TW202208475A - resin composition - Google Patents

resin composition Download PDF

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Publication number
TW202208475A
TW202208475A TW110118057A TW110118057A TW202208475A TW 202208475 A TW202208475 A TW 202208475A TW 110118057 A TW110118057 A TW 110118057A TW 110118057 A TW110118057 A TW 110118057A TW 202208475 A TW202208475 A TW 202208475A
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resin composition
component
mass
group
carbon atoms
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TW110118057A
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Chinese (zh)
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川合賢司
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日商味之素股份有限公司
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    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12Unsaturated polyimide precursors
    • C08G73/121Preparatory processes from unsaturated precursors and polyamines
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/20Layered products comprising a layer of metal comprising aluminium or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/28Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022Non-woven fabric
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/042Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • H05K1/0313Organic insulating material
    • H05K1/032Organic insulating material consisting of one material
    • H05K1/0346Organic insulating material consisting of one material containing N
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • H05K1/0313Organic insulating material
    • H05K1/0353Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02Composition of the impregnated, bonded or embedded layer
    • B32B2260/021Fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04Impregnation, embedding, or binder material
    • B32B2260/046Synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02Synthetic macromolecular fibres
    • B32B2262/0261Polyamide fibres
    • B32B2262/0269Aromatic polyamide fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10Inorganic fibres
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • C08J2479/00Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract

Provided is a resin composition with which it is possible to obtain a cured product having a low relative dielectric constant (Dk) and a low dielectric loss tangent (Df) and having excellent peel strength of a plated conductor layer. The resin composition containing (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) a maleimide compound not having an aliphatic chain having 7 or more carbon atoms.

Description

樹脂組成物resin composition

本發明係有關包含馬來醯亞胺的樹脂組成物。此外,有關使用該樹脂組成物所得的硬化物、薄片狀積層材料、樹脂薄片、印刷配線板,及半導體裝置。The present invention relates to a resin composition containing maleimide. In addition, it relates to a cured product, a sheet-like laminate, a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition.

作為印刷配線板之製造技術,例如藉由將絕緣層與導體層交互堆積之增層方式的製造方法為人所知。增層方式之製造方法中,一般,絕緣層係將樹脂組成物硬化所形成。近年,要求進一步提高絕緣層之介電常數及介電正切等之介電特性,及電鍍導體層之剝離強度。As a manufacturing technique of a printed wiring board, the manufacturing method of the build-up method by alternately stacking an insulating layer and a conductor layer is known, for example. In the manufacturing method of the build-up method, generally, the insulating layer is formed by curing the resin composition. In recent years, it is required to further improve the dielectric properties such as the dielectric constant and the dielectric tangent of the insulating layer, and the peel strength of the electroplated conductor layer.

目前為止,已知有各種的馬來醯亞胺化合物(專利文獻1~3)。 [先前技術文獻] [專利文獻]Various maleimide compounds have been known so far (Patent Documents 1 to 3). [Prior Art Literature] [Patent Literature]

[專利文獻1]日本特開2019-203122號公報 [專利文獻2]國際公開第2018/212116號 [專利文獻3]國際公開第2020/045489號[Patent Document 1] Japanese Patent Laid-Open No. 2019-203122 [Patent Document 2] International Publication No. 2018/212116 [Patent Document 3] International Publication No. 2020/045489

[發明所欲解決之課題][The problem to be solved by the invention]

本發明之課題係提供可得到比電容量(Dk)及介電正切(Df)低,且電鍍導體層之剝離強度優異之硬化物的樹脂組成物。 [用以解決課題之手段]The subject of this invention is to provide the resin composition which can obtain the hardened|cured material which is low in specific capacitance (Dk) and dielectric tangent (Df), and is excellent in the peeling strength of a plated conductor layer. [means to solve the problem]

為了達成本發明之課題,本發明人等精心檢討的結果,藉由使用包含(A)具有聯苯骨架之胺化合物、(B)具有碳原子數為7以上之脂肪鏈之馬來醯亞胺化合物,及(C)不具有碳原子數為7以上之脂肪鏈之馬來醯亞胺化合物的樹脂組成物,意外地發現可得到比電容量(Dk)及介電正切(Df)低,且電鍍導體層之剝離強度優異的硬化物,遂完成本發明。In order to achieve the subject of the present invention, as a result of careful examination by the present inventors, by using (A) an amine compound having a biphenyl skeleton and (B) maleimide having an aliphatic chain having 7 or more carbon atoms A compound, and (C) a resin composition of a maleimide compound having no aliphatic chain having a carbon number of 7 or more, unexpectedly found that a specific capacitance (Dk) and a low dielectric tangent (Df) can be obtained, and A hardened product having excellent peel strength of a plated conductor layer has completed the present invention.

亦即,本發明包含以下的內容。 [1] 一種樹脂組成物,其係包含(A)具有聯苯骨架之胺化合物、 (B)具有碳原子數為7以上之脂肪鏈之馬來醯亞胺化合物,及 (C)不具有碳原子數為7以上之脂肪鏈之馬來醯亞胺化合物。 [2] 如上述[1]之樹脂組成物,其中(B)成分具有直接鍵結於未構成芳香環之碳原子的馬來醯亞胺基。 [3] 如上述[1]或[2]之樹脂組成物,其中(C)成分具有直接鍵結於構成芳香環之碳原子的馬來醯亞胺基。 [4] 如上述[1]~[3]中任一項之樹脂組成物,其中(A)成分具有一級胺基。 [5] 如上述[1]~[4]中任一項之樹脂組成物,其中(A)成分具有直接鍵結於構成芳香環之碳原子的胺基。 [6] 如上述[1]~[5]中任一項之樹脂組成物,其中(A)成分包含具有式(A1):That is, the present invention includes the following contents. [1] A resin composition comprising (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) A maleimide compound which does not have an aliphatic chain having 7 or more carbon atoms. [2] The resin composition according to the above [1], wherein the component (B) has a maleimide group directly bonded to a carbon atom not constituting an aromatic ring. [3] The resin composition according to the above [1] or [2], wherein the component (C) has a maleimide group directly bonded to a carbon atom constituting an aromatic ring. [4] The resin composition according to any one of the above [1] to [3], wherein the component (A) has a primary amine group. [5] The resin composition according to any one of the above [1] to [4], wherein the component (A) has an amine group directly bonded to a carbon atom constituting an aromatic ring. [6] The resin composition according to any one of the above [1] to [5], wherein the component (A) contains the formula (A1):

Figure 02_image001
Figure 02_image001

[式中,V及W各自獨立表示-C(R’)2 -、-O-、 -CO-、-S-、-SO-、-SO2 -、-CONH-、或-NHCO-,R各自獨立表示取代基,R’各自獨立表示氫原子或取代基,h、i及j各自獨立表示0~2之整數]表示之重複單位的胺化合物。 [7] 如上述[1]~[6]中任一項之樹脂組成物,其中樹脂組成物中之不揮發成分設為100質量%時,(A)成分之含量為3質量%~40質量%。 [8] 如上述[1]~[7]中任一項之樹脂組成物,其中樹脂組成物中之不揮發成分設為100質量%時,(B)成分之含量為3質量%~40質量%。 [9] 如上述[1]~[8]中任一項之樹脂組成物,其中樹脂組成物中之不揮發成分設為100質量%時,(C)成分之含量為3質量%~40質量%。 [10] 如上述[1]~[9]中任一項之樹脂組成物,其中(C)成分相對於(B)成分之質量比((C)成分/(B)成分)為0.5~20。 [11] 如上述[1]~[10]中任一項之樹脂組成物,其中(A)成分相對於(B)成分及(C)成分之合計之質量比((A)成分/(B)成分及(C)成分之合計)為0.1~0.5。 [12] 如上述[1]~[11]中任一項之樹脂組成物,其係進一步包含(B)成分及(C)成分以外的(D)自由基聚合性化合物。 [13] 如上述[1]~[12]中任一項之樹脂組成物,其係進一步包含(E)無機填充材。 [14] 如上述[13]之樹脂組成物,其中樹脂組成物中之不揮發成分設為100質量%時,(E)成分之含量為25質量%以上。 [15] 如上述[1]~[14]中任一項之樹脂組成物,其中在5.8GHz、23℃測定時,樹脂組成物之硬化物的介電正切為0.004以下。 [16] 如上述[1]~[15]中任一項之樹脂組成物,其中在5.8GHz、23℃測定時,樹脂組成物之硬化物的比電容量為2.9以下。 [17] 一種硬化物,其係如上述[1]~[16]中任一項之樹脂組成物的硬化物。 [18] 一種薄片狀積層材料,其係含有如上述[1]~[16]中任一項之樹脂組成物。 [19] 一種樹脂薄片,其係具有支撐體,及設置於該支撐體上由上述[1]~[16]中任一項之樹脂組成物所形成之樹脂組成物層。 [20] 一種印刷配線板,其係具備由上述[1]~[16]中任一項之樹脂組成物之硬化物所構成的絕緣層。 [21] 一種半導體裝置,其係包含上述[20]之印刷配線板。 [發明效果][wherein, V and W each independently represent -C(R') 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH-, or -NHCO-, R Each independently represents a substituent, R' each independently represents a hydrogen atom or a substituent, and h, i and j each independently represent an integer of 0 to 2] The amine compound represented by the repeating unit. [7] The resin composition according to any one of the above [1] to [6], wherein the content of the component (A) is 3 to 40 mass % when the nonvolatile content in the resin composition is 100 mass % %. [8] The resin composition according to any one of the above [1] to [7], wherein the content of the (B) component is 3 to 40 mass % when the non-volatile content in the resin composition is 100 mass % %. [9] The resin composition according to any one of the above [1] to [8], wherein the content of the component (C) is 3 to 40 mass % when the non-volatile content in the resin composition is 100 mass % %. [10] The resin composition according to any one of the above [1] to [9], wherein the mass ratio of (C) component to (B) component ((C) component/(B) component) is 0.5 to 20 . [11] The resin composition according to any one of the above [1] to [10], wherein the mass ratio of (A) component to the total of (B) component and (C) component ((A) component/(B) ) component and (C) component total) is 0.1-0.5. [12] The resin composition according to any one of the above [1] to [11], which further contains (D) a radically polymerizable compound other than the (B) component and the (C) component. [13] The resin composition according to any one of the above [1] to [12], further comprising (E) an inorganic filler. [14] The resin composition according to the above [13], wherein the content of the component (E) is 25% by mass or more when the nonvolatile content in the resin composition is 100% by mass. [15] The resin composition according to any one of the above [1] to [14], wherein the dielectric tangent of the cured product of the resin composition is 0.004 or less when measured at 5.8 GHz and 23°C. [16] The resin composition according to any one of the above [1] to [15], wherein the specific capacitance of the cured product of the resin composition is 2.9 or less when measured at 5.8 GHz and 23°C. [17] A cured product, which is a cured product of the resin composition according to any one of the above [1] to [16]. [18] A sheet-like laminate comprising the resin composition according to any one of the above [1] to [16]. [19] A resin sheet comprising a support, and a resin composition layer formed of the resin composition of any one of the above [1] to [16] provided on the support. [20] A printed wiring board including an insulating layer composed of a cured product of the resin composition according to any one of the above [1] to [16]. [21] A semiconductor device comprising the printed wiring board of the above [20]. [Inventive effect]

依據本發明之樹脂組成物時,可得到比電容量(Dk)及介電正切(Df)低,且電鍍導體層之剝離強度優異的硬化物。 [實施發明之形態]According to the resin composition of the present invention, a cured product having low specific capacitance (Dk) and dielectric tangent (Df) and excellent peel strength of the electroplated conductor layer can be obtained. [Form of implementing the invention]

以下依據較佳的實施形態,詳細地說明本發明。但是本發明不限定於下述實施形態及例示物,在不超脫本發明之申請專利範圍及其均等之範圍的範圍內,可任意變更實施。Hereinafter, the present invention will be described in detail based on preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be implemented with arbitrary modifications within the scope of the claims and equivalents of the present invention.

<樹脂組成物> 本發明之樹脂組成物係包含(A)具有聯苯骨架之胺化合物、(B)具有碳原子數為7以上之脂肪鏈之馬來醯亞胺化合物、及(C)不具有碳原子數為7以上之脂肪鏈之馬來醯亞胺化合物。藉由使用這種樹脂組成物,可得到比電容量(Dk)及介電正切(Df)低,且電鍍導體層之剝離強度優異的硬化物。<Resin composition> The resin composition of the present invention comprises (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) a Maleimide compounds with aliphatic chains above 7. By using such a resin composition, a cured product having low specific capacitance (Dk) and dielectric tangent (Df) and excellent peel strength of the plated conductor layer can be obtained.

本發明之樹脂組成物除了(A)具有聯苯骨架之胺化合物、(B)具有碳原子數為7以上之脂肪鏈之馬來醯亞胺化合物、及(C)不具有碳原子數為7以上之脂肪鏈之馬來醯亞胺化合物外,也可進一步包含任意的成分。任意的成分,可列舉例如(D)任意的自由基聚合性化合物、(E)無機填充材、(F)硬化促進劑、(G)其他的添加劑、及(H)有機溶劑。以下,詳細地說明樹脂組成物所含有的各成分。The resin composition of the present invention does not have (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) no amine compound having 7 carbon atoms. In addition to the maleimide compound of the aliphatic chain described above, optional components may be further contained. Examples of the arbitrary components include (D) arbitrary radically polymerizable compounds, (E) inorganic fillers, (F) curing accelerators, (G) other additives, and (H) organic solvents. Hereinafter, each component contained in the resin composition will be described in detail.

<(A)具有聯苯骨架之胺化合物> 本發明之樹脂組成物含有(A)具有聯苯骨架之胺化合物。(A)成分可1種類單獨使用,也可2種類以上任意組合使用。一實施形態中,(A)成分所含有的胺基,可與(B)成分及(C)成分(及包含(D)成分時為(D)成分)等進行加成反應。一實施形態中,(A)成分,較佳為1分子中具有2個以上的胺基,更佳為具有3個以上之胺基。(A)成分可具有作為胺基之一級胺基、二級胺基、及三級胺基之任一個,一實施形態中,較佳為具有一級胺基。一實施形態中,(A)成分,較佳為具有直接鍵結於構成芳香環之碳原子的胺基(芳香族胺基)作為胺基,更佳為具有一級芳香族胺基,特佳為(A)成分所含有之胺基僅為一級芳香族胺基。<(A) Amine compound having biphenyl skeleton> The resin composition of the present invention contains (A) an amine compound having a biphenyl skeleton. (A) A component may be used individually by 1 type, and may be used in arbitrary combination of 2 or more types. In one embodiment, the amine group contained in the (A) component can undergo an addition reaction with the (B) component, the (C) component (and when the (D) component is included, the (D) component) or the like. In one embodiment, the component (A) preferably has two or more amino groups in one molecule, and more preferably has three or more amino groups. The component (A) may have any one of a primary amino group, a secondary amino group, and a tertiary amino group as an amino group, and in one embodiment, it is preferable to have a primary amino group. In one embodiment, the component (A) preferably has an amine group (aromatic amine group) directly bonded to a carbon atom constituting an aromatic ring as the amine group, more preferably has a primary aromatic amine group, particularly preferably The amine group contained in the component (A) is only a primary aromatic amine group.

一實施形態中,(A)成分較佳為包含具有式(A1):In one embodiment, component (A) preferably contains formula (A1):

Figure 02_image003
Figure 02_image003

[式中,V及W各自獨立表示-C(R’)2 -、-O-、 -CO-、-S-、-SO-、-SO2 -、-CONH-、或-NHCO-(較佳為 -C(R’)2 -),R各自獨立表示取代基,R’各自獨立表示氫原子或取代基(較佳為氫原子),h、i及j各自獨立表示0~2之整數(較佳為0)]表示之重複單位(repeat unit)的胺化合物。又,h單位、i單位及j單位各單位可相同或不同。[wherein, V and W each independently represent -C(R') 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH-, or -NHCO- (comparatively Preferably -C(R') 2 -), R each independently represents a substituent, R' each independently represents a hydrogen atom or a substituent (preferably a hydrogen atom), and h, i and j each independently represent an integer of 0 to 2 (preferably 0)] is an amine compound represented by a repeat unit. In addition, the units of the h unit, the i unit, and the j unit may be the same or different.

本說明書中,作為取代基無特別限定,可列舉例如烷基、烯基、芳基、烷基-芳基(被1個以上之烷基取代的芳基)、芳基-芳基(被1個以上之芳基取代的芳基)、芳基-烷基(被1個以上之芳基取代的烷基)、烷基-氧基、烯基-氧基、芳基-氧基、烷基-羰基、烯基-羰基、芳基-羰基、烷基-氧基-羰基、烯基-氧基-羰基、芳基-氧基-羰基、烷基-羰基-氧基、烯基-羰基-氧基、芳基-羰基-氧基等之1價的取代基,可取代時,也可包含側氧基(=O)等之2價的取代基。In the present specification, the substituent is not particularly limited, and examples thereof include an alkyl group, an alkenyl group, an aryl group, an alkyl-aryl group (an aryl group substituted by one or more alkyl groups), an aryl-aryl group (a group substituted by 1 or more Aryl substituted with more than one aryl group), aryl-alkyl (alkyl substituted with more than one aryl group), alkyl-oxy, alkenyl-oxy, aryl-oxy, alkyl -carbonyl, alkenyl-carbonyl, aryl-carbonyl, alkyl-oxy-carbonyl, alkenyl-oxy-carbonyl, aryl-oxy-carbonyl, alkyl-carbonyl-oxy, alkenyl-carbonyl- When a monovalent substituent such as an oxy group and an aryl-carbonyl-oxy group may be substituted, a divalent substituent such as a pendant oxy group (=O) may be included.

烷基(基)係指直鏈、支鏈及/或環狀之1價的飽和烴基。烷基(基)無特別限定,較佳為碳原子數1~14,更佳為碳原子數1~10,又更佳為碳原子數1~6或4~10之烷基。烷基(基)可列舉例如甲基、乙基、丙基、異丙基、丁基、異丁基、sec-丁基、tert-丁基、戊基、己基、庚基、辛基、壬基、癸基、環戊基、環己基、甲基環己基、二甲基環己基、三甲基環己基、環戊基甲基、環己基甲基等。烯基(基)係指具有至少1個碳-碳雙鍵之直鏈、支鏈及/或環狀之1價的脂肪族不飽和烴基。烯基(基)無特別限定,較佳為碳原子數2~14,更佳為碳原子數2~10,又更佳為碳原子數2~6或4~10之烯基。烯基(基)可列舉例如乙烯基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、環己烯基等。芳基(基)係指1價的芳香族烴基。芳基(基),較佳為碳原子數6~14之芳基(基)。芳基(基)可列舉例如苯基、1-萘基、2-萘基等。Alkyl (group) refers to a linear, branched and/or cyclic monovalent saturated hydrocarbon group. The alkyl group (group) is not particularly limited, but is preferably an alkyl group having 1 to 14 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 6 or 4 to 10 carbon atoms. Examples of the alkyl (group) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl cyclohexyl, decyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, cyclopentylmethyl, cyclohexylmethyl and the like. Alkenyl (group) refers to a linear, branched and/or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The alkenyl group (group) is not particularly limited, but is preferably an alkenyl group having 2 to 14 carbon atoms, more preferably 2 to 10 carbon atoms, and still more preferably an alkenyl group having 2 to 6 or 4 to 10 carbon atoms. As an alkenyl group (group), a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a cyclohexenyl group, etc. are mentioned, for example. An aryl group (group) means a monovalent aromatic hydrocarbon group. The aryl group (group) is preferably an aryl group (group) having 6 to 14 carbon atoms. As an aryl group (group), a phenyl group, a 1-naphthyl group, a 2-naphthyl group, etc. are mentioned, for example.

(A)成分之重量平均分子量(Mw),較佳為300 ~4000,更佳為300~3000,又更佳為300~2000。(A)成分之重量平均分子量可藉由凝膠滲透層析儀(GPC)法,以聚苯乙烯換算之值測定。The weight average molecular weight (Mw) of the component (A) is preferably 300-4000, more preferably 300-3000, still more preferably 300-2000. The weight average molecular weight of the component (A) can be measured in terms of polystyrene by a gel permeation chromatography (GPC) method.

(A)成分之胺基的官能基當量,較佳為100 g/eq.~1000g/eq.,更佳為100g/eq.~500g/eq.。(A)成分之胺基的官能基當量係胺基1當量之(A)成分的質量。The functional group equivalent of the amine group of the component (A) is preferably 100 g/eq. to 1000 g/eq., more preferably 100 g/eq. to 500 g/eq. The functional group equivalent of the amine group of the component (A) is the mass of the component (A) per 1 equivalent of the amine group.

(A)成分之具體例,可列舉例如具有式(A2):A specific example of the component (A) includes, for example, the formula (A2):

Figure 02_image005
Figure 02_image005

表示之重複單位的胺化合物。The amine compound represented by the repeating unit.

(A)成分之市售品,可列舉例如日本化藥公司製之「BAN」(上述式(A2)的胺化合物)等。As a commercial item of (A) component, "BAN" (the amine compound of the said formula (A2)) by Nippon Kayaku Co., Ltd., etc. are mentioned, for example.

