TWI737649B - Resin composition - Google Patents

Resin composition Download PDF

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TWI737649B
TWI737649B TW105137480A TW105137480A TWI737649B TW I737649 B TWI737649 B TW I737649B TW 105137480 A TW105137480 A TW 105137480A TW 105137480 A TW105137480 A TW 105137480A TW I737649 B TWI737649 B TW I737649B
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resin composition
resin
epoxy resin
layer
component
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TW105137480A
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TW201731947A (en
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中村茂雄
柚木誠
巽志朗
阪內啓之
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日商味之素股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4688—Composite multilayer circuits, i.e. comprising insulating layers having different properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Abstract

本發明的課題為提供一種可降低絕緣層表面的粗糙度，粗糙化處理後之絕緣層與導體層的剝離強度、鍍敷潛入深度、零件嵌入性、及阻燃性良好之樹脂組成物；含有該樹脂組成物之薄片狀層合材料、包含藉由該樹脂組成物之硬化物所形成之絕緣層的印刷配線板、及半導體裝置。 The subject of the present invention is to provide a resin composition that can reduce the roughness of the insulating layer surface, the peeling strength of the insulating layer and the conductor layer after the roughening treatment, the plating penetration depth, the part embedding property, and the flame retardant resin composition; The sheet-like laminated material of the resin composition, a printed wiring board including an insulating layer formed by a cured product of the resin composition, and a semiconductor device.

本發明的解決手段為一種樹脂組成物，其係含有(A)環氧樹脂、(B)硬化劑、(C)含有氟原子之烷氧基矽烷化合物、及(D)無機填充材。 The solution of the present invention is a resin composition containing (A) epoxy resin, (B) hardener, (C) alkoxysilane compound containing fluorine atoms, and (D) inorganic filler.

Description

樹脂組成物 Resin composition

本發明係關於樹脂組成物。進而係關於含有該樹脂組成物之薄片狀層合材料、包含藉由該樹脂組成物之硬化物所形成之絕緣層的印刷配線板、及半導體裝置。 The present invention relates to a resin composition. Furthermore, it relates to a sheet-like laminated material containing the resin composition, a printed wiring board containing an insulating layer formed by a cured product of the resin composition, and a semiconductor device.

作為印刷配線板之製造技術，已知有於內層基板上藉由交替堆疊絕緣層與導體層之積聚(Build up)方式的製造方法。絕緣層一般而言係藉由使樹脂組成物硬化而形成。 As a manufacturing technology of a printed wiring board, a build-up manufacturing method in which insulating layers and conductor layers are alternately stacked on an inner substrate is known. The insulating layer is generally formed by curing the resin composition.

例如，專利文獻1中，揭示有一種樹脂組成物，其係含有環氧樹脂、硬化劑及以烷氧基矽烷化合物表面處理之無機填充材的樹脂組成物，該無機填充材之平均粒徑為0.01μm~5μm，將樹脂組成物中之不揮發成分定為100質量%時，該無機填充材的含量為30質量%~90質量%。 For example, Patent Document 1 discloses a resin composition containing an epoxy resin, a curing agent, and an inorganic filler surface-treated with an alkoxysilane compound. The average particle diameter of the inorganic filler is 0.01 μm to 5 μm, and when the non-volatile content in the resin composition is 100% by mass, the content of the inorganic filler is 30% to 90% by mass.

又，專利文獻2中，揭示有一種樹脂組成物，其係含有環氧樹脂、硬化劑及無機填充材之樹脂組成物，該無機填充材以胺基烷基矽烷表面處理，將樹脂組成 物中之不揮發成分定為100質量%時，該無機填充材的含量為55質量%~90質量%。 In addition, Patent Document 2 discloses a resin composition containing an epoxy resin, a curing agent, and an inorganic filler. The inorganic filler is surface-treated with an aminoalkylsilane to form a resin composition. When the non-volatile content in the substance is set at 100% by mass, the content of the inorganic filler is 55% by mass to 90% by mass.

[先前技術文獻] [Prior Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2014-12763號公報 [Patent Document 1] JP 2014-12763 A

[專利文獻2]日本特開2014-28880號公報 [Patent Document 2] JP 2014-28880 A

近年來，電子機器之小型化、高性能化進化，在印刷配線板，正期望積聚層複層化、微細配線化及高密度化。藉由使用引用文獻1及引用文獻2所揭示之樹脂組成物，雖然在濕式粗糙化步驟可降低絕緣層表面之算術平均粗糙度，可形成具有充分剝離強度之導體層，但針對鍍敷潛入深度、零件嵌入性、及阻燃性等，期待更進一步之高性能化。 In recent years, the miniaturization and high performance of electronic devices have evolved. In printed wiring boards, multilayer accumulation, fine wiring, and high density are expected. By using the resin composition disclosed in Citation 1 and Citation 2, although the arithmetic average roughness of the insulating layer surface can be reduced in the wet roughening step, a conductor layer with sufficient peeling strength can be formed, but it can be used for plating. Depth, part embedding, and flame retardancy are expected to be further enhanced.

本發明之課題為提供一種可降低絕緣層表面的粗糙度，粗糙化處理後之絕緣層與導體層的剝離強度、鍍敷潛入深度、零件嵌入性、及阻燃性良好之樹脂組成物；含有該樹脂組成物之薄片狀層合材料、包含藉由該樹脂組成物之硬化物所形成之絕緣層的印刷配線板、及半導體裝置。 The subject of the present invention is to provide a resin composition that can reduce the roughness of the insulating layer surface, the peeling strength of the insulating layer and the conductor layer after the roughening treatment, the plating penetration depth, the part embedding property, and the flame retardant resin composition; The sheet-like laminated material of the resin composition, a printed wiring board including an insulating layer formed by a cured product of the resin composition, and a semiconductor device.

本發明者們對於上述課題進行努力研究的結果，發現藉由使用含有氟原子之烷氧基矽烷化合物，可解決上述課題，而終至完成本發明。 As a result of diligent research on the above-mentioned subject, the inventors found that the above-mentioned subject can be solved by using an alkoxysilane compound containing a fluorine atom, and finally completed the present invention.

亦即，本發明係包含以下之內容。 That is, the present invention includes the following contents.

[1]一種樹脂組成物，其係含有(A)環氧樹脂、(B)硬化劑、(C)含有氟原子之烷氧基矽烷化合物、及(D)無機填充材。 [1] A resin composition containing (A) an epoxy resin, (B) a curing agent, (C) an alkoxysilane compound containing a fluorine atom, and (D) an inorganic filler.

[2]如[1]之樹脂組成物，其中，將樹脂組成物中之不揮發成分定為100質量%時，(D)成分的含量為60質量%以上。 [2] The resin composition according to [1], wherein when the non-volatile content in the resin composition is 100% by mass, the content of the component (D) is 60% by mass or more.

[3]如[1]或[2]之樹脂組成物，其中，(D)成分之平均粒徑為0.01μm~2μm。 [3] The resin composition according to [1] or [2], wherein the average particle size of the component (D) is 0.01 μm to 2 μm.

[4]如[1]~[3]中任一項之樹脂組成物，其中，(D)成分為二氧化矽或氧化鋁。 [4] The resin composition according to any one of [1] to [3], wherein the component (D) is silica or alumina.

[5]如[1]~[4]中任一項之樹脂組成物，其中，(C)成分1分子中之氟原子的數目為1~10。 [5] The resin composition according to any one of [1] to [4], wherein the number of fluorine atoms in one molecule of the component (C) is 1-10.

[6]如[1]~[5]中任一項之樹脂組成物，其中，(C)成分1分子中之烷氧基的數目為1~5。 [6] The resin composition according to any one of [1] to [5], wherein the number of alkoxy groups in one molecule of the component (C) is 1 to 5.

[7]如[1]~[6]中任一項之樹脂組成物，其中，(C)成分為3,3,3-三氟丙基三甲氧基矽烷。 [7] The resin composition according to any one of [1] to [6], wherein the component (C) is 3,3,3-trifluoropropyltrimethoxysilane.

[8]如[1]~[7]中任一項之樹脂組成物，其中，(D)成分係以(C)成分表面處理。 [8] The resin composition according to any one of [1] to [7], wherein the component (D) is surface-treated with the component (C).

[9]如[1]~[8]中任一項之樹脂組成物，其係印刷配線板之絕緣層形成用。 [9] The resin composition of any one of [1] to [8], which is used for forming an insulating layer of a printed wiring board.

[10]如[1]~[9]中任一項之樹脂組成物，其係印刷配線板之積聚層用。 [10] The resin composition of any one of [1] to [9], which is used for the accumulation layer of a printed wiring board.

[11]一種薄片狀層合材料，其係包含如[1]~[10]中任一項之樹脂組成物。 [11] A sheet-like laminate material comprising the resin composition as described in any one of [1] to [10].

[12]一種薄片狀層合材料，其係包含以如[1]~[10]中任一項之樹脂組成物形成之樹脂組成物層。 [12] A sheet-like laminate material comprising a resin composition layer formed of the resin composition of any one of [1] to [10].

[13]如[12]之薄片狀層合材料，其中，樹脂組成物層的厚度為10μm以下。 [13] The sheet-like laminate material according to [12], wherein the thickness of the resin composition layer is 10 μm or less.

[14]一種印刷配線板，其係包含藉由如[1]~[10]中任一項之樹脂組成物的硬化物所形成之絕緣層。 [14] A printed wiring board comprising an insulating layer formed by a cured product of the resin composition as described in any one of [1] to [10].

[15]一種半導體裝置，其係包含如[14]之印刷配線板。 [15] A semiconductor device comprising the printed wiring board as in [14].

根據本發明，可提供一種可降低絕緣層表面的粗糙度，粗糙化處理後之絕緣層與導體層的剝離強度、鍍敷潛入深度、零件嵌入性、及阻燃性良好之樹脂組成物；含有該樹脂組成物之薄片狀層合材料、包含藉由該樹脂組成物之硬化物所形成之絕緣層的印刷配線板、及半導體裝置。 According to the present invention, it is possible to provide a resin composition that can reduce the roughness of the insulating layer surface, the peeling strength of the insulating layer and the conductor layer after the roughening treatment, the plating penetration depth, the part embedding property, and the good flame retardancy; The sheet-like laminated material of the resin composition, a printed wiring board including an insulating layer formed by a cured product of the resin composition, and a semiconductor device.

1‧‧‧內層基板 1‧‧‧Inner substrate

1a‧‧‧孔洞 1a‧‧‧Hole

2‧‧‧暫時配附之材料 2‧‧‧Materials attached temporarily

3‧‧‧零件 3‧‧‧Parts

4‧‧‧電路配線 4‧‧‧Circuit wiring

11‧‧‧第1主面 11‧‧‧The first main surface

12‧‧‧第2主面 12‧‧‧Second main surface

100‧‧‧暫時配附零件之內層基板(孔洞基板) 100‧‧‧Inner substrate (hole substrate) temporarily equipped with parts

[圖1]圖1係表示暫時配附零件之內層基板的剖面之一例之模式圖。 [Fig. 1] Fig. 1 is a schematic view showing an example of a cross-section of an inner substrate to which parts are temporarily attached.

以下，針對本發明之樹脂組成物、含有該樹脂組成物之薄片狀層合材料、印刷配線板、及半導體裝置進行詳細說明。 Hereinafter, the resin composition of the present invention, the sheet-like laminate containing the resin composition, the printed wiring board, and the semiconductor device will be described in detail.

[樹脂組成物] [Resin composition]

本發明之樹脂組成物係含有(A)環氧樹脂、(B)硬化劑、(C)含有氟原子之烷氧基矽烷化合物、及(D)無機填充材。 The resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent, (C) an alkoxysilane compound containing a fluorine atom, and (D) an inorganic filler.

以下，針對本發明之樹脂組成物所包含之各成分進行詳細說明。 Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

<(A)環氧樹脂> <(A) Epoxy resin>

作為環氧樹脂，例如可列舉雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚AF型環氧樹脂、雙環戊二烯型環氧樹脂、參酚型環氧樹脂、萘酚酚醛清漆型環氧樹脂、酚酚醛清漆型環氧樹脂、tert-丁基-鄰苯二酚型環氧樹脂、萘型環氧樹脂、萘酚型環氧樹脂、蔥型環氧樹脂、縮水甘油胺型環氧樹脂、縮水甘油酯型環氧樹脂、甲酚酚醛清漆型環氧樹脂、聯苯型環氧樹脂、線狀 脂肪族環氧樹脂、具有丁二烯構造之環氧樹脂、脂環式環氧樹脂、雜環式環氧樹脂、含有螺環之環氧樹脂、環己烷二甲醇型環氧樹脂、萘醚型環氧樹脂、三羥甲基型環氧樹脂、四苯基乙烷型環氧樹脂、二羥基二甲苯(bixylenol)型環氧樹脂等。環氧樹脂可1種單獨使用、或亦可組合2種以上使用。(A)成分較佳為選自雙酚A型環氧樹脂、雙酚F型環氧樹脂、及聯苯型環氧樹脂中之1種以上。 As the epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, ginseng Phenolic epoxy resin, naphthol novolak epoxy resin, phenol novolak epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, Onion type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear Aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane dimethanol type epoxy resin, naphthyl ether Type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, bixylenol type epoxy resin, etc. An epoxy resin may be used individually by 1 type, or may be used in combination of 2 or more types. (A) The component is preferably one or more selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, and biphenyl type epoxy resin.

環氧樹脂較佳為於1分子中包含具有2個以上環氧基之環氧樹脂。將環氧樹脂之不揮發成分定為100質量%的情況下，較佳為至少50質量%以上為於1分子中具有2個以上環氧基之環氧樹脂。其中，較佳為包含於1分子中包含具有2個以上環氧基，於溫度20℃為液狀之環氧樹脂(以下稱為「液狀環氧樹脂」)、與於1分子中具有3個以上環氧基，於溫度20℃為固體狀之環氧樹脂(以下稱為「固體狀環氧樹脂」)。作為環氧樹脂，藉由併用液狀環氧樹脂與固體狀環氧樹脂，而得到具有優異可撓性之樹脂組成物。又，亦提昇樹脂組成物之硬化物的斷裂強度。 The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile content of the epoxy resin is set to 100% by mass, it is preferable that at least 50% by mass is an epoxy resin having two or more epoxy groups in one molecule. Among them, it is preferable to include an epoxy resin that has two or more epoxy groups in a molecule and is liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resin"), and that contains 3 or more epoxy groups in a molecule. A solid epoxy resin with more than one epoxy group at a temperature of 20°C (hereinafter referred to as "solid epoxy resin"). As the epoxy resin, by using a liquid epoxy resin and a solid epoxy resin in combination, a resin composition having excellent flexibility is obtained. In addition, the breaking strength of the cured product of the resin composition is also improved.

