WO2011077679A1 - 導電接続材料、電子部品の製造方法、導電接続材料付き電子部材および電子部品 - Google Patents
導電接続材料、電子部品の製造方法、導電接続材料付き電子部材および電子部品 Download PDFInfo
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- WO2011077679A1 WO2011077679A1 PCT/JP2010/007323 JP2010007323W WO2011077679A1 WO 2011077679 A1 WO2011077679 A1 WO 2011077679A1 JP 2010007323 W JP2010007323 W JP 2010007323W WO 2011077679 A1 WO2011077679 A1 WO 2011077679A1
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- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
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- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3489—Composition of fluxes; Methods of application thereof; Other methods of activating the contact surfaces
-
- 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
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/4007—Surface contacts, e.g. bumps
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31688—Next to aldehyde or ketone condensation product
Definitions
- the present invention relates to a conductive connection material, a method for manufacturing an electronic component, an electronic member with a conductive connection material, and an electronic component.
- An anisotropic conductive adhesive or anisotropic conductive film is a film or paste in which conductive particles are dispersed in an adhesive mainly composed of a thermosetting resin (for example, JP-A-61-276873).
- Patent Document 1 Japanese Patent Application Laid-Open No. 2004-260131 (Patent Document 2)).
- connection terminal on an electrode of an electronic member conventionally, a solder paste is printed on a substrate provided with a metal pad, and the connection terminal is formed by heating and melting the solder paste using a solder reflow device. It was. However, in this method, if the connection terminals have a narrow pitch, the cost of the mask used when printing the solder paste increases. Moreover, if the size of the connection terminal is too small, the solder paste may not be printed. There is also a method of manufacturing the connection terminal by mounting the solder ball on the connection terminal and heating and melting the solder ball using a solder reflow apparatus. However, in this method, if the connection terminal is too small, the manufacturing cost of the solder ball is high, and it may be technically difficult to manufacture a small-diameter solder ball.
- a conductive connecting material used for forming a conductive portion on a plurality of terminals of an electronic member having a substrate and a plurality of terminals provided on the substrate, A metal layer; A resin layer having a resin component and a filler; With A conductive connecting material configured to abut on and heat the a plurality of terminals so that the metal layer aggregates on each terminal and forms the conductive portion on the plurality of terminals is provided.
- the metal layer is formed on the terminal by using a conductive connection material including a metal layer and a resin layer instead of the film in which the conductive particles are dispersed. It has been found that it is easy to agglomerate. For this reason, according to this invention, the favorable electrical connection between the terminals which oppose can be obtained. Moreover, it can suppress that a metal layer remains in a resin layer, and can obtain the high insulation reliability between adjacent terminals. In addition, since the metal layer aggregates on each terminal by heating the conductive connection material, the electronic members having a plurality of terminals can be easily connected, and the connection terminals can be easily formed on the plurality of electrodes of the electronic member. can do.
- the conductive connecting material described above is disposed between the two electronic members facing each other with the plurality of terminals facing inward, and the two electronic members respectively contact the plurality of terminals.
- the step of contacting, the step of heating the conductive connecting material, and connecting the plurality of terminals of the two electronic members to each other via the conductive portions formed on the plurality of terminals, and the resin And a step of curing or solidifying the layer.
- the terminal is an electrode and the conductive part is a connection terminal
- the manufacturing method of an electronic component provided with the process of forming the said electroconductive part on these terminals and the process of hardening or solidifying the said resin layer is provided.
- an electronic member with a conductive connection material formed by adhering the conductive connection material described above on the substrate of the electronic member so as to contact the plurality of terminals.
- the plurality of terminals respectively included in the two electronic members facing the plurality of terminals inward through the conductive portion formed using the conductive connection material described above. Electronic components that are connected to each other.
- the present invention it is possible to obtain good electrical connection between opposing terminals and high insulation reliability between adjacent terminals, and connection between electronic members having a plurality of terminals, It is possible to provide a conductive connection material that facilitates formation of a connection terminal on an electrode.
- connection method of the electronic component of this invention it is sectional drawing which shows roughly an example of the state of the board
- connection method of the electronic component of this invention it is sectional drawing which shows roughly an example of the state of the board
- connection method of the electronic component of this invention it is sectional drawing which shows roughly an example of the state of the board
- manufacturing method of the electronic component of this invention it is sectional drawing which shows roughly an example of the state of a board
- manufacturing method of the electronic component of this invention it is sectional drawing which shows roughly an example of the state of a board
- the conductive connection material of the present invention a method for connecting an electronic component using the conductive connection material, and an electronic component electrically connected using the conductive connection material will be specifically described.
- the conductive connection material of the present invention comprises a resin layer and a metal layer.
- the form is a laminate having a multilayer structure composed of a resin layer and a metal layer, and each of the resin layer and the metal layer may be a single layer or a plurality of layers.
- the laminated structure of the conductive connecting material is not particularly limited, and may be a two-layer structure (resin layer / metal layer) of a resin layer and a metal layer, or a three-layer structure including a plurality of either or both of a resin layer and a metal layer, or A multilayer structure of more than that may be used. When a plurality of resin layers or metal layers are used, the composition of each layer may be the same or different.
- the upper and lower layers of the metal layer are preferably resin layers from the viewpoint of reducing the surface oxide film of the metal layer with a compound having a flux function.
- a three-layer structure resin layer / metal layer / resin layer
- the thicknesses of the resin layers on both sides of the metal layer may be the same or different.
- the thickness of the resin layer may be appropriately adjusted depending on the conductor thickness of the terminal to be connected. For example, when manufacturing a connection terminal using conductive connection materials having different thicknesses of resin layers on both sides of the metal layer, it is preferable to arrange the thinner one on the side of one connection terminal (electrode side). By shortening the distance between the metal layer and the connection terminal, the aggregation of the metal layer on the connection terminal portion can be easily controlled.
- connection terminal on an electronic member such as a semiconductor wafer
- the conductive connection material has a resin layer only on one side of the metal layer, a part of the metal layer is exposed. This is preferable.
- the resin layer side may be disposed so as to be in contact with the connection terminal, or the metal layer side may be disposed so as to be in contact with the connection terminal.
- the conductive connection material is attached to both of the opposing electronic members, and then the electronic member with the conductive connection material is attached. Is preferred.
- the arrangement direction of the conductive connection material may be appropriately selected depending on the pattern shape of the metal layer.
- a resin layer is comprised with the resin composition containing a resin component and a filler.
- the resin composition may be in a liquid or solid form at normal temperature.
- liquid at normal temperature means a state where there is no fixed form at normal temperature (25 ° C.). Paste forms are also included in liquid form.
- any of a curable resin composition and a thermoplastic resin composition may be used as the resin composition.
- the curable resin composition used in the present invention include those that are cured by heating or irradiation with actinic radiation.
- a thermosetting resin composition is preferable in that it is excellent in mechanical properties such as linear expansion coefficient and elastic modulus after curing.
- the thermoplastic resin composition used in the present invention is not particularly limited as long as it is flexible enough to be molded by heating to a predetermined temperature.
- Curable resin composition used in the present invention has a film-forming resin, a curing agent, a curing accelerator, and a flux function as necessary, in addition to the curable resin and the filler.
- a curing agent e.g., a curing accelerator
- a flux function e.g., a flux function of a curable resin composition
- Compounds, silane coupling agents and the like are included.
- curable resin used in the present invention is not particularly limited as long as it can be used as an adhesive component for manufacturing a semiconductor device.
- epoxy resin phenoxy resin, silicone resin, oxetane resin, phenol resin, (meth) acrylate resin, polyester resin (unsaturated polyester resin), diallyl phthalate resin, maleimide resin, polyimide resin (polyimide precursor resin), bismaleimide -Triazine resins and the like.
- thermosetting resin containing at least one selected from the group consisting of epoxy resins, (meth) acrylate resins, phenoxy resins, polyester resins, polyimide resins, silicone resins, maleimide resins, and bismaleimide-triazine resins.
- epoxy resin from a viewpoint that it is excellent in sclerosis
- curable resins may be used alone or in combination of two or more.
- Content of curable resin can be suitably set according to the form of curable resin composition.
- the content of the curable resin is preferably 10% by weight or more, more preferably 15% by weight or more, and more preferably 20% by weight with respect to the total weight of the curable resin composition.
- the above is more preferable, 25% by weight or more is further more preferable, 30% by weight or more is still more preferable, and 35% by weight or more is particularly preferable.
- it is preferably less than 100% by weight, more preferably 95% by weight or less, still more preferably 90% by weight or less, still more preferably 75% by weight or less, still more preferably 65% by weight or less, and particularly preferably 55% by weight or less.
- the content of the curable resin is preferably 5% by weight or more, more preferably 10% by weight or more, and more preferably 15% by weight with respect to the total weight of the curable resin composition.
- the above is more preferable, and 20% by weight or more is particularly preferable.
- 90 weight% or less is preferable, 85 weight% or less is more preferable, 80 weight% or less is further more preferable, 75 weight% or less is still more preferable, 65 weight% or less is still more preferable, 55 weight% or less is especially preferable.
- the content of the curable resin is within the above range, the electrical connection strength and the mechanical adhesive strength between the terminals can be sufficiently secured.
- any epoxy resin that is liquid at room temperature and solid at room temperature may be used.
- An epoxy resin that is liquid at room temperature and an epoxy resin that is solid at room temperature may be used in combination.
- the curable resin composition is liquid, it is preferable to use a liquid epoxy resin at room temperature, and when the curable resin composition is solid, use either a liquid or solid epoxy resin.
- a solid epoxy resin it is preferable to use a film-forming resin in combination.
- Preferred examples of the epoxy resin that is liquid at room temperature include bisphenol A type epoxy resins and bisphenol F type epoxy resins.
- a bisphenol A type epoxy resin and a bisphenol F type epoxy resin may be used in combination.
- the epoxy equivalent of the epoxy resin that is liquid at room temperature is preferably 150 to 300 g / eq, more preferably 160 to 250 g / eq, and particularly preferably 170 to 220 g / eq. If the epoxy equivalent is less than the above lower limit, the shrinkage of the cured product tends to increase, and warping may occur. On the other hand, when the upper limit is exceeded, when a film-forming resin is used in combination, the reactivity with a film-forming resin, particularly a polyimide resin, tends to decrease.
- solid epoxy resins at room temperature examples include bisphenol A type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, glycidyl amine type epoxy resins, and glycidyl ester type epoxies. Resin, trifunctional epoxy resin, tetrafunctional epoxy resin, etc. are mentioned. Among these, solid trifunctional epoxy resin, cresol novolac type epoxy resin and the like are preferable. These epoxy resins may be used alone or in combination of two or more.
- the epoxy equivalent of the epoxy resin solid at room temperature is preferably 150 to 3000 g / eq, more preferably 160 to 2500 g / eq, and particularly preferably 170 to 2000 g / eq.
- the softening point of the epoxy resin solid at room temperature is preferably 40 to 120 ° C, more preferably 50 to 110 ° C, and particularly preferably 60 to 100 ° C. When the softening point is within the above range, tackiness can be suppressed and handling can be easily performed.
- the filler used in the present invention is not particularly limited as long as it does not change quality and is stable during storage at normal temperature or during heating, and an inorganic filler or an organic filler is used. can do.
- a filler may be used individually by 1 type, or may use 2 or more types together.
- the inorganic filler examples include silica, alumina, zinc oxide, magnesium oxide, titanium oxide, antimony oxide, aluminum hydroxide, magnesium hydroxide, boron nitride, calcium carbonate, clay, talc, mica, glass fiber, and glass flake. , Glass beads, barium sulfate and the like, and silica and alumina with few impurities are preferable. These may be used alone or in combination of two or more.
- organic filler examples include cellulose, fluororesin, epoxy resin, urethane resin, melamine resin, phenol resin, acrylic resin, polyester resin, styrene resin, styrene butadiene copolymer, and the like.
- Epoxy resins and phenol resins that have a large effect of reducing the linear expansion coefficient of the product are preferred. These may be used alone or in combination of two or more.
- the shape of the filler is preferably spherical or scaly. Particularly, the spherical filler is more preferable because it has less anisotropy and is excellent in the ability to reduce the linear expansion coefficient of the entire resin composition.
- the particle size of the filler is preferably 10 nm or more, more preferably 50 nm or more, and particularly preferably 100 nm or more. Further, it is preferably 50 ⁇ m or less, more preferably 20 ⁇ m or less, and particularly preferably 10 ⁇ m or less. When the particle size of the filler is less than the lower limit, workability and dispersibility in the resin composition are lowered. On the other hand, when the upper limit is exceeded, the filler exists so as to straddle between the adjacent terminals, and inter-terminal connection by the metal foil is hindered.
- the content of the filler is preferably 1% by weight or more, more preferably 10% by weight or more, and particularly preferably 20% by weight or more with respect to the total weight of the curable resin composition. preferable. Further, it is preferably 80% by weight or less, more preferably 70% by weight or less, and particularly preferably 60% by weight or less. If the filler content is less than the lower limit, the effect of reducing the linear expansion coefficient of the cured resin composition cannot be obtained. On the other hand, when the upper limit is exceeded, the adhesion of the resin composition to the adherend is lowered, the reliability of the electronic component is lowered, and the fluidity of the resin composition is extremely lowered, making it impossible to mold.
