TWI651365B - Composition, laminate for bottom material, laminate, method of manufacturing semiconductor device, and semiconductor device - Google Patents

Composition, laminate for bottom material, laminate, method of manufacturing semiconductor device, and semiconductor device Download PDF

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Publication number
TWI651365B
TWI651365B TW104108889A TW104108889A TWI651365B TW I651365 B TWI651365 B TW I651365B TW 104108889 A TW104108889 A TW 104108889A TW 104108889 A TW104108889 A TW 104108889A TW I651365 B TWI651365 B TW I651365B
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Taiwan
Prior art keywords
composition
meth
laminate
acrylate
general formula
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Application number
TW104108889A
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Chinese (zh)
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TW201602227A (en
Inventor
小山一郎
吉田健太
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日商富士軟片股份有限公司
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Publication of TW201602227A publication Critical patent/TW201602227A/en
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Publication of TWI651365B publication Critical patent/TWI651365B/en

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    • H—ELECTRICITY
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    • H01L23/00—Details of semiconductor or other solid state devices
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    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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Abstract

提供可以形成保存穩定性、塗布性及硬化性優異、吸水性低、耐熱性優異的膜的組成物、底部填料用積層體、使用此等的積層體、半導體裝置之製造方法、及半導體裝置。 Provided are a composition capable of forming a film excellent in storage stability, coatability and curability, low water absorption, and excellent heat resistance, a laminate for underfill, a laminate using these, a method for manufacturing a semiconductor device, and a semiconductor device.

此組成物含有聚碳酸酯樹脂、聚合性化合物、和溶劑，在組成物中含有50質量%以上的溶劑，溶劑當中50質量%以上係沸點為130℃以上、分子量為75以上的非質子性溶劑。聚碳酸酯樹脂較佳為具有通式(1)所表示的重複單元。通式(1)中，Ar1及Ar2各自獨立地表示芳香族基，L表示單鍵或2價的連結基。 This composition contains a polycarbonate resin, a polymerizable compound, and a solvent. The composition contains 50% by mass or more of the solvent. Among the solvents, 50% by mass or more is an aprotic solvent having a boiling point of 130 ° C. or more and a molecular weight of 75 or more. . The polycarbonate resin preferably has a repeating unit represented by the general formula (1). In the general formula (1), Ar 1 and Ar 2 each independently represent an aromatic group, and L represents a single bond or a divalent linking group.

Description

組成物、底部填料用積層體、積層體、半導體裝置之製造方法、及半導體裝置 Composition, laminate for underfill, laminate, method for manufacturing semiconductor device, and semiconductor device

本發明係關於組成物、底部填料用積層體、積層體、半導體裝置之製造方法、及半導體裝置。 The present invention relates to a composition, a laminate for underfill, a laminate, a method for manufacturing a semiconductor device, and a semiconductor device.

於半導體裝置的製造中，在半導體元件彼此的接合、或半導體元件和半導體晶圓的連接之際使用底部填料。 In the manufacture of semiconductor devices, an underfill is used when bonding semiconductor elements or connecting semiconductor elements and semiconductor wafers.

此外，隨著電子機器之更小型化及高性能化的需求，對電子機器所搭載的IC晶片亦要求更小型化及高積體化。 In addition, with the demand for more miniaturization and higher performance of electronic equipment, the IC chip mounted on the electronic equipment is also required to be smaller and more integrated.

為此，在2.5維安裝裝置(mounting device)、或3維安裝裝置中，要求縮短半導體元件上的電極節距(electrode pitch)、及晶片間距離。 For this reason, in the 2.5-dimensional mounting device or the 3-dimensional mounting device, it is required to shorten the electrode pitch on the semiconductor element and the distance between the wafers.

作為利用底部填料的封裝方法，過去以來，係進行在接合半導體元件上的電極後，由半導體元件彼此的間隙填充底部填料以封裝半導體元件間(以下，也稱為後處理底部填料封裝方法)。 As an encapsulation method using an underfill, in the past, after bonding electrodes on a semiconductor element, the underfill was filled with a gap between the semiconductor elements to encapsulate the semiconductor elements (hereinafter, also referred to as post-processing underfill encapsulation method).

然而，後處理底部填料封裝方法的情況，隨著電極節距的細微化、或縮短半導體元件彼此的晶片間距離，有底部填料的填充變困難的傾向，有接合的可靠性降低之虞。 However, in the case of the post-processing underfill encapsulation method, as the electrode pitch becomes finer or the distance between the wafers of the semiconductor elements is shortened, filling of the underfill tends to be difficult, and the reliability of bonding may decrease.

此外，已知有在連接半導體元件彼此的電極之前，在一方半導體元件的表面供給底部填料，壓接另一方的半導體元件以接合電極，並且進行利用底部填料的接著的技術(以下，也稱為預處理底部填料封裝方法)。 In addition, prior to connecting electrodes of semiconductor elements, an underfill is supplied on the surface of one semiconductor element, the other semiconductor element is crimped to bond the electrodes, and a technique of performing an underfill using the underfill (hereinafter, also referred to as Pretreatment underfill encapsulation method).

此時，電極上的底部填料在壓接時被擠出到周圍，藉由利用圖案曝光、顯影步驟來只將電極上的底部填料拿掉來確保半導體元件的電極間的導通。 At this time, the underfill on the electrode is squeezed out to the surroundings during crimping. By using pattern exposure and development steps, only the underfill on the electrode is removed to ensure continuity between the electrodes of the semiconductor element.

作為預處理底部填料封裝方法使用的底部填料，例如，已知有：包含聚醯亞胺樹脂的組成物(專利文獻1~專利文獻3)、包含環氧樹脂的組成物(專利文獻4)、包含含極性基的聚合物的組成物(專利文獻5)等。 As the underfill used as a pretreatment underfill encapsulation method, for example, a composition containing a polyimide resin (Patent Document 1 to Patent Document 3), a composition containing an epoxy resin (Patent Document 4), A composition containing a polar group-containing polymer (Patent Document 5) and the like.

此外，專利文獻6中揭露包含丙烯酸樹脂的UV硬化性樹脂組成物。 In addition, Patent Document 6 discloses a UV-curable resin composition containing an acrylic resin.

另一方面，專利文獻7中揭露使用包含芳香族聚碳酸酯樹脂、具有乙烯性不飽和鍵的光聚合性化合物和光聚合引發劑的感光性樹脂組成物，以形成光碟中的間隔層(spacer layer)。 On the other hand, Patent Document 7 discloses the use of a photosensitive resin composition containing an aromatic polycarbonate resin, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator to form a spacer layer in an optical disc ).

先前技術文獻 Prior technical literature 專利文獻 Patent Literature

專利文獻1 日本特開2010-006983號公報 Patent Literature 1 Japanese Patent Application Publication No. 2010-006983

專利文獻2 日本特開2010-70645號公報 Patent Document 2 Japanese Patent Application Publication No. 2010-70645

專利文獻3 WO 2011/001942號公報 Patent Document 3 WO 2011/001942

專利文獻4 日本特開2009-256588號公報 Patent Document 4 Japanese Patent Laid-Open No. 2009-256588

專利文獻5 國際公開WO 2013/066597號小冊 Patent Literature 5 International Publication WO 2013/066597 Brochure

專利文獻6 日本特開2010-126542號公報 Patent Document 6 Japanese Patent Application Publication No. 2010-126542

專利文獻7 國際公開WO 2004/006235號小冊 Patent Literature 7 International Publication No. WO 2004/006235

根據本發明人等的檢討，已知專利文獻1~專利文獻5所揭露的組成物，吸水性大、硬化性差。此外，已知使用如專利文獻1~專利文獻4所記載的聚醯亞胺樹脂、或環氧樹脂的組成物，由於硬化溫度高，而在接著時有對裝置賦予熱損害的情況。此外，這些樹脂由於硬化時間長，而有半導體裝置的生產性降低的傾向。 According to the review by the present inventors, it is known that the compositions disclosed in Patent Documents 1 to 5 have high water absorption and poor curability. In addition, it is known that a composition using a polyimide resin or an epoxy resin as described in Patent Literature 1 to Patent Literature 4 may have thermal damage to the device at the next time due to the high curing temperature. In addition, since these resins have a long curing time, the productivity of semiconductor devices tends to decrease.

此外，已知如專利文獻6所記載的使用丙烯酸樹脂的組成物，由於樹脂的耐熱性低，而無法承受在電極接合時產生的高溫，接合的可靠性降低。吸水性大。 In addition, it is known that a composition using an acrylic resin as described in Patent Document 6 has low heat resistance of the resin and cannot withstand the high temperature generated during electrode bonding, thereby reducing the reliability of bonding. Great water absorption.

另一方面，專利文獻7中揭露使用包含芳香族聚碳酸酯樹脂、具有乙烯性不飽和鍵的光聚合性化合物和光聚合引發劑的感光性樹脂組成物，以形成光碟中的間隔層。但是，沒有揭露將該感光性樹脂組成物用作底部填料。 On the other hand, Patent Document 7 discloses that a photosensitive resin composition containing an aromatic polycarbonate resin, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator is used to form a spacer layer in an optical disc. However, it is not disclosed that the photosensitive resin composition is used as an underfill.

此外，專利文獻7的段落編號0077中記載和甲醇、乙醇、丙酮、甲乙酮、甲基賽路蘇、乙基賽路蘇、甲苯、 N,N-二甲基甲醯胺、丙二醇單甲基醚等溶劑混合而作成溶液後，塗布在支撐體而能形成感光性樹脂組成物層。但是，本發明人等已知將使用該溶劑而調製的專利文獻7所記載的感光性樹脂組成物用作底部填料，結果保存穩定性差，另外塗布性也差。 In addition, Patent Document 7 describes in paragraph No. 0077, methanol, ethanol, acetone, methyl ethyl ketone, methyl cyclazone, ethyl celazone, toluene, After a solvent such as N, N-dimethylformamide and propylene glycol monomethyl ether is mixed to prepare a solution, it is coated on a support to form a photosensitive resin composition layer. However, the present inventors have known that the photosensitive resin composition described in Patent Document 7 prepared using this solvent is used as an underfill, and as a result, storage stability is poor and coating properties are also poor.

由此，本發明的目的係以提供可以形成保存穩定性、塗布性及硬化性優異、吸水性低、耐熱性優異的膜的組成物、底部填料用積層體、使用此等的積層體、半導體裝置之製造方法、及半導體裝置為目的。 Accordingly, the object of the present invention is to provide a composition capable of forming a film having excellent storage stability, excellent coatability and curability, low water absorption, and excellent heat resistance, a laminate for underfill, a laminate using these, and a semiconductor The manufacturing method of the device and the purpose of the semiconductor device.

本發明人等仔細檢討的結果，發現了藉由作成一種組成物，能作成可以形成保存穩定性、塗布性及硬化性優異、吸水性低、耐熱性優異的膜的組成物，進而完成本發明；該組成物含有聚碳酸酯樹脂、聚合性化合物、和溶劑，在組成物中含有50質量%以上的溶劑，溶劑當中50質量%以上係沸點為130℃以上、分子量為75以上的非質子性溶劑。具體而言，上述課題係利用下述手段<1>，較佳為利用<2>~<28>來解決。 As a result of careful review by the present inventors, it has been found that by making a composition, a composition capable of forming a film having excellent storage stability, coatability and curability, low water absorption, and excellent heat resistance can be formed, and the present invention has been completed The composition contains a polycarbonate resin, a polymerizable compound, and a solvent. The composition contains 50% by mass or more of the solvent. Among the solvents, 50% by mass or more is aprotic with a boiling point of 130 ° C. or more and a molecular weight of 75 or more. Solvent. Specifically, the above problem is solved by the following means <1>, preferably <2> to <28>.

<1>一種組成物，其係含有聚碳酸酯樹脂、聚合性化合物、和溶劑，在組成物中含有50質量%以上的溶劑，溶劑當中50質量%以上係沸點為130℃以上、分子量為75以上的非質子性溶劑。 <1> A composition containing a polycarbonate resin, a polymerizable compound, and a solvent, the composition containing 50% by mass or more of the solvent, 50% by mass or more of the solvent having a boiling point of 130 ° C. or more and a molecular weight of 75 Above aprotic solvents.

<2>如<1>記載的組成物，其中聚碳酸酯樹脂具有下述通式(1)所表示的重複單元； <2> The composition according to <1>, wherein the polycarbonate resin has a repeating unit represented by the following general formula (1);

通式(1)中，Ar1及Ar2各自獨立地表示芳香族基，L表示單鍵或2價的連結基。 In the general formula (1), Ar 1 and Ar 2 each independently represent an aromatic group, and L represents a single bond or a divalent linking group.

<3>如<1>或<2>記載的組成物，其中聚碳酸酯樹脂具有下述通式(2)所表示的重複單元； <3> The composition according to <1> or <2>, wherein the polycarbonate resin has a repeating unit represented by the following general formula (2);

通式(2)中，R1及R2各自獨立地表示氫原子、烷基或芳基，R1及R2可以連結而形成環。 In the general formula (2), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group, and R 1 and R 2 may be linked to form a ring.

<4>如<1>至<3>中任一項記載的組成物，其中聚碳酸酯樹脂具有下述通式(3)所表示的重複單元； <4> The composition according to any one of <1> to <3>, wherein the polycarbonate resin has a repeating unit represented by the following general formula (3);

通式(3)中，R3表示烷基，m係0~10的整數。 In the general formula (3), R 3 represents an alkyl group, and m is an integer of 0 to 10.

<5>如<1>至<4>中任一項記載的組成物，其中聚合性化合物係具有2個以上具乙烯性不飽和鍵的基的化合物。 <5> The composition according to any one of <1> to <4>, wherein the polymerizable compound is a compound having two or more groups having an ethylenically unsaturated bond.

<6>如<1>至<5>中任一項記載的組成物，其中聚合性化合物具有下述式所表示的部分構造；其中，式中的＊係連結鍵(connecting bond)， <6> The composition according to any one of <1> to <5>, wherein the polymerizable compound has a partial structure represented by the following formula; wherein, * in the formula is a connecting bond (connecting bond),

<7>如<1>至<6>中任一項記載的組成物，其還包含光聚合引發劑。 <7> The composition according to any one of <1> to <6>, which further contains a photopolymerization initiator.

<8>如<1>至<7>中任一項記載的組成物，其還包含熱聚合引發劑。 <8> The composition according to any one of <1> to <7>, which further contains a thermal polymerization initiator.

<9>如<1>至<8>中任一項記載的組成物，其還包含填料。 <9> The composition according to any one of <1> to <8>, which further contains a filler.

<10>如<1>至<9>中任一項記載的組成物，其還包含黏合性賦予劑。 <10> The composition according to any one of <1> to <9>, which further contains an adhesiveness-imparting agent.

<11>如<1>至<10>中任一項記載的組成物，其係底部填料用。 <11> The composition according to any one of <1> to <10>, which is used as an underfill.

<12>如<1>至<11>中任一項記載的組成物，其係液狀。 <12> The composition according to any one of <1> to <11>, which is liquid.

<13>一種底部填料用積層體，其係在樹脂薄膜的表面具有包含聚碳酸酯樹脂和聚合性化合物的接著層。 <13> A laminate for an underfill having an adhesive layer containing a polycarbonate resin and a polymerizable compound on the surface of a resin film.

<14>一種積層體，其係在半導體晶圓的表面具有包含聚碳酸酯樹脂和聚合性化合物的接著層。 <14> A laminate having an adhesive layer containing a polycarbonate resin and a polymerizable compound on the surface of a semiconductor wafer.

<15>如<14>記載的積層體，其中聚碳酸酯樹脂具有下述通式(1)所表示的重複單元； <15> The laminate according to <14>, wherein the polycarbonate resin has a repeating unit represented by the following general formula (1);

通式(1)中，Ar1及Ar2各自獨立地表示芳香族基，L表示單鍵或2價的連結基。 In the general formula (1), Ar 1 and Ar 2 each independently represent an aromatic group, and L represents a single bond or a divalent linking group.

<16>如<14>或<15>記載的積層體，其中聚碳酸酯樹脂具有下述通式(2)所表示的重複單元； <16> The laminate according to <14> or <15>, wherein the polycarbonate resin has a repeating unit represented by the following general formula (2);

通式(2)中，R1及R2各自獨立地表示氫原子、烷基或芳基，R1和R2可以連結而形成環。 In the general formula (2), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and R 1 and R 2 may be linked to form a ring.

<17>如<14>至<16>中任一項記載的積層體，其中聚碳酸酯樹脂具有下述通式(3)所表示的重複單元； <17> The laminate according to any one of <14> to <16>, wherein the polycarbonate resin has a repeating unit represented by the following general formula (3);

通式(3)中，R3表示烷基，m係0~10的整數。 In the general formula (3), R 3 represents an alkyl group, and m is an integer of 0 to 10.

<18>如<14>至<17>中任一項記載的積層體，其中聚合性化合物係具有2個以上具乙烯性不飽和鍵的基的化合物。 <18> The laminate according to any one of <14> to <17>, wherein the polymerizable compound is a compound having two or more groups having an ethylenically unsaturated bond.

<19>如<14>至<18>中任一項記載的積層體，其中聚合性化合物具有下述式表示的部分構造；其中，式中的＊係連結鍵， <19> The laminate according to any one of <14> to <18>, wherein the polymerizable compound has a partial structure represented by the following formula; wherein, * in the formula is a linkage bond,

<20>如<14>至<19>中任一項記載的積層體，其還包含光聚合引發劑。 <20> The laminate according to any one of <14> to <19>, which further contains a photopolymerization initiator.

<21>如<14>至<20>中任一項記載的積層體，其還包含熱聚合引發劑。 <21> The laminate according to any one of <14> to <20>, which further contains a thermal polymerization initiator.

<22>如<14>至<21>中任一項記載的積層體，其還包含填料。 <22> The laminate according to any one of <14> to <21>, which further contains a filler.

<23>如<14>至<22>中任一項記載的積層體，其還包含黏合性賦予劑。 <23> The laminate according to any one of <14> to <22>, which further contains an adhesion-imparting agent.

<24>一種半導體裝置之製造方法，其係包含：將如<12>記載的組成物應用於半導體晶圓的步驟； 將已應用於半導體晶圓的組成物乾燥的步驟；和將被接著體加熱壓接在已乾燥的組成物的表面的步驟。 <24> A method of manufacturing a semiconductor device, comprising: the step of applying the composition as described in <12> to a semiconductor wafer; The step of drying the composition applied to the semiconductor wafer; and the step of heating and pressing the adherend to the surface of the dried composition.

<25>如<24>記載的半導體裝置之製造方法，其中在乾燥步驟與加熱壓接步驟之間，包含將已乾燥的組成物曝光的步驟、和將已曝光的組成物顯影的步驟。 <25> The method for manufacturing a semiconductor device according to <24>, wherein a step of exposing the dried composition and a step of developing the exposed composition are included between the drying step and the heat and pressure bonding step.

<26>一種半導體裝置之製造方法，其係包含：將如<13>記載的底部填料用積層體的接著層側的面積層在半導體晶圓，從接著層剝離樹脂薄膜，而將接著層積層在半導體晶圓的步驟；和將被接著體加熱壓接在已積層在半導體晶圓的接著層的表面的步驟。 <26> A method of manufacturing a semiconductor device, comprising: placing an area on the adhesive layer side of the underfill laminate as described in <13> on a semiconductor wafer, peeling the resin film from the adhesive layer, and stacking the adhesive layer The step of the semiconductor wafer; and the step of heating and pressure bonding the bonded body on the surface of the bonding layer that has been deposited on the semiconductor wafer.

<27>如<26>記載的半導體裝置之製造方法，其中在積層步驟與加熱壓接步驟之間，包含將已積層在半導體晶圓的接著層曝光的步驟、和將已曝光的接著層顯影的步驟。 <27> The method for manufacturing a semiconductor device according to <26>, wherein between the lamination step and the heat and pressure bonding step, a step of exposing the adhesion layer deposited on the semiconductor wafer and developing the exposed adhesion layer are included A step of.

<28>一種半導體裝置，係以<24>至<27>中任一項記載的方法製造。 <28> A semiconductor device manufactured by the method according to any one of <24> to <27>.

藉由本發明，變得可提供可以形成保存穩定性、塗布性及硬化性優異、吸水性低、耐熱性優異的膜的組成物、底部填料用積層體、使用此等的積層體、半導體裝置之製造方法、及半導體裝置。 According to the present invention, it becomes possible to provide a composition capable of forming a film having excellent storage stability, coatability and curability, low water absorption, and excellent heat resistance, a laminate for underfill, a laminate using these, a semiconductor device Manufacturing method and semiconductor device.

1‧‧‧薄膜狀接著劑 1‧‧‧ film adhesive

1a‧‧‧接著層圖案 1a‧‧‧Next layer pattern

2‧‧‧覆蓋薄膜 2‧‧‧covering film

3‧‧‧樹脂薄膜 3‧‧‧Resin film

6‧‧‧黏著劑層 6‧‧‧Adhesive layer

7‧‧‧樹脂薄膜 7‧‧‧Resin film

8‧‧‧半導體晶圓 8‧‧‧Semiconductor wafer

11‧‧‧接著層 11‧‧‧Next layer

11a‧‧‧底部填料層 11a‧‧‧Bottom packing layer

12、12a、12b‧‧‧半導體元件 12, 12a, 12b ‧‧‧ semiconductor components

13‧‧‧半導體元件搭載用支撐構件 13‧‧‧Supporting member for mounting semiconductor elements

14‧‧‧導線 14‧‧‧Wire

15‧‧‧封裝材 15‧‧‧Packaging materials

16‧‧‧端子 16‧‧‧terminal

20、20a、20b‧‧‧附接著層的半導體晶圓 20, 20a, 20b ‧‧‧ semiconductor wafer with attached layer

100、110、120‧‧‧接著薄片 100, 110, 120‧‧‧ then thin

200、210、300‧‧‧半導體裝置 200, 210, 300 ‧‧‧ semiconductor device

301a~301d‧‧‧半導體元件 301a ~ 301d‧‧‧Semiconductor components

301‧‧‧半導體元件積層體 301‧‧‧Semiconductor element laminate

302b~302d‧‧‧貫通電極 302b ~ 302d‧‧‧through electrode

303a~303e‧‧‧金屬凸塊 303a ~ 303e‧‧‧Metal bump

305‧‧‧再配線層 305‧‧‧ Redistribution layer

310、310a、310b‧‧‧底部填料層 310, 310a, 310b ‧‧‧ bottom filler layer

315‧‧‧絕緣層 315‧‧‧Insulation

320‧‧‧半導體元件搭載用支撐構件 320‧‧‧Supporting member for mounting semiconductor elements

320a‧‧‧表面電極 320a‧‧‧Surface electrode

第1圖係顯示薄膜狀接著劑的一實施形態的示意剖面圖。 Fig. 1 is a schematic cross-sectional view showing an embodiment of a film-like adhesive.

第2圖係顯示接著薄片的一實施形態的示意剖面圖。 Fig. 2 is a schematic cross-sectional view showing an embodiment of the following sheet.

第3圖係顯示接著薄片的另一實施形態的示意剖面圖。 Fig. 3 is a schematic cross-sectional view showing another embodiment following the sheet.

第4圖係顯示接著薄片的另一實施形態的示意剖面圖。 Fig. 4 is a schematic cross-sectional view showing another embodiment following the sheet.

第5圖係顯示附接著層的半導體晶圓的一實施形態的上視圖。 FIG. 5 is a top view showing an embodiment of a semiconductor wafer with an attached layer.

第6圖係沿著第5圖的VI-VI線的端面圖。 Figure 6 is an end view along the line VI-VI of Figure 5.

第7圖係顯示接著層圖案的一實施形態的上視圖。 FIG. 7 is a top view showing an embodiment of the adhesive layer pattern.

第8圖係沿著第7圖的VIII-VIII線的端面圖。 Figure 8 is an end view taken along the line VIII-VIII of Figure 7.

第9圖係顯示接著層圖案的一實施形態的上視圖。 Fig. 9 is a top view showing an embodiment of the adhesive layer pattern.

第10圖係沿著第9圖的X-X線的端面圖。 Fig. 10 is an end view taken along the line X-X of Fig. 9;

第11圖係顯示本發明的半導體裝置的一實施形態的示意剖面圖。 FIG. 11 is a schematic cross-sectional view showing an embodiment of the semiconductor device of the present invention.

第12圖係顯示本發明的半導體裝置的另一實施形態的示意剖面圖。 FIG. 12 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention.

第13圖係顯示本發明的半導體裝置的另一實施形態的示意剖面圖。 Fig. 13 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention.

[用以實施發明的形態] [Form for carrying out the invention]

以下記載的本發明中的構成要素的說明，係基於本發明的代表性實施態樣而完成的，但本發明並不限於如此的實施態樣。 The description of the constituent elements in the present invention described below is based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

在本說明書中的基(原子團)的標記方面，沒有記明取代及未取代的標記係包含沒有取代基者、和有取代基者。例如，「烷基」不僅包含沒有取代基的烷基(未取代烷基)，也包含有取代基的烷基(取代烷基)。 Regarding the labeling of the group (atomic group) in the present specification, the labeling system which does not specify substitution and unsubstitution includes those without a substituent and those with a substituent. For example, "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group), but also an substituted alkyl group (substituted alkyl group).

