WO2009128530A1 - Adhesive composition, adhesive for circuit connection, connected structure, and semiconductor device - Google Patents
Adhesive composition, adhesive for circuit connection, connected structure, and semiconductor device Download PDFInfo
- Publication number
- WO2009128530A1 WO2009128530A1 PCT/JP2009/057757 JP2009057757W WO2009128530A1 WO 2009128530 A1 WO2009128530 A1 WO 2009128530A1 JP 2009057757 W JP2009057757 W JP 2009057757W WO 2009128530 A1 WO2009128530 A1 WO 2009128530A1
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- adhesive
- weight
- circuit
- adhesive composition
- parts
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- 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
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
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- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
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- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
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- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
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Definitions
- the present invention relates to an adhesive composition, an adhesive for circuit connection using the same, a connection body, and a semiconductor device.
- the adhesives are conventionally used for the purpose of bonding various members in the element.
- the properties required for adhesives are diverse, including adhesiveness, heat resistance, and reliability in high temperature and high humidity conditions.
- the adherends used for adhesion include organic substrates such as printed wiring boards and polyimides, metals such as copper and aluminum, and substrates having various surface states such as ITO, SiN, and SiO 2. Is used. For this reason, it is necessary to molecularly design the adhesive in accordance with each adherend.
- thermosetting resin using an epoxy resin having high adhesiveness and high reliability has been mainly used (for example, see Patent Document 1).
- a resin containing a curing agent such as an epoxy resin, a phenol resin having reactivity with the epoxy resin, and a thermal latent catalyst that promotes the reaction between the epoxy resin and the curing agent as a constituent component is generally used.
- the heat latent catalyst is an important factor for determining the curing temperature and the curing rate, and various compounds have been used from the viewpoint of storage stability at room temperature and curing rate during heating.
- desired adhesiveness can be obtained by curing at a temperature of 170 to 250 ° C. for 1 to 3 hours.
- radical curing type adhesives have a problem that the adhesive strength is inferior compared with the case of using an epoxy resin because the curing shrinkage during curing is large.
- a method for improving the adhesive strength a method of using a urethane acrylate compound imparted with flexibility and flexibility by an ether bond as a radical polymerizable compound has been proposed (see Patent Documents 3 and 4).
- the present invention shows sufficient adhesion even when cured at a low temperature in a short time, and connection reliability even after the connection body is exposed for a long time under high temperature and high humidity conditions (for example, 85 ° C./85% RH). It is an object of the present invention to provide an adhesive composition that is high and that is excellent in storage stability, and an adhesive for circuit connection, a connection body, and a semiconductor device using the same.
- the present invention provides (a) a thermoplastic resin, (b) two or more (meth) acryloyl groups and two or more urethane bonds in one molecule, and a weight average molecular weight of 10,000.
- an adhesive composition containing the above-described radical polymerizable compound (hereinafter also simply referred to as “(b) radical polymerizable compound”) and (c) a radical polymerization initiator.
- the adhesive composition of the present invention comprises (a) 10 to 250 parts by weight of a radically polymerizable compound and (c) 0.05 to 30 parts by weight of a radical polymerization initiator with respect to 100 parts by weight of a thermoplastic resin. It is preferable to contain a part.
- the adhesive composition of the present invention comprises (d) a vinyl compound having at least one phosphate group in the molecule, and (a) 0.1 to 20 parts by weight relative to 100 parts by weight of the thermoplastic resin. It is preferable to contain.
- the adhesive composition of the present invention preferably further contains (e) conductive particles.
- the present invention is also an adhesive for circuit connection that is interposed between substrates having circuit electrodes facing each other and used for bonding the substrates so that the circuit electrodes facing each other are electrically connected to each other.
- An adhesive for circuit connection comprising the adhesive composition of the present invention is provided.
- Such an adhesive for circuit connection uses the adhesive composition of the present invention, it exhibits sufficient adhesion even when cured at a low temperature for a short time, and can be used for a long time under high temperature and high humidity conditions. Even after exposure, connection reliability is high and storage stability is also excellent.
- the present invention also provides a first substrate having a first circuit electrode and a second substrate having a second circuit electrode so that the first circuit electrode and the second circuit electrode face each other.
- the first circuit electrode and the second circuit electrode are disposed between the first substrate and the second substrate disposed opposite to each other by interposing the adhesive for circuit connection according to the present invention and heating and pressing.
- a connection body that is electrically connected.
- the present invention further provides an electrical connection between the semiconductor element and the semiconductor mounting substrate by interposing the circuit connecting adhesive of the present invention between the semiconductor element and the semiconductor mounting substrate opposed to each other, and applying heat and pressure.
- a semiconductor device which is connected.
- connection body and the semiconductor device use the adhesive for circuit connection of the present invention, the connection body and the semiconductor device have sufficiently high adhesiveness and high connection reliability even after being exposed for a long time under high temperature and high humidity conditions.
- (meth) acryl means acryl and methacryl corresponding thereto
- (meth) acrylate means acrylate and methacrylate corresponding thereto
- (meth) acryloyl group means acryloyl group and The corresponding methacryloyl group is meant.
- weight average molecular weight means what was measured using the calibration curve by a standard polystyrene by the gel permeation chromatography method (GPC) on the following conditions.
- GPC gel permeation chromatography method
- Equipment used Hitachi L-6000 (Hitachi, Ltd.) Column: Gel pack GL-R420 + Gel pack GL-R430 + Gel pack GL-R440 (3 in total) [trade name, manufactured by Hitachi Chemical Co., Ltd.]
- the adhesive composition of the present invention contains (a) a thermoplastic resin, (b) a radical polymerizable compound, and (c) a radical polymerization initiator.
- thermoplastic resin a well-known thing can be used without a restriction
- a resin polyimide, polyamide, phenoxy resins, poly (meth) acrylates, polyimides, polyurethanes (urethane resins), polyesters, polyvinyl butyrals, polyurethane esters, and the like can be used. These can be used alone or in combination of two or more, and it is particularly preferable to use a phenoxy resin and a urethane resin in combination. Further, these resins may contain a siloxane bond or a fluorine substituent. These can be suitably used as long as the resins to be mixed are completely compatible with each other or microphase separation occurs and becomes cloudy.
- the molecular weight is not particularly limited, but the general weight average molecular weight is preferably from 5,000 to 150,000, particularly preferably from 10,000 to 80,000. If this value is less than 5,000, the film formability tends to be inferior, and if it exceeds 150,000, the compatibility with other components tends to deteriorate.
- the radically polymerizable compound has two or more (meth) acryloyl groups and two or more urethane bonds in one molecule, and has a weight average molecular weight of 10,000 or more. From the viewpoint of property, fluidity, and adhesiveness, a compound containing at least one structure selected from the following general formula (A) and the following general formula (B) is preferable.
- the weight average molecular weight (Mw) of the radical polymerizable compound is preferably 10,000 to 60,000, particularly preferably more than 30,000 and 50,000 or less. If the Mw is less than 10,000, the adhesive force is reduced due to curing shrinkage, and if it exceeds 60,000, the crosslinking density is lowered, and the connection reliability may be lowered. Since the (b) radical polymerizable compound having an Mw of 10,000 or more is a high molecular weight substance, it may be a reactive component and (a) exhibit characteristics equivalent to or similar to those of a thermoplastic resin. It can be expected, and it is preferable because the design tolerance of the film such as improvement of film formability, fluidity and adhesive force is widened.
- the content of the (b) radical polymerizable compound is preferably 10 to 250 parts by weight, more preferably 30 to 150 parts by weight with respect to 100 parts by weight of the (a) thermoplastic resin.
- known compounds such as conventionally known peroxides and azo compounds can be used. From the viewpoint of stability, reactivity, and compatibility, the half-life of 1 minute Peroxyester derivatives having a temperature of 90 to 175 ° C. and a molecular weight of 180 to 1,000 are preferred. Specific examples thereof include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxynoedecanoate, and t-hexyl.
- the content of the (c) radical polymerization initiator is preferably 0.05 to 30 parts by weight, more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the (a) thermoplastic resin.
