TW201634284A - 疊層結構 - Google Patents
疊層結構 Download PDFInfo
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- TW201634284A TW201634284A TW104110527A TW104110527A TW201634284A TW 201634284 A TW201634284 A TW 201634284A TW 104110527 A TW104110527 A TW 104110527A TW 104110527 A TW104110527 A TW 104110527A TW 201634284 A TW201634284 A TW 201634284A
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- G03F7/004—Photosensitive materials
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133305—Flexible substrates, e.g. plastics, organic film
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- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- 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
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/093—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antistatic means, e.g. for charge depletion
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- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- 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
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Abstract
本發明係關於一種用作乾膜光阻之疊層結構,其包含支撐層、感光性樹脂層及保護層,其中該保護層為具有介於1500nm至2500nm之間之最大表面粗糙度及介於1×108Ω/□至1×1012Ω/□之片電阻之聚酯膜。本發明之疊層結構尤其適用於感光性元件、印刷電路板或導線架之線路製作。
Description
本發明係關於一種用作乾膜光阻(dry film resist)之疊層結構,尤其係適合用於感光性元件、印刷電路板或導線架之線路製程。
乾膜光阻為廣泛用於印刷電路板製程中之感光性材料膜。習知乾膜光阻主要包含支撐層(support film)、感光性樹脂層(即光阻層photoresist layer)及保護層(protection film),其中支撐層係作為支撐感光性樹脂層之基材,保護層則係用於保護感光性樹脂層,避免其於製程中遭受損傷。一般使用具有優異的機械及光學性質、耐熱性、尺寸穩定性等特性之聚酯膜作為支撐層,例如聚對苯二甲酸乙二酯(polyethylene terephthalate)。保護層則可使用聚乙烯、聚丙烯或聚酯等材料。
使用乾膜光阻之方法包括在將乾膜光阻施加於印刷電路板之前,先剝除保護層,將曝露出來的感光性樹脂層與電路板表面(通常為銅板)貼合,此時支撐層位於感光性樹脂層上方。之後,經由曝光及顯影,將所欲產生之電路轉移至感光性樹脂層上。
先前技術已知乾膜光阻中之各層的性質會顯著地影響光阻品質及後續印刷電路板之電路性質。
中華民國第TW531679號專利案發現習知之聚乙烯保護層雖具有柔軟性、耐藥性及良好的剝離性,但聚乙烯在聚合時會產生高分子量
