TWI639371B - Manufacturing method of laminated board - Google Patents
Manufacturing method of laminated board Download PDFInfo
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- TWI639371B TWI639371B TW103130567A TW103130567A TWI639371B TW I639371 B TWI639371 B TW I639371B TW 103130567 A TW103130567 A TW 103130567A TW 103130567 A TW103130567 A TW 103130567A TW I639371 B TWI639371 B TW I639371B
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
- H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
- H05K3/4632—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials laminating thermoplastic or uncured resin sheets comprising printed circuits without added adhesive materials between the sheets
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
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- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Laminated Bodies (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Moulding By Coating Moulds (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
Abstract
本發明之課題係有效製造可維持機械強度,且導體層之密著強度優異之層合板。 An object of the present invention is to efficiently produce a laminated board which can maintain mechanical strength and has excellent adhesive strength of a conductor layer.
本發明提供一種層合板的製造方法,其包含下述步驟(A)與步驟(B):步驟(A)準備於有機支撐體上設置厚度為1μm~10μm,且鉛筆硬度為2B以上之熱硬化性樹脂組成物層之接著片之步驟,步驟(B)於如使熱硬化性樹脂組成物層彼此相互對向之方式配置之2片接著片之間配置1片以上之預浸物,在減壓下、於200℃以上加熱及加壓而一體成型之步驟。 The invention provides a method for manufacturing a laminated board, which comprises the following steps (A) and (B): Step (A) is prepared on an organic support to set a thickness of 1 μm to 10 μm, and the pencil is hardened with a hardness of 2B or more The step of adhering the sheet of the thermosetting resin composition layer. In step (B), one or more prepregs are disposed between the two adhering sheets in which the thermosetting resin composition layers are opposed to each other. The step of pressing, heating and pressing at a temperature above 200 ° C to form a unit.
Description
本發明係關於層合板的製造方法。 This invention relates to the manufacturing method of a laminated board.
電子設備所使用之印刷配線板之製作方法已知有例如包含使附著於金屬箔或脫模薄膜之單面上之樹脂組成物層之B階段樹脂組成物薄片以使該樹脂組成物層朝向預浸物側之方式配置,在真空條件下加熱並加壓而硬化之真空熱壓步驟而一體成型並形成層合板之步驟之製作方法(參考專利文獻1)。 As a method for manufacturing a printed wiring board used in an electronic device, for example, a B-stage resin composition sheet including a resin composition layer attached to one side of a metal foil or a release film is known so that the resin composition layer faces the A manufacturing method of a method in which the material is arranged on the immersed side, and a step of integrally forming and forming a laminated board by a vacuum hot pressing step of heating and pressing under vacuum conditions and hardening (refer to Patent Document 1).
[專利文獻1]日本特開2003-332734號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2003-332734
依據近年來之電子設備小型化之要求,針對 電子設備所使用之印刷配線板,進而印刷配線板等所用之使絕緣層與導體層(配線層)層合而成之層合板,亦要求進一步薄型化、微細配線化。 According to the requirements of miniaturization of electronic equipment in recent years, The printed wiring boards used in electronic equipment, and further the laminated boards formed by laminating an insulating layer and a conductor layer (wiring layer) used in printed wiring boards, etc., are also required to be further thinner and finer wiring.
在該等背景下,針對例如層合板之製作所使 用之樹脂組成物亦要求即使將層合板之厚度設為更薄仍能維持與過去之層合板相同之機械強度,且可防止因與導體層之熱膨脹係數之差而發生翹曲之樹脂組成物。 In these contexts, The resin composition used also requires a resin composition that can maintain the same mechanical strength as the conventional laminate even if the thickness of the laminate is thinner, and can prevent warping due to the difference in thermal expansion coefficient between the laminate and the conductor layer. .
例如,為了維持厚度更薄之層合板的機械強 度,而考慮使用具有更高玻璃轉移溫度(Tg)之樹脂組成物作為層合板之製作中使用之預浸物所使用之樹脂組成物之方法。且為了使樹脂組成物之熱膨脹係數減小,而考慮調配二氧化矽等無機填充材之方法。 For example, to maintain the mechanical strength of thinner laminates Considering a method of using a resin composition having a higher glass transition temperature (Tg) as the resin composition used for the prepreg used in the manufacture of the laminate. In order to reduce the thermal expansion coefficient of the resin composition, a method of blending inorganic fillers such as silicon dioxide is considered.
使用利用此種樹脂組成物之預浸物時,為了 使具有高玻璃轉移溫度之樹脂組成物熱硬化,且由於因無機填充材之調配而降低樹脂組成物之流動性,故有必要在更高溫、高壓下之真空熱壓步驟。 When using prepregs using this resin composition, The resin composition having a high glass transition temperature is thermally hardened, and the flowability of the resin composition is reduced due to the formulation of the inorganic filler, so a vacuum hot pressing step at a higher temperature and pressure is necessary.
然而,實施此種真空熱壓步驟時,於使所得 層合板粗化時,有難以獲得粗糙度不均受抑制之表面之虞,結果有難以藉由鍍敷而形成密著性優異之導體層之虞。 However, when performing this vacuum hot pressing step, When the laminated board is roughened, it may be difficult to obtain a surface with suppressed roughness unevenness, and as a result, it may be difficult to form a conductive layer having excellent adhesion by plating.
藉由鍍敷形成導體層時,亦考慮使銅箔之消光面與預浸物接合之方式使酮箔與預浸物一體成型,隨後去除銅箔,利用銅箔之消光面使預浸物之表面粗化之方法。然而,由於該方法使粗糙度過度增大,故不利於配線之更微 細化。 When forming the conductor layer by plating, it is also considered that the ketone foil and the prepreg are integrally formed by joining the matting surface of the copper foil and the prepreg, and then the copper foil is removed, and the matting surface of the copper foil is used to make the prepreg. Surface roughening method. However, because this method excessively increases the roughness, it is not conducive to finer wiring. Refinement.
為了解決藉鍍敷形成導體層,形成更微細配 線時之上述問題點,而考慮使用使熱硬化性樹脂組成物附著於支撐體之單面上而成之接著薄片等,於預浸物之表面設置可藉由另外鍍敷而可形成微細配線之熱硬化性樹脂組成物層(底塗層)。 In order to solve the problem of forming a conductive layer by plating, a finer composition is formed. For the above problems at the time of wiring, it is considered to use a bonding sheet formed by adhering a thermosetting resin composition to one side of a support body. The surface of the prepreg can be provided by fine plating to form fine wiring. A thermosetting resin composition layer (undercoat layer).
然而,依據本發明人等發現,使藉由在高 溫、高壓之真空熱壓步驟使預浸物與接著薄片一體成型獲得之層合板之表面粗化時,會產生粗糙度不均,使藉鍍敷形成之導體層對層合板之密著性發生偏差,而部分發生容易剝離區域之問題。 However, according to the findings of the present inventors, Warm and high pressure vacuum hot-pressing step roughens the surface of the laminate obtained by integrally forming the prepreg and the subsequent sheet, which will cause uneven roughness, which will cause the adhesion of the conductor layer formed by plating to the laminate. And some problems occur in areas that are easily peeled off.
本發明人等鑑於上述課題而積極檢討之結果,發現在高溫、高壓條件下使熱硬化性樹脂組成物層與預浸物一體成型形成層合板時,若使用具有一定值以上之硬度之熱硬化性樹脂組成物層,則可抑制使熱硬化性樹脂組成物層硬化之硬化體表面之粗糙度不均,可形成密著強度優異之導體層,因而完成本發明。 As a result of active review by the present inventors in view of the above-mentioned problems, it has been found that when a thermosetting resin composition layer and a prepreg are integrally formed under high temperature and high pressure conditions to form a laminate, a thermosetting resin having a hardness of a certain value or more is used. The flexible resin composition layer can suppress uneven unevenness of the surface of the hardened body that hardens the thermosetting resin composition layer, and can form a conductive layer having excellent adhesion strength. Thus, the present invention has been completed.
亦即,本發明提供下述[1]~[14]。 That is, the present invention provides the following [1] to [14].
[1]一種層合板的製造方法,其包含下述步驟(A)與步驟(B),步驟(A)準備於有機支撐體上設置厚度為1μm~10μm,且鉛筆硬度為2B以上之熱硬化性樹脂組成物 層之接著片之步驟,步驟(B)於如使前述熱硬化性樹脂組成物層彼此相互對向之方式配置之2片前述接著片之間配置1片以上之預浸物,在減壓下、於200℃以上加熱及加壓而一體成型之步驟。 [1] A method for manufacturing a laminated board, which includes the following steps (A) and (B). The step (A) is prepared on an organic support by setting a thickness of 1 μm to 10 μm and a pencil hardening with a hardness of 2B or more. Sex resin composition The step of layer-adhering sheet, step (B) is to arrange one or more prepregs between two pieces of the aforementioned adhesive sheet arranged such that the aforementioned thermosetting resin composition layers face each other, and under reduced pressure Step of heating and pressing above 200 ° C for integral molding.
[2]如[1]所記載之層合板的製造方法,其中前述熱硬化性樹脂組成物包含無機填充材,於將前述熱硬化性樹脂組成物中之不揮發成分設為100質量%時,該無機填充材之含量為15質量%以上且80質量%以下。 [2] The method for producing a laminated board according to [1], wherein the thermosetting resin composition includes an inorganic filler, and when a nonvolatile component in the thermosetting resin composition is 100% by mass, The content of the inorganic filler is 15 mass% or more and 80 mass% or less.
[3]如[2]所記載之層合板的製造方法,其中前述無機填充材之含量為35質量%以上且60質量%以下。 [3] The method for producing a laminated board according to [2], wherein the content of the inorganic filler is 35% by mass or more and 60% by mass or less.
[4]如[1]~[3]中任一項所記載之層合板的製造方法,其中前述熱硬化性樹脂組成物包含環氧樹脂、硬化劑。 [4] The method for producing a laminate according to any one of [1] to [3], wherein the thermosetting resin composition contains an epoxy resin and a hardener.
[5]如[1]~[4]中任一項所記載之層合板的製造方法,其中前述熱硬化性樹脂組成物包含有機填充材,於將前述熱硬化性樹脂組成物中之不揮發成分設為100質量%時,有機填充材之含量為1質量%以上且10質量%以下。 [5] The method for producing a laminate according to any one of [1] to [4], wherein the thermosetting resin composition contains an organic filler, and the non-volatile matter in the thermosetting resin composition is non-volatile. When the component is 100% by mass, the content of the organic filler is 1% by mass or more and 10% by mass or less.
[6]如[1]~[5]中任一項所記載之層合板的製造方法,其中前述有機支撐體之玻璃轉移溫度為90℃以上。 [6] The method for producing a laminate according to any one of [1] to [5], wherein the glass transition temperature of the organic support is 90 ° C or higher.
[7]如[1]~[6]中任一項所記載之層合板的製造方法,其中前述有機支撐體之厚度為5μm~50μm。 [7] The method for producing a laminated board according to any one of [1] to [6], wherein a thickness of the organic support is 5 μm to 50 μm.
[8]如[1]~[7]中任一項所記載之層合板的製造方法,其中前述步驟(B)係使用2片以上之預浸物,且預浸物彼此間進一步配置內層電路基板而一體成型之步驟。 [8] The method for manufacturing a laminated board according to any one of [1] to [7], wherein the step (B) uses two or more prepregs, and the prepregs are further arranged with an inner layer therebetween. The step of integrally forming the circuit substrate.
[9]如[1]~[8]中任一項所記載之層合板的製造方法,其中前述熱硬化性樹脂組成物層之最低熔融黏度為20000泊以上。 [9] The method for producing a laminate according to any one of [1] to [8], wherein the minimum melt viscosity of the thermosetting resin composition layer is 20,000 poise or more.
[10]如[1]~[9]中任一項所記載之層合板的製造方法,其進一步包含步驟(C)剝離前述有機支撐體之步驟。 [10] The method for producing a laminated board according to any one of [1] to [9], further comprising a step (C) of removing the organic support.
[11]如[1]~[10]中任一項所記載之層合板的製造方法,其進一步包含步驟(D)形成通孔之步驟。 [11] The method for manufacturing a laminated board according to any one of [1] to [10], further including a step (D) of forming a through hole.
[12]如[10]所記載之層合板的製造方法,其中於前述步驟(C)後進一步包含步驟(E)使層合板進行粗化處理之步驟。 [12] The method for manufacturing a laminated board according to [10], further comprising a step (E) of roughening the laminated board after the step (C).
[13]如[12]所記載之層合板的製造方法,其中於前述步驟(E)後進一步包含步驟(F)藉由鍍敷形成導體層之步驟。 [13] The method for manufacturing a laminated board according to [12], further comprising a step (F) of forming a conductor layer by plating after the aforementioned step (E).
[14]如[13]所記載之層合板的製造方法,其中進一步包含步驟(G)使用前述導體層形成配線層之步驟。 [14] The method for manufacturing a laminated board according to [13], further comprising a step (G) of forming a wiring layer using the aforementioned conductor layer.
依據本發明之層合板的製造方法,可有效製造儘管其厚度較薄仍可維持機械強度,且導體層(配線層)之密著強度優異之層合板。 According to the method for manufacturing a laminated board of the present invention, it is possible to efficiently manufacture a laminated board that can maintain mechanical strength despite its thin thickness and is excellent in the adhesive strength of the conductor layer (wiring layer).
以下,針對本發明之層合體的製造方法加以詳細說明。 Hereinafter, the manufacturing method of the laminated body of this invention is demonstrated in detail.
本發明之層合體的製造方法包含步驟(A)與步 驟(B):步驟(A)準備於有機支撐體上設置厚度為1μm~10μm,且鉛筆硬度為2B以上之熱硬化性樹脂組成物層之接著片之步驟,步驟(B)於以使前述熱硬化性樹脂組成物層彼此相互對向之方式配置之2片前述接著片之間配置1片以上之預浸物,在減壓下、於200℃以上加熱及加壓而一體成型之步驟。 The method for producing a laminated body of the present invention includes steps (A) and Step (B): Step (A) is a step of setting a bonding sheet of a thermosetting resin composition layer having a thickness of 1 μm to 10 μm and a pencil hardness of 2B or more on an organic support. A step in which one or more prepregs are arranged between two of the aforementioned adhesive sheets arranged so that the thermosetting resin composition layers face each other, and are heated and pressurized at 200 ° C. or more under reduced pressure to be integrally molded.
首先,進行準備於有機支撐體上設置厚度為1μm~10μm,且鉛筆硬度為2B以上之熱硬化性樹脂組成物層之接著片之步驟(A)。 First, a step (A) of preparing a bonding sheet for a thermosetting resin composition layer having a thickness of 1 to 10 μm and a pencil hardness of 2B or more on an organic support is performed.
接著片所具備之熱硬化性樹脂組成物層可使用模嘴塗佈器等過去習知之任意較佳塗佈手段將熱硬化性樹脂組成物塗佈於有機支撐體上,藉由乾燥處理塗佈膜而形成熱硬化性樹脂組成物層。 The thermosetting resin composition layer included in the subsequent sheet can be applied to an organic support by any suitable coating method known in the past, such as a die applicator, and then applied by drying. Film to form a thermosetting resin composition layer.
另步驟(A)中之接著薄片可使用例如預先製造之在特定儲存條件下儲存之接著薄片。 The adhesive sheet in the other step (A) may be, for example, a previously prepared adhesive sheet stored under specific storage conditions.
接著薄片所用之有機支撐體係由具有對向兩主面之板狀體或由薄膜所成之構造體。至於有機支撐體亦可使用長 條之薄膜狀構造體。 The organic supporting system used for the flakes is a plate-shaped body with two main surfaces facing each other or a structure formed of a thin film. As for organic supports, long Thin film-like structure.
就可在200℃以上加熱及加壓包含該有機支撐 體之構造體而一體成型之觀點而言,有機支撐體係使用玻璃轉移溫度為90℃以上,較好100℃以上之有機支撐體。 有機支撐體具體而言係選擇由可耐受後述之真空熱壓步驟中之處理條件,尤其是由耐加熱溫度之材料所成之有機支撐體。 Can be heated and pressurized above 200 ° C to include the organic support From the viewpoint of integrally forming a body structure, an organic support system uses an organic support having a glass transition temperature of 90 ° C or higher, preferably 100 ° C or higher. The organic support is specifically an organic support made of a material that can withstand the processing conditions in the vacuum hot pressing step described later, especially a material that is resistant to heating temperature.
該有機支撐體之材料列舉為例如聚萘二甲酸 乙二酯(PEN)等聚酯、聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)等丙烯酸系、環狀聚烯烴、三乙醯纖維素(TAC)、聚醚硫醚(PES)、聚醚酮、聚醚醚酮(PEEK)、聚苯硫醚(PPS)、聚醯亞胺等。其中,就耐熱性之觀點而言以聚萘二甲酸乙二酯、聚醯亞胺較佳。 The material of the organic support is, for example, polynaphthalene dicarboxylic acid. Polyesters such as ethylene glycol (PEN), acrylics such as polycarbonate (PC), polymethyl methacrylate (PMMA), cyclic polyolefins, triethyl cellulose (TAC), polyether sulfide (PES) ), Polyetherketone, polyetheretherketone (PEEK), polyphenylene sulfide (PPS), polyimide, and the like. Among these, polyethylene naphthalate and polyimide are preferred from the viewpoint of heat resistance.
包含前述材料之有機支撐體亦可對與熱硬化 性樹脂組成物層接合之面,亦即對塗佈有熱硬化性樹脂組成物之面施以消光處理、電暈處理。 Organic supports containing the aforementioned materials can also be cured against heat The surface to which the resin composition layer is bonded, that is, the surface coated with the thermosetting resin composition is subjected to a matting treatment or a corona treatment.
且,有機支撐體亦可使用於與熱硬化性樹脂 組成物層接合之側,亦即塗佈熱硬化性樹脂組成物之側上具有脫模層之附脫模層之有機支撐體。形成附脫模層之有機支撐體之脫模層所用之脫模劑列舉為例如由醇酸樹脂、聚烯烴樹脂、胺基甲酸酯樹脂、氟樹脂、及聚矽氧樹脂所組成之群選出之1種以上之脫模劑。 In addition, organic supports can also be used with thermosetting resins. An organic support with a release layer on the side where the composition layer is bonded, that is, the side on which the thermosetting resin composition is applied, has a release layer. The release agent used to form the release layer of the organic support with a release layer is selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, fluororesin, and silicone resin, for example. One or more release agents.