作為液狀環氧樹脂，較佳為雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AF型環氧樹脂、萘型環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、酚酚醛清漆型環氧樹脂、具有酯骨架之脂環式環氧樹脂、環己烷二甲醇型環氧樹脂、縮水甘油胺型環氧樹脂、及具有丁二烯構造之環氧樹脂，更佳為縮水甘油胺型環氧樹 脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AF型環氧樹脂及萘型環氧樹脂。作為液狀環氧樹脂之具體例，可列舉DIC(股)製之「HP4032」、「HP4032D」、「HP4032SS」(萘型環氧樹脂)、三菱化學(股)製之「828US」「jER828EL」(雙酚A型環氧樹脂)、「jER807」(雙酚F型環氧樹脂)、「jER152」(酚酚醛清漆型環氧樹脂)、「630」、「630LSD」(縮水甘油胺型環氧樹脂)、新日鐵住金化學(股)製之「ZX1059」(雙酚A型環氧樹脂與雙酚F型環氧樹脂的混合品)、Nagase ChemteX(股)製之「EX-721」(縮水甘油酯型環氧樹脂)、(股)Daicel製之「Celoxide2021P」(具有酯骨架之脂環式環氧樹脂)、「PB-3600」(具有丁二烯構造之環氧樹脂)、新日鐵化學(股)製之「ZX1658」、「ZX1658GS」(液狀1,4-縮水甘油環己烷)、三菱化學(股)製之「630LSD」(縮水甘油胺型環氧樹脂)等。此等可1種單獨使用，亦可組合2種以上使用。 As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, and glycidol are preferred. Amine type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and those with a butadiene structure Epoxy resin, more preferably glycidylamine epoxy resin Grease, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin and naphthalene type epoxy resin. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation, and "828US" and "jER828EL" manufactured by Mitsubishi Chemical Corporation. (Bisphenol A epoxy resin), "jER807" (bisphenol F epoxy resin), "jER152" (phenol novolac epoxy resin), "630", "630LSD" (glycidylamine epoxy resin) Resin), "ZX1059" (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and "EX-721" manufactured by Nagase ChemteX (Stock) Glycidyl ester type epoxy resin), "Celoxide2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel, "PB-3600" (epoxy resin with butadiene structure), New Japan "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Ferrochemical Co., Ltd., "630LSD" (glycidylamine epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., etc. These can be used individually by 1 type, and can also be used in combination of 2 or more types.

作為固體狀環氧樹脂，較佳為萘型4官能環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙環戊二烯型環氧樹脂、參酚型環氧樹脂、萘酚型環氧樹脂、聯苯型環氧樹脂、萘醚型環氧樹脂、蔥型環氧樹脂、雙酚A型環氧樹脂、四苯基乙烷型環氧樹脂，更佳為萘型4官能環氧樹脂、萘酚型環氧樹脂、及聯苯型環氧樹脂。作為固體狀環氧樹脂之具體例，可列舉DIC(股)製之「HP4032H」(萘型環氧樹脂)、「HP-4700」、「HP-4710」(萘型4 官能環氧樹脂)、「N-690」(甲酚酚醛清漆型環氧樹脂)、「N-695」(甲酚酚醛清漆型環氧樹脂)、「HP-7200」(雙環戊二烯型環氧樹脂)、「HP-7200HH」、「HP-7200H」、「EXA-7311」、「EXA-7311-G3」、「EXA-7311-G4」、「EXA-7311-G4S」、「HP6000」(萘醚型環氧樹脂)、日本化藥(股)製之「EPPN-502H」(參酚型環氧樹脂)、「NC7000L」(萘酚酚醛清漆型環氧樹脂)、「NC3000H」、「NC3000」、「NC3000L」、「NC3100」(聯苯型環氧樹脂)、新日鐵住金化學(股)製之「ESN475V」(萘型環氧樹脂)、「ESN485」(萘酚酚醛清漆型環氧樹脂)、三菱化學(股)製之「YX4000H」、「YL6121」(聯苯型環氧樹脂)、「YX4000HK」(二羥基二甲苯(bixylenol)型環氧樹脂)、「YX8800」(蔥型環氧樹脂)、大阪瓦斯化學(股)製之「PG-100」、「CG-500」、三菱化學(股)製之「YL7760」(雙酚AF型環氧樹脂)、「YL7800」(茀型環氧樹脂)、三菱化學(股)製之「jER1010」(固體狀雙酚A型環氧樹脂)、「jER1031S」(四苯基乙烷型環氧樹脂)等。此等可1種單獨使用，亦可組合2種以上使用。 As the solid epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, ginseng phenol type epoxy resin, naphthol type epoxy resin, Biphenyl type epoxy resin, naphthalene ether type epoxy resin, onion type epoxy resin, bisphenol A type epoxy resin, tetraphenylethane type epoxy resin, more preferably naphthalene type tetrafunctional epoxy resin, naphthalene Phenolic epoxy resin and biphenyl epoxy resin. Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type 4 Functional epoxy resin), "N-690" (cresol novolac epoxy resin), "N-695" (cresol novolac epoxy resin), "HP-7200" (dicyclopentadiene epoxy resin) Oxy resin), "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" ( Naphthyl ether type epoxy resin), "EPPN-502H" (ginseng phenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC7000L" (naphthol novolak type epoxy resin), "NC3000H", "NC3000 ", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., "ESN485" (naphthol novolak type epoxy resin) Resin), "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (onion ring) manufactured by Mitsubishi Chemical Corporation Oxygen resin), "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., and "YL7800" (茀 type) Epoxy resin), "jER1010" (solid bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S" (tetraphenylethane epoxy resin), etc. These can be used individually by 1 type, and can also be used in combination of 2 or more types.

作為環氧樹脂，併用液狀環氧樹脂與固體狀環氧樹脂時，該等之量比(液狀環氧樹脂：固體狀環氧樹脂)以質量比較佳為0：0.1~1：15的範圍。藉由將液狀環氧樹脂與固體狀環氧樹脂的量比定於該範圍，而得到 i)以樹脂薄片之形態使用時帶來適度之黏著性、ii)以樹脂薄片之形態使用時得到充分之可撓性，提昇操作性、以及iii)可得到具有充分斷裂強度之硬化物等之效果。從上述i)~iii)之效果的觀點來看，液狀環氧樹脂與固體狀環氧樹脂的量比(液狀環氧樹脂：固體狀環氧樹脂)以質量比更佳為1：0.3~1：10的範圍，再更佳為1：0.6~1：8的範圍。 When a liquid epoxy resin and a solid epoxy resin are used together as an epoxy resin, the quantity ratio (liquid epoxy resin: solid epoxy resin) is preferably 0:0.1~1:15 in terms of mass ratio. Scope. By setting the ratio of the liquid epoxy resin to the solid epoxy resin in this range, it is obtained i) When used in the form of a resin sheet, it brings moderate adhesiveness, ii) When used in the form of a resin sheet, it has sufficient flexibility to improve handling, and iii) a cured product with sufficient breaking strength can be obtained. Effect. From the viewpoint of the effects of i) to iii) above, the mass ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably 1:0.3 The range of ~1:10 is more preferably the range of 1:0.6~1:8.

樹脂組成物中之環氧樹脂的含量，從得到良好機械強度、顯示絕緣信賴性之絕緣層的觀點來看，較佳為1質量%以上，更佳為2質量%以上，再更佳為3質量%以上。環氧樹脂的含量的上限，只要能發揮本發明的效果下，雖並未特別限定，但較佳為50質量%以下，更佳為30質量%以下，再更佳為20質量%以下。 The content of the epoxy resin in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3 from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. Above mass%. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention are exhibited, but it is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less.

尚，在本發明，樹脂組成物中之各成分的含量，除非另有說明，係將樹脂層中之不揮發成分定為100質量%時的值。 In the present invention, the content of each component in the resin composition, unless otherwise specified, is the value when the non-volatile component in the resin layer is set to 100% by mass.

環氧樹脂的環氧當量較佳為50~5000，更佳為50~3000，再更佳為80~2000，又再更佳為110~1000。藉由成為此範圍，可提供硬化物之交聯密度變充分且表面粗糙度小之絕緣層。尚，環氧當量可依JIS K7236測定，係包含1當量環氧基之樹脂的質量。 The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and still more preferably 110 to 1000. By setting it in this range, it is possible to provide an insulating layer in which the crosslinking density of the cured product becomes sufficient and the surface roughness is small. Furthermore, the epoxy equivalent can be measured in accordance with JIS K7236, which is the mass of a resin containing 1 equivalent of epoxy groups.

環氧樹脂的重量平均分子量較佳為100~5000，更佳為250~3000，再更佳為400~1500。於此，環氧樹脂的重量平均分子量係藉由凝膠滲透層析(GPC) 法所測定之聚苯乙烯換算的重量平均分子量。 The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500. Here, the weight average molecular weight of epoxy resin is determined by gel permeation chromatography (GPC) The weight average molecular weight in terms of polystyrene measured by the method.

<(B)硬化劑> <(B) Hardener>

作為硬化劑，只要是具有硬化環氧樹脂功能則並未特別限定，例如可列舉酚系硬化劑、萘酚系硬化劑、活性酯系硬化劑、苯并噁嗪系硬化劑、氰酸酯系硬化劑、及碳二醯亞胺系硬化劑等。硬化劑可1種單獨使用、或亦可併用2種以上。(B)成分較佳為選自酚系硬化劑、萘酚系硬化劑、活性酯系硬化劑及氰酸酯系硬化劑中之1種以上。 The curing agent is not particularly limited as long as it has the function of curing epoxy resin. Examples include phenolic curing agents, naphthol curing agents, active ester curing agents, benzoxazine curing agents, and cyanate ester curing agents. Hardener, and carbodiimide hardener, etc. The curing agent may be used singly, or two or more of them may be used in combination. (B) The component is preferably one or more selected from a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and a cyanate ester-based curing agent.

作為酚系硬化劑及萘酚系硬化劑，從耐熱性及耐水性的觀點來看，較佳為具有酚醛清漆構造之酚系硬化劑、或具有酚醛清漆構造之萘酚系硬化劑。又，從與導體層之密著性的觀點來看，較佳為含氮酚系硬化劑，更佳為含有三嗪骨架之酚系硬化劑。其中，從高度滿足耐熱性、耐水性、及與導體層之密著性的觀點來看，較佳為含有三嗪骨架之酚酚醛清漆硬化劑。 As the phenolic curing agent and the naphthol curing agent, from the viewpoint of heat resistance and water resistance, a phenol curing agent having a novolak structure or a naphthol curing agent having a novolak structure are preferable. Furthermore, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenolic curing agent is preferred, and a phenolic curing agent containing a triazine skeleton is more preferred. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer, a phenol novolak hardener containing a triazine skeleton is preferred.

作為酚系硬化劑及萘酚系硬化劑之具體例，例如可列舉明和化成(股)製之「MEH-7700」、「MEH-7810」、「MEH-7851」、日本化藥(股)製之「NHN」、「CBN」、「GPH」、新日鐵住金(股)製之「SN170」、「SN180」、「SN190」、「SN475」、「SN485」、「SN495」、「SN375」、「SN395」、DIC(股)製之「TD-2090」、「LA-7052」、「LA-7054」、「LA-1356」、「LA-3018-50P」、「EXB-9500」等。 Specific examples of phenolic hardeners and naphthol hardeners include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Chemical Co., Ltd., and Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395", DIC (stock) system "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", etc.

從得到與導體層的密著性優異之絕緣層的觀點來看，活性酯系硬化劑亦佳。作為活性酯系硬化劑雖並未特別限制，但一般而言較佳為使用於1分子中具有2個以上化合物之酚酯類、硫酚酯類、N-羥基胺酯類、雜環羥基化合物之酯類等之反應活性高之酯基。該活性酯系硬化劑較佳為藉由羧酸化合物及/或硫代羧酸化合物與羥基化合物及/或硫醇化合物的縮合反應所得者。尤其是從提昇耐熱性的觀點來看，較佳為從羧酸化合物與羥基化合物所得之活性酯系硬化劑，更佳為從羧酸化合物與酚化合物及/或萘酚化合物所得之活性酯系硬化劑。作為羧酸化合物，例如可列舉苯甲酸、乙酸、琥珀酸、馬來酸、衣康酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、苯均四酸等。作為酚化合物或萘酚化合物，例如可列舉對苯二酚、間苯二酚、雙酚A、雙酚F、雙酚S、酚酞(Phenolphthalein)、甲基化雙酚A、甲基化雙酚F、甲基化雙酚S、酚、o-甲酚、m-甲酚、p-甲酚、鄰苯二酚、α-萘酚、β-萘酚、1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯甲酮、三羥基二苯甲酮、四羥基二苯甲酮、間苯三酚、苯三酚、雙環戊二烯型二酚化合物、酚酚醛清漆等。於此，所謂「雙環戊二烯型二酚化合物」，係指於雙環戊二烯1分子縮合酚2分子所得之二酚化合物。 From the viewpoint of obtaining an insulating layer excellent in adhesion to the conductor layer, an active ester-based curing agent is also preferable. Although there are no particular restrictions on the active ester curing agent, it is generally preferable to use phenolic esters, thiophenolic esters, N-hydroxyamine esters, and heterocyclic hydroxy compounds having two or more compounds in one molecule. The esters are highly reactive ester groups. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent derived from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent derived from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. hardener. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, and methylated bisphenol F. Methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1 ,6-Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene type Diphenol compounds, phenol novolacs, etc. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

具體而言，較佳為包含雙環戊二烯型二酚構造之活性酯化合物、包含萘構造之活性酯化合物、包含酚 酚醛清漆之乙醯化物之活性酯化合物、包含酚酚醛清漆之苯甲醯基化物之活性酯化合物，其中更佳為包含萘構造之活性酯化合物、包含雙環戊二烯型二酚構造之活性酯化合物。所謂「雙環戊二烯型二酚構造」，係表示由伸苯基-二環伸戊基-伸苯基所成之2價構造單位。 Specifically, it is preferably an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, and an active ester compound containing a phenol structure. The active ester compound of the acetylated compound of novolak, the active ester compound of the benzyl compound containing the phenol novolak, and the active ester compound containing the naphthalene structure is more preferable, and the active ester containing the dicyclopentadiene type diphenol structure is more preferable. Compound. The so-called "dicyclopentadiene-type diphenol structure" refers to a bivalent structural unit formed by phenylene-bicyclopentylene-phenylene.

作為活性酯系硬化劑之市售品，作為包含雙環戊二烯型二酚構造之活性酯化合物，可列舉「EXB9451」、「EXB9460」、「EXB9460S」、「HPC-8000-65T」、「HPC-8000H-65TM」、「EXB-8000L-65TM」(DIC(股)製)，作為包含萘構造之活性酯化合物，可列舉「EXB9416-70BK」(DIC(股)製)，作為包含酚酚醛清漆之乙醯化物之活性酯化合物，可列舉「DC808」(三菱化學(股)製)，作為包含酚酚醛清漆之苯甲醯基化物之活性酯化合物，可列舉「YLH1026」(三菱化學(股)製)，作為酚酚醛清漆之乙醯化物的活性酯系硬化劑，可列舉「DC808」(三菱化學(股)製)，作為酚酚醛清漆之苯甲醯基化物的活性酯化合物，可列舉「YLH1026」(三菱化學(股)製)、「YLH1030」(三菱化學(股)製)、「YLH1048」(三菱化學(股)製)等。 As a commercially available product of an active ester curing agent, as an active ester compound containing a dicyclopentadiene-type diphenol structure, examples include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC -8000H-65TM" and "EXB-8000L-65TM" (manufactured by DIC Co., Ltd.). Examples of the active ester compound containing naphthalene structure include "EXB9416-70BK" (manufactured by DIC Co., Ltd.), which contains novolac The active ester compound of the acetylated compound can include "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.), and the active ester compound of the benzoyl compound containing phenol novolak can include "YLH1026" (Mitsubishi Chemical Co., Ltd.) As the active ester hardener of the acetate of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) can be cited, and the active ester compound of the benzoate of phenol novolak includes "DC808" (manufactured by Mitsubishi Chemical Corporation). "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc.

作為苯并噁嗪系硬化劑之具體例，可列舉昭和高分子(股)製之「HFB2006M」、四國化成工業(股)製之「P-d」、「F-a」。 Specific examples of benzoxazine-based hardeners include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industry Co., Ltd..

