JP2023159622A - 樹脂組成物 - Google Patents
樹脂組成物 Download PDFInfo
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- JP2023159622A JP2023159622A JP2022069431A JP2022069431A JP2023159622A JP 2023159622 A JP2023159622 A JP 2023159622A JP 2022069431 A JP2022069431 A JP 2022069431A JP 2022069431 A JP2022069431 A JP 2022069431A JP 2023159622 A JP2023159622 A JP 2023159622A
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- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
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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
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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
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
-
- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
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Abstract
Description
すなわち、本発明は、下記のものを含む。
R1は、置換基を有していてもよい炭素原子数7以上の鎖状脂肪族炭化水素基を表し、
R2は、置換基を有していてもよい炭化水素基を表し、
nは、1以上の数を表し、
mは、0以上の数を表す。
ただし、R1には、置換基を有していてもよい炭素原子数7以上の鎖状不飽和脂肪族炭化水素基が含まれる。)
[2] (A)成分が、1,000以下の重量平均分子量を有する、[1]に記載の樹脂組成物。
[3] (A)成分が、式(a-1)~式(a-4)のいずれかで表される樹脂又はその組み合わせである、[1]又は[2]に記載の樹脂組成物。
[4] (A)成分の量が、樹脂組成物中の不揮発成分100質量%に対して、0.01質量%以上10質量%以下である、[1]~[3]のいずれか一項に記載の樹脂組成物。
[5] (D)無機充填材を含む、[1]~[4]のいずれか一項に記載の樹脂組成物。
[6] (A)成分及び(C)成分以外の(E)硬化剤を含む、[1]~[5]のいずれか一項に記載の樹脂組成物。
[7] (F)硬化促進剤を含む、[1]~[6]のいずれか一項に記載の樹脂組成物。
[8] (G)熱可塑性樹脂を含む、[1]~[7]のいずれか一項に記載の樹脂組成物。
[9] プリント配線板の絶縁層形成用である、[1]~[8]のいずれか一項に記載の樹脂組成物。
[10] [1]~[9]のいずれか1項に記載の樹脂組成物の硬化物。
[11] [1]~[9]のいずれか1項に記載の樹脂組成物を含む、シート状積層材料。
[12] 支持体と、当該支持体上に形成された樹脂組成物層と、を備え、
樹脂組成物層が、[1]~[9]のいずれか1項に記載の樹脂組成物を含む、樹脂シート。
[13] [1]~[9]の何れか1項に記載の樹脂組成物の硬化物を含む絶縁層を備える、回路基板。
[14] [1]~[9]の何れか1項に記載の樹脂組成物の硬化物を含む、半導体チップパッケージ。
[15] [13]記載の回路基板を備える、半導体装置。
[16] [14]に記載の半導体チップパッケージを備える、半導体装置。
本発明の一実施形態に係る樹脂組成物は、(A)下記式(A-1)で表される樹脂、(B)エポキシ樹脂、及び、(C)活性エステル化合物を含む。「(A)式(A-1)で表される樹脂」を、以下、「(A)長鎖脂肪族フェノール樹脂」ということがある。