- the content of the filler is such that the volume of the filler is Fv, and the volume of the metal layer is Mv.
- Fv / Mv is preferably 0.01 to 10.0, more preferably 0.02 to 8.0, and particularly preferably 0.05 to 5.0.
- the linear expansion coefficient of the cured resin layer is reduced by blending a filler in the resin layer, and further, a thermal cycle test.
- the filler is blended, the resin component content in the resin layer is reduced, so that the moisture absorption and water absorption of the cured resin layer can be reduced, and the moisture absorption heat resistance of the electronic component can be improved.
- blending a filler it is suppressed that the metal layer aggregated on each terminal flows out on a terminal.
- (Iii) Film-forming resin When a solid curable resin composition is used, it is preferable to use the curable resin and the film-forming resin in combination.
- the film-forming resin used in the present invention is not particularly limited as long as it is soluble in an organic solvent and has film-forming properties alone. Either a thermoplastic resin or a thermosetting resin can be used, and these can be used in combination.
- (meth) acrylic resin refers to a polymer of (meth) acrylic acid and its derivatives, or a copolymer of (meth) acrylic acid and its derivatives and other monomers. Means. When expressed as “(meth) acrylic acid” or the like, it means “acrylic acid or methacrylic acid” or the like.
- Examples of the (meth) acrylic resin used in the present invention include polyacrylic acid such as polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, and poly-2-ethylhexyl acrylate.
- esters such as polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polyacrylonitrile, polymethacrylonitrile, polyacrylamide, butyl acrylate-ethyl acrylate-acrylonitrile copolymer, acrylonitrile-butadiene Copolymer, acrylonitrile-butadiene-acrylic acid copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, methyl methacrylate-styrene copolymer, Methyl lurate-acrylonitrile copolymer, methyl methacrylate- ⁇ -methylstyrene copolymer, butyl acrylate-ethyl acrylate-acrylonitrile-2-hydroxyethyl methacrylate-methacrylic acid copolymer, butyl acrylate-ethy
- butyl acrylate-ethyl acrylate-acrylonitrile copolymer and ethyl acrylate-acrylonitrile-N, N-dimethylacrylamide copolymer are preferable.
- These (meth) acrylic resins may be used alone or in combination of two or more.
- the skeleton of the phenoxy resin used in the present invention is not particularly limited, bisphenol A type, bisphenol F type, biphenyl type and the like are preferable.
- the polyimide resin used in the present invention is not particularly limited as long as the resin has an imide bond in the repeating unit.
- the resin has an imide bond in the repeating unit.
- diamine and acid dianhydride react heating the obtained polyamic acid, and carrying out dehydration ring closure is mentioned.
- diamine examples include aromatic diamines such as 3,3′-dimethyl-4,4′-diaminodiphenyl, 4,6-dimethyl-m-phenylenediamine, and 2,5-dimethyl-p-phenylenediamine.
- siloxane diamines such as 3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane.
- a diamine may be used individually by 1 type, or may use 2 or more types together.
- Examples of the acid dianhydride include 3,3 ′, 4,4′-biphenyltetracarboxylic acid, pyromellitic dianhydride, 4,4′-oxydiphthalic dianhydride, and the like.
- An acid dianhydride may be used individually by 1 type, or may use 2 or more types together.
- the polyimide resin may be soluble or insoluble in a solvent, but is preferably a solvent-soluble one because it is easily varnished when mixed with other components and has excellent handleability.
- a siloxane-modified polyimide resin is preferably used because it can be dissolved in various organic solvents.
- the weight average molecular weight of the film-forming resin used in the present invention is preferably 8,000 to 1,000,000, more preferably 8,500 to 950,000, and further preferably 9,000 to 900,000.
- the weight average molecular weight of the film-forming resin can be measured by GPC (gel permeation chromatography).
- a commercially available product can be used as such a film-forming resin.
- a film-forming resin may be blended with various additives such as a plasticizer, a stabilizer, an antistatic agent, an antioxidant, and a pigment.
- the content of the film-forming resin can be appropriately set according to the form of the curable resin composition to be used.
- the content of the film-forming resin is preferably 5% by weight or more with respect to the total weight of the curable resin composition, and is 10% by weight or more. It is more preferable that the content is 15% by weight or more. Further, it is preferably 50% by weight or less, more preferably 45% by weight or less, and particularly preferably 40% by weight or less.
- the content of the film-forming resin is within the above range, the fluidity of the curable resin composition before melting can be suppressed, and the conductive connecting material can be easily handled.
- curing agent used in the present invention include phenols, acid anhydrides, and amine compounds.
- curing agent can be suitably selected according to the kind etc. of curable resin. For example, when an epoxy resin is used as the curable resin, good reactivity with the epoxy resin, low dimensional change during curing, and appropriate physical properties after curing (for example, heat resistance, moisture resistance, etc.) are obtained. Phenols are preferably used as the curing agent, and bifunctional or higher functional phenols are more preferable in terms of excellent physical properties after curing of the curable resin. Moreover, such a hardening
- phenols examples include bisphenol A, tetramethylbisphenol A, diallyl bisphenol A, biphenol, bisphenol F, diallyl bisphenol F, trisphenol, tetrakisphenol, phenol novolac resin, and cresol novolac resin.
- phenol novolac resins and cresol novolac resins are preferable because they have good reactivity with epoxy resins and excellent physical properties after curing.
- the content of the curing agent has a functional group that functions as a curing agent when the compound having a flux function described below and the type of the curable resin or the curing agent to be used have a functional group
- the content should be selected as appropriate. Can do.
- the content of the curing agent is preferably 0.1 to 50% by weight, more preferably 0.2 to 40% by weight, based on the total weight of the curable resin composition. Preferably, 0.5 to 30% by weight is particularly preferable.
- the content of the curing agent is within the above range, the electrical connection strength between the terminals and the mechanical adhesive strength can be sufficiently secured.
- (V) Curing accelerator The curing accelerator used in the present invention includes imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole.
- Content of a hardening accelerator can be suitably set according to the kind of hardening accelerator to be used.
- the content of the imidazole compound is preferably 0.001% by weight or more, more preferably 0.003% by weight or more, based on the total weight of the curable resin composition. 0.005% by weight or more is particularly preferable.
- 1.0 weight% or less is preferable, 0.7 weight% or less is more preferable, and 0.5 weight% or less is especially preferable.
- the content of the imidazole compound is less than the lower limit, the effect as a curing accelerator is not sufficiently exhibited, and the curable resin composition may not be sufficiently cured.
- the metal layer does not move sufficiently to the terminal surface before the curing of the curable resin composition is completed, and the metal layer remains in the insulating region and the insulation is sufficient. May not be secured. In addition, the storage stability of the conductive connection material may be reduced.
- the compound having a flux function used in the present invention has a function of reducing a metal oxide film such as a surface oxide film of a terminal and a metal foil.
- the compound having a flux function is preferably a compound having a phenolic hydroxyl group and / or a carboxyl group.
- Examples of the compound having a phenolic hydroxyl group include phenol, o-cresol, 2,6-xylenol, p-cresol, m-cresol, o-ethylphenol, 2,4-xylenol, 2,5-xylenol, m- Ethylphenol, 2,3-xylenol, mesitol, 3,5-xylenol, p-tert-butylphenol, catechol, p-tert-amylphenol, resorcinol, p-octylphenol, p-phenylphenol, bisphenol F, bisphenol AF, biphenol Monomers containing phenolic hydroxyl groups such as diallyl bisphenol F, diallyl bisphenol A, trisphenol, tetrakisphenol, phenol novolac resins, o-cresol novolac resins, bisphenols Nord F novolak resins, resins containing a phenolic hydroxyl group such as
- Examples of the compound having a carboxyl group include aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides, aliphatic carboxylic acids, and aromatic carboxylic acids.
- Examples of the aliphatic acid anhydride include succinic anhydride, polyadipic acid anhydride, polyazeline acid anhydride, and polysebacic acid anhydride.
- Examples of the alicyclic acid anhydride include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic acid. An anhydride etc. are mentioned.
- Examples of the aromatic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, and glycerol tris trimellitate.
- Examples of the aliphatic carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, acrylic acid, methacrylic acid, crotonic acid, Examples include oleic acid, fumaric acid, maleic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, and pimelic acid.
- n is an integer of 1 to 20
- adipic acid, sebacic acid, and dodecanedioic acid are more preferable.
- the structure of the aromatic carboxylic acid is not particularly limited, but a compound represented by the following formula (2) or (3) is preferable.
- R 1 to R 5 are each independently a monovalent organic group, and at least one of R 1 to R 5 is a hydroxyl group.
- R 6 to R 20 are each independently a monovalent organic group, and at least one of R 6 to R 20 is a hydroxyl group or a carboxyl group.
- Aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, merophanic acid, planitic acid, pyromellitic acid, merit acid, xylyl acid, hemelitonic acid, mesitylene Acid, prenylic acid, toluic acid, cinnamic acid, salicylic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, gentisic acid (2,5-dihydroxybenzoic acid), 2,6-dihydroxybenzoic acid, Benzoic acid derivatives such as 3,5-dihydroxybenzoic acid and gallic acid (3,4,5-trihydroxybenzoic acid); 1,4-dihydroxy-2-naphthoic acid, 3,5-dihydroxy-2-naphthoic acid Naphthoic acid derivatives such as 3,5-2-dihydroxy-2-naphth
- a compound that not only has a flux function but also acts as a curing agent for the curable resin is preferable. That is, as the compound having a flux function used in the present invention, a compound having a functional group capable of reacting with a curable resin and exhibiting an action of reducing a metal surface oxide film such as a metal layer and a terminal is used. preferable.
- the functional group is appropriately selected depending on the type of curable resin. For example, when an epoxy resin is used as the curable resin, the functional group is preferably a functional group capable of reacting with an epoxy group such as a carboxyl group, a hydroxyl group, and an amino group.
- the compound having the flux function also acts as a curing agent, thereby reducing the metal surface oxide film such as the metal layer and the terminal to increase the wettability of the metal surface, facilitating the formation of the conductive region, and conducting After forming the property region, it can be added to the curable resin to increase the elastic modulus or Tg of the resin.
- the compound having a flux function acts as a curing agent, there is an advantage that flux cleaning is not required and the occurrence of ion migration due to the remaining flux component can be suppressed.
- the compound having such a flux function preferably has at least one carboxyl group.
- examples of the compound include aliphatic dicarboxylic acids or compounds having a carboxyl group and a phenolic hydroxyl group.
- Preferred examples of the aliphatic dicarboxylic acid include compounds in which two carboxyl groups are bonded to an aliphatic hydrocarbon group.
- the aliphatic hydrocarbon group may be saturated or unsaturated acyclic, or may be saturated or unsaturated cyclic. Further, when the aliphatic hydrocarbon group is acyclic, it may be linear or branched.
- n in the formula (1) is preferably exemplified.
- n in the formula (1) is within the above range, the balance between the flux activity, the outgas at the time of bonding, the elastic modulus after the conductive connecting material is cured, and the glass transition temperature becomes good.
- n is preferably 3 or more because an increase in the elastic modulus after curing of the conductive connecting material can be suppressed and the adhesion to the adherend can be improved.
- n is preferably 10 or less because it is possible to suppress a decrease in elastic modulus and further improve connection reliability.
- Examples of the aliphatic dicarboxylic acid represented by the formula (1) include glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, and pentadecane.
- Examples include diacid, octadecanedioic acid, nonadecanedioic acid, and eicosanedioic acid.
- adipic acid, suberic acid, sebacic acid and dodencandioic acid are preferable, and sebacic acid is particularly preferable.
- Examples of the compound having a carboxyl group and a phenolic hydroxyl group include salicylic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, gentisic acid (2,5-dihydroxybenzoic acid), and 2,6-dihydroxybenzoic acid.
- Benzoic acid derivatives such as acid, 3,4-dihydroxybenzoic acid, gallic acid (3,4,5-trihydroxybenzoic acid); 1,4-dihydroxy-2-naphthoic acid, 3,5-dihydroxy-2-naphthoic acid
- naphthoic acid derivatives such as acids; phenolphthaline; diphenolic acid and the like. Of these, phenolphthaline, gentisic acid, 2,4-dihydroxybenzoic acid, and 2,6-dihydroxybenzoic acid are preferable, and phenolphthalin and gentisic acid are particularly preferable.
- a compound having a flux function may be used alone or in combination of two or more. Moreover, since any compound easily absorbs moisture and causes voids, it is preferable to dry the compound having a flux function in advance before use.
- Content of the compound which has a flux function can be suitably set according to the form of the resin composition to be used.
- the content of the compound having a flux function is preferably 1% by weight or more, more preferably 2% by weight or more, more preferably 3% by weight with respect to the total weight of the curable resin composition. % Or more is particularly preferable. Moreover, 50 weight% or less is preferable, 40 weight% or less is more preferable, 30 weight% or less is further more preferable, and 25 weight% or less is especially preferable.
- the content of the compound having a flux function is preferably 1% by weight or more, more preferably 2% by weight or more, more preferably 3% by weight with respect to the total weight of the curable resin composition. % Or more is particularly preferable. Moreover, 50 weight% or less is preferable, 40 weight% or less is more preferable, 30 weight% or less is further more preferable, and 25 weight% or less is especially preferable.
