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WO2007023834A1 - Adhesive composition - Google Patents

Adhesive composition Download PDF

Info

Publication number
WO2007023834A1
WO2007023834A1 PCT/JP2006/316458 JP2006316458W WO2007023834A1 WO 2007023834 A1 WO2007023834 A1 WO 2007023834A1 JP 2006316458 W JP2006316458 W JP 2006316458W WO 2007023834 A1 WO2007023834 A1 WO 2007023834A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive composition
composition according
ethyl
adhesive
methyl
Prior art date
Application number
PCT/JP2006/316458
Other languages
French (fr)
Japanese (ja)
Inventor
Takahiro Matsuse
Hideki Kitano
Masami Aoki
Original Assignee
Bridgestone Corporation
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 Bridgestone Corporation filed Critical Bridgestone Corporation
Priority to JP2007532143A priority Critical patent/JPWO2007023834A1/en
Publication of WO2007023834A1 publication Critical patent/WO2007023834A1/en

Links

Classifications

    • 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
    • H05K3/303—Surface mounted components, e.g. affixing before soldering, aligning means, spacing means
    • H05K3/305—Affixing by adhesive
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/711—Monoisocyanates or monoisothiocyanates containing oxygen in addition to isocyanate oxygen
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H01L21/563—Encapsulation of active face of flip-chip device, e.g. underfilling or underencapsulation of flip-chip, encapsulation preform on chip or mounting substrate
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    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
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Definitions

  • the present invention relates to an adhesive composition (hereinafter, also simply referred to as “composition”), and more particularly to an adhesive composition that is suitably used for mounting various electronic components such as an IC package.
  • Underfill is sufficient to penetrate and cure between IC chip substrates, to ensure connection reliability against stresses such as heat and external load, and to satisfy desired electrical characteristics, etc.
  • thermosetting resins such as epoxy resins are most commonly used.
  • a technique using an anisotropic conductive material in which a conductive filler is uniformly dispersed in a resin is also known (for example, , Described in Patent Documents 1 and 2).
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2004-292827 (Claims)
  • Patent Document 2 JP 2004-256650 A (Claims)
  • thermocompression treatment is performed at a high temperature of 100 ° C or more for several tens of seconds in the mounting process or heat treatment process.
  • the electronic component body may be damaged.
  • the connection part contains high internal stress. Insufficient power, causing problems with electrical characteristics and long-term durability It was. Accordingly, there has been a demand for the realization of a material that does not need to be subjected to a high temperature and enables a low-temperature and short-time connection process when applied to mounting electronic components.
  • an object of the present invention is to provide sufficient adhesiveness for mounting electronic components, satisfy desired electrical characteristics and long-term durability, and be used in conventional thermosetting resin. It is to provide an adhesive composition that has no problems.
  • the first adhesive composition of the present invention includes a photoacid generator, 380-: a dye having absorption at LOOOnm, and a photopower thione polymerization system composition, and includes visible light or near-infrared light.
  • a photoacid generator 380-: a dye having absorption at LOOOnm
  • a photopower thione polymerization system composition and includes visible light or near-infrared light.
  • the second adhesive composition of the present invention includes a radical generator, 380-: a dye having absorption at LOOOnm, and a photoradical polymerization composition, and is capable of visible light or near-infrared light.
  • the adhesive composition of the present invention can be suitably used as a film or paste.
  • the adhesive composition of the present invention preferably contains a photosensitizer that preferably contains a conductive filler.
  • the adhesive composition of the present invention can be suitably used as an underfill in flip chip mounting or an adhesive for connecting one electrode to another.
  • an adhesive composition that has sufficient adhesiveness and satisfies desired electrical characteristics and long-term durability.
  • it can be cured by irradiation with visible light or near-infrared radiation, adverse effects due to heat can be eliminated, and even when there is an opaque part with a high degree of concealment, it can be cured reliably. It is possible to do this.
  • visible to near-infrared light used for curing has less adverse effects on the human body than light in the ultraviolet region, and is highly safe, thick, There are also merits such as being able to cure in area.
  • the resin composition is affected by white light. However, in the case of curing in the early modern outside line region, the effect of white light is small, so that the handling property is good.
  • FIGS. 1A and 1B are schematic cross-sectional views showing one embodiment of flip-chip mounting.
  • FIG. 2 is a schematic sectional view of electrode-electrode connection.
  • the first photocurable resin composition of the present invention comprises a photoacid generator, a dye having absorption at 380 to 1000 nm, and a photopower thione polymerization composition, and is irradiated with visible light or near infrared light.
  • An adhesive composition that generates acid and initiates a cationic polymerization reaction to cure, and is used for mounting electronic components. In this case, electron transfer occurs between the dye that has absorbed near infrared rays and the photoacid generator, and the photoacid generator generates an acid.
  • Examples of the dye having absorption in the visible region (approximately 380 to 760 nm) used in the present invention include, for example, ketocoumarin-based dyes such as 3, 3 ', 4, 4, -carborubbis 7- (jetylamino) coumarin.
  • examples of the dye having absorption in the near-infrared region include, for example, powers such as pyrylium, thiopyrylium, cyanine, indolium, and triazine. It is not something.
  • These dyes may be used singly or in combination of two or more.
  • the adhesive composition of the present invention usually 0.1 to 20% by mass, particularly 1 to 10% by mass. It can be contained in%.
  • photoacid generators include 1,2 naphthoquinone-2 diazido 5-sulfonic acid chloride, 1,2 naphthoquinone 1-2 diazido 1-5-sulfonic acid sodium, 1,2 naphthoquinone 1-2 diazido 5-sulfone Potassium acid, 1, 2 Naphthoquinone-2-diazido 5-methyl sulfonate 1, 2-naphthoquinone 2-diazido 5-ethyl sulphonate 1, 2, naphthoquinone-2 diazido 5-sulphonic acid prill, 1, 2 naphthoquinone-2 di Azido 5-cetyl sulfonate, 1,2 naphthoquinone 1-2 diazido 4-sulfonic acid chloride, 1, 2 naphthoquinone 1-2 diazide 4- sodium sulfonate, 1, 2-naphthoquinone 2 diazide 4- sodium
  • Aliphatic diols such as ethylene glycol, 1,3 propanediol, 1,6 hexanediol, 1,10-decanediol, 1,16 hexadecanediol and 1,2 naphthoquinone 1-2 diazido 4 (or 1 5) —Condensates with sulfonic acid chlorides, condensed aromatics such as phenol, hydroquinone, catechol, resorcinol, pyrogallol, etc.
  • 1, 2 —naphthoquinone-2-diazide-4 (or 15) sulfonic acid chloride 2 , 3, 4 trihydroxybenzophenone, 2, 2 ', 4, 4'-tetrahydroxybenzophenone, 2, 2,, 3, 4, 4' pentahydroxybenzophenone, and other polyhydroxybenzophenones 1, 2-naphthoquinone 2 diazide 4 (or 5) sulfonic acid chloride, for example, trihydroxybenzophenone di (1, 2 naphthoquinone-2-diazide 4-sulfonic acid) ester, trihydroxybenzophenone tri (1, 2 naphthoquinone-2-diazide-1-4-sulfonic acid) ester, tetrahydroxybenzophenone di (1,2-naphthoquinone-1-2-diazide-1-4-sulfonic acid) Esters, tetrahydroxybenzophenone tri (1,2 naphthoquinone
  • a group force consisting of allyldiazo-um salt, gallo-rhodonium salt, triarylsulfomum salt, dialkylphenacylsulfomum salt and sulfonate compound is also selected.
  • Any one or more photoacid generators are used.
  • a photoacid generator that generates Bronsted acid or Lewis acid by irradiation with visible light or near infrared light is preferable.
  • Photoacid generator, in the adhesive composition of the present invention usually 0.1 to 20% by weight, in particular can be contained 1-10 wt 0/0 ⁇ trowel.
  • examples of the photothion polymerization composition include a polymerizable monomer having one oxetane ring, and specific examples thereof include 3-ethyl-3-hydroxymethyloxetane, 3- ( (Meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxeta-lmethoxy) methylbenzene, 4-fluoro [1- (3-ethyl-3-oxetal-methoxy) methyl] benzene, 4-methoxy- [1 (3 Ethyl-3-oxetamethyl) methyl] benzene, [1 (3-ethyl-3-oxeta-methoxy) ethyl] ether, isobutoxymethyl (3-ethyl-3-oxeta-methyl) ether, isovoloxyl --Ethyl-3-oxeta-methyl) ether, isobutyl (3-ethyl-3-hydroxymethyloxe
  • polymerizable monomers having two oxetane rings include 1,4 bis ⁇ [(3 ethyl-3-oxeta-l) methoxy] methyl ⁇ benzene, bis ⁇ [((1 ethyl) 3-oxetal-].
  • polymerizable monomer having 3 to 5 tan rings include trimethylolpropane tris (3-ethyl-3-oxeta-methyl) ether, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether. , Pentaerythritol tetrakis (3-ethyl-3-oxeta-methyl) ether, dipentaerythritol pentakis (3-ethyl 3-oxeta-methyl) ether, and the like.
  • examples of glycidyl ether type epoxy compounds include di- or polyglycidyl of polyvalent phenols having an aromatic nucleus or an alkylene oxide adduct thereof. And di- or polyglycidyl ethers of ethers, aliphatic polyhydric alcohols or alkylene oxide adducts thereof.
  • Polyglycidyl ethers diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4 butanediol, 1,6 hexanediol, or alkylene oxide adducts thereof; dialkyl ethers of polyalkylene glycols such as polyethylene glycol and polypropylene glycol Glycidyl ether; neopentyl glycol, dibumonone neopentyl glycol, or diglycidyl ether with an alkylene oxide of these glycols; trimethylol ether , Trimethylolpropane, glycerin, or di- or triglycidyl ethers of alkylene oxides
  • alicyclic epoxy compound for example, a compound having a cycloalkane ring such as cyclohexene or cyclopentene ring is epoxyized with an appropriate oxidizing agent such as hydrogen peroxide or peracid. And cyclohexene oxide-containing compounds containing cyclopentene oxide.
  • Epoxycyclohexylmethyl) ether ethylene bis (3,4-epoxycyclohexanecarboxylate), epoxidized tetrabenzyl alcohol, latataton modified 3, 4 epoxycyclohexenoremethinole 3 ', 4' Examples thereof include epoxycyclohexanecanolevoxylate, latatatone-modified epoxidized tetrahydrobenzyl alcohol, and cyclohexene oxide.
  • a spiro ortho carbonate compound can also be used as the photopower thione polymerization composition.
  • the light-power thione polymerization composition can be contained in the resin composition of the present invention in an amount of usually 10 to 90% by mass, particularly about 50 to 90% by mass.
  • photoacid generators include, for example, UVI-6950, UVI-6970 (bis [4 (di (2-hydroxyethyl) sulfuro) sulfo-)-phenylsulfide, manufactured by Union Carbide Corporation. ], UVI 6974 (Bis [4-diphenylsulfo-phenol] sulfide bishexafluoroantimonate and diphenyl 4-thiophenoxyphenylsulfo-muhexafluoroantimonate ), UVI—6990 (UVI6974 hexafluorophosphate salt), Adeka Optomer made by Asahi Denki Kogyo Co., Ltd.
  • the second photocurable resin composition of the present invention comprises a radical generator, 380-: a dye having absorption in LOOOnm, and a photoradical polymerization composition, and visible light.
  • a radical generator 380-: a dye having absorption in LOOOnm
  • a photoradical polymerization composition e.g., a photoradical polymerization composition
  • visible light e.g., a visible light
  • it is an adhesive composition that starts and cures when exposed to near-infrared rays and is used for mounting electronic components.
  • electron transfer occurs between the dye that absorbs near infrared rays and the radical generator, and radicals are generated.
  • the same dyes as described above can be used, and the blending amount is usually 0.1 to 20% by mass. In particular, 1 to: L0% by mass can be achieved.
  • radical generators radiation photopolymerization initiators
  • organic peroxides bisimidazoles, iodine salts, polyhalogen compounds, titanocenes, borates, sulfonic acid derivatives, and N-phenyldaricin power groups
  • Any one or more selected from force can be suitably used.
  • examples of the salt include pheo-di-ordinium salt, bis (p-phlogo-fuel) oddonium salt, digly-rhodonium salt, bis (p-t-butyl-felt) ododonium salt, bis ( m--trofeol) Jodonium salt, etc.
  • counterions include chloride, bromide, tetrafluoroborate, hexafluorophosphate, trifluoromethane sulfate, etc., respectively.
  • radical photopolymerization initiators include, for example, 2-hydroxy-1,2-methyl-1-phenylpropane 1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl 1 1 (4 (methylthio) phenol) 2
  • Acetophenones such as morpholinopropane 1, benzoins such as benzyldimethyl ketal, benzophenones such as benzophenone, 4-phenylbenzophenone and hydroxybenzophenone, isopropyl Methylphenol glyoxylate and the like can be used as thixanthone series such as norethixanthone, 2-4 jetylthioxanthone, acylphosphine oxide, and other special ones.
  • radical photopolymerization initiators may be optionally combined with one or more known photopolymerization accelerators such as benzoic acid-based compounds such as 4-dimethylaminobenzoic acid or tertiary amine amines. Can be mixed and used. Only one radical photopolymerization initiator can be used, or a mixture of two or more can be used.
  • the radical photopolymerization initiator is preferably contained in the adhesive composition of the present invention in an amount of usually 0.1 to 20% by mass, particularly 1 to L0% by mass.
  • radical photopolymerization initiators as the acetophenone photopolymerization initiator, for example, 4-phenoxydichloroacetophenone, 4-t-butylmonodichloroacetophenone, 4-t —Butyl monotrichloroacetophenone, diethoxyacetophenone, 1— (4-isopropylpropyl) 2 hydroxy-2-methylpropane-1-one, 1— (4 dodecylphenyl) 2 hydroxy-2-methylpropane 1-one, 4- (2 hydroxyethoxy) -phenol (2-hydroxy-1-propyl) ketone, and the like.
  • Benzophenone-based photopolymerization initiators include benzoylbenzoic acid and benzoylbenzoic acid in addition to the above. Examples include methyl acid, 4-benzoyl 4'-methyldiphenyl sulfide, 3,3,1-dimethyl-4-methoxy benzophenone, and the like.
  • Examples of the acyl phosphine oxide include compounds such as 2,4,6 trimethylbenzoyl diphosphine phosphine oxide and bis (2,6 dimethoxybenzoyl) -2,4,4 trimethyl-pentylphosphine oxide. Can be mentioned.
  • acetophenone-based photopolymerization initiators in particular, 2-hydroxy-2-methyl-1-phenylpropane 1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl Lou 1 (4 (methylthio) phenol) 2 Morpholinopropane 1 is preferred.
  • benzophenone photopolymerization initiators benzophenone, benzoylbenzoic acid, and methyl benzoylbenzoate are preferable.
  • tertiary ethanolamine photopolymerization accelerators include triethanolamine, methyljetanolamine, triisopropanolamine, 4,4, -dimethylaminobenzophenone, 4,4, -jetylaminobenzophenone, 2dimethylaminobenzoate.