此外，本說明書中的「活性光線」係指，例如，水銀燈的輝線光譜、以準分子雷射為代表的遠紫外線、極紫外線(EUV光)、X線、電子束等。此外，在本發明中，光係指活性光線或放射線。只要沒有特別說明，本說明書中的「曝光」，不僅包含利用水銀燈、以準分子雷射為代表的遠紫外線、X線、EUV光等的曝光，利用電子束、離子束等粒子束的描繪也包含在曝光內。 In addition, the "active light" in this specification refers to, for example, the glow line spectrum of a mercury lamp, far ultraviolet light represented by excimer laser, extreme ultraviolet light (EUV light), X-ray, electron beam, and the like. In addition, in the present invention, light means active light or radiation. Unless otherwise specified, the "exposure" in this specification includes not only exposure using mercury lamps, excimer lasers, such as far ultraviolet, X-ray, EUV light, etc., but also drawing using particle beams such as electron beams and ion beams. Included in exposure.

在本說明書中，使用「~」所表示的數值範圍係指以記載在「~」的前後的數值為下限值及上限值所包含的範圍。 In this specification, the numerical range indicated by "~" refers to the range included in the lower limit and upper limit with the numerical values described before and after "~".

此外，在本說明書中，「(甲基)丙烯酸酯」表示丙烯酸酯及甲基丙烯酸酯兩者或是其中一者，「(甲基)丙烯酸基」表示丙烯酸基及甲基丙烯酸基兩者或是其中一者，「(甲基)丙烯醯基」表示丙烯醯基及甲基丙烯醯基兩者或是其中一者。 In addition, in this specification, "(meth) acrylate" means both or one of acrylate and methacrylate, and "(meth) acrylate" means both or It is one of them, "(meth) acryloyl" means both or one of acryloyl and methacryloyl.

在本說明書中，所稱「步驟」的用語，不僅包含獨立的步驟，即使為不能與其他步驟作出明確區別的情況，只要可達成該步驟所期望的作用，也包含在本用語內。 In this specification, the term "step" not only includes independent steps, but even if it is impossible to make a clear distinction from other steps, as long as the desired effect of the step can be achieved, it is also included in this term.

在本說明書中，固體成分濃度係指除了溶劑以外的其他成分的重量對組成物的總重量的重量百分率。此外，固體成分係指在25℃下的固體成分。 In this specification, the solid content concentration refers to the weight percentage of the weight of other components than the solvent to the total weight of the composition. In addition, the solid content means the solid content at 25 ° C.

在本說明書中，重量平均分子量係定義為利用GPC測定的聚苯乙烯換算值。在本說明書中，重量平均分子量(Mw)及數量平均分子量(Mn)，係例如，能藉由使用HLC-8220(TOSOH(股)製)，使用TSKgel Super AWM-H(TOSOH(股)製，6.0mmID×15.0cm)作為管柱來求得。只要沒有特別敘述，洗提液係設為使用10mmol/L溴化鋰NMP(N-甲基吡咯啶酮)溶液進行測定者。 In this specification, the weight average molecular weight system is defined as the polystyrene conversion value measured by GPC. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, by using HLC-8220 (manufactured by TOSOH (share)), TSKgel Super AWM-H (manufactured by TOSOH (share), 6.0mmID × 15.0cm) was obtained as the column. Unless otherwise specified, the eluent system was determined to use a 10 mmol / L lithium bromide NMP (N-methylpyrrolidone) solution.

<組成物> <Composition>

本發明的組成物的特徵在於含有聚碳酸酯樹脂、聚合性化合物、和溶劑，在組成物中含有50質量%以上的溶劑，溶劑當中50質量%以上係沸點為130℃以上、分子量為75以上的非質子性溶劑。 The composition of the present invention is characterized by containing a polycarbonate resin, a polymerizable compound, and a solvent. The composition contains 50% by mass or more of the solvent. Among the solvents, 50% by mass or more has a boiling point of 130 ° C. or more and a molecular weight of 75 or more. Of aprotic solvents.

聚碳酸酯樹脂係吸水性低、耐熱性高的樹脂，此外，藉由使聚合性化合物進行反應硬化，快速地發揮其物理特性，因此本發明的組成物係吸水性低、且耐熱性及硬化性優異。而且，溶劑當中50質量%以上係沸點為130℃以上、分子量為75以上的非質子性溶劑，因此保存穩定性變得良好。此外，溶劑的沸點係130℃以上，因此能抑 制烘烤時的起泡，能抑制空隙(void)的發生。此外，溶劑的分子量係75以上，因此具有適度的揮發性，能使應用於半導體晶圓等後的表面狀態良好。 Polycarbonate resins are resins with low water absorption and high heat resistance. In addition, by polymerizing a polymerizable compound by reaction hardening, its physical properties are quickly exhibited. Therefore, the composition of the present invention has low water absorption, heat resistance, and hardening. Excellent. Furthermore, among the solvents, 50% by mass or more is an aprotic solvent having a boiling point of 130 ° C. or more and a molecular weight of 75 or more, so the storage stability becomes good. In addition, the boiling point of the solvent is above 130 ° C, so it can suppress The blistering during the baking process can suppress the occurrence of voids. In addition, since the solvent has a molecular weight of 75 or more, it has moderate volatility and can be applied to semiconductor wafers or the like in good surface condition.

以下，詳細說明本發明。 Hereinafter, the present invention will be described in detail.

<<聚碳酸酯樹脂>> << Polycarbonate resin >>

本發明的組成物含有聚碳酸酯樹脂。 The composition of the present invention contains polycarbonate resin.

在本發明中，聚碳酸酯樹脂較佳為具有下述通式(1)所表示的重複單元。 In the present invention, the polycarbonate resin preferably has a repeating unit represented by the following general formula (1).

通式(1)中，Ar1及Ar2各自獨立地表示芳香族基，L表示單鍵或2價的連結基。 In the general formula (1), Ar 1 and Ar 2 each independently represent an aromatic group, and L represents a single bond or a divalent linking group.

通式(1)中的Ar1及Ar2各自獨立地表示芳香族基。作為芳香族基，可舉出：苯環、萘環、戊搭烯環(pentalene ring)、茚環、薁環、庚搭烯環(heptalene ring)、吲丹烯環(indecene ring)、苝環、稠五苯環、苊烯環(acenaphthalene ring)、菲環、蒽環、稠四苯環(naphthacene ring)、苯并菲環(chrysene ring)、聯三伸苯環(triphenylene ring)、茀環、聯苯環、吡咯環、呋喃環、噻吩環、咪唑環、唑環、噻唑環、吡啶環、吡環、嘧啶環、嗒環(pyridazin ring)、吲環(indolizine ring)、吲哚環、苯并呋喃環(benzofuran ring)、苯并噻吩環、異苯并呋喃環、喹環(quinolizine ring)、喹啉環、呔環(phthalazine ring)、啶環(naphthyridines ring)、 喹啉環(quinoxaline ring)、喹唑啉環(quinoxazolin ring)、異喹啉環、咔唑環、啡啶環、吖啶環、啡啉環、噻蒽環(thianthrene ring)、唏環(chromene ring)、環(xanthene ring)、啡噻環(phenoxathiin ring)、啡噻環、及啡環。其中，較佳為苯環。 Ar 1 and Ar 2 in the general formula (1) each independently represent an aromatic group. Examples of aromatic groups include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, and perylene ring. , Fused pentabenzene ring, acenaphthalene ring (acenaphthalene ring), phenanthrene ring, anthracene ring, fused tetraphenylene ring (naphthacene ring), benzophenanthrene ring (chrysene ring), biphenylene ring (triphenylene ring), stilbene ring , Biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, Azole ring, thiazole ring, pyridine ring, pyridine Ring, pyrimidine ring, clap Ring (pyridazin ring), ind Indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quino Quinolizine ring, quinoline ring, 呔 Phthalazine ring, Naphthyridines ring, quine Quinoxaline ring, quinoxazolin ring, isoquinoline ring, isoquinoline ring, carbazole ring, morphine ring, acridine ring, morpholine ring, thianthrene ring (thianthrene ring), Chromene ring, Ring (xanthene ring), brown Phenoxathiin ring, phenothiazine Ring, and coffee ring. Among them, a benzene ring is preferred.

這些芳香族基可以具有取代基，但較佳為沒有取代基。 These aromatic groups may have a substituent, but preferably no substituent.

作為芳香族基可以具有的取代基的例，可舉出：鹵素原子、烷基、烷氧基、芳基等。 Examples of the substituent that the aromatic group may have include halogen atoms, alkyl groups, alkoxy groups, and aryl groups.

作為鹵素原子，可舉出：氟原子、氯原子、溴原子、碘原子等。 Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

作為烷基，可舉出：碳數1~30的烷基。烷基的碳數更佳為1~20，再更佳為1~10。烷基可以是直鏈、支鏈當中任一者。此外，烷基的一部分或全部氫原子可以以鹵素原子取代。作為鹵素原子，可以舉出：氟原子、氯原子、溴原子、碘原子等，較佳為氟原子。 Examples of the alkyl group include alkyl groups having 1 to 30 carbon atoms. The carbon number of the alkyl group is more preferably 1-20, and even more preferably 1-10. The alkyl group may be either linear or branched. In addition, part or all of the hydrogen atoms of the alkyl group may be substituted with halogen atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and fluorine atoms are preferred.

作為烷氧基，較佳為碳數1~30的烷氧基。烷氧基的碳數，更佳為1~20，再更佳為1~10。烷氧基可以是直鏈、支鏈、環狀當中任一者。 The alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms. The carbon number of the alkoxy group is more preferably 1-20, and even more preferably 1-10. The alkoxy group may be any of linear, branched, and cyclic.

作為芳基，較佳為碳數6~30的芳基，更佳為碳數6~20的芳基。 The aryl group is preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 20 carbon atoms.

通式(1)中的L表示單鍵或2價的連結基。 L in the general formula (1) represents a single bond or a divalent linking group.

作為2價的連結基，可舉出包含從伸烷基、伸芳基、-O-、-NR’-(R’表示氫原子、可以具有取代基的烷基或可以具有取代基的芳基，較佳為氫原子)所表示的構造、-SO2-、-CO-、-O-及-S-所選出的至少一個的基。 Examples of the divalent linking group include alkyl groups, aryl groups, -O-, and -NR '-(R' represents a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent) , Preferably a hydrogen atom), at least one group selected from -SO 2- , -CO-, -O-, and -S-.

作為伸烷基，較佳為碳數2~20的伸烷基，更佳為碳數2~10的伸烷基。 The alkylene group is preferably an alkylene group having 2 to 20 carbon atoms, and more preferably an alkylene group having 2 to 10 carbon atoms.

作為伸芳基，較佳為碳數6~30的伸芳基，更佳為碳數6~20的伸芳基。其中，特佳為伸苯基。 The arylene group is preferably an arylene group having 6 to 30 carbon atoms, and more preferably an arylene group having 6 to 20 carbon atoms. Among them, particularly preferred is phenylene.

伸烷基、伸芳基可以具有取代基。作為取代基，能舉出以Ar1及Ar2說明的取代基。此外，取代基可以具有2個以上。在具有2個以上的取代基的情況，取代基彼此可以鍵結而形成環。作為取代基彼此鍵結而形成的環，可舉出：脂環(非芳香性的烴環)、芳香環、雜環等。環可以是單環，也可以是多環。 The alkylene group and the aryl group may have a substituent. As the substituent, the substituents described by Ar 1 and Ar 2 can be mentioned. In addition, the substituent may have two or more. When there are two or more substituents, the substituents may be bonded to each other to form a ring. Examples of the ring formed by the bonding of substituents include alicyclic (non-aromatic hydrocarbon ring), aromatic ring, and heterocyclic ring. The ring may be a single ring or multiple rings.

本發明使用的聚碳酸酯樹脂較佳為具有下述通式(2)所表示的重複單元。 The polycarbonate resin used in the present invention preferably has a repeating unit represented by the following general formula (2).

通式(2)中，R1及R2各自獨立地表示氫原子、烷基或芳基，R1和R2可以連結而形成環。 In the general formula (2), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and R 1 and R 2 may be linked to form a ring.

通式(2)中，R1及R2各自獨立地表示氫原子、烷基或芳基。 In the general formula (2), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, or an aryl group.

作為烷基，可舉出碳數1~30的烷基。烷基的碳數更佳為1~20，再更佳為1~10。烷基可以是直鏈、支鏈當中任一者。此外，烷基的一部分或全部氫原子可以以鹵素原子取代。作為鹵素原子，可以舉出：氟原子、氯原子、溴原子、碘原子等，較佳為氟原子。 Examples of the alkyl group include an alkyl group having 1 to 30 carbon atoms. The carbon number of the alkyl group is more preferably 1-20, and even more preferably 1-10. The alkyl group may be either linear or branched. In addition, part or all of the hydrogen atoms of the alkyl group may be substituted with halogen atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and fluorine atoms are preferred.

作為芳基，較佳為碳數6~30的芳基，更佳為碳數6~20的芳基，特佳為苯基。 The aryl group is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, and particularly preferably a phenyl group.

R1和R2可以連結而形成環。作為R1和R2連結而形成的環，可舉出：脂環(非芳香性的烴環)、芳香環、雜環等。環可以是單環，也可以是多環。 R 1 and R 2 may be linked to form a ring. Examples of the ring formed by connecting R 1 and R 2 include an alicyclic ring (non-aromatic hydrocarbon ring), aromatic ring, and heterocyclic ring. The ring may be a single ring or multiple rings.

本發明使用的聚碳酸酯樹脂較佳為具有下述通式(3)所表示的重複單元。 The polycarbonate resin used in the present invention preferably has a repeating unit represented by the following general formula (3).

通式(3)中，R3表示烷基，m係0~10的整數。 In the general formula (3), R 3 represents an alkyl group, and m is an integer of 0 to 10.

R3表示烷基。作為烷基，可舉出碳數1~30的烷基。烷基的碳數更佳為1~20，再更佳為1~10。烷基可以是直鏈、支鏈、環狀當中任一者。烷基較佳為甲基。 R 3 represents an alkyl group. Examples of the alkyl group include an alkyl group having 1 to 30 carbon atoms. The carbon number of the alkyl group is more preferably 1-20, and even more preferably 1-10. The alkyl group may be any of linear, branched, and cyclic. The alkyl group is preferably methyl.

m表示0~10的整數。m較佳為0~5，特佳為0~3。 m represents an integer from 0 to 10. m is preferably 0 ~ 5, particularly preferably 0 ~ 3.

在本發明中，作為聚碳酸酯樹脂，也能使用不包含上述通式(1)所表示的重複單元的聚碳酸酯樹脂。 In the present invention, as the polycarbonate resin, a polycarbonate resin that does not include the repeating unit represented by the general formula (1) can also be used.

例如，也能使用日本特開2012-222174號公報的段落編號0012記載的聚碳酸酯樹脂等。 For example, the polycarbonate resin described in Paragraph No. 0012 of Japanese Patent Laid-Open No. 2012-222174 can also be used.

以下，顯示聚碳酸酯樹脂的重複單元的具體例。以下所顯示的重複單元，可以僅包含1種，也可以組合而包含2種以上。其中，從吸水性及耐熱性的觀點來看，較佳為(1-13)、(1-14)的重複單元。 Hereinafter, specific examples of the repeating unit of the polycarbonate resin are shown. The repeating units shown below may contain only one kind, or two or more kinds in combination. Among them, the repeating units of (1-13) and (1-14) are preferred from the viewpoint of water absorption and heat resistance.

聚碳酸酯樹脂的重量平均分子量(Mw)較佳為1,000~1,000,000，更佳為10,000~80,000。若在上述範圍內，則對溶媒的溶解性、耐熱性佳。 The weight average molecular weight (Mw) of the polycarbonate resin is preferably 1,000 to 1,000,000, and more preferably 10,000 to 80,000. Within the above range, the solubility in the solvent and the heat resistance are excellent.

相對於100質量份的沸點為130℃以上、分子量為75以上的非質子性溶劑，本發明所使用的聚碳酸酯樹脂在25℃下的溶解度，較佳為5質量份以上，特佳為15質量份以上。若對上述非質子性溶劑的溶解度為5質量份以上，便能提高組成物中的聚碳酸酯樹脂濃度， 能形成吸水性更低且耐熱性更優異的接著層。作為非質子性溶劑，例如可舉出：苯甲醚(anisole)(沸點154℃，分子量108)、γ-丁內酯(沸點204℃，分子量86)、δ-戊內酯(沸點207℃，分子量100)、環己酮(沸點156℃，分子量98)、環戊酮(沸點130℃，分子量84)、N-甲基-2-吡咯啶酮(沸點202℃，分子量99)、N-乙基-2-吡咯啶酮(沸點225℃，分子量113)、二甲基亞碸(沸點189℃，分子量78)、二甲基乙醯胺(沸點165℃，分子量87)、乙酸1-甲氧基-2丙酯(沸點146℃，分子量132)、甲戊酮(沸點149℃，分子量114)等，上述聚碳酸酯樹脂的溶解度較佳為對這些溶劑的溶解度。 The solubility of the polycarbonate resin used in the present invention at 25 ° C with respect to 100 parts by mass of an aprotic solvent having a boiling point of 130 ° C or higher and a molecular weight of 75 or higher is preferably 5 parts by mass or more, and particularly preferably 15 Above mass. If the solubility in the aprotic solvent is 5 parts by mass or more, the polycarbonate resin concentration in the composition can be increased, It can form an adhesive layer with lower water absorption and more excellent heat resistance. Examples of aprotic solvents include anisole (boiling point 154 ° C, molecular weight 108), γ-butyrolactone (boiling point 204 ° C, molecular weight 86), and δ-valerolactone (boiling point 207 ° C, Molecular weight 100), cyclohexanone (boiling point 156 ° C, molecular weight 98), cyclopentanone (boiling point 130 ° C, molecular weight 84), N-methyl-2-pyrrolidone (boiling point 202 ° C, molecular weight 99), N-B 2-pyrrolidone (boiling point 225 ° C, molecular weight 113), dimethyl sulfoxide (boiling point 189 ° C, molecular weight 78), dimethylacetamide (boiling point 165 ° C, molecular weight 87), 1-methoxyacetic acid The solubility of the above-mentioned polycarbonate resin is preferably based on 2-propyl propyl ester (boiling point 146 ° C, molecular weight 132), methylpentanone (boiling point 149 ° C, molecular weight 114), and the like.

作為聚碳酸酯樹脂的市售品，例如可舉出：PCZ-200、PCZ-300、PCZ-500、PCZ-800(三菱瓦斯化學製)、APEC9379(BAYER製)、PANLITE L-1225LM(帝人製)等。 Examples of commercially available polycarbonate resins include PCZ-200, PCZ-300, PCZ-500, PCZ-800 (manufactured by Mitsubishi Gas Chemical), APEC9379 (manufactured by Bayer), PANLITE L-1225LM (manufactured by Teijin) )Wait.

相對於本發明的組成物的總固體成分，聚碳酸酯樹脂的含量較佳為40~90質量%，更佳為45~85質量%，再更佳為50~85質量%。 The content of the polycarbonate resin with respect to the total solid content of the composition of the present invention is preferably 40 to 90% by mass, more preferably 45 to 85% by mass, and still more preferably 50 to 85% by mass.

相對於100質量份的聚合性化合物，本發明的組成物較佳為含有50~900質量份的聚碳酸酯樹脂，較佳為含有100~600質量份。 The composition of the present invention preferably contains 50 to 900 parts by mass of polycarbonate resin relative to 100 parts by mass of the polymerizable compound, and preferably contains 100 to 600 parts by mass.

聚碳酸酯樹脂能使用1種或2種以上。使用2種以上的情況，較佳為合計量在上述範圍內。 One type or two or more types of polycarbonate resins can be used. When two or more types are used, the total amount is preferably within the above range.

<聚合性化合物> <Polymerizable compound>

本發明的組成物含有聚合性化合物。藉由摻合聚合性化合物，能利用硬化性化合物的硬化來使聚碳酸酯樹脂的物理特性發揮。 The composition of the present invention contains a polymerizable compound. By blending the polymerizable compound, the physical properties of the polycarbonate resin can be exerted by curing the hardening compound.

聚合性化合物係具有聚合性基的化合物，能使用可以利用活性光線、放射線、光、熱、自由基或酸的作用聚合的周知的化合物。這種化合物係在產業領域廣為人知者，在本發明中能夠沒有特別限定地使用此等。此等例如可以是單體、預聚物、寡聚物或此等之混合物以及此等之多量体等的化學形態當中任一者。 The polymerizable compound is a compound having a polymerizable group, and a well-known compound that can be polymerized by the action of active light, radiation, light, heat, free radicals, or acid can be used. Such compounds are widely known in the industrial field, and they can be used in the present invention without particular limitation. These may be, for example, any of the chemical forms of monomers, prepolymers, oligomers, or a mixture of these, and such a plurality of bulks.

在本發明中，單體型式(monomer type)的的聚合性化合物(以下，也稱為聚合性單體)係與高分子化合物不同的化合物。聚合性單體典型上是低分子化合物，較佳為分子量2000以下的低分子化合物，更佳為1500以下的低分子化合物，再更佳為分子量900以下的低分子化合物。又，聚合性單體的分子量通常為100以上。 In the present invention, a monomer type (monomer type) polymerizable compound (hereinafter, also referred to as a polymerizable monomer) is a compound different from a polymer compound. The polymerizable monomer is typically a low-molecular compound, preferably a low-molecular compound with a molecular weight of 2000 or less, more preferably a low-molecular compound with a molecular weight of 1500 or less, and even more preferably a low-molecular compound with a molecular weight of 900 or less. In addition, the molecular weight of the polymerizable monomer is usually 100 or more.

聚合性基，例如，較佳為可以進行加成聚合反應的官能基。作為可以進行加成聚合反應的官能基，可舉出：具有乙烯性不飽和鍵的基、胺基、環氧基等。此外，聚合性基可以是能利用光照射產生自由基的官能基，作為那種聚合性基，例如可舉出：硫醇基、鹵素基等。其中，聚合性基較佳為具有乙烯性不飽和鍵的基。作為乙烯性不飽和鍵基，較佳為苯乙烯基、(甲基)丙烯醯基、烯丙基。 The polymerizable group is, for example, a functional group that can undergo addition polymerization reaction. Examples of the functional group that can undergo addition polymerization reaction include a group having an ethylenically unsaturated bond, an amine group, and an epoxy group. In addition, the polymerizable group may be a functional group capable of generating radicals by light irradiation, and examples of the polymerizable group include a thiol group and a halogen group. Among them, the polymerizable group is preferably a group having an ethylenically unsaturated bond. As the ethylenically unsaturated bond group, styryl, (meth) acryloyl, and allyl are preferred.

即，在本發明中，聚合性化合物較佳為具有具有乙烯性不飽和鍵的基的化合物。 That is, in the present invention, the polymerizable compound is preferably a compound having a group having an ethylenically unsaturated bond.

聚合性化合物，從顯影性及耐熱性的觀點來看，較佳為包含至少1種含有2個以上聚合性基的2官能以上的聚合性化合物，更佳為包含至少1種3官能以上的聚合性化合物。其中，從能更加提升顯影性及耐熱性這種理由來看，特佳為具有2個以上具乙烯性不飽和鍵的基的2官能以上的聚合性化合物。 From the viewpoint of developability and heat resistance, the polymerizable compound is preferably at least one difunctional or more polymerizable compound containing two or more polymerizable groups, and more preferably at least one trifunctional or more polymerizable compound. Sexual compounds. Among them, from the reason that the developability and the heat resistance can be further improved, particularly preferred is a bifunctional or more polymerizable compound having two or more groups having an ethylenically unsaturated bond.

作為聚合性化合物，具體而言，可舉出：自由基聚合性化合物(B1)、離子聚合性化合物(B2)，較佳為自由基聚合性化合物(B1)。 Specific examples of the polymerizable compound include a radically polymerizable compound (B1) and an ionically polymerizable compound (B2), and preferably a radically polymerizable compound (B1).

<<自由基聚合性化合物(B1)>> << Free Radical Polymerizable Compound (B1) >>

作為自由基聚合性化合物(B1)，可舉出：碳數3~35的(甲基)丙烯醯胺化合物(B11)、碳數4~35的(甲基)丙烯酸酯化合物(B12)、碳數6~35的芳香族乙烯化合物(B13)、碳數3~20的乙烯基醚化合物(B14)及其他自由基聚合性化合物(B15)等。自由基聚合性化合物(B1)可以單獨使用1種，也可以併用2種以上。此外，依需要，可以併用氫醌、甲基醚氫醌類等聚合抑制劑。 Examples of the radical polymerizable compound (B1) include (meth) acrylamide compound (B11) having 3 to 35 carbon atoms, (meth) acrylate compound (B12) having 4 to 35 carbon atoms, carbon 6 to 35 aromatic vinyl compounds (B13), C3 to 20 vinyl ether compounds (B14) and other radical polymerizable compounds (B15), etc. The radically polymerizable compound (B1) may be used alone or in combination of two or more. In addition, if necessary, a polymerization inhibitor such as hydroquinone and methyl ether hydroquinone may be used in combination.

作為碳數3~35的(甲基)丙烯醯胺化合物(B11)，例如可舉出：(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-乙基(甲基)丙烯醯胺、N-丙基(甲基)丙烯醯胺、N-正丁基(甲基)丙烯醯胺、N-第三丁基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯 醯胺、N,N-二乙基(甲基)丙烯醯胺及(甲基)丙烯醯基啉。 Examples of the (meth) acrylamide compound (B11) having 3 to 35 carbon atoms include (meth) acrylamide, N-methyl (meth) acrylamide, and N-ethyl (meth Group) acrylamide, N-propyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-third butyl (meth) acrylamide, N-butoxy Methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide , N, N-diethyl (meth) acrylamide and (meth) acrylamide Porphyrin.

作為碳數4~35的(甲基)丙烯酸酯化合物(B12)，例如可舉出以下的單官能~六官能的(甲基)丙烯酸酯。在下文中，EO表示環氧乙烷(ethylene oxide)，PO表示環氧丙烷(propylene oxide)。 Examples of the (meth) acrylate compound (B12) having 4 to 35 carbon atoms include the following monofunctional to hexafunctional (meth) acrylates. In the following, EO means ethylene oxide and PO means propylene oxide.

