JP2011517324A - 非エッチング且つ非レジスト接着剤組成物、並びに加工部品の処理方法 - Google Patents
非エッチング且つ非レジスト接着剤組成物、並びに加工部品の処理方法 Download PDFInfo
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- JP2011517324A JP2011517324A JP2010549061A JP2010549061A JP2011517324A JP 2011517324 A JP2011517324 A JP 2011517324A JP 2010549061 A JP2010549061 A JP 2010549061A JP 2010549061 A JP2010549061 A JP 2010549061A JP 2011517324 A JP2011517324 A JP 2011517324A
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- copper
- copper alloy
- etching
- resist composition
- group
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- 238000007766 curtain coating Methods 0.000 description 1
- APQPRKLAWCIJEK-UHFFFAOYSA-N cystamine Chemical compound NCCSSCCN APQPRKLAWCIJEK-UHFFFAOYSA-N 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 229940078469 dl- cysteine Drugs 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- ZEUUVJSRINKECZ-UHFFFAOYSA-N ethanedithioic acid Chemical compound CC(S)=S ZEUUVJSRINKECZ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- PEYVWSJAZONVQK-UHFFFAOYSA-N hydroperoxy(oxo)borane Chemical compound OOB=O PEYVWSJAZONVQK-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- BOQKCADLPNLYCZ-UHFFFAOYSA-N n-phenylbenzenecarbothioamide Chemical compound C=1C=CC=CC=1C(=S)NC1=CC=CC=C1 BOQKCADLPNLYCZ-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000008427 organic disulfides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000002910 structure generation Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003556 thioamides Chemical class 0.000 description 1
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- USFMMZYROHDWPJ-UHFFFAOYSA-N trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium Chemical compound CC(=C)C(=O)OCC[N+](C)(C)C USFMMZYROHDWPJ-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
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Abstract
Description
{-N+(CH3)2Cl--(CH2)3-NH-CO-NH-(CH2)3-N+(CH3)2Cl--(CH2)2-O-(CH2)2-}x
{N+(R3)(R4)-(CH2)a-N(H)-C(Y)-N(H)-(CH2)b-N+(R3)(R4)-R5}n2nX- II
