201211690 六、發明說明： 【發明所屬之技術領域】 本發明係關於光阻劑用樹脂組成物。 本案係以2010年8月27曰在曰本所提出申請的特願 2〇10-190880號為基礎主張優先權，並爰引其内容於本案中。 【先前技術】 諸如液晶顯示裝置電路或半導體積體電路之類的微細電 路圖案，係在基板上所形成的絕緣膜或導電性金屬膜上，均 勻被覆或塗佈著光阻劑組成物，並在既定形狀遮罩存在下， 對被覆的光阻劑組成物施行曝光而進行顯影，藉此便製得目 標形狀的圖案。然後’將已形成圖案的光阻劑膜使用為遮 罩，經去除金屬膜或絕緣膜後，再將殘存的光阻劑膜予以除 去，便在基板上形成微細電路。此種光阻劑組成物係依照所 曝光部分與光阻劑膜為可溶或不溶，而分類為負型與正型。 一般正型光阻劑組成物係使用萘醌重氮化合物等具g昆重 氮基(quinonediazide group)的感光劑、與驗可溶性樹脂(例如 酚醛清漆型酚樹脂）。由此種組成構成的正型光阻劑組成物 係在曝光後由驗溶液施行顯影而呈現解析力.，被利用於 1C、LSI專半導體製造、LCD專液晶顯示畫面機器的製造、 及印刷原版的製造等。又，酚醛清漆型酚樹脂對於電聚乾式 蚀刻，亦具有歸因於含多數芳香環之構造的高耐熱性，截至 目前為止，已有開發出多數種含有酚醛清漆型酚樹脂與萘g昆 100130624 4 201211690 重氮系感光劑的正型光阻劑’並已然實用化，且可列舉出重 大成果。 就液晶顯示裝置電路用光陴劑組成物的實用面而言，重要 特性為：所形成光阻劑膜的感度、顯影對比、解析度、與基 板間之接著力、殘膜率、耐熱性、以及電路線寬均勻度(CD uniformity)。特別係因屬於薄膜電晶體液晶顯示裝置的特徵 之基板大面積化，而造成在生產線上的較長曝光時間，因而 必定要求提升感度。又，感度與殘膜率係呈反比關係，並顯 現出感度越南則殘膜率越減少的傾向。 液晶顯示裝置電路用正型光阻劑，一般係使用使間/對曱 S分與甲酸，在義媒存在下輯反應顿得㈣料漆型紛 樹脂。而，為調整或提升光阻劑的特性，已就當作原料酚類 使用的間/對甲酚比率、酚樹脂的分子量、分子量分佈等進 行檢討。又，專利文獻i揭示有為提升光阻劑特性，而採取 將酚醛清漆樹脂施行分餾(Fracti〇nati〇n)處理的方法，上述 内容係熟習此技術領域者廣泛已知。201211690 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a resin composition for a photoresist. This case claims priority on the basis of the special offer of No. 2〇10-190880 filed on August 27, 2010 at the Institute, and cites its contents in this case. [Prior Art] A fine circuit pattern such as a liquid crystal display device circuit or a semiconductor integrated circuit is uniformly coated or coated with a photoresist composition on an insulating film or a conductive metal film formed on a substrate, and The coated photoresist composition is exposed and developed in the presence of a predetermined shape mask, whereby a pattern of a target shape is obtained. Then, the patterned photoresist film is used as a mask, and after removing the metal film or the insulating film, the remaining photoresist film is removed to form a fine circuit on the substrate. Such a photoresist composition is classified into a negative type and a positive type depending on whether the exposed portion and the photoresist film are soluble or insoluble. As the general positive type resist composition, a sensitizer having a quinonediazide group such as a naphthoquinone diazo compound or a soluble resin (for example, a novolac type phenol resin) is used. The positive-type photoresist composition having such a composition is developed by the test solution after exposure, and exhibits resolving power. It is used in 1C, LSI-specific semiconductor manufacturing, LCD-specific liquid crystal display screen device manufacturing, and printing originals. Manufacturing and so on. Further, the novolac type phenol resin has high heat resistance due to the structure containing a large number of aromatic rings for electropolymer dry etching, and up to now, many kinds of novolac type phenol resins and naphthalene g Kun 100130624 have been developed. 4 201211690 The positive-type photoresist of diazo-based sensitizers has been put into practical use, and major achievements can be cited. In terms of the practical surface of the photoresist composition for a liquid crystal display device circuit, important characteristics are: sensitivity of the formed photoresist film, development contrast, resolution, adhesion to the substrate, residual film ratio, heat resistance, And circuit uniformity (CD uniformity). In particular, since the substrate which is a feature of the thin film transistor liquid crystal display device has a large area, resulting in a long exposure time on the production line, it is necessary to increase the sensitivity. Further, the sensitivity was inversely proportional to the residual film ratio, and it was found that the sensitivity of Vietnam was decreased as the residual film rate decreased. The positive-type photoresist used in the liquid crystal display device circuit is generally used to make the inter-/parallel S-spot and formic acid, and the reaction is carried out in the presence of a suitable medium (4) paint-type resin. However, in order to adjust or enhance the characteristics of the photoresist, the ratio of the m/p-cresol used as the raw material phenol, the molecular weight of the phenol resin, and the molecular weight distribution have been reviewed. Further, Patent Document i discloses a method of subjecting a novolak resin to fractional distillation in order to improve the characteristics of the photoresist, and the above-mentioned contents are widely known in the art.
-般而言，光阻劑的感度提升係利用降低_清漆樹心 分子量而達成。但是，此項手法會有導㈣熱性變差、或; 曝光部的殘膜率降低、或無法充分獲得與#光_之溶㈣ 度差、或曝光部與未曝光部間之顯影對比降低。因而社果$ 產生解析度降低關題。另—方面，若提高㈣清漆麟白 分子量，雖耐熱性與解析度獲改善，但會發生光阻劑膜的I 100130624 5 201211690 度降低。即’會發生若改良其中—者，另—者便會變差的極 深切不良情況。In general, the sensitivity enhancement of the photoresist is achieved by lowering the molecular weight of the varnish. However, this technique may lead to (4) thermal deterioration, or a decrease in the residual film ratio of the exposed portion, or a sufficient difference in the degree of dissolution between the light and the light, or a decrease in development between the exposed portion and the unexposed portion. Therefore, the fruit of $ produces a lower resolution. On the other hand, if the molecular weight of (4) varnish is increased, the heat resistance and resolution are improved, but the I 100130624 5 201211690 degree of the photoresist film is lowered. That is, if there is a case where it is improved, the other will be worse.
I 截至目前為止’針對此種不良情況已嘗試各種改良。但 是，在諸如感度、殘膜率、顯影對比、解析度、與基板間之 接著力、以及電路線寬均句度等液晶顯示裝置f路用光阻劑 組成物的較佳雜巾之任-雜均未被犧㈣前提下，可提 升上述特性且可適用於各·業錢的各㈣晶顯示裝置 電路用光㈣喊物尚域開發。因而，針項要求仍持 續未消。 ' [先行技術文獻] [專利文獻] [專利文獻1]曰本專利特表2002-508415號公報 【發明内容】 (發明所欲解決之問題） 本發明之目的係在於提供：具有特別高耐熱性，且具有， 好的感度、解析度及高殘膜性，其他特性亦不會較泛用物^ 的光阻劑用樹脂組成物。 (解決問題之手段） 本發明之一態樣的光阻劑用樹脂組成物，係含有：酚醛清 漆型酚樹脂、環狀烯烴樹脂、以及由含萘藏重氣^ (naphthoquinonediazide group)之化合物構成之感光劑者。 上述光阻劑用樹脂組成物中’上述環狀烯烴樹脂亦可為降 100130624 6 201211690 相細樹脂。 上述光阻劑用樹脂組成物中，上述環狀烯烴樹脂亦可為含 有下述—般式⑴所示重複單㈣環__脂。 [化1]I Up to now, various improvements have been attempted for such adverse situations. However, in a liquid crystal display device such as a sensitivity, a residual film ratio, a development contrast, a resolution, an adhesion to a substrate, and a circuit line width uniformity, etc. Under the premise that the miscellaneous average is not sacrificed (4), the above-mentioned characteristics can be improved and the (four) crystal display device circuit for each of the various businesses can be used for light (4). As a result, needle requirements remain unabated. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Patent Application Publication No. 2002-508415 (Draft of the Invention) The object of the present invention is to provide a particularly high heat resistance. And it has a good sensitivity, resolution, and high residual film property, and other characteristics are not more than a resin composition for a photoresist. (Means for Solving the Problem) A resin composition for a photoresist according to an aspect of the present invention comprises: a novolac type phenol resin, a cyclic olefin resin, and a compound composed of a naphthoquinonediazide group; Photosensitive agent. In the above resin composition for a photoresist, the above cyclic olefin resin may be a resin which is reduced by 100130624 6 201211690. In the resin composition for a photoresist, the cyclic olefin resin may contain a repeating mono(tetra)cyclo-lipine represented by the following formula (1). [Chemical 1]