樹脂組成物中之(A)成分的含量無特別限定,樹脂組成物中之不揮發成分設為100質量%時,較佳為60質量%以下,更佳為50質量%以下,又更佳為40質量%以下,再更佳為30質量%以下,特佳為25質量%以下。樹脂組成物中之(A)成分之含量的下限,無特別限定,樹脂組成物中之不揮發成分設為100質量%時,較佳為0.1質量%以上,更佳為1質量%以上,又更佳為3質量%以上,再更佳為5質量%以上,特佳為7質量%以上。The content of the (A) component in the resin composition is not particularly limited, but when the nonvolatile content in the resin composition is 100% by mass, it is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40 mass % or less, more preferably 30 mass % or less, and particularly preferably 25 mass % or less. The lower limit of the content of the component (A) in the resin composition is not particularly limited, but when the nonvolatile content in the resin composition is 100% by mass, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, and More preferably, it is 3 mass % or more, still more preferably 5 mass % or more, and particularly preferably 7 mass % or more.

<(B)具有碳原子數為7以上之脂肪鏈之馬來醯亞胺化合物> 本發明之樹脂組成物含有(B)具有碳原子數為7以上之脂肪鏈之馬來醯亞胺化合物。(B)成分可1種類單獨使用,也可2種類以上任意組合使用。馬來醯亞胺化合物係指1分子中含有至少1個(較佳為2個以上)之馬來醯亞胺基(2,5-二氫-2,5-二氧-1H-吡咯-1-基)的有機化合物。一實施形態中,(B)成分,較佳為具有直接鍵結於未構成芳香環之碳原子的馬來醯亞胺基,(B)成分所含有之馬來醯亞胺基,特佳為僅直接鍵結於未構成芳香環之碳原子的馬來醯亞胺基。<(B) Maleimide compound having an aliphatic chain having 7 or more carbon atoms> The resin composition of the present invention contains (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms. (B) A component may be used individually by 1 type, and may be used in arbitrary combination of 2 or more types. The maleimide compound refers to at least one (preferably two or more) maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrole-1) in one molecule. -based) organic compounds. In one embodiment, the (B) component preferably has a maleimide group directly bonded to a carbon atom that does not constitute an aromatic ring, and the maleimide group contained in the (B) component is particularly preferably Only the maleimide group directly bonded to the carbon atom that does not constitute the aromatic ring.

脂肪鏈係指骨架原子經由單鍵、雙鍵或三鍵連結的脂肪鏈,較佳為骨架原子經由單鍵或雙鍵連結的脂肪鏈,特佳為骨架原子僅經由單鍵連結的脂肪鏈。又,脂肪鏈可具有支鏈,但是未構成環結構一部分或全部。The aliphatic chain refers to an aliphatic chain in which skeleton atoms are connected via a single bond, a double bond or a triple bond, preferably an aliphatic chain in which the skeleton atoms are connected via a single bond or a double bond, and particularly preferably an aliphatic chain in which the skeleton atoms are connected only via a single bond. In addition, the aliphatic chain may have a branch, but does not constitute a part or all of the ring structure.

脂肪鏈可為僅碳原子作為骨架原子之脂肪族碳鏈(例如,伸烷基鏈、伸烯基鏈等),除了碳原子,也可為選自氧原子、氮原子及硫原子之雜原子作為骨架原子之含雜原子之脂肪鏈(例如,聚環氧烷鏈、聚烷撐亞胺鏈等),一實施形態中,較佳為僅碳原子作為骨架原子之脂肪族碳鏈。該脂肪鏈之骨架原子之中碳原子數的上限,無特別限定,例如可為3000以下、1000以下、100以下、50以下等。碳原子數為7以上的脂肪鏈,較佳為脂肪鏈之主鏈之碳原子數為7以上。The aliphatic chain may be an aliphatic carbon chain with only carbon atoms as backbone atoms (eg, alkylene chain, alkenylene chain, etc.), and in addition to carbon atoms, may also be heteroatoms selected from oxygen atoms, nitrogen atoms and sulfur atoms The heteroatom-containing aliphatic chain (eg, polyalkylene oxide chain, polyalkyleneimine chain, etc.) as the skeleton atom is preferably an aliphatic carbon chain having only carbon atoms as the skeleton atom in one embodiment. The upper limit of the number of carbon atoms in the skeleton atoms of the aliphatic chain is not particularly limited, and may be, for example, 3000 or less, 1000 or less, 100 or less, 50 or less, and the like. The aliphatic chain having 7 or more carbon atoms, preferably the main chain of the aliphatic chain, has 7 or more carbon atoms.

一實施形態中,(B)成分之馬來醯亞胺化合物,較佳為包含式(B1):In one embodiment, the maleimide compound of component (B) preferably comprises formula (B1):

Figure 02_image007
Figure 02_image007

[式中,A1 各自獨立表示具有碳原子數為7以上之脂肪鏈之2價有機基,A2 各自獨立表示不具有碳原子數為7以上之脂肪鏈之2價有機基,B1 各自獨立表示具有芳香環及/或非芳香環的4價有機基,n1及n2表示0或1以上之整數(較佳為0或1~100之整數),m1及m2表示任一者為1,其他者為0,n1與m1之合計為1以上] 表示的馬來醯亞胺化合物。又,n1單位及n2單位之順序及各個的配置為任意,包含交互共聚物、嵌段共聚物、無規共聚物等。又,n1單位及n2單位各單位可相同或相異。[In the formula, A 1 each independently represents a divalent organic group having an aliphatic chain having 7 or more carbon atoms, A 2 each independently represents a divalent organic group that does not have an aliphatic chain having a carbon number of 7 or more, and each B 1 independently represent a tetravalent organic group having an aromatic ring and/or a non-aromatic ring, n1 and n2 represent an integer of 0 or more (preferably 0 or an integer from 1 to 100), m1 and m2 represent either 1, Others are 0, and the sum of n1 and m1 is 1 or more. The maleimide compound represented by]. In addition, the order of the n1 unit and the n2 unit and the arrangement of each are arbitrary, and include alternating copolymers, block copolymers, random copolymers, and the like. In addition, each unit of n1 unit and n2 unit may be the same or different.

芳香環係指依據環上之π電子系所含有之電子數為4n+2個(n為自然數)之休克爾法則(Hückel's rule)的環。芳香環也可為以碳原子作為環構成原子的碳環,或作為環構成原子,除了碳原子外,具有氧原子、氮原子、硫原子等之雜原子的雜環,一實施形態中,較佳為碳環。芳香環不僅為單環式之芳香環,及2個以上之單環式芳香環進行縮合的縮合環,也包含1個以上之單環式芳香環上,1個以上之單環式非芳香環進行縮合的縮合環。芳香環之具體例,可列舉苯環、萘環、蒽環、茚滿環、茀環、四氫萘環等。The aromatic ring refers to a ring according to Hückel's rule that the number of electrons contained in the π electron system on the ring is 4n+2 (n is a natural number). The aromatic ring may also be a carbocyclic ring with carbon atoms as ring constituent atoms, or a heterocyclic ring with heteroatoms such as oxygen atoms, nitrogen atoms, sulfur atoms, etc., as ring constituent atoms, in addition to carbon atoms. Preferably it is a carbocyclic ring. Aromatic rings are not only monocyclic aromatic rings and condensed rings in which two or more monocyclic aromatic rings are condensed, but also include one or more monocyclic non-aromatic rings on one or more monocyclic aromatic rings A condensed ring that undergoes condensation. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, an indane ring, a perylene ring, a tetrahydronaphthalene ring, and the like.

非芳香環係指芳香環以外的環。非芳香環可為碳環或雜環,一實施形態中,較佳為碳環。非芳香環可為飽和環,也可為不飽和環,一實施形態中,較佳為飽和環。非芳香環包含環烷環、環烯環等之單環式非芳香環、及交聯烴環等之2個以上之單環式非芳香環進行縮合的縮合非芳香環。環烷環為單環式脂肪族飽和烴環,可列舉例如環丁烷環、環戊烷環、環己烷環、環庚烷環、環辛烷環等之碳原子數3~8的環烷環。環烯環係具有至少1個碳-碳雙鍵之單環式脂肪族不飽和烴環,可列舉例如環丁烯環、環戊烯環、環己烯環、環庚烯環、環辛烯環、環戊二烯環、環己二烯環等之碳原子數4~8的環烯環。交聯烴環係由共有2個以上之原子之2個以上之環所構成的非芳香環,可列舉例如降莰烷環、十氫萘環、金剛烷環、四氫二環戊二烯環等之碳原子數8~15之交聯烴環。A non-aromatic ring means a ring other than an aromatic ring. The non-aromatic ring may be a carbocyclic ring or a heterocyclic ring, and in one embodiment, a carbocyclic ring is preferred. The non-aromatic ring may be a saturated ring or an unsaturated ring, and in one embodiment, a saturated ring is preferable. The non-aromatic ring includes a condensed non-aromatic ring obtained by condensing two or more monocyclic non-aromatic rings such as a cycloalkane ring and a cycloalkene ring, and a monocyclic non-aromatic ring such as a cross-linked hydrocarbon ring. The cycloalkane ring is a monocyclic aliphatic saturated hydrocarbon ring, for example, a ring having 3 to 8 carbon atoms such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring. alkane ring. The cycloolefin ring is a monocyclic aliphatic unsaturated hydrocarbon ring having at least one carbon-carbon double bond, for example, a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, and a cyclooctene ring. A cycloalkene ring having 4 to 8 carbon atoms such as a ring, a cyclopentadiene ring, and a cyclohexadiene ring. The cross-linked hydrocarbon ring is a non-aromatic ring composed of two or more rings having two or more atoms in total, for example, a norbornane ring, a decahydronaphthalene ring, an adamantane ring, and a tetrahydrodicyclopentadiene ring. Equivalent cross-linked hydrocarbon rings with 8 to 15 carbon atoms.

n1為1以上時,n1與n2之比(n2/n1),較佳為5.0以下,更佳為2.0以下,又更佳為1.5以下,特佳為1.2以下。When n1 is 1 or more, the ratio of n1 to n2 (n2/n1) is preferably 5.0 or less, more preferably 2.0 or less, still more preferably 1.5 or less, and particularly preferably 1.2 or less.

A1 各自獨立表示具有碳原子數為7以上之脂肪鏈之2價有機基。A1 表示之「2價有機基」的骨架原子,例如選自碳原子、氧原子、氮原子、及硫原子,骨架原子數無特別限定,例如可為3000以下,1000以下,100以下,50以下等。A 1 each independently represents a divalent organic group having an aliphatic chain having 7 or more carbon atoms. The skeleton atom of the "divalent organic group" represented by A 1 is, for example, selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. The following etc.

A1 在一實施形態中,各自獨立較佳為自二聚物二胺中去除2個胺基而得之2價基。二聚物二胺係指將二聚酸之2個的末端羧基(-COOH)置換成胺基或胺基甲基的化合物,具有碳原子數為7以上的脂肪族碳鏈。二聚酸,例如不飽和脂肪酸(較佳為碳數11~22之不飽和脂肪酸,特佳為油酸、亞麻油酸等之碳數18之不飽和脂肪酸)之二聚物或其氫化物。In one embodiment, each of A 1 is preferably a divalent group obtained by removing two amine groups from dimer diamine. The dimer diamine refers to a compound in which two terminal carboxyl groups (—COOH) of the dimer acid are substituted with an amino group or an aminomethyl group, and has an aliphatic carbon chain having 7 or more carbon atoms. Dimeric acid, for example, dimer of unsaturated fatty acid (preferably unsaturated fatty acid having 11 to 22 carbon atoms, particularly preferably unsaturated fatty acid having 18 carbon atoms such as oleic acid and linoleic acid) or its hydrogenated product.

A1 係在其他的實施形態中,各自獨立較佳為具有碳原子數為7以上之脂肪族碳鏈之2價的非芳香族烴基,更佳為式(b1):In other embodiments, A 1 is each independently preferably a divalent non-aromatic hydrocarbon group having an aliphatic carbon chain having 7 or more carbon atoms, more preferably the formula (b1):

Figure 02_image009
Figure 02_image009

[式中,Y1 各自獨立表示原子數(較佳為伸烷基主鏈之原子數)為7以上之直鏈或支鏈(較佳為直鏈)之伸烷基、或原子數(較佳為伸烯基主鏈之原子數)為7以上之直鏈或支鏈(較佳為直鏈)之伸烯基(較佳為碳原子數為7以上之直鏈或支鏈(較佳為直鏈)之伸烷基),環Zy1 表示可具有選自烷基及烯基之基的環烷環、或可具有選自烷基及烯基之基的環烯基環(較佳為可具有烷基之環己烷環);d表示0或1(較佳為1);*表示鍵結部位] 表示之2價基。[In the formula, Y 1 each independently represents a straight-chain or branched (preferably straight-chain) alkylene group whose number of atoms (preferably the number of atoms in the main chain of the alkylene group) is 7 or more, or the number of atoms (preferably a straight chain) Preferably, the number of atoms in the main chain of the alkenylene group is 7 or more linear or branched (preferably linear) alkenylene (preferably, the number of carbon atoms is 7 or more linear or branched (preferably linear). is a straight chain) alkylidene), ring Z y1 represents a cycloalkane ring which may have a group selected from alkyl and alkenyl, or a cycloalkenyl ring (preferably a cycloalkenyl ring which may have a group selected from alkyl and alkenyl) is a cyclohexane ring which may have an alkyl group); d represents 0 or 1 (preferably 1); * represents a bonding site] represents a divalent group.

伸烷基係指2價之飽和烴基,碳原子數為7以上之直鏈或支鏈之伸烷基的碳原子數,例如為7~200,較佳為7~100,更佳為7~50。伸烯基係指具有至少1個碳-碳雙鍵之2價的脂肪族不飽和烴基,碳原子數為7以上之直鏈或支鏈之伸烯基的碳原子數,例如為7~200,較佳為7~100,更佳為7~50。Alkylene refers to a divalent saturated hydrocarbon group, the number of carbon atoms of a straight-chain or branched alkyl group with a carbon number of 7 or more, such as 7-200, preferably 7-100, more preferably 7- 50. Alkenylene refers to a 2-valent aliphatic unsaturated hydrocarbon group with at least one carbon-carbon double bond, and the number of carbon atoms of a straight-chain or branched alkenylene group with a carbon number of 7 or more is, for example, 7 to 200. , preferably 7~100, more preferably 7~50.

式(b1)表示之2價基的具體例,可列舉下述式表示之2價基:Specific examples of the divalent group represented by the formula (b1) include the divalent group represented by the following formula:

Figure 02_image011
Figure 02_image011

[式中,*表示鍵結部位]。[In the formula, * represents a bond site].

A2 各自獨立表示不具有碳原子數為7以上之脂肪鏈之2價有機基(亦即,具有脂肪鏈時,彼等之脂肪鏈之中,最多碳原子數之脂肪鏈的碳原子數為6以下的2價有機基)。A2 表示之「2價有機基」的骨架原子,例如選自碳原子、氧原子、氮原子、及硫原子,骨架原子數無特別限定,例如可為5~3000,5~1000,5~100,5~50等。A2 例如可為自作為聚醯亞胺之原料,一般使用之不具有碳原子數為7以上之脂肪鏈之二胺化合物中去除2個胺基而成之2價基,但是無特別限定。A 2 each independently represents a divalent organic group that does not have an aliphatic chain having 7 or more carbon atoms (that is, when it has an aliphatic chain, among those aliphatic chains, the number of carbon atoms in the aliphatic chain with the largest number of carbon atoms is 6 or less divalent organic groups). The skeleton atom of the "divalent organic group" represented by A 2 is, for example, selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. The number of skeleton atoms is not particularly limited, for example, it can be 5~3000, 5~1000, 5~ 100, 5~50, etc. A 2 may be, for example, a divalent group obtained by removing two amine groups from a diamine compound generally used as a raw material of polyimide without an aliphatic chain having 7 or more carbon atoms, but it is not particularly limited.

A2 各自獨立較佳為不具有碳原子數為7以上之脂肪鏈,且具有芳香環及/或非芳香環之2價有機基(亦即,具有脂肪鏈時,彼等之脂肪鏈之中,最多碳原子數之脂肪鏈的碳原子數為6以下,且具有芳香環及/或非芳香環之2價有機基),更佳為式(b2):A 2 is each independently preferably a divalent organic group that does not have an aliphatic chain with 7 or more carbon atoms, and has an aromatic ring and/or a non-aromatic ring (that is, when it has an aliphatic chain, among those aliphatic chains , the number of carbon atoms in the aliphatic chain with the largest number of carbon atoms is 6 or less, and has an aromatic ring and/or a non-aromatic ring divalent organic group), more preferably formula (b2):

Figure 02_image013
Figure 02_image013

[式中,Y21 各自獨立表示單鍵,或-C(Rx )2 -(較佳為-C(Rx )2 -);Y22 各自獨立表示單鍵、-C(Ry )2 -、-O-、-CO-、-S-、-SO-、-SO2 -、-CONH-、或-NHCO-(較佳為 -C(Ry )2 -或-O-);Rx 及Ry 各自獨立表示氫原子、甲基、乙基或苯基(較佳為氫原子);環Zy2 各自獨立表示可具有選自碳原子數1~6之烷基及苯基之基的非芳香環,或可具有選自碳原子數1~6之烷基及苯基之基的芳香環,e表示0或1以上之整數(較佳為0或1~5之整數);*表示鍵結部位]表示的2價基。又,e單位之各單位可相同或相異。[In the formula, Y 21 each independently represents a single bond, or -C(R x ) 2 - (preferably -C(R x ) 2 -); Y 22 each independently represents a single bond, -C(R y ) 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH-, or -NHCO- (preferably -C(R y ) 2 - or -O-); R Each of x and R y independently represents a hydrogen atom, a methyl group, an ethyl group or a phenyl group (preferably a hydrogen atom); each of the rings Z y2 independently represents a group which may have an alkyl group selected from 1 to 6 carbon atoms and a phenyl group The non-aromatic ring of , or an aromatic ring that may have a base selected from an alkyl group with 1 to 6 carbon atoms and a phenyl group, e represents an integer of 0 or more (preferably an integer of 0 or 1 to 5); * Represents a divalent group represented by a bonding site]. In addition, each unit of e-unit may be the same or different.

式(b2)表示之2價基的具體例,可列舉下述式表示之2價基:Specific examples of the divalent group represented by the formula (b2) include the divalent group represented by the following formula:

Figure 02_image015
Figure 02_image015

[式中,*表示鍵結部位]。[In the formula, * represents a bond site].

B1 各自獨立表示具有芳香環及/或非芳香環之4價有機基。B1 表示之「4價有機基」之骨架原子,例如選自碳原子、氧原子、氮原子,及硫原子,骨架原子數,無特別限定,例如可為5~3000,5~1000,5~100、5~50等。B1 例如可為自作為聚醯亞胺之原料,一般使用之具有芳香環及/或非芳香環之四羧酸酐去除2個酸酐基(-CO-O-CO-)而成的4價基,但是無特別限定。B 1 each independently represents a tetravalent organic group having an aromatic ring and/or a non-aromatic ring. The skeleton atom of the "tetravalent organic group" represented by B1 is, for example, selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. ~100, 5~50, etc. For example, B1 can be a tetravalent group obtained by removing two acid anhydride groups (-CO-O-CO-) from tetracarboxylic anhydrides having an aromatic ring and/or a non-aromatic ring generally used as a raw material of polyimide , but not particularly limited.

B1 各自獨立較佳為、不具有碳原子數為7以上之脂肪鏈,且具有芳香環及/或非芳香環之4價有機基(亦即,具有脂肪鏈時,彼等之脂肪鏈之中最多碳原子數之脂肪鏈之碳原子數為6以下,且具有芳香環及/或非芳香環之4價有機基),更佳為式(b3):B 1 are each independently preferably a tetravalent organic group that does not have an aliphatic chain with 7 or more carbon atoms and has an aromatic ring and/or a non-aromatic ring (that is, when it has an aliphatic chain, the The number of carbon atoms in the aliphatic chain with the largest number of carbon atoms is 6 or less, and has an aromatic ring and/or a non-aromatic tetravalent organic group), more preferably the formula (b3):

Figure 02_image017
Figure 02_image017

[式中,R1 各自獨立表示碳原子數1~6之烷基或苯基;X1 各自獨立表示單鍵、-C(Rz )2 -、-O-、-CO-、 -S-、-SO-、-SO2 -、-CONH-、或-NHCO-(較佳為-C(Rz )2 -或-O-);Rz 各自獨立表示氫原子、甲基、乙基或苯基(較佳為氫原子);環Zx1 各自獨立表示可具有選自碳原子數1~6之烷基及苯基之基之非芳香環,或可具有選自碳原子數1~6之烷基及苯基之基之芳香環;a各自獨立表示0~2之整數(較佳為0);b表示0或1;c表示0或1以上之整數(較佳為0或1~5之整數);*表示鍵結部位] 表示的4價基。又,a單位及c單位,各單位可相同或相異。[In the formula, R 1 each independently represents an alkyl group or phenyl group with 1 to 6 carbon atoms; X 1 each independently represents a single bond, -C(R z ) 2 -, -O-, -CO-, -S- , -SO-, -SO 2 -, -CONH-, or -NHCO- (preferably -C(R z ) 2 - or -O-); R z each independently represents a hydrogen atom, methyl, ethyl or Phenyl (preferably a hydrogen atom); each of the rings Z x1 independently represents a non-aromatic ring that may have a group selected from an alkyl group with 1 to 6 carbon atoms and a phenyl group, or may have a group selected from 1 to 6 carbon atoms The aromatic ring of the alkyl group and the phenyl group; a each independently represents an integer of 0~2 (preferably 0); b represents 0 or 1; c represents an integer of 0 or more (preferably 0 or 1~ Integer of 5); * represents the tetravalent group represented by the bonding site]. In addition, the a unit and the c unit may be the same or different from each other.

