TWI452083B - Thermosetting resin composition - Google Patents

Thermosetting resin composition Download PDF

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TWI452083B
TWI452083B TW098135436A TW98135436A TWI452083B TW I452083 B TWI452083 B TW I452083B TW 098135436 A TW098135436 A TW 098135436A TW 98135436 A TW98135436 A TW 98135436A TW I452083 B TWI452083 B TW I452083B
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weight
resin composition
film
resin
manufactured
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TW201030083A (en
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Eiichi Hayashi
Masanori Ohkoshi
Yuko Hidehira
Genjin Mago
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Ajinomoto Kk
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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
    • 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
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • 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
    • H05K1/18—Printed circuits structurally associated with non-printed electric components
    • H05K1/182—Printed circuits structurally associated with non-printed electric components associated with components mounted in the printed circuit board, e.g. insert mounted components [IMC]
    • H05K1/185—Components encapsulated in the insulating substrate of the printed circuit or incorporated in internal layers of a multilayer circuit
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/303—Surface mounted components, e.g. affixing before soldering, aligning means, spacing means
    • H05K3/305—Affixing by adhesive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
    • 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
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • 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
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10613—Details of electrical connections of non-printed components, e.g. special leads
    • H05K2201/10621—Components characterised by their electrical contacts
    • H05K2201/10636—Leadless chip, e.g. chip capacitor or resistor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

熱硬化性樹脂組成物Thermosetting resin composition

本發明係關於對於零件內藏基板之製造有用之熱硬化性樹脂組成物、及具有使用該熱硬化性樹脂組成物之接著層的接著薄膜，以及使用該接著薄膜之零件內藏基板的製造方法。The present invention relates to a thermosetting resin composition useful for the production of a component-embedded substrate, and a bonding film having an adhesive layer using the thermosetting resin composition, and a method of manufacturing a component-embedded substrate using the bonding film .

於印刷電路板中，現要求著輕薄短小化而成之高密度化。於零件內藏基板中，被嵌入之零件變小，而於嵌入時之高位置精度則為必要。又，由必需將基板全體之大小縮小一事，於嵌入之零件與零件周邊之電路之間具有高絕緣性之材料則成為必要。In printed circuit boards, high density is required for thinness and shortness. In the built-in substrate of the part, the embedded part becomes smaller, and the high positional accuracy at the time of embedding is necessary. Further, it is necessary to reduce the size of the entire substrate, and it is necessary to have a high insulating property between the embedded component and the circuit around the component.

作為零件內藏基板之製造方法，雖有揭示藉由薄片劑(sheet agent)與附黏著劑之薄片劑將零件予以假固定，將零件以樹脂密封後，將薄片除去之方法(專利文獻1)，但並無揭示具體之組成。又，由於零件密封後有將黏著劑除去之必要而使步驟數增加。As a method of manufacturing a component-embedded substrate, a method of temporarily fixing a component by a sheet agent and a sheet of an adhesive agent, and sealing the component with a resin, and removing the sheet (Patent Document 1) But did not reveal the specific composition. Moreover, the number of steps is increased by the necessity of removing the adhesive after the parts are sealed.

又，有揭示在芯基板之電子零件實際裝載面上，藉由黏著材將零件假固定，將零件以樹脂密封之方法(專利文獻2)。作為黏著材，以具有電絕緣性，進而加上高熱時，會蒸發或成為氣體之材料較佳，而使用之高分子的具體例，可單獨使用丙烯酸樹脂、聚酯樹脂、馬來化油樹脂、聚丁二烯樹脂、環氧樹脂等或將其任意組合之混合物。又，用以賦予此些高分子樹脂黏著性之松香系、萜系、石油樹脂系等之賦予黏著之樹脂可依據需要而添加。然而，其並無揭示黏著材之具體組成。Further, there is a method in which a component is pseudo-fixed by an adhesive material and the component is sealed with a resin on the actual mounting surface of the electronic component of the core substrate (Patent Document 2). As the adhesive material, it is preferable to use a material which is electrically insulating and further heated, and which evaporates or becomes a gas, and a specific example of the polymer to be used may be an acrylic resin, a polyester resin or a maleic oleoresin. , a polybutadiene resin, an epoxy resin, or the like, or a mixture of any combination thereof. Further, a resin for imparting adhesion such as rosin, lanthanide, or petroleum resin to impart adhesion to these polymer resins may be added as needed. However, it does not reveal the specific composition of the adhesive.

又，將接著層不僅在電子零件之接著場所，在全面具備絕緣性基材上將零件假固定，將零件以樹脂進行密封之方法(專利文獻3)。作為接著層，可例示環氧樹脂系、聚胺基甲酸酯系、反應性丙烯酸系、紫外線硬化型或聚矽氧系，而作為例子則有揭示對環氧樹脂系或聚矽氧系等予以混合酚樹脂、有機酸酐、胺或硬化促進劑等之硬化劑而使用。其次，揭示為了將零件固定，在硬化溫度之加熱或藉由照射紫外線照射等使其硬化之手法。但，其並無揭示接著層之具體組成。又，藉由接著層之熱硬化而將電子零件固定之情況，則有因為接著層之熔融而使零件之固定位置精度降低之問題。並且有紫外線所成之硬化其步驟為複雑之問題。In addition, the adhesive layer is a method in which the component is pseudo-fixed on the entire insulating substrate, and the component is sealed with a resin (Patent Document 3). The adhesive layer may, for example, be an epoxy resin, a polyurethane, a reactive acrylic, an ultraviolet curable or a polyoxynoxy, and examples thereof include an epoxy resin or a polyoxyxene. A curing agent such as a phenol resin, an organic acid anhydride, an amine or a curing accelerator is used. Next, a method of hardening a part at a curing temperature or hardening it by irradiation with ultraviolet rays or the like is disclosed. However, it does not reveal the specific composition of the subsequent layers. Further, when the electronic component is fixed by thermal curing of the adhesive layer, there is a problem that the fixing position accuracy of the component is lowered due to the melting of the adhesive layer. And there is a problem that the step of hardening by ultraviolet rays is retanning.

[專利文獻1]特開2002-204045號公報[Patent Document 1] JP-A-2002-204045

[專利文獻2]特開2004-296562號公報[Patent Document 2] JP-A-2004-296562

[專利文獻3]特開2007-42829號公報[Patent Document 3] JP-A-2007-42829

本案發明之課題在於提供對於藉由接著層之黏著性(tack性)而將電子零件固定於接著層，使該接著層熱硬化之情況，可製造零件之固定位置精度及絕緣信賴性為高之零件內藏基板的熱硬化性樹脂組成物。An object of the present invention is to provide a method in which an electronic component is fixed to an adhesive layer by adhesiveness of a bonding layer, and the adhesive layer is thermally cured. The fixed position accuracy and insulation reliability of the manufactured component are high. A thermosetting resin composition of the substrate in the part.

本發明者們為了解決上述課題而進行銳意檢討之結果，藉由使用含有液狀環氧樹脂、酚系硬化劑、無機填料及丙烯酸樹脂之特定的熱硬化性樹脂組成物而完成本發明。As a result of intensive review in order to solve the above problems, the present inventors have completed the present invention by using a specific thermosetting resin composition containing a liquid epoxy resin, a phenolic curing agent, an inorganic filler, and an acrylic resin.

即，本發明為含有以下之內容者。That is, the present invention is intended to contain the following contents.

[1]　一種熱硬化性樹脂組成物，其係零件內藏基板之零件固定及絕緣層形成所用之熱硬化性樹脂組成物，其特徵為在熱硬化性樹脂組成物之不揮發份設為100重量%之情況時，含有25℃下液狀之環氧樹脂25~40重量%、丙烯酸樹脂0.1~5重量%、酚系硬化劑5~30重量%及無機填料20~70重量%。[1] A thermosetting resin composition which is a thermosetting resin composition for fixing a part of a substrate and forming an insulating layer, wherein the non-volatile content of the thermosetting resin composition is 100. In the case of % by weight, it contains 25 to 40% by weight of a liquid epoxy resin at 25 ° C, 0.1 to 5% by weight of an acrylic resin, 5 to 30% by weight of a phenol-based curing agent, and 20 to 70% by weight of an inorganic filler.

[2]　如上述[1]記載之熱硬化性樹脂組成物，其中丙烯酸樹脂為丙烯酸酯共聚物。[2] The thermosetting resin composition according to [1] above, wherein the acrylic resin is an acrylate copolymer.

[3]　如上述[1]或[2]記載之熱硬化性樹脂組成物，其中丙烯酸樹脂為含有丙烯酸甲酯、丙烯酸丁酯、丙烯腈之丙烯酸酯共聚物。[3] The thermosetting resin composition according to the above [1] or [2] wherein the acrylic resin is an acrylate copolymer containing methyl acrylate, butyl acrylate or acrylonitrile.

[4]　如上述[1]~[3]記載之熱硬化性樹脂組成物，其中丙烯酸樹脂含有選自環氧基、羥基、羧基之1種以上之基。[4] The thermosetting resin composition according to the above [1], wherein the acrylic resin contains one or more selected from the group consisting of an epoxy group, a hydroxyl group, and a carboxyl group.

[5]　如上述[1]~[4]記載之熱硬化性樹脂組成物，其中丙烯酸樹脂為含有羥基及羧基。[5] As above [1]~[4] The thermosetting resin composition described above, wherein the acrylic resin contains a hydroxyl group and a carboxyl group.

[6]　一種接著薄膜，其特徵為於支持體上具有由上述[1]~[5]記載之熱硬化性樹脂組成物所形成之接著層，其係為零件內藏基板之零件固定及絕緣層形成所用之接著薄膜。[6] An adhesive film comprising the adhesive layer formed of the thermosetting resin composition according to the above [1] to [5] on the support, which is a component for fixing and insulating the component-embedded substrate. The layer forms the adhesive film used.

[7]　如上述[6]記載之接著薄膜，其中接著層之厚度為5~100μm[7] The adhesive film according to [6] above, wherein the thickness of the adhesive layer is 5 to 100 μm

[8]　如上述[6]或[7]記載之接著薄膜，其中支持體為塑膠薄膜。[8] The adhesive film according to [6] or [7] above, wherein the support is a plastic film.

[9]　如上述[6]~[8]之任一項記載之接著薄膜，其中支持體之接著層側之面為經離型處理者。[9] The adhesive film according to any one of [6] to [8] wherein the surface of the support layer on the side of the support layer is a release type.

[10]　一種零件內藏基板之製造方法，其特徵為包含如上述[1]~[9]中任一項記載之接著薄膜之接著層上將電子零件固定之步驟及使該接著層熱硬化而形成絕緣層之步驟。[10] A method of producing a component-embedded substrate, comprising the step of fixing an electronic component on an adhesive layer of the adhesive film according to any one of the above [1] to [9], and thermally hardening the adhesive layer The step of forming an insulating layer.

依據本發明，藉由使用含有液狀環氧樹脂、酚系硬化劑、無機填料及丙烯酸樹脂之特定的熱硬化性樹脂組成物，可提供對於藉由接著層之黏著性(tack性)將電子零件固定於接著層，使該接著層熱硬化之情況時，可製造零件之固定位置精度及絕緣信賴性為高之零件內藏基板的熱硬化性樹脂組成物。According to the present invention, by using a specific thermosetting resin composition containing a liquid epoxy resin, a phenolic curing agent, an inorganic filler, and an acrylic resin, electrons can be provided for adhesion by a bonding layer (tack property). When the component is fixed to the adhesive layer and the adhesive layer is thermally cured, a thermosetting resin composition of the component-embedded substrate having a high fixed position accuracy and high insulation reliability of the component can be manufactured.