RJ R3 (1) 此處，上述式⑴中，x係0、ch2、CH2CH2中之任一者； n係0〜5的整數；Rl〜R4係從構造中亦可含有〇及的碳 數1〜30之-價有機基、或氫中分別獨立選擇，且~俜 可在单體重複中為不同，但總重複單位的r1〜r4中至少 係具有酸性基β 上述光阻劑用樹脂組成物中，上述酸性基亦可為從叛基、 齡基、㈣基及基所構成群財選擇之丨種以上的 基。 上述光阻劑用樹脂組成物中’上述環狀婦煙樹脂的重量平 均分子量亦可為1000〜500,000道爾賴(1)仏〇11)。 上述光阻劑用樹脂組成物中，上述環狀烯烴樹脂對上述酚 樹脂的混合比率亦可為1〜90重量〇/〇。 (發明效果） 藉由本發明，可提供具有高耐熱性、且具有良好的烕度、 100130624 7 201211690 解析度及高殘膜性，其他特性亦不會較泛用物差的光阻劑用 樹脂組成物。 【實施方式】 以下，針對本發明進行詳細說明。 本發明係關於光阻劑用樹脂組成物。 本發明之光阻劑組成物的製造中所使用的酚醛清漆型酚 樹脂，係依據標準方法，藉由使酚類與醛類在酸觸媒存在下 進行縮合反應而合成。 » 上述反應所使用的酚類並無特別的限定，可舉例如：酚、 鄰甲酚、間曱酚、對曱酚等甲酚類；2,3-二曱酚、2,4-二曱 酚、2,5-二曱酚、2,6-二曱酚、3,4-二曱酚、3,5-二曱酚等二 甲酚類；鄰乙基酚、間乙基酚、對乙基酚等乙基酚類；異丙 酚、丁基酚、對第三丁基酚等烷基酚類；除此以外尚可舉例 如：間苯二酚、兒茶酚、氫醌、五倍子酚、苯三酚等多元酚 類；烷基間苯二酚、烷基兒茶酚、烷基氫醌等烷基多元酚類 (任一者的烷基均係碳數1〜4)。該等係可單獨使用、或組合 使用2種以上。 上述酚類中，特別較佳係使用間曱酚與對曱酚。藉由使用 該等酚類，且調節二者的摻合比率，便可調節當作光阻劑用 的感度、耐熱性等諸特性。此情況，間曱酚與對曱酚的比率 •並無特別的限定，較佳係設為重量比（間曱酚/對曱 酚)=9/1〜1/9。更佳係8/2〜2/8。若間曱酚的比率未滿上述下 100130624 8 201211690 限值’則感度會降低’若超過上述上限值’則耐熱性會降低。 上述反應中所使用的醛類並無特別的限定，可舉例如：ρ 駿、三聚甲酸、三辦、乙路、丙酸、聚縮㈣、三㈣ (chlorai)、六亞甲基四胺、糠經、乙二盤、正丁繼、己酸、 稀丙_I_dehyde)、苯㈣、巴豆盤、叫酸、四 苯乙醛(phenyl acetaldehyde)、鄰甲苯曱醛水揚醛等。該等 之中，就特性而言，較佳係使用曱醛、三聚曱醛。〜 上述齡簡與盤類(F)的反應莫耳比(F/p)並無特別的限 定，在祕清漆型朌樹脂的製造令，利用公知反應莫耳比便 可實施本發明之一態樣。 特另i係田所獍得酚醛清漆型酚樹脂應用為光阻劑使用 時’反應莫耳比較佳係設為0.5〜1.0。藉此便可獲得具有當 作光阻劑用之較佳分子量的樹脂組成物 。若上述反應莫耳比 。k述上限值’树脂組成物在作成光阻劑用時會有過度高 刀子里化、或因反應條件而出現凝膠化之情形。又，若未滿 _述下限值時’因為低核體成分的含有量會相對變多’因而 會有將其除去時的效率降低之情形。 二在上述盼類與_的反應中，一般係使用酸觸媒。酸觸媒 二二寺別的限疋，可舉例如：草酸、醋酸等有機羧酸等等。 1之中’可單獨使用、或混合使用2種以上。酸觸媒的使 用置並無特別的限定，相對於上述酉分類，較佳係使用0.01〜5 〇 ^ ,、匕 ’ g將光阻劑用樹脂使用於光阻劑組成物時’為 100130624 201211690 防止干涉光阻劑的特性，在樹脂中殘留的觸媒較佳為少量。 當然’亦可在合成樹脂的過程中，利用一般的除去方法（中 和、水洗或過濾器過濾等）將觸媒予以除去。 再者’在製造本發明之光阻劑用樹脂組成物時所使用的反 應溶劑’較佳係適度非極性溶劑，可舉例如：己烷、苯、二 曱苯等。 製造本發明之光阻劑用樹脂組成物時所使用的酚樹脂，較 佳係依 GPC(Gel Permeation Chromatography，凝膠渗透色層 分析儀）所測定的重量平均分子量為1000〜20000道爾頓之 紛樹脂’更佳係重量平均分子量為3000〜10000道爾頓。藉 由將所使用酚樹脂的重量平均分子量設在上述範圍内，便可 使光阻劑用樹脂組成物的感度、耐熱性、殘膜率成為最佳狀 態。 上述重量平均分子量係根據使用聚苯乙烯標準物質所作 成的檢量線而計算得。GPC測定係將四氫呋喃當作溶出溶 劑，依流量l.Oml/min、管柱溫度40°C的條件，將示差折射 儀使用為檢測器便可實施。可使用的裝置係分別可使用例 如： 1) 本體：TOSOH公司製「HLC-8020」 2) 檢測器：設於波長280nm的TOSOH公司製「UV-8011」 3) 分析用管柱：昭和電工公司製「SHODEX. KF-802、 KF-803、KF-805」。 100130624 10 201211690 製造本發明之光阻劑用樹脂組成物時所使用的環狀烯烴 樹脂，係主鏈中具有環狀烯烴構造的樹脂，因為源自環狀烯 烴的環構造係具有在聚合物鏈長方向上直接連結的剛性構 造，因而具有較高的玻璃轉移點。此種樹脂中，就從所獲得 光阻劑組成物的性能之觀點，較佳係降稻烯樹脂。降稻烯樹 脂的構造係可舉例如一般式（1)所示者。降捐烯樹脂上的官 能基係配合所獲得光阻劑組成物之使用目的而適當選擇，並 無特別的限制，均可使用。 [化2]RJ R3 (1) Here, in the above formula (1), x is any one of 0, ch2, and CH2CH2; n is an integer of 0 to 5; and R1 to R4 may contain a carbon number of 〇 from the structure. The valence organic group or hydrogen is independently selected, and ~俜 may be different in the monomer repeat, but the total repeating unit of r1 to r4 has at least an acidic group β. The above resin composition for a photoresist In the above, the acidic group may be a group selected from the group consisting of a ruthenium group, an age group, a (4) group, and a group. In the resin composition for a photoresist, the weight average molecular weight of the above-mentioned cyclic vodonic resin may be 1000 to 500,000 Torr (1) 仏〇 11). In the resin composition for a photoresist, the mixing ratio of the cyclic olefin resin to the phenol resin may be 1 to 90% by weight. (Effect of the Invention) According to the present invention, it is possible to provide a resin for a photoresist having high heat resistance, good twist, 100130624 7 201211690 resolution and high residual film property, and other characteristics which are not inferior to general properties. Things. [Embodiment] Hereinafter, the present invention will be described in detail. The present invention relates to a resin composition for a photoresist. The novolac type phenol resin used in the production of the photoresist composition of the present invention is synthesized by a condensation reaction between a phenol and an aldehyde in the presence of an acid catalyst according to a standard method. The phenol to be used in the above reaction is not particularly limited, and examples thereof include phenols such as phenol, o-cresol, m-non-phenol, and p-nonphenol; and 2,3-diinol and 2,4-difluorene. Dimethylphenols such as phenol, 2,5-diinol, 2,6-dioxan, 3,4-dioxan, 3,5-dioxan; o-ethylphenol, m-ethylphenol, p- Ethylphenols such as ethyl phenol; alkylphenols such as propofol, butyl phenol, and p-tert-butylphenol; in addition to, for example, resorcinol, catechol, hydroquinone, gallnut Polyphenols such as phenol and benzenetriol; alkyl polyphenols such as alkyl resorcinol, alkyl catechol, and alkyl hydroquinone (all of which are alkyl groups having a carbon number of 1 to 4). These may be used alone or in combination of two or more. Among the above phenols, it is particularly preferable to use meta-phenol and p-nonylphenol. By using these phenols and adjusting the blending ratio of the two, it is possible to adjust characteristics such as sensitivity and heat resistance for the photoresist. In this case, the ratio of indophenol to p-phenol is not particularly limited, and is preferably a weight ratio (m-cresol/p-phenol) = 9/1 to 1/9. Better system 8/2~2/8. If the ratio of indomethacin is less than the above-mentioned lower limit of 100130624 8 201211690, the sensitivity is lowered. If the ratio exceeds the above upper limit, the heat resistance is lowered. The aldehyde to be used in the above reaction is not particularly limited, and examples thereof include ρ jun, tripoly formic acid, three, ethyl, propionic acid, poly(tetra), chlorai, and hexamethylenetetramine. , 糠, 乙二盘, 正丁继, hexanoic acid, propylene (I_dehyde), benzene (four), croton dish, called acid, phenyl acetaldehyde, o-toluene furfural aldehyde. Among these, in terms of characteristics, furfural or trimeric furfural is preferably used. ～ The reaction molar ratio (F/p) of the above-mentioned age simple type to the disk type (F) is not particularly limited, and in the manufacturing process of the secret varnish-type oxime resin, one of the states of the present invention can be implemented by using a known reaction molar ratio. kind. When the novolac type phenol resin is used as a photoresist, the reaction molar ratio is preferably 0.5 to 1.0. Thereby, a resin composition having a preferred molecular weight as a photoresist can be obtained. If the above reaction is molar ratio. k Represents the upper limit limit. When the resin composition is used as a photoresist, it may be excessively high in knives or gelled due to reaction conditions. In addition, when the lower limit is not described, the amount of the low-nuclear component is relatively large, and the efficiency at the time of removal is lowered. 