TW201540782A - Etch resistant material for oxygen plasma etching, etch resistant film, and a laminate using the same - Google Patents

Etch resistant material for oxygen plasma etching, etch resistant film, and a laminate using the same Download PDF

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TW201540782A
TW201540782A TW104108211A TW104108211A TW201540782A TW 201540782 A TW201540782 A TW 201540782A TW 104108211 A TW104108211 A TW 104108211A TW 104108211 A TW104108211 A TW 104108211A TW 201540782 A TW201540782 A TW 201540782A
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decane
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Naoto Yagi
Takeshi Ibe
Hisashi Tanimoto
Makoto Yada
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Dainippon Ink & Chemicals
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    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
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    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3065—Plasma etching; Reactive-ion etching
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
    • H01L21/32136—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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Abstract

The subject of the present invention is to provide an etch resistant material for oxygen plasma etching, which can appropriately be used in a multi-layer etch resistant agent manufacturing process as a silicon-containing film with excellent dry etching resistance with respect to oxygen plasma and a hydrolysis curing process not requiring baking, thereby providing excellent adhesion to and organic lower film. The silicon-containing film can also be appropriately applied to patterning of UV nano-imprint with higher productivity. This invention solves the aforesaid concerns by providing an etch resistant material for oxygen plasma etching, which contains a specific siloxane resin such that the silicon atom content is specified.

Description

氧電漿蝕刻用抗蝕劑材料、抗蝕劑膜、及使用其之積層體 Resist material for oxygen plasma etching, resist film, and laminated body using the same

本發明係關於一種氧電漿蝕刻用抗蝕劑材料。更詳細而言係關於一種可於多層抗蝕劑製程中用作需要對氧電漿之耐乾式蝕刻性較高之含矽膜、進而亦可藉由UV(ultraviolet，紫外線)奈米壓印而直接圖案化之乾式蝕刻用抗蝕劑材料、抗蝕劑膜、及使用其之積層體。 The present invention relates to a resist material for oxygen plasma etching. More specifically, it relates to a ruthenium-containing film which can be used in a multilayer resist process and which requires high dry etching resistance to oxygen plasma, and can also be embossed by UV (ultraviolet). A resist material for dry etching which is directly patterned, a resist film, and a laminate using the same.

自先前以來，已知對於印刷配線板、液晶顯示元件、電漿顯示器、大規模積體電路、薄型電晶體、半導體封裝體、彩色濾光片、有機電致發光等中之導體電路或電極加工基板等之形成、或金屬之精密加工等，使用感光性組合物及使用其之乾膜抗蝕劑材料作為阻焊劑、蝕刻抗蝕劑或鍍敷抗蝕劑等之抗蝕劑材料。 Since the prior art, it has been known to process conductor circuits or electrodes in printed wiring boards, liquid crystal display elements, plasma displays, large-scale integrated circuits, thin transistors, semiconductor packages, color filters, organic electroluminescence, and the like. For the formation of a substrate or the like, or precision processing of a metal, a photosensitive composition and a dry film resist material using the same are used as a resist material such as a solder resist, an etching resist, or a plating resist.

例如，已知有使用如下感光性圖像形成材料之微影法或雷射直接描繪法，即，於暫時支持膜上塗佈感光性組合物之塗佈液並進行乾燥而形成感光性組合物層，以被覆膜覆蓋該感光性組合物層表面而獲得乾膜抗蝕劑材料，將該材料剝離其被覆膜而積層於被加工基板上，藉此製作感光性圖像形成材料，或於被加工基板上直接塗佈感光性組合物之塗佈液並進行乾燥而形成感光性組合物層，視需要以保護層覆蓋該感光性組合物層表面，藉此而製作感光性圖像形成材料；微影法係使用該感光性圖像形成材料，將其被加工基板上之感光性組合物層經由描繪有電路或電極圖案之遮罩膜進行圖像曝光之後，剝離暫時支持膜、或保護層，利用曝光部與非曝光部對顯影液之溶解性之差進行 顯影處理，藉此形成與電路圖案對應之抗蝕劑圖像，繼而，將該抗蝕劑圖像作為抗蝕劑對被加工基板進行蝕刻加工、鍍敷加工、或焊料加工等，此後，去除抗蝕劑圖像，藉此於基板上形成描繪於遮罩膜之電路或電極圖案，雷射直接描繪法係藉由使用雷射光作為曝光光源，而不使用遮罩膜而根據電腦等之數位資訊直接形成圖像。 For example, a lithography method or a direct laser drawing method using a photosensitive image forming material in which a coating liquid of a photosensitive composition is applied onto a temporary support film and dried to form a photosensitive composition is known. a layer, a surface of the photosensitive composition layer is covered with a coating film to obtain a dry film resist material, and the material is peeled off from the coating film to be laminated on the substrate to be processed, thereby producing a photosensitive image forming material, or The coating liquid of the photosensitive composition is directly applied onto the substrate to be processed and dried to form a photosensitive composition layer, and if necessary, a surface of the photosensitive composition layer is covered with a protective layer, thereby producing a photosensitive image formation. The lithography method uses the photosensitive image forming material, and the photosensitive composition layer on the substrate to be processed is image-exposed by a mask film on which a circuit or an electrode pattern is drawn, and then the temporary support film is peeled off, or The protective layer uses the difference in solubility between the exposed portion and the non-exposed portion to the developer The development process is performed to form a resist image corresponding to the circuit pattern, and then the resist image is used as a resist to etch, plate, or solder the substrate to be processed, and thereafter, remove a resist image, whereby a circuit or an electrode pattern drawn on the mask film is formed on the substrate, and the laser direct drawing method uses a laser light as an exposure light source without using a mask film and is based on a digit of a computer or the like. Information directly forms an image.

進而，於半導體微影之領域，於抗蝕劑圖案之線寬更微細之情形時，作為較為有效之方法之一，進行多層抗蝕劑製程。於多層抗蝕劑製程中，於被加工膜上積層有機下層膜，繼而於該有機膜上積層含矽膜(SOG(spin-on-glass，旋塗玻璃)等)，進而於其上積層抗蝕劑膜，將抗蝕劑圖案作為遮罩對含矽膜進行蝕刻，繼而將含矽膜作為遮罩對有機下層膜進行蝕刻。藉由將如此獲得之有機下層膜之圖案作為遮罩對被加工膜進行蝕刻，與單層抗蝕劑法相比，可使解像性顯著提高。 為了提高與抗蝕劑膜及有機下層膜之蝕刻選擇性，要求上述加工中使用之含矽膜對氧電漿之耐蝕刻性優異、與抗蝕劑膜之密接性優異等。 Further, in the field of semiconductor lithography, when the line width of the resist pattern is finer, a multilayer resist process is performed as one of the more effective methods. In the multilayer resist process, an organic underlayer film is laminated on the film to be processed, and then a ruthenium-containing film (SOG (spin-on-glass), etc.) is laminated on the organic film, and the layer resist is laminated thereon. The etchant film etches the ruthenium-containing film using the resist pattern as a mask, and then etches the organic underlayer film using the ruthenium-containing film as a mask. By etching the film to be processed by using the pattern of the organic underlayer film thus obtained as a mask, the resolution can be remarkably improved as compared with the single layer resist method. In order to improve the etching selectivity with the resist film and the organic underlayer film, the ruthenium-containing film used in the above processing is required to have excellent etching resistance to oxygen plasma and excellent adhesion to a resist film.

然而，多層抗蝕劑製程需要以均勻之膜厚形成並積層非常薄之複數個膜之技術，於產出量及步驟管理上成為較大負擔。又，該製程中使用之含矽膜通常使用含有聚矽氧烷之化合物(例如參照專利文獻1)，於將包含溶解其之醇等有機溶劑之溶液塗佈至有機下層膜上後，為了進行水解縮合而需要加熱、冷卻過程，可以說生產性並不充分。 However, the multilayer resist process requires a technique of forming a uniform film thickness and laminating a very thin plurality of films, which becomes a large burden on throughput and step management. In addition, a ruthenium-containing film to be used in the process is usually a compound containing a polyoxyalkylene (for example, refer to Patent Document 1), and a solution containing an organic solvent such as an alcohol in which the alcohol is dissolved is applied to the organic underlayer film, and then The hydrolysis and condensation require a heating and cooling process, and it can be said that the productivity is not sufficient.

對此，於專利文獻2中揭示有如下技術：使用含有氫化倍半矽氧烷及溶劑之溶液加工材料，將其塗佈膜形成於基板上後，於室溫下進行衝壓，並進行溶劑之去除及水解硬化，藉此獲得微細之圖案。該方法被稱為室溫壓印法，無需進行較含矽膜上層之抗蝕劑膜等之積層步驟，進而可省去加熱、冷卻之循環。然而，衝壓所需之時間較長，可以說產出量尚不充分。 On the other hand, Patent Document 2 discloses a technique in which a coating material containing a hydrogenated silsesquioxane and a solvent is used, and a coating film is formed on a substrate, and then pressed at room temperature to carry out solvent treatment. Removal and hydrolytic hardening, thereby obtaining a fine pattern. This method is called a room temperature imprint method, and it is not necessary to carry out a lamination step of a resist film or the like which is higher than the upper layer of the ruthenium film, and the cycle of heating and cooling can be omitted. However, the time required for stamping is longer, and it can be said that the output is not sufficient.

另一方面，提出有使用利用紫外線進行硬化之光硬化性樹脂之 被稱為UV奈米壓印之技術。該製程係於塗佈光硬化性樹脂後，一面於室溫附近進行衝壓一面藉由紫外線照射使樹脂硬化，自模具剝離而獲得微細圖案之方法。該製程亦無加熱、冷卻之循環，且利用紫外線進行之硬化可於非常短之時間內完成。然而，通常用於UV奈米壓印之樹脂係丙烯酸系有機樹脂，無法於上述多層抗蝕劑製程中應用於需要與抗蝕劑膜及有機下層膜之蝕刻選擇性之含矽膜之用途。 On the other hand, it has been proposed to use a photocurable resin which is cured by ultraviolet rays. Known as the technology of UV nanoimprinting. This process is a method of obtaining a fine pattern by peeling off the mold by ultraviolet irradiation after the photocurable resin is applied, and the resin is cured by ultraviolet irradiation. The process also has no cycles of heating and cooling, and hardening by ultraviolet rays can be completed in a very short time. However, the resin-based acrylic organic resin generally used for UV nanoimprinting cannot be applied to the use of the ruthenium-containing film which requires etching selectivity with the resist film and the organic underlayer film in the above-described multilayer resist process.

作為解決此種問題之方法，於專利文獻3中報告有可進行UV奈米壓印之具有紫外線硬化性之含矽化合物，但由於利用UV陽離子聚合進行硬化，故而可以說生產性尚不充分，進而，由於矽原子之含量較低，故而對氧電漿之耐蝕刻性亦不充分。 As a method for solving such a problem, Patent Document 3 reports an ultraviolet-containing curable cerium-containing compound capable of performing UV nanoimprinting. However, since it is hardened by UV cationic polymerization, productivity can be said to be insufficient. Further, since the content of the ruthenium atoms is low, the etching resistance to the oxygen plasma is also insufficient.

又，於UV奈米壓印中，必須抑制將光硬化性樹脂一面進行衝壓一面進行紫外線硬化後自模具剝離時產生之脫模缺陷。先前之多層抗蝕劑製程中所使用之含矽膜與上層之抗蝕劑膜之密接性存在問題，於直接對含矽膜進行奈米壓印之情形時，為了抑制脫模缺陷，與有機下層膜之密接性更為重要。尤其，由於奈米壓印為接觸式，故而與非接觸之光微影法相比，需要更牢固之含矽膜與有機下層膜之密接性，但迄今為止尚無關注於該方面之報告。 Further, in the UV nanoimprinting, it is necessary to suppress the release defects which occur when the photocurable resin is subjected to ultraviolet curing and then peeled off from the mold. There is a problem in the adhesion between the ruthenium-containing film used in the previous multilayer resist process and the resist film on the upper layer, and in order to suppress the mold release defect and the organic layer directly in the case of performing nanoimprinting on the ruthenium-containing film. The adhesion of the underlying film is more important. In particular, since the nanoimprint is a contact type, it is required to have a stronger adhesion between the ruthenium-containing film and the organic underlayer film than the non-contact photolithography method, but there has been no report on this aspect so far.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開2011-213921號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-213921

[專利文獻2]日本專利特開2003-100609號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-100609

[專利文獻3]日本專利特開2013-131762號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2013-131762

本發明所欲解決之問題在於提供一種氧電漿蝕刻用抗蝕劑材料，其係於多層抗蝕劑製程中作為對氧電漿之耐乾式蝕刻性優異及無 需利用烘烤之水解硬化過程的含矽膜較佳者，進而對有機下層膜之密接性良好，於利用生產性更高之UV奈米壓印進行之圖案化方面亦較佳。 The problem to be solved by the present invention is to provide a resist material for oxygen plasma etching which is excellent in dry etching resistance to oxygen plasma and is not used in a multilayer resist process. The ruthenium-containing film which is required to utilize the hydrolytic hardening process of baking is preferred, and the adhesion to the organic underlayer film is good, and it is also preferable in terms of patterning by using a more productive UV nanoimprint.

又，提供一種含有上述乾式蝕刻抗蝕劑用抗蝕劑材料之抗蝕劑膜、積層該抗蝕劑膜而成之積層體。 Further, a laminate film comprising the resist material for a dry etching resist and a laminate obtained by laminating the resist film is provided.

本發明者等人進行努力研究，結果發現，含有特定之矽氧烷樹脂、進而成為特定矽原子含量之氧電漿蝕刻用抗蝕劑材料可解決上述問題。 As a result of intensive studies, the inventors of the present invention have found that the above-mentioned problem can be solved by a resist material for oxygen plasma etching containing a specific siloxane oxide and further having a specific ruthenium atom content.

本發明如下。 The invention is as follows.

[1]提供一種氧電漿蝕刻用抗蝕劑材料，其特徵在於：其係含有複合樹脂(A)之乾式蝕刻用抗蝕劑材料，該複合樹脂(A)係具有通式(1)及/或通式(2)所表示之結構單元和矽烷醇基及/或水解性矽烷基之聚矽氧烷片段(a1)、與乙烯基系聚合物片段(a2)藉由通式(3)所表示之鍵進行鍵結而成，且該氧電漿蝕刻用抗蝕劑材料之固形物成分量中矽原子之含量為15~45wt%。 [1] Provided is a resist material for oxygen plasma etching, which comprises a resist material for dry etching of a composite resin (A), wherein the composite resin (A) has a general formula (1) and / or a structural unit represented by the formula (2) and a polyoxyalkylene moiety (a1) of a decyl alcohol group and/or a hydrolyzable alkylene group, and a vinyl polymer fragment (a2) by the formula (3) The indicated key is bonded, and the content of the solid content of the resist material for the oxygen plasma etching is 15 to 45 wt%.

[化2] [Chemical 2]

(通式(1)及(2)中，R1、R2及R3分別獨立地表示具有選自由-R4-CH=CH2、-R4-C(CH3)=CH2、-R4-O-CO-C(CH3)=CH2、及-R4-O-CO-CH=CH2所組成之群中之1個聚合性雙鍵之基(其中，R4表示單鍵、芳基或碳原子數1~6之伸烷基)、碳原子數為1~6之烷基、碳原子數為3~8之環烷基、芳基、或碳原子數為7~12之芳烷基，R1、R2及R3中之至少一者為具有聚合性雙鍵之基) (In the general formulae (1) and (2), R 1 , R 2 and R 3 each independently represent a group selected from -R 4 -CH=CH 2 , -R 4 -C(CH 3 )=CH 2 ,- a group of one polymerizable double bond in the group consisting of R 4 —O—CO—C(CH 3 )=CH 2 and —R 4 —O—CO—CH=CH 2 (wherein R 4 represents a single a bond, an aryl group or an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or a carbon number of 7~ a 12-aralkyl group, at least one of R 1 , R 2 and R 3 being a group having a polymerizable double bond)

(通式(3)中，設為碳原子構成上述乙烯基系聚合物片段(a2)之一部分，僅鍵結於氧原子之矽原子構成上述聚矽氧烷片段(a1)之一部分) (In the general formula (3), it is assumed that a carbon atom constitutes a part of the vinyl polymer fragment (a2), and only a germanium atom bonded to an oxygen atom constitutes a part of the polyaluminoxane fragment (a1))

[2]提供一種氧電漿蝕刻用抗蝕劑材料，其係如上述之抗蝕劑材料，上述聚矽氧烷片段(a1)之比率於上述複合樹脂(A)中為70~95wt%。 [2] A resist material for oxygen plasma etching is provided, which is a resist material as described above, and the ratio of the polyoxyalkylene fragment (a1) is 70 to 95% by weight in the composite resin (A).

[3]提供一種抗蝕劑膜，其特徵在於：其係使如[1]或[2]之抗蝕劑材料進行紫外線硬化而成。 [3] A resist film is provided which is obtained by subjecting a resist material of [1] or [2] to ultraviolet curing.

[4]提供一種如上述之抗蝕劑膜，其特徵在於形成有圖案。 [4] A resist film as described above, characterized in that a pattern is formed.

[5]進而提供一種如[3]之抗蝕劑膜，其特徵在於：其藉由奈米壓印而形成有圖案。 [5] Further, there is provided a resist film according to [3], which is characterized in that it is patterned by nanoimprinting.

[6]進而提供一種積層體，其特徵在於：其於基材積層有本發明之抗蝕劑膜。 [6] Further, there is provided a laminate in which a resist film of the present invention is laminated on a substrate.

根據本發明，可獲得如下氧電漿蝕刻用抗蝕劑材料，其係於多層抗蝕劑製程中作為對氧電漿之耐蝕刻性優異及無需利用烘烤之水解硬化過程的含矽膜較佳者，進而對有機下層膜之密接性良好，於利用生產性更高之UV奈米壓印進行之圖案化方面亦較佳。 According to the present invention, the following resist material for oxygen plasma etching can be obtained as a ruthenium-containing film which is excellent in etching resistance to oxygen plasma and which does not require a hydrolysis hardening process by baking in a multilayer resist process. The preferred one is further excellent in adhesion to the organic underlayer film, and is also preferable in patterning using a more productive UV nanoimprint.

(複合樹脂(A)) (composite resin (A))

本發明中使用之複合樹脂(A)係具有上述通式(1)及/或上述通式(2)所表示之結構單元和矽烷醇基及/或水解性矽烷基之聚矽氧烷片段(a1)(以下簡稱為聚矽氧烷片段(a1))、與乙烯基系聚合物片段(a2)(以下簡稱為乙烯基系聚合物片段(a2))藉由上述通式(3)所表示之鍵進行鍵結而成的複合樹脂(A)。上述通式(3)所表示之鍵於獲得之抗蝕劑膜之耐酸性方面尤其優異，又，於耐氧電漿蝕刻性及微細圖案之再現性方面亦優異，故而較佳。 The composite resin (A) used in the present invention has a structural unit represented by the above formula (1) and/or the above formula (2) and a polyoxyalkylene fragment of a stanol group and/or a hydrolyzable decyl group ( A1) (hereinafter abbreviated as polyadenine fragment (a1)) and vinyl polymer fragment (a2) (hereinafter simply referred to as vinyl polymer fragment (a2)) are represented by the above formula (3) The key is a composite resin (A) bonded by a bond. The bond represented by the above formula (3) is particularly excellent in acid resistance of the obtained resist film, and is also excellent in resistance to oxygen plasma etchability and fine pattern reproducibility.

下述聚矽氧烷片段(a1)所具有之矽烷醇基及/或水解性矽烷基與下述乙烯基系聚合物片段(a2)所具有之矽烷醇基及/或水解性矽烷基進行 脫水縮合反應，而產生上述通式(3)所表示之鍵。因此，上述通式(3)中，設為碳原子構成上述乙烯基系聚合物片段(a2)之一部分，僅鍵結於氧原子之矽原子構成上述聚矽氧烷片段(a1)之一部分。 The decyl alcohol group and/or the hydrolyzable decyl group which the polyoxyalkylene fragment (a1) has, and the stanol group and/or hydrolyzable decyl group which the vinyl type polymer fragment (a2) has. The dehydration condensation reaction produces a bond represented by the above formula (3). Therefore, in the above formula (3), a carbon atom constitutes a part of the vinyl polymer segment (a2), and only a germanium atom bonded to an oxygen atom constitutes a part of the polyoxane fragment (a1).

複合樹脂(A)之形態例如可列舉：具有上述聚矽氧烷片段(a1)作為上述聚合物片段(a2)之側鏈進行化學鍵結之接枝結構的複合樹脂、或具有上述聚合物片段(a2)與上述聚矽氧烷片段(a1)進行化學鍵結之嵌段結構的複合樹脂等。 The form of the composite resin (A) may, for example, be a composite resin having the above-mentioned polyoxyalkylene moiety (a1) as a graft structure for chemically bonding a side chain of the polymer fragment (a2), or having the above polymer fragment ( A2) A composite resin or the like having a block structure chemically bonded to the above polyoxyalkylene fragment (a1).

(聚矽氧烷片段(a1)) (polyoxyalkylene fragment (a1))

本發明中之聚矽氧烷片段(a1)係具有通式(1)及/或通式(2)所表示之結構單元與矽烷醇基及/或水解性矽烷基之片段。 The polyoxyalkylene fragment (a1) in the present invention is a fragment having a structural unit represented by the formula (1) and/or the formula (2) and a stanol group and/or a hydrolyzable decyl group.

於通式(1)及/或通式(2)所表示之結構單元中包含具有聚合性雙鍵之基。 The structural unit represented by the formula (1) and/or the formula (2) contains a group having a polymerizable double bond.

又，本發明中之聚矽氧烷片段(a1)亦可進而具有環氧基。 Further, the polyoxyalkylene fragment (a1) in the present invention may further have an epoxy group.

(通式(1)及/或通式(2)所表示之結構單元) (Structural unit represented by the general formula (1) and/or the general formula (2))

上述通式(1)及/或上述通式(2)所表示之結構單元含有具有聚合性雙鍵之基作為必需成分。 The structural unit represented by the above formula (1) and/or the above formula (2) contains a group having a polymerizable double bond as an essential component.

具體而言，上述通式(1)及(2)中之R1、R2及R3分別獨立地表示具有選自由-R4-CH=CH2、-R4-C(CH3)=CH2、-R4-O-CO-C(CH3)=CH2、及-R4-O-CO-CH=CH2所組成之群中之1個聚合性雙鍵之基(其中，R4表示單鍵、芳基、或碳原子數1~6之伸烷基)、碳原子數為1~6之烷基、碳原子數為3~8之環烷基、芳基或碳原子數為7~12之芳烷基，R1、R2及R3中之至少一者為具有聚合性雙鍵之基。又，作為上述R4中之上述碳原子數為1~6之伸烷基，例如可列舉：亞甲基、伸乙基、伸丙基、異伸丙基、伸丁基、異伸丁基、第二伸丁基、第三伸丁基、伸戊基、異伸戊基、新伸戊基、第三伸戊基、1-甲基伸丁基、2-甲基伸丁基、1,2-二甲基伸丙基、1-乙基伸丙基、伸己基、isohesylene、1-甲基 伸戊基、2-甲基伸戊基、3-甲基伸戊基、1,1-二甲基伸丁基、1,2-二甲基伸丁基、2,2-二甲基伸丁基、1-乙基伸丁基、1,1,2-三甲基伸丙基、1,2,2-三甲基伸丙基、1-乙基-2-甲基伸丙基、1-乙基-1-甲基伸丙基等。其中，就原料獲取之容易性而言，R4較佳為單鍵、芳基、或碳原子數為2~4之伸烷基。 Specifically, R 1 , R 2 and R 3 in the above formulae (1) and (2) each independently represent a group selected from -R 4 -CH=CH 2 and -R 4 -C(CH 3 )= a base of one polymerizable double bond in the group consisting of CH 2 , -R 4 -O-CO-C(CH 3 )=CH 2 , and -R 4 -O-CO-CH=CH 2 (wherein R 4 represents a single bond, an aryl group, or an alkylene group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group or a carbon atom. The number is 7 to 12 aralkyl groups, and at least one of R 1 , R 2 and R 3 is a group having a polymerizable double bond. Further, examples of the above-mentioned alkylene group having 1 to 6 carbon atoms in the above R 4 include a methylene group, an exoethyl group, a propyl group, an exo-propyl group, a butyl group, and an isobutylene group. , second butyl, tert-butyl, pentyl, iso-pentyl, neopentyl, pentyl, 1-methylbutyl, 2-methylbutyl, 1 ,2-dimethylmethylpropyl, 1-ethylpropyl, hexyl, isohesylene, 1-methyl-amyl, 2-methyl-amyl, 3-methyl-amyl, 1,1- Dimethylbutylene, 1,2-dimethylbutylene, 2,2-dimethylbutylene, 1-ethylbutylene, 1,1,2-trimethylpropyl, 1 , 2,2-trimethyl-propyl, 1-ethyl-2-methyl-propyl, 1-ethyl-1-methyl-propyl, and the like. Among them, R 4 is preferably a single bond, an aryl group or an alkylene group having 2 to 4 carbon atoms in terms of easiness of obtaining a raw material.

