KR20170094115A - Liquid epoxy resin composition, semiconductor sealing agent, semiconductor device, and method for producing liquid epoxy resin composition - Google Patents
Liquid epoxy resin composition, semiconductor sealing agent, semiconductor device, and method for producing liquid epoxy resin composition Download PDFInfo
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- KR20170094115A KR20170094115A KR1020177005859A KR20177005859A KR20170094115A KR 20170094115 A KR20170094115 A KR 20170094115A KR 1020177005859 A KR1020177005859 A KR 1020177005859A KR 20177005859 A KR20177005859 A KR 20177005859A KR 20170094115 A KR20170094115 A KR 20170094115A
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- 239000000203 mixture Substances 0.000 title claims abstract description 80
- 239000004065 semiconductor Substances 0.000 title claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 15
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 title claims description 76
- 238000007789 sealing Methods 0.000 title description 5
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000003822 epoxy resin Substances 0.000 claims abstract description 54
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 54
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000008393 encapsulating agent Substances 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000009477 glass transition Effects 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims description 17
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 229920001400 block copolymer Polymers 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000002347 injection Methods 0.000 abstract description 10
- 239000007924 injection Substances 0.000 abstract description 10
- 238000005336 cracking Methods 0.000 abstract description 9
- 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 8
- -1 aliphatic amines Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000005382 thermal cycling Methods 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- GHKSKVKCKMGRDU-UHFFFAOYSA-N 2-(3-aminopropylamino)ethanol Chemical compound NCCCNCCO GHKSKVKCKMGRDU-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- QUPKCFBHJFNUEW-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1h-imidazole Chemical compound CCC1=NCCN1 QUPKCFBHJFNUEW-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- VWSLLSXLURJCDF-UHFFFAOYSA-N 2-methyl-4,5-dihydro-1h-imidazole Chemical compound CC1=NCCN1 VWSLLSXLURJCDF-UHFFFAOYSA-N 0.000 description 1
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- PRKPGWQEKNEVEU-UHFFFAOYSA-N 4-methyl-n-(3-triethoxysilylpropyl)pentan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)CC(C)C PRKPGWQEKNEVEU-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005040 ion trap Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- 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
- C08G59/32—Epoxy compounds containing three or more 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
- C08G59/20—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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3227—Compounds containing acyclic nitrogen atoms
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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
- 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
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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
- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- 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
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- C08K5/00—Use of organic ingredients
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- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
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- 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
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Abstract
파인 피치의 배선 패턴을 갖는 플립칩형 반도체 장치에의 주입성에 우수하고, 또한 경화 후에 필렛 크랙을 억제하는 액상 반도체 밀봉제를 제공하는 것을 목적으로 한다. (A) 아미노페놀형 에폭시 수지를 포함하는 액상 에폭시 수지, (B) 아민계 경화제, (C) 실리카 필러 및 (D) 실란 커플링제를 함유하고, (A)성분 100질량부에 대해, 아미노페놀형 에폭시 수지를 10.0∼70질량부를 포함하고, (B)성분이, (A)성분 : 1당량에 대해, 0.7∼1.2당량의 비율이고, 경화 후의 유리 전이 온도가, 110∼200℃인 것을 특징으로 하는, 액상 에폭시 수지 조성물이다.It is an object of the present invention to provide a liquid semiconductor encapsulant that is excellent in injection property into a flip chip type semiconductor device having a fine pitch wiring pattern and suppresses cracking of the fillet after curing. (B) an amine curing agent, (C) a silica filler and (D) a silane coupling agent, wherein the amount of the aminophenol-based epoxy resin (A) (B) is in a ratio of 0.7 to 1.2 equivalents based on 1 equivalent of the component (A), and the glass transition temperature after curing is 110 to 200 DEG C. By weight based on the total weight of the composition.
Description
본 발명은, 액상 에폭시 수지 조성물에 관한 것으로, 특히, 액상 반도체 밀봉제(封止劑), 그 중에서도 플립칩형 반도체 장치용의 액상 반도체 밀봉제에 적합한 액상 에폭시 수지 조성물에 관한 것이다.TECHNICAL FIELD The present invention relates to a liquid epoxy resin composition, and more particularly to a liquid epoxy resin composition suitable for a liquid-state semiconductor encapsulant for a flip-chip type semiconductor device.
반도체 장치의 더한층의 배선 등의 고밀도화, 고출력화에 대응 가능한 반도체 소자의 실장 방식으로, 플립칩 본딩이 이용되고 있다. 일반적으로, 플립칩 본딩에서는, 반도체 소자와 기판을 범프로 접합하고, 반도체 소자와 기판의 간극을, 언더필재라고 불리는 액상 반도체 밀봉제로 밀봉을 행한다.Flip chip bonding is used as a mounting method of a semiconductor device capable of coping with higher density and higher output of wirings for a further layer of a semiconductor device. Generally, in the flip chip bonding, the semiconductor element and the substrate are bonded to each other with a bump, and the gap between the semiconductor element and the substrate is sealed with a liquid semiconductor sealing agent called an underfill material.
근래, 반도체 장치 등의 고밀도화, 고출력화의 요구에 응하기 위해, 액정 드라이버 IC 등을 탑재하는 배선 패턴의 파인 피치화가 진행되고 있다. 이 파인 피치화 및 협(狹) 갭화에 의해, 액상 반도체 밀봉제가 주입될 수 없는 개소가 발생한다는 문제가 발생하고 있다.2. Description of the Related Art In recent years, in order to meet demands for higher density and higher output of semiconductor devices and the like, fine pitching of wiring patterns on which liquid crystal driver ICs are mounted is progressing. Due to this fine pitching and narrowing, there arises a problem that a portion where the liquid-state semiconductor encapsulant can not be injected is generated.
이와 같이, 액상 반도체 밀봉제를, 협 갭의 반도체 장치에 주입하는 경우, 점도가 높으면 주입될 수 없는 문제가 발생하기 때문에, 신뢰성 향상을 위해, 필러 첨가량의 저감에 의한 점도의 저하가 시도되었지만, 필러 첨가량의 저감은, 흡습(吸濕) 리플로나 서멀 사이클 등의 신뢰성 시험에서, 신뢰성의 저하를 초래한다는 다른 문제가 발생한다.As described above, when injecting the liquid-state semiconductor encapsulant into a narrow-gap semiconductor device, there arises a problem that it can not be injected when the viscosity is high. Therefore, in order to improve the reliability, The reduction of the filler addition amount causes another problem that reliability is lowered in a reliability test such as moisture absorption reflow or thermal cycling.
본 발명은, 파인 피치의 배선 패턴을 갖는 플립칩형 반도체 장치에의 주입성에 우수하고, 또한 경화 후에 필렛 크랙을 억제하는 액상 반도체 밀봉제를 제공하는 것을 목적으로 한다.An object of the present invention is to provide a liquid semiconductor encapsulant which is excellent in injection property into a flip-chip type semiconductor device having a fine pitch wiring pattern and which suppresses cracking of the fillet after curing.
본 발명은, 이하의 구성을 가짐에 의해 상기 문제를 해결한 액상 에폭시 수지 조성물, 반도체 밀봉제, 반도체 장치, 및 액상 에폭시 수지 조성물의 제조 방법에 관한 것이다.The present invention relates to a liquid epoxy resin composition, a semiconductor encapsulant, a semiconductor device, and a method for producing a liquid epoxy resin composition which solve the above problems by having the following constitution.
[1] (A) 아미노페놀형 에폭시 수지를 포함하는 액상 에폭시 수지, (B) 아민계 경화제, (C) 실리카 필러 및 (D) 실란 커플링제를 함유하고,(1) A liquid epoxy resin composition comprising (A) a liquid epoxy resin containing an amino phenol type epoxy resin, (B) an amine type curing agent, (C) a silica filler, and (D)
(A)성분 100질량부에 대해, 아미노페놀형 에폭시 수지를 10.0∼70질량부를 포함하고,, 10.0 to 70 parts by mass of an aminophenol type epoxy resin relative to 100 parts by mass of the component (A)
(B)성분이, (A)성분 : 1당량에 대해, 0.7∼1.2당량의 비율이고,(B) is in a ratio of 0.7 to 1.2 equivalents based on 1 equivalent of the component (A)
경화 후의 유리 전이 온도가, 110∼200℃인 것을 특징으로 하는, 액상 에폭시 수지 조성물.Wherein the glass transition temperature after curing is 110 to 200 占 폚.