2. In the above reaction between the desired class and the _, an acid catalyst is generally used. Acid Catalysts Other restrictions on the second two temples include, for example, oxalic acid, acetic acid and other organic carboxylic acids. 1 may be used alone or in combination of two or more. The use of the acid catalyst is not particularly limited, and it is preferable to use 0.01 to 5 〇^ for the 酉 classification, and 匕'g to use the resin for the photoresist for the photoresist composition' as 100130624 201211690 In order to prevent the characteristics of the interference photoresist, the amount of the catalyst remaining in the resin is preferably small. Of course, the catalyst can also be removed by a general removal method (neutralization, water washing or filter filtration, etc.) in the process of synthesizing the resin. Further, the reaction solvent used in the production of the resin composition for a photoresist of the present invention is preferably a moderately nonpolar solvent, and examples thereof include hexane, benzene, and dimethylbenzene. The phenol resin used in the production of the resin composition for a photoresist of the present invention is preferably a weight average molecular weight of 1000 to 20,000 Daltons as measured by GPC (Gel Permeation Chromatography). The resin has a better weight average molecular weight of 3000 to 10,000 Daltons. By setting the weight average molecular weight of the phenol resin to be used in the above range, the sensitivity, heat resistance and residual film ratio of the resin composition for a photoresist can be optimized. The above weight average molecular weight is calculated based on a calibration curve prepared using a polystyrene standard material. In the GPC measurement, tetrahydrofuran was used as a dissolution solvent, and the differential refractometer was used as a detector under the conditions of a flow rate of 1.0 ml/min and a column temperature of 40 °C. For the devices that can be used, for example: 1) Main body: "HLC-8020" manufactured by TOSOH Co., Ltd. 2) Detector: "UV-8011" manufactured by TOSOH Co., Ltd. at a wavelength of 280 nm 3) Column for analysis: Showa Denko "SHODEX. KF-802, KF-803, KF-805". 100130624 10 201211690 The cyclic olefin resin used in the production of the resin composition for a photoresist of the present invention is a resin having a cyclic olefin structure in the main chain because the ring structure derived from the cyclic olefin has a polymer chain. A rigid structure that is directly joined in the long direction and thus has a high glass transition point. Among such resins, from the viewpoint of the properties of the obtained photoresist composition, it is preferred to lower the resin. The structure of the norbornene resin may, for example, be represented by the general formula (1). The functional group on the olefin-reducing resin is appropriately selected in accordance with the purpose of use of the obtained photoresist composition, and is not particularly limited and can be used. [Chemical 2]
此處，式（1)中，X係0、CH2、CH2CH2中之任一者；η 係0〜5的整數。R1〜R4係從構造中亦可含有Ο及/或F的碳 數1〜30之一價有機基、或氳中分別獨立選擇。R1〜R4係可 在單體重複中為不同，但總重複單位的R1〜R4中至少一者係 具有酸性基。 對樹脂賦予驗可溶性的酸性基，係可舉例如：缓基、盼基、 氟醇基、磺醯胺基等，可導入該等中之1種或2種以上。該 等之中，特佳係藉由與感光劑間之交互作用，而可期待高對 比與高殘膜率之顯現的酚基。 一般而言，該等樹脂合成法之例，係可舉例如以一般式(2) 100130624 11 201211690 所示環_ ”單料行聚合。 [化3] 此處，式(2)巾，γ 俜0 S沾敕垂 Χ係0、CH2、CH2CH2中之任一者；n 係0〜5的整數。pi n4 " 〜R係從構造中亦可含有〇及/或F的碳 时1〜30之一價有機基、或氫中分別獨立選擇。r1〜r4係可 在早體重複中為不同’但總重複單位的R1〜R4中至少一者係 具有酸性基。酸性基係可糊如縣、喊、氟醇基、錯酿 胺基，可導入該等中之1種或2種以上。 本發明所使用環狀烯烴單體的具體例，係可舉例如：雙環 [2.2.1]庚-2-稀-5·緩酸、四環[44〇 l2,5 l7，10]十二碳冬稀_8_ 幾酸、8-甲基四環[Row!。]十二碳_3_稀_8_紐、（雙環 [2.2，1]庚-2-稀-5-基）醋酸、2_(雙環[22 ^庚^-烯^•基）丙 ^ 3 (又 ％ [2·2_ 1]庚-2-稀-5-基）丁酸、3-(雙環[2.2.1 ]庚 一2_ 歸5基)戊|久、3-(雙環[2.2.1]庚-2-炸-5-基）己酸、琥轴酸單 -(2-(雙環[2.2.1]庚-2-烯-5-基）羰氧基乙基）酯、琥珀酸單 (2-(雙環[2.2.1]庚-2-婦-5-基）数氧基丙基）g旨、琥站酸單 •(2-(雙環[2.2.1]庚-2-烯-5-基)羰氧基丁基）g旨、酞酸單_(2_(雙 環[2.2.1]庚-2-稀-5-基）幾氧基乙基）酯、己酸單_(2_(雙釋 [2.2.1]庚·2_烯-5-基)幾氧基丁基）酯、（雙環[2.2.1]庚·2_稀 100130624 12 201211690 基）羰氧基醋酸、2-(雙環[2.2.1]庚-2-烯-5-基）曱基酚、3_(雙 裱[2.2.1]庚·2_烯-5-基）甲基酚、4-(雙環[2.2.1]庚-2-烯-5-基） 曱基酚、4·(雙環[2.2.1]庚-2-烯-5-基)酚、4-(雙環[2.2.1]庚_2· 烯―5-基）甲基兒茶酚、3_曱氧基_4_(雙環[2 2 η庚_2_烯_5_基) 曱基酚、3_曱氧基_2-(雙環[2.2.1]庚-2-烯-5·基）曱基酚、2-(雙 環[2·2.1]庚-2-烯基）甲基間苯二酚、M-雙三氟曱基-2-(雙 環[2.2.1]庚烯_5·基）乙醇、丨山雙三氟曱基冬(雙環 庚_2养5-基）丙基醇、U-雙三氟甲基·4-(雙環[2.2.1]庚·2_ 烯基)丁醇、雙三氟甲基-5-(雙環[2.2.1]庚-2-烯-5_基) 戊醇、雙三氟甲基-6·(雙環[2..2.1]庚-2-稀-5-基）己醇等， 但並不僅侷限於該等構造。 或者，取代一般式（2)所示環狀烯烴單體，改為使用未具 有酸性基的環㈣烴單體，施行同制聚合後，再對其殘基 利用南分子反應導人酸性基便可獲得。或者，使用將一般式 (2)所示環狀烯烴單體中酸性基能游離的氫原子，取代為其 他構造的單體，將其施行加成聚合後，再經脫保護而導入原 本的氫原子亦可獲得。利用脫保護施行的酸性基回復係可依 照標準方法實施。 本發明之光阻劑用樹脂組成物之製造中所使用的側鏈具 有酉文性基的％狀稀炫樹脂之酸性基當量，係取決於其分子構 造，在此並無特別的限定，但較佳係600g/莫耳以下、更佳 係400g/莫耳以下。若酸性基當量在上述規定值以下，便可 100130624 13 201211690 溶於顯影時所使用氫氧化納、氫氧化鉀、氨水等無機驗類、 氫氧化四甲錄、乙胺、三乙胺、三乙醇胺類等有機驗類的水 溶液中。若酸性基當量大於上述上限值，便不易顯現出對上 述驗水溶㈣溶解性，導致_加工較難進行。樹脂中的酸 性基量係可利用使用標準鹼溶液的樹脂溶液滴定等進行測 定。 所獲得樹脂的酸性基當量係可利用選擇所使用之具有酸 性基的單體之分子構造，或者改變具麵歸之單體、與未 具有酸性基之單體的存在比進行共聚合等，而進行控制。 製造環狀烯烴樹脂的方法係可應用習知公知手法。例如可 使用屬於配位聚合觸媒的錦化合物或把化合物等，進行加成 聚合。鎳化合物之例係可舉例如化學式：EnNi(C6F5)2所示觸 媒’該化學式中’ η係丨或2，* E係指中性配位基。當n 為1的情況’E較佳係諸如甲笨、苯及均三甲苯之類的n_ 芳配位基。當η為2的情況，E較佳係從二乙峻、τΗρ(四 氮咬喃）、醋酸乙醋、及二哼烷中選擇。可舉例如：（曱苯） 雙(全氟苯基)鎳、（均三甲苯)雙(全氟苯基)錄、（苯)雙(全氟 苯基)鎮、雙(四氫吱喃)雙(全氟苯基)錄、雙(醋酸乙酉旨)雙(全 氟苯基)鎳、及雙（二呤院）雙（全氟笨基)錄等。詳細情形係 如：PCT WO 97/3M98、PCT W0 〇〇/2〇472、曰本專利特表 2010-523766號公報、曰本專利特表平u_5〇588〇號公報等 中所記載。 100130624 14 201211690 該等聚合中所使用的較佳聚合溶劑係包括烴、芳香族溶 劑。烴溶敎則^舉够姚、⑽、庚 舰於鱗。又，芳香麵狀例係：甲苯、二甲苯、均三 甲苯等，仍是不僅揭限於該等。其他尚可使用：四氫哇喃、 二乙驗、醋酸乙自旨、内@旨、酮等。該等溶劑係可單獨使用一 種，此外亦可混合二種以上作為聚合溶劑使用。 關於本發明之光阻劑用樹脂組成物中所含單體的聚合，就 聚合所獲得樹脂的分子量，利關如使觸媒與單體的比率變 化、或聚合溫度、聚合溶劑的極性等亦可進行控制。又，藉 由適當鏈轉移劑的添加，亦可控制聚合所獲得樹脂的分子 量。 本發明之光阻劑用樹脂組成物的製造中所使用的環狀稀 烴樹脂的重量平均分子量係1000〜500 000道爾頓。若重量 平均分子量超越上述範圍，在進行光加工時，樹脂組成物對 鹼水溶液的溶解性會降低，而有無法獲得良好光加工性的疑 慮。另一方面，若重量平均分子量未滿上述下限值，便有無 法充分獲得因添加所造成的性能提升效果的可能性。 環狀稀烴樹脂對紛樹脂的摻合量，較佳係1〜重量％、 更佳係5〜50重量％。添加量係可依照所需耐熱性提升效果 的程度而任意設定，但若添加量過多’便會有導致紛樹脂所 具有感度等性質降低的疑慮。另一方面，若添加量過少，便 會有耐熱性的提升效果不足之情況。 100130624 15 201211690 本發明之光阻劑組成物的製造中所使用的感光劑係含萘 醌重氮基之化合物。