TWI731158B - Resin composition - Google Patents

Resin composition Download PDF

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TWI731158B
TWI731158B TW106130398A TW106130398A TWI731158B TW I731158 B TWI731158 B TW I731158B TW 106130398 A TW106130398 A TW 106130398A TW 106130398 A TW106130398 A TW 106130398A TW I731158 B TWI731158 B TW I731158B
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resin composition
resin
component
mass
manufactured
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TW106130398A
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TW201825586A (en
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長嶋将毅
川合賢司
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日商味之素股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0145—Polyester, e.g. polyethylene terephthalate [PET], polyethylene naphthalate [PEN]

Abstract

[課題]本發明提供一種可製得具有高玻璃轉移溫度、與導體層具有良好密著性，低損耗因子硬化物之樹脂組成物。 　　[解決手段]提供一種含有(A)環氧樹脂、(B)具有碳-碳不飽和鍵結之活性酯化合物，及(C)具有不飽和烴基之樹脂之樹脂組成物。[Question] The present invention provides a resin composition that can produce a cured product with a high glass transition temperature, good adhesion to the conductor layer, and low loss factor.　　[Solution] Provide a resin composition containing (A) epoxy resin, (B) active ester compound with carbon-carbon unsaturated bond, and (C) resin with unsaturated hydrocarbon group.

Description

樹脂組成物Resin composition

[0001] 本發明為有關樹脂組成物之發明。更詳細而言，為有關含有該樹脂組成物之薄片狀層合材料、含有由該樹脂組成物之硬化物所形成的絕緣層之印刷電路板，及半導體裝置。[0001] The present invention is an invention related to a resin composition. More specifically, it relates to a sheet-like laminated material containing the resin composition, a printed circuit board containing an insulating layer formed of a cured product of the resin composition, and a semiconductor device.

[0002] 印刷電路板之製造技術，已知有於內層基板上，使絕緣層與導體層交互層合堆疊方式之製造方法。絕緣層，一般為使樹脂組成物硬化之方式而形成。 　　[0003] 例如，專利文獻1中，揭示一種至少含有(A)環氧樹脂，(B)含有萘結構的活性酯化合物的樹脂組成物中，以不揮發成份為100質量％時，前述(B)含有萘結構的活性酯化合物之含量為0.1～30質量％的熱硬化性環氧樹脂組成物。 　　[0004] 又，專利文獻2中，揭示一種含有(A)自由基聚合性化合物、(B)環氧樹脂、(C)硬化劑及(D)粗化成份的樹脂組成物。 　　[0005] 如上所述般，目前已有多數適合形成內層線路基板的絕緣層之環氧樹脂組成物的提案，但仍更期待一種可形成兼具有極佳平衡的低損耗因子，與優良耐熱性或密著性等特性的絕緣層之樹脂組成物。 [先前技術文獻] [專利文獻] 　　[0006] 　　[專利文獻1]特開2014-47318號公報 　　[專利文獻2]特開2014-34580號公報[0002] The manufacturing technology of printed circuit boards is known as a manufacturing method in which an insulating layer and a conductor layer are alternately laminated on an inner substrate. The insulating layer is generally formed by hardening the resin composition. [0003] For example, Patent Document 1 discloses a resin composition containing at least (A) an epoxy resin and (B) an active ester compound containing a naphthalene structure, when the non-volatile content is 100% by mass, the aforementioned (B) ) A thermosetting epoxy resin composition in which the content of the active ester compound containing a naphthalene structure is 0.1-30% by mass.　　[0004] In addition, Patent Document 2 discloses a resin composition containing (A) a radical polymerizable compound, (B) an epoxy resin, (C) a hardener, and (D) a roughening component. [0005] As mentioned above, there have been many proposals for epoxy resin composition suitable for forming the insulating layer of the inner circuit substrate, but it is still more desirable to form a low loss factor with an excellent balance, and excellent The resin composition of the insulating layer with the characteristics of heat resistance and adhesion. [Prior Art Document] [Patent Document] 　　[0006] 　　[Patent Document 1] JP 2014-47318 No. 　　 [Patent Document 2] JP 2014-34580 No.

[發明所欲解決之問題] 　　[0007] 本發明之課題為提供一種可形成具有低損耗因子、高玻璃轉移溫度、高密著性之絕緣層的樹脂組成物。 [解決問題之方法] 　　[0008] 本發明者們，對前述問題經過深入研究結果，得知含有(A)環氧樹脂、(B)具有碳-碳不飽和鍵結之活性酯化合物，及(C)具有不飽和烴基之樹脂之組合的樹脂組成物，即可解決前述問題，因而完成本發明。 　　即，本發明為包含下述之內容。 　　[0009] [1] 一種樹脂組成物，其為含有(A)環氧樹脂(以下，於本說明書中，亦稱為「(A)成份」)、(B)具有碳-碳不飽和鍵結之活性酯化合物(以下，於本說明書中，亦稱為「(B)成份」)，及(C)具有不飽和烴基之樹脂(以下，於本說明書中，亦稱為「(C)成份」)。 　　[2] 如上述[1]記載之樹脂組成物，其中，前述(B)成份之含量，於樹脂成份為100質量％時，為10質量％～60質量％。 　　[3] 如上述[1]或[2]記載之樹脂組成物，其中，前述(A)成份之含量，於樹脂成份為100質量％時，為10質量％～50質量％，前述(C)成份之含量，於樹脂成份為100質量％時，為3質量％～30質量％。 　　[4] 如上述[1]～[3]中任一項所記載之樹脂組成物，其中，前述(B)成份為具有碳-碳雙鍵之活性酯化合物。 　　[5] 如上述[4]記載之樹脂組成物，其中，前述(B)成份為具有乙烯基、甲基丙烯酸基、丙烯酸基、烯丙基、苯乙烯基或丙烯基之活性酯化合物。 　　[6] 如上述[5]記載之樹脂組成物，其中，前述(B)成份為具有苯乙烯基之活性酯化合物。 　　[7] 如上述[6]記載之樹脂組成物，其中，前述(B)成份為含有下述通式(1)所示之化合物。

Figure 02_image001
(前述通式(1)中，m表示1～6之整數，n表示1～20之整數)。 　　[8] 如上述[1]～[7]中任一項所記載的樹脂組成物，其中，前述(C)成份為具有丙烯酸基、甲基丙烯酸基、苯乙烯基，或烯烴基之樹脂。 　　[9] 如上述[1]～[8]中任一項所記載的樹脂組成物，其為形成印刷電路板之絕緣層者。 　　[10] 一種薄片狀層合材料，其為含有上述[1]～[9]中任一項所記載的樹脂組成物。 　　[11] 一種印刷電路板，其為含有由上述[1]～[9]中任一項所記載的樹脂組成物之硬化物所形成的絕緣層。 　　[12] 一種半導體裝置，其為含有上述[11]記載之印刷電路板。 [發明之效果] 　　[0010] 本發明，可提供一種可製得具有高玻璃轉移溫度、與導體層具有良好密著性，低損耗因子硬化物的樹脂組成物；含有該樹脂組成物之薄片狀層合材料；及含有該樹脂組成物之硬化物的印刷電路板及半導體裝置。 [實施發明之形態] 　　[0011] 以下，將使用實施形態及例示內容詳細說明本發明。但，本發明並不僅限定於下述實施形態及例示內容，只要不超出本發明之申請專利範圍與其均等的範圍之範圍內，皆可進行任意變更而實施。 　　[0012] 以下說明中，樹脂組成物中的各成份之量，於無特別說明時，係指相對於樹脂組成物中的樹脂成份100質量％之值。 　　又，以下說明中，「樹脂成份」於無特別說明時，係指樹脂組成物所含有之不揮發成份中，去除(D)無機填充材料(以下，於本說明書中，亦稱為「(D)成份」)後之成份。 　　[0013] [1. 樹脂組成物之概要] 　　本發明之樹脂組成物為含有(A)環氧樹脂、(B)具有碳-碳不飽和鍵結之活性酯化合物，及(C)具有不飽和烴基之樹脂。本發明之樹脂組成物硬化而形成的硬化物，為含有由(B)成份之不飽和鍵結部位，與(C)成份之不飽和烴基，經反應而形成的分子結構部位。該分子結構部位，經(B)成份之不飽和鍵結部位及(C)成份之不飽和烴基之作用，可降低其極性。因此，可降低硬化物之極性，而降低損耗因子之值。 　　又，本發明之樹脂組成物硬化而形成的硬化物，不僅含有由(B)成份之不飽和鍵結部位，與(C)成份之不飽和烴基經反應而形成的分子結構部位，尚含有由(B)成份之活性酯部位，與(A)成份經反應而形成的分子結構部位。因此，可使交聯密度緻密化(即，構造緻密化)、提高硬化物之玻璃轉移溫度。此外，因交聯密度緻密化，而可提高硬化物的機械性強度，不易造成伴隨硬化物破壞所產生的剝離，而可形成硬化物與導體層具有優良密著性者。 　　[0014] 如前所述，本發明之樹脂組成物，因(B)成份於化合物中，具有由(A)成份及(C)成份經反應而得之反應部位，故可形成一可達到與(A)成份與(C)成份分別單獨使用時所可得到之效果的硬化物。 　　此外，其與分別使用可與(A)成份反應之酯化合物，與可與(C)成份反應之具有不飽和鍵結的化合物的情形相比較時，使用(B)成份之情形中，可提高(A)成份、(B)成份及(C)成份之混合性。因此，可提高硬化物中組成之均勻性，而得以更高水準達成前述之效果。 　　[0015] [2. (A)環氧樹脂] 　　本發明之樹脂組成物為含有(A)成份。因硬化物具有由(A)成份與(B)成份之活性酯部位經反應而形成的分子結構部位，故可形成構造緻密化、提高硬化物之玻璃轉移溫度、優良密著性者。 　　(A)成份，例如，二甲酚型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚AF型環氧樹脂、二環戊二烯型環氧樹脂、三酚型環氧樹脂、萘酚酚醛清漆型環氧樹脂、酚酚醛清漆型環氧樹脂、tert-丁基-兒茶酚型環氧樹脂、萘型環氧樹脂、萘酚型環氧樹脂、蒽型環氧樹脂、縮水甘油胺型環氧樹脂、縮水甘油酯型環氧樹脂、甲酚酚醛清漆型環氧樹脂、聯苯型環氧樹脂、線性脂肪族環氧樹脂、具有丁二烯構造的環氧樹脂、脂環式環氧樹脂、雜環式環氧樹脂、含有螺環的環氧樹脂、環己烷二甲醇型環氧樹脂、伸萘醚型環氧樹脂、三羥甲基型環氧樹脂、四苯基乙烷型環氧樹脂、鹵化環氧樹脂等。 　　[0016] 該些之中，(A)成份，就提高密著性之觀點，以雙酚A型環氧樹脂、雙酚F型環氧樹脂、萘酚型環氧樹脂、萘型環氧樹脂、聯苯型環氧樹脂、伸萘醚型環氧樹脂、縮水甘油酯型環氧樹脂及蒽型環氧樹脂為佳，就降低平均線熱膨張率之觀點，以含有芳香族骨架之環氧樹脂為佳。其中，芳香族骨架，為包含多環芳香族及芳香族雜環之概念。含有芳香族骨架之環氧樹脂，以由雙酚A型環氧樹脂、雙酚F型環氧樹脂、萘型環氧樹脂、聯苯型環氧樹脂、二環戊二烯型環氧樹脂，及萘酚型環氧樹脂所成之群所選出的1種以上之環氧樹脂為佳，又以由雙酚A型環氧樹脂、聯苯型環氧樹脂，及萘型環氧樹脂所成之群所選出的1種以上的環氧樹脂為更佳。 　　[0017] 又，樹脂組成物中，(A)成份以含有1分子中具有2個以上的環氧基之環氧樹脂為佳。相對於(A)成份之不揮發成份100質量％，1分子中具有2個以上的環氧基之環氧樹脂之比例，較佳為50質量％以上，更佳為60質量％以上、特佳為70質量％以上。其中，樹脂組成物中，(A)成份又以含有1分子中具有3個以上的環氧基之、溫度20℃為固體狀的環氧樹脂(以下亦稱為「固體狀環氧樹脂」)為佳。 　　[0018] (A)成份，可單獨使用1種，或將2種以上以任意比例組合使用亦可。因此，樹脂組成物中，(A)成份可僅含有固體狀環氧樹脂亦可，含有固形狀環氧樹脂與其他環氧樹脂之組合者亦可。其中，樹脂組成物中，(A)成份，以含有固體狀環氧樹脂，與1分子中具有2個以上的環氧基、溫度20℃為液狀的環氧樹脂(以下，亦稱為「液狀環氧樹脂」)組合者為佳。(A)成份，於使用液狀環氧樹脂與固體狀環氧樹脂之組合時，可提高樹脂組成物之可撓性，或提高樹脂組成物之硬化物的斷裂強度。 　　[0019] 液狀環氧樹脂，以雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AF型環氧樹脂、萘型環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、酚酚醛清漆型環氧樹脂、具有酯骨架的脂環式環氧樹脂、環己烷二甲醇型環氧樹脂、縮水甘油胺型環氧樹脂，及具有丁二烯構造的環氧樹脂為佳，以縮水甘油胺型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AF型環氧樹脂及萘型環氧樹脂為較佳。 　　[0020] 液狀環氧樹脂，例如，DIC公司製之「HP4032」、「HP4032D」、「HP4032SS」(萘型環氧樹脂)；三菱化學公司製之「YL980」、「828US」、「JER828EL」、「825」、「EPCODA 828EL」(雙酚A型環氧樹脂)；三菱化學公司製之「JER806H」、「JER807」、「YL983U」、「1750」(雙酚F型環氧樹脂)；三菱化學公司製之「JER152」(酚酚醛清漆型環氧樹脂)；三菱化學公司製之「630」、「630LSD」(縮水甘油胺型環氧樹脂)；新日鐵住金化學公司製之「ZX1059」(雙酚A型環氧樹脂與雙酚F型環氧樹脂之混合品)；長瀨化學科技公司製之「EX-721」(縮水甘油酯型環氧樹脂)；DACEL公司製之「CELLOXIDE 2021P」(具有酯骨架的脂環式環氧樹脂)；DACEL公司製之「PB-3600」(具有丁二烯構造的環氧樹脂)；新日鐵化學公司製之「ZX1658」、「ZX1658GS」(液狀1,4-縮水甘油環己烷型環氧樹脂)等。該些可單獨使用1種，或將2種以上以任意比例組合使用亦可。 　　[0021] 固體狀環氧樹脂，例如，萘型環氧樹脂、萘型4官能環氧樹脂、甲酚酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、三酚型環氧樹脂、萘酚型環氧樹脂、聯苯型環氧樹脂、伸萘醚型環氧樹脂、蒽型環氧樹脂、雙酚A型環氧樹脂、四苯基乙烷型環氧樹脂、二甲酚型環氧樹脂為佳，萘型環氧樹脂、萘型4官能環氧樹脂、萘酚型環氧樹脂、二甲酚型環氧樹脂及聯苯型環氧樹脂為較佳。 　　