JP2021187923A - 樹脂組成物 - Google Patents
樹脂組成物 Download PDFInfo
- Publication number
- JP2021187923A JP2021187923A JP2020093146A JP2020093146A JP2021187923A JP 2021187923 A JP2021187923 A JP 2021187923A JP 2020093146 A JP2020093146 A JP 2020093146A JP 2020093146 A JP2020093146 A JP 2020093146A JP 2021187923 A JP2021187923 A JP 2021187923A
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- resin composition
- resin
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- epoxy resin
- Prior art date
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- 239000004065 semiconductor Substances 0.000 claims abstract description 62
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- 125000003118 aryl group Chemical group 0.000 claims abstract description 39
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- 238000004458 analytical method Methods 0.000 description 1
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- RRZKHZBOZDIQJG-UHFFFAOYSA-N azane;manganese Chemical compound N.[Mn] RRZKHZBOZDIQJG-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
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- 229910002115 bismuth titanate Inorganic materials 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
- XSEUMFJMFFMCIU-UHFFFAOYSA-N buformin Chemical compound CCCC\N=C(/N)N=C(N)N XSEUMFJMFFMCIU-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- DAQREMPZDNTSMS-UHFFFAOYSA-M butyl(triphenyl)phosphanium;thiocyanate Chemical compound [S-]C#N.C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 DAQREMPZDNTSMS-UHFFFAOYSA-M 0.000 description 1
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- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- VUFGUVLLDPOSBC-XRZFDKQNSA-M cephalothin sodium Chemical compound [Na+].N([C@H]1[C@@H]2N(C1=O)C(=C(CS2)COC(=O)C)C([O-])=O)C(=O)CC1=CC=CS1 VUFGUVLLDPOSBC-XRZFDKQNSA-M 0.000 description 1
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- FCEOGYWNOSBEPV-FDGPNNRMSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FCEOGYWNOSBEPV-FDGPNNRMSA-N 0.000 description 1
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