R1は、置換基を有していてもよい炭素原子数7以上の鎖状脂肪族炭化水素基を表し、
R2は、置換基を有していてもよい炭化水素基を表し、
nは、1以上の数を表し、
mは、0以上の数を表す。
ただし、R1には、置換基を有していてもよい炭素原子数7以上の鎖状不飽和脂肪族炭化水素基が含まれる。)
本発明の一実施形態に係る樹脂組成物は、(A)成分としての(A)長鎖脂肪族フェノール樹脂を含む。(A)長鎖脂肪族フェノール樹脂は、下記式(A-1)で表されるいずれか又はその組み合わせである。
R1は、置換基を有していてもよい炭素原子数7以上の鎖状脂肪族炭化水素基を表し、
R2は、置換基を有していてもよい炭化水素基を表し、
nは、1以上の数を表し、
mは、0以上の数を表す。
ただし、R1には、置換基を有していてもよい炭素原子数7以上の鎖状不飽和脂肪族炭化水素基が含まれる。)
本発明の一実施形態に係る樹脂組成物は、(B)成分としての(B)エポキシ樹脂を含む。(B)エポキシ樹脂は、エポキシ基を有する硬化性樹脂でありうる。(B)エポキシ樹脂には、上述した(A)成分に該当するものは含めない。
本発明の一実施形態に係る樹脂組成物は、(C)成分としての(C)活性エステル化合物を含む。(C)活性エステル化合物には、上述した(A)~(B)成分に該当するものは含めない。(C)活性エステル化合物は、(B)エポキシ樹脂と反応して樹脂組成物を硬化させるエポキシ樹脂硬化剤としての機能を有しうる。(C)活性エステル化合物は、1種類を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。
本発明の一実施形態に係る樹脂組成物は、任意の成分として、(D)無機充填材を更に含んでいてもよい。(D)成分としての(D)無機充填材には、上述した(A)~(C)成分に該当するものは含めない。(D)無機充填材は、通常、粒子の状態で樹脂組成物に含まれる。
本発明の一実施形態に係る樹脂組成物は、任意の成分として、(E)任意の硬化剤を更に含んでいてもよい。(E)成分としての(E)任意の硬化剤には、上述した(A)~(D)成分に該当するものは含めない。よって、(E)任意の硬化剤は、(B)エポキシ樹脂と反応して樹脂組成物を硬化させるエポキシ樹脂硬化剤のうち、(A)長鎖脂肪族フェノール樹脂及び(C)活性エステル化合物以外の成分を表す。(E)任意の硬化剤は、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。
本発明の一実施形態に係る樹脂組成物は、任意の成分として、(F)硬化促進剤を更に含んでいてもよい。(F)成分としての(F)硬化促進剤には、上述した(A)~(E)成分に該当するものは含めない。(F)硬化促進剤は、(B)エポキシ樹脂の硬化を促進させる硬化触媒としての機能を有する。
本発明の一実施形態に係る樹脂組成物は、任意の成分として、(G)熱可塑性樹脂を更に含んでいてもよい。(G)成分としての(G)熱可塑性樹脂には、上述した(A)~(F)成分に該当するものは含めない。
本発明の一実施形態に係る樹脂組成物は、任意の成分として、(H)任意のラジカル重合性化合物を更に含んでいてもよい。(H)成分としての(H)ラジカル重合性化合物には、上述した(A)~(G)成分に該当するものは含めない。(H)ラジカル重合性化合物は、1種類を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。
本発明の一実施形態に係る樹脂組成物は、任意の成分として(I)任意の添加剤を更に含んでいてもよい。