以不損及本發明目的為條件,有機支撐體之 厚度並無特別限制,但較好為5μm~50μm。又,使用附脫 模層之有機支撐體時,附脫模層之有機支撐體全體厚度較好為上述範圍內。 On the condition that the purpose of the present invention is not impaired, The thickness is not particularly limited, but is preferably 5 μm to 50 μm. Also, use attached In the case of the organic support of the mold layer, the thickness of the entire organic support with the release layer is preferably within the above range.
熱硬化性樹脂組成物層之厚度較好為1μm~10μm。以作成硬化體後可實施粗化步驟為條件,熱硬化性樹脂組成物層之厚度並無特別限制。 The thickness of the thermosetting resin composition layer is preferably 1 μm to 10 μm. The thickness of the thermosetting resin composition layer is not particularly limited on the condition that a roughening step can be performed after the cured body is formed.
熱硬化性樹脂組成物層之鉛筆硬度為2B以上。具體而言,鉛筆硬度較好為2B以上,亦即與2B相等程度之硬度或比2B大之硬度(例如,2B、B、HB、F、H、2H、3H、4H、5H、6H、7H)。 The pencil hardness of the thermosetting resin composition layer is 2B or more. Specifically, the pencil hardness is preferably 2B or more, that is, a hardness equal to or greater than 2B (for example, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H ).
該鉛筆硬度係依據以JIS K5600-5-4規格化之測定方法測定之硬度。 The pencil hardness is a hardness measured in accordance with a measurement method standardized by JIS K5600-5-4.
以不損及本發明目的為條件,熱硬化性樹脂組成物層中之鉛筆硬度上限並無特別限定,但考量乾燥處理所需之時間、無機填充材之含量等時,較好為7H以下。 Provided that the object of the present invention is not impaired, the upper limit of the pencil hardness in the thermosetting resin composition layer is not particularly limited, but when considering the time required for the drying treatment and the content of the inorganic filler, it is preferably 7H or less.
以不損及本發明目的為條件,熱硬化性樹脂組成物層之最低熔融黏度並無特別限制,但較好為20000泊以上,更好為40000泊以上,亦更好為70000泊以上。以不損及 本發明目的為條件,熱硬性樹脂組成物層之最低熔融黏度上限並無特別限制。 Provided that the object of the present invention is not impaired, the minimum melt viscosity of the thermosetting resin composition layer is not particularly limited, but it is preferably 20,000 poise or more, more preferably 40,000 poise or more, and still more preferably 70,000 poise or more. Without compromising The purpose of the present invention is that the upper limit of the minimum melt viscosity of the thermosetting resin composition layer is not particularly limited.
此處,所謂熱硬化性樹脂組成物層之「最低 熔融黏度」係指藉由對構成熱硬化性樹脂組成物層之樹脂(硬化物)進行加熱處理而熔融時,熱硬化性樹脂組成物層所呈現之最低黏度。詳言之,以一定升溫速度加熱處理熱硬化性樹脂組成物層而熔融時,初期階段熔融黏度隨著溫度上升而降低至極小點,超過某溫度時隨著溫度上升熔融黏度上升。所謂「最低熔融黏度」係指該極小點之熔融黏度。 Here, the "minimum of the so-called thermosetting resin composition layer" The "melt viscosity" refers to the lowest viscosity exhibited by the thermosetting resin composition layer when the resin (cured material) constituting the thermosetting resin composition layer is heated and melted. In detail, when the thermosetting resin composition layer is heated and melted at a constant temperature increase rate, the melt viscosity in the initial stage decreases to a minimum point as the temperature rises, and when the temperature exceeds a certain temperature, the melt viscosity rises as the temperature rises. The so-called "minimum melt viscosity" refers to the melt viscosity of the minimum point.
熱硬化性樹脂組成物層之最低熔融黏度可藉 動態黏彈性法測定。具體而言,熱硬化性樹脂組成物層之最低熔融黏度可在測定開始溫度60℃、升溫速度5℃/分鐘、頻率1Hz、偏斜度1度之條件下進行動態黏彈性測定而獲得。至於動態黏彈性測定裝置列舉為例如UBM(股)公司製之「Rheosol-G3000」。 The minimum melt viscosity of the thermosetting resin composition layer can be obtained by Dynamic viscoelasticity. Specifically, the minimum melt viscosity of the thermosetting resin composition layer can be obtained by performing dynamic viscoelasticity measurement under conditions of a measurement start temperature of 60 ° C., a heating rate of 5 ° C./minute, a frequency of 1 Hz, and a skewness of 1 degree. The dynamic viscoelasticity measuring device is, for example, "Rheosol-G3000" manufactured by UBM Corporation.
此處針對熱硬化性樹脂組成物層之形成所用 之熱硬化性樹脂組成物之成分加以說明。又,本說明書中之說明中,各成分之含量係將熱硬化性樹脂組成物中之不揮發成分之合計設為100質量%時之量。 This is used for the formation of a thermosetting resin composition layer The components of the thermosetting resin composition will be described. In addition, in the description in this specification, the content of each component is an amount when the total of the non-volatile components in the thermosetting resin composition is 100% by mass.
接著片係如已說明,包含有機支撐體、及以與有機支撐體接合之方式設置之熱硬化性樹脂組成物層。 Next, as described above, the sheet system includes an organic support and a thermosetting resin composition layer provided so as to be bonded to the organic support.
作為熱硬化性樹脂組成物層之材料使用之熱硬化性樹脂組成物較好包含無機填充材,進而較好包含環 氧樹脂及硬化劑。 The thermosetting resin composition used as the material of the thermosetting resin composition layer preferably contains an inorganic filler, and further preferably contains a ring. Oxygen resin and hardener.
熱硬化性樹脂組成物除了橡膠粒子等有機填 充材外,進而亦可包含硬化促進劑、熱可塑性樹脂及難燃劑等。以下針對該等分別加以說明。 Thermosetting resin composition in addition to organic fillers such as rubber particles The filler may further include a hardening accelerator, a thermoplastic resin, a flame retardant, and the like. Each of these is explained below.
熱硬化性樹脂組成物層之形成所用之熱硬化性樹脂組成物,就抑制因成為硬化體時之熱膨脹率下降之硬化體與預浸物等之熱膨脹率之差造成之龜裂、電路變形等異常發生,且抑制熔融黏度過度降低之觀點而言,將熱硬化性樹脂組成物中之不揮發成分設為100質量%時,無機填充材之含量較好以成為15質量%以上且80質量%以下之方式含有,無機填充材之含量更好為35質量%以上且60質量%以下。 The thermosetting resin composition used for the formation of the thermosetting resin composition layer suppresses cracks and circuit deformation caused by the difference in thermal expansion rate between the cured body and the prepreg when the thermal expansion rate decreases when it becomes a cured body From the viewpoint of abnormal occurrence and suppressing excessive reduction in melt viscosity, when the non-volatile content in the thermosetting resin composition is 100% by mass, the content of the inorganic filler is preferably 15% by mass or more and 80% by mass. It is contained in the following manner, and the content of the inorganic filler is more preferably 35% by mass or more and 60% by mass or less.
通常,作為所謂底塗層發揮功能之熱硬化性 樹脂組成物層雖有不使用無機填充材之情況,但藉由成為前述含量,使熱膨脹係數變得更小,進而可更提高回焊耐性。 Thermosetting that functions as a so-called undercoating Although the resin composition layer may not use an inorganic filler, the thermal expansion coefficient can be made smaller by the content described above, and the reflow resistance can be further improved.
無機填充材列舉為例如二氧化矽、氧化鋁、 玻璃、堇青石(cordierite)、矽氧化物、碳酸鋇、硫酸鋇、滑石、黏土、雲母粉、氧化鋅、水滑石(hydrotalcite)、水鋁石(boehmite)、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、氧化鎂、氮化硼、氮化鋁、氮化錳、硼酸鋁、氧化鋯、磷酸鋯、磷酸鎢酸鋯、碳酸鍶、鈦酸鋇、鈦酸鍶、鈦 酸鈣、鈦酸鎂、鈦酸鉍、鈦酸鋯酸鋇、氧化鈦、鋯酸鋇、及鋯酸鈣等。該等中以無定形二氧化矽、熔融二氧化矽、結晶二氧化矽、合成二氧化矽、中空二氧化矽等二氧化矽最佳。且二氧化矽較好為球狀二氧化矽。無機填充材可單獨使用1種,亦可組合2種以上使用。市售之球狀(熔融)二氧化矽列舉為例如ADMATECHS(股)製之「SOC1」、「SOC2」、「SOC4」、「SOC5」、「SOC6」。 Examples of the inorganic filler include silicon dioxide, aluminum oxide, Glass, cordierite, silicon oxide, barium carbonate, barium sulfate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, carbonic acid Calcium, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, zirconia, zirconium phosphate, zirconium phosphate tungstate, strontium carbonate, barium titanate, strontium titanate, titanium Calcium acid, magnesium titanate, bismuth titanate, barium zirconate titanate, titanium oxide, barium zirconate, and calcium zirconate. Among them, amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, hollow silicon dioxide and the like are the best. The silicon dioxide is preferably spherical silicon dioxide. The inorganic fillers may be used singly or in combination of two or more kinds. The commercially available spherical (fused) silicon dioxide is exemplified by "SOC1", "SOC2", "SOC4", "SOC5", and "SOC6" made by ADMATECHS.
無機填充材之平均粒徑,就提高熱硬化性樹 脂組成物之流動性之觀點而言,較好為0.01μm~4μm之範圍,更好為0.05μm~2.5μm之範圍,又更好為0.1μm~1.5μm之範圍,再更好為0.3μm~1.0μm之範圍。無機填充材之平均粒徑可基於Mie散射理論以雷射繞射‧散射法測定。具體而言可藉雷射繞射散射式粒度分佈測定裝置,以體積基準製作無機填充材之粒度分佈,將其中值徑設為平均粒徑進行測定。該情況下可適當使用以超音波將無機填充材分散於水中之測定樣品。雷射繞射散射式粒度分佈測定裝置可使用崛場製作所(股)製之「LA-500」等。 The average particle size of the inorganic filler increases the thermosetting tree From the viewpoint of the fluidity of the fat composition, a range of 0.01 μm to 4 μm is preferred, a range of 0.05 μm to 2.5 μm is more preferred, a range of 0.1 μm to 1.5 μm is more preferred, and 0.3 μm is even more preferred. The range is ~ 1.0μm. The average particle diameter of the inorganic filler can be measured by the laser diffraction and scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction scattering particle size distribution measurement device, and the median diameter can be measured as the average particle diameter. In this case, a measurement sample in which an inorganic filler is dispersed in water by ultrasonic waves can be suitably used. As the laser diffraction scattering particle size distribution measuring device, "LA-500" manufactured by Horiba Ltd. can be used.
無機填充材,就提高耐濕性及分散性之觀點 而言,較好以胺基矽烷系偶合劑、環氧基矽烷偶合劑、巰基矽烷系偶合劑、矽烷系偶合劑、有機矽氮烷化合物、鈦酸酯系偶合劑等之1種以上之表面處理劑處理。該表面處理劑之市售品列舉為例如信越化學工業(股)製之「KBM403」(3-縮水甘油氧基丙基三甲氧基矽烷)、信越化學工業(股)製之「KBM803」(3-巰基丙基三甲氧基矽 烷)、信越化學工業(股)製之「KBE903」(3-胺基丙基三乙氧基矽烷)、信越化學工業(股)製之「KBM573」(N-苯基-3-胺基丙基三甲氧基矽烷)、信越化學工業(股)製之「SZ-31」(六甲基二矽氮烷)等。 Inorganic filler from the viewpoint of improving moisture resistance and dispersibility In terms of the surface, one or more kinds of amine-based coupling agents, epoxy-based silane coupling agents, mercapto-silane-based coupling agents, silane-based coupling agents, organic silazane compounds, and titanate-based coupling agents are preferred. Treatment agent treatment. Commercially available products of this surface treatment agent are, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "KBM803" (3 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) -Mercaptopropyltrimethoxysilane Alkane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM573" (N-phenyl-3-aminopropyl propyl) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Trimethoxysilane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and the like.
以表面處理劑進行表面處理之無機填充材可 藉溶劑(例如,甲基乙基酮(MEK))進行洗淨處理後,測定無機填充材之每單位表面積之碳量。具體而言,係於經表面處理劑表面處理之無機填充材中添加作為溶劑之足量MEK,在25℃進行超音波洗淨5分鐘。接著,去除上澄液,使不揮發成分乾燥後,使用碳分析計可測定無機填充材之每單位表面積之碳量。碳分析計可使用崛場製作所(股)製之「EMIA-320V」等。 Inorganic fillers with a surface treatment agent After the cleaning treatment with a solvent (for example, methyl ethyl ketone (MEK)), the carbon content per unit surface area of the inorganic filler is measured. Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler treated with the surface treatment agent, and ultrasonic cleaning was performed at 25 ° C for 5 minutes. Next, after removing the upper liquid and drying the non-volatile components, the carbon content per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V", etc., manufactured by Morioka Co., Ltd. can be used.
無機填充材之每單位表面積之碳量,就提高 無機填充材之分散性之觀點而言,較好為0.02mg/m2以上,更好為0.1mg/m2以上,又更好為0.2mg/m2以上。另一方面,就抑制熱硬化性樹脂組成物層之熔融黏度上升之觀點而言,無機填充材之每單位表面積之碳量較好為1mg/m2以下,更好為0.8mg/m2以下,又更好為0.5mg/m2以下。 From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and still more preferably 0.2 mg. / m 2 or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the thermosetting resin composition layer, the carbon content per unit surface area of the inorganic filler is preferably 1 mg / m 2 or less, more preferably 0.8 mg / m 2 or less. , And more preferably 0.5 mg / m 2 or less.
熱硬化性樹脂組成物,就抑制成為硬化體時粗糙度不均之觀點而言,較好含有有機填充材。有機填充材在將熱硬化性樹脂組成物中之不揮發成分設為100質量%時,較 好以含量成為1質量%以上且10質量%以下之方式含有。 The thermosetting resin composition preferably contains an organic filler from the viewpoint of suppressing unevenness in roughness when it becomes a cured body. When the organic filler has a non-volatile content of 100% by mass in the thermosetting resin composition, The content is preferably such that the content is 1% by mass or more and 10% by mass or less.
有機填充材之例列舉為橡膠粒子。有機填充 材的橡膠粒子係使用例如不溶解於後述之有機溶劑中,與後述之環氧樹脂、硬化劑及熱可塑性樹脂等亦不相溶之橡膠粒子。此種橡膠粒子一般係使橡膠粒子成分之分子量增大至不溶解於有機溶劑或樹脂之程度,成為粒子狀而調製。 Examples of the organic filler are rubber particles. Organic filling The rubber particles of the material are, for example, rubber particles which are insoluble in an organic solvent to be described later, and which are not compatible with an epoxy resin, a hardener, and a thermoplastic resin to be described later. Such rubber particles are generally prepared by increasing the molecular weight of the rubber particle components to such an extent that they are insoluble in organic solvents or resins, and are made into particles.
有機填充材的橡膠粒子列舉為例如蕊殼型橡 膠粒子、交聯丙烯腈丁二烯橡膠粒子、交聯苯乙烯丁二烯橡膠粒子、丙烯酸橡膠粒子等。蕊殼型橡膠粒子為聚有蕊層及殼層之橡膠粒子,例如,外層之殼層以玻璃狀聚合物構成,內層之蕊層以橡膠狀聚合物構成之2層構造,或外層之殼層以玻璃狀聚合物構成,中間層以橡膠狀聚合物構成,蕊層以玻璃狀聚合物構成之3層構造之橡膠粒子等。 玻璃狀聚合物層為例如以甲基丙烯酸酯聚合物等構成,橡膠狀聚合物層為例如以丙烯酸丁酯聚合物(丁基橡膠)等構成。可使用之橡膠粒子之例列舉為AICA工業(股)製之「STAFYROID AC3816N」。橡膠粒子可單獨使用1種,或亦可併用2種以上。 Examples of rubber particles of organic fillers include core-shell rubber Rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles, and the like. Core-shell type rubber particles are rubber particles with a core layer and a shell layer. For example, the outer shell layer is composed of a glass-like polymer, the inner core layer is composed of a two-layer structure composed of a rubber-like polymer, or the outer shell The layer is made of glass-like polymer, the middle layer is made of rubber-like polymer, and the core layer is made of glass-like polymer. The glassy polymer layer is composed of, for example, a methacrylate polymer or the like, and the rubbery polymer layer is composed of, for example, butyl acrylate polymer (butyl rubber) or the like. Examples of usable rubber particles are "STAFYROID AC3816N" manufactured by AICA Industrial Co., Ltd. The rubber particles may be used singly or in combination of two or more kinds.
有機填充材的橡膠粒子之平均粒徑較好為 0.005μm~1μm之範圍,更好為0.2μm~0.6μm之範圍。橡膠粒子之平均粒徑可使用動態光散射法測定。例如,可藉超音波等使橡膠粒子均勻分散於適當有機溶劑中,使用濃厚系粒徑分析儀(例如,大塚電子(股)製之「FPAR- 1000」),以質量基準製作橡膠粒子之粒度分佈,以其中值徑作為平均粒徑而測定。熱硬化性樹脂組成物中之有機填充材的橡膠粒子之含量較好為1質量%~10質量%之範圍,更好為3質量%~10質量%之範圍。 The average particle diameter of the rubber particles of the organic filler is preferably The range is from 0.005 μm to 1 μm, and more preferably from 0.2 μm to 0.6 μm. The average particle diameter of the rubber particles can be measured using a dynamic light scattering method. For example, ultrasonic particles can be used to uniformly disperse rubber particles in an appropriate organic solvent, and a thick particle size analyzer (for example, "FPAR- 1000 "), the particle size distribution of the rubber particles was prepared on a mass basis, and the median diameter was measured as the average particle diameter. The content of the rubber particles of the organic filler in the thermosetting resin composition is preferably in a range of 1% to 10% by mass, and more preferably in a range of 3% to 10% by mass.
填充材之含量(無機填充材含量與有機填充材 含量之總和)在將熱硬化性樹脂組成物中之不揮發成分設為100質量%時,較好為16質量%~90質量%之範圍,更好為36質量%~70質量%之範圍。 Filling material content (inorganic filling material content and organic filling material content When the total content of the non-volatile components in the thermosetting resin composition is 100% by mass, the range is preferably from 16% to 90% by mass, and more preferably from 36% to 70% by mass.
