JP7099453B2 - 封止用フィルム、封止構造体及び封止構造体の製造方法 - Google Patents
封止用フィルム、封止構造体及び封止構造体の製造方法 Download PDFInfo
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- JP7099453B2 JP7099453B2 JP2019514667A JP2019514667A JP7099453B2 JP 7099453 B2 JP7099453 B2 JP 7099453B2 JP 2019514667 A JP2019514667 A JP 2019514667A JP 2019514667 A JP2019514667 A JP 2019514667A JP 7099453 B2 JP7099453 B2 JP 7099453B2
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Images
Classifications
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- 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
- 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
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
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- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
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Description
本実施形態の封止用フィルムは、熱硬化性成分及び無機充填材を含有するフィルム状の樹脂組成物である。本実施形態の封止用フィルムは、熱硬化性成分として、下記式(1)で表される構造単位を有する熱硬化性樹脂を含有する。
熱硬化性成分としては、熱硬化性樹脂、硬化剤、硬化促進剤等が挙げられる。熱硬化性成分は、硬化剤及び/又は硬化促進剤を含むことなく、熱硬化性樹脂を含んでいてもよい。また、熱硬化性成分は、少なくとも上記式(1)で表される構造単位を有する熱硬化性樹脂(以下、「第1の熱硬化性樹脂」ともいう。)を含有するが、第1の熱硬化性樹脂以外の熱硬化性樹脂(以下、「第2の熱硬化性樹脂」ともいう。)を更に含有していてもよい。
第1の熱硬化性樹脂は少なくとも上記式(1)で表される構造単位を有する。
第2の熱硬化性樹脂としては、エポキシ樹脂、フェノール樹脂、フェノキシ樹脂、シアネート樹脂、熱硬化性ポリイミド、メラミン樹脂、尿素樹脂、不飽和ポリエステル、アルキド樹脂、ポリウレタン等が挙げられる。第2の熱硬化性樹脂が有する反応性官能基は、第1の熱硬化性樹脂が有する反応性官能基と熱により反応する官能基であることが好ましい。例えば、第1の熱硬化性樹脂が有する反応性官能基が水酸基(フェノール性水酸基)である場合、第2の熱硬化性樹脂が有する反応性官能基はエポキシ基であることが好ましい。換言すれば、第1の熱硬化性樹脂がフェノール樹脂である場合、第2の熱硬化性樹脂はエポキシ樹脂であることが好ましい。この場合、機械的強度に優れると共に、硬化時の収縮が少なく、寸法安定性に優れる。また、耐熱性、耐水性及び耐薬品性に優れ、電気絶縁性に優れる。第2の熱硬化性樹脂が有する反応性官能基は、第1の熱硬化性樹脂が有する反応性官能基と同一であってよい。例えば、第1の熱硬化性樹脂が有する反応性官能基が水酸基(フェノール性水酸基)である場合、第2の熱硬化性樹脂が有する反応性官能基は水酸基(フェノール性水酸基)であってよい。この場合、熱硬化性成分として硬化剤を用いることができる。