  • ethyl 4-ethylaminobenzoate, 4-dimethylaminobenzoate (n-butoxy) ethyl, isoamyl 4-dimethylaminobenzoate, 2-dimethylhexyl 4-dimethylaminobenzoate, and the like can be used.
  • examples of the photopolymerization accelerator include ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate (n-butoxy) ethyl, isoamyl 4-dimethylaminobenzoate, 2-ethylaminobenzoate 4-dimethylaminobenzoate, and the like.
  • the photopolymerization initiator can be combined with components.
  • the photo-radical polymerization composition utilizes a radical polymerization reaction of an unsaturated double bond, and mainly comprises a monomer or oligomer having a photo-polymerizable functional group, and is reactive as required.
  • Polymer may be added.
  • a binder resin can be added to adjust the viscosity.
  • the non-oxidized resin can be used without limitation as long as it can be mixed with a photo-curing resin and does not have a large absorption in the near infrared region.
  • Examples of the reactive polymer having a photopolymerizable functional group include alkyl acrylate (eg, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate) and Z or alkyl methacrylate.
  • alkyl acrylate eg, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate
  • Z or alkyl methacrylate eg, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate
  • Homopolymers or copolymers namely, acrylic resin obtained from a rate (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethyl hexyl methacrylate, etc.)
  • examples thereof include those having a photopolymerizable functional
  • Such a polymer is, for example, a copolymer of one or more types of (meth) acrylate and (meth) acrylate (such as 2-hydroxychetyl (meth) acrylate) having a functional group such as a hydroxyl group. It can be obtained by reacting the obtained polymer with a compound having a photopolymerizable group and reacting with a functional group of the polymer, such as isocyanatoalkyl (meth) acrylate. Therefore, an acrylic resin having a photopolymerizable functional group via a urethane bond is preferred.
  • the photo-radical polymerization composition can be contained in the adhesive composition of the present invention in an amount of usually 10 to 90% by mass, particularly 50 to 90% by mass.
  • it preferably includes a radical photopolymerization composition having at least one ethylenically unsaturated double bond.
  • the adhesive composition of the present invention can be suitably used in the form of a film or a paste, and, as long as it does not impair the effects of the present invention, as other additives, if desired, Solvents, antioxidants, plasticizers, and other components such as solvents, antioxidants, anti-aging agents, thixotropic agents, plasticizers, colorants (dyes), and processing aids. May be.
  • a conductive filler in the composition of the present invention.
  • the composition containing the conductive filler By interposing the composition containing the conductive filler between the electrodes, conduction can be achieved through the composition.
  • the surface of the conductive filler may be coated with a resin, it becomes an insulator in a normal state and can be electrically connected by being compressed and crushed between the electrodes.
  • a strong conductive filler various types can be used as long as they are electrically good conductors.
  • a metal or alloy powder such as copper, silver, nickel, or gold, or a resin or ceramic powder coated with these metal or alloy can be used.
  • the shape can be any shape such as flake shape, dendritic shape, granular shape, pellet shape, and the like.
  • the conductive filler is preferably one having an elastic modulus of 1. OX 10 7 to 1. OX 10 1Q Pa.
  • OX 10 7 to 1. OX 10 1Q Pa the adherend will be cracked or elastically deformed after pressing. It is recommended to use a conductive filler in the above elastic modulus range because there is a possibility that stable conduction performance cannot be obtained due to the occurrence of springback due to recovery. This prevents damage to the adherend, suppresses the occurrence of springback due to recovery of elastic deformation of the particles after crimping, increases the contact area of the conductive filler, and is more stable. Highly reliable conduction performance can be obtained.
  • the elastic modulus is less than 1. OX 10 7 Pa, the particles themselves may be damaged and the conduction characteristics may be degraded. 1. If it is greater than OX 10 1Q Pa, springback may occur. .
  • a conductive filler one in which the surface of the plastic particles having the above elastic modulus is coated with the aforementioned metal or alloy is preferably used.
  • the blending amount of the conductive filler in the composition is preferably 0.1 to 15% by volume with respect to the base resin (light power thione polymerization composition or photo radical polymerization composition).
  • the average particle size of the conductive filler is preferably 0.1 to: LOO / zm.
  • the viscosity at around room temperature is preferably 1 to 1000 Pa's, particularly 10 to 500 Pa's. Therefore, it is desirable to appropriately adjust the blending amounts of the photopolymerizable composition and various additives so that such a viscosity can be obtained.
  • the adhesive composition of the present invention can be cured by irradiation with visible light or near-infrared rays, and the light source that can be used for curing in the present invention emits visible light or near-infrared light.
  • the light source that can be used for curing in the present invention emits visible light or near-infrared light.
  • semiconductor lasers laser diodes, LEDs (Light Emitting Diodes), halogen lamps, VCSEL (Vertical
  • curing can be promoted by heating as necessary after irradiation with visible light or near infrared rays.
  • the irradiation time depends on the type and intensity of the light source – it cannot be roughly determined, but it should be several seconds to several tens of minutes.
  • the temperature Prior to curing, the temperature is about room temperature to about 50 ° C. It is also preferable to perform temporary pressure bonding by applying a pressure of about 0.1 MPa to 1.5 MPa at a temperature.
  • the adhesive composition of the present invention can contain a known UV-curable resin composition that is cured by irradiation with UV light and is not particularly limited.
  • the adhesive composition of the present invention containing an ultraviolet ray curable resin composition component is characterized by being curable with visible light, near infrared rays and ultraviolet rays.
  • the refractive index power of the cured product by irradiation with visible light or near infrared light is preferably higher than the refractive index of the cured product by irradiation with ultraviolet rays.
  • the pigment it is decomposed by irradiation with ultraviolet rays, It is preferable to use a material that decreases the absorption in the near infrared region.
  • the adhesive composition of the present invention can be prepared in a paste form by dissolving and dispersing the photopolymerizable composition and the various additives described above in a solvent in a predetermined combination. It can be filled and applied or injected. Specifically, for example, in the flip chip mounting in which the electrode 1 on the substrate 11 and the BGA (Ball Grid Array) mounting chip 12 are mounted by reflow through the solder bumps 2 as shown in FIG. Then, after mounting, the paste 11 is injected into the gap between the substrate 11 and the chip 12 as an underfill and cured, and the substrate 11 can be sealed as shown in FIG.
  • BGA All Grid Array
  • the thickness of the paste-like composition in the case of application is not particularly limited !, but can be, for example, in the range of 5 to: L00 m and matched to the thickness of the opposing electrode. Thus, the thickness can be appropriately controlled.
  • the adhesive composition of the present invention comprises a photopolymerizable composition and the above-mentioned various additives that are uniformly mixed in a predetermined composition and kneaded with an extruder, a roll, etc.
  • a film can be prepared by forming a film into a predetermined shape by a film forming method such as die extrusion or inflation.
  • a film-like film can be formed by dissolving or dispersing the compounding components of the adhesive composition in a solvent, applying it to the surface of the separator, and then evaporating the solvent. In the film formation, embossing force may be applied for the purpose of preventing blocking and facilitating the pressing with the adherend.
  • the film-like composition of the present invention includes, for example, a BGA (Ball Grid Array) mounting chip 12 on which an electrode 1 and an Au ⁇ t bump 3 are formed on a substrate 11 as shown in FIG. 1 (b). Mounted by thermocompression bonding The flip-chip mounting can be applied, and sealing can be performed by performing pressure bonding in a state where the film-like composition 10 is placed on the substrate.
  • COF Chip On Flex (Film)
  • COB Chip On Board
  • COG Chip On Glass
  • FOF Flux On Flex
  • FOB Felex On Board
  • FOG Felex On Glass
  • the thickness of the film composition is not particularly limited, but can be, for example, about 5 to 100 m, and the thickness can be appropriately controlled according to the thickness of the opposing electrode. it can.
  • polyester resin shown in Table 1 below is dissolved in a mixed solvent of toluene and methylethylketone to prepare a 40% by weight solution. These components were mixed in the amounts shown in the table, and this was applied onto poly (ethylene terephthalate) as a separator with a bar coater to obtain an anisotropic conductive finolem having a width of 2 mm and a thickness of 35 ⁇ m.
  • the obtained film was attached to a non-adhesive type two-layer polyimide flexible printed circuit board and a polyethylene terephthalate (PET) printed circuit board using silver paste as a counter electrode, and the separator was peeled off. Positioning was performed with a monitor, and temporary pressure bonding was performed at 0.5 MPa for 1 second at 50 ° C.
  • PET polyethylene terephthalate
  • IR irradiation ASAHI SPECTRA xenon light source, LAX-102, IR mirror module through the quartz glass serving as the crimping table while crimping at 50 ° C for 60 seconds under the condition of 2MPa.
  • Use and transmission wavelength range of 700-120 nm were performed for the same time.
  • the obtained sample was subjected to a 90 ° peel test (50 mmZmin) using a tensile tester. The adhesive strength was measured. The connection resistance between the opposing wiring patterns was measured with a digital multimeter. Furthermore, the insulation resistance between adjacent wiring patterns (300 m pitch) was measured with an ultrahigh resistance meter. These results are also shown in Table 1 below.
  • a nonconductive film was prepared by the same production method as in Example 1-1, except that the conductive particles were not blended. Using the obtained film, the same substrate as in Example 1-1 was used.
  • IR irradiation (ASAHI SPECTRA xenon light source, LAX-102, IR mirror module through the quartz glass serving as the crimping table through crimping at 3MPa for 60 seconds at 50 ° C. Use and transmission wavelength range of 700-120 nm) were performed for the same time.
  • the anisotropic conductive films and non-conductive films of the examples as the adhesive composition of the present invention may be remarkably excellent in adhesiveness, conductivity, and insulation. It was confirmed.
  • the polyester resin shown in Table 2 below is dissolved in a methyl ethyl ketone solvent to prepare a 65 wt% solution, and the remaining components in Table 2 are expressed with respect to 100 parts by weight of the polyester resin solution.
  • An anisotropic conductive paste was obtained by mixing with three rolls in the amount shown in the figure.
  • the obtained paste is drawn on a polyterephthalate (PET) printed circuit board using silver paste as an electrode, and is adhesive-free. Positioned with a monitor for bonding to a 2-layer polyimide flexible printed circuit board, and temporarily crimped at 0.5 MPa for 1 second at 50 ° C
  • IR irradiation (ASAHI SPECTRA xenon light source, LAX-102, IR mirror module through the quartz glass serving as the crimping table through crimping at 2MPa for 60 seconds at 50 ° C. Use and transmission wavelength range of 700-120 nm) were performed for the same time.
  • the obtained sample was subjected to a 90 ° peel test (50 mmZmin) using a tensile tester. The adhesive strength was measured. The connection resistance between the opposing wiring patterns was measured with a digital multimeter. Furthermore, the insulation resistance between adjacent wiring patterns (300 m pitch) was measured with an ultrahigh resistance meter. These results are also shown in Table 2 below.
  • a non-conductive paste was prepared by the same manufacturing method as Example 2-1 except that the conductive particles were not blended. Using the obtained paste, the same examples as those in Example 2-1 were used.
  • Temporary pressure bonding was performed under the same conditions as in 2-1.
  • IR irradiation (ASAHI SPECTRA xenon light source, LAX-102, IR mirror module through the quartz glass serving as the crimping table through crimping at 3MPa for 60 seconds at 50 ° C. Use, transmission wavelength range 700-: 1020 nm) was performed at the same time.
  • Adhesive strength (N / m (gf / cm)) 519 (530) 549 (560) ⁇ Connection resistance ( ⁇ ) 2 3
  • Adhesive strength connection strength. Adhesive strength. Connection resistance, comprehensive evaluation

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Abstract

Disclosed is an adhesive composition which is free from problems involved in conventional thermosetting resins while having adhesiveness sufficient for electronic component mounting, desired electrical characteristics and long-term durability. Specifically disclosed is an adhesive composition containing a photoacid generator, a dye having an absorption in a range of 380-1000 nm and a cationically photopolymerizable composition. This adhesive composition generates an acid and starts a cationic photopolymerization reaction when irradiated with visible or near infrared light, thereby being cured. Also disclosed is an adhesive composition containing a radical generator, a dye having an absorption in a range of 380-1000 nm and a radically photopolymerizable composition. This adhesive composition is cured by starting a radical polymerization reaction when it is irradiated with visible or near infrared light. These adhesive compositions are used for mounting electronic components.

Description

明 細 書  Specification
接着剤組成物  Adhesive composition
技術分野  Technical field
[0001] 本発明は接着剤組成物（以下、単に「組成物」とも称する）に関し、詳しくは、 ICパッ ケージ等の各種電子部品の実装用として好適に用いられる接着剤組成物に関する。 背景技術  The present invention relates to an adhesive composition (hereinafter, also simply referred to as “composition”), and more particularly to an adhesive composition that is suitably used for mounting various electronic components such as an IC package. Background art
[0002] 近年、電子部品の小型化に伴って、基板に直接 ICチップを実装するベアチップ実 装、中でもフリップチップ方式による実装技術が注目されるようになってきている。フリ ップチップ実装方式は、基板上にバンプを介して ICチップを接続し、 ICチップ—基 板間をアンダーフィルで封止するものであり、はんだバンプを用いる方式と、金、ニッ ケル等の金属バンプを用いる方式とがある。  [0002] In recent years, with the miniaturization of electronic components, bare chip mounting for mounting an IC chip directly on a substrate, in particular, mounting technology using a flip chip method, has attracted attention. In the flip chip mounting method, an IC chip is connected to a substrate via a bump and the IC chip and the substrate are sealed with an underfill. A method using a solder bump and a metal such as gold or nickel are used. There is a method using bumps.
[0003] アンダーフィルには、 ICチップ一基板間に十分に浸透し硬化すること、熱や外的負 荷等の応力に対して接続信頼性を担保できること、所望の電気特性を満足すること などが必要とされ、従来、エポキシ榭脂を初めとする熱硬化性榭脂が最も一般的に 使用されている。また、フリップチップ以外の種々のパッケージ形態や基板間接続な どにも対応した実装方法として、榭脂中に導電性フィラーを均一分散させた異方性 導電材料を用いる技術も公知である（例えば、特許文献 1, 2等に記載)。  [0003] Underfill is sufficient to penetrate and cure between IC chip substrates, to ensure connection reliability against stresses such as heat and external load, and to satisfy desired electrical characteristics, etc. Conventionally, thermosetting resins such as epoxy resins are most commonly used. In addition, as a mounting method corresponding to various package forms other than flip-chip and inter-substrate connection, a technique using an anisotropic conductive material in which a conductive filler is uniformly dispersed in a resin is also known (for example, , Described in Patent Documents 1 and 2).