環氧樹脂列舉為例如雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚AF型環氧樹脂、二環戊二烯型環氧樹脂、參酚環氧樹脂、萘酚酚醛清漆環氧樹脂、酚酚醛清漆型環氧樹脂、第三丁基-兒茶酚型環氧樹脂、萘型環氧樹脂、萘酚型環氧樹脂、蒽型環氧樹脂、縮水甘油基胺型環氧樹脂、縮水甘油酯型環氧樹脂、甲酚酚醛清漆型環氧樹脂、聯苯型環氧樹脂、線狀脂肪族環氧樹脂、具有丁二烯構造之環氧樹脂、脂環式環氧樹脂、雜環式環氧樹脂、含有螺環之環氧樹脂、環己烷二甲醇型環氧樹脂、萘醚型環氧樹脂及三羥甲基型環氧樹脂等。環氧樹脂可單獨使用1種,或併用2種以上。 The epoxy resin is exemplified by bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and ginseng phenol. Epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, third butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy Resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, linear aliphatic epoxy resin, ring with butadiene structure Oxygen resin, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexanedimethanol epoxy resin, naphthalene ether epoxy resin and trimethylol epoxy resin Wait. The epoxy resin may be used alone or in combination of two or more.
環氧樹脂較好包含1分子中具有2個以上環 氧基之環氧樹脂。將環氧樹脂之不揮發成分設為100質量%時,至少50質量%以上為1分子中具有2個以上環氧基 之環氧樹脂。其中,較好包含1分子中具有2個以上環氧基,且在溫度20℃為液狀之環氧樹脂(以下,稱為「液狀環氧樹脂」)、與1分子中具有3個以上環氧基,且在溫度20℃為固體狀環氧樹脂(以下,稱為「固體狀環氧樹脂」)。藉由併用液狀環氧樹脂與固體狀環氧樹脂作為環氧樹脂,可賦予優異的可撓性。且,可提高藉由後述之真空熱壓步驟形成之硬化體(絕緣層)之破裂強度。 The epoxy resin preferably contains two or more rings in one molecule Epoxy resin. When the non-volatile content of the epoxy resin is 100% by mass, at least 50% by mass or more are two or more epoxy groups in one molecule Its epoxy. Among them, an epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C. (hereinafter referred to as a “liquid epoxy resin”) and three or more molecules in one molecule are preferred. An epoxy group and a solid epoxy resin (hereinafter referred to as a "solid epoxy resin") at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin together as the epoxy resin, excellent flexibility can be imparted. In addition, the fracture strength of the hardened body (insulating layer) formed by the vacuum hot pressing step described later can be improved.
液狀環氧樹脂較好為例如雙酚A型環氧樹 脂、雙酚F型環氧樹脂、酚酚醛清漆型環氧樹脂、2官能脂肪族環氧樹脂、或萘型環氧樹脂,列舉為雙酚A型環氧樹脂、雙酚F型環氧樹脂、或萘型環氧樹脂。液狀環氧樹脂之具體例列舉為DIC(股)製之「HP4032」、「HP4032D」、「HP4032SS」(萘型環氧樹脂)、三菱化學(股)製之「jER828EL」、「jER1007」(雙酚A型環氧樹脂)、「jER807」(雙酚F型環氧樹脂)、「jER152」(酚酚醛清漆型環氧樹脂)、新日鐵化學(股)製之「ZX1059」(雙酚A型環氧樹脂與雙酚F型環氧樹脂之混合品)、「YL7410」(2官能脂肪族環氧樹脂)等。該等可單獨使用1種,或亦可併用2種以上。 The liquid epoxy resin is preferably, for example, a bisphenol A epoxy resin. Grease, bisphenol F-type epoxy resin, phenol novolac-type epoxy resin, bifunctional aliphatic epoxy resin, or naphthalene-type epoxy resin, exemplified by bisphenol A-type epoxy resin, bisphenol F-type epoxy resin , Or naphthalene type epoxy resin. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) made by DIC (stock), "jER828EL", "jER1007" (made by Mitsubishi Chemical Corporation) Bisphenol A epoxy resin), "jER807" (bisphenol F epoxy resin), "jER152" (phenol novolac epoxy resin), "ZX1059" (bisphenol manufactured by Nippon Steel Chemical Co., Ltd.) A type epoxy resin and a mixture of bisphenol F type epoxy resin), "YL7410" (bifunctional aliphatic epoxy resin), etc. These may be used individually by 1 type, or may use 2 or more types together.
固體狀環氧樹脂列舉為例如結晶性2官能環 氧樹脂、4官能萘型環氧樹脂、甲酚酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、參酚環氧樹脂、萘酚酚醛清漆環氧樹脂、聯苯型環氧樹脂、萘醚型環氧樹脂。固體狀環氧樹脂之具體例列舉為DIC(股)製之「HP-4700」、 「HP-4710」(4官能萘型環氧樹脂)、「N-690」(甲酚酚醛 清漆型環氧樹脂)、「N-695」(甲酚酚醛清漆型環氧樹脂)、「HP-7200」(二環戊二烯型環氧樹脂)、「EXA7311」、「EXA7311-G3」、「HP6000」(萘醚型環氧樹脂)、日本化藥(股)製之「EPPN-502H」(參酚環氧樹脂)、「NC7000L」(萘酚酚醛清漆環氧樹脂)、「NC3000H」、「NC3000」、「NC3000H」、「NC3000L」、「NC3100」(聯苯型環氧樹脂)、新日鐵化學(股)製之「ESN475」(萘酚酚醛清漆型環氧樹脂)、「ESN485」(萘酚酚醛清漆型環氧樹脂)、三菱化學(股)製之「YX4000H」、「YL6121」(聯苯型環氧樹脂)、結晶性2官能環氧樹脂之「YX4000HK」(聯二甲酚型環氧樹脂)等。 Examples of the solid epoxy resin include a crystalline bifunctional ring Oxygen resin, 4-functional naphthalene epoxy resin, cresol novolac epoxy resin, dicyclopentadiene epoxy resin, ginseng phenol epoxy resin, naphthol novolac epoxy resin, biphenyl epoxy resin Naphthyl ether epoxy resin. Specific examples of the solid epoxy resin include "HP-4700" manufactured by DIC (stock), `` HP-4710 '' (4-functional naphthalene type epoxy resin), `` N-690 '' (cresol novolac Varnish-type epoxy resin), "N-695" (cresol novolac-type epoxy resin), "HP-7200" (dicyclopentadiene-type epoxy resin), "EXA7311", "EXA7311-G3", `` HP6000 '' (naphthyl ether epoxy resin), `` EPPN-502H '' (ginseng phenol epoxy resin), `` NC7000L '' (naphthol novolac epoxy resin), `` NC3000H '', "NC3000", "NC3000H", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475" (naphthol novolac type epoxy resin) made by Nippon Steel Chemical Co., Ltd., and "ESN485" (Naphthol novolac epoxy resin), `` YX4000H '' made by Mitsubishi Chemical Corporation, `` YL6121 '' (biphenyl type epoxy resin), `` YX4000HK '' (dixylenol, crystalline bifunctional epoxy resin) Type epoxy resin) and so on.
併用液狀環氧樹脂與固體狀環氧樹脂作為環 氧樹脂時,該等之量比(液狀環氧樹脂:固體狀環氧樹脂)以質量比計,較好為1:0.1~1:4之範圍。藉由使液狀環氧樹脂與固體狀環氧樹脂之量比落在該範圍,可獲得下述i)~iii)等之效果:i)以接著片之形態使用時具有適度黏著性,ii)以接著片之形態使用時獲得充分之可撓性,且作業性提高,iii)可獲得具有充分破裂強度之硬化體。就上述i)~iii)之效果之觀點而言,液狀環氧樹脂與固體狀環氧樹脂之量比(液狀環氧樹脂:固體狀環氧樹脂)以質量比計,更好為1:0.3~1:3.5之範圍,又更好為1:0.6~1:3之範圍,最好為1:0.8~1:2.5之範圍。 Use liquid epoxy and solid epoxy as ring In the case of an oxygen resin, the amount ratio (liquid epoxy resin: solid epoxy resin) is preferably in a range of 1: 0.1 to 1: 4 in terms of mass ratio. By making the amount ratio of the liquid epoxy resin to the solid epoxy resin fall within this range, the following effects i) to iii) can be obtained: i) moderate adhesion when used in the form of an adhesive sheet, ii ) When used in the form of an adhesive sheet, sufficient flexibility is obtained and workability is improved. Iii) A hardened body having sufficient fracture strength can be obtained. From the viewpoint of the effects of i) to iii) above, the amount ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably 1 in terms of mass ratio. : 0.3 ~ 1: 3.5, more preferably 1: 0.6 ~ 1: 3, and most preferably 1: 0.8 ~ 1: 2.5.
熱硬化性樹脂組成物中之環氧樹脂含量較好 為3質量%~50質量%,更好為5質量%~45質量%,又更好為5質量%~40質量%,最好為7質量%~35質量%。 Good content of epoxy resin in thermosetting resin composition 3 mass% to 50 mass%, more preferably 5 mass% to 45 mass%, still more preferably 5 mass% to 40 mass%, and most preferably 7 mass% to 35 mass%.
環氧樹脂之重量平均分子量較好為 100~5000,更好為250~3000,又更好為400~1500。此處,環氧樹脂之重量平均分子量係以凝膠滲透層析(GPC)法測定之聚苯乙烯換算之重量平均分子量。 The weight average molecular weight of the epoxy resin is preferably 100 ~ 5000, more preferably 250 ~ 3000, and more preferably 400 ~ 1500. Here, the weight average molecular weight of an epoxy resin is the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) method.
環氧樹脂之環氧當量較好為50~3000之範圍,更好為80~2000之範圍,又更好為110~1000之範圍。藉由成為該範圍,可獲得交聯密度充分之硬化體。又,環氧當量可依據JIS K7236而規格化之方法測定。此處環氧當量係包含1當量環氧基之樹脂之質量。 The epoxy equivalent of the epoxy resin is preferably in the range of 50 to 3000, more preferably in the range of 80 to 2000, and still more preferably in the range of 110 to 1,000. By setting it as this range, the hardened | cured material with sufficient crosslinking density can be obtained. The epoxy equivalent can be measured by a method standardized according to JIS K7236. The epoxy equivalent here is the mass of a resin containing 1 equivalent of epoxy groups.
硬化劑只要具有使前述環氧樹脂硬化之功能即無特別限制,列舉為例如酚系硬化劑、萘酚系硬化劑、活性酯系硬化劑、苯并噁嗪系硬化劑、氰酸酯系硬化劑及碳二醯亞胺系硬化劑。硬化劑可單獨使用1種,或亦可併用2種以上。 The hardener is not particularly limited as long as it has a function of hardening the epoxy resin, and examples thereof include a phenol-based hardener, a naphthol-based hardener, an active ester-based hardener, a benzoxazine-based hardener, and a cyanate-based hardener. Agent and carbodiimide hardener. The hardener may be used alone or in combination of two or more.
酚系硬化劑及萘酚系硬化劑列舉為例如具有酚醛清漆構造之酚系硬化劑、具有酚醛清漆構造之萘酚系硬化劑、含氮酚系硬化劑、含有三嗪骨架之甲酚系硬化劑、含有三嗪骨架之酚系硬化劑。 Examples of the phenol-based hardener and naphthol-based hardener include a phenol-based hardener having a novolac structure, a naphthol-based hardener having a novolac structure, a nitrogen-containing phenol-based hardener, and a cresol-based hardener containing a triazine skeleton. Agent, phenolic hardener containing a triazine skeleton.
酚系硬化劑及萘酚系硬化劑之具體例列舉為 例如明和化成(股)製之「MEH-7700」、「MEH-7810」、「MEH-7851」、日本化藥(股)製之「NHN」、「CBN」、「GPH」、東都化成(股)製之「SN170」、「SN180」、「SN190」、「SN475」、「SN485」、「SN495」、「SN375」、「SN395」、DIC(股)製之「LA7052」、「LA7054」、「LA3081」等。 Specific examples of the phenol-based hardener and the naphthol-based hardener are listed below. For example, `` MEH-7700 '', `` MEH-7810 '', `` MEH-7851 '' by Meiwa Kasei Co., Ltd., `` NHN '', `` CBN '', `` GPH '' by Tohoku Kasei Co., Ltd., and Toto Kasei Co., Ltd. ) System "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395", DIC (share) system "LA7052", "LA7054", " LA3081 "and so on.
活性酯系硬化劑並無特別限制,但一般較好 使用酚酯類、噻吩酯類、N-羥基胺酯類、雜環羥基化合物之酯類等之1分子中具有2個以上反應活性高之酯基之化合物。該活性酯系硬化劑較好為藉由羧酸化合物及/或硫代羧酸化合物與羥基化合物及/或硫醇化合物之縮合反應而得之硬化劑。尤其就提高耐熱性之觀點而言,較好為由羧酸化合物與羥基化合物所得之活性酯系硬化劑,更好為由羧酸化合物與酚化合物及/或萘酚化合物所得之活性酯系硬化劑。羧酸化合物列舉為例如苯甲酸、乙酸、琥珀酸、馬來酸、衣康酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、均苯四酸等。酚化合物或萘酚化合物列舉為例如氫醌、間苯二酚、雙酚A、雙酚F、雙酚S、酚酞(phenolphthalein)、甲基化雙酚A、甲基化雙酚F、甲基化雙酚S、苯酚、鄰-甲酚、間-甲酚、對-甲酚、兒茶酚、α-萘酚、β-萘酚、1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯甲酮、三羥基二苯甲酮、四羥基二苯甲酮、苯三酚、苯三醇、二環戊二烯型之二酚化合物、酚酚醛清漆等。 There is no particular limitation on the active ester hardener, but it is generally better Phenol esters, thiophene esters, N-hydroxyamine esters, heterocyclic hydroxy compound esters, and the like are used as compounds having two or more highly reactive ester groups in one molecule. The active ester-based hardener is preferably a hardener obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Especially from the viewpoint of improving heat resistance, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based hardener obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Agent. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methyl Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxy Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, pyrogallol, pyroglycerol, dicyclopentadiene type diphenol compound, Phenolic novolac, etc.
活性酯系硬化劑具體列舉為含二環戊二烯型 二酚縮合構造之活性酯化合物、含萘構造之活性酯化合物、含酚酚醛清漆之乙醯化物之活性酯化合物、含酚酚醛清漆之苯甲醯化合物之活性酯化合物。 Active ester hardeners are specifically listed as dicyclopentadiene-containing An active ester compound of a diphenol condensation structure, an active ester compound of a naphthalene structure, an active ester compound of an acetic acid compound containing a phenol novolac, and an active ester compound of a benzamidine compound containing a phenol novolac.
活性酯系硬化劑之市售品,例如作為含二環 戊二烯型二酚縮合構造之活性酯化合物列舉為「EXB9451」、「EXB9460」、「EXB9460S」、「HPC-8000-65T」(DIC(股)製),作為含萘構造之活性酯化合物列舉為「EXB9416-70BK」(DIC(股)製),作為含酚酚醛清漆之乙醯化合物之活性酯化合物列舉為「DC808」(三菱化學(股)製),作為含酚酚醛清漆之苯甲醯化合物之活性酯化合物列舉為「YLH1026」(三菱化學(股)製)等。 Commercially available active ester hardeners, for example as bicyclic Examples of active ester compounds with a pentadiene-type diphenol condensation structure are "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (manufactured by DIC (stock)), and examples of active ester compounds containing a naphthalene structure "EXB9416-70BK" (manufactured by DIC), listed as the active ester compound of acetic acid compound containing phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.), and benzamidine containing novolac Examples of the active ester compound of the compound include "YLH1026" (manufactured by Mitsubishi Chemical Corporation).
苯并噁嗪系硬化劑之具體例列舉為例如昭和 高分子(股)製之「HFB2006M」、四國化成工業(股)製之「P-d」、「F-a」。 Specific examples of the benzoxazine-based hardener include, for example, Showa "HFB2006M" for polymer (stock) system, "P-d" and "F-a" for Shikoku Chemical Industry (stock) system.
氰酸酯系硬化劑列舉為例如雙酚A二氰酸 酯、聚酚氰酸酯(寡聚(3-亞甲基-1,5-伸苯基氰酸酯)、4,4'-亞甲基雙(2,6-二甲基苯基氰酸酯)、4,4'-亞乙基二苯基二氰酸酯、六氟雙酚A二氰酸酯、2,2-雙(4-氰酸酯基)苯基丙烷、1,1-雙(4-氰酸酯基苯基甲烷)、雙(4-氰酸酯基-3,5-二甲基苯基)甲烷、1,3-雙(4-氰酸酯基苯基-1-(甲基亞乙基))苯、雙(4-氰酸酯基苯基)硫醚、及雙(4-氰酸酯基苯基)醚等2官能氰酸酯樹脂、由酚酚醛清漆及甲酚酚醛清漆等衍生之多官能氰酸酯樹脂、該等氰酸酯樹脂經部分三嗪化 而成之預聚物等。氰酸酯系硬化劑之具體例列舉為日本LONZA(股)製之「PT30」及「PT60」(均為酚酚醛清漆型多官能氰酸酯樹脂)、「BA230」(雙酚A二氰酸酯之一部分或全部經三嗪化成為三聚物之預聚物)等。 Examples of the cyanate-based curing agent include bisphenol A dicyanate Ester, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenyl cyanate) (Ester), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1- Bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1) -Bifunctional cyanate resins such as ((methylethylene)) benzene, bis (4-cyanatephenyl) sulfide, and bis (4-cyanatephenyl) ether; phenol novolac And cresol novolac and other polyfunctional cyanate resins, and these cyanate resins are partially triazinated Prepolymers, etc. Specific examples of the cyanate-based hardener include "PT30" and "PT60" (both phenol novolac-type polyfunctional cyanate resins) and "BA230" (bisphenol A dicyanate) made by Japan LONZA Co., Ltd. One or all of the esters are partially or completely triazinated into a prepolymer of a trimer).
碳二醯亞胺系硬化劑之具體例列舉為日清紡化學(股)製之「V-03」、「V-07」等。 Specific examples of the carbodiimide-based hardener include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.