的凝膠,該凝膠會使聚合後之聚乙烯膜含有微細突起物(即魚眼(fish eye)),使得在剝離保護層,並將感光性樹脂層與電路板貼合時,空氣將混人電路板與感光性樹脂層貼合處,產生氣孔(air hole),導致後續電路板不良,如短路現象等情形發生。為避免產生魚眼現象,TW531679使用具有下列特徵之聚對苯二甲酸乙二酯膜作為保護層:5.0nm≦SRa≦25nm,100nm≦Spv≦250nm及500個≦尖端密度≦10000個,其中SRa為表面粗糙度,Spv為尖端至谷底的高度差,尖端密度為單位面積4點(各為2μm×2μm)內具有高度1nm以上之突起數。根據該案之揭露內容,當SRa、Spv及尖端密度值增大時,會產生粗大粒子,增加感光性樹脂層與保護層間黏著力,導致保護層在剝離時產生破裂現象。反之,當SRa、Spv及尖端密度值降低時,保護層的摩擦係數驟升,造成薄膜製程中之抓痕及靜電問題。
CN180600B指出因保護層之剝離而產生強烈的靜電作用,將造成異物黏附,更可能對感光性樹脂有機溶劑塗料產生火花放電現象,導致乾膜光阻著火。
鑑於上述先前技術之問題,本發明提供一種乾膜光阻疊層結構,其包含具有良好的剝離性之保護層,可減少靜電作用及因乾膜製程所產生之後續電路板不良現象。
如前所述,先前技術的乾膜光阻因各層的性質影響,造成剝離性不佳、抗靜電性不佳等缺點,顯著影響光阻品質及後續印刷電路板之電路性質。本發明之一目的在於提供一種疊層結構,其包含支撐層、感光性樹脂層及保護層,其中該保護層係具有滿足下列條件之表面特性之聚酯膜:1500nm≦最大表面粗糙度≦2500nm;1×108Ω/□≦片電阻值≦1×1012Ω/□。(Ω/□代表歐姆/單位面積)。
本案發明人經研究發現,保護層的最大表面粗糙度和片電阻值對其剝離性和抗靜電作用有關鍵性的影響。申言之,僅在特定保護層性質或條件下(如最大表面粗糙度和片電阻值),方能使保護層於剝離時容易被撕除,減緩撕除保護層時所產生之靜電作用,及避免在剝除時,膜面捲收,產生滑脫現象,及表面出現細紋,感光性樹脂層上發生汙染狀況或氣孔殘留的現象。特定言之,若保護層之最大表面粗糙度低於1500nm,則易產生滑脫現象,表面易出現細紋;反之,若其最大表面粗糙度大於2500nm,則易產生魚眼現象。當保護層具有1500nm≦最大表面粗糙度≦2500nm及1×108Ω/□≦片電阻值≦1×1012Ω/□時,其具有優良的剝離性,亦即,其於剝離時容易撕除且不殘留感光性樹脂組合物。
本發明之疊層結構尤其適用於感光性元件、印刷電路板或導線架之線路製作。
10‧‧‧疊層結構
1‧‧‧支撐層
2‧‧‧保護層
3‧‧‧感光性樹脂層
d1‧‧‧支撐層之厚度
d2‧‧‧保護層之厚度
d3‧‧‧感光性樹脂層之厚度
圖1為根據本發明之疊層結構之剖面圖。
本發明之疊層結構所包含之保護層,係為聚酯膜,其具有以3D干涉儀測得之介於1500nm至2500nm之間,較佳介於約1700nm至2300nm之間,更佳介於約2000nm至2300nm之間之最大表面粗糙度,及以Agilent表面阻抗測定儀43398檢測得之介於1×108Ω/□至1×1012Ω/□,較佳介於1×109Ω/□至1×1011Ω/□之間之片電阻。根據本發明之具體實施例,用於作為保護層之聚酯膜係為聚對苯二甲酸乙二酯膜。本發明之保護層具有優良的防靜電特性。此外,該保護層具有介於約1至100微米(μm)之間之厚度,較佳介於約10至40μm之間之厚度。根據本發明之具體實施例,該保護層較佳為經表面前處理之聚酯膜,例如,在該保護層之表面上,先形成由有機聚矽氧烷、氟化聚烯
烴、聚氟乙烯、聚乙烯醇等之聚合物所構成的下塗層。
本發明之疊層結構所包含之支撐層,為包含聚對苯二甲酸乙二酯之聚酯膜,其具有介於10μm至100μm之間之厚度。
本發明之疊層結構所包含之感光性樹脂層,可包含高分子黏合劑、含雙鍵的光可聚合化合物及光起始劑。添加含雙鍵之光可聚合化合物及光起始劑可使感光性樹脂組合物在紫外線照射下進行自由基鏈聚合反應。本發明之感光性樹脂組合物可視情況包含其他添加物,例如染料(如孔雀石綠、結晶紫或維多利亞藍)、安定劑(如三苯基磷)、助劑(如羧基苯并三唑)、成色劑或填料及其組合。
可用於本發明之含雙鍵的光可聚合化合物包括,但不限於1,4-丁二醇二(甲基)丙烯酸酯(1,4-butanediol di(meth)acrylate)、1,6-己二醇二(甲基)丙烯酸酯(1,6-hexanediol di(meth)acrylate)、新戊基乙二醇二(甲基)丙烯酸酯(neopentylglycol di(meth)acrylate)、聚乙二醇二(甲基)丙烯酸酯(polyethyleneglycol di(meth)acrylate)、新戊基乙二醇二(甲基)丙烯酸酯己二酸酯(neopentylglycol dipate di(meth)acrylate)、新戊基乙二醇二甲基丙烯酸羥基特戊酸酯(neopentylglycol di(meth)acrylate