TWI744365B - Resin composition - Google Patents

Resin composition Download PDF

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TWI744365B
TWI744365B TW106124832A TW106124832A TWI744365B TW I744365 B TWI744365 B TW I744365B TW 106124832 A TW106124832 A TW 106124832A TW 106124832 A TW106124832 A TW 106124832A TW I744365 B TWI744365 B TW I744365B
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resin composition
aforementioned
formula
structural unit
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TW201817754A (en
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菅原由紀
安達勳
坂口崇洋
大竹陽介
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日商日產化學工業股份有限公司
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • G02—OPTICS
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    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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Abstract

［課題］ 　　本發明為提供一種可形成具有優良的耐溶劑性、耐熱性、透明性及平坦化性之硬化膜的樹脂組成物。 　　［解決手段］ 　　一種含有具有下述式（1）所表示之結構單位及下述式（2）所表示之結構單位的自交聯性共聚物，及酸產生劑之樹脂組成物。

Figure 106124832-A0101-11-0001-1
（式中，R0 表示氫原子或甲基，X表示單鍵或伸乙基氧基，R1 表示單鍵或伸甲基，A1 表示碳原子數5或6之環烷基或聯苯基，A2 表示環氧環己基或環氧基）。[Problem] The present invention is to provide a resin composition that can form a cured film having excellent solvent resistance, heat resistance, transparency, and planarization. [Solution] A resin composition containing a self-crosslinking copolymer having a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), and an acid generator.
Figure 106124832-A0101-11-0001-1
(In the formula, R 0 represents a hydrogen atom or a methyl group, X represents a single bond or an ethyleneoxy group, R 1 represents a single bond or a methylidene group, and A 1 represents a cycloalkyl or biphenyl group with 5 or 6 carbon atoms. Group, A 2 represents an epoxy cyclohexyl group or an epoxy group).

Description

樹脂組成物Resin composition

[0001] 本發明為有關一種含有自交聯（self crosslinking）性共聚物、酸產生劑及溶劑之樹脂組成物，及該樹脂組成物所形成之平坦化膜及微透鏡。[0001] The present invention relates to a resin composition containing a self-crosslinking copolymer, an acid generator and a solvent, and a planarization film and microlenses formed by the resin composition.

[0002] 於製造CCD／CMOS影像感測器、液晶顯示器、有機EL顯示器等的電子裝置之步驟中，多使用溶劑或鹼等進行浸漬處理，但就防止因該些處理所造成的元件劣化或損傷時，於元件表面進行設置對該處理具有耐受性之硬化膜。因此，該些硬化膜，多被要求應具有透明性、高度的耐熱性及耐光性、經長期間也不會引起著色等的變質現象、耐溶劑性、耐鹼性等之性能（專利文獻1）。此外，近年來，伴隨CCD／CMOS影像感測器之高精細化，使得感測器之感度需有提升之必要性，因此，為使微透鏡可有效率地集光於受光部，故於濾色膜上等形成硬化膜之情形，該硬化膜於底層基板上所形成之高低差亦要求予以平坦化（專利文獻2及專利文獻3）。又，也開始進行使用該些硬化膜製造微透鏡之研究。 　　[0003] CCD／CMOS影像感測器用微透鏡之製作方法之一，已知有深蝕刻法等（專利文獻4及專利文獻5）。即，於濾色膜上形成的微透鏡用樹脂層上形成光阻圖型，經由熱處理使該光阻圖型回焊（reflow）而形成透鏡圖型。將該經回焊後之光阻圖型所形成的透鏡圖型作為蝕刻遮罩，而對下層微透鏡用樹脂層進行深蝕刻，以將透鏡圖型形狀轉印於微透鏡用樹脂層之方式，以製作微透鏡。又例如專利文獻6至專利文獻8中，則揭示形成微透鏡時所使用的樹脂組成物。但，因任一者皆為感光性（輻射線敏感性）樹脂組成物，故對於使用上述深蝕刻法形成微透鏡時，並非較佳的材料。 ［先前技術文獻］ ［專利文獻］ 　　[0004] 　　［專利文獻1］專利第2921770號 　　［專利文獻2］特開2008-208235號公報 　　［專利文獻3］國際公開第2013／005619號 　　［專利文獻4］特開平1-10666號 　　［專利文獻5］特開平6-112459號公報 　　［專利文獻6］特開2006-251464號公報 　　［專利文獻7］特開2007-033518號公報 　　［專利文獻8］特開2007-171572號公報[0002] In the steps of manufacturing electronic devices such as CCD/CMOS image sensors, liquid crystal displays, organic EL displays, etc., solvents or alkalis are often used for immersion treatment, but it prevents device deterioration or deterioration caused by these treatments. When damaged, a hardened film that is resistant to the treatment is provided on the surface of the element. Therefore, these cured films are often required to have transparency, high heat resistance and light resistance, without causing deterioration such as coloring over a long period of time, solvent resistance, alkali resistance, etc. (Patent Document 1 ). In addition, in recent years, with the high-definition of CCD/CMOS image sensors, it is necessary to improve the sensitivity of the sensor. Therefore, in order to enable the microlens to efficiently collect light on the light receiving part, it is necessary to filter In the case where a cured film is formed on a colored film, the level difference formed by the cured film on the base substrate is also required to be flattened (Patent Document 2 and Patent Document 3). In addition, research on the use of these cured films to produce microlenses has also begun.　　[0003] As one of the methods for manufacturing microlenses for CCD/CMOS image sensors, deep etching methods are known (Patent Document 4 and Patent Document 5). That is, a photoresist pattern is formed on the resin layer for microlenses formed on the color filter film, and the photoresist pattern is reflowed through heat treatment to form a lens pattern. The lens pattern formed by the reflowed photoresist pattern is used as an etching mask, and the lower microlens resin layer is deep-etched to transfer the lens pattern shape to the microlens resin layer , To make micro lenses. In another example, Patent Document 6 to Patent Document 8 disclose resin compositions used when forming microlenses. However, since either of them is a photosensitive (radiation sensitive) resin composition, it is not a preferable material when the microlens is formed by the above-mentioned deep etching method. [Prior Art Documents] [Patent Documents] 　　[0004] 　　 [Patent Document 1] Patent No. 2921770 [Patent Document 2] JP 2008-208235 Publication [Patent Document 3] International Publication No. 2013/005619 [Patent Document 4] Japanese Patent Application Publication No. 1-10666 [Patent Document 5] Japanese Patent Application Publication No. 6-112459 [Patent Document 6] Japanese Patent Application Publication No. 2006-251464 [Patent Document 7] Japanese Patent Application Publication No. 2007-033518 [Patent Document 8] Japanese Patent Application Publication No. 2007 -Bulletin No. 171572

［發明所欲解決之問題］ 　　[0005] 本發明為基於前述情事所提出者，其目的為提供一種可形成具有優良的耐溶劑性、耐熱性、透明性及平坦化性的硬化膜之樹脂組成物。 ［解決問題之方法］ [0006] 本發明者們，就解決前述問題經過深入研究結果，而完成本發明。即，本發明為一種含有：具有下述式（1）所表示之結構單位及下述式（2）所表示之結構單位的自交聯性共聚物、酸產生劑，及溶劑之樹脂組成物。

Figure 02_image005
（式中，R0 表示氫原子或甲基，X表示單鍵或伸乙基氧基，R1 表示單鍵或伸甲基，A1 表示碳原子數5或6之環烷基或聯苯基，A2 表示環氧環己基或環氧基）。 　　[0007] 前述式（1）所表示之結構單位，例如下述式（1-1）、式（1-2）或式（1-3）所表示之結構單位。
Figure 02_image007
[0008] 前述式（2）所表示之結構單位，例如下述式（2-1）或式（2-2）所表示之結構單位。
Figure 02_image009
（式中，R0 表示氫原子或甲基）。 　　[0009] 本發明又提供一種，將前述樹脂組成物塗佈於具有凹部或高低差之基板，於大氣中以1×10-8 Pa至9×104 Pa之減壓下、50℃至200℃之溫度間，對塗佈該樹脂組成物的基板施以減壓燒焙10分鐘至180分鐘，以埋入該基板之方法。 　　[0010] 本發明又為，將前述樹脂組成物塗佈於基板上後，使用加熱手段對塗佈前述樹脂組成物之基板進行燒焙，經由隨後之曝光，而製得硬化膜之方法。亦可於前述曝光後，使用加熱手段進行再燒焙。 ［發明之效果］ 　　[0011] 本發明之樹脂組成物，於使該組成物所含有之共聚物形成自交聯形態時，並非必需要添加交聯劑。又，因含有潛在性之酸，故具有優良的保存安定性。此外，本發明之樹脂組成物所形成之樹脂膜，具有優良的透明性、耐溶劑性，及平坦性。因此，本發明之樹脂組成物所形成之硬化膜，可使形成於底層基板上的高低差平坦化。又，本發明之樹脂組成物於形成硬化膜後塗佈光阻之情形，及本發明之樹脂組成物形成平坦化膜或形成微透鏡後進行電極／配線形成步驟之情形中，可顯著降低前述硬化膜與光阻間之混合（mixing）現象、有機溶劑所造成之平坦化膜或微透鏡之變形及剝離等問題。因此，本發明之樹脂組成物，極適合作為形成平坦化膜及微透鏡之材料。[Problems to be Solved by the Invention] [0005] The present invention is based on the foregoing, and its purpose is to provide a resin composition that can form a cured film with excellent solvent resistance, heat resistance, transparency, and planarization. Things. [Methods to Solve the Problem] [0006] The inventors completed the present invention after in-depth research to solve the aforementioned problems. That is, the present invention is a resin composition containing: a self-crosslinking copolymer having a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), an acid generator, and a solvent .
Figure 02_image005
(In the formula, R 0 represents a hydrogen atom or a methyl group, X represents a single bond or an ethyleneoxy group, R 1 represents a single bond or a methylidene group, and A 1 represents a cycloalkyl or biphenyl group with 5 or 6 carbon atoms. Group, A 2 represents an epoxy cyclohexyl group or an epoxy group). [0007] The structural unit represented by the aforementioned formula (1), for example, the structural unit represented by the following formula (1-1), formula (1-2) or formula (1-3).
Figure 02_image007
[0008] The structural unit represented by the aforementioned formula (2), for example, the structural unit represented by the following formula (2-1) or formula (2-2).
Figure 02_image009
(In the formula, R 0 represents a hydrogen atom or a methyl group). [0009] The present invention also provides a method in which the aforementioned resin composition is coated on a substrate with recesses or height differences, and in the atmosphere at a reduced pressure of 1×10 -8 Pa to 9×10 4 Pa at 50° C. to 200° C. A method of applying reduced pressure baking to the substrate coated with the resin composition at a temperature of 10 minutes to 180 minutes to embed the substrate. [0010] The present invention is also a method of coating the aforementioned resin composition on a substrate, using heating means to fire the substrate coated with the aforementioned resin composition, and then exposing it to obtain a cured film. After the aforementioned exposure, heating means may be used for re-baking. [Effects of the Invention] [0011] In the resin composition of the present invention, when the copolymer contained in the composition is formed into a self-crosslinking form, it is not necessary to add a crosslinking agent. In addition, since it contains latent acid, it has excellent storage stability. In addition, the resin film formed from the resin composition of the present invention has excellent transparency, solvent resistance, and flatness. Therefore, the cured film formed from the resin composition of the present invention can flatten the height difference formed on the base substrate. In addition, when the resin composition of the present invention is coated with a photoresist after the cured film is formed, and when the resin composition of the present invention is formed into a flattened film or formed into a microlens, the electrode/wiring forming step can significantly reduce the aforementioned The mixing phenomenon between the hardened film and the photoresist, the deformation and peeling of the planarization film or the micro lens caused by the organic solvent, etc. Therefore, the resin composition of the present invention is extremely suitable as a material for forming a flattening film and microlenses.

