WO2013187390A1 - 光反射性異方性導電接着剤及び発光装置 - Google Patents
光反射性異方性導電接着剤及び発光装置 Download PDFInfo
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- WO2013187390A1 WO2013187390A1 PCT/JP2013/066032 JP2013066032W WO2013187390A1 WO 2013187390 A1 WO2013187390 A1 WO 2013187390A1 JP 2013066032 W JP2013066032 W JP 2013066032W WO 2013187390 A1 WO2013187390 A1 WO 2013187390A1
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- conductive adhesive
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/44—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the coatings, e.g. passivation layer or anti-reflective coating
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/62—Arrangements for conducting electric current to or from the semiconductor body, e.g. lead-frames, wire-bonds or solder balls
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
- H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
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- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
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- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
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- H01L2224/45001—Core members of the connector
- H01L2224/45099—Material
- H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
- H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
- H01L2224/45144—Gold (Au) as principal constituent
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- H01—ELECTRIC ELEMENTS
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- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
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- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
- H01L2224/48227—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73201—Location after the connecting process on the same surface
- H01L2224/73203—Bump and layer connectors
- H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
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- H01—ELECTRIC ELEMENTS
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- H01L2224/732—Location after the connecting process
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- H01—ELECTRIC ELEMENTS
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- H01L2924/06—Polymers
- H01L2924/078—Adhesive characteristics other than chemical
- H01L2924/0781—Adhesive characteristics other than chemical being an ohmic electrical conductor
- H01L2924/07811—Extrinsic, i.e. with electrical conductive fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/12—Passive devices, e.g. 2 terminal devices
- H01L2924/1204—Optical Diode
- H01L2924/12041—LED
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/181—Encapsulation
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
- H05K2201/10007—Types of components
- H05K2201/10106—Light emitting diode [LED]
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/20—Details of printed circuits not provided for in H05K2201/01 - H05K2201/10
- H05K2201/2054—Light-reflecting surface, e.g. conductors, substrates, coatings, dielectrics
Definitions
- the present invention relates to a light-reflective anisotropic conductive adhesive used for anisotropically conductively connecting a light emitting element to a wiring board, and a light emitting device in which the light emitting element is mounted on the wiring board using the adhesive.
- a light emitting device using a light emitting diode (LED) element is widely used, and the structure of an old type light emitting device is such that, as shown in FIG. 3, an LED element 33 is bonded on a substrate 31 with a die bond adhesive 32, The p electrode 34 and the n electrode 35 on the upper surface are wire-bonded to the connection terminal 36 of the substrate 31 with a gold wire 37, and the entire LED element 33 is sealed with a transparent mold resin 38.
- the gold wire absorbs light having a wavelength of 400 to 500 nm emitted to the upper surface side among the light emitted from the LED element 33, and a part of the light emitted to the lower surface side.
- the luminous efficiency of the LED element 33 is reduced by being absorbed by the die bond adhesive 32.
- the LED element 33 is flip-chip mounted as shown in FIG. 4 from the viewpoint of improving the light emission efficiency regarding the light reflection of the LED element (Patent Document 1).
- bumps 39 are formed on the p electrode 34 and the n electrode 35, respectively, and further, the bump formation surface of the LED element 33 is insulated from the p electrode 34 and the n electrode 35.
- the light reflecting layer 40 is provided on the surface.
- the LED element 33 and the substrate 31 are connected and fixed by using an anisotropic conductive paste 41 or an anisotropic conductive film (not shown) and curing them. Therefore, in the light emitting device of FIG. 4, the light emitted upward of the LED element 33 is not absorbed by the gold wire, and most of the light emitted downward is reflected by the light reflecting layer 40 and emitted upward. Luminous efficiency (light extraction efficiency) does not decrease.
- the anisotropic conductive paste used for mounting the LED element and the insulating resin component in the anisotropic conductive film are accompanied by discoloration due to heat or light.
- a two-component curable methylsilicone resin or a two-component curable phenylsilicone resin excellent in heat resistance and light resistance is used as an anisotropic conductive paste, Attempts have been made to employ an insulating resin component in an anisotropic conductive film.
- the light reflecting layer 40 must be provided on the LED element 33 by a metal vapor deposition method or the like so as to be insulated from the p-electrode 34 and the n-electrode 35, and thus an increase in manufacturing cost is inevitable.
- the surface of the conductive particles coated with gold, nickel or copper in the cured anisotropic conductive paste or anisotropic conductive film is brown or
- the epoxy resin binder itself which exhibits a dark brown color and in which conductive particles are dispersed, also exhibits a brown color because of the imidazole-based latent curing agent that is commonly used for its curing. There is a problem that it is difficult to improve the light emission efficiency (light extraction efficiency).
- An object of the present invention is to solve the above-described problems of the prior art, and light-emitting elements such as light-emitting diodes (LEDs) are flip-chip mounted on a wiring board using an anisotropic conductive adhesive to emit light.
- LEDs light-emitting diodes
- An object is to provide an anisotropic conductive adhesive and a light emitting device in which a light emitting element is flip-chip mounted on a wiring board using the adhesive.
- the inventors of the present invention have assumed that the anisotropic conductive adhesive itself has a light reflecting function, and the light-reflective insulating particles are added to the anisotropic conductive adhesive under the assumption that the luminous efficiency can be prevented. It has been found that by blending, the luminous efficiency of the light emitting device can be prevented from being lowered.