(I)任意の添加剤としては、例えば、ゴム粒子等の有機充填材;有機銅化合物、有機亜鉛化合物、有機コバルト化合物等の有機金属化合物;フタロシアニンブルー、フタロシアニングリーン、アイオディングリーン、ジアゾイエロー、クリスタルバイオレット、酸化チタン、カーボンブラック等の着色剤;ハイドロキノン、カテコール、ピロガロール、フェノチアジン等の重合禁止剤;シリコーン系レベリング剤、アクリルポリマー系レベリング剤等のレベリング剤;ベントン、モンモリロナイト等の増粘剤;シリコーン系消泡剤、アクリル系消泡剤、フッ素系消泡剤、ビニル樹脂系消泡剤等の消泡剤;ベンゾトリアゾール系紫外線吸収剤等の紫外線吸収剤;尿素シラン等の接着性向上剤;トリアゾール系密着性付与剤、テトラゾール系密着性付与剤、トリアジン系密着性付与剤等の密着性付与剤;ヒンダードフェノール系酸化防止剤等の酸化防止剤;スチルベン誘導体等の蛍光増白剤;フッ素系界面活性剤、シリコーン系界面活性剤等の界面活性剤;リン系難燃剤(例えばリン酸エステル化合物、ホスファゼン化合物、ホスフィン酸化合物、赤リン)、窒素系難燃剤(例えば硫酸メラミン)、ハロゲン系難燃剤、無機系難燃剤(例えば三酸化アンチモン)等の難燃剤;リン酸エステル系分散剤、ポリオキシアルキレン系分散剤、アセチレン系分散剤、シリコーン系分散剤、アニオン性分散剤、カチオン性分散剤等の分散剤;ボレート系安定剤、チタネート系安定剤、アルミネート系安定剤、ジルコネート系安定剤、イソシアネート系安定剤、カルボン酸系安定剤、カルボン酸無水物系安定剤等の安定剤、が挙げられる。(I)任意の添加剤は、1種類を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
本発明の一実施形態に係る樹脂組成物は、上述した(A)~(I)成分といった不揮発成分に組み合わせて、任意の揮発性成分として(J)溶剤を更に含んでいてもよい。(J)溶剤としては、通常、有機溶剤を用いる。有機溶剤としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤;酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸イソアミル、プロピオン酸メチル、プロピオン酸エチル、γ-ブチロラクトン等のエステル系溶剤;テトラヒドロピラン、テトラヒドロフラン、1,4-ジオキサン、ジエチルエーテル、ジイソプロピルエーテル、ジブチルエーテル、ジフェニルエーテル、アニソール等のエーテル系溶剤;メタノール、エタノール、プロパノール、ブタノール、エチレングリコール等のアルコール系溶剤;酢酸2-エトキシエチル、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、エチルジグリコールアセテート、γ-ブチロラクトン、メトキシプロピオン酸メチル等のエーテルエステル系溶剤;乳酸メチル、乳酸エチル、2-ヒドロキシイソ酪酸メチル等のエステルアルコール系溶剤;2-メトキシプロパノール、2-メトキシエタノール、2-エトキシエタノール、プロピレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル(ブチルカルビトール)等のエーテルアルコール系溶剤;N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン等のアミド系溶剤;ジメチルスルホキシド等のスルホキシド系溶剤;アセトニトリル、プロピオニトリル等のニトリル系溶剤;ヘキサン、シクロペンタン、シクロヘキサン、メチルシクロヘキサン等の脂肪族炭化水素系溶剤;ベンゼン、トルエン、キシレン、エチルベンゼン、トリメチルベンゼン等の芳香族炭化水素系溶剤等を挙げることができる。(J)溶剤は、1種類を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。
本発明の一実施形態に係る樹脂組成物は、例えば、上述した成分を混合することによって、製造することができる。上述した成分は、一部又は全部を同時に混合してもよく、順に混合してもよい。各成分を混合する過程で、温度を適宜設定してもよく、よって、一時的に又は終始にわたって、加熱及び/又は冷却してもよい。また、各成分を混合する過程において、撹拌又は振盪を行ってもよい。
本発明の一実施形態に係る樹脂組成物を硬化することにより、硬化物が得られる。前記の硬化の際、通常は、樹脂組成物には熱が加えられる。よって、通常、樹脂組成物に含まれる成分のうち、(J)溶剤等の揮発成分は硬化時の熱によって揮発しうるが、(A)~(I)成分といった不揮発成分は、硬化時の熱によっては揮発しない。よって、樹脂組成物の硬化物は、樹脂組成物の不揮発成分又はその反応生成物を含みうる。