含萘醌重氮基之化合物係可舉例如下述 (1)〜(4)、與奈S昆-1,2-重氣-5-續酸或奈S昆-1，2-重氮-4-石黃酸等 含醌重氮基之磺酸的完全酯化合物、部分酯化合物、醯胺化 物或部分醯胺化物等： (1) 2,3,4-三羥基二苯基酮、2,4,4'-三羥基二苯基酮、2,4,6-三羥基二苯基酮、2,3,6-三羥基二苯基酮、2,3,4-三羥基-2’-曱基二苯基酮、2,3,4,4’-四羥基二苯基酮、2,2’，4,4'-四羥基二 苯基酮、2,3',4,4',6-五羥基二苯基酮、2,2',3,4,4'-五羥基二苯 基酮、2,2’，3,4,5-五羥基二苯基酮、2,3',4,4’,5',6-六羥基二苯 基酮、2,3,3'，4,4',5’-六羥基二苯基酮等多羥基二苯基酮類； (2) 雙(2,4-二羥苯基）曱烷、雙(2,3,4-三羥苯基）甲烷、2-(4-羥苯基)-2-(4'-羥苯基）丙烷、2-(2,4-二羥苯基)-2-(2'，4’-二羥 苯基）丙烷、2-(2,3,4-三羥苯基）-2-(2'，3\4’-三羥苯基）丙烷、 4,4’-{l-[4-〔 2-(4-羥苯基）-2-丙基〕苯基]亞乙基}雙酚、3,3，-二甲基-{1-[4-〔2-(3-曱基-4-羥苯基)-2-丙基〕苯基]亞乙基} 雙酚等雙[(多）羥苯基]烷烴類； (3) 參(4-羥苯基）曱烷、雙(4-羥基_3,5_二曱基苯基)-4-羥苯 基曱烷、雙(4-羥基-2,5-二曱基苯基)-4-羥苯基曱烷、雙(4-羥基-3,5-二曱基苯基)-2-羥苯基曱烷、雙(4-羥基-2,5-二曱基 苯基)-2-羥苯基曱烷、雙(4-羥基-2,5-二甲基苯基)-3,4-二羥苯 基曱烷、雙(4-羥基-3,5-二曱基苯基)-3,4-二羥苯基甲烷等參 100130624 16 201211690 (羥苯基）F烷類或其T基取代體； 環己基_4猶基㈣苯基f燒、雙(3_環己基_4· 經苯基)·2·鮮基m(3·環己基_4_經苯基)冰經苯基甲 烧、雙(5·環己基_4_絲·2_甲基苯基)趣苯基甲烧、雜(5 環己基领基_2_甲絲基)_3•鮮基^、雙⑽己^ 經基_2_甲基苯基)·4_經苯基甲烧、雙(3·環己基士經苯基K 經苯基f燒、雙(5·環己基领基_3·ψ基苯基)领苯基甲 烧、雙(5-環己基-4·經基_3_甲基苯基)·3_經苯基甲烧、雙(5_ 環己基-4-經基_3·甲基苯基)_2•經苯基甲烧、雙(3-環己基·2_ 羥苯基)-4-羥笨基曱烷、雙(3_環己基_2_羥苯基)_2_羥苯基曱 烷、雙(5-環己基-2-羥基-4-甲基苯基)_2_羥苯基甲烷、雙(5_ 環己基-2-經基-4-曱基苯基)_4_羥苯基甲烷等雙(環己基羥苯 基)(羥苯基）甲烷類或其曱基取代體等。 此處’上述含萘醌重氮基之化合物成分係可單獨含有1 種、亦可含有2種以上。 本發明的樹脂組成物中，感光劑的摻合量並無特別的限 定’相對於酚樹脂1〇〇重量份，通常可依5〜1〇〇重量份、較 佳為10〜50重量份的範圍摻合。若感光劑的摻合量未滿上述 下限值’圖案便不易獲得忠實的影像，導致轉印性降低。另 一方面’若超過上述上限值，當作光阻劑時會出現感度降低 情形。 本發明組成物中所摻合的溶劑，係在上述酚樹脂、環狀烯 100130624 17 201211690 烴樹脂、及含萘醌重氮基之化合物能溶解的前提下，其餘並 無特別的限定。本發明中，將該等成分溶解於溶劑中使用。 本發明之光阻劑組成物的製造中所使用的溶劑，係可使用： N-曱基-2-吼咯啶酮、γ-丁内酯、Ν,Ν-二曱基乙醯胺、二曱 亞石風、二乙二醇二曱醚、二乙二醇二乙醚、二乙二醇二丁醚、 丙二醇單曱醚、二丙二醇單甲醚、丙二醇單曱醚醋酸酯、乳 酸曱醋、乳酸乙酯、乳酸丁酷、曱基-1,3-丁二醇醋酸酯、1,3-丁二醇20-3-單曱醚、丙酮酸曱酯、丙酮酸乙酯、曱基-3-曱 氧基丙酸酯等，可單獨或混合使用。 另外，本發明的組成物中，除以上所說明成分之外，視需 要尚可使用：抗氧化劑等安定劑、可塑劑、界面活性劑、密 接性提升劑、溶解促進劑等各種添加劑。 本發明組成物的調製方法並無特別的限定，當組成物中沒 有添加填充材、顏料的情況，只要將上述成分依通常方法施 行混合、攪拌便可，當有添加填充材、顏料的情況，只要使 用例如高速攪拌器、均質機、三輥研磨機等分散裝置施行分 散、混合便可。又，視需要亦可進一步使用篩網過濾器、薄 膜過濾、器等施行過滤。 藉由對依此所獲得之本發明的組成物，隔著遮罩施行曝 光，在曝光部中的組成物便會產生構造變化，可促進對鹼顯 影液的溶解性。另一方面，因為在非曝光部中保持對鹼顯影 液較低的溶解性，因而利用依此所產生的溶解性差，便可賦 100130624 18 201211690 予光阻機能。 當將本發明組成物使用為光阻劑的情況，藉由光的照射， 組成物中的含萘醌重氮基之化合物會產生化學變化，在後續 的顯影步驟中會與酚醛清漆樹脂一起溶解於鹼顯影液中，而 在與未被曝光部分間產生明確的溶解速度差，藉此便可利用 顯影而獲得目標圖案。 以下，針對本發明利用合成例與實施例進行說明。惟，本 發明並不因該等合成例與實施例而受限定。又，合成例、實 施例及比較例中所記載的「份」及「％」，岣表示「重量广 及「重量％」。但，甲醛水溶液的濃度(％)除外。 [實施例] 1.盼樹脂之合成 (合成例1) 在具備攪拌裝置、溫度計、熱交換器的3L四口燒瓶中， 裝填入間曱酚60〇g、對曱酚400g、37%甲醛527g、及草酸 5g，依回流條件進行4小時反應。然後，於常壓下施行脫水 至内溫170°C，再於9.3xl〇3Pa減壓下施行脫水及脫單體至 200°C，獲得重量平均分子量4200道爾頓的酚樹脂950g。 2 ♦ ί衣狀細經樹脂之合成 (合成例2) 將[4-(2-雙環[2.2.1]庚_5_烯）苯基]醋酸酿（11.4g， 50mmol)、曱笨（17.6g)、及曱乙酮(27.4g)裝填入具備授拌裝 100130624 19 201211690 置的反應容器中，利用乾燥氮氣取代内部。加熱内容物，在 内溫到達50°C時’添加使（η6-曱苯）Ni(C6F5)2(〇.97g， 2.00mmol)溶解於l〇g曱苯中的溶液。於50°C進行3小時反 應後，冷卻至室溫。添加丁1^(5(^)與i〇%氫氧化鉀水溶液 (80g)，使進行5小時回流反應。然後，添加醋酸進行中和 後’實施利用離子交換水進行的水洗作業3次。將有機層利 用蒸發器施行濃縮後’利用己烧施行再沉澱。所獲得固體利 用60°C真空乾燥機進行整晚乾燥’獲得8.2g淡黃色粉末。 所獲得聚合物的分子量經GPC測定，結果為Mw=ll，〇〇〇、 Mn=5300。 (合成例3) 將3-曱氧基-4-(雙環[2.2.1]庚-2-烯-5_基）曱基酚(5〇g， 18.4mm〇l)、丙酸乙基-3·(3-雙環[2.2.1]庚-5-烯）醋（〇89g， 4.5911^101)、曱苯(28g)、及曱乙_(1〇g)裝填入具備攪拌裝置 的反應容器中，利用乾燥氮氣取代内部。加熱内容物，在内 溫到達6〇。(：日寺，添加使(ηό-甲笨)见仰5)2(〇玛，〇 46_】) 溶解於5g曱苯中的溶液。於6〇t進行3小時反應後，冷卻 至至狐。添加THF(5〇g)與1〇〇/0氫氧化鉀水溶液（5〇幻，使進 行5小時回流反應。然後’添加醋酸進行中和後，實施利用 =子交換水進行的水洗作業3次。將有機層利用蒸發器施行 濃縮後，利用己烷施行再沉澱。所獲得固體利用6〇〇c真空 乾燥機進行整晚乾燥’獲得8 2g淡黃色粉末。所獲得聚合 100130624 20 201211690 物的分子量經GPC測定，結果為Mw=16,000、Mn=9000。 (合成例4) 將丙酸乙基-3-(3-雙環[2.2.1]庚-5-稀）酷（37.3g，0.19mol)、 1，卜雙二氟甲基-2-(雙環[2.2.1]庚-2-烯-5-基）乙醇（13.2g， 0.05mol)、曱苯(55g)、三乙基矽烷（丨4g)、醋酸乙酯（13g)、 及二曱基苯胺鑌肆(五氟苯基)硼酸鹽(〇 〇6g，〇 〇7mm〇1)裝填 入具備攪拌裝置的反應容器中，利用乾燥氮氣取代内部。加 熱内谷物，在内溫到達l〇〇°C時，添加（乙腈）雙（三異丙膦) 鈀（醋酸酯）(五氟苯基硼酸鹽）(0.03g，〇〇2mm〇1)的醋酸乙酯 (6g)溶液。於loot進行16小時反應後，冷卻至室溫，添加 THF與10%氫氧化钾水溶液(3〇〇g)，使進行5小時回流反 應。然後，添加醋酸進行中和後，實施利用離子交換水進行 的水洗作業3次。將有機層利用蒸發器施行濃縮後，利用己 烧施行再減。賴得g)體 6 〇 t真空錢機進行整晚 乾燥，獲得27g白色粉末。所獲得聚合物的分子量經GPC 測定，結果為 Mw=8,200、Mn=4,200。 (合成例5) 將U-雙三氟曱基(雙環[2.2.η庚I烯i基）乙醇 (9.9g，0.036m〇l)、雙環[2.2.1]庚-2H魏三甲基石夕㈣ (2.2g ’ 〇.〇12mol)、醋酸乙醋（l〇〇g)、及環己烷（1〇〇幻裝填入 具備攪拌裝置的反應容器中，利用乾燥氮氣取代内部。加熱 内容物，在内溫到達10(TC時，添加（歸丙基)纪(三環己鱗） 100130624 21 201211690 三氟醋酸鹽（0.006g ’ 0.008mmol)的二氣曱炫(2g)溶液、及肆 (五氟本基)爛酸裡〇.〇34g的曱苯(2g)溶液。進一步添加1_ 己烯(2.6g，〇.〇3mol) ’於20°C進行5小時反應後，冷卻至室 溫。將所獲得聚合物投入曱醇中，將沉澱物凝聚，利用水進 行充分洗淨後，於真空下施行乾燥，獲得7 8g白色粉末。 所獲得聚合物的分子量經GPC測定，結果為Mw=12,200、 Mn=6,100。 (合成例6) 將 5-丁基雙環[2.2.1]庚 _2_ 烯（l3.〇g，〇.〇87mol)、甲笨 (18g)、及曱乙酮（llg)裝填入具備攪拌裝置的反應容器中， 利用乾燥氮氣取代内部。加熱内容物，在内溫到達6叱時， 添加使(η -甲苯)>ii(C6F5)2(〇_42g，〇.87mmol)溶解於 i〇g 曱苯 中的溶液。於_進行3小岐紐，冷卻至室溫。使反 應後的溶餘解於己烧_g巾，實關_子交換水進行 的水洗作業3次。將有機層利用蒸發器施行濃縮後，利用甲 醇施行再沉殿，獲得白色固體。所獲得固體利用_真空 乾燥機進行整晚乾燥，獲得7 5g自色粉末。賴得聚合^ 的分子置經GPC測定，έ士里·^ a f ' ^ '，0 果為 Mw=31，000、Mn=14,〇〇〇。 4.光阻劑用組成物之調製 (實施例1) /合成例1所獲得轉清漆型_脂30份、合成例2所 ㈣環_烴樹脂6份、以及2，w’_四絲二苯基綱與卜 100130624 22 201211690 的鲳6份，溶解於丙二醇 1徑Ι.Ομιη薄膜過濾器施 重氮基-5,6-二氳_5_氧基_蔡小項酸的齡 單甲趟醋酸酿150份中之後，使用孔^ 行過濾，便調製得光阻劑組成物。 (實施例2)Here, in the formula (1), X is any one of 0, CH2, and CH2CH2; and η is an integer of 0 to 5. R1 to R4 may be independently selected from the structure, and may contain one or more carbon atoms of cesium and/or F, respectively. R1 to R4 may be different in the monomer repeat, but at least one of R1 to R4 in the total repeating unit has an acidic group. The acid group which is soluble in the resin is, for example, a slow group, a thiol group, a fluoroalcohol group or a sulfonylamino group, and one or two or more of them may be introduced. Among these, a phenol group which exhibits a high contrast ratio and a high residual film ratio can be expected by interaction with a sensitizer. In general, examples of the resin synthesis method include, for example, polymerization of a ring of the general formula (2) 100130624 11 201211690. [Chemical 3] Here, the formula (2) towel, γ 俜0 S 敕 敕 任一 0 0, CH2, CH2CH2; n is an integer from 0 to 5. pi n4 " ~ R system can also contain 〇 and / or F carbon from the structure 1~30 The one-valent organic group or the hydrogen is independently selected. The r1~r4 system may be different in the early body repetition, but at least one of the R1 to R4 of the total repeating unit has an acidic group. The acidic group may be pasteurized as a county. And one or more of these may be introduced, and the specific examples of the cyclic olefin monomer used in the present invention may be, for example, a bicyclo [2.2.1] g. -2-dilute-5·slow acid, tetracyclic [44〇l2,5 l7,10] twelve carbon winter thin _8_ acid, 8-methyltetracycline [Row!.] twelve carbon _3_ thin _8_纽, (bicyclo[2.2,1]hept-2-ylidene-5-yl)acetic acid, 2_(bicyclo[22 ^heptene]-yl)-propenyl ^ 3 (also % [2·2_ 1] Hept-2-sweet-5-yl)butyric acid, 3-(bicyclo[2.2.1]gino-2_ quinone-5yl)penta], long, 3-(bicyclo[2.2.1]hept-2-expansion-5- Hexanoic acid, Mono-(2-(bicyclo[2.2.1]hept-2-en-5-yl)carbonyloxyethyl) succinate, succinic acid mono(2-(bicyclo[2.2.1]hept-2-one) -5-yl) methoxypropyl)g, succinic acid mono-(2-(bicyclo[2.2.1]hept-2-en-5-yl)carbonyloxybutyl)g, citric acid Mono-(2_(bicyclo[2.2.1]hept-2-ylide-5-yl)oxyethyl) ester, hexanoic acid mono-(2_(double release [2.2.1] g-2·ene-5) -yl) methoxy butyl) ester, (bicyclo[2.2.1] gh. 2 - dilute 100130624 12 