- the present inventors use an anisotropic conductive adhesive by heat or light by using diglycidyl isocyanuryl-modified polysiloxane having a specific structure as an insulating adhesive component of the anisotropic conductive adhesive. Has been found to be able to prevent discoloration and exhibit a practically sufficient die shear strength. And based on these knowledge, it came to complete this invention.
- the present invention is a light-reflective anisotropic conductive adhesive used for anisotropic conductive connection of a light-emitting element to a wiring board, comprising a thermosetting resin composition, conductive particles, and light-reflective insulating particles.
- the thermosetting resin composition contains a diglycidyl isocyanuryl-modified polysiloxane represented by the formula (1) and a curing agent for epoxy resin, and the light-reflective anisotropy A conductive adhesive is provided.
- R is an alkyl group or an aryl group, and n is 1 to 40.
- a light-reflective anisotropic conductive adhesive which is a light-reflective conductive particle comprising a light-reflecting layer formed from at least one kind of inorganic particles selected from particles or aluminum oxide particles.
- the present invention provides a light emitting device in which a light emitting element is mounted on a wiring board by a flip chip method through the above-described light reflective anisotropic conductive adhesive.
- the light-reflective anisotropic conductive adhesive of the present invention used for anisotropically conductively connecting a light-emitting element to a wiring board includes a thermosetting resin composition as a binder, light-reflective insulating particles, and conductive particles. Containing.
- This thermosetting resin composition contains diglycidyl isocyanuryl-modified polysiloxane represented by the formula (1) that is cured by a curing agent for epoxy resin.
- This polysiloxane has a diglycidyl isocyanuryl alkyl group bonded to its side chain. For this reason, it can prevent that an anisotropic conductive adhesive discolors with a heat
- the light-reflective anisotropic conductive adhesive of the present invention contains light-reflective insulating particles, it can reflect light.
- the light-reflective insulating particles are at least one kind of inorganic particles selected from the group consisting of titanium oxide particles, boron nitride particles, zinc oxide particles and aluminum oxide particles, or the surface of scaly or spherical metal particles is an insulating resin.
- the particle itself is almost white, so that the wavelength dependency of the reflection characteristic with respect to visible light is small, so that the light emission efficiency can be improved, and the light emission of the light emitting element can be improved. The color can be reflected as it is.
- conductive particles a core particle coated with a metal material, and a white to gray light reflecting layer formed on the surface thereof from titanium oxide particles, boron nitride particles, zinc oxide particles or aluminum oxide particles.
- the light-reflective conductive particles themselves exhibit a white to gray color, so that the wavelength dependence of the reflection characteristics with respect to visible light is small, thus further improving the luminous efficiency.
- the emission color of the light emitting element can be reflected as it is.
- FIG. 1A is a cross-sectional view of light-reflective conductive particles for the light-reflective anisotropic conductive adhesive of the present invention.
- FIG. 1B is a cross-sectional view of light-reflective conductive particles for the light-reflective anisotropic conductive adhesive of the present invention.
- FIG. 2 is a cross-sectional view of the light emitting device of the present invention.
- FIG. 3 is a cross-sectional view of a conventional light emitting device.
- FIG. 4 is a cross-sectional view of a conventional light emitting device.
- the present invention is a light-reflective anisotropic conductive adhesive used for anisotropically conductively connecting a light-emitting element to a wiring board, and includes a thermosetting resin composition, conductive particles, and light-reflective insulating particles. It is a light-reflective anisotropic conductive adhesive.
- thermosetting resin composition that is a binder will be described.
- thermosetting resin composition contains diglycidyl isocyanuryl-modified polysiloxane represented by the formula (1) and a curing agent for epoxy resin.
- diglycidyl isocyanuryl-modified polysiloxane represented by the formula (1) it is possible to prevent the anisotropic conductive adhesive from being discolored by heat or light, and to have a practically sufficient die shear strength. Can be realized.
- R is an alkyl group such as a lower alkyl group having 1 to 6 carbon atoms, or an aryl group such as a carbocyclic aromatic group or a heterocyclic aromatic group.
- the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group, and a particularly preferable alkyl group is a methyl group.
- a preferred specific example of the aryl group is a phenyl group.
- n is an integer of 1 to 40, preferably an integer of 1 to 4, more preferably 1 or 2.
- the amount is preferably 45 to 65% by mass, more preferably 50 to 60% by mass.
- the diglycidyl isocyanuryl-modified polysiloxane represented by the formula (1) includes a hydrogen polysiloxane of the formula (a) and 1-allyl-3 of the formula (b) as shown in the following reaction formula: , 5-diglycidyl isocyanurate, and then in the presence of a Karstedt catalyst (1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex solution) And can be produced by heating to room temperature to 150 ° C. From the reaction mixture, the compound of the formula (1) can be isolated by a conventional method (concentration treatment, column treatment, etc.).
- thermosetting resin composition is a heterocyclic epoxy compound, an alicyclic epoxy compound, or a hydrogenated epoxy compound as long as the effects of the invention are not impaired. Etc. can be contained.
- heterocyclic epoxy compound examples include an epoxy compound having a triazine ring.
