TW201738312A - 熱硬化性樹脂組合物及電子零件搭載基板 - Google Patents
熱硬化性樹脂組合物及電子零件搭載基板 Download PDFInfo
- Publication number
- TW201738312A TW201738312A TW106112414A TW106112414A TW201738312A TW 201738312 A TW201738312 A TW 201738312A TW 106112414 A TW106112414 A TW 106112414A TW 106112414 A TW106112414 A TW 106112414A TW 201738312 A TW201738312 A TW 201738312A
- Authority
- TW
- Taiwan
- Prior art keywords
- resin composition
- thermosetting resin
- electronic component
- filler
- circuit board
- Prior art date
Links
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 65
- 239000011342 resin composition Substances 0.000 title claims abstract description 59
- 239000000758 substrate Substances 0.000 title claims abstract description 21
- 238000010438 heat treatment Methods 0.000 title abstract description 24
- 239000011148 porous material Substances 0.000 title abstract description 22
- 229910000679 solder Inorganic materials 0.000 title abstract description 19
- 239000003822 epoxy resin Substances 0.000 claims abstract description 48
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 48
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 38
- 239000000945 filler Substances 0.000 claims abstract description 32
- -1 hemiacetal ester Chemical class 0.000 claims abstract description 23
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims abstract description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 229920001289 polyvinyl ether Polymers 0.000 claims abstract description 13
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 238000001723 curing Methods 0.000 claims description 15
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 239000004848 polyfunctional curative Substances 0.000 claims description 8
- 230000001186 cumulative effect Effects 0.000 claims description 5
- 239000010419 fine particle Substances 0.000 claims description 5
- 238000013007 heat curing Methods 0.000 claims description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 22
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 235000012431 wafers Nutrition 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 229960000834 vinyl ether Drugs 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XDZMPRGFOOFSBL-UHFFFAOYSA-N 2-ethoxybenzoic acid Chemical compound CCOC1=CC=CC=C1C(O)=O XDZMPRGFOOFSBL-UHFFFAOYSA-N 0.000 description 2