［實施發明之形態］ 　　[0013] 以下，將詳細說明本發明之各成份。本發明之樹脂組成物去除溶劑後之固形成份，通常為1質量%至80質量%。 　　[0014] 本發明之樹脂組成物，為含有具有前述式（1）所表示之結構單位及前述式（2）所表示之結構單位的自交聯性共聚物、酸產生劑及溶劑。 　　前述共聚物之結構單位中，上述式（1）所表示之結構單位之含量為10mol%至90mol%。 　　[0015] 前述共聚物之重量平均分子量，通常為1,000至80,000，較佳為3,000至50,000。又，重量平均分子量為經凝膠滲透色層分析（GPC）、標準試料使用聚苯乙烯所測得之值。 　　[0016] 又，本發明之樹脂組成物中的前述共聚物之含量，以該樹脂組成物的固形成份中之含量為基準時，通常為5質量%至99.999質量%，例如80質量%至99.999質量%。 　　[0017] 本發明中，製得前述共聚物之方法並未有特別之限定，一般將含有可製得上述共聚物的單體種類的單體混合物，於聚合溶劑中，通常以50℃至120℃之溫度下進行聚合反應而可製得。依此方式製得之共聚物，通常為溶解於溶劑之溶液狀態，該狀態下並無法分離，本發明之樹脂組成物亦可使用該共聚物。 　　[0018] 又，將依上述方式製得之共聚物的溶液，投入攪拌後的己烷、二乙醚、甲醇、水等的貧溶劑中，使該共聚物再沈澱，將生成的沈澱物經過濾、洗淨後，於常壓或減壓下，進行常溫或加熱乾燥，而可將該共聚物製為粉體。經由該些操作，可去除與前述共聚物共存的聚合起始劑或未反應之化合物。本發明中，可無須再處理下使用前述共聚物的粉體，或將該粉體，例如使其再溶解於後述溶劑所製得之溶液的狀態下使用亦可。 　　[0019] 本發明之酸產生劑，為可經由光或熱產生酸，經由酸之作用而使前述環氧基進行陽離子聚合之觸媒。酸產生劑，通常為使用由陽離子成份與陰離子成份形成對位的有機鎓氯化合物，或磺酸酯。 　　[0020] 上述陽離子成份，例如，有機鋶、有機𨦡（organic oxonium）、有機銨、有機鏻、有機錪等的有機陽離子。又，上述陰離子成份，例如，B(C6 F5 )4 - 、SbF6 - 、AsF6 - 、PF6 - 或PF3 (C2 F5 )3 - 、BF4 - 、CF3 SO3 - 、C4 F9 SO3 - 、C(CF3 SO2 )3 - 等。上述磺酸酯，例如，具有CF3 SO3 基之酯、具有C4 F9 SO3 基之酯等。 　　[0021] 酸產生劑，例如， 　　CPI〔註冊商標〕110P、同110B、同210S、同100P、同101A、同200K、TA-60、TA-60B、TA-100、TA-120、TA-160（以上、SAN-APRO（股）製）、 　　IRGACURE〔註冊商標〕250、同270、同290、CGI TPS-C1、GSID-26-1（以上、BASF製）、 　　SAN-AID SI-60L、同SI-80L、同SI-100L、同SI-110L、同SI-150L、同SI-180L、同SI-45、同SI-45L、同SI-60、同SI-80、同SI-100、同SI-110、同SI-150、同SI-180、同SI-B2、同SI-B2A、同SI-B3、同SI-B3A、同SI-B4、同SI-B5、同SI-200、同SI-210、同SI-220、同SI-300、同SI-360（以上、三新化學工業（股）製）、 　　K-PURE〔註冊商標〕TAG-2678、同TAG-2681、同TAG-2689、同TAG-2690、同TAG-2700、同CXC-1612、同CXC-1614、同CXC-1615、同CXC-1616、同CXC-1733、同CXC-1738、同CXC-1742、同CXC-1802、同CXC-1821（以上、King Industries Inc.製）、 　　DPI-105、DPI-106、DPI-109、DPI-201、BI-105、MPI-105、MPI-106、MPI-109、BBI-102、BBI-103、BBI-105、BBI-106、BBI-109、BBI-110、BBI-200、BBI-201、BBI-300、BBI-301TPS-102，TPS-103、TPS-105、TPS-106、TPS-109、TPS-200、TPS-300、TPS-1000、HDS-109、MDS-103、MDS-105、MDS-205、MDS-209、BDS-109、MNPS-109、DTS-102、DTS-103、DTS-105、DTS-200、NDS-103、NDS-105、NDS-155、NDS-165、SI-105、NDI-105、NDI-109、NAI-105、NAI-109（以上、綠化學（股）製）、 　　ADEKARUS〔註冊商標〕SP-056、同SP-066、同SP-140、同SP-141、同SP-082、同SP-601、同SP-606、同SP-701、同SP-150、同SP-170、同SP-171（以上、（股）ADEKA製） 等。該些酸產生劑，可單獨或將2種以上組合使用。 　　[0022] 本發明之樹脂組成物中之酸產生劑之含量，以該樹脂組成物的固形成份中之含量為基準，通常為0.001質量%至20質量%、較佳為0.001質量%至10質量%。 　　[0023] 本發明之樹脂組成物之製造方法，並未有特別之限定，例如，將前述共聚物溶解於溶劑，於該溶液中混合特定比例之酸產生劑，形成均勻的溶液等方法。此外，於該製造方法的適當階段中，必要時，可再添加其他的添加劑予以混合之方法等。 　　[0024] 前述溶劑，只要可溶解前述共聚物、酸產生劑之成份時，並未有特別之限定。該些溶劑，例如，乙二醇單甲醚、乙二醇單乙醚、甲基溶纖劑（cellosolve）乙酸酯、乙基溶纖劑（cellosolve）乙酸酯、二乙二醇單甲醚、二乙二醇單乙醚、丙二醇、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇丙醚乙酸酯、丙二醇單丁醚、丙二醇單丁醚乙酸酯、甲苯、二甲苯、甲基乙酮、環戊酮、環己酮、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁烷酸甲酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸甲酯、丙酮酸甲酯、乙酸乙酯、乙酸丁酯、乳酸乙酯、乳酸丁酯、2-庚酮、γ-丁內酯等。該些溶劑，可單獨使用亦可、將2種以上組合使用亦可。 　　[0025] 該些溶劑之中，就提高於基板上塗佈本發明之樹脂組成物所形成的塗膜之平整性的觀點，以丙二醇單甲醚、丙二醇單甲醚乙酸酯、2-庚酮、乳酸乙酯、乳酸丁酯、環戊酮及環己酮為佳。 　　[0026] 又，本發明之樹脂組成物，就提高塗佈性之目的，亦可含有界面活性劑。該界面活性劑，例如，聚氧乙烯基月桂醚、聚氧乙烯基硬脂醚、聚氧乙烯基鯨蠟醚、聚氧乙烯基油醚等的聚氧乙烯基烷醚類、聚氧乙烯基辛苯醚、聚氧乙烯基壬苯醚等的聚氧乙烯烷基芳醚類、聚氧乙烯基・聚氧丙烯基嵌段共聚物類、山梨糖醇單月桂酸酯、山梨糖醇單棕櫚酸酯、山梨糖醇單硬脂酸酯、山梨糖醇單油酸酯、山梨糖醇三油酸酯、山梨糖醇三硬脂酸酯等的山梨糖醇脂肪酸酯類、聚氧乙烯基山梨糖醇單月桂酸酯、聚氧乙烯基山梨糖醇單棕櫚酸酯、聚氧乙烯基山梨糖醇單硬脂酸酯、聚氧乙烯基山梨糖醇三油酸酯、聚氧乙烯基山梨糖醇三硬脂酸酯等的聚氧乙烯基山梨糖醇脂肪酸酯類等的非離子系界面活性劑、F-TOP〔註冊商標〕EF301、同EF303、同EF352（以上、三菱金屬電子化成（股）製）、美格氟〔註冊商標〕F171、同F173、同R-30、同R-40、同R-40-LM（以上、DIC（股）製）、FLUORD FC430、同FC431（以上、住友3M（股）製）、AsahiGuard〔註冊商標〕AG710、SURFLON〔註冊商標〕S-382、同SC101、同SC102、同SC103、同SC104、同SC105、同SC106（旭硝子（股）製）、DFX-18、FTX-206D、FTX-212D、FTX-218、FTX-220D、FTX-230D、FTX-240D、FTX-212P、FTX-220P、FTX-228P、FTX-240G等FTERGENT系列（（股）NEOS製）等的氟系界面活性劑、有機矽氧烷聚合物KP341（信越化學工業（股）製）等。該些界面活性劑，可單獨或將2種以上組合使用。 　　[0027] 又，使用前述界面活性劑時，本發明之樹脂組成物中之含量，依該樹脂組成物的固形成份中之含量為基準，為3質量%以下，較佳為1質量%以下，更佳為0.5質量%以下。 　　[0028] 又，本發明之樹脂組成物，於無損本發明效果之範圍，於必要時，可含有交聯劑、硬化助劑、紫外線吸收劑、增感劑、可塑劑、抗氧化劑、密著助劑等的添加劑。 　　[0029] 前述交聯劑，以至少具有2個環氧環之化合物，或至少具有1個氧環丁烷環之化合物為佳。 　　[0030] 前述至少具有2個環氧環之化合物，例如，雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AD型環氧樹脂、雙酚S型環氧樹脂等的雙酚型環氧樹脂、酚-酚醛清漆型環氧樹脂、甲酚-酚醛清漆型環氧樹脂等的酚醛清漆型環氧樹脂、茀型環氧樹脂、三酚甲烷三縮水甘油醚等的芳香族環氧樹脂，及該些氫化加物及溴化物、 　　1,4-丁烷二醇二縮水甘油醚、1,6-己烷二醇二縮水甘油醚、新戊基二醇二縮水甘油醚、丙三醇二縮水甘油醚、丙三醇三縮水甘油醚、三羥甲基丙烷二縮水甘油醚、三羥甲基丙烷三縮水甘油醚、季戊四醇四縮水甘油醚、季戊四醇四縮水甘油醚、季戊四醇聚縮水甘油醚、聚乙烯等的碳原子數2至9（較佳為2至4）之含有伸烷基的聚氧烷二醇聚縮水甘油醚、1,4-環己烷二甲醇二縮水甘油醚、肌醇三縮水甘油醚、肌醇聚縮水甘油醚、2,2-雙（羥基甲基）-1-丁醇的1,2-環氧-4-（2-環氧乙烷基）環己烷加成物等的脂肪族環氧樹脂、 　　3,4-環氧環己基甲基-3’,4’-環氧環己烷羧酸酯、3,4-環氧-2-甲基環己基甲基-3’,4’-環氧-2’-甲基環己烷羧酸酯、雙（3,4-環氧環己基）己二酸酯、雙（3,4-環氧環己基甲基己二酸酯、雙（3,4-環氧-6-甲基環己基甲基）己二酸酯、2-（3,4-環氧環己基-5,5-螺-3,4-環氧環己酮-m-二噁烷、雙（2,3-環氧環戊基）醚、二環戊二烯二環氧化物、1,2：8,9-二環氧檸檬烯、（3,4,3’,4’-二環氧）雙環己酯、雙環壬二烯二環氧化物、ε-己內酯變性3’,4’-環氧環己基甲基3,4-環氧環己烷羧酸酯、丁烷四羧酸四（3,4-環氧環己基甲基）修飾ε-己內酯、四氫茚二環氧化物等的脂環式環氧樹脂、 　　苯二甲酸二縮水甘油酯、四氫苯二甲酸二縮水甘油酯、六氫苯二甲酸二縮水甘油酯、二縮水甘油-p-氧代安息香酸、水楊酸之縮水甘油醚-縮水甘油酯、二聚酸縮水甘油酯、富馬酸二縮水甘油、馬來酸二縮水甘油等的、縮水甘油酯型環氧樹脂及該些氫化物、 　　單烯丙基二縮水甘油異三聚氰酸酯、三縮水甘油異三聚氰酸酯、三（4,5-環氧戊基）異三聚氰酸酯、二（4,5-環氧戊基）乙內醯脲、四縮水甘油乙炔脲等的含氮環環氧樹脂等。 　　[0031] 前述至少具有2個環氧環之化合物的市售品，例如， 　　jER〔註冊商標〕825、同827、同828、同828EL、同828US、同828XA、同834、同1001、同1002、同1003、同1055、同1004、同1004AF、同1007、同1009、同1010、同1003F、同1004F、同1005F、同1009F、同1004FS、同1006FS、同1007FS、同834X90、同1001B80、同1001X70、同1001X75、同1001T75、同806、同806H、同807、同4004P、同4005P、同4007P、同4010P、同1256、同4250、同4275、同1256B40、同1255HX30、同YX8100BH30、同YX6954BH30、同YX7200B35、同5046B80、同152、同154、同157S70、同1031S、同1032H60、同604、同630、同630LSD、同871、同872、同872X75、同168V70、同YL6810、同YX7700、同YX8000、同YX8034、同YX8800、同YL980、同YL983U、同YX7105、同YX7110B80、同YX7400、同YX4000、同YX4000H、同YL6121H（以上、三菱化學（股）製）、 　　NC-3000、NC-3000-L、NC-3000-H、NC-3000-FH-75M、NC-3100、CER-3000-L、NC-2000、NC-2000-L、XD-1000、NC-7000L、NC-7300、NC-7300L、EPPN-501、EPPN-501H、EPPN-501HY、EPPN-502、EPPN-502H、EOCN-1020、EOCN-102S、EOCN-103S、EOCN-104S、CER-1020、EPPN-201、EPPN-202、BREN-S、BREN-105、RE-303S-L、RE-310S、RE-602S、LCE-21（以上、日本化藥（股）製）、 　　EPICLON〔註冊商標〕840、同840-S、同850、同850-S、同850-LC、同EXA-850CRP、同860、同1051、同1050、同1055、同2050、同3050、同4050、同7050、同HM-091、同HM-101、同830、同830-S、同835、同EXA-830CRP、同EXA-830LVP、同EXA-835LV、同152、同153、同N-660、同N-665、同N-670、同N-673、同N-680、同N-690、同N-695、同N-665-EXP、同N-672-EXP、同N-655-EXP-S、同N-662-EXP-S、同N-670-EXP-S、同N-685-EXP-S、同N-730A、同N-740、同N-770、同N-775、同N-865、同HP-4032D、同HP-7200L、同HP-7200H、同HP-7200HH、同HP-7200HHH、同HP-4700、同HP-4770、同HP-5000、同HP-6000、同HP-4710、同EXA-4850-150、同EXA-4850-1000、同EXA-4816、同HP-820（以上、DIC（股）製）、 　　Ogsol〔註冊商標〕PG-100、同CG-500、同EG-200、同EG-280、同CG-400（以上、大阪氣體化學（股）製）、 　　Epolite 40E、同100E、同200E、同400E、同70P、同200P、同400P、同1500NP、同1600、同80MF、同100MF、同4000、同3002（N）（以上、共榮社化學（股）製）、 　　Denacol〔註冊商標〕EX-211、同EX-212、同EX-252、同EX-810、同EX-811、同EX-850、同EX-851、同EX-821、同EX-830、同EX-832、同EX-841、同EX-861、同EX-911、同EX-941、同EX-920、同EX-931、同EX-313、同EX-314、同EX-321、同EX-411、同EX-421、同EX-512、同EX-521、同EX-612、同EX-614、同EX-614B、同EX-201、同EX-711、同EX-721、同EX-622、同EX-1310、同EX-1410、同EX-1610、同EX-610U、同EX-211L、同EX-212L、同EX-214L、同EX-216L、同EX-321L、同EX-722L、同EX-850L、同EX-946L、同DLC-201、同DLC-202、同DLC-203、同DLC-204、同DLC-205（以上、長瀨化學科技（股）製）、 　　Epotodo〔註冊商標〕YD-127、同YD-128、同YDF-170、同YD-8125、同YDF-8170C、同ZX-1059、同YD-825GS、同YD-825GSH、同YDF-870GS、同YDPN-138、同YDCN-700、同YDC-1312、同YSLV-80XY、同YSLV-120TE、同ST-3000、同ST-4000D、同YD-171、同FX-289BEK75、同FX-305EK70、同ERF-001M30、PG-207GS、ZX-1658GS（以上、新日鐵住金化學（股）製）、 　　Adeka樹脂〔註冊商標〕EP-4100、同EP-4100G、同EP-4100E、同EP-4100TX、同EP-4100HF、同EP-4300E、同EP-4400、同EP-4520S、同EP-4530、同EP-4901、同EP-4901HF、同EP-5100R、同EP-4000、同EP-4000S、同EP-4000L、同EP-4003S、同EP-4005、同EP-4010S、同EP-4010L、同EP-7001、同EP-4080E、同EP-4082HT、同EP-4088S、同EP-4088L、同EP-3300E、同EP-3300S、同EPU-7N、同EPU-73B、同EPR-1415-1、同EPR-21、同EPR-2000、同EPR-4030、同EPR-49-23、同EP-49-10N、同ED-503、同ED-503G、同ED-506、同ED-523T、同ED-505（以上、（股）ADEKA製）、 　　Celloxide〔註冊商標〕2021P、同2081、同2083、同2085、同3000、同8000、EHPE〔註冊商標〕3150、同3150CE、Epolydo〔註冊商標〕PB3600、同PB4700、同GT-401、同GT-403（以上、（股）DAICEL製）、 　　TEPIC〔註冊商標〕-G、同-S、同-SP、同-SS、同-HP、同-L、同-PAS B26L、同-PAS B22、同-VL、同-FL、同-UC（以上、日產化學工業（股）製）、 　　Epoil〔註冊商標〕G-100、同E-100LC、同E-400、同E-1000、同TMP（以上、日油（股）製）、 　　Rica樹脂〔註冊商標〕HBE-100、同DME-100、同BPO-20E、同BEO-60E（以上、新日本理化（股）製）、 　　CY175、CY177、CY179、CY182、CY184、CY192（以上、BASF日本（股）製）、 　　THI-DE（JXTG能量（股）製） 等。 　　[0032] 前述至少具有1個氧環丁烷環之化合物，例如，3-乙基-3-羥基甲基氧環丁烷、3-乙基-3-（苯氧基甲基）氧環丁烷、3-乙基-3-（2-乙基己氧基甲基）氧環丁烷、（3-乙基氧環丁烷-3-基）甲基丙烯酸酯、（3-乙基氧環丁烷-3-基）甲基甲基丙烯酸酯、3-乙基-3-［（3-乙基氧環丁烷-3-基）甲氧基甲基］氧環丁烷、1,4-雙［（3-乙基氧環丁烷-3-基）甲氧基甲基］苯、1,4-雙［（3-乙基氧環丁烷-3-基）甲氧基甲基］環己烷、4,4’-雙［（3-乙基氧環丁烷-3-基）甲氧基甲基］雙環己酯、4,4’-雙［（3-乙基氧環丁烷-3-基）甲氧基甲基］聯苯等。 　　[0033] 前述至少具有1個氧環丁烷環之化合物的市售品，例如，Aron氧環丁烷〔註冊商標〕OXT-101、同OXT-121、同OXT-211、同OXT-212、同OXT-213、同OXT-221（以上、東亞合成（股）製）、ETERNACOLL〔註冊商標〕EHO、同OXBP、同OXTP、同OXMA（以上、宇部興產（股）製）等。 　　[0034] 前述交聯劑，可單獨使用或將2種以上組合使用皆可。 　　[0035] 使用前述交聯劑時，本發明之樹脂組成物中之含量，依前述共聚物100質量%為基準時，為1質量%至200質量%，較佳為3質量%至100質量%，更佳為5質量%至50質量%。 　　[0036] 前述增感劑，例如，9-羥基甲基蒽、9,10-二甲氧基蒽、9,10-二乙氧基蒽、9,10-二丙氧基蒽、9,10-二丁氧基蒽、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-雙（辛醯氧基）蒽、9,10-二甲氧基蒽-2-磺酸甲酯、9,10-二乙氧基蒽-2-磺酸甲酯、9,10-二甲氧基蒽-2-羧酸甲酯、9-氧硫