特許文献 1：特開 2004— 292827号公報 (特許請求の範囲等）  Patent Document 1: Japanese Patent Application Laid-Open No. 2004-292827 (Claims)
特許文献 2：特開 2004— 256650号公報 (特許請求の範囲等）  Patent Document 2: JP 2004-256650 A (Claims)
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
[0004] し力しながら、従来の熱硬化型の榭脂材料では、その実装工程もしくは熱処理工程 において、 100°C以上の高い温度で数十秒以上の時間を掛けて、熱圧着処理を行 なう必要があり、その結果、電子部品本体に損傷を生ずるおそれがあるという問題が あった。また、熱膨張係数が異なるチップや基板の接続では、高い温度での熱圧着 処理のために、チップや基板が実用温度に戻された際、その接続部分に高い内部 応力を含有するため、接着力が不十分になり、電気特性や長期耐久性に問題があつ た。従って、電子部品の実装に適用するに際し、高い温度を掛ける必要が無い、低 温短時間接続工程が可能となる材料の実現が求められていた。 [0004] However, with conventional thermosetting resin materials, thermocompression treatment is performed at a high temperature of 100 ° C or more for several tens of seconds in the mounting process or heat treatment process. As a result, there is a problem that the electronic component body may be damaged. In addition, when connecting chips and substrates with different coefficients of thermal expansion, when the chip or substrate is returned to a practical temperature due to thermocompression bonding at a high temperature, the connection part contains high internal stress. Insufficient power, causing problems with electrical characteristics and long-term durability It was. Accordingly, there has been a demand for the realization of a material that does not need to be subjected to a high temperature and enables a low-temperature and short-time connection process when applied to mounting electronic components.
[0005] そこで本発明の目的は、電子部品の実装用として、十分な接着性を備えるとともに 所望の電気特性および長期耐久性を満足でき、かつ、従来の熱硬化型榭脂におけ るような問題を有しない接着剤組成物を提供することにある。  [0005] Therefore, an object of the present invention is to provide sufficient adhesiveness for mounting electronic components, satisfy desired electrical characteristics and long-term durability, and be used in conventional thermosetting resin. It is to provide an adhesive composition that has no problems.
課題を解決するための手段  Means for solving the problem
[0006] 本発明者は鋭意検討した結果、下記構成とすることにより、電子部品の実装に好適 な接着剤組成物が得られることを見出して、本発明を完成するに至った。 [0006] As a result of intensive studies, the present inventor has found that an adhesive composition suitable for mounting electronic components can be obtained with the following configuration, and has completed the present invention.
[0007] 即ち、本発明の第一の接着剤組成物は、光酸発生剤と、 380〜： LOOOnmに吸収を 有する色素と、光力チオン重合系組成物とを含み、可視光または近赤外線の照射に より酸を発生し、カチオン重合反応を開始して硬化する接着剤組成物であって、電子 部品の実装用に用いられることを特徴とするものである。 [0007] That is, the first adhesive composition of the present invention includes a photoacid generator, 380-: a dye having absorption at LOOOnm, and a photopower thione polymerization system composition, and includes visible light or near-infrared light. Is an adhesive composition that generates an acid upon irradiation and initiates a cationic polymerization reaction to be cured, and is used for mounting electronic components.
[0008] また、本発明の第二の接着剤組成物は、ラジカル発生剤と、 380〜： LOOOnmに吸 収を有する色素と、光ラジカル重合系組成物とを含み、可視光または近赤外線の照 射により、ラジカル重合反応を開始して硬化する接着剤組成物であって、電子部品 の実装用に用いられることを特徴とするものである。 [0008] The second adhesive composition of the present invention includes a radical generator, 380-: a dye having absorption at LOOOnm, and a photoradical polymerization composition, and is capable of visible light or near-infrared light. An adhesive composition that initiates a radical polymerization reaction upon irradiation and cures, and is used for mounting electronic components.
[0009] 本発明の接着剤組成物は、フィルム状またはペースト状として好適に用いることが できる。また、本発明の接着剤組成物は、導電性フィラーを含有することが好ましぐ 光増感剤を含有することも好まし ヽ。 [0009] The adhesive composition of the present invention can be suitably used as a film or paste. In addition, the adhesive composition of the present invention preferably contains a photosensitizer that preferably contains a conductive filler.
[0010] さらに、本発明の接着剤組成物は、フリップチップ実装におけるアンダーフィルや、 電極一電極間を接続する接着剤として好適に用いることができる。 [0010] Furthermore, the adhesive composition of the present invention can be suitably used as an underfill in flip chip mounting or an adhesive for connecting one electrode to another.
発明の効果  The invention's effect
[0011] 本発明によれば、十分な接着性を備えるとともに所望の電気特性および長期耐久 性を満足する接着剤組成物を実現することができる。また、可視光または近赤外線の 照射により硬化させることができるため、熱による悪影響を排除することができるととも に、ある程度隠蔽性の高い不透明な部分を有する場合であっても、確実に硬化を行 うことが可能である。また、硬化時に用いる可視ないし近赤外領域の光は、例えば、 紫外線領域の光よりも人体に対する悪影響が少なく安全性が高いことや、厚膜、大 面積での硬化が可能であることなどのメリットもある。さらに、紫外線領域の硬化の場 合、榭脂組成物が白色光により影響を受けてしまうが、近世外線領域の硬化では、 白色光による影響が少な 、ために、ハンドリング性が良好である。 [0011] According to the present invention, it is possible to realize an adhesive composition that has sufficient adhesiveness and satisfies desired electrical characteristics and long-term durability. In addition, since it can be cured by irradiation with visible light or near-infrared radiation, adverse effects due to heat can be eliminated, and even when there is an opaque part with a high degree of concealment, it can be cured reliably. It is possible to do this. In addition, visible to near-infrared light used for curing has less adverse effects on the human body than light in the ultraviolet region, and is highly safe, thick, There are also merits such as being able to cure in area. Further, in the case of curing in the ultraviolet region, the resin composition is affected by white light. However, in the case of curing in the early modern outside line region, the effect of white light is small, so that the handling property is good.
図面の簡単な説明  Brief Description of Drawings
[0012] [図 l] (a) , (b)は、フリップチップ実装の一形態を示す概略断面図である。  [0012] FIGS. 1A and 1B are schematic cross-sectional views showing one embodiment of flip-chip mounting.
[図 2]電極-電極間接続の概略断面図である。  FIG. 2 is a schematic sectional view of electrode-electrode connection.
符号の説明  Explanation of symbols
[0013] 1 電極 [0013] 1 electrode
2 はんだバンプ  2 Solder bump
3 Auスタッドバンプ  3 Au stud bump
10 接着剤組成物  10 Adhesive composition
11 基板  11 Board
12 BG A実装チップ  12 BG A mounting chip
21, 22 基板  21, 22 substrate
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0014] 以下、本発明の好適な実施の形態について詳細に説明する。 [0014] Hereinafter, preferred embodiments of the present invention will be described in detail.
本発明の第一の光硬化性榭脂組成物は、光酸発生剤と、 380〜1000nmに吸収 を有する色素と、光力チオン重合系組成物とを含み、可視光または近赤外線の照射 により酸を発生し、カチオン重合反応を開始して硬化する接着剤組成物であり、電子 部品の実装用に用いられる。この場合、近赤外線を吸収した色素と光酸発生剤との 間で電子移動が起こり、光酸発生剤が酸を発生する。  The first photocurable resin composition of the present invention comprises a photoacid generator, a dye having absorption at 380 to 1000 nm, and a photopower thione polymerization composition, and is irradiated with visible light or near infrared light. An adhesive composition that generates acid and initiates a cationic polymerization reaction to cure, and is used for mounting electronic components. In this case, electron transfer occurs between the dye that has absorbed near infrared rays and the photoacid generator, and the photoacid generator generates an acid.
[0015] 本発明に用いる可視領域（およそ 380〜760nm)に吸収を有する色素としては、例 えば、 3, 3' , 4, 4，—カルボ-ルビス 7—（ジェチルァミノ）クマリン等のケトクマリン 系色素、 3, 3，—カルボ-ルビス— 7— (ジェチルァミノ）クマリン、 3— (2，—ベンゾチ ァゾリル） 7— N, N ジェチルァミノクマリン等のクマリン系色素、 4—ブトキシフエ -ル— 2, 6 ジフエ-ルチオピリリウムパーク口レート等のチォピリリウム塩系色素、 4 —tーブチルー 2, 6 ビス（4，ージメチルァミノべンジリデン）シクロへキサノン等の 2 , 6 ビス（ベンジリデン）シクロへキサノン系色素、 [2— [2— [4 （ジメチルァミノ）フ ェ -ル]ェテュル]— 6—メチル—4H—ピラン— 4—イリデン]プロパンジ-トリル等の ピラン系色素等、更にチォキサンテン系色素、キサンテン系色素が挙げられる。 [0015] Examples of the dye having absorption in the visible region (approximately 380 to 760 nm) used in the present invention include, for example, ketocoumarin-based dyes such as 3, 3 ', 4, 4, -carborubbis 7- (jetylamino) coumarin. , 3, 3, -Carborubbis-7- (Jetylamino) coumarin, 3-(2, -benzothiazolyl) 7-N, N Coumarin dyes such as Jetylaminocoumarin, 4-Butoxyphenol-2 6 Thiophyllium salt dyes such as diphenylthiopyrylium percolate, 2, 6-bis (benzylidene) cyclohexanone dyes such as 4 —tert-butyl-2,6 bis (4, -dimethylaminobenzylidene) cyclohexanone, [ 2— [2— [4 (Dimethylamino) F [6] -Methyl-4H-pyran-4-ylidene] pyran dyes such as propanedi-tolyl, and thixanthene dyes and xanthene dyes.
[0016] また、近赤外領域（およそ 760〜1000nm)に吸収を有する色素としては、例えば、 ピリリウム系、チォピリリウム系、シァニン系、インドリウム系、トリアジン系等が挙げられ る力 これらに限定されるものではない。具体的には例えば、 2— [7— (1, 3 ジヒド 口一 1, 1, 3 トリメチル 2H ベンズインドル一 2—イリジン）一 1, 3, 5 ヘプタトリ ェ-ル ]— 1, 1, 3 トリメチル 1H ベンズインドリウムパーク口レート、 3 ェチル 2— [2— [3— [2—（3 ェチノレー 2 (3H) べンゾチアゾリリジン）ェチリジン] 2 —ジフエニルァミノ一 1—シクロペンタン一 1—ィル]ェテュル]ベンゾチアゾリゥムパ 一クロレート、 1—ェチル 2— [7— (1—ェチル 2 (1H)—キノリジン）一 1, 3, 5— ヘプタトリエ-ル]キノリュウムィオダイド、 8— [ (6, 7 ジヒドロ一 2, 4 ジフエ-ル一 5H—1—ベンゾピラン一 8—ィル)メチレン] 5, 6, 7, 8—テトラヒドロ一 2, 4 ジフエ -ル一 1—ベンゾピリリウムパーク口レート、ビス（ジチォベンジル）ニッケル、ビス [2， —クロ口一 3—メトキシ一 4— (2—メトキシエトキシ）ジチォベンジル]ニッケル、 1—ェ チル— 4— [7— (ェチル— 4 (1H)—キノリリジン）— 1, 3, 5 ヘプタトリエ-ル]キノリ ユウムィオダイド、 4—4，一 [3— [2—（1ーェチルー 4 (1H)—キノリ-リジン）ェチリジ ン]プロべ-レン]ビス ( 1―ェチルキノリュウムィオダイド）、株式会社林原生物化学研 究所製の NK— 4432、 NK— 4680、 NK— 5557、 NK— 5559、 NK— 5911、 NK — 2882、 NK— 4489、 NK— 4474、 NK— 5020、 NK— 2014、 NK— 2912など がある。 In addition, examples of the dye having absorption in the near-infrared region (approximately 760 to 1000 nm) include, for example, powers such as pyrylium, thiopyrylium, cyanine, indolium, and triazine. It is not something. Specifically, for example, 2— [7— (1,3 dihydric 1,1,3 trimethyl 2H benzindole 1 2-iridine) 1,3,5 heptatril] — 1, 1,3 trimethyl 1H Benzindolinium Park Mouth Rate, 3 ethyl 2— [2— [3— [2 — (3 ethenolay 2 (3H) benzothiazolylidine) ethyridine] 2 — diphenylamino 1-cyclopentane 1-yl] Etul] benzothiazolympa monochlorate, 1—ethyl 2— [7— (1—ethyl 2 (1H) —quinolidine) 1,3,5—heptatriethyl] quinolium iodide, 8— [( 6, 7 Dihydro-1, 2, 4 Diphenyl 1 5H-1—Benzopyran 1 8-yl) methylene] 5, 6, 7, 8— Tetrahydro 1, 2, 4 Diphenyl 1, 1-Benzopylium , Bis (dithiobenzyl) nickel, bis [2, -black 1-methoxy 4- (2-methoxyethoxy) di Thiobenzyl] nickel, 1-ethyl-4- [7- (ethyl-4 (1H) -quinolilysine)-1, 3, 5 heptatriol] quinoli yuumiodide, 4-4, one [3— [2— (1 -Ethyl 4 (1H) -quinolyl-lysine) ethylidene] probelen] bis (1-ethyl quinolium iodide), NK-4432, NK-4680, NK manufactured by Hayashibara Biochemical Research Institute, Inc. — 5557, NK— 5559, NK— 5911, NK— 2882, NK— 4489, NK— 4474, NK— 5020, NK— 2014, NK— 2912, etc.
[0017] これら色素は、単独で用いても、 2種以上を組み合わせて使用してもよぐ本発明の 接着剤組成物中に、通常 0. 1〜20質量％、特には 1〜10質量％にて含有させるこ とがでさる。  [0017] These dyes may be used singly or in combination of two or more. In the adhesive composition of the present invention, usually 0.1 to 20% by mass, particularly 1 to 10% by mass. It can be contained in%.