[0022] 固體狀環氧樹脂，例如，DIC公司製之「HP4032H」(萘型環氧樹脂)；DIC公司製之「HP-4700」、「HP-4710」(萘型4官能環氧樹脂)；DIC公司製之「N-690」、「N-695」(甲酚酚醛清漆型環氧樹脂)；DIC公司製之「HP-7200」、「HP-7200HH」、「HP-7200H」(二環戊二烯型環氧樹脂)；DIC公司製之「EXA-7311」、「EXA-7311-G3」、「EXA-7311-G4」、「EXA-7311-G4S」、「HP6000」(伸萘醚型環氧樹脂)；日本化藥公司製之「EPPN-502H」(三酚型環氧樹脂)；日本化藥公司製之「NC7000L」(萘酚酚醛清漆型環氧樹脂)；日本化藥公司製之「NC3000H」、「NC3000」、「NC3000L」、「NC3100」(聯苯型環氧樹脂)；新日鐵住金化學公司製之「ESN475V」(萘酚萘型環氧樹脂)；新日鐵住金化學公司製之「ESN485」(萘酚酚醛清漆型環氧樹脂)；三菱化學公司製之「YL6121」(聯苯型環氧樹脂)；三菱化學公司製之「YX4000H」、「YX4000」、「YX4000HK」(二甲酚型環氧樹脂)；三菱化學公司製之「YX8800」(蒽型環氧樹脂)；大阪氣體化學公司製之「PG-100」、「CG-500」；三菱化學公司製之「YL7760」(雙酚AF型環氧樹脂)；三菱化學公司製之「YL7800」(茀型環氧樹脂)；三菱化學公司製之「JER1010」(固體狀雙酚A型環氧樹脂)；三菱化學公司製之「JER1031S」(四苯基乙烷型環氧樹脂)等。該些可單獨使用1種，或將2種以上以任意比例組合使用亦可。 　　[0023] (A)成份，於將液狀環氧樹脂與固體狀環氧樹脂組合使用之情形，該些之質量比(液狀環氧樹脂：固體狀環氧樹脂)較佳為1：0.1～1：15，更佳為1：0.5～1：10、特佳為1：1～1：8。 　　液狀環氧樹脂之質量比於前述範圍時，於以接著薄膜形態使用之情形時，可得到充分之可撓性、提高可處理性，且於層合時可得到充分的流動性。 　　固體狀環氧樹脂之質量比於前述範圍時，就降低環氧樹脂之黏性，而以接著薄膜形態使用之情形，可提高真空層合時之脫氣性。又，於真空層合時可使保護薄膜及支撐體具有良好的剝離性，且可提高硬化後的耐熱性。 　　[0024] (A)成份之環氧當量較佳為50～5000，更佳為50～3000，更佳為80～2000、特佳為110～1000。(A)成份之環氧當量為前述範圍時，樹脂組成物之硬化物可製得具有充分的交聯密度，且表面粗度更小的絕緣層。 　　環氧當量為，含有1當量環氧基的樹脂之質量，為依JIS K7236基準測定而得者。 　　[0025] (A)成份之重量平均分子量，就可更顯製得到本發明所期待之效果的觀點，較佳為100～5000，更佳為250～3000，特佳為400～1500。 　　(A)成份之重量平均分子量，為依凝膠滲透色層分析(GPC)法，所測定之聚苯乙烯換算之值。例如，樹脂之重量平均分子量，可使用作為測定裝置之島津製作所公司製LC-9A/RID-6A，並使用作為管柱的昭和電工公司製Shodex K-800P/K-804L/K-804L，移動相使用氯仿等，於管柱溫度為40℃時之測定結果，並使用標準聚苯乙烯之檢量線而可算出。 　　[0026] 樹脂組成物中之(A)成份之量，就可製得具有高玻璃轉移溫度、高密著性之絕緣層的觀點，一般相對於樹脂組成物中的樹脂成份100質量％，較佳為5質量％以上，更佳為10質量％以上，更佳為20質量％以上。(A)成份之量之上限，只要可達成本發明效果時，可為任意之數值，較佳為70質量％以下，更佳為65質量％以下，特佳為60質量％以下，最佳為50質量％以下。 　　[0027] [3. (B)具有碳-碳不飽和鍵結之活性酯化合物] 　　本發明之樹脂組成物，含有(B)成份。(B)成份可與(A)成份及(C)成份等兩成份進行反應，而形成硬化物。 　　因硬化物中具有由(B)成份之不飽和鍵結部位，與(C)成份經反應而形成的具有分子結構部位，故可降低硬化物之極性，而減低損耗因子之值。 　　又，因硬化物中具有由(B)成份之活性酯部位，與(A)成份經反應而形成的分子結構部位，故可形成具有構造緻密化、提高硬化物之玻璃轉移溫度、優良密著性之物。 　　[0028] 以往，將2個具有不同反應性的樹脂合併使用時，常因各樹脂之混合性惡化，而無法均勻地形成硬化物。因此，要同時以高水準生成兼具有上述效果時為極困難者。 　　又，本案發明之樹脂組成物中，(B)成份中，因具有2個不同反應性的樹脂可與其各別反應的部位為存在同一化合物中。因此，(B)成份可形成由各樹脂鍵結而形成的硬化物，而可形成均勻的硬化物。因此，可同時以高水準生成具有上述特性，而可達成本案發明所期待之效果。 　　此外，使用(B)成份時，可提高(A)成份、(B)成份及(C)成份之混合性。因此，可提高硬化物中的組成之均勻性，而可以更高水準生成上述之效果。 　　[0029] 碳-碳不飽和鍵結，通常為脂肪族不飽和鍵結，例如，碳-碳雙鍵、碳-碳三鍵等。其中，又以碳-碳雙鍵為佳。具有碳-碳雙鍵的較佳(B)成份，例如，具有乙烯基、甲基丙烯酸基、丙烯酸基、烯丙基、苯乙烯基或丙烯基之活性酯化合物等。其中，就具有優良耐熱性之觀點，以苯乙烯基為特佳。 　　[0030] (B)成份，以含有下述通式(1)所示之化合物為佳。
Figure 02_image003
通式(1)中，m表示1～6之整數，n表示1～20之整數。 　　[0031] 通式(1)中，m較佳為1～6之整數，更佳為1～3之整數。又，n較佳為1～10之整數，更佳為1～5之整數，特佳為1～3之整數。於上述數值範圍時，(B)成份可與(C)成份以適當之比例進行反應，而可實現降低損耗因子之目標。 　　[0032] (B)成份，可為具有不同m、n值的通式(1)所示之化合物的化合物之混合物。為混合物之情形，(B)成份，只要含有通式(1)所示之化合物時，亦可含有通式(1)中n為0之化合物(下述式(0-1)所示之化合物)，或n為1～20之整數，m為0之化合物(下述通式(0-2)所示之化合物)。 　　又，相對於(B)成份100質量％，式(0-1)所示之化合物及通式(0-2)所示之化合物之合計比例，較佳為10質量％以下，更佳為5質量％以下，特佳為3質量％以下，最佳為1質量％以下，亦可為0質量％。於該範圍時，可使(B)成份與(C)成份得以適當比例進行反應，而可實現降低損耗因子之目標。
Figure 02_image005
通式(0-2)中，n表示1～20之整數。 　　[0033] 通式(1)所示之化合物可使用市售品，亦可使用合成品。市售品，例如，商品名「PC1300-02-65MA」(Air-Water公司製)等。 　　[0034] 樹脂組成物中(B)成份之量，就可製得具有低損耗因子、高玻璃轉移溫度、高密著性之絕緣層的觀點，相對於樹脂組成物中的樹脂成份100質量％，較佳為5質量％以上，更佳為10質量％以上，最佳為20質量％以上。(B)成份之量之上限，只要可達成本發明效果時，可為任意之比例，較佳為70質量％以下，更佳為65質量％以下，特佳為60質量％以下。 　　[0035] [4. (C)具有不飽和烴基之樹脂] 　　本發明之樹脂組成物，為含有(C)成份。硬化物具有由(C)成份與(B)成份之不飽和鍵結部位經反應而形成的分子結構部位時，可降低硬化物之極性，降低損耗因子之數值。 　　(C)成份，只要具有不飽和烴基時，並未有特別之限定。使用不飽和烴基時，可降低硬化物的損耗因子。不飽和烴基，又以丙烯酸基、甲基丙烯酸基、苯乙烯基、烯烴基等的脂肪族不飽和烴基為佳。其中，就具有優良耐熱性之觀點，以苯乙烯基為較佳。 　　其中，「烯烴基」係指，分子中具有碳-碳雙鍵之脂肪族烴基之意。例如，烯丙基、乙烯基、丙烯基等。 　　[0036] (C)成份，以下述通式(2)所示之化合物為佳。 　　[0037]
Figure 02_image007
通式(2)中，R1 ～R6 ，各自獨立表示氫原子或碳數1～4之烷基，較佳為氫原子。A表示下述通式(3)或下述通式(4)所示之構造。 　　[0038]
Figure 02_image009
通式(3)中，B表示下述通式(B-1)、(B-2)或(B-3)所示之構造。 　　[0039]
Figure 02_image011
通式(4)中，D表示下述通式(5)所示之構造。 　　[0040]
Figure 02_image013
通式(5)中，R7 ～R14 ，各自獨立表示氫原子、碳數6以下之烷基或苯基，較佳為氫原子或甲基。特別是R7 、R8 、R13 、R14 更佳為甲基。a、b為至少一者不為0之0～100之整數。B表示下述通式(B-1)、(B-2)或(B-3)所示之構造。 　　[0041]
Figure 02_image015
通式(B-1)中，R15 ～R18 ，各自獨立表示氫原子、碳數6以下之烷基或苯基，較佳為氫原子或甲基。 　　通式(B-2)中，R19 ～R26 ，各自獨立表示氫原子、碳數6以下之烷基或苯基，較佳為氫原子或甲基。 　　通式(B-3)中，R27 ～R34 ，各自獨立表示氫原子、碳數6以下之烷基或苯基，較佳為氫原子或甲基。E表示碳數20以下之直鏈狀、分支狀或環狀之2價之烴基。 　　[0042] (C)成份，以下述通式(6)、下述式(7)或下述式(8)所示之化合物為較佳。 　　[0043]
Figure 02_image017
通式(6)中，R1 ～R6 與通式(2)中之R1 ～R6 具有相同之意義，B與通式(3)中之B具有相同之意義，a、b，與通式(5)中之a、b具有相同之意義。 　　[0044]
Figure 02_image019
[0045]
Figure 02_image021
[0046] 市售之(C)成份，例如，苯乙烯變性聚苯醚樹脂(三菱瓦斯化學公司製「OPE-2St 1200(數平均分子量1200)」、相當於通式(6))、二甲酚二烯丙醚樹脂(三菱化學公司製「YL7776(數平均分子量331)」、相當於通式(7))、二噁烷丙烯酸基單體二醇二丙烯酸酯(新中村化學工業公司製「A-DOG(數平均分子量326)」、相當於通式(8))等。 　　[0047] (C)成份之數平均分子量，就防止樹脂塗料乾燥時之揮發、防止樹脂組成物的熔融黏度過度上升之觀點，較佳為100～10000之範圍，更佳為200～3000之範圍。又，本發明中之數平均分子量，可使用凝膠滲透色層分析(GPC)法(聚苯乙烯換算)測定。GPC法之數平均分子量，例如，可使用測定裝置之島津製作所公司製LC-9A/RID-6A、管柱之昭和電工公司製Shodex K-800P/K-804L/K-804L、移動相之氯仿等，於管柱溫度40℃下測定之數據，使用標準聚苯乙烯檢量線而算出。 　　[0048] 樹脂組成物中，(C)成份之量，就降低硬化物的損耗因子之數值的觀點，相對於樹脂組成物中之樹脂成份100質量％，較佳為3質量％以上，更佳為5質量％以上，最佳為10質量％以上。(C)成份之量之上限，只要可達成本發明效果時，可為任意之數值，又較佳為50質量％以下，更佳為40質量％以下，特佳為30質量％以下。 　　[0049] [5. 硬化劑] 　　樹脂組成物，於無損本發明效果之範圍，可含有與(B)成份不同之硬化劑。硬化劑，並未有特別限制之內容，例如，酚系硬化劑、萘酚系硬化劑、活性酯系硬化劑、苯併噁
Figure 106130398-A0304-1
系硬化劑、氰酸酯酯系硬化劑，及碳二醯亞胺系硬化劑等。其中，就可得到與導體層具有優良密著性之絕緣層的觀點，以使用活性酯系硬化劑為佳。又，硬化劑可單獨使用1種，或將2種以上以任意比例組合使用亦可。 　　[0050] 酚系硬化劑或萘酚系硬化劑，就耐熱性及耐水性之觀點，以具有酚醛清漆構造之酚系硬化劑或具有酚醛清漆構造之萘酚系硬化劑為佳。又，就與導體層之密著性之觀點，以含氮酚系硬化劑或含氮萘酚系硬化劑為佳，又以含有三
Figure 106130398-A0304-1
骨架之酚系硬化劑或含有三
Figure 106130398-A0304-1
骨架之萘酚系硬化劑為較佳。其中，就可高度滿足耐熱性、耐水性，及與導體層之密著性等觀點，以含有三
Figure 106130398-A0304-1
骨架之酚酚醛清漆硬化劑或含有三
Figure 106130398-A0304-1
骨架之萘酚酚醛清漆硬化劑為佳。 　　[0051] 酚系硬化劑及萘酚系硬化劑，例如，明和化成公司製之「MEH-7700」、「MEH-7810」、「MEH-7851」、日本化藥公司製之「NHN」、「CBN」、「GPH」、新日鐵住金公司製之「SN-170」、「SN-180」、「SN-190」、「SN-475」、「SN-485」、「SN-495」、「SN-375」、「SN-395」、DIC公司製之「TD-2090」、「LA-7052」、「LA-7054」、「LA-1356」、「LA-3018-50P」等。 　　[0052] 活性酯系硬化劑，並未有特別之限定。例如，可使用酚酯類、硫酚酯類、N-羥胺酯類、雜環羥基化合物之酯類等的1分子中具有2個以上的高反應活性之酯基的化合物。該活性酯系硬化劑，以由羧酸化合物及硫代羧酸化合物中至少任一種化合物，與羥基化合物及硫醇化合物中至少任一種化合物，經縮合反應而製得者為佳。特別是就提高耐熱性之觀點，以由羧酸化合物，與羥基化合物所製得之活性酯系硬化劑為佳。 　　[0053] 羧酸化合物，例如，安息香酸、乙酸、琥珀酸、馬來酸、依康酸、苯二甲酸、異苯二甲酸、對苯二甲酸、苯均四酸等。酚化合物或萘酚化合物，例如，氫醌、間苯二酚、雙酚A、雙酚F、雙酚S、酚酞、甲基化雙酚A、甲基化雙酚F、甲基化雙酚S、酚、o-甲酚、m-甲酚、p-甲酚、兒茶酚、α-萘酚、β-萘酚、1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯甲酮、三羥基二苯甲酮、四羥基二苯甲酮、間苯三酚、苯三唑、二環戊二烯型二酚化合物、酚酚醛清漆等。其中，「二環戊二烯型二酚化合物」係指，二環戊二烯1分子與酚2分子經縮合而製得的二酚化合物之意。 　　[0054] 活性酯系硬化劑，以含有二環戊二烯型二酚構造之活性酯化合物、含有萘結構的活性酯化合物、含有酚酚醛清漆的乙醯化物之活性酯化合物、含有酚酚醛清漆之苯甲醯化物之活性酯化合物為佳，以含有萘結構的活性酯化合物、含有二環戊二烯型二酚構造之活性酯化合物為較佳。「二環戊二烯型二酚構造」係指，由伸苯基-二環伸戊基-伸苯基所形成之2價之構造單位。 　　[0055] 活性酯系硬化劑之市售品，例如，DIC公司製之「EXB9451」、「EXB9460」、「EXB9460S」、「HPC-8000-65T」、「EXB-8000L-65TM」、「HPC-8000H-65M」(含有二環戊二烯型二酚構造之活性酯化合物)、DIC公司製之「EXB-9416L-70BK」(含有萘結構的活性酯化合物)、三菱化學公司製之「DC808」(含有酚酚醛清漆的乙醯化物之活性酯化合物)、三菱化學公司製之「YLH1026」(含有酚酚醛清漆的苯甲醯化物之活性酯化合物)、DIC公司製之「EXB-9050L-62M」(含有磷原子之活性酯化合物)等。 　　[0056] 苯併噁
Figure 106130398-A0304-1
系硬化劑，例如，昭和高分子公司製之「HFB2006M」、四國化成工業公司製之「P-d」、「F-a」等。 　　[0057] 氰酸酯酯系硬化劑，並未有特別之限定。例如，酚酚醛清漆型、烷酚酚醛清漆型等的酚醛清漆型氰酸酯酯系硬化劑；二環戊二烯型氰酸酯酯系硬化劑；雙酚A型、雙酚F型、雙酚S型等的、雙酚型氰酸酯酯系硬化劑；及該些中之一部份經三
Figure 106130398-A0304-1
化後之預聚合物等。氰酸酯酯系硬化劑，例如，雙酚A二氰酸酯、聚酚氰酸酯、寡(3-伸甲基-1,5-伸苯基氰酸酯)、4,4’-伸甲基雙(2,6-二甲苯基氰酸酯)、4,4’-亞乙基二苯基二氰酸酯、六氟雙酚A二氰酸酯、2,2-雙(4-氰酸酯)苯基丙烷、1,1-雙(4-氰酸酯苯基甲烷)、雙(4-氰酸酯-3,5-二甲苯基)甲烷、1,3-雙(4-氰酸酯苯基-1-(甲基亞乙基))苯、雙(4-氰酸酯苯基)硫醚，及雙(4-氰酸酯苯基)醚等的2官能氰酸酯樹脂；酚酚醛清漆及甲酚酚醛清漆等所衍生之多官能氰酸酯樹脂；及該些氰酸酯樹脂中之一部份經三
Figure 106130398-A0304-1
化而得之預聚合物等。市售品，可列舉如，Lonza日本公司製之「PT30」、「PT60」(皆為酚酚醛清漆型多官能氰酸酯酯樹脂)、「BA230」(雙酚A二氰酸酯中之一部份或全部經三
Figure 106130398-A0304-1