[2] (A)성분에 포함되는 아미노페놀형 에폭시 수지가, 식(1) :[2] The epoxy resin composition according to [1], wherein the aminophenol type epoxy resin contained in the component (A)
[화학식 1][Chemical Formula 1]
로 표시되는, 상기 [1]에 기재된 액상 에폭시 수지 조성물.The liquid epoxy resin composition according to [1], wherein the liquid epoxy resin composition is represented by the following formula (1).
[3] (B)성분이, 화학식(2)∼(4) :[3] The composition according to [1], wherein the component (B)
[화학식 2](2)
[화학식 3](3)
[화학식 4][Chemical Formula 4]
의 적어도 하나로 표시되는 아민계 경화제를 포함하는, 상기 [1]에 기재된 액상 에폭시 수지 조성물.Based curing agent represented by at least one of the following formula (1): " (1) "
[4] (C)성분의 평균입경이, 0.1∼3.0㎛이고, 또한, 액상 에폭시 수지 조성물 100질량부에 대해, (C)성분이 55∼75질량부인, 상기 [1]에 기재된 액상 에폭시 수지 조성물.[4] The liquid epoxy resin composition according to [1], wherein the average particle diameter of the component (C) is 0.1 to 3.0 탆 and the component (C) is 55 to 75 parts by mass based on 100 parts by mass of the liquid epoxy resin composition. Composition.
[5] 또한, (E) 폴리알킬실록산을 포함하는, 상기 [1]에 기재된 액상 에폭시 수지 조성물.[5] The liquid epoxy resin composition according to [1], further comprising (E) a polyalkylsiloxane.
[6] 또한, (F) 블록코폴리머를 포함하는, 상기 [1]에 기재된 액상 에폭시 수지 조성물.[6] The liquid epoxy resin composition according to [1], further comprising (F) a block copolymer.
[7] (D)성분을, 아미노페놀형 에폭시 수지를 제외한 (A)성분의 적어도 일부에 분산시켜, 마스터배치로 한 후, 마스터배치에, 아미노페놀형 에폭시 수지를 포함하는 (A)성분의 잔부(殘部)와 (B)성분을 혼합함에 의해 얻어지는, 상기 [1]에 기재된 액상 에폭시 수지 조성물.[7] A process for producing a master batch, comprising the steps of: (D) dispersing the component (D) in at least a part of the component (A) except for the aminophenol type epoxy resin to prepare a master batch; The liquid epoxy resin composition according to the above [1], which is obtained by mixing the remainder and the component (B).
[8] 상기 [1]에 기재된 액상 에폭시 수지 조성물을 포함하는, 액상 반도체 밀봉제.[8] A liquid semiconductor encapsulant comprising the liquid epoxy resin composition according to [1] above.
[9] 상기 [8]에 기재된, 기판과 칩 사이의 갭이 5∼25㎛인 플립칩형 반도체 장치용의 액상 반도체 밀봉제.[9] A liquid semiconductor encapsulant for a flip-chip type semiconductor device according to the above [8], wherein the gap between the substrate and the chip is 5 to 25 μm.
[10] 상기 [8]에 기재된 액상 반도체 밀봉제를 이용하여 밀봉된, 반도체 장치.[10] A semiconductor device encapsulated with the liquid semiconductor encapsulant according to the above [8].
[11] 상기 [10]에 기재된, 구리(銅) 필러를 구비하는 플립칩형 반도체 장치.[11] A flip chip type semiconductor device comprising a copper pillar according to [10] above.
[12] (D)성분을, 아미노페놀형 에폭시 수지를 제외한 (A)성분에 분산시켜, 마스터배치로 한 후, 마스터배치에, 아미노페놀형 에폭시 수지와 (B)성분을 혼합하는 것을 특징으로 하는, 상기 [1]에 기재된 액상 에폭시 수지 조성물의 제조 방법.[12] A process for producing a master batch, characterized in that the component (D) is dispersed in a component (A) other than the aminophenol type epoxy resin to prepare a master batch, and then the aminophenol type epoxy resin and the component (B) To the liquid epoxy resin composition according to [1].
본 발명 [1]에 의하면, 파인 피치의 배선 패턴을 갖는 플립칩형 반도체 장치에의 주입성에 우수하고, 또한 경화 후에 필렛 크랙을 억제하는 액상 에폭시 수지 조성물을 제공할 수 있다.According to the present invention [1], it is possible to provide a liquid epoxy resin composition which is excellent in injection property into a flip-chip type semiconductor device having a fine pitch wiring pattern and which suppresses cracking of the fillet after curing.
본 발명 [8]에 의하면, 파인 피치의 배선 패턴에의 주입성에 우수하고, 또한 경화 후에 필렛 크랙을 억제하는 액상 반도체 밀봉제를 용이하게 제공할 수 있다.According to the present invention [8], it is possible to easily provide a liquid-state semiconductor encapsulant which is excellent in injection property into a fine pitch wiring pattern and suppresses cracking of the fillet after curing.
본 발명 [10]에 의하면, 파인 피치의 배선 패턴에 액상 반도체 밀봉제가 양호하게 주입되고, 또한 경화 후의 액상 반도체 밀봉제의 필렛 크랙이 억제된 고신뢰성의 반도체 장치를 용이하게 제공할 수 있다.According to the present invention [10], it is possible to easily provide a highly reliable semiconductor device in which a liquid semiconductor sealing agent is well injected into a fine pitch wiring pattern and a fillet crack of the liquid semiconductor encapsulant after curing is suppressed.
본 발명 [12]에 의하면, 파인 피치의 배선 패턴을 갖는 플립칩형 반도체 장치에의 주입성에 우수하고, 또한 경화 후에 필렛 크랙을 억제하는 액상 에폭시 수지 조성물을 간편하게 제조하는 것이 가능해진다.According to the present invention [12], it is possible to easily produce a liquid epoxy resin composition which is excellent in injection property into a flip-chip type semiconductor device having a fine pitch wiring pattern and which suppresses cracking of the fillet after curing.
도 1은 수지 조성물의 주입성의 평가 방법을 설명하는 모식도.
도 2는 필렛 크랙이 발생하지 않은 개소의 사진.
도 3은 본 발명을 이용하여 필렛 크랙의 발생량을 억제한 개소의 사진.
도 4는 필렛 크랙이 다량으로 발생한 개소의 사진.BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view for explaining a method of evaluating the injectability of a resin composition. Fig.
2 is a photograph of a portion where a fillet crack did not occur.
Fig. 3 is a photograph of a portion where the amount of cracking of the fillet is suppressed by using the present invention. Fig.
Figure 4 is a photograph of a portion where a large number of fillet cracks occurred.
[액상 에폭시 수지 조성물][Liquid Epoxy Resin Composition]
본 발명의 액상 에폭시 수지 조성물(이하, 액상 에폭시 수지 조성물이라고 한다)은,The liquid epoxy resin composition of the present invention (hereinafter referred to as a liquid epoxy resin composition)
(A) 아미노페놀형 에폭시 수지를 포함하는 액상 에폭시 수지, (B) 아민계 경화제, (C) 실리카 필러 및 (D) 실란 커플링제를 함유하고,(A) a liquid epoxy resin comprising an amino phenol type epoxy resin, (B) an amine type curing agent, (C) a silica filler and (D) a silane coupling agent,
(A)성분 100질량부에 대해, 아미노페놀형 에폭시 수지를 10.0∼70질량부를 포함하고,, 10.0 to 70 parts by mass of an aminophenol type epoxy resin relative to 100 parts by mass of the component (A)
(B)성분이, (A)성분 : 1당량에 대해, 0.7∼1.2당량의 비율이고,(B) is in a ratio of 0.7 to 1.2 equivalents based on 1 equivalent of the component (A)
경화 후의 유리 전이 온도(Tg)가, 110∼200℃인 것을 특징으로 한다.And has a glass transition temperature (Tg) after curing of 110 to 200 deg.
