TWI408500B - Photosensitive resin composition, laminate comprising the same, cured product of the same and method for forming pattern using the same (1) - Google Patents
Photosensitive resin composition, laminate comprising the same, cured product of the same and method for forming pattern using the same (1) Download PDFInfo
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本發明係關於可形成高解析性、高長寬比的圖型,而且高感度及液保存安定性優異的感光性樹脂組成物、其層合物、其硬化物及使用該組成物之圖型的形成方法。 The present invention relates to a pattern of a high-sensitivity, high aspect ratio pattern, and a photosensitive resin composition excellent in high sensitivity and liquid storage stability, a laminate thereof, a cured product thereof, and a pattern in which the composition is used. method.
可光微影加工之光阻,最近被廣泛地使用於半導體或MEMS(微機電系統)用途,如此的用途,此光微影加工係在基板上藉由圖型化曝光而進行,接著用顯影液進行顯影,選擇性地去除曝光區域或非曝光區域而逹成。可光微影加工之光阻(光致抗蝕劑)有正型或負型,經由曝光而溶解於顯影液者為正型,不溶者為負型。尖端的電封裝用途(electropackage application)要求高長寬比,另一方面MEMS用途則要求均勻的旋轉塗佈膜的形成能及於100μm以上的厚膜維持直線的形狀,而且高長寬比及可光微影之光阻。其中,長寬比係藉由光阻膜厚/圖型線寬表示,為表示光微影的性能的重要特性。 The photoresist of photolithographic processing has recently been widely used in semiconductor or MEMS (Micro Electro Mechanical Systems) applications. This photolithography process is performed by patterning exposure on a substrate, followed by development. The liquid is developed to selectively remove the exposed or non-exposed areas. The photo-resistance (photoresist) that can be photolithographically processed has a positive or negative type, and is positively dissolved in the developing solution by exposure, and negative in insoluble. The advanced electropackage application requires a high aspect ratio. On the other hand, MEMS applications require uniform spin coating film formation and a thick film of 100 μm or more to maintain a straight shape, and high aspect ratio and photolithography. Light resistance. Among them, the aspect ratio is represented by the photoresist film thickness/pattern line width, and is an important characteristic indicating the performance of photolithography.
以二萘醌-酚醛清漆反應為基礎之先前技術的正型光阻,不適用於要求50μm以上的厚膜之用途,厚膜化時有極限,這是因為一般被使用於光阻曝光的近紫外區域波長(350~450nm)之二萘醌型(DNQ)光反應物具有比較高的光吸收,DNQ型光阻又因為顯影液中曝光區域與非曝光區域之特有的溶解性不同,故側壁形狀不是直線形反而呈 現傾斜形狀。藉由光吸收可使照射在薄膜的頂部至底部的照射強度漸減,但若是此光吸收太高,則光阻的底部與頂部比較下顯得曝光不足,故側壁形狀會呈現傾斜形狀或歪斜形狀。 The positive-type photoresist of the prior art based on the reaction of the naphthoquinone-phenol novolak is not suitable for the use of a thick film requiring 50 μm or more, and has a limit when thick filming, because it is generally used for photoresist exposure. The dinaphthoquinone type (DNQ) photoreactive material with ultraviolet wavelength (350~450nm) has relatively high light absorption, and the DNQ type photoresist has different solubility due to the unique solubility of the exposed area and the non-exposed area in the developing solution. The shape is not linear but instead Now tilted shape. The light intensity can be gradually reduced by the light absorption at the top to the bottom of the film, but if the light absorption is too high, the bottom of the photoresist appears to be underexposed in comparison with the top, so that the side wall shape may have an inclined shape or a skewed shape.
負型的化學增強型之可厚膜光微影加工的組成物,已知在350~450nm波長範圍具有非常低的光吸收,此光阻的組成由多官能雙酚A酚醛清漆環氧樹脂(Resolution Performance Product製EPON SU-8樹脂)、如Dow Chemical製CYRACURE UVI-6974之光致陽離子聚合起始劑(此光致陽離子聚合起始劑為由芳香族六氟銻酸鋶的丙烯碳酸酯溶液所成)所成,此光阻組成物係藉由旋轉塗佈或淋幕式塗佈於各種的基板上,接著經由烘烤使溶劑揮發,形成100μm或此數值以上的厚度的固體光阻層,再使用接觸式曝光、接近式曝光、投射式曝光等之各種曝光方法,隔著光罩照射近紫外光而進行光微影加工,接著,浸漬於顯影液中,使非曝光區域溶解,而在基板上形成高解析的光罩的負影像。 Negative chemically enhanced thick film photolithographic composition, known to have very low light absorption in the 350-450 nm wavelength range, consisting of a polyfunctional bisphenol A novolac epoxy resin ( Resolution Polymer Product EPON SU-8 resin), photo-cationic polymerization initiator of CYRACURE UVI-6974 manufactured by Dow Chemical (this photo-cationic polymerization initiator is a propylene carbonate solution from aromatic hexafluoroantimonate) The photoresist composition is applied to various substrates by spin coating or curtain coating, and then the solvent is volatilized by baking to form a solid photoresist layer having a thickness of 100 μm or more. Then, using various exposure methods such as contact exposure, proximity exposure, and projection exposure, photolithography is performed by irradiating near ultraviolet light through a photomask, and then immersed in a developing solution to dissolve the non-exposed area. A negative image of the high resolution mask is formed on the substrate.
EPON SU-8樹脂,係在厚膜且高長寬比的光微影加工中具有優異的特徵之低分子量環氧低聚物,此優異的特徵係(i)高環氧官能基數、(ii)高支鏈度、(iii)350~450nm的高穿透率、(iv)形成固形物所必須的低分子量;高環氧官能基數及高支鏈度係在強酸觸媒下引起充分的交聯,高穿透率性係穿透厚膜而均勻被光照射,具有形成100μm以上的厚膜且長寬比10以上的圖型之光阻性 能。選擇具有高環氧官能基數與高支鏈度之樹脂,係對於欲形成具有直線的側壁及具有高長寬比之結構物而言為重要項目;選擇低分子量樹脂,係可用最小塗佈階段數在基板上形成厚膜光阻固形物層。 EPON SU-8 resin is a low molecular weight epoxy oligomer with excellent characteristics in thick film and high aspect ratio photolithography. (i) high epoxy functional group, (ii) high branching Degree, (iii) high transmittance of 350 to 450 nm, (iv) low molecular weight necessary for formation of solids; high epoxy functional group and high branching degree cause sufficient crosslinking under strong acid catalyst, high transmittance The system penetrates the thick film and is uniformly irradiated with light, and has a resistive pattern of a thick film having a thickness of 100 μm or more and an aspect ratio of 10 or more. can. Selecting a resin having a high epoxy functional group number and a high degree of branching is an important item for forming a side wall having a straight line and a structure having a high aspect ratio; selecting a low molecular weight resin can be formed on the substrate by a minimum number of coating stages. Thick film photoresist solid layer.
以鋶鹽或碘鎓鹽為基礎的光致陽離子聚合起始劑為人熟知,揭示具有適當的吸光度之有用的光致陽離子聚合起始劑,含有羰基-p-苯撐硫醚(專利文獻1、2),而且亦可添加如2-烷基-9,10-二甲氧基蒽或其他的蒽、萘、綠柱石或吡咯基(pyrryl)化合物之增感劑,亦可導入於光致陽離子聚合起始劑(專利文獻3)。 A photocationic polymerization initiator based on a phosphonium salt or an iodonium salt is well known, and a useful photocationic polymerization initiator having a suitable absorbance is disclosed, which contains a carbonyl-p-phenylene sulfide (Patent Document 1) And 2), and may also add a sensitizer such as 2-alkyl-9,10-dimethoxyanthracene or other anthracene, naphthalene, beryl or pyrryl compound, or may be introduced into the photo-induced Cationic polymerization initiator (Patent Document 3).
以適合旋轉塗佈之如上述揭示的化合物為基礎之負型光阻,由MICRO CHEM公司所販售,特別是在商業上使用於MEMS裝置零件。例如由MICRO CHEM公司所提供的「SU-8系列」,為了形成30~100μm厚的膜而以1000~3000rpm旋轉塗佈,接著曝光‧顯影後,可形成100μm以上的膜厚且長寬比10以上的圖型。 Negative photoresists based on compounds suitable for spin coating as disclosed above are sold by MICRO CHEM, in particular commercially used in MEMS device parts. For example, "SU-8 series" supplied by MICRO CHEM Co., Ltd. can be spin-coated at 1000 to 3000 rpm in order to form a film of 30 to 100 μm thick, and then exposed to ‧ development to form a film thickness of 100 μm or more and an aspect ratio of 10 The above pattern.