化而得三聚物的預聚合物)等。 　　[0058] 碳二醯亞胺系硬化劑，例如，日清紡化學公司製之「V-03」、「V-07」等。 　　[0059] 硬化劑，以由酚系硬化劑、萘酚系硬化劑、活性酯系硬化劑及碳二醯亞胺系硬化劑所選出之1種以上者為佳，以酚系硬化劑及活性酯系硬化劑中之至少任一者為更佳。 　　[0060] (A)成份之環氧基數為1時，就具有良好機械性強度的絕緣層之觀點，該硬化劑的反應基數之下限，較佳為0.1以上，更佳為0.2以上，特佳為0.3以上、最佳為0.4以上。上限較佳為2以下，更佳為1.5以下，特佳為1以下。 　　其中，「硬化劑之反應基」，依活性羥基、活性酯基等，硬化劑之種類而有所差異。又，「(A)成份之環氧基數」係指，樹脂組成物中的各環氧樹脂的固體成份質量除以環氧當量而得之值，作為環氧樹脂中之合計值。又，「硬化劑之反應基數」係指，存在於樹脂組成物中的各硬化劑的固體成份質量除以反應基當量而得之值，作為全部硬化劑之合計值。(A)環氧樹脂與硬化劑之含量比於前述範圍時，可更提高樹脂組成物之硬化物的耐熱性。 　　[0061] 樹脂組成物中硬化劑之含量，並未有特別之限定。例如，相對於樹脂組成物中樹脂成份100質量％，上限較佳為30質量％以下，更佳為25質量％以下，特佳為20質量％以下，最佳為18質量％以下、15質量％以下。又，下限較佳為1質量％以上，更佳為3質量％以上，最佳為5質量％以上、特佳為7質量％以上、10質量％以上。硬化劑含量於前述範圍時，可使樹脂組成物形成具有更優良的線熱膨張係數、損耗因子、與導體層之密著性的硬化物。 　　[0062] [6. (D)無機填充材料] 　　樹脂組成物，通常含有(D)成份。使用(D)成份時，可降低樹脂組成物之硬化物的熱膨張係數，而可抑制絕緣層的回焊變形。 　　[0063] (D)成份之材料並未有特別之限定，例如，二氧化矽、氧化鋁、玻璃、堇青石、矽氧化物、硫酸鋇、碳酸鋇、滑石、黏土、雲母粉、氧化鋅、水滑石、水鋁石、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、氧化鎂、氮化硼、氮化鋁、氮化錳、硼酸鋁、碳酸鍶、鈦酸鋇、鈦酸鍶、鈦酸鈣、鈦酸鎂、鈦酸鉍、氧化鈦、氧化鋯、鈦酸鋯酸鋇、鋯酸鋇、鋯酸鈣、磷酸鋯，及磷酸鎢酸鋯等。該些之中，又以二氧化矽為佳，以無定形二氧化矽、粉碎二氧化矽、熔融二氧化矽、結晶二氧化矽、合成二氧化矽、中空二氧化矽、球狀二氧化矽為更佳，就可降低絕緣層表面粗度之觀點，以熔融二氧化矽、球狀二氧化矽為更佳，以球狀熔融二氧化矽為特佳。(D)成份，可單獨使用1種，或將2種以上以任意比例組合使用亦可。 　　[0064] 通常，(D)成份為以粒子狀態包含於樹脂組成物中。(D)成份之粒子的平均粒徑，就可製得高線路埋入性，低表面粗度之絕緣層的觀點，較佳為5μm以下，更佳為3μm以下，特佳為2μm以下，最佳為1μm以下、0.8μm以下、0.6μm以下、0.4μm以下。該平均粒徑之下限，就作為樹脂塗料之際，防止塗料黏度上升、處理性降低等觀點，較佳為0.01μm以上，更佳為0.03μm以上，特佳為0.05μm以上、最佳為0.07μm以上、0.1μm以上。 　　[0065] 具有前述平均粒徑的(D)成份之市售品，例如，新日鐵住金金屬公司製「SP60-05」、「SP507-05」；Admatechs公司製「YC100C」、「YA050C」、「YA050C-MJE」、「YA010C」；Denka公司製「UFP-30」；德山公司製「Silfile NSS-3N」、「Silfile NSS-4N」、「Silfile NSS-5N」；Admatechs公司製「SC2500SQ」、「SO-C4」、「SO-C2」、「SO-C1」等。 　　[0066] (D)成份等的粒子平均粒徑，可使用米氏(Mie)散亂理論為基礎之雷射繞射-散射法予以測定。例如，可使用雷射繞射散亂式粒徑分佈測定裝置，依體積基準測定粒子之粒徑分佈，並以該粒徑分佈的中位數徑作為平均粒徑。測定樣品，可使用以超音波將粒子分散於水中而得之溶液。雷射繞射散亂式粒徑分佈測定裝置，可使用堀場製作所公司製「LA-500」等。 　　[0067] (D)成份，可使用任意的表面處理劑進行表面處理。表面處理劑，例如，胺基矽烷系耦合劑、環氧矽烷系耦合劑、氫硫基矽烷系耦合劑、烷氧基矽烷化合物、有機矽氮烷化合物、鈦酸鹽系耦合劑等。經使用該些表面處理劑對(D)成份進行表面處理，可提高(D)成份之耐濕性及分散性。 　　[0068] 表面處理劑之市售品，例如，信越化學工業公司製「KBM-22」(二甲基二甲氧基矽烷)、信越化學工業公司製「KBM-403」(3-環氧丙氧基丙基三甲氧基矽烷)、信越化學工業公司製「KBM-803」(3-氫硫基丙基三甲氧基矽烷)、信越化學工業公司製「KBE-903」(3-胺基丙基三乙氧基矽烷)、信越化學工業公司製「KBM-573」(N-苯基-3-胺基丙基三甲氧基矽烷)、信越化學工業公司製「SZ-31」(六甲基二矽氮烷)、信越化學工業公司製「KBM-103」(苯基三甲氧基矽烷)、信越化學工業公司製「KBM-4803」(長鏈環氧型矽烷耦合劑)等。又，表面處理劑可單獨使用1種，或將2種以上以任意比例組合使用亦可。 　　[0069] 使用表面處理劑進行表面處理之程度，可以(D)成份之每一單位表面積的碳量進行評估。(D)成份之每一單位表面積的碳量，就可提高(D)成份之分散性的觀點，較佳為0.02mg/m2 以上，更佳為0.1mg/m2 以上、特佳為0.2mg/m2 以上。又，就可抑制樹脂組成物的熔融黏度及於薄片形態時熔融黏度之上升等觀點，前述碳量，較佳為1mg/m2 以下，更佳為0.8mg/m2 以下，特佳為0.5mg/m2 以下。 　　[0070] (D)成份之每一單位表面積的碳量，為於使用溶劑對表面處理後之(D)成份進行洗淨處理之後所測定者。溶劑，例如，可使用甲基乙酮(以下，亦稱為「MEK」)。例如，將充分量的甲基乙酮，與經表面處理劑進行表面處理後的(D)成份進行混合，於25℃下，使用超音波洗淨5分鐘。隨後，去除上澄液，將固體成份乾燥後，使用碳分析計，測定(D)成份之每一單位表面積的碳量。碳分析計，可使用堀場製作所公司製「EMIA-320V」。 　　[0071] 樹脂組成物中，(D)成份之量的下限，就可製得低熱膨張率的絕緣層之觀點，相對於樹脂組成物中的樹脂成份100質量份，較佳為100質量份以上，更佳為200質量份以上，特佳為250質量份以上。上限，就絕緣層的機械性強度，特別是拉伸性之觀點，較佳為500質量份以下，更佳為400質量份以下，特佳為350質量份以下。 　　[0072] [7. (E)硬化促進劑] 　　本發明之樹脂組成物，必要時，可再含有(E)硬化促進劑(以下，於本說明書中，亦稱為「(E)成份」)。使用(E)成份時，於使樹脂組成物硬化之際，可促進硬化。 　　[0073] (E)成份，例如，磷系硬化促進劑、胺系硬化促進劑、咪唑系硬化促進劑、胍系硬化促進劑、金屬系硬化促進劑、過氧化物系硬化促進劑等。其中，又以磷系硬化促進劑、胺系硬化促進劑、咪唑系硬化促進劑、過氧化物系硬化促進劑或金屬系硬化促進劑為佳，以胺系硬化促進劑、咪唑系硬化促進劑、過氧化物系硬化促進劑或金屬系硬化促進劑為較佳。 　　又，(E)成份，可單獨使用1種，或將2種以上以任意比例組合使用亦可。 　　[0074] 磷系硬化促進劑，例如，三苯基次膦(phosphine)、鏻硼酸鹽化合物、四苯基鏻四苯基硼酸鹽、n-丁基鏻四苯基硼酸鹽、四丁基鏻癸烷酸鹽、(4-甲苯基)三苯基鏻硫代氰酸鹽、四苯基鏻硫代氰酸鹽、丁基三苯基鏻硫代氰酸鹽等。其中，又以三苯基次膦、四丁基鏻癸烷酸鹽為佳。 　　[0075] 胺系硬化促進劑，例如，三乙胺、三丁胺等的三烷胺、4-二甲胺基吡啶、苄二甲胺、2,4,6-三(二甲胺基甲基)酚、1,8-二氮雜雙環[5,4,0]-十一烯等。其中，又以4-二甲胺基吡啶、1,8-二氮雜雙環[5,4,0]-十一烯為佳。 　　[0076] 咪唑系硬化促進劑，例如，2-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-十一烷基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-十一烷基咪唑鹽偏苯三酸酯、1-氰基乙基-2-苯基咪唑鹽偏苯三酸酯、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三
Figure 106130398-A0304-1
、2,4-二胺基-6-[2’-十一烷基咪唑基-(1’)]-乙基-s-三
Figure 106130398-A0304-1
、2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三
Figure 106130398-A0304-1
、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三
Figure 106130398-A0304-1
三聚異氰酸加成物、2-苯基咪唑三聚異氰酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2,3-二氫-1H-吡咯[1,2-a]苯併咪唑、1-十二烷基-2-甲基-3-苄基咪唑鹽氯化物、2-甲基咪唑啉、2-苯基咪唑啉之咪唑化合物及咪唑化合物與環氧樹脂之加成物等。其中，又以2-乙基-4-甲基咪唑、1-苄基-2-苯基咪唑為佳。 　　[0077] 咪唑系硬化促進劑，可使用市售品，例如，三菱化學公司製之「P200-H50」等。 　　[0078] 胍系硬化促進劑，例如，二氰二醯胺、1-甲基胍、1-乙基胍、1-環己基胍、1-苯基胍、1-(o-甲苯基)胍、二甲基胍、二苯基胍、三甲基胍、四甲基胍、五甲基胍、1,5,7-三氮雜雙環[4.4.0]癸-5-烯、7-甲基-1,5,7-三氮雜雙環[4.4.0]癸-5-烯、1-甲基雙胍、1-乙基雙胍、1-n-丁基雙胍、1-n-十七烷基雙胍、1,1-二甲基雙胍、1,1-二乙基雙胍、1-環己基雙胍、1-烯丙基雙胍、1-苯基雙胍、1-(o-甲苯基)雙胍等。其中，又以二氰二醯胺、1,5,7-三氮雜雙環[4.4.0]癸-5-烯為佳。 　　[0079] 金屬系硬化促進劑，例如，鈷、銅、鋅、鐵、鎳、錳、錫等的金屬之有機金屬錯合物或有機金屬鹽等。有機金屬錯合物，例如，乙醯丙酮鈷(II)、乙醯丙酮鈷(III)等的有機鈷錯合物；乙醯丙酮銅(II)等的有機銅錯合物；乙醯丙酮鋅(II)等的有機鋅錯合物；乙醯丙酮鐵(III)等的有機鐵錯合物；乙醯丙酮鎳(II)等的有機鎳錯合物；乙醯丙酮錳(II)等的有機錳錯合物等。有機金屬鹽，例如，辛酸鋅、辛酸錫、環烷酸鋅、環烷酸鈷、硬脂酸錫、硬脂酸鋅等。 　　[0080] 過氧化物系硬化促進劑，例如，過氧化環己酮、過氧化苯甲酸tert-丁酯、過氧化甲基乙酮、過氧化二異丙苯、過氧化異丙苯tert-丁酯、過氧化二-tert-丁酯、過氧化氫二異丙苯、過氧化氫異丙苯、過氧化氫tert-丁酯等。 　　[0081] 過氧化物系硬化促進劑，可使用市售品，例如，日油公司製之「Percumyl D」等。 　　[0082] 樹脂組成物中，(E)成份之量，就使本發明期待之效果更為顯著的觀點，相對於樹脂組成物中之樹脂成份100質量％，以0.01質量％～3質量％之範圍為佳。 　　[0083] [8. (F)熱可塑性樹脂] 　　本發明之樹脂組成物，可再含有(F)熱可塑性樹脂(以下，於本說明書中，亦稱為「(F)成份」)。(F)成份，例如，苯氧基樹脂、聚乙烯縮醛樹脂、聚烯烴樹脂、聚丁二烯樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞胺樹脂、聚碸樹脂、聚醚碸樹脂、聚苯醚樹脂、聚碳酸酯樹脂、聚醚醚酮樹脂、聚酯樹脂、茚苯并呋喃樹脂等。其中，就提高相溶性之觀點，以茚苯并呋喃樹脂為佳。又，(F)成份可單獨使用1種，或將2種以上以任意比例組合使用亦可。 　　[0084] (F)成份之聚苯乙烯換算之重量平均分子量，以8,000～70,000之範圍為佳，以10,000～60,000之範圍為較佳，以20,000～60,000之範圍為更佳。 　　(F)成份之聚苯乙烯換算之重量平均分子量，為使用凝膠滲透色層分析(GPC)法測定者。例如，(F)成份之聚苯乙烯換算之重量平均分子量，可使用測定裝置為島津製作所公司製LC-9A/RID-6A、管柱為昭和電工公司製Shodex K-800P/K-804L/K-804L、移動相為氯仿等，於管柱溫度40℃下測定，並使用標準聚苯乙烯之檢量線算出。 　　[0085] 苯氧基樹脂，例如，具有由雙酚A骨架、雙酚F骨架、雙酚S骨架、雙酚苯乙酮骨架、酚醛清漆骨架、聯苯骨架、茀骨架、二環戊二烯骨架、降莰烯骨架、萘骨架、蒽骨架、金剛烷骨架、萜烯骨架，及三甲基環己烷骨架所成之群所選出之1種以上的骨架之苯氧基樹脂等。苯氧基樹脂之末端，可為酚性羥基、環氧基等的任一官能基。苯氧基樹脂，可單獨使用1種，或將2種以上以任意比例組合使用亦可。 　　[0086] 苯氧基樹脂，例如，三菱化學公司製之「1256」及「4250」(皆為含有雙酚A骨架之苯氧基樹脂)；三菱化學公司製之「YX8100」(含有雙酚S骨架之苯氧基樹脂)；三菱化學公司製之「YX6954」(含有雙酚苯乙酮骨架之苯氧基樹脂)；新日鐵住金化學公司製之「FX280」及「FX293」；三菱化學公司製之「YX6954BH30」、「YX7553」、「YX7553BH30」、「YL7769BH30」、「YL6794」、「YL7213」、「YL7290」、「YL7891BH30」及「YL7482」等。 　　[0087] 茚苯并呋喃樹脂，例如，日塗化學公司製之「H-100」、「WS-100G」、「WS-100H」、「WS-120V」、「WS-100GC」；Nobaresu-Rutogazu公司製之「C10」、「C30」、「CA80」等。 　　[0088] 樹脂組成物中，(F)成份之量的下限，相對於樹脂組成物中的樹脂成份100質量％，較佳為0.1質量％以上，更佳為0.5質量％以上。又，其上限，較佳為10質量％以下，更佳為5質量％以下。於前述範圍時，可發揮薄膜成型能力或提高機械性強度之效果，且可提高熔融黏度或於濕式粗化步驟後降低絕緣層表面之粗度。 　　[0089] [9. 任意成份] 　　本發明之樹脂組成物，除上述成份以外，可含有任意之成份。該些任意成份，例如，難燃劑；有機填充材料；有機銅化合物、有機鋅化合物及有機鈷化合物等的有機金屬化合物；增黏劑；消泡劑；均染劑；密著性賦予劑；著色劑等的樹脂添加劑等。 　　[0090] ＜難燃劑＞ 　　本發明之樹脂組成物，經使用難燃劑時，可更提高樹脂組成物之硬化物之玻璃轉移溫度。 　　難燃劑，例如，有機磷系難燃劑、含有機系氮之磷化合物、氮化合物、聚矽氧系難燃劑、金屬氫氧化物等。難燃劑，可使用市售品，例如，三光公司製之「HCA-HQ」、「HCA-HQ-HS」、大八化學工業公司製之「PX-200」等。又，難燃劑，可單獨使用1種，或將2種以上以任意比例組合使用亦可。 　　[0091] 樹脂組成物中，難燃劑之量，就賦予耐熱性之觀點，相對於樹脂組成物中之樹脂成份100質量％，以0.5質量％～20質量％之範圍為佳，以0.5質量％～15質量％之範圍為較佳，以0.5質量％～10質量％之範圍為更佳。 　　[0092] ＜有機填充材料＞ 　　本發明之樹脂組成物，於使用有機填充材料時，因可提高樹脂組成物之硬化物的柔軟性，故可改善絕緣層之拉伸性。 　　有機填充材料，可使用形成印刷電路板的絕緣層時所使用的任意有機填充材料。例如，橡膠粒子、聚醯胺粒子、聚矽氧粒子等。又，橡膠粒子、可使用市售品，例如，陶氏・化學日本公司製之「EXL-2655」、Aik工業公司製之「AC3816N」等。又，有機填充材料，可單獨使用1種，或將2種以上以任意比例組合使用亦可。 　　[0093] 有機填充材料之粒子的平均粒徑，就使樹脂組成物中的分散性更為優良之觀點，較佳為5μm以下，更佳為4μm以下，特佳為3μm以下。有機填充材料的平均粒徑之下限，較佳為0.05μm以上，更佳為0.08μm以上、特佳為0.10μm以上。 　　[0094] 樹脂組成物中，有機填充材料之量，就將樹脂組成物之硬化物的機械性物性調整至適當範圍之觀點，相對於樹脂組成物中的樹脂成份100質量％，以0.1質量％～20質量％之範圍為佳，以0.2質量％～10質量％之範圍為較佳，以0.3質量％～5質量％之範圍為更佳，以0.5質量％～3質量％之範圍為特佳。 　　[0095] [10. 樹脂組成物之製法及特性] 　　本發明之樹脂組成物之製造方法，並未有特別限制之內容，例如，可將配合成份，必要時可添加溶劑等，使用迴轉攪拌機等進行混合・分散之方法等。 　　[0096] 本發明之樹脂組成物，可形成具有高玻璃轉移溫度之硬化物。本發明之樹脂組成物之硬化物之玻璃轉移溫度，可依後述＜玻璃轉移溫度之測定＞所記載之方法予以測定。具體而言，可列舉如，使用拉伸加重法進行熱機械分析，而可於荷重1g、升溫速度5℃/min下進行測定。本發明之樹脂組成物之硬化物，較佳為具有158℃以上，更佳為160℃以上，更佳為162℃以上之玻璃轉移溫度者。玻璃轉移溫度之上限並未有特別之限定，通常為250℃以下。 　　[0097] 本發明之樹脂組成物，可製得具有低損耗因子的硬化物。本發明之樹脂組成物之硬化物的損耗因子，可依後述＜損耗因子之測定＞所記載之方法測定。具體而言，可列舉如，使用空洞共振器震動法，以周波數5.8GHz、測定溫度23℃下進行測定。損耗因子之值，就防止高周波產生之發熱、降低訊號延遲與雜訊之觀點，較佳為0.0037以下，更佳為0.0035以下。損耗因子之值的下限，以越低越好，通常為0.0001以上等。 　　[0098] 本發明之樹脂組成物，可製得與導體層具有高密著性之硬化物。本發明之樹脂組成物之硬化物的密著性，可依後述＜密著性之測定＞所記載之方法予以評估。所得導體層與絕緣層之密著性，較佳為0.60kgf/cm以上，更佳為0.70kgf/cm以上。密著性之上限並未有特別之限定，通常為1.2kgf/cm以下。 　　[0099] 本發明之樹脂組成物，可製得高玻璃轉移溫度、低損耗因子、與導體層具有良好密著性的硬化物。因此，本發明之樹脂組成物，適合使用於形成印刷電路板的絕緣層所使用的樹脂組成物(印刷電路板之絕緣層用樹脂組成物)、形成印刷電路板之層間絕緣層的樹脂組成物(印刷電路板之層間絕緣層用樹脂組成物)。本發明之樹脂組成物，也適合使用於接著薄膜、預浸體等的薄片狀層合材料、焊劑光阻、底部填充材料(Underfill)、模具接合材料、半導體密封材料、埋穴樹脂、零件埋入樹脂等樹脂組成物的必要用途之廣泛範圍。 　　[0100] [11. 薄片狀層合材料] 　　本發明之樹脂組成物，可以塗料狀態塗佈使用，工業上而言，一般以含有該樹脂組成物的薄片狀層合材料之形態使用為佳。 　　[0101] 薄片狀層合材料，以下示之接著薄膜、預浸體為佳。 　　[0102] 一實施形態中，接著薄膜為含有支撐體，與該支撐體接合之樹脂組成物層(接著層)，其中，樹脂組成物層(接著層)為由本發明之樹脂組成物所形成。 　　[0103] 樹脂組成物層之厚度，就印刷電路板薄型化之觀點，較佳為100μm以下，更佳為80μm以下，特佳為60μm以下，特佳為50μm以下、40μm以下。樹脂組成物層之厚度下限，並未有特別之限定，通常為1μm以上，較佳為5μm以上，特佳為10μm以上等。 　　[0104] 支撐體，例如，由塑膠材料所製得之薄膜、金屬箔、離型紙等，又以由塑膠材料所製得之薄膜、金屬箔為佳。 　　[0105] 支撐體使用由塑膠材料所製得之薄膜時，塑膠材料，例如，聚乙烯對苯二甲酸酯(PET)、聚乙烯萘酯(PEN)等的聚酯；聚碳酸酯(PC)、聚甲基甲基丙烯酸酯(PMMA)等的丙烯酸基；環狀聚烯烴、三乙醯基纖維素(TAC)、聚醚硫醚(PES)、聚醚酮、聚醯亞胺等。其中，又以聚乙烯對苯二甲酸酯、聚乙烯萘酯為佳，又以廉價之聚乙烯對苯二甲酸酯為特佳。 　　[0106] 支撐體使用金屬箔時，金屬箔，例如，銅箔、鋁箔等。其中，又以銅箔為佳。銅箔，可使用僅由銅的單金屬所形成之箔，或使用銅與其他金屬(例如，錫、鉻、銀、鎂、鎳、鋯、矽、鈦等)的合金所形成之箔皆可。 　　[0107] 支撐體，可於與樹脂組成物層接合之側的表面實施消光處理、電暈處理等。又，支撐體，於與樹脂組成物層接合之側的表面，可使用附有具離型層的附離型層之支撐體。使用附離型層之支撐體的離型層之離型劑，例如，由醇酸樹脂、烯烴樹脂、胺基甲酸酯樹脂，及聚矽氧樹脂所成之群所選出之1種以上的離型劑等。離型劑之市售品，例如，醇酸樹脂系離型劑之琳德公司製之「SK-1」、「AL-5」、「AL-7」等。 　　[0108] 支撐體之厚度，並未有特別限定，一般以5μm～75μm之範圍為佳，以10μm～60μm之範圍為較佳。