環氧樹脂與硬化劑之量比以[環氧樹脂之環氧 基合計數]:[硬化劑之反應基合計數]之比率計,較好為1:0.2~1:2之範圍,更好為1:0.3~1:1.5之範圍,又更好為1:0.4~1:1之範圍。此處,所謂硬化劑之反應基為活性羥基、活性酯基等,係隨硬化劑種類而異。此外,環氧樹脂之環氧基合計數為對所有環氧樹脂將各環氧樹脂之不揮發成分之質量除以環氧當量所得之值合計之值,硬化劑之反應基合計數係針對所有硬化劑將各硬化劑之不揮發成分之質量除以反應基當量所得之值合計之值。藉由使環氧樹脂與硬化劑之量比成為該範圍內,而更提高成為硬化體時之耐熱性。 The ratio of epoxy resin to hardener is Basis count]: The ratio of [reaction base count of hardener] is preferably in the range of 1: 0.2 to 1: 2, more preferably in the range of 1: 0.3 to 1: 1.5, and more preferably 1: The range is from 0.4 to 1: 1. Here, the reactive group of the hardener is an active hydroxyl group, an active ester group, and the like, and it depends on the type of the hardener. In addition, the epoxy epoxy group total number is the value obtained by dividing the mass of each epoxy resin by the epoxy equivalent weight for all epoxy resins. The hardener is a value obtained by dividing the mass of the nonvolatile component of each hardener by the equivalent of the reactive group. By setting the amount ratio of the epoxy resin to the hardener within this range, the heat resistance at the time of becoming a hardened body is further improved.
關於硬化劑之含量,環氧樹脂之環氧基合計 數與硬化劑之反應基合計數之比,較好為1:0.2~1:2之範圍,更好為1:0.3~1:1.5之範圍,亦更好為1:0.4~1:1之範圍。 About the content of hardener, total epoxy groups of epoxy resin The ratio of the number to the total number of reactive groups of the hardener is preferably in the range of 1: 0.2 to 1: 2, more preferably in the range of 1: 0.3 to 1: 1.5, and even more preferably in the range of 1: 0.4 to 1: 1. range.
熱硬化性樹脂組成物較好分別包含作為環氧 樹脂之液狀環氧樹脂與固體狀環氧樹脂之混合物(液狀環氧樹脂:固體狀環氧樹脂之質量比較好為1:0.1~1:4之範 圍,更好為1:0.3~1:3.5之範圍,又更好為1:0.6~1:3之範圍,最好為1:0.8~1:2.5之範圍),及作為硬化劑之由酚系硬化劑、萘酚系硬化劑、活性酯系硬化劑及氰酸酯系硬化劑所組成之群選出之1種以上(較好為包含由酚系硬化劑、萘酚系硬化劑所組成之群選出之1種以上,更好由含有三嗪骨架之酚酚醛清漆樹脂、萘酚系硬化劑所組成之群選出之1種以上,又更好為含有三嗪骨架之酚酚醛清漆樹脂之硬化劑)。 The thermosetting resin composition preferably contains each as an epoxy resin. Mixture of liquid epoxy resin and solid epoxy resin (liquid epoxy resin: solid epoxy resin is better in the range of 1: 0.1 ~ 1: 4 Range, more preferably 1: 0.3 ~ 1: 3.5, still more preferably 1: 0.6 ~ 1: 3, most preferably 1: 0.8 ~ 1: 2.5), and phenol as a hardener Hardener, naphthol-based hardener, active ester-based hardener, and cyanate-based hardener selected from one or more (preferably including a phenol-based hardener and a naphthol-based hardener One or more selected from the group, more preferably one or more selected from the group consisting of a phenol novolac resin containing a triazine skeleton, and a naphthol-based hardener, and further preferably a hardening of the phenol novolac resin containing a triazine skeleton剂).
熱可塑性樹脂列舉為例如苯氧樹脂、丙烯酸樹脂、聚乙烯乙縮醛樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚碸樹脂及聚碸樹脂等。熱可塑性樹脂可單獨使用1種,或亦可併用2種以上。 Examples of the thermoplastic resin include a phenoxy resin, an acrylic resin, a polyethylene acetal resin, a polyimide resin, a polyimide resin, a polyimide resin, and a polyimide resin. The thermoplastic resin may be used singly or in combination of two or more kinds.
熱可塑性樹脂之聚苯乙烯換算之重量平均分 子量較好為8000~70000之範圍,更好為10000~60000之範圍,又更好為20000~60000之範圍。熱可塑性樹脂之聚苯乙烯換算之重量平均分子量係以凝膠滲透層析(GPC)法測定。具體而言,熱可塑性樹脂之聚苯乙烯換算之重量平均分子量可使用島津製作所製LC-9A/RID-6A作為測定裝置,使用昭和電工(股)製Shodex K-800P/K-804L/K-804L作為管柱,使用氯仿等作為移動相,將管柱溫度設為40℃進行測定,且使用標準聚苯乙烯之校正線算出。 Polystyrene equivalent weight average of thermoplastic resin The sub-quantity is preferably in the range of 8000 to 70,000, more preferably in the range of 10,000 to 60,000, and more preferably in the range of 20,000 to 60,000. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the weight-average molecular weight in terms of polystyrene of the thermoplastic resin can be measured using LC-9A / RID-6A manufactured by Shimadzu Corporation, and Shodex K-800P / K-804L / K- manufactured by Showa Denko Corporation. 804L was used as a column, and chloroform or the like was used as a mobile phase. The column temperature was measured at 40 ° C, and calculated using a calibration line of standard polystyrene.
作為苯氧樹脂列舉為例如具有由雙酚A骨 架、雙酚F骨架、雙酚S骨架、雙酚苯乙酮骨架、酚醛清漆骨架、聯苯骨架、茀骨架、二環戊二烯骨架、降冰片烯骨架、萘骨架、蒽骨架、金剛烷骨架、萜烯骨架及三甲基環己烷骨架所組成之群選出之1種以上之骨架之苯氧樹脂。苯氧樹脂之末端亦可為酚性羥基、環氧基等任一種官能基。苯氧樹脂可單獨使用1種,或亦可併用2種以上。 苯氧樹脂之具體例列舉為三菱化學(股)製之「1256」及「4250」(均為含有雙酚A骨架之苯氧樹脂)、「YX8100」(含有雙酚S骨架之苯氧樹脂)、及「YX6954」(含有雙酚苯乙酮骨架之苯氧樹脂),另外列舉為東都化成(股)製之「FX280」及「FX293」、三菱化學(股)製之「YX7553」、「YL6794」、「YL7213」、「YL7290」及「YL7482」等。 As the phenoxy resin, for example, bisphenol A Frame, bisphenol F frame, bisphenol S frame, bisphenol acetophenone frame, novolak frame, biphenyl frame, fluorene frame, dicyclopentadiene frame, norbornene frame, naphthalene frame, anthracene frame, adamantane One or more phenoxy resins selected from the group consisting of a skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used singly or in combination of two or more kinds. Specific examples of the phenoxy resin include "1256" and "4250" (both phenoxy resin containing a bisphenol A skeleton) and "YX8100" (phenoxy resin containing a bisphenol S skeleton) made by Mitsubishi Chemical Corporation. And "YX6954" (phenoxy resin containing bisphenol acetophenone skeleton), and other examples are "FX280" and "FX293" made by Totsu Kasei Co., Ltd., and "YX7553" and "YL6794" "," YL7213 "," YL7290 ", and" YL7482 ".
作為丙烯酸樹脂,就使熱膨脹率及彈性率更 低之觀點而言,較好為含官能基之丙烯酸樹脂,更好為玻璃轉移溫度為25℃以下之含環氧基之丙烯酸樹脂。 As an acrylic resin, the thermal expansion rate and elastic modulus are further improved. From a low viewpoint, the functional group-containing acrylic resin is preferable, and the epoxy group-containing acrylic resin having a glass transition temperature of 25 ° C. or lower is more preferred.
含官能基之丙烯酸樹脂之數平均分子量(Mn)較好為10000~1000000,更好為30000~900000。 The number average molecular weight (Mn) of the functional group-containing acrylic resin is preferably 10,000 to 1,000,000, more preferably 30,000 to 900,000.
含官能基之丙烯酸樹脂之官能基當量較好為1000~50000,更好為2500~30000。 The functional group equivalent of the functional group-containing acrylic resin is preferably 1,000 to 50,000, and more preferably 2500 to 30,000.
玻璃轉移溫度為25℃以下之含環氧基之丙烯酸樹脂較好為玻璃轉移溫度為25℃以下之含環氧基之丙烯酸酯共聚物樹脂,其具體例列舉為Nagase Chemtex(股)製之「SG-80H」(含環氧基之丙烯酸酯共聚物樹脂(數平均 分子量Mn:350000g/mol,環氧價0.07eq/kg,Tg 11℃)、Nagase Chemtex(股)製之「SG-P3」(含環氧基之丙烯酸酯共聚物樹脂(數平均分子量Mn:850000g/mol,環氧價0.21eq/kg,玻璃轉移溫度12℃))。 The epoxy group-containing acrylic resin having a glass transition temperature of 25 ° C. or lower is preferably an epoxy group-containing acrylate copolymer resin having a glass transition temperature of 25 ° C. or lower. Specific examples thereof include “made by Nagase Chemtex” SG-80H '' (epoxy-containing acrylate copolymer resin (number average Molecular weight Mn: 350,000 g / mol, epoxy value 0.07 eq / kg, Tg 11 ° C), "SG-P3" (epoxy-containing acrylate copolymer resin (number-average molecular weight Mn: 850000 g) manufactured by Nagase Chemtex / mol, epoxy value 0.21 eq / kg, glass transition temperature 12 ° C)).
聚乙烯乙縮醛樹脂之具體例列舉為電氣化學 工業(股)製之電化丁醛4000-2、5000-A、6000-C、6000-EP、積水化學工業(股)製之SLEC BH系列、BX系列、KSI等之KS系列、BL系列、BM系列等。 Specific examples of polyethylene acetal resin are listed in electrochemistry Electrochemical butyraldehyde 4000-2, 5000-A, 6000-C, 6000-EP made by industrial (stock), SLEC BH series, BX series, KSI, KS series, BL series, BM made by Sekisui Chemical Industry (stock) Series, etc.
聚醯亞胺樹脂之具體例列舉為新日本理化(股) 製之「RIKACOAT SN20」及「RIKACOAT PN20」。聚醯亞胺樹脂之具體例又列舉為使2官能性羥基末端聚丁二烯、二異氰酸酯化合物及四元酸酐反應獲得之線狀聚醯亞胺(日本特開2006-37083號公報記載之聚醯亞胺樹脂)、含聚矽氧烷骨架之聚醯亞胺(日本特開2002-12667號公報及日本特開2000-319386號公報等所記載之聚醯亞胺樹脂)等之改質聚醯亞胺。 Specific examples of polyimide resins are listed as Nippon Physico Chemical Co., Ltd. "RIKACOAT SN20" and "RIKACOAT PN20". Specific examples of the polyimide resin are linear polyimide obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a quaternary acid anhydride (Polyimide described in Japanese Patent Application Laid-Open No. 2006-37083 Polyimide resins), polyimide containing a polysiloxane skeleton (polyimide resins described in JP 2002-12667 and JP 2000-319386, etc.) and other modified polymers醯 imine.
聚醯胺醯亞胺樹脂之具體例列舉為東洋紡績 (股)製之「VYLOMAX HR11NN」及「VYLOMAX HR16NN」。聚醯胺醯亞胺樹脂之具體例列舉為日立化成工業(股)製之含聚矽氧烷骨架之聚醯胺醯亞胺「KS9100」、「KS9300」等改質聚醯胺醯亞胺。 Specific examples of polyimide / imide resins are listed as Toyobo (Share) system "VYLOMAX HR11NN" and "VYLOMAX HR16NN". Specific examples of the polyamidoamine imine resin include modified polyamidoamine imines such as polyamidoamimine "KS9100" and "KS9300" containing a polysiloxane skeleton manufactured by Hitachi Chemical Industries, Ltd.
聚醚碸樹脂之具體例列舉為住友化學(股)製之 「PES5003P」等。 Specific examples of polyether resins are listed by Sumitomo Chemical Co., Ltd. "PES5003P", etc.
聚碸樹脂之具體例列舉為Solvay Advanced Polymers(股)製之聚碸「P1700」、「P3500」等。 Specific examples of polyfluorene resins are Solvay Advanced Polymers (P1700), "P3500", etc.
熱硬化性樹脂組成物中之熱可塑性樹脂含量 較好為0.1質量%~20質量%。藉由使熱可塑性樹脂之含量成為該範圍內,使熱硬化性樹脂組成物之黏度適度,可形成厚度或整體性狀均勻之熱硬化性樹脂組成物層。熱硬化性樹脂組成物中之熱可塑性樹脂之含量更好為0.5質量%~10質量%。 Thermoplastic resin content in thermosetting resin composition It is preferably from 0.1% by mass to 20% by mass. By setting the content of the thermoplastic resin within this range, the viscosity of the thermosetting resin composition is made moderate, and a thermosetting resin composition layer having a uniform thickness or overall properties can be formed. The content of the thermoplastic resin in the thermosetting resin composition is more preferably 0.5% by mass to 10% by mass.
硬化促進劑列舉為例如磷系硬化促進劑、胺系硬化促進劑、咪唑系硬化促進劑、胍系硬化促進劑等。 Examples of the hardening accelerator include a phosphorus-based hardening accelerator, an amine-based hardening accelerator, an imidazole-based hardening accelerator, and a guanidine-based hardening accelerator.
磷系硬化促進劑列舉為例如三苯膦、硼酸鏻 化合物、三苯基鏻四苯基硼酸鹽、正丁基鏻四苯基硼酸鹽、四丁基鏻癸酸鹽、(4-甲基苯基)三苯基鏻硫代氰酸鹽、四苯基鏻硫代氰酸鹽、丁基三苯基鏻硫代氰酸鹽等。 Examples of the phosphorus-based hardening accelerator include triphenylphosphine and lutetium borate Compound, triphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetrabenzene Sulfonium thiocyanate, butyltriphenylsulfonium thiocyanate, and the like.
胺系硬化促進劑列舉為例如三乙胺、三丁胺 等三烷基胺、4-二甲胺基吡啶、苄基二甲基胺、2,4,6-參(二甲胺基甲基)酚、1,8-二氮雜雙環(5.4.0)-十一碳烯等。 Examples of the amine-based hardening accelerator include triethylamine and tributylamine. Isotrialkylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-p- (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5.4.0 ) -Undecene and the like.
咪唑系硬化促進劑列舉為例如2-甲基咪唑、 2-十一烷基咪唑、2-十五烷基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-十一烷基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-十一 烷基咪唑鎓偏苯三酸鹽、1-氰基乙基-2-苯基咪唑鎓偏苯三酸鹽、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基-s-三嗪、2,4-二胺基-6-[2’-十一烷基咪唑基-(1’)]-乙基-s-三嗪、2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三嗪、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪異氰尿酸加成物、2-苯基咪唑異氰尿酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2,3-二羥基-1H-吡咯并[1,2-a]苯并咪唑、1-十二烷基-2-甲基-3-苯并咪唑鎓氯化物、2-甲基咪唑啉、2-苯基咪唑啉等咪唑化合物及咪唑化合物與環氧樹脂之加成物。 Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-pentadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl Imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecane Imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl Alkyl imidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-Ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4 -Diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'- Methyl imidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethyl Imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydroxy-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2- Imidazole compounds such as methyl-3-benzimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and the addition of imidazole compounds to epoxy resins.
胍系硬化促進劑列舉為例如二氰二醯胺、1- 甲基胍、1-乙基胍、1-環己基胍、1-苯基胍、1-(鄰-甲苯基)胍、二甲基胍、二苯基胍、三甲基胍、四甲基胍、五甲基胍、1,5,7-三氮雜雙環[4.4.0]癸-5-烯、7-甲基-1,5,7-三氮雜雙環[4.4.0]癸-5-烯、1-甲基雙胍、1-乙基雙胍、1-正丁基雙胍、1-正十八烷基雙胍、1,1-二甲基雙胍、1,1-二乙基雙胍、1-環己基雙胍、1-烯丙基雙胍、1-苯基雙胍、1-(鄰-甲苯基)雙胍等。 Examples of guanidine-based hardening accelerators include dicyandiamide, 1- Methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethyl Guanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec- 5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1- (o-tolyl) biguanide and the like.
硬化促進劑可單獨使用1種,或亦可組合2 種以上使用。熱硬化性樹脂組成物中之硬化促進劑含量在將環氧樹脂與硬化劑之不揮發成分之合計量設為100質量%時,較好在0.05質量%~3質量%之範圍內使用。 Hardening accelerators can be used alone or in combination of 2 More than one kind of use. When the content of the hardening accelerator in the thermosetting resin composition is 100% by mass, the total amount of the nonvolatile components of the epoxy resin and the hardener is preferably used in the range of 0.05% by mass to 3% by mass.
難燃劑列舉為例如有機磷系難燃劑、有機系含氮之磷化合物、氮化合物、聚矽氧系難燃劑、金屬氫氧化物等。可使用之難燃劑之例列舉為三光(股)製之「HCA-HQ」。難燃劑可單獨使用1種,或亦可併用2種以上。熱硬化性樹脂組成物層中之難燃劑含量並無特別限制,較好為0.5質量%~10質量%之範圍,更好為1質量%~9質量%之範圍,又更好為1.5質量%~8質量%之範圍。 Examples of the flame retardant include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a polysiloxane flame retardant, and a metal hydroxide. Examples of usable flame retardants are "HCA-HQ" manufactured by Mitsuko Corporation. The flame retardant can be used singly or in combination of two or more kinds. The content of the flame retardant in the thermosetting resin composition layer is not particularly limited, but is preferably in the range of 0.5% to 10% by mass, more preferably in the range of 1% to 9% by mass, and even more preferably 1.5% by mass. % To 8% by mass.
熱硬化性樹脂組成物層之形成所用之熱硬化性樹脂組成物亦可視需要含其他添加劑以調整例如熱硬化性樹脂組成物層或硬化體之特性,該其他添加劑列舉為例如有機銅化合物、有機鋅化合物及有機鈷化合物等有機金屬化合物、以及增黏劑、消泡劑、調平劑、密著性賦予劑、及著色劑等樹脂添加劑等。 The thermosetting resin composition used for the formation of the thermosetting resin composition layer may optionally contain other additives to adjust the properties of the thermosetting resin composition layer or the hardened body, for example. The other additives are exemplified by organic copper compounds, organic Organometallic compounds such as zinc compounds and organic cobalt compounds; and resin additives such as tackifiers, defoamers, leveling agents, adhesion-imparting agents, and coloring agents.
