JP6735819B2 - 絶縁層の製造方法および多層印刷回路基板の製造方法 - Google Patents
絶縁層の製造方法および多層印刷回路基板の製造方法 Download PDFInfo
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- JP6735819B2 JP6735819B2 JP2018518421A JP2018518421A JP6735819B2 JP 6735819 B2 JP6735819 B2 JP 6735819B2 JP 2018518421 A JP2018518421 A JP 2018518421A JP 2018518421 A JP2018518421 A JP 2018518421A JP 6735819 B2 JP6735819 B2 JP 6735819B2
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Images
Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4664—Adding a circuit layer by thick film methods, e.g. printing techniques or by other techniques for making conductive patterns by using pastes, inks or powders
- H05K3/4667—Adding a circuit layer by thick film methods, e.g. printing techniques or by other techniques for making conductive patterns by using pastes, inks or powders characterized by using an inorganic intermediate insulating layer
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—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 the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
-
- 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
- H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0017—Etching of the substrate by chemical or physical means
- H05K3/0023—Etching of the substrate by chemical or physical means by exposure and development of a photosensitive insulating layer
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer
- H05K3/4676—Single layer compositions
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Description
本出願は、2016年8月9日付の韓国特許出願第10−2016−0101420号および2017年7月31日付の韓国特許出願第10−2017−0097282号に基づく優先権の利益を主張し、当該韓国特許出願の文献に開示された全ての内容は本明細書の一部として含まれる。
(2)2官能エポキシ樹脂に2官能フェノール、および(または)ジカルボキシ基を反応させた後、多塩基酸無水物を反応させて得られるカルボキシ基含有樹脂、
(3)多官能フェノール樹脂に分子中に1個のエポキシ基を有する化合物を反応させた後、多塩基酸無水物を反応させて得られるカルボキシ基含有樹脂、
(4)分子中に2個以上のアルコール性水酸基を有する化合物に多塩基酸無水物を反応させて得られるカルボキシ基含有樹脂、
(5)ジアミン(diamine)とジアンヒドリド(dianhydride)を反応させたポリアミック酸樹脂またはポリアミック酸樹脂の共重合体樹脂、
(6)アクリル酸を反応させたポリアクリル酸樹脂またはポリアクリル酸樹脂の共重合体、
(7)マレイン酸無水物を反応させたポリマレイン酸無水物樹脂およびポリマレイン酸無水物樹脂共重合体の無水物を弱酸、ジアミン、イミダゾール(imidazole)、ジメチルスルホキシド(dimethyl sulfoxide)で開環させて製造した樹脂などが挙げられるが、これらに限定されるものではない。