作為單官能(甲基)丙烯酸酯，可舉出：(甲基)丙烯酸乙酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸第三辛酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸4-正丁基環己酯、(甲基)丙烯酸冰片酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸苄酯、2-乙基己基二甘醇(甲基)丙烯酸酯、(甲基)丙烯酸丁氧基乙酯、(甲基)丙烯酸2-氯乙酯、(甲基)丙烯酸4-溴丁酯、(甲基)丙烯酸氰基乙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸丁氧基甲酯、單丙烯酸甲氧基丙烯酯、(甲基)丙烯酸3-甲氧基丁酯、(甲基)丙烯酸烷氧基甲酯、2-乙基己基卡必醇(甲基)丙烯酸酯、(甲基)丙烯酸烷氧基乙酯、(甲基)丙烯酸2-(2-甲氧基乙氧基)乙酯、(甲基)丙烯酸2-(2-丁氧基乙氧基)乙酯、(甲基)丙烯酸2,2,2-四氟乙酯、(甲基)丙烯酸1H,1H,2H,2H-全氟癸酯、(甲基)丙烯酸4-丁基苯酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸2,4,5-四甲基苯酯、(甲基)丙烯酸4-氯苯酯、(甲基)丙烯酸苯氧基甲酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸縮水甘油酯、(甲基) 丙烯酸縮水甘油氧基(glycidyloxy)丁酯、(甲基)丙烯酸縮水甘油氧基乙酯、(甲基)丙烯酸縮水甘油氧基丙酯、二乙二醇單乙烯基醚單丙烯酸酯、(甲基)丙烯酸四氫呋喃甲酯、(甲基)丙烯酸羥烷酯、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二乙基胺基乙酯、(甲基)丙烯酸二甲基胺基丙酯、(甲基)丙烯酸二乙基胺基丙酯、(甲基)丙烯酸三甲氧基矽烷基丙酯、(甲基)丙烯酸三甲氧基矽烷基丙酯、(甲基)丙烯酸三甲基矽烷基丙酯、聚環氧乙烷單甲基醚(甲基)丙烯酸酯、寡環氧乙烷單甲基醚(甲基)丙烯酸酯、聚環氧乙烷(甲基)丙烯酸酯、寡環氧乙烷(甲基)丙烯酸酯、寡環氧乙烷單烷基醚(甲基)丙烯酸酯、聚環氧乙烷單烷基醚(甲基)丙烯酸酯、二丙二醇(甲基)丙烯酸酯、聚環氧丙烷單烷基醚(甲基)丙烯酸酯、寡環氧丙烷單烷基醚(甲基)丙烯酸酯、2-甲基丙烯醯氧基乙基丁二酸、2-甲基丙烯醯氧基六氫苯二甲酸、苯二甲酸2-甲基丙烯醯氧基乙基-2-羥丙酯、丁氧基二乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸全氟辛基乙酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、EO改質酚(甲基)丙烯酸酯、EO改質甲酚(甲基)丙烯酸酯、EO改質壬酚(甲基)丙烯酸酯、PO改質壬酚(甲基)丙烯酸酯及EO改質(甲基)丙烯酸-2-乙基己酯等。 Examples of monofunctional (meth) acrylates include ethyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and tert-octyl (meth) acrylate. Ester, isoamyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, (methyl ) Cyclohexyl acrylate, 4-n-butylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl Diethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, cyano (meth) acrylate Ethyl ester, benzyl (meth) acrylate, butoxymethyl (meth) acrylate, methoxypropylacrylate monoacrylate, 3-methoxybutyl (meth) acrylate, alkoxy (meth) acrylate Methyl ester, 2-ethylhexyl carbitol (meth) acrylate, alkoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2- (2-Butoxyethoxy) ethyl (meth) acrylate, (methyl) 2,2,2-tetrafluoroethyl enoate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4-butylphenyl (meth) acrylate, phenyl (meth) acrylate , 2,4,5-tetramethylphenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate , (Meth) glycidyl acrylate, (meth) Glycidyloxybutyl acrylate, glycidoxyethyl (meth) acrylate, glycidoxypropyl (meth) acrylate, diethylene glycol monovinyl ether monoacrylate, (methyl ) Tetrahydrofuran acrylate, hydroxyalkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (A Group) 2-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (methyl) Dimethylaminopropyl acrylate, diethylaminopropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, (meth Base) trimethylsilyl propyl acrylate, polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) Group) acrylate, oligoethylene oxide (meth) acrylate, oligoethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide monoalkyl ether (meth) acrylate, di Propylene glycol (A ) Acrylate, polypropylene oxide monoalkyl ether (meth) acrylate, oligopropylene oxide monoalkyl ether (meth) acrylate, 2-methacryloxyethyl succinic acid, 2- Methacryloyloxyhexahydrophthalic acid, phthalic acid 2-methacryloyloxyethyl-2-hydroxypropyl ester, butoxydiethylene glycol (meth) acrylate, (meth) Trifluoroethyl acrylate, perfluorooctyl ethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, EO modified phenol (meth) acrylate, EO modified methyl Phenol (meth) acrylate, EO-modified nonylphenol (meth) acrylate, PO-modified nonylphenol (meth) acrylate, EO-modified 2-ethylhexyl (meth) acrylate, etc.

作為二官能(甲基)丙烯酸酯，可舉出：1,4-丁烷二(甲基)丙烯酸酯、1,6-己烷二丙烯酸酯、聚丙烯二 丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、新戊基二丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、2,4-二甲基-1,5-戊二醇二(甲基)丙烯酸酯、丁基乙基丙二醇(甲基)丙烯酸酯、乙氧基化環己烷甲醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、寡乙二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、2-乙基-2丁基-丁二醇二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、EO改質雙酚A二(甲基)丙烯酸酯、雙酚F聚乙氧基二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、寡丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、2-乙基-2-丁基-丙二醇二(甲基)丙烯酸酯、1,9-壬烷二(甲基)丙烯酸酯、丙氧基化乙氧基化雙酚A二(甲基)丙烯酸酯及三環癸烷二(甲基)丙烯酸酯等。 Examples of difunctional (meth) acrylates include 1,4-butane di (meth) acrylate, 1,6-hexane diacrylate, and polypropylene diacrylate. Acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl diacrylate, neopentyl glycol di (meth) acrylate Ester, 2,4-dimethyl-1,5-pentanediol di (meth) acrylate, butyl ethyl propylene glycol (meth) acrylate, ethoxylated cyclohexane methanol bis (methyl) Acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2-ethyl-2butyl-butanediol Di (meth) acrylate, hydroxytrimethylacetate neopentyl glycol di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, bisphenol F polyethoxydi (methyl ) Acrylate, polypropylene glycol di (meth) acrylate, oligopropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 2-ethyl-2-butyl-propylene glycol Di (meth) acrylate, 1,9-nonane di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate and tricyclodecane di (methyl) Acrylic esters, etc.

作為三官能的(甲基)丙烯酸酯，可舉出：三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、三羥甲基丙烷的環氧烷(alkylene oxide)改質三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷三((甲基)丙烯醯氧基丙基)醚、異三聚氰酸環氧烷改質三(甲基)丙烯酸酯、丙酸二季戊四醇三(甲基)丙烯酸酯、異三聚氰酸三((甲基)丙烯醯氧基乙基)酯、羥基三甲基乙醛改質二羥甲基丙烷三(甲基)丙烯酸酯、山梨醇三(甲基)丙烯酸酯、丙氧基化三羥甲基丙烷三(甲基)丙烯酸酯及乙氧基化甘油三丙烯酸酯等。 Examples of trifunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and trimethylolpropane epoxy. Alkylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyl propionate ), Ether, isocyanurate modified trialkyl (meth) acrylate, dipentaerythritol propionate tri (meth) acrylate, isocyanuric tris ((meth) acryloyl ethoxylate Base) ester, hydroxytrimethylacetaldehyde modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylic acid Ester and ethoxylated glycerol triacrylate.

作為四官能的(甲基)丙烯酸酯，可舉出：季戊四醇四(甲基)丙烯酸酯、山梨醇四(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、丙酸二季戊四醇四(甲基)丙烯酸酯及乙氧基化季戊四醇四(甲基)丙烯酸酯等。 Examples of tetrafunctional (meth) acrylates include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, and propylene. Acid dipentaerythritol tetra (meth) acrylate and ethoxylated pentaerythritol tetra (meth) acrylate etc.

作為五官能的(甲基)丙烯酸酯，可舉出：山梨醇五(甲基)丙烯酸酯及二季戊四醇五(甲基)丙烯酸酯。 Examples of pentafunctional (meth) acrylates include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.

作為六官能的(甲基)丙烯酸酯，可舉出：二季戊四醇六(甲基)丙烯酸酯、山梨醇六(甲基)丙烯酸酯、磷腈(phosphazene)的環氧烷改質六(甲基)丙烯酸酯及己內酯改質二季戊四醇六(甲基)丙烯酸酯等。 Examples of hexafunctional (meth) acrylates include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, and phosphazene (phosphazene) modified alkylene oxide. ) Acrylate and caprolactone modified dipentaerythritol hexa (meth) acrylate, etc.

作為碳數6~35的芳香族乙烯化合物(B13)，可舉出：乙烯噻吩、乙烯呋喃、乙烯吡啶、苯乙烯、甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、異丙基苯乙烯、氯甲基苯乙烯、甲氧基苯乙烯、乙醯氧基苯乙烯、氯苯乙烯、二氯苯乙烯、溴苯乙烯、乙烯基苯甲酸甲酯、3-甲基苯乙烯、4-甲基苯乙烯、3-乙基苯乙烯、4-乙基苯乙烯、3-丙基苯乙烯、4-丙基苯乙烯、3-丁基苯乙烯、4-丁基苯乙烯、3-己基苯乙烯、4-己基苯乙烯、3-辛基苯乙烯、4-辛基苯乙烯、3-(2-乙基己基)苯乙烯、4-(2-乙基己基)苯乙烯、烯丙基苯乙烯、異丙烯基苯乙烯、丁烯基苯乙烯、辛烯基苯乙烯、4-第三丁氧基羰基苯乙烯、4-甲氧基苯乙烯及4-第三丁氧基苯乙烯等。 Examples of the aromatic vinyl compound having 6 to 35 carbon atoms (B13) include vinylthiophene, ethylenefuran, vinylpyridine, styrene, methylstyrene, trimethylstyrene, ethylstyrene, and isopropyl Styrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl vinyl benzoate, 3-methylstyrene, 4 -Methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3- Hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allyl Styrene, isopropenyl styrene, butenyl styrene, octenyl styrene, 4-third butoxycarbonyl styrene, 4-methoxystyrene and 4-third butoxystyrene Wait.

作為碳數3~35的乙烯基醚化合物(B14)，例如可舉出以下的單官能或多官能乙烯基醚。 Examples of the vinyl ether compound (B14) having 3 to 35 carbon atoms include the following monofunctional or polyfunctional vinyl ethers.

作為單官能乙烯基醚，例如可舉出：甲基乙烯基醚、乙基乙烯基醚、丙基乙烯基醚、正丁基乙烯基醚、第三丁基乙烯基醚、2-乙基己基乙烯基醚、正壬基乙烯基醚、月桂基乙烯基醚、環己基乙烯基醚、環己基甲基乙烯基醚、4-甲基環己基甲基乙烯基醚、苄基乙烯基醚、二環戊烯基乙烯基醚、2-二環戊烯氧基乙基乙烯基醚、甲氧基乙基乙烯基醚、乙氧基乙基乙烯基醚、丁氧基乙基乙烯基醚、甲氧基乙氧基乙基乙烯基醚、乙氧基乙氧基乙基乙烯基醚、甲氧基聚乙二醇乙烯基醚、四氫呋喃甲基乙烯基醚、2-羥乙基乙烯基醚、2-羥丙基乙烯基醚、4-羥丁基乙烯基醚、4-羥甲基環己基甲基乙烯基醚、二乙二醇單乙烯基醚、聚乙二醇乙烯基醚、氯乙基乙烯基醚、氯丁基乙烯基醚、氯乙氧基乙基乙烯基醚、苯基乙基乙烯基醚及苯氧基聚乙二醇乙烯基醚。 Examples of monofunctional vinyl ethers include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, third butyl vinyl ether, and 2-ethylhexyl Vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methyl cyclohexyl methyl vinyl ether, benzyl vinyl ether, di Cyclopentenyl vinyl ether, 2-dicyclopentenyloxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methyl ether Oxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxy polyethylene glycol vinyl ether, tetrahydrofuran methyl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, ethyl chloride Vinyl ether, chlorobutyl vinyl ether, chloroethoxyethyl vinyl ether, phenylethyl vinyl ether and phenoxy polyethylene glycol vinyl ether.

作為多官能乙烯基醚，例如可舉出：乙二醇二乙烯基醚、二乙二醇二乙烯基醚、聚乙二醇二乙烯基醚、丙二醇二乙烯基醚、丁二醇二乙烯基醚、己二醇二乙烯基醚、雙酚A環氧烷二乙烯基醚、雙酚F環氧烷二乙烯基醚等二乙烯基醚類；三羥甲基乙烷三乙烯基醚、三羥甲基丙烷三乙烯基醚、二-三羥甲基丙烷四乙烯基醚、甘油三乙烯基醚、季戊四醇四乙烯基醚、二季戊四醇五乙烯基醚、二季戊四醇六乙烯基醚、環氧乙烷加成三羥甲基丙烷三乙烯基醚、環氧丙烷加成三羥甲基丙 烷三乙烯基醚、環氧乙烷加成二-三羥甲基丙烷四乙烯基醚、環氧丙烷加成二-三羥甲基丙烷四乙烯基醚、環氧乙烷加成季戊四醇四乙烯基醚、環氧丙烷加成季戊四醇四乙烯基醚、環氧乙烷加成二季戊四醇六乙烯基醚及環氧丙烷加成二季戊四醇六乙烯基醚。 Examples of polyfunctional vinyl ethers include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, and butylene glycol divinyl ether. Divinyl ethers such as ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether; trimethylolethane trivinyl ether, tris Hydroxymethylpropane trivinyl ether, di-trimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide Alkane addition trimethylolpropane trivinyl ether, propylene oxide addition trimethylolpropane Alkyl trivinyl ether, ethylene oxide addition di-trimethylolpropane tetravinyl ether, propylene oxide addition di-trimethylol propane tetravinyl ether, ethylene oxide addition pentaerythritol tetraethylene Base ether, propylene oxide addition pentaerythritol tetravinyl ether, ethylene oxide addition dipentaerythritol hexavinyl ether and propylene oxide addition dipentaerythritol hexavinyl ether.

作為其他的自由基聚合性化合物(B15)，可舉出：乙烯酯化合物(乙酸乙烯酯、丙酸乙烯酯及柯赫酸乙烯酯(vinyl versatate)等)、烯丙酯化合物(乙酸烯丙酯等)、含鹵素單體(偏二氯乙烯及氯乙烯等)及烯烴化合物(乙烯及丙烯等)等。 Examples of other radical polymerizable compounds (B15) include vinyl ester compounds (vinyl acetate, vinyl propionate, and vinyl versatate), and allyl ester compounds (allyl acetate Etc.), halogen-containing monomers (vinylidene chloride and vinyl chloride, etc.) and olefin compounds (ethylene and propylene, etc.).

此等之中，從聚合速度的觀點來看，較佳為(甲基)丙烯醯胺化合物(B11)及(甲基)丙烯酸酯化合物(B12)，特佳為(甲基)丙烯酸酯化合物(B12)。 Among these, from the viewpoint of polymerization rate, (meth) acrylamide compound (B11) and (meth) acrylate compound (B12) are preferred, and (meth) acrylate compound ( B12).

<<離子聚合性化合物(B2)>> << Ionic polymerizable compound (B2) >>

作為離子聚合性化合物(B2)，可舉出：碳數3~20的環氧化合物(B21)、碳數4~20的氧雜環丁烷(oxetane)化合物(B22)等。 Examples of the ion-polymerizable compound (B2) include an epoxy compound having 3 to 20 carbon atoms (B21) and an oxetane compound having 4 to 20 carbon atoms (B22).

作為碳數3~20的環氧化合物(B21)，可舉出例如以下的單官能或多官能環氧化合物。 Examples of the epoxy compound (B21) having 3 to 20 carbon atoms include the following monofunctional or polyfunctional epoxy compounds.

作為單官能環氧化合物，例如可舉出：苯基縮水甘油基醚、對第三丁基苯基縮水甘油基醚、丁基縮水甘油基醚、2-乙基己基縮水甘油基醚、烯丙基縮水甘油基醚、1,2-環氧丁烷、1,3-丁二烯一氧化物(1,3 butadiene monooxide)、1,2-環氧十二烷、環氧氯丙烷(epichlorohydrin)、1,2-環氧癸烷、氧化苯乙烯、環氧環 己烷、3-甲基丙烯醯氧基甲基環氧環己烷、3-丙烯醯氧基甲基環氧環己烷及3-乙烯基環氧環己烷。 Examples of monofunctional epoxy compounds include phenyl glycidyl ether, p-third butyl phenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and allyl Glycidyl ether, 1,2-epoxybutane, 1,3-butadiene monooxide, 1,2-epoxydodecane, epichlorohydrin , 1,2-epoxydecane, styrene oxide, epoxy ring Hexane, 3-methacryloxymethylepoxycyclohexane, 3-propenyloxymethylepoxycyclohexane and 3-vinylepoxycyclohexane.

作為多官能環氧化合物，例如可舉出：雙酚A二縮水甘油基醚、雙酚F二縮水甘油基醚、雙酚S二縮水甘油基醚、溴化雙酚A二縮水甘油基醚、溴化雙酚F二縮水甘油基醚、溴化雙酚S二縮水甘油基醚、環氧基酚醛樹脂、氫化雙酚A二縮水甘油基醚、氫化雙酚F二縮水甘油基醚、氫化雙酚S二縮水甘油基醚、3,4-環氧基環己基甲基-3’,4’-環氧基環己烷甲酸酯、2-(3,4-環氧基環己基-5,5-螺-3,4-環氧基)環己烷-間二烷、雙(3,4-環氧基環己基甲基)己二酸酯、乙烯基環氧環己烷、4-乙烯基環氧基環己烷、雙(3,4-環氧基-6-甲基環己基甲基)己二酸酯、3,4-環氧基-6-甲基環己基-3’,4’-環氧基-6’-甲基環己烷甲酸酯、亞甲雙(3,4-環氧基環己烷)、二環戊二烯二環氧化物(dicyclopentadiene diepoxide)、乙二醇二(3,4-環氧基環己基甲基)醚、伸乙基雙(3,4-環氧基環己烷甲酸酯)、環氧基六氫苯二甲酸二辛酯、環氧基六氫苯二甲酸二-2-乙基己酯、1,4-丁二醇二縮水甘油基醚、1,6-己二醇二縮水甘油基醚、甘油三縮水甘油基醚、三羥甲基丙烷三縮水甘油基醚、聚乙二醇二縮水甘油基醚、聚丙二醇二縮水甘油基醚類；1,1,3-十四烷二烯二氧化物(1,1,3-tetradecadiene dioxide)、檸檬烯二氧化物(limonene dioxide)、1,2,7,8-二環氧基辛烷及1,2,5,6-二環氧基環辛烷。 Examples of the polyfunctional epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and brominated bisphenol A diglycidyl ether. Brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy phenolic resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol Phenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5 , 5-spiro-3,4-epoxy) cyclohexane-meta Alkanes, bis (3,4-epoxycyclohexylmethyl) adipate, vinylepoxycyclohexane, 4-vinylepoxycyclohexane, bis (3,4-epoxy- 6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexane formate , Methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide (dicyclopentadiene diepoxide), ethylene glycol bis (3,4-epoxycyclohexylmethyl) ether, Ethylene bis (3,4-epoxycyclohexanecarboxylate), dioctyl hexahydrophthalate, di-2-ethylhexyl hexahydrophthalate, 1 , 4-Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether Ethers, polypropylene glycol diglycidyl ethers; 1,1,3-tetradecadiene dioxide (1,1,3-tetradecadiene dioxide), limonene dioxide, 1,2, 7,8-diepoxyoctane and 1,2,5,6-diepoxycyclooctane.

此等的環氧化合物之中，從所謂聚合速度優異的觀點來看，較佳為芳香族環氧化物及脂環式環氧化物，特佳為脂環式環氧化物。 Among these epoxy compounds, from the viewpoint of excellent so-called polymerization rate, aromatic epoxides and alicyclic epoxides are preferred, and alicyclic epoxides are particularly preferred.

作為碳數為4~20的氧雜環丁烷化合物(B22)，可舉出具有1個~6個氧雜環丁烷環的化合物等。 Examples of the oxetane compound having 4 to 20 carbon atoms (B22) include compounds having 1 to 6 oxetane rings.

作為具有1個氧雜環丁烷環的化合物，例如可舉出：3-乙基-3-羥甲基氧雜環丁烷、3-(甲基)烯丙氧基甲基-3-乙基氧雜環丁烷、(3-乙基-3-氧雜環丁基甲氧基)甲基苯、4-氟-[1-(3-乙基-3-氧雜環丁基甲氧基)甲基]苯、4-甲氧基-[1-(3-乙基-3-氧雜環丁基甲氧基)甲基]苯、[1-(3-乙基-3-氧雜環丁基甲氧基)乙基]苯基醚、異丁氧基甲基(3-乙基-3-氧雜環丁基甲基)醚、異冰片氧基乙基(3-乙基-3-氧雜環丁基甲基)醚、異冰片基(3-乙基-3-氧雜環丁基甲基)醚、2-乙基己基(3-乙基-3-氧雜環丁基甲基)醚、乙基二乙二醇(3-乙基-3-氧雜環丁基甲基)醚、二環戊二烯(3-乙基-3-氧雜環丁基甲基)醚、二環戊烯氧基乙基(3-乙基-3-氧雜環丁基甲基)醚、二環戊烯基(3-乙基-3-氧雜環丁基甲基)醚、四氫呋喃甲基(3-乙基-3-氧雜環丁基甲基)醚、四溴苯基(3-乙基-3-氧雜環丁基甲基)醚、2-四溴苯氧基乙基(3-乙基-3-氧雜環丁基甲基)醚、三溴苯基(3-乙基-3-氧雜環丁基甲基)醚、2-三溴苯氧基乙基(3-乙基-3-氧雜環丁基甲基)醚、2-羥乙基(3-乙基-3-氧雜環丁基甲基)醚、2-羥丙基(3-乙基-3-氧雜環丁基甲基)醚、丁氧基乙基(3-乙基-3-氧雜環丁基甲基)醚、五氯苯基(3-乙基-3-氧雜環丁基甲基)醚、五溴苯基(3-乙基-3- 氧雜環丁基甲基)醚及冰片基(3-乙基-3-氧雜環丁基甲基)醚。 As the compound having one oxetane ring, for example, 3-ethyl-3-hydroxymethyloxetane, 3- (methyl) allyloxymethyl-3-ethyl Oxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl ] Benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-ethyl-3-oxetanylmethoxy) Ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanyl methyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanyl methyl) ether , Isobornyl (3-ethyl-3-oxetanyl methyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanyl methyl) ether, ethyl diethylene glycol (3- Ethyl-3-oxetanyl methyl) ether, dicyclopentadiene (3-ethyl-3-oxetanyl methyl) ether, dicyclopentenyloxyethyl (3-ethyl-3- Oxetanyl methyl) ether, dicyclopentenyl (3-ethyl-3-oxetanyl methyl) ether, tetrahydrofuran methyl (3-ethyl-3-oxetanyl methyl) ether, tetrabromo Phenyl (3-ethyl-3-oxetanyl methyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxa Cyclobutylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanyl methyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanyl methyl) ether , 2-hydroxyethyl (3-ethyl-3-oxetanyl methyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanyl methyl) ether, butoxyethyl (3 -Ethyl-3-oxetanyl methyl) ether, pentachlorophenyl (3-ethyl-3-oxetanyl methyl) ether, pentabromophenyl (3-ethyl-3- Oxetanyl methyl) ether and norbornyl (3-ethyl-3-oxetanyl methyl) ether.