製備樹脂漆料時所用之有機溶劑列舉為例如丙酮、甲基乙基酮及環己酮等酮類、乙酸乙酯、乙酸丁酯、溶纖素乙酸酯、丙二醇單甲基醚乙酸酯及卡必醇乙酸酯等乙酸酯類、溶纖素及丁基卡必醇等卡必醇類、甲苯及二甲苯等芳香族烴類、二甲基甲醯胺、二甲基乙醯胺及N-甲基吡咯啶酮等醯胺系溶劑等。有機溶劑可單獨使用1種,或亦可併用2種以上。 The organic solvents used in the preparation of resin paints include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, lysin acetate, propylene glycol monomethyl ether acetate And acetates such as carbitol acetate, carbitols such as lysin and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide And amine-based solvents such as N-methylpyrrolidone. The organic solvents may be used singly or in combination of two or more kinds.
用於形成熱硬化性樹脂組成物層之熱硬化性樹脂組成物之塗佈膜之乾燥處理可藉由加熱、熱風吹拂等習知任意較佳之乾燥方法實施。塗佈膜藉由該乾燥處理而成為熱硬化性樹脂組成物層。 The drying treatment of the coating film of the thermosetting resin composition for forming the thermosetting resin composition layer can be performed by any known and preferable drying method such as heating and blowing with hot air. The coating film becomes a thermosetting resin composition layer by this drying process.
各乾燥處理之乾燥條件只要考慮樹脂組成物 或樹脂漆料所含之有機溶劑之沸點等而設為任意較佳條件即可。已說明之鉛筆硬度及最低熔融黏度可根據乾燥條件,亦即乾燥方法、乾燥溫度、乾燥處理時間而調節。具體而言,若乾燥溫度相同,則乾燥時間愈長鉛筆硬度及最低熔融黏度愈高。 The drying conditions of each drying process only need to consider the resin composition Or the boiling point of the organic solvent contained in the resin paint can be set to any preferable conditions. The stated pencil hardness and minimum melt viscosity can be adjusted according to the drying conditions, that is, the drying method, drying temperature, and drying processing time. Specifically, if the drying temperature is the same, the longer the drying time, the higher the pencil hardness and the minimum melt viscosity.
該乾燥處理並不限定僅實施一次,亦可重複 實施複數次。重複實施複數次乾燥處理時,各乾燥條件可彼此相同,亦可彼此不同。 This drying process is not limited to being performed only once, and may be repeated Implemented multiple times. When the drying process is repeatedly performed several times, the drying conditions may be the same as or different from each other.
重複複數次乾燥處理時,可例如在較低溫下 進行初次乾燥處理,在比初次乾燥處理更高溫下進行第2次以後之乾燥處理。據此,即使使用沸點不同之複數種有機溶劑時,仍可藉由初次乾燥處理使沸點較低之有機溶劑有效揮發,進而藉由第2次以後之乾燥處理使沸點較高之有機溶劑有效揮發,因此可形成殘留溶劑量較少之高品質熱硬化性樹脂組成物層。 When the drying process is repeated several times, for example, at a lower temperature The first drying process is performed, and the second and subsequent drying processes are performed at a higher temperature than the first drying process. Accordingly, even when plural organic solvents having different boiling points are used, the organic solvent with a lower boiling point can be effectively volatilized by the first drying treatment, and the organic solvent with a higher boiling point can be effectively volatilized by the second and subsequent drying treatments Therefore, a high-quality thermosetting resin composition layer having a small amount of residual solvent can be formed.
步驟(A)較好使用長條之支撐體作為有機支撐 體,以輥對輥方式進行,但亦可以批式方式進行。 Step (A) preferably uses a long support as an organic support The body is carried out in a roll-to-roll manner, but it can also be carried out in a batch manner.
以輥對輥方式之步驟(A)具體可藉由如下進 行:邊將張開跨及於包含捲出輥及捲取輥之至少2個輥之 間之長條有機支撐體連續地輸送,邊將熱硬化性樹脂組成物塗佈於露出於捲出輥及捲取輥之間之支撐體之一主面上,使連續的塗佈膜經乾燥處理而形成熱硬化性樹脂組成物層。 The step (A) of the roll-to-roll method can be specifically performed as follows Row: Spread across at least 2 rolls including the take-up roll and take-up roll The long organic support is continuously conveyed, and the thermosetting resin composition is coated on one of the main surfaces of the support exposed between the take-up roll and the take-up roll, so that the continuous coating film is dried. Process to form a thermosetting resin composition layer.
如此可準備於有機支撐體上設置熱硬化性樹 脂組成物層之接著片。 In this way, it is possible to prepare a thermosetting tree on an organic support Adhesive sheet of lipid composition layer.
所準備之接著薄片在暫時儲存時,亦即暫時 中斷層合板之製造步驟,於經過一段時間再開啟時,較好進一步設置與熱硬化性樹脂組成物層之未與有機支撐體接合之側之露出面(亦即,與有機支撐體相反側之面)接合之保護膜。該保護膜有助於防止污物等附著於熱硬化性樹脂組成物層或防止傷痕。作為保護膜可使用例如聚丙烯膜、聚乙烯膜等。且可使用由與有機支撐體之材料相同之材料所成之薄膜。保護膜厚度並無特別限制,例如為1μm~40μm。保護膜厚度較好薄於有機支撐體之厚度。 When the prepared adhesive sheet is temporarily stored, that is, temporarily When the manufacturing steps of the laminated sheet are discontinued, it is preferable to further set the exposed surface of the side of the thermosetting resin composition layer that is not joined to the organic support (that is, the side opposite to the organic support) when it is opened again after a period of time Surface) bonded protective film. This protective film helps to prevent dirt or the like from adhering to the thermosetting resin composition layer or to prevent scratches. As a protective film, a polypropylene film, a polyethylene film, etc. can be used, for example. A thin film made of the same material as that of the organic support can be used. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. The thickness of the protective film is preferably thinner than the thickness of the organic support.
保護膜對接著片之貼合可使用過去習知之層合機裝置進行。 Bonding of a protective film to an adhesive sheet can be performed using the conventional laminator apparatus.
接著,進行於使熱硬化性樹脂組成物層彼此對向之方式配置之2片接著薄片間配置1片以上之預浸物,在減壓下,於200℃以上加熱及加壓而一體成型之步驟(B)。 Next, two sheets of thermosetting resin composition layers are arranged to face each other, and then one or more prepregs are arranged between the sheets, and they are integrally molded by heating and pressing at 200 ° C or higher under reduced pressure. Step (B).
預浸物係將樹脂組成物含浸於薄片狀纖維基材中而成之薄片狀構造體。本發明之層合板的製造方法可使用之預浸物可依據層合板之用途使用任意較佳之預浸物。預浸物亦可使用市售之預浸物。市售之預浸物列舉為例如日立化成(股)製之「GEA-800G」。 The prepreg is a sheet-like structure in which a resin composition is impregnated into a sheet-like fiber substrate. The prepreg that can be used in the manufacturing method of the laminated board of the present invention can use any preferred prepreg according to the use of the laminated board. As the prepreg, a commercially available prepreg can also be used. Commercially available prepregs are listed, for example, as "GEA-800G" by Hitachi Chemical Co., Ltd.
構成預浸物之薄片狀纖維基材並無特別限 制,可使用玻璃布、芳醯胺不織布、液晶聚合物不織布等預浸物用之作為薄片狀纖維基材常用之基材。依據層合板之用途,預浸物之厚度可為任意較佳厚度,但於多層印刷配線板之絕緣層形成中使用層合板時,較好使用厚度為50μm以下之薄型薄片狀纖維基材,尤其以厚度為10μm~40μm之薄片狀纖維基材較佳,更好為厚度10μm~30μm之薄片狀纖維基材,又更好為厚度10μm~20μm之薄片狀纖維基材。使用層合板作為絕緣性基材(蕊基板)時,較好使用厚度10μm~150μm之薄片狀纖維基材,最好使用厚度10μm~100μm之薄片狀纖維基材。 The sheet-like fibrous substrate constituting the prepreg is not particularly limited It can use glass cloth, aramide, non-woven fabric, liquid crystal polymer non-woven fabric and other prepregs. Depending on the purpose of the laminate, the thickness of the prepreg can be any preferred thickness, but when using a laminate in the formation of an insulating layer of a multilayer printed wiring board, it is preferred to use a thin sheet-like fiber substrate having a thickness of 50 μm or less, especially A sheet-like fibrous substrate having a thickness of 10 μm to 40 μm is preferable, a sheet-like fibrous substrate having a thickness of 10 μm to 30 μm, and a sheet-like fibrous substrate having a thickness of 10 μm to 20 μm is more preferable. When a laminate is used as the insulating substrate (core substrate), a sheet-like fibrous substrate having a thickness of 10 μm to 150 μm is preferably used, and a sheet-like fibrous substrate having a thickness of 10 μm to 100 μm is preferably used.
可使用作為薄片狀纖維基材之玻璃布基材之 具體例列舉為例如ASAHI SCHWEBEL(股)製之「STYLE 1027MS」(經絲密度75條/25mm,緯絲密度75條/25mm,布重量20g/m2,厚度19μm)、ASAHI SCHWEBEL(股)製之「STYLE 1037MS」(經絲密度70條/25mm,緯絲密度73條/25mm,布重量24g/m2,厚度28μm)、有澤製作所(股)製之「1078」(經絲密度54條/25mm,緯絲密度54條/25mm,布重量48g/m2,厚度 43μm)、有澤製作所(股)製之「1037NS」(經絲密度72條/25mm,緯絲密度69條/25mm,布重量23g/m2,厚度21μm)、有澤製作所(股)製之「1027NS」(經絲密度75條/25mm,緯絲密度75條/25mm,布重量19.5g/m2,厚度16μm)、有澤製作所(股)製之「1015NS」(經絲密度95條/25mm,緯絲密度95條/25mm,布重量17.5g/m2,厚度15μm)、有澤製作所(股)製之「1000NS」(經絲密度85條/25mm,緯絲密度85條/25mm,布重量11g/m2,厚度10μm)等。且液晶聚合物不織布之具體例列舉為例如Kuraray(股)製之芳香族聚酯不織布之以熔融吹塑法進行之「VECRUS」(單位面積重量6g/m2~15g/m2)或「VECTRAN」等。 Specific examples of the glass cloth substrate that can be used as a sheet-like fiber substrate include, for example, "STYLE 1027MS" manufactured by ASAHI SCHWEBEL (strand density of 75 warps / 25mm, weft density of 75 / 25mm, and cloth weight of 20g). / m 2 , thickness 19 μm), "STYLE 1037MS" by Asahi Schwebel (strand density 70 warps / 25 mm, weft density 73/25 mm, cloth weight 24 g / m 2 , thickness 28 μm), Arisawa Manufacturing Co., Ltd. ( "1078" (warp density of 54 / 25mm, weft density of 54 / 25mm, cloth weight of 48g / m 2 , thickness of 43μm), "1037NS" (warp density of 72) Article / 25mm, weft density of 69 / 25mm, fabric weight 23g / m 2, a thickness of 21μm), Arisawa (shares) manufactured by the "1027NS" (warp density of 75 / 25mm, weft density of 75 / 25mm, Cloth weight 19.5g / m 2 , thickness 16μm), "1015NS" manufactured by Ariza Seisakusho Co., Ltd. (warp yarn density 95 / 25mm, weft density 95 / 25mm, cloth weight 17.5g / m 2 , thickness 15μm) , Arisawa (shares) manufactured by the "1000NS" (warp density of 85 / 25mm, the weft yarn density of 85 / 25mm, fabric weight 11g / m 2, thickness 10 m) and the like. Specific examples of the liquid crystal polymer nonwoven fabric include, for example, "VECRUS" (unit area weight: 6 g / m 2 to 15 g / m 2 ) or "VECTRAN" of an aromatic polyester nonwoven fabric made by Kuraray (strand) by melt blow molding. "Wait.
預浸物之形成可用之熱硬化性樹脂組成物只 要其硬化物具有充分硬度與絕緣性則無特別限制,例如,亦可使用與用於形成前述接著薄片之熱硬化性樹脂組成物相同組成之熱硬化性樹脂組成物。 The thermosetting resin composition that can be used for prepreg formation is only The cured product is not particularly limited as long as it has sufficient hardness and insulating properties. For example, a thermosetting resin composition having the same composition as the thermosetting resin composition used to form the aforementioned adhesive sheet may be used.
預浸物可利用熱熔融法、溶劑法等習知方法 製造。熱熔融法為不將熱硬化性樹脂組成物溶解於有機溶劑中,而暫時塗佈於對熱硬化性樹脂組成物之剝離性良好之脫模紙上,使之層合於薄片狀纖維基材上,或者藉由模嘴塗佈而直接塗佈於薄片狀纖維基材上等,而製造預浸物。且溶劑法係將薄片狀纖維基材浸自於將熱硬化性樹脂組成物溶解於有機溶劑中而成之漆料中,藉此使熱硬化性樹脂組成物含浸於薄片狀纖維基材中,隨後乾燥,製造預 浸物。進而預浸物亦可藉由以由熱硬化性樹脂組成物所成之2片樹脂薄片自其兩面側夾持薄片狀纖維基材,且在加熱、加壓條件下以層合機連續製造。 The prepreg can use conventional methods such as hot melt method and solvent method. Manufacturing. The hot-melt method is to temporarily apply a thermosetting resin composition to a release paper having good peelability without dissolving the thermosetting resin composition in an organic solvent, and laminating the thermosetting resin composition on a sheet-like fibrous substrate. Or, it can be directly coated on a sheet-like fibrous substrate by die coating, etc., to produce a prepreg. In addition, the solvent method is based on immersing the sheet-like fibrous substrate in a paint made by dissolving a thermosetting resin composition in an organic solvent, thereby impregnating the sheet-like fibrous substrate with the thermosetting resin composition. Then dried to make Dipping. Furthermore, the prepreg can be produced continuously by laminating a fibrous substrate with two resin sheets made of a thermosetting resin composition on both sides of the sheet, and heating and pressing.
接著,說明利用真空熱壓步驟之層合板之具體製造步驟之例。 Next, an example of a specific manufacturing process of a laminate using a vacuum hot pressing step will be described.
首先以使熱硬化性樹脂組成物層彼此成對向之方式配置之2片接著薄片之間配置1片以上之預浸體之方式層合而成之層合構造固定在真空熱壓裝置上。 First, a laminated structure in which two sheets of thermosetting resin composition layers are arranged so as to face each other, and one or more prepregs are arranged between the sheets is fixed to a vacuum hot pressing device.
層合構造較好透過緩衝紙、不鏽鋼板(SUS板)等金屬板、脫模薄膜等固定於真空熱壓裝置上。層合構造係以例如緩衝紙/金屬板/脫模薄膜/層合構造(例如,接著薄片/預浸物/接著片)/脫模薄膜/SUS板/緩衝紙之順序層合而成且固定於真空熱壓裝置上。 The laminated structure is preferably fixed to a vacuum hot pressing device through a metal plate such as a buffer paper, a stainless steel plate (SUS plate), and a release film. The laminated structure is laminated and fixed in the order of, for example, buffer paper / metal plate / release film / laminated structure (for example, adhesive sheet / prepreg / adhesive sheet) / release film / SUS board / buffer paper On a vacuum hot press.
此處之符號「/」係指隔著該符號所示之構成要素彼此相互連接之方式配置(以下,層合構造之說明等中亦相同)。 Here, the symbol "/" means that it is arrange | positioned so that it may mutually connect via the component shown by this symbol (it is the same also in the description of a laminated structure etc. below).
接著,在減壓之真空條件下,邊加熱邊將層 合構造加壓(按壓)進行真空熱壓步驟。 Next, the layers were heated while being heated under reduced pressure. The structure is pressurized (pressed) to perform the vacuum hot pressing step.
真空熱壓步驟可使用利用經加熱之SUS板等 金屬板自兩側按壓成為對象之層合構造體之過去習知之真空熱壓裝置實施。市售之可使用於本發明層合板製造方法之真空熱壓裝置列舉為例如名機製作所(股)製之「MNPC- V-750-5-200」、北川精機(股)製之「VH1-1603」等。 The vacuum hot pressing step can use a heated SUS plate, etc. The conventionally known vacuum hot pressing device is used for pressing a metal plate from both sides as a target laminated structure. Commercially available vacuum hot-pressing apparatuses that can be used in the method for manufacturing the laminated board of the present invention are, for example, "MNPC- "V-750-5-200", "VH1-1603" manufactured by Kitagawa Seiki Co., Ltd., etc.
真空熱壓步驟可僅進行1次處理,但亦可對 處理對象之層合構造進行重複2次以上真空熱壓步驟而處理。 The vacuum hot pressing step can be performed only once, but it can also The laminated structure of the processing target is processed by repeating the vacuum hot pressing step more than 2 times.
真空熱壓步驟中之加壓(按壓)條件較好將壓力 (按壓力)設為50kgf/cm2左右。壓力較好為5kgf/cm2~30kgf/cm2(0.5N/m2~30N/m2)。 The pressure (pressing) condition in the vacuum hot pressing step is preferably set to about 50 kgf / cm 2 . The pressure is preferably 5 kgf / cm 2 to 30 kgf / cm 2 (0.5 N / m 2 to 30 N / m 2 ).
真空熱壓步驟中之真空條件,亦即儲存處理 對象的層合構造之腔室內之減壓時之壓力設為1×10-2MPa左右。壓力通常為5×10-3MPa以下,較好為3×10-2MPa以下。 The vacuum conditions in the vacuum hot-pressing step, that is, the pressure at the time of decompression in the laminated structure storage object to be processed are set to about 1 × 10 -2 MPa. The pressure is usually 5 × 10 -3 MPa or less, and preferably 3 × 10 -2 MPa or less.
真空熱壓步驟中之加熱條件,亦即加熱溫度 隨著接著片及預浸物所用之熱硬化性樹脂組成物之組成與所用之有機支撐體之耐熱性而異,但係設為200℃以上。 加熱溫度上限並無特別限制,一般為240℃以上。加熱溫度較好為210℃以上,更好為220℃以上。 The heating conditions in the vacuum hot pressing step, that is, the heating temperature The composition varies with the composition of the thermosetting resin composition used for the adhesive sheet and the prepreg and the heat resistance of the organic support used, but it is set to 200 ° C or higher. The upper limit of the heating temperature is not particularly limited, but is generally 240 ° C or higher. The heating temperature is preferably 210 ° C or higher, and more preferably 220 ° C or higher.