- the content is less than 0.05 parts by weight, there is a concern about insufficient curing, and when it exceeds 30 parts by weight, the standing stability may be lowered.
- the adhesive composition of the present invention preferably contains (d) a vinyl compound having at least one phosphate group in the molecule.
- a vinyl compound having at least one phosphoric acid group in the molecule known compounds can be used without any particular limitation, and compounds represented by the following general formulas (1) to (3) can be used. preferable.
- R 1 is an acryloyl group or a methacryloyl group
- R 2 is hydrogen or a methyl group
- m and n each independently represents an integer of 1 to 8.
- R 3 is an acryloyl group or a methacryloyl group, l represents an integer of 1-8, m, n an integer of 1 to 8 independently.
- R 4 represents an acryloyl group or a methacryloyl group
- R 5 represents a hydrogen or methyl group
- p and q each independently represents an integer of 1 to 8.
- acid phosphooxyethyl methacrylate acid phosphooxyethyl acrylate, acid phosphooxypropyl methacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, acid phosphooxypolyoxypropylene glycol monomethacrylate, 2,2′- Examples include di (meth) acryloyloxydiethyl phosphate, EO (ethylene oxide) -modified phosphoric acid dimethacrylate, and phosphoric acid-modified epoxy acrylate.
- the content of the vinyl compound having at least one phosphate group in the molecule is preferably 0.1 to 20 parts by weight, more preferably 100 parts by weight of the thermoplastic resin (a). Is 0.5 to 10 parts by weight. When the content is less than 0.1 parts by weight, the effect of improving the adhesive strength tends to be low, and when it exceeds 20 parts by weight, the physical properties of the adhesive after curing are lowered and the connection reliability is lowered. There is a fear.
- the adhesive composition of the present invention preferably contains (e) conductive particles.
- E As electroconductive particle, metal particles, such as Au, Ag, Ni, Cu, and solder, carbon, etc. are mentioned. Further, non-conductive glass, ceramic, plastic, or the like may be used as a core, and the core, metal particles, or carbon may be coated on the core. In the case of conductive particles having plastic as a core, and the core is coated with the metal, metal particles or carbon, or a hot-melt metal particle such as solder, it is deformable by heating and pressurization. This is preferable because the contact area increases, the thickness variation of the electrode is absorbed, and the connection reliability is improved.
- the conductive particles obtained by coating the surface of these conductive particles with polymer resin, fine particles, etc. suppress the short circuit due to contact between the particles when the amount of the conductive particles is increased. Since insulation can be improved, it may be used alone or mixed with conductive particles as appropriate.
- the average particle diameter of the conductive particles is preferably 1 to 18 ⁇ m from the viewpoint of dispersibility and conductivity.
- the content of the conductive particles is not particularly limited, but is preferably 0.1 to 30% by volume, more preferably 0.1 to 10% by volume based on the total amount of the adhesive composition. . If this value is less than 0.1% by volume, the conductivity tends to be inferior, and if it exceeds 30% by volume, a short circuit tends to occur.
- the “volume%” is determined based on the volume of each component before curing at 23 ° C., but the volume of each component can be converted from weight to volume using specific gravity. In addition, do not dissolve or swell the component in a graduated cylinder, etc., but put in a suitable solvent (water, alcohol, etc.) that wets the component well, and add the component to increase the volume as the volume You can ask for it.
- a radical polymerizable compound other than the component (b) can be used in combination with the above-described (b) radical polymerizable compound.
- a radical polymerizable compound a known compound can be used without particular limitation as long as it is a compound that polymerizes by radicals such as a styrene derivative and a maleimide derivative.
- oligomers such as epoxy (meth) acrylate oligomers, polyether (meth) acrylate oligomers, polyester (meth) acrylate oligomers, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, polyalkylene.
- Glycol di (meth) acrylate dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isocyanuric acid modified bifunctional ( Examples include polyfunctional (meth) acrylate compounds such as (meth) acrylate and isocyanuric acid-modified trifunctional (meth) acrylate, especially trifunctional or higher (meth) acrylate (B) it is preferably used together with a radical polymerizable compound.
- monofunctional (meth) acrylate can be used for the purpose of adjusting fluidity.
- specific examples thereof include pentaerythritol (meth) acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2- (2 -Ethoxyethoxy) ethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate , Isobornyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, n-l
- a functional group that is polymerized by an active radical such as an allyl group, a maleimide group, and a vinyl group. You may add suitably the compound which has.
- N-vinylimidazole N-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, 4,4′-vinylidenebis (N, N-dimethylaniline), N-vinyl.
- examples include acetamide, N, N-dimethylacrylamide, N-isopropylacrylamide, N, N-diethylacrylamide, and acrylamide.
- a stabilizer can be added to the adhesive composition of the present invention in order to control the curing rate and impart storage stability.
- known compounds can be used without particular limitation, but quinone derivatives such as benzoquinone and hydroquinone, phenol derivatives such as 4-methoxyphenol and 4-t-butylcatechol, 2,2 Preferred are aminoxyl derivatives such as 1,6,6-tetramethylpiperidine-1-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and hindered amine derivatives such as tetramethylpiperidyl methacrylate.
- the addition amount is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin (a). .
- the content is less than 0.01 parts by weight, there is a concern that the effect of addition is remarkably reduced, and when it is 30 parts by weight or more, the compatibility with other components may be reduced.
- an adhesion aid such as a coupling agent represented by an alkoxysilane derivative or a silazane derivative, an adhesion improver, or a leveling agent may be appropriately added.
- a rubber component may be added to the adhesive composition of the present invention for the purpose of relaxing stress and improving adhesiveness.
- polyisoprene polybutadiene, carboxyl-terminated polybutadiene, hydroxyl-terminated polybutadiene, 1,2-polybutadiene, carboxyl-terminated 1,2-polybutadiene, hydroxyl-terminated 1,2-polybutadiene, acrylic rubber, and styrene-butadiene rubber.
- Hydroxyl-terminated styrene-butadiene rubber acrylonitrile-butadiene rubber, carboxyl group, hydroxyl group, acrylonitrile-butadiene rubber containing a (meth) acryloyl group or morpholine group at the polymer end, carboxylated nitrile rubber, hydroxyl-terminated poly (oxypropylene),
- Examples include alkoxysilyl group-terminated poly (oxypropylene), poly (oxytetramethylene) glycol, polyolefin glycol, poly- ⁇ -caprolactone, and the like.
- a rubber component containing a cyano group or a carboxyl group, which is a highly polar group, in the side chain or terminal is preferable from the viewpoint of improving adhesiveness, and liquid rubber is more preferable from the viewpoint of improving fluidity.
- Specific examples thereof include liquid acrylonitrile-butadiene rubber, liquid acrylonitrile-butadiene rubber containing a carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group at the polymer terminal, and liquid carboxylated nitrile rubber, which are polar groups.
- the acrylonitrile content is preferably 10 to 60% by weight.
- the adhesive composition of the present invention can be used as a paste adhesive when it is liquid at normal temperature (25 ° C.). In the case of a solid at room temperature (25 ° C.), it can be used by heating, or it can be made into a paste using a solvent and used as a paste-like adhesive.
- the solvent that can be used is not particularly limited as long as it has a sufficiently low reactivity with the adhesive composition and additives and exhibits sufficient solubility, but has a boiling point of 50 to 150 at normal pressure. Those having a temperature of ° C are preferred. When the boiling point is 50 ° C. or lower, there is a risk of volatilization if left at room temperature, which limits the use in an open system. Moreover, when the boiling point is 150 ° C. or higher, it is difficult to volatilize the solvent, which may adversely affect the reliability after bonding.
- the adhesive composition of the present invention can also be used as a film adhesive.
- a film-like adhesive is prepared by applying a solution obtained by adding a solvent or the like to the adhesive composition on a peelable substrate such as a fluororesin film, a polyethylene terephthalate film or a release paper, or a substrate such as a nonwoven fabric. It can be prepared by impregnating the above solution with the solution and placing it on a peelable substrate and removing the solvent and the like. Use in the form of a film is more convenient from the viewpoint of handleability.
