた変性ポリウレタン榭脂溶液から、必要に応じて、水による再沈殿法等により 変性ポリウレタン榭脂を取り出すこともできる。  [0048] From the resulting modified polyurethane resin solution, the modified polyurethane resin can be taken out by a reprecipitation method with water or the like, if necessary.
[0049] 以上説明した本発明の変性ポリウレタン榭脂は、例えば、半導体又は液晶ディスプ レイ等の表示システム等において、半導体素子の実装ある 1ヽは回路接続用等のため の接着剤として使用することができる。  [0049] The modified polyurethane resin of the present invention described above is used, for example, as an adhesive for circuit connection or the like, in which a semiconductor element is mounted in a display system such as a semiconductor or a liquid crystal display. Can do.
[0050] 本発明の変性ポリウレタン榭脂は、単独で接着剤として用いられたときでも接着性 に優れるが、硬化性榭脂 (三次元架橋性榭脂)及びその硬化剤を組み合わせた接着 剤組成物の状態で用いることが好まし 、。これにより更に高 、接続信頼性が得られる [0050] The modified polyurethane resin of the present invention is adhesive even when used alone as an adhesive. However, it is preferably used in the state of an adhesive composition in which a curable resin (three-dimensional crosslinkable resin) and its curing agent are combined. This provides higher connection reliability.
[0051] 硬化性榭脂は、硬化により三次元架橋構造を形成する榭脂であればよ！ヽ。硬化性 榭脂の好適な具体例としては、エポキシ榭脂、シァネートエステル榭脂、イミド系榭脂 、ラジカル重合により硬化する榭脂 (ラジカル重合性物質)であるアタリレート、メタタリ レート及びマレイミドィ匕合物等が挙げられる。 [0051] The curable resin may be a resin that forms a three-dimensional crosslinked structure by curing!ヽ. Preferable specific examples of the curable resin include epoxy resin, cyanate ester resin, imide-based resin, and atallate, metatalylate and maleimide resin which are resin (radically polymerizable substance) cured by radical polymerization. Compound etc. are mentioned.
[0052] これら硬化性榭脂は通常その硬化剤とともに用いられる。エポキシ榭脂の場合、硬 ィ匕剤として、例えば、公知のイミダゾール系、ヒドラジド系、三フッ化ホウ素—アミン錯 体、スルホ -ゥム塩、ァミンイミド、ポリアミンの塩、ジシアンジアミド等の硬ィ匕剤又はそ の混合物が用いられる。  [0052] These curable resin are usually used together with the curing agent. In the case of epoxy resin, hardeners such as known imidazole, hydrazide, boron trifluoride-amine complex, sulfo-um salt, aminimide, polyamine salt, dicyandiamide and the like are used as hardeners. Or a mixture thereof is used.
[0053] エポキシ榭脂としては、 1分子内に 2個以上のグリシジル基を有する各種のェポキ シ化合物が用いられる。エポキシ榭脂の具体例としては、ビスフエノール A, F, S及 び AD等力 誘導されるビスフエノール型エポキシ榭脂、フエノールノボラック及びタレ ゾールノボラック力も誘導されるエポキシノボラック型榭脂、ナフタレン骨格を有する ナフタレン型エポキシ榭脂、グリシジルァミン型エポキシ榭脂、上記以外のグリシジル エーテル型エポキシ樹脂、ビフエ-ル型エポキシ樹脂、脂環式エポキシ榭脂がある。 これらは単独で又は複数種を組合わせて用いられる。  [0053] As the epoxy resin, various epoxy compounds having two or more glycidyl groups in one molecule are used. Specific examples of epoxy resins include bisphenol A, F, S, and AD isotropic bisphenol type epoxy resins, phenol novolac and talesol novolac force induced epoxy novolac type resins, and naphthalene skeletons. There are naphthalene type epoxy resin, glycidylamine type epoxy resin, glycidyl ether type epoxy resin, biphenyl type epoxy resin, and alicyclic epoxy resin other than the above. These may be used alone or in combination.
[0054] エポキシ榭脂には、一般に、アルカリ金属イオン、アルカリ土類金属イオン、ハロゲ ンイオン等の不純物イオンが含まれている。エポキシ榭脂としては、これら不純物ィォ ン (特に塩素イオン又は加水分解性塩素）の濃度を 300ppm以下に低減した高純度 品を用いることがエレクト口マイグレーション防止や回路金属導体の腐食防止のため に好ましい。 [0054] Epoxy resin generally contains impurity ions such as alkali metal ions, alkaline earth metal ions, and halogen ions. For epoxy resin, it is necessary to use high-purity products in which the concentration of these impurities (especially chlorine ions or hydrolyzable chlorine) is reduced to 300 ppm or less to prevent electoric port migration and corrosion of circuit metal conductors. preferable.
[0055] シァネートエステル榭脂としては、ビス（4ーシアナトフエ-ル）ェタン、 2, 2 ビス（4 —シアナトフエ-ル）プロパン、 2, 2 ビス（3, 5 ジメチルー 4 シアナトフエ-ル)メ タン、 2, 2 ビス（4 シアナトフェ-ル）—1, 1, 1, 3, 3, 3 へキサフルォロプロノ ンヽ a , a '—ビス（4—シアナトフェ-ル） m ジイソプロピルベンゼン、フエノール 付力卩ジシクロペンタジェン重合体のシァネートエステル化物及びこれらのプレポリマ 一が挙げられる。これらは単独で又は複数種を組合わせて用いられる。これらの中で も、 2, 2—ビス（4ーシアナトフエ-ル）プロパン及び 2, 2—ビス（3, 5—ジメチルー 4 ーシアナトフェニル）が硬化物の誘電特性が特に良好であるため好ま 、。 [0055] Examples of cyanate ester resin include bis (4-cyanatophenol) ethane, 2,2bis (4—cyanatophenol) propane, 2,2bis (3,5 dimethyl-4-cyanatophenol) methane, 2, 2 Bis (4 cyanatophenol) —1, 1, 1, 3, 3, 3 Hexafluoropronone ヽ a, a '-bis (4-cyanatophenol) m Diisopropylbenzene, phenolシ Cyanate esterification products of dicyclopentagen polymers and their prepolymers One is mentioned. These may be used alone or in combination. Of these, 2,2-bis (4-cyanatophenyl) propane and 2,2-bis (3,5-dimethyl-4-cyanatophenyl) are preferred because the dielectric properties of the cured product are particularly good. .
[0056] シァネートエステル榭脂の硬化剤としては、金属系反応触媒類、例えばマンガン、 鉄、コバルト、ニッケル、銅、亜鉛等の金属触媒類が用いられる。具体的には、 2—ェ チルへキサン酸塩やナフテン酸塩等の有機金属塩ィ匕合物及びァセチルアセトン錯 体などの有機金属錯体が硬化剤として用いられる。 [0056] As the curing agent for cyanate ester resin, metal-based reaction catalysts, for example, metal catalysts such as manganese, iron, cobalt, nickel, copper, and zinc are used. Specifically, organometallic complexes such as 2-ethylhexanoate and naphthenate and organometallic complexes such as acetylacetone complex are used as curing agents.
[0057] 金属系反応触媒の配合量は、シァネートエステル榭脂に対して l〜3000ppmとす ることが好ましぐ 1〜： LOOOppmとすることがより好ましぐ 2〜300ppmとすることが更 に好ま ヽ。金属系反応触媒の配合量が lppm未満では反応性及び硬化性が不十 分となる傾向があり、 3000ppmを超えると反応の制御が難しくなつたり、硬化が速く なりすぎる傾向がある。 [0057] The compounding amount of the metal-based reaction catalyst is preferably 1 to 3000 ppm with respect to the cyanate ester resin. 1 to: More preferably LOOOppm and 2 to 300 ppm. More preferred 好. If the compounding amount of the metal-based reaction catalyst is less than 1 ppm, the reactivity and curability tend to be insufficient, and if it exceeds 3000 ppm, the reaction tends to be difficult to control or the curing tends to be too fast.
[0058] ラジカル重合により硬化する榭脂は、ラジカル反応により重合する官能基を有する 化合物 (ラジカル重合性ィ匕合物)からなる。具体的には、（メタ)アタリレート榭脂、マレ イミド榭脂、シトラコンイミド榭脂、ナジイミド榭脂などがあり、これら 2種類以上を混合 して使用してもよい。またラジカル重合性ィ匕合物は、モノマー、オリゴマーいずれの状 態でも使用することができ、モノマーとオリゴマーを混合して用いてもよい。  [0058] The resin cured by radical polymerization is composed of a compound having a functional group that is polymerized by radical reaction (radical polymerizable compound). Specific examples include (meth) acrylate resin, maleimide resin, citraconimide resin, nadiimide resin, and a mixture of two or more of these. The radical polymerizable compound can be used in either a monomer or oligomer state, and a monomer and an oligomer may be mixed and used.