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 208000018459 dissociative disease Diseases 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 150000002373 hemiacetals Chemical class 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- ILUJQPXNXACGAN-UHFFFAOYSA-N ortho-methoxybenzoic acid Natural products COC1=CC=CC=C1C(O)=O ILUJQPXNXACGAN-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000003303 reheating Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- HIYIGPVBMDKPCR-UHFFFAOYSA-N 1,1-bis(ethenoxymethyl)cyclohexane Chemical compound C=COCC1(COC=C)CCCCC1 HIYIGPVBMDKPCR-UHFFFAOYSA-N 0.000 description 1
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- GNUGVECARVKIPH-UHFFFAOYSA-N 2-ethenoxypropane Chemical compound CC(C)OC=C GNUGVECARVKIPH-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229940044949 eucalyptus oil Drugs 0.000 description 1
- 239000010642 eucalyptus oil Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/508—Amines heterocyclic containing only nitrogen as a heteroatom having three nitrogen atoms in the ring
- C08G59/5086—Triazines; Melamines; Guanamines
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
- C08K7/20—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
- H01L21/563—Encapsulation of active face of flip-chip device, e.g. underfilling or underencapsulation of flip-chip, encapsulation preform on chip or mounting substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
-
- 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
-
- 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
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/341—Surface mounted components
- H05K3/3431—Leadless components
- H05K3/3436—Leadless components having an array of bottom contacts, e.g. pad grid array or ball grid array components
-
- 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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L2224/16151—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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
- H01L2224/8319—Arrangement of the layer connectors prior to mounting
- H01L2224/83192—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on another item or body to be connected to the semiconductor or solid-state body
-
- 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
- H05K2201/10613—Details of electrical connections of non-printed components, e.g. special leads
- H05K2201/10954—Other details of electrical connections
- H05K2201/10977—Encapsulated connections
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/08—Treatments involving gases
- H05K2203/085—Using vacuum or low pressure