硬化剤(熱硬化性樹脂に該当する成分は除く)としては、特に限定されないが、フェノール系硬化剤、酸無水物系硬化剤、活性エステル系硬化剤、シアネートエステル系硬化剤などが挙げられる。硬化剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
硬化促進剤としては、特に制限なく用いることができるが、アミン系の硬化促進剤及びリン系の硬化促進剤からなる群より選ばれる少なくとも1種が好ましい。硬化促進剤としては、特に、優れた熱伝導率を有する硬化物が得られやすい観点、誘導体が豊富である観点、及び、所望の活性温度が得られやすい観点から、アミン系の硬化促進剤が好ましく、イミダゾール化合物、脂肪族アミン及び脂環族アミンからなる群より選ばれる少なくとも1種がより好ましく、イミダゾール化合物が更に好ましい。イミダゾール化合物としては、2-フェニル-4-メチルイミダゾール、1-ベンジル-2-メチルイミダゾール等が挙げられる。硬化促進剤は、1種を単独で用いてもよく、2種以上を併用してもよい。硬化促進剤の市販品としては、四国化成工業株式会社製の「2P4MZ」及び「1B2MZ」等が挙げられる。
無機充填剤としては、従来公知の無機充填剤を使用でき、特に限定されない。無機充填剤の構成材料としては、シリカ類(無定形シリカ、結晶性シリカ、溶融シリカ、球状シリカ、合成シリカ、中空シリカ等)、硫酸バリウム、チタン酸バリウム、タルク、クレー、雲母粉、炭酸マグネシウム、炭酸カルシウム、酸化アルミニウム(アルミナ)、水酸化アルミニウム、酸化マグネシウム、水酸化マグネシウム、窒化ケイ素、窒化アルミニウム、ホウ酸アルミニウム、窒化ホウ素、チタン酸バリウム、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸マグネシウム、チタン酸ビスマス、酸化チタン、ジルコン酸バリウム、ジルコン酸カルシウムなどが挙げられる。表面改質(例えば、シラン化合物による表面処理)等により、樹脂組成物中での分散性の向上効果、及び、ワニス中での沈降抑制効果が得られやすい観点、並びに、比較的小さい熱膨張率を有するために所望の硬化膜特性が得られやすい観点では、シリカ類を含む無機充填材が好ましい。高い熱伝導性が得られる観点では、酸化アルミニウムを含む無機充填材が好ましい。無機充填剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
本実施形態の封止用フィルムは、必要に応じて、エラストマー(可とう剤)を含有してもよい。エラストマーは、分散性及び溶解性に優れる観点から、ポリブタジエン粒子、スチレンブタジエン粒子、アクリル系エラストマー、シリコーンパウダ、シリコーンオイル及びシリコーンオリゴマからなる群より選ばれる少なくとも1種を用いることが好ましい。エラストマーは、1種を単独で用いてもよく、2種以上を併用してもよい。
本実施形態の封止用フィルムは、他の添加剤を更に含有することができる。このような添加剤の具体例としては、顔料、染料、離型剤、酸化防止剤、表面張力調整剤等を挙げることができる。
本実施形態の封止用フィルムは、具体的には、次のようにして作製することができる。
本実施形態に係る封止構造体は、被封止体と、当該被封止体を封止する封止部と、を備える。封止部は、本実施形態の封止用フィルムの硬化物であり、本実施形態の樹脂組成物の硬化物を含んでいる。封止構造体は、中空構造を有する中空封止構造体であってよい。中空封止構造体は、例えば、基板と、基板上に設けられた被封止体と、基板と被封止体との間に設けられた中空領域と、被封止体を封止する封止部と、を備える。本実施形態の封止構造体は、複数の被封止体を備えていてもよい。複数の被封止体は、互いに同一の種類であってもよく、互いに異なる種類であってもよい。
A1:ビスフェノールF型エポキシ樹脂(三菱化学株式会社製、商品名「jER806」、エポキシ基当量:160g/eq.)