[0059] (メタ）アクリル榭脂は、 1種又は 2種以上の (メタ）アタリレートイ匕合物をモノマーとし て含む榭脂であり、ラジカル重合により架橋構造を形成する。（メタ)アタリレートイ匕合 物としては、メチル (メタ）アタリレート、ェチル (メタ）アタリレート、イソプロピル (メタ）ァ タリレート、イソブチル (メタ）アタリレート、ェテレングリコールジ（メタ）アタリレート、ジ エチレングリコールジ (メタ）アタリレート、トリメチロールプロパントリ（メタ）アタリレート、 テトラメチレングリコールテトラ (メタ）アタリレート、 2—ヒドロキシ一 1, 3—ジァクリロキ シプロパン、 2, 2—ビス（4—(アタリ口キシメトキシ）フエ-ル）プロパン、 2, 2—ビス（4 - (アタリロキシエトキシ）フエ-ル）プロパン、ジシクロペンテ-ル (メタ）アタリレートトリ シクロデ力-ル (メタ）アタリレート、トリス（アタリ口キシェチル)イソシァヌレート、ウレタ ン (メタ）アタリレート及びイソシァヌール酸エチレンォキシド変性ジアタリレートなどが ある。これらを単独又は 2種類以上を混合して用いられる。また、必要により、ハイド口 キノン、メチルエーテルノヽイドロキノン等のラジカル重合禁止剤を硬化性が損なわれ な!ヽ範囲で使用してもよ ヽ。 [0059] (Meth) acrylic resin is a resin containing one or two or more (meth) atalytoy compound as a monomer, and forms a crosslinked structure by radical polymerization. Examples of (meth) atalytoy compounds include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, ethene glycol di (meth) acrylate, Diethylene glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, tetramethylene glycol tetra (meth) acrylate, 2-hydroxy-1,3-diacryloxypropane, 2, 2-bis (4- ( Atyloxymethoxy) phenol) propane, 2,2-bis (4- (ataryloxyethoxy) phenol) propane, dicyclopentayl (meth) acrylate, cyclodehydryl (meth) acrylate, tris ( Atari mouth kichetil) isocyanurate, urethan (meth) atalylate and isocyanuric acid Examples include ethylene oxide-modified diathalate. These may be used alone or in admixture of two or more. If necessary, hide mouth Radical polymerization inhibitors such as quinone and methyl ether neuroquinone may be used in the range where the curability is not impaired.
[0060] リン酸エステル構造を有するラジカル重合性化合物を使用することにより、金属等 無機物に対する接着力を特に向上することができる。リン酸エステル構造を有するラ ジカル重合性ィ匕合物の使用量は、接着剤組成物 100重量部に対して好ましくは 0. 1 〜： LO重量部であり、より好ましくは 0. 5〜5重量部である。リン酸エステル構造を有す るラジカル重合性ィ匕合物は、例えば、無水リン酸と 2—ヒドロキシェチル (メタ)アタリレ ートの反応生成物として得られる。具体的には、モノ（2—メタクリロイルォキシェチル) アシッドホスフェート、ジ（2—メタクリロイルォキシェチル）アシッドホスフェート等があ る。これらを単独で又は複数種を組合わせて使用することができる。  [0060] By using a radically polymerizable compound having a phosphoric ester structure, it is possible to particularly improve the adhesion to an inorganic substance such as a metal. The amount of the radically polymerizable compound having a phosphate ester structure is preferably 0.1 to: LO parts by weight, more preferably 0.5 to 5 parts per 100 parts by weight of the adhesive composition. Parts by weight. A radically polymerizable compound having a phosphate ester structure is obtained, for example, as a reaction product of phosphoric anhydride and 2-hydroxyethyl (meth) acrylate. Specific examples include mono (2-methacryloyloxychetyl) acid phosphate and di (2-methacryloyloxychetyl) acid phosphate. These can be used alone or in combination of two or more.
[0061] マレイミド榭脂は、分子中にマレイミド基を少なくとも 1個有している化合物力もなる 硬化性榭脂である。例えば、フエ-ルマレイミド、 1—メチル 2, 4 ビスマレイミドべ ンゼン、 N, N， 一m フエ-レンビスマレイミド、 N, N， 一p フエ-レンビスマレイミド 、 N, N， 一4, 4—ビフエ-レンビスマレイミド、 N, N， 一4, 4— (3, 3—ジメチルビフエ -レン）ビスマレイミド、 N, N， 一 4, 4— (3, 3—ジメチルジフエ-ルメタン）ビスマレイ ミド、 N, N，—4, 4— (3, 3—ジェチルジフエ-ルメタン）ビスマレイミド、 N, N，—4, 4—ジフエ-ルメタンビスマレイミド、 N, N， 一 4, 4—ジフエ-ルプロパンビスマレイミド 、 N, N，— 4, 4—ジフエ-ルエーテルビスマレイミド、 N, N，— 4, 4—ジフエ-ルスル ホンビスマレイミド、 2, 2 ビス（4— (4 マレイミドフエノキシ）フエ-ル）プロパン、 2, 2 ビス（3 s ブチル 3, 4— (4 マレイミドフエノキシ）フエ-ル）プロパン、 1, 1 —ビス（4— (4—マレイミドフエノキシ）フエ-ル）デカン、 4, 4，一シクロへキシリデン一 ビス（1— (4 マレイミドフエノキシ）フエノキシ） 2 シクロへキシルベンゼン及び 2, 2 ビス（4— (4 マレイミドフエノキシ）フエ-ル）へキサフルォロプロパンがある。こら れを単独で又は 2種類以上を混合して使用することができる。  [0061] Maleimide resin is a curable resin that also has a compound power having at least one maleimide group in the molecule. For example, phenol maleimide, 1-methyl 2,4 bismaleimide benzene, N, N, 1m phthalene bismaleimide, N, N, 1p phthalene bismaleimide, N, N, 1, 4, 4— Biphenylene bismaleimide, N, N, 1,4, 4- (3,3-dimethylbiphenol-bene) maleimide, N, N, 1,4, 4- (3,3-dimethyldiphenylmethane) bismaleimide, N, N, —4, 4— (3,3—Jetyldiphenylmethane) bismaleimide, N, N, —4,4-Diphenylmethane bismaleimide, N, N, 1,4,4-diphenylpropane bismaleimide , N, N, — 4, 4-Diphenyl ether bismaleimide, N, N, — 4, 4-Diphenyl sulfone bismaleimide, 2, 2 bis (4- (4 maleimide phenol) phenol) Propane, 2, 2 bis (3 s butyl 3, 4— (4 maleimidophenoxy) phenol) propane, 1, 1 —bis (4— (4-Maleimidophenoxy) phenol) decane, 4, 4, monocyclohexylidene monobis (1— (4 maleimidophenoxy) phenoxy) 2 cyclohexylbenzene and 2, 2 bis (4— ( 4 Maleimidophenoxy) Fuel) Hexafluoropropane These can be used alone or in admixture of two or more.