- the content of the compound having the flux function is within the above range, the metal layer and the surface oxide film of the terminal can be removed to such an extent that they can be electrically joined.
- the resin composition when the resin composition is a curable resin, it can be efficiently added to the resin at the time of curing to increase the elastic modulus or Tg of the resin. Moreover, generation
- silane coupling agent examples include an epoxy silane coupling agent and an aromatic-containing aminosilane coupling agent. By adding the silane coupling agent, the adhesion between the bonding member and the conductive connecting material can be enhanced.
- a silane coupling agent may be used individually by 1 type, and may use 2 or more types together.
- the content of the silane coupling agent can be appropriately selected according to the type of the joining member, the curable resin, and the like.
- the content of the silane coupling agent is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and particularly preferably 0.1% by weight or more with respect to the total weight of the curable resin composition. It is preferably 2% by weight or less, more preferably 1.5% by weight or less, and particularly preferably 1% by weight or less.
- the curable resin composition used in the present invention contains a plasticizer, a stabilizer, a tackifier, a lubricant, a filler, an antistatic agent, an antioxidant, a pigment, and the like as long as the effects of the present invention are not impaired. May be.
- the curable resin composition can be prepared by mixing and dispersing the above components.
- the mixing method and dispersion method of each component are not specifically limited, It can mix and disperse
- a liquid curable resin composition may be prepared by mixing the above components in a solvent or without a solvent.
- the solvent used at this time is not particularly limited as long as it is inert to each component.
- acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diisobutyl ketone (DIBK), cyclohexanone Ketones such as diacetone alcohol (DAA); aromatic hydrocarbons such as benzene, xylene and toluene; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and n-butyl alcohol; methyl cellosolve, ethyl cellosolve, butyl cellosolve; Cellosolves such as methyl cellosolve acetate and ethyl cellosolve acetate, N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THMP), t
- thermoplastic resin composition in this invention, can also be used as a resin composition.
- the thermoplastic resin composition used in the present invention includes a compound having a flux function, a silane coupling agent, and the like, if necessary, in addition to the thermoplastic resin and the filler.
- thermoplastic resin used in the present invention examples include vinyl acetate, polyvinyl alcohol resin, polyvinyl butyral resin, vinyl chloride resin, (meth) acrylic resin, phenoxy resin, polyester resin, polyimide resin, and polyamide.
- the softening point of the thermoplastic resin is not particularly limited, but is preferably 10 ° C. or more lower than the melting point of the metal layer constituting the conductive connection material, particularly preferably 20 ° C. or more, and more preferably 30 ° C. or more.
- the decomposition temperature of the thermoplastic resin is not particularly limited, but is preferably 10 ° C. or higher, particularly preferably 20 ° C. or higher, and more preferably 30 ° C. or higher than the melting point of the metal layer constituting the conductive connecting material. More preferred.
- thermoplastic resin composition can be suitably set according to the form of the thermoplastic resin composition to be used.
- the content of the thermoplastic resin is preferably 10% by weight or more, more preferably 15% by weight or more, and more preferably 20% by weight with respect to the total weight of the thermoplastic resin composition.
- the above is more preferable, 25% by weight or more is further more preferable, 30% by weight or more is still more preferable, and 35% by weight or more is particularly preferable.
- 100 weight% or less is preferable, 95 weight% or less is more preferable, 90 weight% or less is more preferable, 75 weight% or less is still more preferable, 65 weight% or less is still more preferable, 55 weight% or less is especially preferable.
- the content of the thermoplastic resin is preferably 5% by weight or more, more preferably 10% by weight or more, and more preferably 15% by weight with respect to the total weight of the thermoplastic resin composition.
- the above is more preferable, and 20% by weight or more is particularly preferable.
- 90 weight% or less is preferable, 85 weight% or less is more preferable, 80 weight% or less is further more preferable, 75 weight% or less is still more preferable, 65 weight% or less is still more preferable, 55 weight% or less is especially preferable.
- the content of the thermoplastic resin is within the above range, the electrical connection strength between the terminals and the mechanical adhesive strength can be sufficiently secured.
- thermoplastic resin composition of the present invention (Ii) Other additives
- the filler, the compound having a flux function, the silane coupling agent, and other additives used in the thermoplastic resin composition of the present invention are described in the above-mentioned "(a) Curable resin composition". The same can be used.
- the content of each component, preferred compounds and preparation methods are also the same as those described for the curable resin composition.
- the epoxy resin is 10 to 90% by weight
- the filler is 1 to 80% by weight
- the curing agent is 0.1 to 50% by weight
- the film-forming resin is 5 to 50% by weight
- the flux function with respect to the total weight of the resin composition. More preferred are those containing 1 to 50% by weight of the compound having The epoxy resin is 20 to 80% by weight
- the filler is 10 to 70% by weight
- the curing agent is 0.2 to 40% by weight
- the film-forming resin is 10 to 45% by weight
- the flux function based on the total weight of the resin composition.
- a compound containing 2 to 40% by weight of a compound having The epoxy resin is 35 to 55% by weight, the filler is 20 to 60% by weight, the curing agent is 0.5 to 30% by weight, the film-forming resin is 15 to 40% by weight, and the flux function based on the total weight of the resin composition.
- Particularly preferred are those containing 3 to 25% by weight of a compound having
- the thickness of each resin layer is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and particularly preferably 5 ⁇ m or more.
- the thickness of the resin layer is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and particularly preferably 100 ⁇ m or less.
- the composition of each resin layer may be the same, or may be different depending on the type of resin component used, the difference in formulation, and the like.
- the physical properties such as melt viscosity and softening temperature of the resin layer may be the same or different.
- a liquid resin layer and a solid resin layer may be used in combination.
- the resin layer of the present invention preferably has an average linear expansion coefficient from room temperature to 100 ° C. of 3 to 70 ppm. In this case, it is possible to reduce the stress applied to the connecting portion that electrically connects the electronic members due to the thermal expansion due to the thermal cycle test or heating during component mounting.
- a metal layer is a layer comprised with metal foil.
- the metal layer should just be formed in at least one part of the resin layer by planar view, and may be formed in the whole surface of the resin layer.
- the shape of the metal layer is not particularly limited, and a certain shape may be repeatedly formed in a pattern shape, or the shape may be irregular. Regular shapes and irregular shapes may be mixed.
- FIG. 1 is a schematic plan view showing an example of the shape of the metal layer.
- Metal layers 110 having various shapes are formed on the resin layer 120.
- As the shape of the metal layer for example, a dotted pattern (a), stripe pattern (b), polka dot pattern (c), rectangular pattern (d), checker pattern (as shown in FIG. e), frame shape (f), lattice pattern shape (g), or multiple frame shape (h). These shapes are examples, and these shapes can be combined or deformed depending on the purpose and application.
- a sheet-like metal layer is formed on the entire surface of the resin layer. Is preferably formed.
- a viewpoint of effectively using the metal layer and between adjacent electrodes From the viewpoint of not leaving the metal layer, it is preferable to form a patterned metal layer repeatedly on at least a part of the resin layer.
- the shape of the metal layer can be appropriately selected depending on the pitch and form of the electrodes.
- the metal layer used in the present invention preferably has a surface oxide film that can be removed by the reducing action of the compound having a flux function, such as tin (Sn), lead (Pb), silver (Ag), bismuth (Bi), Selected from the group consisting of indium (In), zinc (Zn), nickel (Ni), antimony (Sb), iron (Fe), aluminum (Al), gold (Au), germanium (Ge) and copper (Cu) It is preferably made of an alloy of at least two kinds of metals or a simple tin.
- a flux function such as tin (Sn), lead (Pb), silver (Ag), bismuth (Bi), Selected from the group consisting of indium (In), zinc (Zn), nickel (Ni), antimony (Sb), iron (Fe), aluminum (Al), gold (Au), germanium (Ge) and copper (Cu)
- a flux function such as tin (Sn), lead (Pb), silver (Ag), bismuth
- the metal layer is composed of an Sn—Pb alloy, an Sn—Bi alloy which is a lead-free solder, an Sn—Ag—Cu alloy, an Sn—In alloy, Sn.
- a solder foil made of an alloy containing Sn such as an alloy of -Ag is more preferable.
- the content of tin is preferably 30% by weight or more and less than 100% by weight, more preferably 35% by weight or more and less than 100% by weight, and particularly preferably 40% by weight or more. Moreover, less than 100 weight% is preferable.
- the content of tin is preferably 15% by weight or more and less than 100% by weight, more preferably 20% by weight or more and less than 100% by weight, and particularly preferably 25% by weight or more and less than 100% by weight.
- Sn-Pb alloys include Sn63-Pb (melting point 183 ° C), Sn-3.0Ag-0.5Cu (melting point 217 ° C), Sn-3.5Ag (melting point 221 ° C), Sn-58Bi (melting point) 139 ° C.), Sn-9.0Zn (melting point 199 ° C.), Sn-3.5Ag-0.5Bi-3.0In (melting point 193 ° C.), Au-20Sn (melting point 280 ° C.), and the like.
- the metal layer may be appropriately selected according to the heat resistance of the electronic member or semiconductor device to be connected.
- the melting point is 330 ° C. or lower (more preferably 300 ° C. or lower, particularly preferably 280 ° C. or lower, more preferably, in order to prevent the members of the semiconductor device from being damaged by thermal history. It is preferable to use a metal layer that is 260 ° C. or lower.
- a metal layer having a melting point of 100 ° C. or higher more preferably 110 ° C. or higher, particularly preferably 120 ° C. or higher.
- fusing point of a metal layer can be measured with a differential scanning calorimeter (DSC).
- DSC differential scanning calorimeter
- the thickness of the metal layer can be appropriately selected according to the gap between the opposing terminals, the separation distance between adjacent terminals, and the like.
- the thickness of the metal layer is preferably 0.5 ⁇ m or more, more preferably 3 ⁇ m or more, particularly preferably 5 ⁇ m or more, 100 micrometers or less are preferable, 50 micrometers or less are more preferable, and 20 micrometers or less are especially preferable.
- the thickness of the metal layer is less than the lower limit, the metal for constituting the conductive portion is insufficient, and the number of unconnected terminals tends to increase.
- the upper limit is exceeded, the metal becomes surplus, and bridging occurs between adjacent terminals, which tends to cause a short circuit.
- Examples of the method for producing the metal layer include a method of producing from a lump such as an ingot by rolling, and a method of forming the metal layer by direct vapor deposition, sputtering, plating, etc. on the resin layer.
- a method for producing a repetitive patterned metal layer for example, a method of punching a metal layer into a predetermined pattern, a method of forming a predetermined pattern by etching, etc., or using a shielding plate or a mask Examples thereof include a method of forming by vapor deposition, sputtering, plating, and the like.
- the content of the metal layer is preferably 5% by weight or more, more preferably 20% by weight or more, and particularly preferably 30% by weight or more based on the total weight of the conductive connecting material. Moreover, less than 100 weight% is preferable, 80 weight% or less is more preferable, and 70 weight% or less is especially preferable. If the content of the metal layer is less than the above lower limit, the metal for constituting the conductive part may be insufficient, and the number of unconnected terminals may increase. On the other hand, when the content of the metal layer exceeds the above upper limit, the metal becomes surplus and it is easy to cause a bridge between adjacent terminals.
- the content of the metal layer may be defined as a volume ratio with respect to the conductive connection material.
- the content of the metal layer is preferably 1% by volume or more, more preferably 5% by volume or more, and particularly preferably 10% by volume or more with respect to the conductive connection material.
- 90 volume% or less is preferable, 80 volume% or less is more preferable, and 70 volume% or less is especially preferable. If the content of the metal layer is less than the above lower limit, the metal for constituting the conductive part may be insufficient, and the number of unconnected terminals may increase. On the other hand, if the content of the metal layer exceeds the above upper limit, the metal becomes excessive, and bridging is likely to occur between adjacent terminals.
- the form of the conductive connection material can be appropriately selected according to the form of the resin composition.
- the resin composition when the resin composition is in a liquid state, the resin composition is applied on both surfaces of the metal layer, the resin composition is applied on a release substrate such as a polyester sheet, and semi-cured at a predetermined temperature (B stage)
- a film obtained by drying and forming a film and bonding the metal layers to form a film can be used as the conductive connection material.
- the varnish of the resin composition dissolved in an organic solvent is applied onto a release substrate such as a polyester sheet and dried at a predetermined temperature, and then a metal layer is laminated or vapor deposited.
- a film formed using the above method can be used as a conductive connection material.
- the conductive connection material of the present invention and the metal layer used in the conductive connection material can be embossed to enhance contact with the terminal.
- the thickness of the conductive connecting material of the present invention is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, particularly preferably 5 ⁇ m or more, preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and particularly preferably 100 ⁇ m or less. .
- the resin composition can be sufficiently filled in the gap between adjacent terminals.
- the mechanical adhesive strength after the resin component is cured or solidified and the electrical connection between the opposing terminals can be sufficiently ensured.
- the resin composition used in the present invention is liquid at 25 ° C., for example, the metal layer is immersed in the liquid resin composition, and the liquid resin composition is adhered to both surfaces of the metal layer, so that the conductive connecting material of the present invention is used. Can be manufactured.