式(b3)表示之4價基的具體例,可列舉下述式表示之4價基:Specific examples of the tetravalent group represented by the formula (b3) include the tetravalent group represented by the following formula:

Figure 02_image019
Figure 02_image019

[式中,*表示鍵結部位]。[In the formula, * represents a bond site].

一實施形態中,(B)成分之馬來醯亞胺化合物,更佳為式(B2):In one embodiment, the maleimide compound of (B) component is more preferably formula (B2):

Figure 02_image021
Figure 02_image021

[式中,各符號係與式(B1)、(b1)、(b2)及(b3)相同] 表示的化合物(n1單位與n2單位之間為鍵結鍵),又更佳為式(B3):[In the formula, each symbol system is the same as the formula (B1), (b1), (b2) and (b3)] The compound represented (the bond between the n1 unit and the n2 unit) is more preferably the formula (B3):

Figure 02_image023
Figure 02_image023

[式中,各符號係與式(B1)、(b2)及(b3)相同] 表示的化合物(n1單位與n2單位之間為鍵結鍵)。[In the formula, each symbol system is the same as the formula (B1), (b2) and (b3)] The compound represented (the bond between the n1 unit and the n2 unit is a bond).

(B)成分之具體例,可列舉例如式(B4-1)~ (B4-5):Specific examples of the (B) component include, for example, formulas (B4-1) to (B4-5):

Figure 02_image025
Figure 02_image025

[式中,n1’及n2’各自獨立表示1~20之整數(較佳為1~10之整數)] 表示之馬來醯亞胺化合物。又,n1’單位及n2’單位之順序及各個配置為任意,包含交互共聚物、嵌段共聚物、無規共聚物等。[In the formula, n1' and n2' each independently represent an integer of 1 to 20 (preferably an integer of 1 to 10)] Said maleimide compound. The order and arrangement of the n1' units and the n2' units are arbitrary, and include alternating copolymers, block copolymers, random copolymers, and the like.

(B)成分之重量平均分子量(Mw)無特別限定,較佳為200~50000,更佳為300~40000,又更佳為400 ~20000。(B)成分之重量平均分子量可藉由凝膠滲透層析儀(GPC)法,以聚苯乙烯換算之值測定。The weight average molecular weight (Mw) of the component (B) is not particularly limited, but is preferably 200 to 50,000, more preferably 300 to 40,000, and still more preferably 400 to 20,000. The weight average molecular weight of the component (B) can be measured in terms of polystyrene by a gel permeation chromatography (GPC) method.

(B)成分之市售品,可列舉例如Designer molecules公司製之「BMI-689」、「BMI-1500」、「BMI-1700」、「BMI-3000J」、「BMI-2500」等。(B) As a commercial item of a component, "BMI-689", "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-2500" by Designer molecules, etc. are mentioned, for example.

樹脂組成物中之(B)成分的含量,無特別限定,樹脂組成物中之不揮發成分設為100質量%時,較佳為50質量%以下,更佳為40質量%以下,又更佳為30質量%以下,再更佳為25質量%以下,特佳為20質量%以下。樹脂組成物中之(B)成分之含量的下限,無特別限定,樹脂組成物中之不揮發成分設為100質量%時,較佳為1質量%以上,更佳為3質量%以上,又更佳為5質量%以上,再更佳為10質量%以上,特佳為15質量%以上。The content of the (B) component in the resin composition is not particularly limited, but when the non-volatile matter in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably It is 30 mass % or less, More preferably, it is 25 mass % or less, Especially preferably, it is 20 mass % or less. The lower limit of the content of the component (B) in the resin composition is not particularly limited, but when the nonvolatile content in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, and More preferably, it is 5 mass % or more, still more preferably 10 mass % or more, and particularly preferably 15 mass % or more.

<(C)不具有碳原子數為7以上之脂肪鏈之馬來醯亞胺化合物> 本發明之樹脂組成物係含有(B)以外之成分為(C)不具有碳原子數為7以上之脂肪鏈的馬來醯亞胺化合物。亦即,(C)成分為具有脂肪鏈時,彼等之脂肪鏈之中最多碳原子數之脂肪鏈的碳原子數為6以下。(C)成分可1種類單獨使用,也可2種類以上任意組合使用。<(C) Maleimide compound having no aliphatic chain having 7 or more carbon atoms> The resin composition of this invention contains the maleimide compound which does not have an aliphatic chain with 7 or more carbon atoms as components other than (B) (C). That is, when the component (C) has an aliphatic chain, the aliphatic chain having the largest number of carbon atoms among those aliphatic chains has 6 or less carbon atoms. (C) A component may be used individually by 1 type, and may be used in arbitrary combination of 2 or more types.

一實施形態中,(C)成分較佳為具有直接鍵結於構成芳香環之碳原子之馬來醯亞胺基,(C)成分所含有之馬來醯亞胺基,特佳為僅直接鍵結於構成芳香環之碳原子之馬來醯亞胺基。In one embodiment, the component (C) preferably has a maleimide group directly bonded to a carbon atom constituting an aromatic ring, and the maleimide group contained in the component (C) is particularly preferably only directly A maleimide group bonded to a carbon atom constituting an aromatic ring.

一實施形態中,(C)成分之馬來醯亞胺化合物,較佳為包含式(C1-1)或(C1-2):In one embodiment, the maleimide compound of component (C) preferably contains formula (C1-1) or (C1-2):

Figure 02_image027
Figure 02_image027

[式中,B2 各自獨立表示不具有碳原子數為7以上之脂肪鏈之4價有機基;n表示1以上之整數(較佳為1~100之整數);A3 各自獨立表示不具有碳原子數為7以上之脂肪鏈之2價有機基;R3 各自獨立表示碳原子數1~6之烷基或苯基;s表示1或1以上之整數(較佳為1或1~100之整數,更佳為1或1~50之整數,又更佳為1或1~20之整數);t各自獨立表示0~2之整數(較佳為0);其他的符號係與式(B1)相同] 表示之馬來醯亞胺化合物。又,n單位、s單位及t單位,各自單位可相同或相異。[In the formula, B 2 each independently represents a tetravalent organic group that does not have an aliphatic chain with 7 or more carbon atoms; n represents an integer of 1 or more (preferably an integer of 1 to 100); A 3 each independently represents no Divalent organic group of aliphatic chain with 7 or more carbon atoms; R 3 each independently represents an alkyl group or phenyl group with 1 to 6 carbon atoms; s represents an integer of 1 or more (preferably 1 or 1 to 100 The integer of t is preferably 1 or an integer of 1-50, and more preferably an integer of 1 or 1-20); t independently represents an integer of 0-2 (preferably 0); other symbols are the same as those of the formula ( B1) is the same as the maleimide compound represented by]. In addition, the units of n, s, and t may be the same or different from each other.

B2 各自獨立表示不具有碳原子數為7以上之脂肪鏈之4價有機基(亦即,具有脂肪鏈時,彼等之脂肪鏈之中最多碳原子數之脂肪鏈之碳原子數為6以下的4價有機基)。B2 表示之「4價有機基」之骨架原子,例如選自碳原子、氧原子、氮原子,及硫原子,骨架原子數,無特別限定,例如可為5~3000,5~1000,5~100、5~50等。B2 例如可為自作為聚醯亞胺之原料,一般使用之不具有碳原子數為7以上之脂肪鏈之四羧酸酐中去除2個酸酐基(-CO-O-CO-)而成的4價基,但是無特別限定。B2 each independently represents a tetravalent organic group that does not have an aliphatic chain with a carbon number of 7 or more (that is, when there is an aliphatic chain, the carbon number of the aliphatic chain with the highest carbon number among those aliphatic chains is 6 the following tetravalent organic group). The skeleton atom of the "tetravalent organic group" represented by B 2 is, for example, selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. ~100, 5~50, etc. For example, B2 can be obtained by removing two acid anhydride groups (-CO-O-CO-) from tetracarboxylic acid anhydride generally used as a raw material of polyimide without an aliphatic chain with 7 or more carbon atoms A tetravalent base is not particularly limited.

B2 各自獨立較佳為不具有碳原子數為7以上之脂肪鏈,且具有芳香環及/或非芳香環之4價有機基(亦即,具有脂肪鏈時,彼等之脂肪鏈之中最多碳原子數之脂肪鏈之碳原子數為6以下,且具有芳香環及/或非芳香環之4價有機基),更佳為上述式(b3)表示的4價基。B 2 are each independently preferably a tetravalent organic group that does not have an aliphatic chain with 7 or more carbon atoms, and has an aromatic ring and/or a non-aromatic ring (that is, when it has an aliphatic chain, among those aliphatic chains The aliphatic chain having the largest number of carbon atoms has 6 or less carbon atoms and a tetravalent organic group having an aromatic ring and/or a non-aromatic ring), more preferably a tetravalent group represented by the above formula (b3).

A3 各自獨立表示不具有碳原子數為7以上之脂肪鏈之2價有機基。A3 表示之「2價有機基」之骨架原子,例如選自碳原子、氧原子、氮原子,及硫原子,骨架原子數,無特別限定,例如可為1~3000,1~1000,1~100,1~50等。A 3 each independently represents a divalent organic group that does not have an aliphatic chain having 7 or more carbon atoms. The skeleton atom of the "divalent organic group" represented by A 3 is, for example, selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. ~100, 1~50, etc.

式(C1-1)表示之馬來醯亞胺化合物,較佳為式(C2-1):The maleimide compound represented by the formula (C1-1) is preferably the formula (C2-1):

Figure 02_image029
Figure 02_image029

[式中,各符號係與式(C1-1)、(b2)及(b3)相同] 表示之馬來醯亞胺化合物,更佳為式(C3-1):[In the formula, each symbol system is the same as the formula (C1-1), (b2) and (b3)] The maleimide compound represented by the formula is more preferably the formula (C3-1):

Figure 02_image031
Figure 02_image031

[式中,R2 各自獨立表示碳原子數1~6之烷基或苯基;f各自獨立表示0~2之整數;其他的符號係與式(C1-1)、(b2)及(b3)相同。] 表示之馬來醯亞胺化合物。又,f單位係各單位可相同或相異。[In the formula, R 2 each independently represents an alkyl group or phenyl group with 1 to 6 carbon atoms; f each independently represents an integer of 0 to 2; other symbols are the same as those of formulae (C1-1), (b2) and (b3) )same. ] represents the maleimide compound. In addition, each unit of the f unit system may be the same or different.

式(C1-2)表示之馬來醯亞胺化合物,較佳為式(C2-2):The maleimide compound represented by the formula (C1-2) is preferably the formula (C2-2):

Figure 02_image033
Figure 02_image033

[式中,X3 各自獨立表示單鍵、-C(Ra )2 -、 -O-、-CO-、-S-、-SO-、-SO2 -、-CONH-、或-NHCO-;Ra 各自獨立表示氫原子、甲基、乙基或苯基;環Zx3 表示可具有選自碳原子數1~6之烷基及苯基之基的非芳香環、或可具有選自碳原子數1~6之烷基及苯基之基的芳香環;u各自獨立表示0或1以上之整數(較佳為0或1~50之整數);其他的符號係與式(C1-2)相同] 表示之馬來醯亞胺化合物,更佳為、式(C3-2):[wherein, X 3 each independently represents a single bond, -C(R a ) 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH-, or -NHCO- R a each independently represents a hydrogen atom, a methyl group, an ethyl group or a phenyl group; the ring Z x3 represents a non-aromatic ring that may have a base selected from an alkyl group with 1 to 6 carbon atoms and a phenyl group, or may have a group selected from the group consisting of: Aromatic rings of alkyl groups with 1 to 6 carbon atoms and phenyl groups; u each independently represents an integer of 0 or more (preferably an integer of 0 or 1 to 50); other symbols are the same as those of the formula (C1- 2) The maleimide compound represented by the same], more preferably, the formula (C3-2):

Figure 02_image035
Figure 02_image035

[式中,X4 各自獨立表示單鍵、-C(Rb )(Rc )-、-O-、-CO-、-S-、-SO-、-SO2 -、-CONH-、或-NHCO-;R4 及Rb 各自獨立表示氫原子、甲基或苯基;R5 各自獨立表示氫原子、碳原子數1~6之烷基或苯基,Rc 表示氫原子、甲基或苯基,或R5 及Rc 一同相互鍵結,形成可具有選自烷基及烯基之基的環(例如茚滿環)R6 各自獨立表示氫原子、碳原子數1~6之烷基或苯基;v表示0或1以上之整數(較佳為0或1~10之整數);其他的符號係與式(C1-2)相同] 表示之馬來醯亞胺化合物。又,u單位及v單位,各單位可相同或相異。[wherein, X 4 each independently represents a single bond, -C(R b )(R c )-, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH-, or -NHCO-; R 4 and R b each independently represent a hydrogen atom, a methyl group or a phenyl group; R 5 each independently represents a hydrogen atom, an alkyl group with 1 to 6 carbon atoms or a phenyl group, and R c represents a hydrogen atom, a methyl group Or phenyl, or R 5 and R c are bonded together to form a ring (for example, an indan ring) that can have a group selected from an alkyl group and an alkenyl group. R 6 each independently represents a hydrogen atom, a group of 1 to 6 carbon atoms. An alkyl group or a phenyl group; v represents an integer of 0 or more (preferably an integer of 0 or 1 to 10); other symbols are the same as the maleimide compounds represented by the formula (C1-2). In addition, the u unit and the v unit may be the same or different from each other.

(C)成分之具體例,可列舉例如式(C4-1)~ (C4-4):The specific example of (C) component, for example, formula (C4-1)~(C4-4) can be mentioned:

Figure 02_image037
Figure 02_image037

[式中,n’及n”各自獨立表示1~20之整數(較佳為1~10之整數);s’表示1~100之整數(較佳為1~50之整數,更佳為1~20之整數);v’各自獨立表示1~10之整數(較佳為1~5之整數)] 表示之馬來醯亞胺化合物。又,n’單位、n”單位之順序及各個配置為任意,包含交互共聚物、嵌段共聚物、無規共聚物等。[In the formula, n' and n" each independently represent an integer of 1-20 (preferably an integer of 1-10); s' represents an integer of 1-100 (preferably an integer of 1-50, more preferably 1 ~20 integer); v' each independently represents an integer from 1 to 10 (preferably an integer from 1 to 5)] Said maleimide compound. The order and arrangement of the n' units and n" units are arbitrary, and include alternating copolymers, block copolymers, random copolymers, and the like.

(C)成分之重量平均分子量(Mw),無特別限定,較佳為200~50000,更佳為300~40000,又更佳為400~ 20000。(C)成分之重量平均分子量可藉由凝膠滲透層析儀(GPC)法,以聚苯乙烯換算之值測定。The weight average molecular weight (Mw) of the component (C) is not particularly limited, but is preferably 200 to 50,000, more preferably 300 to 40,000, and even more preferably 400 to 20,000. The weight average molecular weight of the component (C) can be measured in terms of polystyrene by a gel permeation chromatography (GPC) method.

(C)成分之市售品,可列舉例如Designer molecules公司製之「BMI-6100」、日本化藥公司製之「MIR-3000-70MT」等。As a commercial item of (C) component, "BMI-6100" by Designer Molecules Co., Ltd., "MIR-3000-70MT" by Nippon Kayaku Co., Ltd., etc. are mentioned, for example.

樹脂組成物中之(C)成分的含量,無特別限定,樹脂組成物中之不揮發成分設為100質量%時,較佳為50質量%以下,更佳為40質量%以下,又更佳為30質量%以下,再更佳為25質量%以下,特佳為20質量%以下。樹脂組成物中之(C)成分之含量的下限,無特別限定,樹脂組成物中之不揮發成分設為100質量%時,較佳為1質量%以上,更佳為3質量%以上,又更佳為5質量%以上,再更佳為10質量%以上,特佳為15質量%以上。The content of the component (C) in the resin composition is not particularly limited, but when the non-volatile matter in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably It is 30 mass % or less, More preferably, it is 25 mass % or less, Especially preferably, it is 20 mass % or less. The lower limit of the content of the component (C) in the resin composition is not particularly limited, but when the nonvolatile content in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, and More preferably, it is 5 mass % or more, still more preferably 10 mass % or more, and particularly preferably 15 mass % or more.

樹脂組成物中,(C)成分相對於(B)成分之質量比((C)成分/(B)成分),無特別限定,較佳為0.01以上,更佳為0.1以上,又更佳為0.5以上,特佳為0.8以上。(C)成分相對於(B)成分之質量比((C)成分/(B)成分)之上限值,無特別限定,較佳為50以下,更佳為40以下,又更佳為20以下,特佳為5以下。In the resin composition, the mass ratio of (C) component to (B) component ((C) component/(B) component) is not particularly limited, but is preferably 0.01 or more, more preferably 0.1 or more, and still more preferably 0.5 or more, particularly preferably 0.8 or more. The upper limit of the mass ratio ((C)component/(B)component) of the component (C) to the component (B) is not particularly limited, but is preferably 50 or less, more preferably 40 or less, and still more preferably 20 Hereinafter, 5 or less is particularly preferred.

樹脂組成物中,(A)成分相對於(B)成分及(C)成分之合計的質量比((A)成分/(B)成分及(C)成分之合計),無特別限定,較佳為0.01以上,更佳為0.05以上,又更佳為0.1以上,特佳為0.2以上。(A)成分相對於(B)成分及(C)成分之合計的質量比((A)成分/(B)成分及(C)成分之合計)的上限,無特別限定,較佳為5以下,更佳為1以下,又更佳為0.5以下,特佳為0.3以下。In the resin composition, the mass ratio of (A) component to the total of (B) component and (C) component ((A) component/(B) component and (C) component total) is not particularly limited, but is preferably It is 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, and particularly preferably 0.2 or more. The upper limit of the mass ratio of (A) component to the total of (B) component and (C) component ((A) component/(B) component and (C) component total) is not particularly limited, but preferably 5 or less , more preferably 1 or less, still more preferably 0.5 or less, particularly preferably 0.3 or less.

<(D)任意之自由基聚合性化合物> 本發明之樹脂組成物,具有包含作為任意成分之(B)成分及(C)成分以外之(D)自由基聚合性化合物的情形。(D)成分可1種類單獨使用,也可2種類以上任意組合使用。<(D) Arbitrary radical polymerizable compound> The resin composition of the present invention may contain (D) radically polymerizable compounds other than (B) component and (C) component as optional components. (D) A component may be used individually by 1 type, and may be used in arbitrary combination of 2 or more types.

(D)成分,例如可為具有自由基聚合性不飽和基的化合物。自由基聚合性不飽和基,可自由基聚合時,即無特別限定,較佳為末端或內部具有碳-碳雙鍵之乙烯性不飽和基,具體而言,可為烯丙基、3-環己烯基等之不飽和脂肪族基;p-乙烯基苯基、m-乙烯基苯基、苯乙烯基等之含有不飽和脂肪族基的芳香族基;丙烯醯基、甲基丙烯醯基、順丁烯二醯基、反丁烯二醯基等之α,β-不飽和羰基等。(D)成分,較佳為具有1個以上之自由基聚合性不飽和基,更佳為具有2個以上。(D)component may be a compound which has a radically polymerizable unsaturated group, for example. The radically polymerizable unsaturated group is not particularly limited when it can be radically polymerized, and is preferably an ethylenically unsaturated group having a carbon-carbon double bond at the terminal or inside, and specifically, allyl, 3- Unsaturated aliphatic groups such as cyclohexenyl; aromatic groups containing unsaturated aliphatic groups such as p-vinylphenyl, m-vinylphenyl, styryl, etc.; acrylyl, methacryloyl α, β-unsaturated carbonyl groups such as base, maleic acid group, fumaric acid group, etc. The component (D) preferably has one or more radically polymerizable unsaturated groups, more preferably two or more.

作為(D)成分,可廣泛使用公知的自由基聚合性化合物,無特別限定,可列舉例如(D-1)乙烯基苯基系自由基聚合性化合物、(D-2)(甲基)丙烯酸系自由基聚合性化合物等。As the component (D), known radically polymerizable compounds can be widely used without particular limitation, and examples thereof include (D-1) vinylphenyl-based radically polymerizable compounds and (D-2) (meth)acrylic acid. Radical polymerizable compounds, etc.

<(D-1)乙烯基苯基系自由基聚合性化合物> (D-1)乙烯基苯基系自由基聚合性化合物為具有乙烯基苯基之自由基聚合性化合物。乙烯基苯基系自由基聚合性化合物,較佳為1分子中具有2個以上之乙烯基苯基。<(D-1) Vinylphenyl-based radically polymerizable compound> (D-1) The vinylphenyl-based radically polymerizable compound is a radically polymerizable compound having a vinylphenyl group. The vinylphenyl-based radically polymerizable compound preferably has two or more vinylphenyl groups in one molecule.