又,就抑制藉真空熱壓步驟而一體成型所形 成之硬化體表面之皺褶產生等之觀點而言,較好邊使溫度階段性或連續上升,及/或邊使溫度階段性或連續下降,而實施真空熱壓步驟。 In addition, it is suppressed from being formed integrally by the vacuum hot pressing step. From the viewpoint of generation of wrinkles on the surface of the cured hardened body, it is preferred to perform the vacuum hot pressing step while gradually increasing the temperature stepwise or continuously and / or decreasing the temperature stepwise or continuously.
真空熱壓步驟具體而言可以特定之升溫率(例 如5℃/分鐘)自常溫升溫至特定加熱溫度(例如205℃),於特定加熱溫度保持特定時間後,以特定降溫率(例如5℃/分鐘)降溫至常溫之加熱條件下進行。 The vacuum hot-pressing step can specifically specify a heating rate (for example, (E.g., 5 ° C / minute) is heated from normal temperature to a specific heating temperature (for example, 205 ° C), and after the specific heating temperature is maintained for a specific time, the heating is performed at a specific cooling rate (for example, 5 ° C / minute) to normal temperature.
真空熱壓步驟中之處理時間可在不損及本發 明目的之範圍內設為任意較佳之處理時間,但通常為15分鐘~90分鐘左右。 The processing time in the vacuum hot pressing step can be The range of the purpose is set to any preferable processing time, but it is usually about 15 minutes to 90 minutes.
步驟(B)亦可係使用2片以上之預浸物,於預 浸物彼此之間進一步配置內層電路基板而一體成型之步驟。 Step (B) can also use more than two pieces of prepreg. The step of further arranging the inner-layer circuit substrate between the immersion materials and forming them integrally.
步驟(B)中可用之內層電路基板可列舉為包含 例如玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板及熱硬化型聚苯醚基板等作為基材,於該基材之單面或兩面上具有經圖型化(形成電路)之導體層(配線層)之過去習知之板狀或薄片狀之構造體。 The inner-layer circuit substrates usable in step (B) can be enumerated as including For example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate are used as the substrate. A conventionally known plate-like or sheet-like structure of a conductor layer (wiring layer) (forming a circuit).
使用2片以上之預浸物時,熱硬化性樹脂組成物之組成、薄片狀纖維基材之材料、厚度中之1種以上亦可彼此不同。 When two or more prepregs are used, one or more of the composition of the thermosetting resin composition, the material of the sheet-like fiber substrate, and the thickness may be different from each other.
步驟(B)中,例如為了接著片之儲存等,而設 置與熱硬化性樹脂組成物層側接合之保護膜時,係剝離保護膜後,或邊剝離邊進行步驟(B)。 In step (B), for example, to When a protective film bonded to the thermosetting resin composition layer is placed, the protective film is peeled off, or step (B) is performed while peeling.
藉由以上之真空熱壓步驟,使接著片之熱硬 化性樹脂組成物層及預浸物(預浸物所含之熱硬化性樹脂組成物)硬化,經一體成型而製造層合板。 With the above vacuum hot pressing step, the adhesive film is hardened. The chemical resin composition layer and the prepreg (thermosetting resin composition contained in the prepreg) are hardened and integrally molded to produce a laminate.
本發明之層合板之製造方法可進一步含剝離有機支撐體之步驟的步驟(C),形成通孔之步驟的步驟(D),粗化處 理之步驟的步驟(E),藉鍍敷形成導體層之步驟的步驟(F),導體層經圖型化而形成配線層之步驟的步驟(G)。以不損及本發明目的為條件,該等步驟(C)至步驟(G)可為本技藝者習知之任意較佳步驟。 The manufacturing method of the laminated board of the present invention may further include step (C) of the step of peeling the organic support, step (D) of the step of forming a through hole, and roughening Step (E) of the logical step, step (F) of the step of forming a conductor layer by plating, and step (G) of the step of forming a wiring layer by patterning the conductor layer. Provided that the purpose of the present invention is not impaired, these steps (C) to (G) may be any preferred steps known to those skilled in the art.
步驟(C)係剝離有機支撐體之步驟。藉由該步驟(C),剝離、去除有機支撐體、使接著片之熱硬化性樹脂組成物層硬化而成之硬化體表面露出。步驟(C)最晚可在步驟(E)之前實施,但較好為步驟(D)之後,步驟(E)之前實施。 Step (C) is a step of peeling off the organic support. In this step (C), the surface of the cured body obtained by peeling and removing the organic support, and curing the thermosetting resin composition layer of the adhesive sheet is exposed. Step (C) can be carried out before step (E) at the latest, but preferably after step (D) and before step (E).
步驟(D)係對所形成之層合板沖孔加工之步驟,藉由該沖孔加工而形成貫穿層合板之通孔之步驟。步驟(D)可藉例如鑽孔機、雷射(二氧化碳氣體雷射、YAG雷射等)、電漿等手段進行。形成之通孔係為了例如使分別設置於層合板兩主面側之導體層(配線層)彼此電性連接而使用。步驟(D)最晚可在步驟(E)之前進行,較好在步驟(C)之前實施。 Step (D) is a step of punching the formed laminated board, and forming a through hole through the laminated board by the punching process. Step (D) can be performed by means of, for example, a drilling machine, a laser (a carbon dioxide gas laser, a YAG laser, etc.), a plasma, or the like. The formed through holes are used, for example, to electrically connect conductor layers (wiring layers) provided on both main surface sides of the laminated board to each other. Step (D) may be carried out before step (E) at the latest, preferably before step (C).
步驟(E)係使層合板、亦即露出之硬化體表面進行粗化處理之步驟。步驟(E)最慢在步驟(G)之前進行,較好在步驟(C)及步驟(D)之後進行。 Step (E) is a step of roughening the laminated board, that is, the surface of the exposed hardened body. Step (E) is performed slowest before step (G), preferably after steps (C) and (D).
粗化處理順序、條件並無特別限制,可採用 過去習知之任意較佳順序、條件。例如,該步驟(E)可藉由依序實施膨潤液之膨潤處理、氧化劑之粗化處理、中和劑之中和處理而進行。膨潤液並無特別限制,列舉為鹼溶液、界面活性劑溶液等,較好為鹼溶液,該鹼溶液較好為氫氧化鈉溶液、氫氧化鉀溶液。市售之膨潤液列舉為例如日本ATOTECH(股)製之Swelling Dip Securiganth P、Swelling Dip Securiganth SBU等。以膨潤液之膨潤處理並無特別限制,例如可藉由將硬化體浸漬於30℃~90℃之膨潤液中1分鐘~20分鐘而進行。基於將硬化體之膨潤抑制在適度程度之觀點而言,較好在40℃~80℃之膨潤液中浸漬5秒~15分鐘。氧化劑並無特別限制,列舉為例如使過錳酸鉀、過錳酸鈉溶解於氫氧化鈉之水溶液中而成之鹼性過錳酸溶液。以鹼性過錳酸溶液等之氧化劑之粗化處理較好在加熱至60℃~80℃之氧化劑溶液中浸漬10分鐘~30分鐘而進行。此外,鹼性過錳酸溶液中之過錳酸鹽濃度較好為5質量%~10質量%。市售之氧化劑列舉為例如日本ATOTECH(股)製之Concentrate Compact P、Doesing Solution Securiganth P等鹼性過錳酸溶液。且,中和液較好為酸性水溶液,市售品列舉為例如日本ATOTECH(股)製之Reduction Solution Securiganth P。以中和液之處理可藉由使以氧化劑溶液進行粗化處理之處理面浸漬於30℃~80℃之中和液中5分鐘~30分鐘而進行。就作業性等方面而言,較好為將以氧化劑溶液進行粗化處理之硬化體 浸漬於40℃~70℃之中和液中5分鐘~20分鐘之方法。 The order and conditions of the roughening treatment are not particularly limited, and can be used Any preferred order and conditions known in the past. For example, step (E) can be performed by sequentially performing a swelling treatment of a swelling liquid, a roughening treatment of an oxidizing agent, and a neutralizing treatment of a neutralizing agent. The swelling liquid is not particularly limited, and examples thereof include an alkali solution, a surfactant solution, and the like, preferably an alkali solution, and the alkali solution is preferably a sodium hydroxide solution or a potassium hydroxide solution. Commercially available swelling liquids include, for example, Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, manufactured by ATOTECH Japan. The swelling treatment with the swelling liquid is not particularly limited. For example, it can be performed by immersing the hardened body in a swelling liquid at 30 ° C to 90 ° C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the hardened body to a moderate degree, it is preferable to immerse it in a swelling liquid at 40 ° C to 80 ° C for 5 seconds to 15 minutes. The oxidizing agent is not particularly limited, and examples thereof include a basic permanganic acid solution obtained by dissolving potassium permanganate and sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidant such as an alkaline permanganic acid solution is preferably performed by immersing in an oxidant solution heated to 60 ° C to 80 ° C for 10 minutes to 30 minutes. In addition, the permanganate concentration in the alkaline permanganic acid solution is preferably 5% to 10% by mass. Commercially available oxidizing agents include, for example, alkaline permanganic acid solutions such as Concentrate Compact P and Doesing Solution Securiganth P manufactured by ATOTECH Japan. The neutralizing solution is preferably an acidic aqueous solution, and commercially available products include, for example, Reduction Solution Securiganth P manufactured by ATOTECH Japan. The treatment with the neutralizing solution can be performed by immersing the treated surface roughened with the oxidant solution in a neutralizing solution at 30 ° C to 80 ° C for 5 to 30 minutes. In terms of workability and the like, a hardened body that is roughened with an oxidant solution is preferred. Method of immersing in 40 ℃ ~ 70 ℃ neutralizing solution for 5 ~ 20 minutes.
步驟(F)係藉鍍敷而於經粗化表面形成導體層之步驟。步驟(F)係在步驟(E)之後實施。 Step (F) is a step of forming a conductor layer on the roughened surface by plating. Step (F) is performed after step (E).
導體層之材料並無特別限制。較佳實施形態 中,導體層係包含由金、鉑、鈀、銀、銅、鋁、鈷、鉻、鋅、鎳、鈦、鎢、鐵、錫及銦所組成之群選出之1種以上之金屬。導體層可為單金屬層亦可為合金層,至於合金層列舉為例如由自上述之群選出之2種以上之金屬之合金(例如,鎳鉻合金、銅鎳合金及銅鈦合金)形成之層。其中,就導體層之形成步驟之廣用性、成本、圖型化之容易性等之觀點,較好為鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅之單金屬層,或鎳鉻合金、銅鎳合金、銅鈦合金之合金層,更好為鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅之單金屬層,或鎳鉻合金之合金層,又更好為銅之單金屬層。 The material of the conductive layer is not particularly limited. Preferred embodiment The conductor layer includes one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy formed of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy) is listed. Floor. Among these, from the viewpoints of versatility, cost, and ease of patterning of the formation step of the conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper is preferred, Or an alloy layer of nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, and More preferably, it is a single metal layer of copper.
導體層可為單層構造,亦可為層合2層以上 之由不同種類之金屬或合金所成之單金屬層或合金層而成之多層構造。導體層為多層構造時,與絕緣層鄰接之層較好為鉻、鋅或鈦之單金屬層,或鎳鉻合金之合金層。 The conductor layer can be a single layer structure, or it can be laminated with two or more layers The multilayer structure is composed of a single metal layer or an alloy layer made of different kinds of metals or alloys. When the conductor layer has a multilayer structure, the layer adjacent to the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of a nickel-chromium alloy.
導體層之厚度一般為3μm~35μm,較好為 5μm~30μm。 The thickness of the conductor layer is generally 3 μm to 35 μm, preferably 5μm ~ 30μm.
本實施形態中導體層係藉鍍敷形成。例如可 藉電解鍍敷法、無電解鍍敷法等過去習知之任意較佳鍍敷 步驟於硬化體表面形成導體層。 In this embodiment, the conductive layer is formed by plating. For example Any preferred plating conventionally known by electrolytic plating, electroless plating, etc. The step of forming a conductor layer on the surface of the hardened body.
步驟(G)係基於所形成之導體層形成配線層之步驟。步驟(G)係在步驟(F)之後實施。步驟(G)可例如藉由於形成之導體層(鍍敷種晶層)上形成配線層之半加成法、全加成法,使形成之導電層圖型化成為配線層之減去法等進行。 Step (G) is a step of forming a wiring layer based on the formed conductor layer. Step (G) is performed after step (F). In step (G), for example, a semi-additive method or a full-additive method for forming a wiring layer on the formed conductor layer (plating seed layer) can be used to pattern the formed conductive layer into a subtractive method for the wiring layer. get on.
此處說明以半加成法形成該配線層之例。 首先,以無電解鍍敷法,於接著片之源自熱硬化性樹脂組成物層之硬化體之經粗化處理表面形成導體層(鍍敷種晶層)。接著,於形成之鍍敷種晶層上形成使對應於期望配線圖型之鍍敷種晶層之一部分露出之遮罩圖型。於露出之鍍敷種晶層上以電解鍍敷法形成厚膜化之導體層後,去除遮罩圖型。隨後,藉由蝕刻步驟等去除不必要之種晶層,可形成具有期望配線圖型之配線層。 Here, an example in which the wiring layer is formed by a semi-additive method will be described. First, a conductive layer (plating seed layer) is formed on the roughened surface of the cured body derived from the thermosetting resin composition layer of the subsequent sheet by the electroless plating method. Next, a mask pattern is formed on the formed plating seed layer so that a part of the plating seed layer corresponding to a desired wiring pattern is exposed. After forming a thick film conductive layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Subsequently, an unnecessary seed layer is removed by an etching step or the like to form a wiring layer having a desired wiring pattern.
藉由該等步驟(F)及步驟(G),亦對藉由步驟(D) 形成之通孔內進行鍍敷,形成通孔內配線。藉由該通孔內配線,可使分別設置於層合板之兩主面側上之導體層或配線層彼此電性連接。 With these steps (F) and (G), also with step (D) Plating is performed in the formed through holes to form wirings in the through holes. Through the wiring in the through hole, the conductor layers or wiring layers respectively provided on the two main surface sides of the laminated board can be electrically connected to each other.
依據本發明之層合板之製造方法,由於使用 玻璃轉移溫度為90℃以上,較好100℃以上之有機支撐體,及鉛筆硬度為2B以上之熱硬化性樹脂組成物層之接著片,即使以過去以來使用之真空熱壓裝置仍可實施,故能有效利用既有設備以降低成本,並且可提供即使厚度較 薄仍可維持機械強度、可使配線更微細化之優異層合板。 According to the method for manufacturing a laminated board according to the present invention, An organic support having a glass transition temperature of 90 ° C or higher, preferably 100 ° C or higher, and an adhesive sheet of a thermosetting resin composition layer having a pencil hardness of 2B or higher can be implemented even with a vacuum hot pressing device used in the past. It can effectively use the existing equipment to reduce costs, and can provide It is an excellent laminated board that can maintain the mechanical strength and make the wiring more fine.
本發明之層合板可使用作為半導體裝置之製造所用之蕊基板等絕緣性基材、多層印刷配線板等配線板之材料。 The laminate of the present invention can be used as a material for wiring boards such as insulating substrates such as core substrates used in the manufacture of semiconductor devices, and multilayer printed wiring boards.
以下針對使用本發明之層合板之配線板製造步驟之例加以說明。 Hereinafter, an example of the manufacturing process of the wiring board using the laminated board of this invention is demonstrated.
配線板可使用本發明之層合板,藉由包含下述(I)及(II)之步驟之方法予以製造。 The wiring board can be manufactured by the method including the following steps (I) and (II) using the laminated board of the present invention.
(I)首先,如上述般準備設置配線層之本發明之層合板,使具備支撐體與設於該支撐體上之樹脂組成物層之接著薄膜以使樹脂組成物層與配線層接合之方式貼合之步驟, (I) First, a method of preparing a laminate of the present invention in which a wiring layer is provided as described above, and a method of bonding a resin composition layer and a wiring layer with a support film including a support and a resin composition layer provided on the support The steps of fit,
(II)使樹脂組成物層硬化形成絕緣層之步驟。 (II) A step of hardening the resin composition layer to form an insulating layer.
步驟(I)中之接著薄膜與層合板之貼合可使用與針對接著薄膜與預浸體之接合中已說明之方法相同之方法實施。 The bonding of the bonding film and the laminate in the step (I) can be carried out using the same method as described for the bonding of the bonding film and the prepreg.
步驟(II)中之樹脂組成物層之硬化可依據樹脂組成物之組成進行任意較佳處理。 The hardening of the resin composition layer in the step (II) can be arbitrarily and preferably performed according to the composition of the resin composition.
步驟(II)之後,進行粗化處理形成配線層。配線層之形成可藉由已說明之半加成法等習知之方法進行。 After step (II), a roughening process is performed to form a wiring layer. The formation of the wiring layer can be performed by a known method such as the semi-additive method described above.
以本發明之製造方法獲得之層合板可使用作為例如電氣製品(例如,電腦、行動電話、數位相機及電視等)及交通工具(例如,機車、汽車、電車、船舶及飛機 等)等之作動控制等使用之各種形態之半導體裝置之構件。 The laminated board obtained by the manufacturing method of the present invention can be used as, for example, electrical products (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., locomotives, automobiles, trams, ships, and airplanes) Various types of semiconductor device components used in operation control, etc.
以下,基於實施例更具體說明本發明,但本發明並不受限於以下實施例。又,只要無特別指明,則以下實施例及比較例中之「份」及「%」分別意指「質量份」及「質量%」。 Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to the following examples. In addition, unless otherwise specified, "part" and "%" in the following examples and comparative examples mean "mass part" and "mass%", respectively.