- the thickness of the resin composition needs to be controlled, it is prepared by passing a metal layer immersed in a liquid resin composition through a bar coater having a certain gap or spraying the liquid resin composition with a spray coater or the like. can do.
- the conductive connecting material can be produced as follows. First, a varnish of a resin composition dissolved in an organic solvent is applied on a release substrate such as a polyester sheet, dried at a predetermined temperature to form a film, and a film-like resin composition is produced. Next, two resin compositions formed into a film on a release substrate were prepared and laminated with a hot roll with a metal layer sandwiched therebetween, whereby resin layers were arranged above and below the metal layer, resin layer / metal layer / A three-layer conductive connecting material made of a resin layer can be produced. In addition, a two-layer conductive connecting material composed of a resin layer / metal layer can be produced by disposing a resin layer on one side of the metal layer by the above-described laminating method.
- the metal layer when using a wound metal layer, the metal layer is used as a base substrate, and the film-like resin composition is laminated on the upper and lower sides or one side of the metal layer with a hot roll, thereby winding the conductive layer.
- a connection material can also be obtained.
- a varnish-like resin composition is directly applied to the upper or lower side or one side of the metal layer, and the solvent is evaporated to produce a wound conductive connection material. it can.
- a patterned metal layer is prepared, and the film-like resin composition may be laminated with a hot roll.
- the resin layer is provided on both surfaces of the patterned metal layer, the release substrate is peeled off, and the film-shaped resin composition is applied to the surface of the patterned metal layer opposite to the surface on which the resin layer is formed. Further lamination may be performed.
- the manufacturing method of a conductive connection material is not restrict
- a first electronic component manufacturing method relates to a method of connecting terminals using the conductive connection material, wherein the conductive connection material is formed by two electrons facing a plurality of terminals inward.
- An arrangement step of arranging between the members and contacting a plurality of terminals of each of the two electronic members, and heating the conductive connecting material to provide the two electronic members via the conductive portions formed on the plurality of terminals. Includes a heating step of connecting a plurality of terminals, respectively, and a curing / solidifying step of curing or solidifying the resin layer.
- the manufacturing method of the 1st electronic component in this invention can be used, for example, when connecting the terminals currently formed in the semiconductor wafer, the semiconductor chip, the rigid board
- the steps of the connection method are slightly different depending on whether the resin composition of the conductive connection material is a curable resin composition or a thermoplastic resin composition.
- the resin layer of the conductive connecting material has a curable resin
- the case where the resin layer includes a thermoplastic resin is described as a second embodiment.
- the step of connecting the electronic members to each other is equal to or higher than the melting point of the metal layer and the curing of the resin layer is completed.
- the step of curing or solidifying the resin layer is performed by heating the conductive connection material at a temperature at which the curing of the resin layer is completed.
- the heat-melted metal layer can be selectively agglomerated between terminals to form a conductive region, and an insulating region can be formed around the curable resin composition.
- insulation between adjacent terminals can be ensured and leakage current can be prevented, so that connection reliability of connection between terminals can be improved.
- electrical connection between a large number of terminals can be performed all at once, and connection between electronic members having a plurality of terminals can be facilitated.
- the mechanical strength of the conductive region or the insulating region can be increased by curing the curable resin composition.
- a substrate 10 provided with a plurality of terminals 11 and a substrate 20 provided with a plurality of terminals 21 are divided into a plurality of terminals 11 and a plurality of terminals 21. Align so that they face each other. And between these terminals, the conductive connection material 30 provided with the metal layer 110 and the resin layer 120 which consists of a curable resin composition provided in both surfaces of the metal layer 110 is arrange
- the conductive connecting material 30 is thermocompression bonded to one side of the substrate 10 or the substrate 20 or both of the substrate 10 and the substrate 20 as shown in FIG. 4 using an apparatus such as a roll laminator or a press. Also good. Further, the surfaces of the terminal 11 and the terminal 21 may be subjected to treatments such as cleaning, polishing, plating, and surface activation as necessary in order to improve electrical connection. Then, the conductive connection material 30 is brought into contact with the plurality of terminals 11 and the plurality of terminals 21.
- the conductive connection material 30 arranged between the terminals in the arrangement step is heated at a temperature equal to or higher than the melting point of the metal layer 110.
- the heating temperature may be equal to or higher than the melting point of the metal layer 110.
- the upper limit is not particularly limited as long as the curing of the resin layer 120 made of is not completed.
- the heating temperature is preferably 5 ° C. or more higher than the melting point of the metal layer 110, more preferably 10 ° C. or more, more preferably 20 ° C. or more, and particularly preferably 30 ° C. or more.
- the heating temperature can be appropriately selected depending on the metal layer to be used and the composition of the curable resin composition, but is preferably 100 ° C or higher, more preferably 130 ° C or higher, particularly preferably 140 ° C or higher, and 150 ° C or higher. Most preferred. In order to prevent thermal degradation of the substrate or the like to be connected, the heating temperature is preferably 260 ° C. or lower, more preferably 250 ° C. or lower, and particularly preferably 240 ° C. or lower.
- the metal layer 110 When the conductive connecting material 30 is heated at such a temperature, the metal layer 110 is melted, and the molten metal layer 110 can move in the resin layer 120 made of the curable resin composition.
- the molten metal layer 110 aggregates on the terminals 11 and 21 due to its wettability. Thereby, as shown in FIG. 3, a conductive portion 130 is formed between the terminals, and the terminals 11 and 21 are electrically connected.
- aggregation on the terminal does not mean that the area in plan view of the metal layer 110 is larger or smaller than the original area, but a good shape for connecting the terminal 11 and the terminal 21. That is, the metal layer 110 moves onto the terminals 11 and 21. Therefore, the case where the area of the metal layer 110 in plan view is reduced or enlarged is included.
- the conductive region 130 is filled with a curable resin composition to form an insulating region 140.
- insulation between adjacent terminals is ensured, and a short circuit between adjacent terminals can be prevented. That is, the conductive connecting material 30 is brought into contact with the plurality of terminals 11 and 21 and heated, thereby taking a structure having anisotropic conductivity.
- the surface oxide film of the metal layer 110 is removed by the reducing action of the compound having the flux function contained in the curable resin composition. This is a state in which the wettability is enhanced, and metal bonding is promoted to easily aggregate between opposing terminals.
- the surface oxide films of the terminals 11 and 21 are also removed by the reducing action of the compound having a flux function and the wettability is enhanced, metal bonding with the metal layer 110 is facilitated.
- heating may be performed by applying pressure so that the distance between opposing terminals is reduced.
- the distance between the terminals facing each other can be controlled to be constant by heating and pressurizing using means such as a known thermocompression bonding apparatus in the direction in which the substrates 10 and 20 in FIG. 2 face each other. It is possible to increase the reliability of electrical connection between the terminals to be performed.
- an ultrasonic wave or an electric field may be applied, or special heating such as laser or electromagnetic induction may be applied.
- (C) Curing Step In the first method for manufacturing an electronic component according to the present invention, after forming the conductive portion 130 and the insulating region 140 in the heating step, the curable resin composition is cured to insulate the insulating region 140. To fix. Thereby, electrical reliability and mechanical connection strength between the terminals can be sufficiently ensured. In particular, in the first method for manufacturing an electronic component according to the present invention, since the curable resin composition having a high insulation resistance value is used, the insulation of the insulating region can be more sufficiently ensured.
- Curing of the curable resin composition can be performed by heating the conductive connection material 30 or the like.
- the curing temperature of the conductive connecting material 30 can be appropriately set according to the composition of the curable resin composition, but is preferably at least 5 ° C. lower than the heating temperature in the heating step, and at least 10 ° C. lower.
- a temperature is particularly preferred. Specifically, it is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, particularly preferably 130 ° C. or higher, and most preferably 150 ° C. or higher. Further, it is preferably 300 ° C. or lower, more preferably 260 ° C. or lower, particularly preferably 250 ° C. or lower, and most preferably 240 ° C. or lower.
- the curing temperature is within the above range, the conductive connecting material 30 is not thermally decomposed and the curable resin composition can be sufficiently cured.
- the step of connecting the electronic members to each other heats the conductive connection material at a temperature equal to or higher than the melting point of the metal layer and the resin layer softening.
- the step of curing or solidifying the resin layer is performed by cooling the conductive connecting material to a temperature at which the resin layer solidifies.
- (A) Arrangement Step When the conductive connection material 30 including the thermoplastic resin composition and the metal layer 110 is used, the conductive connection material 30 including the curable resin composition and the metal layer 110 is used.
- the conductive connection material 30 can be disposed on the substrate.
- the heating step is not particularly limited, the conductive connection material 30 arranged between the terminals in the arrangement step is heated at a melting point or higher of the metal layer 110.
- the heating temperature is preferably 5 ° C. or more higher than the melting point of the metal layer, more preferably 10 ° C. or more, more preferably 20 ° C. or more, and particularly preferably 30 ° C. or more.
- the heating temperature is equal to or higher than the melting point of the metal layer 110, and the resin layer 120 made of the thermoplastic resin composition is softened so that the metal layer 110 can move in the resin layer 120 made of the thermoplastic resin, that is, “thermoplastic resin”.
- the upper limit is not particularly limited as long as the resin layer 120 made of the composition is softened.
- the heating temperature can be appropriately selected depending on the metal layer to be used and the composition of the thermoplastic resin composition. For example, it can be heated at the same heating temperature as the conductive connecting material containing the curable resin composition and the metal layer.
- the metal layer 110 When the conductive connecting material 30 is heated at the above temperature, the metal layer 110 is melted and the molten metal layer 110 can move in the resin layer 120 made of the thermoplastic resin composition.
- the molten metal layer 110 aggregates on the terminals 11 and 21 due to its wettability. Thereby, as shown in FIG. 3, a conductive portion 130 is formed between the terminals, and the terminals 11 and 21 are electrically connected.
- the insulating region 140 is formed by filling the periphery of the conductive portion 130 with the thermoplastic resin composition. As a result, insulation between adjacent terminals is ensured, and a short circuit between adjacent terminals can be prevented. That is, the conductive connecting material 30 is brought into contact with the plurality of terminals 11 and 21 and heated, thereby taking a structure having anisotropic conductivity.
- the surface oxide film of the metal layer 110 is removed by the reducing action of the compound having the flux function contained in the thermoplastic resin composition. This is a state in which the wettability is enhanced, and metal bonding is promoted to easily aggregate between opposing terminals.
- the surface oxide films of the terminals 11 and 21 are also removed by the reducing action of the compound having a flux function and the wettability is enhanced, metal bonding with the metal layer 110 is facilitated.
- thermoplastic resin composition is solidified to form the insulating region 140. Fix the area. Thereby, electrical reliability and mechanical connection strength between the terminals can be sufficiently ensured.
- the solidification of the thermoplastic resin composition can be carried out by cooling and solidifying the conductive connecting material 30 heated and melted in the heating step.
- the cooling and solidification of the conductive connecting material 30 can be appropriately set according to the composition of the thermoplastic resin composition, and is not particularly limited, but may be a method by natural cooling, or may be blown with cold air. The method may be used.
- the solidification temperature of the thermoplastic resin composition is not particularly limited, but is preferably lower than the melting point of the metal layer 110. More specifically, the solidification temperature of the thermoplastic resin composition is preferably 10 ° C. or more lower than the melting point of the metal layer 110, and particularly preferably 20 ° C. or more lower. The solidification temperature of the thermoplastic resin composition is preferably 50 ° C. or higher, particularly preferably 60 ° C. or higher, and further preferably 100 ° C. or higher. When the solidification temperature of the thermoplastic resin composition is within the above range, the conductive portion 130 can be reliably formed, and the insulating region 140 can have a desired heat resistance. For this reason, the insulation between adjacent terminals is ensured, and a short circuit between adjacent terminals can be more reliably prevented.
- a conductive connection material composed of a resin layer and a metal layer is used. For this reason, by heating the conductive connection material, the metal layer can be selectively agglomerated between the terminals facing each other, electrically connecting the terminals facing each other, and ensuring insulation between adjacent terminals. can do. Further, in a fine wiring circuit such as a semiconductor device, a large number of terminals can be brought into conduction at once, and the connection between terminals with excellent reliability can be easily performed.
- the second electronic component manufacturing method according to the present invention includes a placement step of contacting the conductive connection material on the plurality of terminals, a heating step of heating the conductive connection material to form a conductive portion on the plurality of terminals, A curing / solidifying step for curing or solidifying the resin layer.
- the manufacturing method of a 2nd electronic component is based on the method of manufacturing a connection terminal on the electrode of an electronic member, for example using the said conductive connection material.
- the terminal is, for example, an electrode.
- the conductive part is, for example, a connection terminal.
- the second electronic component manufacturing method of the present invention can be used, for example, when manufacturing connection terminals on electrodes of a semiconductor wafer, a semiconductor chip, a rigid substrate, a flexible substrate, and other electronic components.
- connection terminal manufacturing process is slightly different between the case where the resin composition of the conductive connection material is a curable resin composition and the case where the resin composition is a thermoplastic resin composition.
- the resin composition of the conductive connecting material is a curable resin composition
- the case where it is a thermoplastic resin composition will be described as a second embodiment.
- the step of forming the conductive portion is equal to or higher than the melting point of the metal layer, and the curing of the resin layer is not completed.