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1178—Means for venting or for letting gases escape
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1189—Pressing leads, bumps or a die through an insulating layer
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Wire Bonding (AREA)
Abstract
本發明提供一種可藉由回焊後之加熱及真空操作而去除孔隙之熱硬化性樹脂組合物及電子零件搭載基板。 本實施形態之熱硬化性樹脂組合物包含液狀之環氧樹脂、調配單羧酸及聚乙烯醚而成之半縮醛酯、硬化劑、及填料。
Description
本發明係關於一種於電路基板上搭載電子零件(表面安裝零件)時使用之熱硬化性樹脂組合物及使用其之電子零件搭載基板。
先前,作為於電路基板上搭載電子零件之表面安裝技術,已知有以下之方法A、B。方法A係於電路基板上塗佈助焊劑,使用回流裝置安裝電子零件後,將助焊劑洗淨,其後填充底部填充材並進行熱硬化。方法B係首先將具有助焊劑作用之底部填充材塗佈於電路基板,搭載電子零件後,藉由回流裝置而同時進行焊接與底部填充材之熱硬化。 由於伴隨著電子機器之小型化的電子零件之多接腳化與連接間距之縮小化,接合部之焊料體積變小,電路基板與電子零件間之間隙變窄,因此先前之方法存在電子機器之可靠性降低之問題。 於上述方法A中存在如下問題:助焊劑之洗淨變得不充分,離子性成分容易殘留;利用毛細管現象之底部填充材之填充變得困難。又,於上述方法B中存在如下問題:由於回流溫度高於底部填充材之硬化溫度,因此於回流後底部填充材完全硬化,大量產生由去除焊料或銅之氧化膜時產生之水所致之孔隙。又,存在如下問題:於塗佈有底部填充材之電路基板上暫置電子零件時,底部填充材於捲入有空氣之狀態下硬化,產生大量孔隙。 為了解決此種問題,提出有如下方法:於電路基板表面之至少一部分塗佈熱硬化性樹脂組合物,將電子零件搭載於電路基板上,進行回焊,進行真空操作及/或未達塗佈樹脂之硬化溫度之加熱,其後將塗佈樹脂加熱硬化(參照專利文獻1)。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2013-59807號公報
[發明所欲解決之問題] 然而,於上述方法中判明有如下之問題:即便於回焊後進行未達硬化溫度之加熱,亦難以使熱硬化性樹脂組合物發生軟化,難以藉由真空操作去除孔隙。如此,期望可藉由回焊後之加熱及真空操作而去除孔隙之熱硬化性樹脂組合物。 本發明係為了解決上述問題而完成者,其目的在於提供一種可藉由回焊後之加熱及真空操作而去除孔隙的熱硬化性樹脂組合物及電子零件搭載基板。 [解決問題之技術手段] 本發明者等人發現:藉由將回焊結束之時點的環氧基之反應率設為40%以下,可藉由回焊後之加熱及真空操作而去除孔隙。 作為可將回焊結束之時點的環氧基之反應率設為40%以下的熱硬化組合物,本發明包含以下態樣。 [1] 一種熱硬化性樹脂組合物,其包含: 液狀之環氧樹脂; 半縮醛酯,其係將單羧酸及聚乙烯醚合成而成; 硬化劑;及 填料。 [2] 如[1]所記載之熱硬化性樹脂組合物,其中上述半縮醛酯係將相對於上述環氧樹脂之環氧基而為0.2~0.4當量之單羧酸、與相對於上述單羧酸之羧基而為1.0~1.5當量之聚乙烯醚合成而成。 [3] 如[1]或[2]所記載之熱硬化性樹脂組合物,其中上述硬化劑包含氰基胍及三聚氰胺。 [4] 如[1]~[3]中任一項所記載之熱硬化性樹脂組合物,其中上述硬化劑包含相對於上述環氧樹脂之環氧基而為0.4~0.5當量之氰基胍、及相對於上述環氧基而為0.08~0.18當量之三聚氰胺。 [5] 如[1]~[4]中任一項所記載之熱硬化性樹脂組合物,其中上述填料包含10~40質量%之平均粒徑為0.5~5 μm之球狀填料。 [6] 如[1]~[5]中任一項所記載之熱硬化性樹脂組合物,其中上述填料所包含之0.3 μm以下之微粒子之累積含有率為上述填料之總量之10質量%以下。 [7] 如[1]~[6]中任一項所記載之熱硬化性樹脂組合物,其中220~260℃、10~20秒之回流後的上述環氧樹脂中之環氧基之反應率為40%以下。 [8] 一種電子零件搭載基板,其包含: 電路基板; 電子零件,其係安裝於上述電路基板上;及 硬化物,其係設置於上述電路基板與上述電子零件之間,且係將如[1]~[7]中任一項所記載之熱硬化性樹脂組合物熱硬化而獲得。 [發明效果] 根據本發明,可將回焊結束之時點的環氧基之反應率設為40%以下,從而可藉由回焊後之加熱及真空操作而去除孔隙。
以下,視需要一面參照圖式一面對本發明之實施形態(以下稱為「本實施形態」)進行詳細說明,但本發明並不限定於此,可於不脫離其主旨之範圍內進行各種變化。 應用本實施形態之熱硬化性樹脂組合物之表面安裝技術中為了進行電性連接而通常使用之焊料為主要包含錫、銀及銅之合金,其熔點約為220℃,於回焊步驟中,藉由120~160℃之預熱進行1分鐘左右之加熱,且為了進行焊接而進行10秒左右之220~260℃之加熱。 因此,熱硬化性樹脂組合物於回焊步驟中開始各種反應。 1)由半縮醛酯之解離反應所致的羧酸之生成 2)焊料或銅之氧化膜(金屬氧化物)與羧酸之反應 3)羧酸與環氧樹脂之反應 4)羧酸與熱硬化劑之成鹽反應 5)羧酸金屬鹽與環氧樹脂之反應 6)環氧樹脂與熱硬化劑之反應 其結果為,即便於回焊後再次進行加熱,亦難以使熱硬化性樹脂組合物發生軟化,而難以藉由真空操作去除孔隙,難以去除由捲入空氣或去除氧化膜時產生之水所致的孔隙。 