準備使用以4:1之比例含有甲苯及異丙醇之溶劑,將醇酸系樹脂(日立化成聚合物公司製,TESFINE 303,不揮發成分48質量%,與以4:1之比例含有甲苯與異丙醇之溶劑之混合液)100質量份、與對-甲苯磺酸之溶液(日立化成聚合物公司製,DRYER 900,不揮發成分50質量%,與以4:1之比例含有甲苯與異丙醇之溶劑之混合液)2.5質量份稀釋成不揮發成分濃度1.5質量%而成之混合液作為脫模劑,以使該脫膜劑乾燥後之厚度成為0.1μm之方式塗佈於有機支撐體上,在150℃乾燥1分鐘,獲得玻璃轉移溫度為90℃以上之有機支撐體的附脫模層之有機支撐體(有機支撐體1、2)。 To prepare a solvent containing toluene and isopropanol in a ratio of 4: 1, an alkyd resin (manufactured by Hitachi Chemical Co., Ltd., TESFINE 303, 48% by mass of nonvolatile matter), and toluene and 100 parts by mass of a solvent mixture of isopropanol and a solution of p-toluenesulfonic acid (Hitachi Kasei Polymers, DRYER 900, 50% by mass of non-volatile content, containing toluene and isopropyl in a ratio of 4: 1 A mixed solution of a solvent of propanol) 2.5 parts by mass of a mixed solution prepared by diluting a nonvolatile matter concentration of 1.5% by mass as a release agent, and coated on the organic support so that the thickness of the release agent after drying becomes 0.1 μm. On the body, it was dried at 150 ° C for 1 minute to obtain an organic support (organic support 1, 2) with a release layer of an organic support having a glass transition temperature of 90 ° C or higher.
有機支撐體1:PEN薄膜(帝人Dupont Film(股)製之「TEONEX Q83」,厚度25μm,玻璃轉移溫度120℃)之一主面上設置上述脫模層之附脫模層之有機支撐體 Organic support 1: PEN film ("TEONEX Q83" manufactured by Teijin Dupont Film Co., Ltd., thickness 25 μm, glass transition temperature 120 ° C) on one of its main surfaces is provided with an organic support with a release layer and a release layer
有機支撐體2:聚醯亞胺薄膜(KANEKA(股)製之「APICAL AH」,厚度25μm,玻璃轉移溫度300℃以上)之一主面上設置與有機支撐體1同樣之上述脫模層之附脫模層之有機支撐體 Organic support 2: Polyimide film ("APICAL AH" manufactured by KANEKA Co., Ltd., thickness 25 μm, glass transition temperature 300 ° C or higher) on one of the main surfaces is provided with the same release layer as the organic support 1 Organic support with release layer
邊將雙酚型環氧樹脂(新日鐵化學(股)製之「ZX1059」,雙酚A型環氧樹脂與雙酚F型環氧樹脂之1:1混合品,環氧當量169)8份、萘型環氧樹脂(DIC(股)製之「HP4032SS」,環氧當量約144)3份、聯苯型環氧樹脂(三菱化學(股)製之「YX4000HK」,環氧當量約185)6份、聯苯型環氧樹脂(日本化藥(股)製之「NC3000H」,環氧當量約288)15份、苯氧樹脂(三菱化學(股)製之「YX6954BH30」,不揮發成分30質量%(與MEK及環己酮之1:1溶液之混合液)30份於溶劑油(solvent naphtha)5份中邊攪拌加熱溶解。冷卻至室溫後,於其中混合含有三嗪骨架之酚酚醛清漆系硬化劑(DIC(股)製之「LA-7054」,羥基當量125,不揮發成分60%之MEK溶液)12份、萘酚系硬化劑(新日鐵化學(股)製之「SN485」,羥基當量215,不揮發成分60%之MEK溶液)10份、硬化促進劑(4-二甲胺基吡啶(DMAP),不揮發成分5質量%之MEK溶液)2份、加成型硬化促進劑(三菱化學(股)製之「P200H50」,不揮發成分50%)2份、聚乙烯乙縮醛樹脂(積水化學工業(股)製之「KS-1」)之不揮發成分15%之乙 醇與甲苯之1:1溶液)20份、以苯基胺基矽烷系偶合劑(信越化學工業(股)製之「KBM573」)進行表面處理之球形二氧化矽(平均粒徑0.5μm,Adomatech(股)製之「SOC2」,每單位面積之碳量0.39mg/m2)20份、有機填充材的橡膠粒子(MICA工業(股)製之「STAFYROID AC3816N」)(無機填充材)8份,且以高速旋轉混練機均勻分散,調製樹脂漆料1。樹脂漆料1之不揮發成分換算之組成示於表1。 Bien type epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd., a 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent 169) 8 Parts, naphthalene-type epoxy resin ("HP4032SS" manufactured by DIC (stock), epoxy equivalent of about 144), 3 parts, biphenyl epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, and epoxy equivalent of about 185) ) 6 parts, 15 parts for biphenyl epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 288), phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Co., Ltd., non-volatile components 30% by mass (mixed solution with 1: 1 solution of MEK and cyclohexanone) 30 parts are dissolved in 5 parts of solvent naphtha with stirring and heating. After cooling to room temperature, the triazine skeleton-containing solution is mixed therein. 12 parts of phenol novolac-based hardener ("LA-7054" manufactured by DIC Corporation, hydroxyl equivalent 125, MEK solution with 60% non-volatile content), naphthol-based hardener (produced by Nippon Steel Chemical Co., Ltd.) "SN485", hydroxyl equivalent 215, MEK solution with 60% non-volatile content) 10 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), MEK solution with 5 mass% non-volatile content), addition molding Hardening promotion ("P200H50" manufactured by Mitsubishi Chemical Corporation, 50% non-volatile content) 2 parts of polyethylene, 15% non-volatile ethanol of polyethylene acetal resin ("KS-1" manufactured by Sekisui Chemical Industry Co., Ltd.) 20 parts of 1: 1 solution with toluene), spherical silica (average particle size: 0.5 μm, Adomatech (average particle size: 0.5 μm, Adomatech ( 20 parts of "SOC2" made of carbon, 0.39 mg / m 2 carbon per unit area), 8 parts of rubber particles of organic filler ("STAFYROID AC3816N" made of MICA Industrial Co., Ltd.) (inorganic filler), The resin paint 1 is prepared by uniformly dispersing with a high-speed rotary kneader. The composition of the resin varnish 1 in terms of nonvolatile content is shown in Table 1.
將樹脂漆料1均勻塗佈於有機支撐體1之脫模層側,在80℃~140℃(平均120℃)乾燥3分鐘後,再於180℃乾燥4分鐘,製作熱硬化性樹脂組成物層之厚度為3μm之接著片1。又,熱硬化性樹脂組成物層之厚度係使用接觸式層厚計(MitsuToyo(股)製之「MCD-25MJ」)測定(以下之例亦同)。 The resin varnish 1 was evenly coated on the release layer side of the organic support 1, and dried at 80 ° C to 140 ° C (average 120 ° C) for 3 minutes, and then dried at 180 ° C for 4 minutes to produce a thermosetting resin composition. Adhesive sheet 1 with a layer thickness of 3 μm. The thickness of the thermosetting resin composition layer was measured using a contact layer thickness meter ("MCD-25MJ" manufactured by MitsuToyo Co., Ltd.) (the same applies to the following examples).
將雙酚型環氧樹脂(新日鐵化學(股)製之「ZX1059」,雙酚A型環氧樹脂與雙酚F型環氧樹脂之1:1混合品,環氧當量約169)5份、聯苯型環氧樹脂(三菱化學(股)製之「YX4000HK」,環氧當量約185)12份、二環戊二烯型環氧樹脂(DIC(股)製之「HP-7200H」,環氧當量約275)9份、苯氧樹脂(三菱化學(股)製之 「YL7553BH30」,不揮發成分30質量%(與MEK及環己 酮之1:1溶液之混合液)20份於溶劑油30份中攪拌邊加熱溶解。冷卻至室溫後,於其中混合活性酯系硬化劑(DIC(股)製之「HPC-8000-65T」,活性基當量約223,不揮發成分65質量%之甲苯溶液)40份、硬化促進劑(北興化學(股)製之「TBPDA(四丁基鏻癸酸鹽)」,不揮發成分5質量%之MEK溶液)6份、以苯基胺基矽烷系偶合劑(信越化學工業(股)製之「KBM573」)進行表面處理之球形二氧化矽(平均粒徑0.24μm,Adomatech(股)製之「SOC1」,每單位面積之碳量0.36mg/m2)(無機填充材)100份、作為有機填充材之橡膠粒子(MICA工業(股)製之「STAFYROID AC3816N」)5份,以高速旋轉混練機均勻分散,調製樹脂漆料2。樹脂漆料2之不揮發成分換算之組成示於表1。 A bisphenol epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd., a 1: 1 mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, epoxy equivalent of about 169) 5 Parts, biphenyl epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 12 parts, dicyclopentadiene epoxy resin ("HP-7200H" manufactured by DIC, Inc.) , Epoxy equivalent of about 275) 9 parts, phenoxy resin ("YL7553BH30" made by Mitsubishi Chemical Corporation), 30% by mass of nonvolatile matter (mixed solution with 1: 1 solution of MEK and cyclohexanone) in 20 parts Dissolve in 30 parts of solvent oil with heating while stirring. After cooling to room temperature, mix active ester-based hardener ("HPC-8000-65T" manufactured by DIC Corporation) with an active group equivalent of about 223 and a non-volatile content of 65 masses. % Toluene solution) 40 parts, hardening accelerator ("TBPDA (tetrabutylphosphonium decanoate)" manufactured by Beixing Chemical Co., Ltd., 6 parts MEK solution of non-volatile content 5 mass%, phenylamine group Silane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) for surface treatment of spherical silicon dioxide (average particle size 0.24 μm, "SOC1" manufactured by Adomatech (stock), 0.36 mg of carbon per unit area / m 2 ) (Inorganic filler) 100 parts, 5 parts of rubber particles ("STAFYROID AC3816N" manufactured by Mica Industrial Co., Ltd.) as organic filler, uniformly dispersed with a high-speed rotary kneader to prepare resin paint 2. Resin paint 2 The nonvolatile content conversion composition is shown in Table 1.
將樹脂漆料2均勻塗佈於有機支撐體2之脫模層側,在80℃~140℃(平均120℃)乾燥3分鐘,製作熱硬化性樹脂組成物層之厚度為5μm之接著片2。 The resin varnish 2 was evenly coated on the release layer side of the organic support 2 and dried at 80 ° C. to 140 ° C. (average 120 ° C.) for 3 minutes to prepare a bonding sheet 2 having a thermosetting resin composition layer thickness of 5 μm. .
將樹脂漆料1均勻塗佈於有機支撐體1之脫模層側,在80℃~140℃(平均120℃)乾燥3分鐘,製作熱硬化性樹脂組成物層之厚度為3μm之接著片3。 The resin varnish 1 was evenly coated on the release layer side of the organic support 1 and dried at 80 ° C. to 140 ° C. (average 120 ° C.) for 3 minutes to prepare a bonding sheet 3 having a thickness of 3 μm of a thermosetting resin composition layer. .
將雙酚型環氧樹脂(新日鐵化學(股)製之「ZX1059」,雙酚A型環氧樹脂與雙酚F型環氧樹脂之1:1混合品,環氧當量約169)5份、聯苯型環氧樹脂(三菱化學(股)製之「YX4000HK」,環氧當量約185)12份、二環戊二烯型環氧樹脂(DIC(股)製之「HP-7200H」,環氧當量約275)9份、苯氧樹脂(三菱化學(股)製之「YL7553BH30」,不揮發成分30質量%(與MEK及環己酮之1:1溶液之混合液))20份於溶劑油30份中攪拌邊加熱溶解。冷卻至室溫後,於其中混合活性酯系硬化劑(DIC(股)製之「HPC-8000-65T」,活性基當量約223,不揮發成分65質量%之甲苯溶液)40份、硬化促進劑(北興化學(股)製之「TBPDA(四丁基鏻癸酸鹽)」,不揮發成分5質量%之MEK溶液)6份、以苯基胺基矽烷系偶合劑(信越化學工業(股)製之「KBM573」)進行表面處理之球形二氧化矽(平均粒徑0.24μm,Adomatech(股)製之「SOC1」,每單位面積之碳量0.36mg/m2)(無機填充材)220份、作為有機填充材之橡膠粒子(MICA工業(股)製造之「STAFYROID AC3816N」)5份,以高速旋轉混練機均勻分散,調製樹脂漆料3。樹脂漆料3之不揮發成分換算之組成示於表1。 A bisphenol epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd., a 1: 1 mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, epoxy equivalent of about 169) 5 Parts, biphenyl epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 12 parts, dicyclopentadiene epoxy resin ("HP-7200H" manufactured by DIC, Inc.) , 9 parts of epoxy equivalent, phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, 30% by mass of nonvolatile matter (mixed solution with 1: 1 solution of MEK and cyclohexanone)) 20 parts Heat and dissolve in 30 parts of solvent oil while stirring. After cooling to room temperature, 40 parts of an active ester-based hardener ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223, and 65% by mass of a non-volatile matter in toluene solution) was mixed therein, and hardening was promoted. Agent (6 parts of "TBPDA (tetrabutylphosphonium decanoate) manufactured by Beixing Chemical Co., Ltd., non-volatile content of 5% by mass MEK solution), and a phenylaminosilane-based coupling agent (Shin-Etsu Chemical Industry Co., Ltd. ) made of "KBM573") for surface treatment of spherical silicon dioxide (average particle size of 0.24μm, Adomatech (shares) manufactured by the "SOC1", the carbon amount per unit area of 0.36mg / m 2) (inorganic filler) 220 5 parts of rubber particles ("STAFYROID AC3816N" manufactured by Mica Industrial Co., Ltd.) as an organic filler, uniformly dispersed with a high-speed rotary kneader to prepare resin paint 3. The composition of the resin varnish 3 in terms of nonvolatile content is shown in Table 1.
將樹脂漆料3均勻塗佈於有機支撐體1之脫模層側,進行3次之在180℃乾燥5分鐘之乾燥處理,製作熱硬化性樹脂組成物層之厚度為5μm之接著片4。 The resin varnish 3 was uniformly applied to the release layer side of the organic support 1 and dried three times at 180 ° C. for 5 minutes to prepare a bonding sheet 4 having a thickness of 5 μm of a thermosetting resin composition layer.
將樹脂漆料2均勻塗佈於有機支撐體2之脫模層側,在80℃~120℃(平均100℃)乾燥2分鐘,製作熱硬化性樹脂組成物層之厚度為5μm之接著片5。 The resin varnish 2 was evenly coated on the release layer side of the organic support 2 and dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 2 minutes to prepare a bonding sheet 5 having a thickness of 5 μm of a thermosetting resin composition .
將樹脂漆料2均勻塗佈於有機支撐體2之脫模層側,在80℃~140℃(平均120℃)乾燥3分鐘,製作接著片6。 The resin varnish 2 was uniformly applied to the release layer side of the organic support 2, and dried at 80 ° C. to 140 ° C. (average 120 ° C.) for 3 minutes to prepare a bonding sheet 6.
將雙酚型環氧樹脂(新日鐵化學(股)製之「ZX1059」,雙酚A型環氧樹脂與雙酚F型環氧樹脂之1:1混合品,環氧當量約169)5份、聯苯型環氧樹脂(三菱化學(股)製之「YX4000HK」,環氧當量約185)12份、二環戊二烯型環氧樹脂(DIC(股)製之「HP-7200H」,環氧當量約275)9份、苯氧樹脂(三菱化學(股)製之「YL7553BH30」,不揮發成分30質量%(與MEK及環己酮之1:1溶液之混合液)20份於溶劑油30份中攪拌邊加熱溶解。冷卻至室溫後,於其中混合活性酯系硬化劑(DIC(股)製之「HPC-8000-65T」,活性基當量約223,不揮發 成分65質量%之甲苯溶液)40份、硬化促進劑(北興化學(股)製之「TBPDA(四丁基鏻癸酸鹽)」,不揮發成分5質量%之MEK溶液)6份、以苯基胺基矽烷系偶合劑(信越化學工業(股)製之「KBM573」)進行表面處理之球形二氧化矽(平均粒徑0.24μm,Adomatech(股)製之「SOC1」,每單位面積之碳量0.36mg/m2)(無機填充材)280份、作為有機填充材之橡膠粒子(MICA工業(股)製之「STAFYROID AC3816N」)5份,以高速旋轉混練機均勻分散,調製樹脂漆料4。樹脂漆料4之不揮發成分換算之組成示於表1。 A bisphenol epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd., a 1: 1 mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, epoxy equivalent of about 169) 5 Parts, biphenyl epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 12 parts, dicyclopentadiene epoxy resin ("HP-7200H" manufactured by DIC, Inc.) , Epoxy equivalent of about 275) 9 parts, phenoxy resin ("YL7553BH30" made by Mitsubishi Chemical Corporation), 30% by mass of nonvolatile matter (mixed solution with 1: 1 solution of MEK and cyclohexanone) in 20 parts Dissolve in 30 parts of solvent oil with heating while stirring. After cooling to room temperature, mix active ester-based hardener ("HPC-8000-65T" manufactured by DIC Corporation) with an active group equivalent of about 223 and a non-volatile content of 65 masses. % Toluene solution) 40 parts, hardening accelerator ("TBPDA (tetrabutylphosphonium decanoate)" manufactured by Beixing Chemical Co., Ltd., 6 parts MEK solution of non-volatile content 5 mass%, phenylamine group Silane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) for surface treatment of spherical silicon dioxide (average particle size 0.24 μm, "SOC1" manufactured by Adomatech (stock), 0.36 mg of carbon per unit area / m 2 ) (Inorganic filler) 280 parts, 5 parts of rubber particles ("STAFYROID AC3816N" manufactured by Mica Industrial Co., Ltd.) as organic filler, uniformly dispersed with a high-speed rotary kneader to prepare resin paint 4. Resin paint 4 The nonvolatile content conversion composition is shown in Table 1.
將樹脂漆料4均勻塗佈於有機支撐體2之脫模層側,在80℃~140℃(平均120℃)乾燥3分鐘,製作厚度為5μm之接著片7。 The resin varnish 4 was uniformly coated on the release layer side of the organic support 2, and dried at 80 ° C. to 140 ° C. (average 120 ° C.) for 3 minutes to prepare a bonding sheet 7 having a thickness of 5 μm.
測定接著片1~5之各熱硬化性樹脂組成物層之最低熔融黏度。使用UBM(股)製之「Rheosol-G3000」,將樹脂量設為1g,使用直徑18mm之平行板,自起始溫度60℃至結束溫度200℃,升溫速度設為5℃/分鐘,測定溫度間隔設為2.5℃,頻率設為1Hz,偏斜度設為1度之測定條件測定最低熔融黏度(泊)。結果示於表2。 The minimum melt viscosity of each thermosetting resin composition layer of the adhesive sheet 1 to 5 was measured. "Rheosol-G3000" made by UBM (stock) was used, the resin amount was set to 1 g, and a parallel plate with a diameter of 18 mm was used. From the starting temperature of 60 ° C to the ending temperature of 200 ° C, the heating rate was set to 5 ° C / min. The minimum melting viscosity (poise) was measured under the measurement conditions of an interval of 2.5 ° C, a frequency of 1 Hz, and a skewness of 1 degree. The results are shown in Table 2.