(A)성분에 함유되는 아미노페놀형 에폭시 수지는, 분자량이 낮은 에폭시 수지이고, 액상 에폭시 수지 조성물을 저점도로 하여, 주입성을 양호하게 한다. 또한, 경화 후의 액상 에폭시 수지 조성물의 필렛 크랙의 발생을 억제한다. 아미노페놀형 에폭시 수지는, 바람직하게는, 식(5) :The aminophenol-type epoxy resin contained in the component (A) is an epoxy resin having a low molecular weight, and the liquid epoxy resin composition has a low viscosity to improve injectability. Further, the occurrence of fillet cracks in the liquid epoxy resin composition after curing is suppressed. The aminophenol type epoxy resin preferably has the formula (5):
[화학식 5][Chemical Formula 5]
로 표시되고, 2개의 관능기가 오르토 위치 또는 파라 위치에 있는 것이 보다 바람직하고, 식(1) :, And it is more preferable that the two functional groups are in an ortho or para position, and the formula (1):
[화학식 6][Chemical Formula 6]
로 표시되는 것이, 액상 에폭시 수지 조성물의 주입성, 경화성, 내열성, 접착성, 경화 후의 액상 에폭시 수지 조성물의 필렛 크랙 억제 등의 내구성, 내마이그레이션성의 관점에서, 특히 바람직하다. 시판품으로서는, 미쯔비시화학제 아미노페놀형 에폭시 수지(그레이드 : JER630, JER630LSD)를 들 수 있다. 아미노페놀형 에폭시 수지는, 단독이라도 2종 이상을 병용하여도 좋다.Is particularly preferable from the viewpoints of durability such as injectability, curability, heat resistance, adhesiveness, suppression of fillet cracking of the liquid epoxy resin composition after curing, and migration resistance, of the liquid epoxy resin composition. Commercially available products include aminophenol type epoxy resins (grade: JER630, JER630LSD) manufactured by Mitsubishi Chemical Corporation. The aminophenol type epoxy resin may be used alone or in combination of two or more.
아미노페놀형 에폭시 수지 이외의 (A)성분으로서는, 액상 비스페놀A형 에폭시 수지, 액상 비스페놀F형 에폭시 수지, 액상 나프탈렌형 에폭시 수지, 액상 수첨(水添) 비스페놀형 에폭시 수지, 액상 지환식(脂環式) 에폭시 수지, 액상 알코올에테르형 에폭시 수지, 액상 환상(環狀) 지방족형 에폭시 수지, 액상 플루오렌형 에폭시 수지, 액상 실록산계 에폭시 수지 등을 들 수 있고, 액상 비스페놀A형 에폭시 수지, 액상 비스페놀F형 에폭시 수지, 액상 실록산계 에폭시 수지가, 경화성, 내열성, 접착성, 내구성의 관점에서 바람직하다. 또한, 에폭시 당량(當量)은, 점도 조정의 관점에서, 80∼250g/eq가 바람직하다. 시판품으로서는, 신닛데츠화학제 비스페놀A형 에폭시 수지(품명 : YDF8170), 신닛데츠화학제 비스페놀F형 에폭시 수지(품명 : YDF870GS), DIC제 나프탈렌형 에폭시 수지(품명 : HP4032D), 신에츠화학제 실록산계 에폭시 수지(품명 : TSL9906) 등을 들 수 있다. 아미노페놀형 에폭시 수지 이외의 (A)성분은, 단독이라도 2종 이상을 병용하여도 좋다.Examples of the component (A) other than the aminophenol type epoxy resin include liquid bisphenol A type epoxy resins, liquid bisphenol F type epoxy resins, liquid naphthalene type epoxy resins, liquid hydrogenated bisphenol type epoxy resins, liquid phase alicyclic Liquid type bisphenol A type epoxy resin, liquid phase bisphenol type epoxy resin, liquid phase fluorine type epoxy resin, liquid siloxane type epoxy resin and the like. F type epoxy resin, and liquid siloxane-based epoxy resin are preferable from the viewpoints of curability, heat resistance, adhesiveness and durability. The epoxy equivalents are preferably 80 to 250 g / eq from the viewpoint of viscosity adjustment. Examples of commercially available products include bisphenol A type epoxy resin (product name: YDF8170) manufactured by Shin Nittsu Chemical Co., bisphenol F type epoxy resin (product name: YDF870GS) manufactured by Shinetsettsu Chemical Co., dicyclopentadiene type epoxy resin (product name: HP4032D) And an epoxy resin (trade name: TSL9906). The component (A) other than the aminophenol type epoxy resin may be used alone or in combination of two or more.
아미노페놀형 에폭시 수지는, 주입성, 필렛 크랙 억제의 관점에서, (A)성분 : 100중량부에 대해, 10.0∼70중량부 함유된다. 아미노페놀형 에폭시 수지가, 10.0질량부 미만이면, 주입성이 나빠지고, 또한 필렛 크랙이 발생하기 쉽게 되고, 70질량부를 초과하면, 경화 후의 액상 에폭시 수지 조성물의 유리 전이점이 너무 높아지고, 필렛 크랙이 발생하기 쉽게 되어, 신뢰성이 저하된다. 아미노페놀형 에폭시 수지가, 10.0∼70중량부면, 경화 후의 액상 에폭시 수지 조성물의 가교 밀도가 올라가, (A)성분의 결합의 강직성이 유지되고, 필렛 크랙이 신전(伸展)하기 어려워지고, 한편, 아미노페놀형 에폭시 수지가 과잉하게 배합되면, (A)성분의 결합의 강직성이 약하여지고, 경화 후의 액상 에폭시 수지 조성물의 필렛 크랙이 신전하기 쉬워진다, 라고 생각된다.The amino-phenol-type epoxy resin is contained in an amount of 10.0 to 70 parts by weight based on 100 parts by weight of the component (A) from the viewpoint of injectability and suppression of cracking of the fillet. If the amount of the amino-phenol-type epoxy resin is less than 10.0 parts by mass, the injection property is deteriorated and the fillet crack easily occurs. When the amount exceeds 70 parts by mass, the glass transition point of the liquid epoxy resin composition after curing becomes too high, And the reliability is lowered. When the amino-phenol-type epoxy resin is 10.0 to 70 parts by weight, the cross-linking density of the liquid epoxy resin composition after curing is increased, the rigidity of the bond of the component (A) is maintained and the fillet cracks hardly extend, If the aminophenol-type epoxy resin is excessively blended, the rigidity of the bond of the component (A) is weakened, and the fillet crack of the liquid epoxy resin composition after curing is likely to expand.
(B)성분은, 액상 에폭시 수지 조성물에 양호한 반응성(경화 속도), 적당한 점성을 부여한다. (B)성분으로서는, 에폭시기와 부가반응(附加反應)할 수 있는 활성 수소를 분자내에 1개 이상 갖는 것이면 좋다. (B)성분으로서는, 디에틸렌트리아민, 트리에틸렌테트라아민, n-프로필아민, 2-히드록시에틸아미노프로필아민, 시클로헥실아민, 4,4'-디아미노-디시클로헥실메탄 등의 지방족 아민 화합물 ; 4,4'-디아미노디페닐메탄, 2-메틸아닐린 등의 방향족 아민 화합물 ; 이미다졸, 2-메틸이미다졸, 2-에틸이미다졸, 2-이소프로필이미다졸 등의 이미다졸 화합물 ; 이미다졸린, 2-메틸이미다졸린, 2-에틸이미다졸린 등의 이미다졸린 화합물 등을 들 수 있고, 액상인 것과 보존 안정성의 관점에서, 방향족 아민 화합물이 바람직하다.The component (B) imparts good reactivity (curing rate) and proper viscosity to the liquid epoxy resin composition. The component (B) may be one having at least one active hydrogen in the molecule, which can be additionally reacted with an epoxy group. Examples of the component (B) include aliphatic amines such as diethylenetriamine, triethylenetetraamine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine and 4,4'-diamino-dicyclohexylmethane Compound; Aromatic amine compounds such as 4,4'-diaminodiphenylmethane and 2-methylaniline; Imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole, and 2-isopropylimidazole; And imidazoline compounds such as imidazoline, 2-methylimidazoline and 2-ethylimidazoline. From the viewpoint of storage stability, aromatic amine compounds are preferable.