又，作為上述碳原子數為1~6之烷基，例如可列舉：甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、新戊基、第三戊基、1-甲基丁基、2-甲基丁基、1,2-二甲基丙基、1-乙基丙基、己基、isohesyl、1-甲基戊基、2-甲基戊基、3-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、2,2-二甲基丁基、1-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-2-甲基丙基、1-乙基-1-甲基丙基等。 Further, examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a third butyl group, and a pentyl group. Base, isoamyl, neopentyl, third amyl, 1-methylbutyl, 2-methylbutyl, 1,2-dimethylpropyl, 1-ethylpropyl, hexyl, isohesyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl , 1-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-2-methylpropyl, 1-ethyl-1 -Methylpropyl group and the like.

又，作為上述碳原子數為3~8之環烷基，例如可列舉環丙基、環丁基、環戊基、環己基等。又，作為上述芳基，例如可列舉苯基、萘基、2-甲基苯基、3-甲基苯基、4-甲基苯基、4-乙烯基苯基、3-異丙基苯基。 In addition, examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Further, examples of the aryl group include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-vinylphenyl group, and a 3-isopropylbenzene group. base.

又，作為上述碳原子數為7~12之芳烷基，例如可列舉苄基、二苯基甲基、萘基甲基等。 In addition, examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.

於上述分子結構中，就使耐乾式蝕刻性提高之觀點而言，較佳為包含較多芳香環或環狀烴基之結構。 In the above molecular structure, from the viewpoint of improving the dry etching resistance, a structure containing a large number of aromatic rings or cyclic hydrocarbon groups is preferred.

又，R1、R2及R3中之至少一者為上述具有聚合性雙鍵之基。具體而言，較佳為，於聚矽氧烷片段(a1)僅具有通式(1)所表示之結構單元之情形時，R1為上述具有聚合性雙鍵之基，於聚矽氧烷片段(a1)僅具有通式(2)所表示之結構單元之情形時，R2及/或R3為上述具有聚合性雙鍵之基，於聚矽氧烷片段(a1)具有通式(1)與通式(2)所表示之結構單元之兩者之情形時，R1、R2及R3中之至少一者為上述具有聚合性雙鍵 之基。 Further, at least one of R 1 , R 2 and R 3 is a group having a polymerizable double bond. Specifically, in the case where the polyoxyalkylene fragment (a1) has only the structural unit represented by the general formula (1), R 1 is the above-mentioned group having a polymerizable double bond, and is a polyoxyalkylene. In the case where the fragment (a1) has only the structural unit represented by the general formula (2), R 2 and/or R 3 are the above-mentioned group having a polymerizable double bond, and the polyoxonane fragment (a1) has a general formula (a1). 1) In the case of both of the structural units represented by the formula (2), at least one of R 1 , R 2 and R 3 is the group having the above polymerizable double bond.

上述通式(1)及/或上述通式(2)所表示之結構單元係矽之鍵結鍵中之2個或3個參與交聯之三維網狀之聚矽氧烷結構單元。雖然形成三維網狀結構但並未形成緊密之網狀結構，因此亦不會於製造時產生凝膠化等，所獲得之複合樹脂之長期保存穩定性亦變得良好。 Two or three of the bonding bonds of the structural unit system represented by the above formula (1) and/or the above formula (2) are crosslinked three-dimensional network polysiloxane structural units. Although a three-dimensional network structure is formed, but a tight network structure is not formed, gelation or the like is not generated at the time of production, and the long-term storage stability of the obtained composite resin is also good.

(矽烷醇基及/或水解性矽烷基) (stanol-based and/or hydrolyzable decyl)

本發明中，所謂矽烷醇基係指具有直接鍵結於矽原子之羥基之含矽基。具體而言，該矽烷醇基較佳為上述通式(1)及/或上述通式(2)所表示之結構單元之具有鍵結鍵之氧原子與氫原子進行鍵結而產生之矽烷醇基。 In the present invention, the stanol group means a fluorenyl group having a hydroxyl group directly bonded to a ruthenium atom. Specifically, the stanol group is preferably a stanol produced by bonding an oxygen atom having a bonding bond to a hydrogen atom of the structural unit represented by the above formula (1) and/or the above formula (2). base.

又，本發明中，所謂水解性矽烷基係指具有直接鍵結於矽原子之水解性基之含矽基，具體而言，例如可列舉通式(4)所表示之基。 In the present invention, the hydrolyzable decyl group means a fluorenyl group having a hydrolyzable group bonded directly to a ruthenium atom, and specific examples thereof include a group represented by the formula (4).

(通式(4)中，R5為烷基、芳基或芳烷基等一價之有機基，R6為選自由鹵素原子、烷氧基、醯氧基、苯氧基、芳氧基、巰基、胺基、醯胺基、胺基氧基、醯胺氧基及烯氧基所組成之群中之水解性基；又，b為0~2之整數) (In the formula (4), R 5 is a monovalent organic group such as an alkyl group, an aryl group or an arylalkyl group, and R 6 is selected from a halogen atom, an alkoxy group, a decyloxy group, a phenoxy group, an aryloxy group. a hydrolyzable group in the group consisting of a mercapto group, an amine group, an amidino group, an aminooxy group, a decylamino group, and an alkenyloxy group; and, b is an integer of 0 to 2)

上述R5中，作為烷基，例如可列舉：甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、新戊基、第三戊基、1-甲基丁基、2-甲基丁基、1,2-二甲基丙基、1-乙基丙 基、己基、isohesyl、1-甲基戊基、2-甲基戊基、3-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、2,2-二甲基丁基、1-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-2-甲基丙基、1-乙基-1-甲基丙基等。 In the above R 5 , examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a pentyl group, and an isopentyl group. Neopentyl, third amyl, 1-methylbutyl, 2-methylbutyl, 1,2-dimethylpropyl, 1-ethylpropyl, hexyl, isohesyl, 1-methylpentyl , 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1-ethylbutyl Base, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-2-methylpropyl, 1-ethyl-1-methylpropyl, etc. .

又，作為芳基，例如可列舉苯基、萘基、2-甲基苯基、3-甲基苯基、4-甲基苯基、4-乙烯基苯基、3-異丙基苯基等。 Further, examples of the aryl group include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-vinylphenyl group, and a 3-isopropylphenyl group. Wait.

又，作為芳烷基，例如可列舉苄基、二苯基甲基、萘基甲基等。 Further, examples of the aralkyl group include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.

上述R6中，作為鹵素原子，例如可列舉氟原子、氯原子、溴原子、碘原子等。 In the above R 6 , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

作為烷氧基，例如可列舉甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、第二丁氧基、第三丁氧基等。 Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a second butoxy group, and a third butoxy group.

又，作為醯氧基，例如可列舉甲醯氧基、乙醯氧基、丙醯氧基、丁醯氧基、特戊醯氧基、戊醯氧基、苯基乙醯氧基、乙醯乙醯氧基、苯甲醯氧基、萘甲醯氧基等。 Further, examples of the decyloxy group include a methyl methoxy group, an ethyl methoxy group, a propyl methoxy group, a butoxy group, a pentylene group, a pentyloxy group, a phenyl ethoxy group, and an acetamidine group. Ethyloxy, benzamidine, naphthylmethoxy and the like.

又，作為芳氧基，例如可列舉苯氧基、萘氧基等。 Further, examples of the aryloxy group include a phenoxy group and a naphthyloxy group.

作為烯氧基，例如可列舉乙烯氧基、烯丙氧基、1-丙烯氧基、異丙烯氧基、2-丁烯氧基、3-丁烯氧基、2-戊烯氧基、3-甲基-3-丁烯氧基、2-己烯氧基等。 Examples of the alkenyloxy group include a vinyloxy group, an allyloxy group, a 1-propenyloxy group, an isopropenyloxy group, a 2-butenyloxy group, a 3-butenyloxy group, a 2-pentenyloxy group, and 3 -methyl-3-butenyloxy, 2-hexenyloxy, and the like.

又，就使耐氧電漿蝕刻性提高之觀點而言，較佳為包含較多芳香環或環狀烴基之結構。 Moreover, from the viewpoint of improving the etching resistance of the oxygen-resistant plasma, a structure containing a large number of aromatic rings or cyclic hydrocarbon groups is preferred.

藉由使上述R6所表示之水解性基水解，通式(4)所表示之水解性矽烷基成為矽烷醇基。就水解性優異而言，其中較佳為甲氧基及乙氧基。 The hydrolyzable decyl group represented by the formula (4) is a stanol group by hydrolyzing the hydrolyzable group represented by the above R 6 . Among them, in view of excellent hydrolyzability, among them, a methoxy group and an ethoxy group are preferred.

又，具體而言，上述水解性矽烷基較佳為上述通式(1)及/或上述通式(2)所表示之結構單元之具有鍵結鍵之氧原子與上述水解性基鍵 結或被上述水解性基取代之水解性矽烷基。 In addition, the hydrolyzable decyl group is preferably an oxygen atom having a bonding bond and a hydrolyzable group bond of a structural unit represented by the above formula (1) and/or the above formula (2). A hydrolyzable alkylene group substituted by a hydrolyzable group.

上述矽烷醇基或上述水解性矽烷基於利用紫外線硬化形成抗蝕劑膜時，與紫外線硬化反應並行地於矽烷醇基中之羥基或水解性矽烷基中之上述水解性基之間進行水解縮合反應，因此所獲得之抗蝕劑膜之聚矽氧烷結構之交聯密度提高，可形成耐溶劑性等優異之抗蝕劑膜。 When the decyl alcohol group or the hydrolyzable decyl group is formed into a resist film by ultraviolet curing, hydrolysis and condensation reaction is carried out between the hydroxyl group in the stanol group or the hydrolyzable group in the hydrolyzable decyl group in parallel with the ultraviolet curing reaction. Therefore, the crosslinking density of the polyoxyalkylene structure of the obtained resist film is improved, and a resist film excellent in solvent resistance and the like can be formed.

又，於使包含上述矽烷醇基或上述水解性矽烷基之聚矽氧烷片段(a1)與下述乙烯基系聚合物片段(a2)經由上述通式(3)所表示之鍵進行鍵結時使用。 Further, the polyaluminoxane fragment (a1) containing the above stanol group or the hydrolyzable decyl group is bonded to the vinyl polymer fragment (a2) described below via a bond represented by the above formula (3). When used.

聚矽氧烷片段(a1)具有上述通式(1)及/或上述通式(2)所表示之結構單元、與矽烷醇基及/或水解性矽烷基，R1、R2及R3中之至少一者為具有聚合性雙鍵之基，除此以外，並無特別限定，亦可包含其他基。例如， The polyoxyalkylene fragment (a1) has a structural unit represented by the above formula (1) and/or the above formula (2), and a stanol group and/or a hydrolyzable alkyl group, R 1 , R 2 and R 3 At least one of them is a group having a polymerizable double bond, and is not particularly limited, and may contain other groups. E.g,

可為上述通式(1)中之R1為上述具有聚合性雙鍵之基之結構單元、與上述通式(1)中之R1為甲基等烷基之結構單元共存之聚矽氧烷片段(a1)， In the above formula (1), R 1 is a structural unit having a group having a polymerizable double bond, and a polyfluorene which coexists with a structural unit of an alkyl group such as R 1 in the above formula (1). Alkane fragment (a1),

可為上述通式(1)中之R1為上述具有聚合性雙鍵之基之結構單元、上述通式(1)中之R1為甲基等烷基之結構單元、及上述通式(2)中之R2及R3為甲基等烷基之結構單元共存之聚矽氧烷片段(a1)， It may be the general formula R (1) is in one of the structural unit having a polymerizable double bond group of the formula R (1) 1 in the structural units of the alkyl group and the like, and the above general formula ( 2) wherein R 2 and R 3 are a polyoxyalkylene fragment (a1) in which a structural unit of an alkyl group such as a methyl group is present,

可為上述通式(1)中之R1為上述具有聚合性雙鍵之基之結構單元、與上述通式(2)中之R2及R3為甲基等烷基之結構單元共存之聚矽氧烷片段(a1)， The structural unit in which R 1 in the above formula (1) is a group having a polymerizable double bond, and a structural unit in which R 2 and R 3 in the above formula (2) are an alkyl group such as a methyl group may coexist. Polyoxane fragment (a1),

亦可於聚矽氧烷片段(a1)中具有環氧基，並無特別限定。 The polyoxyalkylene fragment (a1) may have an epoxy group, and is not particularly limited.

具體而言，作為聚矽氧烷片段(a1)，例如可列舉具有以下之結構者等。 Specifically, examples of the polyaluminoxane fragment (a1) include those having the following structures.

[化6] [Chemical 6]

[化9] [Chemistry 9]

[化15] [化15]

本發明中，較佳為相對於複合樹脂(A)之總固形物成分量包含上述聚矽氧烷片段(a1)70~95重量%，可兼顧高度之耐酸性、耐氧電漿蝕刻性、微細圖案之再現性等與各種有機膜、矽晶圓、玻璃等之基板密接性之性質。其中，較佳為包含85~95重量%。又，就使耐氧電漿蝕刻性提高之觀點而言，較佳為包含較多芳香環或環狀烴基之結構。 In the present invention, it is preferable that the amount of the total solid content of the composite resin (A) is 70 to 95% by weight based on the polyaluminoxane fragment (a1), and the acid resistance and oxygen plasma etching resistance of the height can be achieved. The reproducibility of the fine pattern and the like are in contact with substrates of various organic films, germanium wafers, and glass. Among them, it is preferably 85 to 95% by weight. Moreover, from the viewpoint of improving the etching resistance of the oxygen-resistant plasma, a structure containing a large number of aromatic rings or cyclic hydrocarbon groups is preferred.

(複合樹脂(A)乙烯基系聚合物片段(a2)) (Composite resin (A) vinyl polymer segment (a2))

本發明中之乙烯基系聚合物片段(a2)係丙烯酸系聚合物、氟代烯烴系聚合物、乙烯酯系聚合物、芳香族系乙烯基系聚合物、聚烯烴系聚合物等乙烯基聚合物片段。藉由乙烯基系聚合物片段(a2)與聚矽氧烷片段(a1)進行化學鍵結，可使對有機下層膜之密接性提高。乙烯基系聚合物片段(a2)較佳為根據所要接觸之有機膜進行適當選擇。 The vinyl polymer chip (a2) in the present invention is a vinyl polymer such as an acrylic polymer, a fluoroolefin polymer, a vinyl ester polymer, an aromatic vinyl polymer or a polyolefin polymer. Fragment of matter. By chemically bonding the vinyl polymer fragment (a2) to the polyoxyalkylene fragment (a1), the adhesion to the organic underlayer film can be improved. The vinyl polymer segment (a2) is preferably appropriately selected depending on the organic film to be contacted.

例如乙烯基系聚合物片段(a2)係使通用之(甲基)丙烯酸系單體進行聚合或共聚而獲得。作為(甲基)丙烯酸系單體，並無特別限定，又，乙烯基單體亦可進行共聚。例如，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯等具有碳原子數為1~22之烷基之(甲基)丙烯酸烷基酯類；(甲基)丙烯酸苄酯、(甲基)丙烯酸2-苯基乙酯等(甲基)丙烯酸芳烷基酯類；(甲基)丙烯酸環己酯、(甲基)丙烯酸異酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸金剛烷基酯等(甲基)丙烯酸環烷基酯類；(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸4-甲氧基丁酯等(甲基)丙烯酸ω-烷氧基烷基酯類；苯乙烯、α-甲基苯乙烯、鄰甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、1,3-二甲基苯乙烯、乙烯基萘、乙烯基蒽等乙烯基芳香族類；乙酸乙烯酯、丙酸乙烯酯、特戊酸乙烯酯、苯甲酸乙烯酯等羧酸乙烯酯類；丁烯酸甲酯、丁烯酸乙酯等丁烯酸之烷基酯類；順丁烯二酸二甲酯、順丁烯二酸二正丁酯、反丁烯二酸二甲酯、衣康酸二甲酯等不飽和二元酸之二烷基酯類；乙烯、丙烯等α-烯烴類；偏二氟乙烯、四氟乙烯、六氟丙烯、三氟氯乙烯等氟代烯烴類；乙基乙烯醚、正丁基乙烯醚等烷基乙烯醚類；環戊基乙烯醚、環己基乙烯醚等環烷基乙烯醚類；N,N-二甲基(甲基)丙烯醯胺、N-(甲 基)丙烯醯基啉、N-(甲基)丙烯醯基吡咯啶、N-乙烯基吡咯啶酮等含有三級醯胺基之單體類等。 For example, the vinyl polymer fragment (a2) is obtained by polymerizing or copolymerizing a general-purpose (meth)acrylic monomer. The (meth)acrylic monomer is not particularly limited, and the vinyl monomer may be copolymerized. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (A) a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 22 carbon atoms such as tributyl acrylate, 2-ethylhexyl (meth) acrylate or lauryl (meth) acrylate; (A) arylalkyl (meth)acrylates such as benzyl (meth)acrylate and 2-phenylethyl (meth)acrylate; cyclohexyl (meth)acrylate, (meth)acrylic acid Ester, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, etc. Cycloalkyl acrylates; 2-methoxyethyl (meth)acrylate; 4-methoxybutyl (meth)acrylate; ω-alkoxyalkyl esters of (meth)acrylic acid; benzene Vinyl aromatics such as ethylene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, vinyl anthracene ; vinyl acetates such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate; alkyl esters of crotonic acid such as methyl crotonate or ethyl crotonate; a dialkyl ester of an unsaturated dibasic acid such as dimethyl enedomethane, di-n-butyl maleate, dimethyl fumarate or dimethyl itaconate; ethylene, propylene, etc. - olefins; fluoroolefins such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene; alkyl vinyl ethers such as ethyl vinyl ether and n-butyl vinyl ether; cyclopentyl vinyl ether, Cyclohexylethylene Cycloalkyl vinyl ethers and the like; N, N- dimethyl (meth) acrylamide, N- (meth) Bing Xixi group A monomer containing a tertiary amide group such as a porphyrin, N-(meth)acrylopyrrolidone or N-vinylpyrrolidone.

又，關於本發明中之乙烯基系聚合物片段(a2)，就使耐乾式蝕刻性提高之觀點而言，更佳為具有芳香環或環狀烴基之(甲基)丙烯酸重複單元。作為上述具有芳香環或環狀烴基之(甲基)丙烯酸重複單元，較佳可列舉：(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯等具有芳香環之(甲基)丙烯酸酯；(甲基)丙烯酸環己酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸三環癸酯、(甲基)丙烯酸四環十二烷基酯、(甲基)丙烯酸二環戊酯、乙二醇二(甲基)丙烯酸酯、丙烯酸異酯、苯乙烯、α-甲基苯乙烯、鄰甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、1,3-二甲基苯乙烯、乙烯基萘、乙烯基蒽等具有環狀烴基之(甲基)丙烯酸酯及乙烯基單體。作為使用之單體，可列舉：乙氧化雙酚A二(甲基)丙烯酸酯、丙氧化雙酚A二(甲基)丙烯酸酯、丙氧化乙氧化雙酚A二(甲基)丙烯酸酯、1,4-環己烷二甲醇二丙烯酸酯、環癸烷二甲醇二(甲基)丙烯酸酯、三環[5.2.1.02,6]癸烷二甲醇(甲基)丙烯酸酯、二(甲基)丙烯酸二環戊烯酯、1,4-苯二甲醇二(甲基)丙烯酸酯、氫化雙酚A二(甲基)丙烯酸酯、1,3-二羥基金剛烷二(甲基)丙烯酸酯等。該等可單獨或組合兩種以上而使用。 In addition, the vinyl polymer segment (a2) in the present invention is more preferably a (meth)acrylic repeating unit having an aromatic ring or a cyclic hydrocarbon group from the viewpoint of improving dry etching resistance. The (meth)acrylic acid repeating unit having an aromatic ring or a cyclic hydrocarbon group is preferably a (meth) acrylate having an aromatic ring such as phenyl (meth) acrylate or benzyl (meth) acrylate; Cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecyl (meth)acrylate, tetracyclododecyl (meth)acrylate , dicyclopentanyl (meth)acrylate, ethylene glycol di(meth)acrylate, acrylic acid Ester, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, vinyl anthracene, etc. Hydroxyalkyl (meth) acrylate and vinyl monomer. Examples of the monomer to be used include ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, and ethoxylated bisphenol A di(meth)acrylate. 1,4-cyclohexanedimethanol diacrylate, cyclodecane dimethanol di(meth)acrylate, tricyclo[5.2.1.02,6]decane dimethanol (meth) acrylate, di(methyl) Dicyclopentyl acrylate, 1,4-benzenedimethanol di(meth) acrylate, hydrogenated bisphenol A di(meth) acrylate, 1,3-dihydroxyadamantane di(meth) acrylate Wait. These may be used alone or in combination of two or more.

使上述單體進行共聚時之聚合方法、溶劑或聚合起始劑亦無特別限定，可藉由公知之方法而獲得乙烯基系聚合物片段(a2)。例如，可藉由塊狀自由基聚合法、溶液自由基聚合法、非水分散自由基聚合法等各種聚合法，使用2,2'-偶氮雙(異丁腈)、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙(2-甲基丁腈)、過氧化特戊酸第三丁酯、過氧化苯甲酸第三丁酯、過氧化2-乙基己酸第三丁酯、過氧化二第三丁基、氫過氧化異丙苯、過氧化碳酸二異丙酯等聚合起始劑而獲得乙烯基系聚合物片段(a2)。 The polymerization method, the solvent or the polymerization initiator which copolymerizes the above monomer is not particularly limited, and the vinyl polymer fragment (a2) can be obtained by a known method. For example, 2,2'-azobis(isobutyronitrile), 2,2'- can be used by various polymerization methods such as bulk radical polymerization, solution radical polymerization, and non-aqueous dispersion radical polymerization. Azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), tert-butyl peroxypivalate, tert-butyl peroxybenzoate a polymerization initiator such as tributyl butyl peroxy-2-ethylhexanoate, dibutyl butyl peroxide, cumene hydroperoxide or diisopropyl peroxycarbonate to obtain a vinyl polymer fragment ( A2).

又，為了與上述聚矽氧烷片段(a1)藉由通式(3)所表示之鍵進行鍵結而製成複合樹脂(A)，上述乙烯基系聚合物片段(a2)較佳為具有直接鍵結於乙烯基系聚合物片段(a2)中之碳原子之矽烷醇基及/或水解性矽烷基。該等矽烷醇基及/或水解性矽烷基由於在下述複合樹脂(A)之製造中成為通式(3)所表示之鍵，故而幾乎不會存在於作為最終產物之複合樹脂(A)中之乙烯基系聚合物片段(a2)。然而，即便於乙烯基系聚合物片段(a2)殘留矽烷醇基及/或水解性矽烷基，亦毫無任何問題，於利用上述具有聚合性雙鍵之基之硬化反應形成塗膜時，與該硬化反應並行地於矽烷醇基中之羥基或水解性矽烷基中之上述水解性基之間進行水解縮合反應，因此所獲得之硬化物之聚矽氧烷結構之交聯密度提高，可形成耐溶劑性等優異之硬化物。 Further, in order to form a composite resin (A) by bonding the polysiloxane derivative (a1) with a bond represented by the formula (3), the vinyl polymer segment (a2) preferably has The stanol group and/or the hydrolyzable decyl group directly bonded to the carbon atom in the vinyl polymer fragment (a2). Since the stanol group and/or the hydrolyzable decyl group are bonds represented by the formula (3) in the production of the composite resin (A) described below, they are hardly present in the composite resin (A) as a final product. The vinyl polymer fragment (a2). However, even if the vinyl polymer segment (a2) remains a stanol group and/or a hydrolyzable decyl group, there is no problem in that a coating film is formed by the hardening reaction using the above-mentioned group having a polymerizable double bond, The hardening reaction is carried out by a hydrolysis condensation reaction between the hydroxyl group in the stanol group or the above hydrolyzable group in the hydrolyzable decyl group, whereby the crosslink density of the obtained polyoxyalkylene structure of the cured product is increased to form A cured product excellent in solvent resistance and the like.