[25℃下液狀之環氧樹脂][Liquid epoxy resin at 25 ° C]

本發明中「25℃下液狀之環氧樹脂」，主要係同時提高硬化物之耐熱性及絕緣性，賦予熱硬化性樹脂組成物之黏著性。作為25℃下液狀之環氧樹脂，具體上有，雙酚A型環氧樹脂、雙酚F型環氧樹脂、酚醛清漆型環氧樹脂、萘型環氧樹脂、三級丁基兒茶酚型環氧樹脂、具有丁二烯構造之環氧樹脂、脂肪族系環氧丙基醚、醇類之環氧丙基醚化物，以及此些之環氧樹脂之鹵化物及加氫物等。此些可1種或將2種以上組合使用。In the present invention, the "liquid epoxy resin at 25 ° C" mainly improves the heat resistance and the insulating property of the cured product at the same time, and imparts adhesion to the thermosetting resin composition. As a liquid epoxy resin at 25 ° C, specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, naphthalene type epoxy resin, tertiary butyl tea a phenol type epoxy resin, an epoxy resin having a butadiene structure, an aliphatic epoxy propyl ether, an epoxy propyl ether compound of an alcohol, and a halide and a hydrogenated product of the epoxy resin, etc. . These may be used alone or in combination of two or more.

此些之中，由耐熱性、絕緣信賴性之觀點，以雙酚A型環氧樹脂、萘酚型環氧樹脂、萘型環氧樹脂、脂肪族系環氧丙基醚、具有丁二烯構造之環氧樹脂為佳。環氧樹脂之具體例，可舉出液狀雙酚A型環氧樹脂(Japan Epoxy Resin(股)製「Epikote 828EL」)、液狀雙酚F型環氧樹脂(Japan Epoxy Resin(股)製「Epikote 807」)、萘型2官能環氧樹脂(大日本油墨化學工業(股)製「HP4032」、「HP4032D」)、脂肪族系環氧丙基醚(東都化成(股)製「ZX-1658」)、具有丁二烯構造之環氧樹脂(Daicel化學工業(股)製「PB-3600」)等。「25℃下液狀之環氧樹脂」亦可將2種以上組合使用。Among these, from the viewpoints of heat resistance and insulation reliability, bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, aliphatic glycidyl ether, and butadiene The epoxy resin constructed is preferred. Specific examples of the epoxy resin include liquid bisphenol A type epoxy resin ("Epikote 828EL" manufactured by Japan Epoxy Resin Co., Ltd.) and liquid bisphenol F type epoxy resin (made by Japan Epoxy Resin Co., Ltd.). "Epikote 807"), naphthalene type 2-functional epoxy resin ("HP4032" and "HP4032D" manufactured by Dainippon Ink Chemical Industry Co., Ltd.), and aliphatic epoxy propyl ether ("XU-Chemical Co., Ltd." 1658"), epoxy resin having a butadiene structure ("PB-3600" manufactured by Daicel Chemical Industry Co., Ltd.). "A liquid epoxy resin at 25 ° C" may be used in combination of two or more kinds.

將熱硬化性樹脂組成物之不揮發成分設為100重量%之情況，25℃下液狀之環氧樹脂之含有量之上限值，由防止黏著力變大而覆蓋薄膜之剝離性變差，又防止於薄膜硬化時容易產生零件之位置偏差之觀點，以40重量%為佳，35重量%為更佳。另一方面，將熱硬化性樹脂組成物之不揮發成分設為100重量%之情況時，25℃下液狀之環氧樹脂之含有量的下限值，由防止零件變得難以固定於接著薄膜之觀點，以25重量%為佳，30重量%為更佳。When the non-volatile content of the thermosetting resin composition is 100% by weight, the upper limit of the content of the liquid epoxy resin at 25 ° C is lowered, and the peeling property of the cover film is deteriorated by preventing the adhesive force from becoming large. Further, from the viewpoint of easily causing positional deviation of the component when the film is cured, it is preferably 40% by weight, more preferably 35% by weight. On the other hand, when the non-volatile content of the thermosetting resin composition is 100% by weight, the lower limit of the content of the liquid epoxy resin at 25 ° C is difficult to prevent the parts from being fixed. The viewpoint of the film is preferably 25% by weight, more preferably 30% by weight.

[丙烯酸樹脂][Acrylic]

本發明中之「丙烯酸樹脂」主要係寄予熱硬化性樹脂組成物之黏著性。作為丙烯酸樹脂可舉出，聚丙烯酸、聚甲基丙烯酸、聚丙烯酸酯、聚甲基丙烯酸酯、聚丙烯酸酯共聚物、聚甲基丙烯酸酯共聚物等。又，丙烯酸樹脂以具有優良黏著性之丙烯酸酯共聚物為佳，更以丙烯酸甲酯共聚物、丙烯酸乙酯共聚物為佳。作為共聚化合物，可舉出丙烯酸甲酯、丙烯酸丁酯、乙酸乙烯酯、丙烯腈、丙烯醯胺等，其中以丙烯酸甲酯、丙烯酸丁酯、丙烯腈為佳。且，丙烯酸甲酯共聚物或丙烯酸乙酯共聚物以更含有選自環氧基、羥基、羧基之1種以上之基為佳，特別以含有羥基及/或羧基為佳。此些可1種或2種以上組合使用。The "acrylic resin" in the present invention mainly imparts adhesion to a thermosetting resin composition. Examples of the acrylic resin include polyacrylic acid, polymethacrylic acid, polyacrylate, polymethacrylate, polyacrylate copolymer, and polymethacrylate copolymer. Further, the acrylic resin is preferably an acrylate copolymer having excellent adhesion, and more preferably a methyl acrylate copolymer or an ethyl acrylate copolymer. The copolymerization compound may, for example, be methyl acrylate, butyl acrylate, vinyl acetate, acrylonitrile or acrylamide. Among them, methyl acrylate, butyl acrylate or acrylonitrile is preferred. Further, the methyl acrylate copolymer or the ethyl acrylate copolymer is preferably one or more groups selected from the group consisting of an epoxy group, a hydroxyl group and a carboxyl group, and particularly preferably a hydroxyl group and/or a carboxyl group. These may be used alone or in combination of two or more.

將熱硬化性樹脂組成物之不揮發成分設為100重量%之情況，丙烯酸樹脂之含有量之上限值，由防止黏著力變大而覆蓋薄膜之剝離性變差、操作性拙劣之觀點，以5重量%為佳，3重量%為更佳。另一方面，將熱硬化性樹脂組成物之不揮發成分設為100重量%之情況，丙烯酸樹脂之含有量之下限值，由防止因為黏著性之降低所造成之難以固定零件之觀點，以0.1重量%為佳，0.5重量%為更佳。When the non-volatile content of the thermosetting resin composition is 100% by weight, the upper limit of the content of the acrylic resin is limited, and the peeling property of the cover film is deteriorated and the workability is deteriorated. It is preferably 5% by weight, more preferably 3% by weight. On the other hand, when the non-volatile content of the thermosetting resin composition is 100% by weight, the lower limit of the content of the acrylic resin is prevented from being fixed due to the decrease in adhesiveness. 0.1% by weight is preferred, and 0.5% by weight is more preferred.

丙烯酸樹脂之重量平均分子量的上限值，由防止對溶劑及環氧樹脂之溶解性降低而製作均勻熱硬化性樹脂組成物變得困難之觀點，以1,200,000為佳，以900,000為更佳。另一方面，丙烯酸樹脂之重量平均分子量的下限值，由防止組成物之黏著性降低而固定零件變得困難之觀點，以400,000為佳，500,000為更佳。尚，本發明中之重量平均分子量係以凝膠滲透層析(GPC)法(以聚苯乙烯換算)所測定。GPC法所得之重量平均分子量，具體而言係以(股)島津製作所製之LC-9A/RID-6A作為測定裝置，以昭和電工(股)公司製Shodex K-800P/K-804L/K-804L作為管柱，使用氯仿等作為流動相，管柱溫度40℃中進行測定，使用標準聚苯乙烯之標準曲線而可算出。The upper limit of the weight average molecular weight of the acrylic resin is difficult to produce a uniform thermosetting resin composition by preventing the solubility in the solvent and the epoxy resin from being lowered, and is preferably 1,200,000 and more preferably 900,000. On the other hand, the lower limit of the weight average molecular weight of the acrylic resin is preferably 400,000, more preferably 500,000, from the viewpoint of preventing the adhesiveness of the composition from being lowered and fixing the component. Further, the weight average molecular weight in the present invention is measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). The weight average molecular weight obtained by the GPC method is, in particular, LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P/K-804L/K-made by Showa Denko Co., Ltd. 804L was used as a column, and chloroform or the like was used as a mobile phase, and the column temperature was measured at 40 ° C, and it was calculated using a standard curve of standard polystyrene.

作為市售之丙烯酸樹脂，具體可舉出Arontack S-1511L、S-1511X、S-1515、S-1517(東亞合成(股)公司製)Toaacron AR-601、AR-602、AR-603((股)TOHPE製)NIPOL AR-31、AR-51、AR-54(日本ZEON(股)公司製)、Noxtite PA-301、PA-501、PA-502(NOK(股)公司製)、Teisan Resin WS-022、WS-023、SG-51、SG-70L、SG-80(Nagase ChemteX(股)公司製)、KH-LT、KH-CT(日立化成工業(股)公司製)等。「丙烯酸樹脂」可將2種以上組合使用。Specific examples of the commercially available acrylic resin include Arontack S-1511L, S-1511X, S-1515, and S-1517 (manufactured by Toago Corporation) Toaacron AR-601, AR-602, and AR-603 (( Co., Ltd.) NIPOL AR-31, AR-51, AR-54 (made by Japan ZEON Co., Ltd.), Noxtite PA-301, PA-501, PA-502 (made by NOK Co., Ltd.), Teisan Resin WS-022, WS-023, SG-51, SG-70L, SG-80 (manufactured by Nagase ChemteX Co., Ltd.), KH-LT, KH-CT (manufactured by Hitachi Chemical Co., Ltd.), and the like. Two or more types of "acrylic resin" can be used in combination.

[酚系硬化劑][phenolic hardener]

本發明中之「酚系硬化劑」主要係作為環氧樹脂之硬化劑運用。作為酚系硬化劑，只要係可作為具有酚性羥基之環氧樹脂之硬化劑運用則無特別限定。一般而言，使用分子內具有2個以上之酚性羥基的酚化合物，具體可舉出苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂等。市售之之酚系硬化劑，可舉出例如MEH-7700、MEH-7810、MEH-7851(明和化成(股)製)、NHN、CBN、GPH(日本化藥(股)製)、SN170、SN180、SN190、SN475、SN485、SN495、SN375、SN395(東都化成(股)製)、TD2090、TD2093、KA1160、KA1163、LA7052、LA7054、LA3018、LA1356(大日本油墨化學工業(股)製)等。「酚系硬化劑」可2種以上組合使用。The "phenolic curing agent" in the present invention is mainly used as a curing agent for an epoxy resin. The phenolic curing agent is not particularly limited as long as it can be used as a curing agent for an epoxy resin having a phenolic hydroxyl group. In general, a phenol compound having two or more phenolic hydroxyl groups in the molecule is used, and specific examples thereof include a phenol novolak resin and a cresol novolak resin. Commercially available phenolic curing agents, for example, MEH-7700, MEH-7810, MEH-7851 (made by Megumi Kasei Co., Ltd.), NHN, CBN, GPH (made by Nippon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Tohto Kasei Co., Ltd.), TD2090, TD2093, KA1160, KA1163, LA7052, LA7054, LA3018, LA1356 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.). The "phenolic curing agent" may be used in combination of two or more kinds.