製造例1
製造温度計、攪拌装置、還流冷却管、水分定量器が装着された加熱および冷却可能な容積2リットルの反応容器に、溶媒としてジメチルホルムアミド(Dimethylformamide、DMF)632g、N−置換マレイミド化合物として、BMI−1100(大和化成工業(株)製)358g、アミン化合物として、4−アミノフェニル酢酸151gを混合し、85℃で24時間攪拌して、固形分含有量50%のアルカリ可溶性樹脂溶液を製造した。
製造温度計、攪拌装置、還流冷却管、水分定量器が装着された加熱および冷却可能な容積2リットルの反応容器に、溶媒としてジメチルホルムアミド(Dimethylformamide、DMF)632g、N−置換マレイミド化合物として、p−カルボキシフェニルマレイミド434g、アミン化合物として、4,4’−ジアミノジフェニルメタン198gを混合し、85℃で24時間攪拌して、固形分含有量50%のアルカリ可溶性樹脂溶液を製造した。
製造温度計、攪拌装置、還流冷却管、水分定量器が装着された加熱および冷却可能な容積2リットルの反応容器に、溶媒としてジメチルアセトアミド(Dimethylacetamide、DMAc)543gを入れて、Cray Valley社製のSMA1000 350g、4−アミノ安息香酸(4−aminobenzoic acid、PABA)144g、4−アミノフェノール(4−aminophenol、PAP)49gを投入した後、混合した。窒素雰囲気下で反応器の温度を80℃とし、24時間持続して酸無水物とアニリン誘導体が反応してアミック酸を形成した後、反応器の温度を150℃とし、24時間持続してイミド化反応を進行して、固形分50%のアルカリ可溶性樹脂溶液を製造した。
製造温度計、攪拌装置、還流冷却管、水分定量器が装着された加熱および冷却可能な容積2リットルの反応容器に、溶媒としてメチルエチルケトン(Methylethylketone、MEK)516gを入れて、p−カルボキシフェニルマレイミド(p−carboxyphenylmaleimide)228g、p−ヒドロキシフェニルマレイミド(p−hydroxyphenylmaleimide)85g、スチレン(styrene)203g、アゾビスイソブチロニトリル(AIBN)0.12gを投入した後、混合した。窒素雰囲気下で反応器の温度を70℃に徐々に上げた後、24時間持続して固形分50%のアルカリ可溶性樹脂溶液を製造した。
<実施例1:絶縁層の製造>
下記図1の内容を参照すれば、前記製造例1で合成したアルカリ可溶性樹脂16g、熱硬化性バインダーとして、MY−510(Huntsman社製)5g、無機フィラーとして、SC2050 MTO(固形分70%、Adamatech社製)35gを混合した高分子樹脂組成物をPETフィルムに塗布し乾燥させて、15μm厚さの高分子樹脂層1を製造した。そして、銅回線2が銅箔積層板3に形成された回路基板上に、前記高分子樹脂層1を85℃で真空ラミネートし、前記PETフィルムを除去した。前記高分子樹脂層1上に15μm厚さの感光性ドライフィルムレジスト(KL1015;コーロンインダストリー(株)製)4を110℃でラミネートした。
下記図2の内容を参照すれば、前記実施例1で製造された絶縁層7の上面とビアホール5の側面にアルゴンと酸素の混合ガスを蒸着装備で供給しながら、スパッタリング法を通してチタニウム(Ti)金属を50nm、銅(Cu)金属を0.5μm厚さに蒸着してシード層(seed layer)8を形成した。
前記高分子樹脂層の製造時、製造例3で合成したアルカリ可溶性樹脂16g、熱硬化性バインダーとしてMY−510(Huntsman社製)6g、無機フィラーとしてSC2050 MTO(固形分70%、Adamatech社製)35gを混合した高分子樹脂組成物を使用したことを除いては、前記実施例1と同様の方法で下記表1のビアホールの直径を有する絶縁層を製造した。
前記実施例1で製造された絶縁層の代わりに、前記実施例3で製造された絶縁層を使用したことを除いては、前記実施例2と同様な方法で多層印刷回路基板を製造した。
前記高分子樹脂層の製造時、製造例1で合成したアルカリ可溶性樹脂16g、熱硬化性バインダーとしてMY−510(Huntsman社製)5g、無機フィラーとしてSC2050 MTO(固形分70%、Adamatech社製)43gを混合した高分子樹脂組成物を使用したことを除いては、前記実施例1と同様の方法で下記表1のビアホールの直径を有する絶縁層を製造した。
前記高分子樹脂層の製造時、製造例2で合成したアルカリ可溶性樹脂16g、熱硬化性バインダーとしてMY−510(Huntsman社製)5g、無機フィラーとしてSC2050 MTO(固形分70%、Adamatech社製)43gを混合した高分子樹脂組成物を使用したことを除いては、前記実施例1と同様の方法で下記表1のビアホールの直径を有する絶縁層を製造した。