又，支撐體為附離型層之支撐體時，附離型層之支撐體全體之厚度以上述範圍為佳。 　　[0109] 接著薄膜，例如，可將樹脂組成物溶解於有機溶劑而製得樹脂塗料，將該樹脂塗料使用狹縫塗佈機等塗佈於支撐體上，再使其乾燥而形成樹脂組成物層之方式而可製得。 　　[0110] 有機溶劑，例如，丙酮、甲基乙酮(MEK)及環己酮等的酮類；乙酸乙基、乙酸丁基、溶纖劑(cellosolve)乙酸酯、丙二醇單甲醚乙酸酯及卡必醇乙酸酯等的乙酸酯類；溶纖劑及丁基卡必醇等的卡必醇類；甲苯及二甲苯等的芳香族烴類；二甲基甲醯胺、二甲基乙醯胺(DMAc)及N-甲基吡咯啶酮等的醯胺系溶劑等。有機溶劑，可單獨使用1種，或將2種以上以任意比例組合使用亦可。 　　[0111] 乾燥，可使用加熱、熱風吹拂等的公知方法予以實施。乾燥條件並未有特別限定，只要可將樹脂組成物層中的有機溶劑之含量降低至10質量％以下，較佳為5質量％以下之方式進行乾燥處理即可。其依樹脂塗料中有機溶劑之沸點而有所不同，例如使用含有30質量％～60質量％有機溶劑的樹脂塗料之情形，為於50℃～150℃下，實施3分鐘～10分鐘乾燥結果，即可形成樹脂組成物層。 　　[0112] 接著薄膜中，於未與樹脂組成物層的支撐體接合之面(即，與支撐體為相反側之面)，可依支撐體之不同再層合保護薄膜。保護薄膜之厚度，並未有特別限制之內容，例如，可為1μm～40μm。層合保護薄膜結果，可防止樹脂組成物層表面附著雜物等或防止碰傷。接著薄膜，可以捲取為滾筒狀予以保存。接著薄膜具有保護薄膜之情形，可將保護薄膜剝離後使用。 　　[0113] 一實施形態中，預浸體為將本發明之樹脂組成物含浸於薄片狀纖維基材中而形成。 　　[0114] 預浸體所使用的薄片狀纖維基材並未有特別之限定，其可使用玻璃纖維、芳香族聚醯胺不織布、液晶聚合物不織布等的常被作為預浸體基材的公知的基材。就印刷電路板薄型化之觀點，薄片狀纖維基材之厚度，較佳為50μm以下，更佳為40μm以下，特佳為30μm以下，最佳為20μm以下。薄片狀纖維基材的厚度下限並未有特別之限定。通常為10μm以上。 　　[0115] 預浸體，可使用熱熔膠法、溶劑法等的公知方法而可製得。 　　[0116] 預浸體之厚度，可與上述接著薄膜中之樹脂組成物層為相同之範圍。 　　[0117] 使用含有由(A)成份、(B)成份，及(C)成份組合的樹脂組成物之本發明中，不僅可製得高玻璃轉移溫度、低損耗因子、與導體層具有良好密著性的硬化物以外，於印刷電路板之製造中，亦為極有用的薄片狀層合材料。 　　[0118] 本發明之薄片狀層合材料，為極適合使用於形成印刷電路板的絕緣層(印刷電路板之絕緣層用)者，因此，其能更適合使用於形成印刷電路板之層間絕緣層(印刷電路板之層間絕緣層用)之材料。 　　[0119] [12. 印刷電路板] 　　本發明之印刷電路板，為含有由本發明之樹脂組成物或本發明之薄片狀層合材料經熱硬化而得之絕緣層。 　　[0120] 一實施形態中，本發明之印刷電路板，為使用上述接著薄膜，依包含下述(I)及(II)之步驟的方法而可製得。 　　(I)於內層基板上，將接著薄膜的該接著薄膜之樹脂組成物層與內層基板接合之方式層合之步驟 　　(II)將樹脂組成物層熱硬化，而形成絕緣層之步驟 　　[0121] 步驟(I)所使用的「內層基板」主要係指，玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚苯醚基板等的基板，或於該基板的單面或兩面進行圖型加工而形成導體層(線路)之線路基板之意。又，於製造印刷電路板之際，再於絕緣層及導體層的至少任一者所形成作為中間產物的內層線路基板，亦包含於本發明所稱之「內層基板」中。印刷電路板為零件內藏線路板之情形，只要使用零件為內藏的內層基板即可。 　　[0122] 內層基板與接著薄膜之層合方法，例如，由支撐體側將接著薄膜向內層基板加熱壓著之方式進行。將接著薄膜向內層基板加熱壓著所使用的構件(以下，亦稱為「加熱壓著構件」)，例如，經加熱之金屬板(SUS鏡板等)或金屬滾筒(SUS滾筒)等。又，加熱壓著構件並無須與接著薄膜直接壓著，一般以使內層基板的表面凹凸充分追隨接著薄膜之方式，介由耐熱橡膠等的彈性材料壓著者為佳。 　　[0123] 內層基板與接著薄膜之層合，可使用真空層合法實施。真空層合法中，加熱壓著溫度較佳為60℃～160℃，更佳為80℃～140℃之範圍。加熱壓著壓力較佳為0.098MPa～1.77MPa，更佳為0.29MPa～1.47MPa之範圍。加熱壓著時間較佳為20秒～400秒鐘，更佳為30秒～300秒鐘之範圍。層合，較佳為於壓力26.7hPa以下的減壓條件下實施。 　　[0124] 層合，可使用市售的真空層合器進行。市售的真空層合器，例如，名機製作所公司製之真空加壓式層合器、日光・金屬公司製之VacuumApplicator等。 　　[0125] 層合後，可於常壓下(大氣壓下)，例如，將加熱壓著構件由支撐體側加壓，對層合後的接著薄膜進行平滑化處理。平滑化處理之加壓條件，可依與上述層合時的加熱壓著條件為相同之條件下進行。平滑化處理，可使用市售之層合器進行。又，層合與平滑化處理，可使用上述市售的真空層合器進行連續性處理。 　　[0126] 支撐體，可於步驟(I)與步驟(II)之間去除，或於步驟(II)之後去除皆可。 　　[0127] 步驟(II)中，為使樹脂組成物層熱硬化而形成絕緣層。 　　[0128] 樹脂組成物層的熱硬化條件並未有特別之限定，其可使用形成印刷電路板之絕緣層時，所通常採用之條件。 　　[0129] 例如，樹脂組成物層之熱硬化條件，依樹脂組成物之種類等而有所不同。例如，硬化溫度通常為120℃～240℃之範圍(較佳為150℃～220℃之範圍，更佳為170℃～200℃之範圍)。硬化時間通常為5分鐘～120分鐘之範圍(較佳為10分鐘～100分鐘，更佳為15分鐘～90分鐘)。 　　[0130] 於使樹脂組成物層熱硬化之前，可使樹脂組成物層於較硬化溫度為更低溫度下進行預熱。例如，於使樹脂組成物層熱硬化之前，通常於50℃以上、未達120℃(較佳為60℃以上、110℃以下，更佳為70℃以上、100℃以下)之溫度，使樹脂組成物層進行通常5分鐘以上(較佳為5～150分鐘，更佳為15～120分鐘)之預熱。 　　[0131] 製造印刷電路板之際，可再實施(III)於絕緣層上開孔之步驟、(IV)對絕緣層進行粗化處理之步驟、(V)於絕緣層表面形成導體層之步驟。該些步驟(III)至(V)，為使用於製造印刷電路板之製程，故熟悉該項技術者，可依公知的各種方法予以實施。又，支撐體於步驟(II)後去除時，去除該支撐體之時間點，可於步驟(II)與步驟(III)之間、步驟(III)與步驟(IV)之間，或步驟(IV)與步驟(V)之間實施。 　　[0132] 其他實施形態中，本發明之印刷電路板可使用上述預浸體而製得。製造方法基本上與使用接著薄膜之情形為相同。 　　[0133] 步驟(III)為於絕緣層上開孔步驟，經此步驟可於絕緣層上形成通孔(via hole)、貫通孔(through hole)等的孔洞(hole)。步驟(III)，可配合形成絕緣層所使用的樹脂組成物之組成內容等，例如，可使用鑽頭、雷射、電漿等實施。孔洞的尺寸或形狀，可配合印刷電路板之設計適當決定即可。 　　[0134] 步驟(IV)為對絕緣層進行粗化處理之步驟。粗化處理之順序、條件，並未有特別之限定，其可使用形成印刷電路板之絕緣層時，所通常使用的公知順序、條件。例如，可依序實施使用膨潤液進行膨潤處理、使用氧化劑進行粗化處理、使用中和液進行中和處理之方法，對絕緣層進行粗化處理。 　　[0135] 膨潤液並未有特別之限定。例如，鹼溶液、界面活性劑溶液等。較佳為鹼溶液，該鹼溶液，又以氫氧化鈉溶液、氫氧化鉀溶液為較佳。市售之膨潤液，例如，Atotech日本公司製之「Swelling Dip Security Gans P」、「Swelling-Dip-Security-GansSBU」等。使用膨潤液進行之膨潤處理，並未有特別之限定。例如，可於30℃～90℃之膨潤液中，將絕緣層浸漬1分鐘～20分鐘之方式進行。就將絕緣層的樹脂之膨潤抑制至適當程度之觀點，以於40℃～80℃之膨潤液中，將硬化體浸漬5分鐘～15分鐘者為佳。 　　[0136] 氧化劑，並未有特別之限定。例如，於氫氧化鈉之水溶液中，溶解過錳酸鉀或過錳酸鈉所製得之鹼性過錳酸溶液等。使用鹼性過錳酸溶液等的氧化劑進行之粗化處理，以於加熱至60℃～80℃的氧化劑溶液中，將絕緣層浸漬10分鐘～30分鐘之方式進行者為佳。又，鹼性過錳酸溶液中之過錳酸鹽的濃度以5質量％～10質量％為佳。市售氧化劑，例如，Atotech日本公司製之「Concentrate Compact CP」、「Dosing solution Security Gans P」等的鹼性過錳酸溶液等。又，中和液，以酸性水溶液為佳，市售品，例如，Atotech日本公司製之「Reduction solutions Security Gantt P」等。 　　[0137] 使用中和液之處理，為將經氧化劑粗化處理後的處理面浸漬於30℃～80℃的中和液5分鐘～30分鐘之方法。就作業性等的觀點，經氧化劑粗化處理後的對象物，以浸潤於40℃～70℃的中和液5分鐘～20分鐘之方法為佳。 　　[0138] 步驟(V)為形成導體層之步驟。 　　[0139] 導體層所使用的導體材料，並未有特別之限定。其較佳的實施形態中，導體層為含有由金、鉑、鈀、銀、銅、鋁、鈷、鉻、鋅、鎳、鈦、鎢、鐵、錫及銦所成之群所選出之1種以上的金屬。導體層，可為單金屬層亦可、合金層亦可。合金層，例如，由上述之群所選出之2種以上的金屬之合金(例如，鎳・鉻合金、銅・鎳合金及銅・鈦合金)所形成的層等。其中，就形成導體層之廣用性、費用、圖型形成(Patterning)之容易性等的觀點，以鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅之單金屬層，或鎳・鉻合金、銅・鎳合金、銅・鈦合金之合金層為佳，以鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅之單金屬層，或鎳・鉻合金之合金層為較佳，以銅之單金屬層為更佳。 　　[0140] 導體層，可為單層構造亦可、由不同種類的金屬或合金所形成的單金屬層或由2層以上的合金層層合而得之多層構造亦可。導體層為多層構造時，與絕緣層相接合之層，以鉻、鋅或鈦之單金屬層，或鎳・鉻合金之合金層為佳。 　　[0141] 導體層之厚度，可配合所期待的印刷電路板之設計，一般為3μm～35μm，較佳為5μm～30μm。 　　[0142] 一實施形態中，導體層可由電鍍所形成。例如，可使用半加成法(Semi-additive Process)、全添加法等的以往公知的技術對絕緣層表面進行電鍍，而可形成具有所期待的配線圖型之導體層。 　　[0143] 其他實施形態中，導體層可使用金屬箔而形成。使用金屬箔形成導體層之情形，步驟(V)，以於步驟(I)與步驟(II)之間實施為佳。例如，於步驟(I)之後，去除支撐體，使露出的樹脂組成物層之表面層合於金屬箔。樹脂組成物層與金屬箔之層合，可使用真空層合法實施。層合之條件，可使用與步驟(I)所說明的條件為相同之方法。其次，實施步驟(II)而形成絕緣層。隨後，利用絕緣層上的金屬箔，使用扣除法(subtractive Process)、改質半加成法(Modified Semi-additive Process)等的以往公知技術，形成具有所期待的配線圖型之導體層。 　　[0144] 金屬箔，例如，可使用電解法、壓延法等的公知方法而可製得。金屬箔之市售品，例如，JX日鑛日石金屬公司製之HLP箔、JXUT-III箔、三井金屬鑛山公司製之3EC-III箔、TP-III箔等。 　　[0145] 使用含有組合(A)成份、(B)成份，及(C)成份的本發明之樹脂組成物，而製造印刷電路板之情形，無關導體層為使用電鍍而形成或使用金屬箔而形成者，皆可顯著提高導體層與絕緣層之密著性。 　　[0146] [13. 半導體裝置] 　　本發明之半導體裝置，為含有本發明之印刷電路板。 　　[0147] 半導體裝置，可列舉如，提供電氣製品(例如，電腦、攜帶電話、數位相機及電視等)及搭乘物(例如，自動二輪車、自動車、電車、船舶及航空機等)等的各種半導體裝置。 　　[0148] 本發明之半導體裝置，可於印刷電路板的導通處，實際裝設零件(半導體晶片)而可製得。「導通處」係指，「印刷電路板中傳導電氣訊號之處」，其場所可為表面，或埋入處皆可，而無任何限定。又，半導體晶片只要為使用半導體作為材料的電氣線路元件時，並未有特別之限定。 　　[0149] 製造本發明之半導體裝置之際，半導體晶片的實際裝設方法，只要可有效發揮半導體晶片之機能時，並未有特別之限定。例如，使用線路接合之實際裝設方法、倒裝晶片之實際裝設方法、無凸點堆疊層(BBUL)之實際裝設方法、異向性導電薄膜(ACF)之實際裝設方法、非導電性薄膜(NCF)之實際裝設方法等。其中，「無凸點堆疊層(BBUL)之實際裝設方法」係指，將「半導體晶片直接埋入印刷電路板之凹部，使半導體晶片與印刷電路板上之配線連接之實際裝設方法」之意。[Problems to be Solved by the Invention] [0007] The subject of the present invention is to provide a resin composition that can form an insulating layer with low loss factor, high glass transition temperature, and high adhesion. [Methods to Solve the Problem] [0008] The inventors of the present invention have conducted in-depth research on the aforementioned problems and found that they contain (A) epoxy resins, (B) active ester compounds with carbon-carbon unsaturated bonds, and ( C) The resin composition of a combination of resins having unsaturated hydrocarbon groups can solve the aforementioned problems, thus completing the present invention. That is, the present invention includes the following contents. [0009] [1] A resin composition containing (A) epoxy resin (hereinafter, also referred to as "(A) component" in this specification), (B) having a carbon-carbon unsaturated bond Active ester compound (hereinafter, also referred to as "(B) component" in this specification), and (C) resin with unsaturated hydrocarbon group (hereinafter, also referred to as "(C) component" in this specification) ). [2] The resin composition described in [1] above, wherein the content of the component (B) is 10% by mass to 60% by mass when the resin component is 100% by mass. [3] The resin composition as described in [1] or [2] above, wherein the content of the aforementioned (A) component is 10% by mass to 50% by mass when the resin component is 100% by mass, and the aforementioned (C) The content of the component is 3% to 30% by mass when the resin component is 100% by mass. [4] The resin composition as described in any one of [1] to [3] above, wherein the component (B) is an active ester compound having a carbon-carbon double bond. [5] The resin composition according to the above [4], wherein the component (B) is an active ester compound having a vinyl group, a methacryl group, an acrylic group, an allyl group, a styryl group, or an acrylic group. [6] The resin composition according to the above [5], wherein the component (B) is an active ester compound having a styryl group. [7] The resin composition according to the above [6], wherein the component (B) contains a compound represented by the following general formula (1).