將熱硬化性樹脂組成物之不揮發成分設為100重量%之情況，酚系硬化劑之含有量的上限值，由防止黏著力之低下或防止硬化劑成分變得過剩，引起耐熱性、絕緣性等之作為絕緣材料之重要特性的降低之觀點，以30重量%為佳，25重量%為更佳，以20重量%為更佳，15重量%為特佳。另一方面，將熱硬化性樹脂組成物之不揮發成分設為100重量%之情況，酚系硬化劑之含有量的下限值，由防止引起硬化劑成分變得過少，樹脂之硬化變得非常慢以外，且防止耐熱性、絕緣性等之作為絕緣材料之重要特性的降低之觀點，以5重量%為佳，10重量%為更佳。When the non-volatile content of the thermosetting resin composition is 100% by weight, the upper limit of the content of the phenol-based curing agent is such that the adhesion is lowered or the curing agent component is prevented from being excessive, thereby causing heat resistance. The insulating property or the like is preferably 30% by weight, more preferably 25% by weight, still more preferably 20% by weight, and particularly preferably 15% by weight. On the other hand, when the non-volatile component of the thermosetting resin composition is 100% by weight, the lower limit of the content of the phenolic curing agent is prevented from causing too little curing agent component, and the curing of the resin becomes In addition to being very slow, it is preferable to use 5% by weight, and more preferably 10% by weight, from the viewpoint of preventing deterioration of important characteristics of the insulating material such as heat resistance and insulation.

[無機填料][Inorganic Filler]

本發明中之「無機填料」主要係使形成之絕緣層的熱膨張率降低而作為目的使用。無機填充材具體可舉出二氧化矽、氧化鋁、硫酸鋇、滑石、白土、雲母粉、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、氧化鎂、氮化硼、硼酸鋁、鈦酸鋇、鈦酸鍶、鈦酸鈣、鈦酸鎂、鈦酸鉍、氧化鈦、鋯酸鋇、鋯酸鈣等，此些之中以無定形二氧化矽、熔融二氧化矽、結晶二氧化矽、合成二氧化矽等之二氧化矽為特別適合。二氧化矽以球狀者為佳。此些可1種或2種以上組合使用。The "inorganic filler" in the present invention is mainly used for the purpose of lowering the thermal expansion rate of the formed insulating layer. Specific examples of the inorganic filler include cerium oxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, and titanic acid. Barium, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium zirconate, calcium zirconate, etc., among which are amorphous ceria, molten ceria, and crystalline ceria. Separation of cerium oxide such as cerium oxide is particularly suitable. It is preferred that the cerium oxide is spherical. These may be used alone or in combination of two or more.

無機填料之平均粒徑的上限值，由絕緣信賴性之觀點，以3μm以下為佳，以1.5μm以下為更佳。另一方面，無機填料之平均粒徑的下限值，由在將熱硬化性樹脂組成物作為樹脂清漆之情況，防止清漆之黏度上昇而操作性降低之觀點，以0.05μm以上為佳。無機填料之最大粒子徑，由絕緣性之觀點，以5μm以下為佳。The upper limit of the average particle diameter of the inorganic filler is preferably 3 μm or less, and more preferably 1.5 μm or less from the viewpoint of insulation reliability. On the other hand, the lower limit of the average particle diameter of the inorganic filler is preferably 0.05 μm or more from the viewpoint of preventing the viscosity of the varnish from increasing and reducing the workability when the thermosetting resin composition is used as the resin varnish. The maximum particle diameter of the inorganic filler is preferably 5 μm or less from the viewpoint of insulation.

無機填料之平均粒徑係可藉由依據Mie散射理論之雷射繞射‧散射法而測定。具體而言，可藉由雷射繞射式粒度分佈測定裝置，將無機填充材之粒度分佈以體積基準製作，以其之中間粒徑作為平均粒徑而測定。測定樣品較佳可使用將無機填充材藉由超音波分散於水中者。雷射繞射式粒度分佈測定裝置可使用(股)堀場製作所製LA-500等。The average particle size of the inorganic filler can be determined by a laser diffraction ‧ scattering method according to the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be produced on a volume basis by a laser diffraction type particle size distribution measuring apparatus, and the intermediate particle diameter can be measured as an average particle diameter. As the measurement sample, those in which the inorganic filler is dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction type particle size distribution measuring apparatus, LA-500 or the like manufactured by Horiba, Ltd. can be used.

將熱硬化性樹脂組成物之不揮發成分設為100重量%之情況，無機填料之含有量的上限值，由防止接著薄膜之流動性降低而在真空層合機等之層合變得困難，接著薄膜硬化物之柔軟性受到大損傷，而引起原本之硬化物特性降低之觀點，以70重量%為佳，60重量%為更佳。另一方面，將熱硬化性樹脂組成物之不揮發成分設為100重量%之情況，無機填料之含有量的下限值，由防止樹脂清漆之流動性變得過高，操作性惡化且薄膜化變得困難之觀點，以30重量%為佳，20重量%為更佳。When the non-volatile content of the thermosetting resin composition is 100% by weight, the upper limit of the content of the inorganic filler is difficult to be laminated in a vacuum laminator or the like by preventing the fluidity of the film from being lowered. Then, the softness of the cured film is greatly impaired, and the viewpoint of lowering the properties of the cured product is preferably 70% by weight, more preferably 60% by weight. On the other hand, when the non-volatile content of the thermosetting resin composition is 100% by weight, the lower limit of the content of the inorganic filler is prevented from being excessively high in fluidity of the resin varnish, and the workability is deteriorated and the film is formed. The viewpoint of becoming difficult is preferably 30% by weight, more preferably 20% by weight.

尚且，為使耐濕性提升，無機填充材以藉由環氧矽烷耦合劑、胺基矽烷耦合劑、鈦酸酯系耦合劑等之表面處理劑經表面處理者為佳。此些可1種或2種以上組合使用。Further, in order to improve the moisture resistance, the inorganic filler is preferably subjected to surface treatment by a surface treatment agent such as an epoxy oxime coupling agent, an amino decane coupling agent, or a titanate coupling agent. These may be used alone or in combination of two or more.

[25℃下固形狀之環氧樹脂][Evaluation of epoxy resin at 25 ° C]

對於本發明之熱硬化性樹脂組成物，以伴隨著樹脂硬化物之交聯密度之提升而硬化物之Tg、斷裂強度之提升等之目的，亦可配合25℃下固形狀之環氧樹脂。25℃下固形狀之環氧樹脂，例如可舉出4官能萘型環氧樹脂、2官能二環戊二烯型環氧樹脂、參酚環氧樹脂等。市售者可舉出大日本油墨化學工業(股)製EXA4700、EXA7200、日本化藥(股)EPPN-502H等。「25℃下固形狀之環氧樹脂」亦可2種以上組合使用。配合25℃下固形狀之環氧樹脂之情況的含有量，將熱硬化性樹脂組成物之不揮發成分設為100重量%之情況，以30重量%以下為佳，較佳為20重量%以下。若含有量過大，接著薄膜在常溫中變脆，其操作性惡化。In the thermosetting resin composition of the present invention, an epoxy resin having a solid shape at 25 ° C may be blended for the purpose of improving the Tg of the cured product, the breaking strength, and the like with an increase in the crosslinking density of the cured resin. Examples of the epoxy resin having a solid shape at 25 ° C include a tetrafunctional naphthalene epoxy resin, a bifunctional dicyclopentadiene epoxy resin, and a phenol epoxy resin. Commercially available persons include EXA4700, EXA7200, and Nippon Chemical Co., Ltd. EPPN-502H manufactured by Dainippon Ink Chemical Industry Co., Ltd. "Epoxy resin having a solid shape at 25 ° C" may be used in combination of two or more kinds. When the amount of the non-volatile component of the thermosetting resin composition is 100% by weight, preferably 30% by weight or less, preferably 20% by weight or less, based on the content of the epoxy resin having a solid shape at 25 ° C. . If the content is too large, then the film becomes brittle at normal temperature, and its workability is deteriorated.

[熱可塑性樹脂][Thermoplastic resin]

對於本發明之熱硬化性樹脂組成物，以賦予硬化後之熱硬化性樹脂組成物適度之可撓性等為目的，可配合熱可塑性樹脂。作為熱可塑性樹脂，例如可舉出苯氧樹脂、聚乙烯縮醛樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚碸樹脂、聚碸樹脂等。「熱可塑性樹脂」可2種以上組合使用。熱硬化性樹脂組成物中之熱可塑性樹脂的含有量，以0.5~60重量%之比進行配合為佳，以3~50重量%之比進行配合為更佳。In the thermosetting resin composition of the present invention, a thermoplastic resin can be blended for the purpose of imparting appropriate flexibility to the thermosetting resin composition after curing. Examples of the thermoplastic resin include a phenoxy resin, a polyvinyl acetal resin, a polyimide resin, a polyamidoximine resin, a polyether oxime resin, and a polyfluorene resin. Two or more types of "thermoplastic resin" can be used in combination. The content of the thermoplastic resin in the thermosetting resin composition is preferably from 0.5 to 60% by weight, more preferably from 3 to 50% by weight.

苯氧樹脂之市售品，例如可舉出東都化成(股)製FX280、FX293、Japan Epoxy Resin(股)製YX8100、YL6954、YL6974等。For example, FX280, FX293, Japan Epoxy Resin Co., Ltd. YX8100, YL6954, YL6974, etc., which are manufactured by Toho Chemical Co., Ltd., may be mentioned.

聚乙烯縮醛樹脂，以聚乙烯丁醛樹脂為佳，聚乙烯縮醛樹脂之市售品，例如可舉出電氣化學工業(股)製、電化丁醛4000-2、5000-A、6000-C、6000-EP、積水化學工業(股)製S-Lec BH系列、BX系列、KS系列、BL系列、BM系列等。The polyvinyl acetal resin is preferably a polyvinyl butyral resin, and a commercially available product of a polyvinyl acetal resin, for example, an electric chemical industry (s), an electrochemical butyral 4000-2, 5000-A, 6000- C, 6000-EP, Sekisui Chemical Industry Co., Ltd. S-Lec BH series, BX series, KS series, BL series, BM series, etc.

聚醯亞胺之市售品，例如可舉出新日本理化(股)製之聚醯亞胺「Rikacoat SN20」及「Rikacoat PN20」。又，使2官能性羥基末端聚丁二烯、二異氰酸酯化合物及四鹼基酸酐而得之線狀聚醯亞胺(於日本特開2006-37083號公報所記載者)、含有聚矽氧烷骨架之聚醯亞胺(於日本特開2002-12667號公報、特開2000-319386號公報等所記載者)等之變性聚醯亞胺。A commercially available product of polyimine is, for example, a polyimine product "Rikacoat SN20" and "Rikacoat PN20" manufactured by Nippon Chemical and Chemical Co., Ltd. Further, a linear polyimine obtained by using a bifunctional hydroxyl terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (described in JP-A-2006-37083) contains a polyoxyalkylene oxide. A modified polyimine such as a polyimine of the skeleton (described in JP-A-2002-12667, JP-A-2000-319386, etc.).