- the above-mentioned paste-like adhesive and film-like adhesive can be suitably used especially as an adhesive for circuit connection.
- the adhesive for circuit connection of the present invention can be bonded by using both heating and pressing.
- the heating temperature is not particularly limited but is preferably 100 to 210 ° C.
- the pressure is not particularly limited as long as it does not damage the adherend, but it is generally preferably 0.1 to 10 MPa. These heating and pressurization are preferably performed in the range of 0.5 to 120 seconds, and can be bonded by heating at 140 to 170 ° C., 3 MPa, and 10 seconds.
- the circuit connecting adhesive of the present invention can be used as an adhesive for different types of adherends having different thermal expansion coefficients. Specifically, it is used as a semiconductor element adhesive material typified by anisotropic conductive adhesive, silver paste, silver film, etc., circuit connection material, CSP elastomer, CSP underfill material, LOC tape, etc. Can do.
- the first circuit electrode and the second circuit electrode face each other between the first substrate having the first circuit electrode and the second substrate having the second circuit electrode.
- the first circuit electrode and the second circuit are arranged by interposing the circuit connecting adhesive of the present invention between the first substrate and the second substrate arranged to face each other and heating and pressing the adhesive.
- the electrode is electrically connected.
- inorganic materials such as semiconductor, glass and ceramic, organic materials such as polyimide resin, polycarbonate resin, polyester resin and polyethersulfone resin, and composite materials such as glass fiber / epoxy resin can be applied.
- organic materials such as polyimide resin, polycarbonate resin, polyester resin and polyethersulfone resin
- composite materials such as glass fiber / epoxy resin
- Example 1 Phenoxy resin and urethane resin were used as the thermoplastic resin.
- phenoxy resin 40 g of phenoxy resin (PKHC, trade name of Union Carbide, average molecular weight 45,000) dissolved in 60 g of methyl ethyl ketone to obtain a solution having a solid content of 40% by weight was used.
- the urethane resin includes 450 parts by weight of polybutylene adipate diol having an average molecular weight of 2,000, 450 parts by weight of polyoxytetramethylene glycol having an average molecular weight of 2,000, and 100 parts by weight of 1,4-butylene glycol in 4000 parts by weight of methyl ethyl ketone.
- a urethane resin having a weight average molecular weight of 350,000 obtained by adding 390 parts by weight of diphenylmethane diisocyanate and reacting at 70 ° C. was used.
- the radical polymerizable compound 50 g of the above U-1 (weight average molecular weight 45,000) or U-2 (weight average molecular weight 4,800) is dissolved in 50 g of methyl ethyl ketone, respectively, and the solid content is 50 wt. % Solution was used.
- pentaerythritol triacrylate (NK ester A-TMM-3L, trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) was used as a radical polymerizable compound other than the component (b).
- C As a radical polymerization initiator, t-hexyl peroxy-2-ethylhexanoate (Perhexyl O, trade name, manufactured by NOF Corporation) was used.
- D As a vinyl compound having at least one phosphate group in the molecule, 2- (meth) acryloyloxyethyl phosphate (light ester P-2M, trade name, manufactured by Kyoeisha Chemical Co., Ltd.) was used.
- (E) As the conductive particles an average particle produced by providing a nickel layer having a thickness of 0.2 ⁇ m on the surface of particles having polystyrene as a core, and providing a gold layer having a thickness of 0.02 ⁇ m outside the nickel layer. Conductive particles having a diameter of 4 ⁇ m and a specific gravity of 2.5 were used. The above components were blended at a solid weight ratio shown in Table 1, and (e) 1.5% by volume of conductive particles were blended and dispersed. The obtained dispersion was applied to a fluororesin film having a thickness of 80 ⁇ m using a coating apparatus, and a film-like adhesive having a thickness of 15 ⁇ m was obtained by hot air drying at 70 ° C. for 10 minutes.
- Example 2 comparative example 2
- phenoxy resin and urethane resin were used as the thermoplastic resin.
- phenoxy resin 40 g of phenoxy resin (PKHC, trade name of Union Carbide, average molecular weight 45,000) dissolved in 60 g of methyl ethyl ketone to obtain a solution having a solid content of 40% by weight was used.
- the urethane resin includes 450 parts by weight of polybutylene adipate diol having an average molecular weight of 2,000, 450 parts by weight of polyoxytetramethylene glycol having an average molecular weight of 2,000, and 100 parts by weight of 1,4-butylene glycol in 4000 parts by weight of methyl ethyl ketone.
- a urethane resin having a weight average molecular weight of 350,000 obtained by adding 390 parts by weight of diphenylmethane diisocyanate and reacting at 70 ° C. was used.
- the radically polymerizable compound the above-mentioned U-1 (weight average molecular weight 45,000) or U-250 g was dissolved in 50 g of methyl ethyl ketone to give a solution having a solid content of 50% by weight. . Further, pentaerythritol triacrylate (NK ester A-TMM-3L, trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) was used as a radical polymerizable compound other than the component (b).
- NK ester A-TMM-3L trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.
- Example 1 Comparative Example 1
- a flexible circuit board (FPC) having 500 copper circuits having a line width of 25 ⁇ m, a pitch of 50 ⁇ m, and a thickness of 8 ⁇ m, and a thin layer of 0.2 ⁇ m indium oxide (ITO)
- the formed glass is used for 10 seconds at a temperature of 160 ° C. and a pressure of 3 MPa using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.).
- a connection body was prepared by connecting over a width of 2 mm.
- the resistance value between adjacent circuits of this connection body was measured with a multimeter immediately after bonding and after being held in a high-temperature and high-humidity bath at 85 ° C. and 85% RH for 250 hours.
- the resistance value was shown as an average of 37 resistances between adjacent circuits.
- Example 2 A flexible circuit board (FPC) having 500 copper circuits having a line width of 100 ⁇ m, a pitch of 200 ⁇ m, and a thickness of 18 ⁇ m, and a copper circuit having a line width of 100 ⁇ m, a pitch of 200 ⁇ m, and a thickness of 35 ⁇ m using the film-like adhesive obtained by the above manufacturing method.
- 500 printed circuit boards (PCB) (thickness: 1.1 mm) were used for 10 seconds at a temperature of 160 ° C. and a pressure of 3 MPa using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.).
- Heating and pressing were performed to connect over a width of 2 mm to produce a connection body.
- the resistance value between adjacent circuits of this connection body was measured with a multimeter immediately after bonding and after being held in a high-temperature and high-humidity bath at 85 ° C. and 85% RH for 250 hours.
- the resistance value was shown as an average of 37 resistances between adjacent circuits.
- connection body was measured by a 90-degree peeling method according to JIS-Z0237 and evaluated.
- Tensilon UTM-4 peeleling speed 50 mm / min, 25 ° C.
- Table 2 shows the results of measurement of the adhesive strength and connection resistance of the connection body performed as described above.
- the film-like adhesives obtained in Examples 1 and 2 containing a urethane (meth) acrylate compound having a weight average molecular weight of 10,000 or more in the composition are a high-temperature and high-humidity tank immediately after bonding and at 85 ° C. and 85% RH. It was found that after holding for 250 hours, it showed good connection resistance and adhesive strength and good properties. On the other hand, in Comparative Examples 1 and 2 in which the urethane (meth) acrylate compound having a weight average molecular weight of 10,000 or more is not included in the composition, the connection resistance value immediately after bonding is good, but the high temperature and high temperature of 85 ° C. and 85% RH are high.
- connection resistance value increased after being kept in the wet tank for 250 hours (after the reliability test).
- the adhesive strength the adhesive strength immediately after the adhesion was higher than that in Examples 1 and 2, but the decrease in the adhesive strength after the reliability test was remarkable. From the above results, it has been clarified that by using the radically polymerizable compound (b) of the present invention, both good connection resistance and adhesive force can be achieved.