(B)성분은, 화학식(2)∼(4) :(B) is a compound represented by any one of formulas (2) to (4):
[화학식 7](7)
[화학식 8][Chemical Formula 8]
[화학식 9][Chemical Formula 9]
의 적어도 하나로 표시되는 아민계 경화제를 포함하면, 액상인 것과 보존 안정성의 관점에서, 바람직하다. (B)성분의 시판품으로서는, ALBEMARLE Co. , Ltd.제 디에틸톨루엔디아민, (화학식(2)의 화합물, 품명 : 에타큐아100), 니혼화약제 아민계 경화제(화학식(3)의 화합물, 품명 : HDAA), ADEKA제 아민계 경화제(화학식(4)의 화합물, 품명 : EH105L)를 들 수 있다. (B)성분은, 단독이라도 2종 이상을 병용하여도 좋다.Based curing agent is preferably in the liquid phase and is preferable from the viewpoint of storage stability. Commercially available products of the component (B) include ALBEMARLE Co. (Compound of formula (3), product name: HDAA), an amine-based curing agent (compound of formula (2), product name: Etacure 100) (4), trade name: EH105L). The component (B) may be used alone or in combination of two or more.
(C)성분에 의해, 액상 에폭시 수지 조성물의 선팽창 계수를 제어할 수 있다. (C)성분으로서는, 콜로이달 실리카, 소수성 실리카, 미세 실리카, 나노 실리카 등을 들 수 있다. 또한, (C)성분의 평균입경(입상이 아닌 경우는, 그 평균 최대 경)은, 특히 한정되지 않지만, 0.1∼3㎛이면, 액상 에폭시 수지 조성물 중에 (C)성분을 균일하게 분산시키는데 바람직하고, 0.3∼2.0㎛이면 더욱 바람직하다. 또한, 액상 에폭시 수지 조성물의 주입성에 우수한 등의 이유로부터 바람직하다. 0.1㎛ 미만이면, 액상 에폭시 수지 조성물의 점도가 상승하고, 주입성이 악화할 우려가 있다. 3㎛ 초과면, 액상 에폭시 수지 조성물 중에 (C)성분을 균일하게 분산시키는 것이 곤란해질 우려가 있다. 시판품으로서는, 아도마텍스제 고순도 합성 구상(球狀) 실리카(품명 : SE2200SEE, 평균입경 : 0.6㎛ ; 품명 : SE1053SEO, 평균입경 : 0.3㎛ ; 품명 : SE5200SEE, 평균입경 : 2.0㎛ ; 품명 : SO-E5, 평균입경 : 2㎛ ; 품명 : SE-2300, 평균입경 : 0.6㎛) 등을 들 수 있다. 또한, (C)성분은, 블리드의 관점에서, 평균입경이 10∼100nm의 나노 실리카를 포함하면, 보다 바람직하다. 여기서, 충전제의 평균입경은, 동적 광산란식 나노 트랙 입도 분석계에 의해 측정한다. (C)성분은, 단독이라도 2종 이상을 병용하여도 좋다.The linear expansion coefficient of the liquid epoxy resin composition can be controlled by the component (C). Examples of the component (C) include colloidal silica, hydrophobic silica, fine silica, and nanosilica. The average particle diameter of the component (C) (the average maximum diameter in the case of not a granular phase) is not particularly limited, but if it is 0.1 to 3 탆, the component (C) is preferably uniformly dispersed in the liquid epoxy resin composition , And more preferably 0.3 to 2.0 m. It is also preferable for reasons such as excellent injection property of liquid epoxy resin composition. If it is less than 0.1 mu m, the viscosity of the liquid epoxy resin composition may increase and the injectability may deteriorate. If it is more than 3 mu m, it may be difficult to uniformly disperse the component (C) in the liquid epoxy resin composition. As a commercially available product, a high purity synthetic spherical silica (trade name: SE2200SEE, average particle diameter: 0.6 mu m, product name: SE1053SEO, average particle diameter: 0.3 mu m; product name: SE5200SEE, average particle diameter: 2.0 mu m; E5, average particle diameter: 2 占 퐉; name: SE-2300, average particle diameter: 0.6 占 퐉). It is more preferable that the component (C) contains nano silica having an average particle diameter of 10 to 100 nm from the viewpoint of bleeding. Here, the average particle diameter of the filler is measured by a dynamic light scattering type nano-track particle size analyzer. The component (C) may be used alone or in combination of two or more.
(D)성분은, 액상 에폭시 수지 조성물에 밀착성을 부여한다. (D)성분으로서는, 3-글리시독시프로필트리메톡시실란, 3-아미노프로필트리메톡시실란, 비닐트리메톡시실란, 3-트리에톡시실릴-N-(1,3-디메틸-부틸리덴)프로필아민, p-스티릴트리메톡시실란, 3-메타크릴록시 프로필메틸 트리메톡시실란, 3-메타크릴옥시프로필트리메톡시실란, 3-우레이도프로필트리에톡시실란, 3-메르캅토프로필트리메톡시실란, 비스(트리에톡시실릴프로필)테트라술피드, 3-이소시아네이트프로필트리에톡시실란 등을 들 수 있고, 3-글리시독시프로필트리메톡시실란, 3-아미노프로필트리메톡시실란, 3-트리에톡시실릴-N-(1,3-디메틸-부틸리덴)프로필아민이 바람직하다. 시판품으로서는, 신에츠화학공업제 3-글리시독시프로필트리메톡시실란(품명 : KBM403), 3-아미노프로필트리에톡시실란(품명 : KBE903), 3-트리에톡시실릴-N-(1,3-디메틸-부틸리덴)프로필아민(품명 : KBE9103) 등을 들 수 있다. (D)성분은, 단독이라도 2종 이상을 병용하여도 좋다.The component (D) imparts adhesion to the liquid epoxy resin composition. Examples of the component (D) include 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl- 3-methacryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, (Triethoxysilylpropyl) tetrasulfide, 3-isocyanatepropyltriethoxysilane, and the like, and examples thereof include 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine is preferable. Examples of commercially available products include 3-glycidoxypropyltrimethoxysilane (trade name: KBM403), 3-aminopropyltriethoxysilane (trade name: KBE903), 3-triethoxysilyl-N- -Dimethyl-butylidene) propylamine (trade name: KBE9103). The component (D) may be used alone or in combination of two or more.
(B)성분은, (A)성분 : 1당량에 대해, 0.7∼1.2당량의 비율이고, 0.7∼1.0 당량의 비율이면, 바람직하다. (A)성분의 당량은 에폭시 당량이고, (B)성분의 당량은 아민 당량이다. 0.7 이상이면, 반응성, 경화 후의 액상 에폭시 수지 조성물의 내습 신뢰성, 내마이그레이션성이 양호하고, 한편, 1.2 이하면, 증점 배율이 너무 높아지지 않고, 보이드의 발생이 억제된다.(B) is a ratio of 0.7 to 1.2 equivalents relative to 1 equivalent of the component (A), preferably 0.7 to 1.0 equivalents. The equivalent amount of the component (A) is the epoxy equivalent, and the equivalent amount of the component (B) is the amine equivalent. If it is 0.7 or more, the reactivity and the moisture-proof reliability and migration resistance of the liquid epoxy resin composition after curing are good. On the other hand, if it is 1.2 or less, the viscosity increase rate is not excessively increased and the generation of voids is suppressed.
