TWI832809B - Method for manufacturing fiber-reinforced plastic precursor, method for manufacturing laminated body, method for manufacturing printed wiring board, and method for manufacturing semiconductor package - Google Patents

Method for manufacturing fiber-reinforced plastic precursor, method for manufacturing laminated body, method for manufacturing printed wiring board, and method for manufacturing semiconductor package Download PDF

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TWI832809B
TWI832809B TW106138823A TW106138823A TWI832809B TW I832809 B TWI832809 B TW I832809B TW 106138823 A TW106138823 A TW 106138823A TW 106138823 A TW106138823 A TW 106138823A TW I832809 B TWI832809 B TW I832809B
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manufacturing
fiber
reinforced plastic
plastic precursor
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TW201829203A (en
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橋本慎太郎
中村幸雄
彈正原和俊
齊藤猛
佐佐木亮太
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日商力森諾科股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/28—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer impregnated with or embedded in a plastic substance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)
  • Moulding By Coating Moulds (AREA)

Abstract

本發明提供一種纖維強化塑膠前驅物的製造方法，該製造方法在將附有支撐體之樹脂薄膜貼合在骨材上之後，能夠容易地將支撐體從樹脂薄膜剝離，並且樹脂成分不會附著在經剝離的支撐體側上。進一步，本發明提供一種積層體的製造方法、印刷線路板的製造方法及半導體封裝體的製造方法，該等製造方法使用了藉由前述纖維強化塑膠前驅物的製造方法所獲得的纖維強化塑膠前驅物。更具體而言，本發明提供一種纖維強化塑膠前驅物的製造方法，該製造方法在將附有支撐體之樹脂薄膜貼合在骨材上之後，從前述附有支撐體之樹脂薄膜將支撐體剝離來製成纖維強化塑膠前驅物，其中，前述樹脂薄膜是包含熱硬化性樹脂組成物而成之樹脂薄膜，該熱硬化性樹脂組成物含有矽氧烷化合物(a)。The present invention provides a method for manufacturing a fiber-reinforced plastic precursor. After the resin film with the support is attached to the aggregate, the manufacturing method can easily peel the support from the resin film and the resin component will not adhere. On the stripped support side. Furthermore, the present invention provides a method for manufacturing a laminated body, a method for manufacturing a printed wiring board, and a method for manufacturing a semiconductor package. These manufacturing methods use a fiber-reinforced plastic precursor obtained by the aforementioned method for manufacturing a fiber-reinforced plastic precursor. things. More specifically, the present invention provides a method for manufacturing a fiber-reinforced plastic precursor. In this manufacturing method, after a resin film with a support is attached to the aggregate, the support is removed from the resin film with a support. It is peeled off to prepare a fiber-reinforced plastic precursor, wherein the resin film is a resin film containing a thermosetting resin composition, and the thermosetting resin composition contains the siloxane compound (a).

Description

纖維強化塑膠前驅物的製造方法、積層體的製造方法、印刷線路板的製造方法及半導體封裝體的製造方法Method for manufacturing fiber-reinforced plastic precursor, method for manufacturing laminated body, method for manufacturing printed wiring board, and method for manufacturing semiconductor package

本發明關於一種纖維強化塑膠前驅物的製造方法、積層體的製造方法、印刷線路板的製造方法及半導體封裝體的製造方法。The present invention relates to a method for manufacturing a fiber-reinforced plastic precursor, a method for manufacturing a laminated body, a method for manufacturing a printed circuit board, and a method for manufacturing a semiconductor package.

FRP(Fiber Reniforced Plastics，纖維強化塑膠)，是一種複合材料，其是將纖維等彈性模數高的材料當作骨材，並將該骨材置入如塑膠這樣的母材(matrix，基質)中使強度提升而成，所以可產生耐候性、耐熱性、耐化學藥品性及輕量性，並且是便宜、輕量且耐久性優異的複合材料。 因為可發揮這些性能，所以纖維強化塑膠被使用在廣泛的技術領域。例如，因為纖維強化塑膠具有造型性和高強度，故被使用在住宅設備機器、船舶、車輛、飛行器等的結構材料。又，因為纖維強化塑膠可發揮絕緣性，所以亦被使用於電子裝置和印刷線路板等電子零件領域中。FRP (Fiber Reniforced Plastics) is a composite material that uses materials with high elastic modulus such as fibers as aggregates and places the aggregates into a base material (matrix) such as plastic. It is made by increasing the strength, so it can produce weather resistance, heat resistance, chemical resistance and lightweight. It is a cheap, lightweight and durable composite material. Because they can exhibit these properties, fiber-reinforced plastics are used in a wide range of technical fields. For example, fiber-reinforced plastics are used as structural materials for residential equipment, ships, vehicles, aircraft, etc. because of their shapeability and high strength. In addition, because fiber-reinforced plastic can exert insulating properties, it is also used in the field of electronic components such as electronic devices and printed wiring boards.

作為纖維強化塑膠的製造方法，可列舉下述方法等：RTM(Resin Transfer Molding，樹脂轉移模製)法，其在平鋪有骨材的模具中注入樹脂；手積(Hand Lay-up)法和噴附(spray up)法，其是一邊鋪上骨材並且將樹脂除氣，一邊進行多層積層；及，SMC(Sheet Molding Compound，片狀模造材料)壓縮法，其利用模具，將已預先混合骨材與樹脂而成的薄片狀材料進行壓縮成型。Examples of fiber-reinforced plastic manufacturing methods include the following methods: RTM (Resin Transfer Molding) method, which injects resin into a mold with aggregates laid flat; Hand Lay-up method and the spray up method, which laminates multiple layers while laying down aggregate and degassing the resin; and the SMC (Sheet Molding Compound) compression method, which uses a mold to preform A sheet-like material made of a mixture of aggregate and resin is compressed and molded.

當將纖維強化塑膠用於印刷線路版時，印刷線路板用的纖維強化塑膠的厚度，被要求相較於其他用途的纖維強化塑膠的厚度薄。又，印刷線路板用的纖維強化塑膠，被要求下述高規格：纖維強化塑膠經成形後之厚度的變異的容許範圍較小、沒有孔隙等。 因此，多數印刷線路板用的纖維強化塑膠大多是以手積(Hand Lay-up；HLU)法所製造。手積法是一種製造方法，其使用塗佈機，在骨材上塗佈經溶解樹脂而成的清漆，然後進行乾燥並且實行溶劑去除和熱硬化(參照專利文獻1)。手積法，若預先在骨材上塗佈了熱硬化性樹脂，可提升作業性，並能夠降低對週邊環境造成的負荷。When fiber-reinforced plastic is used for printed circuit boards, the thickness of the fiber-reinforced plastic used in printed circuit boards is required to be thinner than that of fiber-reinforced plastics for other uses. In addition, fiber-reinforced plastics used in printed wiring boards are required to have the following high specifications: a small allowable range of variation in thickness of fiber-reinforced plastics after molding, and no pores. Therefore, most fiber-reinforced plastics used in printed circuit boards are manufactured by the Hand Lay-up (HLU) method. The hand-laying method is a manufacturing method in which a coater is used to apply a varnish in which a resin is dissolved on an aggregate material, followed by drying, solvent removal, and thermal hardening (see Patent Document 1). In the hand accumulation method, if thermosetting resin is coated on the aggregate in advance, workability can be improved and the load on the surrounding environment can be reduced.

但是，當作為骨材使用未經壓延處理之聚芳醯胺不織布、薄的玻璃纖維紙、薄的織布等時，因為該等骨材作為骨材的強度較低，故在下述情況作業性較差：當塗佈清漆然後實行溶劑去除、乾燥、熱硬化時，空重會增加骨材的荷重量，而造成骨材破裂；或，當為了調整進行塗佈的樹脂量而縮短塗佈機的間距(gap)時，會撕裂骨材等。However, when using non-calendered aramid non-woven fabrics, thin glass fiber paper, thin woven fabrics, etc. as aggregates, the strength of these aggregates as aggregates is low, so the workability will be reduced in the following situations: Poor: When applying varnish and then performing solvent removal, drying, and heat hardening, the empty weight will increase the load capacity of the aggregate and cause the aggregate to break; or when the coating machine is shortened to adjust the amount of resin to be coated. When there is a gap (gap), it will tear the bones etc.

又，印刷線路板用的纖維強化塑膠，有必要兼顧積層後的厚度的高精密度、與樹脂對內層電路圖案的填充性(成型性)。因此，在一種骨材中需要製造複數種纖維強化塑膠前驅物所以繁雜；前述複數種纖維強化塑膠前驅物是：附著在骨材上的樹脂量有數質量%不同者、改變熱硬化性樹脂的硬化時間而成者、組合該等而成者等。進一步，為了改變各種塗佈條件來進行製造，用於製造之材料的損失亦較大。In addition, the fiber-reinforced plastic used for printed circuit boards must have both high precision in thickness after lamination and the ability of the resin to fill the inner circuit pattern (moldability). Therefore, it is complicated to produce multiple types of fiber-reinforced plastic precursors in one type of aggregate. The above-mentioned multiple types of fiber-reinforced plastic precursors are: the amount of resin attached to the aggregate is different in mass %, and the hardening of the thermosetting resin is changed. What is formed by time, what is formed by combining these, etc. Furthermore, in order to perform manufacturing by changing various coating conditions, the loss of materials used for manufacturing is also large.

因此，有下述方法：其並非將熱硬化性樹脂直接塗佈在骨材上，而是預先製作了將熱硬化性樹脂作成薄膜狀之樹脂薄膜，然後將骨材與樹脂薄膜進行加熱和加壓來黏著，而作成纖維強化塑膠前驅物(參照專利文獻2)。 [先前技術文獻] (專利文獻)Therefore, there is a method in which the thermosetting resin is not directly coated on the aggregate, but a resin film in which the thermosetting resin is made into a thin film is prepared in advance, and then the aggregate and the resin film are heated and processed. Press to adhere to form a fiber-reinforced plastic precursor (see Patent Document 2). [Prior art documents] (Patent documents)

專利文獻1：日本特開平01-272416號公報。 專利文獻2：日本特開2011-132535號公報。Patent document 1: Japanese Patent Application Publication No. 01-272416. Patent Document 2: Japanese Patent Application Publication No. 2011-132535.

[發明所欲解決的問題] 然而，專利文獻2所述之方法，在將附有支撐體之樹脂薄膜與骨材黏著後，有時會難以從樹脂薄膜剝離支撐體。當樹脂成分附著在經剝離的支撐體側上時，會因此在製成的纖維強化塑膠前驅物的表面上造成樹脂成分不足，從而會成為積層體、印刷線路板及半導體封裝體等翹曲的原因，進一步，會容易造成引發耐熱性的惡化和外觀不良這樣的問題。[Problems to be Solved by the Invention] However, in the method described in Patent Document 2, after the resin film with the support attached is adhered to the aggregate, it may be difficult to peel the support from the resin film. When the resin component adheres to the peeled support side, the resulting fiber-reinforced plastic precursor surface becomes deficient in the resin component, causing warping of laminates, printed wiring boards, semiconductor packages, etc. Furthermore, it may easily lead to problems such as deterioration of heat resistance and poor appearance.

有鑑於如此的現狀，本發明所欲解決的問題在於提供一種纖維強化塑膠前驅物的製造方法，該製造方法在將附有支撐體之樹脂薄膜貼合在骨材上之後，能夠容易地將支撐體從樹脂薄膜剝離，並且樹脂成分不會附著在經剝離的支撐體側上。進一步，本發明所欲解決的問題在於提供一種積層體的製造方法、印刷線路板的製造方法及半導體封裝體的製造方法，該等製造方法使用了藉由前述纖維強化塑膠前驅物的製造方法所獲得的纖維強化塑膠前驅物。 [解決問題的技術手段]In view of this current situation, the problem to be solved by the present invention is to provide a method for manufacturing a fiber-reinforced plastic precursor, which can easily remove the support after laminating the resin film with the support to the aggregate. The body is peeled off from the resin film, and the resin component does not adhere to the peeled support side. Furthermore, the problem to be solved by the present invention is to provide a method for manufacturing a laminated body, a method for manufacturing a printed wiring board, and a method for manufacturing a semiconductor package. These manufacturing methods use the fiber reinforced plastic precursor produced by the aforementioned manufacturing method. Obtained fiber reinforced plastic precursor. [Technical means to solve problems]

本發明人為了解決前述所欲解決的問題而重覆並努力研究的結果，發現使在與支撐體進行密合的樹脂成分中含有矽氧烷化合物，並藉由特定方法來製造，便能夠解決前述所欲解決的問題，進而完成本發明。As a result of repeated and diligent research in order to solve the aforementioned problems, the inventors found that the problem can be solved by including a siloxane compound in the resin component that is closely adhered to the support and manufacturing it by a specific method. The above-mentioned problems to be solved are further completed by the present invention.

本發明，關於以下[1]～[12]的技術。 [1] 一種纖維強化塑膠前驅物的製造方法，該製造方法在將附有支撐體之樹脂薄膜貼合在骨材上之後，從前述附有支撐體之樹脂薄膜將支撐體剝離來製成纖維強化塑膠前驅物，其中， 前述樹脂薄膜是包含熱硬化性樹脂組成物而成之樹脂薄膜，該熱硬化性樹脂組成物含有矽氧烷化合物(a)。 [2] 如上述[1]所述之纖維強化塑膠前驅物的製造方法，其中，前述矽氧烷化合物(a)是由下述通式(1)表示：通式(1)中，Ra1 、Ra2 、Ra3 及Ra4 各自獨立地表示氫原子、烷基、經取代的烷基、苯基或經取代的苯基，Ra5 和Ra6 各自獨立地表示有機基，m是1～50的整數。 [3] 如上述[1]或[2]所述之纖維強化塑膠前驅物的製造方法，其中，前述熱硬化性樹脂組成物進一步含有熱硬化性樹脂(b)。 [4] 如上述[1]～[3]中任一項所述之纖維強化塑膠前驅物的製造方法，其中，前述熱硬化性樹脂組成物進一步含有馬來醯亞胺化合物(c)，該馬來醯亞胺化合物(c)在1分子中具有至少2個N-取代馬來醯亞胺基。 [5] 如上述[1]～[4]中任一項所述之纖維強化塑膠前驅物的製造方法，其中，前述熱硬化性樹脂組成物進一步含有胺化合物(d)，該胺化合物(d)在1分子中具有至少2個一級胺基。 [6] 如上述[1]～[5]中任一項所述之纖維強化塑膠前驅物的製造方法，其中，前述熱硬化性樹脂組成物進一步含有硬化促進劑(e)。 [7] 如上述[1]～[6]中任一項所述之纖維強化塑膠前驅物的製造方法，其中，前述熱硬化性樹脂組成物進一步含有無機填充材料(f)。 [8] 如上述[1]～[7]中任一項所述之纖維強化塑膠前驅物的製造方法，其中，在常壓下對前述附有支撐體之樹脂薄膜進行加熱和加壓來將其貼合在骨材上。 [9] 如上述[1]～[8]中任一項所述之纖維強化塑膠前驅物的製造方法，其中，前述纖維強化塑膠前驅物用於無芯基板(coreless substrate)。 [10] 一種積層體的製造方法，該製造方法藉由將纖維強化塑膠前驅物積層並進行成形來實行，該纖維強化塑膠前驅物是藉由上述[1]～[8]中任一項所述之纖維強化塑膠前驅物的製造方法所獲得。 [11] 一種印刷線路板的製造方法，該製造方法藉由電路形成在積層體上來實行，該積層體是藉由上述[10]所述之積層體的製造方法所獲得。 [12] 一種半導體封裝體的製造方法，該製造方法藉由半導體元件裝配在印刷線路板上來實行，該印刷線路板是藉由上述[11]所述之印刷線路板的製造方法所獲得。 [發明的效果]The present invention relates to the following technologies [1] to [12]. [1] A method of manufacturing a fiber-reinforced plastic precursor, which involves laminating a resin film with a support to an aggregate, and then peeling off the support from the resin film with a support to produce fibers. Reinforced plastic precursor, wherein the resin film is a resin film containing a thermosetting resin composition, and the thermosetting resin composition contains the siloxane compound (a). [2] The method for producing a fiber-reinforced plastic precursor as described in [1] above, wherein the siloxane compound (a) is represented by the following general formula (1): In the general formula (1), R a1 , R a2 , R a3 and R a4 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and R a5 and R a6 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group. Ground represents an organic group, and m is an integer from 1 to 50. [3] The method for producing a fiber-reinforced plastic precursor according to the above [1] or [2], wherein the thermosetting resin composition further contains a thermosetting resin (b). [4] The method for producing a fiber-reinforced plastic precursor according to any one of the above [1] to [3], wherein the thermosetting resin composition further contains a maleimide compound (c), which The maleimide compound (c) has at least two N-substituted maleimide groups in one molecule. [5] The method for producing a fiber-reinforced plastic precursor according to any one of the above [1] to [4], wherein the thermosetting resin composition further contains an amine compound (d), and the amine compound (d) ) has at least 2 primary amine groups in 1 molecule. [6] The method for producing a fiber-reinforced plastic precursor according to any one of the above [1] to [5], wherein the thermosetting resin composition further contains a hardening accelerator (e). [7] The method for producing a fiber-reinforced plastic precursor according to any one of the above [1] to [6], wherein the thermosetting resin composition further contains an inorganic filler (f). [8] The method for producing a fiber-reinforced plastic precursor according to any one of the above [1] to [7], wherein the resin film with the support is heated and pressurized under normal pressure to It adheres to the bone material. [9] The method for manufacturing a fiber-reinforced plastic precursor according to any one of the above [1] to [8], wherein the fiber-reinforced plastic precursor is used for a coreless substrate. [10] A method for manufacturing a laminated body by laminating and molding a fiber-reinforced plastic precursor obtained by any one of the above [1] to [8]. Obtained by the manufacturing method of the fiber-reinforced plastic precursor. [11] A method of manufacturing a printed wiring board by forming a circuit on a laminated body obtained by the method of manufacturing a laminated body according to the above [10]. [12] A method of manufacturing a semiconductor package, which is performed by mounting semiconductor elements on a printed wiring board obtained by the method of manufacturing a printed wiring board described in the above [11]. [Effects of the invention]

根據本發明，能夠提供一種纖維強化塑膠前驅物的製造方法，該製造方法在將附有支撐體之樹脂薄膜貼合在骨材上之後，能夠容易地將支撐體從樹脂薄膜剝離，並且樹脂成分不會附著在經剝離的支撐體側上。藉由使用由該製造方法而得的纖維強化塑膠前驅物所獲得的積層體、印刷線路板及半導體封裝體，可抑制翹曲並且耐熱性優異。 根據本發明，能夠提供一種積層體的製造方法、印刷線路板的製造方法及半導體封裝體的製造方法，該等製造方法使用了藉由前述纖維強化塑膠前驅物的製造方法所獲得的纖維強化塑膠前驅物。According to the present invention, it is possible to provide a method for manufacturing a fiber-reinforced plastic precursor that, after laminating a resin film with a support to an aggregate, can easily peel the support from the resin film, and the resin component Will not adhere to the stripped support side. Laminates, printed wiring boards, and semiconductor packages obtained by using the fiber-reinforced plastic precursor obtained by this production method can suppress warpage and have excellent heat resistance. According to the present invention, it is possible to provide a method for manufacturing a laminated body, a method for manufacturing a printed wiring board, and a method for manufacturing a semiconductor package, which manufacturing methods use fiber-reinforced plastic obtained by the aforementioned method for manufacturing a fiber-reinforced plastic precursor. precursor.