201211690) carbonyloxyacetic acid, 2-(bicyclo[2.2.1]hept-2-ene-5- Nonylphenol, 3_(biguanidine [2.2.1]hept-2-ene-5-yl)methylphenol, 4-(bicyclo[2.2.1]hept-2-en-5-yl)indolyl Phenol, 4·(bicyclo[2.2.1]hept-2-en-5-yl)phenol, 4-(bicyclo[2.2.1]hept-2-ene-5-yl)methylcatechol, 3_曱oxy_4_(bicyclo[2 2 ηhept-2-ene]-5-yl)nonylphenol, 3-methoxycarbonyl-2-(bicyclo[2.2.1]hept-2-en-5yl) Nonylphenol, 2-(bicyclo[2.2.1]hept-2-enyl)methylresorcinol, M-bistrifluorodecyl-2-(bicyclo[2.2.1]heptene_5·yl Ethanol, Laoshan bistrifluorodecyl sulphate (bicycloheptyl-2-non-5-yl) propyl alcohol, U-bistrifluoromethyl·4-(bicyclo[2.2.1]g·2_ Alkenyl)butanol, bistrifluoromethyl-5-(bicyclo[2.2.1]hept-2-en-5-yl)pentanol, bistrifluoromethyl-6·(bicyclo[2..2.1] Hept-2-ylide-5-yl)hexanol, etc., but not limited to these structures. Alternatively, instead of the cyclic olefin monomer represented by the general formula (2), a cyclic (tetra) hydrocarbon monomer having no acidic group is used instead, and the same polymerization is carried out, and then the residue is subjected to a south molecular reaction to conduct an acidic group. Available. Alternatively, a hydrogen atom free from an acidic group in the cyclic olefin monomer represented by the general formula (2) is substituted with a monomer having another structure, and subjected to addition polymerization, followed by deprotection to introduce the original hydrogen. Atoms are also available. The acid-based recovery system using deprotection can be carried out according to standard methods. The acidic base equivalent of the %-like thin resin having a fluorene-based group in the side chain used for the production of the resin composition for a photoresist of the present invention is not particularly limited, but is not particularly limited herein. It is preferably 600 g/mole or less, more preferably 400 g/mole or less. If the acid base equivalent is below the above specified value, it can be used in the inorganic test such as sodium hydroxide, potassium hydroxide or ammonia water dissolved in the development, tetramethyl hydride, ethylamine, triethylamine and triethanolamine. In an aqueous solution such as a class of organic tests. If the acid group equivalent is more than the above upper limit, it is difficult to exhibit solubility in the above-mentioned water-soluble solution (IV), which makes _processing difficult. The amount of the acid group in the resin can be measured by titration with a resin solution using a standard alkali solution or the like. The acidic group equivalent of the obtained resin can be obtained by selecting the molecular structure of the monomer having an acidic group used, or by changing the presence ratio of the monomer having a surface group and the monomer having no acidic group, and the like. Take control. A method of producing a cyclic olefin resin can be applied to a conventionally known method. For example, a ruthenium compound which is a coordination polymerization catalyst or a compound or the like can be used for addition polymerization. An example of the nickel compound is, for example, a chemical formula: EnNi(C6F5)2, which is a catalyst. In the chemical formula, 'η system 丨 or 2, * E means a neutral ligand. In the case where n is 1, 'E is preferably an n-aryl ligand such as azide, benzene or mesitylene. When η is 2, E is preferably selected from the group consisting of dithizone, τΗρ (tetrazide), ethyl acetate, and dioxane. For example: (nonylbenzene) bis(perfluorophenyl)nickel, (mesitylene)bis(perfluorophenyl), (phenyl)bis(perfluorophenyl), bis(tetrahydrofuran) Double (perfluorophenyl) recording, double (acetate) bis(perfluorophenyl) nickel, and double (two brothel) double (perfluoro stupyl) recording. The details are as follows: PCT WO 97/3M98, PCT W0 〇〇/2〇472, 曰本本特特表 2010-523766, and Japanese Patent Laid-Open Publication No. Hei-5-588. 100130624 14 201211690 Preferred polymerization solvents for use in such polymerizations include hydrocarbons, aromatic solvents. Hydrocarbon dissolved ^ is enough to raise Yao, (10), Geng ship in scales. Further, examples of the aromatic surface type: toluene, xylene, and mesitylene are not limited to these. Others can still be used: tetrahydro-Wan, Er-Bai, Acetic Acid, X--, ketone, etc. These solvents may be used singly or in combination of two or more kinds as a polymerization solvent. The polymerization of the monomer contained in the resin composition for a photoresist of the present invention is such that the molecular weight of the resin obtained by the polymerization is such that the ratio of the catalyst to the monomer changes, or the polymerization temperature and the polarity of the polymerization solvent are also Can be controlled. Further, the molecular weight of the resin obtained by the polymerization can also be controlled by the addition of a suitable chain transfer agent. The cyclic dilute hydrocarbon resin used in the production of the resin composition for a photoresist of the present invention has a weight average molecular weight of 1,000 to 500,000 Daltons. When the weight average molecular weight exceeds the above range, the solubility of the resin composition in the aqueous alkali solution is lowered during photoprocessing, and there is a concern that good photoprocessability cannot be obtained. On the other hand, if the weight average molecular weight is less than the above lower limit value, it is impossible to sufficiently obtain the effect of the performance improvement effect by the addition. The blending amount of the cyclic dilute hydrocarbon resin to the resin is preferably 1 to wt%, more preferably 5 to 50% by weight. The amount of addition can be arbitrarily set according to the degree of improvement of the heat resistance required. However, if the amount of addition is too large, there is a fear that the properties such as sensitivity of the resin are lowered. On the other hand, if the amount added is too small, the effect of improving the heat resistance may be insufficient. 