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- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
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- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
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- 239000006082 mold release agent Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- MZYHMUONCNKCHE-UHFFFAOYSA-N naphthalene-1,2,3,4-tetracarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=C(C(O)=O)C(C(O)=O)=C21 MZYHMUONCNKCHE-UHFFFAOYSA-N 0.000 description 1
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- JFOJYGMDZRCSPA-UHFFFAOYSA-J octadecanoate;tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JFOJYGMDZRCSPA-UHFFFAOYSA-J 0.000 description 1
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- PRCNQQRRDGMPKS-UHFFFAOYSA-N pentane-2,4-dione;zinc Chemical compound [Zn].CC(=O)CC(C)=O.CC(=O)CC(C)=O PRCNQQRRDGMPKS-UHFFFAOYSA-N 0.000 description 1
- CUQCMXFWIMOWRP-UHFFFAOYSA-N phenyl biguanide Chemical compound NC(N)=NC(N)=NC1=CC=CC=C1 CUQCMXFWIMOWRP-UHFFFAOYSA-N 0.000 description 1
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- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- GHPYAGKTTCKKDF-UHFFFAOYSA-M tetraphenylphosphanium;thiocyanate Chemical compound [S-]C#N.C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 GHPYAGKTTCKKDF-UHFFFAOYSA-M 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
-
- 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
- C08G59/42—Polycarboxylic 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
- 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
-
- 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
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- C—CHEMISTRY; METALLURGY
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/12—Mountings, e.g. non-detachable insulating substrates
- H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
- H01L23/145—Organic substrates, e.g. plastic
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- 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