[纖維強化塑膠前驅物的製造方法] 本發明具有使用含有矽氧烷化合物(a)之熱硬化性樹脂組成物這樣的特徵，並且包含下述步驟：在將附有支撐體之樹脂薄膜貼合在骨材上之後，將支撐體從附有支撐體之樹脂薄膜剝離。在此處，所謂的「貼合」，除了附有支撐體之樹脂薄膜的樹脂成分與骨材相接的狀態之外，亦包含了前述樹脂薄膜中的樹脂成分填入骨材中的空隙部的狀態，尤其較佳是後者的狀態。 首先，詳述纖維強化塑膠前驅物的具體的製造方法的一態樣，之後再詳述熱硬化性樹脂組成物。[Production method of fiber-reinforced plastic precursor] The present invention is characterized by using a thermosetting resin composition containing a siloxane compound (a), and includes the following steps: laminating a resin film with a support After being attached to the aggregate, the support body is peeled off from the resin film attached to the support body. Here, the so-called "bonding" includes, in addition to the state in which the resin component of the resin film with the support is in contact with the aggregate, and the resin component in the resin film filling the voids in the aggregate. state, especially the latter state is preferred. First, an aspect of a specific manufacturing method of the fiber-reinforced plastic precursor will be described in detail, and then the thermosetting resin composition will be described in detail.

作為本發明的一較佳態樣，可列舉：在常壓下對前述附有支撐體之樹脂薄膜進行加熱和加壓來將其貼合在骨材上而成的態樣。 以下，一邊參照第1圖，一邊具體地說明本發明中的纖維強化塑膠前驅物的製造方法和纖維強化塑膠前驅物的製造裝置1的一較佳實施態樣。再者，雖然將纖維強化塑膠前驅物的製造裝置1設為將一對樹脂薄膜(由熱硬化性樹脂組成物製成的薄膜)54各自熔融並貼合在薄片狀的骨材40的雙面上的裝置來說明，但亦可以設為僅將1片樹脂薄膜54熔融並貼合在薄片狀的骨材40的其中一表面上的裝置。此時，在第1圖中，不需要位於比骨材40更下側(或更上側)的其中一樹脂送出裝置3、保護薄膜剝除機構4及保護薄膜捲取裝置5。 纖維強化塑膠前驅物的製造裝置1置於常壓下。本發明中的纖維強化塑膠前驅物的製造方法，能夠利用纖維強化塑膠前驅物的製造裝置1來實行。在此處，本說明書中，「常壓下」與「大氣壓下」為同義。也就是說，所謂的「在常壓下對附有支撐體之樹脂薄膜進行加熱和加壓來將其貼合在骨材上」，意指「在置於常壓下的纖維強化塑膠前驅物的製造裝置1中，利用加熱加壓裝置6，對附有支撐體之樹脂薄膜進行加熱和加壓來將其貼合在骨材上」。藉由該方法來製造纖維強化塑膠前驅物時，例如，因為會有傾向不易產生當採用真空疊層機等時易於發生的作業性的問題，所以較佳。As a preferred aspect of the present invention, there is an aspect in which the resin film with the support is heated and pressed under normal pressure to bond it to the aggregate. Hereinafter, a preferred embodiment of the fiber-reinforced plastic precursor manufacturing method and the fiber-reinforced plastic precursor manufacturing apparatus 1 of the present invention will be described in detail with reference to FIG. 1 . Furthermore, the fiber-reinforced plastic precursor manufacturing device 1 is configured such that a pair of resin films (films made of a thermosetting resin composition) 54 are each melted and bonded to both sides of a sheet-like aggregate 40. Although the above device will be described, it may also be a device in which only one resin film 54 is melted and bonded to one surface of the sheet-shaped aggregate 40 . At this time, in FIG. 1 , one of the resin feeding devices 3 , the protective film peeling mechanism 4 and the protective film winding device 5 located below (or above) the frame 40 are not required. The fiber-reinforced plastic precursor manufacturing device 1 is placed under normal pressure. The manufacturing method of the fiber-reinforced plastic precursor in the present invention can be carried out using the fiber-reinforced plastic precursor manufacturing device 1 . Here, in this specification, "normal pressure" and "atmospheric pressure" are synonymous. In other words, the so-called "heating and pressurizing the resin film with the support to adhere to the aggregate under normal pressure" means "the fiber-reinforced plastic precursor is placed under normal pressure. In the manufacturing device 1, the heating and pressurizing device 6 is used to heat and pressurize the resin film with the support to bond it to the aggregate." When a fiber-reinforced plastic precursor is produced by this method, for example, it tends to be less likely to cause workability problems that tend to occur when a vacuum laminating machine or the like is used, so it is preferable.

纖維強化塑膠前驅物的製造裝置1具備：骨材送出裝置2；一對樹脂薄膜送出裝置3和3；薄片加熱加壓裝置6；及，纖維強化塑膠前驅物捲取裝置8。纖維強化塑膠前驅物的製造裝置1，較佳是進一步具備：骨材加熱裝置(未圖示)；薄片加壓冷卻裝置7；一對樹脂薄膜加熱裝置(未圖示)；一對保護薄膜剝除機構4和4；及，一對保護薄膜捲取裝置5和5。The fiber-reinforced plastic precursor manufacturing device 1 includes: an aggregate feeding device 2; a pair of resin film feeding devices 3 and 3; a sheet heating and pressurizing device 6; and a fiber-reinforced plastic precursor winding device 8. The fiber-reinforced plastic precursor manufacturing device 1 preferably further includes: an aggregate heating device (not shown); a sheet pressurizing and cooling device 7; a pair of resin film heating devices (not shown); a pair of protective film peeling devices In addition to mechanisms 4 and 4; and, a pair of protective film winding devices 5 and 5.

骨材送出裝置2，是使捲有薄片狀的骨材40之滾輪往捲取方向的相反方向進行旋轉，來將捲在滾輪上的骨材40送出的裝置。在第1圖中，骨材送出裝置2，將骨材40從滾輪的下側朝向薄片加熱加壓裝置6送出。The aggregate material feeding device 2 is a device that rotates the roller on which the sheet-like aggregate material 40 is wound in the opposite direction to the winding direction, thereby feeding out the aggregate material 40 wound on the roller. In FIG. 1 , the aggregate material feeding device 2 sends the aggregate material 40 from the lower side of the roller toward the sheet heating and pressing device 6 .

一對樹脂薄膜送出裝置3和3具有：滾輪，其捲有附有保護薄膜之樹脂薄膜50；及，支撐機構，其一邊對被送出的附有保護薄膜之樹脂薄膜50賦予一定的張力，一邊以能夠使滾輪旋轉的方式進行支撐；並且一對樹脂薄膜送出裝置3和3是一種送出裝置，其使捲有樹脂薄膜50(附有保護薄膜)之滾輪往捲取方向的相反方向進行旋轉，而將被捲在滾輪上的附有保護薄膜之樹脂薄膜50送出。如同後述，附有保護薄膜之樹脂薄膜50，是一薄片狀的薄膜，其包含樹脂薄膜54及保護薄膜52，該保護薄膜52被積層在位於樹脂薄膜54其中一面的骨材側薄膜表面(在樹脂薄膜54的雙面之中，骨材40側的表面)54a。 再者，在附有保護薄膜之樹脂薄膜50中，保護薄膜52的相反側上，附有支撐體。也就是說，成為支撐體/樹脂薄膜/保護薄膜這樣的構成。The pair of resin film feeding devices 3 and 3 includes rollers on which the resin film 50 with a protective film is rolled, and a support mechanism that imparts a certain tension to the resin film 50 with a protective film that is fed out. The roller is supported in a manner capable of rotating; and a pair of resin film feeding devices 3 and 3 are feeding devices that rotate the roller on which the resin film 50 (with protective film attached) is wound in the opposite direction to the winding direction, The resin film 50 with the protective film rolled up on the roller is sent out. As will be described later, the protective film-attached resin film 50 is a thin sheet-like film including a resin film 54 and a protective film 52. The protective film 52 is laminated on the surface of the frame-side film located on one side of the resin film 54 (at Among the two sides of the resin film 54, the surface on the side of the aggregate 40 is 54a. Furthermore, in the resin film 50 with a protective film, a support is attached on the opposite side to the protective film 52 . In other words, it has a structure of support/resin film/protective film.

一對樹脂薄膜送出裝置3和3，各自位於被送出的骨材40的表面40a側和背面40b側。 其中一樹脂薄膜送出裝置3，位於被送出的骨材40的表面40a側，該送出裝置，是以保護薄膜52會位於被送出的骨材40側的方式，將其中一附有保護薄膜之樹脂薄膜50，從滾輪的下側朝向其中一保護薄膜剝除機構4送出。 同樣地，另一樹脂薄膜送出裝置3，位於被送出的骨材40的背面40b側，該送出裝置，是以保護薄膜52會位於被送出的骨材40側的方式，將另一附有保護薄膜之樹脂薄膜50，從滾輪的上側朝向另一保護薄膜剝除機構4送出。The pair of resin film feeding devices 3 and 3 are respectively located on the front surface 40a side and the back surface 40b side of the aggregate material 40 to be fed out. One of the resin film feeding devices 3 is located on the surface 40a side of the fed-out aggregate 40. This feeding device feeds one of the resin sheets with a protective film in such a manner that the protective film 52 is located on the side of the fed-out aggregate 40. The film 50 is sent out from the lower side of the roller toward one of the protective film peeling mechanisms 4 . Similarly, another resin film feeding device 3 is located on the back 40b side of the fed-out aggregate 40. This feeding device puts the other resin film 52 with a protective film 52 on the side of the fed-out aggregate 40. The resin film 50 is sent out from the upper side of the roller toward the other protective film peeling mechanism 4 .

一對保護薄膜剝除機構4和4，是各自位於被送出的骨材40的表面40a側和背面40b側的旋轉滾輪。 其中一保護薄膜剝除機構4，是從其中一附有保護薄膜之樹脂薄膜50剝除其中一保護薄膜52的機構，該剝除機構是藉由下述方式來剝除：將附有保護薄膜之樹脂薄膜50抵著進行旋轉的旋轉滾輪的表面，然後使樹脂薄膜54朝向薄片加熱加壓裝置6前進，並且使其中一保護薄膜52朝向其中一保護薄膜捲取裝置5前進；前述附有保護薄膜之樹脂薄膜50，是從其中一樹脂薄膜送出裝置3被送出，並且朝向其中一保護薄膜剝除機構4前進；前述樹脂薄膜54位於中一附有保護薄膜之樹脂薄膜50上。藉此，來露出其中一樹脂薄膜54的骨材側薄膜表面54a。 同樣地，另一保護薄膜剝除機構4，是從另一附有保護薄膜之樹脂薄膜50剝除另一保護薄膜52的機構，該剝除機構是藉由下述方式來剝除：將另一附有保護薄膜之樹脂薄膜50抵著進行旋轉的旋轉滾輪的表面，然後使樹脂薄膜54朝向薄片加熱加壓裝置6前進，並且使另一保護薄膜52朝向另一保護薄膜捲取裝置5前進；前述另一附有保護薄膜之樹脂薄膜50，是從另一樹脂薄膜送出裝置3所送出，並且朝向另一保護薄膜剝除機構4前進；前述樹脂薄膜54位於另一附有保護薄膜之樹脂薄膜50上。藉此，來露出另一樹脂薄膜54的骨材側薄膜表面54a。The pair of protective film peeling mechanisms 4 and 4 are rotating rollers located respectively on the front surface 40a side and the back surface 40b side of the fed-out aggregate 40. One of the protective film peeling mechanisms 4 is a mechanism that peels off one of the protective films 52 from one of the resin films 50 attached with the protective film. The peeling mechanism peels off the protective film by removing the protective film. The resin film 50 is pressed against the surface of the rotating rotating roller, and then the resin film 54 is advanced toward the sheet heating and pressing device 6, and one of the protective films 52 is advanced toward one of the protective film winding devices 5; The resin film 50 is sent out from one of the resin film feeding devices 3 and moves toward one of the protective film peeling mechanisms 4; the resin film 54 is located on one of the resin films 50 with a protective film attached thereto. Thereby, the aggregate-side film surface 54a of one of the resin films 54 is exposed. Similarly, another protective film peeling mechanism 4 is a mechanism that peels off another protective film 52 from another resin film 50 with a protective film. The peeling mechanism peels off the other protective film 52 in the following manner: A resin film 50 with a protective film is pressed against the surface of the rotating rotating roller, and then the resin film 54 is advanced toward the sheet heating and pressing device 6 , and another protective film 52 is advanced toward another protective film winding device 5 ; The aforementioned other resin film 50 with a protective film is sent out from another resin film feeding device 3 and moves toward another protective film peeling mechanism 4 ; the aforementioned resin film 54 is located on another resin film with a protective film on the film 50. Thereby, the aggregate-side film surface 54a of the other resin film 54 is exposed.

一對保護薄膜捲取裝置5和5，各自位於被送出的骨材40的表面40a側和背面40b側，並且是捲取保護薄膜52和52之捲取裝置，前述保護薄膜52和52是利用一對保護薄膜剝除機構4和4剝除而得。A pair of protective film winding devices 5 and 5 are respectively located on the surface 40a side and the back 40b side of the fed-out aggregate 40, and are used to wind the protective films 52 and 52. The protective films 52 and 52 are used It is obtained by peeling off a pair of protective film peeling mechanisms 4 and 4 .

骨材加熱裝置(未圖示)，具有加熱體(未圖示)，其各自位於被送出的骨材40的表面40a側和背面40b側。作為該加熱體，較佳是具有：在常壓下對骨材40的表面40a進行加熱的輻射型加熱體、及在常壓下對骨材40的背面40b進行加熱的輻射型加熱體。 再者，骨材的加熱方法，能夠利用輻射、接觸、對流等各種方法，但是利用後述的樹脂薄膜的加熱方法會變得簡便所以較佳。加熱位置，從抑制輻射冷卻的觀點來看，較佳是在具有薄片加熱加壓裝置6之加熱壓縮滾輪的前方，並且是以直線速度計算為距離加熱壓縮滾輪20秒以內的位置，更佳是5秒以內的位置，進一步較佳是1～5秒的位置。 在骨材表面加熱步驟中，骨材40的表面40a和背面40b的加熱溫度，較佳是各自比之後的薄膜壓接步驟的加熱溫度高於5～70℃的溫度，更佳是高於7～60℃的溫度，進一步較佳是高於10～50℃的溫度。The aggregate heating device (not shown) has heating bodies (not shown), which are respectively located on the front surface 40a side and the back surface 40b side of the sent aggregate 40. As this heating element, it is preferable to have a radiation type heating element that heats the surface 40a of the aggregate 40 under normal pressure, and a radiation type heating element that heats the back surface 40b of the aggregate 40 under normal pressure. In addition, various methods such as radiation, contact, and convection can be used to heat the aggregates. However, the heating method using a resin film described below is preferable because it is simple. From the viewpoint of suppressing radiation cooling, the heating position is preferably in front of the heating and compression roller having the sheet heating and pressing device 6, and is within 20 seconds of the heating and compression roller based on linear speed. More preferably, The position is within 5 seconds, and more preferably, the position is between 1 and 5 seconds. In the step of heating the surface of the aggregate material, the heating temperature of the surface 40a and the back surface 40b of the aggregate material 40 is preferably 5 to 70°C higher than the heating temperature in the subsequent film crimping step, and more preferably is higher than 70°C. The temperature is ∼60°C, and more preferably, the temperature is higher than 10°C to 50°C.

樹脂薄膜加熱裝置(未圖示)的其中之一，較佳是以能夠將被送出的其中一樹脂薄膜54的骨材側薄膜表面54a進行加熱的方式，位於被送出的骨材40的表面40a、與其中一樹脂薄膜54的骨材側薄膜表面54a之間。 另一樹脂薄膜加熱裝置，較佳是以能夠將被送出的另一樹脂薄膜54的骨材側薄膜表面54a進行加熱的方式，位於被送出的骨材40的背面40b、與另一樹脂薄膜54的骨材側薄膜表面54a之間。 該等樹脂薄膜加熱裝置，是一種加熱體，其在常壓下對樹脂薄膜54的骨材側薄膜表面54a進行加熱。加熱體例如是輻射型加熱體。One of the resin film heating devices (not shown) is preferably located on the surface 40a of the fed-out aggregate 40 in a manner that can heat the aggregate-side film surface 54a of one of the resin films 54 being fed out. , and between the film surface 54a on the aggregate side of one of the resin films 54. The other resin film heating device is preferably located between the back surface 40b of the fed-out aggregate 40 and the other resin film 54 in a manner that can heat the aggregate-side film surface 54a of the other resin film 54 being fed out. between the aggregate side film surfaces 54a. These resin film heating devices are heating bodies that heat the frame-side film surface 54a of the resin film 54 under normal pressure. The heating element is, for example, a radiation heating element.

前述輻射型加熱體的熱源可以是任一種，設為紅外線或包含紅外線的可見光較簡便，並容易實行加熱。藉此，便能夠抑制由於薄膜的變異所造成的樹脂面的變形、表面的變異等。加熱位置，從抑制輻射冷卻的觀點來看，較佳是在具有薄片加熱加壓裝置6之加熱壓縮滾輪的前方，並且是以直線速度計算為距離加熱壓縮滾輪20秒以內的位置，更佳是5秒以內的位置，進一步較佳是1～5秒的位置。又，進行加熱的溫度，較佳是樹脂的表面溫度在最低熔融黏度溫度的負20～正30℃的範圍，該最低熔融黏度溫度是利用流變儀測定熱硬化性樹脂組成物而得。 又，在薄膜預加熱步驟中，一對樹脂薄膜54和54各自的骨材側薄膜表面54a和54a的加熱溫度，較佳是各自比之後的壓接步驟的加熱溫度高於5～70℃的溫度，更佳是高於7～60℃的溫度，進一步較佳是高於10～50℃的溫度。The heat source of the radiation-type heating element may be any type, but it is simple to use infrared rays or visible light including infrared rays, and it is easy to perform heating. This can suppress deformation of the resin surface, surface variation, etc. caused by variation of the thin film. From the viewpoint of suppressing radiation cooling, the heating position is preferably in front of the heating and compression roller having the sheet heating and pressing device 6, and is within 20 seconds of the heating and compression roller based on linear speed. More preferably, The position is within 5 seconds, and more preferably, the position is between 1 and 5 seconds. In addition, the heating temperature is preferably such that the surface temperature of the resin is in the range of minus 20 to plus 30°C, which is the minimum melt viscosity temperature obtained by measuring the thermosetting resin composition using a rheometer. Furthermore, in the film preheating step, it is preferable that the heating temperature of the frame-side film surfaces 54a and 54a of the pair of resin films 54 and 54 is 5 to 70°C higher than the heating temperature in the subsequent pressure bonding step. The temperature is more preferably higher than 7 to 60°C, further preferably higher than 10 to 50°C.