本發明者進行銳意研究之結果判明:藉由將回流後之環氧樹脂之反應率設為40%以下,可藉由回流後之加熱及真空操作而去除電路基板與電子零件之間之孔隙。 (熱硬化性樹脂組合物) 為了將回流後之環氧樹脂之反應率設為40%以下,本實施形態之熱硬化性樹脂組合物包含液狀之環氧樹脂、將單羧酸及聚乙烯醚調配而成之半縮醛酯、硬化劑、及填料。以下,對本實施形態之熱硬化性樹脂組合物所包含之各成分之詳細情況進行說明。 於本申請案之表面安裝技術所使用之熱硬化性樹脂組合物中,含有液狀之環氧樹脂。環氧樹脂具有作為基質樹脂之功能。又,環氧樹脂具有於硬化反應時亦與下述活性劑(羧酸)反應,從而使活性劑失活之功能。藉此,硬化後之塗佈樹脂變得非常熱穩定,於加熱時(例如底部填充樹脂之加熱硬化時),不會產生腐蝕反應或分解氣體。 熱硬化性樹脂組合物較理想為實質上不含溶劑,包含於常溫下為液狀之環氧樹脂。藉由熱硬化性樹脂組合物不含溶劑,可防止由溶劑揮發時產生之氣體導致的孔隙產生。 液狀之環氧樹脂係指於常溫下為液狀之環氧樹脂,例如可列舉於常溫下具有流動性之環氧樹脂。作為此種液狀環氧樹脂,例如黏度(室溫,mPa・s)較佳為20000以下,尤其較佳為1000~10000。液狀環氧樹脂之環氧基當量(EEW,Epoxy Equivalent per Weight)為100~400,較佳為100~200。又,液狀環氧樹脂之重量平均分子量(Mw)為200~1000,較佳為300~600。 作為液狀環氧樹脂,較佳為有雙酚A型環氧樹脂、雙酚F型環氧樹脂、縮水甘油胺型環氧樹脂、脂環式環氧樹脂等,可使用該等之1種以上。 雙酚A型環氧樹脂係以下式表示: [化1][上述式中,n表示0或1。G表示縮水甘油基],可使用該等之一種以上。 液狀雙酚F型環氧樹脂係以下式表示: [化2][上述式中,n表示0或1。G表示縮水甘油基],可使用該等之一種以上。 半縮醛酯係藉由使單羧酸及聚乙烯醚反應而合成。半縮醛酯中之羧酸作為用以提昇焊接性之活性劑而發揮功能。羧酸若直接使用則會於室溫下與環氧樹脂中之環氧基反應,因此藉由使羧酸與乙烯醚反應製成半縮醛酯,可抑制羧酸與環氧樹脂之反應。進而,為了不於預熱時解離而發生反應,半縮醛酯之解離溫度較適合為170℃以上。藉由將羧酸加以半縮醛酯化,可抑制熱硬化性樹脂之低溫副反應,從而可提昇熱硬化性樹脂組合物之保存穩定性。 作為半縮醛酯化之羧酸,為了於解離後即便與環氧樹脂發生反應亦不會因交聯反應而發生凝膠化,使用於1分子中具有1個羧基之單羧酸。單羧酸可為脂肪族系、芳香族系、多環芳香族系、雜環系之任一種,由於與環氧基發生反應而成為非反應性之支鏈,因此自耐熱性之方面而言較佳為芳香族單羧酸或多環芳香族單羧酸。 單羧酸之調配量較佳為相對於環氧樹脂之環氧基而為0.2~0.4當量。於相對於1當量之環氧基而單羧酸未達0.2當量之情形時,焊料之氧化膜去除性變差而發生連接不良,於超過0.4當量之情形時,因與環氧基之反應而消耗之環氧基減少,硬化性降低。 作為半縮醛酯化之乙烯醚,可使用於1分子中具有2個以上乙烯基之聚乙烯化合物,為了降低半縮醛酯本身之黏度,較佳為脂肪族聚乙烯醚或脂環式聚乙烯醚。 聚乙烯醚之調配量較佳為相對於單羧酸之羧基而為1至1.5當量。於相對於單羧酸1當量而聚乙烯醚未達1.0當量之情形時,未半縮醛化之羧酸於室溫下亦與環氧樹脂發生反應而被消耗,導致連接性降低,於超過1.5當量之情形時,過剩之乙烯醚殘留而成為孔隙之原因,且硬化物之耐熱性降低。 於使用單乙烯醚作為乙烯醚之情形時,存在用以進行半縮醛化之乙烯醚調配量變多,而發生產生孔隙或硬化物之耐熱性降低等問題的情形。又,關於使用聚羧酸與聚乙烯醚之半縮醛酯,會高分子量化而生成凝膠,因此與環氧樹脂之相溶性降低,調配物無法均勻化。 對於單羧酸與聚乙烯醚,為了使其等本身不會氣體化而產生孔隙,使用沸點為200℃以上者。 硬化劑係用以與環氧樹脂發生反應而形成三維交聯構造者。作為硬化劑,為了使回焊後之環氧基之反應率為40%以下,並且於通常之硬化溫度(150~180℃)下完全硬化,較佳為使用氰基胍及三聚氰胺。藉由使用氰基胍及三聚氰胺,藉由使用氰基胍及三聚氰胺,於短時間之加熱下不會發生硬化反應,因此即便於回流時亦可防止熱硬化性樹脂組合物硬化。 氰基胍之調配量較佳為相對於環氧樹脂之環氧基而為0.4~0.5當量。於氰基胍未達0.4當量之情形時,環氧基之反應未完成而發生硬化不良,於超過0.5當量之情形時,因回流步驟而硬化反應過度進行,後消泡性降低,孔隙殘留。 三聚氰胺之調配量較佳為相對於環氧樹脂之環氧基而為0.08~0.18當量。於三聚氰胺未達0.08當量之情形時亦同樣地,環氧基之反應未完成而發生硬化不良,於超過0.12當量之情形時,因回流步驟而硬化反應過度進行,後消泡性降低,孔隙殘留。 填料係為了使硬化後之環氧樹脂組合物之熱膨脹係數變小,提昇熱導率而添加,較佳為使用氧化矽或氧化鋁等微小球狀填料。 關於球狀填料,為了抑制環氧樹脂組合物之黏度上升,較佳為平均粒徑為0.5 μm以上者,又,為了不妨礙焊料凸塊之潤濕擴散,平均粒徑較佳為5 μm以下。於使用平均粒徑未達0.5 μm之球狀填料之情形時,填料之表面積變得過大而組合物之黏度變高,後消泡性降低,於超過5 μm之情形時,於焊接時發生填料之咬入,連接性降低。 又,進而較佳為球狀填料中包含之0.3 μm以下之微粒子之合計為球狀填料之10質量%以下。其原因在於:於球狀填料所包含之0.3 μm以下之微粒子之累積含有率超過10質量%之情形時,填料之表面積增大,因此組合物之黏度變高,後消泡性降低。 球狀填料之含量較佳為10質量%以上且40質量%以下。於球狀填料之含量未達10質量%之情形時硬化收縮變大,於晶片或電路基板與環氧樹脂組合物之間容易產生間隙,於50質量%以上之情形時,後消泡性與連接性降低。 於熱硬化性樹脂組合物中,亦可含有矽油等消泡劑、矽烷偶合劑、艾羅技等作為其他添加劑。 本實施形態之熱硬化性樹脂組合物於220~260℃、10~20秒之熱處理後的上述環氧樹脂中之環氧基之反應率為40%以下。