亦揭示關於塗佈於如聚酯薄膜的基材上之乾膜光阻的用途(專利文獻4)。 The use of a dry film photoresist coated on a substrate such as a polyester film is also disclosed (Patent Document 4).
揭示適合作為防焊劑(soldermask)使用之可感光的陽離子聚合性難燃劑的組成物(專利文獻5、6、7),此為由含有10~80重量%之雙酚A與表氯醇的縮合物之混合物所成,由含有20~90重量%的雙酚A酚醛清漆環氧樹脂、35~50重量%的環氧化四溴雙酚A、0.1~15重量%的光致陽離子聚合起始劑之組成而成。 A composition for a photosensitive cationically polymerizable flame retardant suitable for use as a solder mask (Patent Documents 5, 6, and 7) is disclosed, which is composed of 10 to 80% by weight of bisphenol A and epichlorohydrin. a mixture of condensates, starting from 20 to 90% by weight of bisphenol A novolac epoxy resin, 35 to 50% by weight of epoxidized tetrabromobisphenol A, 0.1 to 15% by weight of photocationic polymerization The composition of the agent.
亦揭示以含羥基之添加物、光致陽離子聚合起始劑及官能基數15以上的環氧樹脂為基礎之光聚合性化合物,已有報告提出含羥基之添加物,增加可撓性或降低100μm厚以上的厚膜之應力(專利文獻8)。 Also disclosed are photopolymerizable compounds based on a hydroxyl group-containing additive, a photocationic polymerization initiator, and an epoxy resin having a functional group number of 15 or more. It has been reported to add a hydroxyl group-containing additive to increase flexibility or reduce 100 μm. Stress of thick film above thickness (Patent Document 8).
專利文獻9中,揭示在可EB硬化的用途中使用硬質環氧樹脂系製作之方法,其中主要的改善重點,係經照射硬化的環氧樹脂的易碎性,大多數的構造物或耗材用的樹脂(環氧樹脂),為了承受多年的嚴格使用,一定要具有充分的強度與耐衝擊性,其中揭示包括SU-8樹脂之廣泛的強韌材料,關於增加的強度,於專利文獻9中權利要求之發明的有效性,係藉由破壞韌性與彎曲彈性率表示,此強韌材料係由各種的熱塑性塑膠、含羥基之熱塑性塑膠低聚物、含環氧之熱塑性塑膠低聚物、反應性柔軟性、彈性體、橡膠及此等的混合物所成。惟,專利文獻9所記載的組成物,係適用於以非圖型EB照射而被影像化的膜之組成物,被用UV、X射線、EB照射進行圖型化曝光時,此等的組成物的特性不能作為感光用途的參考。 Patent Document 9 discloses a method of producing a hard epoxy resin in an EB-curable application, in which the main improvement point is the friability of the epoxy resin which is hardened by irradiation, and most of the structures or consumables are used. Resin (epoxy resin), in order to withstand years of strict use, must have sufficient strength and impact resistance, which reveals a wide range of tough materials including SU-8 resin, regarding the increased strength, in Patent Document 9 The effectiveness of the invention of the claims is expressed by the fracture toughness and the flexural modulus, which are composed of various thermoplastic plastics, hydroxyl-containing thermoplastic oligomers, epoxy-containing thermoplastic oligomers, and reactions. Sexual softness, elastomer, rubber and a mixture of these. However, the composition described in Patent Document 9 is applied to a composition of a film that is imaged by non-pattern EB irradiation, and is patterned by UV, X-ray, or EB irradiation. The properties of the substance cannot be used as a reference for sensitized use.
提議許多關於含環氧之光阻組成物(專利文獻10),其中,例如揭示調製適用於旋轉塗佈法之光阻組成物之必要性,要求流變學的特性,再加上此處的組成物對於如通過膜厚後光分解光起始劑之曝光照射必須具有充分的穿透率。此外,此光阻組成物為了承受各種的用途,必須具有耐焊性或耐油墨性或強度不會明顯的劣化或密著性不會降低之適當的物理的、化學的特性。如果此光阻組成物被使 用於如蝕刻用光阻之其他用途時,則要求其他的特性,惟,如此之滿足所有的各種要件之特定的環氧樹脂目前不存在,已揭示許多不同的組合或各種的環氧樹脂的混合物,著名的專利皆記載著關於光硬化組成物用的各種樹脂、光起始劑,其中多半為適合作為永久膜用途之可感光的光阻,惟,此等皆未揭示我們試圖完成的最適合於MEMS用途的組成,實際上可塑劑、軟化劑、強韌劑的例子大部份會使微影性能降低。 Many proposals have been made for an epoxy-containing photoresist composition (Patent Document 10) in which, for example, the necessity of modulating a photoresist composition suitable for a spin coating method is required, and rheological properties are required, plus here. The composition must have sufficient transmittance for exposure irradiation such as photodegradation of the photoinitiator after passing through the film thickness. Further, in order to withstand various applications, the photoresist composition must have appropriate physical and chemical properties such as solder resistance or ink resistance, deterioration of strength, or deterioration of adhesion. If this photoresist composition is made For other applications such as photoresist for etching, other characteristics are required, but the specific epoxy resin that satisfies all of the various requirements is currently absent, and many different combinations or various epoxy resins have been disclosed. Mixtures, well-known patents, describe various resins and photoinitiators for photohardenable compositions, most of which are photo-sensitive photoresists suitable for permanent film applications. However, none of these reveals the best we have tried to accomplish. For compositions that are suitable for MEMS applications, virtually all examples of plasticizers, softeners, and tougheners can degrade lithography performance.
〔專利文獻1〕美國專利第5502083號說明書 [Patent Document 1] US Patent No. 5502083
〔專利文獻2〕美國專利第6368769號說明書 [Patent Document 2] US Patent No. 6368769
〔專利文獻3〕美國專利第5102772號說明書 [Patent Document 3] US Patent No. 5102772
〔專利文獻4〕美國專利第4882245號說明書 [Patent Document 4] US Patent No. 4882245
〔專利文獻5〕美國專利第5026624號說明書 [Patent Document 5] US Patent No. 5026624
〔專利文獻6〕美國專利第5278010號說明書 [Patent Document 6] US Patent No. 5278010
〔專利文獻7〕美國專利第5304457號說明書 [Patent Document 7] US Patent No. 5304457
〔專利文獻8〕美國專利第4256828號說明書 [Patent Document 8] US Patent No. 4256828
〔專利文獻9〕美國專利第5726216號說明書 [Patent Document 9] US Patent No. 5726216
〔專利文獻10〕美國專利第5264325號說明書 [Patent Document 10] US Patent No. 5264325
使用酚醛清漆型環氧樹脂等之多官能環氧樹脂之先前技術的感光性樹脂組成物,因為所含有的光致陽離子聚合起始劑的感度低,需要大量的起始劑,故會有無法於短時 間內將光罩圖型忠實重現於樹脂圖型之問題點,此外,含有SbF6 -之光致陽離子聚合起始劑較屬於高感度,但會有因其毒性的問題而使用用途受到限制之問題。 A photosensitive resin composition of the prior art using a polyfunctional epoxy resin such as a novolac type epoxy resin, because the photocationic polymerization initiator contained therein has low sensitivity and requires a large amount of an initiator, In a short period of time, the reticle pattern faithfully reproduces the problem of the resin pattern. In addition, the photo-cationic polymerization initiator containing SbF 6 - is relatively high-sensitivity, but it may be used for its toxicity problem. Restricted issues.
本發明係鑑於上述先前技術的事情所完成之發明,其課題係提供可形成高解析性、高長寬比的圖型,而且高感度及毒性少之感光性樹脂組成物。 The present invention has been made in view of the above-described problems of the prior art, and an object of the invention is to provide a photosensitive resin composition which can form a pattern having high resolution and a high aspect ratio and which has high sensitivity and low toxicity.
本發明者等為了解決上述課題,關於感光性樹脂組成物之高感度化、高解析度化,重複精心研究、實驗及檢討的結果,發現組合特定的多官能環氧樹脂與特定的光致陽離子聚合起始劑調製感光性樹脂組成物,若使用此感光性樹脂組成物形成樹脂圖型,可形成高感度且長寬比高的樹脂圖型。亦即,本發明的構成如下述。 In order to solve the above problems, the inventors of the present invention have repeatedly studied, experimented, and reviewed the results of high sensitivity and high resolution of the photosensitive resin composition, and found that a specific polyfunctional epoxy resin and a specific photocation are combined. The polymerization initiator prepares a photosensitive resin composition, and when the photosensitive resin composition is used to form a resin pattern, a resin pattern having high sensitivity and a high aspect ratio can be formed. That is, the constitution of the present invention is as follows.