- 6- (1H, 3H, 5H) -trione in other words triglycidyl isocyanurate.
- Preferred examples of the alicyclic epoxy compound include those having two or more epoxy groups in the molecule. These may be liquid or solid. Among these, glycidyl hexahydrobisphenol A, 3,4-epoxycyclohexenylmethyl-3 ′, 4 is preferable because it can ensure light transmission suitable for mounting LED elements on the cured product and is excellent in rapid curing. '-Epoxycyclohexenecarboxylate can be preferably used.
- hydrogenated epoxy compound hydrogenated products of the aforementioned heterocyclic epoxy compounds and alicyclic epoxy compounds, and other known hydrogenated epoxy resins can be used.
- alicyclic epoxy compounds, heterocyclic epoxy compounds, and hydrogenated epoxy compounds may be used alone or in combination with two or more of the diglycidyl isocyanuryl-modified polysiloxane of formula (1). May be.
- other epoxy compounds may be used in combination as long as the effects of the present invention are not impaired.
- epoxy resin curing agent a known epoxy resin curing agent can be used.
- amine curing agent, polyamide curing agent, acid anhydride curing agent, imidazole curing agent, polymercaptan curing agent, polysulfide curing agent, boron trifluoride-amine complex curing agent, dicyandiamide, organic acid It can be selected from among hydrazides and the like.
- acid anhydride curing agents can be preferably used from the viewpoints of light transmittance, heat resistance, and the like.
- Acid anhydride curing agents include succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydro Phthalic anhydride, or a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornane-2,3-dicarboxylic acid An acid anhydride, methylnorbornane-2,3-dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, etc. can be mentioned.
- the amount of the epoxy resin curing agent such as an acid anhydride curing agent in the thermosetting resin composition is small relative to 100 parts by mass of the diglycidyl isocyanuryl-modified polysiloxane represented by the formula (1). If the amount is too large, the amount of the uncured epoxy component tends to be excessive. If the amount is too large, corrosion of the adherend material tends to be accelerated by the influence of the excess curing agent.
- the amount is preferably 60 to 100 parts by mass.
- the thermosetting resin composition can contain a known curing accelerator in order to complete the curing reaction smoothly and in a short time.
- Preferred curing accelerators include quaternary phosphonium salt-based curing accelerators and imidazole-based curing accelerators. Specific examples include quaternary phosphonium bromide salts (“U-CAT5003” (trademark), San Apro Co., Ltd.), 2-ethyl-4-methylimidazole, and the like.
- an imidazole curing accelerator can be preferably used as a curing accelerator for an acid anhydride curing agent.
- the imidazole curing accelerator is preferably 0.20 to 2.00 parts by mass, and more preferably 0.60 to 1.00 parts by mass with respect to parts.
- thermosetting resin composition described above is preferably as colorless and transparent as possible. This is because the light reflecting efficiency of the light-reflective conductive particles in the anisotropic conductive adhesive is reflected without reducing the light color of the incident light.
- colorless and transparent means that the cured product of anisotropic conductive adhesive has a light transmittance of 1 mm (JIS K7105) with respect to visible light having a wavelength of 380 to 780 nm of 80% or more, preferably 90% or more.
- the light-reflective insulating particles contained in the light-reflective anisotropic conductive adhesive of the present invention are for reflecting light incident on the anisotropic conductive adhesive to the outside.
- the light-reflective particles include metal particles, particles coated with metal particles, inorganic particles such as metal oxides, metal nitrides, and metal sulfides that are gray to white under natural light, resin core particles
- corrugation on the surface are contained irrespective of the material of particle
- the light-reflective insulating particles that can be used in the present invention do not include metal particles that are not covered with insulation because they are required to exhibit insulating properties.
- Such light-reflective insulating particles include titanium oxide (TiO 2 ) particles, boron nitride (BN) particles, zinc oxide (ZnO) particles, and aluminum oxide (Al 2 O 3 ) particles.
- TiO 2 titanium oxide
- BN boron nitride
- ZnO zinc oxide
- Al 2 O 3 aluminum oxide
- TiO 2 it is preferable to use TiO 2 from the viewpoint of a high refractive index.
- the shape of the light-reflective insulating particles may be spherical, scaly, indeterminate, acicular, etc. In consideration of reflection efficiency, spherical and scaly are preferable. In the case of a spherical shape, if it is too small, the reflectance is low, and if it is too large, the anisotropic conductive connection tends to be inhibited. Therefore, it is preferably 0.02 to 20 ⁇ m, more preferably 0.
- the major axis is preferably 0.1 to 100 ⁇ m, more preferably 1 to 50 ⁇ m, and the minor axis is preferably 0.01 to 10 ⁇ m, more preferably 0.1 to The thickness is preferably 5 ⁇ m, and the thickness is preferably 0.01 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m.
- the light-reflective insulating particles made of inorganic particles have a refractive index (JIS K7142) that is preferably larger than the refractive index of a cured product of the thermosetting resin composition (JIS K7142), more preferably at least 0.02. It is preferable that the degree is large. This is because when the difference in refractive index is small, the reflection efficiency at the interface between them decreases.
- the inorganic particles described above may be used, but resin-coated metal particles obtained by coating the surface of scale-like or spherical metal particles with a transparent insulating resin may be used.