藉此,即便於在此種熱處理條件下進行回焊之情形時,亦可抑制熱硬化性樹脂硬化。 根據本實施形態之熱硬化性樹脂組合物,於回焊後,可藉由較該回焊之熱處理溫度更低之溫度(80℃~160℃)之再加熱而軟化,藉由進行真空操作,而可去除樹脂中包含之孔隙。 (表面安裝方法) 其次,對應用本實施形態之熱硬化性樹脂組合物之表面安裝方法進行說明。 如圖1A所示,準備印刷配線基板等電路基板1。其次,如圖1B所示,於電路基板1表面上之至少一部分(包含整個表面)塗佈本申請案之熱硬化性樹脂組合物3。例如可於電路基板1上之至少金屬表面之一部分塗佈。作為金屬,例如可列舉純金屬(銅等)及合金(焊料等),可為該等之一種以上。熱硬化性樹脂組合物3之層厚通常為10~50 μm。 其次,如圖1C所示,將電子零件4暫置於電路基板1上。於該暫置之步驟中,存在因空氣之捲入而產生氣泡10之情況。本實施形態之熱硬化性樹脂組合物亦可應用於大型之電子零件、例如50 mm見方以上之表面安裝技術。作為電子零件4,具體而言可列舉封裝零件(BGA(Ball Grid Array,球狀柵格陣列)零件、CSP(Chip Scale Package,晶片尺度封裝)零件、MCM(MultiChip Module,多晶片模組)零件、IPM(Intelligent Power Module,智慧功率模組)零件、IGBT(Insulated Gate Bipolar Transistor,絕緣閘雙極性電晶體)零件等)、半導體晶片等。 其次,如圖1D所示,進行回焊。回焊包含預熱步驟(120~140℃、40~80秒)、升溫步驟(140~220℃、5~15秒)、及回流步驟(220~260℃,10秒~30秒)。若加熱時間過長,則存在引起塗佈樹脂之硬化反應之情況,因此欠佳。於該回焊時存在如下情況:存在於熔融焊料之表面之氧化物等因熱硬化性樹脂組合物中之半縮醛酯而被還原等,其結果生成水等。該生成之水等蒸發膨脹,進一步產生氣泡10。 其次,如圖1E所示,為了進行消泡,而進行真空操作及/或未達熱硬化性樹脂組合物之硬化溫度之加熱。藉此,去除由電子零件之暫置時之空氣之捲入(圖1C)、或於回流步驟中去除焊料氧化膜(圖1D)所致之水或氣泡10。真空操作條件例如較佳為真空度1~500(尤其較佳為50~300)kPa、1~60(尤其較佳為5~30)分鐘。 用以進行消泡之加熱係於未達熱硬化性樹脂組合物之硬化溫度之溫度下進行。不僅藉由該加熱而熱硬化性樹脂組合物軟化,進行脫水、消泡,而且藉由該軟化之熱硬化性樹脂組合物而將電路基板表面上之凹凸吸收(平坦化)、使其均勻。具體而言,作為用以進行消泡之加熱條件,例如較佳為60~150(尤其較佳為80~130)℃、1~60(尤其較佳為10~20)分鐘。 其後,如圖1F所示,使熱硬化性樹脂組合物加熱硬化,製成硬化物10。作為加熱硬化條件,可為硬化劑之硬化反應起始溫度以上,具體而言為150~200℃、1~4小時。藉此,環氧樹脂與硬化劑發生反應,形成三維交聯構造。又,此時藉由半縮醛酯之解離反應而生成羧酸,羧酸與環氧樹脂發生反應,藉此失去作為活性劑之活性力。因此,不會殘留羧酸,所以可消除因腐蝕等導致可靠性降低之原因。 以上述方式製造本申請案之電子零件搭載基板。於如上所述之電子零件搭載基板之製造方法中,無須設置另外之助焊劑。 以上述方式製造之本實施形態之電子零件搭載基板包含:電路基板1;電子零件4,其係安裝於電路基板1上;及硬化物10,其係設置於電路基板1與電子零件4之間,且係將本實施形態之熱硬化性樹脂組合物3熱硬化而獲得。 根據本實施形態之電子零件搭載基板,可抑制於電路基板1與電子零件4之間之接合材10中產生孔隙,因此可提昇電路基板1與電子零件4之電性連接及機械接合之可靠性,進而可提昇電子零件搭載基板之可靠性。 (實施例) 以下,使用實施例及比較例對本發明更具體地進行說明。本發明不受以下實施例之任何限定。 如下述表1、2所示,分別計量環氧樹脂、半縮醛酯、氰基胍、三聚氰胺、及球狀填料,使用攪拌機混合30分鐘,以三輥磨機使其分散。對於所得之環氧樹脂組合物,於真空下(100 kPa)下進行10分鐘攪拌、消泡,獲得實施例及比較例之熱硬化性樹脂組合物。表1、2所示之數值表示將環氧樹脂設為100質量份之情形時之質量份。又,於表1、2中,所謂「0.3 μm以下」意指0.3 μm以下之累積含有率。於表1、2中記載所使用之填料之平均粒徑,平均粒徑係藉由雷射繞射散射法而測定。 [表1]
[表2]
[半縮醛酯之合成] 表1、2所示之半縮醛酯係以下述方式合成。 合成例1(參照實施例1) 將25.34質量份(相對於環氧樹脂之環氧基而相當於0.29當量)之乙氧基苯甲酸(當量166、沸點315℃)與18.13重量份(相對於乙氧基苯甲酸之羧基而相當於1.35當量)之環己烷二甲醇二乙烯醚(當量88、沸點310℃)混合,於80℃下攪拌10小時使其反應。反應結束後,進行反應物之FT-IR(Fourier Transform Infrared Radiation,傅立葉變換紅外線光譜)測定,確認到羧基之吸收消失。 合成例2(實施例16) 使用24.00質量份(相對於環氧樹脂之環氧基而相當於0.30當量)之甲氧基苯甲酸(當量152、沸點200℃)與21.53質量份(相對於甲氧基苯甲酸之羧基而相當於1.35當量)之三乙二醇二乙烯醚(當量101、沸點220℃),除此以外,與合成例1同樣地進行反應,進行反應物之FT-IR測定,確認到羧基之吸收消失。 合成例3(比較例1) 使用15.95質量份(相對於環氧樹脂之環氧基而相當於0.30當量)之作為二官能羧酸之癸二酸(當量101、沸點386℃)與18.33質量份(相對於甲氧基苯甲酸之羧基而相當於1.35當量)之作為單乙烯醚之異丙基單乙烯醚(當量86、沸點55℃),除此以外,與合成例1同樣地進行反應,進行反應物之FT-IR測定,確認到羧基之吸收消失。 