(1)一種感光性樹脂組成物,其係含有參(五氟乙基)三氟磷酸鋶之光致陽離子聚合起始劑(A)、與下述式(1)所表示的特定結構的多官能環氧樹脂(B)所成。 (1) A photosensitive resin composition containing a photocationic polymerization initiator (A) of ruthenium (pentafluoroethyl)trifluorophosphonate and a specific structure represented by the following formula (1) Made of functional epoxy resin (B).
(2)如上述(1)所記載之感光性樹脂組成物,其中光致陽離子聚合起始劑(A)為下述式(2)所表示之化合物。 (2) The photosensitive resin composition according to the above (1), wherein the photocationic polymerization initiator (A) is a compound represented by the following formula (2).
(3)如上述(1)或(2)所記載之感光性樹脂組成物,其係含有反應性環氧單體(C)。 (3) The photosensitive resin composition according to the above (1) or (2), which contains a reactive epoxy monomer (C).
(4)如上述(1)至(3)中任一項所記載之感光性樹脂組成物,其中於含有溶劑(D)之感光性樹脂組成物中,其固體成份濃度為5~95重量%。 (4) The photosensitive resin composition according to any one of the above (1) to (3), wherein the solid content of the photosensitive resin composition containing the solvent (D) is 5 to 95% by weight. .
(5)一種感光性樹脂組成物層合物,其係用基材挾入上述(1)至(4)中任一項所記載之感光性樹脂組成物。 (5) A photosensitive resin composition laminate according to any one of the above (1) to (4), wherein the photosensitive resin composition according to any one of the above (1) to (4) is used.
(6)一種硬化物,其係含有上述(1)至(4)中任一項所記載之感光性樹脂組成物所成。 (6) A cured product comprising the photosensitive resin composition according to any one of the above (1) to (4).
(7)一種圖型形成方法,其係包含將於所望的支撐體上塗佈上述(1)至(4)中任一項所記載之感光性樹脂組成物所得到的感光性樹脂組成物層,乾燥後,依所定的圖型曝光,曝光後烘烤,顯影樹脂組成物層,加熱處理所得到的樹脂圖型後,得到所定形狀的硬化樹脂圖型之步驟所成。 (7) A pattern forming method comprising the photosensitive resin composition layer obtained by applying the photosensitive resin composition according to any one of the above (1) to (4) to a desired support. After drying, the film is exposed according to a predetermined pattern, baked after exposure, and the resin composition layer is developed, and the obtained resin pattern is heat-treated to obtain a cured resin pattern of a predetermined shape.
(8)一種圖型形成方法,其係包含將從上述(5)所記載的層合物去除基材後殘留的感光性樹脂組成物層,貼合於上述所望的支撐體上後層合,將此感光性樹脂組成物層依所定的圖型曝光,曝光後烘烤,顯影樹脂組成物層,加熱處理所得到的樹脂圖型後,得到所定形狀的硬化樹脂圖型之步驟所成。 (8) A pattern forming method comprising the photosensitive resin composition layer remaining after the substrate is removed from the laminate according to the above (5), laminated on the desired support, and laminated. The photosensitive resin composition layer is exposed to a predetermined pattern, baked after exposure, and the resin composition layer is developed, and the obtained resin pattern is heat-treated to obtain a cured resin pattern having a predetermined shape.
(9)一種感光性樹脂組成物,其係含有參(五氟乙基)三氟磷酸鋶之光致陽離子聚合起始劑(A)、與下述式(3)所表示的特定結構的多官能環氧樹脂(B)所成。 (9) A photosensitive resin composition containing a photo-cationic polymerization initiator (A) of ruthenium (pentafluoroethyl)trifluorophosphonate and a specific structure represented by the following formula (3) Made of functional epoxy resin (B).
(10)如上述(9)所記載之感光性樹脂組成物,其中光致陽離子聚合起始劑(A)為下述式(4)所表示之化合物。 (10) The photosensitive resin composition according to the above (9), wherein the photocationic polymerization initiator (A) is a compound represented by the following formula (4).
(11)如上述(9)或(10)所記載之感光性樹脂組 成物,其係含有反應性環氧單體(C)。 (11) The photosensitive resin group as described in the above (9) or (10) A product containing a reactive epoxy monomer (C).
(12)如上述(9)至(11)中任一項所記載之感光性樹脂組成物,其中於含有溶劑(D)之感光性樹脂組成物中,其固體成份濃度為5~95重量%。 (12) The photosensitive resin composition according to any one of the above-mentioned (9), wherein the solid content of the photosensitive resin composition containing the solvent (D) is 5 to 95% by weight. .
(13)一種感光性樹脂組成物層合物,其係用基材挾入上述(1)至(12)中任一項所記載之感光性樹脂組成物。 (13) A photosensitive resin composition laminate according to any one of the above (1) to (12).
(14)一種硬化物,其係含有上述(1)至(12)中任一項所記載之感光性樹脂組成物所成。 (14) A cured product comprising the photosensitive resin composition according to any one of the above (1) to (12).
(15)一種圖型形成方法,其係包含將於所望的支撐體上塗佈上述(9)至(12)中任一項所記載之感光性樹脂組成物所得到的感光性樹脂組成物層,乾燥後,依所定的圖型曝光,曝光後烘烤,顯影樹脂組成物層,加熱處理所得到的樹脂圖型後,得到所定形狀的硬化樹脂圖型之步驟所成。 (15) A pattern forming method comprising the photosensitive resin composition layer obtained by applying the photosensitive resin composition according to any one of the above (9) to (12) to a desired support. After drying, the film is exposed according to a predetermined pattern, baked after exposure, and the resin composition layer is developed, and the obtained resin pattern is heat-treated to obtain a cured resin pattern of a predetermined shape.
(16)一種圖型形成方法,其係包含將從上述(13)所記載的層合物去除基材後殘留的感光性樹脂組成物層,貼合於上述所望的支撐體上後層合,將此感光性樹脂組成物層依所定的圖型曝光,曝光後烘烤,顯影樹脂組成物層,加熱處理所得到的樹脂圖型後,得到所定形狀的硬化樹脂圖型之步驟所成。 (16) A method of forming a pattern comprising a photosensitive resin composition layer remaining after removing a substrate from the laminate according to the above (13), and bonding the layer to the desired support, followed by lamination. The photosensitive resin composition layer is exposed to a predetermined pattern, baked after exposure, and the resin composition layer is developed, and the obtained resin pattern is heat-treated to obtain a cured resin pattern having a predetermined shape.
本發明的感光性樹脂組成物,適用於具有高長寬比的 外形之樹脂圖型的形成,特別是適用於微細尺寸的電子裝置等中之尺寸安定性高的樹脂成形。 The photosensitive resin composition of the present invention is suitable for having a high aspect ratio The formation of the resin pattern of the outer shape is particularly suitable for resin molding having high dimensional stability in an electronic device of a fine size.
以下說明關於本發明的實施形態。 Embodiments of the present invention will be described below.
本發明的感光性樹脂組成物,其特徵係含有鋶的參(五氟乙基)三氟磷酸鹽離子的鹽之光致陽離子聚合起始劑(A)、與特定結構的多官能環氧樹脂(B),可形成高感度且高長寬比的樹脂圖型,而且形成上述樹脂圖型的能力不會劣化,可賦予可長時間發揮之特性。此等的組合有各種可能,但特別是上述式(3)所表示的特定構造的多官能環氧樹脂(例如日本化藥(股)製NC6300)與上述式(2)所表示的化合物之光致陽離子聚合起始劑之組合最佳。 The photosensitive resin composition of the present invention is characterized in that it contains a photo-cationic polymerization initiator (A) of a salt of cerium (pentafluoroethyl)trifluorophosphate ion of cerium, and a polyfunctional epoxy resin having a specific structure. (B) A resin pattern having a high sensitivity and a high aspect ratio can be formed, and the ability to form the above resin pattern is not deteriorated, and the characteristics which can be exhibited for a long period of time can be imparted. There are various possibilities for such a combination, and in particular, a light of a polyfunctional epoxy resin having a specific structure represented by the above formula (3) (for example, NC6300 manufactured by Nippon Kayaku Co., Ltd.) and a compound represented by the above formula (2) The combination of cationic polymerization initiators is optimal.
本發明之光致陽離子聚合起始劑,係受到紫外線、遠紫外線、KrF、ArF等之準分子雷射、X射線、及電子束等之放射線的照射後產生陽離子,而此陽離子可變成聚合起始劑之化合物。 The photocationic cationic polymerization initiator of the present invention is subjected to irradiation with radiation of excimer laser, X-ray, electron beam or the like of ultraviolet rays, far ultraviolet rays, KrF, ArF or the like to generate cations, and the cation can be polymerized. The compound of the starting agent.