hydroxypivalate)、二(甲基)丙烯酸二環戊二烯酯(dicyclopentdienyl di(meth)acrylate)、己內酯改質的二(甲基)丙烯酸二環戊二烯酯(caprolactone modified dicyclopentdienyl di(meth)acrylate)、烯丙基化的二(甲基)丙烯酸環己酯(allylated cyclohexyl di(meth)acrylate)、二(甲基)丙烯酸異氰尿酸酯(isocyanurate di(meth)acrylate)、三羥甲基丙烷三(甲基)丙烯酸酯(trimethylol propane tri(meth)acrylate)、二戊赤藓醇三(甲基)丙烯酸酯(dipentaerythriol tri(meth)acrylate)、戊赤藓醇三(甲基)丙烯酸酯、三甲基三(甲基)丙烯酸甲酯、三(丙烯氧乙基)異氰酸尿酯(tris(acryloxyethyl)isocyanurate)、二戊赤藓醇五(甲基)丙烯酸酯、二戊赤藓醇六(甲基)酸酯、乙氧基改質之三甲醇丙烷三丙烯酸
酯、脂肪族胺基甲酸酯寡聚體及其混合物所構成的群組。
可用於本發明之光起始劑,包括但不限於二苯乙醇酮(benzoin)、二苯乙醇酮烷基醚(benzoin alkyl ether)、二苯乙二醛(benzyl)、縮酮(ketals)、苯乙酮化合物(acetophenones)、二苯甲酮(benzophenone)、4,4-二甲基-胺基-二苯甲酮(4,4-dimethtl-amino-benzophenone)、硫化氧雜蒽酮化合物(thioxanthones)、馬福林-丙酮化合物(morpholono-propanone)、n-苯基甘胺酸、咪唑二聚體等。
添加高分子黏合劑之目的係為了使乾膜組成具有成膜性。可用於本發明之黏合劑包括丙烯酸系高分子、苯乙烯系高分子、聚胺基甲酸乙酯、聚碳酸酯、聚酯、環氧乙烯等有機高分子。
根據本發明,該感光性樹脂層具有介於5μm至300μm之間之厚度。
如圖1所示,本發明之疊層結構(10)依序為支撐層(1)、感光性樹脂層(3)及保護層(2)。本發明之疊層結構作為乾式薄膜光阻使用時,須先撕除保護層,透過熱壓滾輪將曝露出來的感光性樹脂層貼合於基材上,再撕除位於感光性樹脂層上方之支撐層。之後,經由曝光及顯影,將所欲產生之圖案轉移至感光性樹脂層上,並藉由蝕刻或者電鍍處理,將感光性樹脂層移除後,即可得到配有電路圖案的基材。
以下將具體地描述根據本發明之部分具體實施態樣;惟,在不背離本發明之精神下,本發明尚可以多種不同形式之態樣來實踐,不應將本發明保護範圍解釋為限於說明書所陳述者。此外,除非文中有另外說明,於本說明書中(尤其是在後述專利申請範圍中),所使用之「一」、「該」及類似用語應理解為包含單數及複數形式。另,為明確起見,圖式中可能誇示各元件及區域的尺寸,而未按照實際比例繪示。本文中所使用術語「約」意指包含如由一般熟習此項技術者所測定之特定值的可接受誤差,其部分地視如何量測或測定該值而定。
感光性樹脂组合物1係藉由混合(a)高分子黏合劑,例如60重量份之丙烯酸樹脂(100%固體,配方係由以下組合物所構成:224克甲基丙烯酸,288克甲基丙烯酸甲酯,104克丙烯酸丁酯,120克苯乙烯,64克甲基丙烯酸丁酯,8克2,2'-偶氮雙異丁腈、(b)含雙鍵的光可聚合化合物,例如20重量份之乙氧基改質之三甲醇丙烷三丙烯酸酯(PHOTOMER 4155,Cognis)及15.6重量份之脂肪族胺基甲酸酯寡聚體、(c)光起始劑,例如0.1重量份之n-苯基甘胺酸(NPG,Hampford)及3.6重量份之咪唑二聚體(BCIM,黑金)及(d)溶劑,例如20重量份之丁酮所製得,如下表一所示。該感光性樹脂组合物可另外包含孔雀石綠作為染料(e)。
下表二比較以經表面前處理且具有低片電阻值之商用聚酯膜作為保護層,及以商用聚酯膜或聚乙烯膜作為保護層之性質。
S100H16:三菱化學製PET film(經表面前處理、低片電阻)
T100H16:三菱化學製PET film(經表面前處理)
R310:三菱化學製PET film
GF-102:Tamapoly PE film
將支撐層剪切成寬度為40cm和長度為25cm的大小,將表1之感光性樹脂組合物1的溶液均勻地塗佈於厚為16μm的支撐層上,利用80至100℃的熱風對流式乾燥機乾燥2至10分鐘,即於支撐層上形成了感光性樹脂層,厚度為40μm,並以冷壓滾輪將表二所列之保護層黏著至感光型樹脂上。
將上述的樣品裁剪為寬度為30cm且長度為20cm的大小,在50℃及92%相對溼度(RH)的環境下靜置24小時,以肉眼觀察保護層與