再者,表1、2所示之合成例1、2及3中之羧酸之欄之數值表示相對於合成所使用之羧酸之環氧基的當量。又,乙烯醚之欄中之數值表示相對於合成所使用之乙烯醚之羧基的當量。 又,關於利用二官能以上之羧酸與二官能以上之乙烯醚之半縮醛化,因反應中產生聚合物而生成凝膠化物,故而欠佳。 [電路基板與晶片] 為了進行熱硬化性樹脂組合物之評價,使用設置有連接焊盤之電路基板(30 mm見方、厚度0.4 mm、連接焊盤數196、連接焊盤間距300 μm、連接焊盤表面處理為鍍鎳-金)作為電路基板1,使用試驗用TEG(Test Element Group,測試元件組)晶片(4.2 mm見方、厚度0.4 mm、凸塊數196、凸塊間距300 μm,焊料種類為錫96.5質量%、銀3.0質量%及銅0.5質量%之合金)作為電子零件。又,為了進行導通試驗,電路基板與評價用TEG晶片構成菊鏈電路。 [試驗方法] 於電路基板之焊盤部,使用分注器塗佈實施例及比較例之熱硬化性樹脂組合物3 mg。於其上載置評價用TEG晶片,使用回流裝置(預熱120~140℃、60秒,升溫140~220℃、8秒,回流220~260℃、12秒)進行焊接。焊接結束後,使用附有加熱板之真空腔室加熱至120℃,進行真空操作(極限真空度100 kPa、15分鐘)。於真空操作後,自真空腔室取出,使用乾燥機於160℃下進行2小時加熱並硬化,獲得TEG安裝基板。 [評價方法與判定基準] 對於以上述方式獲得之TEG安裝基板,如表1、2所示,自孔隙(後消泡性)、硬化性、焊接性、低硬化收縮性之觀點進行評價。以下示出各評價之評價方法與判定基準。 (孔隙:後消泡性) 孔隙之確認係使用研磨機磨削安裝基板之TEG晶片直至熱硬化性樹脂之硬化物露出為止,使用20倍之顯微鏡以目視進行觀察。將完全不存在孔隙者視為◎,將孔隙之大小為凸塊間距離之一半即75 μm以下者為3個以下者視為○,將孔隙之大小超過75 μm者、及存在4個以上孔隙者視為×。 (硬化性) 硬化性係於與上述相同之電路基板上,使用具有2 mm見方之開口之150 Mesh之網板以約50 μ之厚度進行印刷,對於在與上述相同之條件下硬化之熱硬化性樹脂組合物,依照JIS K 5600-5-4劃痕硬度(鉛筆法)進行測定,將鉛筆硬度為2 H以上,且進一步將該測定塗膜再次於160℃下加熱1小時而加熱後鉛筆之劃痕未變化(塌陷或消失)者視為○,將鉛筆硬度為H以下或因再加熱而鉛筆之劃痕變化者視為×。 (焊接性) 焊接性係使用對安裝基板實施之菊鏈電路進行導通試驗,將導通者視為○,將未導通者視為×。 (低硬化收縮性) 低硬化收縮性係對於安裝有評價用TEG晶片之電路基板削出截面,以50倍之顯微鏡觀察截面,將截面完全經填充者視為○,將電路基板側或TEG晶片側存在間隙者視為×。 [回流後之環氧基之反應率] 根據於試驗前之熱硬化性樹脂組合物之FT-IR圖中,位於910 cm-1之環氧基之吸收波峰相對於位於1508 cm-1之苯環之吸收波峰之強度的比、及回流後之熱硬化性樹脂組合物之FT-IR圖中之苯環與環氧基之吸收波峰之強度比,計算出環氧基之反應率。 [關於實施例及比較例之結果] 實施例總體而言確認到孔隙少,且後消泡性優異。尤其實施例1~16於表1列舉之所有評價試驗中均獲得了較高之評價,該實施例1~16包含:1)液狀之環氧樹脂、2)將相對於環氧樹脂之環氧基而為0.2~0.4當量之單羧酸(苯甲酸)與相對於上述單羧酸之羧基而為1.0~1.5當量之聚乙烯醚合成而成之半縮醛酯、3)包含相對於環氧樹脂之環氧基而為0.4~0.5當量之氰基胍及相對於環氧基而為0.08~0.18當量之三聚氰胺的硬化劑、及4)10~40質量%之平均粒徑為0.5~5 μm之球狀填料,而且5)填料所含之0.3 μm以下之微粒子之累積含有率為上述填料之總量之10質量%以下,且6)220~260℃、10~20秒之回流後的環氧樹脂中之環氧基之反應率為40%以下。 實施例17~31與實施例1~16相比成為較差之結果。具體而言如下述所示。 於實施例17中,羧酸被環氧基消耗,氧化膜去除性變得不充分。 於實施例18中,羧酸與環氧基反應,硬化所必需之環氧基變得不充分。 於實施例19中,硬化劑不足。 於實施例20中,回流時之反應進行而發生凝膠化。 於實施例21中,硬化劑不足,硬化變得不充分。 於實施例22中,回流時之反應進行而發生凝膠化。又,樹脂於焊料熔融前固化,無法連接。 於實施例23中,硬化後之截面觀察中,於TEG側產生間隙。 於實施例24中,組合物之黏度上升,無法進行後消泡,粒子妨礙焊料之潤濕性,導致連接不良。 於實施例25中,組合物之黏度上升,無法進行後消泡。 於實施例26中,大粒子妨礙焊料之潤濕性,導致連接不良。 於實施例27中,組合物之黏度上升,無法進行後消泡。 於實施例28~31中,回流時之反應進行而發生凝膠化。於焊料熔融前固化,無法連接。 比較例1使用二官能之癸二酸作為羧酸,但因回流之加熱而進行環氧樹脂之三維硬化,妨礙焊接性,進而消泡性降低而孔隙大量殘留。 比較例2由於未加入填料,因此硬化收縮變大,產生底部填充劑與TEG晶片之剝離。
1‧‧‧電路基板
2‧‧‧焊墊焊料
3‧‧‧未硬化之熱硬化性樹脂組合物
4‧‧‧電子零件
5‧‧‧裸晶
6‧‧‧已硬化之底部填充樹脂
8‧‧‧電路
9‧‧‧凸塊焊料
10‧‧‧熱硬化性樹脂組合物之硬化物
10‧‧‧氣泡
2‧‧‧焊墊焊料
3‧‧‧未硬化之熱硬化性樹脂組合物
4‧‧‧電子零件
5‧‧‧裸晶
6‧‧‧已硬化之底部填充樹脂
8‧‧‧電路
9‧‧‧凸塊焊料
10‧‧‧熱硬化性樹脂組合物之硬化物
10‧‧‧氣泡
圖1(A)~(F)係用以對應用本實施形態之熱硬化性樹脂組合物之表面安裝技術之一態樣進行說明的步驟剖視圖。
無
Claims (8)
- 一種熱硬化性樹脂組合物,其包含: 液狀之環氧樹脂; 半縮醛酯,其係將單羧酸及聚乙烯醚合成而成; 硬化劑;及 填料。