- Example 3 The film adhesive obtained in Example 1 was vacuum-packed and allowed to stand at 40 ° C. for 3 days, and then FPC and ITO were thermocompression bonded at 160 ° C., 3 MPa, 10 seconds as in Example 1. went. Measurement of the adhesive strength and connection resistance of the connection body carried out as described above revealed an adhesive strength of 840 to 880 N / m and a connection resistance of 1.0 to 1.3 ⁇ . Since there was almost no change in the value, it was found that the storage stability was excellent.
- Example 4 Thickness 1mm with connecting terminals corresponding to bump arrangement of semiconductor chip (3x10mm, height 0.5mm, 100 ⁇ m square called bumps around the four sides of the main surface, and 20 ⁇ m high protruding gold electrodes)
- substrate for semiconductor mounting produced from the glass epoxy board
- the circuit surface of the semiconductor mounting substrate was subjected to nickel / gold plating.
- the protruding electrode of the semiconductor chip and the semiconductor mounting substrate were connected using the film adhesive of Example 1 as follows.
- a film adhesive is temporarily bonded to the circuit surface of the semiconductor mounting substrate at 80 ° C., 1 MPa for 3 seconds, and after peeling the peelable fluororesin film, the semiconductor chip protruding electrode and the semiconductor mounting substrate are aligned. Then, thermocompression bonding was performed for 20 seconds at a temperature and pressure of 180 kg, 10 kgf / chip. As a result, the protruding electrode of the semiconductor chip and the circuit of the semiconductor mounting substrate are electrically connected via the film adhesive, and at the same time, the connection of the semiconductor chip and the electrode of the semiconductor mounting substrate by the curing of the film adhesive. Retained state.
- the semiconductor device obtained by connecting the semiconductor chip and the semiconductor mounting substrate thus obtained was subjected to a repeated thermal cycle test under the conditions of ( ⁇ 55 ° C., 30 minutes) / (125 ° C., 30 minutes).
- a repeated thermal cycle test under the conditions of ( ⁇ 55 ° C., 30 minutes) / (125 ° C., 30 minutes).
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Abstract
Description
〈GPC条件〉
使用機器:日立L-6000型〔株式会社日立製作所〕
カラム:ゲルパックGL-R420+ゲルパックGL-R430+ゲルパックGL-R440(計3本)〔日立化成工業株式会社製商品名〕
溶離液:テトラヒドロフラン
測定温度:40℃
流量:1.75ml/min
検出器:L-3300RI〔株式会社日立製作所〕 Moreover, in this specification, "weight average molecular weight" means what was measured using the calibration curve by a standard polystyrene by the gel permeation chromatography method (GPC) on the following conditions.
<GPC conditions>
Equipment used: Hitachi L-6000 (Hitachi, Ltd.)
Column: Gel pack GL-R420 + Gel pack GL-R430 + Gel pack GL-R440 (3 in total) [trade name, manufactured by Hitachi Chemical Co., Ltd.]
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 1.75 ml / min
Detector: L-3300RI [Hitachi, Ltd.]
さらに、これら樹脂中には、シロキサン結合やフッ素置換基が含まれていてもよい。これらは、混合する樹脂同士が完全に相溶するか、もしくはミクロ相分離が生じて白濁する状態であれば好適に用いることができる。
上記熱可塑性樹脂の分子量は、大きいほどフィルム形成性が容易に得られ、また接着剤としての流動性に影響する溶融粘度を広範囲に設定できる。分子量は特に制限を受けるものではないが、一般的な重量平均分子量としては5,000~150,000が好ましく、10,000~80,000が特に好ましい。この値が、5,000未満ではフィルム形成性が劣る傾向があり、また150,000を超えると他の成分との相溶性が悪くなる傾向がある。 (A) As a thermoplastic resin, a well-known thing can be used without a restriction | limiting in particular. As such a resin, polyimide, polyamide, phenoxy resins, poly (meth) acrylates, polyimides, polyurethanes (urethane resins), polyesters, polyvinyl butyrals, polyurethane esters, and the like can be used. These can be used alone or in combination of two or more, and it is particularly preferable to use a phenoxy resin and a urethane resin in combination.
Further, these resins may contain a siloxane bond or a fluorine substituent. These can be suitably used as long as the resins to be mixed are completely compatible with each other or microphase separation occurs and becomes cloudy.
The larger the molecular weight of the thermoplastic resin, the easier it is to form a film, and the melt viscosity that affects the fluidity as an adhesive can be set over a wide range. The molecular weight is not particularly limited, but the general weight average molecular weight is preferably from 5,000 to 150,000, particularly preferably from 10,000 to 80,000. If this value is less than 5,000, the film formability tends to be inferior, and if it exceeds 150,000, the compatibility with other components tends to deteriorate.
Mwが10,000未満では硬化収縮により接着力が低下し、60,000を超えた場合では架橋密度が低下し、接続信頼性が低下するおそれがある。
Mwが10,000以上である(b)ラジカル重合性化合物は、高分子量体であることから、反応性成分であると同時に(a)熱可塑性樹脂と同等あるいはそれに類似した特性を発現することが期待でき、フィルム形成性、流動性や接着力の向上といったフィルムの設計裕度が広がることから好ましい。 (B) The weight average molecular weight (Mw) of the radical polymerizable compound is preferably 10,000 to 60,000, particularly preferably more than 30,000 and 50,000 or less.
If the Mw is less than 10,000, the adhesive force is reduced due to curing shrinkage, and if it exceeds 60,000, the crosslinking density is lowered, and the connection reliability may be lowered.
Since the (b) radical polymerizable compound having an Mw of 10,000 or more is a high molecular weight substance, it may be a reactive component and (a) exhibit characteristics equivalent to or similar to those of a thermoplastic resin. It can be expected, and it is preferable because the design tolerance of the film such as improvement of film formability, fluidity and adhesive force is widened.
(b)ラジカル重合性化合物の含有量が10重量部未満の場合には、硬化後の耐熱性低下が懸念され、また、250重量部以上の場合には、フィルムとして使用する場合にフィルム形成性が低下するおそれがある。 The content of the (b) radical polymerizable compound is preferably 10 to 250 parts by weight, more preferably 30 to 150 parts by weight with respect to 100 parts by weight of the (a) thermoplastic resin.
(B) When the content of the radically polymerizable compound is less than 10 parts by weight, there is a concern about a decrease in heat resistance after curing, and when it is 250 parts by weight or more, film formability when used as a film. May decrease.
その具体例としては、クミルパーオキシネオデカノエート、1,1,3,3-テトラメチルブチルパーオキシネオデカノエート、1-シクロヘキシル-1-メチルエチルパーオキシノエデカノエート、t-ヘキシルパーオキシネオデカノエート、t-ブチルパーオキシネオデカノエート、t-ブチルパーオキシピバレート、1,1,3,3-テトラメチルブチルパーオキシ-2-エチルヘキサノエート、2,5-ジメチル-2,5-ジ(2-エチルヘキサノイルパーオキシ)ヘキサン、t-ヘキシルパーオキシ-2-エチルヘキサノエート、t-ブチルパーオキシ-2-エチルヘキサノエート、t-ブチルパーオキシネオヘプタノエート、t-アミルパーオキシ-2-エチルヘキサノエート、ジ-t-ブチルパーオキシヘキサヒドロテレフタレート、t-アミルパーオキシ-3,5,5-トリメチルヘキサノエート、3-ヒドロキシ-1,1-ジメチルブチルパーオキシネオデカノエート、1,1,3,3-テトラメチルブチルパーオキシ-2-エチルヘキサノエート、t-アミルパーオキシネオデカノエート、t-アミルパーオキシ-2-エチルヘキサノエート、2,2’-アゾビス-2,4-ジメチルバレロニトリル、1,1’-アゾビス(1-アセトキシ-1-フェニルエタン)、2,2’-アゾビスイソブチロニトリル、2,2’-アゾビス(2-メチルブチロニトリル)、ジメチル-2,2’-アゾビスイソブチロニトリル、4,4’-アゾビス(4-シアノバレリン酸)、1,1’-アゾビス(1-シクロヘキサンカルボニトリル)、t-ヘキシルパーオキシイソプロピルモノカーボネート、t-ブチルパーオキシマレイン酸、t-ブチルパーオキシ-3,5,5-トリメチルヘキサノエート、t-ブチルパーオキシラウレート、2,5-ジメチル-2,5-ジ(3-メチルベンゾイルパーオキシ)ヘキサン、t-ブチルパーオキシ-2-エチルヘキシルモノカーボネート、t-ヘキシルパーオキシベンゾエート、2,5-ジメチル-2,5-ジ(ベンゾイルパーオキシ)ヘキサン、t-ブチルパーオキシベンゾエート、ジブチルパーオキシトリメチルアジペート、t-アミルパーオキシノルマルオクトエート、t-アミルパーオキシイソノナノエート、t-アミルパーオキシベンゾエート等が挙げられる。これらの化合物は、単独で用いても、2種以上の化合物を混合して用いてもよい。 (C) As the radical polymerization initiator, known compounds such as conventionally known peroxides and azo compounds can be used. From the viewpoint of stability, reactivity, and compatibility, the half-life of 1 minute Peroxyester derivatives having a temperature of 90 to 175 ° C. and a molecular weight of 180 to 1,000 are preferred.