根據JIS K5600-5-4測定上述接著片1~5之各熱硬化性樹脂組成物層之鉛筆硬度。結果示於表2。 The pencil hardness of each of the thermosetting resin composition layers of the above-mentioned adhesive sheets 1 to 5 was measured in accordance with JIS K5600-5-4. The results are shown in Table 2.
將250mm×250mm見方尺寸之已形成內層電路之玻璃布基材環氧樹脂層合板(內層電路厚度為18μm,基板厚度為0.3mm,Panasonic(股)製之「R1515A」)之兩面浸漬於Merck(股)製之「CZ8100」中,進行銅表面之粗化處理。 250mm × 250mm square-shaped glass cloth substrate epoxy resin laminated board with inner layer circuit (inner layer circuit thickness is 18μm, substrate thickness is 0.3mm, and “R1515A” manufactured by Panasonic Co., Ltd.) are immersed on both sides In "CZ8100" manufactured by Merck, the copper surface is roughened.
使用真空熱壓裝置(北川精機(股)製 商品名VH1-1603),使接著片1成型為層合體。 The adhesive sheet 1 was formed into a laminate using a vacuum hot-pressing device (trade name VH1-1603, manufactured by Kitagawa Seiki Co., Ltd.).
真空熱壓步驟係以下述構造設為1組,使之在三組重疊之狀態以真空熱壓裝置進行。 The vacuum hot-pressing step is performed in a group with the following structure, and is performed in a vacuum hot-pressing device in a state where the three groups overlap.
構造:緩衝紙(阿波製紙(股)製之「AACP-9N」,厚度800μm)/SUS板(厚度1mm)/脫模薄膜(旭硝子(股)製之「AFLEX 50N NT」、厚度50μm)/接著片1/預浸物(日立化成(股)製之「GEA-800G」,厚度0.06mm)/內層電路基板/預浸物/接著片1/脫模薄膜/SUS板/緩衝紙 Structure: Buffer paper ("AACP-9N" made by Awa Paper Co., Ltd., thickness 800 μm) / SUS board (1 mm thick) / Release film ("AFLEX 50N NT" made by Asahi Glass Co., Ltd., 50 μm thickness) Sheet 1 / prepreg ("GEA-800G" manufactured by Hitachi Chemical Co., Ltd., thickness 0.06mm) / Inner circuit board / prepreg / adhesive sheet 1 / Release film / SUS board / Buffer paper
真空熱壓步驟之實施條件如下述。 The implementation conditions of the vacuum hot pressing step are as follows.
溫度:以升溫率5℃/分鐘自室溫(常溫)升溫至205℃,在205℃維持90分鐘,隨後以降溫率5℃/分鐘降溫 至室溫 Temperature: The temperature is raised from room temperature (normal temperature) to 205 ° C at a temperature increase rate of 5 ° C / min, and maintained at 205 ° C for 90 minutes, and then the temperature is decreased at a temperature decrease rate of 5 ° C / min. To room temperature
按壓力:將自室溫開始升溫時之按壓力設為50kgf/cm2,且保持至降溫結束時 Pressing pressure: Set the pressing pressure at the time of increasing the temperature from room temperature to 50kgf / cm 2 and keep it until the end of the cooling
環境壓力:70mm/hg~74mm/hg(9.3×10-3MPa~9.9×10-3MPa) Ambient pressure: 70mm / hg ~ 74mm / hg (9.3 × 10 -3 MPa ~ 9.9 × 10 -3 MPa)
真空熱壓步驟結束後,自所形成之熱硬化性樹脂組成物層剝離有機支撐體1,以下述基準評價其剝離性。結果示於表2。 After the vacuum hot-pressing step was completed, the organic support 1 was peeled from the formed thermosetting resin composition layer, and the peelability was evaluated based on the following criteria. The results are shown in Table 2.
可剝離:○ Peelable: ○
無法剝離:× Cannot be stripped: ×
首先在60℃下將所得層合體浸漬於膨潤液的日本ATOTECH(股)製之含有二乙二醇單丁基醚之Swelling Dip Securiganth P中10分鐘。接著在80℃下浸漬於粗化液的日本ATOTECH(股)製之Concentrate Compact P(KMnO4:60g/L及NaOH:40g/L之水溶液)中20分鐘。層合體水洗處理後,最後在40℃下浸漬於作為中和液的ATOTECH(股)之Reduction Solution Securiganth P中5分鐘。隨後在130℃乾燥15分鐘。藉以上處理使熱硬化性樹脂組成物層之表面經粗化處理(及除膠渣處理)。 First, the obtained laminate was immersed in Swelling Dip Securiganth P containing diethylene glycol monobutyl ether manufactured by Japan ATOTECH Co., Ltd. at a swelling liquid at 60 ° C for 10 minutes. Next, it was immersed in a roughened solution of Concentrate Compact P (KMnO 4 : 60 g / L and NaOH: 40 g / L aqueous solution) made by Japan ATOTECH Co., Ltd. at 80 ° C. for 20 minutes. After the laminate was washed with water, it was finally immersed in ATOTECH (strand) Reduction Solution Securiganth P for 5 minutes at 40 ° C. It was then dried at 130 ° C for 15 minutes. By the above treatment, the surface of the thermosetting resin composition layer is subjected to a roughening treatment (and a slag removing treatment).
自將粗化處理後之層合板使用非接觸型表面粗糙度計 (VEECO Instrument公司製之「WYKO NT3300」,以VSI接觸模式、50倍透鏡,測定範圍設為121μm×92μm所得之數值,求出表面粗糙度(Ra值)。針對3片所得層合板,每片各5點進行合計15點之測定,求出Ra值之15點之平均值與表面粗糙度之最大值與最小值之差(表面粗糙度偏差)。 Non-contact type surface roughness meter ("WYKO NT3300" manufactured by VEECO Instrument Co., Ltd.) The surface roughness (Ra value) was obtained by using a VSI contact mode, a 50-fold lens, and a measurement range of 121 μm × 92 μm. For each of the three laminates obtained A total of 15 points were measured at each of the 5 points, and the difference between the average value of the 15 points of the Ra value and the maximum and minimum values of the surface roughness (surface roughness deviation) was obtained.
表面粗糙度偏差愈小則與導體層(配線層)之密 著性愈高,故能使配線更微細化。表面粗糙度偏差較好未達150nm。 The smaller the surface roughness deviation, the closer it is to the conductor layer (wiring layer) The higher the adhesion, the finer the wiring can be made. The surface roughness deviation is preferably less than 150 nm.
偏差判定係以下述基準進行。結果示於表2。 The deviation determination is performed based on the following criteria. The results are shown in Table 2.
(表面粗糙度之最大值與最小值之差)未達150nm之層合板判定為○。 (Difference between the maximum value and the minimum value of the surface roughness) The laminate having a thickness of less than 150 nm was determined as ○.
(表面粗糙度之最大值與最小值之差)為150nm以上之層合板判定為×。 A laminated plate (the difference between the maximum value and the minimum value of the surface roughness) of 150 nm or more was judged as ×.
為了在經粗化處理之層合板表面形成導體層,而進行無電解銅鍍敷步驟(使用日本ATOTECH(股)製之藥液之無電解銅鍍敷步驟)。該步驟係以使無電解銅鍍敷層之厚度成為1μm之方式進行。無電解銅鍍敷步驟及電解銅鍍敷步驟之詳情如下述。 In order to form a conductor layer on the surface of the roughened laminate, an electroless copper plating step (an electroless copper plating step using a chemical solution made by Japan ATOTECH Co., Ltd.) is performed. This step is performed so that the thickness of the electroless copper plating layer may be 1 μm. Details of the electroless copper plating step and the electrolytic copper plating step are as follows.
1.鹼洗淨(層合板表面之洗淨及電荷調整) 1. Alkali cleaning (cleaning and charge adjustment of laminate surface)
使用Cleaning cleaner Securigarth 902(商品名),在60℃洗淨5分鐘。 Using Cleaning cleaner Securigarth 902 (trade name), washing was performed at 60 ° C for 5 minutes.
2.軟蝕刻(無電解銅鍍敷層之洗淨) 2. Soft etching (cleaning of electroless copper plating layer)
使用硫酸酸性過氧二硫酸鈉水溶液在30℃洗淨1分鐘。 It was washed with sulfuric acid acid sodium peroxodisulfate aqueous solution at 30 ° C for 1 minute.
3.預浸(用以賦予Pd之層合板表面之電荷調整) 3.Pre-impregnation (used to adjust the charge on the surface of the laminate of Pd)
使用Pre.Dip Neoganth B(商品名),在室溫處理1分鐘。 Pre.Dip Neoganth B (trade name) was used and treated at room temperature for 1 minute.
4.活化劑(activator)(對層合板表面賦予Pd) 4.Activator (Pd on the surface of the laminate)
使用Activator Neoganth 834(商品名),在35℃處理5分鐘。 Activator Neoganth 834 (trade name) was used for 5 minutes at 35 ° C.
5.還原(對賦予至層合板之Pd之還原) 5. Reduction (reduction of Pd imparted to the laminate)
使用Reducer Neoganth WA(商品名)及Reducer Acceralator 810 mod.(商品名)之混合液,在30℃處理5分鐘。 A mixed solution of Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. (Trade name) was used and treated at 30 ° C for 5 minutes.
6.無電解銅鍍敷(使銅析出於層合板表面(經賦予Pd之表面)) 6. Electroless copper plating (to precipitate copper on the surface of the laminate (the surface imparted with Pd))
使Basic Solution Printganth MSK-DK(商品名)、Copper Solution Printganth MSK(商品名)、Stabilizer Printganth MSK-DK(商品名)及Reducer Cu(商品名)之混合液,在35℃處理20分鐘。 A mixed solution of Basic Solution Printganth MSK-DK (trade name), Copper Solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name) was treated at 35 ° C for 20 minutes.
接著,進行電解銅鍍敷步驟,以厚度總計成為30μm 之方式形成厚膜化之導體層(銅層)。接著在190℃進行60分鐘之退火處理,製造附導體層之層合板。 Next, an electrolytic copper plating step was performed to a total thickness of 30 μm. In this way, a thick film conductor layer (copper layer) is formed. Then, an annealing treatment was performed at 190 ° C for 60 minutes to manufacture a laminated board with a conductor layer.
於附導體層之層合板之導體層上,包圍寬10mm、長100mm之部分區域進行切割。剝離其一端側且以夾具(DSI(股)製之Autograph型試驗機「AC-50C-SL」)夾緊,在室溫(25℃)中,測定以50mm/分鐘之速度朝垂直方向撕離35mm時之荷重(kgf/cm(N/cm))。針對成型之附導體層之層合板3片,進行各5點/片,合計15點之測定,求出每個附導體層之層合板之平均值及剝離強度偏差(剝離強度之最大值與最小值之差)。 On the conductor layer of the laminated board with a conductor layer, a part of a region with a width of 10 mm and a length of 100 mm is cut. One end side was peeled off, and it was clamped with a jig (Autograph type testing machine "AC-50C-SL" made by DSI), and at room temperature (25 ° C), it was measured to be perpendicularly peeled off at a speed of 50 mm / min. Load at 35mm (kgf / cm (N / cm)). For the three laminated plates with conductor layers, 5 points / piece were measured for a total of 15 points, and the average and peel strength deviation of each laminated plate with conductor layers were determined (the maximum and minimum peel strengths). Value difference).
剝離強度偏差愈小則顯示與導體層(配線層)之 接著性愈高,故而可使配線更微細化。剝離強度偏差較好未達0.15kgf/cm。 The smaller the deviation in peel strength is, the smaller the deviation from the conductor layer (wiring layer) is. The higher the adhesion, the finer the wiring can be. The deviation in peel strength is preferably less than 0.15 kgf / cm.
偏差判定係以下述基準進行。結果示於表2。 The deviation determination is performed based on the following criteria. The results are shown in Table 2.
(剝離強度之最大值與最小值之差)未達0.15kgf/cm:○ (Difference between the maximum value and the minimum value of the peel strength) Less than 0.15 kgf / cm: ○
(剝離強度之最大值與最小值之差)為0.15kgf/cm以上:× (The difference between the maximum and minimum peel strength) is 0.15kgf / cm or more: ×
針對附導體層之層合板,使用峰值溫度260℃之回焊裝置(日本ANTOM(股)製之「HAS-6116」),依據 IPC/JEDEC J-STD-020C之溫度分佈重複10次模擬之回焊步驟。隨後,以目視確認導體層與熱硬化性樹脂組成物層之間之密著狀態,亦即有無剝離異常。評價係以下述基準進行。結果示於表2。 For laminates with a conductor layer, a reflow device with a peak temperature of 260 ° C ("HAS-6116" manufactured by Japan Antim Corporation) is used. The temperature distribution of IPC / JEDEC J-STD-020C repeats the reflow step for 10 simulations. Subsequently, the state of adhesion between the conductor layer and the thermosetting resin composition layer was visually confirmed, that is, whether there was abnormality in peeling. The evaluation was performed based on the following criteria. The results are shown in Table 2.
無異常:○ No exception: ○
剝離有異常:× Abnormal peeling: ×
〈實施例2〉 <Example 2>
除了使用接著片2取代接著片1以外,餘與實施例1同樣,進行製造、測定、評價。又,「(2)真空熱壓步驟」中,溫度設為「首先以5℃/分鐘之升溫率自室溫升溫至230℃,在230℃維持90分鐘,隨後以5℃/分鐘之降溫率降溫至室溫」。 Except having used the adhesive sheet 2 instead of the adhesive sheet 1, it manufactured, measured, and evaluated similarly to Example 1. In the "(2) Vacuum Hot Pressing Step", the temperature is set to "first increase the temperature from room temperature to 230 ° C at a temperature increase rate of 5 ° C / min, maintain it at 230 ° C for 90 minutes, and then decrease the temperature at a temperature decrease rate of 5 ° C / min. To room temperature. "
〈實施例3〉 <Example 3>
除了使用接著片3取代接著片1以外,餘與實施例1同樣,進行製造、測定、評價。又,「(2)真空熱壓步驟」中,溫度設為「首先以5℃/分鐘之升溫率自室溫升溫至205℃,在205℃維持90分鐘,隨後以5℃/分鐘之降溫率降溫至室溫」。 Production, measurement, and evaluation were performed in the same manner as in Example 1 except that the adhesive sheet 3 was used instead of the adhesive sheet 1. Also, in the "(2) vacuum hot pressing step", the temperature is set to "first increase the temperature from room temperature to 205 ° C at a temperature increase rate of 5 ° C / min, maintain it at 205 ° C for 90 minutes, and then cool down at a temperature decrease rate of 5 ° C / min To room temperature. "
〈實施例4〉 <Example 4>
除了使用接著片4取代接著片1以外,餘與實施例1同樣,進行製造、測定、評價。又,「(2)真空熱壓步 驟」中,溫度設為「首先以5℃/分鐘之升溫率自室溫升溫至205℃,在205℃維持90分鐘,隨後以5℃/分鐘之降溫率降溫至室溫」。 Production, measurement, and evaluation were performed in the same manner as in Example 1 except that the adhesive sheet 4 was used instead of the adhesive sheet 1. Also, "(2) Vacuum hot pressing In the step, the temperature is set to "first increase the temperature from room temperature to 205 ° C at a temperature increase rate of 5 ° C / min, maintain it at 205 ° C for 90 minutes, and then reduce the temperature to room temperature at a decrease rate of 5 ° C / min.
〈比較例1〉 <Comparative Example 1>
除了使用接著片5取代接著片1以外,餘與實施例1同樣,進行製造、測定、評價。又,「(2)真空熱壓步驟」中,溫度設為「首先以5℃/分鐘之升溫率自室溫升溫至230℃,在230℃維持90分鐘,隨後以5℃/分鐘之降溫率降溫至室溫」。 Except having used the adhesive sheet 5 instead of the adhesive sheet 1, it manufactured, measured, and evaluated similarly to Example 1. Also, in the "(2) vacuum hot pressing step", the temperature is set to "first increase the temperature from room temperature to 230 ° C at a temperature increase rate of 5 ° C / min, maintain it at 230 ° C for 90 minutes, and then cool down at a temperature decrease rate of 5 ° C / min To room temperature. "
〈比較例3〉 <Comparative Example 3>
除了使用接著片7取代接著片1以外,餘與實施例1同樣,進行製造、測定、評價。又,「(2)真空熱壓步驟」中,溫度設為「首先以5℃/分鐘之升溫率自室溫升溫至230℃,在230℃維持90分鐘,隨後以5℃/分鐘之降溫率降溫至室溫」。 Except having used the adhesive sheet 7 instead of the adhesive sheet 1, it manufactured, measured, and evaluated similarly to Example 1. In the "(2) Vacuum Hot Pressing Step", the temperature is set to "first increase the temperature from room temperature to 230 ° C at a temperature increase rate of 5 ° C / min, maintain it at 230 ° C for 90 minutes, and then decrease the temperature at a temperature decrease rate of 5 ° C / min. To room temperature. "
上述實施例及比較例中使用之樹脂漆料之組成示於下述表1,實施例及比較例中該測定結果及評價結果彙整示於下述表2。 The composition of the resin paint used in the above examples and comparative examples is shown in Table 1 below, and the measurement results and evaluation results of the examples and comparative examples are shown in Table 2 below.
由表2可了解,熱硬化性樹脂組成物層之鉛筆硬度為2B以上之實施例1、2、3及4之該層合板與比較例1及3比較,表面粗糙度之偏差,亦即粗化不均及剝離強度偏差均較小。因此教示若使用本發明之層合板,可使配線更微細化。且,與比較例3比較,實施例1、2、3及4之表面粗糙度小,剝離強度大,且回焊耐性優異,故教示所形成之配線之信賴性高。 As can be understood from Table 2, the laminates of Examples 1, 2, 3, and 4 having a pencil hardness of a thermosetting resin composition layer of 2B or more were compared with Comparative Examples 1 and 3, and the deviations in surface roughness, that is, rough Both unevenness in variation and variation in peel strength were small. Therefore, it is taught that the use of the laminated board of the present invention can make the wiring finer. Moreover, compared with Comparative Example 3, the surface roughness of Examples 1, 2, 3, and 4 is small, the peeling strength is large, and the reflow resistance is excellent, so the reliability of the wiring formed is taught to be high.
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