一實施形態中,(D-1)乙烯基苯基系自由基聚合性化合物,較佳為具有乙烯基苄基及聚苯醚骨架之乙烯基苄基改性聚苯醚,特佳為具有式(D1):In one embodiment, the (D-1) vinylphenyl-based radically polymerizable compound is preferably a vinylbenzyl-modified polyphenylene ether having a vinylbenzyl group and a polyphenylene ether skeleton, and particularly preferably has the formula (D1):

Figure 02_image039
Figure 02_image039

[式中,R11 、R12 、R13 及R14 各自獨立表示氫原子或取代基(較佳為氫原子或烷基,特佳為氫原子或甲基)] 表示之重複單位(重複單位數,較佳為2~300,更佳為2~100)及具有乙烯基苄基的乙烯基苄基改性聚苯醚(特別是將聚苯醚之兩末端羥基之氫原子取代為乙烯基苄基之兩末端乙烯基苄基改性聚苯醚)。[wherein, R 11 , R 12 , R 13 and R 14 each independently represent a hydrogen atom or a substituent (preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a methyl group)] Repetitive unit represented by (repetitive unit number, preferably 2~300, more preferably 2~100) and vinylbenzyl modified polyphenylene ether with vinylbenzyl group (especially the hydrogen atoms of the hydroxyl groups at both ends of the polyphenylene ether are replaced with vinyl groups Both ends of the benzyl group are vinylbenzyl modified polyphenylene ether).

其他的實施形態中,(D-1)乙烯基苯基系自由基聚合性化合物,較佳為具有式(D2):In other embodiments, the (D-1) vinylphenyl-based radically polymerizable compound preferably has the formula (D2):

Figure 02_image041
Figure 02_image041

[式中,R15 、R16 及R17 各自獨立表示氫原子或取代基(較佳為氫原子)] 表示之重複單位(重複單位數,較佳為2~200)的二乙烯基苯聚合物。該二乙烯基苯聚合物,可為再具有苯乙烯單元、乙基苯乙烯單元等之其他的苯乙烯骨架單位的共聚物。具有其他之苯乙烯骨架單元時,較佳為相對於全苯乙烯骨架單位,式(D2)之重複單位之比例為5~70莫耳%。[In the formula, R 15 , R 16 and R 17 each independently represent a hydrogen atom or a substituent (preferably a hydrogen atom)] Divinylbenzene polymerization of repeating units (the number of repeating units, preferably 2 to 200) thing. The divinylbenzene polymer may be a copolymer having other styrene skeleton units such as a styrene unit, an ethylstyrene unit, or the like. When it has other styrene skeleton unit, it is preferable that the ratio of the repeating unit of formula (D2) is 5-70 mol% with respect to all styrene skeleton units.

(D-1)乙烯基苯基系自由基聚合性化合物之數平均分子量,無特別限定,較佳為500~100000,更佳為700~80000。(D)成分之數平均分子量可藉由凝膠滲透層析儀(GPC)法,以聚苯乙烯換算之值測定。(D-1)乙烯基苯基系自由基聚合性化合物之乙烯基的官能基當量,無特別限定,較佳為200g/eq.~3000g/eq.,更佳為200g/eq.~2000 g/eq.。(D-1) The number-average molecular weight of the vinylphenyl-based radically polymerizable compound is not particularly limited, but is preferably 500 to 100,000, more preferably 700 to 80,000. The number-average molecular weight of the component (D) can be measured in terms of polystyrene by a gel permeation chromatography (GPC) method. (D-1) The functional group equivalent of the vinyl group of the vinylphenyl-based radically polymerizable compound is not particularly limited, but is preferably 200 g/eq. to 3000 g/eq., more preferably 200 g/eq. to 2000 g /eq..

(D-1)乙烯基苯基系自由基聚合性化合物的市售品,可列舉例如三菱氣體化學公司製之「OPE-2St 1200」、「OPE-2St 2200」(乙烯基苄基改性聚苯醚);NIPPON STEEL Chemical & Material股份公司製之「ODV-XET-X03」、「ODV-XET-X04」、「ODV-XET-X05」(二乙烯基苯聚合物)等。(D-1) Commercial products of vinylphenyl-based radically polymerizable compounds include, for example, "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified poly Phenyl ether); "ODV-XET-X03", "ODV-XET-X04", "ODV-XET-X05" (divinylbenzene polymer) manufactured by NIPPON STEEL Chemical & Material Co., Ltd.

<(D-2)(甲基)丙烯酸系自由基聚合性化合物> (D-2)(甲基)丙烯酸系自由基聚合性化合物係具有丙烯醯基及/或甲基丙烯醯基的自由基聚合性化合物。(D-2)(甲基)丙烯酸系自由基聚合性化合物,較佳為1分子內,具有2個以上之丙烯醯基及/或甲基丙烯醯基。(D-2)(甲基)丙烯酸系自由基聚合性化合物,較佳為具有丙烯醯基及/或甲基丙烯醯基及聚苯醚骨架的(甲基)丙烯酸改性聚苯醚,特佳為具有式(D3):<(D-2) (Meth)acrylic radical polymerizable compound> (D-2) The (meth)acrylic radical polymerizable compound is a radical polymerizable compound having an acryl group and/or a methacryl group. (D-2) The (meth)acrylic radical polymerizable compound preferably has two or more acryl group and/or methacryl group in one molecule. (D-2) A (meth)acrylic radical polymerizable compound, preferably a (meth)acrylic modified polyphenylene ether having an acryl group and/or a methacryloyl group and a polyphenylene ether skeleton, especially It is better to have the formula (D3):

Figure 02_image043
Figure 02_image043

[式中,R21 、R22 、R23 及R24 各自獨立表示氫原子或取代基(較佳為氫原子或烷基,特佳為氫原子或甲基)] 表示之重複單位(重複單位數,較佳為2~300,更佳為2~100)及丙烯醯基及/或甲基丙烯醯基的(甲基)丙烯酸改性聚苯醚(特別是將聚苯醚之兩末端羥基的氫原子取代為丙烯醯基及/或甲基丙烯醯基之兩末端(甲基)丙烯酸改性聚苯醚)。[In the formula, R 21 , R 22 , R 23 and R 24 each independently represent a hydrogen atom or a substituent (preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a methyl group)] Repetitive unit represented by (repetitive unit number, preferably 2 to 300, more preferably 2 to 100) and acrylyl and/or methacryloyl (meth)acrylic modified polyphenylene ether (especially the hydroxyl groups at both ends of the polyphenylene ether) The hydrogen atoms of , are substituted with acrylyl and/or methacrylyl groups at both ends (meth)acrylic acid-modified polyphenylene ether).

(D-2)(甲基)丙烯酸系自由基聚合性化合物之數平均分子量,無特別限定,較佳為500~10000,更佳為700~5000。(D-2)(甲基)丙烯酸系自由基聚合性化合物之丙烯醯基及甲基丙烯醯基的官能基當量,無特別限定,較佳為200g/eq.~3000g/eq.,更佳為300g/eq.~2000g/eq.。(D-2) The number average molecular weight of the (meth)acrylic radical polymerizable compound is not particularly limited, but is preferably 500 to 10,000, more preferably 700 to 5,000. (D-2) The functional group equivalents of the acryl group and the methacryl group of the (meth)acrylic radically polymerizable compound are not particularly limited, but are preferably 200 g/eq. to 3000 g/eq., more preferably It is 300g/eq.~2000g/eq..

(D-2)(甲基)丙烯酸系自由基聚合性化合物的市售品,可列舉例如SABIC Innovative Plastics公司製之「SA9000」、「SA9000-111」(甲基丙烯酸改性聚苯醚)等。(D-2) Commercial products of the (meth)acrylic radical polymerizable compound include, for example, "SA9000" and "SA9000-111" (methacrylic acid-modified polyphenylene ether) manufactured by SABIC Innovative Plastics. .

樹脂組成物中之(D)成分之含量,無特別限定,樹脂組成物中之不揮發成分設為100質量%時,較佳為60質量%以下,更佳為50質量%以下,又更佳為40質量%以下,再更佳為30質量%以下,特佳為20質量%以下。樹脂組成物中之(D)成分之含量之下限無特別限定,樹脂組成物中之不揮發成分設為100質量%時,例如可為0質量%,0.1質量%以上,1質量%以上,3質量%以上,5質量%以上,7質量%以上等。The content of the component (D) in the resin composition is not particularly limited, but when the non-volatile matter in the resin composition is 100% by mass, it is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably It is 40 mass % or less, More preferably, it is 30 mass % or less, Especially preferably, it is 20 mass % or less. The lower limit of the content of component (D) in the resin composition is not particularly limited, but when the nonvolatile content in the resin composition is 100% by mass, for example, it can be 0% by mass, 0.1% by mass or more, 1% by mass or more, 3% by mass or more. mass % or more, 5 mass % or more, 7 mass % or more, etc.

<(E)無機填充材> 本發明之樹脂組成物,含有作為任意成分之(E)無機填充材的情形。(E)無機填充材係以粒子狀態包含於樹脂組成物中。<(E) Inorganic fillers> The resin composition of the present invention contains (E) an inorganic filler as an optional component. (E) The inorganic filler is contained in the resin composition in a particle state.

(E)無機填充材的材料,使用無機化合物。(E)無機填充材的材料,可列舉例如二氧化矽、氧化鋁、玻璃、菫藍石、二氧化矽、硫酸鋇、碳酸鋇、滑石、黏土、雲母粉、氧化鋅、水滑石、水鋁石、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、氧化鎂、氮化硼、氮化鋁、氮化錳、硼酸鋁、碳酸鍶、鈦酸鍶、鈦酸鈣、鈦酸鎂、鈦酸鉍、氧化鈦、氧化鋯、鈦酸鋇、鈦酸鋯酸鋇、鋯酸鋇、鋯酸鈣、磷酸鋯、磷鎢酸鋯、肥粒鐵、鐵系合金等。此等之中,特佳為二氧化矽。二氧化矽,可列舉例如非晶質二氧化矽、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。又,二氧化矽,較佳為球形二氧化矽。(E)無機填充材可1種類單獨使用,也可2種以上以任意比率組合使用。(E) As the material of the inorganic filler, an inorganic compound is used. (E) Materials for the inorganic filler include, for example, silica, alumina, glass, lapis lazuli, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, hydrated aluminum Stone, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, titanium Bismuth acid, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphotungstate, ferric iron, iron alloys, etc. Of these, particularly preferred is silicon dioxide. Silica includes, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. Also, the silica is preferably spherical silica. (E) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

(E)無機填充材之市售品,可列舉例如電化化學工業公司製之「UFP-30」;NIPPON STEEL & SUMIKIN MATERIALS公司製之「SP60-05」、「SP507-05」;admatechs公司製之「YC100C」、「YA050C」、「YA050C-MJE」、「YA010C」;Denka公司製之「UFP-30」;德山公司製之「SilFileNSS-3N」、「SilFileNSS-4N」、「SilFileNSS-5N」;admatechs公司製之「SC2500SQ」、「SO-C4」、「SO-C2」、「SO-C1」;Denka公司製之「DAW-03」、「FB-105FD」等。(E) Commercial products of inorganic fillers include, for example, "UFP-30" manufactured by Denka Chemical Industries, Ltd.; "SP60-05" and "SP507-05" manufactured by NIPPON STEEL & SUMIKIN MATERIALS; "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka Corporation; "SilFileNSS-3N", "SilFileNSS-4N", "SilFileNSS-5N" manufactured by Tokuyama Corporation ; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" made by admatechs company; "DAW-03", "FB-105FD" made by Denka company, etc.

(E)無機填充材之平均粒徑,無特別限定,較佳為10μm以下,更佳為5μm以下,又更佳為2μm以下,再更佳為1μm以下,特佳為0.7μm以下。(E)無機填充材之平均粒徑的下限,無特別限定,較佳為0.01μm以上,更佳為0.05μm以上,又更佳為0.1μm以上,特佳為0.2μm以上。(E)無機填充材之平均粒徑,可藉由依據Mie散射理論之雷射繞射•散射法測定。具體而言,藉由雷射繞射散射式粒徑分布測定裝置,以體積基準製作無機填充材之粒徑分布,可將該中值粒徑作為平均粒徑進行測定。測定樣品可使用以小玻璃瓶秤取無機填充材100mg、甲基乙基酮10g,並以超音波分散10分鐘者。使用雷射繞射式粒徑分布測定裝置,並使用光源波長為藍色及紅色,將測定樣品以液流電池方式測定無機填充材之體積基準的粒徑分布,由所得之粒徑分布,以中值粒徑算出平均粒徑。雷射繞射式粒徑分布測定裝置,可列舉例如堀場製作所公司製「LA-960」等。(E) The average particle size of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 2 μm or less, still more preferably 1 μm or less, and particularly preferably 0.7 μm or less. (E) The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. (E) The average particle size of the inorganic filler can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis by a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size can be measured as an average particle size. As the measurement sample, one that weighs 100 mg of the inorganic filler and 10 g of methyl ethyl ketone in a small glass bottle and disperses it with ultrasonic waves for 10 minutes can be used. Using a laser diffraction particle size distribution measuring device, and using the light source wavelengths as blue and red, the measurement sample is measured by a flow battery method to measure the volume-based particle size distribution of the inorganic filler, and from the obtained particle size distribution, as The median particle diameter was used to calculate the average particle diameter. As a laser diffraction particle size distribution measuring apparatus, "LA-960" manufactured by Horiba, Ltd., etc. is mentioned, for example.

(E)無機填充材之比表面積,無特別限定,較佳為0.1m2 /g以上,更佳為0.5m2 /g以上,又更佳為1m2 /g以上,特佳為3m2 /g以上。(E)無機填充材之比表面積的上限,無特別限定,較佳為100m2 /g以下,更佳為70m2 /g以下,又更佳為50m2 /g以下,特佳為40m2 /g以下。無機填充材的比表面積係依據BET法,使用比表面積測定裝置(MOUNTECH 公司製Macsorb HM-1210),使試料表面吸附氮氣,使用BET多點法算出比表面積而得到。(E) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m 2 /g or more, more preferably 0.5 m 2 /g or more, still more preferably 1 m 2 /g or more, and particularly preferably 3 m 2 /g or more g or more. (E) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100 m 2 /g or less, more preferably 70 m 2 /g or less, still more preferably 50 m 2 /g or less, particularly preferably 40 m 2 /g g or less. The specific surface area of the inorganic filler was obtained by using a specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH Co., Ltd.) according to the BET method, adsorbing nitrogen gas on the surface of the sample, and calculating the specific surface area using the BET multipoint method.

(E)無機填充材,較佳為以適當的表面處理劑進行表面處理。藉由表面處理,可提高(E)無機填充材之耐濕性及分散性。表面處理劑,可列舉例如乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷等之乙烯基系矽烷偶合劑;2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷等之環氧系矽烷偶合劑;p-苯乙烯基三甲氧基矽烷等之苯乙烯基系矽烷偶合劑;3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷等之甲基丙烯醯基系矽烷偶合劑;3-丙烯醯氧基丙基三甲氧基矽烷等之丙烯酸系矽烷偶合劑;N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽基-N-(1,3-二甲基-亞丁基)丙基胺、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-8-胺基辛基三甲氧基矽烷、N-(乙烯基苄基)-2-胺基乙基-3-胺基丙基三甲氧基矽烷等之胺基系矽烷偶合劑;三-(三甲氧基矽基丙基)異氰脲酸酯等之異氰脲酸酯系矽烷偶合劑;3-脲基丙基三烷氧基矽烷等之等之脲基系矽烷偶合劑;3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷等之巰基系矽烷偶合劑;3-異氰酸酯丙基三乙氧基矽烷等之異氰酸酯系矽烷偶合劑;3-三甲氧基矽基丙基琥珀酸酐等之酸酐系矽烷偶合劑;等之矽烷偶合劑;甲基三甲氧基矽烷、二甲基二甲氧基矽烷、苯基三甲氧基矽烷、甲基三乙氧基矽烷、二甲基二乙氧基矽烷、苯基三乙氧基矽烷、n-丙基三甲氧基矽烷、n-丙基三乙氧基矽烷、己基三甲氧基矽烷、己基三乙氧基矽烷、辛基三乙氧基矽烷、癸基三甲氧基矽烷、1,6-雙(三甲氧基矽基)己烷、三氟丙基三甲氧基矽烷等之非矽烷偶合-烷氧基矽烷化合物等。又,表面處理劑可1種類單獨使用,也可2種以上以任意比率組合使用。(E) The inorganic filler is preferably surface-treated with an appropriate surface-treating agent. The moisture resistance and dispersibility of the (E) inorganic filler can be improved by surface treatment. Examples of surface treatment agents include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane Epoxy silane coupling agents such as glycidoxypropyltriethoxysilane; styryl silane coupling agents such as p-styryltrimethoxysilane; 3-methacryloyloxypropyl Methyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyl Methacryloyl-based silane coupling agents such as triethoxysilane; acrylic silane coupling agents such as 3-acryloyloxypropyltrimethoxysilane; N-2-(aminoethyl)-3 -aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Propyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane , N-phenyl-8-aminooctyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, etc. Mixtures; isocyanurate-based silane coupling agents such as tris-(trimethoxysilylpropyl)isocyanurate; ureido-based silane coupling agents such as 3-ureidopropyltrialkoxysilane, etc. Mixtures; mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.; isocyanate-based silane coupling agents such as 3-isocyanatopropyltriethoxysilane; Anhydride-based silane coupling agents such as 3-trimethoxysilylpropyl succinic anhydride; etc. silane coupling agents; methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyl Triethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane Non-silane-coupled-alkanes of ethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane, etc. Oxysilane compounds, etc. Moreover, a surface treatment agent may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

表面處理劑之市售品,可列舉例如信越化學工業公司製之「KBM-1003」、「KBE-1003」(乙烯基系矽烷偶合劑);「KBM-303」、「KBM-402」、「KBM-403」、「KBE-402」、「KBE-403」(環氧系矽烷偶合劑);「KBM-1403」(苯乙烯基系矽烷偶合劑);「KBM-502」、「KBM-503」、「KBE-502」、「KBE-503」(甲基丙烯醯基系矽烷偶合劑);「KBM-5103」(丙烯酸系矽烷偶合劑);「KBM-602」、「KBM-603」、「KBM-903」、「KBE-903」、「KBE-9103P」、「KBM-573」、「KBM-575」(胺基系矽烷偶合劑);「KBM-9659」(異氰脲酸酯系矽烷偶合劑);「KBE-585」(脲基系矽烷偶合劑);「KBM-802」、「KBM-803」(巰基系矽烷偶合劑);「KBE-9007N」(異氰酸酯系矽烷偶合劑);「X-12-967C」(酸酐系矽烷偶合劑);「KBM-13」、「KBM-22」、「KBM-103」、「KBE-13」、「KBE-22」、「KBE-103」、「KBM-3033」、「KBE-3033」、「KBM-3063」、「KBE-3063」、「KBE-3083」、「KBM-3103C」、「KBM-3066」、「KBM-7103」(非矽烷偶合-烷氧基矽烷化合物)等。Commercially available surface treatment agents include, for example, "KBM-1003", "KBE-1003" (vinyl silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd.; "KBM-303", "KBM-402", " "KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agent); "KBM-1403" (styryl silane coupling agent); "KBM-502", "KBM-503" ", "KBE-502", "KBE-503" (methacryloyl silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575" (amine-based silane coupling agent); "KBM-9659" (isocyanurate-based silane coupling agent); "KBE-585" (urea-based silane coupling agent); "KBM-802", "KBM-803" (mercapto-based silane coupling agent); "KBE-9007N" (isocyanate-based silane coupling agent) ; "X-12-967C" (acid anhydride silane coupling agent); "KBM-13", "KBM-22", "KBM-103", "KBE-13", "KBE-22", "KBE-103" ", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" ( non-silane coupling-alkoxysilane compounds), etc.

藉由表面處理劑之表面處理的程度,就無機填充材之分散性提昇的觀點,較佳為在特定之範圍內。具體而言,無機填充材100質量%,較佳為以0.2質量%~5質量%之表面處理劑進行表面處理,更佳為以0.2質量%~3質量%進行表面處理,又更佳為以0.3質量%~2質量%進行表面處理。The degree of surface treatment by the surface treatment agent is preferably within a specific range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, the inorganic filler is 100% by mass, preferably 0.2% by mass to 5% by mass of the surface treatment agent, more preferably 0.2% by mass to 3% by mass, and more preferably 0.2% by mass to 3% by mass. 0.3 mass % to 2 mass % are surface-treated.

藉由表面處理劑之表面處理的程度,可藉由無機填充材之每單位表面積的碳量來進行評價。無機填充材之每單位表面積的碳量,就無機填充材之分散性提昇的觀點,較佳為0.02mg/m2 以上,更佳為0.1mg/m2 以上,又更佳為0.2mg/m2 以上。此外,就防止樹脂組成物之熔融黏度或薄片形態之熔融黏度上昇的觀點,較佳為1.0mg/m2 以下,更佳為0.8mg/m2 以下,又更佳為0.5mg/m2 以下。The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area 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 from the viewpoint of improving the dispersibility of the inorganic filler. 2 or more. In addition, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity of the sheet form, it is preferably 1.0 mg/m 2 or less, more preferably 0.8 mg/m 2 or less, and still more preferably 0.5 mg/m 2 or less. .