薄片加熱加壓裝置6具有：一對加熱壓縮滾輪；及，壓縮力賦予機構(未圖示)，其將壓縮力賦予在一對加熱壓縮滾輪上。一對加熱壓縮滾輪，在內部具有加熱體，而能夠以經設定的特定溫度來進行加熱。 薄片加熱加壓裝置6，利用進行旋轉的一對加熱壓縮滾輪，使樹脂薄膜54和54壓接在經送入的骨材40上，來形成薄片狀的纖維強化塑膠前驅物60(薄膜壓接步驟)，並且將纖維強化塑膠前驅物60朝向薄片加壓冷卻裝置7送出。具體而言，是在從骨材送出裝置2被送出的骨材40的表面40a和背面40b上，各自以從一對保護薄膜剝除裝置4和4所送出的樹脂薄膜54和54進行積層的方式，將從骨材送出裝置2被送出的骨材40、與從一對保護薄膜剝除機構4和4各自被送出的樹脂薄膜54和54，送入一對加熱壓縮滾輪之間。 此時，以其中一樹脂薄膜54的骨材側薄膜表面54a側黏著在骨材40的表面40a側的方式，使其中一樹脂薄膜54積層在骨材40上，又，以另一樹脂薄膜54的骨材側薄膜表面54a側黏著在骨材40的背面40b側的方式，使另一樹脂薄膜54積層在骨材40上，來形成纖維強化塑膠前驅物60。從薄片加熱加壓裝置6被送出的纖維強化塑膠前驅物60是高溫狀態。The sheet heating and pressing device 6 includes a pair of heated compression rollers and a compression force applying mechanism (not shown) that applies compressive force to the pair of heated compression rollers. A pair of heated compression rollers has a heating body inside and can be heated at a set specific temperature. The sheet heating and pressurizing device 6 uses a pair of rotating heated compression rollers to press the resin films 54 and 54 onto the fed aggregate 40 to form a sheet-like fiber-reinforced plastic precursor 60 (film press-bonding). step), and send the fiber-reinforced plastic precursor 60 toward the sheet pressurized cooling device 7 . Specifically, the resin films 54 and 54 fed out from the pair of protective film peeling devices 4 and 4 are laminated on the front surface 40a and the back surface 40b of the aggregate material 40 fed out from the aggregate material feeding device 2, respectively. In this way, the aggregate 40 fed out from the aggregate feeding device 2 and the resin films 54 and 54 respectively fed out from the pair of protective film peeling mechanisms 4 and 4 are fed between a pair of heated compression rollers. At this time, one of the resin films 54 is laminated on the aggregate 40 so that the film surface 54a on the aggregate side is adhered to the surface 40a of the aggregate 40, and the other resin film 54 is laminated on the aggregate 40. The surface 54a of the aggregate-side film is adhered to the back 40b side of the aggregate 40, so that another resin film 54 is laminated on the aggregate 40 to form the fiber-reinforced plastic precursor 60. The fiber-reinforced plastic precursor 60 sent out from the sheet heating and pressing device 6 is in a high-temperature state.

薄片加壓冷卻裝置7具有：一對冷卻壓縮滾輪；及，壓縮力賦予機構(未圖示)，其將壓縮力賦予在一對冷卻壓縮滾輪上。一對冷卻壓縮滾輪，利用進行旋轉的一對冷卻壓縮滾輪，能夠將從薄片加熱加壓裝置6被送出的高溫的纖維強化塑膠前驅物60進行壓縮並且冷卻，然後送往纖維強化塑膠前驅物捲取裝置8。The sheet pressure cooling device 7 includes a pair of cooling compression rollers, and a compression force imparting mechanism (not shown) that applies compression force to the pair of cooling compression rollers. A pair of cooling compression rollers. The pair of rotating cooling compression rollers can compress and cool the high-temperature fiber-reinforced plastic precursor 60 sent out from the sheet heating and pressurizing device 6, and then send it to the fiber-reinforced plastic precursor roll. Take device 8.

纖維強化塑膠前驅物捲取裝置8具有：捲取滾輪，其捲取從薄片加壓冷卻裝置7被送出的薄片狀的纖維強化塑膠前驅物60；及，驅動機構(未圖示)，其使滾輪進行旋轉。The fiber-reinforced plastic precursor winding device 8 has: a winding roller that winds the sheet-shaped fiber-reinforced plastic precursor 60 sent out from the sheet pressurizing and cooling device 7; and a driving mechanism (not shown) that allows the fiber-reinforced plastic precursor to be wound up. The wheel rotates.

再者，因為纖維強化塑膠前驅物的製造裝置1採用了所謂的滾輪疊層法，所以在薄片加熱加壓裝置6中進行滾輪疊層時的骨材40和樹脂薄膜54的加熱溫度，較佳是在該等的寬度方向上，中央溫度較高且端部溫度較低。更具體而言，較佳是在該等的寬度方向上，中央的溫度比端部的溫度高5～20℃。滾輪疊層的加壓，是對滾輪端部施加壓力，來利用滾輪的剛性而對全體施加線壓力，此時，滾輪會稍微變形為弓形。因此，若為相同黏度則會助長弓形的變形，所以可藉由降低樹脂薄膜54的中央部的黏度並提高端部的黏度，使中央部與端部之間的流動性產生差異，從而來抑制弓形的變形。 又，若對寬度方向上的加熱溫度施加差異，在寬度方向中經熔融的樹脂的硬化性就會產生差異，所以較佳是下述方式：以加熱量相同但是使輥壓時的溫度不同的方式，將加熱體配置為V字形來控制中央部與端部至滾輪為止的距離。又，較佳是在輥壓後利用冷卻壓縮滾輪進行冷卻，來去除不必要的熱與實行製品的平坦化。Furthermore, since the fiber-reinforced plastic precursor manufacturing device 1 adopts the so-called roller lamination method, the heating temperature of the aggregate 40 and the resin film 54 when the roller lamination is performed in the sheet heating and pressing device 6 is preferably In the width direction, the center temperature is higher and the end temperature is lower. More specifically, it is preferable that the temperature at the center is 5 to 20°C higher than the temperature at the ends in the width direction. The pressurization of the roller stack is to apply pressure to the end of the roller, using the rigidity of the roller to apply linear pressure to the entire roller. At this time, the roller will be slightly deformed into an arcuate shape. Therefore, if the viscosity is the same, the deformation of the bow will be promoted. Therefore, by lowering the viscosity of the center portion of the resin film 54 and increasing the viscosity of the end portions, a difference in fluidity between the center portion and the end portions can be suppressed. Deformation of the bow. In addition, if the heating temperature in the width direction is different, the curability of the molten resin will be different in the width direction. Therefore, the following method is preferred: the heating amount is the same but the temperature during rolling is different. In this way, the heating element is arranged in a V shape to control the distance from the center part and the end part to the roller. In addition, it is preferable to use cooling compression rollers for cooling after rolling to remove unnecessary heat and achieve flattening of the product.

以上的纖維強化塑膠前驅物的製造裝置1，利用以下的方式來動作。 首先，從骨材送出裝置2，將薄片狀的骨材40朝向薄片加熱加壓裝置6送出。此時，會露出骨材40的表面40a和背面40b。 繼而，依據需要，各自在常壓下利用骨材加熱裝置等加熱體(未圖示)，對骨材40的表面40a和背面40b進行加熱(骨材表面加熱步驟)。 另一方面，保護薄膜52以位於被送出的骨材40側的方式，將其中一附有保護薄膜之樹脂薄膜50，從其中一樹脂薄膜送出裝置3的滾輪下側朝向其中一保護薄膜剝除機構4送出。又，保護薄膜52以位於被送出的骨材40側的方式，將另一附有保護薄膜之樹脂薄膜50，從另一樹脂薄膜送出裝置3的滾輪上側朝向另一保護薄膜剝除機構4送出。The above fiber-reinforced plastic precursor manufacturing device 1 operates in the following manner. First, the sheet-like aggregate material 40 is sent out from the aggregate material feeding device 2 toward the sheet heating and pressing device 6 . At this time, the front surface 40a and the back surface 40b of the aggregate 40 will be exposed. Then, if necessary, the surface 40a and the back surface 40b of the aggregate 40 are heated using a heating body (not shown) such as an aggregate heating device under normal pressure (aggregate surface heating step). On the other hand, the protective film 52 is positioned on the side of the aggregate 40 being fed out, and one of the resin films 50 with the protective film is peeled off from the lower side of the roller of one of the resin film feeding devices 3 toward one of the protective films. Sent by Organization 4. In addition, the other resin film 50 with the protective film is fed out from the upper side of the roller of the other resin film feeding device 3 toward the other protective film peeling mechanism 4 so that the protective film 52 is located on the side of the frame 40 being fed out. .

繼而，被送出的其中一附有保護薄膜之樹脂薄膜50，被掛在其中一保護薄膜剝除機構4也就是旋轉滾輪來進行旋轉時，以露出骨材側薄膜表面54a的方式，從其中一附有保護薄膜之樹脂薄膜50剝除其中一保護薄膜52，並且使其中一樹脂薄膜54朝向薄片加熱加壓裝置6前進。藉此，露出其中一樹脂薄膜54的骨材側薄膜表面54a。同樣地，被送出的另一附有保護薄膜之樹脂薄膜50，被掛在另一保護薄膜剝除機構4也就是旋轉滾輪來進行旋轉時，以露出骨材側薄膜表面54a的方式，從另一附有保護薄膜之樹脂薄膜50剝除另一保護薄膜52，並且使另一樹脂薄膜54朝向薄片加熱加壓裝置6前進。藉此，露出另一樹脂薄膜54的骨材側薄膜表面54a。 經剝除的一對保護薄膜52和52，各自可利用一對保護薄膜捲取裝置5和5來捲取。 在已露出骨材側薄膜表面54a的樹脂薄膜54到達薄片加熱加壓裝置6之前，可利用樹脂薄膜加熱裝置(未圖示)，藉由輻射，從樹脂薄膜54的骨材側薄膜表面54a側將樹脂薄膜54進行加熱 (薄膜預加熱步驟)。藉此，來熔融樹脂薄膜54的骨材側薄膜表面54a。Then, when one of the resin films 50 with a protective film that is sent out is hung on one of the protective film peeling mechanisms 4, that is, a rotating roller, it is exposed from one of the film surfaces 54a on the aggregate side. One of the protective films 52 of the resin film 50 with the protective film is peeled off, and one of the resin films 54 is advanced toward the sheet heating and pressing device 6 . Thereby, the aggregate-side film surface 54a of one of the resin films 54 is exposed. Similarly, another resin film 50 with a protective film that is fed out is hung on another protective film peeling mechanism 4, that is, a rotating roller, and is rotated to expose the aggregate side film surface 54a. The resin film 50 with the protective film is peeled off the other protective film 52, and the other resin film 54 is advanced toward the sheet heating and pressing device 6. Thereby, the aggregate-side film surface 54a of the other resin film 54 is exposed. The stripped pair of protective films 52 and 52 can each be wound up using a pair of protective film winding devices 5 and 5 . Before the resin film 54 with the aggregate-side film surface 54a exposed reaches the sheet heating and pressing device 6, a resin film heating device (not shown) can be used to heat the resin film 54 from the aggregate-side film surface 54a side by radiation. The resin film 54 is heated (film preheating step). Thereby, the aggregate-side film surface 54a of the resin film 54 is melted.

在從骨材送出裝置2被送出且表面40a和背面40b經加熱的骨材40上，各自以骨材側薄膜表面54a和54a經熔融的樹脂薄膜54和54進行積層的方式，將從骨材送出裝置2被送出的骨材40、與從一對保護薄膜剝除機構4和4各自被送出的樹脂薄膜54和54，送入一對加熱壓縮滾輪6之間。進一步，在常壓下，利用薄片加熱加壓裝置6，使一對樹脂薄膜54和54的骨材側薄膜表面54a和54a各自壓接在表面40a和背面40b經加熱的骨材40上，來獲得纖維強化塑膠前驅物60(薄膜壓接步驟)。此時，藉由控制位於一對加熱壓縮滾輪內部的加熱體的溫度，便可使一對加熱壓縮滾輪維持一定的溫度，並且可在進行薄膜壓接步驟時一邊加熱一邊加壓。On the aggregate 40 fed out from the aggregate feeding device 2 and heated on the surface 40 a and the back surface 40 b, resin films 54 and 54 are laminated on the aggregate-side film surfaces 54 a and 54 a, respectively. The aggregate 40 fed out by the feeding device 2 and the resin films 54 and 54 fed out respectively from the pair of protective film peeling mechanisms 4 and 4 are fed between the pair of heated compression rollers 6 . Further, under normal pressure, the sheet heating and pressurizing device 6 is used to press the aggregate side film surfaces 54a and 54a of the pair of resin films 54 and 54 respectively onto the heated aggregate 40 on the surface 40a and the back surface 40b. A fiber-reinforced plastic precursor 60 is obtained (film crimping step). At this time, by controlling the temperature of the heating element located inside the pair of heated compression rollers, the pair of heated compression rollers can be maintained at a certain temperature, and the film pressure bonding step can be performed while heating and pressing.

將樹脂薄膜加熱加壓來黏著在骨材上時，加熱壓縮滾輪的溫度，較佳是在最低熔融黏度溫度的負40℃～正20℃的範圍內，該最低熔融黏度溫度是利用流變儀來測定要使用於樹脂薄膜的形成中的熱硬化性組成物而得。壓力可以是任意的線壓力，但是以IPC-TM-650的No.2.3.17.1的試驗方法，利用輥壓來實施加熱加壓時，較佳是1.6mm的沖孔的滲出是50μm以上且6.4mm的沖孔的滲出是1200μm以下，更佳是1.6mm的沖孔的滲出是100μm以上且6.4mm的沖孔的滲出是500μm以下。When the resin film is heated and pressed to adhere to the aggregate, the temperature of the heated compression roller is preferably within the range of minus 40°C to plus 20°C of the lowest melt viscosity temperature. The lowest melt viscosity temperature is measured using a rheometer. It is obtained by measuring the thermosetting composition used in the formation of the resin film. The pressure can be any linear pressure. However, when heat and pressure are applied by roller pressing according to the test method of IPC-TM-650 No. 2.3.17.1, it is preferable that the bleeding out of the 1.6 mm punched hole is 50 μm or more and 6.4 The bleedout of a 1.6 mm punched hole is 1200 μm or less, and more preferably the bleedout of a 1.6 mm punched hole is 100 μm or less, and the bleedout of a 6.4 mm punched hole is 500 μm or less.

又，熱硬化性樹脂組成物的最低熔融黏度溫度，從纖維強化塑膠前驅物的生產性的觀點來看，較佳是60～150℃，更佳是80～140℃，進一步較佳是100～130℃。In addition, the minimum melt viscosity temperature of the thermosetting resin composition is preferably 60 to 150°C, more preferably 80 to 140°C, and further preferably 100 to 100°C from the viewpoint of productivity of the fiber-reinforced plastic precursor. 130℃.

薄膜壓接步驟，在作業性良好的大氣中將樹脂薄膜54黏著在骨材40上。此時，藉由利用薄片加熱加壓裝置6的加熱壓縮滾輪，透過承載膜(carrier film)來對骨材側薄膜表面54a的加溫，並非使樹脂薄膜54熔融而進行流動，而是從樹脂薄膜54的要黏著在骨材40上的一側進行加熱、或預先將骨材40進行加熱。藉此，因為能夠在骨材40的表面40a和背面40b上預先將樹脂成分高溫化而使其低黏度化，藉此可提升對骨材的含浸性，並且可抑制由於過剩的加熱造成與骨材40的填充無關的部分的樹脂黏度的降低，該過剩的加熱是來自薄片加熱加壓裝置6的加熱壓縮滾輪。也就是說，可兼顧樹脂對骨材40中的空隙部的填充性與防止樹脂從端部擠出，而能夠使纖維強化塑膠前驅物60的生產性良好。 如上所述，較佳是下述態樣：在常壓下，對前述附有支撐體之樹脂薄膜和前述骨材各自相對向的面之中的至少一面進行加熱，繼而，利用加熱壓縮滾輪一邊夾持兩者一邊進行加熱和加壓，藉此，來將前述附有支撐體之樹脂薄膜貼合在前述骨材上。In the film crimping step, the resin film 54 is adhered to the frame 40 in an atmosphere with good workability. At this time, by using the heating and compression roller of the sheet heating and pressing device 6 to heat the aggregate side film surface 54a through the carrier film, the resin film 54 does not melt and flow, but the resin film 54 is heated. The side of the film 54 to be adhered to the aggregate 40 is heated, or the aggregate 40 is heated in advance. In this way, the resin component can be preliminarily heated to a high temperature on the surface 40a and the back surface 40b of the aggregate 40 to reduce its viscosity. This can improve the impregnation of the aggregate and prevent excessive heating from causing damage to the bone. The viscosity of the resin in the portion irrelevant to the filling of the material 40 is reduced. This excess heating comes from the heating and compression roller of the sheet heating and pressing device 6 . That is to say, it is possible to achieve both the filling property of the resin in the voids in the aggregate 40 and the prevention of extrusion of the resin from the end portions, so that the productivity of the fiber-reinforced plastic precursor 60 can be improved. As mentioned above, it is preferable that at least one of the opposing surfaces of the resin film with the support and the aggregate is heated under normal pressure, and then one side of the roller is compressed by heating. The two sides are sandwiched and heated and pressed, thereby bonding the resin film with the support to the aggregate.

將從薄片加熱加壓裝置6被送出的纖維強化塑膠前驅物60，藉由薄片加壓冷卻裝置7進一步加壓並冷卻。 將從薄片加壓冷卻裝置7被送出的纖維強化塑膠前驅物60，藉由纖維強化塑膠前驅物捲取裝置8來進行捲取。The fiber-reinforced plastic precursor 60 sent out from the sheet heating and pressurizing device 6 is further pressurized and cooled by the sheet pressurizing and cooling device 7 . The fiber-reinforced plastic precursor 60 sent out from the sheet pressure cooling device 7 is wound by the fiber-reinforced plastic precursor winding device 8 .

如上所述，本發明的纖維強化塑膠前驅物的製造方法，並非所謂的真空疊層法，而是藉由在作業性良好的常壓下(大氣壓下)，從要黏著在樹脂薄膜的骨材之側進行加熱、或預先將骨材加熱，而能夠兼顧樹脂對骨材中的空隙部的填充性與防止樹脂從端部擠出，而能夠生產性良好地製造纖維強化塑膠前驅物。As mentioned above, the method for manufacturing the fiber-reinforced plastic precursor of the present invention is not the so-called vacuum lamination method, but is performed under normal pressure (atmospheric pressure) with good workability from the aggregate to be adhered to the resin film. The fiber-reinforced plastic precursor can be produced with good productivity by heating the resin on the other side or by heating the aggregate in advance, thereby balancing the filling ability of the resin in the voids in the aggregate and preventing the resin from being extruded from the ends.

繼而，說明用於本發明中的樹脂薄膜的製造中所用的熱硬化性樹脂組成物。用於本發明中的樹脂薄膜，是包含該熱硬化性樹脂組成物而成的樹脂薄膜，可以是附有支撐體的「附有支撐體之樹脂薄膜」的狀態。 [熱硬化性樹脂組成物] 作為樹脂薄膜的材料使用的熱硬化性樹脂組成物，是含有矽氧烷化合物(a)(以下，亦稱為「(a)成分」)之熱硬化性樹脂組成物。藉由使用包含如此的熱硬化性樹脂組成物而成的樹脂薄膜，在將附有支撐體之樹脂薄膜貼合在骨材上之後，能夠容易地將支撐體從樹脂薄膜剝離，並且樹脂成分不會附著在經剝離的支撐體側上。Next, the thermosetting resin composition used for producing the resin film in the present invention will be described. The resin film used in the present invention is a resin film containing the thermosetting resin composition, and may be in the state of a "resin film with a support" to which a support is attached. [Thermosetting resin composition] The thermosetting resin composition used as a material for a resin film is a thermosetting resin composition containing a siloxane compound (a) (hereinafter also referred to as "component (a)") things. By using a resin film containing such a thermosetting resin composition, after the resin film with the support is attached to the aggregate, the support can be easily peeled off from the resin film, and the resin component does not Will adhere to the peeled support side.

〈矽氧烷化合物(a)〉 矽氧烷化合物(a)，只要是含有矽氧烷骨架之化合物，並無特別限定，可以單獨使用1種，亦可以併用2種以上。矽氧烷化合物(a)，為了提高在熱硬化性樹脂組成物中的相溶性，較佳是與後述的(c)成分或(d)成分具有反應性。 作為矽氧烷化合物(a)，從剝離時對支撐體的樹脂殘留性較小、耐熱性優異且可降低翹曲量(以下，稱為低翹曲性)這樣的觀點來看，較佳例如是由下述通式(1)表示的矽氧烷化合物。<Siloxane compound (a)> The siloxane compound (a) is not particularly limited as long as it is a compound containing a siloxane skeleton. One type may be used alone, or two or more types may be used in combination. In order to improve the compatibility in the thermosetting resin composition, the siloxane compound (a) is preferably reactive with component (c) or component (d) described below. As the siloxane compound (a), from the viewpoint of small resin residue on the support during peeling, excellent heat resistance, and the ability to reduce the amount of warpage (hereinafter referred to as low warpage), for example, preferred examples are the siloxane compound (a). It is a siloxane compound represented by the following general formula (1).