- the step of curing or solidifying the resin layer is performed by heating the conductive connection material at a temperature
- the step of curing or solidifying the resin layer is performed by heating the conductive connection material at a temperature at which the curing of the resin layer is completed.
- a metal layer that has been heated and melted is selectively aggregated on electrodes on a substrate to form connection terminals, and an insulating region is formed around the curable resin composition. Can do.
- connection terminal since the periphery of the connection terminal can be covered with the curable resin composition, the conductive region is fixed. Moreover, since the insulation between adjacent connection terminals is ensured by the insulating region, the connection reliability can be improved. According to this method, a large number of connection terminals can be manufactured at once even in a fine wiring circuit, and the connection terminals can be easily formed on the electrodes.
- a conductive connection material 50 having a resin layer 120 made of a curable resin composition and a metal layer 110 is arranged on a substrate 40 provided with a plurality of electrodes 41. To do. At this time, when the patterned metal layer 110 is used, it is necessary to align the conductive connecting material 50 and the electrode 41 on the substrate 40.
- the resin layer 120 made of the curable resin composition is formed on one side of the metal layer 110, but the resin layer 120 made of the curable resin composition is the same as the metal layer 110. It may be formed on both sides.
- the resin layer 120 made of the curable resin composition is disposed so as to face the electrode 41, but the metal foil 110 may be disposed so as to face the electrode 41.
- the conductive connection material 50 may be thermocompression bonded to the substrate 40 using an apparatus such as a roll laminator or a press.
- the resin layer 120 made of the curable resin composition covers the electrode 41, but the thickness of the resin layer 120 made of the thermosetting resin composition may be smaller than the thickness of the electrode 41, It may be thicker than the thickness of the electrode 41, and can be appropriately adjusted according to the purpose and application.
- the surface of the electrode 41 may be cleaned, polished, plated, surface activated, or the like, if necessary, in order to improve electrical connection or to improve the bondability with the metal layer 110. Processing may be performed.
- (B) Heating step In the heating step, the conductive connecting material 50 placed on the electrode 41 on the substrate 40 in the placement step is equal to or higher than the melting point of the metal layer 110, and the curing of the curable resin composition is completed. Heat at a temperature that does not. Thereby, the connection terminal 150 can be formed on the electrode 41 as shown in FIG. On the other hand, a curable resin composition is filled around the connection terminal 150 to form an insulating region 140. As a result, insulation between the adjacent connection terminals 150 is ensured, and a short circuit between the adjacent connection terminals 150 can be prevented.
- the heating temperature and the pressurizing condition of the curable resin composition are as follows.
- the terminal is connected using a conductive connecting material having the curable resin composition and a metal layer. It can be performed under the same conditions.
- (C) Curing Step In the curing step, after forming the connection terminal 150 and the insulating region 140 in the heating step, the curable resin composition is cured and the insulating region 140 is fixed. Thereby, joining of the electrode 41 and the connection terminal 150 on the board
- this curing step is preferably performed after the connection terminal 150 is formed and then the substrate 60 is mounted and connected to another electronic component or substrate.
- the heating temperature of the conductive connection material in the curing step is the same as that in the case of performing inter-terminal connection using the conductive connection material having the curable resin composition and the metal layer in the first electronic component manufacturing method. Can be done under conditions.
- the step of forming the conductive part is heating the conductive connection material at a temperature that is equal to or higher than the melting point of the metal layer and the resin layer is softened.
- the step of curing or solidifying the resin layer is performed by cooling the conductive connection material to a temperature at which the resin layer is solidified.
- the metal layer that has been heated and melted can be selectively agglomerated on the electrodes on the substrate to form connection terminals, and an insulating region can be formed around the thermoplastic resin composition. .
- connection terminal since the periphery of the connection terminal can be covered with the thermoplastic resin composition, the conductive region is fixed. Moreover, since the insulation between adjacent connection terminals is ensured by the insulating region, the connection reliability can be improved. According to this method, a large number of connection terminals can be manufactured at once even in a fine wiring circuit.
- (A) Arrangement step When a conductive connection material including a thermoplastic resin composition and a metal layer is used, a conductive connection material including the curable resin composition of the first embodiment and a metal layer is used. Similarly, the conductive connection material can be disposed on a substrate provided with electrodes.
- the conductive connecting material 50 placed on the electrode provided on the substrate in the placing step is a melting point of the metal layer 110 or more and a resin layer made of the thermoplastic resin composition. Heat at a temperature at which 120 softens.
- the connection terminal 150 can be manufactured on the electrode 41 similarly to the first embodiment.
- the insulating region 140 is formed by filling the periphery of the connection terminal 150 with the thermoplastic resin composition. As a result, insulation between the adjacent connection terminals 150 is ensured, and a short circuit between the adjacent connection terminals 150 can be prevented.
- thermoplastic resin composition the heating temperature and pressurizing conditions of the thermoplastic resin composition are as follows.
- terminal-to-terminal connection is performed using a conductive connection material having the thermoplastic resin composition and a metal foil. It can be performed under the same conditions as in the case of.
- thermoplastic resin composition is cooled and solidified to fix the insulating region 140, thereby forming the electrode 41.
- connection terminal 150 can be reinforced.
- the cooling method and preferable solidification temperature of a thermoplastic resin composition in the manufacturing method of a 1st electronic component, it uses the conductive connection material which has the said thermoplastic resin composition and a metal layer, and connects between terminals. It is the same as the case where it went.
- connection terminal is simplified. Can be manufactured by a simple method.
- a plurality of connection terminals can be manufactured at once in a fine wiring circuit such as a semiconductor device.
- an insulating region can be formed around the plurality of connection terminals, the connection terminals can be fixed and insulation between adjacent connection terminals can be secured. Thereby, the connection terminal excellent in connection reliability can be manufactured easily.
- the present invention also includes an electronic member with a conductive connection material formed by bonding the conductive connection material of the present invention to an electrical connection surface on which a plurality of terminals are formed among the electronic members.
- the adhesive surface of the conductive connection material with the electrical connection surface of the electronic member is preferably a resin layer.
- the resin layer may be directly bonded to the electrical connection surface of the electronic member, or may be bonded via an adhesive layer.
- the electronic members with the conductive connection material of the present invention are bonded to each other, or the electronic members with the conductive connection material of the present invention are bonded to the electrical connection surfaces of the other electronic members and thermocompression bonded so that the electronic members are electrically connected. Can be connected.
- the present invention includes a semiconductor wafer, a semiconductor chip, a rigid substrate and a flexible substrate, and other electronic components in which electronic members are electrically connected using the conductive connection material of the present invention thus obtained. To do.
- Examples 1 to 7 (1) Preparation of curable resin composition Each component shown in Table 1 was dissolved in methyl ethyl ketone (MEK) to obtain a resin composition varnish having a resin solid content of 40%. The obtained varnish was applied to a polyester sheet using a comma coater and dried at 90 ° C. for 5 minutes to obtain a curable resin composition having a film thickness of 30 ⁇ m. (2) Measurement of average linear expansion coefficient of resin composition The average linear expansion coefficient of the resin composition was obtained by curing the curable resin composition obtained in (1) at 180 ° C. for 1 hour.
- MEK methyl ethyl ketone
- thermomechanical analyzer manufactured by Seiko Instruments Inc., SS6100
- connection terminal (terminal diameter) made of a FR-4 base material (thickness 0.1 mm) and a circuit layer (copper circuit, thickness 12 ⁇ m) as a substrate, and Ni / Au plating (thickness 3 ⁇ m) formed on the copper circuit. Two sheets having 100 ⁇ m and a center distance of 200 ⁇ m between adjacent terminals were prepared and used for connection.
- the conductive connection material is disposed between the substrates having such connection terminals, and using a thermocompression bonding apparatus (“TMV1-200ASB” manufactured by Tsukuba Mechanics Co., Ltd.) under the conditions of 230 ° C., 0.5 MPa, 120 seconds.
- Thermocompression bonding (gap between substrates: 50 ⁇ m) was applied to connect the terminals. Then, it heated at 180 degreeC for 1 hour, the curable resin composition was hardened, and the laminated body was obtained.
- Example 1 A curable resin composition containing no filler was prepared in the same manner as in Example 1, and the obtained curable resin composition having a thickness of 30 ⁇ m was laminated on both surfaces of the solder foil shown in Table 1 to have a thickness of 70 ⁇ m.
- the conductive connection material was manufactured. Furthermore, the terminal connection of the board
- connection resistance between opposing terminals, conduction path formation between opposing terminals, and conduction resistance after a thermal cycle test were evaluated by methods described below.
- connection resistance between opposing terminals
- the connection resistance is a four-terminal method (resistance meter: “Digital” manufactured by Iwasaki Tsushinki Co., Ltd.) in the laminates obtained in Examples and Comparative Examples. 12 points were measured by “Multimeter VOA7510”, measurement probe: “Pin type lead 9771” manufactured by Hioki Electric Co., Ltd.). The case where the average value was less than 30 m ⁇ was determined as “A”, and the case where the average value was 30 m ⁇ or more was determined as “B”.
- connection resistance after thermal cycle test The connection resistance between the terminals facing each other in the laminates obtained in the examples and comparative examples was determined by the four-terminal method (resistance meter: “Digital Multimeter VOA7510” manufactured by Iwasaki Tsushinki Co., Ltd.) Measurement probe: “Pin type lead 9771” manufactured by Hioki Electric Co., Ltd.) Next, the laminate was subjected to 1000 cycles and 1500 cycles of a thermal cycle test at ⁇ 40 ° C., 10 minutes to 85 ° C. for 10 minutes, and the connection resistance between terminals was measured in the same manner as described above. “A” when the appearance is normal and the rate of change from the initial value of all connection resistances is less than ⁇ 5%.
- Epoxy resin bisphenol A type epoxy resin, “EPICLON-840S” manufactured by Dainippon Ink and Chemicals, epoxy equivalent of 185 g / eq Curing agent: phenol novolac, “PR-53647” manufactured by Sumitomo Bakelite Co., Ltd.
- Film-forming resin modified biphenol type phenoxy resin, “YX-6654” manufactured by Japan Epoxy Resin Co., Ltd., weight average molecular weight 39,000
- Compound having flux function 1 Sebacic acid, “Sebacic acid” manufactured by Tokyo Chemical Industry Co., Ltd.
- Compound 2 having flux function Phenolphthalene, “Phenolphthalin” manufactured by Tokyo Chemical Industry Co., Ltd.
- Silane coupling agent 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, “KBM-303” manufactured by Shin-Etsu Chemical Co., Ltd.
- Imidazole 2-Phenyl-4-methylimidazole, “Cureazole 2P4MZ” manufactured by Shikoku Chemicals Co., Ltd.
- Filler 1 Silica Admatech, SE2050, average particle size 0.5 ⁇ m, specific gravity 2.2
- Filler 2 Alumina Showa Denko, AS-50, average particle size 9 ⁇ m, specific gravity 3.8
- the resin layer containing the resin component and the filler is used as the resin layer of the conductive connecting material, so that the linear expansion coefficient of the cured resin layer is reduced. It was shown that the stress of the connection part due to thermal expansion due to heating during mounting can be reduced, and the reliability of the electronic component can be improved. Furthermore, it is also shown that by using a resin layer containing a filler as the resin layer of the conductive connection material, the moisture absorption and water absorption of the cured resin layer can be reduced, and the moisture absorption heat resistance of the electronic component can be improved. It was.
- the conductive connection material of the present invention can be suitably used when electrically connecting electronic members in an electronic component or manufacturing a connection terminal on a substrate.
- By using the conductive connection material of the present invention it is possible to achieve both good electrical connection between electronic members and high insulation reliability.
- connection between terminals in a fine wiring circuit is also possible.
- By using the conductive connection material of the present invention it is possible to meet the demand for higher functionality and downsizing of electronic devices.