ここで、R3及びR4は互いに関係なくメチル、エチル、イロプロピル、ヒドロキシメチル、ヒドロキシエチル、又は-CH2CH2(OCH2CH2)cOHであり、R5は(CH2)d又は{(CH2)eO(CH2)f}gであり、YはO,S又はNHであり、a,b,c,d,e及びfはそれぞれ互いに関係なく1〜約6までの整数であり、gは1から約4までの整数である。
nは少なくとも1の整数であって、最大で200、好ましくは最大で100、より好ましくは最大で50、最も好ましくは最大で20であってもよい。さらに、X-はハロゲン化物(フッ化物、塩化物、臭化物、沃化物、最も好ましくは塩化物)イオンである。
R8は、H又はC1−C3アルキルであり、
R9は、H、Li、Na、K及びNH4から成る群から選択され、
R10及びR11は、H、CH3、及びC2H5から成る群から互いに関係なく選択され、
R6及びR7の少なくとも一つがSR9であって、その際R9は、好ましくはHであるという条件を備えている。
R2はC1−C20アルキルであって、OHと、非置換及び置換フェニルと、非置換及び置換フェノキシと、アミノと、アルキレン(アルキルアミノ)と、アルキレン(ジアルキルアミノ)と、アルキレン(トリアルキルアンモニウムイオン)と及びアルキレンオキシランとから成る群から選択された、少なくとも一つの置換基によって置換されてもよい。
一般化学式Iを有するアクリル系化合物のC=O基は、銅表面に対する強力な結合に有効であると信じられている一方で、当該分子のアクリル基における不飽和構造要素は、高分子被覆物に対し強力に結合すると信じられている。
R2は(CH2)m−R12であり、ここで、
mは1〜20の整数であり、
(CH2)mとして、(CH2)mはCH2基のうち少なくとも一つがOHで置換されてもよく、且つ直鎖状である代わりに枝分かれしていてもよいことを示唆しており、
R12は、H、フェニル、O−フェニル、NR13R14、N+R13R14R15Z−又はオキシラン環であり、ここで、フェニルは非置換又は置換され、
R13、R14、及びR15は互いに関係がなく、
H又はC1−C5アルキル、オキシラン環は非置換又は置換され、且つ、Z−はアニオンである。
(a)加工部品の少なくとも片側に銅被覆物を有しており、前記キャリヤ内の個々の回路面と電気的に接触するために用いられる通し穴がさらに設けられた加工部品が一般的に用いられ、
(b)この加工部品には最初に外側と孔壁に、一般的には無電解銅メッキのみによって、又は無電解銅メッキと続く電解銅メッキによって、又は電解銅メッキのみによって銅が被覆される。
パネルメッキ法の変更では、一般的に銅被覆(17μm厚みの銅外側層)材料が用いられ、通し穴を形成するために穴あけがされて、次に通し穴内に導電性を施すために電解銅メッキがされる。パネルメッキ法は以下の一般的方法工程をさらに含む。
(c)方法工程(b)において形成された銅層を本発明の非エッチング且つ非レジスト組成物で前処理する工程と、
(d)銅張り表面にレジストを取り付けてレジストに画像形成を行い、それによってレジスト空隙を形成する工程と、
(e)レジスト空隙内において露出した銅を除去する工程と、及び、
(f)銅表面からレジストを剥ぎ取る工程であって、当該レジストは光画像形成型レジストであることが好ましい、工程である。
(c)加工部品の外側表面上に方法工程(b)で形成された銅層を、本発明の非エッチング且つ非レジスト組成物で前処理する工程と、
(d)銅張り表面にレジストを塗布して当該レジストに画像作成する工程であって、それによってレジスト空隙を形成する工程と、
(e)前記レジスト空隙内に銅を被覆する工程と、
(f)前記銅表面からレジストを剥ぎ取る工程と、及び、
(g)前記レジストによって予め被覆されたこれら領域内の銅を溶蝕除去する工程であって、前記レジストは光画像形成型レジストであることが好ましい、工程である。
タイプA)銅張り(35μm銅)FR4誘電性積層材であって、約1μm厚みの無電解銅層が設けられている((登録商標)Printoganth PV、アトテックドイツ社製、独国)。
タイプB)18μmDC亜鉛メッキ銅を有する銅張りであって、約1μm厚みの無電解銅層が設けられている((登録商標)Printoganth PV、アトテックドイツ社製、独国)(非常に平滑な表面を象徴している)。
タイプC)銅張り(35μm銅)を有するFR4パネルであって、エポキシ樹脂被覆物(味の素ファインテクノ株式会社製、(登録商標)味の素GX−13))でさらに被覆されており、その後、約1μm厚みの無電解銅層によってさらに覆われている。