Specific examples thereof include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxynoedecanoate, and t-hexyl. Peroxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5- Dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneo Heptanoate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate Tate, t-amylperoxy-3,5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxy -2-ethylhexanoate, t-amylperoxyneodecanoate, t-amylperoxy-2-ethylhexanoate, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1 ' -Azobis (1-acetoxy-1-phenylethane), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobisiso Butyronitrile, 4,4′-azobis (4-cyanovaleric acid), 1,1′-azobis (1-cyclohexanecarbonitrile), t-hexylperoxyisopropyl monocarbonate Bonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (3-methyl Benzoylperoxy) hexane, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, Examples thereof include dibutyl peroxytrimethyl adipate, t-amyl peroxy normal octoate, t-amyl peroxy isononanoate, and t-amyl peroxybenzoate. These compounds may be used alone or as a mixture of two or more compounds.
含有量が0.05重量部未満の場合、硬化不足が懸念され、また、30重量部を超える場合には、放置安定性が低下するおそれがある。 The content of the (c) radical polymerization initiator is preferably 0.05 to 30 parts by weight, more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the (a) thermoplastic resin.
When the content is less than 0.05 parts by weight, there is a concern about insufficient curing, and when it exceeds 30 parts by weight, the standing stability may be lowered.
含有量が0.1重量部未満の場合、接着強度向上効果が低い傾向にあり、また、20重量部を超える場合には、硬化後の接着剤の物性が低下し、接続信頼性が低下するおそれがある。 (D) The content of the vinyl compound having at least one phosphate group in the molecule is preferably 0.1 to 20 parts by weight, more preferably 100 parts by weight of the thermoplastic resin (a). Is 0.5 to 10 parts by weight.
When the content is less than 0.1 parts by weight, the effect of improving the adhesive strength tends to be low, and when it exceeds 20 parts by weight, the physical properties of the adhesive after curing are lowered and the connection reliability is lowered. There is a fear.
また、非導電性のガラス、セラミック、プラスチック等を核とし、この核に前記金属、金属粒子やカーボンを被覆したものでもよい。
導電性粒子が、プラスチックを核とし、この核に前記金属、金属粒子やカーボンを被覆したものやはんだのような熱溶融金属粒子の場合、加熱加圧により変形性を有するので接続時に電極との接触面積が増加し電極の厚みばらつきを吸収し、接続信頼性が向上するので好ましい。
またこれらの導電性粒子の表面を、さらに高分子樹脂、微粒子などで被覆した導電性粒子は、導電性粒子の配合量を増加した場合の粒子同士の接触による短絡を抑制し、電極回路間の絶縁性が向上できることから、適宜これを単独あるいは導電性粒子と混合して用いてもよい。 The adhesive composition of the present invention preferably contains (e) conductive particles. (E) As electroconductive particle, metal particles, such as Au, Ag, Ni, Cu, and solder, carbon, etc. are mentioned.
Further, non-conductive glass, ceramic, plastic, or the like may be used as a core, and the core, metal particles, or carbon may be coated on the core.
In the case of conductive particles having plastic as a core, and the core is coated with the metal, metal particles or carbon, or a hot-melt metal particle such as solder, it is deformable by heating and pressurization. This is preferable because the contact area increases, the thickness variation of the electrode is absorbed, and the connection reliability is improved.
In addition, the conductive particles obtained by coating the surface of these conductive particles with polymer resin, fine particles, etc. suppress the short circuit due to contact between the particles when the amount of the conductive particles is increased. Since insulation can be improved, it may be used alone or mixed with conductive particles as appropriate.
この値が、0.1体積%未満であると導電性が劣る傾向があり、30体積%を超えると回路の短絡が起こりやすい傾向がある。
なお、「体積%」は23℃の硬化前の各成分の体積をもとに決定されるが、各成分の体積は、比重を利用して重量から体積に換算することができる。また、メスシリンダー等にその成分を溶解したり膨潤させたりせず、その成分をよく濡らす適当な溶媒(水、アルコール等)を入れたものに、その成分を投入し増加した体積をその体積として求めることもできる。 The average particle diameter of the conductive particles is preferably 1 to 18 μm from the viewpoint of dispersibility and conductivity. The content of the conductive particles is not particularly limited, but is preferably 0.1 to 30% by volume, more preferably 0.1 to 10% by volume based on the total amount of the adhesive composition. .
If this value is less than 0.1% by volume, the conductivity tends to be inferior, and if it exceeds 30% by volume, a short circuit tends to occur.
The “volume%” is determined based on the volume of each component before curing at 23 ° C., but the volume of each component can be converted from weight to volume using specific gravity. In addition, do not dissolve or swell the component in a graduated cylinder, etc., but put in a suitable solvent (water, alcohol, etc.) that wets the component well, and add the component to increase the volume as the volume You can ask for it.
このような安定化剤としては、特に制限なく公知の化合物を使用することができるが、ベンゾキノンやハイドロキノン等のキノン誘導体、4-メトキシフェノールや4-t-ブチルカテコール等のフェノール誘導体、2,2,6,6-テトラメチルピペリジン-1-オキシルや4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン-1-オキシル等のアミノキシル誘導体、テトラメチルピペリジルメタクリレート等のヒンダードアミン誘導体が好ましい。 A stabilizer can be added to the adhesive composition of the present invention in order to control the curing rate and impart storage stability.
As such a stabilizer, known compounds can be used without particular limitation, but quinone derivatives such as benzoquinone and hydroquinone, phenol derivatives such as 4-methoxyphenol and 4-t-butylcatechol, 2,2 Preferred are aminoxyl derivatives such as 1,6,6-tetramethylpiperidine-1-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and hindered amine derivatives such as tetramethylpiperidyl methacrylate.
使用できる溶剤としては、接着剤組成物及び添加剤と反応性が十分に小さく、かつ、十分な溶解性を示すものであれば、特に制限は受けないが、常圧での沸点が50~150℃であるものが好ましい。沸点が50℃以下の場合、室温で放置すると揮発するおそれがあり、開放系での使用が制限される。また、沸点が150℃以上だと、溶剤を揮発させることが難しく、接着後の信頼性に悪影響を及ぼすおそれがある。 The adhesive composition of the present invention can be used as a paste adhesive when it is liquid at normal temperature (25 ° C.). In the case of a solid at room temperature (25 ° C.), it can be used by heating, or it can be made into a paste using a solvent and used as a paste-like adhesive.
The solvent that can be used is not particularly limited as long as it has a sufficiently low reactivity with the adhesive composition and additives and exhibits sufficient solubility, but has a boiling point of 50 to 150 at normal pressure. Those having a temperature of ° C are preferred. When the boiling point is 50 ° C. or lower, there is a risk of volatilization if left at room temperature, which limits the use in an open system. Moreover, when the boiling point is 150 ° C. or higher, it is difficult to volatilize the solvent, which may adversely affect the reliability after bonding.