可將表面處理後之無機填充材藉由溶劑(例如,甲基乙基酮(MEK))進行洗淨處理後測定(E)無機填充材之每單位表面積的碳量。具體而言,將作為溶劑之充分量的MEK加入於以表面處理劑經表面處理的無機填充材中,在25℃下經5分鐘超音波洗淨。去除上清液,使固體成分乾燥後,使用碳分析計,可測定無機填充材之每單位表面積的碳量。碳分析計,可使用堀場製作所公司製「EMIA-320V」等。The surface-treated inorganic filler can be washed with a solvent (eg, methyl ethyl ketone (MEK)), and then (E) the amount of carbon per unit surface area of the inorganic filler can be measured. Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler surface-treated with a surface-treating agent, followed by ultrasonic cleaning at 25° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd., etc. can be used.

樹脂組成物中之(E)無機填充材之含量,無特別限定,樹脂組成物中之不揮發成分設為100質量%時,較佳可為90質量%以下,更佳可為80質量%以下,又更佳可為75質量%以下,特佳可為70質量%以下。樹脂組成物中之(E)無機填充材之含量的下限,無特別限定,樹脂組成物中之不揮發成分設為100質量%時,例如可為0質量%以上,1質量%以上,5質量%以上,10質量%以上等,較佳可為20質量%以上,更佳可為25質量%以上,又更佳可為35質量%以上,特佳可為40質量%以上等。The content of the (E) inorganic filler in the resin composition is not particularly limited, but when the nonvolatile content in the resin composition is 100% by mass, it is preferably 90% by mass or less, more preferably 80% by mass or less , more preferably 75 mass % or less, and particularly preferably 70 mass % or less. The lower limit of the content of the (E) inorganic filler in the resin composition is not particularly limited, but when the nonvolatile content in the resin composition is 100% by mass, for example, it may be 0% by mass or more, 1% by mass or more, and 5% by mass or more. % or more, 10 mass % or more, etc., preferably 20 mass % or more, more preferably 25 mass % or more, still more preferably 35 mass % or more, particularly preferably 40 mass % or more.

<(F)硬化促進劑> 本發明之樹脂組成物,有包含作為任意成分之(F)硬化促進劑的情形。一實施形態中,(F)硬化促進劑可有促進(A)成分與(B)成分及(C)成分(及當包含(D)成分時(D)成分)等之加成反應之觸媒的機能。<(F) Hardening accelerator> The resin composition of the present invention may contain (F) a curing accelerator as an optional component. In one embodiment, the hardening accelerator (F) may have a catalyst that promotes the addition reaction of the component (A), the component (B), the component (C) (and the component (D) when the component (D) is included), etc. function.

(F)硬化促進劑,可列舉例如(F-1)咪唑系硬化促進劑、(F-2)磷系硬化促進劑、(F-3)脲系硬化促進劑、(F-4)胍系硬化促進劑、(F-5)金屬系硬化促進劑、(F-6)胺系硬化促進劑等。一實施形態中,(F)硬化促進劑,較佳為包含(F-1)咪唑系硬化促進劑。(F)硬化促進劑可1種單獨使用,亦可組合2種以上來使用。(F) Curing accelerators, for example, (F-1) imidazole-based curing accelerators, (F-2) phosphorus-based curing accelerators, (F-3) urea-based curing accelerators, (F-4) guanidine-based curing accelerators Hardening accelerators, (F-5) metal-based hardening accelerators, (F-6) amine-based hardening accelerators, and the like. In one embodiment, the (F) curing accelerator preferably contains (F-1) an imidazole-based curing accelerator. (F) A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

(F-1)咪唑系硬化促進劑,可列舉例如2-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、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甲酸鹽、1-氰基乙基-2-苯基咪唑鎓偏苯三甲酸鹽、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-三嗪異三聚氰酸加成物、2-苯基咪唑異三聚氰酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2,3-二氫-1H-吡咯並[1,2-a]苯并咪唑、1-十二烷基-2-甲基-3-苄基咪唑鎓氯化物、2-甲基咪唑啉、2-苯基咪唑啉等之咪唑化合物及咪唑化合物與環氧樹脂的加合物。(F-1) Imidazole-based hardening accelerators, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl- 4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2- Methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 2-Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl yl-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'-methylimidazolyl-(1')]-ethyl-s -Triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl -5-Hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride , 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds and adducts of imidazole compounds and epoxy resins.

(F-1)咪唑系硬化促進劑,可使用市售品,可列舉例如四國化成工業公司製之「1B2PZ」、「2MZA-PW」、「2PHZ-PW」、Mitsubishi Chemical公司製之「P200-H50」等。(F-1) Imidazole-based hardening accelerator, commercially available products can be used, for example, "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Chemical Co., Ltd., "P200" manufactured by Mitsubishi Chemical Co., Ltd. -H50" etc.

(F-2)磷系硬化促進劑,可列舉例如四丁基溴化鏻、四丁基氯化膦、四丁基鏻乙酸酯、四丁基鏻癸酸酯、四丁基鏻月桂酸酯、雙(四丁基鏻)均苯四酸酯、四丁基鏻氫六氫化苯二甲酸酯、四丁基鏻2,6-雙[(2-羥基-5-甲基苯基)甲基]-4-甲基苯酚鹽(Phenolate)、二-tert-丁基甲基鏻四苯基硼酸鹽等之脂肪族鏻鹽;甲基三苯基溴化鏻、乙基三苯基溴化鏻、丙基三苯基溴化鏻、丁基三苯基溴化鏻、苄基三苯基鏻氯化物、四苯基鏻溴化物、p-甲苯基三苯基鏻四-p-甲苯基硼酸鹽、四苯基鏻四苯基硼酸鹽、四苯基鏻四p-甲苯基硼酸鹽、三苯基乙基鏻四苯基硼酸鹽、三(3-甲基苯基)乙基鏻四苯基硼酸鹽、三(2-甲氧基苯基)乙基鏻四苯基硼酸鹽、(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之芳香族鏻鹽;三苯基膦•三苯基硼烷等之芳香族膦•硼烷複合體;三苯基膦•p-苯醌加成反應物等之芳香族膦•醌加成反應物;三丁基膦、三-tert-丁基膦、三辛基膦、二-tert-丁基(2-丁烯基)膦、二-tert-丁基(3-甲基-2-丁烯基)膦、三環己基膦等之脂肪族膦;二丁基苯基膦、二-tert-丁基苯基膦、甲基二苯基膦、乙基二苯基膦、丁基二苯基膦、二苯基環己基膦、三苯基膦、三-o-甲苯基膦、三-m-甲苯基膦、三-p-甲苯基膦、三(4-乙基苯基)膦、三(4-丙基苯基)膦、三(4-異丙基苯基)膦、三(4-丁基苯基)膦、三(4-tert-丁基苯基)膦、三(2,4-二甲基苯基)膦、三(2,5-二甲基苯基)膦、三(2,6-二甲基苯基)膦、三(3,5-二甲基苯基)膦、三(2,4,6-三甲基苯基)膦、三(2,6-二甲基-4-乙氧基苯基)膦、三(2-甲氧基苯基)膦、三(4-甲氧基苯基)膦、三(4-乙氧基苯基)膦、三(4-tert-丁氧基苯基)膦、二苯基-2-吡啶基膦、1,2-雙(二苯基膦基)乙烷、1,3-雙(二苯基膦基)丙烷、1,4-雙(二苯基膦基)丁烷、1,2-雙(二苯基膦基)乙炔、2,2’-雙(二苯基膦基)二苯醚等之芳香族膦等。(F-2) Phosphorus-based curing accelerator, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium caprate, tetrabutylphosphonium lauric acid Esters, bis(tetrabutylphosphonium) pyromellitic acid ester, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl) Aliphatic phosphonium salts such as methyl]-4-methylphenolate (Phenolate), di-tert-butylmethylphosphonium tetraphenylborate, etc.; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide , propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylboronic acid salt, tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium tetra-p-tolyl borate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenyl borate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate , Aromatic phosphonium salts such as butyltriphenylphosphonium thiocyanate, etc.; aromatic phosphine-borane complexes such as triphenylphosphine, triphenylborane, etc.; triphenylphosphine, p-benzoquinone, etc. Aromatic phosphine and quinone addition reactants such as reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di- Aliphatic phosphines such as tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine, etc.; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine Phosphine, Ethyldiphenylphosphine, Butyldiphenylphosphine, Diphenylcyclohexylphosphine, Triphenylphosphine, Tris-o-Tolylphosphine, Tris-m-Tolylphosphine, Tris-p-Tolylphosphine phosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-isopropylphenyl)phosphine -tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl) Phosphine, Tris(3,5-dimethylphenyl)phosphine, Tris(2,4,6-trimethylphenyl)phosphine, Tris(2,6-dimethyl-4-ethoxyphenyl) Phosphine, Tris(2-methoxyphenyl)phosphine, Tris(4-methoxyphenyl)phosphine, Tris(4-ethoxyphenyl)phosphine, Tris(4-tert-butoxyphenyl) Phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenyl) Aromatic phosphines such as phosphino)butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino)diphenyl ether, and the like.

(F-3)脲系硬化促進劑,可列舉例如1,1-二甲基脲;1,1,3-三甲基脲、3-乙基-1,1-二甲基脲、3-環己基-1,1-二甲基脲、3-環辛基-1,1-二甲基脲等之脂肪族二甲基脲;3-苯基-1,1-二甲基脲、3-(4-氯苯基)-1,1-二甲基脲、3-(3,4-二氯苯基)-1,1-二甲基脲、3-(3-氯-4-甲基苯基)-1,1-二甲基脲、3-(2-甲基苯基)-1,1-二甲基脲、3-(4-甲基苯基)-1,1-二甲基脲、3-(3,4-二甲基苯基)-1,1-二甲基脲、3-(4-異丙基苯基)-1,1-二甲基脲、3-(4-甲氧基苯基)-1,1-二甲基脲、3-(4-硝基苯基)-1,1-二甲基脲、3-[4-(4-甲氧基苯氧基)苯基]-1,1-二甲基脲、3-[4-(4-氯苯氧基)苯基]-1,1-二甲基脲、3-[3-(三氟甲基)苯基]-1,1-二甲基脲、N,N-(1,4-伸苯基)雙(N’,N’-二甲基脲)、N,N-(4-甲基-1,3-伸苯基)雙(N’,N’-二甲基脲)[甲苯雙二甲基脲]等之芳香族二甲基脲等。(F-3) Urea-based hardening accelerators, for example, 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3- Aliphatic dimethyl urea such as cyclohexyl-1,1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3 -(4-Chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylurea phenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-di Methyl urea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3- (4-Methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxy Phenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trimethylurea Fluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4 Aromatic dimethylurea such as -methyl-1,3-phenylene)bis(N',N'-dimethylurea)[toluenebisdimethylurea], etc.

(F-4)胍系硬化促進劑,可列舉例如雙氰胺、1-甲基胍、1-乙基胍、1-環己基胍、1-苯基胍、1-(o-甲苯基)胍、二甲基胍、二苯基胍、三甲基胍、四甲基胍、五甲基胍、1,5,7-三氮雙環[4.4.0]癸-5-烯、7-甲基-1,5,7-三氮雙環[4.4.0]癸-5-烯、1-甲基雙胍、1-乙基雙胍、1-n-丁基雙胍、1-n-十八烷基雙胍、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-(o-甲苯基)雙胍等。(F-4) A guanidine-based curing accelerator, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, and 1-(o-tolyl) Guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methylguanidine yl-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.

(F-5)金屬系硬化促進劑,可列舉例如鈷、銅、鋅、鐵、鎳、錳、錫等之金屬之有機金屬錯合物或有機金屬鹽。有機金屬錯合物之具體例,可列舉乙醯丙酮鈷(II)、乙醯丙酮鈷(III)等之有機鈷錯合物、乙醯丙酮銅(II)等之有機銅錯合物、乙醯丙酮鋅(II)等之有機鋅錯合物、乙醯丙酮鐵(III)等之有機鐵錯合物、乙醯丙酮鎳(II)等之有機鎳錯合物、乙醯丙酮錳(II)等之有機錳錯合物等。有機金屬鹽,可列舉例如辛酸鋅、辛酸錫、環烷酸鋅、環烷酸鈷、硬脂酸錫、硬脂酸鋅等。(F-5) Metal-based hardening accelerators include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organocobalt complexes such as cobalt acetylacetonate (II), cobalt acetylacetonate (III), etc., organocopper complexes such as copper acetylacetonate (II), etc. Organozinc complexes such as zinc (II) acetylacetonate, organoiron complexes such as iron (III) acetylacetonate, organonickel complexes such as nickel (II) acetylacetonate, manganese (II) acetylacetonate ) and other organic manganese complexes, etc. The organic metal salts include, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

(F-6)胺系硬化促進劑,可列舉例如三乙基胺、三丁基胺等之三烷基胺、4-二甲基胺基吡啶、苄基二甲基胺、2,4,6,-三(二甲基胺基甲基)苯酚、1,8-二氮雙環(5,4,0)-十一碳烯等。(F-6) Amine-based hardening accelerators, such as triethylamine, tributylamine and other trialkylamines, 4-dimethylaminopyridine, benzyldimethylamine, 2,4, 6,-Tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc.

(F-6)胺系硬化促進劑,可使用市售品,可列舉例如ajinomoto-fine-techno公司製之「MY-25」等。(F-6) As an amine-based hardening accelerator, a commercial item can be used, for example, "MY-25" manufactured by ajinomoto-fine-techno company, etc. are mentioned.

樹脂組成物中之(F)硬化促進劑之含量,無特別限定,樹脂組成物中之不揮發成分設為100質量%時,較佳為10質量%以下,更佳為5質量%以下,又更佳為3質量%以下,特佳為1質量%以下。樹脂組成物中之(F)硬化促進劑之含量的下限,無特別限定,樹脂組成物中之不揮發成分設為100質量%時、例如可為0質量%以上,0.001質量%以上,0.01質量%以上,0.1質量%以上,0.5質量%以上等。The content of the (F) hardening accelerator in the resin composition is not particularly limited, but when the nonvolatile content in the resin composition is 100% by mass, it is preferably 10% by mass or less, more preferably 5% by mass or less, and More preferably, it is 3 mass % or less, and particularly preferably 1 mass % or less. The lower limit of the content of the (F) hardening accelerator in the resin composition is not particularly limited, and when the nonvolatile content in the resin composition is 100% by mass, for example, it may be 0% by mass or more, 0.001% by mass or more, and 0.01% by mass. % or more, 0.1 mass % or more, 0.5 mass % or more, etc.

<(G)其他的添加劑> 本發明之樹脂組成物,也可包含作為不揮發成分之任意的添加劑。這種添加劑,可列舉例如酚系硬化劑、硫醇系硬化劑等之(A)成分以外的硬化劑;環氧樹脂、環氧丙烯酸酯樹脂、胺基甲酸酯丙烯酸酯樹脂、胺基甲酸酯樹脂、氰酸酯樹脂、苯並噁嗪樹脂、不飽和聚酯樹脂、酚樹脂、三聚氰胺樹脂、聚矽氧樹脂、苯氧基樹脂等之熱硬化性樹脂;過氧化物系自由基聚合起始劑、偶氮系自由基聚合起始劑等之自由基聚合起始劑;聚乙烯醇縮乙醛樹脂、聚烯烴樹脂、聚碸樹脂、聚醚碸樹脂、聚苯醚樹脂、聚碳酸酯樹脂、聚醚醚酮樹脂、聚酯樹脂等之熱塑性樹脂;橡膠粒子等之有機填充材;有機銅化合物、有機鋅化合物、有機鈷化合物等之有機金屬化合物;酞菁藍、酞菁綠、碘綠、重氮黃、結晶紫、氧化鈦、碳黑等之著色劑;對苯二酚、兒茶酚、鄰苯三酚、吩噻嗪等之聚合抑制劑;聚矽氧系平坦劑、丙烯酸聚合物系平坦劑等之平坦劑;Benton、微晶高嶺石等之增黏劑;聚矽氧系消泡劑、丙烯酸系消泡劑、氟系消泡劑、乙烯基樹脂系消泡劑等之消泡劑;苯并三唑系紫外線吸收劑等之紫外線吸收劑;脲矽烷等之接著性提昇劑;三唑系密著性賦予劑、四唑系密著性賦予劑、三嗪系密著性賦予劑等之密著性賦予劑;受阻酚系抗氧化劑、受阻胺系抗氧化劑等之抗氧化劑;茋衍生物等之螢光增白劑;氟系界面活性劑、聚矽氧系界面活性劑等之界面活性劑;磷系難燃劑(例如磷酸酯化合物、磷腈化合物、膦酸化合物、紅磷)、氮系難燃劑(例如硫酸三聚氰胺)、鹵素系難燃劑、無機系難燃劑(例如三氧化銻)等之難燃劑;磷酸酯系分散劑、聚氧化烯系分散劑、乙炔系分散劑、聚矽氧系分散劑、陰離子性分散劑、陽離子性分散劑等之分散劑;硼酸鹽系安定劑、鈦酸酯系安定劑、鋁酸鹽系安定劑、鋯酸鹽系安定劑、異氰酸酯系安定劑、羧酸系安定劑、羧酸酐系安定劑等之安定劑等。(G)其他的添加劑,可1種類單獨使用,也可2種以上以任意比率組合使用。(G)其他的添加劑之含量,只要是熟悉該項技藝者可適宜設定。<(G) Other additives> The resin composition of the present invention may contain optional additives as nonvolatile components. Examples of such additives include curing agents other than the component (A) such as phenol-based curing agents and thiol-based curing agents; epoxy resins, epoxy acrylate resins, urethane acrylate resins, and urethane resins. Thermosetting resins such as ester resins, cyanate ester resins, benzoxazine resins, unsaturated polyester resins, phenol resins, melamine resins, polysiloxane resins, phenoxy resins, etc.; peroxide-based radical polymerization Radical polymerization initiators such as initiators, azo radical polymerization initiators, etc.; Thermoplastic resins such as ester resins, polyetheretherketone resins, polyester resins, etc.; organic fillers such as rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds, organic cobalt compounds; phthalocyanine blue, phthalocyanine green, Coloring agents for iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, etc.; polymerization inhibitors for hydroquinone, catechol, pyrogallol, phenothiazine, etc.; polysiloxane-based leveling agent, Acrylic polymer-based leveling agent and other flattening agents; Benton, microcrystalline kaolinite and other tackifiers; polysiloxane-based defoamer, acrylic-based defoamer, fluorine-based defoamer, vinyl resin-based defoamer Defoamers such as benzotriazole-based UV absorbers; UV absorbers such as benzotriazole-based UV absorbers; adhesion promoters such as urea silanes; Adhesion-imparting agents such as adhesion-imparting agents; antioxidants such as hindered phenol-based antioxidants, hindered amine-based antioxidants, etc.; optical brighteners such as stilbene derivatives; fluorine-based surfactants, polysiloxane-based Surfactants such as surfactants; phosphorus-based flame retardants (such as phosphate ester compounds, phosphazene compounds, phosphonic acid compounds, red phosphorus), nitrogen-based flame retardants (such as melamine sulfate), halogen-based flame retardants, inorganic flame retardants Flame retardants such as flame retardants (such as antimony trioxide); phosphate ester dispersants, polyoxyalkylene dispersants, acetylene dispersants, polysiloxane dispersants, anionic dispersants, cationic dispersants Dispersants such as borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, carboxylic acid anhydride stabilizers, etc. Stabilizers, etc. (G) Other additives may be used alone or in combination of two or more in any ratio. (G) The content of other additives can be appropriately set as long as those skilled in the art are skilled in the art.

<(H)有機溶劑> 本發明之樹脂組成物,除上述不揮發成分以外,作為揮發性成分,有再含有任意有機溶劑的情形。(H)有機溶劑,可適宜使用公知者,其種類無特別限定。(H)有機溶劑,可列舉例如丙酮、甲基乙基酮、甲基異丁酮、環己酮等之酮系溶劑;乙酸甲酯、乙酸乙酯、乙酸丁酯、乙酸異丁酯、乙酸異戊酯、丙酸甲酯、丙酸乙酯、γ-丁內酯等之酯系溶劑;四氫吡喃、四氫呋喃、1,4-二噁烷、二乙醚、二異丙醚、二丁醚、二苯醚等之醚系溶劑;甲醇、乙醇、丙醇、丁醇、乙二醇等之醇系溶劑;乙酸2-乙氧基乙基、丙二醇單甲醚乙酸酯、二乙二醇單乙醚乙酸酯、乙基二乙二醇乙酸酯、γ-丁內酯、甲氧基丙酸甲酯等之醚酯系溶劑;乳酸甲酯、乳酸乙酯、2-羥基異丁酸甲酯等之酯醇系溶劑;2-甲氧基丙醇、2-甲氧基乙醇、2-乙氧基乙醇、丙二醇單甲醚、二乙二醇單丁醚(丁基卡必醇)等之醚醇系溶劑;N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮等之醯胺系溶劑;二甲基亞碸等之亞碸系溶劑;乙腈、丙腈等之腈系溶劑;己烷、環戊烷、環己烷、甲基環己烷等之脂肪族烴系溶劑;苯、甲苯、二甲苯、乙基苯、三甲基苯等之芳香族烴系溶劑等。(H)有機溶劑可1種類單獨使用,也可2種以上以任意比率組合使用。<(H) Organic solvent> The resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the above-mentioned nonvolatile components. (H) As an organic solvent, a well-known thing can be used suitably, and the kind is not specifically limited. (H) Organic solvent, for example, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, acetic acid Ester solvents such as isopentyl, methyl propionate, ethyl propionate, γ-butyrolactone, etc.; tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl Ether, diphenyl ether and other ether solvents; methanol, ethanol, propanol, butanol, ethylene glycol and other alcohol solvents; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol Alcohol monoethyl ether acetate, ethyl diethylene glycol acetate, γ-butyrolactone, methyl methoxypropionate and other ether ester solvents; methyl lactate, ethyl lactate, 2-hydroxyisobutyl Ester alcohol solvents such as methyl acid; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol) ) and other ether alcohol-based solvents; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other amide-based solvents; dimethylsulfoxide Nitrile-based solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon-based solvents such as hexane, cyclopentane, cyclohexane, methylcyclohexane, etc.; benzene, toluene, xylene, ethyl Aromatic hydrocarbon solvents such as benzene, trimethylbenzene, etc. (H) An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

一實施形態中,(H)有機溶劑之含量,無特別限定,樹脂組成物中之全成分設為100質量%時,例如可為60質量%以下,40質量%以下,30質量%以下,20質量%以下,15質量%以下,10質量%以下等。In one embodiment, the content of (H) the organic solvent is not particularly limited, and when the total components in the resin composition are set to 100% by mass, for example, it may be 60% by mass or less, 40% by mass or less, 30% by mass or less, and 20% by mass or less. mass % or less, 15 mass % or less, 10 mass % or less, etc.