[0062] シトラコンイミド榭脂は、分子中にシトラコンイミド基を少なくとも 1個有しているシトラ コンイミドィ匕合物力もなる硬化性榭脂である。シトラコンイミド化合物としては、例えば 、フエ-ルシトラコンイミド、 1—メチル 2, 4 ビスシトラコンイミドベンゼン、 N, N， - m フエ-レンビスシトラコンイミド、 N, N， 一 p フエ-レンビスシトラコンイミド、 N, N ，一4, 4—ビフエ-レンビスシトラコンイミド、 N, N，一4, 4— (3, 3—ジメチルビフエ- レン）ビスシトラコンイミド、 N, N，一 4, 4— (3, 3—ジメチルジフエ-ルメタン）ビスシト ラコンイミド、 N, N，一 4, 4— (3, 3—ジェチルジフエ-ルメタン）ビスシトラコンイミド、 N, N，一4, 4ージフエ-ルメタンビスシトラコンイミド、 N, N，一4, 4ージフエ-ルプロ ノ ンビスシトラコンイミド、 N, N，一4, 4ージフエニノレエーテノレビスシトラコンイミド、 N , N，一 4, 4 ジフエ-ルスルホンビスシトラコンイミド、 2, 2 ビス（4— (4 シトラコン イミドフエノキシ）フエ-ル）プロパン、 2, 2 ビス（3 s ブチル 3, 4— (4 シトラ コンイミドフエノキシ）フエ-ル）プロパン、 1, 1—ビス（4— (4 シトラコンイミドフエノキ シ）フエ-ル）デカン、 4, 4'—シクロへキシリデン一ビス（1— (4 シトラコンイミドフエ ノキシ）フエノキシ） 2 シクロへキシルベンゼン及び 2, 2 ビス（4— (4 シトラコン イミドフエノキシ）フエ-ル）へキサフルォロプロパンがある。これらを単独で又は 2種類 以上を混合して使用することができる。 [0062] The citraconimide resin is a curable resin that also has a citraconimide compound strength having at least one citraconimide group in the molecule. Examples of the citraconic imide compound include: ferulcitraconimide, 1-methyl 2,4 biscitraconimide benzene, N, N, -m phenylene biscitraconimide, N, N, 1 p phenylene biscitraconimide , N, N , 1,4-Biphenylene biscitraconimide, N, N, 1,4— (3,3-dimethylbiphenylene) biscitraconimide, N, N, 1,4,4— (3,3-dimethyldiphenol -Lumethane) biscitraconimide, N, N, 1,4,4- (3,3-jetyldiphenylmethane) biscitraconeimide, N, N, 1,4-4-diphenylmethane biscitraconimide, N, N, 1-4 , 4-diphenylpronone biscitraconimide, N, N, 1,4-diphenylenoleobiscitraconimide, N, N, 1,4,4 diphenylsulfone biscitraconimide, 2, 2 bis ( 4— (4 Citraconimidophenoxy) phenol) propane, 2,2bis (3 sbutyl 3,4— (4 Citraconimidephenoxy) phenol) propane, 1,1—bis (4— (4 Citraconimide Phenol) Phenol) Decan, 4, 4'-cyclohexylidene Scan (1- (4 citraconimide Hue phenoxy) phenoxy) 2 hexyl benzene and 2-cyclohexylene, 2-bis (4- (4 citraconic Imidofuenokishi) Hue - Le) is hexa full O b propane to. These can be used alone or in admixture of two or more.
[0063] ナジイミド榭脂は、分子中にナジイミド基を少なくとも 1個有しているナジイミド化合 物からなる硬化性榭脂である。ナジイミドィ匕合物としては、例えば、フエ二ルナジイミド 、 1—メチル 2, 4 ビスナジイミドベンゼン、 N, Ν'—m—フエ-レンビスナジイミド 、 N, N，一p フエ-レンビスナジイミド、 N, N，一 4, 4—ビフエ-レンビスナジイミド、 N, N，—4, 4— (3, 3—ジメチルビフエ-レン）ビスナジイミド、 N, N，—4, 4— (3, 3 —ジメチルジフエ-ルメタン）ビスナジイミド、 N, N，一 4, 4— (3, 3—ジェチルジフエ 二ノレメタン）ビスナジイミド、 N, N，一4, 4ージフエ二ノレメタンビスナジイミド、 N, N，一 4, 4—ジフエ-ルプロパンビスナジイミド、 N, N，— 4, 4—ジフエ-ルエーテルビスナ ジイミド、 N, N，一4, 4 ジフエ-ノレスノレホンビスナジイミド、 2, 2 ビス（4— (4 ナ ジイミドフエノキシ）フエ-ル）プロパン、 2, 2 ビス（3 s ブチルー 3, 4—（4 ナジ イミドフエノキシ）フエ-ル）プロパン、 1, 1 ビス（4— (4 ナジイミドフエノキシ）フエ -ル）デカン、 4, 4'—シクロへキシリデン一ビス（1— (4 ナジイミドフエノキシ）フエノ キシ） 2 シクロへキシルベンゼン及び 2, 2 ビス（4— (4 ナジイミドフエノキシ） フエニル）へキサフルォロプロパンがある。これらを単独で又は 2種類以上を混合して 使用することができる。 [0063] Nadiimide resin is a curable resin made of a nadiimide compound having at least one nadiimide group in the molecule. Examples of nadiimide compounds include phenyl nadiimide, 1-methyl 2,4 bis nadiimide benzene, N, Ν'-m-phenol bis nadiimide, N, N, 1-p phenylene bis nadiimide, N, N, 1, 4, 4-biphenylene bisnadiimide, N, N, —4, 4— (3, 3-dimethylbiphenylene) bisnadiimide, N, N, —4, 4— (3, 3 — dimethyldiphenylmethane ) Bisnadiimide, N, N, 1,4,4— (3,3—Jetyldiphenol Ninolemethane) bisnadiimide, N, N, 1,4,4-Diphenolinenomethane bisnadiimide, N, N, 1,4,4-Diphenol Propane bisnadiimide, N, N, — 4, 4—Diphenyl ether bisnadiimide, N, N, 1,4,4 diphenol-norethnorephone bisnadiimide, 2, 2 bis (4— (4 nadiimide phenoxy) ) Phenol) propane, 2,2 bis (3 s butyl-3,4— (4 nadiimidophenol) Cis) phenol) propane, 1,1 bis (4- (4 nadiimidephenoxy) phenol) decane, 4,4'-cyclohexylidene monobis (1— (4 nadiimidephenoxy) Phenoxy) 2 cyclohexylbenzene and 2, 2 bis (4- (4 nadiimidephenoxy) phenyl) hexafluoropropane. These can be used alone or in admixture of two or more.
[0064] ラジカル重合により硬化する硬化性榭脂を用いる場合、硬化剤として重合開始剤を 使用する。重合開始剤としては、熱又は光によって遊離ラジカルを発生する化合物 であれば特に制限はない。重合開始剤としては過酸ィ匕物、ァゾ化合物などがある。 重合開始剤は、 目的とする接続温度、接続時間、保存安定性等を考慮し適宜選択さ れるが、高反応性と保存安定性の点から、半減期 10時間の温度が 40°C以上で半減 期 1分の温度力 180°C以下である有機過酸ィ匕物が好ましぐ半減期 10時間の温度 が 50°C以上で半減期 1分の温度が 170°C以下である有機過酸ィ匕物が特に好ましい 。接着に要する時間 (接続時間)を 10秒とした場合、十分な反応率を得るためには、 硬ィ匕剤の配合量は 1〜20重量％が好ましぐ 2〜15重量％が特に好ましい。 [0064] When a curable resin that is cured by radical polymerization is used, a polymerization initiator is used as a curing agent. use. The polymerization initiator is not particularly limited as long as it is a compound that generates free radicals by heat or light. Examples of the polymerization initiator include peroxides and azo compounds. The polymerization initiator is appropriately selected in consideration of the intended connection temperature, connection time, storage stability, etc. From the viewpoint of high reactivity and storage stability, the temperature of the half-life of 10 hours is 40 ° C or higher. Half-life 1-minute temperature force Organic peroxides with a temperature of 180 ° C or less are preferred Half-life 10-hour temperature is 50 ° C or more and half-life 1-minute temperature is 170 ° C or less Acid acids are particularly preferred. When the time required for bonding (connection time) is 10 seconds, in order to obtain a sufficient reaction rate, the blending amount of the hardener is preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight. .
[0065] 本発明で使用される有機過酸ィ匕物の具体例としては、ジァシルバーオキサイド、パ ーォキシジカーボネート、パーォキシエステル、パーォキシケタール、ジアルキルパ 一オキサイド、ハイド口パーオキサイド及びシリルパーオキサイドがある。これらは 2種 以上を適宜混合して用いることができる。これらの中でも、含まれる塩素イオンや有機 酸の濃度は 5000ppm以下であり加熱分解後に発生する有機酸が少な!/、ことから、 パーォキシエステル、ジアルキルパーオキサイド、ハイド口パーオキサイド及びシリル パーオキサイドが特に好ましい。塩素イオンや有機酸の量が少ないことにより、回路 部材の接続端子の腐食を抑えることができる。  [0065] Specific examples of the organic peroxide used in the present invention include disilver oxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, and hyde-peroxide. There are oxides and silyl peroxides. These can be used by mixing two or more kinds as appropriate. Among these, the concentration of chlorine ions and organic acids contained is 5000 ppm or less, and there are few organic acids generated after thermal decomposition! /, Therefore, peroxyesters, dialkyl peroxides, hydride peroxides and silyl peroxides. Is particularly preferred. Corrosion of the connection terminals of circuit members can be suppressed by reducing the amount of chlorine ions and organic acids.