- 如請求項1之熱硬化性樹脂組合物,其中上述半縮醛酯係將相對於上述環氧樹脂之環氧基而為0.2~0.4當量之單羧酸、及相對於上述單羧酸之羧基而為1.0~1.5當量之聚乙烯醚合成而成。
- 如請求項1或2之熱硬化性樹脂組合物,其中上述硬化劑包含氰基胍及三聚氰胺。
- 如請求項1或2之熱硬化性樹脂組合物,其中上述硬化劑包含相對於上述環氧樹脂之環氧基而為0.4~0.5當量之氰基胍、及相對於上述環氧基而為0.08~0.18當量之三聚氰胺。
- 如請求項1或2之熱硬化性樹脂組合物,其中上述填料包含10~40質量%平均粒徑為0.5~5 μm之球狀填料。
- 如請求項1或2之熱硬化性樹脂組合物,其中上述填料所含之0.3 μm以下之微粒子之累積含有率為上述填料之總量之10質量%以下。
- 如請求項1或2之熱硬化性樹脂組合物,其中220~260℃、10~20秒之回流後的上述環氧樹脂中之環氧基之反應率為40%以下。
- 一種電子零件搭載基板,其包含: 電路基板; 電子零件,其係安裝於上述電路基板上;及 硬化物,其係設置於上述電路基板與上述電子零件之間,且係藉由將如請求項1~7中任一項之熱硬化性樹脂組合物熱硬化而獲得。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016085548A JP6374434B2 (ja) | 2016-04-21 | 2016-04-21 | 熱硬化性樹脂組成物及び電子部品搭載基板 |
JP??2016-085548 | 2016-04-21 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201738312A true TW201738312A (zh) | 2017-11-01 |
TWI629308B TWI629308B (zh) | 2018-07-11 |
Family
ID=60020926
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW106112414A TWI629308B (zh) | 2016-04-21 | 2017-04-13 | Thermosetting resin composition and electronic component mounting substrate |
Country Status (6)
Country | Link |
---|---|
US (1) | US10870725B2 (zh) |
JP (1) | JP6374434B2 (zh) |
KR (1) | KR101900602B1 (zh) |
CN (1) | CN107304282B (zh) |
DE (1) | DE102017108256B4 (zh) |
TW (1) | TWI629308B (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102552077B1 (ko) * | 2018-04-23 | 2023-07-06 | 현대자동차주식회사 | 적층형 파워 모듈 및 이의 제조 방법 |
JP7390824B2 (ja) * | 2019-08-28 | 2023-12-04 | デクセリアルズ株式会社 | 半導体装置の製造方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60262430A (ja) | 1984-06-08 | 1985-12-25 | Matsushita Electric Ind Co Ltd | 半導体装置の製造方法 |
WO2002006399A1 (fr) * | 2000-07-18 | 2002-01-24 | Kyocera Chemical Corporation | Composition de resine epoxyde ignifuge exempte d'halogenes, composition de resine epoxyde ignifuge exempte d'halogenes pour panneaux multicouches, preimpregnes, stratifies plaques cuivre, cartes a circuits imprimes, films de resine avec feuille ou supports de cuivre, et stratifies et panneaux multicouches |
JP2004152936A (ja) | 2002-10-30 | 2004-05-27 | Tamura Kaken Co Ltd | 回路基板はんだ付用フラックス、ソルダーペースト及び回路基板 |
JP2004155919A (ja) | 2002-11-07 | 2004-06-03 | Nof Corp | 分岐状ポリヘミアセタールエステル樹脂、その製造方法及び用途 |
JP4620967B2 (ja) * | 2004-04-26 | 2011-01-26 | 太陽ホールディングス株式会社 | 永久穴埋め用熱硬化性樹脂組成物 |
JP2012131903A (ja) | 2010-12-21 | 2012-07-12 | Nitto Denko Corp | 半導体封止用エポキシ樹脂組成物およびそれを用いてなる半導体装置 |
JP5467469B2 (ja) * | 2011-01-04 | 2014-04-09 | 山栄化学株式会社 | プリント配線基板に表面実装する方法 |
JP5682470B2 (ja) * | 2011-06-16 | 2015-03-11 | 日立化成株式会社 | 電子部品用樹脂組成物及び電子部品装置 |