- the metal particles include nickel, silver, and aluminum.
- the shape of the particles include an amorphous shape, a spherical shape, a scaly shape, and a needle shape. Among these, a spherical shape is preferable from the viewpoint of the light diffusion effect, and a scaly shape is preferable from the viewpoint of the total reflection effect. Particularly preferred are scaly silver particles in terms of light reflectance.
- the size of the resin-coated metal particles as the light-reflective insulating particles varies depending on the shape, generally, if it is too large, there is a possibility of inhibiting the anisotropic conductive connection, and if it is too small, it becomes difficult to reflect light.
- the particle diameter is 0.1 to 30 ⁇ m, more preferably 0.2 to 10 ⁇ m.
- the major axis is preferably 0.1 to 100 ⁇ m, more preferably 1 to 50 ⁇ m.
- the thickness is preferably 0.01 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m.
- the size of the light-reflective insulating particles is the size including the insulating coating when the insulating coating is applied.
- a cured product of acrylic resin can be preferably used.
- a preferable example is a resin obtained by radical copolymerization of methyl methacrylate and 2-hydroxyethyl methacrylate in the presence of a radical initiator such as an organic peroxide such as benzoyl peroxide.
- a radical initiator such as an organic peroxide such as benzoyl peroxide.
- it is more preferably crosslinked with an isocyanate-based crosslinking agent such as 2,4-tolylene diisocyanate.
- the metal particles it is preferable to introduce a ⁇ -glycidoxy group, a vinyl group, or the like into the metal surface in advance with a silane coupling agent.
- Such resin-coated metal particles are prepared, for example, by putting metal particles and a silane coupling agent in a solvent such as toluene and stirring for about 1 hour at room temperature, and then, if necessary, a radical monomer and a radical polymerization initiator. Then, a crosslinking agent is added, and the mixture is stirred by heating to the radical polymerization starting temperature.
- the light-reflective anisotropic conductive adhesive contains light-reflective insulating particles in an amount of preferably 1 to 50% by volume, more preferably 5 to 25% by volume.
- conductive particles constituting the light-reflective anisotropic conductive adhesive of the present invention metal particles used in conventional conductive particles for anisotropic conductive connection can be used. Examples thereof include gold, nickel, copper, silver, solder, palladium, aluminum, alloys thereof, multilayered products thereof (for example, nickel plating / gold flash plating products), and the like. Above all, gold, nickel, and copper turn the conductive particles brown, so that the effects of the present invention can be enjoyed over other metal materials.
- metal-coated resin particles obtained by coating resin particles with a metal material can be used.
- resin particles include styrene resin particles, benzoguanamine resin particles, and nylon resin particles.
- a method of coating the resin particles with a metal material a conventionally known method can be employed, and an electroless plating method, an electrolytic plating method, or the like can be used.
- the layer thickness of the metal material to be coated is sufficient to ensure good connection reliability, and is usually 0.1 to 3 ⁇ m although it depends on the particle size of the resin particles and the type of metal.
- the particle size of the resin particle is preferably 1 to 20 ⁇ m, more preferably 3 to 10 ⁇ m, and particularly preferably 3 to 5 ⁇ m. is there.
- the core particle 1 has a spherical shape, but may have a flake shape or a rugby ball shape.
- the metal-coated resin particles have a spherical shape, and if the particle size is too large, the connection reliability is lowered. Therefore, it is preferably 1 to 20 ⁇ m, more preferably 3 to 10 ⁇ m.
- 1A and 1B are sectional views of such light-reflective conductive particles 10 and 20. First, the light reflective conductive particles in FIG. 1A will be described.
- the light-reflective conductive particles 10 include a core particle 1 coated with a metal material, and titanium oxide (TiO 2 ) particles, boron nitride (BN) particles, zinc oxide (ZnO) particles, or aluminum oxide (Al 2 ) on the surface thereof. And a light reflecting layer 3 formed of at least one kind of inorganic particles 2 selected from O 3 ) particles. Titanium oxide particles, boron nitride particles, zinc oxide particles, or aluminum oxide particles are inorganic particles that exhibit white under sunlight. Accordingly, the light reflecting layer 3 formed from them exhibits white to gray.
- the expression of white to gray means that the wavelength dependency of the reflection characteristic for visible light is small and the visible light is easily reflected.
- titanium oxide particles boron nitride particles, zinc oxide particles or aluminum oxide particles, if there is a concern about photodegradation of the cured product of the cured thermosetting resin composition of anisotropic conductive adhesive, light Zinc oxide which is not catalytic to deterioration and has a high refractive index can be preferably used.
- the surface thereof is made of a metal material.
- the surface is coated with a metal material, as described above, an aspect in which the core particle 1 itself is a metal material, or an aspect in which the surface of the resin particle is coated with a metal material can be given.
- the thickness of the light reflecting layer 3 formed from the inorganic particles 2 is too low with respect to the particle size of the core particle 1. If it is too large, poor conduction will occur. Therefore, it is preferably 0.5 to 50%, more preferably 1 to 25%.
- the particle size of the inorganic particles 2 constituting the light-reflecting layer 3 is preferably 0.02 to 4 ⁇ m, more preferably 0.1 to 1 ⁇ m, and particularly preferably 0.2 to 0.5 ⁇ m.