[0066] ジァシルバーオキサイドとしては、イソブチルパーオキサイド、 2, 4ージクロ口べンゾ ィルパーオキサイド、 3、 5、 5—トリメチルへキサノィルパーオキサイド、オタタノィルパ 一オキサイド、ラウロイルパーオキサイド、ステアロイルパーオキサイド、スクシニックパ 一オキサイド、ベンゾィルパーォキシトルエン、ベンゾィルパーオキサイド等が挙げら れる。  [0066] Examples of disilver oxide include isobutyl peroxide, 2,4-dichlorobenzoic peroxide, 3, 5, 5-trimethylhexanoyl peroxide, otatanyl peroxide, lauroyl peroxide, stearoyl peroxide Succinic peroxide, benzoylperoxytoluene, benzoyl peroxide and the like.
[0067] パーォキシジカーボネートとしては、ジー n—プロピノレバーオキシジカーボネート、 ジイソプロピルパーォキシジカーボネート、ビス（4—tーブチルシクロへキシル）パー ォキシジカーボネト、ジー 2—エトキシメトキシバーオキシジカーボネート、ジ（2—ェ チルへキシルバーォキシ）ジカーボネート、ジメトキシブチルバ一才キシジカーボネ ート、ジ（3—メチルー 3—メトキシブチルバ一才キシ)ジカーボネート等が挙げられる  [0067] Peroxydicarbonates include di-n-propinolever oxydicarbonate, diisopropyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, and di-2-ethoxymethoxy bar. Examples include oxydicarbonate, di (2-ethylhexyloxy) dicarbonate, dimethoxybutylbadium oxydicarbonate, di (3-methyl-3-methoxybutylbaxyxy) dicarbonate, and the like.
[0068] パーォキシエステル類としては、タミルパーォ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ォキシネオデカノエート、 1ーシクロへキシルー 1ーメチルェ チルパーォキシノエデカノエート、 t一へキシルバーォキシネオデカノエート、 tーブチ ルパーォキシビバレート、 1, 1, 3, 3—テトラメチルブチルパーォキシ 2 ェチル へキサノネート、 2, 5 ジメチルー 2, 5 ジ（2 ェチルへキサノィルパーォキシ）へ キサン、 1 シクロへキシル 1ーメチノレエチノレバーォキシ 2—ェチノレへキサノネ ート、 t一へキシルバーォキシ 2—ェチルへキサノネート、 t ブチルパーォキシ 2—ェチルへキサノネート、 t ブチルパーォキシイソブチレート、 1, 1 ビス（tーブ チルバ一才キシ）シクロへキサン、 t一へキシルバーォキシイソプロピルモノカーボネ ート、 t—ブチルパーォキシ 3, 5, 5—トリメチルへキサノネート、 t ブチルバーオ キシラウレート、 2, 5 ジメチルー 2, 5 ジ（m—トルオイルパーォキシ）へキサン、 t ブチノレパーォキシイソプロピノレモノカーボネート、 t ブチノレパーォキシ 2—ェチ ルへキシルモノカーボネート、 t一へキシルパーォキシベンゾエート、 tーブチノレノ ー ォキシアセテート等が挙られる。 [0068] Peroxyesters include Tamil peroxyneodecanoate, 1, 1, 3, 3— Tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl 1-methylethylperoxynoedecanoate, tert-hexyloxyneodecanoate, tert-peroxybivalate, 1, 1, 3 , 3-Tetramethylbutylperoxy-2-ethylhexanate, 2,5-dimethyl-2,5-di (2-ethylhexylperoxy) hexane, 1-cyclohexyl, 1-methinoleethinolevoxy-2-ethylenole Hexanone, t-hexyloxy 2-ethyl hexanoate, t-butyl peroxy 2-ethyl hexanoate, t-butyl peroxyisobutyrate, 1, 1 bis (t-tylba monoyl) cyclohexane, t Hexasilveroxyisopropyl monocarbonate, t-butylperoxy 3, 5, 5-trimethylhexanoate, t-butyl Oxylaurate, 2,5 dimethyl-2,5 di (m-toluoylperoxy) hexane, t-butinoleperoxyisopropinole monocarbonate, t-butinoreperoxy 2-ethylhexyl monocarbonate, Examples include t-hexyl peroxybenzoate and t-butenolenoxyacetate.
[0069] パーォキシケタールとしては、 1, 1—ビス（t—へキシルバーォキシ）一3, 3, 5 トリ メチルシクロへキサン、 1, 1—ビス（t へキシルバーォキシ）シクロへキサン、 1, 1— ビス（t ブチルパーォキシ）ー 3, 3, 5 トリメチルシクロへキサン、 1, l—(tーブチ ルバーオキシ）シクロドデカン、 2, 2—ビス（t ブチルパーォキシ）デカン等が挙げら れる。 [0069] Peroxyketals include 1,1-bis (t-hexyloxy) -1,3,5 trimethylcyclohexane, 1,1-bis (thexyloxy) cyclohexane, 1, 1- Bis (t-butylperoxy) -3,3,5 trimethylcyclohexane, 1,1- (tert-butyloxy) cyclododecane, 2,2-bis (t-butylperoxy) decane and the like.
[0070] ジアルキルパーオキサイドとしては、 a , α，一ビス（t—ブチルパーォキシ）ジィソプ 口ピルベンゼン、ジクミルパーオキサイド、 2, 5 ジメチルー 2, 5 ジ（tーブチルバ ーォキシ)へキサン、 t—ブチルタミルパーオキサイド等が挙げられる。  [0070] Examples of the dialkyl peroxide include a, α, monobis (t-butylperoxy) diisopropyl pyrbenzene, dicumyl peroxide, 2,5 dimethyl-2,5 di (t-butyloxy) hexane, and t-butyltamperper. Examples include oxides.
[0071] ハイド口パーオキサイドとしては、ジイソプロピルベンゼンハイド口パーオキサイド、ク メンノヽイド口パーオキサイド等が挙げられる。  [0071] Examples of the hydride-peroxide include diisopropylbenzene hydride-peroxide and cumene hydride-peroxide.
[0072] シリルパーオキサイドとしては、 tーブチルトリメチルシリルパーオキサイド、ビス (t- ブチル）ジメチルシリルパーオキサイド、 t—ブチルトリビュルシリルパーオキサイド、ビ ス（t ブチル）ジビュルシリルパーオキサイド、トリス（t ブチル）ビュルシリルバーオ キサイド、 tーブチルトリアリルシリルパーオキサイド、ビス（tーブチル）ジァリルシリル パーオキサイド、トリス (t—プチル)ァリルシリルパーオキサイド等が挙げられる。 [0073] 回路部材の接続端子 (電極)の腐食を抑えるために、硬化剤中に含有される塩素ィ オンや有機酸の濃度は 5000ppm以下であることが好ましい。更に、加熱分解後に 発生する有機酸が少ない硬化剤がより好ましい。また、接着剤組成物（回路接続材 料)の安定性が向上することから、硬化剤は室温、常圧下で 24時間の開放放置後に 20重量％以上の重量保持率を有することが好ま 、。 [0072] Examples of silyl peroxides include t-butyltrimethylsilyl peroxide, bis (t-butyl) dimethylsilyl peroxide, t-butyltributylsilyl peroxide, bis (tbutyl) dibulylsilyl peroxide, tris ( Examples thereof include t-butyl) butylsilyl peroxide, t-butyltriallylsilyl peroxide, bis (t-butyl) diallylsilyl peroxide, and tris (t-butyl) allylsilyl peroxide. [0073] In order to suppress corrosion of the connection terminal (electrode) of the circuit member, the concentration of chlorine ion or organic acid contained in the curing agent is preferably 5000 ppm or less. Furthermore, a curing agent with less organic acid generated after thermal decomposition is more preferable. In addition, since the stability of the adhesive composition (circuit connecting material) is improved, the curing agent preferably has a weight retention of 20% by weight or more after being left open at room temperature and normal pressure for 24 hours.
[0074] これらの重合開始剤 (遊離ラジカル発生剤）は単独又は混合して使用することがで きる。重合開始剤と分解促進剤、抑制剤等とを混合して用いてもよい。  [0074] These polymerization initiators (free radical generators) can be used alone or in combination. You may mix and use a polymerization initiator, a decomposition accelerator, an inhibitor, etc.