作為具有2~6個氧雜環丁烷環的化合物，例如可舉出：3,7-雙(3-氧雜環丁基)-5-氧雜-壬烷、3,3’-(1,3-(2-甲烯基)丙二基雙(氧基亞甲基))雙-(3-乙基氧雜環丁烷)、1,4-雙[(3-乙基-3-氧雜環丁基甲氧基)甲基]苯、1,2-雙[(3-乙基-3-氧雜環丁基甲氧基)甲基]乙烷、1,3-雙[(3-乙基-3-氧雜環丁基甲氧基)甲基]丙烷、乙二醇雙(3-乙基-3-氧雜環丁基甲基)醚、二環戊烯基雙(3-乙基-3-氧雜環丁基甲基)醚、三乙二醇雙(3-乙基-3-氧雜環丁基甲基)醚、四乙二醇雙(3-乙基-3-氧雜環丁基甲基)醚、三環癸烷二基二亞甲基(3-乙基-3-氧雜環丁基甲基)醚、三羥甲基丙烷參(3-乙基-3-氧雜環丁基甲基)醚、1,4-雙(3-乙基-3-氧雜環丁基甲氧基)丁烷、1,6-雙(3-乙基-3-氧雜環丁基甲氧基)己烷、季戊四醇參(3-乙基-3-氧雜環丁基甲基)醚、季戊四醇肆(3-乙基-3-氧雜環丁基甲基)醚、聚乙二醇雙(3-乙基-3-氧雜環丁基甲基)醚、二季戊四醇陸(3-乙基-3-氧雜環丁基甲基)醚、二季戊四醇伍(3-乙基-3-氧雜環丁基甲基)醚、二季戊四醇肆(3-乙基-3-氧雜環丁基甲基)醚、己內酯改質二季戊四醇陸(3-乙基-3-氧雜環丁基甲基)醚、己內酯改質二季戊四醇伍(3-乙基-3-氧雜環丁基甲基)醚、二-三羥甲基丙烷肆(3-乙基-3-氧雜環丁基甲基)醚、EO改質雙酚A雙(3-乙基-3-氧雜環丁基甲基)醚、PO改質雙酚A雙(3-乙基-3-氧雜環丁基甲基)醚、EO改質氫化雙酚A雙(3-乙基-3-氧雜環丁基甲基)醚、PO改 質氫化雙酚A雙(3-乙基-3-氧雜環丁基甲基)醚及EO改質雙酚F(3-乙基-3-氧雜環丁基甲基)醚。 As the compound having 2 to 6 oxetane rings, for example, 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 '-(1 , 3- (2-Methenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3- Oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl -3-oxetanyl methoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanyl methyl) ether, dicyclopentenyl bis (3-ethyl-3-oxo Heterocyclobutyl methyl) ether, triethylene glycol bis (3-ethyl-3-oxetanyl methyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanyl methyl) ether, tri Cyclodecanediyl dimethylene (3-ethyl-3-oxetanyl methyl) ether, trimethylolpropane ginseng (3-ethyl-3-oxetanyl methyl) ether, 1,4 -Bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol ginseng (3-ethyl -3-oxetanyl methyl) ether, pentaerythritol (3-ethyl-3-oxetanyl methyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanyl methyl) ether , Dipentaerythritol (3-ethyl-3-oxetanyl methyl) ether, dipentaerythritol and (3-ethyl-3-oxetanyl methyl) ether, dipentaerythritol (3-ethyl-3- Oxetanyl methyl) ether, caprolactone modified dipentaerythritol Lu (3-ethyl-3-oxetanyl methyl) ether, caprolactone modified dipentaerythritol and (3-ethyl-3-oxa Cyclobutylmethyl) ether, di-trimethylolpropane (3-ethyl-3-oxetanyl methyl) ether, EO modified bisphenol A bis (3-ethyl-3-oxetanyl methyl ) Ether, PO modified bisphenol A bis (3-ethyl-3-oxetanyl methyl) ether, EO modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanyl methyl) ether, PO change Hydrogenated bisphenol A bis (3-ethyl-3-oxetanyl methyl) ether and EO modified bisphenol F (3-ethyl-3-oxetanyl methyl) ether.

聚合性化合物較佳為具有2個以上從環氧基、丙烯酸基、甲基丙烯酸基、烯丙基及苯乙烯基所選出的1種以上的聚合性基的化合物，更佳為具有2個以上從丙烯酸基、甲基丙烯酸基、烯丙基及苯乙烯基所選出的1種以上的聚合性基的化合物，再更佳為具有2個以上從丙烯酸基、甲基丙烯酸基、烯丙基及苯乙烯基所選出的1種以上的聚合性基且具有下述部分構造的化合物。藉由聚合性化合物具有下述部分構造能更加提升耐熱性。 The polymerizable compound is preferably a compound having two or more polymerizable groups selected from an epoxy group, an acrylic group, a methacrylic group, an allyl group, and a styryl group, and more preferably has two or more polymerizable groups. Compounds of at least one polymerizable group selected from acrylic groups, methacrylic groups, allyl groups and styryl groups are even more preferably those having at least two selected from acrylic groups, methacrylic groups, allyl groups and A compound having one or more polymerizable groups selected from styrene groups and having the following partial structure. Since the polymerizable compound has the following partial structure, the heat resistance can be further improved.

式中的＊係連結鍵。 * In the formula is the link key.

作為聚合性化合物的市售品，例如可舉出：A-9300、A-TMP、A-TMPT、A-TMMT、AD-TMP、A-DPH、A-BPE-4、A-BPE-10、4G(新中村化學工業製，多官能(甲基)丙烯酸酯化合物)、TAIC(TCI，3官能烯丙基化合物)、VISCOAT 802(大阪有機化學，多官能(甲基)丙烯酸酯化合物)、TEGMA(aldrich，2官能(甲基)丙烯酸酯化合物)、CD401(SARTOMER製，2官能(甲基)丙烯酸酯化合物)、EPIKOTE(三菱化學，2官能環氧化合物)等。 Examples of commercially available products of polymerizable compounds include A-9300, A-TMP, A-TMPT, A-TMMT, AD-TMP, A-DPH, A-BPE-4, A-BPE-10, 4G (manufactured by Shin Nakamura Chemical Industry, multifunctional (meth) acrylate compound), TAIC (TCI, trifunctional allyl compound), VISCOAT 802 (Osaka Organic Chemistry, multifunctional (meth) acrylate compound), TEGMA (aldrich, bifunctional (meth) acrylate compound), CD401 (manufactured by SARTOMER, bifunctional (meth) acrylate compound), EPIKOTE (Mitsubishi Chemical, bifunctional epoxy compound), etc.

從良好的接著強度、耐熱性的觀點來看，相對於組成物的總固體成分，本發明的組成物中的聚合性化合物的含量較佳為5~75質量%，更佳為10~70質量%，再更佳為10~60質量%。 From the viewpoint of good adhesive strength and heat resistance, the content of the polymerizable compound in the composition of the present invention is preferably 5 to 75% by mass relative to the total solid content of the composition, more preferably 10 to 70% by mass %, Even better is 10 ~ 60% by mass.

聚合性化合物可以僅為1種，也可以為2種以上。溶劑為2種以上的情況，較佳為其合計在上述範圍內。 The polymerizable compound may be only one kind, or two or more kinds. When there are two or more solvents, the total amount is preferably within the above range.

此外，聚合性化合物和上述的聚碳酸酯樹脂的比率(質量比)，較佳為(聚合性化合物/聚碳酸酯樹脂)=90/10~10/90，更佳為20/80~80/20。 In addition, the ratio (mass ratio) of the polymerizable compound to the polycarbonate resin described above is preferably (polymerizable compound / polycarbonate resin) = 90/10 to 10/90, more preferably 20/80 to 80 / 20.

<<溶劑>> << Solvent >>

本發明的組成物含有溶劑。 The composition of the present invention contains a solvent.

作為溶劑，使用含有50質量%以上的沸點為130℃以上、分子量為75以上的非質子性溶劑者。 As the solvent, an aprotic solvent containing 50% by mass or more and having a boiling point of 130 ° C. or more and a molecular weight of 75 or more is used.

藉由使用上述的非質子性溶劑，組成物的保存穩定性良好。此外，因為沸點為130℃以上，而能抑制烘烤時的起泡，能抑制空隙的發生。此外，因為分子量為75以上，而具有適度的揮發性，能使應用於半導體晶圓等之後的表面狀態良好。 By using the above-mentioned aprotic solvent, the storage stability of the composition is good. In addition, since the boiling point is 130 ° C. or higher, blistering during baking can be suppressed, and the occurrence of voids can be suppressed. In addition, because the molecular weight is 75 or more, and has moderate volatility, it can improve the surface condition after being applied to a semiconductor wafer or the like.

非質子性溶劑的沸點較佳為130~230℃，更佳為150~210℃。 The boiling point of the aprotic solvent is preferably 130 to 230 ° C, more preferably 150 to 210 ° C.

非質子性溶劑的分子量較佳為75~150，更佳為80~110。 The molecular weight of the aprotic solvent is preferably 75-150, more preferably 80-110.

作為沸點為130℃以上、分子量為75以上的非質子性溶劑，可舉出：苯甲醚(沸點154℃，分子量108)、γ-丁內酯(沸點204℃，分子量86)、δ-戊內酯(沸點 207℃，分子量100)、環己酮(沸點156℃，分子量98)、環戊酮(沸點130℃，分子量84)、N-甲基-2-吡咯啶酮(沸點202℃，分子量99)、N-乙基-2-吡咯啶酮(沸點225℃，分子量113)、二甲基亞碸(沸點189℃，分子量78)、二甲基乙醯胺(沸點165℃，分子量87)、乙酸1-甲氧基-丙酯(沸點146℃，分子量132)、甲基戊基酮(沸點149℃，分子量114)等。 Examples of aprotic solvents having a boiling point of 130 ° C. or higher and a molecular weight of 75 or more include anisole (boiling point 154 ° C., molecular weight 108), γ-butyrolactone (boiling point 204 ° C., molecular weight 86), and δ-pentane Lactone (boiling point 207 ℃, molecular weight 100), cyclohexanone (boiling point 156 ℃, molecular weight 98), cyclopentanone (boiling point 130 ℃, molecular weight 84), N-methyl-2-pyrrolidone (boiling point 202 ℃, molecular weight 99), N-ethyl-2-pyrrolidone (boiling point 225 ° C, molecular weight 113), dimethyl sulfoxide (boiling point 189 ° C, molecular weight 78), dimethylacetamide (boiling point 165 ° C, molecular weight 87), acetic acid 1 -Methoxy-propyl ester (boiling point 146 ° C, molecular weight 132), methyl amyl ketone (boiling point 149 ° C, molecular weight 114), etc.

在本發明中，作為溶劑，可以僅使用上述非質子性溶劑，也可以併用上述非質子性溶劑、和上述非質子性溶劑以外的溶劑(以下也稱為其他溶劑)。也可以使用複數種上述非質子性溶劑。 In the present invention, as the solvent, only the aprotic solvent may be used, or the aprotic solvent and a solvent other than the aprotic solvent (hereinafter also referred to as other solvents) may be used in combination. A plurality of the above-mentioned aprotic solvents can also be used.

其他溶劑的含量，必須小於溶劑總量的50質量%，較佳為20質量%以下，更佳為10質量%以下，再更佳為5質量%以下，特佳為實質上不含有。實質上不含有係例如，溶劑總量中的含量較佳為1質量%以下，更佳為0.5質量%以下，再更佳為0.1質量%以下，特佳為不含有。 The content of other solvents must be less than 50% by mass of the total solvent, preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably not substantially contained. Substantially no content is included. For example, the content in the total amount of the solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, and particularly preferably does not contain.

作為其他溶劑，能沒有限制地使用周知的溶劑。可舉出：酯類、醚類、酮類、醯胺類、醇類、烴等。例如，能使用日本特開2009-256588號公報的段落編號0072、日本特開2010-70645號公報的段落編號0036、日本特開2010-6983號公報的段落編號0053所記載的溶劑等。 As other solvents, well-known solvents can be used without limitation. Examples include esters, ethers, ketones, amides, alcohols, and hydrocarbons. For example, the solvents described in paragraph number 0972 of Japanese Patent Application Publication No. 2009-256588, paragraph number 0036 of Japanese Patent Application Publication No. 2010-70645, paragraph 0005 of Japanese Patent Application Publication No. 2010-6983, and the like can be used.

本發明的組成物含有50質量%以上的溶劑，較佳為含有50~90質量%，更佳為50~80質量%以上。若溶劑的含量為50質量%以上，便能作出塗布作業性佳的組成物。 The composition of the present invention contains 50% by mass or more of a solvent, preferably 50 to 90% by mass, and more preferably 50 to 80% by mass or more. If the content of the solvent is 50% by mass or more, a composition with good coating workability can be produced.

溶劑可以僅為1種，也可以為2種以上。溶劑為2種以上的情況，較佳為其合計在上述範圍內。 The solvent may be only one kind, or two or more kinds. When there are two or more solvents, the total amount is preferably within the above range.

<光聚合引發劑> <Photoinitiator>

本發明的組成物能含有光聚合引發劑。 The composition of the present invention can contain a photopolymerization initiator.

本發明的組成物藉由含有光聚合引發劑，在將組成物應用於半導體晶圓等而形成層狀的接著層後，利用照射光來引起由自由基或酸所造成的硬化，能使在光照射部的接著性降低。因此，例如，若透過具有僅遮蔽電極部的圖案的光罩而對接著層表面進行，便有能按照電極的圖案，簡便地作出溶解性不同的區域的優勢。 The composition of the present invention contains a photopolymerization initiator. After applying the composition to a semiconductor wafer or the like to form a layered adhesive layer, the irradiation of light is used to cause hardening caused by free radicals or acids. The adhesion of the light irradiated part is reduced. Therefore, for example, if the surface of the adhesive layer is passed through a mask having a pattern that only shields the electrode portion, there is an advantage that regions with different solubility can be easily formed according to the pattern of the electrode.

作為光聚合引發劑，只要是具有引發聚合性化合物的聚合反應(交聯反應)的能力，便沒有特別的限制，能從周知的光聚合引發劑之中適宜選擇。例如，較佳為對從紫外線區域到可見的光線具有感光性者。此外，可以是與經光激發的增感劑產生任何作用以生成活性自由基的活性劑。較佳為藉由光照射來產生自由基或酸的化合物。 The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization reaction (crosslinking reaction) of the polymerizable compound, and can be appropriately selected from well-known photopolymerization initiators. For example, those having sensitivity to visible light from the ultraviolet region are preferred. In addition, it may be an active agent that produces any action with a light-excited sensitizer to generate active free radicals. Compounds that generate free radicals or acids by light irradiation are preferred.

此外，光聚合引發劑，較佳為含有至少1種在約300nm~800nm(較佳為330nm~500nm)的範圍內具有至少約50的分子吸光係數的化合物。 In addition, the photopolymerization initiator preferably contains at least one compound having a molecular absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm (preferably 330 nm to 500 nm).

作為光聚合引發劑，能沒有限制地使用周知的化合物。例如可舉出：鹵化烴衍生物(例如，具有三骨架者、具有二唑骨架者、具有三鹵甲基(trihalomethyl)者等)、醯基膦氧化物(acylphosphine oxide)等醯基膦化合物、六芳基聯咪唑 (hexaarylbiimidazole)、肟衍生物等肟化合物、有機過氧化物、硫化合物、酮化合物、芳香族鎓鹽、酮肟醚、胺基苯乙酮化合物、羥基苯乙酮、偶氮系化合物、疊氮化合物、茂金屬化合物、有機硼化合物、鐵芳烴錯合物等。 As the photopolymerization initiator, well-known compounds can be used without limitation. For example, halogenated hydrocarbon derivatives (for example, having three Skeletons, have Diazole skeletons, trihalomethyl groups, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives such as oxime derivatives, organic compounds Oxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron aromatic hydrocarbons Compound etc.

作為具有三骨架的鹵化烴化合物，例如可舉出：若林等人著的Bull.Chem.Soc.Japan,42,2924(1969)記載的化合物、英國專利1388492號說明書記載的化合物、日本特開昭53-133428號公報記載的化合物、德國專利3337024號說明書記載的化合物、F.C.Schaefer等人的J.Org.Chem.；29,1527(1964)記載的化合物、日本特開昭62-58241號公報記載的化合物、日本特開平5-281728號公報記載的化合物、日本特開平5-34920號公報記載的化合物、美國專利第4212976號說明書所記載的化合物等。 As having three Examples of the halogenated hydrocarbon compounds of the skeleton include compounds described in Bull. Chem. Soc. Japan, 42, 2924 (1969) by Wakabayashi et al., Compounds described in British Patent No. 1384492, and Japanese Patent Laid-Open No. 53-133428. The compound described in the Japanese Patent Publication, the compound described in the German Patent No. 3337024, the compound described in FC Schaefer et al. J. Org. Chem .; 29,1527 (1964), the compound described in Japanese Patent Laid-Open No. 62-58241, Japan The compound described in Japanese Patent Laid-Open No. 5-281728, the compound described in Japanese Patent Laid-Open No. 5-34920, the compound described in US Patent No. 4212976, and the like.

作為美國專利第4212976號說明書所記載的化合物，例如可舉出：具有二唑骨架的化合物(例如，2-三氯甲基-5-苯基-1,3,4-二唑、2-三氯甲基-5-(4-氯苯基)-1,3,4-二唑、2-三氯甲基-5-(1-萘基)-1,3,4-二唑、2-三氯甲基-5-(2-萘基)-1,3,4-二唑、2-三溴甲基-5-苯基-1,3,4-二唑、2-三溴甲基-5-(2-萘基)-1,3,4-二唑；2-三氯甲基-5-苯乙烯基-1,3,4-二唑、2-三氯甲基-5-(4-氯苯乙烯基)-1,3,4-二唑、2-三氯甲基-5-(4-甲氧基苯乙烯基)-1,3,4-二唑、2-三氯甲基-5-(1-萘基)-1,3,4-二唑、2-三氯甲基-5-(4-正丁氧基苯乙烯基)-1,3,4-二唑、2-三溴甲基-5-苯乙烯基-1,3,4-二唑等)等。 Examples of the compounds described in US Patent No. 4212976 include: Diazole skeleton compounds (for example, 2-trichloromethyl-5-phenyl-1,3,4- Diazole, 2-trichloromethyl-5- (4-chlorophenyl) -1,3,4- Diazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4- Diazole, 2-trichloromethyl-5- (2-naphthyl) -1,3,4- Diazole, 2-tribromomethyl-5-phenyl-1,3,4- Diazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4- Oxadiazole; 2-trichloromethyl-5-styryl-1,3,4- Diazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4- Diazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4- Diazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4- Diazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4- Diazole, 2-tribromomethyl-5-styryl-1,3,4- Diazole, etc.).

此外，作為上述以外的光聚合引發劑，可舉出：吖啶衍生物(例如9-苯基吖啶、1,7-雙(9,9'-吖啶基)庚烷等)、N-苯基甘胺酸等、多鹵化合物(例如，四溴化碳、苯基三溴甲基碸、苯基三氯甲基酮等)、香豆素類(例如3-(2-苯并呋喃醯基(benzofuranoyl))-7-二乙胺基香豆素、3-(2-苯并呋喃甲醯基(benzofuroyl))-7-(1-吡咯啶基)香豆素、3-苯甲醯基-7-二乙胺基香豆素、3-(2-甲氧基苯甲醯基)-7-二乙胺基香豆素、3-(4-二甲胺基苯甲醯基)-7-二乙胺基香豆素、3,3'-羰基雙(5,7-二-正丙氧基香豆素)、3,3'-羰基雙(7-二乙胺基香豆素)、3-苯甲醯基-7-甲氧基香豆素、3-(2-呋喃甲醯基)-7-二乙胺基香豆素、3-(4-二乙胺基桂皮醯基)-7-二乙胺基香豆素、7-甲氧基-3-(3-吡啶基羰基)香豆素、3-苯甲醯基-5,7-二丙氧基香豆素、7-苯并三唑-2-基香豆素，此外，日本特開平5-19475號公報、日本特開平7-271028號公報、日本特開2002-363206號公報、日本特開2002-363207號公報、日本特開2002-363208號公報、日本特開2002-363209號公報等記載的香豆素化合物等)、醯基膦氧化物類(例如雙(2,4,6-三甲基苯甲醯基)-苯基膦氧化物、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基-戊基苯基膦氧化物、LucirinTPO等)、茂金屬類(例如雙(η5-2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)-苯基)鈦、η5-環戊二烯基-η6-異丙苯基-鐵(1+)-六氟磷酸鹽(1-)等)、日本特開昭53-133428號公報、日本專利特公昭57-1819號公報、日本特公昭57-6096號公報、及美國專利第3615455號說明書所記載的化合物等。 In addition, as the photopolymerization initiator other than the above, acridine derivatives (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N- Phenylglycine, etc., polyhalogen compounds (e.g., carbon tetrabromide, phenyltribromomethylbenzene, phenyltrichloromethylketone, etc.), coumarins (e.g., 3- (2-benzofuran Benzofuranoyl) -7-diethylamino coumarin, 3- (2-benzofuranyl) benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl Acyl-7-diethylaminocoumarin, 3- (2-methoxybenzyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzyl) ) -7-diethylaminocoumarin, 3,3'-carbonyl bis (5,7-di-n-propoxycoumarin), 3,3'-carbonyl bis (7-diethylamino couma (Coumarin), 3-benzyl-7-methoxycoumarin, 3- (2-furylcarboxyl) -7-diethylaminocoumarin, 3- (4-diethylamino (Cinnamomide) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzyl-5,7-dipropoxy incense Coumarin, 7-benzotriazol-2-yl coumarin, Japanese Patent Laid-Open No. 5-19475, Japanese Patent Laid-Open No. 7-271028, Japan Coumarin compounds described in JP 2002-363206, JP 2002-363207, JP 2002-363208, JP 2002-363209, etc.), acetylphosphine oxides ( For example, bis (2,4,6-trimethylbenzyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzyl) -2,4,4-trimethyl- Amylphenyl phosphine oxide, Lucirin TPO, etc.), metallocenes (e.g. bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole (-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-isopropylphenyl-iron (1 +)-hexafluorophosphate (1-), etc.), Japanese Unexamined Patent Publication 53-133428 The compounds described in Japanese Patent Publication, Japanese Patent Publication No. 57-1819, Japanese Patent Publication No. 57-6096, and US Patent No. 3615455.

作為酮化合物，例如可舉出：二苯基酮、2-甲基二苯基酮、3-甲基二苯基酮、4-甲基二苯基酮、4-甲氧基二苯基酮、2-氯二苯基酮、4-氯二苯基酮、4-溴二苯基酮、2-羧基二苯基酮、2-乙氧基羰基二苯基酮、二苯基酮四甲酸或其四甲酯、4,4'-雙(二烷基胺基)二苯基酮類(例如，4,4’-雙(二甲胺基)二苯基酮、4,4’-雙(二環己胺基)二苯基酮、4,4’-雙(二乙胺基)二苯基酮、4,4'-雙(二羥基乙胺基)二苯基酮、4-甲氧基-4’-二甲胺基二苯基酮、4,4’-二甲氧基二苯基酮、4-二甲胺基二苯基酮、4-二甲胺基苯乙酮、二苯基乙二酮、蒽醌、2-第三丁基蒽醌、2-甲基蒽醌、菲醌、酮(xanthone)、噻噸酮(thioxanthone)、2-氯-噻噸酮、2,4-二乙基噻噸酮、茀酮、2-苄基-二甲胺基-1-(4-啉基苯基)-1-丁酮、2-甲基-1-[4-(甲硫基)苯基]-2-啉基-1-丙酮、2-羥基-2-甲基-[4-(1-甲基乙烯基)苯基]丙醇寡聚物、苯偶姻、苯偶姻醚類(例如苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻丙基醚、苯偶姻異丙基醚、苯偶姻苯基醚、苄基二甲基縮酮)、吖啶酮、氯吖啶酮、N-甲基吖啶酮、N-丁基吖啶酮、N-丁基-氯吖啶酮等。 Examples of ketone compounds include diphenyl ketone, 2-methyl diphenyl ketone, 3-methyl diphenyl ketone, 4-methyl diphenyl ketone, 4-methoxy diphenyl ketone , 2-chlorodiphenyl ketone, 4-chlorodiphenyl ketone, 4-bromodiphenyl ketone, 2-carboxydiphenyl ketone, 2-ethoxycarbonyl diphenyl ketone, diphenyl ketone tetracarboxylic acid Or its tetramethyl ester, 4,4'-bis (dialkylamino) diphenyl ketones (for example, 4,4'-bis (dimethylamino) diphenyl ketone, 4,4'-bis (Dicyclohexylamino) diphenyl ketone, 4,4'-bis (diethylamino) diphenyl ketone, 4,4'-bis (dihydroxyethylamino) diphenyl ketone, 4-methyl Oxy-4'-dimethylaminodiphenylketone, 4,4'-dimethoxydiphenylketone, 4-dimethylaminodiphenylketone, 4-dimethylaminoacetophenone, Diphenylethanedione, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, phenanthrenequinone, Xanthone, thioxanthone, 2-chloro-thioxanthone, 2,4-diethylthioxanthone, stilbene, 2-benzyl-dimethylamino-1- (4- Phenylphenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2- Plinyl-1-acetone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (eg benzoin Methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridinone, chloracridone , N-methylacridone, N-butylacridone, N-butyl-chloroacridone, etc.

作為光聚合引發劑，也能適宜地使用羥基苯乙酮化合物、胺基苯乙酮化合物、及醯基膦化合物。更具體而言，例如，也能使用日本特開平10-291969號公報記載的胺基苯乙酮系引發劑、日本專利第4225898號公報記載的醯基膦氧化物系引發劑。 As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969, or an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.

作為羥基苯乙酮系引發劑，能使用IRGACURE-184、DAROCUR-1173、IRGACURE-500、IRGACURE-2959、IRGACURE-127(商品名：均為BASF公司製)。作為胺基苯乙酮系引發劑，能使用市售品的IRGACURE-907、IRGACURE-369、及IRGACURE-379(商品名：均為BASF公司製)。作為胺基苯乙酮系引發劑，也能使用吸收波長係與365nm或405nm等長波光源匹配(matching)的日本特開2009-191179號公報記載的化合物。另外，作為醯基膦系引發劑，能使用市售品的IRGACURE-819或DAROCUR-TPO(商品名：均為BASF公司製)。 As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in Japanese Patent Laid-Open No. 2009-191179 whose absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm can also be used. In addition, as an acylphosphine-based initiator, commercially available IRGACURE-819 or DAROCUR-TPO (trade names: all manufactured by BASF) can be used.

作為光聚合引發劑，更佳為可舉出肟系化合物。作為肟系引發劑的具體例，能使用日本特開2001-233842號記載的化合物、日本特開2000-80068號記載的化合物、日本特開2006-342166號記載的化合物。 As the photopolymerization initiator, oxime-based compounds are more preferred. As specific examples of the oxime-based initiator, the compounds described in JP 2001-233842, the compounds described in JP 2000-80068, and the compounds described in JP 2006-342166 can be used.