<樹脂組成物之製造方法> 本發明之樹脂組成物,例如藉由在任意的調製容器中,將(A)具有聯苯骨架之胺化合物,(B)具有碳原子數為7以上之脂肪鏈之馬來醯亞胺化合物,(C)不具有碳原子數為7以上之脂肪鏈之馬來醯亞胺化合物,必要時(D)任意的自由基聚合性化合物,必要時(E)無機填充材,必要時(F)硬化促進劑,必要時(G)其他的添加劑,及必要時(H)有機溶劑,以任意的順序,及/或一部分或全部同時加入混合來製造。又,加入各成分進行混合的過程,可適宜設定溫度,可暫時或至始至終進行加熱及/或冷卻。又,在加入進行混合的過程中,或其後,例如可使用混合機等之攪拌裝置或振盪裝置,將樹脂組成物進行攪拌或振盪,使均勻地分散。又,也可攪拌或振盪同時,在真空下等的低壓條件下進行脫泡。<Manufacturing method of resin composition> In the resin composition of the present invention, for example, in an arbitrary preparation container, (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, (C) Maleimide compound not having an aliphatic chain having 7 or more carbon atoms, (D) optional radical polymerizable compound if necessary, (E) inorganic filler if necessary, (F) hardening if necessary Accelerator, (G) other additives if necessary, and (H) organic solvent if necessary, are added and mixed in any order, and/or a part or all of them are simultaneously added and mixed to manufacture. In addition, in the process of adding and mixing each component, the temperature can be appropriately set, and heating and/or cooling can be performed temporarily or throughout. In addition, in the process of adding and mixing, or after that, the resin composition can be uniformly dispersed by stirring or shaking the resin composition using, for example, a stirring device such as a mixer or a shaking device. In addition, the defoaming may be performed under low pressure conditions such as under vacuum while stirring or shaking.

<樹脂組成物之特性> 本發明之樹脂組成物,包含(A)具有聯苯骨架之胺化合物,(B)具有碳原子數為7以上之脂肪鏈之馬來醯亞胺化合物,及(C)不具有碳原子數為7以上之脂肪鏈之馬來醯亞胺化合物。藉由使用這種樹脂組成物,可得到比電容量(Dk)及介電正切(Df)低,且電鍍導體層之剝離強度優異的硬化物。<Characteristics of resin composition> The resin composition of the present invention comprises (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) a Maleimide compounds with aliphatic chains above 7. By using such a resin composition, a cured product having low specific capacitance (Dk) and dielectric tangent (Df) and excellent peel strength of the plated conductor layer can be obtained.

本發明之樹脂組成物之硬化物,可具有介電正切(Df)低的特徵。因此,一實施形態中,如下述試驗例1,以5.8GHz、23℃下測定時之樹脂組成物之硬化物的介電正切(Df),較佳可為0.020以下,0.010以下,更佳可為0.008以下,0.007以下,又更佳可為0.006以下,0.005以下,特佳可為0.004以下,0.003以下。The cured product of the resin composition of the present invention can have a low dielectric tangent (Df). Therefore, in one embodiment, as in Test Example 1 below, the dielectric tangent (Df) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. is preferably 0.020 or less, 0.010 or less, more preferably 0.020 or less. It is 0.008 or less, 0.007 or less, more preferably 0.006 or less, 0.005 or less, particularly preferably 0.004 or less, 0.003 or less.

本發明之樹脂組成物的硬化物,可具有比電容量(Dk)低的特徵。因此,一實施形態中,如下述試驗例1,以5.8GHz、23℃測定時之樹脂組成物之硬化物的比電容量(Dk),較佳可為5.0以下,更佳可為4.0以下,又更佳可為3.5以下,再更佳可為3.0以下,特佳可為2.9以下。The cured product of the resin composition of the present invention may have a low specific capacitance (Dk). Therefore, in one embodiment, as in Test Example 1 below, the specific capacitance (Dk) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. is preferably 5.0 or less, more preferably 4.0 or less, Still more preferably, it is 3.5 or less, still more preferably 3.0 or less, and particularly preferably 2.9 or less.

本發明之樹脂組成物的硬化物,可具有優異之電鍍導體層的剝離強度。因此,一實施形態中,如下述試驗例2,硬化物形成鍍銅導體層,在垂直方向,由鍍銅導體層剝離時的荷重算出的鍍銅剝離強度,較佳可為0.2kgf/cm以上,更佳可為0.3kgf/cm以上,又更佳可為0.35kgf/cm以上,特佳可為0.4kgf/cm以上。上限無特別限定,例如可為10kgf/cm以下等。The cured product of the resin composition of the present invention can have excellent peel strength of the electroplated conductor layer. Therefore, in one embodiment, as in Test Example 2 below, the cured product forms a copper-plated conductor layer, and the copper-plated peel strength calculated from the load when the copper-plated conductor layer is peeled off in the vertical direction is preferably 0.2 kgf/cm or more. , more preferably 0.3kgf/cm or more, still more preferably 0.35kgf/cm or more, and particularly preferably 0.4kgf/cm or more. The upper limit is not particularly limited, but may be, for example, 10 kgf/cm or less.

一實施形態中,本發明之樹脂組成物之硬化物,可具有粗化處理後之表面之算術平均粗糙度(Ra)低的特徵。因此,一實施形態中,如下述試驗例2,測定之粗化處理後之硬化物表面的算術平均粗糙度(Ra),較佳可為300nm以下,更佳可為200nm以下,又更佳可為150nm以下,再更佳可為120nm以下,特佳可為100nm以下。下限無特別限定,例如可為1nm以上,2nm以上等。In one embodiment, the cured product of the resin composition of the present invention may have a feature of low arithmetic mean roughness (Ra) of the surface after roughening treatment. Therefore, in one embodiment, as in the following Test Example 2, the arithmetic mean roughness (Ra) of the surface of the cured product after the roughening treatment measured is preferably 300 nm or less, more preferably 200 nm or less, and more preferably 200 nm or less. It is 150 nm or less, more preferably 120 nm or less, and particularly preferably 100 nm or less. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more, or the like.

<樹脂組成物之用途> 本發明之樹脂組成物,適合作為絕緣用途之樹脂組成物,特別是形成絕緣層用之樹脂組成物使用。具體而言,可適合作為形成於絕緣層上之導體層(包含再配線層)形成用之該絕緣層形成用的樹脂組成物(形成導體層用之絕緣層形成用樹脂組成物)使用。又,後述之印刷配線板中,可適合作為印刷配線板之絕緣層形成用的樹脂組成物(印刷配線板之絕緣層形成用樹脂組成物)使用。本發明之樹脂組成物,可廣範圍使用於樹脂薄片、預浸體等之薄片狀積層材料、阻焊劑、底部填充材料、黏晶材、半導體封裝材料、埋孔樹脂、零件埋入樹脂等需要樹脂組成物的用途。<Application of resin composition> The resin composition of the present invention is suitable for use as a resin composition for insulating purposes, especially a resin composition for forming an insulating layer. Specifically, it can be suitably used as the resin composition for forming the insulating layer (the resin composition for forming the insulating layer for forming the conductor layer) for forming the conductor layer (including the rewiring layer) formed on the insulating layer. Moreover, in the printed wiring board mentioned later, it can be used suitably as the resin composition for insulating layer formation of a printed wiring board (the resin composition for insulating layer formation of a printed wiring board). The resin composition of the present invention can be widely used in sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die-bonding materials, semiconductor packaging materials, buried-hole resins, and parts-embedded resins. Use of resin compositions.

又,例如,經由以下之(1)~(6)步驟,製造半導體晶片封裝時,本發明之樹脂組成物,可適合作為形成再配線層用之絕緣層之再配線形成層用的樹脂組成物(再配線形成層形成用的樹脂組成物),及半導體晶片封裝用之樹脂組成物(半導體晶片封裝用的樹脂組成物)使用。製造半導體晶片封裝時,在密封層上可進一步形成再配線層。 (1)基材上積層暫時固定薄膜的步驟, (2)將半導體晶片暫時固定於暫時固定薄膜上的步驟, (3)半導體晶片上形成密封層的步驟, (4)將基材及暫時固定薄膜由半導體晶片剝離的步驟, (5)在經剝離半導體晶片之基材及暫時固定薄膜的面,形成作為絕緣層之再配線形成層的步驟,及 (6)再配線形成層上,形成作為導體層之再配線層的步驟Further, for example, when a semiconductor chip package is produced through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for a rewiring forming layer for forming an insulating layer for a rewiring layer (resin composition for rewiring formation layer formation), and resin composition for semiconductor wafer encapsulation (resin composition for semiconductor wafer encapsulation) are used. When manufacturing a semiconductor chip package, a rewiring layer may be further formed on the sealing layer. (1) the step of laminating the temporary fixing film on the base material, (2) the step of temporarily fixing the semiconductor wafer on the temporary fixing film, (3) the step of forming the sealing layer on the semiconductor wafer, (4) the step of peeling off the base material and the temporary fixing film from the semiconductor wafer, (5) a step of forming a rewiring formation layer as an insulating layer on the surface of the peeled-off base material of the semiconductor wafer and the temporarily fixed thin film, and (6) Step of forming a rewiring layer as a conductor layer on the rewiring formation layer

又,本發明之樹脂組成物,帶來零件埋入性良好的絕緣層,故適合使用於印刷配線板為零件內藏電路板的情形。In addition, the resin composition of the present invention provides an insulating layer with good component embeddability, so it is suitable for use in a case where the printed wiring board is a component embeddable circuit board.

<薄片狀積層材料> 本發明之樹脂組成物,也可以清漆狀態塗佈使用,工業上,一般適合以含有該樹脂組成物之薄片狀積層材料的形態使用。<Laminated sheet material> The resin composition of the present invention can also be used by coating in a varnish state, and industrially, it is generally suitable for use in the form of a sheet-like laminate containing the resin composition.

薄片狀積層材料,較佳為以下所示之樹脂薄片、預浸體。The sheet-like laminate material is preferably a resin sheet or a prepreg shown below.

一實施形態中,樹脂薄片係含有支撐體與設置於該支撐體上之樹脂組成物層而成,樹脂組成物層係由本發明之樹脂組成物所形成。In one embodiment, the resin sheet includes a support and a resin composition layer provided on the support, and the resin composition layer is formed of the resin composition of the present invention.

樹脂組成物層之厚度,就即使印刷配線板之薄型化、及該樹脂組成物之硬化物為薄膜時,也可提供絕緣性優異之硬化物的觀點,較佳為50μm以下,更佳為40μm以下。樹脂組成物層之厚度的下限,無特別限定,通常可為5μm以上,10μm以上等。The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm from the viewpoint of providing a cured product excellent in insulating properties even when the printed wiring board is thinned and the cured product of the resin composition is a thin film the following. The lower limit of the thickness of the resin composition layer is not particularly limited, but it is usually 5 μm or more, 10 μm or more, or the like.

支撐體可列舉例如由塑膠材料所構成的薄膜、金屬箔、脫模紙,較佳為由塑膠材料所構成的薄膜、金屬箔。Examples of the support include films, metal foils, and release papers made of plastic materials, and preferably films and metal foils made of plastic materials.

作為支撐體使用由塑膠材料所構成的薄膜時,塑膠材料可列舉例如聚對苯二甲酸乙二酯(以下有時簡稱為「PET」)、聚萘二甲酸乙二酯(以下有時簡稱為「PEN」)等之聚酯、聚碳酸酯(以下有時簡稱為「PC」)、聚甲基丙烯酸甲酯(PMMA)等之丙烯酸、環狀聚烯烴、三乙醯基纖維素(TAC)、聚醚硫化物(PES)、聚醚酮、聚醯亞胺等。其中,較佳為聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯,特佳為廉價的聚對苯二甲酸乙二酯。When a film made of a plastic material is used as the support, the plastic material includes, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter sometimes abbreviated as "PET"). Polyester such as "PEN"), polycarbonate (sometimes referred to as "PC" hereinafter), acrylic acid such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC) , polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

作為支撐體使用金屬箔時,金屬箔可列舉例如銅箔、鋁箔等,較佳為銅箔。銅箔可使用由銅之單金屬所構成的箔,也可使用銅與其他的金屬(例如,錫、鉻、銀、鎂、鎳、鋯、矽、鈦等)之合金所構成的箔。When using a metal foil as a support body, a copper foil, an aluminum foil, etc. are mentioned, for example, a copper foil is preferable. As the copper foil, a foil composed of a single metal of copper, or a foil composed of an alloy of copper and other metals (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

支撐體與樹脂組成物層接合的面,可施予消光處理、電暈處理。The surface where the support and the resin composition layer are bonded may be subjected to matting treatment or corona treatment.

又,作為支撐體,也可使用與樹脂組成物層接合之面具有脫模層之附脫模層的支撐體。附脫模層的支撐體之脫模層所使用的脫模劑,可列舉例如選自由醇酸樹脂、聚烯烴樹脂、胺基甲酸酯樹脂、及聚矽氧樹脂所成群之1種以上的脫模劑。附脫模層的支撐體可使用市售品,可列舉例如具有以醇酸樹脂系脫模劑為主成分之脫模層的PET薄膜,Lintec公司製之「SK-1」、「AL-5」、「AL-7」;東麗公司製之「lumirror T60」;帝人公司製之「Purex」;unitika公司製之「unipeel」等。Moreover, as a support body, the support body with a mold release layer which has a mold release layer on the surface joined to the resin composition layer can also be used. The mold release agent used for the mold release layer of the mold release layer-attached support includes, for example, one or more selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and polysiloxane resins. release agent. As the support with a release layer, a commercially available product can be used, for example, a PET film having a release layer containing an alkyd resin-based release agent as a main component, "SK-1" and "AL-5" manufactured by Lintec Co., Ltd. ", "AL-7"; "lumirror T60" made by Toray; "Purex" made by Teijin; "unipeel" made by unitika, etc.

支撐體之厚度,無特別限定,較佳為5μm~ 75μm之範圍,更佳為10μm~60μm之範圍。又,使用附脫模層的支撐體時,附脫模層之支撐體全體的厚度在上述範圍內較佳。The thickness of the support body is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. Moreover, when the support body with a mold release layer is used, it is preferable that the thickness of the whole support body with a mold release layer is in the said range.

一實施形態中,樹脂薄片必要時可進一步含有任意的層。此任意的層,可列舉例如設置於樹脂組成物層之未與支撐體接合的面(亦即,與支撐體相反側之面),依據支撐體的保護薄膜。保護薄膜的厚度,無特別限定,例如為1μm~40μm。藉由積層保護薄膜,可抑制對樹脂組成物層之表面之汙垢等之附著或傷痕。In one embodiment, the resin sheet may further contain an arbitrary layer if necessary. The optional layer includes, for example, a protective film provided on the surface of the resin composition layer not joined to the support (that is, the surface opposite to the support), depending on the support. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion of dirt or the like to the surface of the resin composition layer or scratches.

樹脂薄片,例如液狀之樹脂組成物可直接,或調製將樹脂組成物溶解於有機溶劑的樹脂清漆,將此使用模塗佈機等,塗佈於支撐體上,使乾燥形成樹脂組成物層來製造。The resin sheet, such as a liquid resin composition, can be used as it is, or a resin varnish prepared by dissolving the resin composition in an organic solvent can be applied to a support using a die coater, etc., and dried to form a resin composition layer. to manufacture.

有機溶劑,可列舉與作為樹脂組成物之成分說明之有機溶劑相同者。有機溶劑可1種單獨使用,也可組合2種以上使用。As the organic solvent, the same ones as those described as components of the resin composition can be exemplified. The organic solvent may be used alone or in combination of two or more.

乾燥可藉由加熱、吹熱風等習知的方法來實施。乾燥條件無特別限定,使樹脂組成物層中之有機溶劑之含量乾燥至成為10質量%以下,較佳為成為5質量%以下。也因樹脂組成物或樹脂清漆中之有機溶劑的沸點而異,例如使用含有30質量%~60質量%之有機溶劑之樹脂組成物或樹脂清漆時,藉由在50℃~150℃下使乾燥3分鐘~10分鐘,可形成樹脂組成物層。Drying can be carried out by conventional methods such as heating and blowing hot air. The drying conditions are not particularly limited, but the content of the organic solvent in the resin composition layer is dried to be 10% by mass or less, preferably 5% by mass or less. It also varies depending on the boiling point of the organic solvent in the resin composition or resin varnish. For example, when using a resin composition or resin varnish containing an organic solvent of 30% by mass to 60% by mass, dry it at 50°C to 150°C. The resin composition layer can be formed in 3 minutes to 10 minutes.

樹脂薄片可捲繞成捲筒狀保存。樹脂薄片具有保護薄膜時,可剝離保護薄膜後來使用。The resin sheet can be wound into a roll and stored. When the resin sheet has a protective film, the protective film can be peeled off and used later.

一實施形態中,預浸體係將本發明之樹脂組成物含浸於薄片狀纖維基材所形成。In one embodiment, the prepreg system is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.

預浸體所使用的薄片狀纖維基,無特別限定,可使用作為玻璃布、芳香族聚醯胺不織布、液晶聚合物不織布等之預浸體用基材常用者。就印刷配線板之薄型化的觀點,薄片狀纖維基材的厚度,較佳為50μm以下,更佳為40μm以下,又更佳為30μm以下,特佳為20μm以下。薄片狀纖維基材之厚度的下限,無特別限定。通常為10μm以上。The sheet-like fiber base used for the prepreg is not particularly limited, and those commonly used as substrates for prepregs such as glass cloth, aromatic polyamide nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fibrous base material is not particularly limited. Usually 10 μm or more.

預浸體可藉由熱熔法、溶劑法等之習知的方法來製造。The prepreg can be produced by a conventional method such as a hot melt method and a solvent method.

預浸體之厚度,可與上述樹脂薄片中之樹脂組成物層相同的範圍。The thickness of the prepreg can be in the same range as the resin composition layer in the above-mentioned resin sheet.

本發明之薄片狀積層材料,適合使用於形成印刷配線板之絕緣層(印刷配線板的絕緣層用),適合使用於形成印刷配線板之層間絕緣層(印刷配線板之層間絕緣層用)。The sheet-like laminate material of the present invention is suitable for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and is suitable for forming an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board).

<印刷配線板> 本發明之印刷配線板,包含使本發明之樹脂組成物硬化所得之硬化物所構成的絕緣層。<Printed wiring board> The printed wiring board of the present invention includes an insulating layer composed of a cured product obtained by curing the resin composition of the present invention.

印刷配線板例如使用上述樹脂薄片,可藉由包含下述(I)及(II)之步驟的方法來製造。 (I)在內層基板上,使樹脂薄片之樹脂組成物層與內層基板接合的方式,積層樹脂薄片的步驟 (II)使樹脂組成物層硬化(例如熱硬化),形成絕緣層的步驟The printed wiring board can be manufactured by a method including the steps of the following (I) and (II) using, for example, the above-mentioned resin sheet. (1) The method of bonding the resin composition layer of the resin sheet to the inner-layer substrate on the inner-layer substrate, and the step of laminating the resin sheet (II) Step of curing the resin composition layer (eg, thermosetting) to form an insulating layer

步驟(I)使用之「內層基板」係指成為印刷配線板之基板的構件,可列舉例如玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚苯醚基板等。又,該基板之單面或兩面可具有導體層,此導體層可經圖型加工。基板之單面或兩面形成有導體層(電路)的內層基板,有時稱為「內層電路基板」。又,製造印刷配線板時,進一步,形成有絕緣層及/或導體層之中間製造物也包含在本發明所謂的「內層基板」內。印刷配線板為零件內藏電路板時,可使用內藏零件的內層基板。The "inner layer substrate" used in step (I) refers to a member that becomes a substrate of a printed wiring board, such as glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting type Polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one side or both sides, and the conductor layer may be patterned. An inner layer substrate in which a conductor layer (circuit) is formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit substrate". In addition, when manufacturing a printed wiring board, further, an intermediate product having an insulating layer and/or a conductor layer formed thereon is also included in the so-called "inner layer substrate" of the present invention. When the printed wiring board is a circuit board with built-in components, an inner-layer substrate with built-in components can be used.