[0075] これらの硬化剤をポリウレタン系、ポリエステル系の高分子物質等で被覆してマイク 口カプセルィ匕したものは、可使時間が延長されるために好まし!/ヽ。  [0075] These hardeners coated with a polymer material such as polyurethane or polyester and encapsulated in a microphone mouth are preferred because the pot life is extended!
[0076] 接着剤組成物において、変性ポリウレタン榭脂と硬化性榭脂との配合比は重量比 で変性ポリウレタン榭脂:硬化性榭脂 = 1： 99〜99： 1であることが好ましぐ 10 : 90〜 90： 10であることがより好まし!/、。  [0076] In the adhesive composition, the blending ratio of the modified polyurethane resin and the curable resin is preferably the weight ratio of the modified polyurethane resin: the curable resin = 1:99 to 99: 1. 10: 90-90: 10 is more preferred!
[0077] 接着剤組成物には、流動性や、物性の向上又は導電性、異方導電性、熱伝導性 の機能の付加を目的にフィラーや粒子を添加することができる。このフィラーや粒子と しては、シリカ、三酸化二アンチモン、金、銀、銅、ニッケル、アルミニウム、ステンレス 、カーボン、セラミックがある。又は、上記金属、非導電性のガラス、セラッミク、プラス チック等を核としこの核に上記金属やカーボンを被覆したものでもよ ヽ。フィラーや粒 子の使用量は特に制限は受けないが、変性ポリウレタン榭脂を含む接着剤組成物の 全体量 100体積％に対して 0. 1〜50体積％とすることが好ましい。  [0077] Fillers and particles can be added to the adhesive composition for the purpose of improving fluidity, physical properties, or adding functions of conductivity, anisotropic conductivity, and thermal conductivity. These fillers and particles include silica, antimony trioxide, gold, silver, copper, nickel, aluminum, stainless steel, carbon, and ceramic. Alternatively, the above metal, non-conductive glass, ceramic, plastic or the like may be used as a core, and the core may be coated with the metal or carbon. The amount of filler or particles used is not particularly limited, but is preferably 0.1 to 50% by volume with respect to 100% by volume of the total amount of the adhesive composition containing the modified polyurethane resin.
[0078] 接着剤組成物は、特に、導電粒子をフイラ一として含有して 、ることが好ま U、。好 ましい導電粒子としては、 Ni等の遷移金属や、非導電性のガラス、セラミック、プラス チック等で形成された粒子を核としてその表面を Au等の貴金属カゝらなる被覆層で被 覆したものがある。このような貴金属の被覆層を有する導電粒子を用いた接着剤組 成物は、回路接続材料として用いられたときに、加熱及び加圧により変形すること〖こ より回路電極との接触面積が増カロして、特に高い接続信頼性が得られる。  [0078] The adhesive composition particularly preferably contains conductive particles as a filler. Preferred conductive particles include particles made of transition metals such as Ni, non-conductive glass, ceramics, plastics, etc., and the surface is covered with a coating layer made of a noble metal such as Au. There is what I did. Such an adhesive composition using conductive particles having a precious metal coating layer, when used as a circuit connection material, is deformed by heating and pressurization, thereby increasing the contact area with the circuit electrode. The connection reliability is particularly high.
[0079] 導電性粒子としては、 Au、 Ag、 Ni、 Cu、はんだ等の金属の粒子やカーボン粒子 等が挙げられる。ポットライフを十分に長くするため、導電性粒子は、 Au、 Ag、白金 属の金属を含むことが好ましぐ Auを含むことがより好ましい。 [0080] 接着剤組成物は、接着力及び接着剤の物性の向上を目的として、種々のポリマを 含有していてもよい。使用するポリマは特に制限を受けない。このようなポリマとして は、ビスフエノール A型フエノキシ榭脂ゃビスフエノール F型フエノキシ榭脂、ビスフエ ノール A ·ビスフエノール F共重合型フエノキシ榭脂等の汎用フエノキシ榭脂類、ポリメ タクリレート類、ポリアタリレート類、ポリイミド類、ポリウレタン類、ポリエステル類、ポリ ビュルプチラール、 SBS及びそのエポキシ変性体、 SEBS及びその変性体などを用 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。更 に、これらポリマ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、混合する榭脂同士が完全に相溶するか、又はミクロ相分離が生じて白濁する状 態であれば接着剤組成物中で好適に用いることができる。上記ポリマの分子量は特 に制限を受けるものではないが、一般に、平均分子量としては 5000〜 150000が好 ましぐ 10000〜80000力特〖こ好ましい。この値が 5000未満では接着剤の物性が 低下する傾向があり、 150000を超えると他の成分との相溶性が低下する傾向がある 。使用量は変性ポリウレタン榭脂を含む接着剤組成物 100重量部に対して 20〜320 重量部とすることが好ましい。この使用量が 20重量部未満又は 320重量部を超える 場合は、流動性や接着性が低下する傾向がある。 [0079] Examples of the conductive particles include metal particles such as Au, Ag, Ni, Cu, and solder, and carbon particles. In order to make the pot life sufficiently long, the conductive particles preferably contain Au, Ag, or a platinum group metal, and more preferably contain Au. [0080] The adhesive composition may contain various polymers for the purpose of improving the adhesive strength and the physical properties of the adhesive. The polymer used is not particularly limited. Such polymers include bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol A · bisphenol F copolymer type phenoxy resin, polymethacrylates, polyacrylates, etc. Rates, polyimides, polyurethanes, polyesters, polybutyl petital, SBS and its epoxy modified products, SEBS and its modified products, and the like can be used. These can be used alone or in admixture of two or more. In addition, these polymers may contain siloxane bonds and fluorine substituents. These can be suitably used in the adhesive composition as long as they are completely compatible with each other or mixed with microphase separation and become cloudy. The molecular weight of the polymer is not particularly limited, but in general, the average molecular weight is preferably 5000 to 150,000, more preferably 10,000 to 80,000. If this value is less than 5,000, the physical properties of the adhesive tend to decrease, and if it exceeds 150,000, the compatibility with other components tends to decrease. The amount used is preferably 20 to 320 parts by weight per 100 parts by weight of the adhesive composition containing the modified polyurethane resin. When the amount used is less than 20 parts by weight or more than 320 parts by weight, fluidity and adhesiveness tend to be lowered.
[0081] 接着剤組成物には適宜、軟化剤、促進剤、老化防止剤、着色剤、難燃剤、カツプリ ング剤を添加してもよい。  [0081] A softening agent, an accelerator, an anti-aging agent, a coloring agent, a flame retardant, and a cutting agent may be appropriately added to the adhesive composition.
[0082] 接着剤組成物は、常温で液状である場合にはペースト状の状態で使用することが できる。室温で固体の場合には、加熱により液状ィ匕して使用してもよいし、溶剤を使 用してペーストイ匕してもよい。使用できる溶剤としては、接着剤組成物及び添加剤と 反応性がなぐかつ十分な溶解性を示すものであれば、特に制限は受けないが、常 圧での沸点が 50〜150°Cであるものが好ましい。沸点が 50°C以下の場合、室温で 放置すると揮発するおそれがあり、開放系での使用が制限される。また、沸点が 150 °C以上だと、溶剤を揮発させることが難しぐ接着後の信頼性に悪影響を及ぼすおそ れがある。  [0082] The adhesive composition can be used in a paste state when it is liquid at room temperature. In the case of a solid at room temperature, it may be used in a liquid form by heating, or may be pasted using a solvent. Solvents that can be used are not particularly limited as long as they are not reactive with the adhesive composition and additives and exhibit sufficient solubility, but have a boiling point of 50 to 150 ° C at normal pressure. Those are preferred. If the boiling point is 50 ° C or less, there is a risk of volatilization if left at room temperature, limiting the use in open systems. If the boiling point is 150 ° C or higher, it may be difficult to evaporate the solvent, which may adversely affect the reliability after bonding.
[0083] 接着剤組成物はフィルム状に成形してフィルム状接着剤として用いることもできる。  [0083] The adhesive composition can be formed into a film and used as a film adhesive.
図 1は、本発明に係る接着剤組成物を用いたフィルム状接着剤の一実施形態を示す 断面図である。フィルム状接着剤 1においては、導電粒子 5が接着剤組成物中の他 の成分からなる榭脂層 3中に分散して 、る。 FIG. 1 shows an embodiment of a film adhesive using the adhesive composition according to the present invention. It is sectional drawing. In the film adhesive 1, the conductive particles 5 are dispersed in the resin layer 3 made of other components in the adhesive composition.