攪拌機、温度計、冷却管及び空気ガス導入管を備えた反応容器に空気ガスを導入した後、2-ヒドロキシエチルアクリレート238重量部(2.05モル)、数平均分子量2,000のポリ(ヘキサメチレンカーボネート)ジオール(アルドリッチ社製)4000重量部(2モル)、ハイドロキノンモノメチルエーテル0.49重量部、ジブチルスズジラウレート6.35重量部を仕込み、90~100℃に加熱し、イソフォロンジイソシアネート666重量部(3モル)を3時間で均一に滴下し、反応させた。
滴下完了後約24時間反応を継続し、IR測定によりイソシアネートが消失したことを確認して反応を終了し、重量平均分子量45,000のウレタンアクリレート(U-1)を得た。 (Synthesis of urethane acrylate (U-1))
After introducing air gas into a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe and an air gas introduction pipe, 238 parts by weight (2.05 mol) of 2-hydroxyethyl acrylate, poly (hexahexane) having a number average molecular weight of 2,000 Methylene carbonate) diol (manufactured by Aldrich) 4000 parts by weight (2 moles), hydroquinone monomethyl ether 0.49 parts by weight, dibutyltin dilaurate 6.35 parts by weight, heated to 90-100 ° C., isophorone diisocyanate 666 parts by weight (3 mol) was added dropwise in 3 hours and allowed to react.
The reaction was continued for about 24 hours after the completion of the dropwise addition, and the reaction was terminated by confirming that the isocyanate had disappeared by IR measurement. Thus, urethane acrylate (U-1) having a weight average molecular weight of 45,000 was obtained.
攪拌機、温度計、冷却管及び空気ガス導入管を備えた反応容器に空気ガスを導入した後、2-ヒドロキシエチルアクリレート238重量部(2.05モル)、数平均分子量900のポリ(エチレングリコール)ジオール(アルドリッチ社製)1,800重量部(2モル)、ハイドロキノンモノメチルエーテル0.27重量部、ジブチルスズジラウレート2.70重量部を仕込み、70~75℃に加熱し、イソフォロンジイソシアネート666重量部(3モル)を3時間で均一に滴下し、反応させた。
滴下完了後、約15時間反応を継続し、IR測定によりイソシアネートが消失したことを確認して反応を終了し、重量平均分子量4,800のウレタンアクリレート(U-2)を得た。 (Synthesis of urethane acrylate (U-2))
After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, 238 parts by weight (2.05 mol) of 2-hydroxyethyl acrylate, poly (ethylene glycol) having a number average molecular weight of 900 Diol (manufactured by Aldrich) 1,800 parts by weight (2 moles), hydroquinone monomethyl ether 0.27 parts by weight and dibutyltin dilaurate 2.70 parts by weight were charged and heated to 70 to 75 ° C. to obtain 666 parts by weight of isophorone diisocyanate ( 3 mol) was added dropwise uniformly over 3 hours to allow reaction.
After completion of the dropwise addition, the reaction was continued for about 15 hours. After confirming that the isocyanate had disappeared by IR measurement, the reaction was terminated, and urethane acrylate (U-2) having a weight average molecular weight of 4,800 was obtained.
(a)熱可塑性樹脂として、フェノキシ樹脂及びウレタン樹脂を使用した。
フェノキシ樹脂としては、フェノキシ樹脂(PKHC、ユニオンカーバイト社製商品名、平均分子量45,000)40gを、メチルエチルケトン60gに溶解して、固形分40重量%の溶液としたものを用いた。
またウレタン樹脂としては、平均分子量2,000のポリブチレンアジペートジオール450重量部と平均分子量2,000のポリオキシテトラメチレングリコール450重量部、1,4-ブチレングリコール100重量部をメチルエチルケトン4000重量部中で均一に混合し、ジフェニルメタンジイソシアネート390重量部を加えて70℃にて反応させて得られた重量平均分子量35万のウレタン樹脂を使用した。
(b)ラジカル重合性化合物としては、上述のU-1(重量平均分子量45,000)又はU-2(重量平均分子量4,800)50gを、それぞれメチルエチルケトン50gに溶解して、固形分50重量%の溶液としたものを使用した。
また(b)成分以外のラジカル重合性化合物として、ペンタエリスリトールトリアクリレート(NKエステルA-TMM-3L、新中村化学工業株式会社製商品名)を用いた。
(c)ラジカル重合開始剤として、t-ヘキシルパーオキシ-2-エチルヘキサノエート(パーヘキシルO、日本油脂株式会社製商品名)を用いた。
(d)分子内に少なくとも1個以上のリン酸基を有するビニル化合物として、2-(メタ)アクリロイロキシエチルホスフェート(ライトエステルP-2M、共栄社化学株式会社製商品名)を用いた。
(e)導電性粒子としては、ポリスチレンを核とする粒子の表面に、厚み0.2μmのニッケル層を設け、このニッケル層の外側に、厚み0.02μmの金層を設けて作製した平均粒径4μm、比重2.5の導電性粒子を用いた。
上述の成分を、表1に示す固形重量比で配合し、さらに(e)導電性粒子を1.5体積%配合分散させた。得られた分散液を、厚み80μmのフッ素樹脂フィルムに塗工装置を用いて塗布し、70℃、10分の熱風乾燥によって接着剤層の厚みが15μmのフィルム状接着剤を得た。 (Example 1, Comparative Example 1)
(A) Phenoxy resin and urethane resin were used as the thermoplastic resin.
As the phenoxy resin, 40 g of phenoxy resin (PKHC, trade name of Union Carbide, average molecular weight 45,000) dissolved in 60 g of methyl ethyl ketone to obtain a solution having a solid content of 40% by weight was used.
The urethane resin includes 450 parts by weight of polybutylene adipate diol having an average molecular weight of 2,000, 450 parts by weight of polyoxytetramethylene glycol having an average molecular weight of 2,000, and 100 parts by weight of 1,4-butylene glycol in 4000 parts by weight of methyl ethyl ketone. Then, a urethane resin having a weight average molecular weight of 350,000 obtained by adding 390 parts by weight of diphenylmethane diisocyanate and reacting at 70 ° C. was used.
(B) As the radical polymerizable compound, 50 g of the above U-1 (weight average molecular weight 45,000) or U-2 (weight average molecular weight 4,800) is dissolved in 50 g of methyl ethyl ketone, respectively, and the solid content is 50 wt. % Solution was used.
Further, pentaerythritol triacrylate (NK ester A-TMM-3L, trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) was used as a radical polymerizable compound other than the component (b).
(C) As a radical polymerization initiator, t-hexyl peroxy-2-ethylhexanoate (Perhexyl O, trade name, manufactured by NOF Corporation) was used.
(D) As a vinyl compound having at least one phosphate group in the molecule, 2- (meth) acryloyloxyethyl phosphate (light ester P-2M, trade name, manufactured by Kyoeisha Chemical Co., Ltd.) was used.
(E) As the conductive particles, an average particle produced by providing a nickel layer having a thickness of 0.2 μm on the surface of particles having polystyrene as a core, and providing a gold layer having a thickness of 0.02 μm outside the nickel layer. Conductive particles having a diameter of 4 μm and a specific gravity of 2.5 were used.
The above components were blended at a solid weight ratio shown in Table 1, and (e) 1.5% by volume of conductive particles were blended and dispersed. The obtained dispersion was applied to a fluororesin film having a thickness of 80 μm using a coating apparatus, and a film-like adhesive having a thickness of 15 μm was obtained by hot air drying at 70 ° C. for 10 minutes.