Figure 106124832-A0304-12-0019-1
Figure 106124832-A0304-xxxx-3
、2-異丙基9-氧硫
Figure 106124832-A0304-12-0019-1
Figure 106124832-A0304-xxxx-3
、4-異丙基9-氧硫
Figure 106124832-A0304-12-0019-1
Figure 106124832-A0304-xxxx-3
、2-氯9-氧硫
Figure 106124832-A0304-12-0019-1
Figure 106124832-A0304-xxxx-3
、2,4-二甲基9-氧硫
Figure 106124832-A0304-12-0019-1
Figure 106124832-A0304-xxxx-3
、2,4-二乙基9-氧硫
Figure 106124832-A0304-12-0019-1
Figure 106124832-A0304-xxxx-3
、2,4-二異丙基9-氧硫
Figure 106124832-A0304-12-0019-1
Figure 106124832-A0304-xxxx-3
、蒽醌、1,2-二羥基蒽醌、2-乙基蒽醌、1,4-二乙氧基萘等。 　　[0037] 前述增感劑之市售品，例如，ANTHRACYCLINE〔註冊商標〕UVS-1331、同UVS-1101、同UVS-581（以上、川崎化成工業（股）製）、KAYACURE〔註冊商標〕DETX-S、同EPA（以上、日本化藥（股）製）等。 　　[0038] 前述增感劑，可單獨使用或將2種以上組合使用皆可。 　　[0039] 使用前述增感劑時，本發明之樹脂組成物中之含量，依前述酸產生劑100質量%為基準，為50質量%以下，較佳為30質量%以下，更佳為20質量%以下。 　　[0040] 以下，將說明本發明之樹脂組成物之使用例。 　　使用旋轉塗佈機、塗佈機（Coater）等的適當塗佈方法，將本發明之樹脂組成物塗佈於基板｛例如，氧化矽膜覆蓋之矽等的半導體基板、氮化矽膜或氧化氮化矽膜覆蓋之矽等的半導體基板、形成濾色膜之矽等的半導體基板、氮化矽基板、石英基板、玻璃基板（包含無鹼玻璃、低鹼玻璃、結晶化玻璃）、形成ITO膜之玻璃基板｝上。隨後，使用加熱板、烘箱等的加熱手段，進行預燒焙而形成塗膜。又，於後述進行減壓燒焙之情形，並非必須實施預燒焙。亦可將本發明之樹脂組成物塗佈於前述基板上之後，不進行預燒焙下進行減壓燒焙。 　　[0041] 預燒焙條件，可於燒焙溫度30℃至200℃、燒焙時間0.3分至60分鐘之中，進行適當選擇。較佳為燒焙溫度50℃至180℃、燒焙時間0.5分鐘至30分鐘。預燒焙，可於大氣中，或氮、氬氣、氦等的惰性氣體中進行。 　　[0042] 又，本發明之樹脂組成物所形成之硬化膜之膜厚為0.001μm至1000μm，較佳為0.01μm至600μm。 　　[0043] 預燒焙後、必要時，可進行減壓燒焙。減壓燒焙之條件，可於1×10-8 Pa至9×104 Pa或1×10-7 Pa至5×104 Pa之減壓下、50℃至200℃之溫度、10分至180分鐘之時間中適當地選擇。減壓燒焙，可於大氣中，或氮、氬氣、氦等的惰性氣體中進行。經由該減壓燒焙，可使基板的凹部或高低差埋入本發明之樹脂組成物。 　　[0044] 其次，必要時，可於上述所得之膜上，進行曝光。曝光，例如，可使用紫外線（例如，g線、h線、i線）、KrF準分子雷射、ArF準分子雷射等。曝光後，可使用加熱板、烘箱等的加熱手段進行後燒焙。後燒焙條件，可於燒焙溫度100℃至300℃、燒焙時間0.5分鐘至180分鐘中適當地選擇。又，後燒焙，可於大氣中，或氮、氬氣、氦等的惰性氣體中進行。 　　[0045] 形成微透鏡之方法，可將光阻溶液塗佈於由本發明之樹脂組成物所形成的硬化膜，並經由特定之遮罩進行曝光，必要時，可進行曝光後加熱（PEB），經鹼顯影、洗滌及乾燥處理，而可形成特定之光阻圖型。曝光，例如，可使用紫外線（例如，g線、h線、i線）、KrF準分子雷射、ArF準分子雷射等。 　　[0046] 其次，經由加熱處理（通常為不超過200℃之溫度），可經由回焊上述光阻圖型而形成透鏡圖型。將此透鏡圖型作為蝕刻遮罩，對下層的微透鏡用硬化膜進行深蝕刻處理，將透鏡圖型形狀轉印於微透鏡用樹脂層，而製得微透鏡。 ［實施例］ 　　[0047] 以下，將以實施例為基礎對本發明作更詳細之說，但本發明並不受該些實施例所限定。 〔下述合成例所得之共聚物之重量平均分子量之測定〕 　　裝置：日本分光（股）製GPC系統 　　管柱：SHODEX〔註冊商標〕KF-804L及803L 　　管柱烘箱：40℃ 　　流量：1mL／分鐘 　　溶離液：四氫呋喃 　　[0048] ［共聚物的合成］ ＜合成例1＞ 　　將3,4-環氧環己基甲基甲基丙烯酸酯（CYCLEMA〔註冊商標〕M100（（股）DAICEL製））7.61g、環己基丙烯酸酯40.0g，及2,2’-偶氮二異丁腈1.96g，溶解於丙二醇單甲醚乙酸酯74.3g之後，將該溶液以3小時時間滴入使丙二醇單甲醚乙酸酯41.3g保持於70℃之燒瓶中。滴入結束後，進行18小時反應，使用甲醇進行再沈澱，製得具有前述式（1-1）所表示之結構單位及前述式（2-1）（式中，R0 表示甲基）所表示之結構單位的共聚物。所得共聚物之重量平均分子量Mw為27,000（聚苯乙烯換算）。 　　[0049] ＜合成例2＞ 　　將縮水甘油甲基丙烯酸酯4.72g、環己基丙烯酸酯25.0g，及2,2’-偶氮二異丁腈1.28g，溶解於丙二醇單甲醚乙酸酯57.6g之後，將該溶液以3小時時間滴入使丙二醇單甲醚乙酸酯35.4g保持70℃之燒瓶中。滴入結束後，進行18小時反應，使用甲醇進行再沈澱，製得具有前述式（1-1）所表示之結構單位及前述式（2-2）（式中，R0 表示甲基）所表示之結構單位的共聚物。所得共聚物之重量平均分子量Mw為30,000（聚苯乙烯換算）。 　　[0050] ＜合成例3＞ 　　將3,4-環氧環己基甲基甲基丙烯酸酯（CYCLEMA〔註冊商標〕M100（（股）DAICEL製））12.5g、環己基丙烯酸酯20.0g，及2,2’-偶氮二異丁腈1.27g，溶解於丙二醇單甲醚乙酸酯62.8g之後，將該溶液以3小時時間滴入使丙二醇單甲醚乙酸酯38.6g保持80℃之燒瓶中。滴入結束後，進行18小時反應，使用甲醇進行再沈澱，製得具有前述式（1-1）所表示之結構單位及前述式（2-1）（式中，R0 表示甲基）所表示之結構單位的共聚物。所得共聚物之重量平均分子量Mw為11,000（聚苯乙烯換算）。 　　[0051] ＜合成例4＞ 　　將3,4-環氧環己基甲基甲基丙烯酸酯（CYCLEMA〔註冊商標〕M100（（股）DAICEL製））19.7g、乙氧基化正苯酚丙烯酸酯（NK酯〔註冊商標〕A-LEN-10（新中村化學工業（股）製））40.0g，及2,2’-偶氮二異丁腈3.7g，溶解於丙二醇單甲醚乙酸酯148.0g之後，將該溶液以3小時時間滴入使丙二醇單甲醚乙酸酯105.7g保持70℃之燒瓶中。滴入結束後，進行18小時反應，使用甲醇進行再沈澱，製得具有前述式（1-3）所表示之結構單位及前述式（2-1）（式中，R0 表示甲基）所表示之結構單位的共聚物。所得共聚物之重量平均分子量Mw為15,000（聚苯乙烯換算）。 　　[0052] ＜合成例5＞ 　　將3,4-環氧環己基甲基甲基丙烯酸酯（CYCLEMA〔註冊商標〕M100（（股）DAICEL製））43.9g、乙氧基化正苯酚丙烯酸酯（NK酯〔註冊商標〕A-LEN-10（新中村化學工業（股）製））15.0g，及2,2’-偶氮二異丁腈2.9g，溶解於丙二醇單甲醚乙酸酯92.7g之後，將該溶液以3小時時間滴入使丙二醇單甲醚乙酸酯51.5g保持80℃之燒瓶中。滴入結束後，進行18小時之反應，製得具有前述式（1-3）所表示之結構單位及前述式（2-1）（式中，R0 表示甲基）所表示之結構單位的共聚物之溶液（固形成份濃度30質量%）所得共聚物之重量平均分子量Mw為8,000（聚苯乙烯換算）。 　　[0053] ＜合成例6＞ 　　將3,4-環氧環己基甲基甲基丙烯酸酯7.00g、甲基丙烯酸酯15.0g，及2,2’-偶氮二異丁腈1.38g，溶解於丙二醇單甲醚乙酸酯43.4g之後，將該溶液以3小時時間滴入使丙二醇單甲醚乙酸酯26.7g保持70℃之燒瓶中。滴入結束後，進行18小時之反應，製得共聚物之溶液（固形成份濃度25質量%）。所得共聚物之重量平均分子量Mw為18,000（聚苯乙烯換算）。 　　[0054] ＜合成例7＞ 　　將3,4-環氧環己基甲基甲基丙烯酸酯11.4g、1-丙烯醯氧基-3-羥基金剛烷24.0g，及2,2’-偶氮二異丁腈1.09g，溶解於丙二醇單甲醚乙酸酯67.9g之後，將該溶液以3小時時間滴入使丙二醇單甲醚乙酸酯41.7g保持70℃之燒瓶中。滴入結束後，進行18小時之反應，製得共聚物之溶液（固形成份濃度25質量%）。所得共聚物之重量平均分子量Mw為11,000（聚苯乙烯換算）。 　　[0055] ＜合成例8＞ 　　將3,4-環氧環己基甲基甲基丙烯酸酯7.72g、異莰基丙烯酸酯40.0g，及2,2’-偶氮二異丁腈1.52g，溶解於丙二醇單甲醚乙酸酯91.4g之後，將該溶液以3小時時間滴入使丙二醇單甲醚乙酸酯56.3g保持70℃之燒瓶中。滴入結束後，進行18小時之反應，製得共聚物之溶液（固形成份濃度25質量%）。所得共聚物之重量平均分子量Mw為24，000（聚苯乙烯換算）。 　　[0056] ［樹脂組成物之製造］ ＜實施例1＞ 　　將合成例1所得之共聚物3.49g、光酸產生劑之陽離子成份為由（4-苯基硫代苯基）二苯基鋶所構成之陰離子成份為由B(C6 F5 )4 - 所構成的有機鎓氯化合物之CPI-110B（SAN-APRO（股）製）0.000204g，及界面活性劑之DFX-18（NEOS（股）製）0.00170g，溶解於丙二醇單甲醚乙酸酯16.7g中作為溶液。隨後，使用孔徑0.45μm之聚乙烯製微過濾器過濾，而製得樹脂組成物。 　　[0057] ＜實施例2＞ 　　合成例2所得之共聚物3.00g、光酸產生劑之CPI-110B（SAN-APRO（股）製）0.000180g，及界面活性劑之DFX-18（NEOS（股）製）0.00150g，溶解於丙二醇單甲醚乙酸酯15.1g中作為溶液。隨後，使用孔徑0.45μm之聚乙烯製微過濾器過濾，而製得樹脂組成物。 　　[0058] ＜實施例3＞ 　　將合成例3所得之共聚物16.0g、交聯劑之三｛2,2-雙［（環氧乙烷-2-基甲氧基）甲基］丁基｝-3,3’,3”-［1,3,5-三
Figure 106124832-A0304-12-0020-4
-2,4,6（1H,3H,5H）-三酮-1,3,5-三基］三丙酸酯（TEPIC〔註冊商標〕-UC（日產化學工業（股）製））4.0g、光酸產生劑之陽離子成份為由（4-苯基硫代苯基）二苯基鋶所構成之陰離子成份為由PF3 （C2 F5 ）3 - 所構成的有機鎓氯化合物之CPI-210S（SAN-APRO（股）製）1.0g、增感劑之9,10-雙（辛醯氧基）蒽（ANTHRACYCLINE〔註冊商標〕UVS-581（川崎化成工業（股）製））0.20g，及界面活性劑之DFX-18（NEOS（股）製）0.020g，溶解於丙二醇單甲醚乙酸酯89.3g中作為溶液。隨後，使用孔徑0.45μm之聚乙烯製微過濾器過濾，而製得樹脂組成物。 　　[0059] ＜實施例4＞ 　　將合成例4所得之共聚物16.0g、交聯劑之三（4,5-環氧戊基）異三聚氰酸酯（TEPIC〔註冊商標〕-VL（日產化學工業（股）製））4.0g、光酸產生劑之CPI-210S（SAN-APRO（股）製）1.0g、增感劑之9,10-二丁氧基蒽（ANTHRACYCLINE〔註冊商標〕UVS-1331（川崎化成工業（股）製））0.20g，及界面活性劑之DFX-18（NEOS（股）製）0.020g，溶解於丙二醇單甲醚乙酸酯89.3g中作為溶液。隨後，使用孔徑0.45μm之聚乙烯製微過濾器過濾，而製得樹脂組成物。 　　[0060] ＜實施例5＞ 　　將合成例5所得之共聚物之溶液53.3g（含固形成份16.0g）、交聯劑之三（4,5-環氧戊基）異三聚氰酸酯（TEPIC〔註冊商標〕-VL（日產化學工業（股）製））4.0g、光酸產生劑之CPI-210S（SAN-APRO（股）製）1.0g，及界面活性劑之DFX-18（NEOS（股）製）0.020g，溶解於丙二醇單甲醚乙酸酯51.1g中作為溶液。隨後，使用孔徑0.45μm之聚乙烯製微過濾器過濾，而製得樹脂組成物。 　　[0061] ＜實施例6＞ 　　將合成例4所得之共聚物8.0g、交聯劑之三（4,5-環氧戊基）異三聚氰酸酯（TEPIC〔註冊商標〕-VL（日產化學工業（股）製））2.0g、光酸產生劑的三氟甲烷磺酸酯之Adekagus〔註冊商標〕SP-606（（股）ADEKA製）0.1g，及界面活性劑之DFX-18（NEOS（股）製）0.020g，溶解於丙二醇單甲醚乙酸酯43.0g中作為溶液。隨後，使用孔徑0.45μm之聚乙烯製微過濾器過濾，而製得樹脂組成物。 　　[0062] ＜實施例7＞ 　　將合成例4所得之共聚物10.0g、光酸產生劑的三氟甲烷磺酸酯之Adekagus〔註冊商標〕SP-606（（股）ADEKA製）0.1g，及界面活性劑之DFX-18（NEOS（股）製）0.020g，溶解於丙二醇單甲醚乙酸酯43.0g中作為溶液。隨後，使用孔徑0.45μm之聚乙烯製微過濾器過濾，而製得樹脂組成物。 　　[0063] ＜實施例8＞ 　　將合成例1所得之共聚物10.0g及光酸產生劑之CPI-110B（SAN-APRO（股）製）0.0006g，溶解於丙二醇單甲醚乙酸酯15.0g中作為溶液。隨後，使用孔徑5μm之聚乙烯製微過濾器過濾，而製得樹脂組成物。 　　[0064] ＜實施例9＞ 　　將合成例4所得之共聚物10.0g，及光酸產生劑之陽離子成份為有機鋶所構成之陰離子成份為由C（CF3 SO2 ）3 - 所構成的有機鎓氯化合物之GSID-26-1（BASF公司製）0.0003g，溶解於丙二醇單甲醚乙酸酯15.0g中作為溶液。隨後，使用孔徑5μm之聚乙烯製微過濾器過濾，而製得樹脂組成物。 　　[0065] ＜比較例1＞ 　　將合成例1所得之共聚物3.13g，及界面活性劑之DFX-18（NEOS（股）製）0.00150g，溶解於丙二醇單甲醚乙酸酯16.9g中作為溶液。隨後，使用孔徑0.45μm之聚乙烯製微過濾器過濾，而製得樹脂組成物。 　　[0066] ＜比較例2＞ 　　將合成例6所得之共聚物之溶液13.0g（含固形成份3.25g）、光酸產生劑之CPI-110B（SAN-APRO（股）製）0.000191g，及界面活性劑之DFX-18（NEOS（股）製）0.00160g，溶解於丙二醇單甲醚乙酸酯6.13g中作為溶液。隨後，使用孔徑0.45μm之聚乙烯製微過濾器過濾，而製得樹脂組成物。 　　[0067] ＜比較例3＞ 　　將合成例7所得之共聚物之溶液13.0g（含固形成份3.25g）、光酸產生劑之CPI-110B（SAN-APRO（股）製）0.000192g，及界面活性劑之DFX-18（NEOS（股）製）0.00160g，溶解於丙二醇單甲醚9.72g中作為溶液。隨後，使用孔徑0.45μm之聚乙烯製微過濾器過濾，而製得樹脂組成物。 　　[0068] ＜比較例4＞ 　　將合成例8所得之共聚物之溶液13.0g（含固形成份3.25g）、光酸產生劑之CPI-110B（SAN-APRO（股）製）0.000195g，及界面活性劑之DFX-18（NEOS（股）製）0.00171g，溶解於丙二醇單甲醚乙酸酯6.28g中作為溶液。隨後，使用孔徑0.45μm之聚乙烯製微過濾器過濾，而製得樹脂組成物。 　　[0069] ［耐溶劑性試驗］ 　　將實施例1至實施例7及比較例1至比較例4所製得之樹脂組成物，分別使用旋轉塗佈器塗佈於矽晶圓上，再於加熱板上進行100℃、1分鐘之預燒焙。其次，使用具有380nm強化燈之無電極燈電源系統（（股）Oak 製作所製）全面照射於365nm中之曝光量為1000mJ／cm2 之紫外線。其次，於加熱板上進行220℃、10分鐘之後燒焙，而形成膜厚1.0μm之膜。前述預燒焙及後燒焙中之任一者皆為於大氣中實施者。將該些硬化膜，分別於丙二醇單甲醚、丙二醇單甲醚乙酸酯、環戊酮、乳酸乙酯、乙酸丁酯、3-甲氧基丙酸甲酯，及2.38質量%濃度之氫氧化四甲基銨（TMAH）水溶液中，於23℃之溫度條件下，進行5分鐘浸漬試驗。並測定浸漬前後中之膜厚變化，只要於浸潤溶劑之任一種中，相對於浸漬前之膜厚產生5%以上膜厚之增減者，則標記為“×”，於全部溶劑中，膜厚增減皆未達5%者，則標記為“○”之方式評估其耐溶劑性。評估結果如表1所示。 　　[0070] ［透過率測定］ 　　將實施例1至實施例7及比較例1至比較例4所製得之樹脂組成物，分別使用旋轉塗佈器塗佈於石英基板上，再於加熱板上進行100℃、1分鐘之預燒焙。其次，使用具有380nm強化燈之無電極燈電源系統（（股）Oak 製作所製）全面照射於365nm中之曝光量為1000mJ／cm2 之紫外線。其次，於加熱板上進行220℃、10分鐘之後燒焙，而形成膜厚1.0μm之膜。前述預燒焙及後燒焙中之任一者皆為於大氣中實施者。使用紫外線可見分光光度計UV-2600（（股）島津製作所製），測定該些硬化膜於波長400nm之透過率。評估結果如表1所示。 　　[0071] ［高低差平坦化性］ 　　將實施例1至實施例7及比較例1至比較例4所製得之樹脂組成物，分別使用旋轉塗佈器塗佈於高0.5μm、線路寬10μm、線路間空間10μm的高低差基板（圖1）上，再於加熱板上進行100℃、1分鐘之預燒焙。其次，使用具有380nm強化燈之無電極燈電源系統（（股）Oak 製作所製）全面照射於365nm中之曝光量為1000mJ／cm2 之紫外線。其次，於加熱板上進行220℃、10分鐘之後燒焙，而形成膜厚1.0μm之膜。前述預燒焙及後燒焙中之任一者皆為於大氣中實施者。由圖1所示之h1（高低差基板1之高低差）與h2（硬化膜2之高低差，即線路上之硬化膜的高度與空間上之硬化膜的高度之高低差），使用“式：（1-（h2／h1））×100”求取其平坦化率。評估結果如表1所示。 　　[0072]
Figure 02_image011
[0073] 由表1結果得知，使用本發明之樹脂組成物所形成的硬化膜，除具有高耐溶劑性的同時亦具有高透明性。此外，由本發明之樹脂組成物所形成的硬化膜，為具有平坦化率80%以上的優良高低差平坦化性者。另一方面，使用比較例1所製得之樹脂組成物所形成的硬化膜，因不含有光酸產生劑，又，比較例2至比較例4所製得之樹脂組成物所形成的硬化膜於220℃之燒焙溫度下未能充份硬化等，故得到未能滿足耐溶劑性之結果，而確認其皆無法適用於平坦化膜及微透鏡用硬化膜之用途。此外，使用比較例3及比較例4所製得之樹脂組成物所形成的硬化膜，因平坦化率未達80%，故與由本發明之樹脂組成物所形成的硬化膜相比較時，得到其為高低差平坦化性低劣之結果。 　　[0074] ［埋入性］ 　　將實施例8及實施例9所製得之樹脂組成物，塗佈於具有孔洞（hole)寬200μm四方、150μm四方，及100μm四方的凹部（孔洞深400μm）的矽晶圓上，於加熱板上進行150℃、10分鐘預燒焙後，使用烘箱於3×102 Pa之減壓下，進行150℃、20分鐘之減壓燒焙。其次，使用具有380nm強化燈之無電極燈電源系統（（股）Oak製作所製）全面照射於365nm中之曝光量為1000mJ／cm2 之紫外線。其次，使用烘箱於常壓下，進行220℃、60分鐘之後燒焙。前述預燒焙、減壓燒焙及後燒焙中之任一者皆為於大氣中實施者。使用掃瞄型電子微透鏡（SEM）觀察於具有凹部的矽晶圓上塗佈實施例8及實施例9所製得之樹脂組成物所得之斷面結果，皆未觀察出孔洞內部產生空隙及縫隙，而確認形成均勻的埋入狀態。[Modes for Implementing the Invention] [0013] Hereinafter, each component of the present invention will be described in detail. The solid content of the resin composition of the present invention after removing the solvent is usually 1% to 80% by mass. [0014] The resin composition of the present invention contains a self-crosslinkable copolymer having the structural unit represented by the aforementioned formula (1) and the structural unit represented by the aforementioned formula (2), an acid generator, and a solvent. In the structural unit of the aforementioned copolymer, the content of the structural unit represented by the above formula (1) is 10 mol% to 90 mol%. [0015] The weight average molecular weight of the aforementioned copolymer is usually 1,000 to 80,000, preferably 3,000 to 50,000. In addition, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard sample. [0016] In addition, the content of the aforementioned copolymer in the resin composition of the present invention, when based on the content of the solid content of the resin composition, is usually 5 mass% to 99.999 mass%, for example, 80 mass% to 99.999 quality%. [0017] In the present invention, the method for preparing the aforementioned copolymer is not particularly limited. Generally, a monomer mixture containing the monomer types that can be used to prepare the aforementioned copolymer is used in a polymerization solvent, usually at a temperature of 50°C to 120°C. It can be obtained by polymerization reaction at a temperature of ℃. The copolymer prepared in this way is usually in the state of a solution dissolved in a solvent and cannot be separated in this state. The resin composition of the present invention can also use the copolymer. [0018] In addition, the solution of the