[0018] また、光酸発生剤としては、 1, 2 ナフトキノンー2 ジアジドー 5—スルホン酸クロ リド、 1, 2 ナフトキノン一 2 ジアジド一 5—スルホン酸ナトリウム、 1, 2 ナフトキノ ン一 2 ジアジドー 5—スルホン酸カリウム、 1, 2 ナフトキノン一 2 ジアジドー 5— スルホン酸メチル、 1, 2 ナフトキノン— 2 ジアジドー 5—スルホン酸ェチル、 1, 2 ナフトキノンー2 ジアジドー 5—スルホン酸力プリル、 1, 2 ナフトキノンー2 ジ アジドー 5—スルホン酸セチルなどや、 1, 2 ナフトキノン一 2 ジアジドー 4—スル ホン酸クロリド、 1, 2 ナフトキノン一 2 ジアジド一 4—スルホン酸ナトリウム、 1, 2- ナフトキノン 2 ジアジドー 4ースルホン酸カリウム、 1, 2 ナフトキノン 2 ジアジ ドー 4—スルホン酸メチル、 1, 2 ナフトキノン— 2 ジアジドー 4—スルホン酸ェチ ル、 1, 2 ナフトキノン一 2 ジアジドー 5—スルホン酸へキシル、 1, 2 ナフトキノン —2 ジアジド一 5—スルホン酸ラウロイル、 1, 2 ナフトキノン一 2 ジアジド一 5— スルホン酸ステアリルなど、 1, 2 ベンゾキノン一 2 ジアジドー 4—スルホン酸クロリ ド、 1, 2 ベンゾキノン一 2 ジアジド一 4—スルホン酸ナトリウム、 1, 2 ベンゾキノ ン一 2 ジアジドー 4—スルホン酸カリウム、 1, 2 ベンゾキノン一 2 ジアジドー 4— スルホン酸メチル、 1, 2 ベンゾキノン— 2 ジアジドー 4—スルホン酸ェチル、 1, 2 一べンゾキノン 2 ジアジドー 4ースルホン酸力プロィル、 1, 2 べンゾキノン 2 —ジアジドー 4—スルホン酸デシル、 1, 2 ベンゾキノン— 2 ジアジドー 4—スルホ ン酸ステアリル、 1, 2—ベンゾキノン一 2—ジアジドなどを挙げることができる。 [0018] In addition, photoacid generators include 1,2 naphthoquinone-2 diazido 5-sulfonic acid chloride, 1,2 naphthoquinone 1-2 diazido 1-5-sulfonic acid sodium, 1,2 naphthoquinone 1-2 diazido 5-sulfone Potassium acid, 1, 2 Naphthoquinone-2-diazido 5-methyl sulfonate 1, 2-naphthoquinone 2-diazido 5-ethyl sulphonate 1, 2, naphthoquinone-2 diazido 5-sulphonic acid prill, 1, 2 naphthoquinone-2 di Azido 5-cetyl sulfonate, 1,2 naphthoquinone 1-2 diazido 4-sulfonic acid chloride, 1, 2 naphthoquinone 1-2 diazide 4- sodium sulfonate, 1, 2-naphthoquinone 2 diazide 4-potassium sulfonate, 1 , 2 Naphthoquinone 2 Diazido 4-methyl sulfonate, 1, 2 Naphthoquinone-2 Diazide 4-Ethyl sulfonate, 1, 2 Naphthoquinone 1 2-Diazide 5-Hexyl sulfonate, 1, 2 Naphthoquinone 2 Diazide 1 5 —Lauroyl sulfonate, 1,2 naphthoquinone 1-2 diazide 1-5—stearyl sulfonate, 1,2 benzoquinone 1-2 diazido 4-sulfonic acid chloride, 1, 2 benzoquinone 1-2 diazide 4-sodium sulfonate 1, 2 Benzoquinone 1 2 Diazido 4-potassium sulfonate, 1, 2 Benzoquinone 1 2 Diazido 4- Methyl sulfonate, 1, 2 benzoquinone-2 diazido 4-ethyl sulfonate, 1, 2 monobenzoquinone 2 diazido 4-sulfonic acid profile, 1,2 benzoquinone 2 —diazido 4-decyl sulfonate, 1, 2 benzoquinone— 2 Diazido 4-stearyl sulfonate, 1,2-benzoquinone-2-diazide, and the like.
また、その他、次のようなものも用いることができる。  In addition, the following can also be used.
エチレングリコール、 1, 3 プロパンジオール、 1, 6 へキサンジオール、 1, 10— デカンジオール、 1, 16 へキサデカンジオールなどの脂肪族ジオールと 1, 2 ナ フトキノン一 2 ジアジドー 4 (または一 5)—スルホン酸クロリドとの縮合物、フエノー ル、ヒドロキノン、カテコール、レゾルシノール、ピロガロール等の水酸化芳香族と 1, 2 —ナフトキノン一 2 ジアジド一 4 (または一 5)スルホン酸クロリドとの縮合物、 2, 3, 4 トリヒドロキシベンゾフエノン、 2, 2' , 4, 4'ーテトラヒドロキシベンゾフエノン、 2, 2， , 3, 4, 4' ペンタヒドロキシベンゾフエノン、などのポリヒドロキシベンゾフエノンと 1, 2 -ナフトキノン 2 ジアジド 4 (または 5)スルホン酸クロリドとの縮合物、例え ば、トリヒドロキシベンゾフエノンジ（1, 2 ナフトキノン一 2 ジアジドー 4—スルホン 酸）エステル、トリヒドロキシベンゾフエノントリ（1, 2 ナフトキノン一 2 ジアジド一 4 —スルホン酸）エステル、テトラヒドロキシベンゾフエノンジ（1, 2—ナフトキノン一 2— ジアジド一 4—スルホン酸）エステル、テトラヒドロキシベンゾフエノントリ（1, 2 ナフト キノン一 2 ジアジド一 4 スルホン酸）エステル、テトラヒドロキシベンゾフエノンテトラ (1, 2—ナフトキノン一 2—ジアジドー 4—スルホン酸）エステル、トリヒドロキシベンゾフ エノンジ（1, 2 ナフトキノン一 2 ジアジドー 5—スルホン酸）エステル、トリヒドロキシ ベンゾフエノントリ（1, 2 ナフトキノン一 2 ジアジド一 5—スルホン酸）エステル、テ トラヒドロキシベンゾフエノンジ（ 1 , 2 ナフトキノン 2 ジアジド 5—スノレホン酸） エステル、テトラヒドロキシベンゾフエノントリ（1, 2 ナフトキノン一 2 ジアジド一 5— スルホン酸）エステル、テトラヒドロキシベンゾフエノンテトラ（1, 2—ナフトキノン一 2— ジアジドー 5—スルホン酸）エステルなどや、 2 ジァゾ 5, 5 ジメチルーシクロへ キサン— 1, 3 ジオン、 2, 2 ジメチルー 5 ジアジドー 4, 6 ジケトー 1, 3 ジォ キサンなどである。 Aliphatic diols such as ethylene glycol, 1,3 propanediol, 1,6 hexanediol, 1,10-decanediol, 1,16 hexadecanediol and 1,2 naphthoquinone 1-2 diazido 4 (or 1 5) —Condensates with sulfonic acid chlorides, condensed aromatics such as phenol, hydroquinone, catechol, resorcinol, pyrogallol, etc. with 1, 2 —naphthoquinone-2-diazide-4 (or 15) sulfonic acid chloride, 2 , 3, 4 trihydroxybenzophenone, 2, 2 ', 4, 4'-tetrahydroxybenzophenone, 2, 2,, 3, 4, 4' pentahydroxybenzophenone, and other polyhydroxybenzophenones 1, 2-naphthoquinone 2 diazide 4 (or 5) sulfonic acid chloride, for example, trihydroxybenzophenone di (1, 2 naphthoquinone-2-diazide 4-sulfonic acid) ester, trihydroxybenzophenone tri (1, 2 naphthoquinone-2-diazide-1-4-sulfonic acid) ester, tetrahydroxybenzophenone di (1,2-naphthoquinone-1-2-diazide-1-4-sulfonic acid) Esters, tetrahydroxybenzophenone tri (1,2 naphthoquinone-2-diazide-4-sulfonic acid) ester, tetrahydroxybenzophenone tetra (1,2-naphthoquinone-1-2-diazido-4-sulfonic acid) ester, trihydroxybenzo F Enone di (1,2 naphthoquinone 1-2 diazido 5-sulfonic acid) ester, trihydroxy benzophenone tri (1, 2 naphthoquinone 1-2 diazido 1-5-sulfonic acid) ester, tetrahydroxybenzophenone di (1, 2 naphthoquinone 2 Diazido 5-solephonic acid) ester, tetrahydroxybenzophenone tri (1,2 naphthoquinone-2-diazide-1-5-sulfonic acid) ester, tetrahydroxybenzophenone tetra (1,2-naphthoquinone-1-2-diazido 5-sulfonic acid ) Esters, 2 diazo 5,5 dimethyl-cyclohexane-1,3 dione, 2,2 dimethyl-5 diazido 4,6 diketose 1,3 dioxane.
[0020] 特には、ァリールジァゾ -ゥム塩、ジァリールョードニゥム塩、トリアリールスルホ-ゥ ム塩、ジアルキルフエナシルスルホ -ゥム塩およびスルホン酸エステル化合物からな る群力も選ばれるいずれか 1種以上の光酸発生剤を用いる。また、可視光または近 赤外線の照射により、ブレンステッド酸またはルイス酸を発生する光酸発生剤が好適 である。光酸発生剤は、本発明の接着剤組成物中に、通常 0. 1〜20質量％、特に は 1〜 10質量0 /0〖こて含有させることができる。 [0020] In particular, a group force consisting of allyldiazo-um salt, gallo-rhodonium salt, triarylsulfomum salt, dialkylphenacylsulfomum salt and sulfonate compound is also selected. Any one or more photoacid generators are used. In addition, a photoacid generator that generates Bronsted acid or Lewis acid by irradiation with visible light or near infrared light is preferable. Photoacid generator, in the adhesive composition of the present invention, usually 0.1 to 20% by weight, in particular can be contained 1-10 wt 0/0 〖trowel.
[0021] また、光力チオン重合系組成物としては、例えば、ォキセタン環を 1個有する重合性 モノマーが挙げられ、その具体例としては、 3—ェチルー 3—ヒドロキシメチルォキセ タン、 3—（メタ）ァリルォキシメチルー 3—ェチルォキセタン、（3—ェチルー 3—ォキ セタ -ルメトキシ）メチルベンゼン、 4 フルオロー〔1— (3 ェチル 3—ォキセタ- ルメトキシ)メチル〕ベンゼン、 4ーメトキシー〔1 （3 ェチルー 3—ォキセタ-ルメト キシ)メチル〕ベンゼン、〔1 （3 ェチルー 3—ォキセタ -ルメトキシ）ェチル〕フエ- ルエーテル、イソブトキシメチル（3—ェチルー 3—ォキセタ -ルメチル）エーテル、ィ ソボル-ルォキシェチル（3—ェチルー 3—ォキセタ -ルメチル）エーテル、イソボル -ル（3 ェチル 3 ォキセタ -ルメチル）エーテル、 2 ェチルへキシル（3 ェチ ルー 3—ォキセタ -ルメチル）エーテル、ェチルジエチレングリコール（3—ェチルー 3 ォキセタ -ルメチル）エーテル、ジシクロペンタジェン（ 3—ェチル 3—ォキセタ- ルメチル）エーテル、ジシクロペンテ-ルォキシェチル（3—ェチルー 3—ォキセタ- ルメチル）エーテル、ジシクロペンテ-ルェチル（3—ェチルー 3—ォキセタ-ルメチ ル）エーテル、テトラヒドロフルフリル（3—ェチルー 3—ォキセタ -ルメチル）エーテル 、テトラブロモフエニル（3 ェチルー 3—ォキセタニルメチル）エーテル、 2—テトラブ ロモフエノキシェチル（3—ェチルー 3—ォキセタニルメチル）エーテル、トリブロモフエ -ル（3 ェチルー 3—ォキセタ -ルメチル）エーテル、 2 トリブロモフエノキシェチ ル（3 ェチル 3 ォキセタ -ルメチル）エーテル、 2 ヒドロキシェチル（3 ェチ ルー 3 ォキセタ -ルメチル）エーテル、 2 -ヒドロキシプロピル ( 3 -ェチル 3 ォ キセタ -ルメチル）エーテル、ブトキシェチル（3—ェチル— 3—ォキセタ -ルメチル） エーテル、ペンタクロロフエ-ル（3—ェチルー 3—ォキセタ -ルメチル）エーテル、ぺ ンタブロモフエ-ル（3—ェチルー 3—ォキセタ -ルメチル）エーテル、ボル-ル（3— ェチルー 3—ォキセタニルメチル)エーテル等が挙げられる。ォキセタン環を 2個有す る重合性モノマーの具体例としては、 1, 4 ビス {〔（3 ェチルー 3—ォキセタ -ル） メトキシ〕メチル }ベンゼン、ビス {〔（1 ェチル）3—ォキセタ -ル〕メチル }エーテル、 1, 4 ビス〔（3 ェチル 3—ォキセタ -ル）メトキシ〕ベンゼン、 1, 3 ビス〔（3 ェ チルー 3—ォキセタ -ル)メトキシ〕ベンゼン、 3, 7—ビス（3—ォキセタ-ル）ー5—ォ キサ一ノナン、 1, 4 ビス〔（3 ェチル 3—ォキセタ -ルメトキシ)メチル〕ベンゼン 、 1, 2 ビス〔（3 ェチル 3—ォキセタ -ルメトキシ)メチル〕ェタン、 1, 2 ビス〔（3 ーェチノレー 3—ォキセタ -ルメトキシ）メチル〕プロパン、エチレングリコールビス（3— ェチルー 3—ォキセタ -ルメチル）エーテル、ジシクロペンテ-ルビス（3—ェチルー 3 ォキセタ -ルメチル）エーテル、トリエチレングリコールビス ( 3 ェチル 3—ォキ セタ -ルメチル）エーテル、テトラエチレンダリコールビス（3—ェチルー 3—ォキセタ -ルメチル）エーテル、トリシクロデカンジィルジメチレンビス（3—ェチル— 3—ォキセ タ -ルメチル）エーテル、 1, 4 ビス [ (3 ェチルー 3—ォキセタ -ルメトキシ)メチル ]ブタン、 1, 6 ビス〔（3 ェチルー 3—ォキセタ -ルメトキシ)メチル〕へキサン、ポリ エチレングリコールビス（3—ェチルー 3—ォキセタ -ルメチル）エーテル、 EO変性ビ スフエノール Aビス（3—ェチル— 3—ォキセタ -ルメチル）エーテル、 PO変性ビスフ ェノール Aビス（3—ェチル— 3—ォキセタ -ルメチル）エーテル、 EO変性水添ビスフ ェノール Aビス（3—ェチル— 3—ォキセタ -ルメチル）エーテル、 PO変性水添ビスフ ェノール Aビス（3—ェチル 3—ォキセタ -ルメチル）エーテル、 EO変性ビスフエノ ール Fビス（3—ェチルー 3—ォキセタ -ルメチル）エーテル等が挙げられる。ォキセ タン環を 3乃至 5個有する重合性モノマーの具体例としては、トリメチロールプロパント リス（3—ェチル— 3—ォキセタ -ルメチル）エーテル、ペンタエリスリトールトリス（3 - ェチル 3—ォキセタニルメチル）エーテル、ペンタエリスリトールテトラキス（ 3—ェチ ルー 3—ォキセタ -ルメチル）エーテル、ジペンタエリスリトールペンタキス（3—ェチ ルー 3—ォキセタ -ルメチル）エーテル等が挙げられる。 [0021] In addition, examples of the photothion polymerization composition include a polymerizable monomer having one oxetane ring, and specific examples thereof include 3-ethyl-3-hydroxymethyloxetane, 3- ( (Meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxeta-lmethoxy) methylbenzene, 4-fluoro [1- (3-ethyl-3-oxetal-methoxy) methyl] benzene, 4-methoxy- [1 (3 Ethyl-3-oxetamethyl) methyl] benzene, [1 (3-ethyl-3-oxeta-methoxy) ethyl] ether, isobutoxymethyl (3-ethyl-3-oxeta-methyl) ether, isovoloxyl --Ethyl-3-oxeta-methyl) ether, isobutyl (3-ethyl-3-oxeta-methyl) ether, 2 ethyl Sil (3 ethyl 3-oxeta-methyl) ether, ethyl diethylene glycol (3-ethyl 3-oxeta-methyl) ether, dicyclopentagen (3-ethyl 3-oxeta-methyl) ether, dicyclopentyl-luxhetyl (3- Ethyl 3-ethyl ether), dicyclopent-ruethyl (3-ethyl 3-ethyl ether), tetrahydrofurfuryl (3-ethyl 3-ethyl ether) ether , Tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxychetyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenol (3-ethyl-3-oxetayl-methyl) Ether, 2 Tribromophenoxy (3 ethyl 3 oxeta-methyl) ether, 2 Hydroxy ethyl (3 ethyl 3 oxeta-methyl) ether, 2-Hydroxypropyl (3 -Ethyl 3 oxeta-methyl) Ether, butoxetyl (3-ethyl-3-ethyl) -ether, pentachlorophenyl (3-ethyl-3-ethyl) ether, pentabromophenol (3-ethyl-3-ethyl) ether, bor -(3-ethyl-3-oxycetanylmethyl) ether and the like. Specific examples of polymerizable monomers having two oxetane rings include 1,4 bis {[(3 ethyl-3-oxeta-l) methoxy] methyl} benzene, bis {[((1 ethyl) 3-oxetal-]. ] Methyl} ether, 1,4 bis [(3 ethyl 3-oxetal) methoxy] benzene, 1,3 bis [(3 ethyl-3-oxetal) methoxy] benzene, 3, 7-bis (3— Oxetal) -5-oxanonone, 1,4 bis [(3 ethyl 3-oxeta-lmethoxy) methyl] benzene, 1,2 bis [(3 ethyl 3-oxeta-lmethoxy) methyl] ethane, 1, 2 Bis [(3-ethynole-3-oxeta-methoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxeta-methyl) ether, dicyclopentabis (3-ethyl-3-oxeta-methyl) ether, triethyl Glycol bis (3-ethyl-3-oxeta-methyl) ether, tetraethylenedaricol bis (3-ethyl-3-oxeta-methyl) ether, tricyclodecanedyldimethylene bis (3-ethyl-3-oxeta) Rumethyl) ether, 1,4bis [(3 ethyl-3-oxeta-lmethoxy) methyl] butane, 1,6 bis [(3 ethyl-3-oxeta-lmethoxy) methyl] hexane, poly (ethylene glycol bis (3-ethyl-3) —Oxeta-lmethyl) ether, EO-modified Bisphenol A bis (3-Ethyl-3-Ecetal-methyl) ether, PO-modified Bisphenol A bis (3-Ethyl-3-oxeta-lmethyl) ether, EO-modified Hydrogenated Bisph Enol A bis (3-ethyl-3-oxeta-rumethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl) 3-oxeta-methyl) ether, EO-modified bisphenol F bis (3-ethyl-3-ethyl) -ether, and the like. Oxe Specific examples of the polymerizable monomer having 3 to 5 tan rings include trimethylolpropane tris (3-ethyl-3-oxeta-methyl) ether, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether. , Pentaerythritol tetrakis (3-ethyl-3-oxeta-methyl) ether, dipentaerythritol pentakis (3-ethyl 3-oxeta-methyl) ether, and the like.