具體而言，具有直接鍵結於碳原子之矽烷醇基及/或水解性矽烷基之乙烯基系聚合物片段(a2)係使上述通用單體與含有直接鍵結於碳鍵之矽烷醇基及/或水解性矽烷基之乙烯基系單體進行共聚而獲得。 Specifically, the vinyl-based polymer fragment (a2) having a stanol group and/or a hydrolyzable decyl group directly bonded to a carbon atom is such that the above-mentioned general-purpose monomer and a stanol group having a bond directly bonded to a carbon bond And/or a hydrolyzable vinyl group-based vinyl monomer is obtained by copolymerization.

作為含有直接鍵結於碳原子之矽烷醇基及/或水解性矽烷基之乙烯基系單體，例如可列舉：乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基甲基二甲氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、乙烯基三乙醯氧基矽烷、乙烯基三氯矽烷、2-三甲氧基矽烷基乙基乙烯醚、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基甲基二甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三氯矽烷、苯乙烯基三甲氧基矽烷、金剛烷基三甲氧基矽烷、金剛烷基三乙氧基矽烷、雙金剛烷基三甲氧基矽烷等。其中，就可易於進行水解反應，且可易於去除反應後之副產物而言，較佳為乙烯基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷。就使耐乾式蝕刻性提高之觀點而言，較佳為包含較多芳香環或環狀烴基之結構，較佳為苯乙烯基三甲氧基矽烷、金剛烷基三甲氧基矽 烷、金剛烷基三乙氧基矽烷、雙金剛烷基三甲氧基矽烷等。 Examples of the vinyl monomer having a stanol group and/or a hydrolyzable decyl group directly bonded to a carbon atom include vinyl trimethoxy decane, vinyl triethoxy decane, and vinyl methyl group. Methoxy decane, vinyl tris(2-methoxyethoxy) decane, vinyl triethoxy decane, vinyl trichloro decane, 2-trimethoxy decyl ethyl vinyl ether, 3-( Methyl) propylene methoxy propyl trimethoxy decane, 3-(methyl) propylene methoxy propyl triethoxy decane, 3-(methyl) propylene methoxy propyl methyl dimethoxy Decane, 3-(meth)acryloxypropyltrichlorodecane, styryltrimethoxydecane, adamantyltrimethoxydecane, adamantyltriethoxydecane, bisadamantyltrimethoxy Decane and so on. Among them, a hydrolysis reaction can be easily carried out, and a by-product after the reaction can be easily removed, preferably vinyltrimethoxydecane or 3-(meth)acryloxypropyltrimethoxydecane. From the viewpoint of improving dry etching resistance, a structure containing a large number of aromatic rings or cyclic hydrocarbon groups is preferred, and styryltrimethoxydecane and adamantyltrimethoxyantane are preferred. Alkane, adamantyltriethoxydecane, bisadamantyltrimethoxydecane, and the like.

又，於含有下述多異氰酸酯(B)等反應性化合物時，上述乙烯基系聚合物片段(a2)較佳為具有醇性羥基等反應性官能基。具有例如醇性羥基之乙烯基系聚合物片段(a2)可使具有醇羥基之(甲基)丙烯酸系單體進行共聚而獲得。作為具有醇羥基之(甲基)丙烯酸系單體，具體而言，可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸3-氯-2-羥基丙酯、反丁烯二酸二-2-羥基乙酯、反丁烯二酸單-2-羥基乙基單丁酯、聚乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、「PLACCEL FM或PLACCEL FA」[DAICEL CHEMICAL股份有限公司製造之己內酯加成單體]等各種α、β-乙烯性不飽和羧酸之羥基烷基酯類、或其等與ε-己內酯之加成物等。 In addition, when the reactive compound such as the following polyisocyanate (B) is contained, the vinyl polymer fragment (a2) preferably has a reactive functional group such as an alcoholic hydroxyl group. The vinyl polymer fragment (a2) having, for example, an alcoholic hydroxyl group can be obtained by copolymerizing a (meth)acrylic monomer having an alcoholic hydroxyl group. Specific examples of the (meth)acrylic monomer having an alcoholic hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 3- Hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropionate (meth)acrylate Ester, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl monobutyl methacrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (methyl) a hydroxyalkyl ester of various α,β-ethylenically unsaturated carboxylic acids, such as acrylate, "PLACCEL FM or PLACCEL FA" [caprolactone addition monomer manufactured by DAICEL CHEMICAL Co., Ltd.], or the like - an adduct of caprolactone or the like.

其中，(甲基)丙烯酸2-羥基乙酯易於進行反應，故而較佳。 Among them, 2-hydroxyethyl (meth)acrylate is preferred because it is easy to carry out the reaction.

上述醇性羥基量較佳為根據下述多異氰酸酯之添加量算出而適當決定。 The amount of the above-mentioned alcoholic hydroxyl group is preferably determined as appropriate based on the amount of addition of the polyisocyanate described below.

(複合樹脂(A)之製造方法) (Manufacturing method of composite resin (A))

具體而言，本發明中使用之複合樹脂(A)係藉由下述(方法1)~(方法3)所示之方法而製造。 Specifically, the composite resin (A) used in the present invention is produced by the methods shown in the following (Method 1) to (Method 3).

(方法1)使上述通用之(甲基)丙烯酸系單體等與上述含有直接鍵結於碳鍵之矽烷醇基及/或水解性矽烷基之乙烯基系單體進行共聚，而獲得含有直接鍵結於碳鍵之矽烷醇基及/或水解性矽烷基之乙烯基系聚合物片段(a2)。於其中混合一併具有矽烷醇基及/或水解性矽烷基與聚合性雙鍵之矽烷化合物、及視需要之通用之矽烷化合物，進行水解縮合反應。 (Method 1) The above-mentioned general (meth)acrylic monomer or the like is copolymerized with the above-mentioned vinyl monomer containing a quinol group directly bonded to a carbon bond and/or a hydrolyzable alkylene group, and obtained directly A vinyl polymer fragment (a2) bonded to a carbon bond sterol group and/or a hydrolyzable decyl group. A decane compound having a decyl alcohol group and/or a hydrolyzable decyl group and a polymerizable double bond, and a decane compound which is generally used as needed, are mixed and subjected to a hydrolysis condensation reaction.

該方法中，一併具有矽烷醇基及/或水解性矽烷基和聚合性雙鍵 之矽烷化合物之矽烷醇基或水解性矽烷基、與含有直接鍵結於碳鍵之矽烷醇基及/或水解性矽烷基之乙烯基系聚合物片段(a2)所具有之矽烷醇基及/或水解性矽烷基進行水解縮合反應，形成上述聚矽氧烷片段(a1)，並且獲得上述聚矽氧烷片段(a1)與具有醇性羥基之乙烯基系聚合物片段(a2)藉由上述通式(3)所表示之鍵進行複合化而成的複合樹脂(A)。 In the method, the decyl alcohol group and/or the hydrolyzable decyl group and the polymerizable double bond are combined. a stanol group or a hydrolyzable decyl group of a decane compound, and a stanol group having a vinyl polymer fragment (a2) having a stanol group directly bonded to a carbon bond and/or a hydrolyzable decyl group and/or Or a hydrolyzable decyl group undergoes a hydrolysis condensation reaction to form the above polyoxyalkylene fragment (a1), and obtains the above polyoxyalkylene fragment (a1) and a vinyl polymer fragment (a2) having an alcoholic hydroxyl group by the above A composite resin (A) obtained by combining the bonds represented by the formula (3).

(方法2)以與方法1同樣之方式，獲得含有直接鍵結於碳鍵之矽烷醇基及/或水解性矽烷基之乙烯基系聚合物片段(a2)。 (Method 2) A vinyl polymer fragment (a2) containing a decyl alcohol group and/or a hydrolyzable decyl group directly bonded to a carbon bond is obtained in the same manner as in the method 1.

另一方面，使一併具有矽烷醇基及/或水解性矽烷基與聚合性雙鍵之矽烷化合物、視需要之通用之矽烷化合物進行水解縮合反應，獲得聚矽氧烷片段(a1)。繼而，使乙烯基系聚合物片段(a2)所具有之矽烷醇基及/或水解性矽烷基和聚矽氧烷片段(a1)所具有之矽烷醇基及/或水解性矽烷基進行水解縮合反應。 On the other hand, a decane compound having a decyl alcohol group and/or a hydrolyzable decyl group and a polymerizable double bond, and a decane compound which is generally used as usual are subjected to a hydrolysis condensation reaction to obtain a polyoxyalkylene moiety (a1). Then, the decyl alcohol group and/or the hydrolyzable decyl group which the decyl alcohol group and/or the hydrolyzable decyl group of the vinyl polymer fragment (a2) and the polyoxyalkylene fragment (a1) have are hydrolyzed and condensed. reaction.

(方法3)與方法1同樣地，獲得含有直接鍵結於碳鍵之矽烷醇基及/或水解性矽烷基之乙烯基系聚合物片段(a2)。另一方面，以與方法2同樣之方式獲得聚矽氧烷片段(a1)。進而，將含有一併具有聚合性雙鍵之矽烷化合物之矽烷化合物與視需要之通用之矽烷化合物進行混合，進行水解縮合反應。 (Method 3) In the same manner as in Method 1, a vinyl polymer fragment (a2) containing a decyl alcohol group and/or a hydrolyzable decyl group directly bonded to a carbon bond is obtained. On the other hand, a polyoxyalkylene fragment (a1) was obtained in the same manner as in the method 2. Further, a decane compound containing a decane compound having a polymerizable double bond is mixed with a common decane compound as necessary to carry out a hydrolysis condensation reaction.

作為上述(方法1)~(方法3)中使用之一併具有矽烷醇基及/或水解性矽烷基與聚合性雙鍵之矽烷化合物，具體而言，例如可列舉：乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基甲基二甲氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、乙烯基三乙醯氧基矽烷、乙烯基三氯矽烷、2-三甲氧基矽烷基乙基乙烯醚、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基甲基二甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三氯矽烷等。其中，就可易於進行水解反應，且可易於去除反應後之副產物而 言，較佳為乙烯基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷。 The decane compound which is one of the above (method 1) to (method 3) and has a decyl alcohol group and/or a hydrolyzable decyl group and a polymerizable double bond, specifically, for example, vinyl trimethoxy decane , vinyl triethoxy decane, vinyl methyl dimethoxy decane, vinyl tris(2-methoxyethoxy) decane, vinyl triethoxy decane, vinyl trichloro decane, 2 -trimethoxydecylethylethyl vinyl ether, 3-(meth)acryloxypropyltrimethoxydecane, 3-(methyl)propenyloxypropyltriethoxydecane, 3-(A Base) acryloxypropylmethyldimethoxydecane, 3-(meth)acryloxypropyltrichlorodecane, and the like. Among them, the hydrolysis reaction can be easily carried out, and the by-products after the reaction can be easily removed. In other words, vinyltrimethoxydecane and 3-(meth)acryloxypropyltrimethoxydecane are preferred.

又，作為上述(方法1)~(方法3)中使用之通用之矽烷化合物，例如可列舉：甲基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三正丁氧基矽烷、乙基三甲氧基矽烷、正丙基三甲氧基矽烷、異丁基三甲氧基矽烷、環己基三甲氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷等各種有機三烷氧基矽烷類；二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二甲基二正丁氧基矽烷、二乙基二甲氧基矽烷、二苯基二甲氧基矽烷、甲基環己基二甲氧基矽烷或甲基苯基二甲氧基矽烷等各種二有機二烷氧基矽烷類；甲基三氯矽烷、乙基三氯矽烷、苯基三氯矽烷、乙烯基三氯矽烷、二甲基二氯矽烷、二乙基二氯矽烷或二苯基二氯矽烷等氯矽烷類。其中，較佳為可易於進行水解反應且易於去除反應後之副產物之有機三烷氧基矽烷或二有機二烷氧基矽烷。 Further, examples of the general decane compound used in the above (Method 1) to (Method 3) include methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-butoxydecane, and B. Various organic trialkoxy groups such as methoxymethoxydecane, n-propyltrimethoxydecane, isobutyltrimethoxydecane, cyclohexyltrimethoxynonane, phenyltrimethoxydecane, phenyltriethoxydecane Teroxane; dimethyldimethoxydecane, dimethyldiethoxydecane, dimethyldi-n-butoxydecane, diethyldimethoxydecane, diphenyldimethoxydecane, A Various diorganodialkoxydecanes such as cyclohexyldimethoxydecane or methylphenyldimethoxydecane; methyltrichlorodecane, ethyltrichlorodecane, phenyltrichlorodecane, vinyl three Chlorotropins such as chlorodecane, dimethyldichlorodecane, diethyldichlorodecane or diphenyldichlorodecane. Among them, an organotrialkoxydecane or a diorganodialkoxydecane which can easily carry out a hydrolysis reaction and easily remove a by-product after the reaction is preferred.

又，於聚矽氧烷片段(a1)具有環氧基之情形時，只要使用含有環氧基之矽烷化合物即可。 Further, in the case where the polyoxyalkylene fragment (a1) has an epoxy group, an epoxy group-containing decane compound may be used.

作為含有環氧基之矽烷化合物，可列舉：γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基三乙氧基矽烷、γ-縮水甘油氧基丙基三甲氧基乙氧基矽烷、γ-縮水甘油氧基丙基三乙醯氧基矽烷、β-(3、4-環氧環己基)乙基三甲氧基矽烷、β-(3、4-環氧環己基)乙基三乙氧基矽烷、β-(3、4-環氧環己基)乙基三甲氧基乙氧基矽烷、β-(3、4-環氧環己基)乙基三乙醯氧基矽烷、γ-縮水甘油氧基丙基二甲氧基甲基矽烷、γ-縮水甘油氧基丙基二乙氧基甲基矽烷、γ-縮水甘油氧基丙基二甲氧基乙氧基甲基矽烷、γ-縮水甘油氧基丙基二乙醯氧基甲基矽烷、β-(3、4-環氧環己基)乙基二甲氧基甲基矽烷、β-(3、4-環氧環己基)乙基二乙氧基甲基矽烷、β-(3、4-環氧環己基)乙基二甲氧基乙氧基甲基矽烷、β-(3、4-環氧環己基)乙基二乙醯氧基甲基矽烷、γ-縮水 甘油氧基丙基二甲氧基乙基矽烷、γ-縮水甘油氧基丙基二乙氧基乙基矽烷、γ-縮水甘油氧基丙基二甲氧基乙氧基乙基矽烷、γ-縮水甘油氧基丙基二乙醯氧基乙基矽烷、β-(3、4-環氧環己基)乙基二甲氧基乙基矽烷、β-(3、4-環氧環己基)乙基二乙氧基乙基矽烷、β-(3、4-環氧環己基)乙基二甲氧基乙氧基乙基矽烷、β-(3、4-環氧環己基)乙基二乙醯氧基乙基矽烷、γ-縮水甘油氧基丙基二甲氧基異丙基矽烷、γ-縮水甘油氧基丙基二乙氧基異丙基矽烷、γ-縮水甘油氧基丙基二甲氧基乙氧基異丙基矽烷、γ-縮水甘油氧基丙基二乙醯氧基異丙基矽烷、β-(3、4-環氧環己基)乙基二乙氧基異丙基矽烷、β-(3、4-環氧環己基)乙基二乙氧基異丙基矽烷、β-(3、4-環氧環己基)乙基二甲氧基乙氧基異丙基矽烷、β-(3、4-環氧環己基)乙基二乙醯氧基異丙基矽烷、γ-縮水甘油氧基丙基甲氧基二甲基矽烷、γ-縮水甘油氧基丙基乙氧基二甲基矽烷、γ-縮水甘油氧基丙基甲氧基乙氧基二甲基矽烷、γ-縮水甘油氧基丙基乙醯氧基二甲基矽烷、β-(3、4-環氧環己基)乙基甲氧基二甲基矽烷、β-(3、4-環氧環己基)乙基乙氧基二甲基矽烷、β-(3、4-環氧環己基)乙基甲氧基乙氧基二甲基矽烷、β-(3、4-環氧環己基)乙基乙醯氧基二甲基矽烷、γ-縮水甘油氧基丙基甲氧基二乙基矽烷、γ-縮水甘油氧基丙基乙氧基二乙基矽烷、γ-縮水甘油氧基丙基甲氧基乙氧基二乙基矽烷、γ-縮水甘油氧基丙基乙醯氧基二乙基矽烷、β-(3、4-環氧環己基)乙基甲氧基二乙基矽烷、β-(3、4-環氧環己基)乙基乙氧基二乙基矽烷、β-(3、4-環氧環己基)乙基甲氧基乙氧基二乙基矽烷、β-(3、4-環氧環己基)乙基乙醯氧基二乙基矽烷、γ-縮水甘油氧基丙基甲氧基二異丙基矽烷、γ-縮水甘油氧基丙基乙氧基二異丙基矽烷、γ-縮水甘油氧基丙基甲氧基乙氧基二異丙基矽烷、γ-縮水甘油氧基丙基乙醯氧基二異丙基矽烷、β-(3、4-環氧環己基)乙基甲氧基二異丙基矽烷、β-(3、4-環氧環己基)乙基乙氧基二異丙基矽烷、β-(3、4-環氧環 己基)乙基甲氧基乙氧基二異丙基矽烷、β-(3、4-環氧環己基)乙基乙醯氧基二異丙基矽烷、γ-縮水甘油氧基丙基甲氧基乙氧基甲基矽烷、γ-縮水甘油氧基丙基乙醯氧基甲氧基甲基矽烷、γ-縮水甘油氧基丙基乙醯氧基乙氧基甲基矽烷、β-(3、4-環氧環己基)乙基甲氧基乙氧基甲基矽烷、β-(3、4-環氧環己基)乙基甲氧基乙醯氧基甲基矽烷、β-(3、4-環氧環己基)乙基乙氧基乙醯氧基甲基矽烷、γ-縮水甘油氧基丙基甲氧基乙氧基乙基矽烷、γ-縮水甘油氧基丙基乙醯氧基甲氧基乙基矽烷、γ-縮水甘油氧基丙基乙醯氧基乙氧基乙基矽烷、β-(3、4-環氧環己基)乙基甲氧基乙氧基乙基矽烷、β-(3、4-環氧環己基)乙基甲氧基乙醯氧基乙基矽烷、β-(3、4-環氧環己基)乙基乙氧基乙醯氧基乙基矽烷、γ-縮水甘油氧基丙基甲氧基乙氧基異丙基矽烷、γ-縮水甘油氧基丙基乙醯氧基甲氧基異丙基矽烷、γ-縮水甘油氧基丙基乙醯氧基乙氧基異丙基矽烷、β-(3、4-環氧環己基)乙基甲氧基乙氧基異丙基矽烷、β-(3、4-環氧環己基)乙基甲氧基乙醯氧基異丙基矽烷、β-(3、4-環氧環己基)乙基乙氧基乙醯氧基異丙基矽烷、縮水甘油氧基甲基三甲氧基矽烷、縮水甘油氧基甲基三乙氧基矽烷、α-縮水甘油氧基乙基三甲氧基矽烷、α-縮水甘油氧基甲基三甲氧基矽烷、β-縮水甘油氧基乙基三甲氧基矽烷、β-縮水甘油氧基甲基三甲氧基矽烷、α-縮水甘油氧基丙基三甲氧基矽烷、α-縮水甘油氧基丙基三乙氧基矽烷、β-縮水甘油氧基丙基三甲氧基矽烷、β-縮水甘油氧基丙基三乙氧基矽烷、γ-縮水甘油氧基丙基三丙氧基矽烷、γ-縮水甘油氧基丙基三丁氧基矽烷、γ-縮水甘油氧基丙基三苯氧基矽烷、α-縮水甘油氧基丁基三甲氧基矽烷、α-縮水甘油氧基丁基三乙氧基矽烷、β-縮水甘油氧基丁基三甲氧基矽烷、β-縮水甘油氧基丁基三乙氧基矽烷、γ-縮水甘油氧基丁基三甲氧基矽烷、γ-縮水甘油氧基丁基三乙氧基矽烷、(3,4-環氧環己基)甲基三甲氧基矽烷、(3,4-環氧環己基)甲基三乙氧基矽烷、β-(3,4-環 氧環己基)乙基三丙氧基矽烷、β-(3,4-環氧環己基)乙基三丁氧基矽烷、β-(3,4-環氧環己基)乙基三苯氧基矽烷、γ-(3,4-環氧環己基)丙基三甲氧基矽烷、γ-(3,4-環氧環己基)丙基三乙氧基矽烷、α-(3,4-環氧環己基)丁基三甲氧基矽烷、δ-(3,4-環氧環己基)丁基三乙氧基矽烷、縮水甘油氧基甲基甲基二甲氧基矽烷、縮水甘油氧基甲基甲基二乙氧基矽烷、α-縮水甘油氧基乙基甲基二甲氧基矽烷、α-縮水甘油氧基乙基甲基二乙氧基矽烷、β-縮水甘油氧基乙基甲基二甲氧基矽烷、β-縮水甘油氧基乙基甲基二乙氧基矽烷、α-縮水甘油氧基丙基甲基二甲氧基矽烷、α-縮水甘油氧基丙基甲基二乙氧基矽烷、β-縮水甘油氧基丙基甲基二甲氧基矽烷、β-縮水甘油氧基丙基甲基二乙氧基矽烷、γ-縮水甘油氧基丙基甲基二甲氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷、γ-縮水甘油氧基丙基甲基二丙氧基矽烷、γ-縮水甘油氧基丙基甲基二丁氧基矽烷、γ-縮水甘油氧基丙基甲基二甲氧基乙氧基矽烷、γ-縮水甘油氧基丙基甲基二苯氧基矽烷、γ-縮水甘油氧基丙基乙基二甲氧基矽烷、γ-縮水甘油氧基丙基乙基二乙氧基矽烷、γ-縮水甘油氧基丙基乙基二丙氧基矽烷、γ-縮水甘油氧基丙基乙烯基二甲氧基矽烷、γ-縮水甘油氧基丙基乙烯基二乙氧基矽烷等。 Examples of the decyl group-containing decane compound include γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, and γ-glycidoxypropyltrimethoxy group. Ethoxy decane, γ-glycidoxypropyltriethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, β-(3,4-epoxycyclohexyl Ethyltriethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxyethoxydecane, β-(3,4-epoxycyclohexyl)ethyltriethoxycarbonyl Decane, γ-glycidoxypropyl dimethoxymethyl decane, γ-glycidoxypropyl diethoxymethyl decane, γ-glycidoxypropyl dimethoxy ethoxy group Base decane, γ-glycidoxypropyl dimethyl ethoxymethyl decane, β-(3,4-epoxycyclohexyl)ethyldimethoxymethyl decane, β-(3,4-ring Oxycyclohexyl)ethyldiethoxymethyldecane, β-(3,4-epoxycyclohexyl)ethyldimethoxyethoxymethyldecane, β-(3,4-epoxycyclohexyl Ethyl diethyloxymethyl decane, γ-shrinkage Glyceroxypropyl dimethoxyethyl decane, γ-glycidoxypropyl diethoxyethyl decane, γ-glycidoxypropyl dimethoxyethoxyethyl decane, γ- Glycidoxypropyl diethoxymethoxyethyl decane, β-(3,4-epoxycyclohexyl)ethyldimethoxyethyl decane, β-(3,4-epoxycyclohexyl)B Diethoxyethyl decane, β-(3,4-epoxycyclohexyl)ethyldimethoxyethoxyethyl decane, β-(3,4-epoxycyclohexyl)ethyldiethyl醯-oxyethyl decane, γ-glycidoxypropyl dimethoxy isopropyl decane, γ-glycidoxypropyl diethoxy isopropyl decane, γ-glycidoxy propyl Methoxyethoxyisopropyl decane, γ-glycidoxypropyl diethoxy isopropyl decane, β-(3,4-epoxycyclohexyl)ethyl diethoxy isopropyl Decane, β-(3,4-epoxycyclohexyl)ethyldiethoxyisopropyldecane, β-(3,4-epoxycyclohexyl)ethyldimethoxyethoxyisopropyl decane , β-(3,4-epoxycyclohexyl)ethyldiethoxycarbonylisopropyl decane, γ-glycidoxypropyl methoxy Dimethyl decane, γ-glycidoxypropyl ethoxy dimethyl decane, γ-glycidoxypropyl methoxy ethoxy dimethyl decane, γ-glycidoxy propyl B醯oxydimethyl decane, β-(3,4-epoxycyclohexyl)ethyl methoxy dimethyl decane, β-(3,4-epoxycyclohexyl)ethyl ethoxy dimethyl矽, β-(3,4-epoxycyclohexyl)ethylmethoxyethoxydimethyl decane, β-(3,4-epoxycyclohexyl)ethylethoxycarbonyl dimethyl decane, Γ-glycidoxypropyl methoxydiethyl decane, γ-glycidoxypropyl ethoxydiethyl decane, γ-glycidoxypropyl methoxy ethoxydiethyl decane , γ-glycidoxypropyl ethoxylated diethyl decane, β-(3,4-epoxycyclohexyl)ethyl methoxydiethyl decane, β-(3,4-epoxy ring Hexyl)ethylethoxydiethyldecane, β-(3,4-epoxycyclohexyl)ethylmethoxyethoxydiethyldecane, β-(3,4-epoxycyclohexyl)B Ethyl ethoxylated diethyl decane, γ-glycidoxypropyl methoxy diisopropyl decane, γ-glycidoxy propyl Ethyl ethoxy diisopropyl decane, γ-glycidoxypropyl methoxy ethoxy diisopropyl decane, γ-glycidoxypropyl ethoxylated diisopropyl decane, β- (3, 4-epoxycyclohexyl)ethylmethoxydiisopropyldecane, β-(3,4-epoxycyclohexyl)ethylethoxydiisopropyldecane, β-(3, 4 - epoxy ring Hexyl)ethylmethoxyethoxydiisopropyldecane, β-(3,4-epoxycyclohexyl)ethylethoxylated diisopropyldecane, γ-glycidoxypropylmethoxy Ethyl ethoxymethyl decane, γ-glycidoxypropyl ethoxy methoxy methoxy methyl decane, γ-glycidoxy propyl ethoxy ethoxy ethoxymethyl decane, β-(3 , 4-epoxycyclohexyl)ethylmethoxyethoxymethyl decane, β-(3,4-epoxycyclohexyl)ethylmethoxyethoxymethoxymethyl decane, β-(3, 4-epoxycyclohexyl)ethylethoxyethoxycarbonyloxymethyl decane, γ-glycidoxypropyl methoxyethoxyethyl decane, γ-glycidoxypropyl ethoxylate Methoxyethyl decane, γ-glycidoxypropyl ethoxylated ethoxyethoxyethyl decane, β-(3,4-epoxycyclohexyl)ethyl methoxyethoxyethyl decane, --(3,4-epoxycyclohexyl)ethylmethoxyethoxymethoxyethyl decane, β-(3,4-epoxycyclohexyl)ethylethoxyethoxyethoxyethyl decane, Γ-glycidoxypropyl methoxyethoxy isopropyl decane, γ-glycidoxypropyl ethoxy methoxy methoxy Isopropyl decane, γ-glycidoxypropyl ethoxy ethoxy ethoxy isopropyl decane, β-(3,4-epoxycyclohexyl)ethyl methoxyethoxy isopropyl decane, --(3,4-epoxycyclohexyl)ethylmethoxyethoxymethoxyisopropyl decane, β-(3,4-epoxycyclohexyl)ethylethoxyethoxycarbonyloxyisopropyl Decane, glycidoxymethyltrimethoxydecane, glycidoxymethyltriethoxydecane, α-glycidoxyethyltrimethoxydecane, α-glycidoxymethyltrimethoxydecane , β-glycidoxyethyltrimethoxydecane, β-glycidoxymethyltrimethoxydecane, α-glycidoxypropyltrimethoxydecane, α-glycidoxypropyltriethyl Oxydecane, β-glycidoxypropyltrimethoxydecane, β-glycidoxypropyltriethoxydecane, γ-glycidoxypropyltripropoxydecane, γ-glycidyloxy Propyl tributoxy decane, γ-glycidoxypropyl triphenoxy decane, α-glycidoxy butyl trimethoxy decane, α-glycidoxy butyl triethoxy矽, β-glycidoxybutyl trimethoxy decane, β-glycidoxy butyl triethoxy decane, γ-glycidoxy butyl trimethoxy decane, γ-glycidoxy butyl Triethoxydecane, (3,4-epoxycyclohexyl)methyltrimethoxydecane, (3,4-epoxycyclohexyl)methyltriethoxydecane, β-(3,4-ring Oxycyclohexyl)ethyltripropoxydecane, β-(3,4-epoxycyclohexyl)ethyltributoxydecane, β-(3,4-epoxycyclohexyl)ethyltriphenoxy Decane, γ-(3,4-epoxycyclohexyl)propyltrimethoxydecane, γ-(3,4-epoxycyclohexyl)propyltriethoxydecane, α-(3,4-epoxy Cyclohexyl)butyltrimethoxydecane, δ-(3,4-epoxycyclohexyl)butyltriethoxydecane, glycidoxymethylmethyldimethoxydecane, glycidoxymethyl Methyl diethoxy decane, α-glycidoxyethyl methyl dimethoxy decane, α-glycidoxyethyl methyl diethoxy decane, β-glycidoxyethyl methyl Dimethoxydecane, β-glycidoxyethylmethyldiethoxydecane, α-glycidoxypropylmethyldimethoxydecane, α-glycidoxypropylmethyldiethyl Oxydecane, β-glycidoxypropylmethyldimethoxydecane, β-glycidoxypropylmethyldiethoxydecane, γ-glycidoxypropylmethyldimethoxy矽, γ-glycidoxypropylmethyldiethoxy decane, γ-glycidyl Oloxypropylmethyldipropoxydecane, γ-glycidoxypropylmethyldibutoxydecane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ- Glycidoxypropylmethyldiphenoxydecane, γ-glycidoxypropylethyldimethoxydecane, γ-glycidoxypropylethyldiethoxydecane, γ-glycidol Oxypropylethyldipropoxydecane, γ-glycidoxypropylvinyldimethoxydecane, γ-glycidoxypropylvinyldiethoxydecane, and the like.