copolymer prepared in the above manner is poured into a poor solvent such as hexane, diethyl ether, methanol, water, etc. after stirring to re-precipitate the copolymer, and the resulting precipitate is filtered , After washing, under normal pressure or reduced pressure, drying at normal temperature or heating, the copolymer can be made into powder. Through these operations, the polymerization initiator or unreacted compound coexisting with the aforementioned copolymer can be removed. In the present invention, the powder of the aforementioned copolymer can be used without reprocessing, or the powder can be used in a state of, for example, re-dissolving the powder in a solution prepared by the solvent described below. [0019] The acid generator of the present invention is a catalyst that can generate an acid through light or heat, and through the action of the acid, the aforementioned epoxy group undergoes cationic polymerization. The acid generator is usually an organic onium chloride compound or sulfonic acid ester in which a cationic component and an anionic component form a para position. [0020] The above-mentioned cationic components are, for example, organic cations such as organic oxonium, organic ammonium, organic phosphonium, and organic oxonium. Further, the anionic ingredients, e.g., B (C 6 F 5) 4 -, SbF 6 -, AsF 6 -, PF 6 - or PF 3 (C 2 F 5) 3 -, BF 4 -, CF 3 SO 3 - , C 4 F 9 SO 3 - , C (CF 3 SO 2) 3 - and the like. The above-mentioned sulfonic acid esters, for example, esters having CF 3 SO 3 groups, esters having C 4 F 9 SO 3 groups, and the like. [0021] Acid generators, for example, CPI [registered trademark] 110P, the same 110B, the same 210S, the same 100P, the same 101A, the same 200K, TA-60, TA-60B, TA-100, TA-120, TA-160 (Above, SAN-APRO (share) system), IRGACURE [registered trademark] 250, the same 270, the same 290, CGI TPS-C1, GSID-26-1 (above, BASF system), SAN-AID SI-60L, the same SI-80L, same SI-100L, same SI-110L, same SI-150L, same SI-180L, same SI-45, same SI-45L, same SI-60, same SI-80, same SI-100, same SI-110, same SI-150, same SI-180, same SI-B2, same SI-B2A, same SI-B3, same SI-B3A, same SI-B4, same SI-B5, same SI-200, same SI-210, same as SI-220, same as SI-300, same as SI-360 (above, manufactured by Sanxin Chemical Industry Co., Ltd.), K-PURE [registered trademark] TAG-2678, same as TAG-2681, same as TAG- 2689, same TAG-2690, same TAG-2700, same CXC-1612, same CXC-1614, same CXC-1615, same CXC-1616, same CXC-1733, same CXC-1738, same CXC-1742, same CXC- 1802 Same as CXC-1821 (above, manufactured by King Industries Inc.), DPI-105, DPI-106, DPI-109, DPI-201, BI-105, MPI-105, MPI-106, MPI-109, BBI- 102, BBI-103, BBI-105, BBI-106, BBI-109, BBI-110, BBI-200, BBI-201, BBI-300, BBI-301TPS-102, TPS-103, TPS-105, TPS- 106, TPS-109, TPS-200, TPS-300, TPS-1000, HDS-109, MDS-103, MDS-105, MDS-205, MDS-209, BDS-109, MNPS-109, DTS-102, DTS-103, DTS-105, DTS-200, NDS-103, NDS-105, NDS-155, NDS-165, SI-105, NDI-105, NDI-109, NAI-105, NAI-109 (above, Green Chemical Co., Ltd.), ADEKARUS [registered trademark] SP-056, the same as SP-066, the same as SP-140, the same SP-141, same SP-082, same SP-601, same SP-606, same SP-701, same SP-150, same SP-170, same SP-171 (above, (share) ADEKA system), etc. These acid generators can be used alone or in combination of two or more kinds. [0022] The content of the acid generator in the resin composition of the present invention, based on the content of the solid content of the resin composition, is usually 0.001% to 20% by mass, preferably 0.001% to 10% by mass %. [0023] The manufacturing method of the resin composition of the present invention is not particularly limited. For example, the aforementioned copolymer is dissolved in a solvent, and a specific ratio of acid generator is mixed in the solution to form a uniform solution. In addition, in an appropriate stage of the manufacturing method, if necessary, other additives may be added and mixed. [0024] The aforementioned solvent is not particularly limited as long as it can dissolve the components of the aforementioned copolymer and acid generator. These solvents, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve (cellosolve) acetate, ethyl cellosolve (cellosolve) acetate, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol monobutyl ether, propylene glycol monobutyl ether acetate, toluene, xylene, methyl Ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3- Methyl methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, pyruvic acid Methyl ester, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, γ-butyrolactone, etc. These solvents may be used alone or in combination of two or more kinds. [0025] Among these solvents, from the viewpoint of improving the flatness of the coating film formed by coating the resin composition of the present invention on a substrate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptane Ketones, ethyl lactate, butyl lactate, cyclopentanone and cyclohexanone are preferred. [0026] In addition, the resin composition of the present invention may contain a surfactant for the purpose of improving coatability. The surfactant, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, etc., polyoxyethylene Polyoxyethylene alkyl aryl ethers such as octyl phenyl ether and polyoxyethylene nonphenyl ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitol monolaurate, sorbitol monopalm Sorbitol fatty acid esters such as sorbitan, sorbitol monostearate, sorbitol monooleate, sorbitol trioleate, sorbitol tristearate, etc., polyoxyethylene sorbitan Sugar alcohol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, polyoxyethylene sorbitol Non-ionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as alcohol tristearate, F-TOP [registered trademark] EF301, the same as EF303, the same as EF352 (above, Mitsubishi Metal Electron Chemical Co., Ltd. ) System), Mega Fluor [registered trademark] F171, the same F173, the same R-30, the same R-40, the same R-40-LM (above, DIC (share) system), FLUORD FC430, the same as FC431 (above, Sumitomo 3M (share) system), AsahiGuard [registered trademark] AG710, SURFLON [registered trademark] S-382, same as SC101, same as SC102, same as SC103, same as SC104, same as SC105, same as SC106 (Asahi Glass (share) system), DFX -18, FTX-206D, FTX-212D, FTX-218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FTX-240G and other FTERGENT series ((shares) NEOS Fluorine-based surfactants, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. These surfactants can be used alone or in combination of two or more kinds. [0027] In addition, when the aforementioned surfactant is used, the content of the resin composition of the present invention, based on the content of the solid content of the resin composition, is 3% by mass or less, preferably 1% by mass or less, More preferably, it is 0.5% by mass or less. [0028] In addition, the resin composition of the present invention may contain a crosslinking agent, a hardening aid, an ultraviolet absorber, a sensitizer, a plasticizer, an antioxidant, and an adhesive if necessary, within a range that does not impair the effects of the present invention. Additives such as auxiliaries. [0029] The aforementioned crosslinking agent is preferably a compound having at least two epoxy rings, or a compound having at least one oxetane ring. [0030] The aforementioned compound having at least two epoxy rings, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, etc. Phenolic epoxy resins, phenol-novolac epoxy resins, cresol-novolac epoxy resins and other novolac epoxy resins, sulphur-type epoxy resins, aromatics such as trisphenol methane triglycidyl ether Epoxy resin, and these hydrogenated adducts and bromides, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, Glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol polyglycidyl ether Polyoxyalkylene glycol polyglycidyl ether containing alkylene groups, such as glycidyl ether and polyethylene, having 2 to 9 carbon atoms (preferably 2 to 4), 1,4-cyclohexane dimethanol diglycidol Ether, inositol triglycidyl ether, inositol polyglycidyl ether, 1,2-epoxy-4-(2-oxirane) of 2,2-bis(hydroxymethyl)-1-butanol Aliphatic epoxy resins such as cyclohexane adducts, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, 3,4-epoxy-2-methyl Cyclohexylmethyl-3',4'-epoxy-2'-methylcyclohexane carboxylate, bis(3,4-epoxycyclohexyl) adipate, bis(3,4-cyclic Oxycyclohexyl methyl adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2-(3,4-epoxycyclohexyl-5,5-spiro -3,4-Epoxycyclohexanone-m-dioxane, bis(2,3-epoxycyclopentyl) ether, dicyclopentadiene diepoxide, 1,2:8,9-bis Epoxylimonene, (3,4,3',4'-diepoxy) dicyclohexyl ester, bicyclononadiene diepoxide, ε-caprolactone modified 3',4'-epoxycyclohexyl methyl 3,4-epoxycyclohexane carboxylate, butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone, tetrahydroindene diepoxide, etc. Epoxy resin, diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl-p-oxobenzoic acid, glycidyl ether of salicylic acid -Glycidyl ester, dimer acid glycidyl ester, fumaric acid diglycidyl, maleic acid diglycidyl, etc., glycidyl ester type epoxy resins and these hydrides, monoallyl diglycidyl isotriglycerides Polycyanurate, triglycidyl isocyanurate, tris(4,5-epoxypentyl) isocyanurate, bis(4,5-epoxypentyl)hydantoin, four Nitrogen-containing cyclic epoxy resins such as glycidyl acetylene carbamide, etc. [0031] Commercial products of the aforementioned compounds having at least two epoxy rings, for example, jER [registered trademark] 825, the same 827, the same 828, the same 828EL, Same as 828US, same 828XA, same 834, same 1001, same 1002, same 1003, same 1055, same 1004, same 1004AF, same 1007, same 1009, same 1010, same 1003F, same 1004F, same 1005F, same 1009F, same 1004FS, same 1006FS, same 1007FS, same 834X90, same 1001B80, The same 1001X70, the same 1001X75, the same 1001T75, the same 806, the same 806H, the same 807, the same 4004P, the same 4005P, the same 4007P, the same 4010P, the same 1256, the same 4250, the same 4275, the same 1256B40, the same 1255HX30, the same YX8100BH30, the same YX6954BH30 , Same YX7200B35, same 5046B80, same 152, same 154, same 157S70, same 1031S, same 