作為氰酸酯系硬化劑，例如可列舉雙酚A二 氰酸酯、聚酚氰酸酯、寡(3-亞甲基-1,5-伸苯基氰酸酯)、4,4’-亞甲基雙(2,6-二甲基苯基氰酸酯)、4,4’-亞乙基二苯基二氰酸酯、六氟雙酚A二氰酸酯、2,2-雙(4-氰酸酯)苯基丙烷、1,1-雙(4-氰酸酯苯基甲烷)、雙(4-氰酸酯-3,5-二甲基苯基)甲烷、1,3-雙(4-氰酸酯苯基-1-(甲基亞乙基))苯、雙(4-氰酸酯苯基)硫醚、及雙(4-氰酸酯苯基)醚等之由2官能氰酸酯樹脂、酚酚醛清漆及甲酚酚醛清漆等所衍生之多官能氰酸酯樹脂、此等氰酸酯樹脂經一部分三嗪化之預聚物等。作為氰酸酯系硬化劑之具體例，可列舉Lonza Japan(股)製之「PT30」及「PT60」(皆酚酚醛清漆型多官能氰酸酯樹脂)、「BA230」、「BA230S75」(成為雙酚A二氰酸酯之一部分或全部經三嗪化之三聚物之預聚物)等。 As the cyanate ester curing agent, for example, bisphenol A two Cyanate ester, polyphenol cyanate ester, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylene bis(2,6-dimethylbenzonitrile) Acid ester), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate) phenyl propane, 1,1- Bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methyl) Ethylene)) benzene, bis(4-cyanate phenyl) sulfide, and bis(4-cyanate phenyl) ether, etc. are made of bifunctional cyanate resin, phenol novolac and cresol phenol Multifunctional cyanate resins derived from varnishes, prepolymers of these cyanate resins with a part of triazine, etc. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolak type polyfunctional cyanate resin) manufactured by Lonza Japan (Stock), "BA230", and "BA230S75" (becomes Part or all of the bisphenol A dicyanate is a prepolymer of the trimer of triazine), etc.

作為碳二醯亞胺系硬化劑之具體例，可列舉日清紡化工(股)製之「V-03」、「V-07」等。 Specific examples of the carbodiimide-based hardener include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd., and the like.

環氧樹脂與硬化劑的量比以[環氧樹脂之環氧基的合計數]：[硬化劑之反應基的合計數]的比率，較佳為1：0.01~1：2的範圍，更佳為1：0.015~1：1.5，再更佳為1：0.02~1：1。於此，所謂硬化劑之反應基係指活性羥基、活性酯基等，因硬化劑的種類而有所不同。又，所謂環氧樹脂之環氧基的合計數，係指將各環氧樹脂之固形分質量除以環氧當量之值針對全部環氧樹脂進行合計之值，所謂硬化劑之反應基的合計數，係指將各硬化劑之固形分質量除以反應基當量之值，針對全部硬化劑進行合計 之值。藉由將環氧樹脂與硬化劑的量比定為該範圍，可更加提昇樹脂組成物之硬化物的耐熱性。 The ratio of the amount of epoxy resin to hardener is based on the ratio of [total number of epoxy groups in epoxy resin]: [total number of reactive groups in hardener], preferably in the range of 1:0.01 to 1:2, more Preferably, it is 1:0.015~1:1.5, and even more preferably is 1:0.02~1:1. Here, the so-called reactive groups of the hardener refer to active hydroxyl groups, active ester groups, etc., which vary depending on the type of hardener. In addition, the so-called total number of epoxy groups of epoxy resin refers to the value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins. The so-called total of the reactive groups of the hardener The number refers to the value obtained by dividing the solid content of each hardener by the equivalent of the reactive base, and totaling it for all hardeners The value. By setting the ratio of the amount of the epoxy resin to the curing agent within this range, the heat resistance of the cured product of the resin composition can be further improved.

在一實施形態，樹脂組成物係包含先述之(A)環氧樹脂及(B)硬化劑。樹脂組成物較佳為分別包含：作為(A)環氧樹脂之液狀環氧樹脂與固體狀環氧樹脂的混合物(液狀環氧樹脂：固體狀環氧樹脂的質量比較佳為1：0.1~1：15，更佳為1：0.3~1：10，再更佳為1：0.6~1：8)、與作為(B)硬化劑之選自由酚系硬化劑、萘酚系硬化劑、活性酯系硬化劑及氰酸酯系硬化劑所構成之群組中之1種以上(較佳為選自由酚系硬化劑、萘酚系硬化劑及活性酯系硬化劑所構成之群組中之1種以上)。 In one embodiment, the resin composition includes the aforementioned (A) epoxy resin and (B) hardener. The resin composition preferably contains: (A) a mixture of a liquid epoxy resin and a solid epoxy resin as the epoxy resin (liquid epoxy resin: the mass ratio of the solid epoxy resin is preferably 1:0.1 ~1:15, more preferably 1:0.3~1:10, and even more preferably 1:0.6~1:8), and as (B) the hardener is selected from phenolic hardeners, naphthol hardeners, One or more of the group consisting of active ester hardeners and cyanate ester hardeners (preferably selected from the group consisting of phenol hardeners, naphthol hardeners, and active ester hardeners One or more of them).

樹脂組成物中之硬化劑的含量雖並未特別限定，但較佳為30質量%以下，更佳為25質量%以下，再更佳為20質量%以下，又再更佳為15質量%以下。又，下限並未特別限制，較佳為0.5質量%以上。 Although the content of the hardener in the resin composition is not particularly limited, it is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, and still more preferably 15% by mass or less . In addition, the lower limit is not particularly limited, but is preferably 0.5% by mass or more.

<(C)含有氟原子之烷氧基矽烷化合物> <(C) Alkoxysilane compound containing fluorine atom>

本發明之樹脂組成物係包含(C)成分。本發明者們努力研究結果，發現藉由包含(C)成分，可降低絕緣層表面的粗糙度，可形成具有充分剝離強度之導體層，同時鍍敷潛入深度、零件嵌入性、及阻燃性變良好。(C)成分係化學性安定。因此，相對於氧化劑(除膠渣液(Desmear liquid))之耐性提高，且可降低粗糙度及鍍 敷潛入深度，伴隨此可提昇剝離強度。又，由於(C)成分有阻燃性，即使不包含後述之阻燃劑亦可賦予阻燃性。 The resin composition of the present invention contains the component (C). As a result of diligent research, the inventors found that by including the component (C), the surface roughness of the insulating layer can be reduced, and a conductor layer with sufficient peel strength can be formed. At the same time, the plating penetration depth, part embedding property, and flame retardancy Become good. (C) The ingredients are chemically stable. Therefore, the resistance to oxidants (Desmear liquid) is improved, and the roughness and plating can be reduced. Apply the depth of penetration, which can increase the peel strength. In addition, since the component (C) has flame retardancy, flame retardancy can be imparted even if the flame retardant described later is not included.

(C)成分從降低相對於粗糙化處理所使用之氧化劑的耐性及鍍敷潛入深度的觀點來看，較佳為(C)成分1分子中之氟原子數為1~10，更佳為氟原子數為1~5，再更佳為氟原子數為1~3。 From the viewpoint of reducing the resistance to the oxidizing agent used in the roughening treatment and the plating penetration depth of the component (C), the number of fluorine atoms in one molecule of the component (C) is preferably 1 to 10, and more preferably fluorine The number of atoms is 1 to 5, and more preferably the number of fluorine atoms is 1 to 3.

(C)成分從降低相對於粗糙化處理所使用之氧化劑的耐性及鍍敷潛入深度的觀點來看，較佳為具有氟化烷基，氟化烷基較佳為於末端具有氟原子。氟化烷基較佳為碳原子數1~20之氟化烷基，更佳為碳原子數1~10之氟化烷基，再更佳為碳原子數1~6之氟化烷基。作為如此之氟化烷基，例如可列舉-CF3、-CH2CF3、-CF2CF3、-CH2CH2CF3、-CH(CF3)2、-CH2CH2CH2CF3、-CH2CH(CF3)2、-C(CF3)3等，較佳為-CH2CH2CF3。 The component (C) preferably has a fluorinated alkyl group, and the fluorinated alkyl group preferably has a fluorine atom at the end, from the viewpoint of reducing the resistance to the oxidizing agent used in the roughening treatment and the plating penetration depth. The fluorinated alkyl group is preferably a fluorinated alkyl group having 1 to 20 carbon atoms, more preferably a fluorinated alkyl group having 1 to 10 carbon atoms, and still more preferably a fluorinated alkyl group having 1 to 6 carbon atoms. Examples of such fluorinated alkyl groups include -CF 3 , -CH 2 CF 3 , -CF 2 CF 3 , -CH 2 CH 2 CF 3 , -CH(CF 3 ) 2 , and -CH 2 CH 2 CH 2 CF 3 , -CH 2 CH(CF 3 ) 2 , -C(CF 3 ) 3, etc., preferably -CH 2 CH 2 CF 3 .

又，(C)成分從提昇反應性的觀點來看，較佳為(C)成分1分子中之烷氧基的數目為1~5，更佳為烷氧基的數目為1~3，再更佳為烷氧基的數目為2~3。 In addition, from the viewpoint of improving the reactivity of the component (C), the number of alkoxy groups in one molecule of the component (C) is preferably 1 to 5, and more preferably the number of alkoxy groups is 1 to 3. More preferably, the number of alkoxy groups is 2 to 3.

作為在(C)成分之烷氧基，從提昇反應性的觀點來看，較佳為碳原子數1~20之烷氧基，更佳為碳原子數1~10之烷氧基，再更佳為碳原子數1~6之烷氧基。作為如此之烷氧基，例如可列舉甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、s-丁氧基、異丁氧基、t-丁氧基、戊氧基、己氧基、庚氧基、辛氧基、壬氧基、及癸氧基，較佳為甲氧基。 As the alkoxy group in the component (C), from the viewpoint of improving reactivity, an alkoxy group having 1 to 20 carbon atoms is preferred, an alkoxy group having 1 to 10 carbon atoms is more preferred, and even more Preferably, it is an alkoxy group having 1 to 6 carbon atoms. Examples of such alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, s-butoxy, isobutoxy, t-butoxy, and pentoxy. Group, hexyloxy, heptyloxy, octyloxy, nonyloxy, and decyloxy, preferably methoxy.

烷氧基可具有取代基。作為取代基並未特別限制，例如可列舉鹵素原子、-OH、-O-C1-6烷基、-N(C1-6烷基)2、C1-6烷基、C6-10芳基、-NH2、-CN、-C(O)O-C1-6烷基、-COOH、-C(O)H、-NO2等。 The alkoxy group may have a substituent. The substituent is not particularly limited, and examples thereof include halogen atoms, -OH, -OC 1-6 alkyl, -N(C 1-6 alkyl) 2 , C 1-6 alkyl, and C 6-10 aryl. , -NH 2 , -CN, -C(O)OC 1-6 alkyl, -COOH, -C(O)H, -NO 2 and so on.

於此，所謂「Cp-q」(p及q為正整數，滿足p<q)之用語，係表示僅接此用語所記載之有機基的碳原子數為p~q。例如「C1-6烷基」的表現係表示碳原子數1~6之烷基。 Here, the term "C pq "(p and q are positive integers and satisfy p<q) means that only the number of carbon atoms of the organic group described in this term is p~q. For example , the expression of "C 1-6 alkyl" means an alkyl group with 1 to 6 carbon atoms.

上述之取代基可進一步具有取代基(以下有稱為「二次取代基」的情況)。作為二次取代基，除非另有說明，可使用與上述之取代基相同者。 The above-mentioned substituent may further have a substituent (hereinafter, it may be referred to as a "secondary substituent"). As the secondary substituent, unless otherwise specified, the same ones as the above-mentioned substituents can be used.

作為(C)成分之分子量，從提昇相溶性的觀點來看，較佳為50~2000，更佳為75~100，再更佳為100~500。 As the molecular weight of the component (C), from the viewpoint of improving compatibility, it is preferably 50 to 2000, more preferably 75 to 100, and still more preferably 100 to 500.

此等當中，作為(C)成分，可列舉3,3,3-三氟丙基三甲氧基矽烷、含有全氟(聚)醚基之烷氧基矽烷化合物等。此等可1種單獨使用，亦可組合2種以上使用。其中，作為(C)成分，較佳為3,3,3-三氟丙基三甲氧基矽烷。(C)成分可使用市售品，例如可列舉信越化學工業(股)製「KBM-7103」、「OPTOOLDSX」。 Among these, as the component (C), 3,3,3-trifluoropropyltrimethoxysilane, perfluoro(poly)ether group-containing alkoxysilane compounds, and the like can be cited. These can be used individually by 1 type, and can also be used in combination of 2 or more types. Among them, as the component (C), 3,3,3-trifluoropropyltrimethoxysilane is preferred. For the component (C), commercially available products can be used. Examples include "KBM-7103" and "OPTOOLDSX" manufactured by Shin-Etsu Chemical Co., Ltd.

本發明之樹脂組成物中所包含之(C)成分的態樣雖並未特別限定，但較佳為以下述(i)~(iii)之態樣含在樹脂組成物中，更佳為以(i)或(iii)之態樣含在樹脂組成物中，再更佳為以(i)之態樣含在樹脂組 成物中。亦即，(C)成分作為(D)成分之表面處理劑，較佳為含在樹脂組成物中。 Although the aspect of the component (C) contained in the resin composition of the present invention is not particularly limited, it is preferably contained in the resin composition in the following aspects (i) to (iii), more preferably The form of (i) or (iii) is contained in the resin composition, and more preferably the form of (i) is contained in the resin composition Chengzhong. That is, the component (C) as the surface treatment agent of the component (D) is preferably contained in the resin composition.

(i)(C)成分作為(D)成分之表面處理劑含有 (i) (C) component is contained as a surface treatment agent of (D) component

(ii)以(C)成分單獨含有在樹脂組成物中 (ii) Component (C) is separately contained in the resin composition

(iii)(C)成分可作為(D)成分之表面處理劑含有，同時以(C)成分單獨含有在樹脂組成物中 (iii) Component (C) can be included as a surface treatment agent for component (D), and component (C) can be contained in the resin composition alone

所謂「(C)成分作為(D)成分之表面處理劑含有」，係表示(D)成分以(C)成分表面處理。此情況下，(C)成分通常在(D)成分之表面。又，所謂「以(C)成分單獨含在樹脂組成物中」，係表示(C)成分並未作為(D)成分之表面處理劑含有。尚，(C)成分未作為(D)成分之表面處理劑含有的情況下，(D)成分游離在樹脂組成物中，對絕緣層表面之低粗糙度化有效。 "The component (C) is contained as a surface treatment agent of the component (D)" means that the component (D) is surface-treated with the component (C). In this case, the component (C) is usually on the surface of the component (D). In addition, the phrase "the component (C) is contained in the resin composition alone" means that the component (C) is not contained as the surface treatment agent of the component (D). However, when the component (C) is not contained as the surface treatment agent of the component (D), the component (D) is released in the resin composition and is effective for reducing the surface roughness of the insulating layer.

(C)成分的含量以(C)成分單獨含有在樹脂組成物中的情況下，較佳為0.1質量%以上，更佳為0.15質量%以上，再更佳為0.2質量%以上。上限雖並未特別限定，但較佳為10質量%以下，更佳為8質量%以下，再更佳為6質量%以下。 When the content of the component (C) is contained in the resin composition as the component (C) alone, it is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and still more preferably 0.2% by mass or more. Although the upper limit is not particularly limited, it is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 6% by mass or less.

將(C)成分作為(D)成分之表面處理劑含有的情況下，藉由(C)成分之表面處理的程度，從降低絕緣層表面之粗糙度及鍍敷潛入深度的觀點來看，相對於(D)成分100質量份，較佳為以0.2質量份~5質量份之(C)成分進行表面處理，更佳為以0.3質量份~3質量 份之(C)成分進行表面處理，再更佳為以0.5質量份~2.5質量份之(C)成分進行表面處理。 When the (C) component is contained as the surface treatment agent of the (D) component, the degree of the surface treatment of the (C) component will reduce the surface roughness of the insulating layer and the plating penetration depth. 100 parts by mass of (D) component, preferably 0.2 parts by mass to 5 parts by mass of (C) component for surface treatment, more preferably 0.3 parts by mass to 3 parts by mass Part (C) component is surface treated, and more preferably 0.5 to 2.5 parts by mass (C) component is surface treated.