Figure 02_image001
(In the aforementioned general formula (1), m represents an integer of 1 to 6, and n represents an integer of 1 to 20). [8] The resin composition according to any one of [1] to [7] above, wherein the component (C) is a resin having an acrylic group, a methacrylic group, a styrene group, or an olefin group. [9] The resin composition as described in any one of [1] to [8] above, which forms an insulating layer of a printed circuit board. [10] A sheet-like laminate material containing the resin composition described in any one of [1] to [9] above. [11] A printed circuit board comprising an insulating layer formed of a cured product of the resin composition described in any one of [1] to [9] above. [12] A semiconductor device comprising the printed circuit board described in [11] above. [Effects of the Invention] [0010] The present invention can provide a resin composition that can produce a cured product with a high glass transition temperature, good adhesion to the conductor layer, and low loss factor; a sheet-like resin composition containing the resin composition Laminated materials; and printed circuit boards and semiconductor devices containing the cured resin composition. [Modes for Implementing the Invention] [0011] Hereinafter, the present invention will be described in detail using embodiments and exemplified contents. However, the present invention is not limited to the following embodiments and exemplified contents, and can be implemented with arbitrarily changed as long as it does not exceed the scope of the present invention and its equivalent scope. [0012] In the following description, the amount of each component in the resin composition, unless otherwise specified, refers to a value relative to 100% by mass of the resin component in the resin composition. In addition, in the following description, "resin component", unless otherwise specified, refers to the removal of (D) inorganic fillers from the non-volatile components contained in the resin composition (hereinafter, in this specification, also referred to as "(D) ) Ingredients"). [0013] [1. Overview of the resin composition] The resin composition of the present invention contains (A) an epoxy resin, (B) an active ester compound having carbon-carbon unsaturated bonds, and (C) an unsaturation Hydrocarbon-based resin. The cured product formed by curing the resin composition of the present invention contains a molecular structure formed by the reaction between the unsaturated bonding site of the component (B) and the unsaturated hydrocarbon group of the component (C). The molecular structure part can reduce its polarity by the action of the unsaturated bonding part of component (B) and the unsaturated hydrocarbon group of component (C). Therefore, the polarity of the hardened material can be reduced, and the value of the loss factor can be reduced. In addition, the cured product formed by curing the resin composition of the present invention contains not only the unsaturated bonding site of component (B) but also the molecular structure site formed by the reaction with the unsaturated hydrocarbon group of component (C), but also (B) The active ester part of the component, and the molecular structure formed by the reaction of the component (A). Therefore, the crosslinking density can be densified (that is, the structure can be densified), and the glass transition temperature of the hardened product can be increased. In addition, due to the densification of the cross-linking density, the mechanical strength of the cured product can be improved, the peeling caused by the destruction of the cured product is not easily caused, and the cured product can be formed with excellent adhesion to the conductor layer. [0014] As described above, the resin composition of the present invention, because the (B) component in the compound has a reaction site obtained by the reaction of the (A) component and the (C) component, it can form a (A) component and (C) component are used separately to obtain the effect of the hardened product. In addition, when compared with the case of using an ester compound that can react with the component (A) and a compound with an unsaturated bond that can react with the component (C), compared with the case of using the component (B), it can improve Mixability of (A) component, (B) component and (C) component. Therefore, the uniformity of the composition in the hardened product can be improved, and the aforementioned effects can be achieved at a higher level. [0015] [2. (A) Epoxy resin] The resin composition of the present invention contains the component (A). Since the cured product has a molecular structure formed by the reaction of the active ester parts of the component (A) and the active ester of the component (B), the structure can be densified, the glass transition temperature of the cured product can be increased, and the adhesiveness of the cured product can be improved. (A) Ingredients, for example, xylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentane Diene type epoxy resin, triphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, Naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin Resins, epoxy resins with butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins Resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, halogenated epoxy resin, etc. [0016] Among these, the component (A), from the viewpoint of improving adhesion, uses bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol type epoxy resin, and naphthalene type epoxy resin. , Biphenyl type epoxy resin, naphthylene ether type epoxy resin, glycidyl ester type epoxy resin and anthracene type epoxy resin are better. From the viewpoint of reducing the average linear thermal expansion rate, the epoxy resin containing aromatic skeleton Resin is better. Among them, the aromatic skeleton is a concept including polycyclic aromatics and aromatic heterocyclic rings. The epoxy resin containing aromatic skeleton is composed of bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, and dicyclopentadiene epoxy resin. And one or more epoxy resins selected from the group of naphthol epoxy resins are preferred, and they are also made of bisphenol A epoxy resins, biphenyl epoxy resins, and naphthalene epoxy resins. One or more epoxy resins selected by the group are more preferable. [0017] In addition, in the resin composition, the component (A) is preferably an epoxy resin containing two or more epoxy groups in one molecule. The ratio of epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the non-volatile content of component (A) is preferably 50% by mass or more, more preferably 60% by mass or more, especially preferred It is 70% by mass or more. Among them, in the resin composition, component (A) is a solid epoxy resin (hereinafter also referred to as "solid epoxy resin") that contains 3 or more epoxy groups in one molecule and is at a temperature of 20°C. Better. [0018] The component (A) may be used singly or in combination of two or more in any ratio. Therefore, in the resin composition, the component (A) may contain only a solid epoxy resin, or may contain a combination of a solid epoxy resin and other epoxy resins. Among them, in the resin composition, the component (A) contains a solid epoxy resin, and an epoxy resin that has two or more epoxy groups in one molecule and is liquid at a temperature of 20°C (hereinafter, also referred to as " Liquid epoxy resin") combination is preferred. The component (A), when a combination of liquid epoxy resin and solid epoxy resin is used, can increase the flexibility of the resin composition or increase the breaking strength of the hardened resin composition. [0019] Liquid epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, and glycidol Amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and those with a butadiene structure Epoxy resins are preferred, and glycidylamine epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol AF epoxy resins, and naphthalene epoxy resins are preferred. [0020] Liquid epoxy resins, for example, "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "YL980", "828US", "JER828EL" manufactured by Mitsubishi Chemical Corporation , "825", "EPCODA 828EL" (bisphenol A type epoxy resin); "JER806H", "JER807", "YL983U", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi "JER152" (phenol novolac type epoxy resin) manufactured by Chemical Corporation; "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (Mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemical Technology Co., Ltd.; "CELLOXIDE 2021P" manufactured by DAEL "(Alicyclic epoxy resin with ester skeleton); "PB-3600" (epoxy resin with butadiene structure) manufactured by DACEL; "ZX1658" and "ZX1658GS" manufactured by Nippon Steel Chemical Corporation ( Liquid 1,4-glycidyl cyclohexane type epoxy resin) etc. These may be used individually by 1 type, or may be used in combination of 2 or more types by arbitrary ratios. [0021] Solid epoxy resin, for example, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin , Naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, tetraphenylethane type epoxy resin, xylenol Type epoxy resins are preferable, and naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, naphthol type epoxy resins, xylenol type epoxy resins and biphenyl type epoxy resins are preferable. [0022] Solid epoxy resins, for example, "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC ; "N-690", "N-695" (cresol novolak type epoxy resin) made by DIC; "HP-7200", "HP-7200HH", "HP-7200H" made by DIC (two Cyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (made by DIC) Ether type epoxy resin); "EPPN-502H" (triphenol type epoxy resin) manufactured by Nippon Kayaku Corporation; "NC7000L" (naphthol novolak type epoxy resin) manufactured by Nippon Kayaku Corporation; Nippon Kayaku Corporation "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by the company; "ESN475V" (naphthol naphthalene type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co.; "ESN485" (naphthol novolac type epoxy resin) manufactured by Iron & Steel Chemical Corporation; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000H", "YX4000" manufactured by Mitsubishi Chemical Corporation, "YX4000HK" (xylenol type epoxy resin); "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Corporation; Mitsubishi Chemical Corporation "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (茀 type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "JER1010" (solid bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Corporation ; "JER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These may be used individually by 1 type, or may be used in combination of 2 or more types by arbitrary ratios. [0023] For component (A), when a liquid epoxy resin and a solid epoxy resin are used in combination, the mass ratio of these (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 ～1:15, more preferably 1:0.5 to 1:10, particularly preferably 1:1 to 1:8. When the mass ratio of the liquid epoxy resin is within the aforementioned range, sufficient flexibility can be obtained when used in the form of an adhesive film, the handleability can be improved, and sufficient fluidity can be obtained during lamination. When the mass ratio of the solid epoxy resin is within the aforementioned range, the viscosity of the epoxy resin is reduced, and when it is used in the form of an adhesive film, the outgassing performance during vacuum lamination can be improved. In addition, during vacuum lamination, the protective film and the support can have good peelability, and the heat resistance after curing can be improved. [0024] The epoxy equivalent of the component (A) is preferably 50-5000, more preferably 50-3000, more preferably 80-2000, particularly preferably 110-1000. When the epoxy equivalent of the component (A) is in the aforementioned range, the cured product of the resin composition can be obtained as an insulating layer having a sufficient crosslinking density and a smaller surface roughness. The epoxy equivalent is the mass of the resin containing 1 equivalent of epoxy group, measured in accordance with the JIS K7236 standard. [0025] (A) The weight average molecular weight of the component can more clearly obtain the desired effect of the present invention, and it is preferably 100-5000, more preferably 250-3000, particularly preferably 400-1500. (A) The weight-average molecular weight of the component is a value converted from polystyrene measured by the Gel Permeation Chromatography (GPC) method. For example, the weight average molecular weight of the resin can be measured using LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Corporation as a column. The phase uses chloroform, etc., the measurement result when the column temperature is 40℃, and the calibration curve of standard polystyrene can be used to calculate. [0026] The amount of the component (A) in the resin composition can be used to obtain an insulating layer with high glass transition temperature and high adhesion. Generally, it is preferably 100% by mass relative to the resin component in the resin composition. It is 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more. (A) The upper limit of the amount of the component can be any value as long as the effect of the invention can be achieved. It is preferably 70% by mass or less, more preferably 65% by mass or less, particularly preferably 60% by mass or less, and most preferably 50% by mass or less. [0027] [3. (B) Active ester compound with carbon-carbon unsaturated bond] The resin composition of the present invention contains the component (B). The component (B) can react with the two components (A) and (C) to form a hardened product. Because the hardened material has the unsaturated bonding sites of (B) component and the molecular structure formed by the reaction of (C) component, the polarity of hardened material can be reduced, and the value of loss factor can be reduced. In addition, since the cured product contains the active ester site of the component (B) and the molecular structure site formed by the reaction of the component (A), the structure can be densified, the glass transition temperature of the cured product can be increased, and the glass transition temperature of the cured product can be improved. Sexual things. [0028] In the past, when two resins with different reactivity were used in combination, the mixing properties of the resins were often deteriorated, and the cured product could not be uniformly formed. Therefore, it is extremely difficult to simultaneously produce the above-mentioned effects at a high level. In addition, in the resin composition of the present invention, in the component (B), since two resins with different reactivity can react with each other separately, they exist in the same compound. Therefore, the component (B) can form a cured product formed by bonding each resin, and can form a uniform cured product. Therefore, it is possible to produce the above-mentioned characteristics at a high level at the same time, and achieve the desired effect of the present invention. In addition, when (B) component is used, the mixing of (A) component, (B) component and (C) component can be improved. Therefore, the uniformity of the composition in the hardened product can be improved, and the above-mentioned effects can be produced at a higher level. [0029] The carbon-carbon unsaturated bond is usually an aliphatic unsaturated bond, for example, a carbon-carbon double bond, a carbon-carbon triple bond, and the like. Among them, the carbon-carbon double bond is preferred. The preferred component (B) having a carbon-carbon double bond is, for example, an active ester compound having a vinyl group, a methacryl group, an acrylic group, an allyl group, a styryl group, or an acrylic group. Among them, from the viewpoint of having excellent heat resistance, styrene-based is particularly preferred. [0030] The component (B) preferably contains a compound represented by the following general formula (1).
Figure 02_image003
In the general formula (1), m represents an integer of 1 to 6, and n represents an integer of 1 to 20. [0031] In the general formula (1), m is preferably an integer of 1 to 6, and more preferably an integer of 1 to 3. Moreover, n is preferably an integer of 1-10, more preferably an integer of 1-5, and particularly preferably an integer of 1-3. In the above numerical range, the component (B) can react with the component (C) in an appropriate ratio, and the goal of reducing the loss factor can be achieved. [0032] The component (B) may be a mixture of compounds of the general formula (1) having different values of m and n. In the case of a mixture, component (B), as long as it contains the compound represented by the general formula (1), may also contain the compound in which n is 0 in the general formula (1) (the compound represented by the following formula (0-1)) ), or a compound in which n is an integer of 1-20 and m is 0 (a compound represented by the following general formula (0-2)). In addition, the total ratio of the compound represented by the formula (0-1) and the compound represented by the general formula (0-2) relative to 100% by mass of the component (B) is preferably 10% by mass or less, more preferably 5 Mass% or less, particularly preferably 3% by mass or less, most preferably 1% by mass or less, and may also be 0% by mass. In this range, the (B) component and the (C) component can be reacted in an appropriate ratio, and the goal of reducing the loss factor can be achieved.
Figure 02_image005
In the general formula (0-2), n represents an integer of 1-20. [0033] The compound represented by the general formula (1) can be a commercially available product or a synthetic product. Commercially available products, for example, brand name "PC1300-02-65MA" (manufactured by Air-Water Corporation) and the like. [0034] The amount of component (B) in the resin composition can be used to obtain an insulating layer with low loss factor, high glass transition temperature, and high adhesion, relative to 100% by mass of the resin component in the resin composition, It is preferably 5% by mass or more, more preferably 10% by mass or more, and most preferably 20% by mass or more. (B) The upper limit of the amount of the component may be any ratio as long as the effect of the invention can be achieved, and it is preferably 70% by mass or less, more preferably 65% by mass or less, and particularly preferably 60% by mass or less. [0035] [4. (C) Resin with unsaturated hydrocarbon group] The resin composition of the present invention contains the component (C). When the hardened product has a molecular structure formed by the reaction of the unsaturated bonding sites of the (C) component and the (B) component, the polarity of the hardened product can be reduced, and the loss factor value can be reduced. The component (C) is not particularly limited as long as it has an unsaturated hydrocarbon group. When unsaturated hydrocarbon groups are used, the loss factor of the hardened product can be reduced. The unsaturated hydrocarbon group is preferably an aliphatic unsaturated hydrocarbon group such as an acrylic group, a methacrylic group, a styryl group, and an alkene group. Among them, from the viewpoint of having excellent heat resistance, a styryl group is preferred. Among them, "alkene group" means an aliphatic hydrocarbon group having a carbon-carbon double bond in the molecule. For example, allyl, vinyl, propenyl and the like. [0036] The component (C) is preferably a compound represented by the following general formula (2). [0037]
Figure 02_image007
In the general formula (2), R 1 to R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. A represents the structure represented by the following general formula (3) or the following general formula (4). [0038]
Figure 02_image009
In the general formula (3), B represents the structure represented by the following general formula (B-1), (B-2) or (B-3). [0039]
Figure 02_image011
In the general formula (4), D represents the structure represented by the following general formula (5). [0040]
Figure 02_image013
In the general formula (5), R 7 to R 14 each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and preferably a hydrogen atom or a methyl group. In particular, R 7 , R 8 , R 13 , and R 14 are more preferably methyl groups. a, b is an integer of 0-100 at least one of which is not 0. B represents the structure represented by the following general formula (B-1), (B-2) or (B-3). [0041]
Figure 02_image015
In the general formula (B-1), R 15 to R 18 each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and preferably a hydrogen atom or a methyl group. In the general formula (B-2), R 19 to R 26 each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and preferably a hydrogen atom or a methyl group. In the general formula (B-3), R 27 to R 34 each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and preferably a hydrogen atom or a methyl group. E represents a linear, branched, or cyclic divalent hydrocarbon group with a carbon number of 20 or less. [0042] The component (C) is preferably a compound represented by the following general formula (6), the following formula (7) or the following formula (8). [0043]
Figure 02_image017
In the general formula (6), R 1 ~ R 6 in the general formula R (2) in the 1 ~ R 6 have the same meaning, B in the general formula (3) in the same meaning of B, a, b, and A and b in the general formula (5) have the same meaning. [0044]
Figure 02_image019
[0045]
Figure 02_image021
[0046] Commercially available component (C), for example, styrene modified polyphenylene ether resin (manufactured by Mitsubishi Gas Chemical Corporation "OPE-2St 1200 (number average molecular weight 1200)", equivalent to general formula (6)), dimethyl Phenol diallyl ether resin (manufactured by Mitsubishi Chemical Corporation "YL7776 (number average molecular weight 331)", equivalent to general formula (7)), dioxane acrylic acid-based monomer diol diacrylate (manufactured by Shinnakamura Chemical Industry Co., Ltd.) A-DOG (number average molecular weight 326)", corresponding to general formula (8)), etc. [0047] (C) The number average molecular weight of the component is preferably in the range of 100 to 10,000, more preferably in the range of 200 to 3,000 from the viewpoint of preventing volatilization of the resin coating during drying and preventing excessive increase in the melt viscosity of the resin composition . In addition, the number average molecular weight in the present invention can be measured using a gel permeation chromatography (GPC) method (in terms of polystyrene). For the number average molecular weight of the GPC method, for example, LC-9A/RID-6A manufactured by Shimadzu Corporation, a measuring device, Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Corporation, a mobile phase chloroform can be used Etc., the data measured at a column temperature of 40°C is calculated using a standard polystyrene calibration curve. [0048] In the resin composition, the amount of the (C) component is, from the viewpoint of reducing the value of the loss factor of the cured product, relative to 100% by mass of the resin component in the resin composition, preferably 3% by mass or more, more preferably It is 5% by mass or more, most preferably 10% by mass or more. (C) The upper limit of the amount of the component can be any value as long as the effect of the invention can be achieved, and it is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less. [0049] [5. Hardener] The resin composition may contain a hardener with a different component from (B) within a range that does not impair the effect of the present invention. The hardener is not particularly limited. For example, phenol hardener, naphthol hardener, active ester hardener, benzoxan
Figure 106130398-A0304-1
Series hardeners, cyanate ester hardeners, and carbodiimide hardeners, etc. Among them, from the viewpoint that an insulating layer having excellent adhesion to the conductor layer can be obtained, it is preferable to use an active ester curing agent. Moreover, a hardening agent may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios. [0050] The phenolic hardener or naphthol hardener is preferably a phenol hardener having a novolak structure or a naphthol hardener having a novolak structure in terms of heat resistance and water resistance. In addition, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol hardener or a nitrogen-containing naphthol hardener is preferred, and it also contains three
Figure 106130398-A0304-1
The phenolic hardener of the skeleton or contains three
Figure 106130398-A0304-1
The naphthol-based hardener of the skeleton is preferred. Among them, the viewpoints of heat resistance, water resistance, and adhesion to the conductor layer can be highly satisfied.