(a)熱可塑性樹脂として、フェノキシ樹脂及びウレタン樹脂を使用した。
フェノキシ樹脂としては、フェノキシ樹脂(PKHC、ユニオンカーバイト社製商品名、平均分子量45,000)40gを、メチルエチルケトン60gに溶解して、固形分40重量%の溶液としたものを用いた。
またウレタン樹脂としては、平均分子量2,000のポリブチレンアジペートジオール450重量部と平均分子量2,000のポリオキシテトラメチレングリコール450重量部、1,4-ブチレングリコール100重量部をメチルエチルケトン4000重量部中で均一に混合し、ジフェニルメタンジイソシアネート390重量部を加えて70℃にて反応させて得られた重量平均分子量35万のウレタン樹脂を使用した。
(b)ラジカル重合性化合物としては、上述のU-1(重量平均分子量45,000)又はU-250gを、それぞれメチルエチルケトン50gに溶解して、固形分50重量%の溶液としたものを使用した。
また(b)成分以外のラジカル重合性化合物として、ペンタエリスリトールトリアクリレート(NKエステルA-TMM-3L、新中村化学工業株式会社製商品名)を用いた。
(c)ラジカル重合開始剤として、t-ヘキシルパーオキシ-2-エチルヘキサノエート(パーヘキシルO、日本油脂株式会社製商品名)を用いた。
(d)分子内に少なくとも1個以上のリン酸基を有するビニル化合物として、2-(メタ)アクリロイロキシエチルホスフェート(ライトエステルP-2M、共栄社化学株式会社製商品名)を用いた。
上述の成分を表1に示す固形重量比で配合し、さらに(e)導電性粒子としてのNi粒子を1.5体積%配合分散させた。得られた分散液を、厚み80μmのフッ素樹脂フィルムに塗工装置を用いて塗布し、70℃、10分の熱風乾燥によって接着剤層の厚みが40μmのフィルム状接着剤を得た。 (Example 2, comparative example 2)
(A) Phenoxy resin and urethane resin were used as the thermoplastic resin.
As the phenoxy resin, 40 g of phenoxy resin (PKHC, trade name of Union Carbide, average molecular weight 45,000) dissolved in 60 g of methyl ethyl ketone to obtain a solution having a solid content of 40% by weight was used.
The urethane resin includes 450 parts by weight of polybutylene adipate diol having an average molecular weight of 2,000, 450 parts by weight of polyoxytetramethylene glycol having an average molecular weight of 2,000, and 100 parts by weight of 1,4-butylene glycol in 4000 parts by weight of methyl ethyl ketone. Then, a urethane resin having a weight average molecular weight of 350,000 obtained by adding 390 parts by weight of diphenylmethane diisocyanate and reacting at 70 ° C. was used.
(B) As the radically polymerizable compound, the above-mentioned U-1 (weight average molecular weight 45,000) or U-250 g was dissolved in 50 g of methyl ethyl ketone to give a solution having a solid content of 50% by weight. .
Further, pentaerythritol triacrylate (NK ester A-TMM-3L, trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) was used as a radical polymerizable compound other than the component (b).
(C) As a radical polymerization initiator, t-hexyl peroxy-2-ethylhexanoate (Perhexyl O, trade name, manufactured by NOF Corporation) was used.
(D) As a vinyl compound having at least one phosphate group in the molecule, 2- (meth) acryloyloxyethyl phosphate (light ester P-2M, trade name, manufactured by Kyoeisha Chemical Co., Ltd.) was used.
The above-mentioned components were blended at a solid weight ratio shown in Table 1, and (e) Ni particles as conductive particles were blended and dispersed at 1.5% by volume. The obtained dispersion was applied to a fluororesin film having a thickness of 80 μm using a coating apparatus, and a film adhesive having a thickness of 40 μm was obtained by drying with hot air at 70 ° C. for 10 minutes.
(実施例1、比較例1)
上記製法によって得たフィルム状接着剤を用いて、ライン幅25μm、ピッチ50μm、厚み8μmの銅回路を500本有するフレキシブル回路板(FPC)と、0.2μmの酸化インジウム(ITO)の薄層を形成したガラス(厚み1.1mm、表面抵抗20Ω/□)とを、熱圧着装置(加熱方式:コンスタントヒート型、東レエンジニアリング株式会社製)を用いて、160℃の温度、3MPaの圧力で10秒間の加熱加圧を行って幅2mmにわたり接続し、接続体を作製した。
この接続体の隣接回路間の抵抗値を、接着直後と、85℃、85%RHの高温高湿槽中に250時間保持した後にマルチメータで測定した。抵抗値は隣接回路間の抵抗37点の平均で示した。 [Measurement of adhesive strength and connection resistance]
(Example 1, Comparative Example 1)
Using the film-like adhesive obtained by the above manufacturing method, a flexible circuit board (FPC) having 500 copper circuits having a line width of 25 μm, a pitch of 50 μm, and a thickness of 8 μm, and a thin layer of 0.2 μm indium oxide (ITO) The formed glass (thickness 1.1 mm, surface resistance 20 Ω / □) is used for 10 seconds at a temperature of 160 ° C. and a pressure of 3 MPa using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.). Then, a connection body was prepared by connecting over a width of 2 mm.
The resistance value between adjacent circuits of this connection body was measured with a multimeter immediately after bonding and after being held in a high-temperature and high-humidity bath at 85 ° C. and 85% RH for 250 hours. The resistance value was shown as an average of 37 resistances between adjacent circuits.
(実施例2、比較例2)
上記製法によって得たフィルム状接着剤を用いて、ライン幅100μm、ピッチ200μm、厚み18μmの銅回路を500本有するフレキシブル回路板(FPC)と、ライン幅100μm、ピッチ200μm、厚み35μmの銅回路を500本有するプリント基板(PCB)(厚み1.1mm)とを、熱圧着装置(加熱方式:コンスタントヒート型、東レエンジニアリング株式会社製)を用いて、160℃の温度、3MPaの圧力で10秒間の加熱加圧を行って幅2mmにわたり接続し、接続体を作製した。
この接続体の隣接回路間の抵抗値を、接着直後と、85℃、85%RHの高温高湿槽中に250時間保持した後にマルチメータで測定した。抵抗値は隣接回路間の抵抗37点の平均で示した。 [Measurement of adhesive strength and connection resistance]
(Example 2, comparative example 2)
A flexible circuit board (FPC) having 500 copper circuits having a line width of 100 μm, a pitch of 200 μm, and a thickness of 18 μm, and a copper circuit having a line width of 100 μm, a pitch of 200 μm, and a thickness of 35 μm using the film-like adhesive obtained by the above manufacturing method. 500 printed circuit boards (PCB) (thickness: 1.1 mm) were used for 10 seconds at a temperature of 160 ° C. and a pressure of 3 MPa using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.). Heating and pressing were performed to connect over a width of 2 mm to produce a connection body.
The resistance value between adjacent circuits of this connection body was measured with a multimeter immediately after bonding and after being held in a high-temperature and high-humidity bath at 85 ° C. and 85% RH for 250 hours. The resistance value was shown as an average of 37 resistances between adjacent circuits.
以上のようにして行った接続体の接着強度、接続抵抗の測定の結果を表2に示した。 Further, the adhesive strength of this connection body was measured by a 90-degree peeling method according to JIS-Z0237 and evaluated. Here, Tensilon UTM-4 (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used as an adhesive strength measuring apparatus.
Table 2 shows the results of measurement of the adhesive strength and connection resistance of the connection body performed as described above.
一方、重量平均分子量が10,000以上のウレタン(メタ)アクリレート化合物を組成中に含まない比較例1~2では、接着直後の接続抵抗値は良好なものの、85℃、85%RHの高温高湿槽中に250時間保持した後(信頼性試験後)では接続抵抗値が上昇した。また、接着力についても、実施例1~2と比較して接着直後の接着力は高いが、信頼性試験後の接着力低下が顕著であった。
以上の結果から、本発明の(b)ラジカル重合性化合物を用いることで、良好な接続抵抗と接着力を両立できることが明らかになった。 The film-like adhesives obtained in Examples 1 and 2 containing a urethane (meth) acrylate compound having a weight average molecular weight of 10,000 or more in the composition are a high-temperature and high-humidity tank immediately after bonding and at 85 ° C. and 85% RH. It was found that after holding for 250 hours, it showed good connection resistance and adhesive strength and good properties.