[0022] また、他の光力チオン重合系組成物として、グリシジルエーテル型エポキシィ匕合物 としては、例えば、芳香族核を有する多価フエノール類またはそのアルキレンォキサ イド付加体のジまたはポリグリシジルエーテル、脂肪族多価アルコールまたはそのァ ルキレンオキサイド付加体のジまたはポリグリシジルエーテル等が挙げられる。具体 的には、ビスフエノーノレ A、ビスフエノーノレ F、ビスフエノーノレ S、水添ビスフエノール A 、水添ビスフエノール F、水添ビスフエノール S、ビスフエノールフルオレンまたはこれ らフエノール類のアルキレンオキサイド付カ卩体のジまたはポリグリシジルエーテル；ェ チレングリコール、プロピレングリコール、 1, 4 ブタンジオール、 1, 6 へキサンジ オールまたはそのアルキレンオキサイド付加体等のアルキレングリコールのジグリシ ジルエーテル；ポリエチレングリコール、ポリプロピレングリコール等のポリアルキレン グリコールのジグリシジルエーテル；ネオペンチルグリコール、ジブ口モネオペンチル グリコールまたはこれらグリコールのアルキレンオキサイド付カ卩体のジグリシジルエー テル；トリメチロールェタン、トリメチロールプロパン、グリセリンまたはこれら 3価アルコ ールのアルキレンオキサイド付カ卩体のジまたはトリグリシジルエーテル；ペンタエリスリ トールのジ、トリまたはテトラグリシジルエーテル等の多価アルトールまたはそのアル キレンオキサイド付加体のポリグリシジルエーテル；ノボラック型エポキシ榭脂；クレゾ 一ルノボラック榭脂；並びにこれら化合物の芳香族核がハロゲン置換された化合物； などが挙げられる。 [0022] Further, as another photothion polymerization composition, examples of glycidyl ether type epoxy compounds include di- or polyglycidyl of polyvalent phenols having an aromatic nucleus or an alkylene oxide adduct thereof. And di- or polyglycidyl ethers of ethers, aliphatic polyhydric alcohols or alkylene oxide adducts thereof. Specifically, bisphenol nore A, bisphenol nore F, bisphenol nore S, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, bisphenol fluorene, or alkylene oxides of these phenols with alkylene oxide Polyglycidyl ethers; diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4 butanediol, 1,6 hexanediol, or alkylene oxide adducts thereof; dialkyl ethers of polyalkylene glycols such as polyethylene glycol and polypropylene glycol Glycidyl ether; neopentyl glycol, dibumonone neopentyl glycol, or diglycidyl ether with an alkylene oxide of these glycols; trimethylol ether , Trimethylolpropane, glycerin, or di- or triglycidyl ethers of alkylene oxides of these trivalent alcohols; polyalterols such as di-, tri-, or tetraglycidyl ethers of pentaerythritol or adducts thereof. And polyglycidyl ethers; novolac-type epoxy resins; creso-one novolac resins; and compounds in which the aromatic nucleus of these compounds is halogen-substituted.
[0023] さらに、脂環式エポキシィ匕合物としては、例えば、シクロへキセンまたはシクロペン テン環等のシクロアルカン環を有する化合物を、過酸化水素や過酸等の適当な酸化 剤でエポキシィ匕することによって得られる、シクロへキセンオキサイドまたはシクロペン テンオキサイド含有ィ匕合物等が挙げられる。具体的には、 3, 4 エポキシシクロへキ シルメチルー 3' , 4 '—エポキシシクロへキサンカルボキシレート、 2- (3, 4 ェポキ シシクロへキシノレ 5, 5—スピロ 3, 4—エポキシ）シクロへキサン一メタージォキサ ン、ビス（3, 4—エポキシシクロへキシルメチル）アジペート、ビュルシクロへキセンォ キサイド、 4 ビュルエポキシシクロへキサン、ビス（3, 4—エポキシ 6—メチルシク 口へキシルメチル）アジペート、 3, 4—エポキシ一 6—メチルシクロへキシル 3' , 4， エポキシ 6'—メチルシクロへキサンカルボキシレート、メチレンビス（3, 4—ェポ キシシクロへキサン）、ジシクロペンタジェンジェポキサイド、エチレングリコールのジ（[0023] Further, as the alicyclic epoxy compound, for example, a compound having a cycloalkane ring such as cyclohexene or cyclopentene ring is epoxyized with an appropriate oxidizing agent such as hydrogen peroxide or peracid. And cyclohexene oxide-containing compounds containing cyclopentene oxide. Specifically, 3, 4 epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 2- (3,4 epoxy Cycyclohexenole 5,5-spiro 3,4-epoxy) cyclohexane monomethadioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bulcyclohexene oxide, 4 burepoxycyclohexane, bis (3, 4-epoxy 6-methylcyclohexylmethyl) adipate, 3, 4-epoxy mono 6-methylcyclohexyl 3 ', 4, epoxy 6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane) , Dicyclopentagenjepoxide, ethylene glycol di (
3, 4 エポキシシクロへキシルメチル）エーテル、エチレンビス（3, 4—エポキシシク 口へキサンカルボキシレート）、エポキシ化テトラべンジルアルコール、ラタトン変性 3, 4 エポキシシクロへキシノレメチノレー 3' , 4' エポキシシクロへキサンカノレボキシレ ート、ラタトン変性エポキシ化テトラヒドロべンジルアルコール、シクロへキセンォキサ イド等が挙げられる。また、光力チオン重合系組成物としては、スピロオルトカーボネ ート化合物も使用可能である。光力チオン重合系組成物は、本発明の榭脂組成物中 に、通常 10〜90質量％、特には 50〜90質量％程度にて含有させることができる。 光酸発生剤の市販品としては、例えば、ユニオンカーバイド社製の UVI— 6950、 UVI— 6970 (ビス [4 （ジ（4一（2 ヒドロキシェチル）フエ-ル）スルホ-ォ）—フエ ニルスルフイド]、 UVI 6974 (ビス [4 -ジフエ-ルスルホ -ォ] フエ-ル）スルフィ ドビスへキサフルォロアンチモネートとジフエ二ルー 4ーチオフエノキシフエニルスルホ -ゥムへキサフルォロアンチモネートとの混合物）、 UVI— 6990 (UVI6974のへキ サフルォロホスフェイトの塩）、旭電ィ匕工業 (株)製のアデカオプトマー SP— 151、 SP — 170 (ビス [4 (ジ（4— (2 ヒドロキシェチル）フエ-ル）スルホ -ォ）一フエ-ルス ルフイド]、 SP— 150 (SP— 170のへキサフルォロホスフェイト）、チバガイギ一社製 の Irgacure 261 5— 2, 4 シクロペンタジェン— 1—ィル） [ (1, 2, 3, 4, 5, 6 — )— (1—メチルェチル）ベンゼン]—鉄（1 + )—へキサフルオロフォスフェート（1 一））、 日本曹達 (株）製の CI— 2481、 CI— 5102、 CI— 2855、 CI— 2064CD— 10 10、サートマ一社製の KI85、 CD— 1011、 CD— 1012 (4— (2 ヒドロキシテトラデ 力-ルォキシ）ジフエ-ルョードニゥムへキサフルォロアンチモネート）、みどり化学（ 株）製の DTS— 102、 DTS— 103、 NAT— 103、 NDS— 103 ( (4—ヒドロキシナフ チル）—ジメチルスルホ -ゥムへキサフルォロアンチモネート）、 TPS— 102 (トリフエ ニルスルホ -ゥムへキサフルォロホスフェイト）、 TPS - 103 (トリフエ-ルスルホ -ゥム へキサフルォロアンチモネート）、 MDS— 103 (4—メトキシフエ-ルージフエ-ルス ルホ -ゥムへキサフルォロアンチモネート）、 MPI- 103 (4—メトキシフエ-ルョード -ゥムへキサフルォロアンチモネート）、 BBI— 101 (ビス（4— tert—ブチルフエ-ル） ョードニゥムテトラフルォロボレート）、 BBI- 102 (ビス（4— tert—ブチルフエ-ル）ョ 一ドニゥムへキサフルォロホスフェート）、 BBI— 103 (ビス（4— tert—フエ-ル）ョード -ゥムへキサフルォロアンチモネート）、デグサ社製の Degacure K126 (ビス [4— ( ジフエ-ノレスノレホニォ）一フエ-ル]スルフイドビスへキサフノレオ口ホスフェイト）、ロー ディア社製のロードシルフオトイニシエータ 2074等の商品名で入手できるものが挙 げられる。これらは、 1種単独あるいは 2種以上を組み合わせて用いることができる。 3, 4 Epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), epoxidized tetrabenzyl alcohol, latataton modified 3, 4 epoxycyclohexenoremethinole 3 ', 4' Examples thereof include epoxycyclohexanecanolevoxylate, latatatone-modified epoxidized tetrahydrobenzyl alcohol, and cyclohexene oxide. A spiro ortho carbonate compound can also be used as the photopower thione polymerization composition. The light-power thione polymerization composition can be contained in the resin composition of the present invention in an amount of usually 10 to 90% by mass, particularly about 50 to 90% by mass. Commercially available photoacid generators include, for example, UVI-6950, UVI-6970 (bis [4 (di (2-hydroxyethyl) sulfuro) sulfo-)-phenylsulfide, manufactured by Union Carbide Corporation. ], UVI 6974 (Bis [4-diphenylsulfo-phenol] sulfide bishexafluoroantimonate and diphenyl 4-thiophenoxyphenylsulfo-muhexafluoroantimonate ), UVI—6990 (UVI6974 hexafluorophosphate salt), Adeka Optomer made by Asahi Denki Kogyo Co., Ltd. SP—151, SP—170 (Bis [4 (Di (4 — (2 hydroxyethyl) felt) sulfo-o) monosulfur sulfide], SP—150 (SP—170 hexafluorophosphate), Irgacure 261 5— 2, manufactured by Ciba Gigi 4 cyclopentadiene— 1—yl) [(1, 2, 3, 4, 5, 6 —) — (1-methylethyl) NZEN] —Iron (1 +) —Hexafluorophosphate (1), manufactured by Nippon Soda Co., Ltd. CI-2481, CI-5102, CI-2855, CI-2064CD-10 10 manufactured by Sartoma KI85, CD-1011, CD-1012 (4— (2 hydroxytetrade-ruxy) diphenol-hexafluoroantimonate), DTS—102, DTS—103, NATURAL CHEMICAL CO., LTD., NAT — 103, NDS—103 ((4-Hydroxynaphthyl) —dimethylsulfo-hexafluoroantimonate), TPS—102 (Triphenyl) Nylsulfo-Humhexafluorophosphate), TPS-103 (Triphenylsulfo-Hexafluoroantimonate), MDS—103 (4-Methoxyphenol-Luju-Fuels Rupho-Humhexaful) Oloantimonate), MPI-103 (4-methoxyphenol-umhexafluoroantimonate), BBI-101 (bis (4-tert-butylphenol) jordontetrafluorobo ), BBI-102 (Bis (4-tert-butylphenol) o-monohexafluorophosphate), BBI-103 (Bis (4-tert-butyl-phenol) iodo-umhexafluoro) (Roantimonate), Degussa Degacure K126 (bis [4— (Diphe-Noresnorejonio) 1-Fuel] sulfide bishexa-no-renophosphate phosphate), Rhodia Rhodosyl Photo Initiator 2074, etc. Can be listed. These can be used alone or in combination of two or more.
[0025] 次に、本発明の第二の光硬化性榭脂組成物は、ラジカル発生剤と、 380〜： LOOOn mに吸収を有する色素と、光ラジカル重合系組成物とを含み、可視光または近赤外 線の照射により、ラジカル重合反応を開始して硬化する接着剤組成物であり、電子 部品の実装用に用いられる。この場合、近赤外線を吸収した色素とラジカル発生剤と の間で電子移動が起こり、ラジカルが発生される。このうち、可視ないし近赤外領域（ 380〜1000nm)に吸収を有する色素については、前述のものと同様のものを用い ることができ、その配合量としては、通常 0. 1〜20質量％、特には 1〜： L0質量％とす ることがでさる。 [0025] Next, the second photocurable resin composition of the present invention comprises a radical generator, 380-: a dye having absorption in LOOOnm, and a photoradical polymerization composition, and visible light. Alternatively, it is an adhesive composition that starts and cures when exposed to near-infrared rays and is used for mounting electronic components. In this case, electron transfer occurs between the dye that absorbs near infrared rays and the radical generator, and radicals are generated. Among these, for the dye having absorption in the visible to near-infrared region (380 to 1000 nm), the same dyes as described above can be used, and the blending amount is usually 0.1 to 20% by mass. In particular, 1 to: L0% by mass can be achieved.