[0084] フィルム状接着剤 1は、例えば、接着剤組成物に必要により溶剤等を加えるなどし た溶液を、フッ素榭脂フィルム、ポリエチレンテレフタレートフィルム、離形紙等の剥離 性基材上に塗布し、ある！、は不織布等の基材に溶液を含浸させて剥離性基材上に 載置し、溶剤等を除去して得られる。接着剤組成物をフィルム状で使用すると取扱性 等の点から一層便利である。  [0084] The film-like adhesive 1 is, for example, a solution obtained by adding a solvent or the like to the adhesive composition as necessary on a peelable substrate such as a fluorine resin film, a polyethylene terephthalate film, or a release paper. There is! Is obtained by impregnating a base material such as a non-woven fabric with a solution and placing it on a peelable base material and removing the solvent. Use of the adhesive composition in the form of a film is more convenient from the viewpoint of handleability.
[0085] 接着剤組成物は熱膨張係数の異なる異種の被着体同士を接着するための接着剤 として好適に使用することができる。具体的には、回路電極を有する回路部材同士を 接着するとともに電気的に接続するために用いられる回路接続材料や、 CSP用エラ ストマー、 CSP用アンダーフィル材、 LOCテープ及びダイボンド接着材等に代表され る半導体素子接着剤として使用することができる。銀ペースト、銀フィルム及び異方 導電接着剤に代表される回路接続材料は、例えば、半導体チップ、抵抗体チップ、 コンデンサチップ等のチップ部品や、プリント基板等のような回路部材同士を接続す るために用いられる。  [0085] The adhesive composition can be suitably used as an adhesive for bonding different types of adherends having different thermal expansion coefficients. Specific examples include circuit connection materials used for bonding and electrically connecting circuit members having circuit electrodes, CSP elastomers, CSP underfill materials, LOC tapes, and die bond adhesives. It can be used as a semiconductor element adhesive. Circuit connection materials typified by silver paste, silver film and anisotropic conductive adhesive connect, for example, chip components such as semiconductor chips, resistor chips, capacitor chips, and circuit members such as printed boards. Used for.
[0086] 図 2は、本発明に係る回路部材の接続構造の一実施形態を示す断面図である。図 2に示す回路部材の接続構造 101は、第一の基板 11及びこれの主面上に接着剤層 12を介して形成された第一の回路電極 13を有する第一の回路部材 10と、第二の基 板 21及びこれの主面上に形成された第二の回路電極 23を有する第二の回路部材 2 0とを備えている。そして、第一の回路電極 13と第二の回路電極 23とが電気的に接 続されるように第一の回路部材 10と第二の回路部材 20とがフィルム状接着剤 1で接 着されている。第一の回路部材 10及び第二の回路部材 20の対向面間を充填するよ うに、フィルム状接着剤 1が硬化して形成される硬化物である回路接続部材 laが形 成されている。  FIG. 2 is a cross-sectional view showing an embodiment of a circuit member connection structure according to the present invention. A circuit member connection structure 101 shown in FIG. 2 includes a first circuit member 10 having a first substrate 11 and a first circuit electrode 13 formed on the main surface thereof via an adhesive layer 12; And a second circuit member 20 having a second circuit electrode 23 and a second circuit electrode 23 formed on the main surface thereof. Then, the first circuit member 10 and the second circuit member 20 are bonded with the film adhesive 1 so that the first circuit electrode 13 and the second circuit electrode 23 are electrically connected. ing. The circuit connecting member la, which is a cured product formed by curing the film adhesive 1, is formed so as to fill the space between the opposing surfaces of the first circuit member 10 and the second circuit member 20.
[0087] 回路部材の接続構造 101においては、第一の回路電極 13と第二の回路電極 23と が対畤するとともに電気的に接続されている。  [0087] In the circuit member connection structure 101, the first circuit electrode 13 and the second circuit electrode 23 face each other and are electrically connected.
[0088] 回路接続部材 laは、榭脂層 3に由来する絶縁層 3a及びこれに分散している導電 粒子 5から構成される。第一の回路電極 13と第二の回路電極 23とは、導電粒子 5を 介して電気的に接続されて!、る。 [0088] The circuit connecting member la is composed of an insulating layer 3a derived from the resin layer 3 and conductive particles 5 dispersed therein. The first circuit electrode 13 and the second circuit electrode 23 It is electrically connected through!
[0089] 第一の基板 11は、ポリエステルテレフタレート、ポリエーテルサルフォン、エポキシ 榭脂、アクリル榭脂及びポリイミド榭脂からなる群より選ばれる少なくとも 1種の榭脂を 含む榭脂フィルムである。  [0089] The first substrate 11 is a resin film containing at least one resin selected from the group consisting of polyester terephthalate, polyethersulfone, epoxy resin, acrylic resin, and polyimide resin.
[0090] 回路電極 13は、電極として機能し得る程度の導電性を有する材料 (好ましくは金、 銀、錫、白金族の金属及びインジウム 錫酸化物からなる群より選ばれる少なくとも 一種)で形成されている。複数の回路電極 13が、接着剤層 12を介して第一の基板 1 1の主面上に接着されている。接着剤層 12は、フレキシブル配線板等の回路部材に ぉ 、て通常用いられる接着剤等で形成される。  [0090] The circuit electrode 13 is formed of a material having conductivity sufficient to function as an electrode (preferably at least one selected from the group consisting of gold, silver, tin, platinum group metals, and indium tin oxide). ing. A plurality of circuit electrodes 13 are bonded onto the main surface of the first substrate 11 via the adhesive layer 12. The adhesive layer 12 is formed of a commonly used adhesive or the like for circuit members such as flexible wiring boards.
[0091] 第二の基板 21はガラス基板であり、第二の基板 21の主面上には、複数の第二の 回路電極 23が形成されて 、る。  The second substrate 21 is a glass substrate, and a plurality of second circuit electrodes 23 are formed on the main surface of the second substrate 21.
[0092] 回路部材の接続構造 101は、例えば、第一の回路部材 10と、上記のフィルム状接 着剤 1と、第二の回路部材 20とを、第一の回路電極 13と第二の回路電極 23とが対 畤するようにこの順に積層した積層体を加熱及び加圧することにより、第一の回路電 極 13と第二の回路電極 23とが電気的に接続されるように第一の回路部材 10と第二 の回路部材 20とを接着する方法によって、得られる。  [0092] The circuit member connection structure 101 includes, for example, the first circuit member 10, the film-like adhesive 1 and the second circuit member 20, and the first circuit electrode 13 and the second circuit member 20. The first and second circuit electrodes 13 and 23 are electrically connected to each other by heating and pressurizing the laminate laminated in this order so that the circuit electrode 23 and the circuit electrode 23 are opposed to each other. The circuit member 10 and the second circuit member 20 are bonded to each other.
[0093] この方法においては、まず、支持フィルム上に形成されているフィルム状接着剤 1を 第二の回路部材 20上に貼り合わせた状態で加熱及び加圧して回路接続材料 1を仮 接着し、支持フィルムを剥離してから、第一の回路部材 10を回路電極を位置合わせ しながら載せて、積層体を準備することができる。  [0093] In this method, first, the circuit-connecting material 1 is temporarily bonded by heating and pressurizing the film-like adhesive 1 formed on the support film on the second circuit member 20. After the support film is peeled off, the first circuit member 10 can be placed while aligning the circuit electrodes to prepare a laminate.
[0094] 上記積層体を加熱及び加圧する条件は、接着剤組成物の硬化性等に応じて、接 着剤組成物が硬化して十分な接着強度が得られるように、適宜調整される。  [0094] The conditions for heating and pressurizing the laminate are appropriately adjusted according to the curability and the like of the adhesive composition so that the adhesive composition is cured and sufficient adhesive strength is obtained.
[0095] 本発明に係る回路部材の接続構造は、上記実施形態に限定されないことは言うま でもない。例えば、第一の回路部材において、第一の基板の主面上に第一の回路 電極 13が接着剤層を介することなく直接形成されいてもよい。  It goes without saying that the circuit member connection structure according to the present invention is not limited to the above embodiment. For example, in the first circuit member, the first circuit electrode 13 may be directly formed on the main surface of the first substrate without an adhesive layer interposed therebetween.