- the particle size of the inorganic particles 2 is set so that the light to be reflected (that is, the light emitted from the light emitting element) is not transmitted. It is preferable that it is 50% or more.
- examples of the shape of the inorganic particles 2 include an amorphous shape, a spherical shape, a scaly shape, and a needle shape.
- a spherical shape is preferable from the viewpoint of the light diffusion effect
- a scaly shape is preferable from the viewpoint of the total reflection effect.
- the light-reflective conductive particles 10 in FIG. 1A are formed by a known film forming technique (so-called mechano-fusion method) in which a film composed of small-sized particles is formed on the surface of large-sized particles by physically colliding large and small powders. ).
- the inorganic particles 2 are fixed so as to bite into the metal material on the surface of the core particle 1, and on the other hand, the inorganic particles monolithically constitute the light reflecting layer 3 because the inorganic particles are not easily fused and fixed together. Therefore, in the case of FIG. 1A, the layer thickness of the light reflecting layer 3 is considered to be equivalent to or slightly thinner than the particle size of the inorganic particles 2.
- the light reflective conductive particles 20 in FIG. 1B will be described.
- the light-reflecting layer 3 contains a thermoplastic resin 4 that functions as an adhesive
- the inorganic particles 2 are also fixed together by this thermoplastic resin 4, and the inorganic particles 2 are multilayered (for example, It differs from the light-reflective conductive particle 10 of FIG. 1A in that it is multi-layered into two or three layers.
- thermoplastic resin 4 By including such a thermoplastic resin 4, the mechanical strength of the light reflecting layer 3 is improved, and the inorganic particles are less likely to be peeled off.
- thermoplastic resin 4 a halogen-free thermoplastic resin can be preferably used for the purpose of low environmental load, and for example, polyolefins such as polyethylene and polypropylene, polystyrene, acrylic resins and the like can be preferably used.
- Such light-reflective conductive particles 20 can also be manufactured by a mechanofusion method. If the particle size of the thermoplastic resin 4 applied to the mechano-fusion method is too small, the adhesion function is lowered, and if it is too large, it is difficult to adhere to the core particle 1, so that it is preferably 0.02 to 4 ⁇ m, more preferably 0.8. 1 to 1 ⁇ m. Further, if the amount of the thermoplastic resin 4 is too small, the adhesive function is lowered, and if it is too large, aggregates of particles are formed. The amount is 2 to 500 parts by mass, more preferably 4 to 25 parts by mass.
- the blending amount of the conductive particles such as the light-reflective conductive particles in the light-reflective anisotropic conductive adhesive of the present invention is too small, conduction failure tends to occur, and if it is too large, there is a tendency to cause a short circuit between patterns. Therefore, the blending amount of conductive particles such as light-reflective conductive particles with respect to 100 parts by mass of the thermosetting resin composition is preferably 1 to 100 parts by mass, more preferably 10 to 50 parts by mass.
- the light-reflective anisotropic conductive adhesive of the present invention can be produced by uniformly mixing the light-reflective insulating particles, the conductive particles, and the thermosetting resin composition described above according to a conventional method.
- they are dispersed and mixed together with a solvent such as toluene, and applied to the peeled PET film so as to have a desired thickness. What is necessary is just to dry at temperature.
- the reflection characteristic of the light-reflective anisotropic conductive adhesive of the present invention is such that the reflectance of the cured light-reflective anisotropic conductive adhesive to light having a wavelength of 450 nm (JIS) is improved in order to improve the light emission efficiency of the light-emitting element.
- K7105 is at least 30%.
- the reflection characteristics and blending amount of the light-reflective insulating particles to be used, the blending composition of the thermosetting resin composition, and the like may be appropriately adjusted. Usually, if the amount of the light-reflective insulating particles having good reflection characteristics is increased, the reflectance tends to increase.
- the reflection characteristics of the light-reflective anisotropic conductive adhesive can be evaluated from the viewpoint of refractive index. That is, if the refractive index of the cured product is larger than the refractive index of the cured product of the thermosetting resin composition excluding the conductive particles and the light-reflective insulating particles, the light-reflective insulating particles and the thermosetting surrounding them. This is because the amount of light reflection at the interface with the cured product of the conductive resin composition increases.
- the difference obtained by subtracting the refractive index of the cured product of the thermosetting resin composition (JIS K7142) from the refractive index of the light reflective particles (JIS K7142) is preferably 0.02 or more, more preferably It is desired to be 0.2 or more.
- the refractive index of a thermosetting resin composition mainly composed of an epoxy resin is about 1.5.
- the light-emitting device 200 includes the connection terminal 22 on the substrate 21 and the connection bumps 26 formed on the n-electrode 24 and the p-electrode 25 of the LED element 23 as light-emitting elements.
- This is a light emitting device in which a light reflective anisotropic conductive adhesive is applied and the substrate 21 and the LED element 23 are flip-chip mounted.
- the light-reflective anisotropic conductive adhesive cured product 100 includes light-reflective insulating particles and conductive particles, preferably the light-reflective conductive particles 10 dispersed in the cured product 11 of the thermosetting resin composition. It will be. In addition, you may seal with transparent mold resin so that the whole LED element 23 may be covered as needed. Moreover, you may provide a light reflection layer in the LED element 23 similarly to the past.