1032H60, same 604, same 630, same 630LSD, same 871, same 872, same 872X75, same 168V70, same YL6810, same YX7700, same YX8000, same YX8034, same YX8800, same YL980, same YL983U, same YX7105, same YX7110B80, same YX7400, same YX4000, same YX4000H, same YL6121H (above, manufactured by Mitsubishi Chemical Corporation), NC-3000, NC-3000- L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000, NC-2000-L, XD-1000, NC-7000L, NC-7300, NC- 7300L, EPPN-501, EPPN-501H, EPPN-501HY, EPPN-502, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, EPPN-202, BREN-S, BREN-105, RE-303S-L, RE-310S, RE-602S, LCE-21 (above, Nippon Kayaku Co., Ltd.), EPICLON (registered trademark) 840, the same as 840-S, the same 850, same 850-S, same 850-LC, same EXA-850CRP, same 860, same 1051, same 1050, same 1055, same 2050, same 3050, same 4050, same 7050, same HM-091, same HM-101 , Same 830, Same 830-S, Same 835, Same EXA-830CRP, Same EXA-830LVP, Same EXA-835LV, Same 152, Same 153, Same N-660, Same N-665, Same N-670, Same N -673, same as N-680, same as N-690, same as N-695, same as N- 665-EXP, same as N-672-EXP, same as N-655-EXP-S, same as N-662-EXP-S, same as N-670-EXP-S, same as N-685-EXP-S, same as N- 730A, same N-740, same N-770, same N-775, same N-865, same HP-4032D, same HP-7200L, same HP-7200H, same HP-7200HH, same HP-7200HHH, same HP- 4700, same HP-4770, same HP-5000, same HP-6000, same HP-4710, same EXA-4850-150, same EXA-4850-1000, same EXA-4816, same HP-820 (above, DIC ( Stock system), Ogsol (registered trademark) PG-100, same as CG-500, same as EG-200, same as EG-280, same as CG-400 (above, manufactured by Osaka Gas Chemical Co., Ltd.), Epolite 40E, same as 100E , The same 200E, the same 400E, the same 70P, the same 200P, the same 400P, the same 1500NP, the same 1600, the same 80MF, the same 100MF, the same 4000, the same 3002 (N) (above, Kyoeisha Chemical (stock) system), Denacol [Registered trademark] EX-211, same EX-212, same EX-252, same EX-810, same EX-811, same EX-850, same EX-851, same EX-821, same EX-830, same EX -832, same EX-841, same EX-861, same EX-911, same EX-941, same EX-920, same EX-931, same EX-313, same EX-314, same EX-321, same EX -411, same EX-421, same EX-512, same EX-521, same EX-612, same EX-614, same EX-614B, same EX-201, same EX-711, same EX-721, same EX -622, same EX-1310, same EX-1410, same EX-1610, same EX-610U, same EX-211L, same EX-212L, same EX-214L, same EX-216L, same EX-321L, same EX -722L, same EX-850L, same EX-946L, same DLC-201, same DLC-202, same DLC-203, same DLC-204, same DLC-205 (above, manufactured by Nagase Chemical Technology (Stock)), Epotodo〔registered trademark〕YD-127, same YD-128, same YDF-170, same YD-8125, same YDF-8170C, same ZX-1059, same YD-825GS, same YD-825GSH, same YDF-870GS, same YDPN-138, same as YDCN-700, same as YDC-1312, same as YSLV-8 0XY, same YSLV-120TE, same ST-3000, same ST-4000D, same YD-171, same FX-289BEK75, same FX-305EK70, same ERF-001M30, PG-207GS, ZX-1658GS (above, Nippon Steel Sumikin Chemical Co., Ltd.), Adeka resin [registered trademark] EP-4100, the same EP-4100G, the same EP-4100E, the same EP-4100TX, the same EP-4100HF, the same EP-4300E, the same EP-4400, the same EP -4520S, same EP-4530, same EP-4901, same EP-4901HF, same EP-5100R, same EP-4000, same EP-4000S, same EP-4000L, same EP-4003S, same EP-4005, same EP -4010S, same EP-4010L, same EP-7001, same EP-4080E, same EP-4082HT, same EP-4088S, same EP-4088L, same EP-3300E, same EP-3300S, same EPU-7N, same EPU -73B, same EPR-1415-1, same EPR-21, same EPR-2000, same EPR-4030, same EPR-49-23, same EP-49-10N, same ED-503, same ED-503G, same ED-506, same ED-523T, same ED-505 (above, (share) ADEKA system), Celloxide [registered trademark] 2021P, same 2081, same 2083, same 2085, same 3000, same 8000, EHPE [registered trademark] 3150, same as 3150CE, Epolydo〔registered trademark〕PB3600, same Same-SS, same-HP, same-L, same-PAS B26L, same-PAS B22, same-VL, same-FL, same-UC (above, manufactured by Nissan Chemical Industry Co., Ltd.), Epoil (registered trademark) G-100, same as E-100LC, same as E-400, same as E-1000, same as TMP (above, manufactured by NOF Corporation), Rica resin [registered trademark] HBE-100, same as DME-100, same as BPO- 20E, same as BEO-60E (above, new Japan physical and chemical (share) system), CY175, CY177, CY179, CY182, CY184, CY192 (above, BASF Japan (share) system), THI-DE (JXTG energy (share) system ) Wait. [0032] The aforementioned compound having at least one oxetane ring, for example, 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3-(phenoxymethyl) oxetane Alkane, 3-ethyl-3-(2-ethylhexyloxymethyl) oxobutane, (3-ethyloxobutan-3-yl) methacrylate, (3-ethyloxy Cyclobutan-3-yl) methyl methacrylate, 3-ethyl-3-[(3-ethyloxetan-3-yl) methoxymethyl] oxetane, 1, 4-bis[(3-ethyloxybutan-3-yl)methoxymethyl]benzene, 1,4-bis[(3-ethyloxybutan-3-yl)methoxymethyl Cyclohexane, 4,4'-bis[(3-ethyloxetan-3-yl)methoxymethyl]bicyclohexyl ester, 4,4'-bis[(3-ethyloxy Cyclobutan-3-yl) methoxymethyl] biphenyl and so on. [0033] Commercial products of the aforementioned compounds having at least one oxetane ring, for example, Aron oxetane [registered trademark] OXT-101, the same as OXT-121, the same as OXT-211, the same as OXT-212, The same OXT-213, the same OXT-221 (above, East Asia Synthetic (stock) system), ETERNACOLL [registered trademark] EHO, the same OXBP, the same OXTP, the same OXMA (above, Ube Industries (stock) system), etc. [0034] The aforementioned crosslinking agent can be used alone or in combination of two or more. [0035] When the aforementioned crosslinking agent is used, the content of the resin composition of the present invention is 1% to 200% by mass, preferably 3% to 100% by mass, based on 100% by mass of the aforementioned copolymer. , More preferably 5% to 50% by mass. [0036] The aforementioned sensitizers, for example, 9-hydroxymethylanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10 -Dibutoxyanthracene, 9,10-dimethoxy-2-ethylanthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-dipropoxy-2-ethyl Anthracene, 9,10-dimethoxy-2-chloroanthracene, 9,10-bis(octyloxy)anthracene, 9,10-dimethoxyanthracene-2-methylsulfonate, 9,10- Diethoxy anthracene-2-methyl sulfonate, 9,10-dimethoxyanthracene-2-methyl carboxylate, 9-oxysulfur
Figure 106124832-A0304-12-0019-1
Figure 106124832-A0304-xxxx-3
, 2-isopropyl 9-oxysulfur
Figure 106124832-A0304-12-0019-1
Figure 106124832-A0304-xxxx-3
, 4-isopropyl 9-oxysulfur
Figure 106124832-A0304-12-0019-1
Figure 106124832-A0304-xxxx-3
, 2-Chloro 9-oxysulfur
Figure 106124832-A0304-12-0019-1
Figure 106124832-A0304-xxxx-3
, 2,4-Dimethyl 9-oxysulfur
Figure 106124832-A0304-12-0019-1
Figure 106124832-A0304-xxxx-3
, 2,4-Diethyl 9-oxysulfur
Figure 106124832-A0304-12-0019-1
Figure 106124832-A0304-xxxx-3
, 2,4-Diisopropyl 9-oxysulfur
Figure 106124832-A0304-12-0019-1
Figure 106124832-A0304-xxxx-3
, Anthraquinone, 1,2-Dihydroxyanthraquinone, 2-Ethylanthraquinone, 1,4-diethoxynaphthalene, etc. [0037] Commercial products of the aforementioned sensitizers, for example, ANTHRACYCLINE [registered trademark] UVS-1331, the same as UVS-1101, the same as UVS-581 (above, manufactured by Kawasaki Chemical Industry Co., Ltd.), KAYACURE [registered trademark] DETX -S, same as EPA (above, Nippon Kayaku (stock) system), etc. [0038] The aforementioned sensitizers can be used alone or in combination of two or more. [0039] When the aforementioned sensitizer is used, the content of the resin composition of the present invention is 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass based on 100% by mass of the aforementioned acid generator. %the following. [0040] Hereinafter, examples of the use of the resin composition of the present invention will be described. Use a suitable coating method such as a spin coater, a coater, etc., to coat the resin composition of the present invention on a substrate {e.g., a semiconductor substrate such as silicon covered with a silicon oxide film, a silicon nitride film or an oxide Semiconductor substrates such as silicon covered with silicon nitride film, semiconductor substrates such as silicon used to form color filters, silicon nitride substrates, quartz substrates, glass substrates (including alkali-free glass, low-alkali glass, and crystallized glass), forming ITO Film on the glass substrate}. Subsequently, using heating means such as a hot plate, an oven, etc., pre-baking is performed to form a coating film. In addition, in the case of performing reduced-pressure baking described later, it is not necessary to perform pre-baking. After the resin composition of the present invention is coated on the aforementioned substrate, it may be baked under reduced pressure without pre-baking. [0041] The pre-baking conditions can be appropriately selected among the baking temperature of 30°C to 200°C and the baking time of 0.3 minutes to 60 minutes. Preferably, the firing temperature is 50°C to 180°C, and the firing time is 0.5 minutes to 30 minutes. Pre-baking can be carried out in the atmosphere or in inert gas such as nitrogen, argon, helium, etc. [0042] Furthermore, the thickness of the cured film formed from the resin composition of the present invention is 0.001 μm to 1000 μm, preferably 0.01 μm to 600 μm. [0043] After pre-sintering and roasting, if necessary, pressure-reduced roasting can be carried out. The conditions of reduced pressure roasting can be under reduced pressure of 1×10 -8 Pa to 9×10 4 Pa or 1×10 -7 Pa to 5×10 4 Pa, temperature of 50 ℃ to 200 ℃, 10 minutes to Choose appropriately from 180 minutes. Decompression baking can be carried out in the atmosphere or in inert gas such as nitrogen, argon, helium, etc. Through this reduced-pressure firing, the recesses or height differences of the substrate can be embedded in the resin composition of the present invention. [0044] Secondly, if necessary, exposure can be performed on the film obtained above. For exposure, for example, ultraviolet rays (for example, g-line, h-line, i-line), KrF excimer laser, ArF excimer laser, etc. can be used. After exposure, post-baking can be performed using heating means such as a hot plate and an oven. The post-baking conditions can be appropriately