該光致陽離子聚合起始劑(A)為參(五氟乙基)三氟磷酸鋶。 The photocationic polymerization initiator (A) is ruthenium (pentafluoroethyl)trifluorophosphate.
該光致陽離子聚合起始劑的鋶,可列舉三苯基鋶、三-p-甲苯基鋶、三-o-甲苯基鋶、參(4-甲氧基苯基)鋶、1-萘基二苯基鋶、2-萘基二苯基鋶、參(4-氟苯基)鋶、三-1-萘基鋶、三-2-萘基鋶、參(4-羥基苯基)鋶、 4-(苯基硫)苯基二苯基鋶、4-(p-甲苯基硫)苯基二-p-甲苯基鋶、4-(4-甲氧基苯基硫)苯基雙(4-甲氧基苯基)鋶、4-(苯基硫)苯基雙(4-氟苯基)鋶、4-(苯基硫)苯基雙(4-甲氧基苯基)鋶、4-(苯基硫)苯基二-p-甲苯基鋶、雙[4-(二苯基琉基)苯基]硫醚、雙[4-(雙[4-(2-羥基乙氧基)苯基]琉基)苯基]硫醚、雙(4-[雙(4-氟苯基)琉基]苯基)硫醚、雙(4-[雙(4-甲基苯基)琉基]苯基)硫醚、雙(4-[雙(4-甲氧基苯基)琉基]苯基)硫醚、4-(4-苯甲醯-4-氯苯基硫)苯基雙(4-氟苯基)鋶、4-(4-苯甲醯-4-氯苯基硫)苯基二苯基鋶、4-(4-苯甲醯苯基硫)苯基雙(4-氟苯基)鋶、4-(4-苯甲醯苯基硫)苯基二苯基鋶、4-異丙基-4-氧代-10-硫雜-9,10-二氫蒽-2-基二-p-甲苯基鋶、7-異丙基-9-氧代-10-硫雜-9,10-二氫蒽-2-基二-苯基鋶、2-[(二-p-甲苯基)琉基]噻噸酮、2-[(二苯基)琉基]噻噸酮、4-[4-(4-tert-丁基苯甲醯)苯基硫]苯基二-p-甲苯基鋶、4-[4-(4-tert-丁基苯甲醯)苯基硫]苯基二苯基鋶、4-[4-(苯甲醯苯基硫)]苯基二-p-甲苯基鋶、4-[4-(苯甲醯苯基硫)]苯基二苯基鋶、5-(4-甲氧基苯基)硫雜anthrenium、5-苯基硫雜anthrenium、5-甲苯基硫雜anthrenium、5-(4-乙氧基苯基)硫雜anthrenium、5-(2,4,6-三甲基苯基)硫雜anthrenium等之三芳基鋶;二苯基苯醯甲基鋶、二苯基4-硝基苯醯甲基鋶、二苯基苄基鋶、二苯基甲基鋶等之二芳基鋶;苯基甲基苄基鋶、4-羥基苯基甲基苄基鋶、4-甲氧 基苯基甲基苄基鋶、4-乙醯羰基氧化苯基甲基苄基鋶、2-萘基甲基苄基鋶、2-萘基甲基(1-乙氧基羰基)乙基鋶、苯基甲基苯醯甲基鋶、4-羥基苯基甲基苯醯甲基鋶、4-甲氧基苯基甲基苯醯甲基鋶、4-乙醯羰基氧化苯基甲基苯醯甲基鋶、2-萘基甲基苯醯甲基鋶、2-萘基十八烷基苯醯甲基鋶、9-蒽基甲基苯醯甲基鋶等之單芳基鋶;二甲基苯醯甲基鋶、苯醯甲基四氫噻吩鎓、二甲基苄基鋶、苄基四氫噻吩鎓、十八烷基甲基苯醯甲基鋶等之三烷基鋶等。此等記載於以下文獻。 The ruthenium of the photocationic polymerization initiator may, for example, be triphenylsulfonium, tri-p-methylphenylphosphonium, tri-o-methylphenylphosphonium, stilbene (4-methoxyphenyl)fluorene or 1-naphthyl. Diphenyl hydrazine, 2-naphthyldiphenyl fluorene, stilbene (4-fluorophenyl) fluorene, tri-1-naphthyl anthracene, tri-2-naphthyl anthracene, ginseng (4-hydroxyphenyl) fluorene, 4-(phenylthio)phenyldiphenylphosphonium, 4-(p-tolylthio)phenyldi-p-methylphenyl, 4-(4-methoxyphenylthio)phenyl bis (4 -Methoxyphenyl)anthracene, 4-(phenylthio)phenylbis(4-fluorophenyl)anthracene, 4-(phenylthio)phenylbis(4-methoxyphenyl)anthracene, 4 -(phenylthio)phenyldi-p-tolylhydrazine, bis[4-(diphenylfluorenyl)phenyl] sulfide, bis[4-(bis[4-(2-hydroxyethoxy)) Phenyl]fluorenyl)phenyl] sulfide, bis(4-[bis(4-fluorophenyl)indenyl]phenyl) sulfide, bis(4-[bis(4-methylphenyl)fluorenyl) Phenyl) thioether, bis(4-[bis(4-methoxyphenyl)indenyl]phenyl) sulfide, 4-(4-benzylidene-4-chlorophenylthio)phenyl double (4-fluorophenyl)anthracene, 4-(4-benzhydrazin-4-chlorophenylsulfanyl)phenyldiphenylphosphonium, 4-(4-benzylidenephenylsulfonyl)phenylbis(4- Fluorophenyl)anthracene, 4-(4-benzylidenephenylthio)phenyldiphenylphosphonium, 4-isopropyl-4-oxo-10-thia-9,10-dihydroindole-2 - bis-p-tolylhydrazine, 7-isopropyl-9-oxo-10-thia-9,10-dihydroindol-2-yldi-phenylindole, 2-[(di-p) -tolyl)mercapto]thioxanthone, 2-[(diphenyl)indenyl]thioxanthone, 4-[4-(4-tert-butylbenzylidene)phenylthio]phenyldi- P-tolyl oxime, 4-[4 -(4-tert-butylbenzhydrazide)phenylthio]phenyldiphenylphosphonium, 4-[4-(benzhydrylphenylsulfonyl)]phenyldi-p-methylphenyl, 4-[ 4-(benzimidylthio)]phenyldiphenylphosphonium, 5-(4-methoxyphenyl)thiaanthrenium, 5-phenylthiaanthenium, 5-tolylthioanthenium, 5 -(4-ethoxyphenyl)thiaanthrenium, 5-(2,4,6-trimethylphenyl)thiaanthrenium, etc. triarylsulfonium; diphenylbenzoquinonemethylhydrazine, diphenyl a diaryl fluorene such as 4-nitrophenylhydrazine methyl hydrazine, diphenylbenzyl hydrazine or diphenylmethyl hydrazine; phenylmethylbenzyl hydrazine, 4-hydroxyphenylmethylbenzyl hydrazine, 4 -methoxy Phenylmethylbenzyl hydrazine, 4-ethyl hydrazine carbonyl phenyl methyl benzyl hydrazine, 2-naphthylmethyl benzyl hydrazine, 2-naphthylmethyl (1-ethoxycarbonyl) ethyl hydrazine Phenylmethylphenylhydrazine methylhydrazine, 4-hydroxyphenylmethylphenylhydrazinemethylhydrazine, 4-methoxyphenylmethylphenylhydrazinemethylhydrazine, 4-ethylhydrazinecarbonyloxyphenylenebenzene a monoaryl fluorene such as methyl hydrazine, 2-naphthylmethyl benzoquinone methyl hydrazine, 2-naphthyl octadecyl phenyl hydrazine methyl hydrazine, 9-fluorenylmethyl phenyl hydrazine methyl hydrazine; A trialkylhydrazine such as methyl benzoquinone methyl hydrazine, benzoquinone methyl tetrahydrothiophene hydrazine, dimethyl benzyl hydrazine, benzyl tetrahydrothiophene hydrazine or octadecylmethyl benzoquinone methyl hydrazine. These are described in the following documents.