[0026] また、ラジカル発生剤 (ラジカル光重合開始剤）としては、有機過酸化物、ビスイミダ ゾール、ョードニゥム塩、多ハロゲン化合物、チタノセン、ホウ酸塩、スルホン酸誘導 体および N—フエニルダリシン力 なる群力 選ばれるいずれか 1種以上を好適に用 いることができる。このうちョードニゥム塩としては、例えば、ジフエ-ルョードニゥム塩 、ビス（p クロ口フエ-ル）ョードニゥム塩、ジトリルョードニゥム塩、ビス（p— t—ブチ ルフエ-ル）ョードニゥム塩、ビス（m—-トロフエ-ル）ョードニゥム塩などがあり、それ ぞれにおいて、対イオンとして、クロライド、ブロマイド、テトラフルォロボレート、へキサ フルオロフォスフェート、トリフルォロメタンサルフェートなどがある。  [0026] In addition, as radical generators (radical photopolymerization initiators), organic peroxides, bisimidazoles, iodine salts, polyhalogen compounds, titanocenes, borates, sulfonic acid derivatives, and N-phenyldaricin power groups Any one or more selected from force can be suitably used. Among these, examples of the salt include pheo-di-ordinium salt, bis (p-phlogo-fuel) oddonium salt, digly-rhodonium salt, bis (p-t-butyl-felt) ododonium salt, bis ( m--trofeol) Jodonium salt, etc., and counterions include chloride, bromide, tetrafluoroborate, hexafluorophosphate, trifluoromethane sulfate, etc., respectively.
[0027] その他のラジカル光重合開始剤としては、例えば、 2 ヒドロキシ一 2—メチルー 1 フエニルプロパン 1 オン、 1ーヒドロキシシクロへキシルフェニルケトン、 2—メチ ルー 1一（4 （メチルチオ）フエ-ル） 2 モルホリノプロパン 1などのァセトフエノ ン系、ベンジルジメチルケタールなどのべンゾイン系、ベンゾフエノン、 4—フエニルべ ンゾフエノン、ヒドロキシベンゾフエノンなどのべンゾフエノン系、イソプロピノレチォキサ ントン、 2— 4 ジェチルチオキサントンなどのチォキサントン系、ァシルホスフィンォ キサイド系、その他特殊なものとしては、メチルフエ-ルグリオキシレートなどが使用で きる。特に好ましくは、 2—ヒドロキシ— 2—メチル—1—フエ-ルプロパン— 1—オン、 1ーヒドロキシシクロへキシルフエ-ルケトン、 2—メチルー 1一（4 （メチルチオ）フエ -ル） 2—モルホリノプロパン一 1、ベンゾフエノン等が挙げられる。これらラジカル 光重合開始剤は、必要に応じて、 4ージメチルァミノ安息香酸などの安息香酸系また は、第 3級ァミン系などの公知慣用の光重合促進剤の 1種または 2種以上を任意の割 合で混合して使用することができる。また、ラジカル光重合開始剤のみを 1種または 2 種以上混合して使用することができる。ラジカル光重合開始剤は、本発明の接着剤 組成物中に、通常 0. 1〜20質量％、特には 1〜： L0質量％にて含有させることが好ま しい。 [0027] Other radical photopolymerization initiators include, for example, 2-hydroxy-1,2-methyl-1-phenylpropane 1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl 1 1 (4 (methylthio) phenol) 2 Acetophenones such as morpholinopropane 1, benzoins such as benzyldimethyl ketal, benzophenones such as benzophenone, 4-phenylbenzophenone and hydroxybenzophenone, isopropyl Methylphenol glyoxylate and the like can be used as thixanthone series such as norethixanthone, 2-4 jetylthioxanthone, acylphosphine oxide, and other special ones. Particularly preferably, 2-hydroxy-2-methyl-1-phenolpropane-1-one, 1-hydroxycyclohexylphenol ketone, 2-methyl-1-one (4- (methylthio) phenol) 2-morpholinopropane-one 1, benzophenone and the like. These radical photopolymerization initiators may be optionally combined with one or more known photopolymerization accelerators such as benzoic acid-based compounds such as 4-dimethylaminobenzoic acid or tertiary amine amines. Can be mixed and used. Only one radical photopolymerization initiator can be used, or a mixture of two or more can be used. The radical photopolymerization initiator is preferably contained in the adhesive composition of the present invention in an amount of usually 0.1 to 20% by mass, particularly 1 to L0% by mass.
[0028] ラジカル光重合開始剤のうち、ァセトフエノン系光重合開始剤としては、上記の他、 例えば、 4—フエノキシジクロロアセトフエノン、 4— t—ブチル一ジクロロアセトフエノン 、 4— t—ブチル一トリクロロアセトフエノン、ジエトキシァセトフエノン、 1— (4—イソプロ ピルフエ-ル） 2 ヒドロキシ一 2—メチルプロパン一 1—オン、 1— (4 ドデシルフ ェニル） 2 ヒドロキシ一 2—メチルプロパン一 1—オン、 4— (2 ヒドロキシエトキシ )—フエ-ル（2—ヒドロキシ一 2—プロピル）ケトン等が挙げられ、ベンゾフエノン系光 重合開始剤としては、上記の他、ベンゾィル安息香酸、ベンゾィル安息香酸メチル、 4一べンゾィルー 4'ーメチルジフエ-ルサルファイド、 3, 3， 一ジメチルー 4ーメトキシ ベンゾフエノン等が挙げられる。また、ァシルホスフィンオキサイド系としては、例えば 、 2, 4, 6 トリメチルベンゾィルジフエ-ルホスフィンオキサイド、ビス（2, 6 ジメトキ シベンゾィル）—2, 4, 4 トリメチル—ペンチルホスフィンオキサイド等の化合物が挙 げられる。  [0028] Among radical photopolymerization initiators, as the acetophenone photopolymerization initiator, in addition to the above, for example, 4-phenoxydichloroacetophenone, 4-t-butylmonodichloroacetophenone, 4-t —Butyl monotrichloroacetophenone, diethoxyacetophenone, 1— (4-isopropylpropyl) 2 hydroxy-2-methylpropane-1-one, 1— (4 dodecylphenyl) 2 hydroxy-2-methylpropane 1-one, 4- (2 hydroxyethoxy) -phenol (2-hydroxy-1-propyl) ketone, and the like. Benzophenone-based photopolymerization initiators include benzoylbenzoic acid and benzoylbenzoic acid in addition to the above. Examples include methyl acid, 4-benzoyl 4'-methyldiphenyl sulfide, 3,3,1-dimethyl-4-methoxy benzophenone, and the like. Examples of the acyl phosphine oxide include compounds such as 2,4,6 trimethylbenzoyl diphosphine phosphine oxide and bis (2,6 dimethoxybenzoyl) -2,4,4 trimethyl-pentylphosphine oxide. Can be mentioned.
[0029] 上記ァセトフエノン系光重合開始剤の中でも、特に、 2 ヒドロキシー2—メチルー 1 フエニルプロパン 1 オン、 1ーヒドロキシシクロへキシルフェニルケトン、 2—メチ ルー 1一（4 （メチルチオ）フエ-ル） 2 モルホリノプロパン 1が好ましい。また、 上記べンゾフエノン系光重合開始剤の中でも、ベンゾフヱノン、ベンゾィル安息香酸 、ベンゾィル安息香酸メチルが好ましい。 [0029] Among the above-mentioned acetophenone-based photopolymerization initiators, in particular, 2-hydroxy-2-methyl-1-phenylpropane 1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl Lou 1 (4 (methylthio) phenol) 2 Morpholinopropane 1 is preferred. Among the benzophenone photopolymerization initiators, benzophenone, benzoylbenzoic acid, and methyl benzoylbenzoate are preferable.
[0030] さらに、第 3級ァミン系の光重合促進剤としては、トリエタノールァミン、メチルジェタ ノールァミン、トリイソプロパノールァミン、 4, 4，ージメチルァミノべンゾフエノン、 4, 4 ，ージェチルァミノべンゾフエノン、 2 ジメチルァミノ安息香酸ェチル、 4ージメチル ァミノ安息香酸ェチル、 4 ジメチルァミノ安息香酸 (n ブトキシ)ェチル、 4 ジメチ ルァミノ安息香酸イソァミル、 4 ジメチルァミノ安息香酸 2 ェチルへキシルなどが 使用できる。特に好ましくは、光重合促進剤としては、 4—ジメチルァミノ安息香酸ェ チル、 4 ジメチルァミノ安息香酸 (n ブトキシ)ェチル、 4 ジメチルァミノ安息香酸 イソァミル、 4ージメチルァミノ安息香酸 2 ェチルへキシルなどが挙げられる。以上 のように、光重合開始剤は、成分を組み合わせることも可能である。  [0030] Furthermore, tertiary ethanolamine photopolymerization accelerators include triethanolamine, methyljetanolamine, triisopropanolamine, 4,4, -dimethylaminobenzophenone, 4,4, -jetylaminobenzophenone, 2dimethylaminobenzoate. For example, ethyl 4-ethylaminobenzoate, 4-dimethylaminobenzoate (n-butoxy) ethyl, isoamyl 4-dimethylaminobenzoate, 2-dimethylhexyl 4-dimethylaminobenzoate, and the like can be used. Particularly preferably, examples of the photopolymerization accelerator include ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate (n-butoxy) ethyl, isoamyl 4-dimethylaminobenzoate, 2-ethylaminobenzoate 4-dimethylaminobenzoate, and the like. As described above, the photopolymerization initiator can be combined with components.
[0031] また、光ラジカル重合系組成物は、不飽和二重結合のラジカル重合反応を利用す るものであり、主として光重合性官能基を有するモノマーやオリゴマー力 なり、必要 に応じて反応性ポリマーを加えてもよい。また、粘度調製のためにバインダー榭脂を 加えることができる。ノ^ンダー榭脂は、光硬化樹脂と混合することができ、近赤外領 域に大きな吸収を持たな 、ものであれば、制限なく使用できる。  [0031] Further, the photo-radical polymerization composition utilizes a radical polymerization reaction of an unsaturated double bond, and mainly comprises a monomer or oligomer having a photo-polymerizable functional group, and is reactive as required. Polymer may be added. In addition, a binder resin can be added to adjust the viscosity. The non-oxidized resin can be used without limitation as long as it can be mixed with a photo-curing resin and does not have a large absorption in the near infrared region.
[0032] 光重合性官能基を有する反応性ポリマーとしては、例えば、アルキルアタリレート (メ チルアタリレート、ェチルアタリレート、ブチルアタリレート、 2—ェチルへキシルアタリ レート等）および Zまたはアルキルメタタリレート (メチルメタタリレート、ェチルメタクリレ ート、ブチルメタタリレート、 2—ェチルへキシルメタタリレート等）から得られる単独重 合体または共重合体 (即ち、アクリル榭脂)であって、かつ、主鎖または側鎖に光重 合性官能基を有するものを挙げることができる。このような重合体は、例えば、 1種以 上の (メタ)アタリレートと、ヒドロキシル基等の官能基を有する (メタ）アタリレート（2—ヒ ドロキシェチル (メタ)アタリレート等）とを共重合させ、得られた重合体とイソシアナトァ ルキル (メタ)アタリレートなどの、重合体の官能基と反応しかつ光重合性基を有する 化合物と反応させることにより得ることができる。従って、光重合性官能基をウレタン 結合を介して有するアクリル榭脂が好まし ヽ。 [0033] 光ラジカル重合系組成物は、本発明の接着剤組成物中に、通常 10〜90質量％、 特には 50〜90質量％にて含有させることができる。本発明においては、好ましくは、 エチレン性不飽和二重結合を少なくとも 1個有する光ラジカル重合系組成物を含む。 [0032] Examples of the reactive polymer having a photopolymerizable functional group include alkyl acrylate (eg, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate) and Z or alkyl methacrylate. Homopolymers or copolymers (namely, acrylic resin) obtained from a rate (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethyl hexyl methacrylate, etc.) Examples thereof include those having a photopolymerizable functional group in the chain or side chain. Such a polymer is, for example, a copolymer of one or more types of (meth) acrylate and (meth) acrylate (such as 2-hydroxychetyl (meth) acrylate) having a functional group such as a hydroxyl group. It can be obtained by reacting the obtained polymer with a compound having a photopolymerizable group and reacting with a functional group of the polymer, such as isocyanatoalkyl (meth) acrylate. Therefore, an acrylic resin having a photopolymerizable functional group via a urethane bond is preferred. [0033] The photo-radical polymerization composition can be contained in the adhesive composition of the present invention in an amount of usually 10 to 90% by mass, particularly 50 to 90% by mass. In the present invention, it preferably includes a radical photopolymerization composition having at least one ethylenically unsaturated double bond.
[0034] 本発明の接着剤組成物は、フィルム状またはペースト状として好適に用いることが でき、本発明の効果を阻害しない範囲内で、所望により他の添加剤として、フィルム 状の場合には溶剤、酸化防止剤、可塑剤など、ペースト状の場合には溶剤、酸化防 止剤、老化防止剤、チクソトロピック剤、可塑剤、着色剤 (染料)、加工助剤などの成 分を含有してもよい。  [0034] The adhesive composition of the present invention can be suitably used in the form of a film or a paste, and, as long as it does not impair the effects of the present invention, as other additives, if desired, Solvents, antioxidants, plasticizers, and other components such as solvents, antioxidants, anti-aging agents, thixotropic agents, plasticizers, colorants (dyes), and processing aids. May be.
[0035] また、本発明の組成物中には、導電性フィラーを配合することが好ましい。導電性 フィラーを含有する組成物を電極 電極間に介在させることで、組成物を介して導通 を図ることが可能となる。さらに、導電性フィラー表面を榭脂により被覆してもよぐこ の場合には、常態では絶縁体となるとともに、電極 電極間では圧縮され、潰される ことで導通を図ることができる。  [0035] In addition, it is preferable to mix a conductive filler in the composition of the present invention. By interposing the composition containing the conductive filler between the electrodes, conduction can be achieved through the composition. Furthermore, in the case where the surface of the conductive filler may be coated with a resin, it becomes an insulator in a normal state and can be electrically connected by being compressed and crushed between the electrodes.
[0036] 力かる導電性フイラ一としては、電気的に良好な導体であればよぐ種々のものを使 用することができる。例えば、銅、銀、ニッケル、金等の金属ないし合金粉末や、榭脂 材またはセラミック粉体の周囲をこれら金属または合金で被覆したものなどを使用す ることができる。また、その形状についても特に制限はなぐりん片状、樹枝状、粒状、 ペレット状等の任意の形状をとることができる。  [0036] As a strong conductive filler, various types can be used as long as they are electrically good conductors. For example, a metal or alloy powder such as copper, silver, nickel, or gold, or a resin or ceramic powder coated with these metal or alloy can be used. Also, the shape can be any shape such as flake shape, dendritic shape, granular shape, pellet shape, and the like.