聚醯胺醯亞胺之市售品，例如可舉出東洋紡績(股)製之聚醯胺醯亞胺「Vylomax HR11NN」及「Vylomax HR16NN」。又，日立化成工業(股)製之含有聚矽氧烷骨架的聚醯胺醯亞胺「KS9100」、「KS9300」等之變性聚醯胺醯亞胺。For example, a polyamido quinone imine "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd. are mentioned. In addition, denatured polyamidoximines such as polyacrylamide skeletons "KS9100" and "KS9300" which are made of a polyoxyalkylene skeleton manufactured by Hitachi Chemical Co., Ltd.

聚醚碸之市售品，例如可舉出住友化學(股)公司製之聚醚碸「PES5003P」。For example, a polyether oxime "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. is mentioned.

聚碸之市售品，例如可舉出Solvay Advanced Polymers(股)公司製之聚碸「P1700」、「P3500」等。For example, the "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd. may be mentioned.

[硬化促進劑][hardening accelerator]

對於本發明之熱硬化性樹脂組成物，以加入硬化劑使硬化時間縮短等之目的，可使其更含有硬化促進劑。作為硬化促進劑，例如可舉出咪唑系化合物、有機膦系化合物等，具體例可舉出2-甲基咪唑、三苯基膦等。此些可1種或2種以上組合使用。使用硬化促進劑之情況，較佳以硬化促進劑相對於環氧樹脂的0.1~3.0質量%之範圍內使用。The thermosetting resin composition of the present invention may further contain a curing accelerator for the purpose of shortening the curing time by adding a curing agent. Examples of the curing accelerator include an imidazole compound and an organic phosphine compound. Specific examples thereof include 2-methylimidazole and triphenylphosphine. These may be used alone or in combination of two or more. In the case of using a hardening accelerator, it is preferred to use the curing accelerator in an amount of 0.1 to 3.0% by mass based on the epoxy resin.

[添加劑][additive]

本發明之熱硬化性樹脂組成物，依據需要可更使其含有其他之成分。其他成分，例如可舉出有機磷系難燃劑、含有有機系氮之磷化合物、氮化合物、聚矽氧系難燃劑、金屬氫氧化物等之難燃劑；聚矽氧粉末、耐隆粉末、氟粉末等之有機充填劑；Orben、Benton等之增黏劑；聚矽氧系、氟系等之高分子系消泡劑或調平劑；咪唑系、噻唑系、***系、矽烷系耦合劑等之密著性賦予劑；酞花青藍、酞花青綠、碘綠、重氮黃、碳黑等之著色劑等。此些可1種或2種以上組合使用。The thermosetting resin composition of the present invention may further contain other components as needed. Examples of other components include an organic phosphorus-based flame retardant, a phosphorus compound containing an organic nitrogen, a nitrogen compound, a polysulfonium-based flame retardant, a metal hydroxide, and the like, and a flame retardant; Organic fillers such as powders and fluorine powders; tackifiers such as Orben and Benton; polymer antifoaming agents or leveling agents such as polyfluorene and fluorine; imidazole, thiazole, triazole and decane It is a tackifier for a coupling agent or the like; a coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, carbon black, or the like. These may be used alone or in combination of two or more.

[有機溶劑][Organic solvents]

作為調製清漆之情況的有機溶劑，例如可舉出丙酮、甲基乙基酮、環己酮等之酮類、乙酸乙酯、乙酸丁酯、溶纖劑乙酸酯、丙二醇單甲基醚乙酸酯、卡必醇乙酸酯等之乙酸酯類、溶纖劑、丁基卡必醇等之卡必醇類、甲苯、茬等之芳香族烴類、二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮等。此些可1種或2種以上組合使用。Examples of the organic solvent in the case of preparing a varnish include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl ether B. Acetate such as acid ester or carbitol acetate, cellosolve, carbitol such as butyl carbitol, aromatic hydrocarbon such as toluene or hydrazine, dimethylformamide, and dimethyl Ethyl acetamide, N-methylpyrrolidone, and the like. These may be used alone or in combination of two or more.

[接著薄膜][Next film]

本發明之接著薄膜係由支持體層、於該支持體層上藉由熱硬化性樹脂組成物所形成之具有黏著性的接著層所構成。接著層亦可形成於支持體層之兩面。The adhesive film of the present invention comprises a support layer and an adhesive adhesive layer formed of a thermosetting resin composition on the support layer. Subsequent layers may also be formed on both sides of the support layer.

支持體層可適宜使用塑膠薄膜。除塑膠薄膜以外，離型紙或銅箔、鋁箔等之金屬箔等也可作為支持體層使用。塑膠薄膜，可舉出聚對酞酸乙二酯(以下有略稱為「PET」)、聚萘二甲酸乙二酯等之聚酯、聚碳酸酯、丙烯、環狀聚烯烴、三乙醯纖維素、聚醚硫化物、聚醚酮、聚醯亞胺等。其中，以聚對酞酸乙二酯薄膜、聚萘二甲酸乙二酯薄膜為佳，特別係以便宜之聚對酞酸乙二酯薄膜為佳。於支持體中，特別係使用塑膠薄膜之情況，為了可由熱硬化性樹脂組成物之硬化物層剝離，以使用熱硬化性樹脂組成物層之被形成面經離型處理而具有離型層之支持體為佳。金屬箔雖也可藉由蝕刻溶液進行去除，將塑膠薄膜作為支持體而使熱硬化性樹脂組成物熱硬化之情況，如無離型層，由硬化物將塑膠薄膜剝離則變得困難。作為離型處理所使用之離型劑，只要係可將硬化物由支持體剝離者則無特別限定，例如可舉出聚矽氧系離型劑、醇酸樹脂系離型劑等。尚，亦可使用市售之附離型層的塑膠薄膜，較佳者例如可舉出具有將醇酸樹脂系離型劑作為主成分之離型層的PET薄膜，Lintec(股)製之SK-1、AL-5、AL-7等。又，塑膠薄膜可施以拋光處理、電暈處理，亦可在該處理面上形成離型層。並且，將銅箔作為支持體使用之情況，可無剝離地將該銅箔作為導體層使用。支持體之厚度並無特別限定，以10~150μm為佳，較佳使用25~50μm。A plastic film can be suitably used for the support layer. In addition to the plastic film, a metal foil such as a release paper or a copper foil or an aluminum foil can also be used as the support layer. Examples of the plastic film include polyesters of polyethylene terephthalate (hereinafter abbreviated as "PET"), polyethylene naphthalate, polycarbonate, propylene, cyclic polyolefin, and triethylene sulfonate. Cellulose, polyether sulfide, polyether ketone, polyimine, and the like. Among them, polyethylene terephthalate film and polyethylene naphthalate film are preferred, and in particular, a cheap polyethylene terephthalate film is preferred. In the case of using a plastic film, in particular, in order to peel off the cured layer of the thermosetting resin composition, the formed surface of the thermosetting resin composition layer is subjected to release treatment to have a release layer. The support is better. The metal foil may be removed by an etching solution, and the plastic film may be used as a support to thermally cure the thermosetting resin composition. If the release layer is not provided, it is difficult to peel off the plastic film from the cured product. The release agent to be used for the release treatment is not particularly limited as long as the cured product can be peeled off from the support, and examples thereof include a polyfluorene-based release agent and an alkyd-based release agent. Further, a commercially available release film of a release layer may be used. For example, a PET film having a release layer containing an alkyd resin release agent as a main component, and a SK manufactured by Lintec Co., Ltd. may be used. -1, AL-5, AL-7, etc. Further, the plastic film may be subjected to a buffing treatment or a corona treatment, and a release layer may be formed on the treated surface. Further, when the copper foil is used as a support, the copper foil can be used as a conductor layer without peeling. The thickness of the support is not particularly limited, and is preferably 10 to 150 μm, more preferably 25 to 50 μm.

熱硬化性樹脂組成物之接著層的厚度以1~200μm為佳，而作為適合薄型化之絕緣樹脂薄片，以5~100μm之範圍為較佳，5~40μ之範圍為更佳，5~30μm之範圍為特佳。接著層之厚度若過薄，則有電子零件之外部端子與電路之絕緣變得不足之傾向，又也有製造變得困難之傾向。且，接著層之厚度若過厚，則有多層印刷電路板之薄型化變得困難之傾向。The thickness of the adhesive layer of the thermosetting resin composition is preferably from 1 to 200 μm, and the insulating resin sheet suitable for thinning is preferably in the range of 5 to 100 μm, more preferably in the range of 5 to 40 μ, and 5 to 30 μm. The range is particularly good. If the thickness of the layer is too thin, the insulation between the external terminals of the electronic component and the circuit tends to be insufficient, and manufacturing tends to be difficult. Further, if the thickness of the subsequent layer is too thick, the thickness of the multilayer printed wiring board tends to be thin.

本發明之接著薄膜係首先將熱硬化性樹脂組成物溶解於有機溶劑作成樹脂清漆後，將此塗佈於支持體層上，藉由吹熱風等使溶劑乾燥，而可以既述之既定之厚度形成。In the adhesive film of the present invention, the thermosetting resin composition is first dissolved in an organic solvent to form a resin varnish, and then applied to a support layer, and the solvent is dried by blowing hot air or the like to form a predetermined thickness. .

接著層之保護薄膜可防止接著層表面上之灰塵等之附著或傷痕，且有效於提升使用絕緣樹脂薄片而製造之印刷電路板的信賴性。在此，作為保護薄膜可舉出聚乙烯、聚丙烯、聚氯乙烯等之聚烯烴、聚對酞酸乙二酯等之聚酯、聚碳酸酯、聚醯亞胺，更且可舉出離型紙、鋁箔等。尚，保護薄膜亦可施予拋光處理、電暈處理、設置聚矽氧系離型薄膜層等之離型處理。又，保護薄膜之厚度以作為1~40μm為佳。The protective film of the next layer can prevent adhesion or scratches of dust or the like on the surface of the adhesive layer, and is effective for improving the reliability of a printed circuit board manufactured using the insulating resin sheet. Here, examples of the protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, and polyesters such as polyethylene terephthalate, polycarbonate, and polyimine, and further examples thereof include Type paper, aluminum foil, etc. Further, the protective film may be subjected to a release treatment such as a buffing treatment, a corona treatment, or a polyfluorinated release film layer. Further, the thickness of the protective film is preferably 1 to 40 μm.

[零件內藏基板之製造方法][Method of Manufacturing Part Built-in Substrate]

藉由本發明之接著薄膜製造零件內藏基板之方法，其至少包含，(A)於接著薄膜之接著層上將電子零件固定之步驟、(B)使該接著層熱硬化形成絕緣層之步驟。本發明之接著薄膜，其特徵為具有可強固地進行固定零件的黏著力。The method for producing a component-embedded substrate by the adhesive film of the present invention comprises at least (A) a step of fixing an electronic component on a subsequent adhesive layer of the film, and (B) a step of thermally hardening the adhesive layer to form an insulating layer. The adhesive film of the present invention is characterized in that it has an adhesive force capable of firmly fixing a component.

具體而言，經過(A)於接著薄膜之接著層上將電子零件或電子零件與電路基板予以固定之步驟、(B)將該接著層熱硬化而形成絕緣層之步驟、(C)藉由密封用樹脂組成物、接著薄膜或預浸體，將電子零件或電子零件與電路基板予以密封之步驟，而製造出零件內藏基板。Specifically, (A) a step of fixing an electronic component or an electronic component to a circuit board on a subsequent layer of the film, (B) a step of thermally curing the adhesive layer to form an insulating layer, and (C) The resin composition for sealing, the film or the prepreg, and the step of sealing the electronic component or the electronic component and the circuit board to produce the component-embedded substrate.