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Abstract
Description
すなわち、本発明は、下記の内容を含む。
[1] (A)エポキシ樹脂、
(B)酸無水物系硬化剤、アミン系硬化剤、及びフェノール系硬化剤から選ばれる少なくとも1種の硬化剤、
(C)芳香族構造を有するポリエステルポリオール樹脂、及び
(D)無機充填材、を含み、
(C)成分の含有量が、樹脂組成物中の不揮発成分を100質量%とした場合、2質量%以上20質量%以下である、樹脂組成物。
[2] (A)成分が、縮合環骨格を含む、[1]に記載の樹脂組成物。
[3] (C)成分の末端が、ヒドロキシ基及びカルボキシル基のいずれかである、[1]又は[2]に記載の樹脂組成物。
[4] (D)成分の含有量が、樹脂組成物中の不揮発成分を100質量%とした場合、60質量%以上95質量%以下である、[1]〜[3]のいずれかに記載の樹脂組成物。
[5] (C)成分が、ポリエステル由来の構造及びポリオール由来の構造を有する樹脂である、[1]〜[4]のいずれかに記載の樹脂組成物。
[6] ポリオール由来の構造が、エチレンオキシド構造、プロピレンオキシド構造、及びブチレンオキシド構造のいずれかを含む、[5]に記載の樹脂組成物。
[7] (C)成分が、ビスフェノール骨格を有する、[1]〜[6]のいずれかに記載の樹脂組成物。
[8] (C)成分の樹脂組成物中の不揮発成分を100質量%とした場合の含有量をc1とし、(D)成分の樹脂組成物中の不揮発成分を100質量%とした場合の含有量をd1としたとき、d1/c1が、5以上70以下である、[1]〜[7]のいずれかに記載の樹脂組成物。
[9] 封止層用である、[1]〜[8]のいずれかに記載の樹脂組成物。
[10] 支持体と、該支持体上に設けられた、[1]〜[9]のいずれかに記載の樹脂組成物を含む樹脂組成物層とを含む、樹脂シート。
[11] [1]〜[9]のいずれかに記載の樹脂組成物の硬化物により形成された硬化物層を含む、回路基板。
[12] [11]に記載の回路基板と、該回路基板上に搭載された半導体チップとを含む、半導体チップパッケージ。
[13] [1]〜[9]のいずれかに記載の樹脂組成物、もしくは[10]に記載の樹脂シートにより封止された半導体チップを含む半導体チップパッケージ。
本発明の樹脂組成物は、(A)エポキシ樹脂、(B)酸無水物系硬化剤、アミン系硬化剤、及びフェノール系硬化剤から選ばれる少なくとも1種の硬化剤、(C)芳香族構造を有するポリエステルポリオール樹脂、及び(D)無機充填材、を含み、(C)成分の含有量が、樹脂組成物中の不揮発成分を100質量%とした場合、2質量%以上20質量%以下である。このような樹脂組成物を用いることにより、高い接合強度を有し且つ反りの発生が抑制された硬化物を得ることが可能となる。また、本発明では、通常、熱膨張係数(CTE)が低い硬化物を得ることもできる。
樹脂組成物は、(A)成分として、(A)エポキシ樹脂を含有する。(A)エポキシ樹脂としては、例えば、ビキシレノール型エポキシ樹脂;ビスフェノールA型エポキシ樹脂;ビスフェノールF型エポキシ樹脂;ビスフェノールS型エポキシ樹脂;ビスフェノールAF型エポキシ樹脂;ジシクロペンタジエン型エポキシ樹脂;トリスフェノール型エポキシ樹脂;フェノールノボラック型エポキシ樹脂;グリシジルアミン型エポキシ樹脂;グリシジルエステル型エポキシ樹脂;クレゾールノボラック型エポキシ樹脂;ビフェニル型エポキシ樹脂;線状脂肪族エポキシ樹脂;ブタジエン構造を有するエポキシ樹脂;脂環式エポキシ樹脂;複素環式エポキシ樹脂;スピロ環含有エポキシ樹脂;シクロヘキサン型エポキシ樹脂;シクロヘキサンジメタノール型エポキシ樹脂;トリメチロール型エポキシ樹脂;テトラフェニルエタン型エポキシ樹脂;ナフチレンエーテル型エポキシ樹脂、tert−ブチル−カテコール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ナフトール型エポキシ樹脂、アントラセン型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂等の縮合環骨格を含有するエポキシ樹脂等が挙げられる。エポキシ樹脂は、1種類単独で用いてもよく、2種類以上を組み合わせて用いてもよい。中でも、(A)エポキシ樹脂としては、本発明の効果を顕著に得る観点から、縮合環骨格を含有するエポキシ樹脂を含むことが好ましい。
樹脂の重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)法により、ポリスチレン換算の値として測定できる。