前記高分子樹脂層の製造時、製造例3で合成したアルカリ可溶性樹脂16g、熱硬化性バインダーとしてMY−510(Huntsman社製)5g、無機フィラーとしてSC2050 MTO(固形分70%、Adamatech社製)43gを混合した高分子樹脂組成物を使用したことを除いては、前記実施例1と同様の方法で下記表1のビアホールの直径を有する絶縁層を製造した。
前記高分子樹脂層の製造時、製造例4で合成したアルカリ可溶性樹脂16g、熱硬化性バインダーとしてMY−510(Huntsman社製)5g、無機フィラーとしてSC2050 MTO(固形分70%、Adamatech社製)43gを混合した高分子樹脂組成物を使用したことを除いては、前記実施例1と同様の方法で下記表1のビアホールの直径を有する絶縁層を製造した。
<比較例1:絶縁層の製造>
前記実施例1のように、前記製造例1で合成したアルカリ可溶性樹脂16g、熱硬化性バインダーとしてMY−510(Huntsman社製)5g、無機フィラーとしてSC2050 MTO(固形分70%、Adamatech社製)35gを混合した高分子樹脂組成物をPETフィルムに塗布し乾燥させて、15μm厚さの高分子樹脂層1を製造した。そして、銅回線2が銅箔積層板3に形成された回路基板上に前記高分子樹脂層1を85℃で真空ラミネートし、前記PETフィルムを除去した。
酸変性アクリレート樹脂としてCCR−1291H(日本化薬(株)製)30g、多官能アクリレートモノマーとしてTMPTA(ETNIS社製)5g、光開始剤としてIrgacure TPO−L(BASF社製)2g、多官能エポキシとしてYDCN−500−8P(国都化学(株)製)6g、熱硬化触媒として2E4MZ(四国化成工業(株)製)0.2gを混合した感光性樹脂組成物を回路基板上に塗布し乾燥して感光性樹脂層を製造した。
実施例1で製造された絶縁層の代わりに、比較例2で製造された絶縁層を使用したことを除いては、前記実施例2と同様に多層印刷回路基板を製造した。
前記実施例5のように、製造例1で合成したアルカリ可溶性樹脂16g、熱硬化性バインダーとしてMY−510(Huntsman社製)6g、無機フィラーとしてSC2050 MTO(固形分70%、Adamatech社製)43gを混合した高分子樹脂組成物をPETフィルムに塗布し乾燥させて、15μm厚さの高分子樹脂層1を製造した。そして、銅回線2が銅箔積層板3に形成された回路基板上に前記高分子樹脂層1を85℃で真空ラミネートし、前記PETフィルムを除去した。
前記実施例7のように、製造例3で合成したアルカリ可溶性樹脂16g、熱硬化性バインダーとしてMY−510(Huntsman社製)5g、無機フィラーとしてSC2050 MTO(固形分70%、Adamatech社製)43gを混合した高分子樹脂組成物をPETフィルムに塗布し乾燥させて、15μm厚さの高分子樹脂層1を製造した。そして、銅回線2が銅箔積層板3に形成された回路基板上に前記高分子樹脂層1を85℃で真空ラミネートし、前記PETフィルムを除去した。
酸変性アクリレート樹脂としてCCR−1291H(日本化薬(株)製)30g、多官能アクリレートモノマーとしてTMPTA(ETNIS社製)5g、光開始剤としてIrgacure TPO−L(BASF社製)2g、多官能エポキシとしてYDCN−500−8P(国都化学(株)製)6g、熱硬化触媒として2E4MZ(四国化成工業(株)製)0.2g、無機フィラーとしてSC2050 MTO(固形分70%、Adamatech社製)49gを混合した感光性樹脂組成物を回路基板上に塗布し乾燥して感光性樹脂層を製造した。
前記実施例および比較例で得られた絶縁層の物性を下記方法で測定し、その結果を表1に示した。
前記実施例1、3、5−8および比較例1、2、4、5、6で得られた絶縁層に対して、光学顕微鏡を通して上段開口面(ビアホール)の直径を測定した。
前記実施例2、4および比較例3で得られた多層印刷回路基板に対して、135℃、85%吸湿状態で48時間放置させた後、IPC−TM−650基準により、金属の剥離強度を測定して、これより金属密着力を求めた。
前記実施例2、4および比較例3で得られた多層印刷回路基板に対して、JESD22−A101基準により、HAST特性を確認した。具体的に、幅、間隔、厚さがそれぞれ50μm、50μm、12μmの試片回路基板に対して、3Vの電圧を印加し、168時間放置した後、以下の基準下に試片回路基板の外観上の異常の有無を確認した。
OK:被膜外観に異常が観察されない
NG:被膜に水泡または剥がれが観察される
2:銅回線
3:銅箔積層板
4:感光性ドライフィルムレジスト(DFR)
5:ビアホール
6:金属層
7:絶縁層
8:シード層
9:感光性樹脂パターン
10:金属基板
<1>乃至<6>:工程の進行順序
Claims (16)
- 導体配線上にアルカリ可溶性樹脂および熱硬化性バインダーを含む高分子樹脂層を形成する段階;