Abstract
Description
金属層と、
樹脂成分と充填剤とを有する樹脂層と、
を備え、
前記複数の端子上に当接し、加熱することによって、前記金属層が各端子上に凝集し、前記複数の端子上に前記導電部を形成するように構成された導電接続材料が提供される。
本発明の導電接続材料は、樹脂層と金属層とから構成される。その形態は、樹脂層と金属層とからなる多層構造を有する積層体であり、樹脂層及び金属層は各々一層であっても複数層であってもよい。導電接続材料の積層構造は特に制限されず、樹脂層と金属層との二層構造(樹脂層/金属層)でもよいし、樹脂層あるいは金属層の何れか又は両方を複数含む三層構造又はそれ以上の多層構造でもよい。なお、樹脂層又は金属層を複数用いる場合、各層の組成は同一でもよく、異なっていてもよい。
本発明において、樹脂層は、樹脂成分及び充填剤を含有する樹脂組成物で構成される。樹脂組成物は、常温で液状又は固形状のいずれの形態であってもよい。ここで「常温で液状」とは、常温(25℃)で一定の形態を持たない状態を意味する。ペースト状も液状に含まれる。
本発明で用いる硬化性樹脂組成物には、硬化性樹脂及び充填剤のほか、必要に応じて、フィルム形成性樹脂、硬化剤、硬化促進剤、フラックス機能を有する化合物、シランカップリング剤などが含まれる。
本発明で用いる硬化性樹脂は、通常、半導体装置製造用の接着剤成分として使用できるものであれば特に限定されない。例えば、エポキシ樹脂、フェノキシ樹脂、シリコーン樹脂、オキセタン樹脂、フェノール樹脂、(メタ)アクリレート樹脂、ポリエステル樹脂(不飽和ポリエステル樹脂)、ジアリルフタレート樹脂、マレイミド樹脂、ポリイミド樹脂(ポリイミド前駆体樹脂)、ビスマレイミド-トリアジン樹脂などが挙げられる。特に、エポキシ樹脂、(メタ)アクリレート樹脂、フェノキシ樹脂、ポリエステル樹脂、ポリイミド樹脂、シリコーン樹脂、マレイミド樹脂、ビスマレイミド-トリアジン樹脂からなる群より選ばれる少なくとも1種を含む熱硬化性樹脂を用いることが好ましい。中でも、硬化性と保存性、硬化物の耐熱性、耐湿性、耐薬品性に優れるという観点からエポキシ樹脂を用いることが好ましい。これらの硬化性樹脂は1種単独で用いても、2種以上を併用してもよい。
例えば、硬化性樹脂組成物が液状の場合、硬化性樹脂の含有量は、硬化性樹脂組成物の全重量に対して、10重量%以上が好ましく、15重量%以上がより好ましく、20重量%以上がさらに好ましく、25重量%以上がさらにより好ましく、30重量%以上がなお好ましく、35重量%以上が特に好ましい。また、100重量%未満が好ましく、95重量%以下がより好ましく、90重量%以下がさらに好ましく、75重量%以下がさらにより好ましく、65重量%以下がなお好ましく、55重量%以下が特に好ましい。
硬化性樹脂組成物が固形状の場合は、硬化性樹脂の含有量は、硬化性樹脂組成物の全重量に対して、5重量%以上が好ましく、10重量%以上がより好ましく、15重量%以上がさらに好ましく、20重量%以上が特に好ましい。また、90重量%以下が好ましく、85重量%以下がより好ましく、80重量%以下がさらに好ましく、75重量%以下がさらにより好ましく、65重量%以下がなお好ましく、55重量%以下が特に好ましい。
硬化性樹脂の含有量が前記範囲内にあると端子間の電気的接続強度及び機械的接着強度を十分に確保することができる。
室温で液状のエポキシ樹脂のエポキシ当量は、150~300g/eqが好ましく、160~250g/eqがより好ましく、170~220g/eqが特に好ましい。前記エポキシ当量が上記下限未満になると硬化物の収縮率が大きくなる傾向があり、反りが生じることがある。他方、前記上限を超えると、フィルム形成性樹脂を併用した場合に、フィルム形成性樹脂、特にポリイミド樹脂との反応性が低下する傾向にある。
室温で固形状のエポキシ樹脂のエポキシ当量は、150~3000g/eqが好ましく、160~2500g/eqがより好ましく、170~2000g/eqが特に好ましい。
室温で固形状のエポキシ樹脂の軟化点は、40~120℃が好ましく、50~110℃がより好ましく、60~100℃が特に好ましい。前記軟化点が前記範囲内にあると、タック性を抑えることができ、容易に取り扱うことが可能となる。
本発明に用いる充填剤は、常温保管時や加熱時に、変質することがなく性能が安定しているものであれば特に制限はなく、無機充填剤や有機充填剤などを使用することができる。充填剤は1種単独で用いても、2種以上を併用してもよい。
Fv/Mvが0.01~10.0であることが好ましく、さらに、0.02~8.0であることが好ましく、0.05~5.0であることが特に好ましい。Fv/Mvを上記下限値以上とすることで、硬化後の樹脂組成物の線膨張係数を効果的に低下させることができるため、電子部品の信頼性を向上させることができる。また、Fv/Mvを上記上限値以下とすることで、金属層が加熱工程(後述する)で樹脂組成物中を確実に移動することができるため、良好な端子間接続を実現することができる。
固形状の硬化性樹脂組成物を使用する場合、前記硬化性樹脂とフィルム形成性樹脂とを併用することが好ましい。本発明で用いるフィルム形成性樹脂としては、有機溶媒に可溶であり、単独で製膜性を有するものであれば特に制限はない。熱可塑性樹脂又は熱硬化性樹脂のいずれのものも使用することができ、また、これらを併用することもできる。具体的に、フィルム形成性樹脂としては、(メタ)アクリル系樹脂、フェノキシ樹脂、ポリエステル樹脂(飽和ポリエステル樹脂)、ポリウレタン樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、シロキサン変性ポリイミド樹脂、ポリブタジエン樹脂、ポリプロピレン樹脂、スチレン-ブタジエン-スチレン共重合体、スチレン-エチレン-ブチレン-スチレン共重合体、ポリアセタール樹脂、ポリビニルブチラール樹脂、ポリビニルアセタール樹脂、ブチルゴム、クロロプレンゴム、ポリアミド樹脂、アクリロニトリル-ブタジエン共重合体、アクリロニトリル-ブタジエン-アクリル酸共重合体、アクリロニトリル-ブタジエン-スチレン共重合体、ポリ酢酸ビニル、ナイロンなどが挙げられる。中でも、(メタ)アクリル系樹脂、フェノキシ樹脂、ポリエステル樹脂及びポリイミド樹脂が好ましい。フィルム形成性樹脂は1種単独で用いても、2種以上を併用してもよい。
例えば、固形状の硬化性樹脂組成物の場合には、フィルム形成性樹脂の含有量は、硬化性樹脂組成物の全重量に対して、5重量%以上であることが好ましく、10重量%以上であることがより好ましく、15重量%以上であることが特に好ましい。また、50重量%以下であることが好ましく、45重量%以下であることがより好ましく、40重量%以下であることが特に好ましい。フィルム形成性樹脂の含有量が前記範囲内にあると溶融前の硬化性樹脂組成物の流動性を抑制することができ、導電接続材料を容易に取り扱うことが可能となる。
本発明で用いる硬化剤としては、フェノール類、酸無水物及びアミン化合物が好ましく挙げられる。硬化剤は、硬化性樹脂の種類などに応じて適宜選択することができる。例えば、硬化性樹脂としてエポキシ樹脂を使用する場合、エポキシ樹脂との良好な反応性、硬化時の低寸法変化及び硬化後の適切な物性(例えば、耐熱性、耐湿性など)が得られる点で硬化剤としてフェノール類を用いることが好ましく、硬化性樹脂の硬化後の物性が優れている点で2官能以上のフェノール類がより好ましい。また、このような硬化剤は1種単独で用いてもよいし、2種以上を併用してもよい。
例えば、硬化性樹脂としてエポキシ樹脂を用いた場合、硬化剤の含有量は硬化性樹脂組成物の全重量に対して、0.1~50重量%が好ましく、0.2~40重量%がより好ましく、0.5~30重量%が特に好ましい。硬化剤の含有量が前記範囲内にあると端子間の電気的接続強度及び機械的接着強度を十分に確保することができる。
本発明で用いる硬化促進剤としては、イミダゾール、2-メチルイミダゾール、2-ウンデシルイミダゾール、2-ヘプタデシルイミダゾール、1,2-ジメチルイミダゾール、2-エチル-4-メチルイミダゾール、2-フェニルイミダゾール、2-フェニル-4-メチルイミダゾール、1-ベンジル-2-フェニルイミダゾール、1-ベンジル-2-メチルイミダゾール、1-シアノエチル-2-メチルイミダゾール、1-シアノエチル-2-エチル-4-メチルイミダゾール、1-シアノエチル-2-ウンデシルイミダゾール、1-シアノエチル-2-フェニルイミダゾール、1-シアノエチル-2-ウンデシルイミダゾリウムトリメリテイト、1-シアノエチル-2-フェニルイミダゾリウムトリメリテイト、2,4-ジアミノ-6-[2'-メチルイミダゾリル(1')]-エチル-s-トリアジン、2,4-ジアミノ-6-[2'-ウンデシルイミダゾリル(1')]-エチル-s-トリアジン、2,4-ジアミノ-6-[2'-エチル-4-メチルイミダゾリル(1')]-エチル-s-トリアジン、2,4-ジアミノ-6-[2'-メチルイミダゾリル(1')]-エチル-s-トリアジンのイソシアヌル酸付加物、2-フェニルイミダゾールのイソシアヌル酸付加物、2-メチルイミダゾールのイソシアヌル酸付加物、2-フェニル-4,5-ジヒドロキシジメチルイミダゾール、2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾールなどのイミダゾール化合物が挙げられる。
例えば、イミダゾール化合物を使用する場合には、イミダゾール化合物の含有量は、硬化性樹脂組成物の全重量に対して、0.001重量%以上が好ましく、0.003重量%以上がより好ましく、0.005重量%以上が特に好ましい。また、1.0重量%以下が好ましく、0.7重量%以下がより好ましく、0.5重量%以下が特に好ましい。イミダゾール化合物の含有量が前記下限未満になると硬化促進剤としての作用が十分に発揮されず、硬化性樹脂組成物を十分に硬化できない場合がある。他方、イミダゾール化合物の含有量が前記上限を超えると、硬化性樹脂組成物の硬化が完了する前に金属層が端子表面に十分に移動せず、絶縁性領域に金属層が残り絶縁性が十分に確保できない場合がある。また、導電接続材料の保存安定性が低下する場合がある。
本発明で用いるフラックス機能を有する化合物は、端子及び金属箔の表面酸化膜など金属酸化膜を還元する作用を有するものである。例えば、フラックス機能を有する化合物としては、フェノール性水酸基及び/又はカルボキシル基を有する化合物が好ましい。フェノール性水酸基を有する化合物としては、例えば、フェノール、o-クレゾール、2,6-キシレノール、p-クレゾール、m-クレゾール、o-エチルフェノール、2,4-キシレノール、2,5-キシレノール、m-エチルフェノール、2,3-キシレノール、メシトール、3,5-キシレノール、p-tert-ブチルフェノール、カテコール、p-tert-アミルフェノール、レゾルシノール、p-オクチルフェノール、p-フェニルフェノール、ビスフェノールF、ビスフェノールAF、ビフェノール、ジアリルビスフェノールF、ジアリルビスフェノールA、トリスフェノール、テトラキスフェノールなどのフェノール性水酸基を含有するモノマー類、フェノールノボラック樹脂、o-クレゾールノボラック樹脂、ビスフェノールFノボラック樹脂、ビスフェノールAノボラック樹脂などのフェノール性水酸基を含有する樹脂が挙げられる。
HOOC-(CH2)n-COOH (1)
(式(1)中、nは1~20の整数である。)
で表される脂肪族カルボン酸が好ましく、アジピン酸、セバシン酸、ドデカンジオン酸がより好ましい。
脂肪族ジカルボン酸としては、脂肪族炭化水素基にカルボキシル基が2個結合した化合物が好ましく挙げられる。脂肪族炭化水素基は、飽和又は不飽和の非環式であってもよいし、飽和又は不飽和の環式であってもよい。また、脂肪族炭化水素基が非環式の場合には直鎖状でも分岐状でもよい。
例えば、樹脂組成物が液状の場合、フラックス機能を有する化合物の含有量は、硬化性樹脂組成物の全重量に対して、1重量%以上が好ましく、2重量部%以上がより好ましく、3重量%以上が特に好ましい。また、50重量%以下が好ましく、40重量%以下がより好ましく、30重量%以下がさらに好ましく、25重量%以下が特に好ましい。
固形状の樹脂組成物の場合には、フラックス機能を有する化合物の含有量は、硬化性樹脂組成物の全重量に対して、1重量%以上が好ましく、2重量%以上がより好ましく、3重量%以上が特に好ましい。また、50重量%以下が好ましく、40重量%以下がより好ましく、30重量%以下がさらに好ましく、25重量%以下が特に好ましい。
フラックス機能を有する化合物の含有量が上記範囲内であると、金属層及び端子の表面酸化膜を電気的に接合できる程度に除去することができる。さらに、樹脂組成物が硬化性樹脂の場合、硬化時に、樹脂に効率よく付加して樹脂の弾性率又はTgを高めることができる。また、未反応のフラックス機能を有する化合物に起因するイオンマイグレーションの発生を抑制することができる。
本発明で用いるシランカップリング剤としては、エポキシシランカップリング剤、芳香族含有アミノシランカップリング剤などが挙げられる。シランカップリング剤を添加することにより、接合部材と導電接続材料との密着性を高めることができる。シランカップリング剤は1種単独で用いてもよいし、2種以上を併用してもよい。
本発明においては、樹脂組成物として熱可塑性樹脂組成物を用いることもできる。
本発明で用いる熱可塑性樹脂組成物は、熱可塑性樹脂及び充填剤のほか、必要に応じて、フラックス機能を有する化合物、シランカップリング剤などが含まれる。