內層基板與樹脂薄片之積層,例如可將樹脂薄片由支撐體側加熱壓接於內層基板來進行。將樹脂薄片加熱壓接於內層基板的構件(以下稱為「加熱壓接構件」),可列舉例如被加熱之金屬板(SUS鏡板等)或金屬輥(SUS輥)等。又,並非將加熱壓接構件直接壓製於樹脂薄片,而是使樹脂薄片充分地追随內層基板之表面凹凸,經由耐熱橡膠等之彈性材進行壓製較佳。The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding of the resin sheet to the inner layer substrate from the support side. The member for thermocompression bonding of the resin sheet to the inner layer substrate (hereinafter referred to as "thermocompression bonding member") includes, for example, a heated metal plate (SUS mirror plate, etc.), a metal roll (SUS roll), and the like. In addition, instead of pressing the thermocompression-bonding member directly on the resin sheet, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface unevenness of the inner layer substrate.

內層基板與樹脂薄片之積層,可藉由真空積層法實施。真空積層法中,加熱壓接溫度,較佳為60℃~160℃,更佳為80℃~140℃之範圍,加熱壓接壓力,較佳為0.098MPa~1.77MPa,更佳為0.29MPa~1.47MPa之範圍,加熱壓接時間,較佳為20秒鐘~400秒鐘,更佳為30秒鐘~300秒鐘的範圍。積層較佳為壓力26.7hPa以下的減壓條件下實施。The lamination of the inner layer substrate and the resin sheet can be carried out by a vacuum lamination method. In the vacuum lamination method, the heating and crimping temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heating and crimping pressure is preferably 0.098MPa to 1.77MPa, more preferably 0.29MPa~ In the range of 1.47MPa, the heating and crimping time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure at a pressure of 26.7 hPa or less.

積層可藉由市售之真空積層機進行。市售之真空積層機,可列舉例如名機製作所公司製之真空加壓式積層機、nikko-materials公司製之真空塗佈機、分批式真空加壓積層機等。Lamination can be performed by a commercially available vacuum laminator. As a commercially available vacuum laminator, the vacuum pressurization type|mold laminator by Meiki Seisakusho Co., Ltd., the vacuum coater by Nikko-Materials Co., Ltd., the batch type vacuum pressurization lamination machine, etc. are mentioned, for example.

積層後,在常壓下(大氣壓下),例如可藉由將加熱壓接構件由支撐體側進行壓製,經積層之樹脂薄片可進行平滑化處理。平滑化處理之壓製條件,可與上述積層之加熱壓接條件相同的條件。平滑化處理可藉由市售積層機進行。又,積層與平滑化處理可使用上述市售真空積層機,連續地進行。After lamination, the laminated resin sheet can be smoothed under normal pressure (atmospheric pressure), for example, by pressing the thermocompression-bonding member from the support side. The pressing conditions for the smoothing treatment may be the same as the above-mentioned thermocompression bonding conditions for the laminate. The smoothing process can be performed by a commercially available laminator. In addition, the lamination and smoothing process can be performed continuously using the above-mentioned commercially available vacuum lamination machine.

支撐體可在步驟(I)與步驟(II)之間去除,也可在步驟(II)後去除。The support may be removed between step (I) and step (II), or may be removed after step (II).

步驟(II)中,將樹脂組成物層硬化(例如熱硬化),形成由樹脂組成物之硬化物所構成的絕緣層。樹脂組成物層之硬化條件,無特別限定,形成印刷配線板之絕緣層時,可使用通常採用的條件。In step (II), the resin composition layer is cured (eg, thermally cured) to form an insulating layer composed of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and generally used conditions can be used when forming the insulating layer of the printed wiring board.

例如,樹脂組成物層之熱硬化條件係因樹脂組成物的種類等而異,一實施形態中,硬化溫度較佳可為120℃~240℃,更佳為150℃~220℃,又更佳為170℃~210℃。硬化時間,較佳為5分鐘~120分鐘,更佳為10分鐘間~100分鐘,又更佳為15分鐘~100分鐘。For example, the thermal curing conditions of the resin composition layer vary depending on the type of the resin composition. In one embodiment, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and more It is 170℃~210℃. The hardening time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and still more preferably 15 minutes to 100 minutes.

使樹脂組成物層熱硬化之前,可將樹脂組成物層以比硬化溫度低的溫度,進行預備加熱。例如,將樹脂組成物層熱硬化之前,以50℃~120℃,較佳為60℃~115℃,更佳為70℃~110℃的溫度,可將樹脂組成物層預備加熱5分鐘以上,較佳為5分鐘~150分鐘,更佳為15分鐘~120分鐘,又更佳為15分鐘~100分鐘。Before thermally curing the resin composition layer, the resin composition layer may be pre-heated at a temperature lower than the curing temperature. For example, before thermosetting the resin composition layer, the resin composition layer may be preliminarily heated for 5 minutes or more at a temperature of 50°C to 120°C, preferably 60°C to 115°C, and more preferably 70°C to 110°C. It is preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and still more preferably 15 minutes to 100 minutes.

製造印刷配線板時,可進一步實施(III)在絕緣層進行開孔的步驟、(IV)將絕緣層進行粗化處理的步驟、(V)形成導體層的步驟。此等之步驟(III)至步驟(V),用於印刷配線板製造之熟悉該項技藝者,可依據公知的各種方法來實施。又,在步驟(II)後去除支撐體時,該支撐體之去除,可在步驟(II)與步驟(III)之間、步驟(III)與步驟(IV)之間、或步驟(IV)與步驟(V)之間實施。又,必要時,步驟(II)~步驟(V)之絕緣層及導體層之形成,可重複實施形成多層配線板。When manufacturing a printed wiring board, (III) the step of opening a hole in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming the conductor layer can be further carried out. These steps (III) to (V), for those skilled in the art for the manufacture of printed wiring boards, can be implemented according to various known methods. In addition, when the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or between step (IV) between step (V). In addition, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) can be repeated to form a multilayer wiring board.

其他的實施形態中,本發明之印刷配線板可使用上述預浸體來製造。製造方法,基本上與使用樹脂薄片的情形相同。In other embodiment, the printed wiring board of this invention can be manufactured using the said prepreg. The manufacturing method is basically the same as the case of using the resin sheet.

步驟(III)係在絕緣層開孔的步驟,藉此在絕緣層,可形成導通孔、通孔等之孔。步驟(III)係因應絕緣層形成所使用之樹脂組成物的組成等,例如可使用鑽頭、雷射、電漿等來實施。孔之尺寸或形狀可依據印刷配線板之設計適宜決定。Step (III) is a step of opening holes in the insulating layer, whereby holes such as via holes, through holes, etc. can be formed in the insulating layer. The step (III) can be implemented by using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used for forming the insulating layer. The size or shape of the holes can be appropriately determined according to the design of the printed wiring board.

步驟(IV)係將絕緣層進行粗化處理的步驟。通常,此步驟(IV)中,去除膠渣。粗化處理之順序、條件,無特別限定,形成印刷配線板的絕緣層時,可採用通常使用之公知之順序、條件。例如,藉由膨潤液之膨潤處理、利用氧化劑之粗化處理、利用中和液之中和處理依此順序實施,可將絕緣層進行粗化處理。Step (IV) is a step of roughening the insulating layer. Typically, in this step (IV), the smear is removed. The order and conditions of the roughening treatment are not particularly limited, and when the insulating layer of the printed wiring board is formed, well-known procedures and conditions generally used can be adopted. For example, the insulating layer can be roughened by performing swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

粗化步驟可使用之膨潤液,無特別限定,可列舉鹼溶液、界面活性劑溶液等,較佳為鹼溶液,該鹼溶液,更佳為氫氧化鈉溶液、氫氧化鉀溶液。市售的膨潤液,可列舉例如atotech Japan公司製「Swelling Dip Securiganth P」、「Swelling Dip Securiganth SBU」等。藉由膨潤液之膨潤處理,無特別限定,例如,在30℃~90℃之膨潤液中,將絕緣層浸漬1分鐘~20分鐘來進行。就絕緣層之樹脂的膨潤壓抑至適度水平的觀點,較佳為在40℃~80℃之膨潤液中,使絕緣層浸漬5分鐘~15分鐘。The swelling liquid that can be used in the roughening step is not particularly limited, and examples thereof include alkali solutions, surfactant solutions, etc., preferably alkali solutions, and more preferably sodium hydroxide solutions and potassium hydroxide solutions. Commercially available swelling liquids include, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. The swelling treatment by the swelling liquid is not particularly limited, but for example, the insulating layer is immersed in the swelling liquid at 30° C. to 90° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid of 40° C. to 80° C. for 5 minutes to 15 minutes.

粗化處理所使用的氧化劑,無特別限定,可列舉例如氫氧化鈉之水溶液中溶解有過錳酸鉀或過錳酸鈉的鹼性過錳酸溶液。藉由鹼性過錳酸溶液等之氧化劑的粗化處理,較佳為加熱至60℃~100℃的氧化劑溶液中,將絕緣層浸漬10分鐘~30分鐘。又,鹼性過錳酸溶液中之過錳酸鹽的濃度,較佳為5質量%~10質量%。市售之氧化劑,可列舉例如atotech Japan公司製之「Concentrate Compact CP」、「Dosing Solution Securiganth P」等之鹼性過錳酸溶液。The oxidizing agent used for the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. By the roughening treatment of an oxidizing agent such as an alkaline permanganic acid solution, the insulating layer is preferably immersed in an oxidizing agent solution heated to 60° C. to 100° C. for 10 minutes to 30 minutes. In addition, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan.

又,粗化處理所使用的中和液,較佳為酸性的水溶液,市售品可列舉例如atotech Japan公司製之「Reduction solution Securiganth P」。In addition, the neutralizing liquid used for the roughening treatment is preferably an acidic aqueous solution, and as a commercial product, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan can be mentioned.

利用中和液之處理係將經氧化劑之粗化處理的處理面,在30℃~80℃之中和液中浸漬5分鐘~30分鐘來進行。從作業性等的觀點,較佳為將藉由氧化劑之粗化處理的對象物,在40℃~70℃之中和液中,浸漬5分鐘~20分鐘的方法。The treatment with the neutralizing solution is performed by immersing the treated surface roughened by the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object to be roughened by the oxidizing agent in a neutralizing liquid at 40° C. to 70° C. for 5 minutes to 20 minutes is preferable.

一實施形態中,粗化處理後之絕緣層表面的均方根粗糙度(Rq),較佳為500nm以下,更佳為400nm以下,又更佳為300nm以下。下限無特別限定,例如可為1nm以上、2nm以上等。均方根粗糙度(Rq)可使用非接觸型表面粗糙度計測定。In one embodiment, the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and still more preferably 300 nm or less. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more, or the like. The root mean square roughness (Rq) can be measured using a non-contact surface roughness meter.

步驟(V)係形成導體層的步驟,在絕緣層上形成導體層。導體層所使用之導體材料,無特別限定。較佳實施形態中,導體層含有選自由金、鉑、鈀、銀、銅、鋁、鈷、鉻、鋅、鎳、鈦、鎢、鐵、錫及銦所構成群組中之1種以上的金屬。導體層可為單金屬層,也可為合金層,合金層可列舉例如由選自上述群之2種以上之金屬合金(例如,鎳•鉻合金、銅•鎳合金及銅•鈦合金)所形成的層。其中,就導體層形成之泛用性、成本、圖型化之容易性等的觀點,較佳為鉻、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,更佳為鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅之單金屬層、或鎳•鉻合金之合金層,又更佳為銅之單金屬層。The step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains at least one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, formed of two or more metal alloys (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy) selected from the above-mentioned group. formed layer. Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or a single metal layer of nickel, from the viewpoints of versatility, cost, easiness of patterning, etc., for forming the conductor layer is preferred. •Alloy layer of 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 a single metal layer of copper.

導體層也可為單層構造,也可為不同種類之金屬或合金所構成的單金屬層或合金層積層2層以上的多層構造。導體層為多層構造時,與絕緣層接觸的層,較佳為鉻、鋅或鈦之單金屬層、或鎳•鉻合金之合金層。The conductor layer may be a single-layer structure, or may be a multi-layer structure in which two or more layers of a single metal layer or an alloy layer of different kinds of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

導體層之厚度係因所期望之印刷配線板之設計,一般為3μm~35μm,較佳為5μm~30μm。The thickness of the conductor layer depends on the desired design of the printed wiring board, and is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

一實施形態中,導體層可藉由鍍敷形成。例如,藉由半加成法、全加成法等之以往公知的技術,在絕緣層表面鍍敷,可形成具有所期望之配線圖型的導體層,就製造之簡便性的觀點,較佳為藉由半加成法形成。以下,顯示藉由半加成法形成導體層之例。In one embodiment, the conductor layer can be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method, which is preferable from the viewpoint of easiness of manufacture. to be formed by the semi-additive method. Hereinafter, an example in which the conductor layer is formed by the semi-additive method is shown.

首先,在絕緣層表面,藉由無電鍍形成電鍍晶種層。接著,在形成之電鍍晶種層上,形成與所期望之配線圖型對應,使電鍍晶種層之一部分露出的遮罩圖型。露出的電鍍晶種層上,藉由電鍍形成金屬層後,去除遮罩圖型。然後,藉由蝕刻等去除不要的電鍍晶種層,可形成具有所期望之配線圖型的導體層。First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern for exposing a part of the plating seed layer corresponding to a desired wiring pattern is formed. On the exposed electroplating seed layer, after forming a metal layer by electroplating, the mask pattern is removed. Then, by removing the unnecessary plating seed layer by etching or the like, a conductor layer having a desired wiring pattern can be formed.

其他的實施形態中,導體層可使用金屬箔形成。使用金屬箔,形成導體層時,步驟(V)在步驟(I)與步驟(II)之間實施較佳。例如,步驟(I)後,去除支撐體,在露出之樹脂組成物層的表面,積層金屬箔。樹脂組成物層與金屬箔之積層,可藉由真空積層法實施。積層之條件,可與步驟(I)說明之條件相同。接著,實施步驟(II),形成絕緣層。然後,利用絕緣層上之金屬箔,藉由減去性製程、模擬半加成法等之以往公知的技術,可形成具有所期望之配線圖型的導體層。In other embodiments, the conductor layer may be formed using metal foil. When the conductor layer is formed using metal foil, the step (V) is preferably performed between the step (I) and the step (II). For example, after the step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil can be carried out by a vacuum lamination method. The conditions for lamination may be the same as those described in step (I). Next, step (II) is carried out to form an insulating layer. Then, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by conventionally known techniques such as a subtractive process and an analog semi-additive method.

金屬箔例如可藉由電解法、壓延法等之習知的方法製造。金屬箔之市售品,可列舉例如JX日礦日石金屬公司製之HLP箔、JXUT-III箔、三井金屬礦山公司製之3EC-III箔、TP-III箔等。The metal foil can be produced by a conventional method such as an electrolytic method and a rolling method, for example. As a commercial item of metal foil, HLP foil, JXUT-III foil, 3EC-III foil, TP-III foil by Mitsui Metal Mining Co., Ltd. made by JX Nippon Mining Co., Ltd., etc. are mentioned, for example.

<半導體裝置> 本發明之半導體裝置,包含本發明之印刷配線板。本發明之半導體裝置可使用本發明之印刷配線板製造。<Semiconductor device> The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

半導體裝置,可列舉供給電氣製品(例如,電腦、行動電話、數位相機及電視等)及交通工具(例如,摩托車、汽車、電車、船舶及航空機等)等之各種半導體裝置。Examples of semiconductor devices include various semiconductor devices supplied to electrical products (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

[實施例][Example]

以下藉由實施例更具體說明本發明。本發明不受此等之實施例限定。又,以下,表示量的「份」及「%」,無特別聲明時,分別表示「質量份」及「質量%」。特別是無指定溫度時之溫度條件為室溫(25℃)。Hereinafter, the present invention will be described in more detail by way of examples. The present invention is not limited by these embodiments. In addition, in the following, "part" and "%" indicating the amount, unless otherwise specified, indicate "part by mass" and "% by mass", respectively. In particular, the temperature condition when there is no specified temperature is room temperature (25°C).

<實施例1> 將含有聯苯骨架之胺化合物(日本化藥公司製「BAN」)10份、脂肪族馬來醯亞胺化合物(Designer molecules公司製「BMI-689」)20份、芳香族馬來醯亞胺化合物(日本化藥公司製「MIR-3000-70MT」、固體成分70%之MEK/甲苯混合溶液)28.6份、咪唑系硬化促進劑(四國化成工業公司製「1B2PZ」、1-苄基-2-苯基咪唑)1份,以矽烷偶合劑(信越化學工業公司製「KBM-573」、N-苯基-3-胺基丙基三甲氧基矽烷)進行表面處理的球形二氧化矽(admatechs公司製「SO-C2」、平均粒徑0.5μm、比表面積5.8m2 /g)60份混合,使用高速旋轉混合機均勻地分散,調製樹脂組成物。<Example 1> 10 parts of an amine compound containing a biphenyl skeleton (“BAN” manufactured by Nippon Kayaku Co., Ltd.), 20 parts of an aliphatic maleimide compound (“BMI-689” manufactured by Designer molecules Co., Ltd.), and an aromatic Maleimide compound ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., MEK/toluene mixed solution with a solid content of 70%) 28.6 parts, imidazole-based hardening accelerator ("1B2PZ" manufactured by Shikoku Chemical Industry Co., Ltd., 1 part of 1-benzyl-2-phenylimidazole), surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane) 60 parts of spherical silica ("SO-C2" manufactured by Admatechs, average particle size 0.5 μm, specific surface area 5.8 m 2 /g) were mixed and uniformly dispersed using a high-speed rotary mixer to prepare a resin composition.

<實施例2> 除了使用脂肪族馬來醯亞胺化合物(Designer molecules公司製「BMI-1500」)20份,取代脂肪族馬來醯亞胺化合物(Designer molecules公司製「BMI-689」)20份外,與實施例1相同調製樹脂組成物。<Example 2> Except using 20 parts of aliphatic maleimide compound (“BMI-1500” manufactured by Designer molecules) in place of 20 parts of aliphatic maleimide compound (“BMI-689” manufactured by Designer molecules), the same Example 1 The resin composition was prepared in the same manner.

<實施例3> 除了使用脂肪族馬來醯亞胺化合物(Designer molecules公司製「BMI-2500」)20份,取代脂肪族馬來醯亞胺化合物(Designer molecules公司製「BMI-689」)20份外,與實施例1相同調製樹脂組成物。<Example 3> Except using 20 parts of aliphatic maleimide compound (“BMI-2500” manufactured by Designer Molecules Co., Ltd.) instead of 20 parts of aliphatic maleimide compound (“BMI-689” manufactured by Designer molecules Co., Ltd.) Example 1 The resin composition was prepared in the same manner.

<實施例4> 除了使用脂肪族馬來醯亞胺化合物(Designer molecules公司製「BMI-3000J」)20份,取代脂肪族馬來醯亞胺化合物(Designer molecules公司製「BMI-689」)20份外,與實施例1相同調製樹脂組成物。<Example 4> Except using 20 parts of aliphatic maleimide compound (“BMI-3000J” manufactured by Designer Molecules Co., Ltd.) instead of 20 parts of aliphatic maleimide compound (“BMI-689” manufactured by Designer molecules Co., Ltd.) Example 1 The resin composition was prepared in the same manner.

<實施例5> 除了使用芳香族馬來醯亞胺化合物(Designer molecules公司製「BMI-6100」)20份,取代芳香族馬來醯亞胺化合物(日本化藥公司製「MIR-3000-70MT」、固體成分70%之MEK/甲苯混合溶液)28.6份外,實施例2同樣調製樹脂組成物。<Example 5> In addition to using 20 parts of an aromatic maleimide compound (“BMI-6100” manufactured by Designer Molecules), instead of an aromatic maleimide compound (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd.), 70 parts of solid content % MEK/toluene mixed solution) 28.6 parts, the resin composition was prepared in the same manner as in Example 2.

<實施例6> 除了使用芳香族馬來醯亞胺化合物(Designer molecules公司製「BMI-6100」)20份,取代芳香族馬來醯亞胺化合物(日本化藥公司製「MIR-3000-70MT」、固體成分70%之MEK/甲苯混合溶液)28.6份外,實施例3同樣調製樹脂組成物。<Example 6> In addition to using 20 parts of an aromatic maleimide compound (“BMI-6100” manufactured by Designer Molecules), instead of an aromatic maleimide compound (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd.), 70 parts of solid content % MEK/toluene mixed solution) 28.6 parts, the resin composition was prepared similarly in Example 3.

<實施例7> 除了將芳香族馬來醯亞胺化合物(日本化藥公司製「MIR-3000-70MT」、固體成分70%之MEK/甲苯混合溶液)之使用量由28.6份變更為14.3份,進一步使用芳香族馬來醯亞胺化合物(Designer molecules公司製「BMI-6100」)10份外,與實施例2同樣調製樹脂組成物。<Example 7> In addition to changing the usage amount of the aromatic maleimide compound (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd., a MEK/toluene mixed solution with a solid content of 70%) from 28.6 parts to 14.3 parts, an aromatic A resin composition was prepared in the same manner as in Example 2 except for 10 parts of a maleimide compound (“BMI-6100” manufactured by Designer Molecules).