又，亦可於無損本發明之效果之範圍內併用四甲氧基矽烷、四乙氧基矽烷或四正丙氧基矽烷等四官能烷氧基矽烷化合物或該四官能烷氧基矽烷化合物之部分水解縮合物。 Further, a tetrafunctional alkoxydecane compound such as tetramethoxynonane, tetraethoxysilane or tetra-n-propoxydecane or a tetrafunctional alkoxydecane compound may be used in combination with the effect of the present invention. Partial hydrolysis of the condensate.

又，於上述矽烷化合物中，亦可於無損本發明之效果之範圍內併用硼、鈦、鋯或鋁等除矽原子以外之金屬烷氧化物化合物。例如，相對於構成聚矽氧烷片段(a1)之全體矽原子，較佳為以不超過25莫耳%之範圍併用上述金屬烷氧化物化合物所具有之金屬原子。 Further, in the above decane compound, a metal alkoxide compound other than a ruthenium atom such as boron, titanium, zirconium or aluminum may be used in the range which does not impair the effects of the present invention. For example, it is preferable to use a metal atom of the above metal alkoxide compound in a range of not more than 25 mol% with respect to the entire ruthenium atom constituting the polyoxyalkylene fragment (a1).

上述(方法1)~(方法3)中之水解縮合反應係指上述水解性基之一部分因水等之影響而被水解而形成羥基，繼而該羥基彼此、或於該羥 基與水解性基之間進行之縮合反應。該水解縮合反應可藉由公知之方法使反應進行，但藉由於上述製造步驟中供給水與觸媒而使反應進行之方法較為簡便，故而較佳。 The hydrolytic condensation reaction in the above (Method 1) to (Method 3) means that a part of the above hydrolyzable group is hydrolyzed by the influence of water or the like to form a hydroxyl group, and then the hydroxyl group or the hydroxy group The condensation reaction between the group and the hydrolyzable group. The hydrolysis condensation reaction can be carried out by a known method. However, it is preferred that the reaction is carried out by supplying water and a catalyst in the above production step.

作為使用之觸媒，例如可列舉：鹽酸、硫酸、磷酸等無機酸類；對甲苯磺酸、磷酸單異丙酯、乙酸等有機酸類；氫氧化鈉或氫氧化鉀等無機鹼類；鈦酸四異丙酯、鈦酸四丁酯等鈦酸酯類；1,8-二氮雙環[5.4.0]十一烯-7(DBU)、1,5-二氮雙環[4.3.0]壬烯-5(DBN)、1,4-二氮雙環[2.2.2]辛烷(DABCO)、三正丁基胺、二甲基苄基胺、單乙醇胺、咪唑、1-甲基咪唑等含有各種鹼性氮原子之化合物類；四甲基銨鹽、四丁基銨鹽、二月桂基二甲基銨鹽等各種四級銨鹽類，且具有氯化物、溴化物、羧酸酯或氫氧化物等作為抗衡陰離子之四級銨鹽類；二乙酸二丁基錫、二辛酸二丁基錫、二月桂酸二丁基錫、二乙醯丙酮酸二丁基錫、辛酸錫或硬脂酸錫等羧酸錫等。觸媒可單獨使用，亦可併用兩種以上。 Examples of the catalyst to be used include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate, and acetic acid; and inorganic bases such as sodium hydroxide or potassium hydroxide; Titanates such as isopropyl ester and tetrabutyl titanate; 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]decene -5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole, 1-methylimidazole, etc. a compound of a basic nitrogen atom; various quaternary ammonium salts such as tetramethylammonium salt, tetrabutylammonium salt, dilauryldimethylammonium salt, and having chloride, bromide, carboxylate or hydroxide The substance is a quaternary ammonium salt of a counter anion; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, tin octylate or tin stearate. The catalyst may be used singly or in combination of two or more.

上述觸媒之添加量並無特別限定，一般而言，相對於上述具有矽烷醇基或水解性矽烷基之各種化合物總量，較佳為於0.0001~10重量%之範圍使用，更佳為於0.0005~3重量%之範圍使用，尤佳為於0.001~1重量%之範圍使用。 The amount of the catalyst to be added is not particularly limited. In general, the total amount of each of the compounds having a stanol group or a hydrolyzable decyl group is preferably from 0.0001 to 10% by weight, more preferably It is used in the range of 0.0005 to 3% by weight, and more preferably in the range of 0.001 to 1% by weight.

又，供給之水之量相對於上述具有矽烷醇基或水解性矽烷基之各種化合物所具有之矽烷醇基或水解性矽烷基1莫耳較佳為0.05莫耳以上，更佳為0.1莫耳以上，尤佳為0.5莫耳以上。該等觸媒及水可一次供給，亦可逐次供給，還可供給預先混合有觸媒與水者。 Further, the amount of the supplied water is preferably 0.05 mol or more, more preferably 0.1 mol, based on the stanol group or the hydrolyzable decyl group 1 mole of each of the compounds having a stanol group or a hydrolyzable decyl group. Above, it is especially preferably 0.5 mol or more. The catalyst and water may be supplied at a time, or may be supplied one by one, and may be supplied with a catalyst and water mixed in advance.

上述(方法1)~(方法3)中之進行水解縮合反應時之反應溫度適宜為0℃~150℃之範圍，較佳為20℃~100℃之範圍內。又，作為反應之壓力，可於常壓、加壓下或減壓下之任一條件下進行。又，作為上述水解縮合反應中可能生成之副產物之醇或水亦可視需要藉由蒸餾等 方法而去除。 The reaction temperature in the hydrolysis condensation reaction in the above (Method 1) to (Method 3) is suitably in the range of 0 ° C to 150 ° C, preferably in the range of 20 ° C to 100 ° C. Further, the pressure of the reaction can be carried out under any of normal pressure, pressure or reduced pressure. Further, the alcohol or water which is a by-product which may be formed in the above hydrolysis and condensation reaction may be optionally distilled, etc. Remove by method.

上述(方法1)~(方法3)中，作為將聚矽氧烷片段與乙烯基系聚合物片段嵌段狀地複合化之具體方法，可列舉如下方法：使用如僅於聚合物鏈之單末端或兩末端具有上述矽烷醇基及/或水解性矽烷基般之結構之乙烯基系聚合物片段作為中間體，例如當為(方法1)時，於該乙烯基系聚合物片段中混合一併具有矽烷醇基及/或水解性矽烷基與聚合性雙鍵之矽烷化合物、視需要之通用之矽烷化合物，從而進行水解縮合反應。 In the above (Method 1) to (Method 3), as a specific method of combining the polyoxyalkylene fragment and the vinyl polymer fragment in a block form, a method of using a single polymer chain alone may be mentioned. a vinyl-based polymer fragment having a stanol group and/or a hydrolyzable alkylene group structure at the terminal or both ends as an intermediate, for example, when (Method 1), a vinyl polymer segment is mixed Further, a decane compound having a decyl alcohol group and/or a hydrolyzable decyl group and a polymerizable double bond, and a decane compound which is generally used as needed, is subjected to a hydrolysis condensation reaction.

另一方面，於上述(方法1)~(方法3)中，作為使聚矽氧烷片段相對於乙烯基系聚合物片段接枝狀地複合化之具體方法，可列舉如下方法：使用具有使上述矽烷醇基及/或水解性矽烷基相對於乙烯基系聚合物片段之主鏈無規地分佈之結構的乙烯基系聚合物片段作為中間體，例如當為(方法2)時，使該乙烯基系聚合物片段所具有之矽烷醇基及/或水解性矽烷基與上述聚矽氧烷片段所具有之矽烷醇基及/或水解性矽烷基進行水解縮合反應。 On the other hand, in the above (Method 1) to (Method 3), as a specific method of graft-polymerizing a polyoxyalkylene fragment with respect to a vinyl polymer fragment, the following method may be mentioned: The vinyl polymer segment having a structure in which the above stanol group and/or hydrolyzable decyl group are randomly distributed with respect to the main chain of the vinyl polymer segment is used as an intermediate, for example, when (Method 2), The stanol group and/or the hydrolyzable decyl group which the vinyl type polymer fragment has is hydrolyzed and condensed with the stanol group and/or the hydrolyzable decyl group which the said poly oxane part has.

(氧電漿蝕刻抗蝕劑材料) (oxygen plasma etching resist material)

本發明之氧電漿蝕刻抗蝕劑材料含有上述複合樹脂(A)。於氧電漿蝕刻抗蝕劑材料中，藉由總固形物成分中之矽原子之含量為15-45wt%，可製成耐氧電漿蝕刻性優異之抗蝕劑材料。於矽原子少於15%之情形時，耐蝕刻性較差，當為45%以上時，難以進行樹脂合成。矽原子之含量較佳為18~45%。 The oxygen plasma etching resist material of the present invention contains the above composite resin (A). In the oxygen plasma etching resist material, a resist material excellent in oxygen-resistant plasma etching property can be obtained by containing 15 to 45 wt% of the total atomic component in the solid content. When the atomic weight is less than 15%, the etching resistance is inferior, and when it is 45% or more, it is difficult to perform resin synthesis. The content of the ruthenium atom is preferably from 18 to 45%.

本發明之氧電漿蝕刻抗蝕劑材料由於含有具有聚合性雙鍵之基，故而可進行活性能量線硬化，尤其可進行紫外線硬化。紫外線硬化具有如下特徵：硬化速度較快，而且無需加熱、冷卻步驟，因此生產性優異。 Since the oxygen plasma etching resist material of the present invention contains a group having a polymerizable double bond, it can be subjected to active energy ray hardening, and in particular, ultraviolet curing can be performed. The ultraviolet curing has the following characteristics: the curing speed is fast, and the heating and cooling steps are not required, so that the productivity is excellent.

於進行光硬化時，較佳為含有光聚合起始劑。 When photocuring is carried out, it is preferred to contain a photopolymerization initiator.

作為光聚合起始劑，於抗蝕劑材料中使用公知者即可，例如可較佳地使用選自由苯乙酮類、苯偶醯縮酮類、二苯甲酮類所組成之群中之一種以上。作為上述苯乙酮類，可列舉二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、4-(2-羥基乙氧基)苯基-(2-羥基-2-丙基)酮等。作為上述苯偶醯縮酮類，例如可列舉1-羥基環己基-苯基酮、苯偶醯二甲基縮酮等。作為上述二苯甲酮類，例如可列舉二苯甲酮、鄰苯甲醯苯甲酸甲酯等。 作為上述安息香類等，例如可列舉安息香、安息香甲醚、安息香異丙醚等。光聚合起始劑可單獨使用，亦可併用兩種以上。 As the photopolymerization initiator, a known one may be used for the resist material, and for example, a group selected from the group consisting of acetophenones, benzoin ketals, and benzophenones can be preferably used. More than one. Examples of the acetophenones include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-(4-isopropylphenyl)-2- Hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, and the like. Examples of the benzoin ketal include 1-hydroxycyclohexyl-phenyl ketone and benzoin dimethyl ketal. Examples of the benzophenones include benzophenone and methyl phthalic acid benzoate. Examples of the benzoin or the like include benzoin, benzoin methyl ether, and benzoin isopropyl ether. The photopolymerization initiator may be used singly or in combination of two or more.

又，於上述複合樹脂(A)中具有乙烯醚基或環氧基等光陽離子聚合性基之情形時，可併用光陽離子起始劑。作為光陽離子起始劑，可列舉路易斯酸之重氮鎓鹽、路易斯酸之錪鹽、路易斯酸之鋶鹽等，該等係陽離子部分分別為芳香族重氮鎓離子、芳香族錪離子、芳香族鋶離子、且陰離子部分包含BF4-、PF6-、SbF6-、[BY4]-(其中，Y為經至少兩個以上之氟原子或三氟甲基取代之苯基)等之鎓鹽，就穩定性之觀點而言，較佳為作為磷系化合物之陽離子聚合起始劑。具體而言，可列舉：四氟化硼之苯基重氮鎓鹽、六氟化磷之二苯基錪鹽、六氟化銻之二苯基錪鹽、六氟化砷之三-4-甲基苯基鋶鹽、四氟化銻之三-4-甲基苯基鋶鹽、四(五氟苯基)硼之二苯基錪鹽、乙醯丙酮鋁鹽與鄰硝基苄基矽烷醚混合體、苯硫基吡啶鹽、六氟化磷-鐵錯合物等。 In the case where the composite resin (A) has a photocationic polymerizable group such as a vinyl ether group or an epoxy group, a photocationic initiator can be used in combination. Examples of the photocationic initiator include a diazonium salt of a Lewis acid, a sulfonium salt of a Lewis acid, a sulfonium salt of a Lewis acid, and the like, and the cation portions are aromatic diazonium ions, aromatic cesium ions, and aromatics. a cerium ion and an anion moiety comprising bismuth salts such as BF4-, PF6-, SbF6-, [BY4]- (wherein Y is a phenyl group substituted with at least two fluorine atoms or a trifluoromethyl group), From the viewpoint of stability, a cationic polymerization initiator which is a phosphorus compound is preferred. Specific examples thereof include a phenyldiazonium salt of boron tetrafluoride, a diphenylphosphonium salt of phosphorus hexafluoride, a diphenylsulfonium salt of ruthenium hexafluoride, and a trisium -4-hexafluoride. Methylphenyl sulfonium salt, tris-methylphenyl sulfonium salt of ruthenium tetrafluoride, diphenyl sulfonium salt of tetrakis(pentafluorophenyl)boron, aluminum acetoacetate and o-nitrobenzyl decane An ether mixture, a phenylthiopyridine salt, a phosphorus hexafluoride-iron complex, and the like.

作為市售之光聚合起始劑，可列舉IRGACURE 651、IRGACURE 184、IRGACURE 819、IRGACURE 907、IRGACURE 1870、IRGACURE 500、IRGACURE 369、IRGACURE 1173、IRGACURE 2959、IRGACURE 4265、IRGACURE 4263、DAROCURE TPO、IRGACURE OXE01等(汽巴精化股份有限公司製造)。又，亦可使用IRGACURE 250(汽巴精化股份有限公司製造)、CPI100P、CPI101A、 CPI-200K、CPI210S(SAN-APRO股份有限公司製造)、ADEKA OPTOMER SP300、SP150(ADEKA股份有限公司製造)等陽離子系光聚合起始劑。 As a commercially available photopolymerization initiator, IRGACURE 651, IRGACURE 184, IRGACURE 819, IRGACURE 907, IRGACURE 1870, IRGACURE 500, IRGACURE 369, IRGACURE 1173, IRGACURE 2959, IRGACURE 4265, IRGACURE 4263, DAROCURE TPO, IRGACURE OXE01 Etc. (Manufactured by Ciba Specialty Chemicals Co., Ltd.). Also, IRGACURE 250 (manufactured by Ciba Specialty Chemicals Co., Ltd.), CPI100P, CPI101A, A cationic photopolymerization initiator such as CPI-200K, CPI210S (manufactured by SAN-APRO Co., Ltd.), ADEKA OPTOMER SP300, and SP150 (manufactured by ADEKA Co., Ltd.).

上述光聚合起始劑之使用量相對於上述複合樹脂(A)100重量%較佳為1~15重量%，更佳為2~10重量%。 The amount of the photopolymerization initiator to be used is preferably from 1 to 15% by weight, more preferably from 2 to 10% by weight, based on 100% by weight of the composite resin (A).

又，藉由與上述光聚合起始劑組合地併用增感色素，可使感光性大幅提高。作為增感色素之具體例，可列舉硫系、系、酮系、硫代吡喃鹽系、基礎苯乙烯基系、部花青素系、3-取代香豆素系、花青系、吖啶系、噻嗪系等之色素類。 Further, by using a sensitizing dye in combination with the above photopolymerization initiator, the photosensitivity can be greatly improved. Specific examples of the sensitizing dye include sulfur system, A pigment such as a ketone system, a thiopyranium salt system, a basic styrene group, a merocyanine system, a 3-substituted coumarin system, a cyanine system, an acridine system or a thiazine system.

(反應性化合物) (reactive compound)

於本發明中之氧電漿蝕刻抗蝕劑材料中，除複合樹脂(A)以外，亦可於無損本發明之效果之範圍內含有反應性化合物。 In the oxygen plasma etching resist material of the present invention, in addition to the composite resin (A), a reactive compound may be contained within a range not impairing the effects of the present invention.

作為反應性化合物，可使用具有直接有助於與複合樹脂(A)之硬化反應之反應性基之聚合物或單體。尤其，尤佳為多異氰酸酯(B)或活性能量線硬化性單體、或含有矽原子之反應性單體及低聚物等反應性稀釋劑。 As the reactive compound, a polymer or a monomer having a reactive group which directly contributes to the hardening reaction with the composite resin (A) can be used. In particular, a polyisocyanate (B), an active energy ray-curable monomer, or a reactive diluent such as a reactive monomer or oligomer containing a ruthenium atom is preferable.

藉由於上述複合樹脂(A)中導入反應性官能基，複合樹脂(A)與反應性稀釋劑進行三維交聯，因此一般而言可獲得硬化性上升且氧電漿蝕刻時之圖案保持性優異之抗蝕劑膜。又，若使用含有矽之反應性稀釋劑，則可防止因稀釋所引起之抗蝕劑材料中之矽含量之降低。 Since the composite resin (A) and the reactive diluent are three-dimensionally crosslinked by introducing a reactive functional group into the composite resin (A), generally, the curability is improved and the pattern retention property in the oxygen plasma etching is excellent. Resist film. Further, if a reactive diluent containing ruthenium is used, it is possible to prevent a decrease in the ruthenium content in the resist material due to dilution.

於使用多異氰酸酯(B)作為反應性化合物之情形時，上述複合樹脂(A)中之上述乙烯基系聚合物片段(a2)較佳為具有醇性羥基。此時之多異氰酸酯(B)相對於本發明之氧電漿蝕刻抗蝕劑材料總量較佳為含有0~50重量%。 When the polyisocyanate (B) is used as the reactive compound, the vinyl polymer fragment (a2) in the above composite resin (A) preferably has an alcoholic hydroxyl group. The polyisocyanate (B) at this time preferably contains 0 to 50% by weight based on the total amount of the oxygen plasma etching resist material of the present invention.