前記高分子樹脂層上に感光性樹脂層を形成する段階;
前記感光性樹脂層を露光およびアルカリ現像して感光性樹脂パターンを形成し、かつ前記感光性樹脂パターンによって露出した高分子樹脂層もアルカリ現像する段階;
前記アルカリ現像以降、前記高分子樹脂層を熱硬化する段階;および
前記感光性樹脂パターンを剥離する段階を含み、
前記アルカリ可溶性樹脂は、1)酸性作用基;およびアミノ基で置換された環状イミド作用基をそれぞれ少なくとも1つ以上含むか、または2)下記の化学式3で表示される反復単位;および下記の化学式4で表される反復単位をそれぞれ少なくとも1つ以上含み、
前記の酸性作用基;およびアミノ基で置換された環状イミド作用基をそれぞれ少なくとも1つ以上含むアルカリ可溶性樹脂は、環状不飽和イミド化合物;およびアミン化合物の反応を通して製造され、前記環状不飽和イミド化合物は末端に置換された酸性作用基を含み、
前記の化学式3で表示される反復単位;および下記の化学式4で表される反復単位をそれぞれ少なくとも1つ以上含むアルカリ可溶性樹脂は、下記の化学式5で表される反復単位を含む重合体、下記の化学式6で表示されるアミン、および下記の化学式7で表されるアミンの反応で製造される、絶縁層の製造方法:
R4は−H、−OH、−NR5R6、ハロゲン、または炭素数1〜20のアルキル基であり、
前記R5およびR6はそれぞれ独立に、水素、炭素数1〜20のアルキル基、または炭素数6〜20のアリール基であってもよく、
“*”は結合点を意味し、
- 前記の酸性作用基;およびアミノ基で置換された環状イミド作用基をそれぞれ少なくとも1つ以上含むアルカリ可溶性樹脂は、酸性作用基;およびアミノ基で置換された環状イミド作用基をそれぞれ少なくとも2つ以上含む、請求項1に記載の絶縁層の製造方法。
- 前記アミン化合物は、アミノ基で置換されたカルボン酸化合物、および2つ以上のアミノ基を含む多官能アミン化合物からなる群より選択された1種以上を含む、請求項1に記載の絶縁層の製造方法。
- 前記アルカリ可溶性樹脂は、KOH滴定によって求められる酸価(acid value)が50mgKOH/g乃至250mgKOH/gである、請求項1に記載の絶縁層の製造方法。
- 前記高分子樹脂層は、アルカリ可溶性樹脂100重量部に対して、熱硬化性バインダー1重量部乃至150重量部を含む、請求項1に記載の絶縁層の製造方法。
- 前記熱硬化性バインダーは、オキセタニル基、環状エーテル基、環状チオエーテル基、シアノ基、マレイミド基およびベンゾオキサジン基からなる群より選択された1種以上の作用基およびエポキシ基を含む、請求項1に記載の絶縁層の製造方法。
- 前記高分子樹脂層に含まれている光開始剤の含有量が、全体高分子樹脂層の重量対比0.01重量%以下である、請求項1に記載の絶縁層の製造方法。
- 前記感光性樹脂層を露光およびアルカリ現像して感光性樹脂パターンを形成し、かつ前記感光性樹脂パターンによって露出した高分子樹脂層もアルカリ現像する段階で、
前記感光性樹脂パターンが除去される比率が、全体感光性樹脂パターン重量対比0.01重量%以下である、請求項1に記載の絶縁層の製造方法。 - 前記感光性樹脂層を露光およびアルカリ現像して感光性樹脂パターンを形成し、かつ前記感光性樹脂パターンによって露出した高分子樹脂層もアルカリ現像する段階以降に、
前記感光性樹脂パターンによって露出した高分子樹脂層の全体重量を基準に0.1重量%乃至85重量%が残留する、請求項1に記載の絶縁層の製造方法。 - 前記感光性樹脂パターンを剥離する段階で、
高分子樹脂層が除去される比率が、全体高分子樹脂層の重量対比10重量%以下である、請求項1に記載の絶縁層の製造方法。 - 前記高分子樹脂層は、アルカリ可溶性樹脂と熱硬化性バインダーの重量合計100重量部に対して、無機フィラーを100重量部以上含む、請求項1に記載の絶縁層の製造方法。
- 前記高分子樹脂層または感光性樹脂層の厚さは1μm乃至500μmである、請求項1に記載の絶縁層の製造方法。
- 請求項1乃至16のいずれか一項に記載の方法によって製造された絶縁層上にパターンが形成された金属基板を形成する段階を含む、多層印刷回路基板の製造方法。
- 前記絶縁層は、アルカリ可溶性樹脂および熱硬化性バインダーの熱硬化物を含む、請求項14に記載の多層印刷回路基板の製造方法。
- 前記絶縁層上にパターンが形成された金属基板を形成する段階は、
前記絶縁層上に金属箔膜を形成する段階;
前記金属箔膜上にパターンが形成された感光性樹脂層を形成する段階;および
前記感光性樹脂層パターンによって露出した金属箔膜上に金属を蒸着させる段階;および
前記感光性樹脂層を除去し、露出した金属箔膜を除去する段階を含む、請求項14に記載の多層印刷回路基板の製造方法。
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