(C)성분은, 경화 후의 액상 에폭시 수지 조성물의 선팽창 계수의 관점에서, 액상 에폭시 수지 조성물 100질량부에 대해, 55∼75질량부면 바람직하다.The component (C) is preferably 55 to 75 parts by mass with respect to 100 parts by mass of the liquid epoxy resin composition, from the viewpoint of the linear expansion coefficient of the liquid epoxy resin composition after curing.
(D)성분은, (A)성분 : 100질량부에 대해, 바람직하게는 0.05∼5.0질량부, 보다 바람직하게는 0.1∼3.0질량부 함유된다. 0.05질량부 이상이면, 액상 에폭시 수지 조성물의 밀착성이 향상하고, 경화 후의 액상 에폭시 수지 조성물의 내습 신뢰성이 보다 양호하게 되고, 5.0질량부 이하면, 액상 에폭시 수지 조성물의 발포가 억제된다.(D) is contained in an amount of preferably 0.05 to 5.0 parts by mass, more preferably 0.1 to 3.0 parts by mass, per 100 parts by mass of the component (A). When the amount is 0.05 parts by mass or more, the adhesion of the liquid epoxy resin composition is improved, and the humidity resistant reliability of the liquid epoxy resin composition after curing becomes better. When the amount is 5.0 parts by mass or less, foaming of the liquid epoxy resin composition is suppressed.
액상 에폭시 수지 조성물은, 또한, (E) 폴리알킬실록산(Si에 결합하는 알킬기로서는, 메틸, 디메틸, 에틸 등을 들 수 있다)을 포함하면, 액상 에폭시 수지 조성물의 유동 특성을 개량하고, 필렛 형상을 변화시킬 수 있기 때문에, 바람직하다. (E)성분으로서는, 폴리알킬디메틸실록산이면, 보다 바람직하다. (E)성분의 시판품으로서는, 도레·다우코닝제 폴리알킬디메틸실록산(품명 : SF8421)을 들 수 있다. (E)성분은, 단독이라도 2종 이상을 병용하여도 좋다.When the liquid epoxy resin composition further contains (E) a polyalkylsiloxane (the alkyl group bonded to Si is exemplified by methyl, dimethyl, ethyl and the like), the flow property of the liquid epoxy resin composition is improved, Can be changed. As the component (E), a polyalkyldimethylsiloxane is more preferred. As a commercially available product of the component (E), a polyalkyl dimethyl siloxane (trade name: SF8421) manufactured by Dow Corning Toray Co., Ltd. may be mentioned. The component (E) may be used alone or in combination of two or more.
액상 에폭시 수지 조성물은, (F) 블록코폴리머를 포함하면, 액상 에폭시 수지 조성물의 유동 특성을 개량하고, 필렛 형상을 변화시킬 수 있기 때문에, 바람직하다. 이 (F)성분으로서는, 아크릴 코폴리머 등의 블록코폴리머를 들 수 있고, 메타크릴산메틸과 아크릴산부틸의 블록코폴리머이면, 보다 바람직하다. (F)성분의 시판품으로서는, 알케마제 블록코폴리머의 아크릴 코폴리머, 품명 : M52N, 분자량 : 80000∼100000을 들 수 있다. (F)성분은, 단독이라도 2종 이상을 병용하여도 좋다.The liquid epoxy resin composition is preferably a (F) block copolymer because it can improve the flow characteristics of the liquid epoxy resin composition and change the shape of the fillet. As the component (F), a block copolymer such as an acrylic copolymer may be mentioned, and a block copolymer of methyl methacrylate and butyl acrylate is more preferable. As a commercially available product of the component (F), an acrylic copolymer of an alchimer block copolymer, trade name: M52N, molecular weight: 80000 to 100000 can be mentioned. The component (F) may be used alone or in combination of two or more.
(E)성분은, 필렛 형상의 관점에서, 액상 에폭시 수지 조성물 100질량부에 대해, 2∼8질량부면 바람직하다.The component (E) is preferably 2 to 8 parts by mass with respect to 100 parts by mass of the liquid epoxy resin composition from the viewpoint of the fillet shape.
(F)성분은, 필렛 형상의 관점에서, 액상 에폭시 수지 조성물 100질량부에 대해, 4∼10질량부면 바람직하다.The component (F) is preferably 4 to 10 parts by mass with respect to 100 parts by mass of the liquid epoxy resin composition from the viewpoint of the fillet shape.
본 발명의 액상 에폭시 수지 조성물에는, 본 발명의 목적을 손상시키지 않는 범위에서, 또한 필요에 응하여, 경화 촉진제, 포접(包接) 화합물, 레벨링제, 이온 트랩제, 소포제, 요변제(搖變劑), 산화 방지제, 안료, 염료 등의 첨가제를 배합할 수 있다.The liquid epoxy resin composition of the present invention may contain a curing accelerator, an inclusion compound, a leveling agent, an ion trap agent, an antifoaming agent, a thixotropic agent ), An antioxidant, a pigment, and a dye.
액상 에폭시 수지 조성물은, 경화 후의 유리 전이 온도(Tg)가, 110∼200℃이고, 120∼200℃면 바람직하다. Tg가 110℃ 미만에서는, 고온에서의 강도가 저하되기 때문에, 최고 온도가 110∼120℃인 환경 시험에서의 신뢰성에 뒤떨어져 버리고, Tg가 200℃를 초과하면, 너무 단단해져서, 필렛 크랙이 발생하기 쉬워지고, 또한, 경화시의 수축이 커짐에 의해, 반도체 장치에 휘어짐이 발생하기 쉽게 되고, 흡수율도 높아지기 쉽게 되어 버린다.The liquid epoxy resin composition preferably has a glass transition temperature (Tg) after curing of 110 to 200 캜 and 120 to 200 캜. If the Tg is less than 110 deg. C, the strength at high temperature is lowered, and thus the reliability of the environmental test at the maximum temperature of 110 to 120 deg. C is inferior. When the Tg exceeds 200 deg. C, And the shrinkage at the time of curing becomes large, warping easily occurs in the semiconductor device, and the water absorption rate tends to become high.
액상 에폭시 수지 조성물은, 온도 : 25℃에서의 점도가 5∼20Pa·s면, 주입성의 관점에서 바람직하다. 여기서, 점도는, 브룩필드제 HBT형 점도계(형번 : DV-I)로 측정한다.The liquid epoxy resin composition is preferable from the viewpoint of injection property if the viscosity at 25 ° C is 5 to 20 Pa · s. Here, the viscosity is measured with a Brookfield HBT type viscometer (Model No. DV-I).
본 발명의 에폭시 수지 조성물은, 칩과 기판의 간극이 5∼25㎛인 파인 피치의 배선 패턴을 갖는 플립칩 본딩을 이용하는 액상 반도체 밀봉제에 적합하다.The epoxy resin composition of the present invention is suitable for a liquid-state semiconductor encapsulant using flip-chip bonding having a fine-pitch wiring pattern having a gap of 5 to 25 mu m between the chip and the substrate.
[액상 에폭시 수지 조성물의 제조 방법][Method of producing liquid epoxy resin composition]
본 발명의 액상 에폭시 수지 조성물의 제조 방법은, (D)성분을, 아미노페놀형 에폭시 수지를 제외한 (A)성분에 분산시켜, 마스터배치로 한 후, 마스터배치에, 아미노페놀형 에폭시 수지와 (B)성분을 혼합하는 것을 특징으로 한다.The method for producing a liquid epoxy resin composition of the present invention is a method for producing a liquid epoxy resin composition which comprises dispersing a component (D) in a component (A) except for an aminophenol type epoxy resin to prepare a master batch, B) are mixed together.