關於三芳基鋶,可列舉美國專利第4231951號、美國專利第4256828號、特開平7-61964號、特開平8-165290號、特開平7-10914號、特開平7-25922號、特開平8-27208號、特開平8-27209號、特開平8-165290號、特開平8-301991號、特開平9-143212號、特開平9-278813號、特開平10-7680號、特開平10-287643號、特開平10-245378號、特開平8-157510號、特開平10-204083號、特開平8-245566號、特開平8-157451號、特開平7-324069號、特開平9-268205號、特開平9-278935號、特開2001-288205號、特開平11-80118號、特開平10-182825號、特開平10-330353號、特開平10-152495號、特開平5-239213號、特開平7-333834號、特開平9-12537號、特開平8-325259號、特開平8-160606號、特開2000-186071號(美國專利第6368769號)等;關於二芳基鋶,可列舉特開平7-300504號、特開昭64-45357 號、特開昭64-29419號等;關於單芳基鋶,可列舉特開平6-345726號、特開平8-325225號、特開平9-118663號(美國專利第6093753號)、特開平2-196812號、特開平2-1470號、特開平2-196812號、特開平3-237107號、特開平3-17101號、特開平6-228086號、特開平10-152469號、特開平7-300505號、特開2003-277353號、特開2003-277352號等;關於三烷基鋶,可列舉特開平4-308563號、特開平5-140210號、特開平5-140209號、特開平5-230189號、特開平6-271532號、特開昭58-37003號、特開平2-178303號、特開平10-338688號、特開平9-328506號、特開平11-228534號、特開平8-27102號、特開平7-333834號、特開平5-222167號、特開平11-21307號、特開平11-35613號、美國專利第6031014號等。 Examples of the triaryl sulfonium include U.S. Patent No. 4,231,951, U.S. Patent No. 4,256,828, Japanese Patent Publication No. 4-61964, Japanese Patent Application No. Hei 8-165290, No. Hei No. Hei 7-10914, No. Hei 7-25922, and JP-A-8 -27208, special Kaiping 8-27209, special Kaiping 8-165290, special Kaiping 8-301991, special Kaiping 9-143212, special Kaiping 9-278813, special Kaiping 10-7680, special Kaiping 10- 287643, special Kaiping 10-245378, special Kaiping 8-157510, special Kaiping 10-204083, special Kaiping 8-245566, special Kaiping 8-157451, special Kaiping 7-324069, special Kaiping 9-268205 No. 9-278935, special opening 2001-288205, special Kaiping 11-80118, special Kaiping 10-182825, special Kaiping 10-330353, special Kaiping 10-152495, special Kaiping 5-239213 Japanese Patent Application Laid-Open No. Hei 7-333834, No. Hei 9-12537, No. Hei 8-325259, No. Hei 8-160606, No. 2000-186071 (U.S. Patent No. 6,368,769), and the like; Except for the special Kaikai 7-300504, special opening 64-45357 No. 64-29419, and the like. For the monoaryl hydrazine, JP-A-6-345726, JP-A-8-325225, JP-A-9-118663 (U.S. Patent No. 6,093,537), and JP-A No. 2 -196812, special Kaiping 2-1470, special Kaiping 2-196812, special Kaiping 3-237107, special Kaiping 3-17101, special Kaiping 6-228086, special Kaiping 10-152469, special Kaiping 7- 300505, JP-A-2003-277353, JP-A-2003-277352, etc.; for the trialkylsulfonium, JP-A-4-308563, JP-A-5-14010, JP-A-5-140209, and JP-A-5 -230189, Special Kaiping 6-271532, Special Kaikai 58-37003, Special Kaiping 2-178303, Special Kaiping 10-338688, Special Kaiping 9-328506, Special Kaiping 11-228534, Special Kaiping 8 No. -27,102, JP-A-H07-333834, JP-A No. 5-222167, No. Hei 11-21307
特別是上述光致陽離子聚合起始劑的鋶,以三苯基鋶、4-(苯基硫)苯基二苯基鋶較佳,下述式(2)所表示的4-(苯基硫)苯基二苯基鋶最佳。 In particular, the ruthenium of the photocationic polymerization initiator is preferably triphenylphosphonium or 4-(phenylthio)phenyldiphenylphosphonium, 4-(phenylsulfate) represented by the following formula (2). Phenyldiphenylphosphonium is most preferred.
本發明中之具有上述特定結構之多官能環氧樹脂(B),只要是用於形成厚膜的圖型之一分子中含有充分的環氧基之多官能環氧樹脂即可,可為任何環氧樹脂,此等具有上述特定結構之多官能環氧樹脂的環氧當量為150~400較佳,小於此範圍,由硬化收縮大而易發生硬化物的翹曲或裂縫之觀點而言較不佳,另一方面,大於此範圍時,因為交聯密度變小、硬化膜的強度或耐藥品性、耐熱性、耐裂縫性差而較不佳。符合上述範圍的多官能環氧樹脂,以上述特定結構的多官能環氧樹脂(例如NC6300日本化藥(股)製)為特別佳。 The polyfunctional epoxy resin (B) having the above specific structure in the present invention may be any polyfunctional epoxy resin having a sufficient epoxy group in a molecule for forming a thick film. The epoxy resin, such a polyfunctional epoxy resin having the above specific structure has an epoxy equivalent of 150 to 400, preferably less than this range, and is superior in hardening shrinkage to warpage or cracking of the cured product. On the other hand, when it is larger than this range, the crosslinking density becomes small, the strength of the cured film or the chemical resistance, heat resistance, and crack resistance are poor. A polyfunctional epoxy resin having a specific range as described above is particularly preferred as a polyfunctional epoxy resin having a specific structure as described above (for example, manufactured by Nippon Chemical Co., Ltd.).
具有上述特定結構之多官能環氧樹脂(B),以下述式(3)表示。 The polyfunctional epoxy resin (B) having the above specific structure is represented by the following formula (3).
多官能環氧樹脂的軟化點低時,圖型化時易發生光罩黏著,而且,作為乾膜光阻使用時,因為於常溫中軟化而較不佳,另一方面,多官能環氧樹脂的軟化點高時,將乾膜光阻層壓於基板時不易軟化,與基板的貼合性變差,故較不佳。基於上述理由,多官能環氧樹脂的較佳軟化點為40~120℃,更佳為50~100℃。 When the softening point of the polyfunctional epoxy resin is low, the mask is likely to adhere when patterning, and when used as a dry film photoresist, it is less preferred to soften at room temperature, and on the other hand, a multifunctional epoxy resin. When the softening point is high, when the dry film photoresist is laminated on the substrate, it is hard to soften, and the adhesion to the substrate is deteriorated, which is not preferable. For the above reasons, the polyfunctional epoxy resin preferably has a softening point of 40 to 120 ° C, more preferably 50 to 100 ° C.
上述光致陽離子聚合起始劑(A)於該感光性樹脂組成物中的含量太高,具有上述特定結構之多官能環氧樹脂(B)於上述感光性樹脂組成物中的含量太低時,該樹脂組成物的顯影困難,而且硬化後的膜變脆,故較不佳。相反的,上述光致陽離子聚合起始劑(A)於該感光性樹脂組成物中的含量太低,具有上述特定結構之多官能環氧樹脂(B)於上述感光性樹脂組成物中的含量太高時,塗佈 於基板上時該樹脂組成物之藉由放射線曝光的硬化時間變長而較不佳。考量上述問題之下,光致陽離子聚合起始劑(A)與具有上述特定結構之多官能環氧樹脂(B)的使用比例以0.1:99.9~15:85為佳,較佳為0.5:99.5~10:90。 The content of the photocationic polymerization initiator (A) in the photosensitive resin composition is too high, and when the content of the polyfunctional epoxy resin (B) having the specific structure described above is too low in the photosensitive resin composition The development of the resin composition is difficult, and the cured film becomes brittle, which is less preferable. On the contrary, the content of the above photo-cationic polymerization initiator (A) in the photosensitive resin composition is too low, and the content of the polyfunctional epoxy resin (B) having the above specific structure in the above-mentioned photosensitive resin composition is When it is too high, coating When the resin composition is on the substrate, the hardening time by the radiation exposure becomes longer and it is less preferable. In view of the above problems, the ratio of use of the photocationic polymerization initiator (A) to the polyfunctional epoxy resin (B) having the above specific structure is preferably 0.1:99.9 to 15:85, preferably 0.5:99.5. ~10:90.