首先，在(A)於接著薄膜之接著層上將電子零件，或電子零件與電路基板固定之步驟中，將電子零件及依據需要之電路基板固定於具有黏著性之接著層表面的既定位置。固定時之溫度的上限值，由效率良好進行作業之觀點，以70℃為佳，60℃為較佳，55℃為更佳，50℃為又更佳，45℃為特佳，40℃為最佳。另一方面，固定時之溫度的下限值，由使黏著性降低之觀點，以-20℃為佳，-10℃為較佳，-5℃為更佳，0℃為又更佳，5℃為特佳，10℃為最佳。First, in the step of (A) fixing the electronic component or the electronic component to the circuit board on the adhesive layer following the film, the electronic component and the circuit substrate as needed are fixed to a predetermined position on the surface of the adhesive adhesive layer. The upper limit of the temperature at the time of fixing is preferably 70 ° C from the viewpoint of efficient operation, preferably 60 ° C, more preferably 55 ° C, more preferably 50 ° C, and 45 ° C is particularly good, 40 ° C For the best. On the other hand, the lower limit of the temperature at the time of fixing is preferably -20 ° C from the viewpoint of lowering the adhesion, preferably -10 ° C, more preferably -5 ° C, and more preferably 0 ° C, 5 °C is especially good, 10 °C is the best.

其次，藉由(B)使該接著層熱硬化而形成絕緣層之步驟，電子零件或電路基板被更強固地固定於所形成之絕緣層上。熱硬化之硬化溫度以140~200℃為佳，150~180℃為更佳。又，硬化時間以15分~2小時為佳，30~90分之範圍為更佳。Next, the step of forming the insulating layer by (B) thermally curing the adhesive layer, the electronic component or the circuit substrate is more firmly fixed to the formed insulating layer. The hardening temperature of the heat hardening is preferably 140 to 200 ° C, and more preferably 150 to 180 ° C. Further, the hardening time is preferably 15 minutes to 2 hours, and the range of 30 to 90 minutes is more preferable.

其後，(C)藉由密封用樹脂組成物、接著薄膜或預浸體將電子零件或電子零件與電路基板予以密封。密封可採用對當業者而言公知之方法。例如可舉出，於支持體上將已形成熱硬化性樹脂組成物層的接著薄膜藉由真空層合機等之層合機進行層合而後熱硬化之方法，將預浸體藉由加壓層合而層合後熱硬化之方法等。Thereafter, (C) the electronic component or the electronic component is sealed to the circuit board by the resin composition for sealing, the film or the prepreg. The sealing can be carried out by a method known to the practitioner. For example, a film obtained by laminating a film of a thermosetting resin composition layer on a support by a laminator such as a vacuum laminator and then thermally hardening may be used to pressurize the prepreg by pressurization. A method of laminating and laminating and then thermally hardening.

藉由使用本發明之接著薄膜，(A)步驟、(B)步驟、(C)步驟中，以使用可伴隨振動之運送機帶為佳。又，藉由使用本發明之接著薄膜，可使接著層可直接作為熱硬化層。且，藉由使用本發明之接著薄膜，在高位置精度下將電子零件予以密封則成為可能。另外，由於步驟數也受到削減，成為也可更便宜地製造零件內藏基板。By using the adhesive film of the present invention, in the steps (A), (B), and (C), it is preferred to use a conveyor belt that can accompany vibration. Further, by using the adhesive film of the present invention, the adhesive layer can be directly used as the thermosetting layer. Further, by using the adhesive film of the present invention, it is possible to seal the electronic component with high positional accuracy. Further, since the number of steps is also reduced, it is also possible to manufacture the component built-in substrate more inexpensively.

[實施例][Examples]

以下，展示實施例更加詳細說明本發明，而此無論在任何意義中皆非係為限制本發明者。尚，以下之記載中，「份」則係指「重量份」。In the following, the present invention will be described in more detail, and it is not intended to limit the invention in any way. In the following description, "parts" means "parts by weight".

(實施例1)(Example 1)

將雙酚型環氧樹脂(東都化成(股)製「ZX1059」、環氧當量約165)20重量份、環氧化聚丁二烯(Daicel化學(股)製「PB3600M」、不揮發份80重量%之MEK溶液)8重量份、萘型4官能環氧樹脂(大日本油墨(股)製「HP-4700」)14重量份、酚醛清漆型酚樹脂(大日本油墨(股)製「LA7054」、羥基當量約125、不揮發份60重量%之甲基乙基酮(以下略稱為MEK)溶液)25重量份、球形二氧化矽((股)Admatechs製「SO-C4」)40重量份、難燃填料(三光(股)製「HCA-HQ」)6重量份、有機填料(Ganz化成(股)製「AC3816N」)3重量份、丁醛樹脂(將積水化學(股)製「BL-1」與甲苯及甲醇以1：1進行稀釋而成之不揮發份為15%之溶液者)10重量份，及以丙烯酸酯共聚樹脂作為丙烯酸樹脂((股)Nagase ChemteX(股)製「SG-70L」、不揮發份12.5重量%之MEK與甲苯之1.3：1混合溶液)0.85重量份，與石油腦(純正化學(股)製「IP solvent 150」)5重量份及MEK21重量份一起進行混合，以高速回轉混合機均勻分散，製成熱硬化性樹脂組成物清漆(樹脂組成物(不揮發份)中之液狀環氧樹脂25重量%、酚系硬化劑14.2重量%、丙烯酸樹脂0.10重量%)。其次，將樹脂組成物清漆在經離型處理之聚對酞酸乙二酯薄膜(厚度38μm)(Lintec(股)製AL-5)(以下，略稱為38μm離型PET)上，以刮條塗佈機進行均勻塗佈使其乾燥後之樹脂組成物層(接著層)之厚度成為40μm，在65~120℃(平均100℃)下乾燥10分鐘(樹脂組成物層中之殘留溶劑量：約1重量%)。在乾燥後之樹脂組成物層表面上貼合經離型處理之聚酞酸乙二酯薄膜(厚度25μm)(Lintec(股)製AL-5)(以下，略稱為25μm離型PET)，製成薄片狀之具有3層構造的接著薄膜。Bisphenol type epoxy resin ("ZX1059" manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 165) 20 parts by weight, epoxidized polybutadiene ("PB3600M" manufactured by Daicel Chemical Co., Ltd., 80 parts by weight of nonvolatile matter) 8 parts by weight of the MEK solution, 14 parts by weight of a naphthalene type tetrafunctional epoxy resin ("HP-4700" manufactured by Dainippon Ink Co., Ltd.), and a novolak type phenol resin ("LA7054" manufactured by Dainippon Ink Co., Ltd." 25 parts by weight of a methyl ethyl ketone (hereinafter abbreviated as MEK) solution having a hydroxyl group equivalent of about 125 and a nonvolatile content of 60% by weight, and 40 parts by weight of spherical cerium oxide ("SO-C4" manufactured by Admatechs). 6 parts by weight of a flame-retardant filler ("HCA-HQ" manufactured by Sanko Co., Ltd.), 3 parts by weight of an organic filler ("AC3816N" manufactured by Ganz Chemical Co., Ltd.), and butyral resin ("BL" -1" 10 parts by weight of a solution having a nonvolatile content of 15% with toluene and methanol diluted by 1:1), and an acrylate copolymer resin as an acrylic resin ("Nagase ChemteX") SG-70L", a non-volatile content of 12.5% by weight of a 1.3:1 mixed solution of MEK and toluene), 0.85 parts by weight, and 5 parts by weight of petroleum brain ("IP solvent 150" manufactured by Junsei Chemical Co., Ltd.) and MEK21 weight. The mixture was mixed together and uniformly dispersed in a high-speed rotary mixer to obtain a thermosetting resin composition varnish (25% by weight of a liquid epoxy resin in a resin composition (nonvolatile matter), 14.2% by weight of a phenolic curing agent, and acrylic acid. Resin 0.10% by weight). Next, the resin composition varnish was subjected to a release-treated polyethylene terephthalate film (thickness: 38 μm) (AL-5 manufactured by Lintec) (hereinafter, abbreviated as 38 μm release PET) to scrape The thickness of the resin composition layer (adhesive layer) after uniform coating by the strip coater was 40 μm, and dried at 65 to 120 ° C (average 100 ° C) for 10 minutes (the amount of residual solvent in the resin composition layer) : about 1% by weight). A release-treated polyethylene terephthalate film (thickness 25 μm) (AL-5 manufactured by Lintec Co., Ltd.) (hereinafter, abbreviated as 25 μm release PET) was attached to the surface of the dried resin composition layer. A sheet-like adhesive film having a three-layer structure was formed.

(實施例2)(Example 2)

除了將實施例1之雙酚型環氧樹脂(東都化成(股)製「ZX1059」、環氧當量約165)變更為21重量份，丙烯酸酯共聚樹脂(Nagase ChemteX(股)製「SG-70L」、不揮發份12.5重量%之MEK與甲苯之1.3：1混合溶液)變更為17.2重量份(樹脂組成物(不揮發份)中之液狀環氧樹脂25.0重量%、酚系硬化劑13.9重量%、丙烯酸樹脂2重量%)以外，其他藉由與實施例1相同之方法得到接著薄膜。In addition, the bisphenol type epoxy resin ("ZX1059" manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 was changed to 21 parts by weight, and acrylate copolymer resin ("SG-70L" manufactured by Nagase ChemteX Co., Ltd. The non-volatile content of 12.5% by weight of a 1.3:1 mixed solution of MEK and toluene was changed to 17.2 parts by weight (25.0% by weight of the liquid epoxy resin in the resin composition (nonvolatile matter), and 13.9 weight of the phenolic curing agent). An adhesive film was obtained by the same method as in Example 1 except that % and acrylic resin (2% by weight).

(實施例3)(Example 3)

除了將實施例1之雙酚型環氧樹脂(東都化成(股)製「ZX1059」、環氧當量約165)變更為22重量份，萘型4官能環氧樹脂(大日本油墨(股)製「HP-4700」)變更為13重量份，更將丙烯酸酯共聚樹脂(Nagase ChemteX(股)製「SG-70L」、不揮發份12.5重量%之MEK與甲苯之1.3：1混合溶液)變更為44.5重量份(樹脂組成物(不揮發份)中之液狀環氧樹脂25.0重量%、酚系硬化劑13.5重量%、丙烯酸樹脂5重量%)以外，其他藉由與實施例1相同之方法得到接著薄膜。In addition, the bisphenol type epoxy resin (ZX1059, manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: 165) of the first embodiment was changed to 22 parts by weight, and a naphthalene type tetrafunctional epoxy resin (manufactured by Dainippon Ink Co., Ltd.) was used. "HP-4700" was changed to 13 parts by weight, and an acrylate copolymer resin ("SG-70L" manufactured by Nagase ChemteX Co., Ltd., a 1.3:1 mixed solution of a nonvolatile portion of MEK and toluene) was changed to 4: 4 parts by weight (25.0% by weight of the liquid epoxy resin in the resin composition (nonvolatile matter), 13.5% by weight of the phenolic curing agent, and 5% by weight of the acrylic resin) were obtained by the same method as in Example 1. Then the film.

(實施例4)(Example 4)

除了將實施例1之雙酚型環氧樹脂(東都化成(股)製「ZX1059」、環氧當量約165)變更為26重量份，更將萘型4官能環氧樹脂(大日本油墨(股)製「HP-4700」)變更為9重量份(樹脂組成物(不揮發份)中之液狀環氧樹脂30重量%、酚系硬化劑14.2重量%、丙烯酸樹脂0.1重量%)以外，其他藉由與實施例1相同之方法得到接著薄膜。In addition, the bisphenol type epoxy resin ("ZX1059" manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 was changed to 26 parts by weight, and a naphthalene type 4-functional epoxy resin (large Japanese ink) The "HP-4700" was changed to 9 parts by weight (30% by weight of the liquid epoxy resin in the resin composition (nonvolatile matter), 14.2% by weight of the phenolic curing agent, and 0.1% by weight of the acrylic resin). The adhesive film was obtained by the same method as in Example 1.