Figure 106130398-A0304-1
The hardener of the phenol novolac of the skeleton or contains three
Figure 106130398-A0304-1
Naphthol novolac hardener for the skeleton is better. [0051] Phenol-based hardeners and naphthol-based hardeners, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Chemical Co., Ltd., and "NHN", "Nippon Kayaku Co., Ltd."CBN","GPH","SN-170","SN-180","SN-190","SN-475","SN-485","SN-495", manufactured by Nippon Steel & Sumitomo Metal Corporation "SN-375", "SN-395", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", etc. manufactured by DIC. [0052] The active ester hardener is not particularly limited. For example, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds, can be used. The active ester hardener is preferably prepared from at least one compound of a carboxylic acid compound and a thiocarboxylic acid compound and at least one compound of a hydroxyl compound and a thiol compound through a condensation reaction. In particular, from the viewpoint of improving heat resistance, an active ester hardener made from a carboxylic acid compound and a hydroxy compound is preferred. [0053] Carboxylic acid compounds, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. Phenol compound or naphthol compound, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 ,6-Dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzotriazole, dicyclopentadiene type diphenol compound, phenol novolac Wait. Among them, "dicyclopentadiene-type diphenol compound" means a diphenol compound obtained by condensing 1 molecule of dicyclopentadiene and 2 molecules of phenol. [0054] Active ester hardener, including active ester compound containing dicyclopentadiene type diphenol structure, active ester compound containing naphthalene structure, active ester compound containing acetone of phenol novolak, and phenol novolak containing The active ester compound of the benzoic acid compound is preferable, and the active ester compound containing the naphthalene structure and the active ester compound containing the dicyclopentadiene type diphenol structure are preferable. "Dicyclopentadiene-type diphenol structure" refers to a bivalent structural unit formed by phenylene-bicyclopentylene-phenylene. [0055] Commercial products of active ester hardeners, for example, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "EXB-8000L-65TM", "HPC- 8000H-65M" (active ester compound containing dicyclopentadiene-type diphenol structure), "EXB-9416L-70BK" (active ester compound containing naphthalene structure) manufactured by DIC, and "DC808" manufactured by Mitsubishi Chemical Corporation (Active ester compound containing phenol novolac acetate), "YLH1026" manufactured by Mitsubishi Chemical Corporation (active ester compound containing phenol novolac benzoate), "EXB-9050L-62M" manufactured by DIC (Reactive ester compound containing phosphorus atom) and so on. [0056] Benzox
Figure 106130398-A0304-1
It is a hardener, such as "HFB2006M" manufactured by Showa Polymer Corporation, "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd., etc. [0057] The cyanate ester-based curing agent is not particularly limited. For example, novolak type cyanate ester hardeners such as phenol novolak type, alkylphenol novolak type, etc.; dicyclopentadiene type cyanate ester hardener; bisphenol A type, bisphenol F type, double Phenol S type, bisphenol type cyanate ester hardener; and some of these hardeners
Figure 106130398-A0304-1
Pre-polymer after chemical conversion, etc. Cyanate ester hardeners, for example, bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylidene-1,5-phenylene cyanate), 4,4'- Methyl bis(2,6-xylyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4- Cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-xylyl)methane, 1,3-bis(4- Cyanate phenyl-1-(methylethylene)) benzene, bis(4-cyanate phenyl) sulfide, and bis(4-cyanate phenyl) ether and other bifunctional cyanate esters Resins; polyfunctional cyanate ester resins derived from phenol novolac and cresol novolac; and a part of these cyanate ester resins
Figure 106130398-A0304-1
Pre-polymer obtained by chemical conversion. Commercial products include, for example, "PT30", "PT60" (both phenol novolak type polyfunctional cyanate ester resin) manufactured by Lonza Japan, and "BA230" (one of bisphenol A dicyanate) Part or all of the three
Figure 106130398-A0304-1
The prepolymer of the terpolymer) and so on. [0058] Carbodiimide-based hardeners, for example, "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd., etc. [0059] The hardener is preferably one or more selected from phenolic hardeners, naphthol hardeners, active ester hardeners, and carbodiimide hardeners, and phenolic hardeners and active At least any one of ester hardeners is more preferable. [0060] When the number of epoxy groups of the component (A) is 1, from the viewpoint of an insulating layer with good mechanical strength, the lower limit of the reaction base of the hardener is preferably 0.1 or more, more preferably 0.2 or more, particularly preferred It is 0.3 or more, most preferably 0.4 or more. The upper limit is preferably 2 or less, more preferably 1.5 or less, and particularly preferably 1 or less. Among them, the "reactive group of the hardener" differs according to the type of hardener such as active hydroxyl group, active ester group, etc. In addition, "the number of epoxy groups of the component (A)" refers to the value obtained by dividing the mass of the solid content of each epoxy resin in the resin composition by the epoxy equivalent, which is used as the total value in the epoxy resin. In addition, the "reaction base number of the hardening agent" refers to the value obtained by dividing the mass of the solid content of each hardening agent present in the resin composition by the equivalent of the reaction group, as the total value of all hardening agents. (A) When the content ratio of the epoxy resin and the curing agent is within the aforementioned range, the heat resistance of the cured product of the resin composition can be further improved. [0061] The content of the hardener in the resin composition is not particularly limited. For example, relative to 100% by mass of the resin component in the resin composition, the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, particularly preferably 20% by mass or less, most preferably 18% by mass or less, 15% by mass the following. Furthermore, the lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, most preferably 5% by mass or more, particularly preferably 7% by mass or more, and 10% by mass or more. When the content of the curing agent is within the aforementioned range, the resin composition can be formed into a cured product having better linear thermal expansion coefficient, loss factor, and adhesion to the conductor layer. [0062] [6. (D) Inorganic filler material] The resin composition usually contains the component (D). When the component (D) is used, the thermal expansion coefficient of the hardened resin composition can be reduced, and the reflow deformation of the insulating layer can be suppressed. [0063] (D) The material of the component is not particularly limited, for example, silica, alumina, glass, cordierite, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, Hydrotalcite, diaspore, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, barium titanate, strontium titanate, Calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among these, silica is preferred, amorphous silica, crushed silica, fused silica, crystalline silica, synthetic silica, hollow silica, spherical silica To be better, it is possible to reduce the surface roughness of the insulating layer, and fused silica and spherical silica are more preferable, and spherical fused silica is particularly preferable. (D) Ingredients can be used alone or in combination of two or more in any ratio. [0064] Generally, the component (D) is contained in the resin composition in the form of particles. (D) The average particle size of the component particles can be used to obtain an insulating layer with high circuit embedding properties and low surface roughness. It is preferably 5μm or less, more preferably 3μm or less, particularly preferably 2μm or less, most preferably It is preferably 1 μm or less, 0.8 μm or less, 0.6 μm or less, or 0.4 μm or less. The lower limit of the average particle size is preferably 0.01 μm or more, more preferably 0.03 μm or more, particularly preferably 0.05 μm or more, and most preferably 0.07 from the viewpoint of preventing the increase in paint viscosity and decrease in handling properties when used as a resin coating. μm or more, 0.1 μm or more. [0065] Commercial products with the aforementioned average particle size (D) component, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metals; "YC100C" and "YA050C" manufactured by Admatechs, "YA050C-MJE" and "YA010C";"UFP-30" manufactured by Denka; "Silfile NSS-3N", "Silfile NSS-4N" and "Silfile NSS-5N" manufactured by Tokuyama; "SC2500SQ" manufactured by Admatechs , "SO-C4", "SO-C2", "SO-C1", etc. [0066] (D) The average particle size of the components, etc., can be measured using the laser diffraction-scattering method based on the Mie dispersion theory. For example, a laser diffraction scattering type particle size distribution measuring device can be used to measure the particle size distribution of particles on a volume basis, and the median diameter of the particle size distribution can be used as the average particle size. For the measurement sample, a solution obtained by dispersing particles in water with ultrasonic waves can be used. The laser diffraction scattering type particle size distribution measuring device can be used "LA-500" manufactured by Horiba Manufacturing Co., Ltd., etc. [0067] For component (D), any surface treatment agent can be used for surface treatment. Surface treatment agents include, for example, aminosilane-based coupling agents, epoxysilane-based coupling agents, sulfhydrylsilane-based coupling agents, alkoxysilane compounds, organosilazane compounds, titanate-based coupling agents, and the like. The surface treatment of (D) component by using these surface treatment agents can improve the moisture resistance and dispersibility of (D) component. [0068] Commercial products of surface treatment agents, for example, "KBM-22" (dimethyldimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM-403" (3-epoxypropylene) manufactured by Shin-Etsu Chemical Co., Ltd. Oxypropyl trimethoxysilane), "KBM-803" (3-hydrothiopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE-903" (3-aminopropyl) manufactured by Shin-Etsu Chemical Co., Ltd. Triethoxysilane), "KBM-573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyl) manufactured by Shin-Etsu Chemical Co., Ltd. Disilazane), "KBM-103" manufactured by Shin-Etsu Chemical Co., Ltd. (phenyltrimethoxysilane), "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy silane coupling agent), etc. Moreover, a surface treatment agent may be used individually by 1 type, or may be used in combination of 2 or more types by arbitrary ratios. [0069] The degree of surface treatment using a surface treatment agent can be evaluated by the amount of carbon per unit surface area of component (D). (D) The amount of carbon per unit surface area of the component can improve the dispersibility of the (D) component, preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, particularly preferably 0.2 mg/m 2 or more. In addition, from the viewpoint of suppressing the melt viscosity of the resin composition and the increase in melt viscosity in the sheet form, the carbon content is preferably 1 mg/m 2 or less, more preferably 0.8 mg/m 2 or less, and particularly preferably 0.5 mg/m 2 or less. [0070] The amount of carbon per unit surface area of the (D) component is measured after the surface treatment of the (D) component is washed with a solvent. As the solvent, for example, methyl ethyl ketone (hereinafter, also referred to as "MEK") can be used. For example, a sufficient amount of methyl ethyl ketone is mixed with component (D) after surface treatment with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. Then, after removing the supernatant liquid and drying the solid content, use a carbon analyzer to measure the amount of carbon per unit surface area of the component (D). For the carbon analyzer, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd. can be used. [0071] In the resin composition, the lower limit of the amount of the component (D), from the viewpoint that an insulating layer with a low thermal expansion rate can be obtained, relative to 100 parts by mass of the resin component in the resin composition, preferably 100 parts by mass or more , More preferably 200 parts by mass or more, particularly preferably 250 parts by mass or more. The upper limit is preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and particularly preferably 350 parts by mass or less from the viewpoint of mechanical strength of the insulating layer, particularly stretchability. [0072] [7. (E) Hardening accelerator] The resin composition of the present invention may further contain (E) hardening accelerator (hereinafter, in this specification, also referred to as "(E) component") if necessary . When the component (E) is used, the curing can be accelerated when the resin composition is cured. [0073] The component (E), for example, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, metal-based hardening accelerators, peroxide-based hardening accelerators, and the like. Among them, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, peroxide-based curing accelerators, or metal-based curing accelerators are preferred, and amine-based curing accelerators and imidazole-based curing accelerators are preferred. , Peroxide-based hardening accelerators or metal-based hardening accelerators are preferred. In addition, (E) component may be used individually by 1 type, or may be used in combination of 2 or more types by arbitrary ratios. [0074] Phosphorus-based hardening accelerators, for example, triphenyl phosphine (phosphine), phosphonium borate compound, tetraphenyl phosphonium tetraphenyl borate, n-butyl phosphonium tetraphenyl borate, tetrabutyl phosphonium Decanoate, (4-methylphenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc. Among them, triphenylphosphine and tetrabutylphosphonium decanoate are preferred. [0075] Amine-based hardening accelerators, for example, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl) Base) phenol, 1,8-diazabicyclo[5,4,0]-undecene, etc. Among them, 4-dimethylaminopyridine and 1,8-diazabicyclo[5,4,0]-undecene are preferred. [0076] Imidazole-based hardening accelerators, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl 2-phenylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2 -Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole , 1-cyanoethyl-2-undecylimidazole salt trimellitate, 1-cyanoethyl-2-phenylimidazole salt trimellitate, 2,4-diamino-6 -[2'-Methylimidazolyl-(1')]-ethyl-s-tri
Figure 106130398-A0304-1
, 2,4-Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-tri
Figure 106130398-A0304-1
, 2,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-tri
Figure 106130398-A0304-1
, 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-tri
Figure 106130398-A0304-1
Trimeric isocyanate adduct, 2-phenylimidazole trimeric isocyanate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazole salt chloride, 2-methyl Imidazoline, 2-phenylimidazoline and the adduct of imidazole compound and epoxy resin, etc. Among them, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred. [0077] As the imidazole-based hardening accelerator, commercially available products can be used, for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation. [0078] Guanidine-based hardening accelerators, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine , Dimethylguanidine, Diphenylguanidine, Trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-Triazabicyclo[4.4.0]dec-5-ene, 7-methyl Yl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-heptadecane Biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc. . Among them, dicyanodiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred. [0079] Metal-based hardening accelerators, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Organometallic complexes, for example, organic cobalt complexes such as cobalt(II) acetone and cobalt(III) acetone; organic copper complexes such as copper(II) acetone; zinc acetone Organic zinc complexes such as (II); organic iron complexes such as iron (III) acetone; organic nickel complexes such as nickel (II) acetone; manganese (II) acetone Organic manganese complexes and so on. Organic metal salts, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like. [0080] Peroxide-based hardening accelerators, for example, cyclohexanone peroxide, tert-butyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, cumene peroxide tert-butyl Ester, di-tert-butyl peroxide, dicumyl hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, etc. [0081] As the peroxide-based hardening accelerator, commercially available products can be used, for example, "Percumyl D" manufactured by NOF Corporation and the like. [0082] In the resin composition, the amount of the (E) component makes the effect expected by the present invention more significant, and it is 0.01% to 3% by mass relative to 100% by mass of the resin component in the resin composition. The range is better. [8. (F) Thermoplastic resin] The resin composition of the present invention may further contain (F) thermoplastic resin (hereinafter, also referred to as "(F) component" in this specification). (F) Ingredients, for example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyimide resin, polyetherimide resin, poly Waste resin, polyether waste resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, indene coumarone resin, etc. Among them, from the viewpoint of improving compatibility, indene coumarone resin is preferred. Moreover, (F) component may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios. [0084] The weight average molecular weight of the component (F) in terms of polystyrene is preferably in the range of 8,000 to 70,000, preferably in the range of 10,000 to 60,000, and more preferably in the range of 20,000 to 60,000. (F) The weight average molecular weight in terms of polystyrene of the component is measured by the gel permeation chromatography (GPC) method. For example, the weight average molecular weight of the component (F) in terms of polystyrene can be measured using LC-9A/RID-6A manufactured by Shimadzu Corporation, and Shodex K-800P/K-804L/K manufactured by Showa Denko Corporation. -804L, the mobile phase is chloroform, etc., measured at a column temperature of 40°C, and calculated using the calibration curve of standard polystyrene. [0085] The phenoxy resin has, for example, a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolak skeleton, a biphenyl skeleton, a sulphur skeleton, and a dicyclopentadiene skeleton. Phenoxy resins with one or more skeletons selected from the group consisting of skeletons, norbornene skeletons, naphthalene skeletons, anthracene skeletons, adamantane skeletons, terpene skeletons, and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group. The phenoxy resin may be used alone or in combination of two or more in any ratio. [0086] Phenoxy resins, for example, "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are phenoxy resins containing bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (containing bisphenol S Frame phenoxy resin); "YX6954" (phenoxy resin containing bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation; "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Chemical Corporation; Mitsubishi Chemical Corporation "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7891BH30" and "YL7482" etc. [0087] Indene benzofuran resin, for example, "H-100", "WS-100G", "WS-100H", "WS-120V", "WS-100GC" manufactured by Nitto Chemical Co.; Nobaresu-Rutogazu Corporate system "C10", "C30", "CA80", etc. [0088] In the resin composition, the lower limit of the amount of the (F) component relative to 100% by mass of the resin component in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more. In addition, the upper limit thereof is preferably 10% by mass or less, and more preferably 5% by mass or less. In the aforementioned range, the film forming ability or the effect of improving the mechanical strength can be exerted, and the melt viscosity can be increased or the surface roughness of the insulating layer can be reduced after the wet roughening step. [0089] [9. Optional Components] The resin composition of the present invention may contain optional components in addition to the above-mentioned components. These optional ingredients, for example, flame retardants; organic fillers; organic copper compounds, organic zinc compounds, organic cobalt compounds and other organic metal compounds; tackifiers; defoamers; leveling agents; adhesion imparting agents; Resin additives such as colorants, etc. [0090] <Flame retardant> The resin composition of the present invention, when a flame retardant is used, can further increase the glass transition temperature of the hardened resin composition. Flame retardants, for example, organic phosphorus flame retardants, phosphorus compounds containing organic nitrogen, nitrogen compounds, silicone flame retardants, metal hydroxides, and the like. As the flame retardant, commercially available products can be used, for example, "HCA-HQ" and "HCA-HQ-HS" manufactured by Sankoh Co., Ltd., and "PX-200" manufactured by Dahachi Chemical Industry Co., Ltd., etc. In addition, the flame retardant may be used alone or in combination of two or more in any ratio. [0091] The amount of the flame retardant in the resin composition, from the viewpoint of imparting heat resistance, relative to 100% by mass of the resin component in the resin composition, the range is preferably 0.5% by mass to 20% by mass, and 0.5% by mass The range of% to 15% by mass is preferable, and the range of 0.5% to 10% by mass is more preferable. [0092] <Organic Filler> The resin composition of the present invention, when an organic filler is used, can improve the flexibility of the cured resin composition, so that the stretchability of the insulating layer can be improved. The organic filling material may be any organic filling material used when forming the insulating layer of the printed circuit board. For example, rubber particles, polyamide particles, polysiloxane particles, and the like. In addition, as rubber particles, commercially available products can be used, for example, "EXL-2655" manufactured by Dow Chemical Japan Co., Ltd., "AC3816N" manufactured by Aik Industrial Co., Ltd., and the like. In addition, the organic filler may be used alone or in combination of two or more in any ratio. [0093] The average particle diameter of the particles of the organic filler is preferably 5 μm or less, more preferably 4 μm or less, particularly preferably 3 μm or less from the viewpoint of better dispersibility in the resin composition. The lower limit of the average particle size of the organic filler is preferably 0.05 μm or more, more preferably 0.08 μm or more, and particularly