本発明の一実施形態に係る樹脂組成物は、絶縁用途の樹脂組成物として使用でき、特に、絶縁層を形成するための樹脂組成物(絶縁層形成用の樹脂組成物)として好適に使用することができる。例えば、本実施形態に係る樹脂組成物は、半導体チップパッケージの絶縁層を形成するための樹脂組成物(半導体チップパッケージの絶縁層用の樹脂組成物)、及び、回路基板(プリント配線板を含む。)の絶縁層を形成するための樹脂組成物(回路基板の絶縁層用の樹脂組成物)として、好適に使用することができる。特に、樹脂組成物は、導体層と導体層との間に設けられる層間絶縁層を形成するために好適である。また、樹脂組成物は、プリント配線板の絶縁層を形成するための樹脂組成物(プリント配線板の絶縁層形成用の樹脂組成物)として特に好適である。
樹脂組成物は、ワニス状態で塗布して使用してもよいが、工業的には、該樹脂組成物を含むシート状積層材料の形態で用いることが好適である。
本発明の一実施形態に係る回路基板は、樹脂組成物の硬化物を含む。通常、回路基板は、樹脂組成物の硬化物で形成された絶縁層を備える。絶縁層は、上述した樹脂組成物の硬化物を含み、好ましくは上述した樹脂組成物の硬化物のみを含む。この回路基板は、例えば、下記の工程(I)及び工程(II)を含む製造方法によって、製造できる。
(I)内層基板上に、樹脂組成物層を形成する工程。
(II)樹脂組成物層を硬化して、絶縁層を形成する工程。
本発明の一実施形態に係る半導体チップパッケージは、樹脂組成物の硬化物を含む。通常、半導体チップパッケージは、樹脂組成物の硬化物で形成された絶縁層を含む。絶縁層は、上述した樹脂組成物の硬化物を含み、好ましくは上述した樹脂組成物の硬化物のみを含む。この半導体チップパッケージとしては、例えば、下記のものが挙げられる。
(i)基材に仮固定フィルムを積層する工程、
(ii)半導体チップを、仮固定フィルム上に仮固定する工程、
(iii)半導体チップ上に封止層を形成する工程、
(iv)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、
(v)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を形成する工程、
(vi)再配線形成層上に、導体層としての再配線層を形成する工程、並びに、
(vii)再配線層上にソルダーレジスト層を形成する工程、
を含む。また、前記の半導体チップパッケージの製造方法は、
(viii)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
を含んでいてもよい。
工程(i)は、基材に仮固定フィルムを積層する工程である。基材と仮固定フィルムとの積層条件は、回路基板の製造方法における内層基板と樹脂シートとの積層条件と同様でありうる。
工程(ii)は、半導体チップを、仮固定フィルム上に仮固定する工程である。半導体チップの仮固定は、例えば、フリップチップボンダー、ダイボンダー等の装置を用いて行うことができる。半導体チップの配置のレイアウト及び配置数は、仮固定フィルムの形状、大きさ、目的とする半導体チップパッケージの生産数等に応じて適切に設定できる。例えば、複数行で、かつ複数列のマトリックス状に半導体チップを整列させて、仮固定してもよい。
工程(iii)は、半導体チップ上に封止層を形成する工程である。封止層は、例えば、感光性樹脂組成物又は熱硬化性樹脂組成物によって形成しうる。この封止層を、上述した実施形態に係る樹脂組成物の硬化物によって形成してもよい。封止層は、通常、半導体チップ上に樹脂組成物層を形成する工程と、この樹脂組成物層を硬化させて封止層を形成する工程とを含む方法で形成できる。
工程(iv)は、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である。剥離方法は、仮固定フィルムの材質に応じた適切な方法を採用することが望ましい。剥離方法としては、例えば、仮固定フィルムを加熱、発泡又は膨張させて剥離する方法が挙げられる。また、剥離方法としては、例えば、基材を通して仮固定フィルムに紫外線を照射して、仮固定フィルムの粘着力を低下させて剥離する方法が挙げられる。