最初の試験は、タイプAの試験パネルに実施した。アクリル系化合物A、B、C及びDによって得られた各場合における結果を、本発明に係るヘテロ環式化合物Eによって得られた結果と、及び基準サンプルX(図2〜5)によって得られた結果と比較した。(登録商標)Scotch tapeを貼り付ける前に試験した個々の化合物と基準サンプルの間ではいかなる顕著な違いも検出されなかったので、図2〜5中に示したグラフは、テープ試験後の線完全性に関する。
この実験は、線の完全性に関して溶媒とパネルタイプの効果を観察するために実施した。したがって全ての試験を、タイプAとタイプBの試験パネルにおいて行った。また、アクリル系化合物C及びDは、溶媒の影響を直接的に比較するために、両者とも脱イオン水中又はエチレングリコールモノブチルエーテル中に溶解した。接着剤組成物中のこれら化合物の濃度は10mg/lであった。
これら実験では、化合物D、E、F及びG(濃度:1〜100mg/l)を調査し、Fについては、1−ヒドロキシエチリデン−1,1−ジホスホン酸の水溶液中にさらなる後浸漬あり又はなしで調査し、標準サンプルXと比較した。試験はタイプA材料において実施した(図11において「PD」は後浸漬)。視覚的検査をテープ試験前後に行った(「TT」)。
他の実験では、化合物E(0.02g+130ml/l conc.H2SO4)で銅線の処理が行われた後にレジスト−銅接着性を測定し、2−メルカプトベンゾチアゾール(0.5g/l+20g/l KOH)で処理したものと、及び硫酸(130ml/l conc.H2SO4)処理したものと比較した。テープ試験後銅線上に残存するレジストの量として接着性を求めた。
化合物A、B、C、D(比較例)と化合物E(本発明の例)を含有する接着剤組成物で前処理を行い(濃度10mg/l)、乾燥膜を貼り付け、先のように露光して現像した。次に15μm厚の銅被覆物を実現するために、パネルを電解銅メッキした。
Claims (23)
- 銅又は銅合金の処理用非エッチング且つ非レジスト組成物において、前記組成物は、
少なくとも一つのチオール基を含むヘテロ環式化合物と、及び、
一般化学式IIを有する四級アンモニウムポリマーとで構成される群から選択された、少なくとも一つの接着剤を含有し、
R3とR4は互いに関係なくメチル、エチル、イソプロピル、ヒドロキシメチル、ヒドロキシエチル、又は−CH2CH2(OCH2CH2)cOHであり、
R5は(CH2)d又は{(CH2)eO(CH2)f}gであり、
YはO、S、又はNHであり、
a、b、c、d、e及びfは、それぞれ互いに関係なく1から約6の整数であり、
gは1から約4の整数であり、
nは少なくとも1である整数であり、及び、
X−はハロゲン化物イオンである、組成物。 - 少なくとも一つのチオール基を含むヘテロ環式化合物が、少なくとも一つのチオール基で置換されたトリアゾール化合物である、請求項1に記載の、銅又は銅合金の処理用非エッチング且つ非レジスト組成物。
- 少なくとも一つのチオール基を含むヘテロ環式化合物が、1H−1,2,4−トリアゾール−3−チオール、及び3−アミノ−1,2,4−トリアゾール−5−チオールから成る群から選択される、請求項1〜3のいずれか一項に記載の、銅又は銅合金の処理用非エッチング且つ非レジスト組成物。
- R3とR4がメチルである、請求項1〜4のいずれか一項に記載の、銅又は銅合金の処理用非エッチング且つ非レジスト組成物。
- aとbが3である、請求項1〜5のいずれか一項に記載の、銅又は銅合金の処理用非エッチング且つ非レジスト組成物。
- YがOである、請求項1〜6のいずれか一項に記載の、銅又は銅合金の処理用非エッチング且つ非レジスト組成物。
- R5が{(CH2)eO(CH2)f}gである、請求項1〜7のいずれか一項に記載の、銅又は銅合金の処理用非エッチング且つ非レジスト組成物。
- eとfが2である、請求項1〜8のいずれか一項に記載の、銅又は銅合金の処理用非エッチング且つ非レジスト組成物。
- gが1である、請求項1〜9のいずれか一項に記載の、銅又は銅合金の処理用非エッチング且つ非レジスト組成物。
- X−が塩化物イオンである、請求項1〜10のいずれか一項に記載の、銅又は銅合金の処理用非エッチング且つ非レジスト組成物。
- 接着剤を、1mg/lから1000mg/lの濃度で前記組成物中に含有する、請求項1〜12のいずれか一項に記載の、銅又は銅合金の処理用非エッチング且つ非レジスト組成物。
- 前記組成物には、銅又は銅合金用の酸化剤が入っていない、請求項1〜13のいずれか一項に記載の、銅又は銅合金の処理用非エッチング且つ非レジスト組成物。
- 少なくとも一つの鉱酸、又は少なくとも一つの有機酸をさらに含む、請求項1〜14のいずれか一項に記載の、銅又は銅合金の処理用非エッチング且つ非レジスト組成物。
- 鉱酸が、硫酸及びリン酸から成る群から選択される、請求項1〜15のいずれか一項に記載の、銅又は銅合金の処理用非エッチング且つ非レジスト組成物。