(實施例5)(Example 5)

除了將實施例1之雙酚型環氧樹脂(東都化成(股)製「ZX1059」、環氧當量約165)變更為26重量份，萘型4官能環氧樹脂(大日本油墨(.股)製「HP-4700」)變更為8重量份，更將丙烯酸酯共聚樹脂(Nagase ChemteX(股)製「SG-70L」、不揮發份12.5重量%之MEK與甲苯之1.3：1混合溶液)變更為17.3重量份(樹脂組成物(不揮發份)中之液狀環氧樹脂30重量%、酚系硬化劑13.9重量%、丙烯酸樹脂2重量%)以外，其他藉由與實施例1相同之方法得到接著薄膜。In addition to changing the bisphenol type epoxy resin ("ZX1059" manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 to 26 parts by weight, a naphthalene type 4-functional epoxy resin (Daily Ink (.) The amount of the "HP-4700" was changed to 8 parts by weight, and the acrylate copolymer resin ("SG-70L" manufactured by Nagase ChemteX Co., Ltd., and the 1.3:1 mixed solution of MEK and toluene having a nonvolatile content of 12.5% by weight) was changed. The same method as in Example 1 except for 17.3 parts by weight (30% by weight of the liquid epoxy resin in the resin composition (nonvolatile matter), 13.9% by weight of the phenolic curing agent, and 2% by weight of the acrylic resin) A follow-up film is obtained.

(實施例6)(Example 6)

除了將實施例1之雙酚型環氧樹脂(東都化成(股)製「ZX1059」、環氧當量約165)變更為27重量份，萘型4官能環氧樹脂(大日本油墨(股)製「HP-4700」)變更為7重量份，更將丙烯酸酯共聚樹脂(Nagase ChemteX(股)製「SG-70L」、不揮發份12.5重量%之MEK與甲苯之1.3：1混合溶液)變更44.5重量份(樹脂組成物(不揮發份)中之液狀環氧樹脂30重量%、酚系硬化劑13.5重量%、丙烯酸樹脂5重量%)以外，其他藉由與實施例1相同之方法得到接著薄膜。In addition, the bisphenol type epoxy resin (ZX1059, manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 was changed to 27 parts by weight, and a naphthalene type 4-functional epoxy resin (manufactured by Dainippon Ink Co., Ltd.) was used. "HP-4700") was changed to 7 parts by weight, and an acrylate copolymer resin ("SG-70L" manufactured by Nagase ChemteX Co., Ltd., a 1.3:1 mixed solution of 0.15 wt% of non-volatile MEK and toluene) was changed to 44.5. The same procedure as in Example 1 was carried out except for a part by weight (30% by weight of the liquid epoxy resin in the resin composition (nonvolatile matter), 13.5% by weight of the phenolic curing agent, and 5% by weight of the acrylic resin). film.

(實施例7)(Example 7)

除了將實施例1之雙酚型環氧樹脂(東都化成(股)製「ZX1059」、環氧當量約165)變更為35重量份，去除萘型4官能環氧樹脂(大日本油墨(股)製「HP-4700」)，將球形二氧化矽((股)Admatechs製「SO-C4」)變更為37重量份，丙烯酸酯共聚樹脂(Nagase ChemteX(股)製「SG-70L」、不揮發份12.5重量%之MEK與甲苯之1.3：1混合溶液)變更為0.83重量份，更將MEK變更為5量份(樹脂組成物(不揮發份)中之液狀環氧樹脂39.8重量%、酚系硬化劑14.5重量%、丙烯酸樹脂0.1重量%)以外，其他藉由與實施例1相同之方法得到接著薄膜。In addition, the bisphenol type epoxy resin (ZX1059, manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 was changed to 35 parts by weight, and the naphthalene type 4-functional epoxy resin (Daily Ink) was removed. "HP-4700", the spherical cerium oxide ("SO-C4" manufactured by Admatechs) was changed to 37 parts by weight, acrylate copolymer resin ("SG-70L" manufactured by Nagase ChemteX Co., Ltd., non-volatile The content of 12.5% by weight of a 1.3:1 mixed solution of MEK and toluene was changed to 0.83 parts by weight, and the MEK was changed to 5 parts by weight (the liquid epoxy resin in the resin composition (nonvolatile matter) was 39.8 wt%, and phenol An adhesive film was obtained by the same method as in Example 1 except that the curing agent was 14.5% by weight and the acrylic resin was 0.1% by weight.

(實施例8)(Example 8)

除了將實施例1之雙酚型環氧樹脂(東都化成(股)製「ZX1059」、環氧當量約165)變更為35重量份，去除萘型4官能環氧樹脂(大日本油墨(股)製「HP-4700」)，將球形二氧化矽((股)Admatechs製「SO-C4」)變更35重量份，更將丙烯酸酯共聚樹脂(Nagase ChemteX(股)製「SG-70L」、不揮發份12.5重量%之MEK與甲苯之1.3：1混合溶液)變更為16.4重量份，更將MEK變更為5量份(樹脂組成物(不揮發份)中之液狀環氧樹脂39.8重量%、酚系硬化劑14.6重量%、丙烯酸樹脂1.99重量%)以外，其他藉由與實施例1相同之方法得到接著薄膜。In addition, the bisphenol type epoxy resin (ZX1059, manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 was changed to 35 parts by weight, and the naphthalene type 4-functional epoxy resin (Daily Ink) was removed. "HP-4700"), 35 parts by weight of spherical cerium oxide ("SO-C4" manufactured by Admatechs), and acrylate copolymer resin ("SG-70L" manufactured by Nagase ChemteX Co., Ltd.) The volatile solution (12.5 wt% of a 1.3:1 mixed solution of MEK and toluene) was changed to 16.4 parts by weight, and the MEK was changed to 5 parts by weight (the liquid epoxy resin in the resin composition (nonvolatile matter) was 39.8 wt%, An adhesive film was obtained by the same method as in Example 1 except that the phenolic curing agent was 14.6% by weight and the acrylic resin was 1.99% by weight.

(實施例9)(Example 9)

除了將實施例1之雙酚型環氧樹脂(東都化成(股)製「ZX1059」、環氧當量約165)變更35重量份，去除萘型4官能環氧樹脂(大日本油墨(股)製「HP-4700」)，將球形二氧化矽((股)Admatechs製「SO-C4」)變更為32重量份，且將丙烯酸酯共聚樹脂(Nagase ChemteX(股)製「SG-70L」、不揮發份12.5重量%之MEK與甲苯之1.3：1混合溶液)變更為41重量份，更將MEK變更為5量份(樹脂組成物(不揮發份)中之液狀環氧樹脂40重量%、酚系硬化劑14.6重量%、丙烯酸樹脂4.99重量%)以外，其他藉由與實施例1相同之方法得到接著薄膜。The bisphenol-type epoxy resin (ZX1059, manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 was changed by 35 parts by weight to remove a naphthalene type tetrafunctional epoxy resin (manufactured by Dainippon Ink Co., Ltd.). "HP-4700"), the spherical cerium oxide ("SO-C4" manufactured by Admatechs) was changed to 32 parts by weight, and the acrylate copolymer resin ("SG-70L" manufactured by Nagase ChemteX Co., Ltd.) was not used. The volatile solution (12.5 wt% of a 1.3:1 mixed solution of MEK and toluene) was changed to 41 parts by weight, and the MEK was changed to 5 parts by weight (40% by weight of the liquid epoxy resin in the resin composition (nonvolatile matter), An adhesive film was obtained by the same method as in Example 1 except that the phenolic curing agent was 14.6% by weight and the acrylic resin was 4.99% by weight.

(比較例1)(Comparative Example 1)

除了將實施例1之丙烯酸酯共聚樹脂(Nagase ChemteX(股)製「SG-70L」、不揮發份12.5重量%之MEK與甲苯之1.3：1混合溶液)變更為0.43重量份(樹脂組成物(不揮發份)中之液狀環氧樹脂25重量%、酚系硬化劑14.2重量%、丙烯酸樹脂0.05重量%)以外，其他藉由與實施例1相同之方法得到接著薄膜。In addition, the acrylate copolymer resin of Example 1 ("SG-70L" manufactured by Nagase ChemteX Co., Ltd., a 1.3:1 mixed solution of non-volatile 12.5% by weight of MEK and toluene) was changed to 0.43 parts by weight (resin composition ( A film was obtained by the same method as in Example 1 except that 25% by weight of the liquid epoxy resin, 14.2% by weight of the phenolic curing agent, and 0.05% by weight of the acrylic resin in the nonvolatile matter.

(比較例2)(Comparative Example 2)

除了將實施例1之雙酚型環氧樹脂(東都化成(股)製「ZX1059」、環氧當量約165)變更為22重量份，萘型4官能環氧樹脂(大日本油墨(股)製「HP-4700」)變更13重量份，更將丙烯酸酯共聚樹脂(Nagase ChemteX(股)製「SG-70L」、不揮發份12.5重量%之MEK與甲苯之1.3：1混合溶液)變更為53.9重量份(樹脂組成物(不揮發份)中之液狀環氧樹脂25重量%、酚系硬化劑13.4重量%、丙烯酸樹脂6重量%)以外，其他藉由與實施例1相同之方法得到接著薄膜。In addition, the bisphenol type epoxy resin (ZX1059, manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: 165) of the first embodiment was changed to 22 parts by weight, and a naphthalene type tetrafunctional epoxy resin (manufactured by Dainippon Ink Co., Ltd.) was used. "HP-4700") was changed to 13 parts by weight, and an acrylate copolymer resin ("SG-70L" manufactured by Nagase ChemteX Co., Ltd., a 1.3:1 mixed solution of 0.10% by weight of MEK and toluene) was changed to 53.9. The same procedure as in Example 1 was carried out except for a part by weight (25% by weight of the liquid epoxy resin in the resin composition (nonvolatile matter), 13.4% by weight of the phenolic curing agent, and 6% by weight of the acrylic resin). film.

(比較例3)(Comparative Example 3)

除了將實施例1之雙酚型環氧樹脂(東都化成(股)製「ZX1059」、環氧當量約165)變更為26重量份，萘型4官能環氧樹脂(大日本油墨(股)製「HP-4700」)變更為9重量份，更將丙烯酸酯共聚樹脂(Nagase ChemteX(股)製「SG-70L」、不揮發份12.5重量%之MEK與甲苯之1.3：1混合溶液)變更為0.43重量份(樹脂組成物(不揮發份)中之液狀環氧樹脂30重量%、酚系硬化劑14.2重量%、丙烯酸樹脂0.05重量%)以外，其他藉由與實施例1相同之方法得到接著薄膜。In addition, the bisphenol type epoxy resin (ZX1059, manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: 165) of the first embodiment was changed to 26 parts by weight, and a naphthalene type tetrafunctional epoxy resin (manufactured by Dainippon Ink Co., Ltd.) was used. "HP-4700") was changed to 9 parts by weight, and an acrylate copolymer resin ("SG-70L" manufactured by Nagase ChemteX Co., Ltd., a 1.3:1 mixed solution of 0.10% by weight of MEK and toluene) was changed to 0.43 parts by weight (30% by weight of the liquid epoxy resin in the resin composition (nonvolatile matter), 14.2% by weight of the phenolic curing agent, and 0.05% by weight of the acrylic resin) were obtained by the same method as in Example 1. Then the film.