<(D)無機填充材> <(D) Inorganic filler>

無機填充材的材料雖並未特別限定，但例如可列舉二氧化矽、氧化鋁、玻璃、堇青石、矽氧化物、硫酸鋇、碳酸鋇、滑石、黏土、雲母粉、氧化鋅、水滑石、薄水鋁石、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、及磷酸鎢酸鋯等。此等當中，尤其適合二氧化矽、氧化鋁。又作為二氧化矽，較佳為球狀二氧化矽。無機填充材可1種單獨使用，亦可組合2種以上使用。 Although the material of the inorganic filler is not particularly limited, for example, silica, alumina, glass, cordierite, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, titanic acid Magnesium, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among these, silica and alumina are particularly suitable. As the silica, spherical silica is preferred. The inorganic filler may be used singly or in combination of two or more kinds.

無機填充材的平均粒徑雖並未特別限定，但從得到表面粗糙度小之絕緣層或提昇微細配線形成性的觀點來看，較佳為2μm以下，更佳為1.5μm以下，再更佳為1μm以下。該平均粒徑的下限雖並未特別限定，但較佳為0.01μm以上，更佳為0.1μm以上，再更佳為0.3μm以上。作為具有如此平均粒徑之無機填充材之市售品，例如可列舉(股)Admatechs製「YC100C」、「YA050C」、「YA050C-MJE」、「YA010C」、電氣化學工業製「UFP-30」、德山製「Sifil NSS-3N」、「Sifil NSS-4N」、「Sifil NSS-5N」、(股)Admatechs製 「SC2500SQ」、「SO-C4」、「SO-C2」、「SO-C1」等。 Although the average particle size of the inorganic filler is not particularly limited, it is preferably 2 μm or less, more preferably 1.5 μm or less, from the viewpoint of obtaining an insulating layer with small surface roughness or improving the formation of fine wiring. It is 1μm or less. Although the lower limit of the average particle diameter is not particularly limited, it is preferably 0.01 μm or more, more preferably 0.1 μm or more, and still more preferably 0.3 μm or more. Commercial products of inorganic fillers having such an average particle size include, for example, "YC100C", "YA050C", "YA050C-MJE", "YA010C", and "UFP-30" manufactured by Admatechs Corporation. , Tokuyama made "Sifil NSS-3N", "Sifil NSS-4N", "Sifil NSS-5N", (stock) Admatechs system "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", etc.

無機填充材之平均粒徑可根據米氏(Mie)散射理論藉由雷射繞射暨散射法測定。具體而言，藉由雷射繞射散射式粒度分布測定裝置，將無機填充材之粒度分布以體積基準作成，可藉由將其中位徑作為平均粒徑來測定。測定樣品較佳可使用將無機填充材藉由超音波而使其分散於水中者。作為雷射繞射散射式粒度分布測定裝置，可使用(股)堀場製作所製「LA-500」等。 The average particle size of the inorganic filler can be measured by the laser diffraction and scattering method according to the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is created on a volume basis by a laser diffraction scattering type particle size distribution measuring device, and the median diameter can be measured as the average particle size. It is preferable to use an inorganic filler dispersed in water by ultrasonic waves as the measurement sample. As a laser diffraction scattering type particle size distribution measuring device, "LA-500" manufactured by Horiba Manufacturing Co., Ltd., etc. can be used.

無機填充材較佳為以表面處理劑進行表面處理。作為表面處理劑，可列舉(C)成分、及(C)成分以外之表面處理劑(以下亦稱為「其他表面處理劑」)。無機填充材可以(C)成分進行表面處理，亦可以其他表面處理劑進行表面處理。從提高耐濕性及分散性、以及降低絕緣層表面之粗糙度及鍍敷潛入深度的觀點來看，較佳為以(C)成分進行表面處理，除了(C)成分之外亦可以其他表面處理劑進行表面處理。 The inorganic filler is preferably surface-treated with a surface treatment agent. Examples of the surface treatment agent include (C) component and surface treatment agents other than (C) component (hereinafter also referred to as "other surface treatment agents"). The inorganic filler may be surface-treated with the component (C), or may be surface-treated with other surface treatment agents. From the viewpoint of improving moisture resistance and dispersibility, as well as reducing the surface roughness of the insulating layer and the depth of plating penetration, it is preferable to use the (C) component for surface treatment, and other surfaces other than the (C) component may be used. The treatment agent performs surface treatment.

作為其他表面處理劑，例如可列舉胺基矽烷系偶合劑、環氧矽烷系偶合劑、巰基矽烷系偶合劑、烷氧基矽烷化合物、有機矽氮烷化合物、鈦酸酯系偶合劑等。此等可1種單獨使用，亦可組合2種以上使用。作為如此之其他表面處理劑的市售品，例如可列舉信越化學工業(股)製「KBM-403」(3-環氧甘油氧基丙基三甲氧基矽烷)、信越化學工業(股)製「KBM-803」(3-巰基丙基 三甲氧基矽烷)、信越化學工業(股)製「KBE-903」(3-胺基丙基三乙氧基矽烷)、信越化學工業(股)製「KBM-573」(N-苯基-3-胺基丙基三甲氧基矽烷)、信越化學工業(股)製「SZ-31」(六甲基矽氮烷)、信越化學工業(股)製「KBM-103」(苯基三甲氧基矽烷)、信越化學工業(股)製「KBM-4803」(長鏈環氧型矽烷偶合劑)等。 Examples of other surface treatment agents include aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, alkoxysilane compounds, organosilazane compounds, titanate-based coupling agents, and the like. These can be used individually by 1 type, and can also be used in combination of 2 or more types. Commercial products of such other surface treatment agents include, for example, "KBM-403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBM-803" (3-mercaptopropyl Trimethoxysilane), "KBE-903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM-573" (N-phenyl-) manufactured by Shin-Etsu Chemical Co., Ltd. 3-aminopropyltrimethoxysilane), "SZ-31" (hexamethylsilazane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM-103" (phenyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Base silane), "KBM-4803" (long-chain epoxy silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

藉由表面處理劑之表面處理的程度可藉由每一無機填充材之單位表面積之碳量來評估。每一無機填充材之單位表面積之碳量，從無機填充材之分散性提昇的觀點來看，較佳為0.05mg/m2以上，更佳為0.1mg/m2以上，再更佳為0.2mg/m2以上。另外，從防止樹脂清漆之熔融黏度或以薄片形態之熔融黏度的上昇觀點來看，較佳為1mg/m2以下，更佳為0.8mg/m2以下，再更佳為0.5mg/m2以下。每一無機填充材之單位表面積的碳量可依照後述之<每一單位表面積之碳量的算出>所記載之方法測定。 The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of each inorganic filler. The amount of carbon per unit surface area of each inorganic filler, from the viewpoint of improving the dispersibility of the inorganic filler, is preferably 0.05 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and still more preferably 0.2 mg/m 2 or more. In addition, from the viewpoint of preventing the melt viscosity of the resin varnish or the melt viscosity in the form of a sheet from increasing, it is preferably 1 mg/m 2 or less, more preferably 0.8 mg/m 2 or less, and still more preferably 0.5 mg/m 2 the following. The amount of carbon per unit surface area of each inorganic filler can be measured according to the method described in <Calculation of the amount of carbon per unit surface area> described later.

樹脂組成物中之無機填充材的含量從得到熱膨脹率較低之絕緣層的觀點來看，較佳為60質量%以上，更佳為65質量%以上，再更佳為70質量%以上。樹脂組成物中之無機填充材的含量的上限，從絕緣層之機械強度的觀點來看，較佳為95質量%以下，更佳為90質量%以下，再更佳為85質量%以下。(D)成分以(C)成分進行表面處理的情況下，上述無機填充材的含量係包含 (C)成分的含量。 The content of the inorganic filler in the resin composition is preferably 60% by mass or more, more preferably 65% by mass or more, and still more preferably 70% by mass or more from the viewpoint of obtaining an insulating layer with a low thermal expansion rate. From the viewpoint of the mechanical strength of the insulating layer, the upper limit of the content of the inorganic filler in the resin composition is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less. When the component (D) is surface-treated with the component (C), the content of the above-mentioned inorganic filler includes (C) Content of ingredients.

<(E)熱塑性樹脂> <(E) Thermoplastic resin>

本發明之樹脂組成物除了(A)~(D)成分之外亦可含有(E)熱塑性樹脂。 The resin composition of the present invention may contain (E) thermoplastic resin in addition to the components (A) to (D).

作為熱塑性樹脂，例如可列舉苯氧基樹脂、聚乙烯縮醛樹脂、聚烯烴樹脂、聚丁二烯樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞胺樹脂、聚碸樹脂、聚醚碸樹脂、聚苯醚樹脂、聚碳酸酯樹脂、聚醚醚酮樹脂、聚酯樹脂，較佳為苯氧基樹脂。熱塑性樹脂可1種單獨使用、或亦可組合2種以上使用。 Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyimide resins, polyetherimide resins, and polyimide resins. The ash resin, polyether ash resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, preferably phenoxy resin. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more types.

熱塑性樹脂之聚苯乙烯換算之重量平均分子量較佳為8,000~70,000的範圍，更佳為10,000~60,000的範圍，再更佳為20,000~60,000的範圍。熱塑性樹脂之聚苯乙烯換算之重量平均分子量係以凝膠滲透層析(GPC)法測定。具體而言，熱塑性樹脂之聚苯乙烯換算之重量平均分子量，係使用(股)島津製作所製LC-9A/RID-6A作為測定裝置，使用昭和電工(股)製Shodex K-800P/K-804L/K-804L作為管柱，使用氯仿作為移動相等，在管柱溫度40℃測定，可使用標準聚苯乙烯之檢量線算出。 The weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The weight average molecular weight of the thermoplastic resin in terms of polystyrene is measured by the gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured using LC-9A/RID-6A manufactured by Shimadzu Corporation and Shodex K-800P/K-804L manufactured by Showa Denko Corporation. /K-804L is used as the column, and chloroform is used as the moving equivalent. It is measured at the column temperature of 40°C and can be calculated using the calibration curve of standard polystyrene.

作為苯氧基樹脂，例如可列舉具有選自由雙酚A骨架、雙酚F骨架、雙酚S骨架、雙酚苯乙酮骨架、酚醛清漆骨架、聯苯骨架、茀骨架、雙環戊二烯骨 架、降莰烯骨架、萘骨架、蔥骨架、金剛烷骨架、萜烯骨架、及三甲基環己烷骨架所構成之群組中之1種以上骨架的苯氧基樹脂。苯氧基樹脂之末端可為酚性羥基、環氧基等任一種之官能基。苯氧基樹脂可1種單獨使用，亦可組合2種以上使用。作為苯氧基樹脂之具體例，可列舉三菱化學(股)製之「1256」及「4250」(皆為含有雙酚A骨架之苯氧基樹脂)、「YX8100」(含有雙酚S骨架之苯氧基樹脂)、及「YX6954BH30」(含有雙酚苯乙酮骨架之苯氧基樹脂)，其他當中，亦可列舉新日鐵住金化學(股)製之「FX280」及「FX293」、三菱化學(股)製之「YX6954BH30」、「YX7553BH30」、「YL7769BH30」、「YL6794BH30」、「YL7213BH30」、「YL7290BH30」及「YL7482BH30」等。 Examples of phenoxy resins include those having a skeleton selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, stilbene skeleton, and dicyclopentadiene skeleton. A phenoxy resin with at least one type of skeleton in the group consisting of a framework, a norbornene skeleton, a naphthalene skeleton, an onion skeleton, adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The end of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types. As specific examples of phenoxy resins, "1256" and "4250" (both phenoxy resins containing bisphenol A skeleton) manufactured by Mitsubishi Chemical Co., Ltd., and "YX8100" (containing bisphenol S skeleton) Phenoxy resin), and "YX6954BH30" (phenoxy resin containing bisphenol acetophenone skeleton), among others, "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Mitsubishi "YX6954BH30", "YX7553BH30", "YL7769BH30", "YL6794BH30", "YL7213BH30", "YL7290BH30", "YL7482BH30", etc. manufactured by Chemical Corporation.

作為聚乙烯縮醛樹脂，例如可列舉聚乙烯縮甲醛樹脂、聚乙烯縮丁醛樹脂，較佳為聚乙烯縮丁醛樹脂。作為聚乙烯縮醛樹脂之具體例，可列舉電氣化學工業(股)製之「電化縮丁醛4000-2」、「電化縮丁醛5000-A」、「電化縮丁醛6000-C」、「電化縮丁醛6000-EP」、積水化學工業(股)製之S-LEC BH系列、BX系列(例如BX-5Z)、KS系列(例如KS-1)、BL系列、BM系列等。 Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of polyvinyl acetal resins include "Electrochemical Butyral 4000-2", "Electrochemical Butyral 5000-A", "Electrochemical Butyral 6000-C" manufactured by Denki Chemical Industry Co., Ltd. "Electrochemical Butyral 6000-EP", S-LEC BH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series manufactured by Sekisui Chemical Industry Co., Ltd.

作為聚醯亞胺樹脂之具體例，可列舉新日本理化(股)製之「RIKACOAT SN20」及「RIKACOAT PN20」。又，作為聚醯亞胺樹脂之具體例，可列舉使2官能性羥基末端聚丁二烯、二異氰酸酯化合物及四元酸酐進行反應所得之線狀聚醯亞胺(日本特開2006-37083號公報之聚醯亞胺)、含有聚矽氧烷骨架之聚醯亞胺(日本特開2002-12667號公報及日本特開2000-319386號公報等所記載之聚醯亞胺)等之改質聚醯亞胺。 Specific examples of polyimide resins include "RIKACOAT SN20" and "RIKACOAT PN20". In addition, as a specific example of the polyimide resin, a linear polyimide obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (Japanese Patent Laid-Open No. 2006-37083) The modification of polyimide in the bulletin), polyimide containing a polysiloxane skeleton (polyimide described in JP 2002-12667 and JP 2000-319386, etc.), etc. Polyimide.

作為聚醯胺醯亞胺樹脂之具體例，可列舉東洋紡績(股)製之「VYLOMAX HR11NN」及「VYLOMAX HR16NN」。作為聚醯胺醯亞胺樹脂之具體例，又可列舉日立化成工業(股)製之「KS9100」、「KS9300」(含有聚矽氧烷骨架之聚醯胺醯亞胺)等之改質聚醯胺醯亞胺。 Specific examples of polyimide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. As specific examples of polyimide resins, modified polyimide resins such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyimide imide) manufactured by Hitachi Chemical Co., Ltd. can also be cited. Amide imine.

作為聚醚碸樹脂之具體例，可列舉住友化學(股)製之「PES5003P」等。 As a specific example of the polyether sulfite resin, "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. and the like can be cited.

作為聚苯醚樹脂之具體例，可列舉三菱瓦斯化學(股)製之寡苯醚．苯乙烯樹脂「OPE-2St 1200」等。 As a specific example of polyphenylene ether resin, oligophenylene ether manufactured by Mitsubishi Gas Chemical Co., Ltd. can be cited. Styrene resin "OPE-2St 1200", etc.

作為聚碸樹脂之具體例，可列舉Solvay Advanced Polymers(股)製之聚碸「P1700」、「P3500」等。 As a specific example of the polyimide resin, the polyimide "P1700" and "P3500" manufactured by Solvay Advanced Polymers (stocks) can be cited.

其中，作為熱塑性樹脂，較佳為苯氧基樹脂、聚乙烯縮醛樹脂。據此，在適合之一實施形態，熱塑性樹脂係包含由苯氧基樹脂及聚乙烯縮醛樹脂所構成之群組中之1種以上。 Among them, as the thermoplastic resin, phenoxy resin and polyvinyl acetal resin are preferred. According to this, in a suitable embodiment, the thermoplastic resin system includes one or more of the group consisting of phenoxy resin and polyvinyl acetal resin.