作為使用之多異氰酸酯(B)，並無特別限定，可使用公知者。例如，可列舉：以甲苯二異氰酸酯、二苯基甲烷-4,4'-二異氰酸酯等芳 香族二異氰酸酯類、或間苯二甲基二異氰酸酯、α,α,α',α'-四甲基-間苯二甲基二異氰酸酯等芳烷基二異氰酸酯類作為主原料的多異氰酸酯、四亞甲基二異氰酸酯、1,5-五亞甲基二異氰酸酯、1,6-六亞甲基二異氰酸酯(以下簡稱為「HDI」)、2,2,4-(或2,4,4-三甲基-1,6-六亞甲基diisoicyanate、離胺酸異氰酸酯、異佛爾酮二異氰酸酯、氫化二甲苯二異氰酸酯、氫化二苯基甲烷二異氰酸酯、1,4-二異氰酸酯環己烷、1,3-雙(二異氰酸酯基甲基)環己烷、4,4'-二環己基甲烷二異氰酸酯、脲基甲酸酯型多異氰酸酯、縮二脲型多異氰酸酯、加成物型多異氰酸酯及異氰尿酸酯型多異氰酸酯。 The polyisocyanate (B) to be used is not particularly limited, and a known one can be used. For example, examples thereof include toluene diisocyanate and diphenylmethane-4,4'-diisocyanate. a polyisocyanate having a arylalkyl diisocyanate such as an aromatic diisocyanate or m-xylylene diisocyanate or α,α,α',α'-tetramethyl-m-xylylene diisocyanate or the like as a main raw material, Tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (hereinafter referred to as "HDI"), 2,2,4- (or 2,4,4 -trimethyl-1,6-hexamethylene diisoicyanate, isocyanate isocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,4-diisocyanate cyclohexane , 1,3-bis(diisocyanatemethyl)cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, allophanate type polyisocyanate, biuret type polyisocyanate, and addition type Isocyanate and isocyanurate type polyisocyanate.

多異氰酸酯(B)與系中之羥基(其係具有上述乙烯基系聚合物片段(a2)中之羥基或下述醇性羥基之上述活性能量線硬化性單體中之羥基)之反應無需特別進行加熱等，藉由放置於室溫下而逐漸進行反應。 又，亦可視需要於80℃下加熱數分鐘~數小時(20分鐘~4小時)，而促進醇性羥基與異氰酸酯之反應。於此情形時，亦可視需要使用公知之胺基甲酸酯化觸媒。胺基甲酸酯化觸媒係根據所期望之反應溫度而適當選擇。 The reaction of the polyisocyanate (B) with a hydroxyl group in the system (which is a hydroxyl group in the above-mentioned active energy ray-curable monomer having a hydroxyl group in the above vinyl polymer segment (a2) or an alcoholic hydroxyl group described below) does not need to be particularly Heating or the like is carried out, and the reaction is gradually carried out by standing at room temperature. Further, it is also possible to heat at 80 ° C for several minutes to several hours (20 minutes to 4 hours) to promote the reaction of the alcoholic hydroxyl group with the isocyanate. In this case, a known urethane catalyst can also be used as needed. The urethane-based catalyst is appropriately selected depending on the desired reaction temperature.

又，作為上述多官能(甲基)丙烯酸酯，亦可併用單官能(甲基)丙烯酸酯。例如，可列舉：(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基丁酯、己內酯改性羥基(甲基)丙烯酸酯(例如DAICEL CHEMICAL工業股份有限公司製造，商品名「PLACCEL」)、由苯二甲酸與丙二醇所獲得之聚酯二醇之單(甲基)丙烯酸酯、由琥珀酸與丙二醇所獲得之聚酯二醇之單(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、季戊四醇單(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、各種環氧酯之(甲基)丙烯酸加成物等含有羥基之(甲基)丙烯酸酯；(甲基)丙烯酸、丁烯酸、衣康酸、順丁烯二酸、反丁烯二酸等含 有羧基之乙烯基單體；乙烯基磺酸、苯乙烯磺酸、(甲基)丙烯酸磺乙酯等含有磺酸基之乙烯基單體；2-(甲基)丙烯醯氧基乙基酸式磷酸酯、2-(甲基)丙烯醯氧基丙基酸式磷酸酯、2-(甲基)丙烯醯氧基-3-氯-丙基酸式磷酸酯、2-甲基丙烯醯氧基乙基苯基磷酸等酸性磷酸酯系乙烯基單體；N-羥甲基(甲基)丙烯醯胺等具有羥甲基之乙烯基單體等。 該等可使用一種或兩種以上。作為單體，尤佳為具有羥基之(甲基)丙烯酸酯。 Further, as the polyfunctional (meth) acrylate, a monofunctional (meth) acrylate may be used in combination. For example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and caprolactone-modified hydroxy (meth) acrylate (for example, DAICEL CHEMICAL Industrial Co., Ltd.) Made by the company, trade name "PLACCEL"), mono (meth) acrylate of polyester diol obtained from phthalic acid and propylene glycol, monoester of methyl diol obtained from succinic acid and propylene glycol Acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, pentaerythritol mono(meth)acrylate, 2-hydroxy-3-(methyl)(meth)acrylate a hydroxy-containing (meth) acrylate such as propylene methoxypropyl ester or a (meth)acrylic acid addition product of various epoxy esters; (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid , fumaric acid, etc. a vinyl monomer having a carboxyl group; a vinyl monomer having a sulfonic acid group such as vinylsulfonic acid, styrenesulfonic acid or sulfoethyl (meth)acrylate; 2-(meth)acryloxyethylate Phosphate, 2-(methyl)propenyloxypropyl phosphate, 2-(methyl)propenyloxy-3-chloro-propyl acid phosphate, 2-methylpropene oxide An acid phosphate-based vinyl monomer such as ethethylphenylphosphoric acid; a vinyl monomer having a methylol group such as N-methylol (meth) acrylamide or the like. These may be used alone or in combination of two or more. As the monomer, a (meth) acrylate having a hydroxyl group is particularly preferable.

又，於使用活性能量線硬化性單體作為上述反應性化合物之情形時，可視需要含有多官能(甲基)丙烯酸酯或單官能(甲基)丙烯酸酯。 Further, when an active energy ray-curable monomer is used as the reactive compound, a polyfunctional (meth) acrylate or a monofunctional (meth) acrylate may optionally be contained.

作為多官能(甲基)丙烯酸酯，可列舉：1,2-乙二醇二(甲基)丙烯酸酯、1,2-丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三(2-(甲基)丙烯醯氧基)異氰尿酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二(三羥甲基丙烷)四(甲基)丙烯酸酯、二(季戊四醇)五(甲基)丙烯酸酯、二(季戊四醇)六(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、環氧乙烷加成雙酚A二(甲基)丙烯酸酯、環氧乙烷加成雙酚F二(甲基)丙烯酸酯、環氧丙烷加成雙酚A二(甲基)丙烯酸酯、環氧丙烷加成雙酚F二(甲基)丙烯酸酯、具有9、9聯苯茀骨架之二(甲基)丙烯酸酯等於1分子中具有2個以上之聚合性雙鍵之多官能(甲基)丙烯酸酯等。尤其就使耐乾式蝕刻性提高之觀點而言，較佳為包含較多芳香環或環狀烴基之結構，較佳為三環癸烷二甲醇二(甲基)丙烯酸酯、環氧乙烷加成雙酚A二(甲基)丙烯酸酯、環氧乙烷加成雙酚F二(甲基)丙烯酸酯、環氧丙烷加成雙酚A二(甲基)丙烯酸酯、環氧丙烷加成雙酚F 二(甲基)丙烯酸酯、具有9、9聯苯茀骨架之二(甲基)丙烯酸酯等。 Examples of the polyfunctional (meth) acrylate include 1,2-ethanediol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, and 1,4-butanediol di(II). Methyl) acrylate, 1,6-hexanediol di(meth) acrylate, dipropylene glycol di(meth) acrylate, neopentyl glycol di(meth) acrylate, tripropylene glycol di(methyl) Acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(2-(methyl)acryloxy)isocyanurate, pentaerythritol III (meth) acrylate, pentaerythritol tetra (meth) acrylate, bis (trimethylolpropane) tetra (meth) acrylate, bis (pentaerythritol) penta (meth) acrylate, bis (pentaerythritol) hexa Methyl) acrylate, tricyclodecane dimethanol di(meth) acrylate, ethylene oxide addition bisphenol A di(meth) acrylate, ethylene oxide addition bisphenol F bis (methyl) Acrylate, propylene oxide addition bisphenol A di(meth) acrylate, propylene oxide addition bisphenol F di(meth) acrylate, bis(methyl) having 9,9 biphenyl fluorene skeleton Acrylate is equal to 2 in 1 molecule The polymerizable double bonds as many functional (meth) acrylate. In particular, from the viewpoint of improving the dry etching resistance, a structure containing a large number of aromatic rings or cyclic hydrocarbon groups is preferred, and tricyclodecane dimethanol di(meth)acrylate or ethylene oxide is preferred. Bisphenol A di(meth) acrylate, ethylene oxide addition bisphenol F di(meth) acrylate, propylene oxide addition bisphenol A di(meth) acrylate, propylene oxide addition Bisphenol F Di(meth)acrylate, di(meth)acrylate having a 9,9 biphenyl fluorene skeleton, and the like.

作為單官能(甲基)丙烯酸酯，可列舉：(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基丁酯、己內酯改性羥基(甲基)丙烯酸酯(例如DAICEL CHEMICAL工業股份有限公司製造，商品名「PLACCEL」)、由苯二甲酸與丙二醇所獲得之聚酯二醇之單(甲基)丙烯酸酯、由琥珀酸與丙二醇所獲得之聚酯二醇之單(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、季戊四醇單(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、各種環氧酯之(甲基)丙烯酸加成物等含有羥基之(甲基)丙烯酸酯；(甲基)丙烯酸、丁烯酸、衣康酸、順丁烯二酸、反丁烯二酸等含有羧基之乙烯基單體；乙烯基磺酸、苯乙烯磺酸、(甲基)丙烯酸磺乙酯等含有磺酸基之乙烯基單體；2-(甲基)丙烯醯氧基乙基酸式磷酸酯、2-(甲基)丙烯醯氧基丙基酸式磷酸酯、2-(甲基)丙烯醯氧基-3-氯-丙基酸式磷酸酯、2-甲基丙烯醯氧基乙基苯基磷酸等酸性磷酸酯系乙烯基單體；N-羥甲基(甲基)丙烯醯胺等具有羥甲基之乙烯基單體、zylacrylate、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯基苄酯、(甲基)丙烯酸苯氧基苄酯、苯酚EO改性(甲基)丙烯酸酯、鄰苯基苯酚EO改性(甲基)丙烯酸酯、對異丙苯基苯酚EO改性(甲基)丙烯酸酯、壬基苯酚EO改性(甲基)丙烯酸酯、鄰苯二甲酸單羥基乙酯(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、(甲基)丙烯酸2-(苯硫基)乙酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸四氫呋喃甲酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸異酯、(甲基)丙烯酸金剛烷基酯等。該等可使用一種或兩種以上。尤其就使耐乾式蝕刻性提高之觀點而言，較佳為包含較多芳香環或環狀烴基之結構，較佳為(甲基)丙烯酸苄酯、(甲基)丙烯酸苯基苄酯、(甲基)丙烯酸苯氧基苄酯、苯酚EO改性(甲基)丙烯酸酯、鄰 苯基苯酚EO改性(甲基)丙烯酸酯、對異丙苯基苯酚EO改性(甲基)丙烯酸酯、壬基苯酚EO改性(甲基)丙烯酸酯、鄰苯二甲酸單羥基乙酯(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、(甲基)丙烯酸2-(苯硫基)乙酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸四氫呋喃甲酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸異酯、(甲基)丙烯酸金剛烷基酯等。 Examples of the monofunctional (meth) acrylate include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and caprolactone-modified hydroxy (methyl). Acrylate (for example, manufactured by DAICEL CHEMICAL CO., LTD., trade name "PLACCEL"), mono(meth) acrylate of polyester diol obtained from phthalic acid and propylene glycol, and polycondensation obtained from succinic acid and propylene glycol Mono(meth) acrylate of ester diol, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol mono (meth) acrylate, (meth) acrylate 2 (hydroxy)-containing (meth) acrylate such as hydroxy-3-(methyl) propylene methoxy propyl ester or various epoxy ester (meth) acrylate adducts; (meth)acrylic acid, crotonic acid, clothing a vinyl monomer having a carboxyl group such as a benic acid, a maleic acid or a fumaric acid; a vinyl group containing a sulfonic acid group such as a vinylsulfonic acid, a styrenesulfonic acid or a sulfoethyl (meth)acrylate 2-(methyl)propenyloxyethyl acid phosphate, 2-(meth)acryloxypropyl phosphate, 2-( Acidic phosphate ester vinyl monomer such as acryloxy-3-chloro-propyl acid phosphate or 2-methylpropenyloxyethyl phenyl phosphate; N-hydroxymethyl (methyl) a vinyl monomer having a methylol group such as acrylamide, zylacrylate, benzyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxybenzyl (meth)acrylate, phenol EO modified ( Methyl) acrylate, o-phenylphenol EO modified (meth) acrylate, p-cumyl phenol EO modified (meth) acrylate, nonyl phenol EO modified (meth) acrylate, adjacent Monohydroxyethyl methacrylate (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-(phenylthio)ethyl (meth) acrylate, (methyl) Cyclohexyl acrylate, tetrahydrofuran methyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, ( Methyl) acrylate Ester, adamantyl (meth)acrylate, and the like. These may be used alone or in combination of two or more. In particular, from the viewpoint of improving the dry etching resistance, a structure containing a large number of aromatic rings or cyclic hydrocarbon groups is preferred, and benzyl (meth)acrylate or phenylbenzyl (meth)acrylate is preferred. Phenyloxybenzyl methacrylate, EO modified (meth) acrylate, o-phenylphenol EO modified (meth) acrylate, p-cumylphenol EO modified (meth) acrylate , nonylphenol EO modified (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, (methyl) 2-(phenylthio)ethyl acrylate, cyclohexyl (meth) acrylate, tetrahydrofuran (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentene (meth) acrylate Ethyl ethyl ester, dicyclopentyl (meth)acrylate, (meth)acrylic acid Ester, adamantyl (meth)acrylate, and the like.

同樣地，於使用活性能量線硬化性單體之情形時，可視需要含有多官能或單官能環氧樹脂。作為環氧樹脂，可使用雙酚A型、雙酚F型、甲酚酚醛清漆型、苯酚酚醛清漆型、環氧多元醇等。 Similarly, in the case of using an active energy ray-curable monomer, it may optionally contain a polyfunctional or monofunctional epoxy resin. As the epoxy resin, a bisphenol A type, a bisphenol F type, a cresol novolac type, a phenol novolak type, an epoxy polyol, or the like can be used.

作為使用上述多官能及單官能丙烯酸酯之情形時之使用量，相對於本發明之乾式蝕刻抗蝕劑材料之總固形物成分量較佳為0~80重量%，更佳為0~50重量%。藉由於上述範圍內使用上述多官能丙烯酸酯，可改善所獲得之抗蝕劑膜之硬度等物性。 The amount of the total solid content of the dry etching resist material of the present invention is preferably from 0 to 80% by weight, more preferably from 0 to 50% by weight, in the case of using the above polyfunctional and monofunctional acrylate. %. By using the above polyfunctional acrylate in the above range, physical properties such as hardness of the obtained resist film can be improved.

又，於使用含有矽之反應性單體及低聚物作為上述反應性化合物之情形時，可列舉：乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基甲基二甲氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、乙烯基三乙醯氧基矽烷、乙烯基三氯矽烷、2-三甲氧基矽烷基乙基乙烯醚、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基甲基二甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三氯矽烷、苯乙烯基三甲氧基矽烷、金剛烷基三甲氧基矽烷、金剛烷基三乙氧基矽烷、雙金剛烷基三甲氧基矽烷等矽烷化合物、或其等之縮合物、丙烯醯基POSS(Polyhedral Oligomeric Silsesquioxane，多面體低聚倍半矽氧烷)、丙烯醯基異丁基POSS、甲基丙烯醯基異丁基POSS、甲基丙烯酸酯環己基POSS、甲基丙烯酸酯異丁基POSS、甲基丙烯酸酯乙基POSS、甲基丙烯醯基乙基POSS、甲基丙烯酸酯異辛基POSS、甲基丙烯醯基異辛基POSS、甲基丙烯醯基 苯基POSS等化合物。 Further, when a reactive monomer or oligomer containing ruthenium is used as the above-mentioned reactive compound, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl methyl dimethoxy group is exemplified. Decane, vinyl tris(2-methoxyethoxy)decane, vinyltriethoxydecane, vinyltrichlorodecane, 2-trimethoxydecylethylvinylether, 3-(methyl) Propylene methoxypropyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, 3-(meth)acryloxypropylmethyldimethoxydecane, 3 - (Methyl) propylene methoxy propyl trichloro decane, styryl trimethoxy decane, adamantyl trimethoxy decane, adamantyl triethoxy decane, bis-adamantyl trimethoxy decane, etc. a compound, or a condensate thereof, acryl-based POSS (Polyhedral Oligomeric Silsesquioxane, polyhedral oligomeric sesquioxane), propylene oxime isobutyl POSS, methacryl oxime isobutyl POSS, methacrylate Cyclohexyl POSS, methacrylate isobutyl POSS, methacrylate ethyl POSS, methacrylic acid oxime Ethyl POSS, isooctyl methacrylate POSS, methyl iso-octyl group Bingxi Xi POSS, methyl group Bing Xixi Compounds such as phenyl POSS.

作為使用上述含有矽之反應性單體及低聚物之情形時之使用量，相對於本發明之乾式蝕刻抗蝕劑材料之總固形物成分量較佳為0~80重量%，更佳為10~70重量%。藉由於上述範圍內使用上述含有矽之反應性單體及低聚物，可保持抗蝕劑材料中之矽含量並且調整為適於對基板或下層膜之塗佈方法及奈米壓印之黏度。 The amount of the total solid content of the dry etching resist material of the present invention is preferably from 0 to 80% by weight, more preferably from 0 to 80% by weight, based on the amount of the above-mentioned reactive monomer and oligomer containing cerium. 10 to 70% by weight. By using the above-mentioned ruthenium-containing reactive monomer and oligomer in the above range, the ruthenium content in the resist material can be maintained and adjusted to the coating method for the substrate or the underlying film and the viscosity of the nanoimprinting. .

於使本發明之氧電漿蝕刻抗蝕劑材料硬化之情形時，可進行熱硬化及光硬化，就硬化速度之觀點而言，較佳為光硬化。尤佳為活性能量線硬化，其中尤佳為紫外線硬化。 When the oxygen plasma etching resist material of the present invention is cured, thermal curing and photo hardening can be performed, and from the viewpoint of curing speed, photohardening is preferred. It is especially preferred for active energy ray hardening, of which UV curing is particularly preferred.

用於進行紫外線硬化時之光例如可使用低壓水銀燈、高壓水銀燈、金屬鹵化物燈、氙氣燈、氬雷射、氦、鎘雷射、紫外線發光二極體等。可藉由使用該等將波長約180~400nm之紫外線照射至上述硬化性樹脂組合物之塗佈面而進行硬化。作為紫外線之照射量，根據所使用之光聚合起始劑之種類及量而適當選擇。 For the light used for ultraviolet curing, for example, a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, an argon laser, a krypton, a cadmium laser, an ultraviolet light emitting diode, or the like can be used. The curing can be carried out by irradiating the coated surface of the curable resin composition with ultraviolet rays having a wavelength of about 180 to 400 nm. The amount of ultraviolet light to be irradiated is appropriately selected depending on the type and amount of the photopolymerization initiator to be used.

又，為了調整塗敷時之黏度，亦可含有有機溶劑。作為有機溶劑，例如可將正己烷、正庚烷、正辛烷、環己烷、環戊烷等脂肪族系或脂環族系烴類；甲苯、二甲苯、乙基苯等芳香族烴類；甲醇、乙醇、正丁醇、乙二醇單甲醚、丙二醇單甲醚等醇類；乙酸乙酯、乙酸丁酯、乙酸正丁酯、乙酸正戊酯、乙二醇單甲醚乙酸酯、丙二醇單甲醚乙酸酯等酯類；丙酮、甲基乙基酮、甲基異丁基酮、甲基正戊基酮、環己酮等酮類；二乙二醇二甲醚、二乙二醇二丁醚等聚伸烷基二醇二烷基醚類；1,2-二甲氧基乙烷、四氫呋喃、二烷等醚類；N-甲基吡咯啶酮、二甲基甲醯胺、二甲基乙醯胺或碳酸乙二酯單獨使用或併用兩種以上而使用。 Further, in order to adjust the viscosity at the time of coating, an organic solvent may be contained. Examples of the organic solvent include aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, cyclohexane, and cyclopentane; and aromatic hydrocarbons such as toluene, xylene, and ethylbenzene. Alcohols such as methanol, ethanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; ethyl acetate, butyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate Esters such as esters, propylene glycol monomethyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, cyclohexanone; diethylene glycol dimethyl ether, Diethylene glycol dibutyl ether, such as polyalkylene glycol dialkyl ethers; 1,2-dimethoxyethane, tetrahydrofuran, two An ether such as an alkyl group; N-methylpyrrolidone, dimethylformamide, dimethylacetamide or ethylene carbonate may be used singly or in combination of two or more.

此外，於本發明中使用之乾式蝕刻抗蝕劑材料中，亦可視需要使用有機溶劑、無機顏料、有機顏料、體質顏料、黏土礦物、蠟、界 面活性劑、穩定劑、流動調整劑、染料、調平劑、流變控制劑、紫外線吸收劑、抗氧化劑、或塑化劑等各種添加劑等。 In addition, in the dry etching resist material used in the present invention, an organic solvent, an inorganic pigment, an organic pigment, an extender pigment, a clay mineral, a wax, and a boundary may also be used as needed. Various additives such as surfactants, stabilizers, flow regulators, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, or plasticizers.

本發明中使用之乾式蝕刻抗蝕劑材料所含有之複合樹脂(A)具有聚矽氧烷片段(a1)與乙烯基系聚合物片段(a2)之兩者，因此可使塗膜之表面滑性等提高之矽樹脂、丙烯酸系樹脂或活性能量線硬化性單體均相對容易相溶。因此，可獲得相溶性良好之組合物。 The composite resin (A) contained in the dry etching resist material used in the present invention has both a polyoxymethane fragment (a1) and a vinyl polymer fragment (a2), so that the surface of the coating film can be slipped The resin, the acrylic resin, or the active energy ray-curable monomer which are improved in properties and the like are relatively easily compatible. Therefore, a composition having good compatibility can be obtained.

本發明之乾式蝕刻抗蝕劑材料亦可於無損本發明之效果之範圍內視需要含有其他成分。例如，可列舉：包含縮水甘油氧基烷基三甲氧基矽烷或(甲基)丙烯醯氧基丙烯酸基三烷氧基矽烷矽烷等通用之矽烷偶合劑之接著性助劑、滑石、雲母、黏土、二氧化矽、氧化鋁、絹雲母、白碳、石膏、雲母、硫酸鋇、碳酸鋇或碳酸鎂等無機微粒子、顏料或染料等著色物質、防退色劑、抗氧化劑、UV吸收劑、塑化劑或潤滑劑等塗料添加劑。 The dry etching resist material of the present invention may contain other components as needed within the range not impairing the effects of the present invention. For example, a auxiliary decane coupling agent such as glycidoxyalkyltrimethoxydecane or (meth)acryloxy methoxytrialtrialkoxide, such as talc, mica or clay, may be mentioned. , inorganic particles such as cerium oxide, alumina, sericite, white carbon, gypsum, mica, barium sulfate, barium carbonate or magnesium carbonate, coloring substances such as pigments or dyes, anti-fading agents, antioxidants, UV absorbers, plasticizing Coating additives such as agents or lubricants.

(抗蝕劑膜) (resist film)

藉由將本發明之氧電漿蝕刻抗蝕劑材料積層於基材並進行硬化，可獲得抗蝕劑膜及具有抗蝕劑膜之積層體。 A resist film and a laminate having a resist film can be obtained by laminating the oxygen plasma etching resist material of the present invention on a substrate and curing it.