B1:炭化水素基含有フェノール樹脂(フェノール性水酸基当量:140g/eq.、重量平均分子量:12万)
B2:炭化水素基含有フェノール樹脂(フェノール性水酸基当量:185g/eq.、重量平均分子量:12万)
B3:炭化水素基含有フェノール樹脂(フェノール性水酸基当量:243g/eq.、重量平均分子量:12万)
B4:炭化水素基含有フェノール樹脂(フェノール性水酸基当量:205g/eq.、重量平均分子量:12万)
B5:ノボラック型フェノール樹脂(明和化成株式会社製、商品名「DL-92」、フェノール性水酸基当量:103g/eq.、重量平均分子量:5万)
C1:イミダゾール(四国化成工業株式会社製、商品名「2P4MZ」)
D1:アクリル酸エステルポリマー(ナガセケムテックス株式会社製、商品名「SG-280 EK23」、分子量90万)
E1:シリカ(株式会社アドマテックス製、商品名「5μm SX-E2」、フェニルアミノシラン処理、平均粒径:5.8μm)
まず、カルダノールと、メタノールと、50%ホルムアルデヒド水溶液とを混合して、混合液を得た。次いで、得られた混合液に30%水酸化ナトリウム水溶液を滴下して反応させた後、得られた反応液に35%塩酸を添加して水酸化ナトリウムを中和した。次いで、反応液にフェノールを添加した後、更にシュウ酸を添加した。次いで、反応液の水洗を行った後、過剰のフェノールを留去した。これにより、下記式(5)で表される構造単位40モル%と、下記式(6)で表される構造単位60モル%とからなる樹脂B1を得た。
まず、4-tert-ブチルフェノールと、メタノールと、50%ホルムアルデヒド水溶液とを混合して、混合液を得た。次いで、得られた混合液に30%水酸化ナトリウム水溶液を滴下して反応させた後、得られた反応液に35%塩酸を添加して水酸化ナトリウムを中和した。次いで、反応液に4-フェニルフェノールを添加した後、更にシュウ酸を添加した。次いで、反応液の水洗を行った後、過剰の4-フェニルフェノールを留去した。これにより、下記式(7)で表される構造単位50モル%と、下記式(8)で表される構造単位50モル%とからなる樹脂B2を得た。
まず、4-(1,1,3,3-テトラメチルブチル)フェノールと、メタノールと、50%ホルムアルデヒド水溶液とを混合して、混合液を得た。次いで、得られた混合液に30%水酸化ナトリウム水溶液を滴下して反応させた。これにより、下記式(9)で表される構造単位からなる樹脂B3を得た。
まず、カルダノールと、メタノールと、50%ホルムアルデヒド水溶液とを混合して、混合液を得た。次いで、得られた混合液に30%水酸化ナトリウム水溶液を滴下して反応させた後、得られた反応液に35%塩酸を添加して水酸化ナトリウムを中和した。次いで、反応液にペンチルフェノールを添加した後、更にシュウ酸を添加した。次いで、反応液の水洗を行った後、過剰のペンチルフェノールを留去した。これにより、上記式(5)で表される構造単位75モル%と、下記式(10)で表される構造単位25モル%からなる樹脂B4を得た。
(実施例1)
0.5Lのポリエチレン容器に、表1に示す量(質量部)のA1、B1、D1、及びE1を加えて、撹拌羽で撹拌し、無機充填材E1を分散した。その後、表1に示す量(質量部)のC1を加えて、更に30分撹拌した。得られた混合液をナイロン製#150メッシュ(開口106μm)でろ過して、ろ液を採取した。これによりワニス状エポキシ樹脂組成物を得た。このワニス状エポキシ樹脂組成物を、塗工機を使用してPETフィルム上に、以下の条件で塗布した。これにより、厚さ110μmの封止用フィルムを支持体(PETフィルム)上に作製した。
・塗布ヘッド方式:コンマ
・塗布及び乾燥速度:1m/分
・乾燥条件(温度/炉長):80℃/1.5m、100℃/1.5m
・支持体:厚さ38μmのPETフィルム