100130624 15 201211690 The sensitizer used in the production of the photoresist composition of the present invention is a naphthoquinonediazide-containing compound. The naphthoquinonediazide-containing compound may, for example, be the following (1) to (4), and Nai S Kun-1,2-heavy gas-5-supply acid or Nai S Kun-1,2-diazo-4. a complete ester compound, a partial ester compound, a amide or a partial amide of a sulfonic acid-containing sulfonic acid such as tarnish; (1) 2,3,4-trihydroxydiphenyl ketone, 2, 4,4'-trihydroxydiphenyl ketone, 2,4,6-trihydroxydiphenyl ketone, 2,3,6-trihydroxydiphenyl ketone, 2,3,4-trihydroxy-2'- Mercapto diphenyl ketone, 2,3,4,4'-tetrahydroxydiphenyl ketone, 2,2',4,4'-tetrahydroxydiphenyl ketone, 2,3',4,4', 6-pentahydroxydiphenyl ketone, 2,2',3,4,4'-pentahydroxydiphenyl ketone, 2,2',3,4,5-pentahydroxydiphenyl ketone, 2,3' , 4,4',5',6-hexahydroxydiphenyl ketone, 2,3,3',4,4',5'-hexahydroxydiphenyl ketone and other polyhydroxydiphenyl ketones; (2 Bis(2,4-dihydroxyphenyl)decane, bis(2,3,4-trihydroxyphenyl)methane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl) Propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(2) ',3\4'-trihydroxyphenyl)propane, 4,4'-{l-[4-[2-(4-hydroxyphenyl)-2-propyl]phenyl] Ethyl}bisphenol, 3,3,-dimethyl-{1-[4-[2-(3-indolyl-4-hydroxyphenyl)-2-propyl]phenyl]ethylidene} Bis[(poly)hydroxyphenyl]alkane such as phenol; (3) ginseng (4-hydroxyphenyl)decane, bis(4-hydroxy-3,5-didecylphenyl)-4-hydroxyphenyl Decane, bis(4-hydroxy-2,5-diamidinophenyl)-4-hydroxyphenylnonane, bis(4-hydroxy-3,5-dianonylphenyl)-2-hydroxyphenyl Decane, bis(4-hydroxy-2,5-diamidinophenyl)-2-hydroxyphenylnonane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-di Hydroxyphenyl decane, bis(4-hydroxy-3,5-dimercaptophenyl)-3,4-dihydroxyphenylmethane, etc. 100130624 16 201211690 (hydroxyphenyl) F alkane or its T group substitution Cyclohexyl _4 heptyl (tetra)phenyl f-sinter, bis(3_cyclohexyl _4· phenyl)·2·fresh base m(3·cyclohexyl _4_phenyl) phenyl Burning, bis(5·cyclohexyl_4_ silk·2_methylphenyl) funyl phenylacetate, hetero (5-cyclohexyl collaryl-2-methylsilyl)_3• fresh base ^, double (10) already ^ Benzyl-2-methylphenyl)·4_ by phenylmethyl, bis (3·cyclohexyl phenyl) via phenyl f, bis(5·cyclohexyl collar _3· decyl benzene Phenyl ketone, bis(5-cyclohexyl-4)-based _3-methyl Phenyl)·3_ by phenylmethyl, bis(5-cyclohexyl-4-transmethyl-3-methylphenyl)_2• by phenylmethyl, bis(3-cyclohexyl·2_hydroxyphenyl) 4-hydroxyphenyl decane, bis(3-cyclohexyl-2-hydroxyphenyl)-2-hydroxyphenyl decane, bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)_2_ Bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methane or its thiol group substituted with hydroxyphenylmethane or bis(5-cyclohexyl-2-yl-4-ylphenyl)-4-hydroxyphenylmethane Body and so on. Here, the above naphthoquinonediazide-containing compound component may be contained alone or in combination of two or more. In the resin composition of the present invention, the blending amount of the sensitizer is not particularly limited to 1 part by weight based on 1 part by weight of the phenol resin, and usually 5 to 1 part by weight, preferably 10 to 50 parts by weight. Range blending. If the blending amount of the sensitizer is less than the above lower limit value, it is difficult to obtain a faithful image, resulting in a decrease in transferability. On the other hand, if it exceeds the above upper limit value, the sensitivity may decrease when it is used as a photoresist. The solvent to be blended in the composition of the present invention is not particularly limited as long as the phenol resin, the cyclic olefin 100130624 17 201211690 hydrocarbon resin, and the naphthoquinonediazide-containing compound are soluble. In the present invention, these components are dissolved in a solvent and used. The solvent used in the production of the photoresist composition of the present invention may be: N-mercapto-2-oxaridone, γ-butyrolactone, hydrazine, fluorenyl-dimercaptoacetamide,曱亚石风, diethylene glycol dioxime ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monoterpene ether, dipropylene glycol monomethyl ether, propylene glycol monoterpene ether acetate, lactic acid vinegar, Ethyl lactate, butyl ketone, decyl-1,3-butanediol acetate, 1,3-butanediol 20-3-monodecyl ether, decyl pyruvate, ethyl pyruvate, thiol-3 - methoxypropionate or the like, which may be used singly or in combination. Further, in the composition of the present invention, in addition to the above-described components, various additives such as a stabilizer such as an antioxidant, a plasticizer, a surfactant, a adhesion improving agent, and a dissolution promoter may be used. The preparation method of the composition of the present invention is not particularly limited. When the filler or the pigment is not added to the composition, the above components may be mixed and stirred according to a usual method, and when a filler or a pigment is added, Dispersion and mixing may be carried out by using a dispersing device such as a high-speed agitator, a homogenizer, or a three-roll mill. Further, filtration may be further carried out using a sieve filter, a membrane filter, or the like as needed. By subjecting the composition of the present invention thus obtained to exposure through a mask, a structural change occurs in the composition in the exposed portion, and the solubility in the alkali developing solution can be promoted. On the other hand, since the solubility in the alkali developing solution is kept low in the non-exposed portion, it is possible to impart a light-resistance function to the 100130624 18 201211690 by utilizing the poor solubility resulting therefrom. When the composition of the present invention is used as a photoresist, the naphthoquinonediazide-containing compound in the composition undergoes chemical change by irradiation of light, and is dissolved together with the novolak resin in a subsequent development step. In the alkali developing solution, a clear difference in dissolution speed is generated between the unexposed portions, whereby the target pattern can be obtained by development. Hereinafter, a synthesis example and an example will be described with respect to the present invention. However, the present invention is not limited by the synthesis examples and examples. Further, "parts" and "%" described in the synthesis examples, the examples, and the comparative examples indicate "total weight and "% by weight". However, the concentration (%) of the aqueous formaldehyde solution is excluded. [Examples] 1. Synthesis of a resin (Synthesis Example 1) A 3 L four-necked flask equipped with a stirring device, a thermometer, and a heat exchanger was charged with 60 g of metaxanthine, 400 g of p-nonylphenol, and 527 g of 37% formaldehyde. 5 g of oxalic acid was reacted for 4 hours under reflux conditions. Then, dehydration was carried out under normal pressure to an internal temperature of 170 ° C, and dehydration and de-monomerization were carried out at 9.3 x 1 Torr 3 Pa to 200 ° C to obtain 950 g of a phenol resin having a weight average molecular weight of 4,200 daltons. 