工程(v)は、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、絶縁層としての再配線形成層を形成する工程である。通常、この再配線形成層は、半導体チップ及び封止層上に形成される。再配線形成層は、上述した実施形態に係る樹脂組成物の硬化物によって形成しうる。再配線形成層は、通常、半導体チップ上に樹脂組成物層を形成する工程と、この樹脂組成物層を硬化させて再配線形成層を形成する工程とを含む方法で形成できる。半導体チップ上への樹脂組成物層の形成は、例えば、内層基板の代わりに半導体チップを用いること以外は、前記の回路基板の製造方法で説明した内層基板上への樹脂組成物層の形成方法と同じ方法で行いうる。
工程(vi)は、再配線形成層上に、導体層としての再配線層を形成する工程である。再配線形成層上に再配線層を形成する方法は、回路基板の製造方法における絶縁層上への導体層の形成方法と同様でありうる。また、工程(v)及び工程(vi)を繰り返し行い、再配線層及び再配線形成層を交互に積み上げて(ビルドアップ)もよい。
工程(vii)は、再配線層上にソルダーレジスト層を形成する工程である。ソルダーレジスト層の材料は、絶縁性を有する任意の材料を用いることができる。中でも、半導体チップパッケージの製造のしやすさの観点から、感光性樹脂組成物及び熱硬化性樹脂組成物が好ましい。ソルダーレジスト層は、上述した実施形態に係る樹脂組成物の硬化物によって形成してもよい。
半導体チップパッケージの製造方法は、工程(i)~(vii)以外に、工程(viii)を含んでいてもよい。工程(viii)は、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、個片化する工程である。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する方法は特に限定されない。
半導体装置は、上述した回路基板又は半導体チップパッケージを備える。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。
長鎖脂肪族フェノール樹脂(東北化工社製「LB-7000」、活性基当量約262g/eq.)は、下記式(a-1-1)で表されるカルダノール90%と、下記式(a-2-1)で表されるカードル10%とを含む樹脂であった。
長鎖脂肪族フェノール樹脂(東北化工社製「LB-7250」、活性基当量約273g/eq.)は、下記式(a-1-1)で表されるカルダノール95%と、下記式(a-2-1)で表されるカードル5%とを含む樹脂であった。
反応容器に、2官能性ヒドロキシ基末端ポリブタジエン(日本曹達社製「G-3000」、数平均分子量=3000、ヒドロキシ基当量=1800g/eq.)69gと、芳香族炭化水素系混合溶剤(出光興産社製「イプゾール150」)40gと、ジブチル錫ラウレート0.005gとを入れ、混合して均一に溶解させた。均一になったところで60℃に昇温し、更に撹拌しながらイソホロンジイソシアネート(エボニックジャパン社製「IPDI」、イソシアネート基当量=113g/eq.)8gを添加し、約3時間反応を行った。
ビフェニル型エポキシ樹脂(日本化薬社製「NC3000L」、エポキシ当量約269g/eq.)15部とビスフェノール型エポキシ樹脂(日鉄ケミカル&マテリアル社製「ZX1059」、ビスフェノールA型とビスフェノールF型の1:1混合品、エポキシ当量約169g/eq.)5部を、ソルベントナフサ25部に撹拌しながら加熱溶解させて、溶液を得た。この溶液を室温にまで冷却し、エポキシ樹脂の溶解組成物を調製した。
実施例1において、ビフェニル型エポキシ樹脂(日本化薬社製「NC3000L」、エポキシ当量約269g/eq.)15部とビスフェノール型エポキシ樹脂(日鉄ケミカル&マテリアル社製「ZX1059」、ビスフェノールA型とビスフェノールF型の1:1混合品、エポキシ当量約169g/eq.)5部の代わりに、ナフタレン型エポキシ樹脂(DIC社製「HP-4032-SS」、1,6-ビス(グリシジルオキシ)ナフタレン、エポキシ当量約145g/eq.)20部を用いた。また、長鎖脂肪族フェノール樹脂(東北化工社製「LB-7000」、活性基当量約262g/eq.)の量を、2部から4部に増量した。さらに、活性エステル化合物(DIC社製「HPC-8150-62T」、活性エステル基当量約220g/eq.、不揮発成分率62質量%のトルエン溶液)68部の代わりに活性エステル化合物(DIC社製「HPC-8000-65T」、活性エステル基当量約223g/eq.、不揮発成分率65%のトルエン溶液)62部用いた。以上の事項以外は、実施例1と同様にして、樹脂組成物を調製した。