<實施例8> 準備以發明協會公開技報公技編號2020-500211號之合成例1所記載之方法合成之下述式(X)表示之馬來醯亞胺化合物A(Mw/Mn=1.81、v”=1.47(主要為1、2或3))之MEK溶液(不揮發成分70質量%)。<Example 8> A maleimide compound A represented by the following formula (X) (Mw/Mn=1.81, v”=1.47 was prepared by the method described in Synthesis Example 1 of the Invention Association Publication No. 2020-500211 (mainly 1, 2 or 3)) of MEK solution (non-volatile content 70 mass %).

Figure 02_image045
Figure 02_image045

除了使用芳香族馬來醯亞胺化合物(式(X)表示之馬來醯亞胺化合物A、固體成分70質量%之MEK溶液)28.6份,取代芳香族馬來醯亞胺化合物(日本化藥公司製「MIR-3000-70MT」、固體成分70%之MEK/甲苯混合溶液)28.6份外,與實施例2同樣調製樹脂組成物。In addition to using 28.6 parts of an aromatic maleimide compound (maleimide compound A represented by the formula (X), a MEK solution with a solid content of 70% by mass), instead of an aromatic maleimide compound (Nihon Kayaku) A resin composition was prepared in the same manner as in Example 2, except that the company's "MIR-3000-70MT", a MEK/toluene mixed solution with a solid content of 70%) was 28.6 parts.

<實施例9> 除了將以矽烷偶合劑(信越化學工業公司製「KBM-573」、N-苯基-3-胺基丙基三甲氧基矽烷)進行表面處理之球形二氧化矽(admatechs公司製「SO-C2」)之使用量由60份變更為70份,進一步使用乙烯基苄基改性聚苯醚(三菱瓦斯化學公司製「OPE-2St 2200」、固體成分65%之甲苯溶液)15.4份外,與實施例2同樣調製樹脂組成物。<Example 9> Except for spherical silica ("SO-C2" manufactured by admatechs, Inc. ”) was changed from 60 parts to 70 parts, and 15.4 parts of vinylbenzyl-modified polyphenylene ether (“OPE-2St 2200” manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a solid content of 65%) was used in addition to 15.4 parts. In Example 2, a resin composition was prepared in the same manner.

<實施例10> 除了將以矽烷偶合劑(信越化學工業公司製「KBM-573」、N-苯基-3-胺基丙基三甲氧基矽烷)進行表面處理的球形二氧化矽(admatechs公司製「SO-C2」)之使用量,由60份變更為70份,進一步使用甲基丙烯酸改性聚苯醚(將SABIC Innovative Plastics公司製「SA9000-111」作為固體成分50%之甲苯溶液者)20份外,與實施例2同樣調製樹脂組成物。<Example 10> Except for spherical silica (“SO-C2” manufactured by Admatechs, Inc.) treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane) ”) was changed from 60 parts to 70 parts, and 20 parts of methacrylic acid-modified polyphenylene ether (“SA9000-111” manufactured by SABIC Innovative Plastics Co., Ltd. was used as a toluene solution with a solid content of 50%) was used. A resin composition was prepared in the same manner as in Example 2.

<實施例11> 除了將以矽烷偶合劑(信越化學工業公司製「KBM-573」、N-苯基-3-胺基丙基三甲氧基矽烷)進行表面處理的球形二氧化矽(admatechs公司製「SO-C2」)之使用量,由60份變更為70份,進一步使用二乙烯基苯/苯乙烯共聚物(NIPPON STEEL Chemical & Material公司製「ODV-XET-X04」、固體成分65%之甲苯溶液)15.4份外,與實施例2同樣調製樹脂組成物。<Example 11> Except for spherical silica (“SO-C2” manufactured by Admatechs, Inc.) treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane) ”) was changed from 60 parts to 70 parts, and a divinylbenzene/styrene copolymer (“ODV-XET-X04” manufactured by NIPPON STEEL Chemical & Material Co., Ltd., a toluene solution with a solid content of 65%) was used for 15.4 A resin composition was prepared in the same manner as in Example 2 except for the parts.

<比較例1> 除了未使用脂肪族馬來醯亞胺化合物(Designer molecules公司製「BMI-689」)20份,且將芳香族馬來醯亞胺化合物(日本化藥公司製「MIR-3000-70MT」、固體成分70%之MEK/甲苯混合溶液)之使用量,由28.6份變更為57.1份外,與實施例1相同調製樹脂組成物。<Comparative Example 1> In addition to not using 20 parts of an aliphatic maleimide compound (“BMI-689” manufactured by Designer molecules), an aromatic maleimide compound (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd.), solid A resin composition was prepared in the same manner as in Example 1, except that the usage amount of MEK/toluene mixed solution with a composition of 70%) was changed from 28.6 parts to 57.1 parts.

<比較例2> 除了將脂肪族馬來醯亞胺化合物(Designer molecules公司製「BMI-689」)之使用量,由20份變更為10份,使用不含聯苯骨架之胺化合物(日本化藥公司製「A-A」)10份,取代含有聯苯骨架之胺化合物(日本化藥公司製「BAN」)10份外,與實施例1相同調製樹脂組成物。<Comparative Example 2> In addition to changing the amount of the aliphatic maleimide compound (“BMI-689” manufactured by Designer molecules) from 20 parts to 10 parts, an amine compound without a biphenyl skeleton (“A-A” manufactured by Nippon Kayaku Co., Ltd.) was used. ”) 10 parts, except that 10 parts of the amine compound (“BAN” manufactured by Nippon Kayaku Co., Ltd.) containing a biphenyl skeleton was replaced, a resin composition was prepared in the same manner as in Example 1.

<試驗例1:比電容量(Dk)及介電正切(Df)之測定> 準備具備脫模層之聚對苯二甲酸乙二酯薄膜(琳得科公司製「AL5」、厚度38μm),作為支撐體。此支撐體之脫模層上,均勻地塗佈實施例及比較例所得之樹脂組成物,使乾燥後之樹脂組成物層的厚度成為40μm。然後,將樹脂組成物以80℃~100℃(平均90℃)使乾燥4分鐘,得到包含支撐體及樹脂組成物層的樹脂薄片A。<Test example 1: Measurement of specific capacitance (Dk) and dielectric tangent (Df)> A polyethylene terephthalate film (“AL5” manufactured by Lintec Co., Ltd., thickness 38 μm) provided with a mold release layer was prepared as a support. On the mold release layer of this support, the resin compositions obtained in Examples and Comparative Examples were uniformly coated so that the thickness of the resin composition layer after drying was 40 μm. Then, the resin composition was dried at 80° C. to 100° C. (average 90° C.) for 4 minutes to obtain a resin sheet A including a support and a resin composition layer.

將所得之樹脂薄片A以190℃的烤箱,硬化90分鐘。藉由從烤箱取出的樹脂薄片A,剝離支撐體後,得到樹脂組成物層的硬化物。將其硬化物切成長度80mm、寬2mm,作為評價用硬化物B。The obtained resin sheet A was cured in an oven at 190° C. for 90 minutes. The cured product of the resin composition layer was obtained by peeling the support from the resin sheet A taken out from the oven. The cured product was cut into pieces with a length of 80 mm and a width of 2 mm, and was used as a cured product B for evaluation.

關於評價用硬化物B,使用Agilent Technologies(AgilentTechnologies)公司製「HP8362B」,藉由共振腔微擾法(Cavity Perturbation Method),在測定頻率5.8GHz、測定溫度23℃下,測定介電常數之值(Dk值)及介電正切之值(Df值)。以2支的試驗片進行測定,算出其平均。Regarding the cured product B for evaluation, the value of the dielectric constant was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by using “HP8362B” manufactured by Agilent Technologies, Inc. by the Cavity Perturbation Method. (Dk value) and the value of dielectric tangent (Df value). The measurement was performed on two test pieces, and the average was calculated.

<試驗例2:剝離強度及算術平均粗糙度(Ra)之測定> (1)內層基板之準備 形成有內層電路支玻璃布基材環氧樹脂兩面貼銅積層板(銅箔之厚度18μm、基板之厚度0.4mm、panasonic公司製「R1515A」)的兩面以微蝕刻劑(MEC公司製「CZ8101」)蝕刻1μm,進行銅表面之粗化處理。<Test example 2: Measurement of peel strength and arithmetic mean roughness (Ra)> (1) Preparation of inner layer substrate On both sides of the epoxy resin double-sided copper-clad laminate (copper foil thickness 18μm, substrate thickness 0.4mm, "R1515A" manufactured by Panasonic Corporation) with inner layer circuit support glass cloth base material ”) to etch 1 μm to roughen the copper surface.

(2)樹脂薄片A之積層 使用分批式真空加壓積層機(nikko-materials公司製、2載台增層積層機「CVP700」),使樹脂組成物層接觸內層基板方式,將試驗例1得到的樹脂薄片A積層於內層基板的兩面。積層係30秒鐘減壓,將氣壓調整為13hPa以下後,以120℃,壓力0.74MPa,壓接30秒來實施。接著,以100℃、壓力0.5MPa下,熱壓60秒鐘。(2) Lamination of resin sheet A Using a batch-type vacuum pressure laminator (manufactured by Nikko-Materials, Inc., 2-stage build-up laminator "CVP700"), the resin composition layer was brought into contact with the inner layer substrate, and the resin sheet A obtained in Test Example 1 was laminated on Both sides of the inner substrate. The lamination system was decompressed for 30 seconds, and the air pressure was adjusted to 13 hPa or less, followed by pressure bonding at 120° C. and a pressure of 0.74 MPa for 30 seconds. Next, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 60 seconds.

(3)樹脂組成物層之熱硬化 然後,將積層有樹脂薄片A的內層基板投入130℃的烤箱中,加熱30分鐘,接著,移入190℃的烤箱,加熱30分鐘,使樹脂組成物層熱硬化,形成絕緣層。然後,將支撐體剝離,得到依序具有絕緣層、內層基板及絕緣層的硬化基板A。(3) Thermosetting of the resin composition layer Then, the inner layer substrate on which the resin sheet A was laminated was put into an oven at 130°C and heated for 30 minutes, then moved into an oven at 190°C and heated for 30 minutes to thermally harden the resin composition layer to form an insulating layer. Then, the support body was peeled off, and the cured board|substrate A which has an insulating layer, an inner-layer board|substrate, and an insulating layer in this order was obtained.

(4)粗化處理 對硬化基板A進行粗化處理之除膠渣處理。作為除膠渣處理,實施下述的濕式除膠渣處理。(4) Coarsening treatment The hardened substrate A is subjected to desmear treatment for roughening treatment. As the desmear treatment, the following wet desmear treatment was performed.

(濕式除膠渣處理) 將硬化基板A在膨潤液(atotech Japan公司製「Swelling Dip Securiganth P」、二乙二醇單丁醚及氫氧化鈉之水溶液)在60℃下浸漬5分鐘,接著,氧化劑溶液(atotech Japan公司製「Concentrate Compact CP」、過錳酸鉀濃度約6%、氫氧化鈉濃度約4%之水溶液)中,在80℃下,浸漬20分鐘。接著,中和液(atotech Japan公司製「Reduction solution Securiganth P」、硫酸水溶液)40℃下,浸漬5分鐘後,以80℃乾燥15分鐘。(Wet degreaser treatment) The cured substrate A was immersed in a swelling solution (“Swelling Dip Securiganth P” manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60° C. for 5 minutes, followed by an oxidizing agent solution (manufactured by Atotech Japan). "Concentrate Compact CP", an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%), immersed at 80°C for 20 minutes. Next, after immersion for 5 minutes in a neutralizing solution (“Reduction solution Securiganth P” manufactured by Atotech Japan, an aqueous sulfuric acid solution) at 40° C., it was dried at 80° C. for 15 minutes.

(5)粗化處理後之絕緣層表面之算術平均粗糙度(Ra)之測定 使用非接觸型表面粗糙度計(Bruker公司製WYKO NT3300),藉由VSI模式,50倍透鏡,測定範圍設為121μm×92μm,所得之數值求得粗化處理後之硬化基板A之絕緣層表面的算術平均粗糙度(Ra)。求各自10點的平均值來測定。(5) Determination of the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening treatment Using a non-contact surface roughness meter (WYKO NT3300 manufactured by Bruker), the surface of the insulating layer of the hardened substrate A after the roughening treatment was obtained from the values obtained by using a VSI mode, a 50x lens, and a measurement range of 121 μm × 92 μm. The arithmetic mean roughness (Ra). The average value of each 10 points was calculated.

(6)導體層之形成 依據半加成法,在硬化基板A之絕緣層的粗化面形成導體層。亦即,將粗化處理後的基板在含有PdCl2 之無電電鍍液中,在40℃下浸漬5分鐘後,在無電鍍銅液中,25℃下浸漬20分鐘。接著,以150℃加熱30分鐘,進行退火處理後,形成蝕刻阻劑,藉由蝕刻形成圖型。然後,進行硫酸銅電鍍,形成厚度25μm的導體層,以190℃進行退火處理60分鐘。將所得之基板稱為「評價基板B」。(6) Formation of Conductor Layer The conductor layer was formed on the roughened surface of the insulating layer of the hardened substrate A according to the semi-additive method. That is, the roughened substrate was immersed in an electroless plating solution containing PdCl 2 at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes. Next, after heating at 150° C. for 30 minutes and performing annealing treatment, an etching resist was formed, and a pattern was formed by etching. Then, copper sulfate electroplating was performed to form a conductor layer with a thickness of 25 μm, and annealing treatment was performed at 190° C. for 60 minutes. The obtained board|substrate is called "evaluation board|substrate B".

(7)電鍍導體層之剝離強度之測定 依據日本工業規格(JIS C6481)進行絕緣層與導體層之剝離強度之測定。具體而言,在評價基板B之導體層,在寬10mm、長度100mm之部分切割,將此一端剝離,且以抓具抓住,在室溫下,以50mm/分鐘的速度,測定在垂直方向拉剝離35mm時的荷重(kgf/cm),求剝離強度。測定係使用拉伸試驗機(TSE公司製「AC-50C-SL」)。(7) Determination of peel strength of electroplated conductor layer The peel strength of the insulating layer and the conductor layer was measured according to Japanese Industrial Standards (JIS C6481). Specifically, the conductor layer of the evaluation substrate B was cut at a width of 10 mm and a length of 100 mm, the end was peeled off, and grasped with a gripper. At room temperature, at a speed of 50 mm/min, the vertical direction was measured. The load (kgf/cm) when pulling and peeling 35 mm was used to obtain the peeling strength. The measurement system used a tensile tester ("AC-50C-SL" manufactured by TSE).

實施例及比較例之樹脂組成物之不揮發成分之使用量、試驗例之測定結果示於下述表1。The usage-amount of the non-volatile matter of the resin compositions of Examples and Comparative Examples and the measurement results of the test examples are shown in Table 1 below.

Figure 02_image047
Figure 02_image047

以上,藉由使用包含(A)具有聯苯骨架之胺化合物、(B)具有碳原子數為7以上之脂肪鏈之馬來醯亞胺化合物,及(C)不具有碳原子數為7以上之脂肪鏈之馬來醯亞胺化合物的樹脂組成物,可得到比電容量(Dk)及介電正切(Df)低,且電鍍導體層之剝離強度優異的硬化物。In the above, by using (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) no compound having 7 or more carbon atoms The resin composition of the maleimide compound in the aliphatic chain can obtain a cured product with low specific capacitance (Dk) and dielectric tangent (Df) and excellent peel strength of the electroplated conductor layer.

Claims (21)

一種樹脂組成物,其係包含(A)具有聯苯骨架之胺化合物, (B)具有碳原子數為7以上之脂肪鏈之馬來醯亞胺化合物,及 (C)不具有碳原子數為7以上之脂肪鏈之馬來醯亞胺化合物。A resin composition comprising (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) A maleimide compound which does not have an aliphatic chain having 7 or more carbon atoms. 如請求項1之樹脂組成物,其中(B)成分具有直接鍵結於未構成芳香環之碳原子的馬來醯亞胺基。The resin composition according to claim 1, wherein the component (B) has a maleimide group directly bonded to a carbon atom not constituting an aromatic ring. 如請求項1之樹脂組成物,其中(C)成分具有直接鍵結於構成芳香環之碳原子的馬來醯亞胺基。The resin composition according to claim 1, wherein the component (C) has a maleimide group directly bonded to a carbon atom constituting an aromatic ring. 如請求項1之樹脂組成物,其中(A)成分具有一級胺基。The resin composition according to claim 1, wherein the component (A) has a primary amine group. 如請求項1之樹脂組成物,其中(A)成分具有直接鍵結於構成芳香環之碳原子的胺基。The resin composition according to claim 1, wherein the component (A) has an amine group directly bonded to a carbon atom constituting an aromatic ring. 如請求項1之樹脂組成物,其中(A)成分包含具有式(A1):
Figure 03_image001
[式中,V及W各自獨立表示-C(R’)2 -、-O-、-CO-、-S-、-SO-、-SO2 -、-CONH-、或-NHCO-,R各自獨立表示取代基,R’各自獨立表示氫原子或取代基,h、i及j各自獨立表示0~2之整數]表示之重複單位的胺化合物。
As the resin composition of claim 1, wherein (A) component comprises formula (A1):
Figure 03_image001
[wherein, V and W each independently represent -C(R') 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH-, or -NHCO-, R Each independently represents a substituent, R' each independently represents a hydrogen atom or a substituent, and h, i and j each independently represent an integer of 0 to 2] The amine compound represented by the repeating unit.
如請求項1之樹脂組成物,其中樹脂組成物中之不揮發成分設為100質量%時,(A)成分之含量為3質量%~40質量%。As in the resin composition of claim 1, when the non-volatile matter in the resin composition is set to 100% by mass, the content of component (A) is 3% by mass to 40% by mass. 如請求項1之樹脂組成物,其中樹脂組成物中之不揮發成分設為100質量%時,(B)成分之含量為3質量%~40質量%。As in the resin composition of claim 1, when the nonvolatile matter in the resin composition is set to 100% by mass, the content of component (B) is 3% by mass to 40% by mass. 如請求項1之樹脂組成物,其中樹脂組成物中之不揮發成分設為100質量%時,(C)成分之含量為3質量%~40質量%。The resin composition of claim 1, wherein when the non-volatile matter in the resin composition is set to 100% by mass, the content of component (C) is 3% by mass to 40% by mass. 如請求項1之樹脂組成物,其中(C)成分相對於(B)成分之質量比((C)成分/(B)成分)為0.5~20。The resin composition of claim 1, wherein the mass ratio of (C) component to (B) component ((C) component/(B) component) is 0.5 to 20. 如請求項1之樹脂組成物,其中(A)成分相對於(B)成分及(C)成分之合計之質量比((A)成分/(B)成分及(C)成分之合計)為0.1~0.5。The resin composition of claim 1, wherein the mass ratio of component (A) to the total of components (B) and (C) (component (A)/total of components (B) and (C)) is 0.1 ~0.5. 如請求項1之樹脂組成物,其係進一步包含(B)成分及(C)成分以外的(D)自由基聚合性化合物。The resin composition of Claim 1 which further contains (D) a radical polymerizable compound other than (B) component and (C) component. 如請求項1之樹脂組成物,其係進一步包含(E)無機填充材。The resin composition according to claim 1, further comprising (E) an inorganic filler. 如請求項13之樹脂組成物,其中樹脂組成物中之不揮發成分設為100質量%時,(E)成分之含量為25質量%以上。The resin composition of claim 13, wherein the content of the component (E) is 25 mass % or more when the non-volatile content in the resin composition is 100 mass %. 如請求項1之樹脂組成物,其中在5.8GHz、23℃測定時,樹脂組成物之硬化物的介電正切為0.004以下。The resin composition of claim 1, wherein the dielectric tangent of the cured product of the resin composition is 0.004 or less when measured at 5.8 GHz and 23°C. 如請求項1之樹脂組成物,其中在5.8GHz、23℃測定時,樹脂組成物之硬化物的比電容量為2.9以下。The resin composition of claim 1, wherein the specific capacitance of the cured product of the resin composition is 2.9 or less when measured at 5.8 GHz and 23°C. 一種硬化物,其係如請求項1~16中任一項之樹脂組成物的硬化物。A hardened product, which is the hardened product of the resin composition according to any one of claims 1 to 16. 一種薄片狀積層材料,其係含有如請求項1~16中任一項之樹脂組成物。A sheet-like laminated material containing the resin composition according to any one of claims 1 to 16. 一種樹脂薄片,其係具有支撐體,及設置於該支撐體上由請求項1~16中任一項之樹脂組成物所形成的樹脂組成物層。A resin sheet having a support body and a resin composition layer formed of the resin composition of any one of claims 1 to 16 provided on the support body. 一種印刷配線板,其係具備由請求項1~16中任一項之樹脂組成物之硬化物所構成的絕緣層。A printed wiring board including an insulating layer composed of a cured product of the resin composition of any one of claims 1 to 16. 一種半導體裝置,其係包含請求項20之印刷配線板。A semiconductor device comprising the printed wiring board of claim 20.
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