使用した材料(A1、B1、C1、D1、及びE1)の種類及び配合量を表1に示すように変更したこと以外は、実施例1と同様にして、実施例2~4及び比較例1~2のワニス状エポキシ樹脂組成物を得た。次いで、実施例1のワニス状エポキシ樹脂に代えて、実施例2~4及び比較例1~2のワニス状エポキシ樹脂組成物をそれぞれ用いたこと以外は、実施例1と同様にして、実施例2~4及び比較例1~2の封止用フィルム(厚さ110μm)を得た。
以下の方法で、封止用フィルムの溶融粘度、埋め込み性及び中空非充填性、並びに、封止用フィルムの硬化後の弾性率及びガラス転移温度の評価を行った。
封止用フィルム0.6gを量り取り、圧縮成型機にて直径2cmのタブレット状に成形した。得られた成形物を評価用サンプルとし、以下の条件にて、封止用フィルムの溶融粘度を測定した。測定は、温度を40℃から200℃まで昇温することにより行った。
測定装置:レオメータ製品名:TAインスツルメントジャパン株式会社製ARES-G2
測定モード:Dynamic Temperature Ramp
周波数:1.0Hz
温度範囲:40℃~200℃
昇温速度:5℃/分
以下の方法で、封止温度70℃における封止用フィルムの埋め込み性及び中空非充填性を評価した。まず、主面の中央に貫通孔(直径1mm)を設けた基板(5cm×5cm)を用意した。次いで、当該基板の一方の主面上における上記貫通孔の縁から2cm離れた位置に両面テープを張り付け、両面テープを介して基板上にガラス板を貼り付けた。得られた積層体を、ガラス板側の面を下にして配置し、基板のガラス板とは反対側の面上に、貫通孔を塞ぐように、1cm角サイズの封止用フィルムを配置した。次いで、封止フィルム上に100gの重りを載せた後70℃のオーブン(エスペック株式会社製、商品名「SAFETY OVEN SPH-201」)内で1時間加熱した。
[埋め込み性]
A:ガラス基板まで樹脂が到達
B:ガラス基板まで樹脂が未到達
[中空非充填性]
A:流れ込み面積≦2.5mm2
B:流れ込み面積≦5mm2、>2.5mm2
C:流れ込み面積>5mm2
評価Aの溶融粘度の測定結果に基づき、封止用フィルムの溶融粘度が7000Pa・sとなる温度で封止を行ったこと以外は、評価Bと同様の方法で埋め込み性及び中空非充填性を評価した。
以下の条件で、実施例及び比較例の封止用フィルムを銅箔にラミネートし、銅箔付き封止用フィルムを得た。
・ラミネータ装置:名機製作所製真空加圧ラミネータMVLP-500
・ラミネート温度:110℃
・ラミネート圧力:0.5MPa
・真空引き時間:30秒
・ラミネート時間:40秒
・オーブン:エスペック株式会社製SAFETY OVEN SPH-201
・オーブン温度:140℃
・時間:120分
・測定装置:DVE(株式会社レオロジ製DVE-V4)
・測定温度:25~300℃
・昇温速度:5℃/min
A:弾性率(30℃)≦15GPa
B:弾性率(30℃)>15GPa
A:ガラス転移温度(℃)≧100
B:ガラス転移温度(℃)<100
結果を表1に示す。なお、表1中の各成分の配合量は、固形分量(溶剤の量を除いた量)である。
Claims (8)
- 前記熱硬化性樹脂の重量平均分子量は500以上である、請求項1又は2に記載の封止用フィルム。
- 膜厚は20~250μmである、請求項1~3のいずれか一項に記載の封止用フィルム。
- 基板と、当該基板上にバンプを介して設けられた被封止体と、を備え、前記基板と前記被封止体との間に中空領域が設けられている、中空構造体を用意し、
請求項1~4のいずれか一項に記載の封止用フィルムにより前記被封止体を封止する、封止構造体の製造方法。 - 前記被封止体は、前記中空領域側に電極を有するSAWデバイスである、請求項5に記載の封止構造体の製造方法。
- 基板と、当該基板上にバンプを介して設けられた被封止体と、当該被封止体を封止する請求項1~4のいずれか一項に記載の封止用フィルムの硬化物と、を備え、
前記基板と前記被封止体との間に中空領域が設けられている、封止構造体。 - 前記被封止体は、前記中空領域側に電極を有するSAWデバイスである、請求項7に記載の封止構造体。
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