実施例1において、ビフェニル型エポキシ樹脂(日本化薬社製「NC3000L」、エポキシ当量約269g/eq.)15部の代わりに、ナフトール型エポキシ樹脂(日鉄ケミカル&マテリアル社製「ESN475V」、エポキシ当量約330g/eq.)15部を用いた。また、長鎖脂肪族フェノール樹脂(東北化工社製「LB-7000」、活性基当量約262g/eq.)2部の代わりに、別の長鎖脂肪族フェノール樹脂(東北化工社製「LB-7250」、活性基当量約273g/eq.)2部を用いた。以上の事項以外は、実施例1と同様にして、樹脂組成物を調製した。
実施例3において、長鎖脂肪族フェノール樹脂(東北化工社製「LB-7250」、活性基当量約273g/eq.)2部の代わりに、別の長鎖脂肪族フェノール樹脂(東京化成工業社製「ウルシオール」、活性基当量約174g/eq.)2部を用いた。以上の事項以外は、実施例3と同様にして、樹脂組成物を調製した。
実施例1において、樹脂組成物にビフェニルアラルキルノボラック型マレイミド(日本化薬社製「MIR-3000-70MT」、不揮発成分率70%のMEK/トルエン混合溶液)を4部追加した。以上の事項以外は、実施例1と同様にして、樹脂組成物を調製した。
実施例1において、樹脂組成物にビマレイミド末端ポリイミド化合物(DMI社製「BMI-1500」)を3部追加した。以上の事項以外は、実施例1と同様にして、樹脂組成物を調製した。
実施例1において、樹脂組成物にメタクリル変性ポリフェニレンエーテル(SABICイノベーティブプラスチックス社製「SA9000-111」)を3部追加した。以上の事項以外は、実施例1と同様にして、樹脂組成物を調製した。
実施例1において、樹脂組成物にビニルベンジル変性ポリフェニレンエーテル(三菱瓦斯化学社製「OPE-2St 2200」、不揮発成分率65%のトルエン溶液)を4部追加した。以上の事項以外は、実施例1と同様にして、樹脂組成物を調製した。
実施例1において、長鎖脂肪族フェノール樹脂(東北化工社製「LB-7000」、活性基当量約262g/eq.)2部を用いなかった。以上の事項以外は、実施例1と同様にして、樹脂組成物を調製した。
実施例2において、長鎖脂肪族フェノール樹脂(東北化工社製「LB-7000」、活性基当量約262g/eq.)4部の代わりに、ノボラック型フェノール系硬化剤(DIC社製「TD-2090」、活性基当量約105g/eq.)4部を用いた。以上の事項以外は、実施例2と同様にして、樹脂組成物を調製した。
実施例1において、長鎖脂肪族フェノール樹脂(東北化工社製「LB-7000」、活性基当量約262g/eq.)2部の代わりに、応力緩和成分としてのエポキシ化ポリブタジエン樹脂(ダイセル社製「PB3600M」、エポキシ当量約193g/eq.)2.5部を用いた。以上の事項以外は、実施例1と同様にして、樹脂組成物を調製した。
実施例1において、長鎖脂肪族フェノール樹脂(東北化工社製「LB-7000」、活性基当量約262g/eq.)2部の代わりに、応力緩和成分として合成例1で調製したエラストマーXを10部用いた。以上の事項以外は、実施例1と同様にして、樹脂組成物を調製した。
支持体として、離型層を備えたポリエチレンテレフタレートフィルム(リンテック社製「AL5」、厚さ38μm)を用意した。この支持体の離型層上に、上述した実施例及び比較例で得られた樹脂組成物を、乾燥後の樹脂組成物層の厚さが40μmとなるように均一に塗布した。その後、樹脂組成物を80℃~100℃(平均90℃)で4分間乾燥させて、支持体及び樹脂組成物層を含む樹脂シートを得た。
前記の樹脂シートを200℃にて90分間加熱して樹脂組成物層を熱硬化させた後、支持体を剥離することで、樹脂組成物の硬化物で形成された硬化物フィルムを得た。硬化物フィルムを、幅2mm、長さ80mmに切り出し、評価用硬化物Aを得た。