樹脂組成物は、(B)成分として、(B)酸無水物系硬化剤、アミン系硬化剤、及びフェノール系硬化剤から選ばれる少なくとも1種の硬化剤を含有する。硬化剤は、通常、(A)成分と反応して樹脂組成物を硬化させる機能を有するが、特にこれら硬化剤を樹脂組成物に含有させることで、(A)成分と反応して樹脂組成物を硬化させる機能に加えて、反りの発生が抑制された硬化物を得ることが可能となる。(B)成分は、1種類単独で用いてもよく、2種類以上を組み合わせて用いてもよい。
樹脂組成物は、(C)成分として(C)芳香族構造を有するポリエステルポリオール樹脂を含有する。(C)成分を樹脂組成物に含有させることでその硬化物の応力が緩和され、その結果、高い接合強度を有し且つ硬化物の反りの発生が抑制された硬化物を得ることが可能となる。また、(C)成分が応力を緩和する作用を発揮できるので、通常、硬化物の熱膨張係数(CTE)を低くできる。(C)成分は、1種類単独で用いてもよく、2種類以上を組み合わせて用いてもよい。
樹脂組成物は、(D)無機充填材を含有する。(D)無機充填材を樹脂組成物に含有させることで、熱膨張係数に優れた硬化物を得ることが可能となる。
樹脂組成物は、上述した成分以外に、任意の成分として、更に、(E)硬化促進剤を含んでいてもよい。(E)硬化促進剤を含有させることにより、硬化時間等を効率的に調整することができる。
樹脂組成物は、揮発性成分として、さらに任意の溶剤を含有していてもよい。溶剤としては、例えば、有機溶剤が挙げられる。また、溶剤は、1種を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。溶剤は、量が少ないほど好ましい。溶剤の量は、樹脂組成物中の不揮発成分100質量%に対して、好ましくは3質量%以下、より好ましくは1質量%以下、更に好ましくは0.5質量%以下、更に好ましくは0.1質量%以下、更に好ましくは0.01質量%以下であり、含まないこと(0質量%)が特に好ましい。また、樹脂組成物は、このように溶剤の量が少ない場合に、ペースト状であってもよい。ペースト状の樹脂組成物の25℃における粘度は、20Pa・s〜1000Pa・sの範囲内にあることが好ましい。
樹脂組成物は、上述した成分以外に、任意の成分として、更にその他の添加剤を含んでいてもよい。このような添加剤としては、例えば、熱可塑性樹脂;(B)成分以外の硬化剤;有機充填材;増粘剤、消泡剤、レベリング剤、密着性付与剤、難燃剤等の樹脂添加剤;などが挙げられる。これらの添加剤は、1種類単独で用いてもよく、2種類以上を組み合わせて用いてもよい。
樹脂組成物を180℃で90分間熱硬化させた硬化物は、接合強度が優れるという特性を示す。接合強度は、例えば、シェア強度によって表しうる。よって、前記の硬化物は、通常、シェア強度に優れる絶縁層又は封止層をもたらす。シェア強度としては、好ましくは2kgf/mm2以上である。シェア強度の評価は、後述する実施例に記載の方法に従って測定することができる。
本発明の樹脂シートは、支持体と、該支持体上に設けられた樹脂組成物層と、を有する。樹脂組成物層は、本発明の樹脂組成物を含む層であり、通常は、樹脂組成物で形成されている。
本発明の回路基板は、本発明の樹脂組成物の硬化物により形成された硬化物層を含む。硬化物層は絶縁層又は封止層となりうる。この回路基板は、例えば、下記の工程(1)及び工程(2)を含む製造方法によって、製造できる。
(1)基材上に、樹脂組成物層を形成する工程。
(2)樹脂組成物層を熱硬化して、絶縁層を形成する工程。
例えば、樹脂シートを用いて回路基板を製造した場合、回路基板の製造方法は、樹脂シートの支持体を剥離する工程を含んでいてもよい。支持体は、樹脂組成物層の熱硬化の前に剥離してもよく、樹脂組成物層の熱硬化の後に剥離してもよい。
本発明の第一実施形態に係る半導体チップパッケージは、上述した回路基板と、この回路基板に搭載された半導体チップとを含む。この半導体チップパッケージは、回路基板に半導体チップを接合することにより、製造することができる。
(A)基材に仮固定フィルムを積層する工程、
(B)半導体チップを、仮固定フィルム上に仮固定する工程、
(C)本発明の樹脂シートの樹脂組成物層を、半導体チップ上に積層、又は本発明の樹脂組成物を半導体チップ上に塗布し、熱硬化させて封止層を形成する工程、
(D)基材及び仮固定フィルムを半導体チップから剥離する工程、
(E)半導体チップの基材及び仮固定フィルムを剥離した面に再配線形成層(絶縁層)を形成する工程、
(F)再配線形成層(絶縁層)上に導体層(再配線層)を形成する工程、及び
(G)導体層上にソルダーレジスト層を形成する工程、を含む。また、半導体チップパッケージの製造方法は、(H)複数の半導体チップパッケージを個々の半導体チップパッケージにダイシングし、個片化する工程を含み得る。