(D)성분을, 아미노페놀형 에폭시 수지를 제외한 (A)성분에 분산시켜, 마스터배치로 하는 공정에 의해, 액상 에폭시 수지 조성물 중에서의 (D)성분의 분리, (D)성분과 아미노페놀형 에폭시 수지와의 튕김(ハジキ)을 억제할 수 있고, 모든 원료를 동시에 혼합하는 경우와 비교하여, 용이하게 액상 에폭시 수지 조성물을 제조할 수 있다.(D) in the liquid epoxy resin composition by a step of dispersing the component (D) in the component (A) except for the aminophenol-type epoxy resin to obtain a master batch, The liquid epoxy resin composition can be easily produced as compared with the case where all the raw materials are mixed at the same time.
여기서, 마스터배치를 제작할 때, (D)성분과 혼합하는 아미노페놀형 에폭시 수지를 제외한 (A)성분은, (C)성분 : 100질량부에 대해, 10∼1000질량부면 바람직하고, 50∼500질량부면, 보다 바람직하다.When preparing the master batch, the component (A) except for the aminophenol type epoxy resin to be mixed with the component (D) is preferably 10 to 1000 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of the component (C) Mass surface, more preferably.
마스터배치를 제작할 때에는, 필요에 의해 가열 처리를 가하면서, 교반, 용융, 혼합, 분산시킴에 의해 얻을 수 있다. 이들 혼합, 교반, 분산 등의 장치로서는, 특히 한정되는 것은 아니지만, 교반, 가열 장치를 구비하는 뢰괴기, 3본 롤밀, 볼밀, 플라네터리 믹서, 비즈밀 등을 사용할 수 있다. 또한, 이들 장치를 적절히 조합시켜서 사용하여도 좋다.When the master batch is produced, it can be obtained by stirring, melting, mixing and dispersing, while applying a heat treatment as necessary. The mixing, stirring, and dispersing apparatuses are not particularly limited, and examples thereof include a stirring apparatus, a crucible having a heating device, a three-roll mill, a ball mill, a planetary mixer, and a bead mill. These devices may be used in appropriate combination.
마스터배치에, 아미노페놀형 에폭시 수지를 포함하는 (A)성분의 잔부와 (D)성분을 혼합할 때에, 혼합하는 순서는, 특히, 한정되지 않는다. 혼합하는 방법은, 마스터배치를 제작하는 경우와 마찬가지면 좋다.The order of mixing the remainder of the component (A) containing the aminophenol type epoxy resin and the component (D) in the master batch is not particularly limited. The mixing method may be the same as in the case of producing the master batch.
본 발명의 액상 에폭시 수지 조성물은, 디스펜서, 인쇄 등으로 기판의 소망하는 위치에 형성·도포된다. 여기서, 액상 에폭시 수지 조성물은, 플렉시블 배선 기판 등의 기판과 반도체 소자와의 사이에, 적어도 일부가 기판의 배선상에 접하도록 형성한다.The liquid epoxy resin composition of the present invention is formed and applied at desired positions on a substrate by a dispenser, printing, or the like. Here, the liquid epoxy resin composition is formed such that at least a part of the liquid epoxy resin composition is in contact with a substrate such as a flexible wiring substrate and a semiconductor element on the wirings of the substrate.
본 발명의 액상 수지 조성물의 경화는, 90∼170℃, 60∼180분간 행하는 것이 바람직하고, 특히 120분 이내에 경화시키면, 반도체 장치에 이용하는 밀봉제로서 생산성 향상 때문에 바람직하다.The liquid resin composition of the present invention is preferably cured at 90 to 170 DEG C for 60 to 180 minutes, and particularly preferably when it is cured within 120 minutes because of the improvement in productivity as a sealing agent for semiconductor devices.
[액상 반도체 밀봉제][Liquid semiconductor sealing agent]
본 발명의 액상 반도체 밀봉제는, 상술한 액상 에폭시 수지 조성물을 포함하고, 칩과 기판의 간극이 5∼25㎛인 플립칩형 반도체 장치용의 액상 반도체 밀봉제에 적합하다.The liquid-state semiconductor encapsulant of the present invention is suitable for a liquid-semiconductor encapsulant for a flip-chip type semiconductor device which contains the above-described liquid epoxy resin composition and has a gap between the chip and the substrate of 5 to 25 mu m.
[반도체 장치][Semiconductor device]
본 발명의 반도체 장치는, 상술한 액상 반도체 밀봉제를 이용하여 밀봉된다. 반도체 소자, 기판은, 소망하는 것을 사용할 수 있지만, 칩과 기판의 간극이 5∼25㎛인 플립칩형 반도체 장치라면, 본 발명의 효과를 발휘하기 위해 적합하다. 또한, 구리(銅) 필러를 구비하는 플립칩형 반도체 장치에 대해서도, 본 발명의 효과를 발휘할 수 있다.The semiconductor device of the present invention is sealed using the liquid semiconductor encapsulant described above. Any desired semiconductor device or substrate can be used, but it is preferable to use the flip-chip type semiconductor device having a gap between the chip and the substrate of 5 to 25 mu m in order to exert the effect of the present invention. Further, the effect of the present invention can be exerted also for a flip-chip type semiconductor device having a copper (Cu) filler.
실시례Example
본 발명에 관해, 실시례에 의해 설명하지만, 본 발명은 이들로 한정되는 것이 아니다. 또한, 이하의 실시례에서, 부, %는 단서가 없는 한, 질량부, 질량%를 나타낸다.The present invention will be described by way of examples, but the present invention is not limited thereto. In the following examples, "parts" and "%" denote parts by mass and% by mass, respectively, unless otherwise specified.
[실시례 1∼14, 비교례 1∼6][Examples 1 to 14, Comparative Examples 1 to 6]
표 1∼3에 표시하는 배합으로 원료를 혼합한 후, 실온에서 3본 롤밀을 이용하여 분산하여, 액상 에폭시 수지 조성물(이하, 「수지 조성물」이라고 한다)을 제작하였다. 또한, 실시례 14만은, (D)성분을, 아미노페놀형 에폭시 수지를 제외한 (A)성분과 (C)성분으로, 실온에서 혼합한 후, 3본 롤밀로 분산시켜, 마스터배치로 한 후, 마스터배치에, 아미노페놀형 에폭시 수지와 (B)성분을, 실온에서 혼합한 후, 3본 롤밀로 분산함에 의해 제작하였다.The raw materials were mixed in the formulations shown in Tables 1 to 3 and then dispersed at room temperature using a three-roll mill to prepare a liquid epoxy resin composition (hereinafter referred to as "resin composition"). In Example 14 only, the component (D) was mixed with the components (A) and (C) except for the aminophenol type epoxy resin at room temperature and then dispersed with a three-roll mill to prepare a master batch. The masterbatch was prepared by mixing the aminophenol type epoxy resin and the component (B) at room temperature and then dispersing the resulting mixture in a three-roll mill.