本發明的感光性樹脂組成物,為了更加改良圖型的性能,可添加具有混合性之反應性環氧單體(C),反應性環氧單體,可使用縮水甘油醚化合物,可列舉例如二乙二醇二縮水甘油醚、己二醇二縮水甘油醚、二羥甲基丙烷二縮水甘油醚、聚丙二醇二縮水甘油醚(旭電化工業(股)製,ED506)、三羥甲基丙烷三縮水甘油醚(旭電化工業(股)製,ED505)、季戊四醇四縮水甘油醚等;此等可單獨使用或混合2種以上使用。反應性環氧單體(C)成份,其目的係被使用於改善光阻的反應性或硬化膜的物性,反應性環氧單體成份以液狀較多,該成份為液狀時,若摻合多於20重量%,則溶劑去除後的皮膜上易發生沾黏而引起光罩黏著等,而較不適當,由此觀點而言,摻合反應性環氧單體成份時,其摻合比例係(A)成份、(B)成份及(C)成份的合計,以光阻的固體成份而言,相對於此固體成份以1~10重量%為佳,特別是以2~7重量%較適合。 In the photosensitive resin composition of the present invention, in order to further improve the performance of the pattern, a reactive epoxy monomer (C) having a miscibility may be added, and a reactive epoxy monomer may be used. For example, a glycidyl ether compound may be used. Diethylene glycol diglycidyl ether, hexanediol diglycidyl ether, dimethylolpropane diglycidyl ether, polypropylene glycol diglycidyl ether (made by Asahi Kasei Co., Ltd., ED506), trimethylolpropane Triglycidyl ether (ED50, manufactured by Asahi Kasei Co., Ltd.), pentaerythritol tetraglycidyl ether, etc.; these may be used alone or in combination of two or more. The reactive epoxy monomer (C) component is used for improving the reactivity of the photoresist or the physical properties of the cured film. The reactive epoxy monomer component is more in liquid form, and when the component is in a liquid state, When the blending is more than 20% by weight, the film after the solvent is removed is liable to stick to the reticle, and is less suitable. From this point of view, when the reactive epoxy monomer component is blended, the blending is carried out. The total amount of the components (A), (B) and (C) is preferably 1 to 10% by weight, particularly 2 to 7 by weight, based on the solid content of the photoresist. % is more suitable.
降低本發明的感光性樹脂組成物的黏度,可使用提升塗膜性之溶劑(D),溶劑係可使用一般所使用的有機溶劑且可溶解各成份者皆可使用,如此的有機溶劑可列舉丙 酮、甲基乙基酮、環己酮等之酮類,甲苯、二甲苯、四甲基苯等之芳香族烴類,二丙二醇二甲基醚、二丙二醇二乙基醚等之二醇醚類,乙酸乙酯、乙酸丁酯、丁基溶纖劑乙酸酯、卡必醇乙酸酯、丙二醇單甲基醚乙酸酯、γ-丁內酯等之酯類,甲醇、乙醇、溶纖劑、甲基溶纖劑等之醇類,辛烷、癸烷等之脂肪族烴、石油醚、石腦油、氫化石腦油、溶劑石腦油等之石油系溶劑等之有機溶劑類等。 When the viscosity of the photosensitive resin composition of the present invention is lowered, a solvent (D) which improves the coating property can be used, and a solvent can be used by using an organic solvent which is generally used and which can dissolve each component. Such an organic solvent can be exemplified. C a ketone such as a ketone, methyl ethyl ketone or cyclohexanone; an aromatic hydrocarbon such as toluene, xylene or tetramethylbenzene; a glycol ether such as dipropylene glycol dimethyl ether or dipropylene glycol diethyl ether; Ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, etc., methanol, ethanol, cellosolve An alcohol such as a methyl cellosolve, an organic solvent such as an aliphatic hydrocarbon such as octane or decane, a petroleum solvent such as petroleum ether, naphtha, hydrogenated naphtha or solvent naphtha.
此等溶劑可單獨使用或組合2種以上使用,溶劑成份的添加目的係調整塗佈於基材時的膜厚或塗佈性,為了保持適當的主成份的溶解性、成份的揮發性、組成物的液黏度,相對於感光性樹脂組成物而言以5重量%~95重量%較佳,特別佳為10重量%~90重量%。 These solvents may be used singly or in combination of two or more. The purpose of the solvent component is to adjust the film thickness or coatability when applied to a substrate, in order to maintain proper solubility of the main component, volatility of the component, and composition. The liquid viscosity of the material is preferably from 5% by weight to 95% by weight, particularly preferably from 10% by weight to 90% by weight, based on the photosensitive resin composition.
本發明的感光性樹脂組成物,為了更提升組成物對於基板的密著性之目的,亦可使用具有混合性之密著性賦予劑,密著性賦予劑可使用矽烷偶合劑、鈦偶合劑等之偶合劑,較佳者為矽烷偶合劑。 In the photosensitive resin composition of the present invention, in order to further improve the adhesion of the composition to the substrate, a miscibility imparting agent having a miscibility may be used, and a decane coupling agent or a titanium coupling agent may be used as the adhesion imparting agent. The coupling agent is preferably a decane coupling agent.
上述矽烷偶合劑,可列舉3-氯丙基三甲氧基矽烷、乙烯基三氯矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基‧參(2-甲氧基乙氧基)矽烷、3-甲基丙烯氧基丙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、3-醯脲丙基三乙氧基矽烷等。此等密著性賦予劑,可單獨使用或組合2種以上使 用,密著性賦予劑因為主成份為未反應性,故除了於基材界面作用的成份以外,在硬化後以殘存成份存在,所以,大量使用則會產生物性降低等之壞影響,依基材的不同,由即使少量亦可發揮效果之觀點而言,在不產生壞影響的範圍內使用較為適當,其使用比例係相對於感光性樹脂組成物而言15重量%以下為佳,特別佳為10重量%以下。 The above decane coupling agent may, for example, be 3-chloropropyltrimethoxydecane, vinyltrichlorodecane, vinyltriethoxydecane, vinyltrimethoxydecane or vinyltrisole (2-methoxyethoxyl). Base) decane, 3-methacryloxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane , 3-mercaptopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, 3-anthracene Triethoxy decane and the like. These adhesion imparting agents may be used alone or in combination of two or more. Since the main component is unreacted, the adhesion imparting agent is present as a residual component in addition to the component acting on the interface of the substrate. Therefore, when used in a large amount, the physical properties are deteriorated, and the like. The difference in the amount of the material is preferably within a range that does not adversely affect the effect, and the use ratio is preferably 15% by weight or less based on the photosensitive resin composition, particularly preferably. It is 10% by weight or less.
本發明的感光性樹脂組成物中,亦可再使用目的為吸收紫外線而將所吸收的光能量供予光致陽離子聚合起始劑之增感劑,作為增感劑,較佳為例如9位與10位上具有烷氧基之蒽化合物(9,10-二烷氧基蒽衍生物),烷氧基可列舉例如甲氧基、乙氧基、丙氧基等之C1~C4的烷氧基。9,10-二烷氧基蒽衍生物,亦可再具有取代基,取代基可列舉例如氟原子、氯原子、溴原子、碘原子等之鹵素原子,甲基、乙基、丙基等之C1~C4的烷基或磺酸烷基酯基、羧酸烷基酯基等。磺酸烷基酯基或羧酸烷基酯之烷基,可列舉例如甲基、乙基、丙基等之C1~C4之烷基,此等的取代基的取代位置為2位較佳。 In the photosensitive resin composition of the present invention, a sensitizer which absorbs ultraviolet light and supplies the absorbed light energy to the photocationic polymerization initiator may be further used as the sensitizer, preferably, for example, 9-position. And a hydrazine compound having an alkoxy group at the 10-position (9,10-dialkoxyfluorene derivative), and the alkoxy group may, for example, a C1 to C4 alkoxy group such as a methoxy group, an ethoxy group or a propoxy group. base. The 9,10-dialkoxyfluorene derivative may further have a substituent, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a methyl group, an ethyl group, a propyl group or the like. An alkyl group or a sulfonic acid alkyl ester group or a carboxylic acid alkyl ester group of C1 to C4. The alkyl group of the alkyl sulfonate group or the alkyl carboxylate may, for example, be a C1 to C4 alkyl group such as a methyl group, an ethyl group or a propyl group, and the substitution position of these substituents is preferably 2 positions.
9,10-二烷氧基蒽衍生物,可列舉例如9,10-二甲氧基蒽、9,10-二乙氧基蒽、9,10-二丙氧基蒽、9,10-二甲氧基-2-乙基蒽、9,10-二乙氧基-2-乙基蒽、9,10-二丙氧基-2-乙基蒽、9,10-二甲氧基-2-氯蒽、9,10-二甲氧基蒽-2-磺酸甲基酯、9,10-二乙氧基蒽-2-磺酸甲基酯、9,10-二甲氧基蒽-2-羧酸甲基酯等;此等可單獨使用或混合2種以上使用。增感劑成份,因為少量即可發揮效果,故其使用比例係相 對於光致陽離子聚合起始劑(A)而言3重量%以下為佳,特別佳為1重量%以下。 The 9,10-dialkoxypurine derivative may, for example, be 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-di Methoxy-2-ethyl hydrazine, 9,10-diethoxy-2-ethyl hydrazine, 9,10-dipropoxy-2-ethyl hydrazine, 9,10-dimethoxy-2 -chloropurine, 9,10-dimethoxyindole-2-sulfonic acid methyl ester, 9,10-diethoxyindole-2-sulfonic acid methyl ester, 9,10-dimethoxyanthracene- 2-carboxylic acid methyl ester or the like; these may be used singly or in combination of two or more. The sensitizer component, because a small amount can exert its effect, so it uses a proportional phase The photo-cationic polymerization initiator (A) is preferably 3% by weight or less, particularly preferably 1% by weight or less.