樹脂組成物含有熱塑性樹脂的情況下，熱塑 性樹脂的含量較佳為0.5質量%~10質量%，更佳為0.6質量%~5質量%，再更佳為0.7質量%~3質量%。 When the resin composition contains a thermoplastic resin, the thermoplastic The content of the sexual resin is preferably 0.5% by mass to 10% by mass, more preferably 0.6% by mass to 5% by mass, and still more preferably 0.7% by mass to 3% by mass.

<(F)硬化促進劑> <(F) Hardening accelerator>

本發明之樹脂組成物除了(A)~(D)成分之外可含有(F)硬化促進劑。 The resin composition of the present invention may contain (F) a hardening accelerator in addition to the components (A) to (D).

作為硬化促進劑，例如可列舉磷系硬化促進劑、胺系硬化促進劑、咪唑系硬化促進劑、胍系硬化促進劑、金屬系硬化促進劑等，較佳為磷系硬化促進劑、胺系硬化促進劑、咪唑系硬化促進劑、金屬系硬化促進劑，更佳為胺系硬化促進劑、咪唑系硬化促進劑、金屬系硬化促進劑。硬化促進劑可1種單獨使用，亦可組合2種以上使用。 Examples of the hardening accelerator include phosphorus hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, guanidine hardening accelerators, metal hardening accelerators, etc., preferably phosphorus hardening accelerators, amine hardening accelerators, etc. The hardening accelerator, the imidazole-based hardening accelerator, and the metal-based hardening accelerator are more preferably an amine-based hardening accelerator, an imidazole-based hardening accelerator, or a metal-based hardening accelerator. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

作為磷系硬化促進劑，例如可列舉三苯基膦、鏻硼酸酯化合物、四苯基鏻四苯基硼酸酯、n-丁基鏻四苯基硼酸酯、四丁基鏻癸酸鹽、(4-甲基苯基)三苯基鏻硫氰酸酯、四苯基鏻硫氰酸酯、丁基三苯基鏻硫氰酸酯等，較佳為三苯基膦、四丁基鏻癸酸鹽。 Examples of phosphorus-based hardening accelerators include triphenyl phosphine, phosphonium borate compounds, tetraphenyl phosphonium tetraphenyl borate, n-butyl phosphonium tetraphenyl borate, and tetrabutyl phosphonium decanoic acid. Salt, (4-methylphenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc., preferably triphenyl phosphine, tetrabutyl Base phosphonium caprate.

作為胺系硬化促進劑，例如可列舉三乙基胺、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,-參(二甲基胺基甲基)酚、1,8-二氮雜聯環(5,4,0)-十一碳烯等，較佳為4-二甲基胺基吡啶、1,8-二氮雜聯環(5,4,0)-十一碳烯。 Examples of amine-based hardening accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, and (Dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine, 1,8- Diazabicyclo(5,4,0)-undecene.

作為咪唑系硬化促進劑，例如可列舉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-氰乙基-2-甲基咪唑、1-氰乙基-2-十一烷基咪唑、1-氰乙基-2-乙基-4-甲基咪唑、1-氰乙基-2-苯基咪唑、1-氰乙基-2-十一烷基咪唑鎓偏苯三酸酯、1-氰乙基-2-苯基咪唑鎓偏苯三酸酯、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪、2,4-二胺基-6-[2’-十一烷基咪唑基-(1’)]-乙基-s-三嗪、2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三嗪、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪異氰脲酸加成物、2-苯基咪唑異氰脲酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2,3-二氫-1H-吡咯[1,2-a]苯并咪唑、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之加合物，較佳為2-乙基-4-甲基咪唑、1-苄基-2-苯基咪唑。 Examples of imidazole-based hardening accelerators include 2-methyl Imidazole, 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-cyano Ethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenyl Imidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-Methylimidazolyl-(1')]-Ethyl-s-triazine, 2,4-Diamino-6-[2'-Undecylimidazolyl-(1')]- Ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4 -Diamino-6-[2'-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-pyrrole[1,2-a]benzene Imidazole compounds such as bisimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, etc. and the addition of imidazole compounds and epoxy resin The compound is preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

作為咪唑系硬化促進劑可使用市售品，例如可列舉三菱化學公司製之「P200-H50」等。 Commercially available products can be used as the imidazole-based hardening accelerator, and examples include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

作為胍系硬化促進劑，例如可列舉雙氰胺、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、1,5,7-三氮雜雙環[4.4.0]癸-5-烯、7-甲基-1,5,7-三氮雜雙環[4.4.0]癸-5-烯、1-甲基雙胍、1-乙基雙 胍、1-n-丁基雙胍、1-n-十八烷基雙胍、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，較佳為雙氰胺、1,5,7-三氮雜雙環[4.4.0]癸-5-烯。 As the guanidine-based hardening accelerator, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, metformin Guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1 ,5,7-Triazabicyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl bis Guanidine, 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, etc., preferably dicyandiamide, 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

作為金屬系硬化促進劑，例如可列舉鈷、銅、鋅、鐵、鎳、錳、錫等金屬之有機金屬錯合物或有機金屬鹽。作為有機金屬錯合物之具體例，可列舉鈷(II)乙醯丙酮酸鹽、鈷(III)乙醯丙酮酸鹽等之有機鈷錯合物、銅(II)乙醯丙酮酸鹽等之有機銅錯合物、鋅(II)乙醯丙酮酸鹽等之有機鋅錯合物、鐵(III)乙醯丙酮酸鹽等之有機鐵錯合物、鎳(II)乙醯丙酮酸鹽等之有機鎳錯合物、錳(II)乙醯丙酮酸鹽等之有機錳錯合物等。作為有機金屬鹽，例如可列舉辛酸鋅、辛酸錫、環烷酸鋅、環烷酸鈷、硬脂酸錫、硬脂酸鋅等。 Examples of the metal-based hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetylpyruvate, cobalt (III) acetylpyruvate, and copper (II) acetylpyruvate. Organocopper complexes, organic zinc complexes such as zinc (II) acetopyruvate, organic iron complexes such as iron (III) acetopyruvate, nickel (II) acetylpyruvate, etc. The organic nickel complexes, manganese (II) acetopyruvate and other organic manganese complexes. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

樹脂組成物中之硬化促進劑的含量雖並未特別限定，但較佳為將環氧樹脂與硬化劑之不揮發成分合計量定為100質量%時，為0.01質量%~9質量%。 Although the content of the hardening accelerator in the resin composition is not particularly limited, it is preferably 0.01 to 9% by mass when the total amount of the non-volatile components of the epoxy resin and the hardener is 100% by mass.

<(G)阻燃劑> <(G) Flame Retardant>

本發明之樹脂組成物即使不包含阻燃劑，阻燃性亦優異，但可包含(G)阻燃劑。作為阻燃劑，例如可列舉有機磷系阻燃劑、含有有機系氮之磷化合物、氮化合物、金屬氫氧化物等。阻燃劑可1種單獨使用、或亦可併用2種以上。 Even if the resin composition of the present invention does not contain a flame retardant, it has excellent flame retardancy, but it may contain (G) a flame retardant. Examples of flame retardants include organic phosphorus flame retardants, phosphorus compounds containing organic nitrogen, nitrogen compounds, metal hydroxides, and the like. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

作為阻燃劑可使用市售品，例如可列舉三光公司製之「HCA-HQ」、大八化學工業(股)製之「PX-200」等。 Commercially available products can be used as the flame retardant, and examples include "HCA-HQ" manufactured by Sanko Co., Ltd., "PX-200" manufactured by Dahachi Chemical Industry Co., Ltd., and the like.

樹脂組成物含有阻燃劑的情況下，阻燃劑的含量雖並未特別限定，但以較佳為0.5質量%~20質量%，更佳為0.5質量%~15質量%，再更佳為0.5質量%~10質量%更佳。 When the resin composition contains a flame retardant, although the content of the flame retardant is not particularly limited, it is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and still more preferably It is more preferably 0.5% by mass to 10% by mass.

<(H)有機填充材> <(H) Organic Filling Material>

樹脂組成物從使拉伸提昇的觀點來看，可包含(H)有機填充材。作為有機填充材，可使用形成印刷配線板之絕緣層時可使用之任意有機填充材，例如可列舉橡膠粒子、聚醯胺微粒子、矽氧粒子等。 The resin composition may contain (H) an organic filler from the viewpoint of improving stretching. As the organic filler, any organic filler that can be used when forming the insulating layer of a printed wiring board can be used, and examples thereof include rubber particles, polyamide fine particles, and silica particles.

作為橡膠粒子可使用市售品，例如可列舉陶氏化學日本(股)製之「EXL2655」、甘茲化成(股)製之「AC3816N」等。 As the rubber particles, commercially available products can be used. For example, "EXL2655" manufactured by Dow Chemical Japan Co., Ltd., "AC3816N" manufactured by Ganz Chemicals Co., Ltd., and the like can be cited.

樹脂組成物含有有機填充材的情況下，有機填充材的含量較佳為0.1質量%~20質量%，更佳為0.2質量%~10質量%，再更佳為0.3質量%~5質量%、或0.5質量%~3質量%。 When the resin composition contains an organic filler, the content of the organic filler is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass, and still more preferably 0.3% by mass to 5% by mass, Or 0.5% by mass to 3% by mass.

<(I)任意之添加劑> <(I) Any additives>

樹脂組成物如有必要可包含其他添加劑，作為該其他添加劑，例如可列舉有機銅化合物、有機鋅化合物及有機 鈷化合物等之有機金屬化合物、以及增黏劑、消泡劑、整平劑、密著性賦予劑、及著色劑等之樹脂添加劑等。 The resin composition may contain other additives if necessary. Examples of the other additives include organic copper compounds, organic zinc compounds, and organic Organometallic compounds such as cobalt compounds, and resin additives such as tackifiers, defoamers, levelers, adhesion imparting agents, and coloring agents.

又，樹脂組成物從製造可撓之印刷配線板的觀點來看，較佳為進一步含有於分子內具有聚丁二烯構造、胺基甲酸乙酯構造、醯亞胺構造、及於分子末端具有酚構造之聚醯亞胺樹脂。含有該聚醯亞胺樹脂的情況下，含量較佳為10質量%~85質量%，更佳為15質量%~50質量%，再更佳為20質量%~30質量%。 In addition, from the viewpoint of manufacturing a flexible printed wiring board, the resin composition preferably further contains a polybutadiene structure, a urethane structure, an amide structure, and a molecular end having a polybutadiene structure in the molecule. Phenolic structure of polyimide resin. When the polyimide resin is contained, the content is preferably 10% by mass to 85% by mass, more preferably 15% by mass to 50% by mass, and still more preferably 20% by mass to 30% by mass.

該聚醯亞胺的細節可參酌國際公開第2008/153208號之記載，將此內容組入本說明書。 The details of the polyimide can refer to the record of International Publication No. 2008/153208, and this content is incorporated into this specification.

本發明之樹脂組成物帶來熱硬化物表面的粗糙度、剝離強度、鍍敷潛入深度、零件嵌入性、及阻燃性良好之絕緣層。據此，本發明之樹脂組成物可適合作為用以形成印刷配線板之絕緣層的樹脂組成物(印刷配線板之絕緣層用樹脂組成物)使用，更適合作為用以形成印刷配線板之層間絕緣層的樹脂組成物(印刷配線板之層間絕緣層用樹脂組成物)使用。又，本發明之樹脂組成物由於帶來零件嵌入性良好之絕緣層，即使印刷配線板為零件內藏電路板的情況亦可適合使用。 The resin composition of the present invention provides an insulating layer with good surface roughness, peel strength, plating penetration depth, part embedding properties, and flame retardancy of the thermoset surface. Accordingly, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board), and is more suitable for use as an interlayer for forming a printed wiring board The resin composition of the insulating layer (the resin composition for the interlayer insulating layer of a printed wiring board) is used. In addition, since the resin composition of the present invention provides an insulating layer with good parts embedding, it can be suitably used even when the printed wiring board is a circuit board with a built-in part.

[薄片狀層合材料] [Flake Laminated Material]

本發明之樹脂組成物雖亦可以清漆狀態塗佈使用，但工業上一般而言適合以包含該樹脂組成物之薄片狀層合材料的形態使用。 Although the resin composition of the present invention can be applied and used in a varnish state, it is generally industrially suitable for use in the form of a sheet-like laminate containing the resin composition.

作為薄片狀層合材料，較佳為以下所示之樹脂薄片、預浸料。 As the sheet-like laminate material, the following resin sheets and prepregs are preferred.

在一實施形態，樹脂薄片已包含支持體、與和該支持體接合之樹脂組成物層，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 already includes a support and a resin composition layer bonded to the support, and the resin composition layer is formed of the resin composition of the present invention.

樹脂組成物層的厚度，較佳為900μm以下，更佳為800μm以下，再更佳為700μm以下，又再更佳為600μm以下。尤其是本發明由於可將鍍敷潛入深度抑制在小，故較佳為30μm以下，更佳為20μm以下，再更佳為10μm以下。樹脂組成物層的厚度的下限雖並未特別限定，但通常可為1μm以上、1.5μm以上、2μm以上等。 The thickness of the resin composition layer is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, and still more preferably 600 μm or less. In particular, in the present invention, since the plating penetration depth can be suppressed to be small, it is preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 10 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can usually be 1 μm or more, 1.5 μm or more, 2 μm or more.

作為支持體，例如可列舉由塑膠材料所成之薄膜、金屬箔、脫模紙，較佳為由塑膠材料所成之薄膜、金屬箔。 Examples of the support include films made of plastic materials, metal foils, and release paper, and films made of plastic materials and metal foils are preferred.

作為支持體使用由塑膠材料所成之薄膜的情況下，作為塑膠材料，例如可列舉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)等之丙烯醯基、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，特佳為便宜之聚對苯二甲酸乙二酯。 When a film made of a plastic material is used as the support, as the plastic material, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter Sometimes abbreviated as "PEN") such as polyester, polycarbonate (hereinafter sometimes referred to as "PC"), polymethylmethacrylate (PMMA) and other acryl, cyclic polyolefin, triacetin Base 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.

作為支持體使用金屬箔的情況下，作為金屬 箔，例如可列舉銅箔、鋁箔等，較佳為銅箔。作為銅箔，可使用由銅之單金屬所成之箔，亦可使用由銅與其他金屬(例如錫、鉻、銀、鎂、鎳、鋯、矽、鈦等)之合金所成之箔。 When using metal foil as a support, as a metal Examples of the foil include copper foil and aluminum foil, and copper foil is preferred. As the copper foil, a foil made of a single metal of copper can be used, and a foil made of an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can also be used.

支持體可於與樹脂組成物層接合的面實施磨砂處理、電暈處理。 The support may be frosted or corona treated on the surface joined with the resin composition layer.

又，作為支持體，可使用於與樹脂組成物層接合的面具有脫模層之附脫模層之支持體。作為附脫模層之支持體的脫模層所使用之脫模劑，例如可列舉選自由酸醇樹脂、聚烯烴樹脂、胺基甲酸乙酯樹脂、及矽氧樹脂所構成之群組中之1種以上的脫模劑。附脫模層之支持體可使用市售品，例如可列舉具有將酸醇樹脂系脫模劑作為主成分之脫模層之PET薄膜即Lintec(股)製之「SK-1」、「AL-5」、「AL-7」、東麗(股)製「LumirrorT6AM」等。 In addition, as the support, a support with a mold release layer having a mold release layer on the surface to be bonded to the resin composition layer can be used. As the mold release agent used for the mold release layer of the support with the mold release layer, for example, it may be selected from the group consisting of alcohol resins, polyolefin resins, urethane resins, and silicone resins. One or more release agents. Commercial products can be used for the support with a release layer. Examples include PET film with a release layer based on an acid-alcohol resin-based release agent, namely "SK-1" and "AL" made by Lintec. -5", "AL-7", Toray's "LumirrorT6AM", etc.