上述した半導体チップパッケージが実装される半導体装置としては、例えば、電気製品(例えば、コンピューター、携帯電話、スマートフォン、タブレット型デバイス、ウェラブルデバイス、デジタルカメラ、医療機器、及びテレビ等)及び乗物(例えば、自動二輪車、自動車、電車、船舶及び航空機等)等に供される各種半導体装置が挙げられる。
シリカA:平均粒径1.8μm、比表面積3.5m2/g、N−フェニル−3−アミノプロピルトリメトキシシラン(信越化学工業社製「KBM−573」)で表面処理されたシリカ。
シリカB:平均粒径3.2μm、比表面積4.6m2/g、3−グリシドキシプロピルトリメトキシシラン(信越化学工業社製「KBM−403」)で表面処理されたシリカ。
アルミナA:平均粒径6.2μm、比表面積1.7m2/g、N−フェニル−3−アミノプロピルトリメトキシシラン(信越化学工業社製「KBM−573」)で表面処理されたアルミナ。
反応装置に、ビスフェノールA型グリコールエーテル(ハイブロックスMDB−561、DIC社製)を779.1質量部と、イソフタル酸を132.9質量部と、セバシン酸を40.4質量部仕込み、昇温と撹拌を開始した。
次いで、内温を230℃に上昇した後、テトライソプロピルチタネートを0.10質量部仕込み、230℃で24時間反応させ芳香族構造を有するポリエステルポリオール樹脂Aを合成した。得られた芳香族構造を有するポリエステルポリオール樹脂Aは、両末端にOH基を有し、その水酸基価は36.9mgKOH/g、数平均分子量は3040、ガラス転移温度は−14℃、75℃における粘度は9Pa・sであった。
反応装置に、ビスフェノールA型グリコールエーテル(ハイブロックスMDB−561、DIC社製)を596.8質量部と、セバシン酸257.4質量部を仕込み昇温と攪拌を開始した。
次いで、内温を230℃に上昇した後、テトライソプロピルチタネート0.10質量部仕込み、230℃で24時間反応させ芳香族構造を有するポリエステルポリオール樹脂Bを合成した。得られた芳香族構造を有するポリエステルポリオール樹脂Bは、その両末端に−COOH基を有し、その酸価は36.6mgKOH/g、数平均分子量は3070、ガラス転移温度は−33℃、75℃における粘度は12Pa・sであった。
脂環式エポキシ樹脂(ダイセル社製、「CEL2021P」、エポキシ当量136g/eq.)6.6部、ナフタレン型エポキシ樹脂(DIC社製、「HP4032D」、エポキシ当量142g/eq.)8部、アミン系硬化剤(日本化薬社製、「カヤハードA−A」)0.5部、合成例1で合成した芳香族構造を有するポリエステルポリオール樹脂A 2.5部、シリカA 80部、硬化促進剤(四国化成社製、「2MA−OK」)0.4部をミキサーを用いて均一に分散して樹脂組成物1を得た。
実施例1において、芳香族構造を有するポリエステルポリオール樹脂A 0.5部を、芳香族構造を有するポリエステルポリオール樹脂B 0.5部に変えた。以上の事項以外は実施例1と同様にして樹脂組成物2を作製した。
脂環式エポキシ樹脂(ダイセル社製、「CEL2021P」、エポキシ当量136g/eq.)3部、ナフタレン型エポキシ樹脂(DIC社製、「HP4032D」、エポキシ当量142g/eq.)3部、酸無水物系硬化剤(新日本理化社製、「MH−700」)10部、合成例1で合成した芳香族構造を有するポリエステルポリオール樹脂A 4部、シリカA 100部、硬化促進剤(四国化成社製、「2MA−OK」)0.5部をミキサーを用いて均一に分散して樹脂組成物3を得た。
実施例3において、
芳香族構造を有するポリエステルポリオール樹脂A 4部を、芳香族構造を有するポリエステルポリオール樹脂B 8部に変え、
シリカA 100部を、アルミナA 130部に変えた。
以上の事項以外は実施例3と同様にして樹脂組成物4を作製した。
脂環式エポキシ樹脂(ダイセル社製、「CEL2021P」、エポキシ当量136g/eq.)7部、ナフタレン型エポキシ樹脂(DIC社製、「HP4032D」、エポキシ当量142g/eq.)8部、フェノール系硬化剤(2、2―ジアリルビスフェノールA)1部、合成例1で合成した芳香族構造を有するポリエステルポリオール樹脂A 2部、シリカA 70部、硬化促進剤(四国化成社製、「2MA−OK」)0.4部をミキサーを用いて均一に分散して樹脂組成物5を得た。
実施例2において、芳香族構造を有するポリエステルポリオール樹脂A 2.5部を用いなかった。以上の事項以外は実施例2と同様にして樹脂組成物6を作製した。
実施例3において、芳香族構造を有するポリエステルポリオール樹脂Aの量を4部から0.5部に変えた。以上の事項以外は実施例3と同様にして樹脂組成物7を作製した。
実施例3において、芳香族構造を有するポリエステルポリオール樹脂Aの量を4部から35部に変えた。以上の事項以外は実施例3と同様にして樹脂組成物8を作製した。