- the light emitting device 200 configured as described above, among the light emitted from the LED element 23, the light emitted toward the substrate 21 is light in the cured product 100 of the light-reflective anisotropic conductive adhesive. The light is reflected by the reflective insulating particles or the light-reflective conductive particles 10 and emitted from the upper surface of the LED element 23. Accordingly, it is possible to prevent a decrease in luminous efficiency.
- Configurations other than the light-reflective anisotropic conductive adhesive (the LED element 23, the bump 26, the substrate 21, the connection terminal 22, and the like) in the light-emitting device 200 of the present invention can be the same as the configuration of the conventional light-emitting device. .
- the light emitting device 200 of the present invention can be manufactured by using a conventional anisotropic conductive connection technique except that the light reflective anisotropic conductive adhesive of the present invention is used.
- a well-known light emitting element can be applied in the range which does not impair the effect of this invention other than an LED element.
- Example 1 and Comparative Example 1-3 A light-reflective anisotropic conductive adhesive was prepared by uniformly mixing the components having the composition shown in Table 1.
- Example 1 an epoxy compound and an acid anhydride curing agent were blended so that the ratio of the number of functional groups of epoxy group / acid anhydride was 1 / 1.1.
- the anisotropic conductive adhesive of Comparative Example 2 is a mixture of light-reflective insulating particles and conductive particles in a two-part curable dimethyl silicone resin (IVS4742, Momentive Performance Materials).
- the anisotropic conductive adhesive of Example 3 is a two-component curable phenyl silicone resin (SCR-1012, Shin-Etsu Chemical Co., Ltd.) blended with light-reflective insulating particles and conductive particles.
- the die shear strength of the obtained light-reflective anisotropic conductive adhesive was measured as described below.
- the remaining thermosetting resin composition obtained by removing the light-reflective insulating particles and the conductive particles from the light-reflective anisotropic conductive adhesive was subjected to a heat resistance test and a heat resistance light test as described below. It was. The obtained results are shown in Table 2.
- a glass epoxy substrate for LED (special order product, Kansai Electronics Co., Ltd.) having a silver solid electrode with a thickness of 10 ⁇ m on which gold bumps (high 10 ⁇ m, diameter 80 ⁇ m, pitch 190 ⁇ m) are formed so that the diameter is 4 mm.
- a curable resin composition is applied, and a 0.3 mm square flip chip type LED element (GM35R460G, Showa Denko KK) is placed thereon, and the glass epoxy substrate is placed at 80 ° C. so that the flip chip type LED element is on the front side.
- the LED element was temporarily fixed to the glass epoxy substrate for LED by heating for 2 minutes.
- the glass epoxy substrate for LED to which this LED element is temporarily fixed, is applied to a thermocompression bonding apparatus and subjected to thermocompression bonding at 230 ° C. for 15 seconds while applying a pressure of 80 gf / chip to the LED element.
- An LED device having LED elements mounted on a substrate was created.
- a reflow treatment at 260 ° C. for 20 seconds was further performed after the thermocompression treatment.
- the die shear strength (gf / chip) of the LED device thus created was measured.
- the die shear strength is desired to be at least 200 gf / chip, preferably 250 gf / chip or more.
- thermosetting resin composition is sandwiched between two aluminum flat plates (length 100 mm ⁇ width 50.0 mm ⁇ thickness 0.500 mm) in which spacers having a height of 1 mm are arranged at the four corners, and thermosetting of Example 1 and Comparative Example 1
- the curable resin composition was first heated at 120 ° C. for 30 minutes, and then heated at 140 ° C. for 1 hour to prepare a cured resin sheet.
- the thermosetting resin composition of the comparative examples 2 and 3 the cured resin sheet was created by heating at 80 degreeC for 1 hour first, and then heating at 150 degreeC for 2 hours.
- the obtained cured resin sheet is left in an oven set at 150 ° C. for 1000 hours, and the spectral characteristics (L * , a * , b * ) before and after being left are measured with a spectrocolorimeter (CM-3600d, Konica Minolta).
- CM-3600d spectrocolorimeter
- the color difference ( ⁇ E) was calculated from the measured values. In practice, ⁇ E is desirably 35 or less.
- ⁇ Heat-resistant light test> A cured resin sheet similar to the cured resin sheet subjected to the heat resistance test was prepared, and the cured resin sheet was heated at 120 ° C. with a light intensity of 16 mW / cm 2 (Superwin Mini, Daipura Wintes Co., Ltd.) Used in a metal halide lamp) for 1000 hours, and the resulting cured resin sheet is left in an oven set at 150 ° C. for 1000 hours to obtain spectral characteristics (L * , a * , b * ) before and after being left.
- the color difference ( ⁇ E) was calculated from the obtained measurement value using a spectrocolorimeter (CM-3600d, Konica Minolta Co., Ltd.). Practically, ⁇ E is desired to be 20 or less.
- the light-reflective anisotropic conductive adhesive of Example 1 was practically preferable in terms of die shear strength, heat resistance test, and heat resistance light test. Since a thermosetting epoxy resin composition is used, favorable results were obtained with respect to die shear strength, but since the diglycidyl isocyanuryl-modified polysiloxane of formula (1a) was not used, The test did not give satisfactory results.