本發明中,必須降低因為來自光致陽離子起始聚合劑(A)的離子所產生的壞影響時,亦可添加參甲氧基鋁、參乙氧基鋁、參異丙氧基鋁、異丙氧基二乙氧基鋁、參丁氧基鋁等之烷氧基鋁,參苯氧基鋁、參對甲基苯氧基鋁等之苯氧基鋁,參乙醯氧基鋁、參硬脂酸鋁、參丁酸鋁、參丙酸鋁、參乙醯丙酮鋁、參三氟乙醯丙酮鋁、參乙基乙醯乙酸鋁、二乙醯丙酮二(三甲基乙醯)甲酸鋁、二異丙氧基(乙基乙醯乙酸)鋁等之有機鋁化合物等之離子捕捉劑;此等成份可單獨使用或組合2種以上使用,此外,其摻合量係可為相對於固體成份而言10重量%以下。 In the present invention, it is necessary to reduce the adverse effects caused by ions derived from the photocationic cationic starting polymerization agent (A), and it is also possible to add methoxy aluminum, ethoxylated aluminum, and isopropoxy aluminum. Aluminum alkoxide such as propoxydiethoxyaluminum or butylaluminum hydride; phenoxy aluminum such as phenoxy aluminum or para-methylphenoxy aluminum; Aluminum stearate, aluminum arsenate, aluminum propionate, aluminum acetonide, aluminum hexafluoroacetate, aluminum acetoacetate, diethyl acetonide acetonate An ion scavenger such as an organoaluminum compound such as aluminum or diisopropoxy (ethyl acetoacetate) aluminum; these components may be used singly or in combination of two or more kinds, and the blending amount thereof may be relative to The solid content is 10% by weight or less.
而且本發明中必要時,可使用熱塑性樹脂、著色劑、增黏劑、消泡劑、塗平劑等之各種添加劑。熱塑性樹脂可列舉例如聚醚碸、聚苯乙烯、聚碳酸酯等;著色劑可列舉例如酞菁藍、酞菁綠、碘綠、結晶紫、氧化鈦、碳黑、萘黑等。增黏劑可列舉例如Orben、潘通、蒙脫石等;消泡劑可列舉例如聚矽氧烷系、氟系及高分子系等之消泡劑。使用此等添加劑等,其使用量係在本發明的感光性樹脂組成物中,例如各自為0.1~30重量%左右為大概的簡單標準,可依其使用目的而適當增減。 Further, in the case of the present invention, various additives such as a thermoplastic resin, a coloring agent, a tackifier, an antifoaming agent, and a leveling agent can be used. Examples of the thermoplastic resin include polyether oxime, polystyrene, and polycarbonate; and examples of the coloring agent include phthalocyanine blue, phthalocyanine green, iodine green, crystal violet, titanium oxide, carbon black, and naphthalene black. Examples of the tackifier include Orben, Pantone, and montmorillonite. Examples of the antifoaming agent include antifoaming agents such as polyoxyalkylene-based, fluorine-based, and polymeric. The amount of the additive to be used in the photosensitive resin composition of the present invention is, for example, about 0.1 to 30% by weight, which is an approximate simple standard, and can be appropriately increased or decreased depending on the purpose of use.
此外,本發明中,可使用硫酸鋇、鈦酸鋇、氧化矽、無定形二氧化矽、滑石、黏土、碳酸鎂、碳酸鈣、氧化鋁、氫氧化鋁、雲母粉等之無機填充劑,其摻合比例可為 組成物中的0~60重量%。 Further, in the present invention, an inorganic filler such as barium sulfate, barium titanate, cerium oxide, amorphous cerium oxide, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide or mica powder may be used. Blending ratio can be 0 to 60% by weight of the composition.
本發明的感光性樹脂組成物,較佳為依下述表1的比例添加,必要時亦可添加上述密著性賦予劑、增感劑、離子捕捉劑、熱塑性樹脂、著色劑、增黏劑、消泡劑、塗平劑及無機填充劑。以一般的方法混合,亦可僅攪拌,必要時亦可使用溶解器、均化器、3輥機等之分散機進行分散、混合,混合後可再用、網狀篩、膜濾器等過濾。 The photosensitive resin composition of the present invention is preferably added in the proportions shown in Table 1 below, and if necessary, the above-mentioned adhesion imparting agent, sensitizer, ion trapping agent, thermoplastic resin, coloring agent, and tackifier may be added. , antifoaming agent, coating agent and inorganic filler. The mixture may be mixed by a general method, or may be stirred only, and if necessary, it may be dispersed and mixed using a disperser such as a dissolver, a homogenizer or a 3-roller, and after mixing, it may be reused, filtered by a mesh sieve, a membrane filter or the like.
本發明的感光性樹脂組成物,較佳為以液狀使用,使用本發明的感光性樹脂組成物時,例如可使用旋轉塗佈機等以0.1~1000μm的厚度塗佈於矽晶圓、玻璃等基板上,以60~130℃熱處理5~60分鐘左右,去除溶劑而形成感光性樹脂組成物層後,載置具有所定圖型的光罩後照射紫外線,以50~130℃進行1~50分鐘左右的加熱處理後,將未曝光部份用顯影液以室溫~50℃顯影1~180分鐘左右後形成圖型,接著以130~200℃加熱處理,得到符合諸特性之永久保護膜。顯影液可使用例如γ-丁內酯、三乙二醇二甲基醚、丙二醇單甲基醚乙酸酯等之有機溶劑、或上述有機溶劑與水的混合液,顯影亦可使用攪拌型、噴霧型、噴 淋型等之顯影裝置,必要時亦可進行超音波照射。 The photosensitive resin composition of the present invention is preferably used in the form of a liquid. When the photosensitive resin composition of the present invention is used, for example, it can be applied to a ruthenium wafer or a glass with a thickness of 0.1 to 1000 μm using a spin coater or the like. After heat treatment at 60 to 130 ° C for 5 to 60 minutes, the solvent is removed to form a photosensitive resin composition layer, and then a mask having a predetermined pattern is placed, and then ultraviolet rays are irradiated, and 50 to 130 ° C is performed for 1 to 50. After the heat treatment for about a minute, the unexposed portion is developed with a developing solution at room temperature to 50 ° C for about 1 to 180 minutes to form a pattern, and then heat-treated at 130 to 200 ° C to obtain a permanent protective film conforming to various characteristics. As the developer, for example, an organic solvent such as γ-butyrolactone, triethylene glycol dimethyl ether or propylene glycol monomethyl ether acetate, or a mixture of the above organic solvent and water may be used, and a development type may be used. Spray type, spray A developing device such as a shower type or the like can be subjected to ultrasonic irradiation if necessary.
本發明的感光性樹脂組成物,係使用滾軸塗佈機、狹縫式塗佈機(die coater)、刮刀塗佈機、棒塗佈機、照相凹版印刷塗佈機等塗佈該組成物於基礎薄膜上後,用設定在45~100℃的乾燥爐進行乾燥,藉由去除所定量的溶劑,又必要時藉由層合外層膜作為乾膜光阻。此時,基礎薄膜上的光阻的厚度調製為2~100μm,基礎薄膜及外層膜,可使用例如聚酯、聚丙烯、聚乙烯、TAC、聚醯亞胺等之薄膜,此等薄膜必要時可使用藉由矽系離型處理劑或非矽系離型處理劑被離型處理的薄膜。使用此乾膜光阻,例如藉由手動式滾軸、層壓機等剝離外層膜,以40℃~100℃、壓力0.05~2MPa轉印於基板,可進行與上述相同的曝光、曝光後烘烤、顯影、加熱處理。 The photosensitive resin composition of the present invention is coated with a roller coater, a die coater, a knife coater, a bar coater, a gravure coater, or the like. After drying on the base film, it is dried in a drying oven set at 45 to 100 ° C, by removing the amount of solvent, and if necessary, by laminating the outer layer film as a dry film photoresist. In this case, the thickness of the photoresist on the base film is adjusted to 2 to 100 μm, and the base film and the outer layer film may be films such as polyester, polypropylene, polyethylene, TAC, polyimide, etc., if necessary, such films are necessary. A film which is subjected to release treatment by an oxime release treatment agent or a non-oxime release treatment agent can be used. By using the dry film photoresist, for example, by peeling off the outer layer film by a manual roller, a laminator or the like, and transferring the substrate to the substrate at 40 to 100 ° C and a pressure of 0.05 to 2 MPa, the same exposure and post-exposure baking as described above can be performed. Bake, develop, heat treatment.
將上述的感光性樹脂組成物以薄膜供給,可省略塗佈於支撐體、及乾燥的步驟,可更簡便地進行圖型形成。 The above-mentioned photosensitive resin composition is supplied as a film, and the step of applying to the support and drying can be omitted, and pattern formation can be performed more easily.