作為可在本發明適宜地用作光聚合引發劑的肟化合物，例如可舉出：3-苯甲醯氧基亞胺基丁烷-2-酮、3-乙醯氧基亞胺基丁烷-2-酮、3-丙醯氧基亞胺基丁烷-2-酮、2-乙醯氧基亞胺基戊烷-3-酮、2-乙醯氧基亞胺基-1-苯基丙烷-1-酮、2-苯甲醯氧基亞胺基-1-苯基丙烷-1-酮、3-(4-甲苯磺醯氧基)亞胺基丁烷-2-酮、以及2-乙氧基羰氧基亞胺基-1-苯基丙烷-1-酮等。 Examples of the oxime compound which can be suitably used as a photopolymerization initiator in the present invention include, for example, 3-benzyloxyiminobutane-2-one and 3-ethoxyimidobutane-2-one -2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-benzene Propan-1-one, 2-benzyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one and the like.

作為肟酯化合物，可舉出：J.C.S.Perkin II(1979年)pp.1653-1660、J.C.S.Perkin II(1979年)pp.156-162、Journal of Photopolymer Science and Technology(1995年)pp.202-232、日本特開2000-66385號公報記載的化合物、日本特開2000-80068號公報、日本特表2004-534797號公報、日本特開2006-342166號公報之各公報記載的化合物等。 Examples of oxime ester compounds include: J.C.S. Perkin II (1979) pp.1653-1660, J.C.S.Perkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in Japanese Patent Laid-Open No. 2000-66385, Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2004-534797, Japanese Patent Laid-Open No. 2006-342166 The compounds described in each publication.

在市售品方面，也可適宜地使用IRGACURE-OXE01(BASF公司製)、IRGACURE-OXE02(BASF公司製)、N-1919(ADEKA公司製)。 For commercial products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), and N-1919 (manufactured by ADEKA) can also be used as appropriate.

此外，作為上述記載以外的肟酯化合物，可以使用於咔唑的N位連結有肟的日本特表2009-519904號公報記載的化合物、於二苯基酮部位導入有雜取代基的美國專利7626957號公報記載的化合物、於色素部位導入有硝基的日本特開2010-15025號公報及美國專利公開2009-292039號記載的化合物、國際公開專利2009-131189號公報記載的酮肟系化合物、同一分子內含有三骨架與肟骨架的美國專利7556910號公報記載的化合物、於405nm具有吸收極大值且對g線光源具有良好感度的日本專利特開2009-221114號公報記載的化合物等。 In addition, as an oxime ester compound other than the above, a compound described in Japanese Patent Publication No. 2009-519904 in which oxazole is linked to the N-position of carbazole, and US Patent No. 7,626,957 in which a hetero substituent is introduced into a diphenyl ketone site The compound described in the Japanese Patent Publication, the compound described in Japanese Patent Laid-Open No. 2010-15025 and U.S. Patent Publication No. 2009-292039 in which the nitro group is introduced into the pigment portion, the ketoxime-based compound described in the International Publication Patent No. 2009-131189 The molecule contains three The compounds described in US Patent No. 7556910 of the skeleton and the oxime skeleton, the compounds described in Japanese Patent Laid-Open No. 2009-221114, etc., which have an absorption maximum at 405 nm and have good sensitivity to the g-line light source.

較佳還能適宜地使用日本特開2007-231000號公報、及日本特開2007-322744號公報記載的環狀肟化合物。環狀肟化合物當中，尤其是日本特開2010-32985號公報、日本特開2010-185072號公報記載的於咔唑色素縮環而成的環狀肟化合物，具有高的光吸收性，從高感度化的觀點來看較佳。 Preferably, the cyclic oxime compounds described in Japanese Patent Laid-Open No. 2007-231000 and Japanese Patent Laid-Open No. 2007-322744 can also be suitably used. Among the cyclic oxime compounds, in particular, the cyclic oxime compounds described in Japanese Patent Laid-Open Nos. 2010-32985 and JP 2010-185072, which are condensed with a carbazole pigment ring, have high light absorbency The point of view of sensitivity is better.

此外，於肟化合物的特定部位具有不飽和鍵的日本特開2009-242469號公報記載的化合物，亦能藉由從聚合惰性自由基再產生活性自由基來達成高感度化而能適宜地使用。 In addition, the compound described in Japanese Patent Laid-Open No. 2009-242469 having an unsaturated bond at a specific part of an oxime compound can also be suitably used by regenerating active radicals from polymerization inert radicals to achieve high sensitivity.

最佳可舉出：日本特開2007-269779號公報所示的具有特定取代基的肟化合物、或日本特開2009-191061號公報所示的具有硫代芳基的肟化合物。 The best examples include: an oxime compound having a specific substituent shown in Japanese Patent Laid-Open No. 2007-269779, or an oxime compound having a thioaryl group shown in Japanese Patent Laid-Open No. 2009-191061.

從曝光感度的觀點來看，光聚合引發劑，較佳為從包含三鹵甲基三化合物、苄基二甲基縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、醯基膦化合物、膦氧化物化合物、茂金屬化合物、肟化合物、三烯丙基咪唑二聚體、鎓化合物、苯并噻唑化合物、二苯基酮化合物、苯乙酮化合物及其衍生物、環戊二烯-苯-鐵錯合物及其鹽、鹵甲基二唑化合物、3-芳基取代香豆素化合物的群組所選出的化合物。更佳為三鹵甲基三化合物、α-胺基酮化合物、醯基膦化合物、膦氧化物化合物、肟化合物、三烯丙基咪唑二聚體、鎓化合物、二苯基酮化合物、苯乙酮化合物。特佳為從包含三鹵甲基三化合物、α-胺基酮化合物、肟化合物、三烯丙基咪唑二聚體、二苯基酮化合物的群組所選出的至少一種化合物。特佳為肟化合物。 From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably Compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acetylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallyl imidazole dimer Onium compounds, benzothiazole compounds, diphenyl ketone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyl A compound selected from the group of diazole compounds and 3-aryl-substituted coumarin compounds. More preferably trihalomethyl tri Compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, diphenylketone compounds, acetophenone compounds. Tejia is a compound containing trihalomethyl At least one compound selected from the group of compounds, α-aminoketone compounds, oxime compounds, triallyl imidazole dimers, and diphenyl ketone compounds. Particularly preferred are oxime compounds.

此外，光聚合引發劑，較佳為使用產生pKa為4以下的酸的化合物，更佳為產生pKa為3以下的酸的化合物。 In addition, the photopolymerization initiator is preferably a compound that generates an acid with a pKa of 4 or less, and more preferably a compound that generates an acid with a pKa of 3 or less.

作為產生酸的化合物的例，可舉出：三氯甲基-s-三類、鋶鹽或錪鹽、四級銨鹽類、重氮甲烷化合物、醯亞胺磺酸鹽化合物、及肟磺酸鹽化合物等。此等之中，從高感度的觀點來看，較佳為使用肟磺酸鹽化合物。此等酸產生劑能單獨使用1種或者組合2種以上使用。 Examples of acid-generating compounds include trichloromethyl-s-tris Class, manganese salt or iodonium salt, quaternary ammonium salt, diazomethane compound, amide imine sulfonate compound, oxime sulfonate compound, etc. Among these, from the viewpoint of high sensitivity, it is preferable to use an oxime sulfonate compound. These acid generators can be used alone or in combination of two or more.

具體而言，能舉出：日本特開2012-8223號公報的段落編號[0073]~[0095]記載的酸產生劑。 Specifically, the acid generators described in paragraph numbers [0073] to [0095] of Japanese Patent Laid-Open No. 2012-8223 can be cited.

光聚合引發劑的莫耳吸光係數能使用周知的方法。具體而言，例如，較佳為利用紫外線可見光分光光度計(Varian公司製的Carry-5 spctrophotometer)，使用乙酸乙酯溶媒，在0.01g/L的濃度下進行測定。 A well-known method can be used for the molar absorption coefficient of a photoinitiator. Specifically, for example, it is preferable to use an ultraviolet-visible light spectrophotometer (Carry-5 spctrophotometer manufactured by Varian) using an ethyl acetate solvent to perform measurement at a concentration of 0.01 g / L.

本發明的組成物，較佳為相對於組成物的總固體成分，含有0.1~30質量%的光聚合引發劑，更佳為含有0.1~20質量%，特佳為含有0.1~10質量%。 The composition of the present invention preferably contains 0.1 to 30% by mass of the photopolymerization initiator relative to the total solid content of the composition, more preferably contains 0.1 to 20% by mass, and particularly preferably contains 0.1 to 10% by mass.

此外，本發明的組成物，較佳為相對於100質量份的聚合性化合物，含有1~20質量份的光聚合引發劑，更佳為含有3~10質量份。 In addition, the composition of the present invention preferably contains 1 to 20 parts by mass of the photopolymerization initiator relative to 100 parts by mass of the polymerizable compound, and more preferably contains 3 to 10 parts by mass.

光聚合引發劑，可以僅為1種，也可以併用2種以上。併用2種以上的情況，合計為上述含量較佳。 The photopolymerization initiator may be only one kind, or two or more kinds may be used in combination. When two or more types are used in combination, the above content is preferable.

<<熱聚合引發劑>> << Thermal polymerization initiator >>

本發明的組成物能含有熱聚合引發劑。 The composition of the present invention can contain a thermal polymerization initiator.

本發明的組成物藉由含有熱聚合引發劑而具有下述優勢：在將組成物應用於半導體晶圓等而形成層狀的組成物層後，藉由接著被接著體，加熱至熱聚合引發劑的 分解溫度以上，而使組成物層硬化，可以進行耐熱性更高、高強度的接著。 The composition of the present invention has the following advantages by containing a thermal polymerization initiator: after the composition is applied to a semiconductor wafer or the like to form a layered composition layer, it is heated to thermal polymerization initiation by the adherend Pharmaceutical Above the decomposition temperature, the composition layer is hardened, and higher heat resistance and high strength bonding can be performed.

熱聚合引發劑能較佳地使用利用熱產生自由基或酸的化合物。 The thermal polymerization initiator can preferably use a compound that generates free radicals or acids using heat.

<<<利用熱產生自由基的化合物>>> <<< Compounds that use heat to generate free radicals >>>

作為利用熱產生自由基的化合物(以下，也簡稱為熱自由基產生劑)，能使用周知的熱自由基產生劑。 As a compound that generates radicals by heat (hereinafter, also simply referred to as a thermal radical generator), a well-known thermal radical generator can be used.

熱自由基產生劑係利用熱能來產生自由基，引發或促進聚合性化合物的聚合反應的化合物。 Thermal radical generators are compounds that use thermal energy to generate free radicals and initiate or promote the polymerization reaction of polymerizable compounds.

作為較佳的熱自由基產生劑，可舉出上述的利用活性光線或放射線的照射產生酸或自由基的化合物，但能較佳地使用熱分解點為130℃~250℃(較佳為150℃~220℃)範圍的化合物。 As a preferred thermal radical generating agent, there may be mentioned the above-mentioned compounds that generate acid or radicals by irradiation with active light or radiation, but a thermal decomposition point of 130 ° C to 250 ° C (preferably 150 ℃ ~ 220 ℃).

作為熱自由基產生劑，可舉出：芳香族酮類、鎓鹽化合物、有機過氧化物、硫化合物、六芳基聯咪唑化合物、酮肟酯化合物、硼酸鹽化合物、吖鎓(azinium)化合物、茂金屬化合物、活性酯化合物、具有碳鹵素鍵(carbon-halogen bond)的化合物、偶氮系化合物等。其中，更佳為有機過氧化物或偶氮系化合物，特佳為有機過氧化物。 Examples of thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, sulfur compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, and acridine. An azinium compound, a metallocene compound, an active ester compound, a compound having a carbon-halogen bond, an azo compound, and the like. Among them, organic peroxides or azo compounds are more preferred, and organic peroxides are particularly preferred.

具體而言，可舉出日本特開2008-63554號公報的段落0074~0118所記載的化合物。 Specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Laid-Open No. 2008-63554 can be mentioned.

此外，在市售品方面，可適合使用PERCUMYL D(雙異丙苯基過氧化物，日油製)等。 In addition, in terms of commercially available products, PERCUMYL D (bis-cumyl peroxide, manufactured by NOF) and the like can be suitably used.

<<<利用熱產生酸的化合物>>> <<< Compounds that generate acid using heat >>>

作為利用熱產生酸的化合物(以下，也簡稱為熱酸產生劑)，能使用周知的熱酸產生劑。 As a compound that generates acid by heat (hereinafter, also simply referred to as a thermal acid generator), a well-known thermal acid generator can be used.

熱酸產生劑，較佳可舉出熱分解點為130℃~250℃(更佳為150℃~220℃)的範圍的化合物。 The thermal acid generator preferably includes compounds having a thermal decomposition point in the range of 130 ° C to 250 ° C (more preferably 150 ° C to 220 ° C).

作為熱酸產生劑係例如，利用加熱而產生磺酸、羧酸、二磺醯基醯亞胺等的低親核性的酸的化合物。作為從熱酸產生劑產生的酸，較佳為pKa為2以下的酸。 As the thermal acid generator system, for example, a compound that generates a low-nucleophilic acid such as sulfonic acid, carboxylic acid, or disulfonyl imide by heating. The acid generated from the thermal acid generator is preferably an acid having a pKa of 2 or less.

例如，較佳為磺酸或者以電子吸引基取代的烷基羧酸、芳基羧酸、二磺醯基醯亞胺等。作為電子吸引基，能舉出：氟原子等鹵素原子、三氟甲基等鹵烷基、硝基、氰基。 For example, a sulfonic acid or an alkyl carboxylic acid substituted with an electron attracting group, an aryl carboxylic acid, a disulfonyl amide imine, etc. are preferable. Examples of the electron attracting group include halogen atoms such as fluorine atoms, haloalkyl groups such as trifluoromethyl groups, nitro groups, and cyano groups.

作為熱酸產生劑，較佳為使用實質上不因活性光線或放射線的照射而產生酸，而是利用熱來產生酸的磺酸酯。實質上不因活性光線或放射線的照射而產生酸的情形，能利用在化合物的曝光前後的紅外線吸收(IR)光譜、核磁共振(NMR)光譜測定，根據光譜沒有變化來判定。 As the thermal acid generator, it is preferable to use a sulfonic acid ester that generates substantially no acid by irradiation of active light or radiation, but generates acid by heat. When the acid is not substantially generated by the irradiation of active light or radiation, it can be determined by infrared absorption (IR) spectrum and nuclear magnetic resonance (NMR) spectrum before and after exposure of the compound, and it can be determined that the spectrum does not change.

磺酸酯的分子量較佳為230~1,000，更佳為230~800。 The molecular weight of the sulfonate is preferably 230 to 1,000, and more preferably 230 to 800.

磺酸酯可以使用市售者，也可以使用以周知的方法合成者。磺酸酯，例如，能藉由在鹼性條件下使磺醯氯(sulfonyl chloride)或磺酸酐與對應的多元醇反應來合成。 The sulfonate may be a commercially available one, or a one synthesized by a well-known method. Sulfonates, for example, can be synthesized by reacting sulfonyl chloride or sulfonic anhydride with the corresponding polyol under alkaline conditions.

本發明的組成物，較佳為相對於組成物的總固體成分，含有0.01~30質量%的熱聚合引發劑，更佳為含有0.1~20質量%，特佳為含有0.5~10質量%。 The composition of the present invention preferably contains 0.01 to 30% by mass of a thermal polymerization initiator relative to the total solid content of the composition, more preferably contains 0.1 to 20% by mass, and particularly preferably contains 0.5 to 10% by mass.

此外，本發明的組成物，較佳為相對於100質量份的光聚合引發劑，含有10~200質量份的熱聚合引發劑，更佳為含有33~100質量份。 In addition, the composition of the present invention preferably contains 10 to 200 parts by mass of a thermal polymerization initiator relative to 100 parts by mass of the photopolymerization initiator, and more preferably contains 33 to 100 parts by mass.

此外，本發明的組成物，較佳為相對於100質量份的聚合性化合物，含有1~10質量份的熱聚合引發劑，更佳為含有2~5質量份。 In addition, the composition of the present invention preferably contains 1 to 10 parts by mass of a thermal polymerization initiator relative to 100 parts by mass of the polymerizable compound, and more preferably contains 2 to 5 parts by mass.

熱聚合引發劑，可以僅為1種，也可以併用2種以上。併用2種以上的情況，合計為上述含量較佳。 The thermal polymerization initiator may be only one kind, or two or more kinds may be used in combination. When two or more types are used in combination, the above content is preferable.

此外，本發明的組成物，也能以光聚合引發劑、熱聚合引發劑皆不添加的方法使用。例如，能以非導電性膏NCP(Non-Conductive Paste)、非導電性薄膜NCF(Non-Conductive Film)的形狀使用，能不對已成膜的底部填料層進行曝光和顯影而在接著時使單體熱硬化來進行接著。 In addition, the composition of the present invention can also be used by a method in which neither a photopolymerization initiator nor a thermal polymerization initiator is added. For example, it can be used in the form of a non-conductive paste NCP (Non-Conductive Paste) or a non-conductive film NCF (Non-Conductive Film). Body heat hardening to proceed.

<<填料>> << Filling >>

本發明的組成物能含有填料。 The composition of the present invention can contain a filler.

在本發明中，填料若為不在膜中進行分子分散，而是以固體的狀態進行分散者，便沒有特別的限定。作為能用於本發明的填料，可舉出有機填料及無機填料。 In the present invention, the filler is not particularly limited as long as it does not disperse molecules in the film but disperses in a solid state. Examples of the filler that can be used in the present invention include organic fillers and inorganic fillers.

作為有機填料，可舉出：有機交聯聚合物(較佳為PMMA交聯粒子)、低密度聚乙烯粒子、高密度聚乙烯粒子、聚苯乙烯粒子、各種有機顏料、微型中空球(micro-balloon)、脲-福馬林填料、聚酯顆粒(polyester particle)、纖維素填料、有機金屬等。 Examples of organic fillers include organic cross-linked polymers (preferably PMMA cross-linked particles), low-density polyethylene particles, high-density polyethylene particles, polystyrene particles, various organic pigments, and micro hollow balls (micro- balloon), urea-formalin filler, polyester particle, cellulose filler, organic metal, etc.

作為有機顏料，可舉出周知者，能使用：靛藍系顏料、喹吖酮系顏料、二系顏料、異吲哚啉酮系顏料、喹啉黃(quinophthalone)系顏料、染色色澱顏料(dyeing lake pigment)、吖(azine)顏料、亞硝基顏料、硝基顏料、天然顏料、螢光顏料、碳黑等。此外，可以含有無機顏料。 As organic pigments, well-known ones can be mentioned, and indigo-based pigments, quinacridone-based pigments, Pigments, isoindolinone pigments, quinophthalone pigments, dyeing lake pigments, acridine (azine) pigment, nitroso pigment, nitro pigment, natural pigment, fluorescent pigment, carbon black, etc. In addition, inorganic pigments may be contained.

作為無機顏料，可舉出：氧化鋁、氧化鈦、氧化鋯、高嶺土、煅燒高嶺土、滑石、蠟石、矽藻土、碳酸鈉、碳酸鈣、氫氧化鋁、氫氧化鎂、氧化鋅、鋅鋇白(lithopone)、矽酸鹽礦物粒子(較佳為非晶質氧化矽、膠體氧化矽、煅燒石膏、氧化矽)、碳酸鎂、氧化鈦、氧化鋁、碳酸鋇、硫酸鋇、雲母等。 Examples of inorganic pigments include alumina, titania, zirconia, kaolin, calcined kaolin, talc, waxite, diatomaceous earth, sodium carbonate, calcium carbonate, aluminum hydroxide, magnesium hydroxide, zinc oxide, and zinc barium Lithopone, silicate mineral particles (preferably amorphous silica, colloidal silica, calcined gypsum, silica), magnesium carbonate, titanium oxide, alumina, barium carbonate, barium sulfate, mica, etc.

作為填料的形狀，沒有特別的限制，但能舉出：球狀、層狀、纖維狀、中空球的形狀。 The shape of the filler is not particularly limited, but examples include spherical, layered, fibrous, and hollow sphere shapes.

填料的平均粒徑(平均一次粒徑)較佳為5nm以上20μm以下，更佳為10nm以上10μm以下，特佳為50nm以上1μm以下。若在上述範圍內，則膜中的分散穩定性良好，再者，膜表面狀態或曝光、顯影後的圖案形狀優異。 The average particle size (average primary particle size) of the filler is preferably 5 nm or more and 20 μm or less, more preferably 10 nm or more and 10 μm or less, and particularly preferably 50 nm or more and 1 μm or less. Within the above range, the dispersion stability in the film is good, and the film surface state or the pattern shape after exposure and development is excellent.

作為層狀的填料，較佳地可舉出具有薄平板狀的無機質的層狀化合物，例如可舉出：下述式(1)所表示的天然雲母、合成雲母等雲母群、3MgO‧4SiO‧H2O所表示的滑石、帶雲母、蒙脫石、皂石、鋰蒙脫石、磷酸鋯等。 As the layered filler, preferably, an inorganic layered compound having a thin flat plate shape, for example, a mica group such as natural mica or synthetic mica represented by the following formula (1), 3MgO‧4SiO‧ Talc, mica, montmorillonite, saponite, hectorite, zirconium phosphate, etc. represented by H 2 O.

A(B,C)2~5D4O10(OH,F,O)2...(1) A (B, C) 2 ~ 5 D 4 O 10 (OH, F, O) 2 ... (1)

式(1)中，A表示K、Na、Ca當中任一者，B及C表示Fe(II)、Fe(III)、Mn、Al、Mg、V當中任一者，D表示Si或Al。 In formula (1), A represents any one of K, Na, and Ca, B and C represent any one of Fe (II), Fe (III), Mn, Al, Mg, and V, and D represents Si or Al.

層狀的填料的粒徑，平均長徑較佳為0.3~20μm，更佳為0.5~10μm，特佳為1~5μm。此外，平均厚度較佳為0.1μm以下，更佳為0.05μm以下，特佳為0.01μm以下。 The particle size and average long diameter of the layered filler are preferably 0.3 to 20 μm, more preferably 0.5 to 10 μm, and particularly preferably 1 to 5 μm. In addition, the average thickness is preferably 0.1 μm or less, more preferably 0.05 μm or less, and particularly preferably 0.01 μm or less.

例如，層狀的填料之中，膨潤性合成雲母係厚度為1~50nm，面尺寸為1~20μm左右。 For example, among layered fillers, the swelling synthetic mica system has a thickness of 1 to 50 nm and a surface size of about 1 to 20 μm.

填料可以使用市售品。作為市售品，可舉出：R-972(氧化矽，日本AEROSIL製)、AKP-50(氧化鋁，住友化學製)等。 As the filler, commercially available products can be used. Examples of commercially available products include R-972 (silica, manufactured by Japan Aerosil), AKP-50 (alumina, manufactured by Sumitomo Chemical), and the like.

本發明所使用的填料，較佳為氧化鋁、矽酸鹽礦物粒子、苯乙烯粒子、有機交聯聚合物、碳酸鈉、雲母、或膨潤石，更佳為氧化鋁、矽酸鹽礦物粒子、有機交聯聚合物或膨潤石，再更佳為氧化鋁或矽酸鹽礦物粒子。 The filler used in the present invention is preferably alumina, silicate mineral particles, styrene particles, organic cross-linked polymer, sodium carbonate, mica, or bentonite, more preferably alumina, silicate mineral particles, Organic cross-linked polymers or bentonite, and even more preferably alumina or silicate mineral particles.

本發明的組成物，可以不含有填料，但含有填料的情況，相對於組成物的總固體成分，較佳為1~30質量%，更佳為1~25質量%，特佳為1~20質量%。 The composition of the present invention may not contain a filler, but when it contains a filler, it is preferably 1 to 30% by mass, more preferably 1 to 25% by mass, and particularly preferably 1 to 20 relative to the total solid content of the composition. quality%.

填料，可以僅為1種，也可以併用2種以上。併用2種以上的情況，合計為上述含量較佳。 The filler may be only one kind, or two or more kinds may be used in combination. When two or more types are used in combination, the above content is preferable.

<<黏合性賦予劑>> << Adhesiveness imparting agent >>

本發明的組成物，為了改善異種材料間的界面結合，也能含有黏合性賦予劑。作為黏合性賦予劑，例如 可舉出：矽烷系偶合劑、鈦系偶合劑、鋁系偶合劑等，其中，於效果高的觀點，較佳為矽烷系偶合劑(矽烷偶合劑)。黏合性賦予劑的含量，從其效果或耐熱性及成本的方面來看，較佳為相對於組成物的總固體成分為0.01~20質量%，更佳為0.1~15質量%。 The composition of the present invention may contain an adhesion-imparting agent in order to improve the interfacial bonding between different materials. As an adhesion-imparting agent, for example Examples thereof include silane-based coupling agents, titanium-based coupling agents, and aluminum-based coupling agents. Among them, from the viewpoint of high effects, silane-based coupling agents (silane coupling agents) are preferred. The content of the adhesion-imparting agent is preferably 0.01 to 20% by mass, and more preferably 0.1 to 15% by mass with respect to the total solid content of the composition from the viewpoint of its effect, heat resistance, and cost.

<<<矽烷系偶合劑>>> <<< Silane-based coupling agent >>>

在本發明中，矽烷偶合劑係指分子中具有1個以上「至少1個烷氧基或鹵素基與Si原子直接鍵結的官能基(以下也稱為矽烷偶合基)」的化合物。矽烷偶合基較佳為2個以上的烷氧基或鹵素基與Si原子直接鍵結者，特佳為3個以上的烷氧基或鹵素基與Si原子直接鍵結者。 In the present invention, the silane coupling agent refers to a compound having at least one "functional group in which at least one alkoxy group or halogen group is directly bonded to a Si atom (hereinafter also referred to as a silane coupling group)" in the molecule. The silane coupling group is preferably a group in which two or more alkoxy groups or halogen groups are directly bonded to Si atoms, and particularly preferably a group in which three or more alkoxy groups or halogen groups are directly bonded to Si atoms.