作為支持體的厚度雖並未特別限定，但較佳為5μm~75μm的範圍，更佳為10μm~60μm的範圍。尚，使用附脫模層之支持體的情況下，較佳為附脫模層之支持體全體的厚度為上述範圍。 Although the thickness of the support is not particularly limited, it is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In the case of using a support with a release layer, it is preferable that the thickness of the entire support with a release layer is in the above-mentioned range.

樹脂薄片，例如於有機溶劑調製溶解樹脂組成物之樹脂清漆，可藉由將此樹脂清漆使用模塗佈機等塗佈在支持體上，進而使其乾燥而形成樹脂組成物層來製造。 The resin sheet, for example, a resin varnish in which a resin composition is dissolved in an organic solvent can be prepared by coating the resin varnish on a support using a die coater or the like, and then drying it to form a resin composition layer.

作為有機溶劑，例如可列舉丙酮、甲基乙基 酮(MEK)及環己酮等之酮類、乙酸乙酯、乙酸丁酯、溶纖劑乙酸酯、丙二醇單甲基醚乙酸酯及卡必醇乙酸酯等之乙酸酯類、溶纖劑及丁基卡必醇等之卡必醇類、甲苯及二甲苯等之芳香族烴類、二甲基甲醯胺、二甲基乙醯胺(DMAc)及N-甲基吡咯啶酮等之醯胺系溶媒等。有機溶劑可1種單獨使用，亦可組合2種以上使用。 As the organic solvent, for example, acetone, methyl ethyl Ketones such as ketones (MEK) and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate and other acetates, solvents Carbitols such as fiber and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone And other amide-based solvents. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

乾燥可藉由加熱、吹送熱風等之周知的乾燥方法實施。乾燥條件雖並未特別限定，但樹脂組成物層中之有機溶劑的含量成為10質量%以下，較佳為成為5質量%以下的方式來乾燥。雖因樹脂清漆中之有機溶劑的沸點而不同，但例如使用包含30質量%~60質量%之有機溶劑的樹脂清漆時，藉由使其於50℃~150℃乾燥3分鐘~10分鐘，可形成樹脂組成物層。 Drying can be performed by a well-known drying method such as heating and blowing hot air. Although the drying conditions are not particularly limited, the content of the organic solvent in the resin composition layer is 10% by mass or less, and drying is preferably performed so that it is 5% by mass or less. Although it differs depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% to 60% by mass of organic solvent is used, it can be dried at 50°C to 150°C for 3 minutes to 10 minutes. A resin composition layer is formed.

在樹脂薄片，在未與樹脂組成物層之支持體接合的面(亦即，與支持體相反側的面)中，可進一步層合依照支持體之保護薄膜。保護薄膜的厚度雖並非被特別限定者，但例如為1μm~40μm。藉由層合保護薄膜，可防止對樹脂組成物層的表面之塵埃等之附著或傷痕。樹脂薄片可捲繞成輥狀保存。樹脂薄片具有保護薄膜的情況下，可藉由剝離保護薄膜來使用。 In the resin sheet, on the surface not bonded to the support of the resin composition layer (that is, the surface on the opposite side to the support), a protective film corresponding to the support may be further laminated. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent adhesion or scratches of dust and the like on the surface of the resin composition layer. The resin sheet can be wound into a roll for storage. When the resin sheet has a protective film, it can be used by peeling off the protective film.

在一實施形態，預浸料係於薄片狀纖維基材含浸本發明之樹脂組成物而形成。 In one embodiment, the prepreg is formed by impregnating a sheet-like fiber substrate with the resin composition of the present invention.

預浸料所使用之薄片狀纖維基材並未特別限定，可使用常被作為玻璃布、芳香族聚醯胺(Aramid)不 織布、液晶聚合物不織布等之預浸料用基材使用者。從印刷配線板之薄型化的觀點來看，薄片狀纖維基材的厚度較佳為900μm以下，更佳為800μm以下，再更佳為700μm以下，又再更佳為600μm以下。尤其是由於本發明可將鍍敷潛入深度抑制在小，故較佳為30μm以下，更佳為20μm以下，再更佳為10μm以下。薄片狀纖維基材的厚度之下限雖並未特別限定，但通常可為1μm以上、1.5μm以上、2μm以上等。 The sheet-like fibrous substrate used for the prepreg is not particularly limited. It can be used as glass cloth, aromatic polyamide (Aramid) Users of substrates for prepregs such as woven fabrics and liquid crystal polymer non-woven fabrics. From the viewpoint of thinning of the printed wiring board, the thickness of the sheet-like fiber substrate is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, and still more preferably 600 μm or less. In particular, because the present invention can suppress the plating penetration depth to be small, it is preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 10 μm or less. Although the lower limit of the thickness of the sheet-like fibrous base material is not particularly limited, it can usually be 1 μm or more, 1.5 μm or more, 2 μm or more.

預浸料可藉由熱熔法、溶劑法等之周知方法製造。 The prepreg can be manufactured by a well-known method such as a hot melt method and a solvent method.

預浸料的厚度可與在上述之樹脂薄片之樹脂組成物層為相同的範圍。 The thickness of the prepreg may be in the same range as the resin composition layer of the above-mentioned resin sheet.

在薄片狀層合材料樹脂組成物層(預浸料的情況下，含浸在薄片狀纖維基材之樹脂組成物)的最低熔融黏度，從得到良好之零件嵌入性的觀點來看，較佳為12000poise(1200Pa．s)以下，更佳為10000poise(1000Pa．s)以下，再更佳為8000poise(800Pa．s)以下、5000poise(500Pa．s)以下、或4000poise(400Pa．s)以下。該最低熔融黏度的下限，從安定維持樹脂組成物層既薄且厚度的觀點來看，較佳為100poise(10Pa．s)以上，更佳為200poise(20Pa．s)以上，再更佳為250poise(25Pa．s)以上。 The lowest melt viscosity of the sheet-like laminate resin composition layer (in the case of a prepreg, the resin composition impregnated in the sheet-like fiber substrate) is preferably from the viewpoint of obtaining good part embedding properties 12000poise (1200Pa.s) or less, more preferably 10000poise (1000Pa.s) or less, still more preferably 8000poise (800Pa.s) or less, 5000poise (500Pa.s) or less, or 4000poise (400Pa.s) or less. The lower limit of the minimum melt viscosity is preferably 100 poise (10 Pa·s) or more, more preferably 200 poise (20 Pa·s) or more, and still more preferably 250 poise from the viewpoint of stably maintaining the thinness and thickness of the resin composition layer. (25Pa.s) or more.

所謂樹脂組成物層之最低熔融黏度，係指熔融樹脂組成物層之樹脂時，樹脂組成物層呈現最低的黏 度。詳細而言，係以一定之昇溫速度加熱樹脂組成物層使樹脂熔融時，初期階段熔融黏度伴隨溫度上昇而下降，然後當溫度超過某種程度時，與溫度上昇一起提昇熔融黏度。所謂最低熔融黏度，係指該極小點之熔融黏度。樹脂組成物層之最低熔融黏度，可使用動態黏彈法測定，例如可依後述之<樹脂組成物層之最低熔融黏度的測定>所記載之方法測定。 The so-called minimum melt viscosity of the resin composition layer means that when the resin of the resin composition layer is melted, the resin composition layer exhibits the lowest viscosity. Spend. Specifically, when the resin composition layer is heated at a constant temperature increase rate to melt the resin, the melt viscosity decreases with the temperature rise in the initial stage, and then when the temperature exceeds a certain level, the melt viscosity increases together with the temperature rise. The so-called minimum melt viscosity refers to the minimum melt viscosity. The minimum melt viscosity of the resin composition layer can be measured using the dynamic viscoelastic method, for example, it can be measured according to the method described in the below-mentioned "Measuring the minimum melt viscosity of the resin composition layer".

在本發明之樹脂組成物(或樹脂組成物層)的硬化物(例如將樹脂組成物以190℃熱硬化90分鐘)，顯示阻燃性優異之特性。該阻燃性較佳為根據UL-94V規格之V-0或較V-0更為優異。阻燃性的評估可依後述之<阻燃性的評估>所記載之方法測定。 The cured product of the resin composition (or resin composition layer) of the present invention (for example, the resin composition is thermally cured at 190°C for 90 minutes) exhibits excellent flame retardancy characteristics. The flame retardancy is preferably V-0 according to UL-94V standard or better than V-0. The evaluation of flame retardancy can be measured according to the method described in <Evaluation of flame retardancy> described later.

[印刷配線板] [Printed Wiring Board]

本發明之印刷配線板係包含藉由本發明之樹脂組成物的硬化物所形成之絕緣層。 The printed wiring board of the present invention includes an insulating layer formed by a cured product of the resin composition of the present invention.

例如，本發明之印刷配線板係使用上述之樹脂薄片，可藉由包含下述步驟(I)及(II)之方法製造。 For example, the printed wiring board of the present invention uses the above-mentioned resin sheet, and can be manufactured by a method including the following steps (I) and (II).

(I)將樹脂薄片以該樹脂薄片之樹脂組成物層與內層基板接合的方式，層合於內層基板上之步驟 (I) The step of laminating the resin sheet on the inner substrate by bonding the resin composition layer of the resin sheet to the inner substrate

(II)熱硬化樹脂組成物層形成絕緣層之步驟 (II) Steps of forming insulating layer from thermosetting resin composition layer

所謂步驟(I)所使用之「內層基板」，主要係指玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚苯醚基板等之基板、或形 成圖型加工於該基板之單面或兩面之導體層(電路)的電路基板。又製造印刷配線板時，進而要形成絕緣層及/或導體層之中間製造物的內層電路基板亦包含在本發明之「內層基板」。印刷配線板為零件內藏電路板的情況下，使用內藏零件之內層基板即可(導體層亦稱為配線層)。 The "inner substrate" used in step (I) mainly refers to substrates such as glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. Or form A circuit substrate with a conductor layer (circuit) on one or both sides of the substrate is patterned. When a printed wiring board is manufactured, an inner layer circuit board in which an insulating layer and/or a conductor layer is to be formed as an intermediate product is also included in the "inner layer substrate" of the present invention. When the printed wiring board is a circuit board with built-in parts, it is sufficient to use an inner-layer substrate with built-in parts (the conductor layer is also referred to as a wiring layer).

內層基板與樹脂薄片的層合，例如可藉由從支持體側將樹脂薄片加熱壓著在內層基板來進行。作為將樹脂薄片加熱壓著在內層基板之構件(以下亦稱為「加熱壓著構件」)，例如可列舉經加熱之金屬板(SUS鏡板等)或金屬輥(SUS輥)等。尚，較佳為並非將加熱壓著構件直接沖壓在樹脂薄片，而是於內層基板的表面凹凸以樹脂薄片充分追隨的方式，透過耐熱橡膠等之彈性材進行沖壓。 The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet against the inner layer substrate from the support side. As a member for heat-pressing the resin sheet to the inner layer substrate (hereinafter also referred to as "heating and pressing member"), for example, a heated metal plate (SUS mirror plate, etc.) or metal roller (SUS roller) can be cited. However, it is preferable not to directly press the heating and pressing member on the resin sheet, but to press through an elastic material such as heat-resistant rubber so that the surface irregularities of the inner substrate are fully followed by the resin sheet.

內層基板與樹脂薄片的層合，可藉由真空層合法實施。在真空層合法，加熱壓著溫度較佳為60℃~160℃，更佳為80℃~140℃的範圍，加熱壓著壓力較佳為0.098MPa~1.77MPa，更佳為0.29MPa~1.47MPa的範圍，加熱壓著時間較佳為20秒~400秒，更佳為30秒~300秒的範圍。層合較佳為以壓力26.7hPa以下之減壓條件下實施。 The lamination of the inner substrate and the resin sheet can be implemented by a vacuum lamination method. In the vacuum lamination method, the heating and pressing temperature is preferably 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heating and pressing pressure is preferably 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa The heating and pressing 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.

層合處理可使用市售之真空層合機來實施。作為市售之真空層合機，例如可列舉(股)名機製作所製之真空加壓式層合機、Nichigo-Morton(股)製之真空敷料器等。 The lamination process can be implemented using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressure laminator manufactured by Meiji Seisakusho Co., Ltd., and a vacuum applicator manufactured by Nichigo-Morton Co., Ltd. can be cited.

層合之後，於常壓(大氣壓)下，例如藉由將加熱壓著構件從支持體側進行沖壓，可進行經層合之樹脂薄片的平滑化處理。平滑化處理的沖壓條件可成為與上述層合之加熱壓著條件相同的條件。平滑化處理可藉由市售之層合機進行。尚，層合與平滑化處理可使用市售之真空層合機連續性進行。 After lamination, under normal pressure (atmospheric pressure), for example, by pressing the heating and pressing member from the support side, smoothing treatment of the laminated resin sheet can be performed. The pressing conditions of the smoothing treatment can be the same conditions as the heating and pressing conditions of the above-mentioned lamination. The smoothing treatment can be performed by a commercially available laminator. Still, the lamination and smoothing process can be continuously performed using a commercially available vacuum laminator.

支持體可於步驟(I)與步驟(II)之間去除，亦可於步驟(II)之後去除。 The support can be removed between step (I) and step (II), or after step (II).

在步驟(II)，熱硬化樹脂組成物層而形成絕緣層。 In step (II), the resin composition layer is thermoset to form an insulating layer.

樹脂組成物層之熱硬化條件並未特別限定，可使用形成印刷配線板之絕緣層時通常所採用之條件。 The thermosetting conditions of the resin composition layer are not particularly limited, and the conditions generally used when forming the insulating layer of a printed wiring board can be used.

例如，樹脂組成物層之熱硬化條件，雖因樹脂組成物的種類等而不同，但硬化溫度可成為120℃~240℃的範圍(較佳為150℃~220℃的範圍，更佳為170℃~200℃的範圍)，硬化時間可成為5分鐘~120分鐘的範圍(較佳為10分鐘~100分鐘，更佳為15分鐘~90分鐘)。 For example, although the thermosetting conditions of the resin composition layer vary depending on the type of resin composition, etc., the curing temperature can be in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably 170 ℃~200℃), the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

熱硬化樹脂組成物層之前，可將樹脂組成物層在較硬化溫度更低之溫度進行預備加熱。例如，在熱硬化樹脂組成物層之前，可在50℃以上未滿120℃(較佳為60℃以上110℃以下，更佳為70℃以上100℃以下)之溫度，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)。 Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before the thermosetting resin composition layer, the resin composition layer can be prepared at a temperature above 50°C but less than 120°C (preferably 60°C or more and 110°C or less, more preferably 70°C or more and 100°C or less). Heating for more than 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

製造印刷配線板時，可進一步實施(III)鑽孔於絕緣層之步驟、(IV)粗糙化處理絕緣層之步驟、(V)形成導體層之步驟。此等之步驟(III)~(V)可依用在印刷配線板之製造，本發明領域具有通常知識者所周知之各種方法來實施。尚，將支持體於步驟(II)之後去除的情況下，可於步驟(II)與步驟(III)之間、步驟(III)與步驟(IV)之間、或步驟((IV)與步驟(V)之間來實施。 When manufacturing a printed wiring board, (III) a step of drilling a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer can be further implemented. These steps (III) to (V) can be implemented in various methods known to those with ordinary knowledge in the field of the invention in the manufacture of printed wiring boards. Still, in the case of removing the support after step (II), it can be done between step (II) and step (III), between step (III) and step (IV), or between step ((IV) and step (IV)). (V) Implemented in between.