[0037] なお、導電性フィラーとしては、弾性率が 1. O X 107〜1. O X 101QPaであるものが 好ましい。即ち、接着剤組成物を適用する被接着体の材質によっては、導電性フイラ 一として弾性率の高いものを用いると、被接着体にクラックが生じるなどの破壊や圧 着後の粒子の弾性変形回復によるスプリングバックなどが発生し、安定した導通性能 を得ることができな 、おそれがあるため、上記弾性率範囲の導電性フィラーを用いる ことが推奨される。これにより、被接着体の破壊を防止して、圧着後の粒子の弾性変 形回復によるスプリングバックの発生を抑制し、導電性フィラーの接触面積を広くする ことが可能になって、より安定した信頼性の高い導通性能を得ることができる。なお、 弾性率が 1. O X 107Paより小さいと、粒子自身の損傷が生じて導通特性が低下する 場合があり、 1. O X 101QPaより大きいと、スプリングバックの発生が生じる恐れがある。 このような導電性フイラ一としては、上記のような弾性率を有するプラスチック粒子の 表面を前述の金属または合金で被覆したものが好適に用いられる。 [0037] The conductive filler is preferably one having an elastic modulus of 1. OX 10 7 to 1. OX 10 1Q Pa. In other words, depending on the material of the adherend to which the adhesive composition is applied, if a conductive filler having a high elastic modulus is used, the adherend will be cracked or elastically deformed after pressing. It is recommended to use a conductive filler in the above elastic modulus range because there is a possibility that stable conduction performance cannot be obtained due to the occurrence of springback due to recovery. This prevents damage to the adherend, suppresses the occurrence of springback due to recovery of elastic deformation of the particles after crimping, increases the contact area of the conductive filler, and is more stable. Highly reliable conduction performance can be obtained. If the elastic modulus is less than 1. OX 10 7 Pa, the particles themselves may be damaged and the conduction characteristics may be degraded. 1. If it is greater than OX 10 1Q Pa, springback may occur. . As such a conductive filler, one in which the surface of the plastic particles having the above elastic modulus is coated with the aforementioned metal or alloy is preferably used.
[0038] 組成物中における導電性フィラーの配合量としては、ベース榭脂（光力チオン重合 系組成物ないし光ラジカル重合系組成物）に対して 0. 1〜15容量％であることが好 ましぐまた、この導電性フィラーの平均粒径は 0. 1〜： LOO /z mであることが好ましい 。このように配合量および粒径を規定することにより、隣接した回路間で導電性フイラ 一が凝縮し、短絡し難くなり、良好な導電性を得ることが可能となる。  [0038] The blending amount of the conductive filler in the composition is preferably 0.1 to 15% by volume with respect to the base resin (light power thione polymerization composition or photo radical polymerization composition). Moreover, the average particle size of the conductive filler is preferably 0.1 to: LOO / zm. By defining the blending amount and the particle size in this way, the conductive filler is condensed between adjacent circuits, and it becomes difficult to short-circuit, and good conductivity can be obtained.
[0039] 本発明の接着剤組成物をペースト状とする場合には、室温付近での粘度が 1〜10 00Pa' s、特には、 10〜500Pa ' sであることが好ましい。従って、このような粘度が得 られるように、光重合性組成物および各種添加剤の配合量を適宜調整することが望 ましい。  [0039] When the adhesive composition of the present invention is made into a paste, the viscosity at around room temperature is preferably 1 to 1000 Pa's, particularly 10 to 500 Pa's. Therefore, it is desirable to appropriately adjust the blending amounts of the photopolymerizable composition and various additives so that such a viscosity can be obtained.
[0040] 上記本発明の接着剤組成物は、可視光または近赤外線の照射により硬化させるこ とができるものであり、本発明において硬化に使用できる光源としては、可視光また は近赤外線を発光するものであれば特に制限はないが、半導体レーザー、レーザー ダイオード、 LED (Light Emitting Diodes)、ハロゲンランプ、 VCSEL (Vertical [0040] The adhesive composition of the present invention can be cured by irradiation with visible light or near-infrared rays, and the light source that can be used for curing in the present invention emits visible light or near-infrared light. There are no particular restrictions, but semiconductor lasers, laser diodes, LEDs (Light Emitting Diodes), halogen lamps, VCSEL (Vertical
Cavity Surface Emitting Laser Diode,面発光型レーザー）などが挙げら れる。また、可視光または近赤外線の照射後に、必要に応じて加熱することで、硬化 を促進させることも可能である。照射時間は、光源の種類および強さによるためー概 には決められないが、数秒〜数十分程度とする。なお、本発明の組成物を用いて接 着を行う際には、 l〜4MPa程度の圧力を付与しながら硬化を行うことが好ましぐま た、硬化に先立って、室温〜 50°C程度の温度で 0. lMPa〜l . 5MPa程度の圧力 を付与することにより、仮圧着を行うことも好ましい。 Cavity Surface Emitting Laser Diode). In addition, curing can be promoted by heating as necessary after irradiation with visible light or near infrared rays. The irradiation time depends on the type and intensity of the light source – it cannot be roughly determined, but it should be several seconds to several tens of minutes. In addition, when performing adhesion using the composition of the present invention, it is preferable to cure while applying a pressure of about 1 to 4 MPa. Prior to curing, the temperature is about room temperature to about 50 ° C. It is also preferable to perform temporary pressure bonding by applying a pressure of about 0.1 MPa to 1.5 MPa at a temperature.
[0041] 本発明の接着剤組成物には、さら〖こ、紫外線の照射により硬化する既知の紫外線 硬化型榭脂組成物成分を含有させることもでき、特に制限されるものではない。紫外 線硬化型榭脂組成物成分を含有させた本発明の接着剤組成物は、可視光な!ヽし近 赤外線と紫外線との双方で硬化可能であるという特徴を有する。この場合、可視光ま たは近赤外線の照射による硬化物の屈折率力 紫外線の照射による硬化物の屈折 率よりも高いことが好ましい。また、前記色素として、紫外線の照射により分解されて、 近赤外領域の吸収が低下するものを用いることが好ま 、。 [0041] The adhesive composition of the present invention can contain a known UV-curable resin composition that is cured by irradiation with UV light and is not particularly limited. The adhesive composition of the present invention containing an ultraviolet ray curable resin composition component is characterized by being curable with visible light, near infrared rays and ultraviolet rays. In this case, the refractive index power of the cured product by irradiation with visible light or near infrared light is preferably higher than the refractive index of the cured product by irradiation with ultraviolet rays. Further, as the pigment, it is decomposed by irradiation with ultraviolet rays, It is preferable to use a material that decreases the absorption in the near infrared region.
[0042] 本発明の接着剤組成物は、光重合性組成物および前述の各種添加剤を所定の配 合で溶媒に溶解な 、し分散させることでペースト状に調製することができ、デイスペン サ一に充填して塗布または注入することができる。具体的には例えば、図 1 (a)に示 すような、基板 11上の電極 1と BGA (Ball Grid Array)実装チップ 12とをはんだ バンプ 2を介してリフローにより実装したフリップチップ実装においては、実装後に基 板 11—チップ 12間の隙間にアンダーフィルとしてペースト状の組成物 10を注入、硬 化させることで封止を行うことができ、同図（b)に示すような、基板 11上の電極 1と Au スタッドバンプ 3を形成したチップ 12とを熱圧着により実装したフリップチップ実装に お!、ては、基板上にあら力じめペースト状の組成物 10を塗布した状態で圧着を行え ばよい。また、例えば、 COF (Chip On Flex (Film) ) , COB (Chip On Board) , COG (Chip On Glass) , FOF (Flex On Flex) , FOB (Flex On Board) , FOG (Flex On Glass)等の各種パッケージ形態（図 1)や基板間接続（図 2)に示 すような基板 21上の電極 1と基板 22上の電極 1との間を接続する場合についても、 一方の基板上にあら力じめペースト状の組成物 10を塗布して接着を行えばよぐい ずれの場合にも、良好な導通および接着性を得ることができる。  [0042] The adhesive composition of the present invention can be prepared in a paste form by dissolving and dispersing the photopolymerizable composition and the various additives described above in a solvent in a predetermined combination. It can be filled and applied or injected. Specifically, for example, in the flip chip mounting in which the electrode 1 on the substrate 11 and the BGA (Ball Grid Array) mounting chip 12 are mounted by reflow through the solder bumps 2 as shown in FIG. Then, after mounting, the paste 11 is injected into the gap between the substrate 11 and the chip 12 as an underfill and cured, and the substrate 11 can be sealed as shown in FIG. For flip chip mounting in which the upper electrode 1 and the chip 12 with the Au stud bump 3 are mounted by thermocompression bonding, press the paste composition 10 applied onto the substrate. Can be done. Also, for example, COF (Chip On Flex (Film)), COB (Chip On Board), COG (Chip On Glass), FOF (Flex On Flex), FOB (Flex On Board), FOG (Flex On Glass), etc. When connecting between electrode 1 on substrate 21 and electrode 1 on substrate 22 as shown in various package configurations (Fig. 1) and board-to-board connections (Fig. 2), force is exerted on one substrate. Even if the paste 10 is applied and adhered, good conduction and adhesion can be obtained.
[0043] ここで、塗布する場合のペースト状組成物の厚みとしては、特に制限されな!、が、 例えば、 5〜： L00 mの範囲内とすることができ、対向する電極の厚みに合わせて、 適宜厚みを制御することができる。  [0043] Here, the thickness of the paste-like composition in the case of application is not particularly limited !, but can be, for example, in the range of 5 to: L00 m and matched to the thickness of the opposing electrode. Thus, the thickness can be appropriately controlled.
[0044] また、本発明の接着剤組成物は、光重合性組成物および前述の各種添加剤を所 定の配合で均一に混合し、押出機、ロール等で混練した後、カレンダーロール、 Tダ ィ押出、インフレーション等の成膜法により所定の形状に成膜することによりフィルム 状に調製することができる。また、接着剤組成物の配合成分を溶媒に溶解ないし分 散させ、セパレーターの表面に塗布した後、溶媒を蒸発させることによつてもフィルム 状に成膜することができる。なお、成膜に際しては、ブロッキング防止、被着体との圧 着を容易にするため等の目的で、エンボス力卩ェを施してもよい。本発明のフィルム状 組成物は、具体的には例えば、図 1 (b)に示すような、基板 11上の電極 1と Au^タツ ドバンプ 3を形成した BGA (Ball Grid Array)実装チップ 12とを熱圧着により実装 したフリップチップ実装に適用することができ、基板上にフィルム状の組成物 10を載 置した状態で圧着を行うことで、封止を行うことができる。また、例えば、 COF (Chip On Flex (Film) ) , COB (Chip On Board) , COG (Chip On Glass) , FOF ( Flex On Flex) , FOB (Flex On Board) , FOG (Flex On Glass)等の各種 ノ ッケージ形態（図 1)や基板間接続 (図 2)に示すような基板 21上の電極 1と基板 22 上の電極 1との間を接続する場合についても、一方の基板上にあらカゝじめフィルム状 の組成物 10を載置、圧着して接着を行えばよぐいずれの場合にも、良好な導通お よび接着性を得ることができる。 [0044] Further, the adhesive composition of the present invention comprises a photopolymerizable composition and the above-mentioned various additives that are uniformly mixed in a predetermined composition and kneaded with an extruder, a roll, etc. A film can be prepared by forming a film into a predetermined shape by a film forming method such as die extrusion or inflation. Also, a film-like film can be formed by dissolving or dispersing the compounding components of the adhesive composition in a solvent, applying it to the surface of the separator, and then evaporating the solvent. In the film formation, embossing force may be applied for the purpose of preventing blocking and facilitating the pressing with the adherend. Specifically, the film-like composition of the present invention includes, for example, a BGA (Ball Grid Array) mounting chip 12 on which an electrode 1 and an Au ^ t bump 3 are formed on a substrate 11 as shown in FIG. 1 (b). Mounted by thermocompression bonding The flip-chip mounting can be applied, and sealing can be performed by performing pressure bonding in a state where the film-like composition 10 is placed on the substrate. Also, for example, COF (Chip On Flex (Film)), COB (Chip On Board), COG (Chip On Glass), FOF (Flex On Flex), FOB (Flex On Board), FOG (Flex On Glass), etc. When connecting between the electrode 1 on the substrate 21 and the electrode 1 on the substrate 22 as shown in various types of knocking (Fig. 1) and inter-substrate connections (Fig. 2) In any case where the bullying film-like composition 10 is placed and bonded by pressure bonding, good conduction and adhesion can be obtained.
[0045] この場合、フィルム状組成物の厚みとしては、特に制限されないが、例えば、 5〜10 0 m程度とすることができ、対向する電極の厚みに合わせて、適宜厚みを制御する ことができる。 [0045] In this case, the thickness of the film composition is not particularly limited, but can be, for example, about 5 to 100 m, and the thickness can be appropriately controlled according to the thickness of the opposing electrode. it can.
実施例  Example
[0046] 以下、本発明を、実施例を用いてより詳細に説明する。  Hereinafter, the present invention will be described in more detail using examples.
(実施例 1 1)  (Example 1 1)
下記の表 1に示すポリエステル榭脂をトルエンとメチルェチルケトンとの混合溶媒に 溶解し、 40重量％溶液を調製して、このポリエステル榭脂溶液 100重量部に対して、 表 1中の残りの成分を表中に示す量で混合し、これをバーコ一ターによりセパレータ 一であるポリテレフタル酸エチレン上に塗布し、幅 2mm、厚さ 35 μ mの異方性導電 フイノレムを得た。  The polyester resin shown in Table 1 below is dissolved in a mixed solvent of toluene and methylethylketone to prepare a 40% by weight solution. These components were mixed in the amounts shown in the table, and this was applied onto poly (ethylene terephthalate) as a separator with a bar coater to obtain an anisotropic conductive finolem having a width of 2 mm and a thickness of 35 μm.
[0047] 得られたフィルムを、無接着剤タイプ 2層ポリイミド製フレキシブルプリント基板と銀 ペーストを対向電極とするポリテレフタル酸エチレン (PET)製プリント基板同士の接 着用として、セパレーターを剥離して、モニターで位置決めをし、 50°Cで 1秒間、 0. 5MPaにお!/、て仮圧着を行なった。  [0047] The obtained film was attached to a non-adhesive type two-layer polyimide flexible printed circuit board and a polyethylene terephthalate (PET) printed circuit board using silver paste as a counter electrode, and the separator was peeled off. Positioning was performed with a monitor, and temporary pressure bonding was performed at 0.5 MPa for 1 second at 50 ° C.
[0048] 引き続き、 50°C60秒間、 2MPaの条件で圧着を行ないながら、圧着テーブルとな る石英ガラスを通して、 PET製基板側から IR照射 (ASAHI SPECTRA製 キセノ ン光源、 LAX— 102、 IRミラーモジュール使用、透過波長域 700〜1020nm)を同 時間行なった。  [0048] Next, IR irradiation (ASAHI SPECTRA xenon light source, LAX-102, IR mirror module through the quartz glass serving as the crimping table while crimping at 50 ° C for 60 seconds under the condition of 2MPa. Use and transmission wavelength range of 700-120 nm) were performed for the same time.
[0049] 得られたサンプルについて、引張試験機による 90° 剥離試験（50mmZmin)によ り接着力を測定した。また、対向する配線パターン間の接続抵抗を、デジタルマルチ メーターにて測定した。さらに、隣り合う配線パターン間（300 mピッチ）の絶縁抵抗 を超高抵抗計にて測定した。これらの結果を、下記の表 1中に併せて示す。 [0049] The obtained sample was subjected to a 90 ° peel test (50 mmZmin) using a tensile tester. The adhesive strength was measured. The connection resistance between the opposing wiring patterns was measured with a digital multimeter. Furthermore, the insulation resistance between adjacent wiring patterns (300 m pitch) was measured with an ultrahigh resistance meter. These results are also shown in Table 1 below.