通式(1)中，Ra1 、Ra2 、Ra3 及Ra4 各自獨立地表示氫原子、烷基、經取代的烷基、苯基或經取代的苯基，Ra5 和Ra6 各自獨立地表示有機基，m是1～50的整數。 In the general formula (1), R a1 , R a2 , R a3 and R a4 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and R a5 and R a6 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group. Ground represents an organic group, and m is an integer from 1 to 50.

通式(1)中，作為Ra1 、Ra2 、Ra3 及Ra4 表示的烷基，例如可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、三級丁基、正戊基等。作為該烷基，較佳是碳數1～5的烷基，更佳是碳數1～3的烷基，進一步較佳是甲基。 作為經取代的烷基中的烷基，與說明於Ra1 、Ra2 、Ra3 及Ra4 表示的烷基相同，較佳者亦同。又，作為經取代的烷基中的取代基，較佳是選自由胺基、環氧基、脂環式環氧基、聚醚殘基、苯基、羥基、巰基、羧基及(甲基)丙烯酸基所組成之群組中的至少1種，更佳是羥基。也就是說，作為經取代的烷基，較佳是甲醇基(羥甲基)。作為前述脂環式環氧基，可列舉環氧基環己基等。 作為經取代的苯基中苯基所具有的取代基，例如可列舉：碳數1～5的烷基、碳數2～5的烯基、碳數2～5的炔基。作為該碳數1～5的烷基，可列舉與已於前述者相同的烷基。作為該碳數2～5的烯基，可列舉乙烯基、烯丙基等。作為碳數2～5的炔基，可列舉乙炔基、炔丙基(propargyl)等。 以上之中，作為Ra1 、Ra2 、Ra3 及Ra4 ，較佳是甲基、苯基、甲醇基，並且較佳是全部皆為甲基。又，當m是2時，較佳是複數個Ra1 中的至少1個Ra1 是甲醇基，並且不為甲醇基的Ra1 和Ra2 、Ra3 及Ra4 皆為甲基。In the general formula (1), examples of the alkyl groups represented by R a1 , R a2 , R a3 and R a4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Tertiary butyl, n-pentyl, etc. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group. The alkyl group in the substituted alkyl group is the same as the alkyl group represented by R a1 , R a2 , R a3 and R a4 described above, and the preferred ones are also the same. Furthermore, the substituent in the substituted alkyl group is preferably selected from an amino group, an epoxy group, an alicyclic epoxy group, a polyether residue, a phenyl group, a hydroxyl group, a thiol group, a carboxyl group, and a (methyl) group. At least one type of the group consisting of acrylic groups, preferably a hydroxyl group. That is, as the substituted alkyl group, a carbinol group (hydroxymethyl) is preferred. Examples of the alicyclic epoxy group include epoxycyclohexyl group and the like. Examples of the substituent of the phenyl group in the substituted phenyl group include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an alkynyl group having 2 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include the same alkyl groups as described above. Examples of the alkenyl group having 2 to 5 carbon atoms include vinyl, allyl, and the like. Examples of the alkynyl group having 2 to 5 carbon atoms include an ethynyl group, a propargyl group, and the like. Among the above, R a1 , R a2 , R a3 and R a4 are preferably a methyl group, a phenyl group, and a carbinol group, and all of them are preferably a methyl group. Moreover, when m is 2, it is preferable that at least one R a1 among the plurality of R a1 is a methanol group, and R a1 and R a2 , R a3 and R a4 that are not methanol groups are all methyl groups.

Ra5 和Ra6 表示的有機基，較佳是經取代或未被取代的有機基，較佳是經取代或未被取代的碳數1～5的烷基，更佳是經取代或未被取代的甲基。作為被取代時的取代基，較佳是選自由胺基、環氧基、脂環式環氧基、羥基、巰基、羧基及(甲基)丙烯酸基所組成之群組中的至少1種。作為前述脂環式環氧基，可列舉環氧基環己基等。 作為Ra5 和Ra6 表示的有機基，較佳是：甲基；被環氧基取代之烷基；被胺基取代之烷基。再者，有時會將Ra5 和Ra6 表示的有機基是被環氧基取代的烷基或被胺基取代的烷基之矽氧烷化合物(a)，分別稱為環氧基改質矽氧烷化合物、胺改質矽氧烷化合物。並且，有時會將Ra5 和Ra6 皆是被環氧基取代的烷基之矽氧烷化合物(a)，稱為兩末端環氧基改質矽氧烷化合物，並將Ra5 和Ra6 皆是被胺基取代的烷基之矽氧烷化合物(a)，稱為兩末端胺改質矽氧烷化合物。 m是1～50的整數，較佳是3～50的整數，更佳是8～50的整數，進一步較佳是10～40的整數，特佳是15～40的整數。當m是2以上的整數時，複數個Ra1 彼此、複數個Ra2 彼此，可以各自相同，亦可以不同。The organic group represented by R a5 and R a6 is preferably a substituted or unsubstituted organic group, preferably a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, more preferably a substituted or unsubstituted alkyl group. Substituted methyl. When substituted, the substituent is preferably at least one selected from the group consisting of an amino group, an epoxy group, an alicyclic epoxy group, a hydroxyl group, a mercapto group, a carboxyl group, and a (meth)acrylic acid group. Examples of the alicyclic epoxy group include epoxycyclohexyl group and the like. As the organic group represented by R a5 and R a6 , preferred are: methyl group; alkyl group substituted by epoxy group; alkyl group substituted by amino group. Furthermore, siloxane compounds (a) in which the organic groups represented by R a5 and R a6 are an alkyl group substituted by an epoxy group or an alkyl group substituted by an amino group are sometimes referred to as epoxy modified siloxane compounds. Siloxane compounds, amine modified siloxane compounds. In addition, the siloxane compound (a) in which R a5 and R a6 are both alkyl groups substituted by epoxy groups is sometimes called a siloxane compound modified with both terminal epoxy groups, and R a5 and R The siloxane compound (a) in which a6 is an alkyl group substituted by an amine group is called an amine-modified siloxane compound at both ends. m is an integer of 1 to 50, preferably an integer of 3 to 50, more preferably an integer of 8 to 50, further preferably an integer of 10 to 40, particularly preferably an integer of 15 to 40. When m is an integer of 2 or more, the plurality of R a1 and the plurality of R a2 may be the same or different from each other.

作為矽氧烷化合物(a)，從剝離時對支撐體的樹脂殘留性較小、耐熱性優異且低翹曲性這樣的觀點來看，較佳是前述Ra1 ～Ra6 之中的至少1個是烷基(尤其是甲基)以外的基之化合物，亦即，較佳是改質矽氧烷化合物。該改質矽氧烷化合物之中，較佳是：在1分子中具有2個一級胺基之矽氧烷化合物(也就是胺基改質矽氧烷化合物)、在1分子中具有2個環氧基之矽氧烷化合物(也就是環氧基改質矽氧烷化合物)。該等化合物，只要在矽氧烷骨架的側鏈或末端中的任一者或雙方上具有一級胺基或環氧基即可，從取得容易性的觀點和低翹曲性這樣的觀點來看，較佳是在末端上具有一級胺基或環氧基，更佳是在兩末端上具有一級胺基或環氧基(有時稱為兩末端改質)。胺基改質矽氧烷化合物與環氧基改質矽氧烷化合物，可以各自單獨使用，亦可以併用。 又，除了上述以外，作為改質矽氧烷化合物，較佳是在側鏈上具有甲醇基之矽氧烷化合物(以下，有時稱為側鏈甲醇改質矽氧烷化合物)。The siloxane compound (a) is preferably at least 1 of the above-mentioned R a1 to R a6 from the viewpoint of small resin residue on the support during peeling, excellent heat resistance, and low warpage. The first is a compound having a group other than an alkyl group (especially a methyl group), that is, a modified siloxane compound is preferred. Among the modified siloxane compounds, a siloxane compound having two primary amine groups per molecule (that is, an amine modified siloxane compound) and a siloxane compound having two primary amine groups per molecule are preferred. Oxygen-based siloxane compounds (that is, epoxy-modified siloxane compounds). These compounds only need to have a primary amino group or an epoxy group on either or both side chains or terminals of the siloxane skeleton. From the viewpoint of ease of acquisition and low warpage, , it is preferable to have primary amine groups or epoxy groups on the terminals, and more preferably to have primary amine groups or epoxy groups on both terminals (sometimes referred to as two-terminal modification). The amine-modified siloxane compound and the epoxy-modified siloxane compound may be used alone or in combination. In addition to the above, as the modified siloxane compound, a siloxane compound having a methanol group in a side chain (hereinafter, sometimes referred to as a side chain methanol-modified siloxane compound) is preferred.

作為(a)成分，能夠使用市售品。 例如，作為在側鏈上具有甲基之「在1分子中具有2個一級胺基之矽氧烷化合物」，可列舉：「KF-8010」(胺基的官能基當量430g/mol)、「X-22-161A」(胺基的官能基當量800g/mol)、「X-22-161B」(胺基的官能基當量1500g/mol)、「KF-8012」(胺基的官能基當量2200g/mol)、「KF-8008」(胺基的官能基當量5700g/mol)、「X-22-9409」(胺基的官能基當量700g/mol，以上為信越化學工業股份有限公司製造)等。 作為在側鏈上具有苯基之「在1分子中具有2個一級胺基之矽氧烷化合物」，可列舉：「X-22-1660B-3」(胺基的官能基當量2200g/mol，信越化學工業股份有限公司製造)；「BY-16-853U」(胺基的官能基當量460g/mol)、「BY-16-853」(胺基的官能基當量650g/mol)、「BY-16-853B」(胺基的官能基當量2200g/mol，以上為東麗道康寧股份有限公司製造)等。 作為兩末端環氧基改質矽氧烷化合物，例如可列舉：「X-22-163」(環氧基的官能基當量200g/mol)、「X-22-163A」(環氧基的官能基當量1000g/mol)、「X-22-163B」(環氧基的官能基當量1800g/mol)、「KF-105」(環氧基的官能基當量490g/mol)等。 作為側鏈甲醇改質矽氧烷化合物，例如可列舉：「X-22-4015」(羥基價30mg KOH/g)、「X-22-4039」(羥基價58mg KOH/g)等。 該等化合物可以單獨使用1種，亦可以併用2種以上。 該等之中，從剝離時對支撐體的樹脂殘留性較小、耐熱性優異且低翹曲性這樣的觀點來看，較佳是「X-22-163B」、「X-22-4039」、「X-22-161A」。As the component (a), a commercially available product can be used. For example, as a "siloxane compound having two primary amino groups in one molecule" having a methyl group on the side chain, "KF-8010" (the functional group equivalent of the amine group is 430 g/mol), " " /mol), "KF-8008" (amine group functional group equivalent weight 5700g/mol), "X-22-9409" (amine group functional group equivalent weight 700g/mol, the above are manufactured by Shin-Etsu Chemical Industry Co., Ltd.), etc. . Examples of "siloxane compounds having two primary amino groups in one molecule" having a phenyl group on the side chain include: "X-22-1660B-3" (the functional group equivalent of the amine group is 2200 g/mol, Manufactured by Shin-Etsu Chemical Industry Co., Ltd.); "BY-16-853U" (functional group equivalent of amine group 460g/mol), "BY-16-853" (functional group equivalent of amine group 650g/mol), "BY- 16-853B" (the functional group equivalent of the amine group is 2200g/mol, the above is manufactured by Toray Dow Corning Co., Ltd.), etc. Examples of siloxane compounds modified with epoxy groups at both ends include "X-22-163" (functional group equivalent of epoxy group: 200 g/mol), "X-22-163A" (functional group of epoxy group) group equivalent of 1000g/mol), "X-22-163B" (functional group equivalent of epoxy group 1800g/mol), "KF-105" (functional group equivalent of epoxy group 490g/mol), etc. Examples of side chain methanol-modified siloxane compounds include "X-22-4015" (hydroxyl value: 30 mg KOH/g), "X-22-4039" (hydroxyl value: 58 mg KOH/g), and the like. One type of these compounds may be used alone, or two or more types may be used in combination. Among them, "X-22-163B" and "X-22-4039" are preferred from the viewpoint of small resin residue on the support during peeling, excellent heat resistance, and low warpage. , "X-22-161A".

當(a)成分是在兩末端上具有官能基之矽氧烷化合物時，官能基當量較佳是300～3000g/mol，更佳是400～2500g/mol，進一步較佳是600～1500 g/mol。 又，當是在側鏈上具有羥基之矽氧烷化合物時，羥基價較佳是20～100mg KOH/g，更佳是25～70mg KOH/g。When component (a) is a siloxane compound having functional groups at both ends, the functional group equivalent is preferably 300 to 3000 g/mol, more preferably 400 to 2500 g/mol, and further preferably 600 to 1500 g/mol. mol. Moreover, in the case of a siloxane compound having a hydroxyl group on the side chain, the hydroxyl value is preferably 20 to 100 mg KOH/g, more preferably 25 to 70 mg KOH/g.

熱硬化性樹脂組成物中的矽氧烷化合物(a)的含量，從剝離時對支撐體的樹脂殘留性較小、耐熱性優異且低翹曲性這樣的觀點來看，相對於熱硬化性樹脂組成物中的樹脂成分的固體成分100質量份，較佳是2～30質量份，更佳是2～25質量份，進一步較佳是3～20質量份。 在此處，所謂的本實施形態中的固體成分，意指熱硬化性樹脂組成物中的水分、後述的溶劑等可揮發的物質以外的成分。亦即，固體成分，意指包含在25℃左右的室溫中為液狀、糖漿狀及蠟狀的成分，並且不一定是固體。再者，當稱為樹脂成分的固體成分時，意指不包含(f)無機填充材料等無機物。The content of the siloxane compound (a) in the thermosetting resin composition is smaller than the thermosetting property from the viewpoint of small resin residue on the support during peeling, excellent heat resistance, and low warpage. The solid content of the resin component in the resin composition is preferably 2 to 30 parts by mass, more preferably 2 to 25 parts by mass, and further preferably 3 to 20 parts by mass per 100 parts by mass of the resin component. Here, the solid content in this embodiment means components in the thermosetting resin composition other than volatile substances such as moisture and solvents described below. That is, the solid component means a component that is liquid, syrupy, or waxy at room temperature of about 25° C., and is not necessarily solid. In addition, when it is called the solid content of a resin component, it means that inorganic substances, such as (f) an inorganic filler, are not included.

〈熱硬化性樹脂(b)〉 熱硬化性樹脂組成物，進一步可含有熱硬化性樹脂(b)。但是，該熱硬化性樹脂(b)，不包含前述(a)成分和後述的(c)成分。 作為熱硬化性樹脂(b)，例如可列舉：環氧樹脂、酚樹脂、不飽和醯亞胺樹脂(但是，不包含後述的(c)成分)、氰酸酯樹脂、異氰酸酯樹脂、苯并噁嗪(benzoxazine)樹脂、環氧丙烷樹脂、胺樹脂、不飽和聚酯樹脂、烯丙樹脂、雙環戊二烯樹脂、矽氧樹脂、三氮雜苯樹脂、三聚氰胺樹脂等。該等可以單獨使用1種，亦可以併用2種以上。該等之中，從成形性和電絕緣性的觀點、以及與金屬電路的黏著強度的觀點來看，較佳是選自由環氧樹脂和氰酸酯樹脂所組成之群組中的1種以上，更佳是環氧樹脂。<Thermosetting resin (b)> The thermosetting resin composition may further contain a thermosetting resin (b). However, the thermosetting resin (b) does not contain the aforementioned component (a) and the component (c) described below. Examples of the thermosetting resin (b) include epoxy resin, phenol resin, unsaturated acyl imine resin (however, component (c) described below is not included), cyanate resin, isocyanate resin, benzox benzoxazine resin, propylene oxide resin, amine resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, triazine resin, melamine resin, etc. One type of these may be used alone, or two or more types may be used in combination. Among these, from the viewpoint of formability, electrical insulation, and adhesion strength to a metal circuit, one or more types selected from the group consisting of epoxy resin and cyanate ester resin is preferred. , preferably epoxy resin.

作為環氧樹脂，例如可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、α-萘酚/甲酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、雙酚F酚醛清漆型環氧樹脂、二苯乙烯型環氧樹脂、含有三氮雜苯骨架之環氧樹脂、含有茀骨架之環氧樹脂、三苯甲烷型環氧樹脂、聯苯型環氧樹脂、二甲苯型環氧樹脂、聯苯芳烷型環氧樹脂、萘型環氧樹脂、雙環戊二烯型環氧樹脂、脂環式環氧樹脂、多官能酚類及蒽等多環芳香族類的二環氧丙基醚化合物、及在該等環氧樹脂中導入磷化合物而成之含有磷之環氧樹脂等。該等環氧樹脂可以單獨使用1種，亦可以併用2種以上。在該等之中，從耐熱性和難燃性的觀點來看，較佳是聯苯芳烷型環氧樹脂、α-萘酚/甲酚酚醛清漆型環氧樹脂。Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, α-naphthol/cresol novolak type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolak type epoxy resin, stilbene type epoxy resin, ring containing triazine skeleton Oxygen resin, epoxy resin containing fluorine skeleton, triphenylmethane epoxy resin, biphenyl epoxy resin, xylene epoxy resin, biphenyl aralkyl epoxy resin, naphthalene epoxy resin, dicyclopentanol Diene epoxy resins, alicyclic epoxy resins, polycyclic aromatic diepoxypropyl ether compounds such as polyfunctional phenols and anthracenes, and compounds containing phosphorus compounds introduced into these epoxy resins Phosphorus epoxy resin, etc. One type of these epoxy resins may be used alone, or two or more types may be used in combination. Among these, from the viewpoint of heat resistance and flame retardancy, biphenyl aralkyl type epoxy resin and α-naphthol/cresol novolac type epoxy resin are preferred.

當熱硬化性樹脂組成物含有熱硬化性樹脂(b)時，其含量，從低翹曲性的觀點來看，相對於熱硬化性樹脂組成物中的樹脂成分的固體成分100質量份，較佳是1～85質量份，更佳是2～80質量份，進一步較佳是5～80質量份，特佳是10～80質量份。When the thermosetting resin composition contains the thermosetting resin (b), its content is relatively small relative to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition from the viewpoint of low warpage. It is preferably 1 to 85 parts by mass, more preferably 2 to 80 parts by mass, still more preferably 5 to 80 parts by mass, and particularly preferably 10 to 80 parts by mass.

〈在1分子中具有至少2個N-取代馬來醯亞胺基之馬來醯亞胺化合物(c)〉 (c)成分只要是在1分子中具有至少2個N-取代馬來醯亞胺基之馬來醯亞胺化合物(以下，有時略稱為馬來醯亞胺化合物(c))，並無特別限定。 作為馬來醯亞胺化合物(c)，較佳是在1分子中具有2個N-取代馬來醯亞胺基之馬來醯亞胺化合物，更佳是由下述通式(c-1)表示的化合物。<Maleimine compound (c) having at least 2 N-substituted maleimide groups in 1 molecule> The component (c) must have at least 2 N-substituted maleimide groups in 1 molecule The amino maleimide compound (hereinafter, may be simply referred to as the maleimine compound (c)) is not particularly limited. The maleimide compound (c) is preferably a maleimide compound having two N-substituted maleimide groups in one molecule, and more preferably a maleimide compound represented by the following general formula (c-1 ) represents the compound.