前記の樹脂シートの樹脂組成物層を25枚重ね合わせて、1mm厚の樹脂組成物層を得た。この樹脂組成物層を直径20mmに打ち抜き、測定試料を調製した。調製した測定試料について、動的粘弾性測定装置(UBM社製「Rheogel-G3000」)を使用して、開始温度60℃から200℃まで、昇温速度5℃/min、測定温度間隔2.5℃、振動周波数1Hzの測定条件にて動的粘弾性率を測定することで、最低溶融粘度(poise)を求めた。
(1)内装基板の下地処理:
内層基板として、表面に銅箔を有するガラス布基材エポキシ樹脂両面銅張積層板(銅箔の厚さ18μm、基板の厚さ0.8mm、パナソニック社製「R1515A」)を用意した。この内層基板の表面の銅箔を、マイクロエッチング剤(メック社製「CZ8101」)を用いて、銅エッチング量1μmにてエッチングして、粗化処理を行った。その後、190℃にて30分乾燥を行った。
前記の樹脂シートを、バッチ式真空加圧ラミネーター(ニッコー・マテリアルズ社製2ステージビルドアップラミネーター「CVP700」)を用いて、樹脂組成物層が前記の内層基板と接合するように、内層基板の両面にラミネートした。このラミネートは、30秒間減圧して気圧を13hPa以下とした後、温度100℃、圧力0.74MPaにて30秒間圧着することにより、実施した。
ビアメカニクス社製のCO2レーザー加工機(LK-2K212/2C)を使用して、周波数2000Hz、パルス幅3μ秒、出力0.95W、ショット数3の条件で絶縁層を加工して、ビアホールを形成した。絶縁層表面におけるビアホールの開口径(トップ径、直径)は50μm、絶縁層底面におけるビアホールの直径は40μmであった。その後、支持体としてのポリエチレンテレフタレートフィルムを剥離して、絶縁層/内層基板/絶縁層の層構成を有する試料基板を得た。
試料基板を、膨潤液であるアトテックジャパン社製のスエリングディップ・セキュリガントPに60℃で10分間浸漬した。次に、試料基板を、粗化液であるアトテックジャパン社製のコンセントレート・コンパクトP(KMnO4:60g/L、NaOH:40g/Lの水溶液)に80℃で20分間浸漬した。最後に、試料基板を、中和液であるアトテックジャパン社製のリダクションソリューション・セキュリガントPに40℃で5分間浸漬して、デスミア処理後の試料基板として評価基板Aを得た。
得られた評価基板Aの絶縁層の表面の算術平均粗さRaを、非接触型表面粗さ計(ビーコインスツルメンツ社製WYKO NT3300)を用いて、VSIモード、50倍レンズ、測定範囲121μm×92μmの測定条件で測定した。それぞれの評価基板Aについて、無作為に選んだ10点で算術平均粗さRaを測定し、その平均値を求めた。
前記の試験例3と同様の方法で工程「(4)デスミア処理」において得た評価基板Aを、PdCl2を含む無電解めっき用溶液に40℃で5分間浸漬し、次に無電解銅めっき液に25℃で20分間浸漬した。150℃にて30分間加熱してアニール処理を行った後に、エッチングレジストを形成し、エッチングによるパターン形成の後に硫酸銅電解めっきを行い、絶縁層上に30μmの厚さの導体層を形成した。次に、アニール処理を200℃にて60分間行って、評価基板Bを得た。
(1)樹脂シートのラミネート:
L/S=8μm/8μmの配線パターンにて形成された回路導体(銅)を両面に有する内層基板(日立化成社製「MCL-E700G」、導体層の厚さ35μm、計0.4mm厚、残銅率40%)を用意した。この内層基板の両面に、樹脂組成物層が内層基板と接するように、樹脂シートをラミネートした。かかるラミネートは、真空加圧式ラミネーター(名機製作所社製「MVLP-500」)を用い、温度120℃にて30秒間真空吸引後、温度120℃、圧力7.0kg/cm2の条件で、支持体上から、耐熱ゴムを介して30秒間プレスすることにより行った。次に、大気圧下で、SUS鏡板を用いて、温度120℃、圧力5.5kg/cm2の条件で60秒間プレスを行った。
130℃で30分間加熱し、次いで170℃で30分間加熱して、樹脂組成物層を熱硬化させて、樹脂組成物の硬化物からなる硬化物層としての絶縁層を得た。その後、支持体を剥離して、絶縁層/内層基板/絶縁層の層構成を有する試料基板を得た。