- the light-reflective anisotropic conductive adhesive of the present invention is used to produce a light-emitting device by flip-chip mounting a light-emitting element such as a light-emitting diode (LED) element on a wiring board using an anisotropic conductive adhesive, Even if a light reflecting layer that causes an increase in manufacturing cost is not provided in the light emitting element, the light emission efficiency can be prevented from being lowered. In addition, the die shear strength can be maintained high, and the heat resistance and heat resistance are excellent. Therefore, the light-reflective anisotropic conductive adhesive of the present invention is useful when the LED element is flip-lip mounted.
- a light-emitting element such as a light-emitting diode (LED) element
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Abstract
Description
本発明において、熱硬化性樹脂組成物は、式(1)で表されるジグリシジルイソシアヌリル変性ポリシロキサンと、エポキシ樹脂用硬化剤とを含有する。式(1)で表されるジグリシジルイソシアヌリル変性ポリシロキサンを含有することにより、熱や光により異方性導電接着剤が変色してしまうことを防止でき、しかも実用上十分なダイシェア強度を実現することができる。
本発明の光反射性異方性導電接着剤が含有する光反射性絶縁粒子は、異方性導電接着剤に入射した光を外部に反射するためのものである。
本発明の光反射性異方性導電接着剤を構成する導電粒子としては、異方性導電接続用の従来の導電粒子において用いられている金属の粒子を利用することができる。例えば、金、ニッケル、銅、銀、半田、パラジウム、アルミニウム、それらの合金、それらの多層化物(例えば、ニッケルメッキ/金フラッシュメッキ物)等を挙げることができる。中でも、金、ニッケル、銅は、導電粒子を茶色としてしまうことから、本発明の効果を他の金属材料よりも享受することができる。
本発明の光反射性異方性導電接着剤は、以上説明した光反射性絶縁粒子と導電粒子と熱硬化性樹脂組成物とを、常法に従って均一に混合することにより製造することができる。また、光反射性異方性導電接着フィルムとする場合には、それらをトルエン等の溶媒とともに分散混合し、剥離処理したPETフィルムに所期の厚さとなるように塗布し、約80℃程度の温度で乾燥すればよい。
本発明の光反射性異方性導電接着剤の反射特性は、発光素子の発光効率を向上させるために、光反射性異方性導電接着剤の硬化物の波長450nmの光に対する反射率(JIS K7105)が、少なくとも30%であること望ましい。このような反射率とするためには、使用する光反射性絶縁粒子の反射特性や配合量、熱硬化性樹脂組成物の配合組成などを適宜調整すればよい。通常、反射特性の良好な光反射性絶縁粒子の配合量を増量すれば、反射率も増大する傾向がある。
次に、本発明の発光装置について図2を参照しながら説明する。発光装置200は、基板21上の接続端子22と、発光素子としてLED素子23のn電極24とp電極25とのそれぞれに形成された接続用のバンプ26との間に、前述の本発明の光反射性異方性導電接着剤を塗布し、基板21とLED素子23とがフリップチップ実装されている発光装置である。ここで、光反射性異方性導電接着剤の硬化物100は、光反射性絶縁粒子や導電粒子、好ましくは光反射性導電粒子10が熱硬化性樹脂組成物の硬化物11中に分散してなるものである。なお、必要に応じて、LED素子23の全体を覆うように透明モールド樹脂で封止してもよい。また、LED素子23に従来と同様に光反射層を設けてもよい。
窒素気流中、還流冷却管と磁気撹拌子とを備えた100ml三口フラスコに、28.12g(100.00mmol)の1-アリル-3,5-ジグリシジルイソシアヌレート(MADGIC、四国化成工業(株))と、11.31g(40.02mmol)の1,3-ビス(トリメチルシロキシ)-1,3-ジメチルジシロキサン(SIB1838.0、Gelest Inc.)とを投入し、混合物を80℃で均一に溶融するまで撹拌した。続いて、)この溶融混合物に2%Karstedt触媒溶液(キシレン溶液)45.0μLを添加し、撹拌しながら120℃になるまで加熱し、溶融混合物の温度が120℃に到達してから、その温度を9時間保持して、1-アリル-3,5-ジグリシジルイソシアヌレートと1,3-ビス(トリメチルシロキシ)-1,3-ジメチルジシロキサンとを反応させた。
表1に示す配合組成の成分を均一に混合することにより光反射性異方性導電接着剤を調製した。
得られた光反射性異方性導電接着剤のダイシェア強度を以下に説明するように測定した。また、光反射性異方性導電接着剤から光反射性絶縁粒子と導電粒子とを除いた残りの熱硬化性樹脂組成物について、以下に説明するように、耐熱試験と耐熱光試験とを行った。得られた結果を表2に示す。