[0050] (実施例 1 2) [0050] (Example 1 2)
導電性粒子を配合しな ヽこと以外は実施例 1— 1と同一製法にて、非導電性フィル ムを調製した。得られたフィルムを用いて、実施例 1—1と同様の基板につき、実施例 A nonconductive film was prepared by the same production method as in Example 1-1, except that the conductive particles were not blended. Using the obtained film, the same substrate as in Example 1-1 was used.
1— 1と同条件にて仮圧着を行なった。 Temporary pressure bonding was performed under the same conditions as 1-1.
[0051] 引き続き、 50°C60秒間、 3MPaの条件で圧着を行ないながら、圧着テーブルとな る石英ガラスを通して、 PET製基板側から IR照射 (ASAHI SPECTRA製 キセノ ン光源、 LAX— 102、 IRミラーモジュール使用、透過波長域 700〜1020nm)を同 時間行なった。 [0051] Subsequently, IR irradiation (ASAHI SPECTRA xenon light source, LAX-102, IR mirror module through the quartz glass serving as the crimping table through crimping at 3MPa for 60 seconds at 50 ° C. Use and transmission wavelength range of 700-120 nm) were performed for the same time.
[0052] 得られたサンプルにつ 、て、実施例 1— 1と同様にして評価を行った結果を、下記 の表 1中に併せて示す。  [0052] The obtained samples were evaluated in the same manner as in Example 1-1, and the results are also shown in Table 1 below.
[0053] [表 1] [0053] [Table 1]
Figure imgf000018_0001
Figure imgf000018_0001
* 1 :ュニチカ株式会社製 飽和共重合ポリエステル，エリーテル UE3600の解重合 物のメタクリロキシ基導入ィ匕合物 * 1: Depolymerization of Saturated Copolyester, Elitel UE3600, manufactured by Unitika Ltd. Methacryloxy group introduction compound
* 2 : 8— [ (6, 7—ジヒドロ一 2, 4—ジフエ-ル一 5H—1—ベンゾピラン一 8—ィル)メ チレン] 5, 6, 7, 8—テトラヒドロ一 2, 4—ジフエ-ル一 1—ベンゾピリリウムパークロレ ート  * 2: 8— [(6,7-Dihydro-1,2,4-Diphenyl-5H-1—Benzopyran-8-yl) methylene] 5, 6, 7, 8—Tetrahydro 1,2,4-Diphenol -Le 1—benzopyrylium perchlorate
* 3：ジフエ-ルョードニゥムクロライド  * 3: Jihue-Rheuddenum Chloride
* 4： N—フエ-ルグリシン  * 4: N—Fuel-glycine
* 5：ペンタエリエストールテトラアタリレート  * 5: Pentaeliestor tetra acrylate
* 6：ネオペンチルグリコールジメタタリレート  * 6: Neopentyl glycol dimetatalylate
* 7 : γ—メタクリロキシプロピルトリメトキシシラン  * 7: γ-Methacryloxypropyltrimethoxysilane
* 8：積水化学株式会社製 Au205,平均粒子径 5 μ m (但し、導電性粒子の配合 量のみ、ベース榭脂（ポリエステル不飽和化合物）に対する体積％である。 )  * 8: Au205 manufactured by Sekisui Chemical Co., Ltd., average particle size 5 μm (however, only the amount of conductive particles is volume% based on the base resin (polyester unsaturated compound).)
[0054] 上記表 1の結果より、本発明の接着剤組成物としての実施例の異方性導電フィルム および非導電性フィルムは、いずれも著しく接着性、導通性および絶縁性に優れるこ とが確かめられた。  [0054] From the results in Table 1 above, the anisotropic conductive films and non-conductive films of the examples as the adhesive composition of the present invention may be remarkably excellent in adhesiveness, conductivity, and insulation. It was confirmed.
[0055] (実施例 2— 1)  [0055] (Example 2-1)
下記の表 2に示すポリエステル榭脂をメチルェチルケトンの溶媒に溶解し、 65重量 %溶液を調製して、このポリエステル榭脂溶液 100重量部に対して、表 2中の残りの 成分を表中に示す量で 3本ロールにて混合し、異方性導電ペーストを得た。  The polyester resin shown in Table 2 below is dissolved in a methyl ethyl ketone solvent to prepare a 65 wt% solution, and the remaining components in Table 2 are expressed with respect to 100 parts by weight of the polyester resin solution. An anisotropic conductive paste was obtained by mixing with three rolls in the amount shown in the figure.
[0056] 得られたペーストを、ディスペンサー（ショットマスター：武蔵エンジニアリング (株）製 )を用いて、銀ペーストを電極とするポリテレフタル酸エチレン (PET)製プリント基板 上に描画し、無接着剤タイプ 2層ポリイミド製フレキシブルプリント基板との接着用とし て、モニターで位置決めをし、 50°Cで 1秒間、 0. 5MPaにおいて仮圧着を行なった  [0056] Using a dispenser (Shot Master: manufactured by Musashi Engineering Co., Ltd.), the obtained paste is drawn on a polyterephthalate (PET) printed circuit board using silver paste as an electrode, and is adhesive-free. Positioned with a monitor for bonding to a 2-layer polyimide flexible printed circuit board, and temporarily crimped at 0.5 MPa for 1 second at 50 ° C
[0057] 引き続き、 50°C60秒間、 2MPaの条件で圧着を行ないながら、圧着テーブルとな る石英ガラスを通して、 PET製基板側から IR照射 (ASAHI SPECTRA製 キセノ ン光源、 LAX— 102、 IRミラーモジュール使用、透過波長域 700〜1020nm)を同 時間行なった。 [0057] Subsequently, IR irradiation (ASAHI SPECTRA xenon light source, LAX-102, IR mirror module through the quartz glass serving as the crimping table through crimping at 2MPa for 60 seconds at 50 ° C. Use and transmission wavelength range of 700-120 nm) were performed for the same time.
[0058] 得られたサンプルについて、引張試験機による 90° 剥離試験（50mmZmin)によ り接着力を測定した。また、対向する配線パターン間の接続抵抗を、デジタルマルチ メーターにて測定した。さらに、隣り合う配線パターン間（300 mピッチ）の絶縁抵抗 を超高抵抗計にて測定した。これらの結果を、下記の表 2中に併せて示す。 [0058] The obtained sample was subjected to a 90 ° peel test (50 mmZmin) using a tensile tester. The adhesive strength was measured. The connection resistance between the opposing wiring patterns was measured with a digital multimeter. Furthermore, the insulation resistance between adjacent wiring patterns (300 m pitch) was measured with an ultrahigh resistance meter. These results are also shown in Table 2 below.
[0059] (実施例 2— 2) [0059] (Example 2-2)
導電性粒子を配合しないこと以外は実施例 2— 1と同一製法にて、非導電性ペース トを調製した。得られたペーストを用いて、実施例 2—1と同様の基板につき、実施例 A non-conductive paste was prepared by the same manufacturing method as Example 2-1 except that the conductive particles were not blended. Using the obtained paste, the same examples as those in Example 2-1 were used.
2—1と同条件にて仮圧着を行なった。 Temporary pressure bonding was performed under the same conditions as in 2-1.
[0060] 引き続き、 50°C60秒間、 3MPaの条件で圧着を行ないながら、圧着テーブルとな る石英ガラスを通して、 PET製基板側から IR照射 (ASAHI SPECTRA製 キセノ ン光源、 LAX— 102、 IRミラーモジュール使用、透過波長域 700〜： 1020nm)を同 時間行なった。 [0060] Next, IR irradiation (ASAHI SPECTRA xenon light source, LAX-102, IR mirror module through the quartz glass serving as the crimping table through crimping at 3MPa for 60 seconds at 50 ° C. Use, transmission wavelength range 700-: 1020 nm) was performed at the same time.
[0061] 得られたサンプルについて、実施例 2—1と同様にして評価を行った結果を、下記 の表 2中に併せて示す。  [0061] The results of evaluation of the obtained samples in the same manner as in Example 2-1 are also shown in Table 2 below.
[0062] [表 2] — 実施例 2 - 1 実施例 2-2 ポリエステル不飽和化合物 *9 100 100 [0062] [Table 2] — Example 2-1 Example 2-2 Polyester unsaturated compound * 9 100 100
IR吸収色素 *2 10 10  IR absorbing dye * 2 10 10
ラジカル光重合開删 *3 3 3 Radical photopolymerization * 3 3 3
配  Arrangement
□ ラジカル光重合開始剤 *4 1 1  □ Radical photoinitiator * 4 1 1
ァクリ口キシ基含有化合物 *5 5 5  Acrylic group-containing compound * 5 5 5
メ夕クリロキシ基含有化合物 *6 3 3  Mebutyloxy group-containing compound * 6 3 3
シランカップリング剤 *7 1 1 Silane coupling agent * 7 1 1
チクソトロピック剤 0 2 2  Thixotropic agent 0 2 2
導電性粒子 *8 5 ―  Conductive particles * 8 5 ―
接着力 （N/m (gf/cm) ) 519 (530) 549 (560) ϊ 接続抵抗 (Ω) 2 3  Adhesive strength (N / m (gf / cm)) 519 (530) 549 (560) ϊ Connection resistance (Ω) 2 3
騰職 (Ω) 1.E+11 1.E+12  Employment (Ω) 1.E + 11 1.E + 12
接着力 .接続雕 . 接着力 .接続抵抗， 総合評価  Adhesive strength. Connection strength. Adhesive strength. Connection resistance, comprehensive evaluation
隱^:良好 抗良好 * 2〜* 8 :上記表 1と同様のものを用いた。 （但し、導電性粒子の配合量のみ、ベー ス榭脂（ポリエステル不飽和化合物）に対する体積％である。 ) 隱 ^: Good Anti-good * 2 to * 8: The same as in Table 1 above was used. (However, only the blending amount of the conductive particles is volume% with respect to the base resin (polyester unsaturated compound).)
* 9 :ュ-チカ株式会社製 飽和共重合ポリエステル，エリーテル UE3200の解重合 物のメタクリロキシ基導入ィ匕合物  * 9: Saturated copolyester made by Utica Co., Ltd. Elitel UE3200 depolymerized methacryloxy group-introduced compound
* 10 :楠本化成株式会社製 ディスパロン 6820— 10M  * 10: Disparon 6820-10M manufactured by Enomoto Kasei Co., Ltd.
上記表 2の結果より、本発明の接着剤組成物としての実施例の異方性導電ペース トおよび非導電性ペーストは、いずれも著しく接着性、導通性および絶縁性に優れる ことが確かめられた。  From the results of Table 2 above, it was confirmed that the anisotropic conductive pastes and non-conductive pastes of the examples as the adhesive composition of the present invention were remarkably excellent in adhesiveness, conductivity and insulation. .

Claims

請求の範囲 The scope of the claims
[I] 光酸発生剤と、 380〜： LOOOnmに吸収を有する色素と、光力チオン重合系組成物 とを含み、可視光または近赤外線の照射により酸を発生し、カチオン重合反応を開 始して硬化する接着剤組成物であって、電子部品の実装用に用いられることを特徴 とする接着剤組成物。  [I] Photoacid generator, 380 ~: A dye having absorption at LOOOnm, and a photopower thione polymerization composition, generate acid by irradiation with visible light or near infrared ray, and start cationic polymerization reaction An adhesive composition that cures when used, and is used for mounting electronic components.
[2] 前記光酸発生剤が、可視光または近赤外線の照射により、ブレンステッド酸または ルイス酸を発生する請求項 1記載の接着剤組成物。  [2] The adhesive composition according to [1], wherein the photoacid generator generates Bronsted acid or Lewis acid upon irradiation with visible light or near infrared rays.
[3] 前記光酸発生剤が、ァリールジァゾニゥム塩、ジァリールョードニゥム塩、トリアリー ルスルホ -ゥム塩、ジアルキルフエナシルスルホ -ゥム塩およびスルホン酸エステル 化合物からなる群力 選ばれるいずれか 1種以上である請求項 1または 2記載の接着 剤組成物。 [3] The photoacid generator is selected from allyldiazonium salt, dialyrhodonium salt, triarylsulfo-um salt, dialkylphenacylsulfo-um salt and sulfonate compound. The adhesive composition according to claim 1 or 2, wherein the adhesive composition is one or more selected.
[4] ラジカル発生剤と、 380〜： LOOOnmに吸収を有する色素と、光ラジカル重合系組成 物とを含み、可視光または近赤外線の照射により、ラジカル重合反応を開始して硬 化する接着剤組成物であって、電子部品の実装用に用いられることを特徴とする接 着剤組成物。  [4] Adhesive containing a radical generator, 380-: a dye having absorption at LOOOnm, and a photo-radical polymerization composition, which starts and cures when exposed to visible light or near-infrared radiation. An adhesive composition characterized by being used for mounting electronic components.
[5] 前記ラジカル発生剤が、有機過酸化物、ビスイミダゾール、ョードニゥム塩、多ハロ ゲン化合物、チタノセン、ホウ酸塩、スルホン酸誘導体および N—フエ-ルグリシンか らなる群カゝら選ばれるいずれか 1種以上である請求項 4記載の接着剤組成物。  [5] The radical generator may be selected from the group consisting of organic peroxides, bisimidazoles, iodine salts, polyhalogen compounds, titanocene, borates, sulfonic acid derivatives, and N-phenol glycine. The adhesive composition according to claim 4, wherein the adhesive composition is one or more.
[6] エチレン性不飽和二重結合を少なくとも 1個有するラジカル重合性ィ匕合物を含む請 求項 4または 5記載の接着剤組成物。 [6] The adhesive composition according to claim 4 or 5, comprising a radical polymerizable compound having at least one ethylenically unsaturated double bond.
[7] フィルム状である請求項 1〜6のうち 、ずれか一項記載の接着剤組成物。 [7] The adhesive composition according to any one of [1] to [6], wherein the adhesive composition is in the form of a film.
[8] ペースト状である請求項 1〜6のうち 、ずれか一項記載の接着剤組成物。 [8] The adhesive composition according to any one of claims 1 to 6, which is in a paste form.
[9] さらに、紫外線の照射により硬化する紫外線硬化型榭脂組成物成分を含む請求項[9] The method further comprises an ultraviolet curable resin composition component that is cured by irradiation with ultraviolet rays.
1〜8のうち 、ずれか一項記載の接着剤組成物。 The adhesive composition according to any one of 1 to 8.
[10] 導電性フィラーを含有する請求項 1〜9のうちいずれか一項記載の接着剤組成物。 [10] The adhesive composition according to any one of claims 1 to 9, comprising a conductive filler.
[II] 光増感剤を含有する請求項 1〜10のうちいずれか一項記載の接着剤組成物。  [II] The adhesive composition according to any one of claims 1 to 10, comprising a photosensitizer.
[12] フリップチップ実装におけるアンダーフィルとして用いられる請求項 1〜： L 1のうちい ずれか一項記載の接着剤組成物。 電極 電極間を接続する接着剤として用いられる請求項 1〜： L Iのうちいずれか一 項記載の接着剤組成物。 [12] The adhesive composition according to any one of claims 1 to L1, which is used as an underfill in flip chip mounting. The adhesive composition according to claim 1, which is used as an adhesive for connecting electrodes.
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