在矽烷偶合劑中，作為與Si原子直接鍵結的官能基，具有烷氧基及鹵素基當中至少1個以上的官能基，從化合物的操作簡便性的觀點來看，較佳為具有烷氧基者。 In the silane coupling agent, as the functional group directly bonded to the Si atom, it has at least one functional group among the alkoxy group and the halogen group, and from the viewpoint of ease of handling of the compound, it is preferable to have an alkoxy group Base.

作為烷氧基，從反應性的觀點來看，較佳為碳數1~30的烷氧基，更佳為碳數1~15的烷氧基，特佳為碳數1~5的烷氧基。 The alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 15 carbon atoms, and particularly preferably an alkoxy group having 1 to 5 carbon atoms from the viewpoint of reactivity. base.

作為鹵素原子，可舉出：F原子、Cl原子、Br原子、I原子，於合成的簡便性及穩定性的觀點，較佳可舉出Cl原子及Br原子，更佳為Cl原子。 Examples of halogen atoms include F atoms, Cl atoms, Br atoms, and I atoms. From the viewpoint of simplicity and stability of synthesis, Cl atoms and Br atoms are preferred, and Cl atoms are more preferred.

本發明中的矽烷偶合劑，於良好地保持黏合性的觀點，較佳為分子內包含1個以上10個以下的矽烷偶合基，更佳為1個以上5個以下，特佳為1個以上2個以下。 The silane coupling agent in the present invention preferably contains one or more silane coupling groups in the molecule from the viewpoint of maintaining good adhesion, more preferably one or more silane coupling groups, and particularly preferably one or more silane coupling groups. 2 or less.

以下，作為可應用於本發明的矽烷偶合劑的具體例，例如能舉出：乙烯基三氯矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、β-(3,4-環氧基環己基)乙基三甲氧基矽烷、γ-縮水甘油氧基(glycidoxy)丙基三甲氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷、γ-縮水甘油氧基丙基三乙氧基矽烷、γ-甲基丙烯醯氧基(methacryloxy)丙基甲基二甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、γ-甲基丙烯醯氧基丙基三乙氧基矽烷、γ-丙烯醯氧基丙基三甲氧基矽烷、N-(β-胺乙基)-γ-胺丙基甲基二甲氧基矽烷、N-(β-胺乙基)-γ-胺丙基三甲氧基矽烷、N-(β-胺乙基)-γ-胺丙基三乙氧基矽烷、γ-胺丙基三甲氧基矽烷、γ-胺丙基三乙氧基矽烷、N-苯基-γ-胺丙基三甲氧基矽烷、γ-巰丙基三甲氧基矽烷、γ-氯丙基三甲氧基矽烷、γ-脲丙基三乙氧基矽烷等。 Hereinafter, as specific examples of the silane coupling agent applicable to the present invention, for example, vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, β- (3,4-cyclo Oxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyl diethoxysilane, γ-glycidoxy Propyltriethoxysilane, γ-methacryloxypropylmethydimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacrylamide Oxypropylmethyl diethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriazine Ethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane , Γ-chloropropyltrimethoxysilane, γ-urea propylene Based on triethoxysilane and so on.

作為市售品，例如可舉出KBE-503(信越SILICONE製)等。 Examples of commercially available products include KBE-503 (manufactured by Shin-Etsu Silicone).

矽烷偶合劑，可以僅使用1種，也可以併用2種以上。 Only one kind of silane coupling agent may be used, or two or more kinds may be used in combination.

<<界面活性劑>> << Surface Active Agent >>

本發明的感光性樹脂組成，從更加提升塗布性的觀點來看，可以含有界面活性劑。作為界面活性劑，能使用氟系界面活性劑、非離子系界面活性劑、陽離子系界面活性劑、陰離子系界面活性劑、矽酮系界面活性劑等各種界面活性劑。 The photosensitive resin composition of the present invention may contain a surfactant from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

尤其是，本發明的組成物藉由含有氟系界面活性劑，而當調製為塗布液時的液體特性(特別是流動性)更加提升，因此能更加改善塗布厚度的均勻性或省液性。 In particular, the composition of the present invention contains a fluorine-based surfactant, and the liquid characteristics (especially fluidity) when prepared as a coating liquid are further improved, so that the uniformity or liquidity of the coating thickness can be further improved.

即，在使用包含氟系界面活性劑的組成物進行成膜的情況，藉由使被塗布面與塗布液的界面張力降低，而改善對被塗布面的潤濕性，提升對被塗布面的塗布性。因此，即使是以小量的液量形成數μm左右的薄膜的情況，在能更適宜地進行厚度不均小的均勻厚度的成膜的觀點仍然是有效的。 That is, in the case of forming a film using a composition containing a fluorine-based surfactant, by reducing the interfacial tension between the coated surface and the coating liquid, the wettability to the coated surface is improved, and the coating surface is improved. Spreadability. Therefore, even in the case of forming a thin film of about several μm with a small amount of liquid, it is still effective from the viewpoint that it is possible to more suitably form a uniform thickness film with a small thickness unevenness.

氟系界面活性劑中的氟含有率，適合為3~40質量%，更佳為5~30質量%，特佳為7~25質量%。氟含有率在此範圍內的氟系界面活性劑，在塗布膜的厚度均勻性或省液性的觀點是有效的，在保護層形成用組成物中的溶解性也是良好的。 The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content rate within this range is effective from the viewpoint of the thickness uniformity or liquid-saving property of the coating film, and its solubility in the protective layer forming composition is also good.

作為氟系界面活性劑，例如可舉出：Megafac F171、Megafac F172、Megafac F173、Megafac F176、Megafac F177、Megafac F141、Megafac F142、Megafac F143、Megafac F144、Megafac R30、Megafac F437、Megafac F475、Megafac F479、Megafac F482、Megafac F554、Megafac F780、Megafac F781(以上，DIC(股)製)，Fluorad FC430、Fluorad FC431、Fluorad FC171(以上，住友3M(股)製)，Surflon S-382、Surflon SC-101、Surflon SC-103、Surflon SC-104、Surflon SC-105、Surflon SC1068、Surflon SC-381、Surflon SC-383、Surflon S393、 Surflon KH-40(以上，旭硝子(股)製)，PF636、PF656、PF6320、PF6520、PF7002(OMNOVA公司製)等。 Examples of fluorine-based surfactants include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, and Megafac F475 , Megafac F482, Megafac F554, Megafac F780, Megafac F781 (above, DIC (stock) system), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above, Sumitomo 3M (stock) system), Surflon S-382, Surflon SC-101 , Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), etc.

作為非離子系界面活性劑，具體而言，可舉出：甘油、三羥甲基丙烷、三羥甲基乙烷以及此等的乙氧基化物及丙氧基化物(例如甘油丙氧基化物、甘油乙氧基化物等)、聚氧乙烯基月桂基醚、聚氧乙烯基硬脂基醚、聚氧乙烯基油烯基(oleyl)醚、聚氧乙烯基辛基苯基醚、聚氧乙烯基壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、去水山梨醇脂肪酸酯(BASF公司製的Pluronic L10、L31、L61、L62、10R5、17R2、25R2，Tetronic 304、701、704、901、904、150R1，Solsperse 20000(日本Lubrizol(股)製)等。 Specific examples of the nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, glycerol propoxylate) , Glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxy Vinyl nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, manufactured by BASF Corporation, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Solsperse 20000 (made by Japan Lubrizol Co., Ltd.), etc.

作為陽離子系界面活性劑，具體而言，可舉出：酞花青衍生物(商品名：EFKA-745，森下產業(股)製)、有機矽氧烷聚合物KP341(信越化學工業(股)製)、(甲基)丙烯酸系(共)聚合物Polyflow No.75、No.90、No.95(共榮社化學(股)製)、W001(裕商(股)製)等。 Specific examples of the cationic surfactants include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Industry Co., Ltd.), and organosiloxane polymer KP341 (Shin-Etsu Chemical Industry Co., Ltd.) ), (Meth) acrylic (co) polymer Polyflow No. 75, No. 90, No. 95 (Kyoeisha Chemical Co., Ltd.), W001 (Yushang Co., Ltd.), etc.

作為陰離子系界面活性劑，具體而言，可舉出：W004、W005、W017(裕商(股)公司製)等。 Specific examples of the anionic surfactants include W004, W005, and W017 (manufactured by Yushang Corporation).

作為矽酮系界面活性劑，例如可舉出：TORAY．DOW CORNING(股)製的「Toray Silicone DC3PA」、「Toray Silicone SH7PA」、「Toray Silicone DC11PA」、「Toray Silicone SH21PA」、「Toray Silicone SH28PA」、「Toray Silicone SH29PA」、「Toray Silicone SH30PA」、「Toray Silicone SH8400」，Momentive Performance Materials公司製的「TSF-4440」、「TSF-4300」、「TSF-4445」、「TSF-4460」、「TSF-4452」，信越SILICONE股份公司製造「KP341」、「KF6001」、「KF6002」，BYK-CHEMIE公司製的「BYK307」、「BYK323」、「BYK330」等。 Examples of silicone-based surfactants include TORAY. DOW CORNING (Toray Silicone DC3PA), `` Toray Silicone SH7PA '', `` Toray Silicone DC11PA '', `` Toray Silicone SH21PA '', `` Toray Silicone SH28PA '', `` Toray Silicone SH29PA '', `` Toray Silicone SH30PA '', `` Toray Silicone SH30PA '' Toray Silicone SH8400 ", Momentive "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF-4452" made by Performance Materials, Shin-Etsu Silicon Corporation "KP341", "KF6001", "KF6002" ", BYK-CHEMIE's" BYK307 "," BYK323 "," BYK330 "and so on.

本發明的樹脂組成物具有界面活性劑的情況，相對於組成物的總固體成分，界面活性劑的添加量較佳為0.001質量%~2.0質量%，更佳為0.005質量%~1.0質量%。 When the resin composition of the present invention has a surfactant, the amount of the surfactant added is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass relative to the total solid content of the composition.

界面活性劑可以僅為1種，也可以為2種以上。界面活性劑為2種以上的情況，較佳為其合計在上述範圍內。 The surfactant may be only one kind, or two or more kinds. When there are two or more surfactants, it is preferable that the total amount is within the above range.

<<抗氧化劑>> << Antioxidant >>

從防止因加熱時的氧化所造成的組成物的低分子化或凝膠化的觀點來看，本發明的組成物可以添加抗氧化劑。作為抗氧化劑，能使用酚系抗氧化劑、硫系抗氧化劑、醌系抗氧化劑、胺系抗氧化劑等。 From the viewpoint of preventing the low-molecularization or gelation of the composition due to oxidation during heating, the composition of the present invention may contain an antioxidant. As the antioxidant, a phenol-based antioxidant, a sulfur-based antioxidant, a quinone-based antioxidant, an amine-based antioxidant, or the like can be used.

作為酚系抗氧化劑，例如可舉出：對甲氧基酚、2,6-二-第三丁基-4-甲基酚、BASF(股)製的「Irganox 1010」、「Irganox 1330」、「Irganox 3114」、「Irganox 1035」，住友化學(股)製的「Sumilizer MDP-S」、「Sumilizer GA-80」等。 Examples of the phenolic antioxidants include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, "Irganox 1010", "Irganox 1330" manufactured by BASF Corporation, "Irganox 3114", "Irganox 1035", "Sumilizer MDP-S" and "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd.

作為硫系抗氧化劑，例如可舉出：3,3’-硫二丙酸二硬脂酯、住友化學(股)製的「Sumilizer TPM」、「Sumilizer TPS」、「Sumilizer TP-D」等。 Examples of sulfur-based antioxidants include 3,3'-thiodipropionate distearate, Sumitomo Chemical Co., Ltd. "Sumilizer TPM", "Sumilizer TPS", "Sumilizer TP-D" and the like.

作為醌系抗氧化劑，例如可舉出：對苯醌、2-第三丁基-1,4-苯醌等。 Examples of the quinone-based antioxidant include p-benzoquinone and 2-tert-butyl-1,4-benzoquinone.

作為胺系抗氧化劑，例如可舉出：二甲基苯胺或啡噻(phenothiazine)等。 Examples of the amine-based antioxidant include dimethylaniline and phenothiazine (phenothiazine) etc.

上述抗氧化劑之中，較佳為「Irganox 1010」、「Irganox 1330」、3,3’-硫二丙酸二硬脂酯、「Sumilizer TP-D」，更佳為「Irganox 1010」、「Irganox 1330」，特佳為「Irganox 1010」。 Among the above antioxidants, "Irganox 1010", "Irganox 1330", 3,3'-distearyl thiodipropionate, "Sumilizer TP-D" are preferred, and "Irganox 1010" and "Irganox" are more preferred 1330 ", the best is" Irganox 1010 ".

此外，上述抗氧化劑之中，再更佳為併用酚系抗氧化劑和硫系抗氧化劑。在半導體加工中，220℃這種高溫的加工步驟進行長達30分鐘以上的時間，單獨的抗氧化劑無法得到對該加工步驟的耐久性。藉由進行上述組合，在高溫加工步驟中，硫系抗氧化劑吸收酚系抗氧化劑受到的損害，即使在30分鐘以上的長時間的步驟時間中也能防止組成物變質。作為抗氧化劑的組合，較佳為「Irganox 1010」和「Sumilizer TP-D」的組合、「Irganox 1330」和「Sumilizer TP-D」的組合、及「Sumilizer GA-80」和「Sumilizer TP-D」的組合，更佳為「Irganox 1010」和「Sumilizer TP-D」的組合、「Irganox 1330」和「Sumilizer TP-D」的組合，特佳為「Irganox 1010」和「Sumilizer TP-D」的組合。 In addition, among the above-mentioned antioxidants, it is even more preferable to use a phenol-based antioxidant and a sulfur-based antioxidant together. In semiconductor processing, high-temperature processing steps such as 220 ° C are carried out for more than 30 minutes, and the antioxidant alone cannot provide durability to the processing steps. By performing the above combination, in the high-temperature processing step, the sulfur-based antioxidant absorbs the damage to the phenol-based antioxidant, and the composition can be prevented from being deteriorated even during a long step time of 30 minutes or more. The combination of antioxidants is preferably a combination of "Irganox 1010" and "Sumilizer TP-D", a combination of "Irganox 1330" and "Sumilizer TP-D", and a combination of "Sumilizer GA-80" and "Sumilizer TP-D" ", The combination of" Irganox 1010 "and" Sumilizer TP-D ", the combination of" Irganox 1330 "and" Sumilizer TP-D ", especially the combination of" Irganox 1010 "and" Sumilizer TP-D " combination.

從防止加熱中的昇華的觀點來看，抗氧化劑的分子量較佳為400以上，更佳為600以上，特佳為750以上。 From the viewpoint of preventing sublimation during heating, the molecular weight of the antioxidant is preferably 400 or more, more preferably 600 or more, and particularly preferably 750 or more.

本發明的組成物具有抗氧化劑的情況，相對於組成物的總固體成分，抗氧化劑的含量較佳為0.001~20.0質量%，更佳為0.005~10.0質量%。經歷180℃以上的高溫步驟的情況，特佳為5.0~10.0質量%。 When the composition of the present invention has an antioxidant, the content of the antioxidant is preferably 0.001 to 20.0% by mass, and more preferably 0.005 to 10.0% by mass relative to the total solid content of the composition. In the case of experiencing a high temperature step of 180 ° C. or higher, it is particularly preferably 5.0 to 10.0% by mass.

抗氧化劑可以僅為1種，也可以為2種以上。抗氧化劑為2種以上的情況，較佳為其合計在上述範圍內。 The antioxidant may be only one kind, or two or more kinds. When there are two or more antioxidants, the total amount is preferably within the above range.

<<離子捕捉劑>> << ion trapping agent >>

本發明的組成物，為了吸附離子性雜質，而改良吸濕時的絕緣可靠性，也能進一步含有離子捕捉劑。作為離子捕捉劑，沒有特別的限制，例如可舉出：三硫醇化合物、酚系還原劑等的已知作為防止銅離子化而溶出用的防銅害劑的化合物、粉末狀的鉍系、銻系、鎂系、鋁系、鋯系、鈣系、鈦系、錫系及此等的混合系等無機化合物。作為具體例，沒有特別的限定，但有東亞合成(股)製的無機離子捕捉劑，商品名IXE-300(銻系)、IXE-500(鉍系)、IXE-600(銻、鉍混合系)、IXE-700(鎂、鋁混合系)、IXE-800(鋯系)、IXE-1100(鈣系)等。此等能單獨使用或是混合2種以上使用。 The composition of the present invention may further contain an ion trapping agent in order to adsorb ionic impurities and improve insulation reliability during moisture absorption. The ion trapping agent is not particularly limited, and examples include: three Compounds known as thiol compounds, phenol-based reducing agents, etc. as copper inhibitors for preventing copper ionization and elution, powdered bismuth, antimony, magnesium, aluminum, zirconium, calcium, titanium Inorganic compounds such as series, tin series and these mixed series. As a specific example, there is no particular limitation, but there are inorganic ion scavengers made by East Asia Synthetic Co., Ltd., trade names IXE-300 (antimony series), IXE-500 (bismuth series), IXE-600 (antimony, bismuth mixed system) ), IXE-700 (magnesium, aluminum mixed system), IXE-800 (zirconium system), IXE-1100 (calcium system), etc. These can be used alone or in combination of two or more.

本發明的組成物具有離子捕捉劑的情況，從因添加所造成的效果或耐熱性、成本等觀點來看，相對於組成物的總固體成分，離子捕捉劑的含量較佳為0.01~10質量%。 In the case where the composition of the present invention has an ion scavenger, the content of the ion scavenger is preferably 0.01 to 10% by mass relative to the total solid content of the composition from the viewpoint of effects due to addition, heat resistance, cost, etc. %.

離子捕捉劑可以僅為1種，也可以為2種以上。離子捕捉劑為2種以上的情況，較佳為其合計在上述範圍內。 The ion trapping agent may be only one kind, or two or more kinds. When there are two or more ion scavengers, the total amount is preferably within the above range.

<組成物的調製> <Modulation of composition>

本發明的組成物能混合上述各成分而調製。混合方法沒有特別的限定，能以過去以來周知的方法進行。 The composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and can be carried out by a method known in the past.

<組成物的用途及形態> <Use and form of composition>

本發明的組成物，因為耐熱性及顯影性優異，而能較佳地用作半導體裝置的底部填料。尤其是，能較佳地用作3維安裝裝置中的底部填料等。 Since the composition of the present invention is excellent in heat resistance and developability, it can be preferably used as an underfill for semiconductor devices. In particular, it can be preferably used as an underfill in a three-dimensional mounting device.

此外，本發明的組成物，因為保存穩定性也優異，而能較佳地用作液狀的組成物。 In addition, the composition of the present invention is excellent in storage stability and can be preferably used as a liquid composition.

<底部填料用積層體(接著薄片)> <Layered body for underfill (adjacent sheet)>

接下來，針對本發明的底部填料用積層體加以說明。 Next, the laminate for underfill of the present invention will be described.

本發明的底部填料用積層體係在樹脂薄膜的表面具有包含聚碳酸酯樹脂和聚合性化合物的接著層者。以下，使用圖式說明。 The layering system for underfill of the present invention has an adhesive layer containing a polycarbonate resin and a polymerizable compound on the surface of the resin film. Hereinafter, the description will be made using the drawings.

第1圖係顯示薄片狀的組成物的一實施形態的示意剖面圖。第1圖所示的薄膜狀接著劑1係包含聚碳酸酯樹脂和聚合性化合物而成者。再者，可以包含光聚合引發劑、熱聚合引發劑、填料、黏合性賦予劑等。此等係與上述的組成物所說明者同義，較佳的範圍也相同。 Fig. 1 is a schematic cross-sectional view showing an embodiment of a sheet-like composition. The film-like adhesive 1 shown in FIG. 1 is a polycarbonate resin and a polymerizable compound. Furthermore, it may contain a photopolymerization initiator, a thermal polymerization initiator, a filler, an adhesiveness-imparting agent, and the like. These terms are synonymous with those described above for the composition, and the preferred ranges are also the same.

第2圖係顯示將薄膜狀接著劑積層在樹脂薄膜而成之本發明的底部填料用積層體(接著薄片)的一實施形態的示意剖面圖。第2圖所示的接著薄片100係以樹脂薄膜3、和在其一面上所設置的包含薄膜狀接著劑1的接著層所構成。 Fig. 2 is a schematic cross-sectional view showing an embodiment of the laminate (adhesive sheet) for underfill of the present invention formed by laminating a film-like adhesive on a resin film. The adhesive sheet 100 shown in FIG. 2 is composed of a resin film 3 and an adhesive layer including a film-like adhesive 1 provided on one surface thereof.

第3圖係顯示接著薄片的另一實施形態的示意剖面圖。第3圖所示的接著薄片110係以樹脂薄膜3、在其一面上所設置的包含薄膜狀接著劑1的接著層、和積層在薄膜狀接著劑1的覆蓋薄膜(cover film)2所構成。 Fig. 3 is a schematic cross-sectional view showing another embodiment following the sheet. The adhesive sheet 110 shown in FIG. 3 is composed of a resin film 3, an adhesive layer including a film-like adhesive 1 provided on one surface thereof, and a cover film 2 laminated on the film-like adhesive 1 .

薄膜狀接著劑1能以下述的方法得到：在有機溶媒中混合聚碳酸酯樹脂、聚合性化合物、根據需要所添加的其他成分，混練混合液以調製清漆(varnish)，使此清漆的層形成在樹脂薄膜3上，利用加熱乾燥清漆層後除去樹脂薄膜3。此時，也能夠不除去樹脂薄膜3而以接著薄片100、110的狀態保存及使用。 The film-like adhesive 1 can be obtained by mixing a polycarbonate resin, a polymerizable compound, and other components added as needed in an organic solvent, kneading the mixed liquid to prepare a varnish, and forming a layer of the varnish On the resin film 3, the resin film 3 is removed after drying the varnish layer by heating. In this case, it is possible to store and use the sheet 100, 110 in the state where the resin film 3 is not removed.

上述的混合及混練能適宜組合通常的攪拌機、擂潰機、三輥研磨機(three roll mill)、球磨機等分散機來進行。清漆層的乾燥，較佳為在聚合性化合物不充分反應的溫度下且在溶媒充分揮散的條件下進行乾燥。具體而言，較佳為在60~180℃下、加熱0.1~90分鐘而乾燥清漆層。乾燥前的清漆層的厚度較佳為1~100μm。若乾燥前的清漆層的厚度為1μm以上，便可以充分得到接著固定功能。若清漆層的厚度為100μm以下，便能減少殘存揮發成分。 The above-mentioned mixing and kneading can be suitably carried out in combination with a dispersing machine such as a general mixer, a blasting machine, a three-roll mill, and a ball mill. The drying of the varnish layer is preferably carried out at a temperature at which the polymerizable compound does not sufficiently react and under conditions in which the solvent is sufficiently dispersed. Specifically, it is preferable to dry the varnish layer by heating at 60 to 180 ° C. for 0.1 to 90 minutes. The thickness of the varnish layer before drying is preferably 1 to 100 μm. If the thickness of the varnish layer before drying is 1 μm or more, the subsequent fixing function can be sufficiently obtained. If the thickness of the varnish layer is 100 μm or less, the remaining volatile components can be reduced.

乾燥後的清漆層的較佳殘存揮發成分係10質量%以下。若殘存揮發成分小於10質量%，便能難以產生空隙。又，殘存揮發成分的測定條件係如下述。即，針對切斷為50mm×50mm尺寸的薄膜狀接著劑，係將初期的質量設為M1，將在160℃的烘箱中加熱此薄膜狀接著劑3小時後的質量設為M2，而設為[(M2-M1)/M1]×100=殘存揮發成分(%)時的值。 The preferred residual volatile content of the varnish layer after drying is 10% by mass or less. If the remaining volatile components are less than 10% by mass, it is difficult to generate voids. The measurement conditions of the remaining volatile components are as follows. That is, for the film-shaped adhesive agent cut to a size of 50 mm × 50 mm, the initial mass is set to M1, and the mass after heating the film-shaped adhesive agent in an oven at 160 ° C. for 3 hours is set to M2. [(M2-M1) / M1] × 100 = value when remaining volatile components (%).

上述的聚合性化合物無法充分反應的溫度，具體而言係指使用DSC(例如，PerkinElmer公司製的「DSC-7型」(商品名))，以樣品量：10mg、昇溫速度：5℃/min、測定氣體環境：空氣的條件測定時的反應熱的峰值溫度以下的溫度。 The temperature at which the above-mentioned polymerizable compound cannot sufficiently react, specifically refers to the use of DSC (for example, "DSC-7 type" (trade name) manufactured by PerkinElmer), with a sample amount of 10 mg and a heating rate of 5 ° C / min 2. Measuring gas environment: the temperature below the peak temperature of the reaction heat during the measurement of air conditions.

調製清漆使用的有機溶媒，即清漆溶劑，若為能均勻地溶解或分散材料者，便沒有特別的限制。能使用與能用於組成物的溶劑相同者。例如可舉出：二甲基甲醯胺、甲苯、苯、二甲苯、甲乙酮、四氫呋喃、乙基賽路蘇、乙基賽路蘇乙酸酯、二烷、環己酮、乙酸乙酯、及N-甲基-吡咯啶酮。 The organic solvent used for preparing the varnish, that is, the varnish solvent, if it can dissolve or disperse the material uniformly, there is no particular limitation. The same solvent that can be used for the composition can be used. For example, dimethylformamide, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl celulose, ethyl celulose acetate, di Alkanes, cyclohexanone, ethyl acetate, and N-methyl-pyrrolidone.