通式(c-1)中，Xc1 是由下述通式(c1-1)、(c1-2)、(c1-3)或(c1-4)表示的基團。 In the general formula (c-1), X c1 is a group represented by the following general formula (c1-1), (c1-2), (c1-3) or (c1-4).

通式(c1-1)中，Rc1 各自獨立地是碳數1～5的脂肪族烴基或鹵素原子。p是0～4的整數。 In the general formula (c1-1), R c1 is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. p is an integer from 0 to 4.

通式(c1-2)中，Rc2 和Rc3 各自獨立地是碳數1～5的脂肪族烴基或鹵素原子。Xc2 是碳數1～5的伸烷基、碳數2～5的亞烷(alkylidene)基、醚基、硫醚基、磺醯基、羰氧(carbonyloxy)基、酮基、單鍵或由下述通式(c1-2-1)表示的基團。q和r各自獨立地是0～4的整數。 In the general formula (c1-2), R c2 and R c3 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X c2 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyloxy group, a ketone group, a single bond, or A group represented by the following general formula (c1-2-1). q and r are each independently an integer from 0 to 4.

通式(c1-2-1)中，Rc4 和Rc5 各自獨立地是碳數1～5的脂肪族烴基或鹵素原子。Xc3 是碳數1～5的伸烷基、碳數2～5的亞烷(alkylidene)基、醚基、硫醚基、磺醯基、羰氧基[－O－C(＝O)－]、酮基、單鍵。s和t各自獨立地是0～4的整數。 In the general formula (c1-2-1), R c4 and R c5 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X c3 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, or a carbonyloxy group [-O-C(=O)- ], ketone group, single bond. s and t are each independently an integer from 0 to 4.

通式(c1-3)中，n是1～10的整數。 In the general formula (c1-3), n is an integer from 1 to 10.

通式(c1-4)中，Rc6 和Rc7 各自獨立地是氫原子或碳數1～5的脂肪族烴基。u是1～8的整數。 In the general formula (c1-4), R c6 and R c7 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. u is an integer from 1 to 8.

前述通式(c1-1)中，作為Rc1 表示的脂肪族烴基，例如可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、三級丁基、正戊基等。作為該脂肪族烴基，較佳是碳數1～3的脂肪族烴基，更佳是甲基。又，作為鹵素原子，例如可列舉：氟原子、氯原子、溴原子、碘原子等。 以上之中，作為Rc1 ，較佳是碳數1～5的脂肪族烴基。 p是0～4的整數，從取得容易性的觀點來看，較佳是0～2的整數，更佳是0或1，進一步較佳是0。當p是2以上的整數時，複數個Rc1 彼此可以相同，亦可以不同。In the general formula (c1-1), examples of the aliphatic hydrocarbon group represented by R c1 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl etc. As the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, and a methyl group is more preferred. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. Among the above, R c1 is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms. p is an integer of 0 to 4, and from the viewpoint of ease of acquisition, it is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0. When p is an integer of 2 or more, the plural R c1 may be the same as or different from each other.

前述通式(c1-2)中，作為Rc2 和Rc3 表示的碳數1～5的脂肪族烴基、鹵素原子，可列舉與前述Rc1 相同者。作為該脂肪族烴基，較佳是碳數1～3的脂肪族烴基，更佳是甲基和乙基，進一步較佳是乙基。 作為Xc2 表示的碳數1～5的伸烷基，例如可列舉：亞甲基、1,2-伸乙基、1,3-伸丙基、1,4-伸丁基、1,5-伸戊基等。作為該伸烷基，從耐熱性和低熱膨脹性的觀點來看，較佳是碳數1～3的伸烷基，更佳是亞甲基。 作為Xc2 表示的碳數2～5的亞烷基，例如可列舉：亞乙基、亞丙基、亞異丙基、亞丁基、亞異丁基、亞戊基、亞異戊基等。在該等之中，從耐熱性和低熱膨脹性的觀點來看，較佳是亞異丙基。 作為Xc2 ，在上述的選擇之中，較佳是碳數1～5的伸烷基、碳數2～5的亞烷基、由通式(c1-2-1)表示的基團，更佳是碳數1～5的伸烷基、由通式(c1-2-1)表示的基團。進一步較佳者如同前述或後述的選擇。 q和r各自獨立地是0～4的整數，從取得容易性的觀點來看，較佳是皆為0～2的整數，更佳是皆為0或2，當q或r是2以上的整數時，複數個Rc2 彼此或Rc3 彼此，可以各自相同，亦可以不同。In the general formula (c1-2), examples of the aliphatic hydrocarbon group and halogen atom having 1 to 5 carbon atoms represented by R c2 and R c3 include the same ones as those described above for R c1 . As the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, a methyl group and an ethyl group are more preferred, and an ethyl group is still more preferred. Examples of the alkylene group having 1 to 5 carbon atoms represented by - Pentyl etc. As the alkylene group, from the viewpoint of heat resistance and low thermal expansion, an alkylene group having 1 to 3 carbon atoms is preferred, and a methylene group is more preferred. Examples of the alkylene group having 2 to 5 carbon atoms represented by X c2 include ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, isopentylene group, and the like. Among these, isopropylene group is preferable from the viewpoint of heat resistance and low thermal expansion. X c2 is preferably an alkylene group having 1 to 5 carbon atoms, an alkylene group having 2 to 5 carbon atoms, or a group represented by the general formula (c1-2-1) among the above-mentioned choices, and more preferably Preferably, it is an alkylene group having 1 to 5 carbon atoms and a group represented by the general formula (c1-2-1). Further preferred options are as described above or below. q and r are each independently an integer from 0 to 4. From the viewpoint of ease of acquisition, it is preferable that both are an integer from 0 to 2, and more preferably both are 0 or 2. When q or r is 2 or more When it is an integer, the plurality of R c2 or R c3 may be the same or different.

前述通式(c1-2-1)中，作為Rc4 和Rc5 表示的碳數1～5的脂肪族烴基、鹵素原子，可列舉與前述Rc2 和Rc3 的情況相同的基團，較佳者亦相同。 作為Xc3 表示的碳數1～5的伸烷基、碳數2～5的亞烷基，可列舉與前述Xc2 表示的碳數1～5的伸烷基、碳數2～5的亞烷基相同的基團，較佳者亦相同。 作為Xc3 ，在上述選擇之中，較佳是碳數2～5的亞烷基，更佳者如同前述。 s和t是0～4的整數，從取得容易性的觀點來看，較佳是皆為0～2的整數，更佳是0或1，進一步較佳是0。當s或t是2以上的整數時，複數個Rc4 或Rc5 彼此，可以各自相同，亦可以不同。 前述通式(c1-2-1)，較佳是由下述通式(c1-2-1’)表示。In the general formula (c1-2-1), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R c4 and R c5 include the same groups as those in the case of the aforementioned R c2 and R c3 . The same goes for the best. Examples of the alkylene group having 1 to 5 carbon atoms and the alkylene group having 2 to 5 carbon atoms represented by X c3 include the alkylene group having 1 to 5 carbon atoms and the alkylene group having 2 to 5 carbon atoms represented by X c2 mentioned above. The groups having the same alkyl group are preferably also the same. X c3 is preferably an alkylene group having 2 to 5 carbon atoms among the above selections, and more preferably is as described above. s and t are integers from 0 to 4. From the viewpoint of ease of acquisition, both are preferably integers from 0 to 2, more preferably 0 or 1, and still more preferably 0. When s or t is an integer of 2 or more, the plurality of R c4 or R c5 may be the same or different from each other. The aforementioned general formula (c1-2-1) is preferably represented by the following general formula (c1-2-1').

通式(c1-2-1’)中的Xc3 、Rc4 、Rc5 、s及t，與通式(c1-2-1)中的例子相同，較佳者亦相同。 X c3 , R c4 , R c5 , s and t in the general formula (c1-2-1') are the same as those in the general formula (c1-2-1), and the preferred ones are also the same.

由前述通式(c1-2)表示的基團，較佳是由下述(c1-2’)表示的基團，更佳是由下述(c1-i)～(c1-iii) 表示的基團，進一步較佳是由下述(c1-i)或(c1-iii) 表示的基團。The group represented by the general formula (c1-2) is preferably a group represented by the following (c1-2'), and more preferably is represented by the following (c1-i) to (c1-iii) The group is more preferably a group represented by the following (c1-i) or (c1-iii).

通式(c1-2’)中的Xc2 、Rc2 、Rc3 、q及r，與通式(c1-2)中的例子相同，較佳者亦同。 X c2 , R c2 , R c3 , q and r in the general formula (c1-2') are the same as those in the general formula (c1-2), and the preferred ones are also the same.

前述通式(c1-3)中，n是1～10的整數，從取得容易性的觀點來看，較佳是1～5的整數，更佳是1～3的整數。 前述通式(c1-4)中，作為Rc6 和Rc7 表示的碳數1～5的脂肪族烴基、鹵素原子，可列舉與前述通式(c1-1)中的Rc1 相同的例子，較佳者亦相同。u是1～8的整數，較佳是1～3的整數，更佳是1。In the general formula (c1-3), n is an integer of 1 to 10. From the viewpoint of availability, n is preferably an integer of 1 to 5, and more preferably an integer of 1 to 3. In the aforementioned general formula (c1-4), examples of the aliphatic hydrocarbon group and halogen atom having 1 to 5 carbon atoms represented by R c6 and R c7 include the same examples as R c1 in the aforementioned general formula (c1-1). The same goes for the better ones. u is an integer from 1 to 8, preferably an integer from 1 to 3, and more preferably 1.

前述通式(c-1)中，Xc1 ，可以是由前述通式(c1-1)、(c1-2)、(c1-3)或(c1-4)表示的任一基團，在該等之中，從低翹曲性、尺寸穩定性、耐熱性和取得容易性的觀點來看，較佳是由(c1-2)表示的基團。In the aforementioned general formula (c-1), X c1 may be any group represented by the aforementioned general formula (c1-1), (c1-2), (c1-3) or (c1-4), where Among these, the group represented by (c1-2) is preferable from the viewpoint of low warpage, dimensional stability, heat resistance, and ease of acquisition.

作為馬來醯亞胺化合物(c)的具體例，可列舉：雙(4-馬來醯亞胺基苯基)甲烷、聚苯甲烷馬來醯亞胺、雙(4-馬來醯亞胺基苯基)醚、雙(4-馬來醯亞胺基苯基)碸、3,3’-二甲基-5,5’-二乙基-4,4’-二苯甲烷雙馬來醯亞胺、4-甲基-1,3-伸苯基雙馬來醯亞胺、間苯基雙馬來醯亞胺、2,2-雙[4-(4-馬來醯亞胺基苯氧基)苯基]丙烷等。該等可以單獨使用1種，亦可以併用2種以上。 該等之中，從反應性高、並且能夠進一步高耐熱性化這樣的觀點來看，較佳是雙(4-馬來醯亞胺基苯基)甲烷、雙(4-馬來醯亞胺基苯基)碸、3,3’-二甲基-5,5’-二乙基-4,4’-二苯甲烷雙馬來醯亞胺、2,2-雙[4-(4-馬來醯亞胺基苯氧基)苯基]丙烷，從對溶劑的溶解性的觀點來看，更佳是3,3’-二甲基-5,5’-二乙基-4,4’-二苯甲烷雙馬來醯亞胺、雙(4-馬來醯亞胺基苯基)甲烷、2,2-雙[4-(4-馬來醯亞胺基苯氧基)苯基]丙烷，從製造成本的觀點來看，進一步較佳是雙(4-馬來醯亞胺基苯基)甲烷、2,2-雙[4-(4-馬來醯亞胺基苯氧基)苯基]丙烷。Specific examples of the maleimide compound (c) include bis(4-maleimidophenyl)methane, polyphenylmethanemaleimide, and bis(4-maleimide) phenyl) ether, bis(4-maleiminophenyl)terine, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismale Imide, 4-methyl-1,3-phenylbismaleimide, m-phenylbismaleimide, 2,2-bis[4-(4-maleimide) Phenoxy)phenyl]propane, etc. One type of these may be used alone, or two or more types may be used in combination. Among these, bis(4-maleimidophenyl)methane and bis(4-maleimide) are preferred from the viewpoint of high reactivity and the ability to achieve further high heat resistance. basephenyl)terine, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 2,2-bis[4-(4- Maleimidophenoxy)phenyl]propane, more preferably 3,3'-dimethyl-5,5'-diethyl-4,4 from the viewpoint of solubility in solvents '-Diphenylmethane bismaleimide, bis(4-maleiminophenyl)methane, 2,2-bis[4-(4-maleiminophenoxy)phenyl ] propane, and from the viewpoint of production cost, bis(4-maleiminophenyl)methane and 2,2-bis[4-(4-maleimidophenoxy) are more preferred. )phenyl]propane.

當熱硬化性樹脂組成物含有馬來醯亞胺化合物(c)時，其含量，從低翹曲性的觀點來看，相對於熱硬化性樹脂組成物中的樹脂成分的固體成分100質量份，較佳是20～90質量份，更佳是30～85質量份，進一步較佳是30～80質量份。When the thermosetting resin composition contains the maleimide compound (c), its content is, from the viewpoint of low warpage, 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. , preferably 20 to 90 parts by mass, more preferably 30 to 85 parts by mass, further preferably 30 to 80 parts by mass.

〈在1分子中具有至少2個一級胺基之胺化合物(d)〉 在1分子中具有至少2個一級胺基之胺化合物(d)(以下，有時略稱為胺化合物(d))，在分子內沒有矽氧烷鍵而可與前述成分(a)進行區別。 胺化合物(d)所具有的一級胺基的數目，從耐熱性的觀點來看，較佳是2個～4個，更佳是2個或3個，進一步較佳是2個。 作為胺化合物(d)，從耐熱性的觀點來看，較佳是由下述通式(d-1)～(d-3)中的任一通式表示的二胺化合物，更佳是由下述通式(d-1)或(d-3)中的任一通式表示的二胺化合物，進一步較佳是由下述通式(d-1)表示的二胺化合物。<Amine compound (d) having at least 2 primary amine groups per molecule> Amine compound (d) having at least 2 primary amine groups per molecule (hereinafter, may be abbreviated as amine compound (d)) , which has no siloxane bond in the molecule and can be distinguished from the aforementioned component (a). From the viewpoint of heat resistance, the number of primary amine groups the amine compound (d) has is preferably 2 to 4, more preferably 2 or 3, and still more preferably 2. As the amine compound (d), from the viewpoint of heat resistance, a diamine compound represented by any one of the following general formulas (d-1) to (d-3) is preferred, and a diamine compound represented by the following general formulas is more preferred: The diamine compound represented by any of the general formulas (d-1) or (d-3) is more preferably a diamine compound represented by the following general formula (d-1).

上述式中，Xd1 表示單鍵、碳數1～5的伸烷基、碳數2～5的亞烷基、－O－、磺醯基、酮基、茀二(fluorine diyl)基或苯二氧(phenylenedioxy)基。Rd1 和Rd2 ，各自獨立地表示碳數1～5的脂肪族烴基、甲氧基或羥基。v和w，各自獨立地是0～4的整數。 Xd2 ～Xd4 ，各自獨立地表示單鍵、碳數1～5的伸烷基、亞異丙基、－O－或磺醯基。In the above formula , Dioxy (phenylenedioxy) group. R d1 and R d2 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a methoxy group or a hydroxyl group. v and w are each independently an integer from 0 to 4. X d2 to X d4 each independently represent a single bond, an alkylene group having 1 to 5 carbon atoms, an isopropylene group, -O- or a sulfonyl group.

作為Xd1 表示的碳數1～5的伸烷基，例如可列舉：亞甲基、1,2-伸乙基、1,3-伸丙基、1,4-伸丁基、1,5-伸戊基等。作為該伸烷基，從耐熱性的觀點來看，較佳是碳數1～3的伸烷基，更佳是亞甲基。 作為Xd1 表示的碳數2～5的亞烷基，例如可列舉：亞乙基、亞丙基、亞異丙基、亞丁基、亞異丁基、亞戊基、亞異戊基等。在該等之中，從耐熱性的觀點來看，較佳是亞異丙基。 作為Xd1 表示的茀二基，例如可列舉：茀-1,8-二基、茀-1,7-二基、茀-1,6-二基、茀-1,5-二基、茀-2,7-二基、茀-2,6-二基、茀-2,5-二基、茀-3,6-二基、茀-3,5-二基、茀-4,5-二基等。 作為Xd1 表示的苯二氧基，可列舉1,4-苯二氧基、1,3-苯二氧基、1,2-苯二氧基。 作為Xd1 ，在上述選擇之中，較佳是碳數1～5的伸烷基、－O－、磺醯基，更佳是碳數1～5的伸烷基、磺醯基。Examples of the alkylene group having 1 to 5 carbon atoms represented by X d1 include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5 - Pentyl etc. As the alkylene group, from the viewpoint of heat resistance, an alkylene group having 1 to 3 carbon atoms is preferred, and a methylene group is more preferred. Examples of the alkylene group having 2 to 5 carbon atoms represented by X d1 include ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, isopentylene group, and the like. Among these, from the viewpoint of heat resistance, isopropylene group is preferred. Examples of the fluorine diyl group represented by -2,7-diyl, fluorine-2,6-diyl, fluorine-2,5-diyl, fluorine-3,6-diyl, fluorine-3,5-diyl, fluorine-4,5- Erji et al. Examples of the benzenedioxy group represented by X d1 include 1,4-phenylenedioxy group, 1,3-phenylenedioxy group and 1,2-phenylenedioxy group. As X d1 , among the above selections, an alkylene group having 1 to 5 carbon atoms, -O-, or a sulfonyl group is preferred, and an alkylene group having 1 to 5 carbon atoms or a sulfonyl group is more preferred.

作為Rd1 和Rd2 表示的碳數1～5的脂肪族烴基，例如可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、三級丁基、正戊基等。作為該脂肪族烴基，從耐熱性的觀點來看，較佳是碳數1～3的脂肪族烴基，更佳是甲基、乙基，進一步較佳是乙基。 v和w是0～4的整數，從耐熱性的觀點來看，較佳是各自是0～2的整數，更佳是各自是0或1，進一步較佳是各自是1。Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R d1 and R d2 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n- Pentyl etc. From the viewpoint of heat resistance, the aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably an ethyl group. v and w are integers of 0 to 4. From the viewpoint of heat resistance, it is preferable that each is an integer of 0 to 2, more preferably 0 or 1, and still more preferably 1.

作為Xd2 ～Xd4 表示的碳數1～5的伸烷基，例如可列舉：亞甲基、1,2-伸乙基、1,3-伸丙基、1,4-伸丁基、1,5-伸戊基等。作為該伸烷基，從耐熱性的觀點來看，較佳是碳數1～3的伸烷基。 作為Xd2 ～Xd4 ，在上述選擇之中，各自較佳是亞甲基或亞異丙基。Examples of the alkylene group having 1 to 5 carbon atoms represented by X d2 to 1,5-pentyl etc. As the alkylene group, from the viewpoint of heat resistance, an alkylene group having 1 to 3 carbon atoms is preferred. As X d2 to X d4 , among the above-mentioned choices, each is preferably a methylene group or an isopropylene group.