步驟(III)係鑽孔於絕緣層之步驟，藉此，可於絕緣層形成通孔、貫穿孔等之孔。步驟(III)因應絕緣層之形成所使用之樹脂組成物的組成等，例如使用鑽孔機、雷射、電漿等來實施。孔之尺寸或形狀可因應印刷配線板之設計適當決定。 Step (III) is a step of drilling holes in the insulating layer, whereby holes such as through holes and through holes can be formed in the insulating layer. Step (III) is carried out in accordance with the composition of the resin composition used in the formation of the insulating layer, for example, using a drill, a laser, or a plasma. The size or shape of the hole can be appropriately determined according to the design of the printed wiring board.

步驟(IV)係粗糙化處理絕緣層之步驟。粗糙化處理的順序、條件並未特別限定，可採用形成印刷配線板之絕緣層時通常所使用之周知順序、條件。例如，可依藉由膨潤液之膨潤處理、藉由氧化劑之粗糙化處理、藉由中和液之中和處理此順序實施，可粗糙化處理絕緣層。作為膨潤液雖並未特別限定，但可列舉鹼溶液、界面活性劑溶液等，較佳為鹼溶液，作為該鹼溶液，更佳為氫氧化鈉溶液、氫氧化鉀溶液。作為市售之膨潤液，例如可列舉Atotech Japan(股)製之「Swelling Dip Securiganth P」、「Swelling Dip Securiganth SBU」等。藉由膨潤液之膨潤處理雖並未特別限定，但例如可藉由於30℃~90 ℃之膨潤液浸漬1分鐘~20分鐘絕緣層來進行。從將絕緣層之樹脂的膨潤抑制在適當之水準的觀點來看，較佳為於加熱至40℃~80℃之膨潤液浸漬硬化體5分鐘~15分鐘。作為氧化劑(粗糙化液)，雖並未特別限定，但例如可列舉於氫氧化鈉之水溶液溶解過錳酸鉀或過錳酸鈉之鹼性過錳酸溶液。藉由鹼性過錳酸溶液等氧化劑之粗糙化處理，較佳為於加熱至60℃~80℃之氧化劑溶液浸漬10分鐘~30分鐘絕緣層來進行。又，在鹼性過錳酸溶液之過錳酸鹽的濃度較佳為5質量%~10質量%。作為市售之氧化劑，例如可列舉Atotech Japan(股)製之「Concentrate Compact CP」、「Concentrate Compact P」、「Dozing Solusion Securiganth P」等之鹼性過錳酸溶液。又，作為中和液，較佳為酸性之水溶液，作為市售品，例如可列舉Atotech Japan(股)製之「Reduction solution Securiganth P」。藉由中和液之處理，可藉由未進行藉由氧化劑溶液之粗糙化處理的處理面於30℃~80℃之中和液浸漬5分鐘~30分鐘來進行。從作業性等之點來看，較佳為將成為藉由氧化劑之粗糙化處理的對象物於40℃~70℃之中和液浸漬5分鐘~20分鐘之方法。 Step (IV) is a step of roughening the insulating layer. The order and conditions of the roughening treatment are not particularly limited, and the well-known order and conditions generally used when forming the insulating layer of a printed wiring board can be adopted. For example, the swelling treatment with a swelling solution, the roughening treatment with an oxidizing agent, and the neutralization treatment with a neutralization solution can be performed in this order, and the insulating layer can be roughened. Although it does not specifically limit as a swelling liquid, an alkali solution, a surfactant solution, etc. are mentioned, Preferably it is an alkali solution, As this alkali solution, sodium hydroxide solution and potassium hydroxide solution are more preferable. Examples of commercially available swelling fluids include "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, it can be The insulation layer is immersed in the swelling liquid at ℃ 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 impregnate the hardened body with a swelling solution heated to 40°C to 80°C for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent (roughening liquid), for example, the alkaline permanganic acid solution which melt|dissolved potassium permanganate or sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment by an oxidant such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidant solution heated to 60°C to 80°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidants include alkaline permanganic acid solutions such as "Concentrate Compact CP", "Concentrate Compact P", and "Dozing Solusion Securiganth P" manufactured by Atotech Japan. In addition, as the neutralizing liquid, an acidic aqueous solution is preferable, and as a commercially available product, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd. can be cited. The treatment by the neutralization solution can be performed by immersing the treated surface that has not been roughened by the oxidizing agent solution in the neutralization solution for 5 minutes to 30 minutes at 30°C to 80°C. From the viewpoint of workability and the like, a method of immersing an object to be roughened by an oxidizing agent in a neutral solution at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

步驟(V)係形成導體層之步驟。 Step (V) is a step of forming a conductor layer.

導體層所使用之導體材料並未特別限定。於適合之實施形態，導體層係包含選自由金、鉑、鈀、銀、銅、鋁、鈷、鉻、鋅、鎳、鈦、鎢、鐵、錫及銦所構成之群組中之1種以上的金屬。導體層可為單金屬層亦可為合 金層，作為合金層，例如可列舉選自由上述之群組中之2種以上的金屬之合金(例如鎳暨鉻合金、銅暨鎳合金及銅暨鈦合金)所形成之層。其中，從導體層形成之泛用性、成本、圖型化之容易性等之觀點來看，較佳為鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅之單金屬層、或鎳暨鉻合金、銅暨鎳合金、銅暨鈦合金之合金層，更佳為鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅之單金屬層、或鎳暨鉻合金之合金層，再更佳為銅之單金屬層。 The conductor material used in the conductor layer is not particularly limited. For a suitable embodiment, the conductor layer includes one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium Above the metal. The conductor layer can be a single metal layer or a composite The gold layer, as the alloy layer, may be, for example, a layer formed by an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, from the viewpoints of versatility, cost, and ease of patterning of the conductor layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, Or nickel and chromium alloy, copper and nickel alloy, copper and titanium alloy alloy layer, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel and chromium alloy layer The alloy layer is more preferably a single metal layer of copper.

導體層可為單層構造，亦可為由不同種類之金屬或合金所成之單金屬層或層合2層以上合金層之複層構造。導體層為複層構造的情況下，與絕緣層接觸之層較佳為鉻、鋅或鈦之單金屬層、或鎳暨鉻合金之合金層。 The conductor layer can be a single-layer structure, a single metal layer made of different types of metals or alloys, or a multiple-layer structure composed of two or more alloy layers. When the conductor layer has a multi-layer 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 and chromium alloy.

導體層的厚度雖因所期望印刷配線板的設計而異，但一般為3μm~35μm，較佳為5μm~30μm。 Although the thickness of the conductor layer varies depending on the design of the desired printed wiring board, it is generally 3 μm to 35 μm, and preferably 5 μm to 30 μm.

在一實施形態中，導體層可藉由鍍敷形成。例如，藉由半加成法、全加成法等之以往周知之技術鍍敷於絕緣層之表面，可形成具有所期望配線圖型之導體層。以下，表示將導體層藉由半加成法形成之例。 In one embodiment, the conductive layer can be formed by plating. For example, by plating on the surface of the insulating layer by a well-known technique such as a semi-additive method, a full-additive method, etc., a conductor layer with a desired wiring pattern can be formed. The following shows an example in which the conductor layer is formed by the semi-additive method.

首先，於絕緣層之表面，藉由無電解鍍敷形成鍍敷種晶層(seed layer)。其次，於所形成之鍍敷種晶層上，對應所期望之配線圖型，形成使鍍敷種晶層之一部分露出之遮罩圖型。於露出之鍍敷種晶層上，藉由電解鍍敷形成金屬層後，去除遮罩圖型。然後，將不要之鍍敷種晶層藉由蝕刻等去除，可形成具有所期望配線圖型之導 體層。 First, on the surface of the insulating layer, a plating seed layer is formed by electroless plating. Secondly, on the formed plating seed layer, corresponding to the desired wiring pattern, a mask pattern is formed that exposes a part of the plating seed layer. After forming a metal layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like to form a conductor with the desired wiring pattern. Body layer.

本發明之樹脂組成物由於帶來零件嵌入性良好之絕緣層，即使於印刷配線板為零件內藏電路板的情況，亦可適合使用。 Since the resin composition of the present invention provides an insulating layer with good parts embedding properties, it can be suitably used even when the printed wiring board is a circuit board with a built-in part.

作為如此之零件內藏電路板的製造方法，係包含(i)~(v)之步驟，(i)係準備暫時配附零件之步驟，該暫時配附零件之內層基板係具有對向之第1及第2主面，且包含形成貫通該第1及第2主面間之孔洞(Cavity)的內層基板、與和內層基板之第2主面接合之暫時配附之材料、與在內層基板之孔洞的內部藉由暫時配附之材料而暫時配附之零件、(ii)將本發明之樹脂薄片以樹脂組成物層與內層基板之第1主面接合的方式層合之步驟、(iii)從內層基板之第2主面剝離暫時配附之材料之步驟、(iv)將樹脂薄片以樹脂組成物層與內層基板之第2主面接合的方式層合之步驟、及(v)熱硬化樹脂組成物層之步驟。 As such a method of manufacturing a circuit board with a built-in part, it includes the steps (i) to (v). (i) is the step of preparing temporarily attached parts, and the inner substrate of the temporarily attached parts has opposing The first and second main surfaces, and include an inner substrate that forms a cavity (cavity) penetrating between the first and second main surfaces, a temporarily attached material that is bonded to the second main surface of the inner substrate, and A part that is temporarily attached to the inside of the cavity of the inner substrate by temporarily attaching the material, (ii) the resin sheet of the present invention is laminated with the resin composition layer and the first main surface of the inner substrate The step of (iii) the step of peeling the temporarily attached material from the second main surface of the inner layer substrate, (iv) the resin sheet is laminated so that the resin composition layer is bonded to the second main surface of the inner layer substrate Step, and (v) Step of thermosetting the resin composition layer.

如表示一例於圖1，暫時配附零件之內層基板100(亦稱為「孔洞基板」)，係具有對向之第1及第2主面11、12，且包含形成貫通該第1及第2主面間之孔洞1a的內層基板1、與和內層基板1之第2主面12接合之暫時配附之材料2、與在內層基板之孔洞1a的內部藉 由暫時配附之材料2而暫時配附之零件3。內層基板1可準備貫孔(Via)配線、表面配線等之電路配線4。 For example, as shown in Fig. 1, the inner substrate 100 (also referred to as the "hole substrate") for temporarily attaching parts has opposed first and second main surfaces 11, 12, and includes forming through the first and The inner layer substrate 1 of the hole 1a between the second main surfaces, the temporarily attached material 2 that is bonded to the second main surface 12 of the inner layer substrate 1, and the inside of the hole 1a of the inner layer substrate From the temporarily attached material 2 and the temporarily attached part 3. The inner substrate 1 can be prepared with circuit wiring 4 such as via wiring and surface wiring.

內層基板所形成之孔洞考慮內層基板的特性，例如可藉由使用鑽孔機、雷射、電漿、蝕刻媒體等之周知方法形成。孔洞可鑽開預定之間隔複數形成，孔洞之開口形狀並未特別限定，可成為矩形、圓形、略矩形、略圓形等之任意形狀。 The holes formed in the inner layer substrate take into consideration the characteristics of the inner layer substrate, and can be formed, for example, by using a well-known method such as a drill, a laser, a plasma, an etching medium, and the like. The holes can be drilled at predetermined intervals and formed in plural, and the opening shape of the holes is not particularly limited, and can be any shape such as rectangular, circular, slightly rectangular, or slightly circular.

作為暫時配附之材料，為了將零件暫時配附，只要具有表示充分黏著性之黏著面則並未特別限制，於零件內藏電路板的製造時，可使用以往周知之任意暫時配附之材料。作為暫時配附之材料，例如可列舉(股)有澤製作所製之PFDKE-1525TT(附黏著劑之聚醯亞胺薄膜)、古河電氣工業(股)製之UC系列(晶圓切割用UV膠帶)。 As a material for temporary attachment, in order to temporarily attach the part, it is not particularly limited as long as it has an adhesive surface showing sufficient adhesiveness. When manufacturing a circuit board inside the part, any previously known temporary attachment material can be used. . As a material for temporary attachment, for example, PFDKE-1525TT (polyimide film with adhesive) manufactured by Yusawa Manufacturing Co., Ltd., and UC series (UV tape for wafer dicing) manufactured by Furukawa Electric Co., Ltd. .

零件係透過孔洞暫時配附在露出之暫時配附之材料的黏著面。作為零件，因應所期望特性選擇適當之電氣零件即可，例如可列舉電容器、電感器、電阻、層合陶瓷電容器等之受動零件、半導體裸晶片等之現用零件。於全部孔洞可使用相同零件，於每一孔洞可使用不同之零件。 The parts are temporarily attached to the exposed adhesive surface of the temporarily attached material through the holes. As the parts, suitable electrical parts can be selected according to the desired characteristics. Examples include passive parts such as capacitors, inductors, resistors, multilayer ceramic capacitors, and current parts such as semiconductor bare chips. The same parts can be used in all holes, and different parts can be used in each hole.

步驟(ii)係將本發明之樹脂薄片以樹脂組成物層與內層基板之第1主面接合的方式層合之步驟。第1主面與樹脂薄片的層合條件係與上述之步驟(I)的條件相同，較佳範圍亦相同。 Step (ii) is a step of laminating the resin sheet of the present invention such that the resin composition layer is bonded to the first main surface of the inner substrate. The lamination conditions of the first main surface and the resin sheet are the same as the conditions of the above-mentioned step (I), and the preferred ranges are also the same.

可於內層基板之第1主面層合樹脂組成物層後，熱硬化樹脂組成物層。熱硬化樹脂組成物層的條件係與上述之步驟(II)的條件相同，較佳範圍亦相同。 After the resin composition layer is laminated on the first main surface of the inner substrate, the resin composition layer can be thermoset. The conditions of the thermosetting resin composition layer are the same as the conditions of the above-mentioned step (II), and the preferred ranges are also the same.

步驟(iii)係從內層基板之第2主面剝離暫時配附之材料之步驟。暫時配附之材料的剝離，可因應暫時配附之材料的種類，依以往周知之方法進行。 Step (iii) is a step of peeling the temporarily attached material from the second main surface of the inner substrate. The peeling of temporarily attached materials can be carried out according to the type of temporarily attached materials according to the well-known methods in the past.

步驟(iv)係將樹脂薄片以樹脂組成物層與內層基板之第2主面接合的方式層合之步驟。第2主面與樹脂薄片的層合條件係與上述之步驟(I)的條件相同，較佳範圍亦相同。在步驟(iv)之樹脂組成物層，可為與在步驟(ii)之樹脂組成物層為同一樹脂組成物層，亦可為不同樹脂組成物層。 Step (iv) is a step of laminating the resin sheet such that the resin composition layer is bonded to the second main surface of the inner substrate. The lamination conditions of the second main surface and the resin sheet are the same as the conditions of the above step (I), and the preferred ranges are also the same. The resin composition layer in step (iv) may be the same resin composition layer as the resin composition layer in step (ii), or a different resin composition layer.

步驟(v)係熱硬化樹脂組成物層之步驟。熱硬化樹脂組成物層的條件係與上述之步驟(II)的條件相同，較佳範圍亦相同。 Step (v) is a step of thermosetting the resin composition layer. The conditions of the thermosetting resin composition layer are the same as the conditions of the above-mentioned step (II), and the preferred ranges are also the same.

作為零件內藏電路板之製造方法，可進一步包含進而在絕緣層鑽孔之步驟(鑽孔步驟)、粗糙化處理絕緣層的表面之步驟、於經粗糙化之絕緣層表面形成導體層之步驟。此等步驟係如上述。 As a method of manufacturing a circuit board with a built-in part, it may further include a step of drilling a hole in the insulating layer (drilling step), a step of roughening the surface of the insulating layer, and a step of forming a conductor layer on the surface of the roughened insulating layer . These steps are as described above.