[점도의 평가][Evaluation of viscosity]
제작한 액상 에폭시 수지 조성물의 점도(초기 점도, 단위 : Pa·s)를, 브룩필드사제 DV-1형 점도계/14호 스핀들을 이용하여, 25℃, 50rpm으로 1분간 회전시킨 때의 점도(표 1∼3에는, 점도(50rpm)로 기재하였다)를 측정하였다. 다음에, 액상 에폭시 수지 조성물을, DV-1형 점도계/14호 스핀들을 이용하여, 25℃, 50rpm과 5rpm으로 1분간 회전시킨 때의 점도를 측정하였다. 얻어진 [(50rpm에서의 점도)/(5rpm에서의 점도)]로부터 틱소트로픽 지수(TI)를 구하였다. TI는, 0.5∼1.1이면 바람직하다. 표 1∼3에, 결과를 표시한다.Viscosity (initial viscosity, unit: Pa · s) of the prepared liquid epoxy resin composition was measured using a Brookfield DV-1 type viscometer / No. 14 spindle at 25 ° C and 50 rpm for one
[주입성의 평가][Evaluation of injection property]
도 1에, 액상 에폭시 수지 조성물의 주입성의 평가 방법을 설명하는 모식도를 도시한다. 우선, 도 1(A)에 도시하는 바와 같이, 기판(20)상에, 50㎛ 또는 25㎛의 간극(40)을 마련하여, 반도체 소자 대신에 유리판(30)을 고정한 시험편을 제작하였다. 단, 기판(20)으로서는, 플렉시블 기판 대신에 유리 기판을 사용하였다. 다음에, 이 시험편을 110℃로 설정한 핫 플레이트상에 올려놓고, 도 1(B)에 도시하는 바와 같이, 유리판(30)의 일단측에, 제작한 수지 조성물(10)을 도포하고, 도 1(C)에 도시하는 바와 같이, 간극(40)이 수지 조성물(11)로 채워질 때까지의 시간을 측정하였다. 표 1∼3에, 결과를 표시한다.Fig. 1 shows a schematic diagram for explaining a method of evaluating the injectability of a liquid epoxy resin composition. First, as shown in Fig. 1 (A), a
[유리 전이점(Tg)의 평가][Evaluation of glass transition point (Tg)] [
동적 점탄성 측정(DMA)으로 측정하였다. 지지체상에, 폭 : 40㎜, 길이 : 70㎜, 두께 : 2㎜로 도포한 액상 에폭시 수지 조성물을, 165℃로 120분간, 가열 경화시키고, 지지체로부터 박리한 후, 그 접착성 필름으로부터 시험편(10±0.5㎜×50±1㎜)을 절출(切出)하고, 시험편의 폭, 두께를 측정하였다. 그 후, SII제 동적 점탄성 측정 장치(형번 : DMS6100)로 측정을 행하였다(3℃/min 25-300℃). tanD의 피크 온도를 판독하고, Tg로 하였다. 표 1∼3에, 결과를 표시한다.And measured by dynamic viscoelasticity measurement (DMA). The liquid epoxy resin composition coated on the support with a width of 40 mm, a length of 70 mm and a thickness of 2 mm was heated and cured at 165 DEG C for 120 minutes and peeled off from the support. 10 ± 0.5 mm × 50 ± 1 mm) was cut out, and the width and thickness of the test piece were measured. Thereafter, the measurement was carried out with a dynamic viscoelasticity measuring device (model number: DMS 6100) manufactured by SII (3 ° C / min 25-300 ° C). The peak temperature of tanD was read and determined as Tg. The results are shown in Tables 1 to 3.
[필렛 크랙 발생률의 평가][Evaluation of Fillet Crack Occurrence Rate]
Cu 필러의 범프로, 칩 사이즈가 10㎜□, 기판이 30㎜□의 TEG를 사용하였다. 그 TEG에, 액상 에폭시 수지 조성물을 도포하고, 165℃로 120분간, 가열 경화시켰다. 액상 에폭시 수지 조성물을 경화시킨 TEG에, -55℃, 30분간과 125℃, 30분간을 1사이클로 하는 서멀 사이클을 걸었다. 500사이클 후, 필렛 크랙의 길이를 계측하고, 칩 주변의 길이(40㎜)로 나누어, 필렛 크랙 발생률을 산출하였다. 필렛 크랙 발생률은, 65% 이하면 바람직하다. 도 2∼4에, 필렛 크랙을 설명하기 위한 사진을 도시한다. 도 2는, 필렛 크랙이 발생하지 않은 개소의 사진이다. 도 3은, 본 발명을 이용하여 필렛 크랙의 발생량을 억제한 개소의 사진이다. 도 3에서는, 필렛 크랙이 발생한 개소(3개소)를 화살표로 나타낸다. 도 4는, 필렛 크랙이 다량으로 발생한 개소의 사진이다. 도 4에서는, 필렛 크랙이 발생한 개소(7개소)을 화살표로 나타낸다.As the bump of the Cu filler, a TEG having a chip size of 10 mm square and a substrate of 30 mm square was used. The TEG was coated with a liquid epoxy resin composition and cured by heating at 165 DEG C for 120 minutes. The TEG obtained by curing the liquid epoxy resin composition was subjected to thermal cycling at -55 占 폚 for 30 minutes and at 125 占 폚 for 30 minutes as one cycle. After 500 cycles, the length of the fillet crack was measured and divided by the length (40 mm) around the chip to calculate the fillet crack occurrence rate. The incidence of fillet cracks is preferably 65% or less. Figs. 2 to 4 show photographs for explaining a fillet crack. Fig. 2 is a photograph of a portion where a fillet crack did not occur. Fig. 3 is a photograph of a portion where the amount of cracking of the fillet is suppressed by using the present invention. In Fig. 3, the points (three points) where the fillet cracks occur are indicated by arrows. Fig. 4 is a photograph of a place where a large number of fillet cracks occurred. In Fig. 4, the points (7 points) where the fillet cracks occur are indicated by arrows.
[표 1][Table 1]
[표 2][Table 2]
[표 3][Table 3]
표 1∼3으로 부터 알 수 있는 바와 같이, 실시례 1∼18의 전부에서, 점도, 틱소트로픽 계수, 주입성, 유리 전이점, 필렛 크랙 발생률의 평가 결과가 양호하였다. 또한, 표 1에 기재하지 않지만, (D)성분을, 아미노페놀형 에폭시 수지를 제외한 (A)성분과 마스터배치로 한 후, 마스터배치에, 아미노페놀형 에폭시 수지와 (B)성분을, 실온에서 혼합한 실시례 14는, 액상 에폭시 수지 조성물의 보존 특성이, 다른 실시례와 비교하고 양호하였다.As can be seen from Tables 1 to 3, evaluation results of the viscosity, the thixotropic coefficient, the injection property, the glass transition point, and the incidence of fillet cracks were satisfactory in all of Examples 1 to 18. Although not shown in Table 1, the component (D) was masterbatched with the component (A) except for the aminophenol-type epoxy resin, and the aminophenol-type epoxy resin and the component (B) In Example 14, the storage characteristics of the liquid epoxy resin composition were better than those of the other examples.
이에 대해, 아미노페놀 에폭시 수지를 함유하지 않는 비교례 1에서는, 필렛 크랙 발생률이 높았다. 아미노페놀 에폭시 수지의 함유율이 너무 낮은 비교례 2∼4에서는, 20㎛ 간극에서의 주입성이 나쁘고, 필렛 크랙 발생률도 높았다. 아미노페놀 에폭시 수지의 함유율이 너무 높은 비교례 5에서는, 유리 전이점이 너무 높고, 신뢰성을 확보할 수 없는 값이고, 또한 필렛 크랙 발생률도 높았다. (B)성분의 당량비가 낮고, 유리 전이점이 너무 낮은 비교례 6은, 유리 전이점이 너무 낮고, 신뢰성을 확보할 수 없는 값이었다.On the other hand, in Comparative Example 1 in which the aminophenol epoxy resin was not contained, the incidence of fillet cracks was high. In Comparative Examples 2 to 4 where the content of the aminophenol epoxy resin was too low, the injectability at a gap of 20 占 퐉 was poor and the rate of occurrence of fillet crack was also high. In Comparative Example 5 in which the content of the aminophenol epoxy resin was too high, the glass transition point was too high, the reliability could not be ensured, and the rate of occurrence of fillet crack was also high. Comparative Example 6 in which the equivalence ratio of the component (B) was low and the glass transition point was too low had a glass transition point too low, and the reliability could not be ensured.
상기한 바와 같이, 본 발명의 액상 에폭시 수지 조성물은, 파인 피치의 배선 패턴을 갖는 플립칩형 반도체 장치에의 주입성에 우수하고, 또한 경화 후에 필렛 크랙을 억제할 수 있기 때문에, 액상 반도체 밀봉제에 적합하다.As described above, the liquid epoxy resin composition of the present invention is excellent in injectability into a flip-chip type semiconductor device having a fine pitch wiring pattern and can suppress the fillet crack after curing, so that it is suitable for a liquid semiconductor encapsulant Do.