WO2015093281A1 (ja) | 2013-12-16 | 2015-06-25 | 住友精化株式会社 | エポキシ樹脂接着剤 |
TW201625708A (zh) | 2014-10-10 | 2016-07-16 | Mitsubishi Chem Corp | 半導體元件之製造方法 |
-
2016
- 2016-04-21 JP JP2016085548A patent/JP6374434B2/ja active Active
-
2017
- 2017-04-05 US US15/479,457 patent/US10870725B2/en active Active
- 2017-04-13 TW TW106112414A patent/TWI629308B/zh active
- 2017-04-19 DE DE102017108256.5A patent/DE102017108256B4/de active Active
- 2017-04-19 CN CN201710259355.6A patent/CN107304282B/zh active Active
- 2017-04-20 KR KR1020170050743A patent/KR101900602B1/ko active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
JP2017193664A (ja) | 2017-10-26 |
KR20170120513A (ko) | 2017-10-31 |
CN107304282B (zh) | 2019-08-27 |
US20170335049A1 (en) | 2017-11-23 |
DE102017108256B4 (de) | 2024-01-18 |
CN107304282A (zh) | 2017-10-31 |
KR101900602B1 (ko) | 2018-09-19 |
US10870725B2 (en) | 2020-12-22 |
TWI629308B (zh) | 2018-07-11 |
JP6374434B2 (ja) | 2018-08-15 |
DE102017108256A1 (de) | 2017-10-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101432620B1 (ko) | 활성 수지 조성물, 표면 실장 방법 및 프린트 배선판 | |
JP4299140B2 (ja) | ウエハレベル用の二重硬化b−ステージ化可能なアンダーフィル | |
JP2004530740A (ja) | フラックス処理用アンダーフィル組成物 | |
JP2005519169A (ja) | B−ステージに対応可能なアンダーフィル封入材料と、その利用方法 | |
JP3971995B2 (ja) | 電子部品装置 | |
JP6094884B2 (ja) | 半導体装置の製造方法とそれに使用される半導体封止用アクリル樹脂組成物 | |
JP2007500455A (ja) | 予備適用アンダーフィル封入剤の使用方法 | |
JP2007211244A (ja) | ウエハパッケージングのためのアンダーフィル封止材及びその施用のための方法 | |
JP4887850B2 (ja) | アンダーフィル用液状樹脂組成物、並びにそれを用いた半導体装置の製造方法及び半導体装置 | |
JPWO2013125684A1 (ja) | 半導体装置及びその製造方法 | |
WO2021029259A1 (ja) | モールドアンダーフィル封止用の多層シート、モールドアンダーフィル封止方法、電子部品実装基板及び電子部品実装基板の製造方法 | |
JP6094886B2 (ja) | 半導体装置の製造方法とそれに使用される半導体封止用アクリル樹脂組成物 | |
TWI629308B (zh) | Thermosetting resin composition and electronic component mounting substrate | |
JP6094885B2 (ja) | 半導体装置の製造方法とそれに使用される半導体封止用アクリル樹脂組成物 | |
JP2004204047A (ja) | 液状エポキシ樹脂組成物 | |
JP5493327B2 (ja) | 封止充てん用樹脂組成物、並びに半導体装置及びその製造方法 | |
TW201120082A (en) | Cleaning-free activated resinous composition and method for surface mounting using the same | |
JP5557158B2 (ja) | フリップチップ接続用アンダーフィル剤、及びそれを用いる半導体装置の製造方法 | |
JP2018160566A (ja) | ギャングボンディングプロセス用アンダーフィル絶縁フィルム | |
JP2016204645A (ja) | 封止用熱硬化性樹脂組成物、半導体装置の製造方法及び半導体装置 | |
JP2021093412A (ja) | アンダーフィル用のシート状樹脂組成物、及びそれを用いた半導体装置 | |
JP2005350646A (ja) | 電子部品装置 | |
JP6374298B2 (ja) | フラックス及びフラックスを用いた接合方法 | |
JP2019029599A (ja) | 生産性に優れたギャングボンディングプロセス用アンダーフィル絶縁フィルム | |
JP2005272547A (ja) | 一液型エポキシ樹脂組成物 |