- 銅又は銅合金表面を有する加工部品を、次に続く前記銅又は銅合金表面への高分子被覆物による被覆のために前処理する方法であって、
(a)加工部品を備える工程と、及び、
(b)加工部品を、請求項1〜16のいずれか一項に記載の非エッチング且つ非レジスト組成物と接触するようにもたらす工程とを有する、方法。 - 加工部品を非エッチング且つ非レジスト組成物中に浸漬することにより、又は、非エッチング且つ非レジスト組成物を加工部品の表面に噴霧することにより、加工部品を非エッチング且つ非レジスト組成物と接触するようにもたらす、請求項17に記載の、銅又は銅合金表面を有する加工部品を、次に続く前記銅又は銅合金表面への高分子被覆物による被覆のために前処理する方法。
- 前記方法が、次の工程、つまり、
(c)接着剤が、一般化学式IIを有する、つまり、
R3とR4は互いに関係なく、メチル、エチル、イソプロピル、ヒドロキシメチル、ヒドロキシエチル、又は−CH2CH2(OCH2CH2)cOHであり、
R5は(CH2)d又は{(CH2)eO(CH2)f}gであり、
YはO、S、又はNHであり、
a、b、c、d、e及びfがそれぞれ互いに関係なく1から約6までの整数であり、
gが1から約4までの整数であり、
nが少なくとも1の整数であり、及び、
X−がハロゲン化物イオンである、
四級アンモニウムポリマーから成る群から選択される場合には、加工部品を少なくとも一つのホスホン酸化合物と接触するようにもたらす工程を、さらに含む、請求項17又は18に記載の、銅又は銅合金表面を有する加工部品を、次に続く前記銅又は銅合金表面への高分子被覆物による被覆のために前処理する方法。 - ホスホン酸化合物が、ヒドロキシエチリデンジホスホン酸、アミノトリ(メチレンホスホン酸)、ジエチレントリアミンペンタ(メチレンホスホン酸)、ポリアミノホスホン酸、ビス(ヘキサメチレントリアミンペンタ(メチレンホスホン酸))及び2−ホスホノブタン−1,2,4−トリカルボン酸から成る群から選択される、請求項19に記載の、銅又は銅合金表面を有する加工部品を、次に続く前記銅又は銅合金表面への高分子被覆物による被覆のために前処理する方法。
- ホスホン酸化合物がヒドロキシエチリデンジホスホン酸である、請求項19又は20に記載の、銅又は銅合金表面を有する加工部品を、次に続く前記銅又は銅合金表面への高分子被覆物による被覆のために前処理する方法。
- 前記方法が、次の工程、つまり、
(c)接着剤が、一般化学式IIを有する四級アンモニウムポリマーから成る群から選択される場合には、一般化学式Iを有する少なくとも一つのアクリル系化合物であって、
R1はH又はC1−C4アルキルであり、
R2はC1−C20アルキルであって、OHと、非置換及び置換フェニルと、非置換及び置換フェノキシと、アミノと、アルキレン(アルキルアミノ)と、アルキレン(ジアルキルアミノ)と、アルキレン(トリアルキルアンモニウムイオン)と及びアルキレンオキシランとから成る群から選択された、少なくとも一つの置換基によって置換されてもよい、
少なくとも一つのアクリル系化合物と、加工部品とを接触するようにもたらす工程をさらに含む、請求項19〜21のいずれか一項に記載の、銅又は銅合金表面を有する加工部品を、次に続く前記銅又は銅合金表面への高分子被覆物による被覆のために前処理する方法。 - 加工部品が銅表面を有する回路キャリヤであり、且つ、高分子被覆物がレジスト被覆物である、請求項17〜22のいずれか一項に記載の、銅又は銅合金表面を有する加工部品を、次に続く前記銅又は銅合金表面への高分子被覆物による被覆のために前処理する方法。
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EP2248402B1 (en) | 2019-05-01 |
US20100323099A1 (en) | 2010-12-23 |
JP5538243B2 (ja) | 2014-07-02 |
EP2248402A1 (en) | 2010-11-10 |
EP2099268A1 (en) | 2009-09-09 |
TWI457469B (zh) | 2014-10-21 |
TW200944616A (en) | 2009-11-01 |
US8945298B2 (en) | 2015-02-03 |
KR101614169B1 (ko) | 2016-04-20 |
CN101926235A (zh) | 2010-12-22 |
WO2009109391A1 (en) | 2009-09-11 |
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