ポリイミドが塗布されたシリコンウエハ上に、直径4mmにくり抜いたシリコンラバー枠を用いて、実施例及び比較例で作製した樹脂組成物1〜8を高さ5mmの円柱状に充填した。180℃90分加熱した後、シリコンラバー枠を外すことで、樹脂組成物の硬化物からなる試験片を作製した。ボンドテスター(Dage社製 シリーズ4000)にてヘッド位置が基材から1mm、ヘッドスピード700μm/sの条件でポリイミドと試験片の界面のシェア強度を測定した。試験は5回実施し、その平均値を用い、以下の基準で評価した。
〇:2kgf/mm2以上の場合
×:2kgf/mm2未満の場合
12インチシリコンウエハ上に、実施例及び比較例で調製した樹脂組成物を、コンプレッションモールド装置(金型温度:130℃、圧力:6MPa、キュアタイム:10分)を用いて圧縮成型して、厚さ300μmの樹脂組成物層を形成した。その後、180℃で90分加熱して、樹脂組成物層を熱硬化させた。これにより、シリコンウエハと樹脂組成物の硬化物層とを含む試料基板を得た。シャドウモアレ測定装置(Akorometrix社製「ThermoireAXP」)を用いて、前記の試料基板を25℃での反り量を測定した。測定は、電子情報技術産業協会規格のJEITA EDX−7311−24に準拠して行った。具体的には、測定領域の基板面の全データの最小二乗法によって算出した仮想平面を基準面として、その基準面から垂直方向の最小値と最大値との差を反り量として求めた。反り量が2mm未満を「○」、2mm以上を「×」と評価した。
離型処理した12インチシリコンウエハ上に、実施例及び比較例で作製した樹脂組成物1〜8を、コンプレッションモールド装置(金型温度:130℃、圧力:6MPa、キュアタイム:10分)を用いて圧縮成型して、厚さ300μmの樹脂組成物層を形成した。その後、離型処理したシリコンウエハから樹脂組成物層を剥がし、180℃で90分間加熱して樹脂組成物層を熱硬化させ硬化物サンプルを作製した。硬化物サンプルを幅5mm、長さ15mmに切断して、試験片を得た。この試験片について、熱機械分析装置(リガク社製「ThermoPlus TMA8310」)を用いて、引張加重法にて熱機械分析を行った。詳細には、試験片を前記熱機械分析装置に装着した後、荷重1g、昇温速度5℃/分の測定条件にて、連続して2回測定を行った。そして、2回目の測定において、25℃から150℃までの範囲における平面方向の熱膨張係数(ppm/℃)を算出し、以下の基準で評価した。
〇:13ppm/℃未満の場合
×:13ppm/℃以上の場合
Claims (13)
- (A)エポキシ樹脂、
(B)酸無水物系硬化剤、アミン系硬化剤、及びフェノール系硬化剤から選ばれる少なくとも1種の硬化剤、
(C)芳香族構造を有するポリエステルポリオール樹脂、及び
(D)無機充填材、を含み、
(C)成分の含有量が、樹脂組成物中の不揮発成分を100質量%とした場合、2質量%以上20質量%以下である、樹脂組成物。 - (A)成分が、縮合環骨格を含む、請求項1に記載の樹脂組成物。
- (C)成分の末端が、ヒドロキシ基及びカルボキシル基のいずれかである、請求項1又は2に記載の樹脂組成物。
- (D)成分の含有量が、樹脂組成物中の不揮発成分を100質量%とした場合、60質量%以上95質量%以下である、請求項1〜3のいずれか1項に記載の樹脂組成物。
- (C)成分が、ポリエステル由来の構造及びポリオール由来の構造を有する樹脂である、請求項1〜4のいずれか1項に記載の樹脂組成物。
- ポリオール由来の構造が、エチレンオキシド構造、プロピレンオキシド構造、及びブチレンオキシド構造のいずれかを含む、請求項5に記載の樹脂組成物。
- (C)成分が、ビスフェノール骨格を有する、請求項1〜6のいずれか1項に記載の樹脂組成物。
- (C)成分の樹脂組成物中の不揮発成分を100質量%とした場合の含有量をc1とし、(D)成分の樹脂組成物中の不揮発成分を100質量%とした場合の含有量をd1としたとき、d1/c1が、5以上70以下である、請求項1〜7のいずれか1項に記載の樹脂組成物。
- 封止層用である、請求項1〜8のいずれか1項に記載の樹脂組成物。
- 支持体と、該支持体上に設けられた、請求項1〜9のいずれか1項に記載の樹脂組成物を含む樹脂組成物層とを含む、樹脂シート。
- 請求項1〜9のいずれか1項に記載の樹脂組成物の硬化物により形成された硬化物層を含む、回路基板。
- 請求項11に記載の回路基板と、該回路基板上に搭載された半導体チップとを含む、半導体チップパッケージ。
- 請求項1〜9のいずれか1項に記載の樹脂組成物、もしくは請求項10に記載の樹脂シートにより封止された半導体チップを含む半導体チップパッケージ。
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