本発明で用いる熱可塑性樹脂としては、例えば、酢酸ビニル系、ポリビニルアルコール樹脂、ポリビニルブチラール樹脂、塩化ビニル樹脂、(メタ)アクリル樹脂、フェノキシ樹脂、ポリエステル樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、シロキサン変性ポリイミド樹脂、ポリブタジエン樹脂、アクリル樹脂、スチレン樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ポリアミド樹脂、セルロース樹脂、イソブチレン樹脂、ビニルエーテル樹脂、液晶ポリマー樹脂、ポリフェニレンスルフィド樹脂、ポリフェニレンエーテル樹脂、ポリエーテルサルフォン樹脂、ポリエーテルイミド樹脂、ポリエーテルエーテルケトン樹脂、ポリウレタン樹脂、スチレン-ブタジエン-スチレン共重合体、スチレン-エチレン-ブチレン-スチレン共重合体、ポリアセタール樹脂、ポリビニルアセタール樹脂、ブチルゴム、クロロプレンゴム、アクリロニトリル-ブタジエン共重合体、アクリロニトリル-ブタジエン-アクリル酸共重合体、アクリロニトリル-ブタジエン-スチレン共重合体、ポリ酢酸ビニル等が挙げられる。熱可塑性樹脂は、単一の重合体でもよく、上記熱可塑樹脂の2種以上の共重合体でもよい。
例えば、熱可塑性樹脂組成物が液状の場合、熱可塑性樹脂の含有量は、熱可塑性樹脂組成物の全重量に対して、10重量%以上が好ましく、15重量%以上がより好ましく、20重量%以上がさらに好ましく、25重量%以上がさらにより好ましく、30重量%以上がなお好ましく、35重量%以上が特に好ましい。また、100重量%以下が好ましく、95重量%以下がより好ましく、90重量%以下がさらに好ましく、75重量%以下がさらにより好ましく、65重量%以下がなお好ましく、55重量%以下が特に好ましい。
熱可塑性樹脂組成物が固形状の場合は、熱可塑性樹脂の含有量は、熱可塑性樹脂組成物の全重量に対して、5重量%以上が好ましく、10重量%以上がより好ましく、15重量%以上がさらに好ましく、20重量%以上が特に好ましい。また、90重量%以下が好ましく、85重量%以下がより好ましく、80重量%以下がさらに好ましく、75重量%以下がさらにより好ましく、65重量%以下がなお好ましく、55重量%以下が特に好ましい。
熱可塑性樹脂の含有量が上記の範囲内であると端子間の電気的接続強度及び機械的接着強度を十分に確保することができる。
本発明の熱可塑性樹脂組成物で用いる充填剤、フラックス機能を有する化合物、シランカップリング剤、その他の添加剤は、前記「(a)硬化性樹脂組成物」において説明したものと同じものを用いることができる。各成分の含有量、好ましい化合物及び調製方法も硬化性樹脂組成物で説明したものと同様である。
本発明において金属層は、金属箔で構成される層である。金属層は平面視で樹脂層の少なくとも一部に形成されていればよく、樹脂層の全面に形成されていてもよい。
本発明で用いる樹脂組成物が25℃で液状の場合、例えば、金属層を液状の樹脂組成物に浸漬させ、金属層の両面に液状の樹脂組成物を付着させて、本発明の導電接続材料を製造することができる。樹脂組成物の厚み制御が必要な場合は、液状の樹脂組成物に浸漬させた金属層を一定の間隙を有するバーコーターを通過させる方法や液状の樹脂組成物をスプレーコーター等により吹き付ける方法により作製することができる。
なお、導電接続材料の製造方法は上記方法に制限されない。導電接続材料の製造方法は、目的や用途に応じて当業者が適宜選択することができる。
次に、本発明における第1の電子部品の製造方法について説明する。
本発明における第1の電子部品の製造方法は、前記導電接続材料を用いて端子間を接続する方法にかかるものであり、導電接続材料を、複数の端子を内側に向けて対向する二つの電子部材間に配置し、二つの電子部材がそれぞれ有する複数の端子に当接させる配置工程と、前記導電接続材料を加熱して、複数の端子上に形成された導電部を介して二つの電子部材がそれぞれ有する複数の端子を互いに接続する加熱工程と、前記樹脂層を硬化又は固化する硬化/固化工程と、を含む。本発明における第1の電子部品の製造方法は、例えば、半導体ウエハ、半導体チップ、リジッド基板、フレキシブル基板、その他の電子部材に形成されている端子同士を接続する際などに用いることができる。
本発明の第1実施態様における第1の電子部品の製造方法において、電子部材を互いに接続する工程は、金属層の融点以上であって、かつ樹脂層の硬化が完了しない温度で導電接続材料を加熱することにより行われ、樹脂層を硬化または固化する工程は、樹脂層の硬化が完了する温度で導電接続材料を加熱することにより行われる。
(a)配置工程
先ず、図2に示すように、複数の端子11が設けられた基板10と、複数の端子21が設けられた基板20とを、複数の端子11と複数の端子21とが対向するように位置あわせする。そして、これらの端子間に、金属層110と、金属層110の両面に設けられた硬化性樹脂組成物からなる樹脂層120と、を備える導電接続材料30を配置する。この時、導電接続材料30はロールラミネータ又はプレス等の装置を使用し、図4に示すように、あらかじめ基板10又は基板20の片側、あるいは、基板10及び基板20の双方に熱圧着されていてもよい。また、端子11および端子21の表面は、電気的な接続を良好にするために、必要により、洗浄、研磨、めっき及び表面活性化などの処理を施してもよい。そして、導電接続材料30を、複数の端子11および複数の端子21へ当接させる。
加熱工程では、前記配置工程において端子間に配置した導電接続材料30を、金属層110の融点以上で加熱する。加熱温度は、金属層110の融点以上であればよく、例えば加熱時間を短くするなど、加熱時間を調整することによって、金属層110が硬化性樹脂中を移動できる範囲すなわち「硬化性樹脂組成物からなる樹脂層120の硬化が完了しない」範囲であれば、その上限は特に制限されない。加熱温度は、金属層110の融点より5℃以上高い温度が好ましく、10℃以上高い温度がより好ましく、20℃以上高い温度がさらに好ましく、30℃以上高い温度が特に好ましい。
さらに、加圧又は加熱する際に超音波や電場などを加えたり、レーザーや電磁誘導などの特殊加熱を適用したりしてもよい。
本発明における第1の電子部品の製造方法においては、前記加熱工程で導電部130と絶縁性領域140とを形成した後、硬化性樹脂組成物を硬化させて絶縁性領域140を固定する。これにより、前記端子間の電気的信頼性及び機械的接続強度を十分に確保することができる。特に本発明における第1の電子部品の製造方法においては、高絶縁抵抗値を有する硬化性樹脂組成物を使用しているため、絶縁性領域の絶縁性をより十分に確保することができる。
次に、本発明の第2実施態様における第1の電子部品の製造方法について説明する。本発明の第2実施態様における第1の電子部品の製造方法において、電子部材を互いに接続する工程は、金属層の融点以上であって、かつ樹脂層が軟化する温度で導電接続材料を加熱することにより行われ、樹脂層を硬化または固化する工程は、樹脂層が固化する温度まで導電接続材料を冷却することにより行われる。
熱可塑性樹脂組成物と金属層110とを含む導電接続材料30を使用した場合も、前記硬化性樹脂組成物と金属層110とを含む導電接続材料30を使用した場合と同様に導電接続材料30を配置することができる。
加熱工程は、特に制限されないが、前記配置工程において端子間に配置した導電接続材料30を、金属層110の融点以上で加熱する。加熱温度は、金属層の融点より5℃以上高い温度が好ましく、10℃以上高い温度がより好ましく、20℃以上高い温度がさらに好ましく、30℃以上高い温度が特に好ましい。加熱温度は、金属層110の融点以上であり、熱可塑性樹脂組成物からなる樹脂層120が軟化して、金属層110が熱可塑性樹脂からなる樹脂層120中を移動できる範囲すなわち「熱可塑性樹脂組成物からなる樹脂層120が軟化する」範囲であれば、その上限は特に制限されない。
本発明における第1の電子部品の製造方法においては、前記加熱工程で導電部130と絶縁性領域140とを形成した後、熱可塑性樹脂組成物を固化させて絶縁性領域140領域を固定する。これにより、前記端子間の電気的信頼性及び機械的接続強度を十分に確保することができる。
次に、本発明における第2の電子部品の製造方法について説明する。
本発明における第2の電子部品の製造方法は、導電接続材料を複数の端子上に当接する配置工程と、導電接続材料を加熱して、複数の端子上に導電部を形成する加熱工程と、樹脂層を硬化または固化する硬化/固化工程と、を備えている。第2の電子部品の製造方法は、例えば前記導電接続材料を用いて電子部材の電極上に接続端子を製造する方法にかかるものである。この場合、上記端子は、例えば電極である。また、上記導電部は、例えば接続端子である。本発明における第2の電子部品の製造方法は、例えば、半導体ウエハ、半導体チップ、リジッド基板、フレキシブル基板、その他の電子部品の電極上に接続端子を製造する際に用いることができる。
本発明の第1実施態様における第2の電子部品の製造方法において、導電部を形成する工程は、金属層の融点以上であって、かつ樹脂層の硬化が完了しない温度で導電接続材料を加熱することにより行われ、樹脂層を硬化または固化する工程は、樹脂層の硬化が完了する温度で導電接続材料を加熱することにより行われる。
この第2の電子部品の製造方法では、加熱溶融した金属層を選択的に基板上の電極に凝集させて接続端子を形成し、その周囲に硬化性樹脂組成物による絶縁性領域を形成することができる。その結果、接続端子の周囲を硬化性樹脂組成物で被覆することができるため、導電性領域が固定される。また、絶縁性領域によって隣接する接続端子間の絶縁性が確保されるので、接続信頼性を高めることができる。この方法によれば、微細な配線回路においても多数の接続端子を一括で製造することが可能となり、電極上への接続端子の形成が容易となる。
先ず、図5に示すように、硬化性樹脂組成物からなる樹脂層120と金属層110とを有する導電接続材料50を、複数の電極41が設けられた基板40上に配置する。この時、パターン状の金属層110を使用した場合は、導電接続材料50と基板40上の電極41との位置合わせが必要となる。なお、図5では、硬化性樹脂組成物からなる樹脂層120が金属層110の片面に形成されたものを使用しているが、硬化性樹脂組成物からなる樹脂層120は、金属層110の両面に形成されていてもよい。また、図5では、硬化性樹脂組成物からなる樹脂層120が電極41と対向するように配置されているが、金属箔110が電極41と対向するように配置されていてもよい。
図5に示すように、導電接続材料50は、ロールラミネータ、プレス等の装置を使用し、基板40に熱圧着されていてもよい。なお、図6では、硬化性樹脂組成物からなる樹脂層120が電極41を被覆しているが、熱硬化樹脂組成物からなる樹脂層120の厚みは、電極41の厚みより薄くてもよく、電極41の厚みより厚くてもよく、目的及び用途等に応じて適宜調整することができる。また、前記電極41の表面は、電気的な接続を良好にするために、あるいはまた、金属層110との接合性を向上させるために、必要により、洗浄、研磨、めっき及び表面活性化などの処理を施してもよい。
加熱工程では、前記配置工程において基板40上の電極41上に配置した導電接続材料50を、金属層110の融点以上であり、且つ、前記硬化性樹脂組成物の硬化が完了しない温度で加熱する。これにより、図7に示すように、電極41上に接続端子150を形成することができる。他方、前記接続端子150の周囲には硬化性樹脂組成物が充填されて絶縁性領域140が形成される。その結果、隣接する接続端子150間の絶縁性が確保され、隣接する接続端子150間のショートを防止することができる。
硬化工程では、前記加熱工程で接続端子150と絶縁性領域140とを形成した後、硬化性樹脂組成物を硬化させて、絶縁性領域140を固定する。これにより、基板40上の電極41と接続端子150の接合を補強することができる。特に本発明の第1実施態様では、高絶縁抵抗値を有する硬化性樹脂組成物を使用しているため、絶縁性領域の絶縁性をより十分に確保することができる。特に制限されないが、この硬化工程は、接続端子150を形成した後、基板60を、別の電子部品又は基板等に搭載し、接続した後に行なうことが好ましい。
硬化工程における導電接続材料の加熱温度は、第1の電子部品の製造方法において、前記硬化性樹脂組成物と金属層とを有する導電接続材料を使用して端子間接続を行った場合と同様の条件で行うことができる。
次に、本発明の第2実施態様における第2の電子部品の製造方法について説明する。
本発明の第2実施態様における第2の電子部品の製造方法において、導電部を形成する工程は、金属層の融点以上であって、かつ樹脂層が軟化する温度で導電接続材料を加熱することにより行われ、樹脂層を硬化または固化する工程は、樹脂層が固化する温度まで導電接続材料を冷却することにより行われる。
第2実施態様の製造方法では、加熱溶融した金属層を選択的に基板上の電極に凝集させて接続端子を形成し、その周囲に熱可塑性樹脂組成物による絶縁性領域を形成することができる。その結果、接続端子の周囲を熱可塑性樹脂組成物で被覆することができるため、導電性領域が固定される。また、絶縁性領域によって隣接する接続端子間の絶縁性が確保されるので、接続信頼性を高めることができる。この方法によれば、微細な配線回路においても多数の接続端子を一括で製造することが可能となる。
熱可塑性樹脂組成物と金属層とを含む導電接続材料を使用した場合も、前記第1実施態様の硬化性樹脂組成物と金属層とを含む導電接続材料を使用した場合と同様に導電接続材料を電極が設けられた基板上に配置することができる。