2 ♦ ί Synthesis of a fine-formed resin (Synthesis Example 2) [4-(2-Bicyclo[2.2.1]hept-5-ene)phenyl]acetic acid (11.4 g, 50 mmol), 曱 stupid (17.6 g), and acetophenone (27.4g) were packed in a reaction vessel equipped with a mix of 100130624 19 201211690, and the inside was replaced with dry nitrogen. The contents were heated, and when the internal temperature reached 50 ° C, a solution of (η6-nonylbenzene)Ni(C6F5)2 (〇.97 g, 2.00 mmol) dissolved in 10 g of benzene was added. After reacting at 50 ° C for 3 hours, it was cooled to room temperature. Adding 1 (5 (^) and i〇% potassium hydroxide aqueous solution (80 g) to carry out a reflux reaction for 5 hours. Then, after adding neutralized acetic acid, the water washing operation by ion-exchange water was performed three times. The organic layer was concentrated by an evaporator, and then reprecipitated by calcination. The obtained solid was dried overnight by a vacuum dryer at 60 ° C to obtain 8.2 g of a pale yellow powder. The molecular weight of the obtained polymer was measured by GPC, and the result was Mw = ll, 〇〇〇, Mn = 5300. (Synthesis Example 3) 3-methoxy-4-(bicyclo[2.2.1]hept-2-en-5-yl)nonylphenol (5 〇g) , 18.4mm〇l), ethyl 3-(propionate) (3-bicyclo[2.2.1]hept-5-ene) vinegar (〇89g, 4.5911^101), benzene (28g), and _B_( 1〇g) Filled in a reaction vessel equipped with a stirring device, and replaced the inside with dry nitrogen gas. The contents were heated and the internal temperature reached 6 〇. (: Japanese temple, added to make (ηό-甲笨) see 5) 2 (〇玛,〇46_]) A solution dissolved in 5 g of benzene. After 3 hours of reaction at 6 Torr, it was cooled to fox. Add THF (5 〇g) and 1 〇〇 / 0 potassium hydroxide solution ( 5 illusion, allowing 5 hours of reflux reaction Then, after adding acetic acid for neutralization, the water washing operation by sub-exchange water was carried out three times. The organic layer was concentrated by an evaporator, and then reprecipitated by hexane. The obtained solid was subjected to a vacuum cleaner of 6 〇〇c. Drying overnight was carried out to obtain 8 2 g of a pale yellow powder. The molecular weight of the obtained polymer 100130624 20 201211690 was measured by GPC and found to be Mw = 16,000 and Mn = 9000. (Synthesis Example 4) Ethyl-3-ethyl propionate -bicyclo[2.2.1]hept-5-lean)cool (37.3 g, 0.19 mol), 1, bis-difluoromethyl-2-(bicyclo[2.2.1]hept-2-en-5-yl) Ethanol (13.2 g, 0.05 mol), toluene (55 g), triethyldecane (丨4 g), ethyl acetate (13 g), and dimercaptoaniline (pentafluorophenyl) borate (〇〇6g) , 〇〇 7mm 〇 1) filled in a reaction vessel equipped with a stirring device, replacing the inside with dry nitrogen. Heating the inner grain, adding (acetonitrile) bis (triisopropylphosphine) when the internal temperature reaches l〇〇 °C Palladium (acetate) (pentafluorophenylborate) (0.03 g, 〇〇 2 mm 〇 1) in ethyl acetate (6 g). After 16 hours of reaction on the loot, cool to room temperature, add TH F and a 10% aqueous potassium hydroxide solution (3 〇〇g) were subjected to a reflux reaction for 5 hours. Then, after neutralizing with acetic acid, the water washing operation by ion-exchanged water was carried out three times. The organic layer was subjected to an evaporator. After concentration, it was further reduced by calcination, and it was dried overnight to obtain 27 g of a white powder. The molecular weight of the obtained polymer was measured by GPC and found to be Mw = 8,200 and Mn = 4,200. (Synthesis Example 5) U-bistrifluorofluorenyl (bicyclo[2.2.ηheptene Ii)ethanol (9.9 g, 0.036 m〇l), bicyclo [2.2.1] g-2H Weitrimethyl Shi Xi (4) (2.2g '〇.〇12mol), ethyl acetate (l〇〇g), and cyclohexane (1〇〇 phantom filled in a reaction vessel equipped with a stirring device, replacing the inside with dry nitrogen. Heating the contents, When the internal temperature reaches 10 (TC), add (propyl group) (tricyclohexyl scale) 100130624 21 201211690 trifluoroacetate (0.006g ' 0.008mmol) of dioxin (2g) solution, and 肆 (five Fluorine base) 〇 〇 〇 〇 g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g The obtained polymer was put into decyl alcohol, and the precipitate was coagulated, washed thoroughly with water, and dried under vacuum to obtain 77 g of a white powder. The molecular weight of the obtained polymer was measured by GPC, and the result was Mw = 12,200. Mn = 6,100. (Synthesis Example 6) 5-butylbicyclo[2.2.1]hept-2-ene (l3.〇g, 〇.〇87 mol), methyl stupid (18 g), and acetophenone (llg) Fill in the counter with the stirring device In the vessel, the inside was replaced with dry nitrogen. The contents were heated, and when the internal temperature reached 6 Torr, (η-toluene) > ii (C6F5) 2 (〇_42g, 〇.87 mmol) was dissolved in i〇g 曱The solution in benzene was subjected to 3 hours of hydrazine and cooled to room temperature. The solution after the reaction was dissolved in a _g towel, and the water washing operation was carried out 3 times. The organic layer was evaporated. After concentration, the apparatus was re-sinked with methanol to obtain a white solid. The obtained solid was dried overnight by a vacuum dryer to obtain 7 5 g of a color powder. The molecular weight of the polymer was determined by GPC, and the gentleman was measured. ·^ af ' ^ ',0 The fruit is Mw=31,000, Mn=14, 〇〇〇 4. Modulation of the composition for the photoresist (Example 1) / The varnish type obtained in Synthesis Example 1 30 parts, Synthesis Example 2 (4) Ring-hydrocarbon resin 6 parts, and 2, w'_Tetra-diphenyl group and Bu 100130624 22 201211690 6 parts, dissolved in propylene glycol 1 Ι. Ομιη membrane filter weight After the nitrogen-based-5,6-di-indole-5-oxyl_caimin acid is aged in 15 parts of monomethylhydrazine acetic acid, the photoresist composition is prepared by using a pore filter. (Example 2)
施行過濾，便調製得光阻劑組成物。 (實施例3) 將合成例1所獲得祕清漆型酉分樹脂3〇份、合成例3所 獲得環狀烯烴樹脂3份、以及2,3,4,4,_四經基二苯基嗣與卜 重氮基-5,6-二氫_5_氧基-萘_丨_磺酸的酯6份，溶解於丙二醇 早曱_醋酸醋150份中之後’使用孔徑丨㈣薄膜過遽器施 行過濾，便調製得光阻劑組成物。 (實施例4) 將合成例1所獲得盼搭清漆型紛樹脂3〇份、合成例4所 後得環狀婦煙樹脂6份、以及2,3,4,4，-四經基二苯基酮與6-重氮基-5,6-一氫-5-氧基-萘_1_續酸的酯6份，溶解於丙二醇 單甲驗醋酸醋15〇份中之後，使用孔徑ι·〇μπ1薄膜過濾器施 4亍過;慮，便调製得光阻劑組成物。 (實施例5) 100130624 23 201211690 將合成例1所獲得酚醛清漆型酚樹脂30份、合成例5所 獲得環狀烯fe樹脂6份、以及2,3,4,4'-四羥基二笨基_與 重氮基-5,6-一氫-5-氧基-萘-1·續酸的酯6份，溶解於丙二醇 單甲趟錯酸S曰150份中之後’使用孔徑1 〇gm薄膜過遽器施 行過濾’便調製得光阻劑組成物。 (實施例6) 將合成例1所獲得祕清漆型盼樹脂3〇份、合成例6戶 獲得環狀雜樹脂3份、以及2,3,4,4，锦基二苯基綱與（ 重氮基-5,6·二氫錢基萘」姻的自旨6份，溶解於丙二 單甲義㈣15G份中之後，使用孔徑1()叫薄膜過遽器 行過濾，便調製得光阻劑組成物。 (比較例1) 將合成例1所獲得酚醛清漆型酚 四經基二苯基酮與6.重氮基_5,6、二/ 7以及2,3,4，’ 酯6份’溶解於丙二醇單甲醚醋酸：土 ： · 徑1.0哗薄膜過濾器施行過濾 0伤中之後’使用 伯田眘#^ , 周製得光阻劑組成物。 使用貫轭例1〜5、及比較例Κ2 彳 f k得光阻劑組成物， 仃下述所不特性評估。結果示於表丨。 