作為胺化合物(d)，可列舉：間苯二胺、對苯二胺、4,6-二甲基間苯二胺、2,5-二甲基對苯二胺、2,3,5,6-四甲基對苯二胺、2,4-二胺基均三甲苯、間二甲苯-2,5-二胺、間荏二胺、對荏二胺、2,4-二胺甲苯、2,5-二胺甲苯、2,4-雙(胺基三級丁基)甲苯、2,4-二胺基二甲苯、2,4-二胺吡啶、2,6-二胺吡啶、2,5-二胺吡啶、2,4-二胺荰、4,5-二胺基-6-羥基-2-巰基嘧啶、3-雙(3-胺基芐基)苯、4-雙(4-胺基芐基)苯、1,4-雙(4-胺基苯基)苯、1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、3-雙(3-(3-胺基苯氧基)苯氧基)苯、4-雙(4-(4-胺基苯氧基)苯氧基)苯、3-雙(3-(3-(3-胺基苯氧基)苯氧基)苯氧基)苯、4-雙(4-(4-(4-胺基苯氧基)苯氧基)苯氧基)苯、3-雙(α,α-二甲基-3-胺基芐基)苯、1,4-雙(α,α-二甲基-3-胺基芐基)苯、3-雙(α,α-二甲基-4-胺基芐基)苯、雙(4-甲基胺戊基)苯、對雙(2-甲基-4-胺戊基)苯、1,4-雙(3-胺丙基二甲基矽基)苯、雙[(4-胺苯基)-2-丙基]1,4-苯、2,5-二胺基苯磺酸、3,3’-二胺基二苯甲烷、4,4’-二胺基二苯甲烷、3,3’-二甲基-4,4’-二胺基二苯甲烷、3,3’,5,5’-四甲基-4,4’-二胺基二苯甲烷、3,3’-二乙基-4,4’-二胺基二苯甲烷、3,3’-二甲基-5,5’-二乙基-4,4’-二胺基二苯甲烷、4,4’-亞甲基-雙(2-氯苯胺)、3,3’-二胺基二苯乙烷、4,4’-二胺基二苯乙烷、2,2’-二胺基二苯丙烷、3,3’-二胺基二苯丙烷、4,4’-二胺基二苯丙烷、2,2’-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2’-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、3-(2’,4’-二胺基苯氧基)丙烷磺酸、雙(4-胺苯基)二乙基矽烷、3,3’-二胺基二苯基酮、4,4’-二胺基二苯基酮、3,3’-二胺基二苯基醚、4,4’-二胺基二苯基醚、3,3’-二甲基-4,4’-二胺基二苯基醚、雙(4-胺基三級丁基苯基)醚、4,4’-二胺基二苯基醚-2,2’-二磺酸、3,3’-二胺基二苯碸、4,4’-二胺基二苯磺碸、雙[4-(4-胺基苯氧基)苯基] 碸、雙[4-(3-胺基苯氧基)苯基] 碸、聯苯胺、2,2’-二甲基-4,4’-二胺基聯苯、3,3’-二甲基-4,4’-二胺基聯苯、3,3’-二甲氧基-4,4’-二胺基聯苯、3,3’-二甲基-4,4’-二胺基聯苯-6,6’-二磺酸、2,2’,5,5’-四氯-4,4’-二胺基聯苯、3,3’-二氯-4,4’-二胺基聯苯、3,3’-二氯-4,4’-二胺基聯苯、4,4’-雙(4-胺基苯氧基)聯苯、4,4’-二胺基二苯硫醚、4,4’-二胺基-3,3’-聯苯二醇、1,5-二胺萘、1,4-二胺萘、2,6-二胺萘、9,9’-雙(4-胺苯基)茀、9,9’-雙(4-胺苯基)茀-2,7-二磺酸、9,9’-雙(4-胺基苯氧基苯基)茀、二胺蒽醌、3,7-二胺基-2,8-二甲基二苯并噻吩碸等含有芳香族基之胺類；Examples of the amine compound (d) include m-phenylenediamine, p-phenylenediamine, 4,6-dimethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,3,5, 6-tetramethyl-p-phenylenediamine, 2,4-diamine mesitylene, m-xylene-2,5-diamine, m-xylenediamine, p-phenylenediamine, 2,4-diaminetoluene, 2,5-diaminetoluene, 2,4-bis(aminotertiary butyl)toluene, 2,4-diaminoxylene, 2,4-diaminepyridine, 2,6-diaminepyridine, 2 , 5-diaminepyridine, 2,4-diamine pyridine, 4,5-diamino-6-hydroxy-2-mercaptopyrimidine, 3-bis(3-aminobenzyl)benzene, 4-bis(4 -Aminobenzyl)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminobenzene) oxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3-bis(3-(3-aminophenoxy)phenoxy)benzene, 4-bis(4-(4 -Aminophenoxy)phenoxy)benzene, 3-bis(3-(3-(3-aminophenoxy)phenoxy)phenoxy)benzene, 4-bis(4-(4- (4-Aminophenoxy)phenoxy)phenoxy)benzene, 3-bis(α,α-dimethyl-3-aminobenzyl)benzene, 1,4-bis(α,α- Dimethyl-3-aminobenzyl)benzene, 3-bis(α,α-dimethyl-4-aminobenzyl)benzene, bis(4-methylaminepentyl)benzene, p-bis(2 -Methyl-4-aminopentyl)benzene, 1,4-bis(3-aminopropyldimethylsilyl)benzene, bis[(4-aminophenyl)-2-propyl]1,4- Benzene, 2,5-diaminobenzenesulfonic acid, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4' -Diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diamine Diphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-methylene-bis(2-chloroaniline ), 3,3'-diaminodiphenylethane, 4,4'-diaminodiphenylethane, 2,2'-diaminodiphenylpropane, 3,3'-diaminodiphenyl Propane, 4,4'-diaminodiphenylpropane, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-amine phenoxy)phenyl]hexafluoropropane, 3-(2',4'-diaminophenoxy)propanesulfonic acid, bis(4-aminophenyl)diethylsilane, 3,3'- Diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3 '-Dimethyl-4,4'-diaminodiphenyl ether, bis(4-amino tertiary butylphenyl) ether, 4,4'-diaminodiphenyl ether-2,2 '-Disulfonic acid, 3,3'-diaminodiphenyl sulfonate, 4,4'-diaminodiphenyl sulfonate, bis[4-(4-aminophenoxy)phenyl] sulfonate, bis [4-(3-Aminophenoxy)phenyl] terine, benzidine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4 ,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl -6,6'-disulfonic acid, 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl Biphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diaminobiphenyl Sulfide, 4,4'-diamino-3,3'-biphenyldiol, 1,5-diaminenaphthalene, 1,4-diaminenaphthalene, 2,6-diaminenaphthalene, 9,9' -Bis (4-aminophenyl) fluorine, 9,9'-bis (4-aminophenyl) fluorine-2,7-disulfonic acid, 9,9'-bis (4-aminophenoxyphenyl) )amines containing aromatic groups such as fluorine, diamine anthraquinone, 3,7-diamino-2,8-dimethyldibenzothiophene;

伸乙二胺、伸丁二胺、伸戊二胺、伸己二胺、伸庚二胺、伸辛二胺、伸壬二胺、伸癸二胺、2,5-二甲基伸己二胺、3-甲氧基伸己二胺、2,5-二甲基伸庚二胺、3-甲基伸庚二胺、4,4’-二甲基伸庚二胺、5-甲基伸壬二胺、1,4-二胺基環己烷、1,3-雙(3-胺丙基)四甲基二矽氧烷、2,5-二胺基-1,3,4-噁二唑、雙(4-胺基環己基)甲烷等脂肪族胺；三聚氰胺、苯并胍胺、乙醯胍胺、2,4-二胺基-6-乙烯基-s-三氮雜苯、2,4-二胺基-6-烯丙基-s-三氮雜苯、2,4-二胺基-6-丙烯醯基氧乙基-s-三氮雜苯、2,4-二胺基-6-甲基丙烯醯基氧乙基-s-三氮雜苯等胍胺系化合物等。Ethylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptenediamine, octylenediamine, nonylenediamine, decanediamine, 2,5-dimethylhexylenediamine Amine, 3-methoxyhexylenediamine, 2,5-dimethylhexylenediamine, 3-methylheptylenediamine, 4,4'-dimethylhexylenediamine, 5-methylhexylenediamine Nonanediamine, 1,4-diaminocyclohexane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 2,5-diamino-1,3,4-oxane Aliphatic amines such as diazole and bis(4-aminocyclohexyl)methane; melamine, benzoguanamine, acetoguanamine, 2,4-diamino-6-vinyl-s-triazaphenyl, 2,4-Diamino-6-allyl-s-triazaphenyl, 2,4-Diamino-6-propenyloxyethyl-s-triazaphenyl, 2,4-di Guanamine-based compounds such as amino-6-methacryloxyethyl-s-triazaphenyl, etc.

該等之中，較佳是：間苯二胺、對苯二胺、1,4-雙(4-胺基苯氧基)苯、4,4’-二胺基二苯甲烷、3,3’-二甲基-4,4’-二胺基二苯甲烷、3,3’-二乙基-4,4’-二胺基二苯甲烷、2,2’-雙[4-(4-胺基苯氧基)苯基]丙烷、4,4’-二胺基二苯基酮、4,4’-二胺基二苯基醚、3,3’-二胺基二苯碸、4,4’-二胺基二苯碸、雙[4-(4-胺基苯氧基)苯基] 碸、聯苯胺、4,4’-雙(4-胺基苯氧基)聯苯、4,4’-二胺基二苯硫醚、4,4’-二胺基-3,3’-聯苯二醇、苯并胍胺，更佳是3,3’-二乙基-4,4’-二胺基二苯甲烷、2,2’-雙[4-(4-胺基苯氧基)苯基]丙烷。 胺化合物(d)，可以單獨使用1種，亦可以併用2種以上。Among these, preferred are: m-phenylenediamine, p-phenylenediamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenylmethane, 3,3 '-Dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 2,2'-bis[4-(4 -Aminophenoxy)phenyl]propane, 4,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-Diaminodiphenyl, bis[4-(4-aminophenoxy)phenyl]terine, benzidine, 4,4'-bis(4-aminophenoxy)biphenyl , 4,4'-diaminodiphenyl sulfide, 4,4'-diamino-3,3'-biphenyldiol, benzoguanamine, more preferably 3,3'-diethyl- 4,4'-Diaminodiphenylmethane, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane. Amine compound (d) may be used individually by 1 type, or may use 2 or more types together.

當熱硬化性樹脂組成物含有胺化合物(d)時，其含量，從低翹曲性的觀點來看，相對於熱硬化性樹脂組成物中的樹脂成分的固體成分100質量份，較佳是1～40質量份，更佳是2～35質量份，進一步較佳是2～30質量份，又，可以是7～30質量份。When the thermosetting resin composition contains the amine compound (d), from the viewpoint of low warpage, the content is preferably: 1 to 40 parts by mass, more preferably 2 to 35 parts by mass, still more preferably 2 to 30 parts by mass, and may be 7 to 30 parts by mass.

〈硬化促進劑(e)〉 熱硬化性樹脂組成物，可以進一步含有硬化促進劑(e)。 作為硬化促進劑(e)，例如可列舉：環烷酸鋅、環烷酸鈷、辛酸錫、辛酸鈷、雙乙醯丙酮鈷(II)、參乙醯丙酮鈷(III)等有機金屬鹽；咪唑類及其衍生物；有機磷系化合物；二級胺類；三級胺類；四級銨鹽等。該等之中，從耐熱性、難燃性及與金屬電路的黏著強度的觀點來看，較佳是咪唑類及其衍生物，從低熱膨脹性的觀點來看，較佳是有機磷系化合物。 硬化促進劑(e)可以單獨使用1種，亦可以併用2種以上。 作為硬化促進劑(e)，可以使用市售品。作為市售品，可列舉：異氰酸酯遮蔽咪唑(isocyanate-masked imidazole，第一工業製藥股份有限公司製造，商品型號G-8009L)、三苯膦-三苯硼烷(北興化學工業股份有限公司製造，商品型號TPP-S)等。 當熱硬化性樹脂組成物含有硬化促進劑(e)時，其含量，相對於熱硬化性樹脂組成物中的樹脂成分的固體成分100質量份，較佳是0.05～10質量份，更佳是0.01～5質量份，進一步較佳是0.1～1質量份。只要硬化促進劑(e)的含量是0.05質量份以上，就會有耐熱性、難燃性及銅箔黏著性優異的傾向，只要是10質量份以下，就會有耐熱性、經時穩定性及加壓成形性優異的傾向。<Curing accelerator (e)> The thermosetting resin composition may further contain a curing accelerator (e). Examples of the hardening accelerator (e) include: organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, cobalt diacetyl acetonate (II), cobalt acetate acetonate (III); Imidazoles and their derivatives; organophosphorus compounds; secondary amines; tertiary amines; quaternary ammonium salts, etc. Among these, imidazoles and their derivatives are preferred from the viewpoint of heat resistance, flame retardancy, and adhesion strength to metal circuits, and organophosphorus compounds are preferred from the viewpoint of low thermal expansion. . One type of hardening accelerator (e) may be used alone, or two or more types may be used in combination. As the hardening accelerator (e), a commercially available product can be used. Commercially available products include: isocyanate-masked imidazole (manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., product model number G-8009L), triphenylphosphine-triphenylborane (manufactured by Bukheung Chemical Industry Co., Ltd., Product model TPP-S), etc. When the thermosetting resin composition contains the hardening accelerator (e), its content is preferably 0.05 to 10 parts by mass relative to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition, and more preferably 0.01 to 5 parts by mass, more preferably 0.1 to 1 part by mass. When the content of the hardening accelerator (e) is 0.05 parts by mass or more, heat resistance, flame retardancy, and copper foil adhesion tend to be excellent, and when it is 10 parts by mass or less, heat resistance and stability over time tend to be excellent. And tend to have excellent press formability.

〈無機填充材料(f)〉 熱硬化性樹脂組成物，可以進一步含有無機填充材料(f)。 作為無機填充材料，例如可列舉：二氧化矽、氧化鋁、氧化鈦、雲母、鈹土、鈦酸鋇、鈦酸鉀、鈦酸鍶、鈦酸鈣、碳酸鋁、氫氧化鎂、氫氧化鋁、矽酸鋁、碳酸鈣、矽酸鈣、矽酸鎂、氮化矽、氮化硼、煅燒黏土等黏土、滑石、硼酸鋁、碳化矽、石英粉末、短玻璃纖維、玻璃微細粉末(glass fine powder)、中空玻璃等。作為玻璃，較佳可列舉E型玻璃、T型玻璃、D型玻璃等。 在該等之中，從介電特性、耐熱性及低熱膨脹性的觀點來看，較佳是二氧化矽。作為二氧化矽，例如可列舉：利用濕式法所製成的含水率高的沉澱二氧化矽、利用乾式法所製成的幾乎不含有結合水等乾式法二氧化矽，作為乾式法二氧化矽，藉由其製造法的不同，可分類為破碎二氧化矽、發煙二氧化矽、熔融球狀二氧化矽等。在該等之中，從低熱膨脹性和當填充在樹脂中時的流動性的觀點來看，較佳是熔融球狀二氧化矽。 無機填充材料(f)可以單獨使用1種，亦可以併用2種以上。<Inorganic filler (f)> The thermosetting resin composition may further contain an inorganic filler (f). Examples of the inorganic filler include silicon dioxide, aluminum oxide, titanium oxide, mica, beryllium earth, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, and aluminum hydroxide. , aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay and other clays, talc, aluminum borate, silicon carbide, quartz powder, short glass fiber, glass fine powder (glass fine powder), insulating glass, etc. Preferred examples of glass include E-type glass, T-type glass, and D-type glass. Among these, silicon dioxide is preferred from the viewpoints of dielectric properties, heat resistance, and low thermal expansion. Examples of silica include precipitated silica with a high moisture content produced by a wet process, dry silica containing little bound water, etc. produced by a dry process, and dry process silica. Silicon, depending on its manufacturing method, can be classified into crushed silica, fumed silica, fused spherical silica, etc. Among these, molten spherical silica is preferable from the viewpoint of low thermal expansion and fluidity when filled in resin. The inorganic filler (f) may be used individually by 1 type, or may be used in combination of 2 or more types.

無機填充材料的平均粒徑，較佳是0.1～10μm，更佳是0.3～8μm，進一步較佳是0.3～3μm。若平均粒徑是0.1μm以上，高度填充至樹脂中時會有良好地保持流動性的傾向，若是10μm以下，可降低粗粒子的混入機率，而會有能夠抑制源自於粗粒子所產生的不良的傾向。在此處，所謂的平均粒徑，是將粒子的總體積設為100%來求得源自粒徑的累積粒度分布曲線時，對應於體積50%的點的粒徑，該平均粒徑能夠藉由使用雷射繞射散射法的粒度分布測定裝置等來測定。 無機填充材料(f)，可以利用耦合劑來進行表面處理而成。藉由耦合劑進行的表面處理的方式，可以是以乾式或濕式來對調配前的無機填充材料(f)進行表面處理的方式，亦可以是整體摻混(integral blending)處理方式，其是在將未經表面處理的無機填充材料(f)調配至其他成分中作成組成物後，在該組成物中添加矽烷耦合劑。 作為耦合劑，例如可列舉：矽烷系耦合劑、鈦酸酯系耦合劑、矽氧寡聚物等。The average particle size of the inorganic filler is preferably 0.1 to 10 μm, more preferably 0.3 to 8 μm, and still more preferably 0.3 to 3 μm. If the average particle diameter is 0.1 μm or more, it will tend to maintain good fluidity when highly filled in the resin. If it is 10 μm or less, the probability of mixing coarse particles can be reduced, and it is possible to suppress the generation of coarse particles. Bad tendencies. Here, the average particle diameter is the particle diameter corresponding to the point of 50% of the volume when the cumulative particle size distribution curve derived from the particle diameter is obtained by setting the total volume of the particles to 100%. This average particle diameter can It is measured by a particle size distribution measuring device using laser diffraction scattering method, etc. The inorganic filler material (f) can be surface-treated with a coupling agent. The surface treatment method by the coupling agent can be a dry or wet method of surface treatment of the inorganic filler material (f) before preparation, or it can be an integral blending treatment method, which is After the inorganic filler material (f) without surface treatment is mixed with other components to prepare a composition, a silane coupling agent is added to the composition. Examples of the coupling agent include silane coupling agents, titanate coupling agents, silicon oxygen oligomers, and the like.

當熱硬化性樹脂組成物含有無機填充材料(f)時，其含量，相對於熱硬化性樹脂組成物中的樹脂成分的固體成分100質量份，較佳是20～400質量份，更佳是50～350質量份，進一步較佳是70～230質量份。若無機填充材料(f)的含量在前述範圍內，成形性和低熱膨脹性為良好。When the thermosetting resin composition contains the inorganic filler (f), its content is preferably 20 to 400 parts by mass based on 100 parts by mass of the solid content of the resin component in the thermosetting resin composition, and more preferably 50 to 350 parts by mass, more preferably 70 to 230 parts by mass. If the content of the inorganic filler (f) is within the aforementioned range, the formability and low thermal expansion will be good.

〈其他成分〉 本發明的熱硬化性樹脂組成物，在不損害熱硬化性的性質的程度內，可以含有有機填充材料、難燃劑、紫外線吸收劑、抗氧化劑、光聚合起始劑、螢光增白劑、黏著性提升劑等。<Other components> The thermosetting resin composition of the present invention may contain organic fillers, flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, and fluorescent materials to the extent that the thermosetting properties are not impaired. Optical brighteners, adhesion enhancers, etc.

作為有機填充材料，例如可列舉：由聚乙烯、聚丙烯、聚苯乙烯、聚苯醚樹脂、矽氧樹脂、四氟乙烯樹脂等所構成的樹脂填料；及，核殼(core shell)結構之樹脂填料等，該核殼結構具有橡膠狀態的核層與玻璃狀態的殼層，該核層由丙烯酸酯系樹脂、甲基丙烯酸酯系樹脂、共軛二烯系樹脂等所構成，該殼層由丙烯酸酯系樹脂、甲基丙烯酸酯系樹脂、芳香族乙烯系樹脂、氰化乙烯系樹脂等所構成。Examples of organic fillers include resin fillers made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, etc.; and those with a core shell structure. Resin fillers, etc., the core-shell structure has a rubber-state core layer and a glass-state shell layer. The core layer is composed of acrylate resin, methacrylate resin, conjugated diene resin, etc., and the shell layer It is composed of acrylate resin, methacrylate resin, aromatic vinyl resin, cyanide vinyl resin, etc.