実施例  Example
[0096] 以下に、本発明を実施例に基づいて具体的に説明する力 本発明はこれに限定さ れるものではない。 [0097] (変性ポリウレタン榭脂 PU—1の合成） [0096] Hereinafter, the present invention will be described specifically based on examples. The present invention is not limited to this. [0097] (Synthesis of modified polyurethane resin PU-1)
ォキシジフタル酸二無水物（1. Omol)、 2 ヒドロキシェチルメタタリレート（0. 2mo 1)、トリェチルァミン（0. Olmol)及びヒドロキノン（0. Olmol)を γ—ブチロラタトン中 で窒素雰囲気下、 80°Cで 5時間攪拌し、ォキシジフタル酸二無水物の一部に 2 ヒ ドロキシェチルメタタリレートが付加したォキシジフタル酸二無水物混合液を得た。  Oxydiphthalic dianhydride (1. Omol), 2 hydroxyethyl methacrylate (0.2 mol), triethylamine (0. Olmol) and hydroquinone (0. Olmol) in γ-butyrolatatone at 80 ° The mixture was stirred at C for 5 hours to obtain a mixed solution of oxydiphthalic dianhydride in which 2 hydroxyxetyl metatalylate was added to a part of oxydiphthalic dianhydride.
[0098] 一方、ジフエ-ルメタン一 4, 4，一ジイソシァネート（1. Omol)、ジフエ-ルメタン一 2 , 4，ージイソシァネート（1. Omol)及び平均分子量 2000のポリテトラメチレングリコ ール（0. 8mol)を 1ーメチルー 2 ピロリドン中で窒素雰囲気下、 100°Cで 2時間反 応させ、そこに、上記ォキシジフタル酸二無水物混合液をカ卩え、更に、 80°Cで 5時間 反応させた。更に、ベンジルアルコールを添加し 80°Cで 2時間攪拌し、反応を終了し た。反応後の溶液を激しく攪拌させた水に入れた。析出した沈殿物を濾別し、メタノ ールで洗浄後、真空中 60°Cで 8時間乾燥させて、一般式 (I)において Z (R) —の 部分が下記化学式 (Ha)、 (Ilia)又は (IVa)で表される 2価の基である分子鎖を含む 変性ポリウレタン榭脂 PU— 1を得た。  [0098] On the other hand, diphenylmethane 1,4,4,1 diisocyanate (1. Omol), diphenylmethane 1,2,4, -diisocyanate (1. Omol) and polytetramethylene glycol having an average molecular weight of 2000 (0.8 mol) was reacted in 1-methyl-2-pyrrolidone under nitrogen atmosphere at 100 ° C for 2 hours, and the above oxydiphthalic dianhydride mixture was added thereto, and further at 80 ° C for 5 hours. Reacted. Further, benzyl alcohol was added and stirred at 80 ° C. for 2 hours to complete the reaction. The solution after the reaction was placed in vigorously stirred water. The deposited precipitate was filtered off, washed with methanol, dried in vacuum at 60 ° C for 8 hours, and in the general formula (I), the part of Z (R) — is represented by the following chemical formula (Ha), (Ilia ) Or (IVa) to obtain a modified polyurethane resin PU-1 containing a molecular chain which is a divalent group represented by (IVa).
[0099] [化 7]  [0099] [Chemical 7]
Figure imgf000023_0001
Figure imgf000023_0001
[0100] 変性ポリウレタン榭脂 PU— 1の GPCを測定したところ、ポリスチレン換算で、 Mw= 27000、 Mn= 12500であった。 [0101] (変性ポリウレタンイミド PU— 2の合成） [0100] When the GPC of the modified polyurethane resin PU-1 was measured, it was Mw = 27000 and Mn = 12,500 in terms of polystyrene. [0101] (Synthesis of modified polyurethaneimide PU-2)
平均分子量 2000のポリテトラメチレングリコール（0. 8mol)を平均分子量 2000の ポリ（へキサメチレンカーボネート） (0. 8mol)に代えた他は PU— 1と同様にして、一 般式 (I)において Z (R) —の部分が下記化学式 (IIa)、 （Ilia)又は (IVa)で表され る 2価の基である分子鎖を含む変性ポリウレタン榭脂 PU— 2を得た。変性ポリウレタ ン榭脂 PU— 2の GPCを測定したところ、ポリスチレン換算で Mw= 25000、 Mn= l 2000であった。  Similar to PU-1, except that polytetramethylene glycol (0.8 mol) with an average molecular weight of 2000 was replaced with poly (hexamethylene carbonate) (0.8 mol) with an average molecular weight of 2000, in general formula (I) A modified polyurethane resin PU-2 containing a molecular chain in which the part of Z (R) — is a divalent group represented by the following chemical formula (IIa), (Ilia) or (IVa) was obtained. When the GPC of the modified polyurethane resin PU-2 was measured, it was Mw = 25,000 and Mn = 2000 in terms of polystyrene.
[0102] (実施例 1)  [0102] (Example 1)
PU—1をメチルェチルケトンに固形分濃度 40質量％で溶解し、硬化剤として 1, 1 —ビス（t—へキシルバーォキシ）一3, 3, 5—トリメチルシクロへキサン（パーへキサ T MH、 日本油脂株式会社製商品名）を固形重量比で PU—1の量 100重量部に対し て 2重量部加え、更に導電粒子を 1. 5体積％加えてこれを分散した。導電性子は、 ポリスチレンを核とする粒子の表面に厚み 0. 2 mのニッケル層を設け、このニッケ ル層の外側に厚み 0. 02 mの金層を設けた平均粒径 5 m、比重 2. 5のものを用 いた。導電粒子を分散した溶液を厚み 80 mのフッ素榭脂フィルムに塗工装置を用 いて塗布し、 70°C、 10分の熱風乾燥によって接着剤層の厚みが 20 mのフィルム 状回路接続用異方導電接着剤 (フィルム状接着剤)を得た。  PU-1 is dissolved in methyl ethyl ketone at a solid concentration of 40% by mass, and 1, 1-bis (t-hexyloxy) -1,3,5-trimethylcyclohexane (perhexane T MH) is used as a curing agent. , Nippon Oil & Fat Co., Ltd. (trade name) was added in an amount of 2 parts by weight based on 100 parts by weight of PU-1 in terms of solid weight ratio, and 1.5% by volume of conductive particles were further dispersed. The conductive element has an average particle size of 5 m and a specific gravity of 2 m, with a 0.2 m thick nickel layer on the surface of polystyrene core particles and a 0.02 m thick gold layer outside the nickel layer. I used 5 items. The conductive particle-dispersed solution is applied to an 80-m thick fluororesin film using a coating device, and dried with hot air at 70 ° C for 10 minutes. The adhesive layer has a thickness of 20 m. A directionally conductive adhesive (film adhesive) was obtained.
[0103] 上記製法によって得たフィルム状接着剤を用いて、 2層フレキシブル回路板 (FPC) と、ガラス基板 (厚み 1. lmm、表面抵抗 20 Ω Ζ口）上に厚み 2 /z mの酸化インジゥ ム (ITO)の薄層が電極として形成されて 、る回路部材とを、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株式会社製)を用いて加熱及び加圧を行 つて幅 2mmにわたり接続し、回路部材の接続構造である接続体を作製した。 FPCは 厚さ 40umのポリイミドフィルム上にライン幅 50 μ m、ピッチ 100 μ m、厚み 10 μ mの 銅回路 500本を蒸着により形成したものを用いた。また、加熱及び加圧は 170°C、 3 MPaで 20秒間行った。 [0103] Using the film-like adhesive obtained by the above-mentioned manufacturing method, a 2-layer flexible circuit board (FPC) and a 2 / zm thick indium oxide oxide on a glass substrate (thickness 1. lmm, surface resistance 20 Ω well) A thin layer of ITO (ITO) is formed as an electrode, and the circuit member is heated and pressed using a thermocompression bonding device (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.) over a width of 2 mm. The connection body which is the connection structure of a circuit member was produced. The FPC used was formed by depositing 500 copper circuits with a line width of 50 μm, a pitch of 100 μm, and a thickness of 10 μm on a polyimide film with a thickness of 40 μm. Heating and pressurization were performed at 170 ° C and 3 MPa for 20 seconds.