關於抗蝕劑膜之形成方法，只要使用公知慣用之方法即可，例如可藉由於基材表面塗佈液狀之氧電漿蝕刻抗蝕劑材料即抗蝕劑液後進行硬化而獲得。於製成液狀之氧電漿蝕刻抗蝕劑材料之情形時，關於氧電漿蝕刻抗蝕劑材料中之總固形物成分之濃度，若考慮塗佈性(例如塗佈及溶劑去除後之膜厚收斂於所期望之範圍內；該膜厚於被加工表面整體為均一性；即便於被加工表面存在少許凹凸，亦追隨於該凹凸而形成均勻厚度之塗膜等)等，則較佳為0.1質量%以上且10質量%以下，更佳為0.1質量%以上且5質量%以下，進而較佳為0.1質量%以上且3質量%以下。具體而言，只要以塗膜之膜厚成為10nm~50μm之方式進行調整即可，更佳為10nm~5μm。 The method for forming the resist film may be any conventionally known method, and may be obtained, for example, by applying a liquid plasma to the surface of the substrate to etch a resist material, that is, a resist liquid. In the case of preparing a liquid oxygen plasma etching resist material, regarding the concentration of the total solid content in the oxygen plasma etching resist material, considering the coating property (for example, after coating and solvent removal) The film thickness converges within a desired range; the film thickness is uniform over the entire surface to be processed; even if there is a slight unevenness on the surface to be processed, a coating film having a uniform thickness is formed following the unevenness, etc., it is preferably It is 0.1% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less, further preferably 0.1% by mass or more and 3% by mass or less. Specifically, the film thickness of the coating film may be adjusted to be 10 nm to 50 μm, and more preferably 10 nm to 5 μm.

本發明之氧電漿蝕刻抗蝕劑材料由於可進行微細圖案加工，因此膜厚亦可為1μm以下。 Since the oxygen plasma etching resist material of the present invention can be processed by fine patterning, the film thickness can be 1 μm or less.

作為所使用之溶劑，只要為用於公知之抗蝕劑材料之有機溶劑即可，例如可將正己烷、正庚烷、正辛烷、環己烷、環戊烷等脂肪族系或脂環族系烴類；甲苯、二甲苯、乙基苯等芳香族烴類；甲醇、乙醇、正丁醇、乙二醇單甲醚、丙二醇單甲醚等醇類；乙酸乙酯、乙酸正丁酯、乙酸異丁酯、乙酸正戊酯、乙二醇單甲醚乙酸酯、丙二醇單甲醚乙酸酯等酯類；丙酮、甲基乙基酮、甲基異丁基酮、甲基正戊基酮、環己酮等酮類；二乙二醇二甲醚、二乙二醇二丁醚等聚伸烷基二醇二烷基醚類；1,2-二甲氧基乙烷、四氫呋喃、二烷等醚類；N-甲基吡咯啶酮、二甲基甲醯胺、二甲基乙醯胺或碳酸乙二酯單獨使用或併用兩種以上而使用。 The solvent to be used may be an organic solvent used for a known resist material, and for example, an aliphatic or alicyclic ring such as n-hexane, n-heptane, n-octane, cyclohexane or cyclopentane may be used. Family hydrocarbons; aromatic hydrocarbons such as toluene, xylene, ethylbenzene; alcohols such as methanol, ethanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; ethyl acetate, n-butyl acetate , isobutyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate and other esters; acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl positive a ketone such as amyl ketone or cyclohexanone; a polyalkylene glycol dialkyl ether such as diethylene glycol dimethyl ether or diethylene glycol dibutyl ether; 1,2-dimethoxyethane; Tetrahydrofuran, two An ether such as an alkyl group; N-methylpyrrolidone, dimethylformamide, dimethylacetamide or ethylene carbonate may be used singly or in combination of two or more.

本發明之抗蝕劑膜亦可為將本發明之氧電漿蝕刻抗蝕劑材料藉由擠出成形等公知之成形方法成膜為膜狀，或塗佈於暫時支持膜上加以乾燥，並視需要加熱壓接於以被覆膜覆蓋所形成之光硬化性組合物層表面而成之作為處理對象之表面並進行積層者。作為此時使用之暫時支持膜，例如可使用聚對苯二甲酸乙二酯膜、聚醯亞胺膜、聚醯胺醯亞胺膜、聚丙烯膜、聚苯乙烯膜等先前公知之膜。此時，於該等膜為具有製作抗蝕劑膜時所需之耐溶劑性或耐熱性等者時，可於該等暫時支持膜上直接塗佈本發明之抗蝕劑材料並進行乾燥而製作本發明之抗蝕劑膜，又，即便該等膜為耐溶劑性或耐熱性等較低者，例如亦可於聚四氟乙烯膜或脫模膜等具有脫模性之膜上先形成本發明之抗蝕劑材料後，於該層上積層耐溶劑性或耐熱性等較低之暫時支持膜，其後將具有脫模性之膜剝離，藉此製作本發明之抗蝕劑膜。 The resist film of the present invention may be formed into a film by a known molding method such as extrusion molding of the present invention, or may be applied to a temporary support film and dried. The surface to be treated, which is formed by covering the surface of the photocurable composition layer formed with the coating film, is heated and bonded as needed, and laminated. As the temporary support film to be used at this time, for example, a conventionally known film such as a polyethylene terephthalate film, a polyimide film, a polyimide film, a polypropylene film, or a polystyrene film can be used. In this case, when the film is required to have solvent resistance or heat resistance required for producing a resist film, the resist material of the present invention may be directly applied onto the temporary support film and dried. When the resist film of the present invention is produced, even if the film is low in solvent resistance or heat resistance, for example, it may be formed on a film having a mold release property such as a polytetrafluoroethylene film or a release film. After the resist material of the present invention, a temporary support film having a low solvent resistance or heat resistance is laminated on the layer, and then a film having mold release property is peeled off to prepare a resist film of the present invention.

又，本發明之抗蝕劑膜亦可為將本發明之氧電漿蝕刻抗蝕劑材料藉由旋塗法或噴墨法等公知之塗佈方法塗佈於作為處理對象之表面 上者。作為塗佈方法，可列舉旋塗法、噴墨法、噴霧法、浸漬法、輥塗法、刮塗法、刮刀輥法、刮刀法、淋幕式塗佈法、狹縫式塗佈法、網版印刷法等。就生產性優異且易於控制膜厚之方面而言，較佳為使用旋塗法。 Further, the resist film of the present invention may be applied to a surface to be treated by a known coating method such as a spin coating method or an inkjet method. The above. Examples of the coating method include a spin coating method, an inkjet method, a spray method, a dipping method, a roll coating method, a knife coating method, a doctor roll method, a doctor blade method, a curtain coating method, and a slit coating method. Screen printing method, etc. In terms of excellent productivity and easy control of film thickness, spin coating is preferably used.

[積層體] [layered body]

本發明之積層體係將本發明之抗蝕劑膜積層於基材而成之積層體。所使用之基材根據本發明之抗蝕劑膜之目的而不同，例如可列舉：石英、藍寶石、玻璃、光學膜、陶瓷材料、蒸鍍膜、磁性膜、反射膜、Al、Ni、Cu、Cr、Fe、不鏽鋼等金屬基材、絲網、紙、木材、矽等合成樹脂、SOG(Spin On Glass，旋塗式玻璃)、聚酯膜、聚碳酸酯膜、聚醯亞胺膜等聚合物基材、TFT(Thin Film Transistor，薄膜電晶體)陣列基材、藍寶石或GaN等發光二極體(LED)基材、玻璃或塑膠基材、氧化銦錫(ITO)或金屬等導電性基材、絕緣性基材、矽、氮化矽、多晶矽、氧化矽、非晶形矽等半導體製作基材等。該等可為透光性，亦可為非透光性。 In the laminated system of the present invention, the resist film of the present invention is laminated on a substrate to form a laminate. The substrate to be used differs depending on the purpose of the resist film of the present invention, and examples thereof include quartz, sapphire, glass, optical film, ceramic material, vapor deposited film, magnetic film, reflective film, Al, Ni, Cu, and Cr. Metal substrates such as Fe, stainless steel, etc., synthetic resins such as wire mesh, paper, wood, and enamel, polymers such as SOG (Spin On Glass), polyester film, polycarbonate film, and polyimide film. Substrate, TFT (Thin Film Transistor) array substrate, light-emitting diode (LED) substrate such as sapphire or GaN, glass or plastic substrate, indium tin oxide (ITO) or metal conductive substrate A semiconductor substrate such as an insulating substrate, tantalum, tantalum nitride, polycrystalline germanium, tantalum oxide or amorphous germanium. These may be light transmissive or non-translucent.

又，基材之形狀亦無特別限定，可為平板、片狀、或於三維形狀整面或一部分具有曲率者等對應目的之任意形狀。又，基材之硬度、厚度等亦無特別限制。 Further, the shape of the substrate is not particularly limited, and may be any shape such as a flat plate, a sheet shape, or a corresponding object such as a curvature of the entire surface or a part of the three-dimensional shape. Further, the hardness, thickness, and the like of the substrate are not particularly limited.

尤其，於基材為合成樹脂或高分子材料、非晶形碳之類之有機材料之情形時，本發明之氧乾式蝕刻材料所含有之上述複合樹脂(A)具有乙烯基系聚合物片段(a-2)，因此密接性優異，故而較佳。例如於多層抗蝕劑製程之情形時，於矽晶圓上積層被稱為有機下層膜之包含有機材料之膜。本發明之抗蝕劑膜對有機下層膜之密接性較高，而且藉由紫外線硬化形成具有充分之耐氧電漿蝕刻性之塗膜，因此抗蝕劑形成/蝕刻步驟成為大幅地省事之步驟。 In particular, in the case where the substrate is an organic material such as a synthetic resin or a polymer material or amorphous carbon, the above-mentioned composite resin (A) contained in the oxygen dry etching material of the present invention has a vinyl polymer segment (a) -2) Therefore, it is preferable because it is excellent in adhesiveness. For example, in the case of a multilayer resist process, a film containing an organic material called an organic underlayer film is laminated on a germanium wafer. Since the resist film of the present invention has high adhesion to the organic underlayer film and forms a coating film having sufficient oxygen plasma etch resistance by ultraviolet curing, the resist formation/etching step becomes a step of greatly saving trouble. .

作為有機下層膜，可使用先前公知者，可使用通常之多層抗蝕 劑法等所使用之有機膜。例如，可列舉：甲酚酚醛清漆、萘酚酚醛清漆、甲酚二環戊二烯酚醛清漆、萘酚二環戊二烯酚醛清漆、茀雙酚酚醛清漆、非晶形碳、類鑽碳、聚羥基苯乙烯、茚樹脂、苊樹脂、三環[2.2.1.02,6]庚烷(nortricyclene)樹脂、(甲基)丙烯酸酯樹脂、聚醯亞胺、聚碸等、及其等之共聚樹脂或聚合物摻合物等。又，作為此種有機下層膜，可為先前用以形成抗有機反射膜(有機BARC)等有機膜之材料。例如，可列舉BREWER SCIENCE公司製造之ARC系列、ROHM AND HAAS公司製造之AR系列、東京應化工業公司製造之SWK系列等。 As the organic underlayer film, a conventionally known one can be used, and a conventional multilayer resist can be used. An organic film used in a reagent method or the like. For example, cresol novolac, naphthol novolac, cresol dicyclopentadiene novolac, naphthol dicyclopentadiene novolac, bisphenol novolac, amorphous carbon, diamond-like carbon, poly a hydroxystyrene, an anthracene resin, an anthracene resin, a tricyclo[2.2.1.02,6]nortricyclene resin, a (meth) acrylate resin, a polyimine, a polyfluorene, etc., and the like, or a copolymer resin thereof Polymer blends and the like. Further, as such an organic underlayer film, a material which is previously used to form an organic film such as an organic reflective film (organic BARC) may be used. For example, an ARC series manufactured by BREWER SCIENCE, an AR series manufactured by ROHM AND HAAS, and a SWK series manufactured by Tokyo Yinghua Industrial Co., Ltd., and the like can be cited.

[圖案形成方法] [Pattern forming method]

本發明中之抗蝕劑膜可藉由各種方法形成圖案。例如亦可為如光微影法、雷射直接描繪法之光阻劑法，於將形成過圖案之模型壓抵於硬化前之抗蝕劑膜之狀態下進行硬化而製成圖案形成抗蝕劑膜，其後將模型剝離，藉此亦可形成圖案。 The resist film of the present invention can be patterned by various methods. For example, it may be a photoresist method such as a photolithography method or a laser direct drawing method, and a pattern is formed by pressing a mold having a patterned pattern against a resist film before curing to form a resist. The film is then peeled off from the mold, whereby a pattern can also be formed.

作為微影法之例，例如於作為處理對象之基板利用上述方法進行成膜而積層硬化前之抗蝕劑膜後，藉由活性光經由遮罩膜進行圖像曝光。曝光時使用之光例如可使用低壓水銀燈、高壓水銀燈、金屬鹵化物燈、氙氣燈、紫外線發光二極體、氬雷射、氦、鎘雷射等。作為光照射量，可根據所使用之光聚合起始劑之種類及量而適當選擇。 As an example of the lithography method, for example, a resist film before film formation and hardening is formed on the substrate to be processed by the above method, and then image exposure is performed by the active light through the mask film. For the light used for the exposure, for example, a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, an ultraviolet light emitting diode, an argon laser, a helium, a cadmium laser or the like can be used. The amount of light irradiation can be appropriately selected depending on the kind and amount of the photopolymerization initiator to be used.

另一方面，作為雷射直接描繪法之例，於利用上述方法進行成膜而積層硬化前之抗蝕劑膜後，藉由波長350~430nm之雷射光進行掃描曝光。作為該曝光光源，可列舉碳弧燈、水銀燈、氙氣燈、金屬鹵化物燈、螢光燈、鎢絲燈、鹵素燈、及HeNe雷射、氬離子雷射、YAG(Yttrium Aluminium Garnet，釔鋁石榴石)雷射、HeCd雷射、半導體雷射、紅寶石雷射等雷射光源，尤佳為產生波長區域350~430nm之藍紫色區域之雷射光之光源，進而較佳為其中心波長為約405nm 者。具體而言，可列舉振盪405nm之氮化銦鎵半導體雷射等。又，利用雷射光源之掃描曝光方法並無特別限定，例如可列舉平面掃描曝光方式、外表面筒式掃描(drum scanning)曝光方式、內表面筒式掃描曝光方式等，作為掃描曝光條件，將雷射之輸出光強度設為較佳為1~100mW、進而較佳為3~70mW，將振盪波長設為較佳為390~430nm、進而較佳為400~420nm，將束斑點直徑設為較佳為2~30μm、進而較佳為4~20μm，將掃描速度設為較佳為50~500m/秒、進而較佳為100~400m/秒，將掃描密度設為較佳為2,000dpi以上、進而較佳為4,000dpi以上，進行掃描曝光。 On the other hand, as an example of the laser direct drawing method, after the film is formed by the above method and the resist film is laminated and cured, scanning exposure is performed by laser light having a wavelength of 350 to 430 nm. Examples of the exposure light source include a carbon arc lamp, a mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a halogen lamp, and a HeNe laser, an argon ion laser, and a YAG (Yttrium Aluminium Garnet). Laser light sources such as garnet lasers, HeCd lasers, semiconductor lasers, and ruby lasers are particularly preferred as sources of laser light that produce a blue-violet region having a wavelength region of 350 to 430 nm, and preferably have a center wavelength of about 405nm By. Specifically, an indium gallium nitride semiconductor laser having an oscillation of 405 nm or the like can be cited. Further, the scanning exposure method using the laser light source is not particularly limited, and examples thereof include a planar scanning exposure method, an outer surface drum scanning exposure method, an inner surface cylindrical scanning exposure method, and the like, and as scanning exposure conditions, The output light intensity of the laser is preferably 1 to 100 mW, more preferably 3 to 70 mW, and the oscillation wavelength is preferably 390 to 430 nm, more preferably 400 to 420 nm, and the beam spot diameter is set to be relatively It is preferably 2 to 30 μm, more preferably 4 to 20 μm, and the scanning speed is preferably 50 to 500 m/sec, more preferably 100 to 400 m/sec, and the scanning density is preferably 2,000 dpi or more. Further, it is preferably 4,000 dpi or more, and scanning exposure is performed.

繼而，使用鹼性水溶液將未曝光部之未硬化部分顯影去除。作為鹼性水溶液，使用碳酸鈉、碳酸鉀等水溶液。該等鹼性水溶液係對照感光性樹脂層之特性而進行選擇，一般而言使用0.5~3質量%之碳酸鈉水溶液。 Then, the uncured portion of the unexposed portion is developed and removed using an alkaline aqueous solution. As the alkaline aqueous solution, an aqueous solution such as sodium carbonate or potassium carbonate is used. These alkaline aqueous solutions are selected in accordance with the characteristics of the photosensitive resin layer, and generally, a sodium carbonate aqueous solution of 0.5 to 3% by mass is used.

於使用模型之圖案形成之情形時，藉由於以將形成有圖案之模型壓抵於利用上述方法製作之膜之方式接觸並保持之狀態下使乾式蝕刻抗蝕劑材料硬化，可於抗蝕劑膜形成圖案。本發明之氧電漿蝕刻抗蝕劑材料尤其可較佳地用於能夠形成100nm以下之圖案之奈米壓印。 In the case of using the pattern formation of the model, the dry etching resist material can be cured by being pressed and held in a state in which the pattern formed by pressing the pattern is contacted and held by the film produced by the above method. The film forms a pattern. The oxygen plasma etch resist material of the present invention is particularly preferably used for nanoimprinting capable of forming a pattern of 100 nm or less.

所謂奈米壓印係指將預先藉由電子束微影等作成有特定之微細凹凸圖案之奈米壓印用模型壓抵於塗佈有抗蝕劑之基板，將奈米壓印用模型之凹凸轉印至基板之抗蝕劑膜的方法。其具有如下特徵：關於一次處理所花費之時間，於例如1平方英吋以上之區域較雷射直接描繪法非常短。 The nanoimprinting method is a method in which a nanoimprinting pattern having a specific fine concavo-convex pattern formed by electron beam lithography or the like is applied to a substrate coated with a resist, and a nanoimprinting model is used. A method of transferring a bump to a resist film of a substrate. It has the feature that the time taken for one treatment is very short compared to the laser direct drawing method in an area of, for example, 1 square inch or more.

具體而言，壓抵具有凹凸結構之奈米壓印用模型之步驟係一面按壓奈米壓印用模型一面將包含上述氧電漿蝕刻抗蝕劑材料之抗蝕劑膜壓入至模型之微細形狀。此時，亦可以上述氧電漿蝕刻抗蝕劑材料進一步追隨於模型之微細形狀之方式，一面進行加熱而降低黏度一面 進行按壓。其後，藉由於照射紫外線而使包含上述氧電漿蝕刻抗蝕劑材料之抗蝕劑膜硬化後分離奈米壓印用模型，可獲得形成於奈米壓印用模型之微細形狀形成於包含上述氧電漿蝕刻抗蝕劑材料之抗蝕劑膜表面的圖案。 Specifically, the step of pressing the nanoimprinting model having the uneven structure is performed by pressing the nanoimprinting mold while pressing the resist film containing the oxygen plasma etching resist material into the model. shape. In this case, the oxygen plasma etching resist material may be heated to reduce the viscosity while further following the fine shape of the mold. Press it. Thereafter, the resist film containing the oxygen plasma etch resist material is cured by irradiation with ultraviolet rays, and the nanoimprint mold is separated to obtain a fine shape formed in the nanoimprint model. The oxygen plasma etches a pattern of the surface of the resist film of the resist material.

具體而言，以於設置於基材表面之包含氧電漿蝕刻抗蝕劑材料之抗蝕劑膜上壓抵奈米壓印用模型之方式進行接觸、夾持。關於奈米壓印用模型，作為高效率地製造大面積之成形體之方法，亦較佳為利用如適於輥製程之平面狀原版之上下方式、帶狀原版之貼合方式、輥狀原版之輥轉印方式、輥帶狀原版之輥轉印方式等方法進行接觸之方法。作為奈米壓印用模型之材質，作為使光透過之材質，可列舉石英玻璃、紫外線透過玻璃、藍寶石、鑽石、聚二甲基矽氧烷等矽材料、氟樹脂、其他使光透過之樹脂材料等。又，只要使用之基材為使光透過之材質，則奈米壓印用模型亦可為不使光透過之材質。作為不使光透過之材質，可列舉金屬、矽、SiC、雲母等。 Specifically, the resist film provided on the surface of the substrate and the resist film containing the oxygen plasma etching resist material are pressed and held in contact with the nanoimprinting mold. Regarding the nanoimprinting model, as a method of efficiently producing a large-sized molded body, it is also preferable to use a planar original plate-up method suitable for a roll process, a tape-like original bonding method, and a roll-shaped original plate. A method of contacting by a method such as a roll transfer method or a roll transfer method of a roll belt original plate. As a material for the nanoimprinting model, examples of the material for transmitting light include bismuth materials such as quartz glass, ultraviolet ray permeable glass, sapphire, diamond, and polydimethyl siloxane, fluororesins, and other resins that transmit light. Materials, etc. Further, as long as the substrate to be used is a material that transmits light, the nanoimprinting model may be a material that does not transmit light. Examples of the material that does not transmit light include metal, ruthenium, SiC, mica, and the like.

如上所述，奈米壓印用模型可選擇平面狀、帶狀、輥狀、輥帶狀等任意形態者。就防止因懸浮污物等所致之原版之污染等目的而言，較佳為對轉印面實施先前公知之脫模處理。 As described above, the nanoimprinting model can be any form such as a flat shape, a belt shape, a roll shape, or a roll belt shape. For the purpose of preventing contamination of the original plate due to suspended dirt or the like, it is preferred to carry out a previously known release treatment on the transfer surface.

(硬化步驟) (hardening step)

硬化方法可列舉於模型為使光透過之材質之情形時自模型側照射光之方法、或於基材為使光透過之材質之情形時自基材側照射光之方法。作為用於光照射之光，只要為光聚合起始劑進行反應之光即可，其中，就光聚合起始劑易於反應，且可於更低溫下進行硬化之方面而言，較佳為波長450nm以下之光(紫外線、X射線、γ射線等活性能量線)。就操作性方面而言，尤佳為波長200至450nm之光。具體而言，可使用上述紫外線硬化時使用之光。 The hardening method may be a method of irradiating light from the model side when the model is a material that transmits light, or a method of irradiating light from the substrate side when the substrate is a material that transmits light. The light used for the light irradiation may be any light that is a reaction of the photopolymerization initiator, and among them, the photopolymerization initiator is easily reacted and can be hardened at a lower temperature, preferably a wavelength. Light below 450 nm (active energy lines such as ultraviolet rays, X-rays, and gamma rays). In terms of operability, light having a wavelength of 200 to 450 nm is particularly preferred. Specifically, the light used in the above ultraviolet curing can be used.

又，若所形成之圖案之追隨性存在不良情況，則亦可於光照射 時加熱至獲得充分之流動性之溫度為止。加熱之情形時之溫度較佳為300℃以下，更佳為0℃至200℃，進而較佳為0℃至150℃，尤佳為20℃至80℃。於該溫度範圍內，形成於包含上述氧電漿蝕刻抗蝕劑材料之抗蝕劑膜之微細圖案形狀之精度被保持得較高。 Moreover, if there is a problem with the followability of the formed pattern, it can also be irradiated with light. Heat until the temperature at which sufficient fluidity is obtained. The temperature in the case of heating is preferably 300 ° C or lower, more preferably 0 ° C to 200 ° C, further preferably 0 ° C to 150 ° C, and particularly preferably 20 ° C to 80 ° C. Within this temperature range, the precision of the shape of the fine pattern formed on the resist film containing the above-described oxygen plasma etching resist material is kept high.

關於上述任一方式，作為高效率地製造大面積之成形體之方法，亦較佳為利用以適於輥製程之方式於反應機內進行搬送之方法進行硬化之方法。 In any of the above embodiments, the method of efficiently producing a large-sized molded body is preferably a method of curing by a method of carrying it in a reactor in a manner suitable for a roll process.

(脫模步驟) (release step)

於硬化步驟後，藉由將成形體自模型剝離，獲得轉印有模型之凹凸圖案之凸凹圖案形成於包含上述氧電漿蝕刻抗蝕劑材料之抗蝕劑膜之硬化物表面的抗蝕劑膜。於抑制基材翹曲等變形或提高凸凹圖案之精度之方面，作為剝離步驟之溫度，較佳為於抗蝕劑膜之溫度冷卻至常溫(25℃)附近後實施之方法，或即便於抗蝕劑膜尚為加熱狀態時進行剝離之情形時，亦於對抗蝕劑膜施加一定張力之狀態下冷卻至常溫(25℃)附近之方法。 After the hardening step, by peeling the formed body from the mold, a convex-concave pattern in which the concave-convex pattern of the model is transferred is formed on the surface of the cured material of the resist film containing the oxygen plasma-etched resist material. membrane. In order to suppress deformation such as warpage of the substrate or to improve the accuracy of the uneven pattern, the temperature of the peeling step is preferably carried out after the temperature of the resist film is cooled to a temperature near normal temperature (25 ° C), or even if it is resistant. When the etching agent film is peeled off in a heated state, it is also cooled to a temperature near normal temperature (25 ° C) while applying a certain tension to the resist film.