加熱工程では、前記配置工程において基板に設けられた電極上に配置した導電接続材料50を、金属層110の融点以上であり、且つ、前記熱可塑性樹脂組成物からなる樹脂層120が軟化する温度で加熱する。これにより、第1実施態様と同様に、電極41上に接続端子150を製造することができる。他方、接続端子150の周囲には熱可塑性樹脂組成物が充填されて絶縁性領域140が形成される。その結果、隣接する接続端子150間の絶縁性が確保され、隣接する接続端子150間のショートを防止することができる。
固化工程では、前記加熱工程で接続端子150と絶縁性領域140とを形成した後、熱可塑性樹脂組成物を冷却固化させて、絶縁性領域140を固定することにより、電極41と接続端子150との接合を補強することができる。
なお、熱可塑性樹脂組成物の冷却方法及び好ましい固化温度については、第1の電子部品の製造方法において、前記熱可塑性樹脂組成物と金属層とを有する導電接続材料を使用して端子間接続を行った場合と同様である。
本発明は、電子部材のうち複数の端子が形成された電気的接続面に、本発明の導電接続材料を接着してなる導電接続材料付き電子部材をも包含する。本発明の導電接続材料付き電子部材において、導電接続材料の電子部材の電気的接続面との接着面は樹脂層であることが好ましい。該樹脂層は、電子部材の電気的接続面に直接接着されていてもよいし、接着剤層を介して接着されていてもよい。本発明の導電接続材料付き電子部材を互いに貼り合わせ、あるいは、本発明の導電接続材料付き電子部材を他の電子部材の電気的接続面と貼り合わせて熱圧着させることで、電子部材間を電気的に接続することができる。
本発明では、このようにして得られた本発明の導電接続材料を用いて電子部材間が電気的に接続されてなる半導体ウエハ、半導体チップ、リジッド基板及びフレキシブル基板、その他の電子部品をも包含する。
(1)硬化性樹脂組成物の調製
表1に示した各成分を、メチルエチルケトン(MEK)に溶解して樹脂固形分40%の樹脂組成物のワニスを得た。得られたワニスを、コンマコーターを用いて、ポリエステルシートに塗布し、90℃で5分間乾燥させてフィルム状の厚さ30μmの硬化性樹脂組成物を得た。
(2)樹脂組成物の平均線膨張係数測定
樹脂組成物の平均線膨張係数は、(1)で得られた硬化性樹脂組成物を180℃、1時間の条件で硬化し、得られたサンプルを用い、熱機械分析装置(TMA;セイコーインスツルメンツ(株)社製、SS6100)で、引っ張り法、昇温速度10℃/min、荷重50mNの条件で測定し、室温から100℃までの線膨張係数の平均値を測定値とした。
得られたフィルム状の硬化性樹脂組成物を60℃、2kgf/cm2、0.3m/minの条件で、表1に示した半田箔の両面にラミネートし、厚み70μmの導電接続材料を製造した。
次に、得られた導電接続材料を用いて基板の端子間接続を行った。基板として、FR-4基材(厚み0.1mm)と回路層(銅回路、厚み12μm)からなり、銅回路上にNi/Auメッキ(厚み3μm)を施して形成される接続端子(端子径100μm、隣接する端子間の中心距離200μm)を有するものを2枚準備し、接続に使用した。このような接続端子を有する基板間に、前記導電接続材料を配置し、熱圧着装置((株)筑波メカニクス製「TMV1-200ASB」)を用いて230℃、0.5MPa、120秒の条件で熱圧着(基板間ギャップ50μm)を施し、端子間を接続した。その後、180℃で1時間加熱して硬化性樹脂組成物を硬化させて、積層体を得た。
実施例1と同様にして充填剤が含まれていない硬化性樹脂組成物を調製し、得られた厚さ30μm硬化性樹脂組成物を表1に示した半田箔の両面にラミネートして厚み70μmの導電接続材料を製造した。さらに、実施例1と同様の方法(前記「(4)端子間接続」記載の方法)で、得られた導電接続材料を用いて基板の端子間接続を行った。
接続抵抗は、実施例および比較例で得られた積層体において対向する端子間の接続抵抗を4端子法(抵抗計:岩崎通信機(株)製「デジタルマルチメータVOA7510」、測定プローブ:日置電機(株)製「ピン型リード9771」)により12点測定した。その平均値が30mΩ未満の場合を「A」、30mΩ以上の場合を「B」と判定した。
実施例および比較例で得られた積層体において対向する端子10組について、その端子間の断面を走査型電子顕微鏡(SEM)(日本電子(株)製「JSM-7401F」)で観察し、10組全てにおいて半田により円柱状の導通路が形成されている場合を「A」、1組でも導通路が形成されていない端子が存在する場合を「B」、隣接している端子とショート接触している場合を「C」と判定した。
実施例および比較例で得られた積層体において対向する端子間の接続抵抗を4端子法(抵抗計:岩崎通信機(株)製「デジタルマルチメータVOA7510」、測定プローブ:日置電機(株)製「ピン型リード9771」)により12点測定した。次に、積層体を-40℃、10分⇔85℃、10分で1サイクルの冷熱サイクル試験を1000サイクル、1500サイクル実施し、上述と同様の方法で端子間の接続抵抗を測定した。
外観に異常がなく、全ての接続抵抗の初期値からの変化率が、±5%未満である場合を「A」。外観に異常がなく、接続抵抗の初期値からの変化率が、±5%以上で±10%未満である場合を「B」。冷熱サイクル試験後外観に膨れ、剥がれ等の異常がある、または接続抵抗の初期値からの変化率が±10%以上である場合を「C」と判定した。
実施例および比較例で得られた導電接続材料が備える樹脂層の吸水率WA[%]を、以下のようにして求めた。まず、製造された導電接続材料が備える樹脂層を、180℃×1時間の条件で硬化を兼ねた乾燥を行う。そして、その直後における樹脂層の重さW0[g]を測定した。次に、導電接続材料を、温度85℃、湿度85%RHの雰囲気下に24時間配置した後の、樹脂層の重さW1[g]を測定した。そして、測定されたW0[g]およびW1[g]から、下記式を用いて吸水率WA[%]を求めた。
WA[%]=(W1-W0)/W0×100
エポキシ樹脂:ビスフェノールA型エポキシ樹脂、大日本インキ化学工業(株)製「EPICLON-840S」、エポキシ当量185g/eq
硬化剤:フェノールノボラック、住友ベークライト(株)製「PR-53647」
フィルム形成性樹脂:変性ビフェノール型フェノキシ樹脂、ジャパンエポキシレジン(株)製「YX-6954」、重量平均分子量39,000
フラックス機能を有する化合物1:セバシン酸、東京化成工業(株)製「セバシン酸」
フラックス機能を有する化合物2:フェノールフタリン、東京化成工業(株)製「フェノールフタリン」
シランカップリング剤:2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、信越化学工業(株)製「KBM-303」
イミダゾール:2-フェニル-4-メチルイミダゾール、四国化成工業(株)製「キュアゾール2P4MZ」
充填剤1:シリカ アドマテック社製、SE2050、平均粒径0.5μm、比重2.2
充填剤2:アルミナ 昭和電工製、AS-50、平均粒径9μm、比重3.8
金属層A:Sn/Pb=63/37(融点:183℃)、厚さ10μm
金属層B:Sn/Ag/Cu=96.5/3.0/0.5(融点:217℃)、厚さ10μm
Claims (22)
- 基板および前記基板上に設けられた複数の端子を有する電子部材の、前記複数の端子上に導電部を形成するために用いられる導電接続材料であって、
金属層と、
樹脂成分と充填剤とを有する樹脂層と、
を備え、
前記複数の端子上に当接し、加熱することによって、前記金属層が各端子上に凝集し、前記複数の端子上に前記導電部を形成するように構成された導電接続材料。 - 請求項1に記載の導電接続材料において、
前記複数の端子上に当接し、加熱することによって、前記金属層が分離して各端子上に凝集するように構成された導電接続材料。 - 請求項1または2に記載の導電接続材料において、
前記金属層のうち、前記樹脂層が設けられている面とは反対側の面に、他の樹脂層が設けられている導電接続材料。 - 請求項1ないし3いずれか1項に記載の導電接続材料において、
前記金属層は、半田または錫によって構成されている導電接続材料。 - 請求項1ないし4いずれか1項に記載の導電接続材料において、
前記充填剤の粒径が、10nm~50μmである導電接続材料。 - 請求項1ないし5いずれか1項に記載の導電接続材料において、
前記充填剤の含有量が、前記樹脂層の全重量に対し1~80重量%である導電接続材料。 - 請求項1ないし6いずれか1項に記載の導電接続材料において、
前記充填剤の体積をFv、前記金属層の体積をMvとしたとき、Fv/Mvが0.01~10である導電接続材料。 - 請求項1ないし7いずれか1項に記載の導電接続材料において、
前記樹脂層の室温から100℃における平均線膨張係数は、3~70ppmである導電接続材料。 - 請求項1ないし8いずれか1項に記載の導電接続材料において、
前記樹脂層は、フラックス機能を有する化合物を含む導電接続材料。 - 請求項9に記載の導電接続材料において、
前記フラックス機能を有する化合物は、フェノール性水酸基及び/またはカルボキシル基を有する導電接続材料。 - 請求項9または10に記載の導電接続材料において、
前記フラックス機能を有する化合物は、下記一般式(1)で示される化合物を含む導電接続材料。
HOOC-(CH2)n-COOH・・・・・(1)
[式中、nは、1~20の整数である。] - 請求項1ないし12いずれか1項に記載の導電接続材料において、
前記金属層の融点が100℃~330℃である導電接続材料。 - 請求項1ないし13いずれか1項に記載の導電接続材料において、
前記端子は、電極であり、
前記導電部は、接続端子である導電接続材料。 - 請求項1ないし13いずれか1項に記載の導電接続材料を、前記複数の端子を内側に向けて対向する二つの前記電子部材間に配置し、前記二つの電子部材がそれぞれ有する前記複数の端子に当接させる工程と、
前記導電接続材料を加熱して、前記複数の端子上に形成された前記導電部を介して前記二つの電子部材がそれぞれ有する前記複数の端子を互いに接続する工程と、
前記樹脂層を硬化または固化する工程と、
を備える電子部品の製造方法。 - 請求項15に記載の電子部品の製造方法であって、
前記樹脂層は、熱硬化性樹脂を有しており、
前記電子部材を互いに接続する工程は、前記金属層の融点以上であって、かつ前記樹脂層の硬化が完了しない温度で前記導電接続材料を加熱することにより行われ、
前記樹脂層を硬化または固化する工程は、前記樹脂層の硬化が完了する温度で前記導電接続材料を加熱することにより行われる電子部品の製造方法。 - 請求項15に記載の電子部品の製造方法であって、
前記樹脂層は、熱可塑性樹脂を有しており、
前記電子部材を互いに接続する工程は、前記金属層の融点以上であって、かつ前記樹脂層が軟化する温度で前記導電接続材料を加熱することにより行われ、
前記樹脂層を硬化または固化する工程は、前記樹脂層が固化する温度まで前記導電接続材料を冷却することにより行われる電子部品の製造方法。 - 請求項14に記載の導電接続材料を、前記複数の端子上に当接する工程と、
前記導電接続材料を加熱して、前記複数の端子上に前記導電部を形成する工程と、
前記樹脂層を硬化または固化する工程と、
を備える電子部品の製造方法。 - 請求項18に記載の電子部品の製造方法であって、
前記樹脂層は、熱硬化性樹脂を有しており、
前記導電部を形成する工程は、前記金属層の融点以上であって、かつ前記樹脂層の硬化が完了しない温度で前記導電接続材料を加熱することにより行われ、
前記樹脂層を硬化または固化する工程は、前記樹脂層の硬化が完了する温度で前記導電接続材料を加熱することにより行われる電子部品の製造方法。 - 請求項18に記載の電子部品の製造方法であって、
前記樹脂層は、熱可塑性樹脂を有しており、
前記導電部を形成する工程は、前記金属層の融点以上であって、かつ前記樹脂層が軟化する温度で前記導電接続材料を加熱することにより行われ、
前記樹脂層を硬化または固化する工程は、前記樹脂層が固化する温度まで前記導電接続材料を冷却することにより行われる電子部品の製造方法。 - 請求項1ないし14いずれか1項に記載の導電接続材料を、前記複数の端子に当接するように前記電子部材の前記基板上に接着してなる導電接続材料付き電子部材。
- 請求項1ないし14いずれか1項に記載の導電接続材料を用いて形成された前記導電部を介して、前記複数の端子を内側に向けて対向する二つの前記電子部材がそれぞれ有する前記複数の端子を互いに接続させてなる電子部品。
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Also Published As
Publication number | Publication date |
---|---|
CN102687603A (zh) | 2012-09-19 |
JPWO2011077679A1 (ja) | 2013-05-02 |
CN102687603B (zh) | 2015-07-15 |
EP2519088A1 (en) | 2012-10-31 |
KR20120070622A (ko) | 2012-06-29 |
US20120261174A1 (en) | 2012-10-18 |
SG181575A1 (en) | 2012-07-30 |
TW201130646A (en) | 2011-09-16 |
KR101191686B1 (ko) | 2012-10-16 |
TWI540039B (zh) | 2016-07-01 |
JP4924773B2 (ja) | 2012-04-25 |
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