[0104] 得られた接続体の接着強度を、 JIS— Z0237に準じて 90度剥離法で測定すること により評価した。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 U TM— 4 (剥離速度 50mmZmin、 25°C)を使用した。 [0105] (実施例 2) [0104] The adhesive strength of the obtained connected body was evaluated by measuring by 90 degree peeling method according to JIS-Z0237. As a measuring device for adhesive strength, Tensilon U TM-4 (peeling speed 50 mmZmin, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used. [0105] (Example 2)
PU- 1に代えて PU— 2を用いた他は実施例 1と同様にしてフィルム状接着剤を作 製し、これを用いて実施例 1と同様に接続体を作製し、その接着強度を測定した。  A film-like adhesive was prepared in the same manner as in Example 1 except that PU-2 was used instead of PU-1, and a connection body was prepared in the same manner as in Example 1 using this film. It was measured.
[0106] (実施例 3) [Example 3]
80重量部の PU— 1、硬化性榭脂としての 20重量部のイソシァヌル酸 EO変性ジァ タリレート (東亞合成製、ァロニックス M215)、及び硬ィ匕剤としての 2重量部の 1, 1 - ビス（t—へキシルバーォキシ）一3, 3, 5—トリメチルシクロへキサン（パーへキサ TM H、 日本油脂株式会社製商品名）を混合した。得られた混合物に実施例 1と同様の 導電粒子を 1. 5体積％加えてこれを分散して接着剤組成物を調製した。この接着剤 を用いて実施例 1と同様にフィルム状接着剤を作製した。そして、得られたフィルム状 接着剤を用いて実施例 1と同様にして接続体を作製し、その接着強度を測定した。  80 parts by weight of PU-1, 20 parts by weight of isocyanuric acid EO-modified ditalylate (Toray Gosei, Alonix M215) as curable resin, and 2 parts by weight of 1,1-bis as a hardener (T-hexyloxy) 1,3,3,5-trimethylcyclohexane (Perhexa ™ H, product name manufactured by NOF Corporation) was mixed. The obtained mixture was dispersed by adding 1.5% by volume of the same conductive particles as in Example 1 to prepare an adhesive composition. A film adhesive was produced in the same manner as in Example 1 using this adhesive. And the connection body was produced like Example 1 using the obtained film adhesive, and the adhesive strength was measured.
[0107] (比較例 1) [0107] (Comparative Example 1)
PU—1に代えてウレタンアタリレート (UA— 511、新中村ィ匕学工業株式会社製)を 用いた他は実施例 1と同様にして、接続体の接着強度を測定した。  The adhesive strength of the connector was measured in the same manner as in Example 1 except that urethane acrylate (UA-511, manufactured by Shin-Nakamura Engineering Co., Ltd.) was used instead of PU-1.
[0108] (比較例 2) [0108] (Comparative Example 2)
PU—1に代えてジフエ-ノレメタン一 4, 4'—ジイソシァネート（0. 5mol)、ジフエ- ルメタン 2, 4'—ジイソシァネート（0. 5mol)及び平均分子量 2000のポリテトラメチ レングリコール（1. Omol)から得られるポリウレタン（平均分子量 Mw= 57000、 Mn = 35000)を用いて実施例 3と同様にして接続体の接着強度を測定した。  Instead of PU-1, diphenylmethane 4,4'-diisocyanate (0.5 mol), diphenylmethane 2,4'-diisocyanate (0.5 mol) and polytetramethylene glycol (1. Omol) with an average molecular weight of 2000 Using the resulting polyurethane (average molecular weight Mw = 57000, Mn = 35000), the adhesive strength of the connection body was measured in the same manner as in Example 3.
[0109] [表 1] [0109] [Table 1]
接着強度（N Zm ) 実施例 1 600 実施例 2 500 実施例 3 580 比較例 1 1 80 比較例 2 200 Adhesive strength (N Zm) Example 1 600 Example 2 500 Example 3 580 Comparative example 1 1 80 Comparative example 2 200
実施例及び比較例の評価結果を表 1にまとめて示す。表 1に示されるように、従来 のポリウレタン榭脂を用いた比較例 1、 2の接続体は接着強度が必ずしも十分でなか つたのに対して、本発明に係る変性ポリウレタン榭脂を用いた実施例の接続体は十 分に大きな接着強度を示した。 The evaluation results of Examples and Comparative Examples are summarized in Table 1. As shown in Table 1, the connecting bodies of Comparative Examples 1 and 2 using conventional polyurethane resin did not necessarily have sufficient adhesive strength, whereas Examples using the modified polyurethane resin according to the present invention were used. The connected body showed sufficiently high adhesive strength.

Claims

請求の範囲 [1] 下記一般式 (I)で表される分子鎖を含む変性ポリウレタン榭脂。 Claims [1] A modified polyurethane resin containing a molecular chain represented by the following general formula (I):
[化 1]  [Chemical 1]
[2]
Figure imgf000027_0001
[2]
Figure imgf000027_0001
[式 (Π)、（III)及び (IV)中、 Aは炭素数 4以上の 4価の有機基、 Rは反応性を有する 基、を示す。 ] [In the formulas (Π), (III) and (IV), A represents a tetravalent organic group having 4 or more carbon atoms, and R represents a reactive group. ]
[3] (a)、（b)及び (c)の合計量を基準として、（a)の割合が 10〜90mol%、（b)の割合 が O〜90mol%、（c)の割合力^〜 90mol%である、請求項 2記載の変性ポリウレタン 樹脂。 [3] Based on the total amount of (a), (b) and (c), the proportion of (a) is 10 to 90 mol%, the proportion of (b) is O to 90 mol%, and the proportion power of (c) ^ The modified polyurethane resin according to claim 2, which is ˜90 mol%.
[4] 前記反応性を有する基が (メタ）アタリレート基を有する基である、請求項 1〜3のい ずれか一項に記載の変性ポリウレタン榭脂。  [4] The modified polyurethane resin according to any one of claims 1 to 3, wherein the reactive group is a group having a (meth) acrylate group.
[5] 請求項 1〜4のいずれか一項に記載の変性ポリウレタン榭脂を含有する接着剤組 成物。 [5] An adhesive composition containing the modified polyurethane resin according to any one of claims 1 to 4.
[6] 硬化性榭脂を更に含有する、請求項 5記載の接着剤組成物。  6. The adhesive composition according to claim 5, further comprising a curable rosin.
[7] 前記硬化性榭脂がラジカル重合により硬化する榭脂であり、 [7] The curable resin is a resin cured by radical polymerization,
光照射又は加熱により遊離ラジカルを発生する硬化剤を含有している、請求項 6記 載の接着剤組成物。  7. The adhesive composition according to claim 6, comprising a curing agent that generates free radicals upon light irradiation or heating.
[8] 導電粒子を更に含有する、請求項 5〜7の ヽずれか一項に記載の接着剤組成物。  [8] The adhesive composition according to any one of claims 5 to 7, further comprising conductive particles.
[9] 第一の基板及びこれの主面上に形成された第一の回路電極を有する第一の回路 部材と、第二の基板及びこれの主面上に形成された第二の回路電極を有する第二 の回路部材とを請求項 5〜8のいずれか一項に記載の接着剤組成物で接着すること により、前記第一の回路電極と前記第二の回路電極とを電気的に接続する、回路部 材の接続方法。 [9] A first circuit member having a first circuit electrode and a first circuit electrode formed on the main surface of the first substrate, and a second circuit electrode formed on the second substrate and the main surface thereof Is bonded to the second circuit member with the adhesive composition according to any one of claims 5 to 8, thereby electrically connecting the first circuit electrode and the second circuit electrode. How to connect circuit components.
[10] 第一の基板及びこれの主面上に形成された第一の回路電極を有する第一の回路 部材と、  [10] a first circuit member having a first substrate and a first circuit electrode formed on the main surface of the first substrate;
第二の基板及びこれの主面上に形成された第二の回路電極を有する第二の回路 部材と、を備え、  A second circuit member having a second circuit electrode and a second circuit electrode formed on the main surface of the second substrate,
前記第一の回路電極と前記第二の回路電極とが電気的に接続されるように前記第 一の回路部材と前記第二の回路部材とが請求項 5〜8のいずれか一項に記載の接 着剤組成物で接着されている、回路部材の接続構造。  9. The first circuit member and the second circuit member according to claim 5, wherein the first circuit member and the second circuit member are electrically connected to each other. A circuit member connection structure bonded with an adhesive composition.
PCT/JP2006/301356 2005-05-27 2006-01-27 Modified polyurethane resin and adhesive composition using the same, method for connecting circuit member and connection structure of circuit member WO2006126305A1 (en)

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