selected from the baking temperature of 100°C to 300°C and the baking time of 0.5 minutes to 180 minutes. In addition, post-baking can be carried out in the atmosphere or in an inert gas such as nitrogen, argon, or helium. [0045] In the method of forming microlenses, a photoresist solution can be applied to the cured film formed by the resin composition of the present invention, and exposed through a specific mask, and if necessary, post-exposure heating (PEB) can be performed, After alkali development, washing and drying treatment, a specific photoresist pattern can be formed. For exposure, for example, ultraviolet rays (for example, g-line, h-line, i-line), KrF excimer laser, ArF excimer laser, etc. can be used. [0046] Secondly, through heat treatment (usually at a temperature not exceeding 200° C.), the above-mentioned photoresist pattern can be reflowed to form a lens pattern. Using this lens pattern as an etching mask, the lower layer of the hardened film for microlenses is deep-etched, and the shape of the lens pattern is transferred to the resin layer for microlenses to produce microlenses. [Examples] [0047] Hereinafter, the present invention will be described in more detail on the basis of examples, but the present invention is not limited by these examples. [Measurement of the weight average molecular weight of the copolymer obtained in the following synthesis example] Apparatus: GPC system manufactured by JASCO Corporation Column: SHODEX [registered trademark] KF-804L and 803L column oven: 40°C Flow rate: 1 mL/min Soluble solution: Tetrahydrofuran [0048] [Synthesis of copolymer] <Synthesis example 1> 3,4-epoxycyclohexyl methyl methacrylate (CYCLEMA [registered trademark] M100 (made by (stock) DAICEL)) 7.61 g , 40.0g of cyclohexyl acrylate, and 1.96g of 2,2'-azobisisobutyronitrile, dissolved in 74.3g of propylene glycol monomethyl ether acetate, the solution was dropped over 3 hours to make propylene glycol monomethyl ether 41.3 g of acetate was kept in a flask at 70°C. After the dripping, the reaction was carried out for 18 hours, and methanol was used for reprecipitation to obtain the structural unit represented by the aforementioned formula (1-1) and the aforementioned formula (2-1) (where R 0 represents a methyl group). Represents the structural unit of the copolymer. The weight average molecular weight Mw of the obtained copolymer was 27,000 (in terms of polystyrene). [0049] <Synthesis Example 2> 4.72 g of glycidyl methacrylate, 25.0 g of cyclohexyl acrylate, and 1.28 g of 2,2'-azobisisobutyronitrile were dissolved in propylene glycol monomethyl ether acetate 57.6 After g, the solution was dropped into a flask in which 35.4 g of propylene glycol monomethyl ether acetate was kept at 70°C over a period of 3 hours. After the dripping, the reaction was carried out for 18 hours, and methanol was used for reprecipitation to obtain the structure unit represented by the aforementioned formula (1-1) and the aforementioned formula (2-2) (where R 0 represents a methyl group). Represents the structural unit of the copolymer. The weight average molecular weight Mw of the obtained copolymer was 30,000 (in terms of polystyrene). [0050] <Synthesis Example 3> 12.5 g of 3,4-epoxycyclohexyl methacrylate (CYCLEMA [registered trademark] M100 (manufactured by DAICEL)), 20.0 g of cyclohexyl acrylate, and 2 After dissolving 1.27 g of 2'-azobisisobutyronitrile in 62.8 g of propylene glycol monomethyl ether acetate, the solution was dropped over a period of 3 hours into a flask keeping 38.6 g of propylene glycol monomethyl ether acetate at 80°C middle. After the dripping, the reaction was carried out for 18 hours, and methanol was used for reprecipitation to obtain the structural unit represented by the aforementioned formula (1-1) and the aforementioned formula (2-1) (where R 0 represents a methyl group). Represents the structural unit of the copolymer. The weight average molecular weight Mw of the obtained copolymer was 11,000 (in terms of polystyrene). [0051] <Synthesis Example 4> 19.7 g of 3,4-epoxycyclohexyl methacrylate (CYCLEMA [registered trademark] M100 (manufactured by DAICEL)) and ethoxylated n-phenol acrylate ( NK ester [registered trademark] A-LEN-10 (manufactured by Shinnakamura Chemical Industry Co., Ltd.)) 40.0g, and 2,2'-azobisisobutyronitrile 3.7g, dissolved in propylene glycol monomethyl ether acetate 148.0 After g, the solution was dropped into a flask in which 105.7 g of propylene glycol monomethyl ether acetate was kept at 70°C over a period of 3 hours. After the dropping, the reaction was carried out for 18 hours, and methanol was used for reprecipitation to obtain the structure unit represented by the aforementioned formula (1-3) and the aforementioned formula (2-1) (where R 0 represents a methyl group). Represents the structural unit of the copolymer. The weight average molecular weight Mw of the obtained copolymer was 15,000 (in terms of polystyrene). [0052] <Synthesis Example 5> 43.9 g of 3,4-epoxycyclohexyl methacrylate (CYCLEMA [registered trademark] M100 (manufactured by DAICEL)) and ethoxylated n-phenol acrylate ( NK ester [registered trademark] A-LEN-10 (manufactured by Shinnakamura Chemical Industry Co., Ltd.)) 15.0g, and 2,2'-azobisisobutyronitrile 2.9g, dissolved in propylene glycol monomethyl ether acetate 92.7 After g, the solution was dropped into a flask in which 51.5 g of propylene glycol monomethyl ether acetate was kept at 80°C over a period of 3 hours. After the dripping, the reaction was carried out for 18 hours to obtain a structural unit represented by the aforementioned formula (1-3) and a structural unit represented by the aforementioned formula (2-1) (where R 0 represents a methyl group) The weight average molecular weight Mw of the copolymer obtained from the copolymer solution (solid content concentration 30% by mass) is 8,000 (in terms of polystyrene). [0053] <Synthesis Example 6> 7.00 g of 3,4-epoxycyclohexyl methacrylate, 15.0 g of methacrylate, and 1.38 g of 2,2'-azobisisobutyronitrile were dissolved in After 43.4 g of propylene glycol monomethyl ether acetate, the solution was dropped into a flask in which 26.7 g of propylene glycol monomethyl ether acetate was maintained at 70°C over a period of 3 hours. After the dripping, the reaction was carried out for 18 hours to obtain a copolymer solution (solid content concentration 25% by mass). The weight average molecular weight Mw of the obtained copolymer was 18,000 (in terms of polystyrene). [0054] <Synthesis Example 7> 11.4 g of 3,4-epoxycyclohexyl methacrylate, 24.0 g of 1-propenyloxy-3-hydroxyadamantane, and 2,2'-azobis After dissolving 1.09 g of isobutyronitrile in 67.9 g of propylene glycol monomethyl ether acetate, the solution was dropped over 3 hours into a flask in which 41.7 g of propylene glycol monomethyl ether acetate was kept at 70°C. After the dripping, the reaction was carried out for 18 hours to obtain a copolymer solution (solid content concentration 25% by mass). The weight average molecular weight Mw of the obtained copolymer was 11,000 (in terms of polystyrene). <Synthesis Example 8> Dissolve 7.72 g of 3,4-epoxycyclohexyl methacrylate, 40.0 g of isobornyl acrylate, and 1.52 g of 2,2'-azobisisobutyronitrile After 91.4 g of propylene glycol monomethyl ether acetate, the solution was dropped into a flask in which 56.3 g of propylene glycol monomethyl ether acetate was kept at 70°C over a period of 3 hours. After the dripping, the reaction was carried out for 18 hours to obtain a copolymer solution (solid content concentration 25% by mass). The weight average molecular weight Mw of the obtained copolymer was 24,000 (in terms of polystyrene). [Production of resin composition] <Example 1> 3.49 g of the copolymer obtained in Synthesis Example 1 and the cationic component of the photoacid generator were made from (4-phenylthiophenyl) diphenyl The anion component is composed of B(C 6 F 5 ) 4 - organic onium chloride compound CPI-110B (manufactured by SAN-APRO (stock)) 0.000204g, and surfactant DFX-18 (NEOS (stock) ) Made) 0.00170g, dissolved in 16.7g of propylene glycol monomethyl ether acetate as a solution. Subsequently, it was filtered using a polyethylene microfilter with a pore size of 0.45 μm to obtain a resin composition. [0057] <Example 2> 3.00g of the copolymer obtained in Synthesis Example 2, CPI-110B (manufactured by SAN-APRO (stock)) 0.000180g of photoacid generator, and DFX-18 (NEOS (stock) ) Made) 0.00150g, dissolved in 15.1g of propylene glycol monomethyl ether acetate as a solution. Subsequently, it was filtered using a polyethylene microfilter with a pore size of 0.45 μm to obtain a resin composition. [0058] <Example 3> 16.0 g of the copolymer obtained in Synthesis Example 3, the third crosslinking agent {2,2-bis[(oxiran-2-ylmethoxy)methyl]butyl} -3,3',3"-[1,3,5-three
Figure 106124832-A0304-12-0020-4