金バンプ(高10μm、径80μm、ピッチ190μm)が形成された10μm厚の銀ベタ電極を有するLED用ガラスエポキシ基板(特注品、関西電子工業(株)))に、径が4mmとなるように硬化性樹脂組成物を塗布し、そこへ0.3mm角のフリップチップ型LED素子(GM35R460G、昭和電工(株))を載せ、フリップチップ型LED素子が表側となるようにガラスエポキシ基板を80℃に保持されたホットプレートに置き、2分間加熱してLED素子をLED用ガラスエポキシ基板に仮固定した。このLED素子が仮固定されたLED用ガラスエポキシ基板を熱圧着装置に適用し、LED素子に80gf/chipの圧力を印加しながら230℃で15秒間熱圧着処理を行うことにより、LED用ガラスエポキシ基板にLED素子が実装されたLED装置を作成した。実施例1又は比較例1の光反射性異方性導電接着剤を使用して作成したLED装置の場合、熱圧着処理後に更に260℃、20秒のリフロー処理を行った。
1mm高さのスペーサが四隅に配置された2枚のアルミニウム平板(長100mm×幅50.0mm×厚0.500mm)で熱硬化性樹脂組成物を挟み、実施例1及び比較例1の熱硬化性樹脂組成物については、まず120℃で30分加熱し、続いて140℃で1時間加熱することにより硬化樹脂シートを作成した。また、比較例2及び3の熱硬化性樹脂組成物については、まず80℃で1時間加熱し、続いて150℃で2時間加熱することにより硬化樹脂シートを作成した。
耐熱試験に供した硬化樹脂シートと同様の硬化樹脂シートを作成し、それを、温度120℃で光強度16mW/cm2に設定された熱光試験機(スーパーウインミニ、ダイプラ・ウィンテス(株);メタルハライドランプ使用)内に1000時間放置し、 得られた硬化樹脂シートを、150℃に設定されたオーブン内に1000時間放置し、放置前後の分光特性(L*、a*、b*)を、分光測色計(CM-3600d、コニカミノルタ(株))を用いて測定し、得られた測定値から色差(ΔE)を算出した。実用上、ΔEは20以下であることが望まれる。
2 無機粒子
3 光反射層
4 熱可塑性樹脂
10、20 光反射性導電粒子
11 熱硬化性樹脂組成物の硬化物
21 基板
22 接続端子
23 LED素子
24 n電極
25 p電極
26 バンプ
100 光反射性異方性導電接着剤の硬化物
200 発光装置
Claims (14)
- Rがメチル基であり、nが1~40の整数である請求項1記載の光反射性異方性導電接着剤。
- 熱硬化性樹脂組成物が、式(1)のジグリシジルイソシアヌリル変性ポリシロキサン100質量部に対し、エポキシ樹脂用硬化剤を50~120質量部含有する請求項1又は2記載の光反射性異方性導電接着剤。
- エポキシ樹脂用硬化剤が、酸無水物系硬化剤である請求項1~3のいずれかに記載の光反射性異方性導電接着剤。
- 熱硬化性樹脂組成物が、更にイミダゾール系硬化促進剤を含有する請求項4記載の光反射性異方性導電接着剤。
- 熱硬化性樹脂組成物が、酸無水物系硬化剤100質量部に対し、イミダゾール系硬化促進剤を0.20~2.00質量部含有する請求項5記載の光反射性異方性導電接着剤。
- 光反射性絶縁粒子が、酸化チタン粒子、窒化ホウ素粒子、酸化亜鉛粒子及び酸化アルミニウム粒子からなる群より選択される少なくとも一種の無機粒子である請求項1~6のいずれかに記載の光反射性異方性導電接着剤。
- 光反射性絶縁粒子の屈折率(JIS K7142)が、熱硬化性樹脂組成物の硬化物の屈折率(JIS K7142)よりも大きい請求項1~7のいずれかに記載の光反射性異方性導電接着剤。
- 光反射性絶縁粒子が、鱗片状又は球状金属粒子の表面を絶縁性樹脂で被覆した樹脂被覆金属粒子である請求項1~8のいずれかに記載の光反射性異方性導電接着剤。
- 光反射性異方性導電接着剤が、光反射性絶縁粒子を1~50体積%で含有している請求項1~9のいずれかに記載の光反射性異方性導電接着剤。
- 導電粒子が、金属材料で被覆されているコア粒子と、その表面に酸化チタン粒子、窒化ホウ素粒子、酸化亜鉛粒子又は酸化アルミニウム粒子から選択された少なくとも一種の無機粒子から形成された光反射層とからなる光反射性導電粒子である請求項1~10のいずれかに記載の光反射性異方性導電接着剤。
- 熱硬化性樹脂組成物100質量部に対する光反射性導電粒子の配合量が、1~100質量部である請求項11記載の光反射性異方性導電接着剤。
- 請求項1~12のいずれかに記載の光反射性異方性導電接着剤を介して、発光素子がフリップチップ方式で配線板に実装されてなる発光装置。
- 発光素子が、発光ダイオードである請求項13記載の発光装置。
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WO2015083306A1 (ja) * | 2013-12-06 | 2015-06-11 | デクセリアルズ株式会社 | 光反射性異方性導電接着剤、ジグリシジルイソシアヌリル変性環状ポリシロキサンの製造方法、及び発光装置 |
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JP2014001273A (ja) | 2014-01-09 |
US10246613B2 (en) | 2019-04-02 |
KR102032414B1 (ko) | 2019-10-16 |
CN104364337A (zh) | 2015-02-18 |
TW201414799A (zh) | 2014-04-16 |
US20150166847A1 (en) | 2015-06-18 |
JP5958107B2 (ja) | 2016-07-27 |
TWI575053B (zh) | 2017-03-21 |
CN104364337B (zh) | 2016-08-17 |
KR20150032519A (ko) | 2015-03-26 |
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