On the other hand, in Comparative Examples 1 and 2 in which the urethane (meth) acrylate compound having a weight average molecular weight of 10,000 or more is not included in the composition, the connection resistance value immediately after bonding is good, but the high temperature and high temperature of 85 ° C. and 85% RH are high. The connection resistance value increased after being kept in the wet tank for 250 hours (after the reliability test). As for the adhesive strength, the adhesive strength immediately after the adhesion was higher than that in Examples 1 and 2, but the decrease in the adhesive strength after the reliability test was remarkable.
From the above results, it has been clarified that by using the radically polymerizable compound (b) of the present invention, both good connection resistance and adhesive force can be achieved.
実施例1で得られたフィルム状接着剤を、真空包装を施して、40℃で3日間放置した後、実施例1と同様にFPCとITOとを160℃、3MPa、10秒で加熱圧着を行った。以上のようにして行った接続体の接着強度、接続抵抗を測定したところ、接着強度は840~880N/m、接続抵抗は1.0~1.3Ωを示し、処理前である実施例1と値に変化がほとんどなかったことから、放置安定性に優れることが分かった。 (Example 3)
The film adhesive obtained in Example 1 was vacuum-packed and allowed to stand at 40 ° C. for 3 days, and then FPC and ITO were thermocompression bonded at 160 ° C., 3 MPa, 10 seconds as in Example 1. went. Measurement of the adhesive strength and connection resistance of the connection body carried out as described above revealed an adhesive strength of 840 to 880 N / m and a connection resistance of 1.0 to 1.3 Ω. Since there was almost no change in the value, it was found that the storage stability was excellent.
半導体チップ(3×10mm,高さ0.5mm,主面の4辺周囲にバンプとよばれる100μm角、高さ20μmの突起した金電極が存在)のバンプ配置と対応した接続端子を有する厚み1mmのガラスエポキシ基板(回路は銅箔で厚み18μm)から作製した半導体搭載用基板を用意した。
半導体搭載用基板の回路表面には、ニッケル/金めっきを施した。半導体チップの突起電極と半導体搭載用基板とを上記実施例1のフィルム状接着剤を用いて次のようにして接続した。
半導体搭載用基板の回路面にフィルム状接着材を80℃、1MPa、3秒で仮圧着し、剥離性フッ素樹脂フィルムを剥離後、半導体チップの突起電極と半導体搭載用基板との位置合せを行い、180℃、10kgf/チップの温度及び圧力で20秒間加熱圧着した。
これによって、フィルム状接着剤を介して半導体チップの突起電極と半導体搭載用基板の回路とを電気的に接続すると同時に半導体チップと半導体搭載用基板の電極はフィルム状接着剤の硬化によって、この接続状態を保持した。このようにして得た半導体チップと半導体搭載用基板を接続した半導体装置を(-55℃、30分)/(125℃、30分)の条件で繰り返す冷熱サイクル試験に曝した。
この冷熱サイクル試験1,000回後の半導体チップの突起電極と基板回路の接続抵抗を測定したところ接続抵抗の上昇がなく、良好な接続信頼性を示した。 Example 4
Thickness 1mm with connecting terminals corresponding to bump arrangement of semiconductor chip (3x10mm, height 0.5mm, 100μm square called bumps around the four sides of the main surface, and 20μm high protruding gold electrodes) The board | substrate for semiconductor mounting produced from the glass epoxy board | substrate (The circuit is copper foil and thickness is 18 micrometers) was prepared.
The circuit surface of the semiconductor mounting substrate was subjected to nickel / gold plating. The protruding electrode of the semiconductor chip and the semiconductor mounting substrate were connected using the film adhesive of Example 1 as follows.
A film adhesive is temporarily bonded to the circuit surface of the semiconductor mounting substrate at 80 ° C., 1 MPa for 3 seconds, and after peeling the peelable fluororesin film, the semiconductor chip protruding electrode and the semiconductor mounting substrate are aligned. Then, thermocompression bonding was performed for 20 seconds at a temperature and pressure of 180 kg, 10 kgf / chip.
As a result, the protruding electrode of the semiconductor chip and the circuit of the semiconductor mounting substrate are electrically connected via the film adhesive, and at the same time, the connection of the semiconductor chip and the electrode of the semiconductor mounting substrate by the curing of the film adhesive. Retained state. The semiconductor device obtained by connecting the semiconductor chip and the semiconductor mounting substrate thus obtained was subjected to a repeated thermal cycle test under the conditions of (−55 ° C., 30 minutes) / (125 ° C., 30 minutes).
When the connection resistance between the protruding electrode of the semiconductor chip and the substrate circuit after 1,000 times of the thermal cycle test was measured, there was no increase in the connection resistance, and good connection reliability was shown.
Claims (7)
- (a)熱可塑性樹脂、(b)1分子中に2個以上の(メタ)アクリロイル基及び2個以上のウレタン結合を有し、かつ重量平均分子量が10,000以上であるラジカル重合性化合物、及び(c)ラジカル重合開始剤を含有する接着剤組成物。 (A) a thermoplastic resin, (b) a radically polymerizable compound having two or more (meth) acryloyl groups and two or more urethane bonds in one molecule, and having a weight average molecular weight of 10,000 or more, And (c) an adhesive composition containing a radical polymerization initiator.
- 前記(a)熱可塑性樹脂100重量部に対して、前記(b)ラジカル重合性化合物を10~250重量部、前記(c)ラジカル重合開始剤を0.05~30重量部含有する、請求項1に記載の接着剤組成物。 The (b) radical polymerizable compound is contained in an amount of 10 to 250 parts by weight and the radical polymerization initiator (c) in an amount of 0.05 to 30 parts by weight with respect to 100 parts by weight of the thermoplastic resin (a). The adhesive composition according to 1.
- (d)分子内に少なくとも1個以上のリン酸基を有するビニル化合物を、前記(a)熱可塑性樹脂100重量部に対して、0.1~20重量部さらに含有する、請求項1又は2に記載の接着剤組成物。 The (d) vinyl compound having at least one phosphate group in the molecule is further contained in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the (a) thermoplastic resin. The adhesive composition described in 1.
- (e)導電性粒子をさらに含有する、請求項1~3のいずれか一項に記載の接着剤組成物。 (E) The adhesive composition according to any one of claims 1 to 3, further comprising conductive particles.
- 相対向する回路電極を有する基板間に介在させ、前記相対向する回路電極同士が電気的に接続されるように前記基板同士を接着するために用いられる回路接続用接着剤であって、
請求項1~4のいずれか一項に記載の接着剤組成物からなる回路接続用接着剤。 An adhesive for circuit connection that is interposed between substrates having circuit electrodes facing each other, and is used for bonding the substrates so that the circuit electrodes facing each other are electrically connected,
An adhesive for circuit connection comprising the adhesive composition according to any one of claims 1 to 4. - 第一の回路電極を有する第一の基板と、
第二の回路電極を有する第二の基板とを、
前記第一の回路電極と前記第二の回路電極とが相対向するように配置し、
対向配置した前記第一の基板と第二の基板との間に、請求項5に記載の回路接続用接着剤を介在させ、加熱加圧して、前記第一の回路電極と前記第二の回路電極とを電気的に接続させてなる接続体。 A first substrate having a first circuit electrode;
A second substrate having a second circuit electrode;
The first circuit electrode and the second circuit electrode are arranged so as to face each other,
The adhesive for circuit connection according to claim 5 is interposed between the first substrate and the second substrate arranged to face each other, and the first circuit electrode and the second circuit are heated and pressed. A connection body in which electrodes are electrically connected. - 対向配置した半導体素子と半導体搭載用基板との間に、請求項5に記載の回路接続用接着剤を介在させ、加熱加圧して、前記半導体素子と前記半導体搭載用基板とを電気的に接続させてなる半導体装置。 The circuit-connecting adhesive according to claim 5 is interposed between the semiconductor element and the semiconductor-mounting substrate arranged to face each other, and the semiconductor element and the semiconductor-mounting substrate are electrically connected by heating and pressing. A semiconductor device.
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