試料基板の絶縁層に、粗化処理を施した。具体的には、試料基板を、膨潤液であるアトテックジャパン社製のスエリングディップ・セキュリガントPに60℃で10分間浸漬した。次に、粗化液であるアトテックジャパン社製のコンセントレート・コンパクトP(KMnO4:60g/L、NaOH:40g/Lの水溶液)に80℃で20分間浸漬した。最後に、中和液であるアトテックジャパン社製のリダクションソリューション・セキュリガントPに40℃で5分間浸漬した。
粗化処理後の絶縁層表面のうち、内層基板の配線パターン上の部分を観察した。100個の内層基板のパターン形状に沿って絶縁層の表面にクラック(割れ)が発生しているか確認し、クラックの発生していないパターン上の部分の数の割合を数えた。この割合を「歩留まり」として算出した。また、算出した歩留まりを以下の基準で点数をつけた。
1点:0%以上20%未満。
2点:20%以上40%未満。
3点:40%以上60%未満。
4点:60%以上80%未満。
5点:80%以上。
3点以上を「○」とし、2点以下を「×」として評価した。
前記の実施例及び比較例の結果を、下記の表に示す。
110 半導体チップ
120 封止層
130 再配線形成層
140 再配線層
150 ソルダーレジスト層
160 バンプ
Claims (16)
- (A)成分が、1,000以下の重量平均分子量を有する、請求項1に記載の樹脂組成物。
- (A)成分の量が、樹脂組成物中の不揮発成分100質量%に対して、0.01質量%以上10質量%以下である、請求項1に記載の樹脂組成物。
- (D)無機充填材を含む、請求項1に記載の樹脂組成物。
- (A)成分及び(C)成分以外の(E)硬化剤を含む、請求項1に記載の樹脂組成物。
- (F)硬化促進剤を含む、請求項1に記載の樹脂組成物。
- (G)熱可塑性樹脂を含む、請求項1に記載の樹脂組成物。
- プリント配線板の絶縁層形成用である、請求項1に記載の樹脂組成物。
- 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。
- 請求項1~9のいずれか1項に記載の樹脂組成物を含む、シート状積層材料。
- 支持体と、当該支持体上に形成された樹脂組成物層と、を備え、
樹脂組成物層が、請求項1~9のいずれか1項に記載の樹脂組成物を含む、樹脂シート。 - 請求項1~9の何れか1項に記載の樹脂組成物の硬化物を含む絶縁層を備える、回路基板。
- 請求項1~9の何れか1項に記載の樹脂組成物の硬化物を含む、半導体チップパッケージ。
- 請求項13に記載の回路基板を備える、半導体装置。
- 請求項14に記載の半導体チップパッケージを備える、半導体装置。
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JP2022069431A Pending JP2023159622A (ja) | 2022-04-20 | 2022-04-20 | 樹脂組成物 |
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KR (1) | KR20230149742A (ja) |
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KR102441075B1 (ko) | 2017-10-31 | 2022-09-06 | 현대자동차주식회사 | 노면표시기반 차량의 위치추정 방법 및 장치 |
KR20200136542A (ko) | 2019-05-27 | 2020-12-08 | 서울대학교산학협력단 | 나노기포를 이용한 침전물 정화 및 캐핑 장치 |
JP2020023714A (ja) | 2019-10-24 | 2020-02-13 | 積水化学工業株式会社 | 樹脂材料及び多層プリント配線板 |
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TW202346444A (zh) | 2023-12-01 |
CN116903992A (zh) | 2023-10-20 |
KR20230149742A (ko) | 2023-10-27 |
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