(比較例4)(Comparative Example 4)

除了將實施例1之雙酚型環氧樹脂(東都化成(股)製「ZX1059」、環氧當量約165)變更為28重量份，萘型4官能環氧樹脂(大日本油墨(股)製「HP-4700」)變更為7重量份，更將丙烯酸酯共聚樹脂(Nagase ChemteX(股)製「SG-70L」、不揮發份12.5重量%之MEK與甲苯之1.3：1混合溶液)變更為54重量份(樹脂組成物(不揮發份)中之液狀環氧樹脂30重量%、酚系硬化劑13.3重量%、丙烯酸樹脂6重量%)以外，其他藉由與實施例1相同之方法得到接著薄膜。In addition, the bisphenol type epoxy resin (ZX1059, manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 was changed to 28 parts by weight, and a naphthalene type 4-functional epoxy resin (manufactured by Dainippon Ink Co., Ltd.) was used. "HP-4700") was changed to 7 parts by weight, and an acrylate copolymer resin ("SG-70L" manufactured by Nagase ChemteX Co., Ltd., a 1.3:1 mixed solution of 0.10% by weight of MEK and toluene) was changed to 54 parts by weight (30% by weight of the liquid epoxy resin in the resin composition (nonvolatile matter), 13.3% by weight of the phenolic curing agent, and 6% by weight of the acrylic resin) were obtained in the same manner as in Example 1. Then the film.

(比較例5)(Comparative Example 5)

除了將實施例1之雙酚型環氧樹脂(東都化成(股)製「ZX1059」、環氧當量約165)變更為35重量份，去除萘型4官能環氧樹脂(大日本油墨(股)製「HP-4700」)，將球形二氧化矽((股)Admatechs製「SO-C4」)變更為37重量份，更將丙烯酸酯共聚樹脂(Nagase ChemteX(股)製「SG-70L」、不揮發份12.5重量%之MEK與甲苯之1.3：1混合溶液)變更為0.4重量份，更將MEK變更5量部(樹脂組成物(不揮發份)中之液狀環氧樹脂40重量%、酚系硬化劑14.6重量%、丙烯酸樹脂0.05重量%)以外，其他藉由與實施例1相同之方法得到接著薄膜。In addition, the bisphenol type epoxy resin (ZX1059, manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 was changed to 35 parts by weight, and the naphthalene type 4-functional epoxy resin (Daily Ink) was removed. "HP-4700", the spherical cerium oxide ("SO-C4" manufactured by Admatechs) was changed to 37 parts by weight, and the acrylate copolymer resin ("SG-70L" manufactured by Nagase ChemteX Co., Ltd.) was further changed. The amount of the non-volatile portion (12.5 wt% of the mixed solution of MEK and toluene of 1.3:1) was changed to 0.4 part by weight, and the MEK was changed by 5 parts (the weight of the liquid epoxy resin in the resin composition (nonvolatile matter) was 40% by weight, An adhesive film was obtained by the same method as in Example 1 except that the phenolic curing agent was 14.6% by weight and the acrylic resin was 0.05% by weight.

(比較例6)(Comparative Example 6)

除了將實施例1之雙酚型環氧樹脂(東都化成(股)製「ZX1059」、環氧當量約165)變更為35重量份，去除萘型4官能環氧樹脂(大日本油墨(股)製「HP-4700」)，將球形二氧化矽((股)Admatechs製「SO-C4」)變更為30重量份，且將丙烯酸酯共聚樹脂(Nagase ChemteX(股)製「SG-70L」、不揮發份12.5重量%之MEK與甲苯之1.3：1混合溶液)變更為49.2重量份，更將MEK變更為5量份(樹脂組成物(不揮發份)中之液狀環氧樹脂40重量%、酚系硬化劑14.6重量%、丙烯酸樹脂6重量%)，其他與藉由實施例1相同之方法得到接著薄膜。In addition, the bisphenol type epoxy resin (ZX1059, manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 was changed to 35 parts by weight, and the naphthalene type 4-functional epoxy resin (Daily Ink) was removed. "HP-4700", the spherical cerium oxide ("SO-C4" manufactured by Admatechs) was changed to 30 parts by weight, and an acrylate copolymer resin ("SG-70L" manufactured by Nagase ChemteX Co., Ltd.) was used. The non-volatile content of 12.5% by weight of a 1.3:1 mixed solution of MEK and toluene was changed to 49.2 parts by weight, and the MEK was changed to 5 parts by weight (40% by weight of the liquid epoxy resin in the resin composition (nonvolatile matter)) Further, a film was obtained in the same manner as in Example 1 except that the phenolic curing agent was 14.6% by weight and the acrylic resin was 6% by weight.

(比較例7)(Comparative Example 7)

除了將實施例1之雙酚型環氧樹脂(東都化成(股)製「ZX1059」、環氧當量約165)變更為16重量份，萘型4官能環氧樹脂(大日本油墨(股)製「HP-4700」)變更為19重量份，更將丙烯酸酯共聚樹脂(Nagase ChemteX(股)製「SG-70L」、不揮發份12.5重量%之MEK與甲苯之1.3：1混合溶液)變更為17.2重量份(樹脂組成物(不揮發份)中之液狀環氧樹脂20重量%、酚系硬化劑13.9重量%、丙烯酸樹脂2重量%)以外，其他藉由與實施例1相同之方法得到接著薄膜。In addition to changing the bisphenol type epoxy resin ("ZX1059" manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 to 16 parts by weight, a naphthalene type tetrafunctional epoxy resin (manufactured by Dainippon Ink Co., Ltd.) "HP-4700") was changed to 19 parts by weight, and an acrylate copolymer resin ("SG-70L" manufactured by Nagase ChemteX Co., Ltd., a 1.3:1 mixed solution of 0.10% by weight of MEK and toluene) was changed to 17.2 parts by weight (20% by weight of the liquid epoxy resin in the resin composition (nonvolatile matter), 13.9% by weight of the phenolic curing agent, and 2% by weight of the acrylic resin) were obtained by the same method as in Example 1. Then the film.

(比較例8)(Comparative Example 8)

除了將實施例1之雙酚型環氧樹脂(東都化成(股)製「ZX1059」、環氧當量約165)變更為35重量份，去除萘型4官能環氧樹脂(大日本油墨(股)製「HP-4700」)，將球形二氧化矽((股)Admatechs製「SO-C4」)變更為23重量份，且將丙烯酸酯共聚樹脂(Nagase ChemteX(股)製「SG-70L」、不揮發份12.5重量%之MEK與甲苯之1.3：1混合溶液)變更為14.5重量份，更將MEK變更為5量份(樹脂組成物(不揮發份)中之液狀環氧樹脂45重量%、酚系硬化劑16.6重量%、丙烯酸樹脂2重量%)以外，其他藉由與實施例1相同之方法得到接著薄膜。In addition, the bisphenol type epoxy resin (ZX1059, manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 was changed to 35 parts by weight, and the naphthalene type 4-functional epoxy resin (Daily Ink) was removed. "HP-4700", a spherical cerium oxide ("SO-C4" manufactured by Admatechs) was changed to 23 parts by weight, and an acrylate copolymer resin ("SG-70L" manufactured by Nagase ChemteX Co., Ltd.) was used. The non-volatile content of 12.5% by weight of a 1.3:1 mixed solution of MEK and toluene was changed to 14.5 parts by weight, and the MEK was changed to 5 parts by weight (45% by weight of the liquid epoxy resin in the resin composition (nonvolatile matter)) An adhesive film was obtained by the same method as in Example 1 except that the phenolic curing agent was 16.6 wt% and the acrylic resin was 2 wt%.

使用實施例及比較例之接著薄膜進行Tg(玻璃轉移溫度)測定、絕緣電阻值之測定、黏著(tack)力之測定、25μm離型PET(覆蓋薄膜)剝離性之評價、零件固定性之評價、最大零件位置偏差量之測定。Tg (glass transition temperature) measurement, measurement of insulation resistance value, measurement of adhesion (tack) force, evaluation of peeling property of 25 μm release PET (cover film), and evaluation of component fixability were carried out using the adhesive films of the examples and the comparative examples. Determination of the maximum part position deviation.

＜Tg(玻璃轉移溫度)測定＞<Tg (glass transition temperature) measurement>

將實施例及比較例所作成之接著薄膜由25μm離型PET剝離，藉由分批式真空加壓層合機(Nichigo-Morton(股)製，「MortoN-724」)，層合於200mm×200mm之聚醯亞胺薄膜(宇部興產(股)製，「UPILEX50S」)。30秒鐘真空吸引後使用耐壓橡膠，30秒鐘1kg/cm2 之壓力下加壓之條件中進行。將以上述所作成之樣品的38μm離型PET剝離，放入分批熱處理機在180℃中加熱90分鐘，使樹脂組成物層(接著層)硬化。將本硬化物之Tg藉由熱分析裝置(Seiko Instruments(股)製、「DMS6100」)進行測定。The film formed in the examples and the comparative examples was peeled off from 25 μm release PET, and laminated by a batch type vacuum pressure laminator (manufactured by Nichigo-Morton Co., Ltd., "Morto N-724") at 200 mm × 200mm polyimide film (made by Ube Hiroshi Co., Ltd., "UPILEX50S"). After vacuum suction for 30 seconds, pressure-resistant rubber was used, and the pressure was applied under a pressure of 1 kg/cm 2 for 30 seconds. The 38 μm release PET of the sample prepared above was peeled off, and placed in a batch heat treatment machine at 180 ° C for 90 minutes to harden the resin composition layer (the subsequent layer). The Tg of the cured product was measured by a thermal analysis apparatus (manufactured by Seiko Instruments Co., Ltd., "DMS6100").

＜絕緣電阻值之測定＞<Measurement of insulation resistance value>

將實施例及比較例所作成之接著薄膜之25μm離型PET剝離，分批式真空加壓層合機(Nichigo-Morton(股)製、「Morton-724」)層合於L/S=15μm/15μm之TAB帶(三井金屬(股)製、「AJ-C0002-30/40」)。層合係以30秒鐘真空吸引後使用耐壓橡膠，30秒鐘1kg/cm2 之壓力下加壓之條件中進行。將上述所作成之樣品的38μm離型PET剝離，分批熱處理機中在180℃中加熱90分鐘，使樹脂組成物層(接著層)硬化。測定硬化後之樣品的電阻值，將其作為初期電阻值。其次，在HAST試驗機(楠本化成(股)製、「ETAC PM422」)中以130℃、85重量%Rh之條件下，放置100小時，測定其後電阻值(HAST電阻值)。The 25 μm release PET of the film formed in the examples and the comparative examples was peeled off, and a batch vacuum pressure laminator (manufactured by Nichigo-Morton Co., Ltd., "Morton-724") was laminated on L/S = 15 μm. /15μm TAB tape (manufactured by Mitsui Metals Co., Ltd., "AJ-C0002-30/40"). The lamination was carried out under vacuum for 30 seconds, and then pressure-resistant rubber was used, and the pressure was applied under a pressure of 1 kg/cm 2 for 30 seconds. The 38 μm release PET of the above-prepared sample was peeled off, and heated in a batch heat treatment machine at 180 ° C for 90 minutes to harden the resin composition layer (adhesion layer). The resistance value of the sample after hardening was measured and used as an initial resistance value. Then, it was allowed to stand at 130 ° C and 85% by weight of Rh under a HAST tester (manufactured by Kanemoto Kasei Co., Ltd., "ETAC PM422") for 100 hours, and the subsequent resistance value (HAST resistance value) was measured.