[氧電漿蝕刻抗蝕劑] [Oxygen plasma etching resist]

藉由對具有利用上述方法形成有圖案之抗蝕劑膜之積層體進行氧電漿蝕刻，可於基板良好地形成圖案，可獲得藉由氧電漿蝕刻形成有圖案之圖案形成物。 By performing oxygen plasma etching on the laminate having the resist film formed by the above method, a pattern can be favorably formed on the substrate, and a pattern-formed product formed by patterning by oxygen plasma etching can be obtained.

本發明之包含氧電漿蝕刻抗蝕劑材料之抗蝕劑膜由於對氧電漿之耐乾式蝕刻性優異，故而於該蝕刻時亦不會發生圖案等變形之情況，可提供微細之蝕刻圖案。藉此，可將形成於抗蝕劑之圖案精度良好地轉印至基板，因此可獲得所獲得之圖案形成物之圖案再現性優異之圖案轉印物。 Since the resist film containing the oxygen plasma etching resist material of the present invention is excellent in dry etching resistance to oxygen plasma, deformation of a pattern or the like does not occur during the etching, and a fine etching pattern can be provided. . Thereby, the pattern formed on the resist can be accurately transferred to the substrate, and thus the pattern transfer product excellent in pattern reproducibility of the obtained pattern formation can be obtained.

作為用於氧電漿蝕刻之氣體，使用產生氧電漿作為主成分之單獨氣體或混合氣體。作為單獨氣體，例如可使用氧氣、一氧化碳、二 氧化碳等含氧原子之氣體，另一方面，作為混合之氣體，亦可於不抑制氧電漿之產生之範圍內適當混合氦氣、氮氣、氬氣等惰性氣體、氯系氣體、氟系氣體、氫氣、氨氣等公知慣用之氣體。 As the gas for oxygen plasma etching, a separate gas or a mixed gas which generates oxygen plasma as a main component is used. As a separate gas, for example, oxygen, carbon monoxide, or two can be used. A gas containing oxygen atoms such as carbon oxide, on the other hand, as a gas to be mixed, an inert gas such as helium gas, nitrogen gas or argon gas, a chlorine gas or a fluorine system may be appropriately mixed in a range in which the generation of the oxygen plasma is not inhibited. A well-known gas such as a gas, hydrogen gas, or ammonia gas.

藉由使用該等蝕刻氣體進行蝕刻，可將本發明之氧電漿蝕刻抗蝕劑材料作為遮罩而於基材形成所期望之圖案。 By etching using the etching gas, the oxygen plasma etching resist material of the present invention can be used as a mask to form a desired pattern on the substrate.

[實施例] [Examples]

其次，根據實施例及比較例具體地說明本發明。例中若無說明，則「份」「%」為重量標準。 Next, the present invention will be specifically described based on examples and comparative examples. In the example, if there is no explanation, "part" "%" is the weight standard.

(合成例1[聚矽氧烷(a1-1)之製備例]) (Synthesis Example 1 [Preparation Example of Polyoxane (a1-1)])

於具備攪拌機、溫度計、滴液漏斗、冷卻管及氮氣導入口之反應容器中，添加二甲基二甲氧基矽烷(DMDMS)304份、甲基三甲氧基矽烷(MTMS)337份、3-丙烯醯氧基丙基三甲氧基矽烷(APTMS)491份，於通入氮氣下一面攪拌一面升溫至60℃。繼而，以5分鐘滴加包含「Phoslex A-4」[堺化學股份有限公司製造之酸式磷酸正丁酯]0.1份與脫離子水141份之混合物。於滴加結束後，將反應容器中升溫至80℃，並攪拌4小時，藉此進行水解縮合反應，獲得反應產物。 In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and a nitrogen inlet, 304 parts of dimethyldimethoxydecane (DMDMS), 337 parts of methyltrimethoxydecane (MTMS), and 3- 491 parts of propylene methoxy propyl trimethoxy decane (APTMS) was heated to 60 ° C while stirring under nitrogen. Then, a mixture containing 0.1 parts of "Phoslex A-4" [n-butyl acid phosphate produced by Sigma Chemical Co., Ltd.] and 141 parts of deionized water was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction vessel was heated to 80 ° C and stirred for 4 hours to carry out a hydrolysis condensation reaction to obtain a reaction product.

藉由將所獲得之反應產物中所含之甲醇及水於1~30千帕(kPa)之減壓下、於40~60℃之條件下去除，而獲得數量平均分子量為1000且有效成分為70.0%之聚矽氧烷(a1-1)1000份。 By removing the methanol and water contained in the obtained reaction product under a reduced pressure of 1 to 30 kPa (kPa) at 40 to 60 ° C, the number average molecular weight is 1000 and the active ingredient is 1000 parts of 70.0% polyoxyalkylene (a1-1).

再者，所謂「有效成分」，係將使用之矽烷單體之甲氧基全部進行水解縮合反應之情形時的理論產量(重量份)除以水解縮合反應後之實際產量(重量份)所得之值、即藉由[矽烷單體之甲氧基全部進行水解縮合反應之情形時之理論產量(重量份)/水解縮合反應後之實際產量(重量份)]之式而算出者。 In addition, the "active ingredient" is obtained by dividing the theoretical yield (parts by weight) of the methoxy group of the decane monomer used in the hydrolytic condensation reaction by the actual yield (parts by weight) after the hydrolysis condensation reaction. The value is calculated by the formula (the theoretical yield (parts by weight) in the case where the methoxy group of the decane monomer is subjected to the hydrolysis condensation reaction/the actual yield (parts by weight after the hydrolysis condensation reaction).

(合成例2[聚矽氧烷(a1-2)之製備例]) (Synthesis Example 2 [Preparation Example of Polyoxane (a1-2)])

於具備攪拌機、溫度計、滴液漏斗、冷卻管及氮氣導入口之反 應容器中，添加DMDMS 106份、MTMS 831份、APTMS 320份，於通入氮氣下一面攪拌一面升溫至60℃。繼而，以5分鐘滴加包含Phoslex A-4 0.1份與脫離子水165份之混合物。於滴加結束後，將反應容器中升溫至80℃並攪拌4小時，藉此進行水解縮合反應，獲得反應產物。 With a blender, thermometer, dropping funnel, cooling tube and nitrogen inlet In the container, 106 parts of DMDMS, 831 parts of MTMS, and 320 parts of APTMS were added, and the temperature was raised to 60 ° C while stirring under nitrogen. Then, a mixture containing 0.1 part of Phoslex A-4 and 165 parts of deionized water was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction vessel was heated to 80 ° C and stirred for 4 hours to carry out a hydrolysis condensation reaction to obtain a reaction product.

藉由將所獲得之反應產物中所含之甲醇及水於1~30千帕(kPa)之減壓下、於40~60℃之條件下去除，獲得數量平均分子量為1000且有效成分為70.0%之聚矽氧烷(a1-2)1000份。 By removing the methanol and water contained in the obtained reaction product under a reduced pressure of 1 to 30 kPa (kPa) at 40 to 60 ° C, the number average molecular weight is 1000 and the active ingredient is 70.0. 1000 parts of polyoxyalkylene (a1-2).

(合成例3[聚矽氧烷(a1-3)之製備例]) (Synthesis Example 3 [Preparation Example of Polyoxane (a1-3)])

於具備攪拌機、溫度計、滴液漏斗、冷卻管及氮氣導入口之反應容器中，添加四乙氧基矽烷(TEOS)2288份、APTMS 58份，於通入氮氣下一面攪拌一面升溫至60℃。繼而，以5分鐘滴加包含Phoslex A-4 0.1份與脫離子水165份之混合物。於滴加結束後，將反應容器中升溫至80℃並攪拌4小時，藉此進行水解縮合反應，獲得反應產物。 In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and a nitrogen gas inlet, 2288 parts of tetraethoxy decane (TEOS) and 58 parts of APTMS were added, and the temperature was raised to 60 ° C while stirring under nitrogen. Then, a mixture containing 0.1 part of Phoslex A-4 and 165 parts of deionized water was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction vessel was heated to 80 ° C and stirred for 4 hours to carry out a hydrolysis condensation reaction to obtain a reaction product.

藉由將所獲得之反應產物中所含之甲醇及水於1~30千帕(kPa)之減壓下、於40~60℃之條件下去除，獲得數量平均分子量為1000且有效成分為70.0%之聚矽氧烷(a1-3)1000份。 By removing the methanol and water contained in the obtained reaction product under a reduced pressure of 1 to 30 kPa (kPa) at 40 to 60 ° C, the number average molecular weight is 1000 and the active ingredient is 70.0. 1000 parts of polyoxyalkylene (a1-3).

(合成例4[聚矽氧烷(a1-9)之製備例]) (Synthesis Example 4 [Preparation Example of Polyoxane (a1-9)])

於具備攪拌機、溫度計、滴液漏斗、冷卻管及氮氣導入口之反應容器中，添加MTMS 387份、3-甲基丙烯醯氧基丙基三甲氧基矽烷(MPTMS)706份，於通入氮氣下一面攪拌一面升溫至60℃。繼而，以5分鐘滴加包含Phoslex A-4 0.1份與脫離子水113份之混合物。於滴加結束後，將反應容器中升溫至80℃並攪拌4小時，藉此進行水解縮合反應，獲得反應產物。 387 parts of MTMS and 706 parts of 3-methylpropenyloxypropyltrimethoxydecane (MPTMS) were added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube and a nitrogen inlet, and nitrogen gas was introduced thereto. The temperature was raised to 60 ° C while stirring. Then, a mixture containing 0.1 parts of Phoslex A-4 and 113 parts of deionized water was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction vessel was heated to 80 ° C and stirred for 4 hours to carry out a hydrolysis condensation reaction to obtain a reaction product.

藉由將所獲得之反應產物中所含之甲醇及水於1~30千帕(kPa)之減壓下、於40~60℃之條件下去除，獲得數量平均分子量為1000且有效成分為70.0%之聚矽氧烷(a1-4)1000份。 By removing the methanol and water contained in the obtained reaction product under a reduced pressure of 1 to 30 kPa (kPa) at 40 to 60 ° C, the number average molecular weight is 1000 and the active ingredient is 70.0. 1000 parts of polyoxyalkylene (a1-4).

(合成例5[聚矽氧烷(a1-5)之製備例]) (Synthesis Example 5 [Preparation Example of Polyoxane (a1-5)])

於具備攪拌機、溫度計、滴液漏斗、冷卻管及氮氣導入口之反應容器中，添加苯基三甲氧基矽烷(PTMS)74.4份、DMDMS 180.4份、MTMS 593.0份、APTMS 351.8份，於通入氮氣下一面攪拌一面升溫至60℃。以5分鐘滴加包含Phoslex A-4 0.1份與脫離子水153.3份之混合物。於滴加結束後，將反應容器中升溫至80℃並攪拌4小時，藉此進行水解縮合反應，獲得反應產物。 74.4 parts of phenyltrimethoxydecane (PTMS), 180.4 parts of DMDMS, 593.0 parts of MTMS, 351.8 parts of APTMS were added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube and a nitrogen inlet. The temperature was raised to 60 ° C while stirring. A mixture containing 0.1 part of Phoslex A-4 and 153.3 parts of deionized water was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction vessel was heated to 80 ° C and stirred for 4 hours to carry out a hydrolysis condensation reaction to obtain a reaction product.

藉由將所獲得之反應產物中所含之甲醇及水於1~30千帕(kPa)之減壓下、於40~60℃之條件下去除，獲得數量平均分子量為1000且有效成分為70.0%之聚矽氧烷(a1-5)1000份。 By removing the methanol and water contained in the obtained reaction product under a reduced pressure of 1 to 30 kPa (kPa) at 40 to 60 ° C, the number average molecular weight is 1000 and the active ingredient is 70.0. 1000 parts of polyoxyalkylene (a1-5).

(合成例6[乙烯基系聚合物(a2-1)之製備例]) (Synthesis Example 6 [Preparation Example of Vinyl Polymer (a2-1)])

於與合成例1相同之反應容器中添加PTMS 60.3份、DMDMS 73.1份、甲基異丁基酮(MIBK)319.2份，於通入氮氣下一面攪拌一面升溫至95℃。繼而，將含有甲基丙烯酸甲酯(MMA)366.3份、甲基丙烯酸正丁酯(BMA)25.4份、丙烯酸(AA)4.5份、丙烯酸正丁酯(BA)4.5份、MPTS 27.0份、甲基丙烯酸2-羥基乙酯(HEMA)22.5份、MIBK 45.0份、過氧化-2-乙基己酸第三丁酯(TBPEH)90份之混合物於該溫度下在通入氮氣下一面攪拌一面向上述反應容器中滴加4小時。進而，於該溫度下攪拌2小時後，於上述反應容器中花費5分鐘滴加「A-4」0.17份與脫離子水38.4份之混合物，並於該溫度下攪拌5小時，藉此使PTMS、DMDMS、MPTS之水解縮合反應進行。利用1H-NMR對反應產物進行分析，結果上述反應容器中之矽烷單體所具有之三甲氧基矽烷基之約100%水解。繼而，藉由於該溫度下攪拌10小時，獲得TBPEH之殘留量為0.1%以下之反應產物即乙烯基系聚合物(a2-1)。 60.3 parts of PTMS, 73.1 parts of DMDMS, and 319.2 parts of methyl isobutyl ketone (MIBK) were added to the same reaction container as in Synthesis Example 1, and the temperature was raised to 95 ° C while stirring under nitrogen. Then, it will contain 366.3 parts of methyl methacrylate (MMA), 25.4 parts of n-butyl methacrylate (BMA), 4.5 parts of acrylic acid (AA), 4.5 parts of n-butyl acrylate (BA), 27.0 parts of MPTS, and methyl group. a mixture of 22.5 parts of 2-hydroxyethyl acrylate (HEMA), 45.0 parts of MIBK, and 90 parts of tert-butyl peroxy-2-ethylhexanoate (TBPEH) were stirred at this temperature under nitrogen gas. The reaction vessel was added dropwise for 4 hours. Further, after stirring at the temperature for 2 hours, a mixture of 0.17 parts of "A-4" and 38.4 parts of deionized water was added dropwise to the reaction vessel for 5 minutes, and stirred at the same temperature for 5 hours, thereby allowing PTMS. The hydrolysis condensation reaction of DMDMS and MPTS is carried out. The reaction product was analyzed by 1H-NMR, and as a result, about 100% of the trimethoxydecyl group of the decane monomer in the above reaction vessel was hydrolyzed. Then, by stirring at this temperature for 10 hours, a vinyl-based polymer (a2-1) which is a reaction product in which the residual amount of TBPEH is 0.1% or less is obtained.

(合成例7[乙烯基系聚合物(a2-2)之製備例]) (Synthesis Example 7 [Preparation Example of Vinyl Polymer (a2-2)])

於與合成例1相同之反應容器中，添加PTMS 60.3份、DMDMS 73.1份、甲基異丁基酮(MIBK)328.2份，於通入氮氣下一面攪拌一面升溫至95℃。繼而，將含有MMA 80.6份、BMA 9.5份、甲基丙烯酸環己酯(CHMA)225.0份、AA4.5份、BA 4.5份、MPTS 13.5份、HEMA 22.5份、MIBK 72.0份、TBPEH 36.0份之混合物於該溫度下在通入氮氣下一面攪拌一面向上述反應容器中滴加4小時。進而，於該溫度下攪拌2小時後，於上述反應容器中花費5分鐘滴加「A-4」0.17份與脫離子水38.4份之混合物，並於該溫度下攪拌5小時，藉此使PTMS、DMDMS、MPTS之水解縮合反應進行。利用1H-NMR對反應產物進行分析，結果上述反應容器中之矽烷單體所具有之三甲氧基矽烷基之約100%水解。繼而，藉由於該溫度下攪拌10小時，獲得TBPEH之殘留量為0.1%以下之反應產物即乙烯基系聚合物(a2-2)。 In the same reaction vessel as in Synthesis Example 1, 60.3 parts of PTMS and DMDMS were added. 73.1 parts of 328.2 parts of methyl isobutyl ketone (MIBK) were heated to 95 ° C while stirring under nitrogen. Then, it will contain 80.6 parts of MMA, 9.5 parts of BMA, 225.0 parts of cyclohexyl methacrylate (CHMA), 4.5 parts of AA, 4.5 parts of BA, 13.5 parts of MPTS, 22.5 parts of HEMA, 72.0 parts of MIBK, and 36.0 parts of TBPEH. At this temperature, while stirring with nitrogen, the mixture was stirred for 4 hours in the above reaction vessel. Further, after stirring at the temperature for 2 hours, a mixture of 0.17 parts of "A-4" and 38.4 parts of deionized water was added dropwise to the reaction vessel for 5 minutes, and stirred at the same temperature for 5 hours, thereby allowing PTMS. The hydrolysis condensation reaction of DMDMS and MPTS is carried out. The reaction product was analyzed by 1H-NMR, and as a result, about 100% of the trimethoxydecyl group of the decane monomer in the above reaction vessel was hydrolyzed. Then, by stirring at this temperature for 10 hours, a vinyl-based polymer (a2-2) which is a reaction product in which the residual amount of TBPEH is 0.1% or less is obtained.

(合成例8[複合樹脂(A-1)之製備例]) (Synthesis Example 8 [Preparation Example of Composite Resin (A-1)])

於與合成例1相同之反應容器中，於上述合成例2中所獲得之乙烯基系聚合物(a2-1)216.4份中添加合成例1中所獲得之聚矽氧烷(a1-1)275.9份，於攪拌5分鐘後添加脫離子水31.2份，於75℃下進行2小時攪拌，進行上述反應產物與聚矽氧烷之水解縮合反應。藉由將所獲得之反應產物於10~300kPa之減壓下、於40~60℃之條件下蒸餾2小時，去除所生成之甲醇及水，繼而添加MIBK 226.4份，獲得具有不揮發成分為50.3%之聚矽氧烷片段(a1-1)與乙烯基系聚合物片段(a2-1)之複合樹脂(A-1)600份。 Into the 216.4 parts of the vinyl polymer (a2-1) obtained in the above Synthesis Example 2, the polyoxoxane (a1-1) obtained in Synthesis Example 1 was added to the same reaction vessel as in Synthesis Example 1. 275.9 parts, after stirring for 5 minutes, 31.2 parts of deionized water was added, and it stirred at 75 degreeC for 2 hours, and the hydrolytic-condensation reaction of the above reaction product and poly The obtained reaction product was distilled under a reduced pressure of 10 to 300 kPa at 40 to 60 ° C for 2 hours to remove the methanol and water formed, and then 226.4 parts of MIBK was added to obtain a nonvolatile content of 50.3. 600 parts of a composite resin (A-1) of a polyoxyalkylene fragment (a1-1) and a vinyl polymer fragment (a2-1).

(合成例9[複合樹脂(A-2)之製備例]) (Synthesis Example 9 [Preparation Example of Composite Resin (A-2)])

於與合成例1相同之反應容器中，於上述合成例2中所獲得之乙烯基系聚合物(a2-1)72.1份添加合成例2中所獲得之聚矽氧烷(a1-2)377.7份，於攪拌5分鐘後添加脫離子水69.4份，於75℃下進行2小時攪拌，進行上述反應產物與聚矽氧烷之水解縮合反應。藉由將所獲得之反應產物於10~300kPa之減壓下、於40~60℃之條件下蒸餾2小 時，去除所生成之甲醇及水，繼而添加MIBK 275.5份，獲得具有不揮發成分為50.1%之聚矽氧烷片段(a1-2)與乙烯基系聚合物片段(a2-1)之複合樹脂(A-2)600份。 In the same reaction vessel as in Synthesis Example 1, 72.1 parts of the vinyl polymer (a2-1) obtained in the above Synthesis Example 2 was added to the polyoxane (a1-2) 377.7 obtained in Synthesis Example 2. After stirring for 5 minutes, 69.4 parts of deionized water was added, and the mixture was stirred at 75 ° C for 2 hours to carry out a hydrolysis condensation reaction of the above reaction product with polyoxyalkylene. By distilling the obtained reaction product under a reduced pressure of 10 to 300 kPa at a temperature of 40 to 60 ° C for 2 hours. At the same time, the methanol and water formed were removed, and then 275.5 parts of MIBK was added to obtain a composite resin having a polyoxonane fragment (a1-2) having a nonvolatile content of 50.1% and a vinyl polymer fragment (a2-1). (A-2) 600 parts.

(合成例10[複合樹脂(A-3)之製備例]) (Synthesis Example 10 [Preparation Example of Composite Resin (A-3)])

於與合成例1相同之反應容器中，於上述合成例2中所獲得之乙烯基系聚合物(a2-1)36.1份中添加合成例3中所獲得之聚矽氧烷(a1-3)403.1份，於攪拌5分鐘後，添加脫離子水189.0份，於75℃下進行2小時攪拌，進行上述反應產物與聚矽氧烷之水解縮合反應。藉由將所獲得之反應產物於10~300kPa之減壓下、於40~60℃之條件下蒸餾2小時，去除生成之甲醇及水，繼而添加MIBK 287.7份，獲得具有不揮發成分為50.4%之聚矽氧烷片段(a1-3)與乙烯基系聚合物片段(a2-1)之複合樹脂(A-3)600份。 Into the same reaction vessel as in Synthesis Example 1, the polyoxoxane (a1-3) obtained in Synthesis Example 3 was added to 36.1 parts of the vinyl polymer (a2-1) obtained in the above Synthesis Example 2. After 40 minutes of stirring, 189.0 parts of deionized water was added, and the mixture was stirred at 75 ° C for 2 hours to carry out a hydrolysis condensation reaction of the above reaction product with polyoxymethane. The obtained reaction product is distilled under a reduced pressure of 10 to 300 kPa at 40 to 60 ° C for 2 hours to remove the formed methanol and water, and then 287.7 parts of MIBK is added to obtain a nonvolatile content of 50.4%. 600 parts of the composite resin (A-3) of the polyoxyalkylene fragment (a1-3) and the vinyl polymer fragment (a2-1).

(合成例11[複合樹脂(A-4)之製備例]) (Synthesis Example 11 [Preparation Example of Composite Resin (A-4)])

於與合成例1相同之反應容器中，於上述合成例2中所獲得之乙烯基系聚合物(a2-2)36.7份中添加合成例4中所獲得之聚矽氧烷(a1-4)174.1份，於攪拌5分鐘後，添加脫離子水17.7份，於75℃下進行2小時攪拌，進行上述反應產物與聚矽氧烷之水解縮合反應。藉由將所獲得之反應產物於10~300kPa之減壓下、於40~60℃之條件下蒸餾2小時，去除所生成之甲醇及水，繼而添加MIBK 177.3份，獲得具有不揮發成分為50.0%之聚矽氧烷片段(a1-4)與乙烯基系聚合物片段(a2-2)之複合樹脂(A-4)600份。 In the same reaction vessel as in Synthesis Example 1, the polyaluminoxane (a1-4) obtained in Synthesis Example 4 was added to 36.7 parts of the vinyl polymer (a2-2) obtained in the above Synthesis Example 2. After 17 minutes of stirring, 17.7 parts of deionized water was added, and the mixture was stirred at 75 ° C for 2 hours to carry out a hydrolysis condensation reaction of the above reaction product with polyoxyalkylene. The obtained reaction product is distilled under a reduced pressure of 10 to 300 kPa at 40 to 60 ° C for 2 hours to remove the formed methanol and water, and then 177.4 parts of MIBK is added to obtain a nonvolatile content of 50.0. 600 parts of a composite resin (A-4) of a polyoxyalkylene fragment (a1-4) and a vinyl polymer fragment (a2-2).