疊層結構的滑脫狀況,並以手動方式將保護層自疊層結構剝離,觀察保護層撕除後之感光性樹脂層表面性質,例如感光性樹脂組合物殘留量、表面污染狀況及氣孔數,評估樣品性質之優劣:
滑脫性:以肉眼觀察保護層與疊層結構間的滑脫狀況
O:膜面捲收後,沒有滑脫,表面沒有細紋
△:膜面捲收後,沒有滑脫,表面一部份出現細紋
x:膜面捲收後,發生滑脫,表面出現細紋
剝離性:觀察保護層撕除後,保護層上是否有殘留感光性樹脂組合物
O:保護層上無殘留感光性樹脂組合物
△:以肉眼觀察保護層,該保護層上殘留佔保護層面積小於5%之感光性樹脂組合物
x:以肉眼觀察保護層,該保護層上殘留佔保護層面積大於5%之感光性樹脂組合物
汙染狀況:以100倍光學顯微鏡觀察感光性樹脂層表面污染狀況
O:觀察無污染狀況
x:觀察有污染狀況
氣孔數(air hole):以100倍光學顯微鏡下觀察,並計數氣孔個數
O:氣孔個數<20個/m2
△:20個/m2<氣孔個數<300個/m2
x:氣孔個數>300個/m2
上述結果示於表三。
綜合比較表二之實施例與比較例保護層之性質及表三所示之表面性質評估結果可知,實施例1之保護層具有介於6×109Ω/□至7×1010Ω/□間之片電阻值及介於1800nm至2200nm間之最大粗糙度,即其滿足本發明保護層之以下特性:1500nm≦最大表面粗糙度≦2500nm及1×108Ω/□≦片電阻值≦1×1012Ω/□,所以將該保護層自感光性樹脂層表面上撕除時,膜面捲收後,未產生滑脫現象,表面未出現細紋,感光性樹脂層上並未觀察汙染狀況且沒有感光性樹脂組合物或大量氣孔殘留的現象。相較之下,比較例1之保護層雖具有與實施例1保護層相同範圍之最大粗糙度,即介於1800nm至2200nm間之最大粗糙度,但是其片電阻值係介於2×1014Ω/□~1×1015Ω/□,即不滿足本發明保護層之1×108Ω/□≦片電阻值≦1×1012Ω/□之要求,由表面性質評估結果可知,比較例1之保護層雖未在膜面捲收後,產生滑脫現象及未於表面出現細紋,但仍在該保護層上觀察到殘留5%感光性樹脂組合物、感光性樹脂層上有汙染狀況或感光性樹脂組合物上有大於300個/m2之氣孔個數等不良現象。另一方面,比較例2之保護層具有50nm~100nm之最大粗糙度,遠低於本發明保護層之最大粗糙度,在剝除時,膜面捲收後,產生滑脫現象,表面出現細紋,且因片電阻值介
於2×1014Ω/□~1×1015Ω/□,所以在該保護層上肉眼觀察到殘留佔大於保護層面積5%感光性樹脂組合物,且感光性樹脂層上有顯著汙染狀況等不良現象。而比較例3之保護層具有介於2500nm至2600nm間之最大粗糙度,因此在剝離保護層後,將感光性樹脂層與電路板貼合時,空氣易混入電路板與感光性樹脂層貼合處,產生氣孔。
由上述說明可知,具有滿足1500nm≦最大表面粗糙度≦2500nm及1×108Ω/□≦片電阻值≦1×1012Ω/□之條件之保護層,在剝離時所產生的剝離帶電電壓較低,較易撕除,可減緩保護層撕除時之靜電作用,避免在剝除時,膜面捲收後,產生滑脫現象,表面出現細紋,感光性樹脂層上發生汙染狀況及有大量感光性樹脂組合物或氣孔殘留的現象,此等優異性質可避免後續使用於電路板上時,因乾膜製程所產生之不良現象。
10‧‧‧疊層結構
1‧‧‧支撐層
2‧‧‧保護層
3‧‧‧感光性樹脂層
d1‧‧‧支撐層之厚度
d2‧‧‧保護層之厚度
d3‧‧‧感光性樹脂層之厚度
Claims (8)
- 一種疊層結構,其包含支撐層、感光性樹脂層及保護層,其中該保護層係具有滿足下列條件之表面特性之聚酯膜:1500nm≦最大表面粗糙度≦2500nm;1×108Ω/□≦片電阻值≦1×1012Ω/□。
- 如請求項1之疊層結構,其中該保護層之厚度係介於約1至100μm。
- 如請求項1之疊層結構,其中該感光性樹脂層包含:(a)高分子黏合劑;(b)含雙鍵的光可聚合化合物;及(c)光起始劑。
- 如請求項1之疊層結構,其中該保護層之最大表面粗糙度係介於約1700nm至2300nm之間。
- 如請求項1之疊層結構,其中該保護層之最大表面粗糙度係介於約2000nm至2300nm之間。
- 如請求項1之疊層結構,其中該保護層之片電阻值係介於1×109Ω/□至1×1011Ω/□之間。
- 如請求項1之疊層結構,其中該保護層具有防靜電特性。
- 一種如請求項1之疊層結構之用途,其係用於感光性元件、印刷電路板或導線架之線路製作。
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