100130624 24 201211690 [表l]The filter composition is applied to prepare a photoresist composition. (Example 3) 3 parts of the secret varnish type bismuth resin obtained in Synthesis Example 1, 3 parts of the cyclic olefin resin obtained in Synthesis Example 3, and 2,3,4,4,_tetramethylenediphenyl fluorene and 6 parts of an ester of diazo-5,6-dihydro-5-oxy-naphthalene-anthracene-sulfonic acid, dissolved in propylene glycol early 曱 _ vinegar vinegar 150 parts, using a pore size 四 (four) film filter After filtering, the photoresist composition is prepared. (Example 4) 3 parts of the varnish type resin obtained in Synthesis Example 1 and 6 parts of the ring-shaped fume resin obtained in Synthesis Example 4, and 2,3,4,4,-tetracarboxylic benzene. 6 parts of an ester of a ketone with 6-diazo-5,6-monohydro-5-oxy-naphthalene-1-one, dissolved in 15 parts of propylene glycol monoacetic acid vinegar, using a pore size ι· The 〇μπ1 membrane filter was applied; the photoresist composition was prepared. (Example 5) 100130624 23 201211690 30 parts of the novolac type phenol resin obtained in Synthesis Example 1, 6 parts of the cyclic olefinic resin obtained in Synthesis Example 5, and 2,3,4,4'-tetrahydroxydiphenyl group 6 parts of ester with diazo-5,6-monohydro-5-oxy-naphthalene-1·suan acid, dissolved in 150 parts of propylene glycol monomethylhydrazone S ' 'Use pore size 1 〇gm film The filter is applied to the filter to prepare the photoresist composition. (Example 6) 3 parts of the secret varnish type anti-resin obtained in Synthesis Example 1, 3 parts of the ring-shaped resin, and 2, 3, 4, 4, and 2, 3, 4, 4, and 2, 3, 4, 4 6 parts of the nitrogen-based-5,6·dihydrocarbylnaphthalene", dissolved in the 15g parts of the propylidene (4), and then filtered using a pore size 1 () as a membrane filter. (Comparative Example 1) The novolac type phenol tetracarboxylic acid diphenyl ketone obtained in Synthesis Example 1 and 6. Diazo _5,6, bis/7 and 2,3,4,' ester 6 Parts 'dissolved in propylene glycol monomethyl ether acetate: soil: · diameter 1.0 哗 membrane filter after filtration 0 injury 'Using Bertian Shen #^, week made photoresist composition. Using yoke examples 1 to 5, And Comparative Example 2 彳fk obtained photoresist composition, 仃 evaluation of the following characteristics. The results are shown in Table 100. 100130624 24 201211690 [Table l]
(1) 耐熱性之評估方法 在經六甲基二石夕氮院處理過的石夕晶圓上，利用旋塗機依乾 無時的膜厚成為之方式施行塗佈，再於就於加轨 板上施行9G秒鐘乾燥1後，使用縮小投影曝光裝置，隔 t賴圖案遮罩施行曝光，再使用顯影液(2遍氫氧化四甲 銨水溶液)施行60秒鐘顯且， 々衫。所獲得矽晶圓在經改變溫度的 加熱板上放置3分鐘，利用p 用知也式電子顯微鏡觀察矽晶圓上 的光阻圖案形狀，將盔法 r …、夬焱侍正㊉光阻圖案時的溫度視為 「耐熱溫度」。 (2) 殘膜率測定方法 了光_組成物_旋塗機在3啊㈣上依成為 施行塗佈，並在㈣加熱板上施請秒鐘 乾燥。將該晶圓在顯影液 、主mama ( .38/0虱氧化四甲銨水溶液）中浸 沒60秒釦後，利用水施行 4丨扭私π 於於not：加熱板上施行1〇〇 秒釦乾燥。將顯影後的膜 子員衫剐的膜厚之比，依百分率 100130624 25 201211690 表示，並視為「殘膜率」。 使用時的殘膜（耐性)程度， (3)感度之測定方法 將光阻劑組烕物在3吋矽晶圓上 約Ιμπι的方式施行塗佈，再於U(rc加熱機依成為厚度 乾燥。接著，在該石夕晶圓上重疊測試 胃τ 〇 &1 20mJ/cm2、40m：T/cm、60mJ/cm2 的紫外繞 匕^ 、’使用顯影液(2.38% 虱氧化四甲叙水浴液）施行90秒鐘顯影料 貝〜針對所獲得圖 用掃描式電子顯微鏡觀察圖案形狀，依照 /L …、下的基準施行評 估。 A於20mJ/cm2以下可形成影像。， B於超過20mJ/cm2、且40mJ/cm2以下可形成今像 C於超過40mJ/cm2、且60mJ/cm2以下可形成$像 (4)解析度之測定 將上述所調製得之光阻劑組成物’使用旋塗機塗佈於矽曰 圓上，施行liot、1〇〇秒鐘預烤，形成膜厚丨5μιη光阻^ 膜。對其隔著經刻劃100〜Ιμιη線寬的圖案遮罩，使用紫外 線施行曝光。經曝光後，馬上利用2.38wt%氫氧化四甲録水 /谷液’於23°C施行60秒鐘顯影，施行水洗、乾燥，便彳被得 正型圖案。此時，將以一定曝光量可解析的最小光阻圖案尺 寸視為「解析度」。 由表1的結果，貫施例1〜5係本發明的光阻劑用樹脂組成 1〇〇13〇624 26 201211690 物，相較於非屬本發明樹脂組成物的比較例1〜2之下，可證 明具有優異的殘膜率、感度、特別係耐熱性。 (產業上之可利用性） 本發明之光阻劑用樹脂組成物係具有良好的熱安定性，且 呈高感度、高解析度，並具有高殘膜性，因而可適用於液晶 • 顯示裝置電路、半導體積體電路的微細電路製造。 100130624 27(1) Evaluation method of heat resistance On the Shixi wafer treated by hexamethyl diaphorus, the coating was applied by a spin coater according to the film thickness of the dry film, and then it was applied. After the rail was dried for 9 G seconds, the exposure was performed using a reduced projection exposure device, and the exposure was applied to the mask, and the developer (2 times aqueous solution of tetramethylammonium hydroxide) was used for 60 seconds. The obtained ruthenium wafer was placed on a hot plate with a changed temperature for 3 minutes, and the shape of the photoresist pattern on the ruthenium wafer was observed by using a p-type electron microscope, and the helmet method was used. The temperature is regarded as "heat resistant temperature". (2) Method for measuring residual film rate The light_composition_rotator is applied on 3 (4) to be applied, and applied to the (4) hot plate for 2 seconds. The wafer was immersed in a developing solution, a main mama (.38/0 四 tetramethylammonium oxide aqueous solution) for 60 seconds, and then subjected to 4 丨 twisting π on the no: hot plate for 1 sec. dry. The ratio of the film thickness of the filmmakers after development is expressed as a percentage of 100130624 25 201211690 and is regarded as the "residual film rate". The degree of residual film (resistance) at the time of use, (3) The method of measuring the sensitivity is applied to the photoresist group on a 3 吋矽 wafer by about Ι μπι, and then the U (rc heating machine is dried to a thickness) Then, on the Shi Xi wafer, the test was performed on the τ 〇 & 1 20 mJ/cm 2 , 40 m : T / cm , 60 mJ / cm 2 of the UV winding 、 ^ , ' using the developer (2.38% 虱 四 四 甲 叙 水 水 水The liquid was applied for 90 seconds, and the shape of the pattern was observed with a scanning electron microscope for the obtained image, and evaluated according to the reference of /L ... and below. A can form an image at 20 mJ/cm 2 or less, and B exceeds 20 mJ / Cm2, and 40 mJ/cm2 or less can form a current image C. When the thickness is more than 40 mJ/cm 2 and 60 mJ/cm 2 or less, a resolution of $4 can be formed. The above-prepared photoresist composition can be used as a spin coater. It is coated on a round circle, and subjected to a lidt and pre-baked for 1 second to form a film thickness 丨5μιη photoresist film. It is covered with a pattern of 100% Ιμιη line width, and is exposed by ultraviolet rays. Immediately after exposure, use 2.38wt% Hydroxide Hydroxide/Valley Solution to perform at 60°C for 23 seconds. The water is washed and dried, and the toilet is patterned into a positive pattern. At this time, the minimum resist pattern size that can be resolved with a certain amount of exposure is regarded as "resolution". From the results of Table 1, the examples 1 to 5 are used. The resin for a photoresist of the present invention has a composition of 1〇〇13〇624 26 201211690, and can be proved to have excellent residual film ratio, sensitivity, and speciality as compared with Comparative Examples 1 to 2 which are not the resin composition of the present invention. Heat resistance. (Industrial Applicability) The resin composition for a photoresist of the present invention has good thermal stability, high sensitivity, high resolution, and high residual film property, and thus is applicable to LCD • Display device circuit, fine circuit manufacturing of semiconductor integrated circuit. 100130624 27