＜黏著力之測定＞<Measurement of adhesion>

將實施例及比較例所製作之接著薄膜的25μm離型PET剝離，裝上裝置専用之冶具，測定樹脂組成物層(接著層)側之黏著力。裝置係使用Probe Tack Tester(Tester產業(股)製，TE6002)、Φ 5.05mm不鏽鋼之針，25℃、荷重1kgf/cm2 、接觸速度5mm/min下將探針壓向接著薄膜之接著層面，且保持10秒鐘。其後，以剝離速度1mm/min使其剝離，測定此時之荷重。進行此測定5次，將去除最大值與最小值的3個測定值之平均值作為黏著力。0.25N以下則為測定誤差內記為ND。The 25 μm release PET of the adhesive film produced in the examples and the comparative examples was peeled off, and the mold for the device was attached, and the adhesive force on the side of the resin composition layer (adhesive layer) was measured. The device was pressed with Probe Tack Tester (Tester Industries, TE6002), Φ 5.05 mm stainless steel needle, 25 ° C, load 1 kgf / cm 2 , contact speed 5 mm / min, the probe was pressed to the subsequent layer of the film. And keep it for 10 seconds. Thereafter, the film was peeled off at a peeling speed of 1 mm/min, and the load at this time was measured. This measurement was performed 5 times, and the average value of the three measured values of the maximum value and the minimum value was removed as the adhesive force. Below 0.25 N, the measurement error is recorded as ND.

＜25μm離型PET(覆蓋薄膜)剝離性之評價＞<25μm release PET (cover film) peelability evaluation>

將實施例及比較例所製作之接著薄膜切出一約10cm棱角，將38μm之離型PET側固定於固定台(藉由減壓可將薄片予以固定之台)。其次，僅將室溫(25℃)下四角之1處之25μm離型PET以手捏起，對接著薄膜以90度之角度垂直地拉起約5cm。在25μm離型PET與接著層之間若剝離之情況記為○，在接著層與38μm離型PET之間若剝離，或接著薄膜在在層間中無剝離而藉由固定台剝離之情況記為×。The adhesive film produced in the examples and the comparative examples was cut out to an angular angle of about 10 cm, and the 38 μm release PET side was fixed to a fixing table (a table in which the sheet was fixed by pressure reduction). Next, only 25 μm of the release PET at one of the four corners at room temperature (25 ° C) was pinched by hand, and the film was pulled up vertically by about 5 cm at an angle of 90 degrees. In the case where the peeling between the 25 μm release PET and the adhesive layer is ○, the peeling between the adhesive layer and the 38 μm release PET, or the peeling of the film by the fixing table without peeling between the layers is recorded as ×.

＜零件固定性之評價＞<Evaluation of part fixing property>

由實施例及比較例所製作之接著薄膜將25μm離型PET剝離，藉由分批式真空加壓層合機(Nichigo-Morton(股)製，「MortoN-724」)，層合於26mm×76mm之載玻片單面上。層合係在室溫(25℃)中30秒鐘真空吸引後使用耐壓橡膠，以30秒鐘1kg/cm2 之壓力加壓之條件下進行。The 25 μm release PET was peeled off from the adhesive film produced in the examples and the comparative examples, and laminated to 26 mm by a batch type vacuum pressure laminator (manufactured by Nichigo-Morton Co., Ltd., "Morto N-724"). The 76mm slide is on one side. The laminate was vacuum-sucked at room temperature (25 ° C) for 30 seconds, and then pressure-resistant rubber was used, and the pressure was applied under a pressure of 1 kg/cm 2 for 30 seconds.

將上述所作成之樣品的38μm離型PET剝離，將1608晶片電容器3個以小鎳子置於接著薄膜上。其次，以分批式真空加壓層合機(Nichigo-Morton(股)製、「Morton-724」)，30秒鐘真空吸引後使用耐壓橡膠，在室溫(25℃)中30秒鐘1kg/cm2 之壓力加壓之條件下將電容器固定於接著薄膜上。The 38 μm release PET of the sample prepared above was peeled off, and 3 of the 1608 wafer capacitors were placed on the adhesive film with small nickel. Next, a batch type vacuum pressure laminator (manufactured by Nichigo-Morton Co., Ltd., "Morton-724") was used, and after 30 seconds of vacuum suction, pressure-resistant rubber was used, and it was 30 seconds at room temperature (25 ° C). The capacitor was fixed to the adhesive film under pressure of 1 kg/cm 2 under pressure.

於接著薄膜上將已固定之電容器以小鎳子朝垂直方向剝離，觀察接著層表面所殘留之電容器的痕跡。如圖1所示般，配合電容器之形狀於接著層表面有痕跡者記為○，只有一部分痕跡者記為△、無痕跡之情況記為×。The fixed capacitor was peeled off in a vertical direction on the film, and the trace of the capacitor remaining on the surface of the layer was observed. As shown in Fig. 1, the shape of the matching capacitor is marked as ○ on the surface of the adhesive layer, and the case where only a part of the trace is marked as Δ and no trace is recorded as ×.

＜最大零件位置偏差量之測定＞<Measurement of the maximum part position deviation amount>

與零件固定性之評價相同之方法作成零件經固定之載玻片，以如圖2所示之要領進行測定電容器之隨及固定後及硬化後中之位置偏差量。The glass slides in which the parts were fixed were prepared in the same manner as the evaluation of the fixing of the parts, and the positional deviation amount of the capacitors after the fixing and after the hardening was measured in the manner shown in FIG.

零件固定後之零件位置之測定係藉由測距機(商品名，MF-UD2017B(股)Mitsutoyo製)，如圖2所示般，決定原點A、B，測定由原點至由零件之角落(4角)的距離(W、X、Y、Z)。The position of the part after the part is fixed is determined by the distance measuring machine (product name, MF-UD2017B (manufactured by Mitsutoyo), as shown in Fig. 2, the origin A, B is determined, and the measurement is performed from the origin to the part. The distance (W, X, Y, Z) of the corner (4 corners).

樣品之硬化係藉由將上述樣品在分批熱處理機中使樹脂成為垂直般而放入，在180℃中加熱30分鐘，而使樹脂組成物層(接著層)硬化。The hardening of the sample was carried out by subjecting the above sample to a vertical state in a batch heat treatment machine, and heating at 180 ° C for 30 minutes to harden the resin composition layer (adhesion layer).

硬化後之零件位置係由硬化前所定之原點A、B與硬化後之零件的角(4角落)測定其距離(W’、X’、Y’、Z’)。將(|W’-W|、|X’-X|、|Y’-Y|、|Z’-Z|)作為零件位置偏差量，將此等4個數值之最大值作為最大零件位置偏差量。對於在硬化中零件由接著層剝離者記為ND。The position of the hardened part is measured by the origins A and B determined before hardening and the angle (4 corners) of the hardened parts (W', X', Y', Z'). Use (|W'-W|, |X'-X|, |Y'-Y|, |Z'-Z|) as the part position deviation amount, and use the maximum value of these four values as the maximum part position deviation. the amount. For the part where the part is peeled off by the adhesive layer during hardening, it is referred to as ND.

由表1可知，實施例之接著薄膜其零件固定性為良好最大零件位置偏差量為小，且覆蓋薄膜(25μm離型PET)之剝離性也為良好一事。另一方面，比較例之接著薄膜，於黏著力為低之情況，因零件固定性拙劣其最大零件位置偏差為大，若黏著力過強則覆蓋薄膜(25μm離型PET)剝離性降低。As can be seen from Table 1, in the film of the example, the component fixing property was good, the maximum part position deviation amount was small, and the peeling property of the cover film (25 μm release PET) was also good. On the other hand, in the case of the adhesive film of the comparative example, when the adhesive force was low, the maximum part position deviation was large due to the poor fixing property of the part, and the peeling property of the cover film (25 μm release type PET) was lowered when the adhesive force was too strong.

[圖1]於零件固定性評價試驗中之評價方法的概念圖。[Fig. 1] A conceptual diagram of an evaluation method in a part fixing evaluation test.

[圖2]於零件位置偏差評價試驗中之評價方法的概念圖。Fig. 2 is a conceptual diagram of an evaluation method in a part position deviation evaluation test.

Claims (10)

一種熱硬化性樹脂組成物，其係為零件內藏基板之零件固定及絕緣層形成所使用之熱硬化性樹脂組成物，其特徵為在熱硬化性樹脂組成物之不揮發份設為100重量%之情況時，含有25℃下液狀之環氧樹脂25~40重量%、丙烯酸樹脂0.1~5重量%、酚系硬化劑5~30重量%及無機填料20~70重量%。 A thermosetting resin composition which is a thermosetting resin composition used for fixing a part of a component-embedded substrate and forming an insulating layer, and is characterized in that a non-volatile content of the thermosetting resin composition is set to 100 by weight. In the case of %, 25 to 40% by weight of a liquid epoxy resin at 25 ° C, 0.1 to 5% by weight of an acrylic resin, 5 to 30% by weight of a phenolic curing agent, and 20 to 70% by weight of an inorganic filler. 如申請專利範圍第1項之熱硬化性樹脂組成物，其中丙烯酸樹脂為丙烯酸酯共聚物。 The thermosetting resin composition of claim 1, wherein the acrylic resin is an acrylate copolymer. 如申請專利範圍第1項或第2項記載之熱硬化性樹脂組成物，其中丙烯酸樹脂係含有丙烯酸甲酯、丙烯酸丁酯、丙烯腈之丙烯酸酯共聚物。 The thermosetting resin composition according to the first or second aspect of the invention, wherein the acrylic resin contains an acrylate copolymer of methyl acrylate, butyl acrylate or acrylonitrile. 如申請專利範圍第1項或第2項中任一項記載之熱硬化性樹脂組成物，其中丙烯酸樹脂含有選自環氧基、羥基、羧基之1種以上之基。 The thermosetting resin composition according to any one of the first aspect, wherein the acrylic resin contains one or more selected from the group consisting of an epoxy group, a hydroxyl group, and a carboxyl group. 如申請專利範圍第1項或第2項中任一項記載之熱硬化性樹脂組成物，其中丙烯酸樹脂含有羥基及羧基。 The thermosetting resin composition according to any one of the preceding claims, wherein the acrylic resin contains a hydroxyl group and a carboxyl group. 一種接著薄膜，其特徵為於支持體上具有由申請專利範圍第1項至第5項中任一項記載之熱硬化性樹脂組成物所形成之接著層，且係用於零件內藏基板之零件固定及絕緣層形成。 An adhesive film comprising the adhesive layer formed of the thermosetting resin composition according to any one of claims 1 to 5, and is used for a component-embedded substrate. Part fixing and insulation layer formation. 如申請專利範圍第6項記載之接著薄膜，其中接著層之厚度為5~100μm。 The film according to item 6 of the patent application, wherein the thickness of the adhesive layer is 5 to 100 μm. 如申請專利範圍第6項記載之接著薄膜，其中支 持體為塑膠薄膜。 If the film is as described in item 6 of the patent application, The holder is a plastic film. 如申請專利範圍第6項記載之接著薄膜，其中支持體之接著層側之面為經離型處理者。 The film according to claim 6, wherein the surface of the support layer on the side of the support layer is a release type. 一種零件內藏基板之製造方法，其特徵為包含於如申請專利範圍第6項記載之接著薄膜的接著層上將電子零件固定之步驟及將該接著層熱硬化而形成絕緣層之步驟。 A method for producing a component-embedded substrate, comprising the step of fixing an electronic component on an adhesive layer of a film as described in claim 6 and the step of thermally curing the adhesive layer to form an insulating layer.
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