-2,4,6(1H,3H,5H)-trione-1,3,5-triyl]tripropionate (TEPIC[registered trademark]-UC (manufactured by Nissan Chemical Industry Co., Ltd.)) 4.0g cationic component by the photoacid generator (4-phenylthio-phenyl) diphenyl sulfonium anion component formed by the PF 3 (2 F 5 C) 3 - CPI organic onium chloride compounds composed of -210S (manufactured by SAN-APRO (stock)) 1.0g, 9,10-bis (octyloxy) anthracene as a sensitizer (ANTHRACYCLINE [registered trademark] UVS-581 (manufactured by Kawasaki Chemical Industry Co., Ltd.)) 0.20 g, and 0.020 g of DFX-18 (manufactured by NEOS) as a surfactant, dissolved in 89.3 g of propylene glycol monomethyl ether acetate as a solution. Subsequently, it was filtered using a polyethylene microfilter with a pore size of 0.45 μm to obtain a resin composition. [0059] <Example 4> 16.0 g of the copolymer obtained in Synthesis Example 4, the third crosslinking agent (4,5-epoxypentyl) isocyanurate (TEPIC [registered trademark]-VL (Nissan) Chemical Industry Co., Ltd.) 4.0g, CPI-210S (manufactured by SAN-APRO Co., Ltd.) 1.0g as a photoacid generator, 9,10-dibutoxyanthracene as a sensitizer (ANTHRACYCLINE [registered trademark] UVS-1331 (manufactured by Kawasaki Chemical Industry Co., Ltd.)) 0.20 g, and 0.020 g of DFX-18 (manufactured by NEOS Co., Ltd.) as a surfactant, dissolved in 89.3 g of propylene glycol monomethyl ether acetate as a solution. Subsequently, it was filtered using a polyethylene microfilter with a pore size of 0.45 μm to obtain a resin composition. [0060] <Example 5> 53.3g of the copolymer solution obtained in Synthesis Example 5 (containing 16.0g of solid content), the third crosslinking agent (4,5-epoxypentyl) isocyanurate ( TEPIC〔registered trademark〕-VL (manufactured by Nissan Chemical Industry Co., Ltd.)) 4.0g, photoacid generator CPI-210S (manufactured by SAN-APRO Co., Ltd.) 1.0g, and surfactant DFX-18 (NEOS) (Product made by stock) 0.020 g, dissolved in 51.1 g of propylene glycol monomethyl ether acetate as a solution. Subsequently, it was filtered using a polyethylene microfilter with a pore size of 0.45 μm to obtain a resin composition. [0061] <Example 6> 8.0 g of the copolymer obtained in Synthesis Example 4, the third crosslinking agent (4,5-epoxypentyl) isocyanurate (TEPIC [registered trademark]-VL (Nissan) Chemical Industry Co., Ltd.) 2.0g, Adekagus [registered trademark] SP-606 (trademark) of trifluoromethane sulfonate as a photoacid generator, 0.1g (made by ADEKA), and DFX-18 as a surfactant As a solution, 0.020 g of NEOS (manufactured by NEOS) was dissolved in 43.0 g of propylene glycol monomethyl ether acetate. Subsequently, it was filtered using a polyethylene microfilter with a pore size of 0.45 μm to obtain a resin composition. [0062] <Example 7> 10.0 g of the copolymer obtained in Synthesis Example 4, Adekagus [registered trademark] SP-606 (manufactured by ADEKA) of the trifluoromethanesulfonate of the photoacid generator, and 0.1 g, and 0.020g of surfactant DFX-18 (manufactured by NEOS) was dissolved in 43.0g of propylene glycol monomethyl ether acetate as a solution. Subsequently, it was filtered using a polyethylene microfilter with a pore size of 0.45 μm to obtain a resin composition. [0063] <Example 8> 10.0 g of the copolymer obtained in Synthesis Example 1 and 0.0006 g of CPI-110B (manufactured by SAN-APRO (stock)) as a photoacid generator were dissolved in 15.0 g of propylene glycol monomethyl ether acetate As a solution. Subsequently, it was filtered using a polyethylene microfilter with a pore size of 5 μm to obtain a resin composition. [0064] <Example 9> The cationic component copolymer obtained in Synthesis Example 4 of 10.0g, and the photoacid generator is an anion of an organic component consisting of sulfonium by C (CF 3 SO 2) 3 - composed of organic 0.0003 g of onium chloride compound GSID-26-1 (manufactured by BASF) was dissolved in 15.0 g of propylene glycol monomethyl ether acetate as a solution. Subsequently, it was filtered using a polyethylene microfilter with a pore size of 5 μm to obtain a resin composition. [0065] <Comparative Example 1> 3.13 g of the copolymer obtained in Synthesis Example 1 and 0.00150 g of DFX-18 (manufactured by NEOS) as a surfactant were dissolved in 16.9 g of propylene glycol monomethyl ether acetate as Solution. Subsequently, it was filtered using a polyethylene microfilter with a pore size of 0.45 μm to obtain a resin composition. [0066] <Comparative Example 2> 13.0 g of the copolymer solution obtained in Synthesis Example 6 (containing 3.25 g of solid content), 0.000191 g of CPI-110B (manufactured by SAN-APRO (stock)), and interface 0.00160g of active agent DFX-18 (manufactured by NEOS) was dissolved in 6.13g of propylene glycol monomethyl ether acetate as a solution. Subsequently, it was filtered using a polyethylene microfilter with a pore size of 0.45 μm to obtain a resin composition. [0067] <Comparative Example 3> 13.0 g of the copolymer solution obtained in Synthesis Example 7 (containing 3.25 g of solid content), 0.000192 g of CPI-110B (manufactured by SAN-APRO (stock)), and interface 0.00160g of DFX-18 (manufactured by NEOS) as the active agent was dissolved in 9.72g of propylene glycol monomethyl ether as a solution. Subsequently, it was filtered using a polyethylene microfilter with a pore size of 0.45 μm to obtain a resin composition. [0068] <Comparative Example 4> 13.0 g of the copolymer solution obtained in Synthesis Example 8 (containing 3.25 g of solid content), 0.000195 g of CPI-110B (manufactured by SAN-APRO (stock)), and interface 0.00171 g of DFX-18 (manufactured by NEOS) as the active agent was dissolved in 6.28 g of propylene glycol monomethyl ether acetate as a solution. Subsequently, it was filtered using a polyethylene microfilter with a pore size of 0.45 μm to obtain a resin composition. [0069] [Solvent Resistance Test] The resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 4 were coated on a silicon wafer using a spin coater, and then heated The board is pre-baked at 100°C for 1 minute. Secondly, the electrodeless lamp power supply system (made by Oak Manufacturing Co., Ltd.) with a 380nm enhanced lamp is used to irradiate the ultraviolet rays with an exposure amount of 1000mJ/cm 2 in 365nm. Next, it was fired on a hot plate at 220°C for 10 minutes to form a film with a thickness of 1.0 μm. Any one of the aforementioned pre-firing roasting and post-firing roasting is carried out in the atmosphere. These cured films were applied to propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclopentanone, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, and 2.38% by mass hydrogen. In a tetramethylammonium oxide (TMAH) aqueous solution, a 5-minute immersion test was carried out at a temperature of 23°C. And measure the change in film thickness before and after immersion. As long as the film thickness increases or decreases by more than 5% relative to the film thickness before immersion in any of the immersion solvents, it is marked as "×". In all solvents, the film If the thickness increase or decrease does not reach 5%, the solvent resistance is evaluated by the method marked as "○". The evaluation results are shown in Table 1. [0070] [Transmittance measurement] The resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 4 were coated on a quartz substrate using a spin coater, and then applied to a heating plate Carry out pre-baking at 100°C for 1 minute. Secondly, the electrodeless lamp power supply system (made by Oak Manufacturing Co., Ltd.) with a 380nm enhanced lamp is used to irradiate the ultraviolet rays with an exposure amount of 1000mJ/cm 2 in 365nm. Next, it was fired on a hot plate at 220°C for 10 minutes to form a film with a thickness of 1.0 μm. Any one of the aforementioned pre-firing roasting and post-firing roasting is carried out in the atmosphere. An ultraviolet-visible spectrophotometer UV-2600 (manufactured by Shimadzu Corporation) was used to measure the transmittance of the cured films at a wavelength of 400 nm. The evaluation results are shown in Table 1. [0071] [Level difference planarization] The resin compositions prepared in Example 1 to Example 7 and Comparative Example 1 to Comparative Example 4 were respectively applied to a height of 0.5 μm and a circuit width of 10 μm using a spin coater. , On the substrate with a height difference of 10μm between the lines (Figure 1), pre-baking is carried out on the heating plate at 100°C for 1 minute. Secondly, the electrodeless lamp power supply system (made by Oak Manufacturing Co., Ltd.) with a 380nm enhanced lamp is used to irradiate the ultraviolet rays with an exposure amount of 1000mJ/cm 2 in 365nm. Next, it was fired on a hot plate at 220°C for 10 minutes to form a film with a thickness of 1.0 μm. Any one of the aforementioned pre-firing roasting and post-firing roasting is carried out in the atmosphere. From the h1 (the height difference of the substrate 1 with the height difference) and h2 (the height difference of the hardened film 2, that is, the height difference between the height of the hardened film on the circuit and the height of the hardened film on the space) shown in Figure 1, use the formula " ：(1-(h2/h1))×100” to find the flattening rate. The evaluation results are shown in Table 1. [0072]
Figure 02_image011
[0073] From the results in Table 1, it is known that the cured film formed using the resin composition of the present invention has high solvent resistance while also having high transparency. In addition, the cured film formed from the resin composition of the present invention has an excellent level difference flatness with a flattening rate of 80% or more. On the other hand, the cured film formed using the resin composition prepared in Comparative Example 1 does not contain a photoacid generator, and the cured film formed from the resin composition prepared in Comparative Examples 2 to 4 It was not sufficiently cured at a baking temperature of 220°C, so it was found that the solvent resistance was not satisfied, and it was confirmed that it was not suitable for the application of flattening film and hardened film for microlenses. In addition, the cured film formed using the resin composition prepared in Comparative Example 3 and Comparative Example 4 has a flattening rate of less than 80%, so when compared with the cured film formed from the resin composition of the present invention, it is obtained This is the result of poor level difference flatness. [Embedding] The resin composition prepared in Example 8 and Example 9 was applied to a hole (hole) with a width of 200 μm square, 150 μm square, and 100 μm square recess (hole depth 400 μm) The silicon wafer is pre-baked at 150°C for 10 minutes on a hot plate, and then baked at 150°C for 20 minutes in an oven under a reduced pressure of 3×10 2 Pa. Secondly, the electrodeless lamp power supply system (made by Oak Manufacturing Co., Ltd.) with a 380nm enhanced lamp was used to irradiate the ultraviolet rays with an exposure amount of 1000mJ/cm 2 in 365nm. Secondly, use an oven at normal pressure to calcinate at 220°C for 60 minutes. Any one of the aforementioned pre-baking, reduced-pressure baking, and post-baking is performed in the atmosphere. Using scanning electron microlens (SEM) to observe the cross-section results obtained by coating the resin composition prepared in Example 8 and Example 9 on a silicon wafer with recesses, no voids and voids inside the holes were observed. The gap is confirmed to form a uniform embedded state.