(合成例12[複合樹脂(A-5)之製備例]) (Synthesis Example 12 [Preparation Example of Composite Resin (A-5)])

於與合成例1相同之反應容器中，添加PTMS 2.0份、DMDMS 73.1份、MIBK 79.0份、MTMS 103.7份、MMA 14.1份、MPTS 0.9份、TBPEH 3份，於通入氮氣下一面攪拌一面花費2小時自75℃升溫至95℃。繼而，添加TBPEH 0.75份、MIBK 0.38份，於該溫度下攪拌 6小時後，添加APTS 62.8份、DMDMS 62.1份，於降溫至75℃後，添加「A-4」0.17份、水65.0份，於75℃下攪拌2小時，進行水解及聚縮合反應。藉由將所獲得之反應產物於10~300kPa之減壓下、於40~60℃之條件下蒸餾2小時，獲得不揮發成分為50.5%之(A-5)330份。 In the same reaction vessel as in Synthesis Example 1, 2.0 parts of PTMS, 73.1 parts of DMDMS, 79.0 parts of MIBK, 103.7 parts of MTMS, 14.1 parts of MMA, 0.9 parts of MPTS, and 3 parts of TBPEH were added, and the mixture was stirred while being purged with nitrogen. The temperature was raised from 75 ° C to 95 ° C. Then, add 0.75 parts of TBPEH and 0.38 parts of MIBK, and stir at this temperature. After 6 hours, 62.8 parts of APTS and 62.1 parts of DMDMS were added, and after cooling to 75 ° C, 0.17 parts of "A-4" and 65.0 parts of water were added, and the mixture was stirred at 75 ° C for 2 hours to carry out hydrolysis and polycondensation reaction. By subjecting the obtained reaction product to distillation under the reduced pressure of 10 to 300 kPa at 40 to 60 ° C for 2 hours, 330 parts of (A-5) having a nonvolatile content of 50.5% was obtained.

(比較合成例1) (Comparative Synthesis Example 1)

於安裝有溫度計及冷卻管之三口燒瓶中，添加1,3,5,7-四甲基環四矽氧烷2.0g(8.3mmol)、3,4-環氧環己烷羧酸烯丙酯6.4g(34.9mmol，以Si-H為基準計為1.05倍)及甲苯50g，於Ar氣流下於室溫下進行攪拌。於其中分4次逐一少量地添加2%二乙烯基四甲基二矽氧烷鉑錯合物之二甲苯溶液0.82g(鉑金屬之重量為原料添加之1000ppm)。於在室溫下攪拌2小時後，於減壓下將甲苯溶劑蒸餾去除。將包含所獲得之反應物之殘留量以固形物成分濃度成為5%之方式溶解於丙二醇單甲基乙酸酯中(相對樹脂-1)。 To a three-necked flask equipped with a thermometer and a cooling tube, 2.0 g (8.3 mmol) of 1,3,5,7-tetramethylcyclotetraoxane and allyl 3,4-epoxycyclohexanecarboxylate were added. 6.4 g (34.9 mmol, 1.05 times based on Si-H) and 50 g of toluene were stirred at room temperature under an Ar gas flow. 0.82 g of a xylene solution of 2% divinyltetramethyldioxane platinum complex was added in a small amount in 4 portions (the weight of the platinum metal was 1000 ppm of the raw material added). After stirring at room temperature for 2 hours, the toluene solvent was distilled off under reduced pressure. The residual amount of the obtained reactant was dissolved in propylene glycol monomethyl acetate (relative resin-1) so that the solid content concentration became 5%.

<有機下層膜用聚合物X-1之合成例> <Synthesis Example of Polymer X-1 for Organic Underlayer Film>

於安裝有溫度計、冷卻管、分餾管、攪拌器之燒瓶中，添加甲酚(75%間甲酚/25%對甲酚)108g(1.0莫耳)、丙二醇單甲醚乙酸酯200g及92%多聚甲醛29.3g(0.9莫耳)。繼而，一面攪拌一面添加草酸1.5g。其後，一面攪拌一面升溫至120℃，反應5小時，獲得酚系樹脂(具有源自甲酚之骨架之酚醛清漆樹脂)X-1 120g。所獲得之聚合物X-1之Mw為7,000。 Add cresol (75% m-cresol/25% p-cresol) 108 g (1.0 mol), propylene glycol monomethyl ether acetate 200 g and 92 to a flask equipped with a thermometer, a cooling tube, a fractionation tube, and a stirrer. % paraformaldehyde 29.3 g (0.9 m). Then, 1.5 g of oxalic acid was added while stirring. Then, the temperature was raised to 120 ° C while stirring, and the reaction was carried out for 5 hours to obtain 120-1 of a phenol resin (a novolak resin having a skeleton derived from cresol) X-1. The Mw of the obtained polymer X-1 was 7,000.

<有機下層膜形成用組合物Y-1之製備> <Preparation of Composition Y-1 for Organic Underlayer Film Formation>

將聚合物(X-1)10質量份、作為熱酸產生劑之二苯基錪三氟甲烷磺酸酯0.3質量份及作為交聯劑之1,3,4,6-四(甲氧基甲基)甘脲1質量份溶解於作為溶劑之丙二醇單甲醚乙酸酯90質量份中。利用孔徑0.1μm之薄膜過濾器(membrane filter)將該溶液進行過濾，製備有機下層膜形成用組合物Y-1。 10 parts by mass of the polymer (X-1), 0.3 parts by mass of diphenylsulfonium trifluoromethanesulfonate as a thermal acid generator, and 1,3,4,6-tetra(methoxy) as a crosslinking agent 1 part by mass of methyl) glycoluril was dissolved in 90 parts by mass of propylene glycol monomethyl ether acetate as a solvent. This solution was filtered through a membrane filter having a pore size of 0.1 μm to prepare an organic underlayer film-forming composition Y-1.

<有機下層膜形成用組合物Y-2之製備> <Preparation of Composition Y-2 for Forming Organic Underlayer Film>

將聚(4-乙烯基苯酚)(SIGMA-ALDRICH公司製造，Mw 11,000)10質量份、作為熱酸產生劑之二苯基錪三氟甲烷磺酸酯0.3質量份及作為交聯劑之1,3,4,6-四(甲氧基甲基)甘脲1質量份溶解於作為溶劑之丙二醇單甲醚乙酸酯90質量份中。利用孔徑0.1μm之薄膜過濾器將該溶液進行過濾，製備有機下層膜形成用組合物Y-2。 10 parts by mass of poly(4-vinylphenol) (manufactured by SIGMA-ALDRICH, Mw 11,000), 0.3 parts by mass of diphenylsulfonium trifluoromethanesulfonate as a thermal acid generator, and 1 as a crosslinking agent. 1 part by mass of 3,4,6-tetrakis(methoxymethyl)glycolil was dissolved in 90 parts by mass of propylene glycol monomethyl ether acetate as a solvent. This solution was filtered through a membrane filter having a pore size of 0.1 μm to prepare a composition Y-2 for forming an organic underlayer film.

(基材1之製作例) (Production Example of Substrate 1)

於以旋塗將所製備之有機下層膜形成用組合物Y-1塗佈於直徑4英吋之矽晶圓上後，利用加熱板於180℃下加熱60秒鐘，繼而於300℃下加熱60秒鐘，製作表面具有膜厚0.1μm之有機下層膜之基材1。 The prepared organic underlayer film forming composition Y-1 was applied onto a 4 inch diameter silicon wafer by spin coating, and then heated at 180 ° C for 60 seconds using a hot plate, followed by heating at 300 ° C. The substrate 1 having an organic underlayer film having a film thickness of 0.1 μm was produced for 60 seconds.

(基材2之製作例) (Production Example of Substrate 2)

以與基材1之製作方法相同之方法將有機下層膜形成用組合物Y-2塗佈於矽晶圓上並使其硬化，藉此獲得表面具有膜厚0.1μm之有機下層膜之基材2。 The organic underlayer film forming composition Y-2 was applied onto a tantalum wafer and hardened in the same manner as in the method of producing the substrate 1, whereby a substrate having an organic underlayer film having a film thickness of 0.1 μm was obtained. 2.

(實施例1) (Example 1) (抗蝕劑材料1之製備例) (Preparation Example of Resist Material 1)

將合成例8中所獲得之複合樹脂(A-1)20份、IRGACURE 907[光聚合起始劑BASF製造]0.2份進行混合，獲得抗蝕劑材料1。 20 parts of the composite resin (A-1) obtained in Synthesis Example 8 and 0.2 parts of IRGACURE 907 [manufactured by Photopolymerization Starter BASF] were mixed to obtain a resist material 1.

(平板積層體1-1之製作) (production of flat laminate 1-1)

使用MIBK將上述抗蝕劑材料1進行稀釋，以膜厚成為300nm之方式旋塗塗佈於基材1上，於氮氣環境下使用峰值波長375±5nm之LED光源以500mJ/cm2之條件進行曝光使其光硬化，形成抗蝕劑膜1，藉此獲得具有抗蝕劑膜之平板積層體1-1。 The above-mentioned resist material 1 was diluted with MIBK, spin-coated on the substrate 1 so as to have a film thickness of 300 nm, and subjected to a condition of 500 mJ/cm 2 using an LED light source having a peak wavelength of 375 ± 5 nm under a nitrogen atmosphere. Exposure exposes the light to form a resist film 1, whereby a flat laminated body 1-1 having a resist film is obtained.

(平板積層體1-2之製作) (Production of flat laminate 1-2)

使用與平板積層體1-1相同之方法於基材2上積層抗蝕劑材料1並使其光硬化，形成抗蝕劑膜1，藉此獲得具有抗蝕劑膜之平板積層體 1-2。 The resist material 1 is laminated on the substrate 2 by the same method as that of the flat laminated body 1-1 and photohardened to form a resist film 1, whereby a flat laminated body having a resist film is obtained. 1-2.

(具有圖案形狀之積層體1-1之製作) (Production of laminated body 1-1 having a pattern shape)

使用MIBK將抗蝕劑材料1進行稀釋，以膜厚成為100nm之方式旋塗塗佈於基材1上，獲得積層體。繼而，於SCIVAX公司製造之奈米壓印裝置X300之下表面載台設置上述積層體，將具有100nm之線/空間圖案且槽深度為100nm之以環烯烴聚合物(日本ZEON股份有限公司，ZEONOR ZF-14)為材質之模型設置於上述裝置之上表面載台。於將裝置內設為真空後，於室溫下以1.5氣壓之壓力使模型壓接於基板，對其自模型之背面使用峰值波長375±5nm之LED光源以500mJ/cm2之條件進行曝光，將模型剝離，藉此形成具有圖案形狀之抗蝕劑膜1，獲得具有圖案形狀之積層體1-1。 The resist material 1 was diluted with MIBK, and spin-coated on the substrate 1 so as to have a film thickness of 100 nm to obtain a laminate. Then, the above-mentioned laminated body was placed under the surface of the nanoimprinting apparatus X300 manufactured by SCIVAX, and a cycloolefin polymer having a line/space pattern of 100 nm and a groove depth of 100 nm (ZEONOR, Japan) ZF-14) is a material model set on the surface carrier of the above device. After the inside of the apparatus was vacuumed, the mold was pressure-bonded to the substrate at a pressure of 1.5 atm at room temperature, and exposed to the back surface of the model using an LED light source having a peak wavelength of 375±5 nm at 500 mJ/cm 2 . The mold is peeled off, whereby a resist film 1 having a pattern shape is formed, and a laminated body 1-1 having a pattern shape is obtained.

(具有圖案形狀之積層體1-2之製作) (Production of laminated body 1-2 having a pattern shape)

使用與具有圖案形狀之積層體1-1之情形相同之方法，於基材2上形成具有圖案形狀之抗蝕劑膜1，製作具有圖案形狀之積層體1-2。 A resist film 1 having a pattern shape is formed on the substrate 2 by the same method as in the case of the laminated body 1-1 having a pattern shape, and a laminated body 1-2 having a pattern shape is produced.

(評價) (Evaluation)

對所獲得之抗蝕劑膜及積層體進行如下評價，將結果示於第1表。 The obtained resist film and laminate were evaluated as follows, and the results are shown in Table 1.

(對基材之密接性評價) (Evaluation of the adhesion of the substrate)

針對平板積層體1-1及平板積層體1-2，基於JIS K-5400評價抗蝕劑膜1對基材(有機下層膜)之密接性。即，於抗蝕劑膜以貫通至基材(有機下層膜)之方式形成直角格子圖案(100塊)，於格子圖案貼附黏著帶(NICHIBAN公司製造之Sellotape(註冊商標)，寬度18mm)。於附著黏著帶後1~2分鐘後，手持黏著帶之一端呈直角地保持於抗蝕劑膜面，進行剝離。根據100塊中未剝離而殘留之棋盤方格(剩餘塊數)之數量評價密接性。將剩餘塊數為95以上者設為◎，將90以上且未達95者設為○，將80以上且未達90者設為△，將未達80者設為×。 The adhesion between the resist film 1 and the substrate (organic underlayer film) was evaluated based on JIS K-5400 with respect to the flat laminate 1-1 and the flat laminate 1-2. In other words, a rectangular lattice pattern (100 pieces) was formed so as to penetrate the base film (organic lower layer film), and an adhesive tape (Sellotape (registered trademark) manufactured by NIKIBAN Co., Ltd., width: 18 mm) was attached to the lattice pattern. One to two minutes after the adhesion of the adhesive tape, one end of the hand-held adhesive tape was held at a right angle on the surface of the resist film to be peeled off. The adhesion was evaluated based on the number of checkerboard squares (the number of remaining blocks) remaining in 100 pieces without being peeled off. The number of remaining blocks is 95 or more, ◎, 90 or more and less than 95 are set to ○, 80 or more and less than 90 are set to Δ, and less than 80 is set to ×.

(圖案形成性評價) (pattern formation evaluation)

於具有圖案形狀之積層體1-1及具有圖案形狀之積層體1-2中，藉由掃描型電子顯微鏡對具有圖案形狀之抗蝕劑膜1之線圖案剖面之形狀進行觀察，評價圖案形成性。將無圖案缺損者設為◎，將圖案破裂、或於與下層膜之界面發生剝離者設為×。 In the laminated body 1-1 having the pattern shape and the laminated body 1-2 having the pattern shape, the shape of the line pattern cross section of the resist film 1 having the pattern shape was observed by a scanning electron microscope, and the pattern formation was evaluated. Sex. The pattern-free defect was set to ◎, and the pattern was broken or the peeling occurred at the interface with the underlayer film was set to ×.

(耐乾式蝕刻性評價-1) (dry etch resistance evaluation-1)

使用SAMCO股份有限公司製造之乾式蝕刻器(dry etcher)RIE-101iPH對平板積層體1-1供給O2/N2=10/10(sccm)之混合氣體，於0.1Pa之真空下進行180秒鐘氧電漿蝕刻後測定硬化膜之殘留膜厚，算出每1秒鐘之蝕刻速度。將所獲得之蝕刻速度以下述比較例-3之值成為1之方式標準化。標準值越小，表示耐乾式蝕刻性越優異，以如下方式進行評價。 The flat laminated body 1-1 was supplied with a mixed gas of O 2 /N 2 = 10/10 (sccm) using a dry etcher RIE-101iPH manufactured by SAMCO Co., Ltd., and subjected to a vacuum of 0.1 Pa for 180 seconds. After the galvanic plasma etching, the residual film thickness of the cured film was measured, and the etching rate per one second was calculated. The etching rate obtained was normalized so that the value of the following Comparative Example-3 became 1. The smaller the standard value, the more excellent the dry etching resistance, and the evaluation was as follows.

◎：標準化後之蝕刻速度為0以上且未達0.5 ◎: The etching rate after standardization is 0 or more and less than 0.5

○：標準化後之蝕刻速度為0.5以上且未達1 ○: The etching rate after standardization is 0.5 or more and less than 1

×：標準化後之蝕刻速度為1以上 ×: The etching rate after standardization is 1 or more

(耐乾式蝕刻性評價-2) (dry etch resistance evaluation -2)

使用混合氣體O2/He=10/5(sccm)代替混合氣體O2/N2=10/10(sccm)，除此以外，以與<耐乾式蝕刻性評價-1>相同之方法進行評價。 Evaluation was performed in the same manner as <dry etching resistance evaluation-1> except that the mixed gas O 2 /He=10/5 (sccm) was used instead of the mixed gas O 2 /N 2 = 10/10 (sccm). .

(耐乾式蝕刻性評價-3) (dry etch resistance evaluation -3)

使用混合氣體O2/CF4=20/5(sccm)代替混合氣體O2/N2=10/10(sccm)，除此以外，以與<耐乾式蝕刻性評價-1>相同之方法進行評價。 In the same manner as <dry etching resistance evaluation-1>, a mixed gas O 2 /CF 4 = 20/5 (sccm) was used instead of the mixed gas O 2 /N 2 = 10/10 (sccm). Evaluation.

(耐乾式蝕刻性評價-4) (dry etch resistance evaluation -4)

使用混合氣體O2/N2=10/5(sccm)代替混合氣體O2/N2=10/10(sccm)，除此以外，以與<耐乾式蝕刻性評價-1>相同之方法進 行評價。 The mixed gas O 2 /N 2 =10/5 (sccm) was used instead of the mixed gas O 2 /N 2 = 10/10 (sccm), except for the same method as <dry etching resistance evaluation-1>. Evaluation.

(實施例2~8及比較例1~5) (Examples 2 to 8 and Comparative Examples 1 to 5)

基於第1表所示之調配，以與實施例1相同之方法製備抗蝕劑材料2~8及比較抗蝕劑材料1~5，以與實施例1相同之方式分別製作抗蝕劑膜及各積層體。將對各積層體之評價結果匯總於表1~3。 Resist materials 2 to 8 and comparative resist materials 1 to 5 were prepared in the same manner as in Example 1 based on the formulation shown in Table 1, and resist films were respectively formed in the same manner as in Example 1. Each laminate. The evaluation results of the respective laminates are summarized in Tables 1 to 3.

關於表1~2之縮略語 Abbreviations for Tables 1~2 數字 digital

(a1)係聚矽氧烷片段(a1)之簡稱。 (a1) is an abbreviation for the polyoxyalkylene fragment (a1).

※1 Si相對於硬化性樹脂組合物之總固形物成分量之含有率(%)。 *1 The content (%) of Si relative to the total solid content of the curable resin composition.

※2聚矽氧烷片段(a1)相對於複合樹脂(A)之總固形物成分量之含有率。 * The content ratio of the polyoxyalkylene fragment (a1) to the total solid content of the composite resin (A).

HSQ：氫倍半矽氧烷之簡稱。 HSQ: Abbreviation for hydrogen sesquioxane.

TMPTA：三羥甲基丙烷三丙烯酸酯之簡稱。 TMPTA: Abbreviation for trimethylolpropane triacrylate.

KBM-5103：信越化學股份有限公司製造之單體。 KBM-5103: Monomer manufactured by Shin-Etsu Chemical Co., Ltd.

Irg-907：BASF製造之光聚合起始劑。 Irg-907: Photopolymerization initiator manufactured by BASF.

TPSHA：三苯基鋶六氟銻酸酯之簡稱。 TPSHA: Abbreviation for triphenylsulfonium hexafluoroantimonate.

其結果為，關於實施例1~8中評價之使用抗蝕劑材料1~8之抗蝕劑膜，任一者之對有機下層膜之密接性、圖案形成性、及耐氧電漿蝕刻性均優異。 As a result, the resist films using the resist materials 1 to 8 evaluated in Examples 1 to 8 were excellent in adhesion to the organic underlayer film, pattern formation property, and oxygen plasma etching resistance. Both are excellent.

比較例1~3中獲得之抗蝕劑膜之耐氧電漿蝕刻性不充分，另一方面，比較例4~5中所獲得之抗蝕劑膜之對基材之密接性及圖案形成性較差。 The resist films obtained in Comparative Examples 1 to 3 were insufficient in oxygen etching resistance, and on the other hand, the adhesion of the resist film obtained in Comparative Examples 4 to 5 to the substrate and the pattern formation property. Poor.

[產業上之可利用性] [Industrial availability]

本發明之使用硬化性組合物之抗蝕劑膜不僅可用於使用多層抗蝕劑製程之半導體用途，而且亦可用於各種應用，例如光罩加工、奈米/微光學要素、光學元件、顯示元件、電子紙、儲存器、MEMS(Microelectromechanical System，微機電系統)/PCB(Printed Circuit Board，印刷電路板)安裝材料、以微量生化學分析或微量化學合成、生物學應用為目的之高功能三維奈米/微流路、下一代電子元件、DNA(Deoxyribonucleic Acid，去氧核糖核酸)晶片等。 The resist film using the curable composition of the present invention can be used not only for semiconductor applications using a multilayer resist process, but also for various applications such as mask processing, nano/micro-optical elements, optical elements, display elements. , electronic paper, storage, MEMS (Microelectromechanical System) / PCB (Printed Circuit Board) mounting materials, high-performance three-dimensional naphthalate for micro-chemical analysis or micro-chemical synthesis, biological applications Meter/micro flow path, next-generation electronic components, DNA (Deoxyribonucleic Acid) wafers, etc.

Claims (7)

一種氧電漿蝕刻用抗蝕劑材料，其特徵在於：其係含有複合樹脂(A)之乾式蝕刻用抗蝕劑材料，該複合樹脂(A)係具有通式(1)及/或通式(2)所表示之結構單元和矽烷醇基及/或水解性矽烷基之聚矽氧烷片段(a1)、與乙烯基系聚合物片段(a2)藉由通式(3)所表示之鍵進行鍵結而成，且該氧電漿蝕刻用抗蝕劑材料之總固形物成分量中矽原子之含量為15~45wt%， (通式(1)及(2)中，R1、R2及R3分別獨立地表示具有選自由-R4-CH=CH2、-R4-C(CH3)=CH2、-R4-O-CO-C(CH3)=CH2、及-R4-O-CO-CH=CH2所組成之群中之1個聚合性雙鍵之基(其中，R4表示單鍵、芳基或碳原子數1~6之伸烷基)、碳原子數為1~6之烷 基、碳原子數為3~8之環烷基、芳基、或碳原子數為7~12之芳烷基，R1、R2及R3中之至少一者為具有聚合性雙鍵之基) (通式(3)中，設為碳原子構成上述乙烯基系聚合物片段(a2)之一部分，僅鍵結於氧原子之矽原子構成上述聚矽氧烷片段(a1)之一部分)。 A resist material for oxygen plasma etching, characterized in that it comprises a resist material for dry etching of a composite resin (A) having a general formula (1) and/or a general formula (2) a structural unit and a polyoxyalkylene fragment (a1) of a decyl alcohol group and/or a hydrolyzable decyl group, and a bond represented by the formula (3) with a vinyl polymer fragment (a2) Bonding is performed, and the content of the total solid content of the resist material for the oxygen plasma etching is 15 to 45 wt%, (In the general formulae (1) and (2), R 1 , R 2 and R 3 each independently represent a group selected from -R 4 -CH=CH 2 , -R 4 -C(CH 3 )=CH 2 ,- a group of one polymerizable double bond in the group consisting of R 4 —O—CO—C(CH 3 )=CH 2 and —R 4 —O—CO—CH=CH 2 (wherein R 4 represents a single a bond, an aryl group or an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or a carbon number of 7~ a 12-aralkyl group, at least one of R 1 , R 2 and R 3 being a group having a polymerizable double bond) (In the formula (3), it is assumed that a carbon atom constitutes a part of the vinyl polymer segment (a2), and only a germanium atom bonded to an oxygen atom constitutes a part of the polyaluminoxane fragment (a1). 如請求項1之氧電漿蝕刻用抗蝕劑材料，其中上述聚矽氧烷片段(a1)之比率於上述複合樹脂(A)中為70~95wt%。 The resist material for oxygen plasma etching according to claim 1, wherein the ratio of the polyoxyalkylene fragment (a1) is 70 to 95% by weight in the above composite resin (A). 一種抗蝕劑膜，其特徵在於：其係將如請求項1或2之該氧電漿蝕刻用抗蝕劑材料紫外線硬化而成。 A resist film obtained by ultraviolet curing a resist material for oxygen plasma etching according to claim 1 or 2. 如請求項3之抗蝕劑膜，其形成有圖案。 The resist film of claim 3, which is formed with a pattern. 如請求項4之抗蝕劑膜，其藉由奈米壓印而形成有圖案。 The resist film of claim 4, which is patterned by nanoimprinting. 一種積層體，其特徵在於：於基材積層有如請求項3至5中任一項之抗蝕劑膜。 A laminate comprising a resist film according to any one of claims 3 to 5 laminated on a substrate. 如請求項6之積層體，其中上述基材為有機材料。 The laminate according to claim 6, wherein the substrate is an organic material.
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