10, 11 : 액상 수지 조성물
20 ; 기판
30 ; 유리판
40 ; 간극10, 11: Liquid resin composition
20; Board
30; Glass plate
40; Clearance
Claims (12)
(A)성분 100질량부에 대해, 아미노페놀형 에폭시 수지를 10.0∼70질량부를 포함하고,
(B)성분이, (A)성분 : 1당량에 대해, 0.7∼1.2당량의 비율이고,
경화 후의 유리 전이 온도가, 110∼200℃인 것을 특징으로 하는, 액상 에폭시 수지 조성물.(A) a liquid epoxy resin comprising an amino phenol type epoxy resin, (B) an amine type curing agent, (C) a silica filler and (D) a silane coupling agent,
, 10.0 to 70 parts by mass of an aminophenol type epoxy resin relative to 100 parts by mass of the component (A)
(B) is in a ratio of 0.7 to 1.2 equivalents based on 1 equivalent of the component (A)
Wherein the glass transition temperature after curing is 110 to 200 占 폚.
(A)성분에 포함되는 아미노페놀형 에폭시 수지가, 식(1) :
[화학식 10]
로 표시되는 것을 특징으로 하는 액상 에폭시 수지 조성물.The method according to claim 1,
Wherein the aminophenol-type epoxy resin contained in the component (A)
[Chemical formula 10]
Lt; RTI ID = 0.0 > 1, < / RTI >
(B)성분이, 화학식(2)∼(4) :
[화학식 11]
[화학식 12]
[화학식 13]
의 적어도 하나로 표시되는 아민계 경화제를 포함하는 것을 특징으로 하는 액상 에폭시 수지 조성물.The method according to claim 1,
(B) is at least one compound selected from the group consisting of formulas (2) to (4):
(11)
[Chemical Formula 12]
[Chemical Formula 13]
And an amine curing agent represented by at least one of the following formula (1).
(C)성분의 평균입경이, 0.1∼3.0㎛이고, 또한, 액상 에폭시 수지 조성물 100질량부에 대해, (C)성분이 55∼75질량부인 것을 특징으로 하는 액상 에폭시 수지 조성물.The method according to claim 1,
Wherein the average particle diameter of the component (C) is 0.1 to 3.0 占 퐉, and the component (C) is 55 to 75 parts by mass based on 100 parts by mass of the liquid epoxy resin composition.
또한, (E) 폴리알킬실록산을 포함하는 것을 특징으로 하는 액상 에폭시 수지 조성물.The method according to claim 1,
The liquid epoxy resin composition according to any one of claims 1 to 3, further comprising (E) a polyalkylsiloxane.
또한, (F) 블록코폴리머를 포함하는 것을 특징으로 하는 액상 에폭시 수지 조성물.The method according to claim 1,
The liquid epoxy resin composition according to claim 1, further comprising (F) a block copolymer.
(D)성분을, 아미노페놀형 에폭시 수지를 제외한 (A)성분의 적어도 일부에 분산시켜, 마스터배치로 한 후, 마스터배치에, 아미노페놀형 에폭시 수지를 포함하는 (A)성분의 잔부와 (B)성분을 혼합함에 의해 얻어지는 것을 특징으로 하는 액상 에폭시 수지 조성물.The method according to claim 1,
(D) is dispersed in at least a part of the component (A) except for the aminophenol type epoxy resin to prepare a master batch, and then the remainder of the component (A) containing the aminophenol type epoxy resin and the (B). ≪ / RTI >
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| JP2018119032A (en) * | 2017-01-23 | 2018-08-02 | 株式会社ダイセル | Curable resin composition for light reflection and cured product thereof, and optical semiconductor device |
| KR20190104063A (en) * | 2017-01-23 | 2019-09-05 | 주식회사 다이셀 | Curable resin composition for light reflecting, its hardened | cured material, and optical semiconductor device |
| KR102489346B1 (en) * | 2017-01-23 | 2023-01-18 | 주식회사 다이셀 | Curable Epoxy Resin Composition |
| WO2018181603A1 (en) * | 2017-03-31 | 2018-10-04 | 日立化成株式会社 | Liquid epoxy resin composition, semiconductor device, and method for producing semiconductor device |
| TWI787295B (en) | 2017-06-29 | 2022-12-21 | 日商昭和電工材料股份有限公司 | Resin composition for encapsulation, semiconductor package and method of producing semiconductor package |
| JP6920723B2 (en) * | 2017-07-14 | 2021-08-18 | ナミックス株式会社 | NCF for pressure mounting |
| CN110527046A (en) * | 2019-08-19 | 2019-12-03 | 湖北三选科技有限公司 | Modify diamine type benzoxazine resin and preparation method and its application in liquid wafer-level packaging material as stress release agent |
| JP7099490B2 (en) * | 2020-05-07 | 2022-07-12 | 昭和電工マテリアルズ株式会社 | Liquid resin composition for encapsulation and electronic component equipment |
| CN112457808A (en) * | 2020-11-20 | 2021-03-09 | 湖北三选科技有限公司 | Low-warpage high-adhesion liquid mold sealing adhesive for gallium nitride power device and preparation method |
| CN118510843A (en) * | 2022-01-18 | 2024-08-16 | 松下知识产权经营株式会社 | Liquid sealing resin composition and semiconductor device |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050068690A (en) * | 2003-12-30 | 2005-07-05 | 제일모직주식회사 | Liquid epoxy compsoition for semiconductor packaging |
| JP2006016429A (en) * | 2004-06-30 | 2006-01-19 | Shin Etsu Chem Co Ltd | Epoxy resin composition for semiconductor sealing |
| JP2012162585A (en) * | 2011-02-03 | 2012-08-30 | Namics Corp | Resin sealng material for semiconductor |
| JP2012193284A (en) | 2011-03-16 | 2012-10-11 | Namics Corp | Liquid epoxy resin composition |
| JP2013001811A (en) * | 2011-06-16 | 2013-01-07 | Hitachi Chemical Co Ltd | Resin composition for electronic component and electronic component device |
| JP2013527869A (en) * | 2010-04-19 | 2013-07-04 | トリリオン サイエンス インク | One-component epoxy resin with low shrinkage adhesive |
| JP2014227465A (en) * | 2013-05-22 | 2014-12-08 | 京セラケミカル株式会社 | Liquid resin compositions for injection molding, and semiconductor device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200948888A (en) * | 2008-04-16 | 2009-12-01 | Henkel Corp | Flow controllable B-stageable composition |
| JP5862176B2 (en) * | 2011-10-06 | 2016-02-16 | 日立化成株式会社 | Selection method and manufacturing method of liquid epoxy resin composition, and manufacturing method of electronic component device |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050068690A (en) * | 2003-12-30 | 2005-07-05 | 제일모직주식회사 | Liquid epoxy compsoition for semiconductor packaging |
| JP2006016429A (en) * | 2004-06-30 | 2006-01-19 | Shin Etsu Chem Co Ltd | Epoxy resin composition for semiconductor sealing |
| JP2013527869A (en) * | 2010-04-19 | 2013-07-04 | トリリオン サイエンス インク | One-component epoxy resin with low shrinkage adhesive |
| JP2012162585A (en) * | 2011-02-03 | 2012-08-30 | Namics Corp | Resin sealng material for semiconductor |
| JP2012193284A (en) | 2011-03-16 | 2012-10-11 | Namics Corp | Liquid epoxy resin composition |
| JP2013001811A (en) * | 2011-06-16 | 2013-01-07 | Hitachi Chemical Co Ltd | Resin composition for electronic component and electronic component device |
| JP2014227465A (en) * | 2013-05-22 | 2014-12-08 | 京セラケミカル株式会社 | Liquid resin compositions for injection molding, and semiconductor device |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20230024030A (en) * | 2021-08-11 | 2023-02-20 | 한국생산기술연구원 | Self-healing epoxy adhesive |
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