[0075]1‧‧‧高低差基板2‧‧‧硬化膜3‧‧‧線路寬4‧‧‧線路間空間h1‧‧‧高低差基板之高低差h2‧‧‧硬化膜之高低差[0075] 1. ‧ ‧ height difference substrate 2. ‧ ‧ hardened film 3. ‧ ‧ circuit width 4 ‧ ‧ inter-circuit space h1 ‧ ‧ height difference substrate height difference h2 ‧ ‧ hardened film height difference

[0012] 　　［圖1］圖1為，於高低差基板上塗佈本發明之樹脂組成物，經燒焙而形成的硬化膜之示意圖。[0012] 　　 [FIG. 1] FIG. 1 is a schematic diagram of a cured film formed by coating the resin composition of the present invention on a high-low difference substrate and firing it.

Figure 106124832-A0101-11-0002-2
Figure 106124832-A0101-11-0002-2

1‧‧‧高低差基板 1‧‧‧High-low difference substrate

2‧‧‧硬化膜 2‧‧‧hardened film

3‧‧‧線路寬 3‧‧‧Line width

4‧‧‧線路間空間 4‧‧‧Space between lines

h1‧‧‧高低差基板之高低差 h1‧‧‧The height difference of the substrate

h2‧‧‧硬化膜之高低差 h2‧‧‧The height difference of the hardened film

Claims (17)

一種樹脂組成物，其特徵為含有：具有下述式(1)所表示之結構單位及下述式(2)所表示之結構單位的自交聯性共聚物、酸產生劑，及溶劑，前述式(1)所表示之結構單位之含量為10mol%至90mol%，樹脂組成物去除前述溶劑後之固形成份，為1質量%至80質量%，前述自交聯性共聚物之含量，以前述固形成份中之含量為基準時，為5質量%至99.999質量%；
Figure 106124832-A0305-02-0036-1
 (式中，R0表示氫原子或甲基，X表示單鍵或伸乙基氧基，R1表示單鍵或伸甲基，A1表示碳原子數5或6之環烷基，A2表示環氧環己基或環氧基)。 A resin composition characterized by containing: a self-crosslinking copolymer having a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), an acid generator, and a solvent. The content of the structural unit represented by formula (1) is 10 mol% to 90 mol%, the solid content of the resin composition after removing the aforementioned solvent is 1% to 80% by mass, and the content of the aforementioned self-crosslinking copolymer is based on the aforementioned When the content in the solid content is a reference, it is 5 mass% to 99.999 mass%;
Figure 106124832-A0305-02-0036-1
 (In the formula, R 0 represents a hydrogen atom or a methyl group, X represents a single bond or an ethyleneoxy group, R 1 represents a single bond or a methylidene group, A 1 represents a cycloalkyl group with 5 or 6 carbon atoms, and A 2 Represents epoxycyclohexyl or epoxy). 如請求項1之樹脂組成物，其中，前述式(1)所表示之結構單位為下述式(1-1)、式(1-2)所表示之結構單位；
Figure 106124832-A0305-02-0037-2
 The resin composition of claim 1, wherein the structural unit represented by the aforementioned formula (1) is the structural unit represented by the following formula (1-1) and formula (1-2);
Figure 106124832-A0305-02-0037-2
 如請求項1或請求項2之樹脂組成物，其中，前述式(2)所表示之結構單位為下述式(2-1)或式(2-2)所表示之結構單位；
Figure 106124832-A0305-02-0037-3
 (式中，R0與請求項1之定義為相同之意義)。 Such as the resin composition of claim 1 or claim 2, wherein the structural unit represented by the aforementioned formula (2) is the structural unit represented by the following formula (2-1) or formula (2-2);
Figure 106124832-A0305-02-0037-3
 (In the formula, R 0 has the same meaning as the definition of claim 1). 如請求項1或請求項2之樹脂組成物，其中，前述自交聯性共聚物之重量平均分子量為1,000至80,000。 The resin composition of claim 1 or claim 2, wherein the weight average molecular weight of the aforementioned self-crosslinking copolymer is 1,000 to 80,000. 如請求項1或請求項2之樹脂組成物，其中，前述酸產生劑為磺酸酯。 The resin composition of claim 1 or claim 2, wherein the acid generator is a sulfonic acid ester. 如請求項5之樹脂組成物，其中，相對於前述自交聯性 聚合物，前述磺酸酯為含有0.001質量%至20質量%。 The resin composition of claim 5, wherein, relative to the aforementioned self-crosslinking The polymer contains the aforementioned sulfonic acid ester from 0.001% by mass to 20% by mass. 如請求項1或請求項2之樹脂組成物，其尚含有界面活性劑。 For example, the resin composition of claim 1 or claim 2 still contains a surfactant. 如請求項1或請求項2之樹脂組成物，其尚含有交聯劑。 For example, the resin composition of claim 1 or claim 2 still contains a crosslinking agent. 如請求項8之樹脂組成物，其中，前述交聯劑為含有：由至少具有2個環氧環之化合物及至少具有1個氧環丁烷環之化合物所成之群所選出之至少1種。 The resin composition of claim 8, wherein the crosslinking agent contains: at least one selected from the group consisting of a compound having at least two epoxy rings and a compound having at least one oxetane ring . 如請求項1或請求項2之樹脂組成物，其尚含有增感劑。 For example, the resin composition of claim 1 or claim 2, which still contains a sensitizer. 如請求項1或請求項2之樹脂組成物，其為平坦化膜形成用者。 Such as the resin composition of claim 1 or claim 2, which is used for forming a flattening film. 如請求項1或請求項2之樹脂組成物，其為微透鏡形成用者。 Such as the resin composition of claim 1 or claim 2, which is used for forming microlenses. 一種基板之埋入方法，其特徵為，將請求項1至請求項10中任一項之樹脂組成物塗佈於具有凹部之基板，再於1×10-8Pa至9×104Pa之減壓下、50℃至200℃之溫度，對塗 佈有該樹脂組成物之基板進行10分至180分鐘減壓燒焙之方法。 A method for embedding a substrate, which is characterized in that the resin composition of any one of claim 1 to claim 10 is applied to a substrate with recessed portions, and then at a temperature of 1×10 -8 Pa to 9×10 4 Pa A method of calcining the substrate coated with the resin composition under reduced pressure at a temperature of 50°C to 200°C for 10 minutes to 180 minutes. 如請求項13之埋入方法，其中，前述減壓燒焙為於大氣中或惰性氣體中進行。 According to the embedding method of claim 13, wherein the aforementioned reduced-pressure baking is carried out in the atmosphere or in an inert gas. 如請求項13或請求項14之埋入方法，其為將塗佈前述樹脂組成物之基板，於大氣中或惰性氣體中，以30℃至200℃之溫度，進行0.3分鐘至60分鐘預燒焙之後，進行前述減壓燒焙之方法。 Such as the embedding method of claim 13 or claim 14, which is to burn the substrate coated with the aforementioned resin composition in the atmosphere or in an inert gas at a temperature of 30°C to 200°C for 0.3 minutes to 60 minutes After roasting, the aforementioned method of roasting under reduced pressure is carried out. 一種硬化膜之製作方法，其特徵為，將請求項1至請求項10中任一項之樹脂組成物塗佈於基板上之後，使用加熱手段對塗佈前述樹脂組成物之基板進行燒焙，隨後進行曝光之方法。 A method for producing a cured film, characterized in that, after the resin composition of any one of claims 1 to 10 is coated on a substrate, the substrate coated with the resin composition is fired by heating means, Subsequent exposure method. 如請求項16之硬化膜之製作方法，其為於前述曝光後，使用加熱手段進行再燒焙之方法。 Such as the manufacturing method of the cured film of claim 16, which is a method of re-baking after the aforementioned exposure using heating means.
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