作為難燃劑，例如可列舉：含有溴、氯等含有鹵素系之難燃劑；磷酸三苯酯、磷酸三甲苯酯、磷酸參二氯丙酯、磷酸酯系化合物、紅磷等磷系難燃劑；胺磺酸胍、硫酸三聚氰胺酯、多磷酸三聚氰胺酯、三聚氰酸三聚氰胺酯等氮系難燃劑；環偶磷氮(cyclophosphazene)、聚偶磷氮(polyphosphazene)等偶磷氮系難燃劑；三氧化二銻等無機系難燃劑等。Examples of the flame retardants include halogen-containing flame retardants such as bromine and chlorine; phosphorus-based flame retardants such as triphenyl phosphate, tricresyl phosphate, dichloropropyl phosphate, phosphate ester compounds, and red phosphorus. Fire agents; Nitrogen-based flame retardants such as guanidine sulfonate, melamine sulfate, melamine polyphosphate, and melamine cyanurate; aphosphorous nitrogen-based flame retardants such as cyclophosphazene and polyphosphazene Flame retardants; antimony trioxide and other inorganic flame retardants.

作為紫外線吸收劑，例如可列舉苯并***系紫外線吸收劑。 作為抗氧化劑，例如可列舉：受阻酚(hindered phenol)系抗氧化劑、受阻胺(hindered amine)系抗氧化劑等。 作為光聚合起始劑，例如可列舉：二苯基酮類、苯甲基縮酮(benzyl ketal)類、9-氧硫[口+山][口+星]系(thioxanthone)等光聚合起始劑。 作為螢光增白劑，例如可列舉二苯乙烯衍生物的螢光增白劑等。 作為黏著性提升劑，例如可列舉：尿素矽烷等尿素化合物、前述耦合劑等。Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers. Examples of antioxidants include hindered phenol antioxidants, hindered amine antioxidants, and the like. Examples of the photopolymerization initiator include benzophenones, benzyl ketals, thioxanthone and other photopolymerizable initiators. starter. Examples of the fluorescent whitening agent include fluorescent whitening agents of stilbene derivatives. Examples of the adhesion improving agent include urea compounds such as ureasilane and the coupling agent described above.

熱硬化性樹脂組成物，可以是清漆狀態，其易於使用在預浸體等的製造中，並且是各成分已溶解或分散在有機溶劑中而成。The thermosetting resin composition may be in a varnish state, is easily used in the production of prepregs, etc., and has each component dissolved or dispersed in an organic solvent.

作為該有機溶劑，例如可列舉：甲醇、乙醇、丙醇、丁醇、甲基賽璐蘇、丁基賽璐蘇、丙二醇單甲基醚等醇系溶劑；丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮系溶劑；乙酸丁酯、丙二醇單甲基醚乙酸酯等酯系溶劑；四氫呋喃等醚系溶劑；甲苯、二甲苯、均三甲苯等芳香族系溶劑；二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮等含有氮原子之溶劑；二甲亞碸等含有硫原子之溶劑等。該等溶劑可以單獨使用1種，亦可以併用2種以上。 該等之中，從各成分的溶解性的觀點來看，較佳是甲基乙基酮、甲基異丁基酮、環己酮、甲基賽璐蘇、丙二醇單甲基醚，更佳是甲基乙基酮，又，從低毒性這樣的觀點來看，更佳是甲基異丁基酮、環己酮、丙二醇單甲基醚。 清漆的固體成分濃度，較佳是40～90質量%，更佳是50～80質量%。若清漆的固體成分濃度在前述範圍內，便能夠獲得良好地保持塗佈性，並且能夠獲得熱硬化性樹脂組成物的含量適當的預浸體。Examples of the organic solvent include alcohol-based solvents such as methanol, ethanol, propanol, butanol, methylcellulose, butylcellulose, and propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methane, etc. Ketone solvents such as isobutyl ketone and cyclohexanone; ester solvents such as butyl acetate and propylene glycol monomethyl ether acetate; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and mesitylene. ; Solvents containing nitrogen atoms such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; solvents containing sulfur atoms such as dimethylsulfoxide, etc. One type of these solvents may be used alone, or two or more types may be used in combination. Among these, from the viewpoint of the solubility of each component, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcellulose, and propylene glycol monomethyl ether are more preferred. It is methyl ethyl ketone, and from the viewpoint of low toxicity, methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferred. The solid content concentration of the varnish is preferably 40 to 90% by mass, more preferably 50 to 80% by mass. When the solid content concentration of the varnish is within the above range, it is possible to obtain a prepreg in which the coating properties are maintained well and the content of the thermosetting resin composition is appropriate.

[骨材] 可用於本發明的骨材，可列舉：玻璃、碳等無機纖維基材；聚芳醯胺、纖維素等有機纖維基材；鐵、銅、鋁、該等金屬的合金等所構成的金屬纖維基材等。該等可以單獨使用1種，亦可以併用2種以上。尤其，從介電特性的觀點來看，較佳是無機物纖維，更佳是低介電玻璃、Q型玻璃。 作為骨材，例如能夠使用具有織布、不織布、粗紗(roving)、切股纖維氈(chopped strand mat)或表面氈(surfacing mat)等形狀者。該等之中，較佳是織布或不織布。 骨材的材質和形狀，可依據設為目的的成形物的用途、性能等來適當選擇，依據需要，可以是由1種材質和1種形狀所組成之纖維基材，亦可以是2種以上的材質所組成之骨材，亦可以是具有2種以上的形狀之骨材。 骨材的厚度，例如是5μm～0.5mm，從能夠作成低翹曲性和高密度線路的觀點來看，較佳是5μm～100μm，更佳是8μm～60μm，進一步較佳是10～30μm。該等骨材，從耐熱性、耐濕性、加工性等觀點來看，較佳是利用矽烷耦合劑等經表面處理而成者、或經施以機械性開纖處理而成者。[Aggregate] Aggregates that can be used in the present invention include inorganic fiber base materials such as glass and carbon; organic fiber base materials such as polyarylamide and cellulose; iron, copper, aluminum, alloys of these metals, etc. Made of metal fiber substrate, etc. One type of these may be used alone, or two or more types may be used in combination. In particular, from the viewpoint of dielectric properties, inorganic fibers are preferred, and low dielectric glass and Q-type glass are more preferred. As the aggregate material, those having a shape such as woven fabric, nonwoven fabric, roving, chopped strand mat, or surfacing mat can be used. Among these, woven or non-woven fabric is preferred. The material and shape of the aggregate can be appropriately selected according to the use and performance of the intended molded article. Depending on the needs, it can be a fiber base material composed of one material and one shape, or it can be two or more types. The aggregates composed of different materials can also be aggregates with two or more shapes. The thickness of the aggregate material is, for example, 5 μm to 0.5 mm. From the viewpoint of producing low warpage and high-density circuits, it is preferably 5 μm to 100 μm, more preferably 8 μm to 60 μm, and still more preferably 10 to 30 μm. From the viewpoints of heat resistance, moisture resistance, processability, etc., it is preferable that these aggregates are surface-treated with a silane coupling agent or the like, or that are subjected to mechanical fiber opening treatment.

纖維強化塑膠前驅物中的熱硬化性樹脂組成物的固體成分的含量，較佳是20～90質量%。The solid content of the thermosetting resin composition in the fiber-reinforced plastic precursor is preferably 20 to 90% by mass.

[附有支撐體之樹脂薄膜] 在本發明中使用於纖維強化塑膠前驅物的製造的附有支撐體之樹脂薄膜，例如能夠藉由將熱硬化性樹脂組成物塗佈在支撐體上，在90～130℃乾燥1～10分鐘來製造。 作為支撐體，並無特別限定，例如可列舉：有機樹脂薄膜、金屬箔、脫模紙等。 作為有機樹脂薄膜的材質，可列舉：聚乙烯、聚氯化乙烯等聚烯烴；聚對苯二甲酸乙二酯(以下，亦稱為「PET」)、聚萘二甲酸乙二酯等聚酯；聚碳酸酯、聚醯亞胺等。在該等之中，從價格和處理性的觀點來看，較佳是PET。也就是說，作為有機樹脂薄膜，較佳是PET薄膜。 作為金屬箔，可列舉銅箔、鋁箔等。當在支撐體上使用銅箔時，銅箔可直接作成導體層，亦能夠形成電路。此時，作為銅箔，能夠使用壓延銅箔、電解銅箔等。又，銅箔的厚度並無特別限定，例如能夠使用具有2～36μm的厚度者。當使用厚度較薄的銅箔時，從使作業性提升的觀點來看，可以使用附有承載(carrier)之銅箔。 支撐體的厚度，並無特別限定，從處理性的觀點來看，較佳是10～120μm，更佳是15～80μm，進一步較佳是15～70μm。 支撐體，不必是如上所述的單一成分，亦可以利用複數層(2層以上)的不同材料來形成。[Resin film with support] The resin film with support used in the production of the fiber-reinforced plastic precursor in the present invention can be formed by coating a thermosetting resin composition on the support, for example. Manufacture by drying at 90 to 130°C for 1 to 10 minutes. The support is not particularly limited, and examples thereof include organic resin films, metal foils, release papers, and the like. Examples of the material of the organic resin film include polyolefins such as polyethylene and polyethylene chloride; and polyesters such as polyethylene terephthalate (hereinafter also referred to as "PET") and polyethylene naphthalate. ; Polycarbonate, polyimide, etc. Among these, PET is preferable from the viewpoint of price and handleability. That is, as the organic resin film, a PET film is preferred. Examples of the metal foil include copper foil, aluminum foil, and the like. When copper foil is used on the support, the copper foil can be directly used as a conductor layer and can also form a circuit. At this time, as the copper foil, rolled copper foil, electrolytic copper foil, etc. can be used. Moreover, the thickness of a copper foil is not specifically limited, For example, what has a thickness of 2-36 micrometers can be used. When using a thin copper foil, from the viewpoint of improving workability, a copper foil with a carrier can be used. The thickness of the support is not particularly limited, but from the viewpoint of handleability, it is preferably 10 to 120 μm, more preferably 15 to 80 μm, and still more preferably 15 to 70 μm. The support does not have to be a single component as described above, but can also be formed using multiple layers (two or more layers) of different materials.

藉由本發明所獲得的纖維強化塑膠前驅物，用於無芯基板方面是有用的。 無芯基板，例如是藉由下述方式來製造：在核心基板(core substrate)上，使用本發明的預浸體來形成導體層與絕緣層交互地積層而成的增層(build-up layer)後，分離去除前述核心基板而成。再者，前述增層的形成方法並無特別限制，能夠採用公知的方法。例如，增層能夠藉由以下的方法來形成。 首先，在核心基板上配置預浸體1。再者，在前述核心基板上配置黏著層後，亦可以配置預浸體2。之後，將預浸體2進行加熱硬化來作成絕緣層。繼而，藉由穿孔切割方法、或使用YAG雷射或二氧化碳雷射等雷射加工方法等，來形成通孔(via hole)後，依據需要來實行表面粗糙化處理和除膠渣(desmear)處理。繼而，藉由減去法(subtractive process)、全加成法(fully-additive process)、半加成法( semi-additive process)、模擬半加成法(mSAP，modified semi additive process)等來形成電路圖案。藉由重複進行以上的過程，便可形成增層。所形成的增層，可藉由從核心基板分離，來獲得無芯基板。The fiber-reinforced plastic precursor obtained by the present invention is useful for coreless substrates. The coreless substrate is manufactured, for example, by using the prepreg of the present invention on a core substrate to form a build-up layer in which conductor layers and insulating layers are alternately laminated. ), the aforementioned core substrate is separated and removed. Furthermore, the method of forming the build-up layer is not particularly limited, and a known method can be used. For example, the build-up layer can be formed by the following method. First, the prepreg 1 is placed on the core substrate. Furthermore, after the adhesive layer is disposed on the core substrate, the prepreg 2 can also be disposed. Thereafter, the prepreg 2 is heated and cured to form an insulating layer. Then, after forming via holes by punch cutting, or using laser processing methods such as YAG laser or carbon dioxide laser, surface roughening and desmearing are performed as needed. . Then, it is formed by subtractive process, fully-additive process, semi-additive process, modified semi-additive process (mSAP, modified semi-additive process), etc. circuit pattern. By repeating the above process, a build-up layer can be formed. The formed build-up layer can be separated from the core substrate to obtain a coreless substrate.

[積層體的製造方法和印刷線路板的製造方法] 本發明亦提供一種積層體的製造方法，該積層體藉由將纖維強化塑膠前驅物積層並進行成形而成，該纖維強化塑膠前驅物藉由前述製造方法所獲得。更具體而言，準備1片利用本發明而得的纖維強化塑膠前驅物(例如預浸體)或重疊2～20片該纖維強化塑膠前驅物而成之纖維強化塑膠前驅物，依據需要，在其中一面或雙面上，以經配置銅、鋁等金屬箔而成的結構來積層並進行成形，藉此便能夠製造積層體(亦稱為積層板)。金屬箔只要是可用於電絕緣材料用途者，並無特別限制，較佳是銅箔。當金屬箔是銅箔時，所獲得的積層體(積層板)，一般而言稱為覆銅積層板。 製造積層體時的成形條件，例如能夠應用電絕緣材料用積層板和多層板的成形條件。具體而言，能夠使用多段加壓、多段真空加壓、連續成形、熱壓成形機等，並利用溫度100～250℃、壓力0.2～10MPa、加熱時間0.1～5小時這樣的條件來進行成形。又，亦能夠將纖維強化塑膠前驅物與內層用線路板組合來積層並進行成形，來製造積層體。 進一步，藉由在前述積層體上形成電路，更具體而言，藉由將前述金屬箔進行電路加工，便能夠製造印刷線路板。[Method for manufacturing a laminated body and a method for manufacturing a printed wiring board] The present invention also provides a method for manufacturing a laminated body formed by laminating and molding a fiber-reinforced plastic precursor. Obtained by the aforementioned manufacturing method. More specifically, one piece of the fiber-reinforced plastic precursor (for example, a prepreg) obtained by the present invention or a fiber-reinforced plastic precursor obtained by stacking 2 to 20 pieces of the fiber-reinforced plastic precursor is prepared. If necessary, A laminated body (also called a laminated board) can be produced by laminating and molding a structure in which metal foils such as copper and aluminum are placed on one or both sides. The metal foil is not particularly limited as long as it can be used as an electrical insulating material, but copper foil is preferred. When the metal foil is copper foil, the obtained laminated body (laminated board) is generally called a copper-clad laminated board. For example, the molding conditions for electrically insulating material laminates and multilayer boards can be applied to the molding conditions when manufacturing the laminated body. Specifically, multi-stage pressurization, multi-stage vacuum pressure, continuous molding, hot press molding machine, etc. can be used, and the molding can be performed using conditions such as a temperature of 100 to 250° C., a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours. Alternatively, a fiber-reinforced plastic precursor and an inner layer wiring board may be combined, laminated, and molded to produce a laminated body. Furthermore, by forming a circuit on the laminated body, more specifically, by subjecting the metal foil to circuit processing, a printed wiring board can be manufactured.

[半導體封裝體] 本發明亦提供一種半導體封裝體的製造方法，該半導體封裝體藉由在印刷線路板上裝配半導體元件而成，該印刷線路板藉由前述製造方法所獲得。半導體封裝體，能夠藉由在前述印刷線路板的特定位置上裝配半導體晶片、記憶體等半導體元件，並藉由密封樹脂等來密封半導體元件來製造。 [實施例][Semiconductor Package] The present invention also provides a method for manufacturing a semiconductor package, which is formed by assembling semiconductor elements on a printed wiring board obtained by the aforementioned manufacturing method. A semiconductor package can be manufactured by mounting a semiconductor chip, a memory, or other semiconductor element at a specific position on the printed circuit board, and sealing the semiconductor element with a sealing resin or the like. [Example]

繼而，藉由下述實施例來進一步詳細地說明本發明，但是該等實施例並非用以限制本發明。 再者，有關利用以下的實施例而獲得的纖維強化塑膠前驅物，利用以下的方法來測定和評價其物性或特性。Next, the present invention will be further described in detail through the following examples, but these examples are not intended to limit the present invention. Furthermore, regarding the fiber-reinforced plastic precursor obtained in the following examples, the physical properties or characteristics thereof were measured and evaluated by the following method.

(1)剝離時對支撐體的樹脂殘留性 在製造纖維強化塑膠前驅物後，以手動的方式從附有支撐體的纖維強化塑膠前驅物剝離該支撐體，並目視觀察支撐體的狀態，然後依據下述評價基準來評價。再者，評價為A時，是樹脂充分地轉印在骨材上的狀態，並且與支撐體的剝離性良好，作為製品為合格。當評價為B和C時，作為製品皆不合格。 A：支撐體上完全沒有樹脂附著。 B：支撐體上附著有一些樹脂。 C：支撐體上附著有許多樹脂。(1) Resin residue on the support during peeling. After manufacturing the fiber-reinforced plastic precursor, manually peel the support from the fiber-reinforced plastic precursor attached to the support, and visually observe the state of the support, and then Evaluation is based on the following evaluation criteria. In addition, when the evaluation is A, the resin is fully transferred to the aggregate and the releasability from the support is good, so the product is acceptable. When the evaluation is B or C, both products are unqualified. A: There is no resin attached to the support at all. B: There is some resin attached to the support. C: A lot of resin is attached to the support.

(2)耐熱性(焊接耐熱性) 使評價基板漂浮在288℃的焊料槽(solder bath)中1分鐘後，藉由目視觀察外觀，來評價焊接耐熱性，該評價基板是由各例製成的覆銅積層板裁切成5cm見方的大小而得。 無法確認到膨脹者評價為「良好」，確認到膨脹者則評價為「有膨脹」。(2) Heat resistance (soldering heat resistance) The evaluation substrate was floated in a 288°C solder bath for 1 minute, and then the appearance was visually observed to evaluate the soldering heat resistance. The evaluation substrate was made from each example. The copper-clad laminated board is cut into 5cm square size. Those whose expansion could not be confirmed were evaluated as "good", and those whose expansion was confirmed were evaluated as "with expansion".

(3)翹曲量 依據下述步驟，由各例製成的覆銅積層板來作成評價用基板，並使用表面形狀測定裝置(AKROMETRIX公司製造，商品型號TherMoire PS200，陰影疊紋(Shadow Moire)分析)，來測定前述評價用基板的翹曲量。 首先，在覆銅積層板的雙面上形成殘銅率40%的電路圖案，在雙面上塗佈阻劑並且焙燒後，切割出40mm×40mm的大小。藉由混有銀粉的環氧樹脂系導電性黏著劑，將20mm×20mm的矽晶片固定在中央部，然後使用環氧樹脂系密封材料進行密封，作成評價用基板。 將處於室溫的評價用基板加熱至260℃，之後，測定當冷卻至50℃時的翹曲量。藉由該方法所測得的翹曲量，較佳是70μm以下，更佳是65μm以下，該翹曲量越少越佳。(3) Warp amount According to the following procedure, a substrate for evaluation was prepared from the copper-clad laminate produced in each example, and a surface shape measuring device (manufactured by AKROMETRIX, product model TherMoire PS200, Shadow Moire) was used analysis) to measure the amount of warpage of the evaluation substrate. First, a circuit pattern with a residual copper rate of 40% is formed on both sides of the copper-clad laminate. After applying resist on both sides and baking, the circuit pattern is cut into a size of 40 mm × 40 mm. A 20 mm × 20 mm silicon wafer was fixed in the center with an epoxy resin-based conductive adhesive mixed with silver powder, and then sealed with an epoxy resin-based sealing material to prepare an evaluation substrate. The evaluation substrate at room temperature was heated to 260°C, and then the amount of warpage when cooled to 50°C was measured. The amount of warpage measured by this method is preferably 70 μm or less, more preferably 65 μm or less, and the smaller the warpage amount, the better.