樹脂薄膜3，若為可承受乾燥條件者便沒有特別的限定。例如可舉出：聚酯薄膜、聚丙烯薄膜、聚對苯二甲酸乙二酯薄膜、聚醯亞胺薄膜、聚醚醯亞胺薄膜、聚醚萘二甲酸酯薄膜、甲基戊烯薄膜等。樹脂薄膜3可以是組合2種以上的多層薄膜，也可以是表面經矽酮系、氧化矽系等脫模劑等處理者。 The resin film 3 is not particularly limited as long as it can withstand drying conditions. For example, polyester film, polypropylene film, polyethylene terephthalate film, polyimide film, polyetherimide film, polyether naphthalate film, methylpentene film Wait. The resin film 3 may be a multilayer film combining two or more types, or may be a surface treated with a silicone-based, silicon oxide-based release agent or the like.

在本發明中，也能將薄膜狀接著劑1和切割薄片(dicing sheet)積層，作成接著薄片。切割薄片係在樹脂薄膜上設置黏著劑層的薄片，上述的黏著劑層可以是壓感型或放射線硬化型當中任一者。此外，上述的樹脂薄膜較佳為可以延展的樹脂薄膜。藉由作成這種接著薄片，可得到兼具作為黏晶薄膜(die bonding film)的功能、和作為切割薄片的功能的切割-黏晶一體型接著薄片。 In the present invention, the film-like adhesive 1 and the dicing sheet can also be laminated to form an adhesive sheet. The dicing sheet is a sheet provided with an adhesive layer on a resin film. The adhesive layer may be either a pressure-sensitive type or a radiation-curing type. In addition, the above-mentioned resin film is preferably a stretchable resin film. By making such an adhesive sheet, a die-bonding integrated adhesive sheet having both the function as a die bonding film and the function as a dicing sheet can be obtained.

作為上述的切割-黏晶一體型接著薄片，具體而言，可舉出如第4圖所示般，依序形成樹脂薄膜7、黏著劑層6及包含本發明的組成物的薄膜狀接著劑1而成的接著薄片120。 As the above-mentioned dicing-adhesive integrated adhesive sheet, specifically, as shown in FIG. 4, a resin film 7, an adhesive layer 6, and a film-like adhesive containing the composition of the present invention are formed in this order. 1 成 的 形成 片 120。 Then the sheet 120 is formed.

<積層體> <Laminate>

接下來，針對本發明的積層體加以說明。 Next, the laminate of the present invention will be described.

本發明的積層體也是在半導體晶圓的表面具有包含聚碳酸酯樹脂和聚合性化合物的接著層者。此等積層體也是附接著層的半導體晶圓。 The laminate of the present invention is also one having a bonding layer containing a polycarbonate resin and a polymerizable compound on the surface of a semiconductor wafer. These laminates are also semiconductor wafers with attached layers.

以下，使用圖式，針對本發明的積層體(附接著層的半導體晶圓)加以說明。 Hereinafter, the laminate (semiconductor wafer with adhesion layer) of the present invention will be described using drawings.

第5圖係顯示本發明的積層體(附接著層的半導體晶圓)的一實施形態的上視圖，第6圖係沿著第5圖的VI-VI線的端面圖。第5、6圖所示的積層體(附接著層的半導體晶圓)20具備半導體晶圓8、和在其一面上所設置的接著層11。 FIG. 5 is a top view showing an embodiment of the laminate (semiconductor wafer with an attached layer) of the present invention, and FIG. 6 is an end view along the line VI-VI of FIG. 5. The laminate (semiconductor wafer with adhesion layer) 20 shown in FIGS. 5 and 6 includes a semiconductor wafer 8 and an adhesion layer 11 provided on one surface thereof.

附接著層的半導體晶圓20，係藉由在半導體晶圓8上積層上述的接著薄片的薄膜狀接著劑1來得到。 The semiconductor wafer 20 with an adhesive layer is obtained by laminating the above-mentioned adhesive sheet film-like adhesive 1 on the semiconductor wafer 8.

此外，附接著層的半導體晶圓20也能藉由將液狀的組成物應用於半導體晶圓8上後，使其在室溫(25℃)~200℃下加熱乾燥來得到。作為將組成物應用於半導體晶圓8的方法，可舉出：旋轉(spinning)、浸漬、刮刀塗布(doctor-blade coating)、懸浮澆鑄(suspended casting)、塗布、噴霧、靜電噴霧、逆輥塗布等。 In addition, the semiconductor wafer 20 with an adhesive layer can also be obtained by applying a liquid composition to the semiconductor wafer 8 and heating and drying it at room temperature (25 ° C) to 200 ° C. Examples of methods for applying the composition to the semiconductor wafer 8 include spinning, dipping, doctor-blade coating, suspended casting, coating, spraying, electrostatic spraying, and reverse roll coating. Wait.

第7圖、第9圖係顯示接著層圖案的一實施形態的上視圖，第8圖係沿著第7圖的VIII-VIII線的端面圖，第10圖係沿著第9圖的X-X線的端面圖。第7、8、9、10圖所示的接著層圖案1a及1b係在作為被接著體的半導體晶圓8上，以具有沿著略正方形的邊的圖案或正方形的圖案的方式形成。 Figures 7 and 9 are top views showing an embodiment of the bonding layer pattern, Figure 8 is an end view along line VIII-VIII of Figure 7, and Figure 10 is along line XX of Figure 9 End view. The adhesive layer patterns 1 a and 1 b shown in FIGS. 7, 8, 9, and 10 are formed on the semiconductor wafer 8 as the object to be adhered, and are formed to have a pattern along a slightly square side or a square pattern.

接著層圖案1a及1b，係藉由透過光罩將附接著層的半導體晶圓20上的接著層11進行曝光，利用鹼顯影液將曝光後的接著層11進行顯影處理來形成。此外，藉此，得到形成有接著層圖案1a及1b的積層體(附接著層的半導體晶圓20a、20b)。 The subsequent layer patterns 1a and 1b are formed by exposing the adhesive layer 11 on the semiconductor wafer 20 of the adhesive layer through a photomask, and developing the exposed adhesive layer 11 with an alkali developing solution. In addition, thereby, a laminate (semiconductor wafers 20a and 20b with adhesion layers) formed with the adhesion layer patterns 1a and 1b is obtained.

能藉由在附接著層的半導體晶圓20上的接著層11加熱壓接半導體元件等的被接著體，使接著層11硬化，來作成半導體裝置。 A semiconductor device can be manufactured by heating and pressure-bonding a to-be-adhered body such as a semiconductor element by the adhesive layer 11 on the semiconductor wafer 20 of the adhesive layer to harden the adhesive layer 11.

<半導體裝置的製造方法> <Manufacturing method of semiconductor device>

接下來，針對本發明的半導體裝置的製造方法加以說明。 Next, the method of manufacturing the semiconductor device of the present invention will be described.

<<半導體裝置的製造方法的第一實施形態>> << First Embodiment of Manufacturing Method of Semiconductor Device >>

本發明的半導體裝置的製造方法的第一實施形態包含：將本發明的液狀的組成物應用於半導體晶圓的步驟；使已應用於半導體晶圓的組成物乾燥的步驟；和將被接著體加熱壓接在已乾燥的組成物的表面的步驟。 The first embodiment of the method for manufacturing a semiconductor device of the present invention includes: the step of applying the liquid composition of the present invention to a semiconductor wafer; the step of drying the composition applied to the semiconductor wafer; and the following The step of heating and pressing the body on the surface of the dried composition.

此外，可以進一步在乾燥步驟與加熱壓接步驟之間包含將已乾燥的組成物曝光的步驟、和將已曝光的組成物顯影的步驟。 In addition, a step of exposing the dried composition and a step of developing the exposed composition may be further included between the drying step and the heat and pressure bonding step.

即，也能在將已應用於半導體晶圓的組成物乾燥後，不進行曝光及顯影而加熱壓接被接著體以製造半導體裝置。此外，也能在將已應用於半導體晶圓的組成物曝光及顯影以形成圖案後，加熱壓接被接著體以製造半導體裝置。以下，針對各步驟詳細地加以說明。 In other words, after the composition applied to the semiconductor wafer is dried, the adherend can be heated and pressure-bonded without exposure and development to manufacture a semiconductor device. In addition, after exposing and developing the composition applied to the semiconductor wafer to form a pattern, the adherend can be heated and pressure-bonded to manufacture a semiconductor device. Hereinafter, each step will be described in detail.

<<<將組成物應用於半導體晶圓的步驟>>> <<< Procedure for applying composition to semiconductor wafer >>>

作為將組成物應用於半導體晶圓的方法，可舉出：旋轉、浸漬、刮刀塗布、懸浮澆鑄(suspended casting)、塗布、噴霧、靜電噴霧、逆輥塗布等。 Examples of the method for applying the composition to a semiconductor wafer include rotation, dipping, blade coating, suspended casting, coating, spraying, electrostatic spraying, and reverse roll coating.

能藉由將本發明的組成物應用於半導體晶圓，來作成在半導體晶圓的表面具有包含本發明的組成物的接著層之本發明的積層體(附接著層的半導體晶圓)。 By applying the composition of the present invention to a semiconductor wafer, a layered body of the present invention (semiconductor wafer with an attached layer) having an adhesive layer including the composition of the present invention on the surface of the semiconductor wafer can be prepared.

將組成物應用於半導體晶圓的量(層的厚度)，例如，較佳為1~50μm。 The amount (layer thickness) of the composition applied to the semiconductor wafer is, for example, preferably 1 to 50 μm.

在將組成物應用於半導體晶圓後，較佳為進行乾燥。乾燥較佳為例如在25℃~200℃下進行30秒鐘~10分鐘。 After the composition is applied to the semiconductor wafer, it is preferably dried. The drying is preferably performed at 25 ° C to 200 ° C for 30 seconds to 10 minutes, for example.

<<<曝光步驟>>> <<< Exposure Step >>>

曝光步驟係對已應用於半導體晶圓的組成物照射既定圖案的活性光線或放射線。此步驟係利用活性光線或放射線的照射，進行聚合性化合物的聚合反應，光照射部位的接著性降低而按照遮罩的圖案形成接著力不同的區域。 The exposure step is to irradiate the composition applied to the semiconductor wafer with a predetermined pattern of active light or radiation. In this step, the polymerization reaction of the polymerizable compound is carried out by the irradiation of active light or radiation, and the adhesion of the light-irradiated part is reduced to form regions with different adhesion according to the pattern of the mask.

活性光線或放射線的波長係依組成物的組成而異，但較佳為200~600nm，更較佳為300~450nm。 The wavelength of active light or radiation varies depending on the composition of the composition, but it is preferably 200 to 600 nm, and more preferably 300 to 450 nm.

作為光源，能使用低壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈(chemical lamp)、LED光源、準分子雷射產生裝置等，能較佳地使用i線(365nm)、h線(405nm)、g線(436nm)等的具有波長300nm以上450nm以下的波長的活性光線。此外，也能根據需要通過如長波長截止濾波器(cut filter)、短波長截止濾波器、帶通濾波器(band-pass filter)的分光濾波器以調整照射光。露光量較佳為1~500mJ/cm2。 As the light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp (chemical lamp), an LED light source, an excimer laser generation device, etc. can be used, and i-line (365nm), h-line (405nm), Active rays with a wavelength of 300 nm or more and 450 nm or less such as g-line (436 nm). In addition, it is possible to adjust the irradiation light by passing through a spectral filter such as a long-wavelength cut filter, a short-wavelength cut filter, and a band-pass filter as necessary. The amount of light exposure is preferably 1 to 500 mJ / cm 2 .

作為曝光裝置，能使用鏡面投射對準器(mirror projection aligner)、步進器(stepper)、掃描器、近接式、接觸式、微透鏡陣列、透鏡掃描器、雷射曝光等各種方式的曝光機。 As an exposure device, various types of exposure machines such as mirror projection aligner, stepper, scanner, proximity type, contact type, microlens array, lens scanner, and laser exposure can be used .

<<<進行顯影處理的步驟>>> <<< Procedure for developing processing >>>

進行顯影處理的步驟係使用顯影液來將組成物的未曝光部分顯影。作為顯影液，能使用水性鹼性顯影液等。 The step of performing the development process is to use a developing solution to develop the unexposed portion of the composition. As the developer, an aqueous alkaline developer or the like can be used.

作為水性鹼性顯影液使用的鹼化合物，例如可舉出：氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、矽酸鈉、矽酸鉀、偏矽酸鈉、偏矽酸鉀、氨或胺等。作為胺，例如可舉出：乙基胺、正丙基胺、二乙基胺、二正丙基胺、三乙基胺、甲基二乙基胺、烷醇胺、二甲基乙醇胺、三乙醇胺、四級銨氫氧化物、氫氧化四甲基銨(TMAH)或氫氧化四乙基銨等。其中，較佳為不含金屬的鹼化合物。 Examples of the alkaline compound used as the aqueous alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, and sodium metasilicate , Potassium metasilicate, ammonia or amine, etc. Examples of amines include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethylamine Ethanolamine, quaternary ammonium hydroxide, tetramethylammonium hydroxide (TMAH) or tetraethylammonium hydroxide, etc. Among them, metal-free alkali compounds are preferred.

鹼化合物可以僅為1種，也可以為2種以上。 The alkali compound may be only one kind, or two or more kinds.

合適的水性鹼性顯影液，一般而言，關於鹼至多為0.5當量濃度，但可以在使用前適當地稀釋。例如，約0.15~0.4當量濃度(較佳為0.20~0.35當量濃度)的水性鹼性顯影液也是適切的。 A suitable aqueous alkaline developer is generally at most 0.5 equivalent concentration with respect to alkali, but can be appropriately diluted before use. For example, an aqueous alkaline developer having a concentration of about 0.15 to 0.4 equivalent concentration (preferably 0.20 to 0.35 equivalent concentration) is also suitable.

<<<加熱壓接被接著體的步驟>>> <<< Procedure for heat-pressing the adherend >>>

能藉由將被接著體加熱壓接在接著層，使接著層硬化，而作成在半導體晶圓的表面具有將本發明的組成物硬化而成的硬化物層的半導體裝置。作為被接著體，可舉出半導體元件等。 A semiconductor device having a hardened layer formed by hardening the composition of the present invention on the surface of a semiconductor wafer can be produced by heating and pressing the adherend to the bonding layer to harden the bonding layer. Examples of the adherend include semiconductor elements.

作為加熱壓接條件，加熱溫度較佳為20~250℃。荷重較佳為0.01~20kgf。加熱時間較佳為0.1~300秒鐘。 As heating and pressure bonding conditions, the heating temperature is preferably 20 to 250 ° C. The load is preferably 0.01 to 20 kgf. The heating time is preferably 0.1 to 300 seconds.

又，本發明的半導體裝置的製造方法也能省略上述的曝光步驟及進行顯影處理的步驟。 In addition, the method of manufacturing the semiconductor device of the present invention can also omit the above-mentioned exposure step and the step of performing the development process.

<<半導體裝置的製造方法的第二實施形態>> << Second Embodiment of Manufacturing Method of Semiconductor Device >>

本發明的半導體裝置的製造方法的第二實施形態包含：將本發明的底部填料用積層體的接著層側的面積層在半導體晶圓，從接著層剝離樹脂薄膜，而將接著層積層在半導體晶圓的步驟；和將被接著體加熱壓接在已積層在半導體晶圓的接著層的表面的步驟。 The second embodiment of the method for manufacturing a semiconductor device of the present invention includes: placing the area of the bonding layer side of the underfill laminate of the invention on a semiconductor wafer, peeling the resin film from the bonding layer, and stacking the bonding layer on the semiconductor The step of the wafer; and the step of heating and pressing the bonded body on the surface of the bonding layer that has been deposited on the semiconductor wafer.

此外，可以進一步在積層步驟與加熱壓接步驟之間包含將已積層在半導體晶圓的接著層曝光的步驟、和將已曝光的接著層顯影的步驟。 In addition, a step of exposing the adhesion layer that has been deposited on the semiconductor wafer and a step of developing the exposed adhesion layer may be further included between the lamination step and the heat and pressure bonding step.

即，也能在將接著層積層於半導體晶圓後，不進行曝光及顯影而加熱壓接被接著體以製造半導體裝置。此外，也能在將已積層在半導體晶圓的接著層曝光及顯影以形成圖案後，加熱壓接被接著體以製造半導體裝置。 That is, it is also possible to manufacture the semiconductor device by heating and pressure-bonding the adherend without exposure and development after laminating the adhesive layer on the semiconductor wafer. In addition, after exposing and developing the adhesion layer that has been laminated on the semiconductor wafer to form a pattern, the adherend can be heated and pressure-bonded to manufacture a semiconductor device.

將接著層積層至半導體晶圓的方法沒有特別的限定，例如可舉出將本發明的底部填料用積層體的接著層側的面積層在半導體晶圓，一面加熱一面從接著層剝離樹脂薄膜而進行積層的方法等。此外，也可以不進行加熱而積層接著層。 The method of laminating the adhesive layer to the semiconductor wafer is not particularly limited. For example, an area layer on the adhesive layer side of the laminate for underfill of the present invention may be placed on the semiconductor wafer, and the resin film may be peeled from the adhesive layer while heating The method of stacking. In addition, the adhesion layer may be laminated without heating.

曝光步驟、顯影步驟、加熱壓接被接著體的步驟能與上述的第一實施形態同樣地進行。 The exposure step, the development step, and the step of heat and pressure bonding the adherend can be performed in the same manner as in the first embodiment described above.

此外，也能省略曝光步驟及進行顯影處理的步驟。 In addition, the exposure step and the step of performing the development process can also be omitted.

<半導體裝置> <Semiconductor device>

接下來，針對將本發明的組成物用作底部填料的半導體裝置，使用圖式具體說明。又，近年來提案有各式各樣構造的半導體裝置，本發明的組成物之作為底部填料的用途，不限於以下說明的構造的半導體裝置。 Next, the semiconductor device using the composition of the present invention as an underfill will be specifically described using drawings. Furthermore, in recent years, semiconductor devices of various structures have been proposed, and the use of the composition of the present invention as an underfill is not limited to semiconductor devices of the structure described below.

第11圖係顯示本發明的半導體裝置的一實施形態的示意剖面圖。在第11圖所示的半導體裝置200中，半導體元件12係透過底部填料層11a而接著在半導體元件搭載用支撐構件13，半導體元件12的連接端子(未圖示)係透過導線(wire)14而與外部連接端子(未圖示)電氣連接，利用封裝材15予以封裝。底部填料層11a係使用本發明的組成物或本發明的積層體(接著薄片)形成而成者。 FIG. 11 is a schematic cross-sectional view showing an embodiment of the semiconductor device of the present invention. In the semiconductor device 200 shown in FIG. 11, the semiconductor element 12 passes through the underfill layer 11 a and then the semiconductor element mounting support member 13, and the connection terminal (not shown) of the semiconductor element 12 passes through the wire 14 On the other hand, it is electrically connected to an external connection terminal (not shown), and is sealed with a sealing material 15. The underfill layer 11a is formed using the composition of the present invention or the laminate (adhesive sheet) of the present invention.

此外，第12圖係顯示本發明的半導體裝置的另一實施形態的示意剖面圖。在第12圖所示的半導體裝置210中，第一層的半導體元件12a係透過底部填料層11a而接著形成有端子16的半導體元件搭載用支撐構件13，在第一層的半導體元件12a上進一步透過底部填料層11a而連接第二層的半導體元件12b。第一層的半導體元件12a及第二層的半導體元件12b的連接端子(未圖示)係透過導線14而與外部連接端子電氣連接，利用封裝材15予以封裝。如此，本發明的組成物或本發明的積層體(接著薄片)也能適合使用於重疊複數個半導體元件的構造的半導體裝置。 FIG. 12 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention. In the semiconductor device 210 shown in FIG. 12, the semiconductor element 12a of the first layer passes through the underfill layer 11a and then the semiconductor element mounting support member 13 on which the terminal 16 is formed, further on the semiconductor element 12a of the first layer The second layer semiconductor element 12b is connected through the underfill layer 11a. The connection terminals (not shown) of the semiconductor element 12a of the first layer and the semiconductor element 12b of the second layer are electrically connected to the external connection terminal through the wire 14, and are encapsulated by the packaging material 15. In this way, the composition of the present invention or the laminate (adhesive sheet) of the present invention can also be suitably used for a semiconductor device having a structure in which a plurality of semiconductor elements are stacked.

第11圖及第12圖所示的半導體裝置(半導體封裝體(semiconductor package))200、210，例如能藉由沿著虛線D切割第9圖所示的附接著層的半導體晶圓20b，將切割後的附接著層的半導體晶圓加熱壓接在半導體元件搭載用支撐構件13以使兩者接著，之後，經歷焊線(wire bonding)步驟、根據需要而利用封裝材的封裝步驟等步驟來得到。加熱壓接中的加熱溫度較佳為20~250℃。荷重較佳為0.01~20kgf。加熱時間較佳為0.1~300秒鐘。 The semiconductor devices (semiconductor packages) 200 and 210 shown in FIGS. 11 and 12 can be obtained by cutting the semiconductor wafer 20b of the adhesion layer shown in FIG. 9 along the broken line D, for example. The diced semiconductor wafer with the adhesive layer is heated and pressure-bonded to the semiconductor element mounting support member 13 to bond the two, and then undergoes a wire bonding step, a packaging step using a packaging material as necessary, and other steps to get. The heating temperature in the thermal compression bonding is preferably 20 to 250 ° C. The load is preferably 0.01 to 20 kgf. The heating time is preferably 0.1 to 300 seconds.

第13圖係顯示本發明的半導體裝置的另一實施形態的示意剖面圖。 Fig. 13 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention.

第13圖所示的半導體裝置300係所謂的3維安裝裝置，積層複數個半導體元件301a~301d的半導體元件積層體301係配置在半導體元件搭載用支撐構件320。 The semiconductor device 300 shown in FIG. 13 is a so-called three-dimensional mounting device, and a semiconductor element layered body 301 in which a plurality of semiconductor elements 301 a to 301 d are stacked is arranged on a semiconductor element mounting support member 320.

又，此實施形態係以半導體元件的積層數為4層的情況為中心加以說明，但半導體元件的積層數沒有特別的限定，例如可以是2層、8層、16層、32層等。此外，也可以是1層。 In addition, this embodiment is described focusing on the case where the number of stacked semiconductor elements is four, but the number of stacked semiconductor elements is not particularly limited, and may be, for example, two layers, eight layers, 16 layers, or 32 layers. In addition, it may be one layer.

301a~301d皆包含矽基板等半導體晶圓。 301a to 301d all include semiconductor wafers such as silicon substrates.

最上層的半導體元件301a沒有貫通電極，在其一面形成有電極墊(electrode pad)(未圖示)。 The semiconductor element 301a at the uppermost layer has no through electrode, and an electrode pad (not shown) is formed on one surface thereof.

半導體元件301b~301d具有貫通電極302b~302d，在各半導體元件的兩面，設置有被一體地設置在貫通電極的連接墊(未圖示)。 The semiconductor elements 301b to 301d have penetration electrodes 302b to 302d, and connection pads (not shown) integrally provided on the penetration electrodes are provided on both surfaces of each semiconductor element.

半導體元件積層體301具有將沒有貫通電極的半導體元件301a、和具有貫通電極302b~302d的半導體元件301b~301d進行倒裝晶片接合的構造。 The semiconductor element laminate 301 has a structure in which a semiconductor element 301a without through electrodes and semiconductor elements 301b to 301d with through electrodes 302b to 302d are flip-chip bonded.

即，沒有貫通電極的半導體元件301a的電極墊、和與其鄰接的具有貫通電極302b的半導體元件301b之半導體元件301a側的連接墊，係以銲點凸塊(solder bump)等金屬凸塊303a連接，具有貫通電極302b的半導體元件301b之另一側的連接墊，係以焊點凸塊等金屬凸塊303b來和與其鄰接的具有貫通電極302c的半導體元件301c之半導體元件301b側的連接墊連接。同樣地，具有貫通電極302c的半導體元件301c之另一側的連接墊，係以焊點凸塊等金屬凸塊303c來和與其鄰接的具有貫通電極302d的半導體元件301d之半導體元件301c側的連接墊連接。 That is, the electrode pad of the semiconductor element 301a without the through electrode and the adjacent connection pad on the semiconductor element 301a side of the semiconductor element 301b with the through electrode 302b are connected by metal bumps 303a such as solder bumps The connection pad on the other side of the semiconductor element 301b having the through electrode 302b is connected to the connection pad on the side of the semiconductor element 301b of the semiconductor element 301c with the through electrode 302c adjacent thereto by metal bumps 303b such as solder bumps . Similarly, the connection pad on the other side of the semiconductor element 301c having the through electrode 302c is connected to the semiconductor element 301c side of the semiconductor element 301d having the through electrode 302d adjacent thereto with metal bumps 303c such as solder bumps Pad connection.

在各半導體元件301a~301d的間隙形成有底部填料層310，各半導體元件301a~301d係透過底部填料層310而積層。底部填料層310係使用本發明的組成物或本發明的積層體(接著薄片)形成而成者。 An underfill layer 310 is formed in the gap between the semiconductor elements 301a to 301d, and the semiconductor elements 301a to 301d are laminated through the underfill layer 310. The underfill layer 310 is formed using the composition of the present invention or the layered product (adhesive sheet) of the present invention.

半導體元件積層體301係積層在半導體元件搭載用支撐構件320。 The semiconductor element layered body 301 is laminated on the support member 320 for mounting a semiconductor element.