preferably 0.10 μm or more. [0094] In the resin composition, the amount of the organic filler is 0.1% by mass relative to 100% by mass of the resin component in the resin composition from the viewpoint of adjusting the mechanical and physical properties of the cured resin composition to an appropriate range The range of -20% by mass is preferred, the range of 0.2% by mass to 10% by mass is more preferred, the range of 0.3% by mass to 5% by mass is more preferred, and the range of 0.5% by mass to 3% by mass is particularly preferred. . [0095] [10. Preparation method and characteristics of the resin composition] The method for preparing the resin composition of the present invention is not particularly limited. For example, the ingredients can be mixed, a solvent can be added if necessary, and a rotary mixer can be used. Methods of mixing and dispersing, etc. [0096] The resin composition of the present invention can be formed into a cured product having a high glass transition temperature. The glass transition temperature of the cured product of the resin composition of the present invention can be measured according to the method described in the below-mentioned <Measurement of Glass Transition Temperature>. Specifically, for example, a thermomechanical analysis can be performed using the tensile-weight method, and the measurement can be performed at a load of 1 g and a temperature increase rate of 5°C/min. The cured product of the resin composition of the present invention preferably has a glass transition temperature of 158°C or higher, more preferably 160°C or higher, and even more preferably 162°C or higher. The upper limit of the glass transition temperature is not particularly limited, but it is usually 250°C or lower. [0097] The resin composition of the present invention can produce a hardened product with a low loss factor. The loss factor of the cured product of the resin composition of the present invention can be measured according to the method described in the below-mentioned <Measurement of Loss Factor>. Specifically, for example, a cavity resonator vibration method is used, and the measurement is performed at a frequency of 5.8 GHz and a measurement temperature of 23°C. The value of the loss factor, from the viewpoint of preventing heat generated by high frequency and reducing signal delay and noise, is preferably less than 0.0037, more preferably less than 0.0035. The lower limit of the value of the loss factor, the lower the better, usually 0.0001 or more. [0098] With the resin composition of the present invention, a cured product having high adhesion to the conductor layer can be obtained. The adhesion of the cured product of the resin composition of the present invention can be evaluated according to the method described in the below-mentioned "Measurement of Adhesion". The resulting adhesion between the conductor layer and the insulating layer is preferably 0.60 kgf/cm or more, more preferably 0.70 kgf/cm or more. The upper limit of the adhesion is not particularly limited, but it is usually 1.2 kgf/cm or less. [0099] The resin composition of the present invention can produce a cured product with high glass transition temperature, low loss factor, and good adhesion to the conductor layer. Therefore, the resin composition of the present invention is suitable for use as a resin composition for forming an insulating layer of a printed circuit board (resin composition for an insulating layer of a printed circuit board), and a resin composition for forming an interlayer insulating layer of a printed circuit board (Resin composition for interlayer insulating layer of printed circuit board). The resin composition of the present invention is also suitable for use in sheet-like laminate materials such as adhesive films and prepregs, flux photoresists, underfill materials, die bonding materials, semiconductor sealing materials, buried resins, and parts embedding Into a wide range of necessary uses of resin compositions such as resins. [11. Sheet-like laminated material] The resin composition of the present invention can be applied and used in the state of coating. Industrially, it is generally preferred to use the form of a sheet-like laminated material containing the resin composition. [0101] The sheet-like laminate material is preferably an adhesive film and a prepreg as shown below. [0102] In one embodiment, the adhesive film is a resin composition layer (adhesive layer) that contains a support and is bonded to the support, wherein the resin composition layer (adhesive layer) is formed of the resin composition of the present invention. [0103] The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, particularly preferably 60 μm or less, and particularly preferably 50 μm or less and 40 μm or less from the viewpoint of thinning of the printed circuit board. The lower limit of the thickness of the resin composition layer is not particularly limited, but it is usually 1 μm or more, preferably 5 μm or more, particularly preferably 10 μm or more. [0104] The support, for example, a film, metal foil, release paper, etc. made of plastic materials, and preferably a film or metal foil made of plastic materials. [0105] When a film made of a plastic material is used for the support, the plastic material, for example, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polycarbonate (PC ), acrylic groups such as polymethacrylate (PMMA); cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and cheap polyethylene terephthalate is particularly preferred. [0106] When metal foil is used as the support, the metal foil is, for example, copper foil, aluminum foil, or the like. Among them, copper foil is preferred. For copper foil, either a foil formed of a single metal of copper alone, or a foil formed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used. . [0107] The support may be subjected to matting treatment, corona treatment, or the like on the surface of the side where it is joined to the resin composition layer. In addition, as the support, a support with a release layer attached with a release layer can be used on the surface of the side to be joined with the resin composition layer. The release agent of the release layer using the support with the release layer, for example, one or more selected from the group of alkyd resin, olefin resin, urethane resin, and silicone resin Release agent, etc. Commercial products of release agents, for example, "SK-1", "AL-5", "AL-7", etc. made by Linde Corporation, which are alkyd resin-based release agents. [0108] The thickness of the support is not particularly limited. Generally, the range of 5 μm to 75 μm is preferable, and the range of 10 μm to 60 μm is more preferable. In addition, when the support is a support with a release layer, the thickness of the entire support with a release layer is preferably within the above-mentioned range. [0109] Next, for the film, for example, the resin composition can be dissolved in an organic solvent to prepare a resin coating, and the resin coating can be applied to the support using a slit coater or the like, and then dried to form the resin composition It can be made by layer. [0110] Organic solvents, for example, ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetic acid Acetate esters such as esters and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethyl Amine-based solvents such as methyl acetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more in any ratio. [0111] Drying can be carried out using known methods such as heating and hot air blowing. The drying conditions are not particularly limited, as long as the content of the organic solvent in the resin composition layer can be reduced to 10% by mass or less, preferably 5% by mass or less, to perform the drying treatment. It depends on the boiling point of the organic solvent in the resin paint. For example, when a resin paint containing 30% to 60% by mass organic solvent is used, it is the result of drying at 50°C to 150°C for 3 minutes to 10 minutes. The resin composition layer can then be formed. [0112] Next, in the film, on the surface that is not bonded to the support of the resin composition layer (that is, the surface on the opposite side to the support), a protective film can be laminated depending on the support. The thickness of the protective film is not particularly limited. For example, it can be 1 μm to 40 μm. As a result of laminating the protective film, it is possible to prevent foreign matter, etc. from adhering to the surface of the resin composition layer or to prevent scratches. The film can then be rolled into a roll for storage. When the film has a protective film, the protective film can be peeled off and used. [0113] In one embodiment, the prepreg is formed by impregnating the resin composition of the present invention in a sheet-like fibrous base material. [0114] The sheet-like fibrous substrate used in the prepreg is not particularly limited, and glass fiber, aromatic polyamide nonwoven fabric, liquid crystal polymer nonwoven fabric, etc., which are commonly known as prepreg substrates, can be used. The substrate. From the viewpoint of thinning the printed circuit board, the thickness of the sheet-like fibrous substrate is preferably 50 μm or less, more preferably 40 μm or less, particularly preferably 30 μm or less, and most preferably 20 μm or less. The lower limit of the thickness of the sheet-like fibrous base material is not particularly limited. It is usually 10 μm or more. [0115] The prepreg can be produced using a known method such as a hot melt adhesive method and a solvent method. [0116] The thickness of the prepreg may be in the same range as the resin composition layer in the adhesive film described above. [0117] In the present invention using a resin composition composed of (A) component, (B) component, and (C) component, not only high glass transition temperature, low loss factor, and good density with the conductor layer can be obtained. In addition to the adhesive hardening material, it is also an extremely useful sheet-like laminate material in the manufacture of printed circuit boards. [0118] The sheet-like laminate material of the present invention is very suitable for forming the insulating layer of a printed circuit board (for the insulating layer of the printed circuit board), therefore, it can be more suitable for forming the interlayer insulation of the printed circuit board The material of the layer (for the interlayer insulating layer of the printed circuit board). [0119] [12. Printed circuit board] The printed circuit board of the present invention contains an insulating layer obtained by thermally curing the resin composition of the present invention or the sheet-like laminate material of the present invention. [0120] In one embodiment, the printed circuit board of the present invention can be manufactured using the above-mentioned adhesive film according to a method including the following steps (I) and (II). (I) The step of bonding the resin composition layer of the adhesive film and the inner substrate on the inner substrate on the inner substrate (II) The step of thermally curing the resin composition layer to form an insulating layer [ 0121] The "inner substrate" used in step (I) mainly refers to substrates such as glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. , Or pattern processing on one or both sides of the substrate to form a conductor layer (line) circuit substrate. In addition, when manufacturing a printed circuit board, the inner layer circuit substrate formed as an intermediate product on at least any one of the insulating layer and the conductor layer is also included in the "inner layer substrate" in the present invention. The printed circuit board is the case where the part has a built-in circuit board, so long as the part is a built-in inner substrate. [0122] The laminating method of the inner layer substrate and the adhesive film is performed by heating and pressing the adhesive film to the inner layer substrate from the support side, for example. The member used for heating and pressing the adhesive film to the inner substrate (hereinafter also referred to as "heating and pressing member"), for example, a heated metal plate (SUS mirror plate, etc.) or metal roller (SUS roller). In addition, the heating and pressing member does not need to be directly pressed against the adhesive film. Generally, it is preferable to press it with an elastic material such as heat-resistant rubber in such a way that the surface irregularities of the inner substrate fully follow the adhesive film. [0123] The lamination of the inner substrate and the adhesive film can be implemented using a vacuum lamination method. In the vacuum lamination method, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C. The heating and pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa. The heating and pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure conditions of a pressure of 26.7 hPa or less. [0124] Lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meike Manufacturing Co., Ltd., and a Vacuum Applicator manufactured by Nikko Metal Co., Ltd., etc. [0125] After lamination, under normal pressure (atmospheric pressure), for example, the heating and pressing member can be pressurized from the support side to smoothen the laminated adhesive film. The pressing conditions for the smoothing treatment can be performed under the same conditions as the heating and pressing conditions at the time of lamination. The smoothing treatment can be carried out using a commercially available laminator. In addition, the lamination and smoothing process can be continuously processed using the above-mentioned commercially available vacuum laminator. [0126] The support can be removed between step (I) and step (II), or removed after step (II). [0127] In step (II), an insulating layer is formed in order to thermally harden the resin composition layer. [0128] The thermal curing conditions of the resin composition layer are not particularly limited, and the conditions commonly used when forming the insulating layer of a printed circuit board can be used. [0129] For example, the thermosetting conditions of the resin composition layer vary depending on the type of resin composition and the like. For example, the curing temperature is usually in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably in the range of 170°C to 200°C). The curing time is usually in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes). [0130] Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before the resin composition layer is thermally cured, the resin is usually set at a temperature above 50°C and below 120°C (preferably above 60°C and below 110°C, more preferably above 70°C and below 100°C). The composition layer is usually preheated for more than 5 minutes (preferably 5 to 150 minutes, more preferably 15 to 120 minutes). [0131] When manufacturing printed circuit boards, (III) the step of opening holes on the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming a conductor layer on the surface of the insulating layer can be carried out. . These steps (III) to (V) are processes used to manufacture printed circuit boards, so those familiar with the technology can implement them in various known methods. In addition, when the support is removed after step (II), the time point for removing the support can be between step (II) and step (III), between step (III) and step (IV), or step ( IV) and step (V). [0132] In other embodiments, the printed circuit board of the present invention can be manufactured using the above-mentioned prepreg. The manufacturing method is basically the same as the case of using the adhesive film. [0133] Step (III) is a step of making holes on the insulating layer, and through this step, holes such as via holes and through holes can be formed on the insulating layer. Step (III), the composition content of the resin composition used to form the insulating layer, etc. can be matched. For example, it can be implemented using drills, lasers, plasma, and the like. The size or shape of the hole can be appropriately determined according to the design of the printed circuit board. [0134] Step (IV) is a step of roughening the insulating layer. The order and conditions of the roughening treatment are not particularly limited, and the well-known order and conditions generally used when forming the insulating layer of a printed circuit board can be used. For example, a method of using a swelling liquid for swelling treatment, using an oxidizing agent for roughening treatment, and using a neutralizing liquid for neutralizing treatment can be carried out in order to roughen the insulating layer. [0135] The swelling fluid is not particularly limited. For example, alkaline solution, surfactant solution, etc. It is preferably an alkaline solution, and the alkaline solution is preferably sodium hydroxide solution or potassium hydroxide solution. Commercially available swelling fluids, for example, "Swelling Dip Security Gans P" and "Swelling-Dip-Security-GansSBU" manufactured by Atotech Japan. The swelling treatment using swelling liquid is not particularly limited. For example, it can be performed by immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the hardened body in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes. [0136] The oxidizing agent is not particularly limited. For example, an alkaline permanganic acid solution prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 80°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Commercially available oxidants include, for example, alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing solution Security Gans P" manufactured by Atotech Japan. In addition, the neutralization liquid is preferably an acidic aqueous solution, and is a commercially available product, for example, "Reduction solutions Security Gantt P" manufactured by Atotech Japan Co., Ltd. and the like. [0137] The treatment using the neutralization liquid is a method of immersing the treated surface after the roughening treatment with an oxidizing agent in a neutralization liquid at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability, etc., the object after the roughening treatment with the oxidizing agent is preferably immersed in a neutralization solution at 40°C to 70°C for 5 minutes to 20 minutes. [0138] Step (V) is a step of forming a conductor layer. [0139] The conductive material used in the conductive layer is not particularly limited. In a preferred embodiment, the conductor layer contains one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. More than species of metals. The conductor layer may be a single metal layer or an alloy layer. The alloy layer is, for example, a layer formed of an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, in terms of the versatility, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or Nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy alloy layer is preferred, single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel-chromium alloy alloy layer The layer is preferable, and a single metal layer of copper is more preferable. [0140] The conductor layer may have a single layer structure, a single metal layer formed of different types of metals or alloys, or a multilayer structure formed by laminating two or more alloy layers. When the conductor layer has a multilayer structure, the layer to be joined to the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy. [0141] The thickness of the conductor layer can match the desired design of the printed circuit board, and is generally 3 μm to 35 μm, preferably 5 μm to 30 μm. [0142] In one embodiment, the conductive layer may be formed by electroplating. For example, the surface of the insulating layer can be electroplated using a conventionally known technique such as a semi-additive process (Semi-additive Process) and a full additive process, and a conductor layer having a desired wiring pattern can be formed. [0143] In other embodiments, the conductor layer may be formed using metal foil. In the case of using metal foil to form the conductor layer, step (V) is preferably implemented between step (I) and step (II). For example, after step (I), the support is removed, and the exposed surface of the resin composition layer is laminated on the metal foil. The lamination of the resin composition layer and the metal foil can be implemented using a vacuum lamination method. The conditions for lamination can be the same as the conditions described in step (I). Next, step (II) is performed to form an insulating layer. Subsequently, the metal foil on the insulating layer is used to form a conductor layer having a desired wiring pattern using conventionally known techniques such as a subtractive process and a modified semi-additive process. [0144] The metal foil can be produced, for example, by using a known method such as an electrolysis method and a rolling method. Commercially available metal foils include, for example, HLP foil, JXUT-III foil, 3EC-III foil, TP-III foil, etc. manufactured by JX Nikkei Nippon Oil Metal Co., Ltd., and Mitsui Metal Mining Co., Ltd. [0145] When using the resin composition of the present invention containing a combination of (A), (B), and (C) components, and manufacturing printed circuit boards, irrespective of whether the conductor layer is formed by electroplating or metal foil is used. If it is formed, it can significantly improve the adhesion between the conductive layer and the insulating layer. [13. Semiconductor device] The semiconductor device of the present invention is a printed circuit board containing the present invention. [0147] Semiconductor devices include, for example, various semiconductor devices that provide electrical products (for example, computers, mobile phones, digital cameras, and televisions, etc.) and rides (for example, motorcycles, automobiles, trams, ships, aircraft, etc.), etc. . [0148] The semiconductor device of the present invention can be manufactured by actually mounting parts (semiconductor chips) on the conductive parts of the printed circuit board. The "conducting point" refers to the "place where electrical signals are conducted on the printed circuit board". The location can be either on the surface or buried, without any limitation. In addition, the semiconductor wafer is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material. [0149] When manufacturing the semiconductor device of the present invention, the actual mounting method of the semiconductor chip is not particularly limited as long as the function of the semiconductor chip can be effectively utilized. For example, the actual installation method using wire bonding, the actual installation method of flip chip, the actual installation method of bumpless stacking layer (BBUL), the actual installation method of anisotropic conductive film (ACF), non-conductive The actual installation method of NCF, etc. Among them, "the actual installation method of bumpless stacked layer (BBUL)" refers to the "actual installation method of directly burying the semiconductor chip in the recess of the printed circuit board to connect the semiconductor chip to the wiring on the printed circuit board" Meaning.