[實施例1～7、比較例1～4] 以表1所示的調配比例(表中的數值的單位是質量份)混合以下所示的各成分，並使用甲基乙基酮作為溶劑，製成固體成分濃度65質量%的清漆。 繼而，將各清漆塗佈在支撐體也就是PET薄膜(帝人杜邦薄膜股份有限公司製造，商品型號G2)上，藉由在90～130℃加熱乾燥3分鐘，獲得附有支撐體之樹脂薄膜(樹脂厚：60μm)。 繼而，以2片附有支撐體之樹脂薄膜各自的樹脂側與骨材(厚度25μm的E型玻璃纖維布)相對向的方式進行配置。藉由加壓滾輪，以滾輪溫度100℃、線壓力0.2MPa、速度2.0m/分鐘的條件將其疊層，來將樹脂組成物加壓含浸在骨材中。 之後，實行捲取，繼而，以手動方式將PET薄膜從雙面剝離，藉此獲得纖維強化塑膠前驅物(預浸體)。 使用1片此纖維強化塑膠前驅物，將12μm的電解銅箔配置在該纖維強化塑膠前驅物的上下，以壓力2.5MPa、溫度200～240℃的條件實行加壓60分鐘，來獲得覆銅積層板。使用所獲得的覆銅積層板，依據前述測定方法來評價各物性。將結果顯示於表1。[Examples 1 to 7, Comparative Examples 1 to 4] The following components were mixed at the mixing ratios shown in Table 1 (the units of values in the table are parts by mass), and methyl ethyl ketone was used as the solvent. A varnish with a solid content concentration of 65% by mass was produced. Next, each varnish is applied to a support, which is a PET film (manufactured by Teijin DuPont Film Co., Ltd., product model G2), and is heated and dried at 90 to 130° C. for 3 minutes to obtain a resin film with a support ( Resin thickness: 60μm). Next, two resin films with a support were arranged so that their respective resin sides faced the aggregate (E-type glass fiber cloth with a thickness of 25 μm). The resin composition is pressure-impregnated into the aggregate by laminating it using a pressurizing roller under the conditions of roller temperature of 100°C, linear pressure of 0.2MPa, and speed of 2.0m/min. Thereafter, winding is performed, and then the PET film is manually peeled off from both sides, thereby obtaining a fiber-reinforced plastic precursor (prepreg). Using one piece of this fiber-reinforced plastic precursor, place 12 μm electrolytic copper foil above and below the fiber-reinforced plastic precursor, and pressurize it for 60 minutes at a pressure of 2.5 MPa and a temperature of 200 to 240°C to obtain a copper-clad laminate. plate. Using the obtained copper-clad laminated board, various physical properties were evaluated according to the aforementioned measurement method. The results are shown in Table 1.

[矽氧烷化合物(a)] (a-1)：兩末端環氧基改質矽氧烷 (信越化學工業股份有限公司製造，商品型號X-22-163A，環氧基的官能基當量1000g/mol) (a-2)：側鏈甲醇改質矽氧烷 (信越化學工業股份有限公司製造，商品型號X-22-4039，羥基價58mg KOH/g) (a-3)：兩末端胺改質矽氧烷 (信越化學工業股份有限公司製造，商品型號X-22-161A，胺基的官能基當量800g/mol)[Siloxane compound (a)] (a-1): Modified siloxane with both terminal epoxy groups (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product model number X-22-163A, functional group equivalent of epoxy group: 1000 g /mol) (a-2): Side chain methanol-modified siloxane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product model number X-22-4039, hydroxyl value 58 mg KOH/g) (a-3): Both terminal amines Modified siloxane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product model number X-22-161A, functional group equivalent of amine group 800g/mol)

[熱硬化性樹脂(b)] (b-1)α-萘酚/甲酚酚醛清漆型環氧樹脂 (日本化藥股份有限公司製造，商品型號NC-7000L，環氧基當量223～238g/eq) (b-2)聯苯芳烷型環氧樹脂 (日本化藥股份有限公司製造，商品型號NC-3000-H，環氧基當量280～300g/eq) (b-3)苯酚樹脂 (DIC股份有限公司製造，苯酚酚醛清漆樹脂，商品型號PHENOLITE(註冊商標)TD-2090，羥基當量105g/eq)[Thermosetting resin (b)] (b-1) α-naphthol/cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product model NC-7000L, epoxy equivalent weight 223 to 238 g/ eq) (b-2) Biphenyl aralkane type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product model NC-3000-H, epoxy equivalent weight 280~300g/eq) (b-3) Phenol resin ( Manufactured by DIC Co., Ltd., phenol novolak resin, product model PHENOLITE (registered trademark) TD-2090, hydroxyl equivalent 105g/eq)

[馬來醯亞胺化合物(c)] (c-1)雙(4-馬來醯亞胺基苯基)甲烷 (K.I.化成股份有限公司製造，商品型號BMI) (c-2)2,2-雙[4-(4-馬來醯亞胺基苯氧基)苯基]丙烷 (大和化成工業股份有限公司製造，商品型號BMI-4000)[Maleimide compound (c)] (c-1) Bis(4-maleimidophenyl)methane (manufactured by K.I. Chemicals Co., Ltd., product model number BMI) (c-2) 2,2 -Bis[4-(4-maleiminophenoxy)phenyl]propane (manufactured by Yamato Chemical Industry Co., Ltd., product model number BMI-4000)

[胺化合物(d)] (d-1)3,3’-二乙基-4,4’-二胺基二苯甲烷 (日本化藥股份有限公司製造，商品型號KAYAHARD A-A) (d-2)2,2’-雙[(4-(4-胺基苯氧基)苯基)丙烷] (和歌山精化工業股份有限公司製造，商品型號BAPP)[Amine compound (d)] (d-1) 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., product model number KAYAHARD A-A) (d-2 )2,2'-bis[(4-(4-aminophenoxy)phenyl)propane] (manufactured by Wakayama Seika Industry Co., Ltd., product model number BAPP)

[硬化促進劑(e)] (e-1) 異氰酸酯遮蔽咪唑 (第一工業製藥股份有限公司製造，商品型號G-8009L) (e-2)四苯基鏻硼酸四對甲苯酯 (北興化學工業股份有限公司製造，商品型號TPP-MK)[Harding accelerator (e)] (e-1) Isocyanate-shielded imidazole (manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., product model number G-8009L) (e-2) Tetraphenylphosphonium borate tetra-p-tolyl (Bukheung Chemical Industry Co., Ltd., product model TPP-MK)

[無機填充材料(f)] (f-1)球狀熔融二氧化矽 (Admatechs股份有限公司製造，平均粒徑0.5μm)[Inorganic filler (f)] (f-1) Spherical fused silica (manufactured by Admatechs Co., Ltd., average particle size 0.5 μm)

[表1] 表示各成分的含量的數值單位是質量份。[Table 1] The numerical unit expressing the content of each component is parts by mass.

由表1可知，實施例在剝離時對支撐體的樹脂殘留性較小、耐熱性優異且可降低基板的翹曲量。另一方面，比較例在剝離時對支撐體的樹脂殘留性、耐熱性及基板的翹曲的評價中，至少有1項較差。 從而可知，根據本發明的纖維強化塑膠前驅物的製造方法，可獲得外觀良好的纖維強化塑膠前驅物，進一步，可獲得具有良好的耐熱性且可抑制翹曲的積層板。 [產業上的可利用性]As can be seen from Table 1, the Examples have less resin residue on the support during peeling, excellent heat resistance, and can reduce the amount of warpage of the substrate. On the other hand, the comparative example was poor in at least one of the evaluations of the resin residue of the support during peeling, the heat resistance, and the warpage of the substrate. Therefore, it can be seen that according to the manufacturing method of the fiber-reinforced plastic precursor of the present invention, a fiber-reinforced plastic precursor with good appearance can be obtained, and further, a laminate having good heat resistance and capable of suppressing warpage can be obtained. [Industrial availability]

因為藉由本發明所獲得的熱硬化性樹脂組成物，能夠獲得具有良好的耐熱性且可抑制翹曲的積層板，所以在經高密度化和高度多層化的印刷線路板的製造用途方面是有用的，進一步，能夠適合用於電子機器的線路板中，該電子機器是高速地處理大量資料的電腦和情報機器終端等。The thermosetting resin composition obtained by the present invention can obtain a laminated board that has good heat resistance and can suppress warpage, so it is useful in the production of high-density and highly multi-layered printed wiring boards. Furthermore, it can be suitably used in circuit boards of electronic equipment such as computers and information equipment terminals that process large amounts of data at high speed.

1‧‧‧纖維強化塑膠前驅物2‧‧‧骨材送出裝置3‧‧‧樹脂薄膜送出裝置4‧‧‧保護薄膜剝除機構5‧‧‧保護薄膜捲取裝置6‧‧‧薄片加熱加壓裝置(薄膜壓接手段)7‧‧‧薄片加壓冷卻裝置8‧‧‧纖維強化塑膠前驅物捲取裝置40‧‧‧骨材40a‧‧‧骨材的表面(骨材的其中一表面，骨材的兩表面的其中一面)40b‧‧‧骨材的背面(骨材的另一表面，骨材的兩表面的另一面)50‧‧‧附有保護薄膜之樹脂薄膜52‧‧‧保護薄膜54‧‧‧樹脂薄膜(薄膜)54a‧‧‧樹脂薄膜的骨材側的表面(骨材側薄膜表面)60‧‧‧纖維強化塑膠前驅物1‧‧‧Fiber reinforced plastic precursor 2‧‧‧Aggregate delivery device 3‧‧‧Resin film delivery device 4‧‧‧Protective film stripping mechanism 5‧‧‧Protective film winding device 6‧‧‧Sheet heating Pressing device (film crimping means) 7‧‧‧Sheet pressurizing and cooling device 8‧‧‧Fiber reinforced plastic precursor winding device 40‧‧‧Aggregate 40a‧‧‧The surface of the aggregate (one of the surfaces of the aggregate , one of the two surfaces of the aggregate) 40b‧‧‧The back of the aggregate (the other surface of the aggregate, the other side of the two surfaces of the aggregate) 50‧‧‧Resin film with protective film 52‧‧‧ Protective film 54‧‧‧Resin film (film) 54a‧‧‧Resin film surface on the aggregate side (aggregate side film surface) 60‧‧‧Fiber reinforced plastic precursor

第1圖是顯示可用於本發明中的纖維強化塑膠前驅物的製造裝置的一態樣的概要圖。FIG. 1 is a schematic diagram showing an aspect of a manufacturing apparatus for a fiber-reinforced plastic precursor that can be used in the present invention.

國內寄存資訊 (請依寄存機構、日期、號碼順序註記) 無Domestic storage information (please note in order of storage institution, date and number) None

國外寄存資訊 (請依寄存國家、機構、日期、號碼順序註記) 無Overseas deposit information (please note in order of deposit country, institution, date and number) None

1‧‧‧纖維強化塑膠前驅物 1‧‧‧Fiber reinforced plastic precursor

2‧‧‧骨材送出裝置 2‧‧‧Aggregate delivery device

3‧‧‧樹脂薄膜送出裝置 3‧‧‧Resin film feeding device

4‧‧‧保護薄膜剝除機構 4‧‧‧Protective film peeling mechanism

5‧‧‧保護薄膜捲取裝置 5‧‧‧Protective film winding device

6‧‧‧薄片加熱加壓裝置(薄膜壓接手段) 6‧‧‧Sheet heating and pressurizing device (film crimping method)

7‧‧‧薄片加壓冷卻裝置 7‧‧‧Sheet pressure cooling device

8‧‧‧纖維強化塑膠前驅物捲取裝置 8‧‧‧Fiber reinforced plastic precursor winding device

40‧‧‧骨材 40‧‧‧Aggregate

40a‧‧‧骨材的表面 40a‧‧‧Surface of aggregate

40b‧‧‧骨材的背面 40b‧‧‧Back side of aggregate

50‧‧‧附有保護薄膜之樹脂薄膜 50‧‧‧Resin film with protective film

52‧‧‧保護薄膜 52‧‧‧Protective film

54‧‧‧樹脂薄膜(薄膜) 54‧‧‧Resin film (film)

54a‧‧‧樹脂薄膜的骨材側的表面(骨材側薄膜表面) 54a‧‧‧The surface of the resin film on the aggregate side (film surface on the aggregate side)

60‧‧‧纖維強化塑膠前驅物 60‧‧‧Fiber reinforced plastic precursor

Claims (11)

一種纖維強化塑膠前驅物的製造方法，該製造方法在將附有支撐體之樹脂薄膜貼合在骨材上之後，從前述附有支撐體之樹脂薄膜將支撐體剝離來製成纖維強化塑膠前驅物，其中，前述樹脂薄膜是包含熱硬化性樹脂組成物而成之樹脂薄膜，該熱硬化性樹脂組成物含有矽氧烷化合物(a)，前述熱硬化性樹脂組成物進一步包含選自由熱硬化性樹脂(b)及在1分子中具有至少2個N-取代馬來醯亞胺基之馬來醯亞胺化合物(c)所組成之群組中的1種以上；前述矽氧烷化合物(a)是由下述通式(1)表示：
Figure 106138823-A0305-02-0057-1
 通式(1)中，Ra1、Ra2、Ra3及Ra4各自獨立地表示氫原子、烷基、經取代的烷基、苯基或經取代的苯基；前述經取代的烷基中的取代基是選自由胺基、環氧基、脂環式環氧基、聚醚殘基、苯基、羥基、巰基、羧基及(甲基)丙烯酸基所組成之群組中的至少1種；前述經取代的苯基中的苯基所具有的取代基是選自由碳數1~5的烷基、碳數2~5的烯基及碳數2~5的炔基所組成之群組中的至少1種； Ra5和Ra6各自獨立地表示經取代或未被取代的碳數1~5的烷基，被取代時的取代基是選自由胺基、環氧基、脂環式環氧基、羥基、巰基、羧基及(甲基)丙烯酸基所組成之群組中的至少1種；m是1~50的整數。 A method of manufacturing a fiber-reinforced plastic precursor. In this manufacturing method, after laminating a resin film with a support to a frame, the support is peeled off from the resin film with a support to produce a fiber-reinforced plastic precursor. object, wherein the aforementioned resin film is a resin film containing a thermosetting resin composition, the thermosetting resin composition contains a siloxane compound (a), and the aforementioned thermosetting resin composition further contains a material selected from the group consisting of thermosetting One or more types of the group consisting of a flexible resin (b) and a maleimide compound (c) having at least 2 N-substituted maleimide groups in 1 molecule; the aforementioned siloxane compound ( a) is represented by the following general formula (1):
Figure 106138823-A0305-02-0057-1
 In the general formula (1), R a1 , R a2 , R a3 and R a4 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group; in the aforementioned substituted alkyl group The substituent is at least one selected from the group consisting of amine group, epoxy group, alicyclic epoxy group, polyether residue, phenyl group, hydroxyl group, mercapto group, carboxyl group and (meth)acrylic acid group ; The substituent of the phenyl group in the aforementioned substituted phenyl group is selected from the group consisting of an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, and an alkynyl group with 2 to 5 carbon atoms. At least one of the following; R a5 and R a6 each independently represent a substituted or unsubstituted alkyl group with 1 to 5 carbon atoms. When substituted, the substituent is selected from the group consisting of an amine group, an epoxy group, and an alicyclic group. At least one kind from the group consisting of epoxy group, hydroxyl group, mercapto group, carboxyl group and (meth)acrylic acid group; m is an integer from 1 to 50. 如請求項1所述之纖維強化塑膠前驅物的製造方法，其中，前述矽氧烷化合物(a)是在1分子中具有2個一級胺基之矽氧烷化合物、在1分子中具有2個環氧基之矽氧烷化合物或在側鏈上具有甲醇基之矽氧烷化合物。 The method for producing a fiber-reinforced plastic precursor according to claim 1, wherein the siloxane compound (a) is a siloxane compound having two primary amine groups in one molecule, and having two primary amine groups in one molecule. A siloxane compound with an epoxy group or a siloxane compound with a carbinol group on the side chain. 如請求項1或2所述之纖維強化塑膠前驅物的製造方法，其中，前述熱硬化性樹脂組成物進一步含有胺化合物(d)，該胺化合物(d)在1分子中具有至少2個一級胺基。 The method for manufacturing a fiber-reinforced plastic precursor according to claim 1 or 2, wherein the thermosetting resin composition further contains an amine compound (d), and the amine compound (d) has at least two primary molecule in one molecule. Amino group. 如請求項1或2所述之纖維強化塑膠前驅物的製造方法，其中，前述熱硬化性樹脂組成物進一步含有硬化促進劑(e)。 The method for manufacturing a fiber-reinforced plastic precursor according to claim 1 or 2, wherein the thermosetting resin composition further contains a hardening accelerator (e). 如請求項1或2所述之纖維強化塑膠前驅物的製造方法，其中，前述熱硬化性樹脂組成物進一步含有無機填充材料(f)。 The method for manufacturing a fiber-reinforced plastic precursor according to claim 1 or 2, wherein the thermosetting resin composition further contains an inorganic filler (f). 如請求項1或2所述之纖維強化塑膠前驅物的製造方法，其中，在常壓下對前述附有支撐體之樹脂薄 膜進行加熱和加壓來將其貼合在骨材上。 The method for manufacturing a fiber-reinforced plastic precursor as claimed in claim 1 or 2, wherein the resin thin film with the support is processed under normal pressure. The membrane is heated and pressured to bond it to the bone. 如請求項1或2所述之纖維強化塑膠前驅物的製造方法，其中，前述骨材的厚度是5μm~30μm。 The manufacturing method of fiber-reinforced plastic precursor according to claim 1 or 2, wherein the thickness of the aforementioned aggregate is 5 μm~30 μm. 如請求項1或2所述之纖維強化塑膠前驅物的製造方法，其中，前述纖維強化塑膠前驅物用於無芯基板。 The method for manufacturing a fiber-reinforced plastic precursor according to claim 1 or 2, wherein the fiber-reinforced plastic precursor is used for a coreless substrate. 一種積層體的製造方法，該製造方法藉由將纖維強化塑膠前驅物積層並進行成形來實行，該纖維強化塑膠前驅物是藉由請求項1~6中任一項所述之纖維強化塑膠前驅物的製造方法所獲得。 A method for manufacturing a laminated body, the manufacturing method being carried out by laminating and shaping a fiber-reinforced plastic precursor, the fiber-reinforced plastic precursor being the fiber-reinforced plastic precursor described in any one of claims 1 to 6 Obtained from the manufacturing method of the object. 一種印刷線路板的製造方法，該製造方法藉由將電路形成在積層體上來實行，該積層體是藉由請求項9所述之積層體的製造方法所獲得。 A method for manufacturing a printed wiring board, the manufacturing method being carried out by forming a circuit on a laminated body obtained by the method for manufacturing a laminated body according to claim 9. 一種半導體封裝體的製造方法，該製造方法藉由將半導體元件裝配在印刷線路板上來實行，該印刷線路板是藉由請求項10所述之印刷線路板的製造方法所獲得。A method of manufacturing a semiconductor package, the manufacturing method being carried out by assembling a semiconductor element on a printed circuit board, the printed circuit board being obtained by the method of manufacturing a printed circuit board according to claim 10.
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