作為半導體元件搭載用支撐構件320，例如可使用將樹脂基板、陶瓷基板、玻璃基板等絕緣基板用作基材的多層配線基板。作為應用樹脂基板的半導體元件搭載用支撐構件320，可舉出多層敷銅層板(多層印刷配線板)等。 As the support member 320 for mounting a semiconductor element, for example, a multilayer wiring board using an insulating substrate such as a resin substrate, a ceramic substrate, a glass substrate, or the like as a base material can be used. Examples of the supporting member 320 for mounting a semiconductor element to which a resin substrate is applied include a multilayer copper-clad laminate (multilayer printed wiring board) and the like.

在半導體元件搭載用支撐構件320的一面設置有表面電極320a。 A surface electrode 320a is provided on one surface of the support member 320 for mounting a semiconductor element.

在半導體元件搭載用支撐構件320與半導體元件積層體301之間配置形成有再配線層305的絕緣層315，半導體元件搭載用支撐構件320和半導體元件積層體301係透過再配線層305而電氣連接。 The insulating layer 315 on which the redistribution layer 305 is formed is arranged between the support member 320 for mounting a semiconductor element and the semiconductor element laminate 301, and the support member 320 for mounting a semiconductor element and the semiconductor element laminate 301 are electrically connected through the redistribution layer 305 .

即，再配線層305的一端係透過焊點凸塊等金屬凸塊303d，而連接於半導體元件301d之在再配線層305側的面所形成的電極墊。此外，再配線層305的另一端係透過焊點凸塊等金屬凸塊303e來和半導體元件搭載用支撐構件的表面電極320a連接。 That is, one end of the rewiring layer 305 is connected to the electrode pad formed on the surface of the semiconductor element 301d on the side of the rewiring layer 305 through metal bumps 303d such as solder bumps. In addition, the other end of the redistribution layer 305 is connected to the surface electrode 320a of the semiconductor element mounting support member through metal bumps 303e such as solder bumps.

然後，在絕緣層315與半導體元件積層體301之間形成有底部填料層310a。此外，在絕緣層315與半導體元件搭載用支撐構件320之間形成有底部填料層310b。 底部填料層310a、310b係使用本發明的組成物或本發明的積層體(接著薄片)形成而成者。 Then, an underfill layer 310a is formed between the insulating layer 315 and the semiconductor element laminate 301. In addition, an underfill layer 310b is formed between the insulating layer 315 and the support member 320 for mounting a semiconductor element. The underfill layers 310a and 310b are formed using the composition of the present invention or the laminate (adhesive sheet) of the present invention.

[實施例] [Example]

以下，利用實施例來更具體地說明本發明，但本發明只要不超出其主旨，便不限於以下的實施例。又，只要沒有特別的說明，「%」及「份」為質量基準。 Hereinafter, the present invention will be described more specifically using examples, but the present invention is not limited to the following examples as long as the gist is not exceeded. In addition, as long as there is no special explanation, "%" and "parts" are quality standards.

<實施例1~36、比較例1~7> <Examples 1 to 36, Comparative Examples 1 to 7>

將下述表所示的各成分混合後，使用具有0.1μm孔徑(pore size)的聚四氟乙烯製過濾器過濾，調製實施例1~36、比較例1~7的組成物的溶液。 After mixing the components shown in the following table, it was filtered using a polytetrafluoroethylene filter having a pore size of 0.1 μm to prepare solutions of the compositions of Examples 1 to 36 and Comparative Examples 1 to 7.

以1000rpm、30秒鐘將所得到的溶液旋轉塗布在4吋矽晶圓，進行110℃、5分鐘，然後150℃、10分鐘的軟烘烤(soft bake)以成膜。所得到的樣品膜的膜厚係約10μm。 The resulting solution was spin-coated on a 4-inch silicon wafer at 1000 rpm for 30 seconds, and soft bake was performed at 110 ° C. for 5 minutes and then at 150 ° C. for 10 minutes to form a film. The film thickness of the obtained sample film was about 10 μm.

表1記載的縮寫係如以下所示。 The abbreviations described in Table 1 are as follows.

樹脂成分 Resin composition

A-1：PCZ-200(三菱瓦斯化學製)下述構造 A-1: PCZ-200 (made by Mitsubishi Gas Chemical)

A-2：PCZ-300(三菱瓦斯化學製)下述構造 A-2: PCZ-300 (made by Mitsubishi Gas Chemical)

A-3：PCZ-500(三菱瓦斯化學製)下述構造 A-3: PCZ-500 (made by Mitsubishi Gas Chemical)

A-4：PCZ-800(三菱瓦斯化學製)下述構造 A-4: PCZ-800 (made by Mitsubishi Gas Chemical)

A-5：下述構造。合成例後述。 A-5: The following structure. The synthesis example will be described later.

A-6：下述構造。合成例後述。 A-6: The following structure. The synthesis example will be described later.

A-7：下述構造。合成例後述。 A-7: The following structure. The synthesis example will be described later.

A-8：下述構造。合成例後述。 A-8: The following structure. The synthesis example will be described later.

A-9：下述構造。合成例後述。 A-9: The following structure. The synthesis example will be described later.

A-10：下述構造。合成例後述。 A-10: The following structure. The synthesis example will be described later.

A-11：APEC9379(BAYER製)下述構造 A-11: APEC9379 (made by Bayer) the following structure

A-12：PANLITE L-1225LM(帝人製)下述構造 A-12: PANLITE L-1225LM (made by Teijin)

A-13：下述構造。合成例後述。 A-13: The following structure. The synthesis example will be described later.

A-14：下述構造。合成例後述。 A-14: The following structure. The synthesis example will be described later.

W116.3：W116.3(丙烯酸樹脂，根上工業製) W116.3: W116.3 (acrylic resin, produced by Negami Industrial)

SG-P3：SG-P3(丙烯酸樹脂，NAGASE CHEMTEX製) SG-P3: SG-P3 (acrylic resin, made by NAGASE CHEMTEX)

RIKACOAT：RIKACOAT(溶劑溶解型聚醯亞胺樹脂，新日本理科製) RIKACOAT: RIKACOAT (solvent-soluble polyimide resin, manufactured by New Japan Science)

EPIKOTE 828XA：EPIKOTE 828XA(液狀環氧樹脂，三菱化學製) EPIKOTE 828XA: EPIKOTE 828XA (liquid epoxy resin, manufactured by Mitsubishi Chemical)

(A-5~A-10、A-13、A-14的合成) (Synthesis of A-5 ~ A-10, A-13, A-14)

在經氮置換的附攪拌器、回流管的3頸燒瓶，混合合計40質量份的各單體二醇(monomer diol)的混合物、60質量份的碳酸二乙酯、60質量份的20%乙氧化鈉乙醇溶液，升溫至120℃。之後，將反應器內減壓30kPa左右，進一步攪拌1小時。之後，在0.1kPa的真空下，攪拌3小時。冷卻至室溫後，將反應物一面攪拌一面滴至500質量份的純水。利用過濾取出所得到的白色粉末，進行送風乾燥得到A-5~A-10、A-13、A-14。 In a 3-necked flask with a stirrer and a reflux tube replaced with nitrogen, a total of 40 parts by mass of a mixture of each monomer diol (monomer diol), 60 parts by mass of diethyl carbonate, and 60 parts by mass of 20% ethyl Sodium oxide ethanol solution was raised to 120 ℃. Thereafter, the pressure in the reactor was reduced by about 30 kPa, and further stirred for 1 hour. Thereafter, it was stirred for 3 hours under a vacuum of 0.1 kPa. After cooling to room temperature, the reactant was dropped to 500 parts by mass of pure water while stirring. The obtained white powder was taken out by filtration and air-dried to obtain A-5 to A-10, A-13, and A-14.

聚合性化合物 Polymerizable compound

B-1：TAIC(TCI製)下述構造 B-1: TAIC (manufactured by TCI)

B-2：A-9300(新中村化學製)下述構造 B-2: A-9300 (manufactured by Shin Nakamura Chemical)

B-3：A-TMP(新中村化學製)下述構造 B-3: A-TMP (manufactured by Shin Nakamura Chemical)

B-4：AD-TMP(新中村化學製)下述構造 B-4: AD-TMP (manufactured by Shin Nakamura Chemical)

B-5：A-DPH(新中村化學製)下述構造 B-5: A-DPH (manufactured by Shin Nakamura Chemical)

B-6：TEGMA(Aldrich製)下述構造 B-6: TEGMA (made by Aldrich) the following structure

B-7：A-BPE-4(新中村化學製)下述構造 B-7: A-BPE-4 (produced by Shin Nakamura Chemical)

B-8：A-BPE-10(新中村化學製)下述構造 B-8: A-BPE-10 (manufactured by Shin Nakamura Chemical)

B-9：EPIKOTE(三菱化學製)下述構造 B-9: EPIKOTE (made by Mitsubishi Chemical Corporation)

CD401：CD401(SARTOMER製) CD401: CD401 (made by SARTOMER)

VISCOAT 802：VISCOAT 802(大阪有機化學) VISCOAT 802: VISCOAT 802 (Osaka Organic Chemistry)

(d)溶劑 (d) Solvent

NMP：N-甲基-2-吡咯啶酮 NMP: N-methyl-2-pyrrolidone

光聚合引發劑 Photopolymerization initiator

IRGACURE OXE01：IRGACURE OXE01(BASF公司製) IRGACURE OXE01: IRGACURE OXE01 (manufactured by BASF)

IRGACURE OXE02：IRGACURE OXE02(BASF公司製) IRGACURE OXE02: IRGACURE OXE02 (manufactured by BASF)

熱聚合引發劑 Thermal polymerization initiator

PERCUMYL D：PERCUMYL D(雙異丙苯基過氧化物，日油製) PERCUMYL D: PERCUMYL D (bis-cumyl peroxide, manufactured by Nippon Oil)

填料 filler

R-972：AEROSIL R-972(氧化矽，日本AEROSIL製) R-972: AEROSIL R-972 (silica, made by Japan AEROSIL)

AKP-50：AKP-50(氧化鋁，住友化學製) AKP-50: AKP-50 (alumina, manufactured by Sumitomo Chemical)

黏合性賦予劑 Tackifier

KBE-503：KBE-503(3-甲基丙烯醯氧基丙基三乙氧基矽烷，信越SILICONE製) KBE-503: KBE-503 (3-methacryloxypropyltriethoxysilane, manufactured by Shin-Etsu Silicone)

<耐熱性> <Heat resistance>

利用熱重量分析裝置Q500(TA公司製)測定所得到的樣品膜的熱重量減少。在60mL/min的氮氣流下，以20℃/min的一定升溫條件使用熱重量分析裝置而測定，用以下的基準評價。 The thermogravimetric analysis device Q500 (manufactured by TA) was used to measure the thermogravimetric reduction of the obtained sample film. Under a nitrogen flow of 60 mL / min, it was measured using a thermogravimetric analyzer under a constant temperature increase condition of 20 ° C./min, and evaluated using the following criteria.

5：殘存重量成為95%的溫度為300℃以上 5: The temperature at which the remaining weight becomes 95% is 300 ° C or higher

4：殘存重量成為95%的溫度為250℃以上小於300℃ 4: The temperature at which the remaining weight becomes 95% is 250 ° C or higher but less than 300 ° C

3：殘存重量成為95%的溫度為220℃以上小於250℃ 3: The temperature at which the remaining weight becomes 95% is 220 ° C or higher but less than 250 ° C

2：殘存重量成為95%的溫度為200℃以上小於220℃ 2: The temperature at which the remaining weight becomes 95% is 200 ° C or higher but less than 220 ° C

1：殘存重量成為95%的溫度小於200℃ 1: The temperature at which the remaining weight becomes 95% is less than 200 ℃

<硬化性> <Hardenability>

在加熱板上將所得到的樣品膜加熱至180℃，以玻璃棒接觸表面，藉此測定變得不具膠黏性(tackiness)的時間，評價硬化性。 The obtained sample film was heated to 180 ° C on a hot plate, and the surface was contacted with a glass rod, thereby measuring the time until tackiness became non-tackiness and evaluating the hardenability.

5：膠黏性在10分鐘以內消失 5: The adhesiveness disappears within 10 minutes

4：膠黏性在超過10分鐘、20分鐘以內消失 4: Adhesiveness disappears within 10 minutes and 20 minutes

3：膠黏性在超過20分鐘、30分鐘以內消失 3: Adhesiveness disappears within 20 minutes and 30 minutes

2：膠黏性在超過30分鐘、60分鐘以內消失 2: Adhesiveness disappears within 30 minutes and 60 minutes

1：膠黏性超過60分鐘才消失 1: The adhesiveness disappears after more than 60 minutes

<吸水性> <Water absorption>

使所得到的樣品在室溫下浸漬在水中1日後，測定在室溫下風乾1小時者的吸水率。吸水率係利用熱重量分析裝置Q500(TA公司製)，在60mL/min的氮氣流下，以20℃/min的一定升溫條件升溫至120℃，在120℃下保持60分鐘後，測定重量減少率，用以下的基準評價吸水性。 After immersing the obtained sample in water at room temperature for 1 day, the water absorption rate of the person who was air-dried at room temperature for 1 hour was measured. The water absorption rate was measured using a thermogravimetric analyzer Q500 (manufactured by TA Co., Ltd.) under a nitrogen flow of 60 mL / min under a constant temperature increase condition of 20 ° C / min to 120 ° C. After holding at 120 ° C for 60 minutes, the weight loss rate was measured , The water absorption was evaluated using the following criteria.

5：重量減少率小於1% 5: Weight reduction rate is less than 1%

4：重量減少率為1%以上小於2% 4: Weight reduction rate is more than 1% and less than 2%

3：重量減少率為2%以上小於3% 3: Weight reduction rate is more than 2% and less than 3%

2：重量減少率為3%以上小於5% 2: Weight reduction rate is more than 3% and less than 5%

1：重量減少率為5%以上 1: Weight reduction rate is more than 5%

<影像形成性> <Image formation>

使用UV曝光裝置(濱松Photonics製，LC8)，透過將100μm正方形點作為遮光區域的光罩，以2000mJ/cm2、365nm，將使用實施例23、24、27、32~36 的組成物所得到的樣品進行曝光。使曝光後的樣品浸漬於環戊酮5分鐘，以光學顯微鏡確認是否形成影像。 Using a UV exposure device (manufactured by Hamamatsu Photonics, LC8), using a mask with a 100 μm square dot as a light-shielding area, the composition of Examples 23, 24, 27, and 32 to 36 was obtained at 2000 mJ / cm 2 and 365 nm. Samples are exposed. The exposed sample was immersed in cyclopentanone for 5 minutes, and it was confirmed with an optical microscope whether an image was formed.

<保存穩定性> <Storage stability>

調製實施例1~36、比較例1~7的組成物的溶液，加以密閉而在40℃下放置1週。利用GPC(凝膠滲透層析)測定溶液中的聚碳酸酯的重量平均分子量，用以下的基準評價保存穩定性。 The solutions of the compositions of Examples 1 to 36 and Comparative Examples 1 to 7 were prepared, sealed, and left at 40 ° C for 1 week. The weight average molecular weight of the polycarbonate in the solution was measured by GPC (gel permeation chromatography), and the storage stability was evaluated according to the following criteria.

2：與剛調液後相比，重量平均分子量的變化率小於5% 2: The rate of change of the weight-average molecular weight is less than 5% compared with immediately after liquid adjustment

1：與剛調液後相比，重量平均分子量的變化率為5%以上 1: The rate of change of the weight-average molecular weight is 5% or more compared with immediately after liquid adjustment

<塗布性> <Coatability>

利用目視確認所得到的樣品膜的平滑性，用以下的基準評價確認塗布性。 The smoothness of the obtained sample film was visually confirmed, and the applicability was confirmed by the following criteria.

2：不能確認表面有凹凸 2: Unable to confirm the unevenness on the surface

1：能確認表面有凹凸者 1: Those who can confirm the unevenness on the surface

根據上述結果，實施例1~36的組成物能形成保存穩定性、塗布性及硬化性優異、吸水性低、耐熱性優異的膜。 Based on the above results, the compositions of Examples 1 to 36 can form a film excellent in storage stability, coatability and curability, low in water absorption, and excellent in heat resistance.

另一方面，使用丙烯酸樹脂取代聚碳酸酯樹脂的比較例1、2係耐熱性差者。再者，吸水性大。 On the other hand, Comparative Examples 1 and 2 in which acrylic resin was used instead of polycarbonate resin had poor heat resistance. Furthermore, the water absorption is large.

此外，使用聚醯亞胺樹脂取代聚碳酸酯樹脂的比較例3係吸水性大。 In addition, the comparative example 3 in which the polyimide resin is used instead of the polycarbonate resin has high water absorption.

此外，使用環氧樹脂取代聚碳酸酯樹脂的比較例4係硬化性差者。 In addition, Comparative Example 4 using epoxy resin instead of polycarbonate resin has poor curability.

此外，使用與本發明中的非質子性溶劑不同的溶劑的比較例5~7係保存穩定性或塗布性差者。 In addition, Comparative Examples 5 to 7 using a solvent different from the aprotic solvent in the present invention are those with poor storage stability or poor coatability.

Claims (28)

一種組成物，其係含有聚碳酸酯樹脂、聚合性化合物、和溶劑，在組成物中含有50質量%以上的該溶劑，該溶劑當中50質量%以上係沸點為130℃以上、分子量為75以上的非質子性溶劑，該聚碳酸酯樹脂的含量，相對於組成物的總固體成分為40~90質量%。A composition containing a polycarbonate resin, a polymerizable compound, and a solvent, the composition containing 50% by mass or more of the solvent, 50% by mass or more of the solvent having a boiling point of 130 ° C or higher and a molecular weight of 75 or more The content of the polycarbonate resin is 40 to 90% by mass relative to the total solid content of the composition. 如請求項1的組成物，其中該聚碳酸酯樹脂具有下述通式(1)所表示的重複單元；
Figure TWI651365B_C0001
通式(1)中，Ar1及Ar2各自獨立地表示芳香族基，L表示單鍵或2價的連結基。The composition according to claim 1, wherein the polycarbonate resin has a repeating unit represented by the following general formula (1);
Figure TWI651365B_C0001
In the general formula (1), Ar 1 and Ar 2 each independently represent an aromatic group, and L represents a single bond or a divalent linking group. 如請求項1或2的組成物，其中該聚碳酸酯樹脂具有下述通式(2)所表示的重複單元；
Figure TWI651365B_C0002
通式(2)中，R1及R2各自獨立地表示氫原子、烷基或芳基，R1和R2可以連結而形成環。The composition according to claim 1 or 2, wherein the polycarbonate resin has a repeating unit represented by the following general formula (2);
Figure TWI651365B_C0002
In the general formula (2), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and R 1 and R 2 may be linked to form a ring. 如請求項1或2的組成物，其中該聚碳酸酯樹脂具有下述通式(3)所表示的重複單元；
Figure TWI651365B_C0003
通式(3)中，R3表示烷基，m係0~10的整數。The composition according to claim 1 or 2, wherein the polycarbonate resin has a repeating unit represented by the following general formula (3);
Figure TWI651365B_C0003
In the general formula (3), R 3 represents an alkyl group, and m is an integer of 0 to 10. 如請求項1或2的組成物，其中該聚合性化合物係具有2個以上具乙烯性不飽和鍵的基的化合物。The composition according to claim 1 or 2, wherein the polymerizable compound is a compound having two or more groups having an ethylenically unsaturated bond. 如請求項1或2的組成物，其中該聚合性化合物具有下述式所表示的部分構造；其中，式中的＊係連結鍵(connecting bond)，
Figure TWI651365B_C0004
The composition according to claim 1 or 2, wherein the polymerizable compound has a partial structure represented by the following formula; wherein, * in the formula is a connecting bond (connecting bond),
Figure TWI651365B_C0004
 如請求項1或2的組成物，其還包含光聚合引發劑。The composition according to claim 1 or 2, which further contains a photopolymerization initiator. 如請求項1或2的組成物，其還包含熱聚合引發劑。The composition according to claim 1 or 2, which further contains a thermal polymerization initiator. 如請求項1或2的組成物，其還包含填料。The composition according to claim 1 or 2 further contains a filler. 如請求項1或2的組成物，其還包含黏合性賦予劑。The composition according to claim 1 or 2 further contains an adhesion-imparting agent. 如請求項1或2的組成物，其係底部填料用。If the composition of claim 1 or 2, it is used as an underfill. 如請求項1或2的組成物，其係液狀。The composition of claim 1 or 2 is liquid. 一種底部填料用積層體，其係在樹脂薄膜的表面具有由如請求項1至12中任一項的組成物所形成的接著層。A laminate for an underfill having an adhesive layer formed of the composition according to any one of claims 1 to 12 on the surface of a resin film. 一種積層體，其係在半導體晶圓的表面具有由如請求項1至12中任一項的組成物所形成的接著層。A laminate having an adhesive layer formed of the composition according to any one of claims 1 to 12 on the surface of a semiconductor wafer. 如請求項14的積層體，其中該組成物中的聚碳酸酯樹脂具有下述通式(1)所表示的重複單元；
Figure TWI651365B_C0005
通式(1)中，Ar1及Ar2各自獨立地表示芳香族基，L表示單鍵或2價的連結基。The laminate according to claim 14, wherein the polycarbonate resin in the composition has a repeating unit represented by the following general formula (1);
Figure TWI651365B_C0005
In the general formula (1), Ar 1 and Ar 2 each independently represent an aromatic group, and L represents a single bond or a divalent linking group. 如請求項14或15的積層體，其中該組成物中的聚碳酸酯樹脂具有下述通式(2)所表示的重複單元；
Figure TWI651365B_C0006
通式(2)中，R1及R2各自獨立地表示氫原子、烷基或芳基，R1和R2可以連結而形成環。The laminate according to claim 14 or 15, wherein the polycarbonate resin in the composition has a repeating unit represented by the following general formula (2);
Figure TWI651365B_C0006
In the general formula (2), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and R 1 and R 2 may be linked to form a ring. 如請求項14或15的積層體，其中該組成物中的聚碳酸酯樹脂具有下述通式(3)所表示的重複單元；
Figure TWI651365B_C0007
通式(3)中，R3表示烷基，m係0~10的整數。The laminate according to claim 14 or 15, wherein the polycarbonate resin in the composition has a repeating unit represented by the following general formula (3);
Figure TWI651365B_C0007
In the general formula (3), R 3 represents an alkyl group, and m is an integer of 0 to 10. 如請求項14或15的積層體，其中該組成物中的聚合性化合物係具有2個以上具乙烯性不飽和鍵的基的化合物。The laminate according to claim 14 or 15, wherein the polymerizable compound in the composition is a compound having two or more groups having an ethylenically unsaturated bond. 如請求項14或15的積層體，其中該組成物中的聚合性化合物具有下述式表示的部分構造；其中，式中的＊係連結鍵，
Figure TWI651365B_C0008
The laminated body according to claim 14 or 15, wherein the polymerizable compound in the composition has a partial structure represented by the following formula; wherein, * in the formula is a bond,
Figure TWI651365B_C0008
 如請求項14或15的積層體，其中該組成物還包含光聚合引發劑。The laminate according to claim 14 or 15, wherein the composition further contains a photopolymerization initiator. 如請求項14或15的積層體，其中該組成物還包含熱聚合引發劑。The laminate according to claim 14 or 15, wherein the composition further contains a thermal polymerization initiator. 如請求項14或15的積層體，其中該組成物還包含填料。The laminate according to claim 14 or 15, wherein the composition further contains a filler. 如請求項14或15的積層體，其中該組成物還包含黏合性賦予劑。The laminate according to claim 14 or 15, wherein the composition further contains an adhesion-imparting agent. 一種半導體裝置之製造方法，其係包含：將如請求項12的組成物應用於半導體晶圓的步驟；將已應用於半導體晶圓的組成物乾燥的步驟；和將被接著體加熱壓接在已乾燥的組成物的表面的步驟。A method of manufacturing a semiconductor device, comprising: the step of applying the composition as claimed in claim 12 to a semiconductor wafer; the step of drying the composition applied to the semiconductor wafer; Step of drying the surface of the composition. 如請求項24的半導體裝置之製造方法，其中在乾燥步驟與加熱壓接步驟之間，包含將已乾燥的組成物曝光的步驟、和將已曝光的組成物顯影的步驟。The method for manufacturing a semiconductor device according to claim 24, wherein a step of exposing the dried composition and a step of developing the exposed composition are included between the drying step and the thermal compression bonding step. 一種半導體裝置之製造方法，其係包含：將如請求項13的底部填料用積層體的接著層側的面積層在半導體晶圓，從該接著層剝離樹脂薄膜，而將接著層積層在半導體晶圓的步驟；和將被接著體加熱壓接在已積層在半導體晶圓的接著層的表面的步驟。A method of manufacturing a semiconductor device, comprising: placing an area of the bonding layer side of the underfill laminate as in claim 13 on a semiconductor wafer, peeling the resin film from the bonding layer, and stacking the bonding layer on the semiconductor crystal A round step; and a step of heating and pressing the bonded body on the surface of the bonding layer that has been laminated on the semiconductor wafer. 如請求項26的半導體裝置之製造方法，其中在積層步驟與加熱壓接步驟之間，包含將已積層在半導體晶圓的接著層曝光的步驟、和將已曝光的接著層顯影的步驟。The method for manufacturing a semiconductor device according to claim 26, wherein between the lamination step and the heat-compression bonding step, a step of exposing the adhesion layer deposited on the semiconductor wafer and a step of developing the exposed adhesion layer are included. 一種半導體裝置，其係以如請求項24至27中任一項的方法製造。A semiconductor device manufactured by the method according to any one of claims 24 to 27.
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