藉由上述方法所得到的本發明的樹脂組成物的硬化物,例如作為永久光阻膜利用於噴射記錄噴頭等MEMS用零件。 The cured product of the resin composition of the present invention obtained by the above method is used as a permanent photoresist film for a MEMS component such as a jet recording head.
以下說明本發明的實施例,此等實施例僅為適當地說明本發明之例子,並非限定本發明。 The embodiments of the present invention are described below, and the examples are merely illustrative of the present invention and are not intended to limit the invention.
依照表2所記載的摻合量(單位為重量份),將多官能環氧樹脂、光致陽離子聚合起始劑、及其他的成份,於附有攪拌機的燒瓶中以60℃攪拌混合1小時,得到感光性樹脂組成物。 The polyfunctional epoxy resin, the photocationic polymerization initiator, and other components were stirred and mixed at 60 ° C for 1 hour in a flask equipped with a stirrer according to the blending amount (unit: parts by weight) described in Table 2. A photosensitive resin composition was obtained.
將此感光性樹脂組成物用旋轉塗佈機塗佈於矽晶圓上後乾燥,而得到具有80μm的膜厚之感光性樹脂組成物層,將此感光性樹脂組成物層藉由加熱板以65℃進行5分鐘及95℃進行20分鐘之預烘烤,然後,使用i線曝光裝置(光罩對準裝置:USHIO電機公司製)進行圖型曝光(軟式接觸,i線),藉由加熱板以95℃進行6分鐘的曝光後烘烤(PEB),接著使用丙二醇單甲基醚乙酸酯,藉由浸漬法以23℃進行7分鐘的顯影處理,於基板上得到硬化樹脂圖型。 The photosensitive resin composition was applied onto a ruthenium wafer by a spin coater and dried to obtain a photosensitive resin composition layer having a film thickness of 80 μm, and the photosensitive resin composition layer was passed through a hot plate. Prebaking at 65 ° C for 5 minutes and 95 ° C for 20 minutes, and then performing pattern exposure (soft contact, i-line) using an i-line exposure apparatus (mask alignment apparatus: manufactured by USHIO Electric Co., Ltd.) by heating The plate was subjected to post-exposure baking (PEB) at 95 ° C for 6 minutes, followed by development treatment at 23 ° C for 7 minutes by immersion using propylene glycol monomethyl ether acetate to obtain a hardened resin pattern on the substrate.
顯影後藉由必要曝光量進行下述評估,結果列示於下述表2。 The following evaluation was carried out by the necessary exposure amount after development, and the results are shown in Table 2 below.
最適曝光量:使光罩轉印精密度為最佳之曝光量 Optimum exposure: the photographic mask transfer precision is the best exposure
長寬比:膜厚/所形成的光阻圖型中所密著之最細的圖型寬 Aspect ratio: film thickness / the thinnest pattern width enclosed in the formed photoresist pattern
(A):光致陽離子聚合起始劑 (A): Photocationic polymerization initiator
(商品名:CPI-210S san-apro(股)製) (trade name: CPI-210S san-apro (share) system)
(B):本發明之多官能環氧樹脂 (B): The multifunctional epoxy resin of the present invention
(商品名:NC6300日本化藥(股)製) (trade name: NC6300 Nippon Chemical Co., Ltd.)
(C):反應性環氧單體 (C): Reactive epoxy monomer
(商品名:ED506旭電化工業(股)製) (trade name: ED506 Asahi Chemical Industry Co., Ltd.)
(D):溶劑環戊酮 (D): Solvent cyclopentanone
(E):塗平劑 (E): coating agent
(商品名:MEGAFAC F-470大日本油墨化學工業(股)製) (trade name: MEGAFAC F-470 Dainippon Ink Chemical Industry Co., Ltd.)
(F):矽烷偶合劑 (F): decane coupling agent
(商品名:S-510 CHISSO(股)製) (trade name: S-510 CHISSO (share) system)
(G):光致陽離子聚合起始劑 (G): Photocationic polymerization initiator
(商品名:UVI-6974 Dow Chemical公司製50%碳酸丙 烯溶液) (trade name: UVI-6974 50% propylene carbonate manufactured by Dow Chemical Co., Ltd. Alkene solution)
如表2所示,實施例1~3皆為好的結果。 As shown in Table 2, Examples 1 to 3 are all good results.
混合100重量份的本發明之多官能樹脂(商品名NC6300日本化藥(股)製)、4.6重量份的光致聚合起始劑(商品名CPI-210S san-apro(股)製)、4重量份的反應性環氧單體(商品名ED506旭電化工業(股)製)、及30重量份的甲基乙基酮,得到感光性樹脂組成物。 100 parts by weight of the polyfunctional resin of the present invention (trade name: NC6300, manufactured by Nippon Chemical Co., Ltd.), and 4.6 parts by weight of a photopolymerization initiator (trade name: CPI-210S san-apro (manufactured by the company)), 4 A photosensitive epoxy resin composition (trade name: ED506, manufactured by Asahi Kasei Kogyo Co., Ltd.) and 30 parts by weight of methyl ethyl ketone were added in a weight ratio to obtain a photosensitive resin composition.
將此感光性樹脂組成物均勻地塗佈於60μm的聚丙烯(PP)薄膜(基礎薄膜,東麗(股)製)上,藉由溫風對流乾燥機以65℃進行10分鐘及80℃進行15分鐘乾燥後,於感光性樹脂組成物層上層合膜厚60μm的PP薄膜(外層膜,東麗(股)製),形成40μm的膜厚的感光性樹脂組成物層合物。 The photosensitive resin composition was uniformly applied onto a 60 μm polypropylene (PP) film (base film, manufactured by Toray Industries, Inc.), and subjected to a warm air convection dryer at 65 ° C for 10 minutes and at 80 ° C. After drying for 15 minutes, a PP film (outer film, manufactured by Toray Industries, Inc.) having a film thickness of 60 μm was laminated on the photosensitive resin composition layer to form a photosensitive resin composition laminate having a film thickness of 40 μm.
剝離此感光性樹脂組成物層合物的外層膜,以滾軸溫度70℃、氣體壓力0.2MPa、速度0.5m/min層合於矽晶圓上,剝離基礎薄膜,再重複此操作而得到80μm的感光性樹脂組成物層。於此感光性樹脂組成物層上,使用i線曝光裝置(光罩對準裝置:USHIO電機公司製)進行圖型曝 光(軟式接觸,i線),然後,藉由加熱板以95℃進行6分鐘的PEB,接著使用丙二醇單甲基醚乙酸酯,藉由浸漬法以23℃進行7分鐘的顯影處理,於基板上得到硬化樹脂圖型。得到最適曝光量350mJ/cm2、長寬比9.1之優良的結果。 The outer layer film of the photosensitive resin composition laminate was peeled off, laminated on a ruthenium wafer at a roll temperature of 70 ° C, a gas pressure of 0.2 MPa, and a speed of 0.5 m/min, and the base film was peeled off, and this operation was repeated to obtain 80 μm. A photosensitive resin composition layer. On the photosensitive resin composition layer, pattern exposure (soft contact, i-line) was performed using an i-ray exposure apparatus (mask alignment apparatus: manufactured by USHIO Electric Co., Ltd.), and then, by a hot plate at 95 ° C. The PEB of the minute was then subjected to development treatment at 23 ° C for 7 minutes by immersion using propylene glycol monomethyl ether acetate to obtain a hardened resin pattern on the substrate. An excellent result of an optimum exposure amount of 350 mJ/cm 2 and an aspect ratio of 9.1 was obtained.
由實施例1~4與比較例1結果的比較,可清楚的知道藉由特定結構的多官能環氧樹脂與特定的光致陽離子聚合起始劑的組合,可得到其他組合所無法得到的高感度且高長寬比的外形的樹脂圖型。 From the comparison of the results of Examples 1 to 4 and Comparative Example 1, it is clear that a combination of a polyfunctional epoxy resin having a specific structure and a specific photocationic polymerization initiator can provide a high which cannot be obtained by other combinations. A resin pattern with a shape of sensitivity and a high aspect ratio.
如上述,本發明該相關的感光性樹脂組成物,適合形成具有高長寬比的外形之樹脂圖型,特別是適合於微細尺寸的電子裝置等之尺寸安定性高的樹脂成形。 As described above, the photosensitive resin composition according to the present invention is suitable for forming a resin pattern having an outer shape having a high aspect ratio, and is particularly suitable for resin molding having high dimensional stability such as an electronic device having a fine size.
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JPH08165333A (en) * | 1994-12-14 | 1996-06-25 | Sumitomo Bakelite Co Ltd | Production of prepreg |
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