[實施例] 　　[0150] 以下，本發明將列舉實施例作具體的說明。但，本發明並不受以下所示之實施例所限定。以下說明中，表示量之「份」及「％」，於無特別限定時，係指質量基準。 　　[0151] ＜實施例1＞ 　　將二甲酚型環氧樹脂(三菱化學公司製「YX4000HK」、環氧當量約185)25份、雙酚A型環氧樹脂(三菱化學公司製「828US」、環氧當量約180)10份加入溶劑石油腦25份中，於攪拌中進行加熱使其溶解，隨後將其冷卻至室溫為止。經其與無機填充材料(Admatechs公司製「SO-C2」、平均粒徑0.5μm、每一單位表面積之碳量0.38mg/m2 )315份混合，使用3輥混練機混練分散。於其中，加入具有乙烯基的活性酯系硬化劑(Air-Water公司製「PC1300-02-65MA」、活性基當量約199的不揮發成份65％之甲基戊酮溶液) 69.2份、具有乙烯基的樹脂(三菱瓦斯化學公司製「OPE-2St 1200」、不揮發成份60％之甲苯溶液)25份、茚苯并呋喃樹脂(日塗化學製「H-100」)15份、硬化促進劑之4-二甲胺基吡啶(DMAP)5％之MEK溶液2份及過氧化二異丙苯(日油公司製「Percumyl D」)0.13份混合，使用迴轉攪拌機均勻分散，製得樹脂塗料1。 　　[0152] 將樹脂塗料1，使用狹縫塗佈機以乾燥後的樹脂組成物層之厚度為40μm之方式均勻地塗佈於附有經醇酸系離型處理的聚乙烯對苯二甲酸酯薄膜(琳德公司製「AL-5」、厚度38μm)之離型面上，再於80℃～110℃(平均95℃)乾燥5分鐘，而製得接著薄膜1。 　　[0153] ＜實施例2＞ 　　將實施例1中，具有乙烯基之活性酯系硬化劑(Air-Water公司製「PC1300-02-65MA」、活性基當量約199之不揮發成份65％之甲基戊酮溶液)69.2份中之30.8份，變更為活性酯系硬化劑(DIC者製「HPC-8000-65T」、活性基當量約223之不揮發成份65％之甲苯溶液)30.8份。除以上事項以外，其他皆依與實施例1相同之方法製得樹脂塗料2及接著薄膜2。 　　[0154] ＜實施例3＞ 　　將實施例1中，二甲酚型環氧樹脂(三菱化學公司製「YX4000HK」、環氧當量約185)25份中之5份，變更為具有乙烯基之樹脂(三菱瓦斯化學公司製「OPE-2St 1200」、不揮發成份60％之甲苯溶液)8.3份。除以上事項以外，其他皆依與實施例1相同之方法製得樹脂塗料3及接著薄膜3。 　　[0155] ＜實施例4＞ 　　將實施例1中，具有乙烯基之樹脂(三菱瓦斯化學公司製「OPE-2St 1200」、不揮發成份60％之甲苯溶液)25份，變更為二噁烷丙烯酸基單體(新中村化學工業公司製「A-DOG」)15份。除以上事項以外，其他皆依與實施例1相同之方法製得樹脂塗料4及接著薄膜4。 　　[0156] ＜比較例1＞ 　　將實施例1中，具有乙烯基之活性酯系硬化劑(Air-Water公司製「PC1300-02-65MA」、活性基當量約199之不揮發成份65％之甲基戊酮溶液)，變更為活性酯系硬化劑(DIC公司製「HPC-8000-65T」、活性基當量約223之不揮發成份65％之甲苯溶液)。除以上事項以外，其他皆依與實施例1相同之方法製得樹脂塗料5及接著薄膜5。 　　[0157] ＜比較例2＞ 　　將實施例1中，具有乙烯基之活性酯系硬化劑(Air-Water公司製「PC1300-02-65MA」、活性基當量約199之不揮發成份65％之甲基戊酮溶液)，變更為活性酯系硬化劑(DIC公司製「EXB-8000L-65TM」、活性基當量約220之不揮發成份65％之甲苯溶液)。除以上事項以外，其他皆依與實施例1相同之方法製得樹脂塗料6及接著薄膜6。 　　[0158] ＜比較例3＞ 　　將實施例1中，具有乙烯基之活性酯系硬化劑(Air-Water公司製「PC1300-02-65MA」、活性基當量約199之不揮發成份65％之甲基戊酮溶液)69.2份，變更為活性酯系硬化劑(DIC公司製「EXB-9416L-70BK」、活性基當量約330之不揮發成份70％之甲苯溶液)64.3份。除以上事項以外，其他皆依與實施例1相同之方法製得樹脂塗料7及接著薄膜7。 　　[0159] [評估方法] 　　上述實施例及比較例所得之接著薄膜，為依下述方法進行評估。 　　[0160] ＜硬化物性評估用樣品之製作＞ 　　將實施例及比較例所得之接著薄膜，於190℃進行90分鐘之熱硬化，經剝離作為支撐體之PET薄膜後，製得薄片狀之硬化物性評估用樣品。 　　[0161] ＜損耗因子之測定＞ 　　由硬化物性評估用樣品中，切取寬2mm、長80mm之試驗片。切出之試驗片，使用Agilent Technologies公司製之測定裝置「HP8362B」，依空洞共振震動法，測定周波數5.8GHz、測定溫度23℃下之損耗因子。 　　又，為0.0035以下之情形時，則評估為「優」，為0.0037以下之情形時，則評估為「良」，超過0.0037之情形，則評估為「不良」。 　　[0162] ＜玻璃轉移溫度之測定＞ 　　將硬化物性評估用樣品切斷為寬約5mm、長約15mm之試驗片，使用熱機械分析裝置(琳德公司製「Thermo Plus TMA8310」)，依拉伸加重法進行熱機械分析。詳細而言，為將試驗片裝設於前述熱機械分析裝置之後，使用荷重1g、升溫速度5℃/分之測定條件連續測定2次。隨後，於第2次之測定中，算出玻璃轉移溫度(Tg；℃)。 　　又超過138℃之情形，評估為「良」，138℃以下之情形，評估為「不良」。 　　[0163] ＜密著性之測定＞ (1)銅箔之底部處理 　　將三井金屬鑛山公司製「3EC-III」(電場銅箔、35μm)之光澤面，浸潤於墨克公司製MEC etch bond「CZ-8101」中，對銅表面進行粗化處理(Ra值=1μm)，並施以防鏽處理(CL8300)。將該銅箔稱為CZ銅箔。隨後，再於130℃之烘箱中進行30分鐘加熱處理。 　　[0164] (2)銅箔之層合與絕緣層之形成 　　將實施例及比較例所製得之接著薄膜，使用批次式真空加壓層合器(名機公司製「MVLP-500」)，以樹脂組成物層接合內層線路基板之方式，對內層線路基板兩面進行層合處理。層合處理為，於經30秒鐘減壓，使氣壓降至13hPa以下後，於100℃、壓力0.74MPa下，進行30秒鐘壓著處理之方式進行。於經層合處理後的接著薄膜，將支撐體之PET薄膜剝離。於該樹脂組成物層上，將「3EC-III」之CZ銅箔的處理面，依與上述相同之條件，進行層合。隨後，於190℃、90分鐘之硬化條件，使樹脂組成物層硬化而形成絕緣層，而製得樣品。 　　[0165] (3)銅箔拉伸剝離強度(密著性)之測定 　　將製得之樣品切斷為150×30mm之小片。於小片的銅箔部份上，使用切斷器對寬10mm、長100mm之部份進行切入。將銅箔的前述部份之一端剝離，並使用夾具(TSE公司製、Autocom型試驗機、「AC-50C-SL」)夾住，向垂直方向進行拉伸剝離。該拉伸剝離，為使用英斯特萬能試驗機，於室溫中，以50mm/分鐘之速度進行。依JIS C6481為基準測定拉伸剝離35mm時之荷重，作為「密著性」評估數據。 　　又，超過0.3kgf/cm之情形，評估為「良」，0.3kgf/cm以下之情形，評估為「不良」。 　　[0166] ＜結果＞ 　　上述實施例及比較例之結果，記載如下述表所示。下述表中，簡稱內容係具有下述之意義。 　　YX4000HK：二甲酚型環氧樹脂(三菱化學公司製「YX4000HK」) 　　828US：雙酚A型環氧樹脂(三菱化學公司製「828US」) 　　PC1300-02：具有乙烯基之活性酯系硬化劑(Air-Water公司製「PC1300-02-65MA」) 　　HPC-8000：活性酯系硬化劑(DIC公司製「HPC-8000-65T」) 　　EXB-8000L：活性酯系硬化劑(DIC公司製「EXB-8000L-65TM」) 　　EXB-9416：活性酯系硬化劑(DIC公司製「EXB-9416L-70BK」) 　　OPE-2St 1200：具有乙烯基之樹脂(三菱瓦斯化學公司製「OPE-2St 1200」) 　　A-DOG：二噁烷丙烯酸基單體(新中村化學工業公司製「A-DOG」) 　　H-100：茚苯并呋喃樹脂(日塗化學製「H-100」) 　　SOC2：球狀二氧化矽(Admatechs公司製「SO-C2」) 　　Percumyl D：過氧化二異丙苯(日油公司製「Percumyl D」) 　　DMAP：4-二甲胺基吡啶 　　又，表中，添加量為固體成份換算值。 　　[0167]

Figure 02_image023
[0168] [結論] 　　使用活性酯系硬化劑之比較例1～3，其玻璃轉移溫度，及密著性皆不良。特別是，比較例3所使用的含有萘結構的活性酯系硬化劑，其損耗因子亦為不良。 　　相對於此，使用(B)成份的實施例1～4，非但損耗因子之值可維持於低值，其玻璃轉移溫度仍為高值，且顯示出良好的密著性。因此，由該些實施例1～4、比較例1～3之結果得知，經組合(A)成份、(B)成份，及(C)成份結果，確認可實現一種可製得具有低損耗因子、高玻璃轉移溫度、與導電層具有良好密著性的絕緣層之樹脂組成物。[Examples] [0150] Hereinafter, the present invention will be specifically described with examples. However, the present invention is not limited to the examples shown below. In the following description, the "parts" and "%" that indicate the amount, unless specifically limited, refer to the quality standard. [0151] <Example 1> 25 parts of xylenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent approximately 185), bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation "828US", Add 10 parts of epoxy equivalent of about 180) to 25 parts of solvent naphtha, heat it while stirring to dissolve, and then cool it to room temperature. It was mixed with 315 parts of an inorganic filler ("SO-C2" manufactured by Admatechs, 0.5 μm average particle size, 0.38 mg/m 2 of carbon per unit surface area), and then kneaded and dispersed using a 3-roll kneader. To this, 69.2 parts of an active ester hardener with vinyl ("PC1300-02-65MA" made by Air-Water, a non-volatile 65% methylpentanone solution with an active group equivalent of about 199) is added, with vinyl Base resin (Mitsubishi Gas Chemical Corporation "OPE-2St 1200", non-volatile content 60% toluene solution) 25 parts, indene benzofuran resin (Nippon Paint Chemical "H-100") 15 parts, hardening accelerator Mix 2 parts of 4-dimethylaminopyridine (DMAP) 5% MEK solution and 0.13 parts of dicumyl peroxide ("Percumyl D" manufactured by NOF Corporation), and use a rotary mixer to evenly disperse to obtain resin coating 1 . [0152] The resin coating 1 was uniformly applied to polyethylene terephthalic acid with alkyd release treatment using a slit coater so that the thickness of the dried resin composition layer was 40 μm. The release surface of the ester film ("AL-5" manufactured by Linde, thickness 38μm) was dried at 80°C to 110°C (average 95°C) for 5 minutes to obtain Adhesive Film 1. [0153] <Example 2> In Example 1, an active ester curing agent having a vinyl group ("PC1300-02-65MA" manufactured by Air-Water Co., Ltd., an active group equivalent of about 199 and a non-volatile content of 65% 30.8 parts of 69.2 parts of methylpentanone solution) were changed to 30.8 parts of an active ester hardener ("HPC-8000-65T" made by DIC, a toluene solution of 65% non-volatile content with an active base equivalent of about 223). Except for the above matters, the resin coating 2 and the adhesive film 2 were prepared in the same manner as in Example 1. [0154] <Example 3> In Example 1, 5 parts out of 25 parts of xylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) were changed to a resin having a vinyl group. (Mitsubishi Gas Chemical Corporation "OPE-2St 1200", a toluene solution of 60% non-volatile content) 8.3 parts. Except for the above matters, the resin coating 3 and the adhesive film 3 were prepared in the same manner as in Example 1. [0155] <Example 4> In Example 1, 25 parts of a resin having a vinyl group (Mitsubishi Gas Chemical Corporation "OPE-2St 1200", a toluene solution of 60% non-volatile content) was changed to dioxane acrylic acid 15 parts of base monomer ("A-DOG" manufactured by Shinnakamura Chemical Industry Co., Ltd.). Except for the above matters, the resin coating 4 and the adhesive film 4 were prepared in the same manner as in Example 1. [0156] <Comparative Example 1> In Example 1, an active ester curing agent having a vinyl group ("PC1300-02-65MA" manufactured by Air-Water Co., Ltd., an active group equivalent of about 199 and a non-volatile content of 65% Benzylpentanone solution) was changed to an active ester hardener ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution of 65% non-volatile content with an active base equivalent of about 223). Except for the above matters, the resin coating 5 and the adhesive film 5 were prepared in the same manner as in Example 1. [0157] <Comparative Example 2> In Example 1, an active ester curing agent having a vinyl group ("PC1300-02-65MA" manufactured by Air-Water Co., Ltd., an active group equivalent of about 199 and a non-volatile content of 65% Benzylpentanone solution) was changed to an active ester hardener ("EXB-8000L-65TM" manufactured by DIC Corporation, a toluene solution of 65% non-volatile content with an active base equivalent of approximately 220). Except for the above matters, the resin coating 6 and the adhesive film 6 were prepared in the same manner as in Example 1. [0158] <Comparative Example 3> In Example 1, an active ester curing agent having a vinyl group ("PC1300-02-65MA" manufactured by Air-Water Co., Ltd., an active group equivalent of approximately 199 and a non-volatile content of 65% 69.2 parts of methylpentanone solution), changed to 64.3 parts of active ester hardener ("EXB-9416L-70BK" manufactured by DIC Corporation, a toluene solution of 70% non-volatile content with an active base equivalent of approximately 330). Except for the above matters, the resin coating 7 and the adhesive film 7 were prepared in the same manner as in Example 1. [Evaluation Method] The adhesive films obtained in the above-mentioned Examples and Comparative Examples were evaluated according to the following method. [0160] <Preparation of Samples for Evaluation of Cured Physical Properties> The adhesive films obtained in the Examples and Comparative Examples were heat-cured at 190°C for 90 minutes, and the PET film as the support was peeled off to obtain sheet-like cured physical properties Samples for evaluation. [0161] <Measurement of loss factor> From the sample for evaluation of hardened physical properties, a test piece with a width of 2 mm and a length of 80 mm was cut out. The cut-out test piece used the measurement device "HP8362B" manufactured by Agilent Technologies, and measured the loss factor at a frequency of 5.8 GHz and a measurement temperature of 23 ℃ by the cavity resonance vibration method. Also, if it is less than 0.0035, it is evaluated as "excellent", if it is less than 0.0037, it is evaluated as "good", and if it exceeds 0.0037, it is evaluated as "bad". [0162] <Measurement of glass transition temperature> The cured physical property evaluation sample was cut into a test piece with a width of about 5 mm and a length of about 15 mm, and a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Linde Co., Ltd.) was used to stretch it. The aggravation method is used for thermomechanical analysis. Specifically, after the test piece was installed in the thermomechanical analyzer, it was continuously measured twice under the measurement conditions of a load of 1 g and a temperature increase rate of 5°C/min. Subsequently, in the second measurement, the glass transition temperature (Tg; °C) was calculated. If it exceeds 138°C, it is evaluated as "good", and if it is below 138°C, it is evaluated as "bad". <Measurement of Adhesion> (1) Bottom treatment of copper foil The glossy surface of "3EC-III" (electric field copper foil, 35 μm) manufactured by Mitsui Metals Mining Co., Ltd. was soaked in MEC etch bond manufactured by Merck In "CZ-8101", the copper surface is roughened (Ra value = 1μm) and rust-proof treatment (CL8300) is applied. This copper foil is called CZ copper foil. Subsequently, heat treatment was performed in an oven at 130°C for 30 minutes. [0164] (2) Laminating of copper foil and formation of insulating layer The adhesive films produced in the Examples and Comparative Examples were used with a batch-type vacuum pressure laminator ("MVLP-500" manufactured by Meiji Co., Ltd.) , Laminate both sides of the inner layer circuit substrate by bonding the resin composition layer to the inner layer circuit substrate. The lamination process is performed by reducing the pressure for 30 seconds to reduce the air pressure to less than 13 hPa, and then performing a pressing process at 100° C. and a pressure of 0.74 MPa for 30 seconds. On the adhesive film after the lamination process, the PET film of the support is peeled off. On the resin composition layer, the processed surface of the "3EC-III" CZ copper foil is laminated under the same conditions as above. Subsequently, the resin composition layer was cured at 190°C for 90 minutes to form an insulating layer, and a sample was prepared. [0165] (3) Measurement of copper foil tensile peel strength (adhesion) The prepared sample was cut into small pieces of 150×30 mm. On the small piece of copper foil, use a cutter to cut the 10mm wide and 100mm long part. One end of the aforementioned part of the copper foil was peeled off, clamped with a jig (manufactured by TSE, Autocom type testing machine, "AC-50C-SL"), and stretched and peeled in the vertical direction. The tensile peeling was carried out at a speed of 50 mm/min at room temperature using an Instron universal testing machine. According to JIS C6481, the load at 35mm tensile peeling was measured as the "adhesion" evaluation data. In addition, cases exceeding 0.3kgf/cm are evaluated as "good", and cases less than 0.3kgf/cm are evaluated as "bad". [0166] <Results> The results of the above-mentioned Examples and Comparative Examples are described in the following table. In the following table, the abbreviated content has the following meanings. YX4000HK: Xylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation) 828US: Bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation) PC1300-02: Active ester hardener with vinyl ( Air-Water Company "PC1300-02-65MA") HPC-8000: Active ester hardener (DIC Company "HPC-8000-65T") EXB-8000L: Active ester hardener (DIC Company "EXB- 8000L-65TM") EXB-9416: Active ester hardener ("EXB-9416L-70BK" made by DIC) OPE-2St 1200: Resin with vinyl ("OPE-2St 1200" made by Mitsubishi Gas Chemical Company) A -DOG: Dioxane acrylic monomer ("A-DOG" manufactured by Shinnakamura Chemical Industry Co., Ltd.) H-100: Indene coumarone resin ("H-100" manufactured by Nitto Chemical Co., Ltd.) SOC2: Spherical silicon dioxide ("SO-C2" manufactured by Admatechs) Percumyl D: Dicumyl peroxide ("Percumyl D" manufactured by NOF Corporation) DMAP: 4-Dimethylaminopyridine. In the table, the added amount is a solid content conversion value . [0167]
Figure 02_image023
[Conclusion] Comparative Examples 1 to 3 using active ester hardeners had poor glass transition temperature and adhesion. In particular, the active ester hardener containing a naphthalene structure used in Comparative Example 3 also had a poor loss factor. In contrast, in Examples 1 to 4 using the component (B), not only the value of the loss factor can be maintained at a low value, the glass transition temperature is still at a high value, and good adhesion is shown. Therefore, based on the results of these Examples 1 to 4 and Comparative Examples 1 to 3, it is confirmed that the combination of (A) component, (B) component, and (C) component results confirms that a product with low loss can be achieved The resin composition of the insulating layer with high factor, high glass transition temperature, and good adhesion to the conductive layer.

Claims (9)

一種樹脂組成物，其特徵為，含有(A)環氧樹脂、(B)具有碳-碳不飽和鍵結之活性酯化合物，及(C)具有不飽和烴基之樹脂，前述(A)成份之含量，於樹脂成份為100質量%時，為10~50質量%，前述(B)成份為具有苯乙烯基之活性酯化合物。 A resin composition characterized in that it contains (A) an epoxy resin, (B) an active ester compound having carbon-carbon unsaturated bonds, and (C) a resin having an unsaturated hydrocarbon group. The aforementioned (A) component The content is 10-50% by mass when the resin component is 100% by mass. The aforementioned component (B) is an active ester compound with a styrene group. 如請求項1之樹脂組成物，其中，前述(B)成份之含量，於樹脂成份為100質量%時，為10質量%~60質量%。 Such as the resin composition of claim 1, wherein the content of the aforementioned (B) component is 10% by mass to 60% by mass when the resin component is 100% by mass. 如請求項1之樹脂組成物，其中，前述(C)成份之含量，於樹脂成份為100質量%時，為3質量%~30質量%。 Such as the resin composition of claim 1, wherein the content of the aforementioned (C) component is 3% by mass to 30% by mass when the resin component is 100% by mass. 如請求項1之樹脂組成物，其中，前述(B)成份為含有下述通式(1)所示之化合物；
Figure 106130398-A0305-02-0060-2
 (前述通式(1)中，m表示1~6之整數，n表示1~20之整數)。 The resin composition of claim 1, wherein the aforementioned component (B) contains a compound represented by the following general formula (1);
Figure 106130398-A0305-02-0060-2
 (In the aforementioned general formula (1), m represents an integer of 1 to 6, and n represents an integer of 1 to 20). 如請求項1之樹脂組成物，其中，前述(C)成份為具有丙烯酸基、甲基丙烯酸基、苯乙烯基，或烯烴基之樹脂。 The resin composition of claim 1, wherein the aforementioned component (C) is a resin having an acrylic group, a methacrylic group, a styrene group, or an olefin group. 如請求項1之樹脂組成物，其中，其為使用於形成印刷電路板之絕緣層。 The resin composition according to claim 1, wherein it is used to form an insulating layer of a printed circuit board. 一種薄片狀層合材料，其特徵為，含有請求項1~6中任一項之樹脂組成物。 A sheet-like laminated material characterized by containing the resin composition of any one of claims 1 to 6. 一種印刷電路板，其特徵為，含有由請求項1~6中任一項之樹脂組成物之硬化物所形成的絕緣層。 A printed circuit board characterized by comprising an insulating layer formed of a cured product of the resin composition of any one of claims 1 to 6. 一種半導體裝置，其特徵為，含有請求項8之印刷電路板。 A semiconductor device characterized by including the printed circuit board of claim 8.
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