本發明之印刷配線板可為具備本發明之樹脂薄片之樹脂組成物層的硬化物即絕緣層、與嵌入絕緣層之嵌入型配線層的態樣。 The printed wiring board of the present invention may include an insulating layer that is a cured product of the resin composition layer of the resin sheet of the present invention, and an embedded wiring layer in which the insulating layer is embedded.

作為如此印刷配線板之製造方法，係包含(1)~(4)之步驟， (1)準備具有內層基板、與該基材之至少一側的面所設置之配線層的附配線層之基材之步驟、(2)將本發明之樹脂薄片以配線層嵌入樹脂組成物層的方式，層合在附配線層之基材上，使其熱硬化而形成絕緣層之步驟、(3)層間連接配線層之步驟、及(4)去除基材之步驟。 As a manufacturing method of such a printed wiring board, it includes the steps (1) to (4), (1) A step of preparing a substrate with a wiring layer having an inner substrate and a wiring layer provided on at least one surface of the substrate; (2) The resin sheet of the present invention is embedded in the resin composition with the wiring layer The method of layering is a step of laminating on a substrate with a wiring layer and thermally curing it to form an insulating layer, (3) a step of connecting the wiring layer between layers, and (4) a step of removing the substrate.

於此製造方法所使用之內層基板的兩面中，較佳為具有由銅箔等所構成之金屬層，更佳為金屬層係層合2層以上金屬層之構成。步驟(1)之細節為於基材上層合乾膜(感光性光阻劑薄膜)，使用光罩以預定之條件進行曝光、顯像而形成圖型乾膜。將經顯像之圖型乾膜作為電鍍遮罩，藉由電解電鍍法形成配線層後，剝離圖型乾膜。 On both sides of the inner layer substrate used in this manufacturing method, it is preferable to have a metal layer composed of copper foil or the like, and it is more preferable to have a structure in which the metal layer is laminated with two or more metal layers. The details of step (1) are laminating a dry film (photosensitive photoresist film) on a substrate, and using a photomask to perform exposure and development under predetermined conditions to form a patterned dry film. The developed pattern dry film is used as a plating mask, the wiring layer is formed by electrolytic plating, and the pattern dry film is peeled off.

內層基板與乾膜的層合條件係與上述之步驟(II)的條件相同，較佳範圍亦相同。 The lamination conditions of the inner substrate and the dry film are the same as the conditions of the above step (II), and the preferred ranges are also the same.

將乾膜層合於內層基板上後，為了對於乾膜形成所期望之圖型，使用光罩以預定的條件進行曝光、顯像。 After the dry film is laminated on the inner substrate, in order to form a desired pattern for the dry film, exposure and development are performed under predetermined conditions using a photomask.

配線層之線(電路寬)/空間(電路間的寬)比雖並未特別限制，但較佳為20/20μm以下(即間距為40μm以下)，更佳為18/18μm以下(間距36μm以下)，再更佳為15/15μm以下(間距30μm以下)。配線層之線/空間比的下限雖並未特別限制，但較佳為 0.5/0.5μm以上，更佳為1/1μm以上。間距係通過配線層的全體不須為同一。 Although the line (circuit width)/space (width between circuits) ratio of the wiring layer is not particularly limited, it is preferably 20/20μm or less (that is, the pitch is 40μm or less), and more preferably 18/18μm or less (the pitch is 36μm or less) ), and more preferably 15/15μm or less (pitch 30μm or less). Although the lower limit of the line/space ratio of the wiring layer is not particularly limited, it is preferably 0.5/0.5μm or more, more preferably 1/1μm or more. The pitch does not have to be the same across the entire wiring layer.

形成乾膜之圖型後，形成配線層，剝離乾膜。於此，配線層的形成，可將形成所期望圖型之乾膜作為鍍敷遮罩使用，且可藉由鍍敷法實施。 After the pattern of the dry film is formed, the wiring layer is formed, and the dry film is peeled off. Here, the formation of the wiring layer can use a dry film forming a desired pattern as a plating mask, and can be implemented by a plating method.

配線層所使用之導體材料並未特別限定。於適合之實施形態，配線層係包含選自由金、鉑、鈀、銀、銅、鋁、鈷、鉻、鋅、鎳、鈦、鎢、鐵、錫及銦所構成之群組中之至少一種以上的金屬。配線層可為單金屬層亦可為合金層，作為合金層，例如可列舉選自由上述之群組中之2種以上的金屬之合金(例如鎳暨鉻合金、銅暨鎳合金及銅暨鈦合金)所形成者。 The conductor material used in the wiring layer is not particularly limited. For a suitable embodiment, the wiring layer includes 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 Above the metal. The wiring layer can be a single metal layer or an alloy layer. As the alloy layer, for example, alloys of two or more metals selected from the above group (such as nickel and chromium alloy, copper and nickel alloy, and copper and titanium Alloy) formed by.

配線層的厚度雖因所期望配線板的設計而定，但較佳為3μm~35μm，更佳為5μm~30μm，再更佳為10~20μm、或15μm。 Although the thickness of the wiring layer depends on the design of the desired wiring board, it is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, and still more preferably 10 to 20 μm, or 15 μm.

形成配線層後剝離乾膜。乾膜的剝離可藉由周知之方法實施。如有必要將不要之配線圖型藉由蝕刻等去除，亦可形成所期望之配線圖型。 After the wiring layer is formed, the dry film is peeled off. The peeling of the dry film can be implemented by a well-known method. If necessary, the unnecessary wiring pattern can be removed by etching or the like, and the desired wiring pattern can also be formed.

步驟(2)係將樹脂薄片以配線層嵌入熱硬化性樹脂組成物層的方式層合於附配線層之基材上，並使其熱硬化而形成絕緣層之步驟。附配線層之基材與樹脂薄片的層合條件係與上述之步驟(II)的條件相同，較佳範圍亦相同。 Step (2) is a step of laminating the resin sheet on the substrate with the wiring layer in such a way that the wiring layer is embedded in the thermosetting resin composition layer, and thermally curing it to form an insulating layer. The lamination conditions of the substrate with the wiring layer and the resin sheet are the same as the conditions of the above step (II), and the preferred ranges are also the same.

步驟(3)若為層間連接配線層雖並未特別限 定，但較佳為於絕緣層形成通孔，形成導體層之步驟、及研磨或研削絕緣層，使配線層露出之步驟中之至少任一種之步驟。於絕緣層形成通孔，形成導體層之步驟係如上述。 Step (3) is not particularly limited if it is an interlayer connection wiring layer However, it is preferably at least one of the steps of forming a through hole in the insulating layer, forming a conductive layer, and grinding or grinding the insulating layer to expose the wiring layer. The steps of forming through holes in the insulating layer and forming the conductor layer are as described above.

作為絕緣層之研磨方法或研削方法，可使配線層曝露，若研磨或研削面為水平，則並未特別限定，可適用以往周知之研磨方法或研削方法，例如可列舉藉由化學機械研磨裝置之化學機械研磨方法、拋光(buff)等之機械研磨方法、藉由砥石回轉之平面研削方法等。 As a polishing method or grinding method of the insulating layer, the wiring layer can be exposed. If the polishing or grinding surface is horizontal, it is not particularly limited, and conventionally known polishing methods or grinding methods can be applied. For example, a chemical mechanical polishing device can be used The chemical mechanical grinding method, the mechanical grinding method such as buffing, and the plane grinding method by turning the wheel.

步驟(4)係去除內層基板，形成本發明之印刷配線板之步驟。內層基板的去除方法並未特別限定。適合之一實施形態，於內層基板上所具有之金屬層的界面從印刷配線板剝離內層基板，將金屬層例如以氯化銅水溶液等蝕刻去除。 Step (4) is a step of removing the inner substrate to form the printed wiring board of the present invention. The method of removing the inner layer substrate is not particularly limited. In a suitable embodiment, the inner layer substrate is peeled from the printed wiring board at the interface of the metal layer on the inner layer substrate, and the metal layer is etched away, for example, with a copper chloride aqueous solution or the like.

在其他實施形態，本發明之印刷配線板可使用上述之預浸料製造。製造方法基本上係與使用樹脂薄片的情況相同。 In other embodiments, the printed wiring board of the present invention can be manufactured using the above-mentioned prepreg. The manufacturing method is basically the same as in the case of using a resin sheet.

本發明之印刷配線板係包含藉由本發明之樹脂組成物的硬化物所形成之絕緣層。因此，表示零件嵌入性優易之特性。亦即，使用本發明之薄片狀層合材料所製造之零件內藏電路板，在全部之孔洞，可成為零件之外周邊以樹脂組成物被覆之構成。零件嵌入性的評估可依後述之<零件嵌入性的評估>所記載之方法測定。 The printed wiring board of the present invention includes an insulating layer formed by a cured product of the resin composition of the present invention. Therefore, it shows that the parts are easy to be embedded. That is, the parts manufactured by using the sheet-like laminated material of the present invention have built-in circuit boards, and all the holes in the parts can be covered with a resin composition. The evaluation of the insertability of parts can be measured according to the method described in <Evaluation of Part Insertion> described later.

本發明之印刷配線板由於包含藉由本發明之 樹脂組成物的硬化物所形成之絕緣層，故可降低粗糙度。具體而言，粗糙化處理後之絕緣層表面的算術平均粗糙度(Ra)及均方根粗糙度(Rq)顯示良好之結果。該算術平均粗糙度(Ra)較佳為500nm以下，更佳為450nm以下，再更佳為400nm以下。針對下限雖並未特別限定，但可為100nm以上。絕緣層表面的均方根粗糙度(Rq)較佳為600nm以下，更佳為550nm以下，再更佳為530nm以下。針對下限雖並未特別限定，但可為100nm以上。算術平均粗糙度(Ra)及均方根粗糙度(Rq)的評估，可依後述之(算術平均粗糙度(Ra)、均方根粗糙度(Rq)的測定)所記載之方法測定。 The printed wiring board of the present invention includes the The insulating layer formed by the hardened resin composition can reduce the roughness. Specifically, the arithmetic average roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface after the roughening treatment showed good results. The arithmetic average roughness (Ra) is preferably 500 nm or less, more preferably 450 nm or less, and still more preferably 400 nm or less. Although the lower limit is not particularly limited, it may be 100 nm or more. The root mean square roughness (Rq) of the surface of the insulating layer is preferably 600 nm or less, more preferably 550 nm or less, and still more preferably 530 nm or less. Although the lower limit is not particularly limited, it may be 100 nm or more. The evaluation of the arithmetic mean roughness (Ra) and the root mean square roughness (Rq) can be measured according to the method described in (Measurement of the arithmetic mean roughness (Ra) and root mean square roughness (Rq)) described later.

本發明之印刷配線板係包含藉由本發明之樹脂組成物的硬化物所形成之絕緣層。因此，粗糙化處理後之絕緣層與導體層的剝離強度(Peel Strength)顯示良好之結果。該剝離強度較佳為0.3kgf/cm以上，更佳為0.40kgf/cm以上，再更佳為0.45kgf/cm以上。上限雖並未特別限定，但可為1.2kgf/cm以下、0.9kgf/cm以下等。在本發明，由於粗糙化處理後之絕緣層的算術平均粗糙度(Ra)及均方根粗糙度(Rq)儘管低，亦可形成呈現如此高之剝離強度的導體層，故顯著有助於印刷配線板之微細配線化。剝離強度的評估可依後述之(剝離強度的測定)所記載之方法測定。 The printed wiring board of the present invention includes an insulating layer formed by a cured product of the resin composition of the present invention. Therefore, the peel strength (Peel Strength) of the insulating layer and the conductor layer after the roughening treatment shows good results. The peel strength is preferably 0.3 kgf/cm or more, more preferably 0.40 kgf/cm or more, and still more preferably 0.45 kgf/cm or more. Although the upper limit is not particularly limited, it may be 1.2 kgf/cm or less, 0.9 kgf/cm or less. In the present invention, even though the arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer after the roughening treatment are low, it is possible to form a conductive layer exhibiting such a high peel strength, which significantly contributes to Fine wiring of printed wiring boards. The evaluation of peel strength can be measured according to the method described in (Measurement of peel strength) described later.

藉由本發明之樹脂組成物(或樹脂組成物層)所形成之絕緣層，顯示良好之鍍敷潛入深度。該鍍敷 潛入深度較佳為3.0μm以下，再更佳為2.5μm以下，更佳為2.0μm以下。下限雖並未特別限定，但可為0.1μm以上等。作為一實施形態，在本發明，由於鍍敷潛入深度較低，即使為使用厚度為10μm以下之樹脂組成物層所製造之絕緣層亦具有絕緣性，藉此，顯著有助於印刷配線板之微細配線化及薄膜化。鍍敷潛入深度的評估可依後述之(鍍敷潛入深度的測定)所記載之方法測定。 The insulating layer formed by the resin composition (or resin composition layer) of the present invention shows a good plating penetration depth. The plating The penetration depth is preferably 3.0 μm or less, more preferably 2.5 μm or less, and even more preferably 2.0 μm or less. Although the lower limit is not particularly limited, it may be 0.1 μm or more. As an embodiment, in the present invention, since the plating penetration depth is low, even an insulating layer manufactured using a resin composition layer with a thickness of 10 μm or less has insulating properties, thereby significantly contributing to the printed wiring board Fine wiring and thinning. The evaluation of the plating penetration depth can be measured in accordance with the method described in (Measurement of plating penetration depth) described later.

[半導體裝置] [Semiconductor device]

本發明之半導體裝置係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。 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.

作為半導體裝置，可列舉供於電氣製品(例如電腦、手機、數位相機及電視等)及車輛(例如摩托車、汽車、電車、船舶及飛機等)等之各種半導體裝置。 Examples of semiconductor devices include various semiconductor devices used in electrical products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trams, ships, and airplanes).

本發明之半導體裝置可藉由於印刷配線板之導通處實裝零件(半導體晶片)來製造。所謂「導通處」，係為「傳達在印刷配線板之電信號之處」，該場所可為表面，亦可為經嵌入之處皆無妨。又，半導體晶片若為將半導體作為材料之電氣電路元件則並未特別限定。 The semiconductor device of the present invention can be manufactured by mounting parts (semiconductor chips) due to the conduction of the printed wiring board. The so-called "conducting point" refers to "the place where the electrical signal is transmitted on the printed wiring board". The place can be a surface or a place where it is embedded. In addition, if the semiconductor wafer is an electrical circuit element using a semiconductor as a material, it is not particularly limited.

製造本發明之半導體裝置時之半導體晶片的實裝方法，只要是能夠使半導體晶片有效進行功能，雖並未特別限定，但具體而言，可列舉引線接合實裝方法、倒裝晶片實裝方法、藉由無凹凸積聚層(BBUL)之實裝方法、藉由各向異性導電薄膜(ACF)之實裝方法、藉由非 導電性薄膜(NCF)之實裝方法、等。於此，所謂「藉由無凹凸積聚層(BBUL)之實裝方法」，係指「將半導體晶片直接嵌入印刷配線板的凹部，使半導體晶片與印刷配線板上之配線連接之實裝方法」。 The mounting method of the semiconductor wafer when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor wafer can effectively perform its functions. Specifically, a wire bonding mounting method and a flip chip mounting method can be cited , By the mounting method of the non-concave accumulation layer (BBUL), by the mounting method of the anisotropic conductive film (ACF), by the non- How to mount conductive film (NCF), etc. Here, the so-called "mounting method by non-convex build-up layer (BBUL)" refers to the "mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board to connect the semiconductor chip to the wiring on the printed wiring board" .

[實施例] [Example]

以下，雖將本發明由實施例具體說明，但本發明並非被限定於此等之實施例。尚，在以下之記載，「份」及「%」除非另有規定分別意指「質量份」及「質量%」。 Hereinafter, although the present invention will be specifically explained by examples, the present invention is not limited to these examples. However, in the following description, "parts" and "%" mean "parts by mass" and "% by mass" respectively unless otherwise specified.

<每一單位表面積之碳量的算出> <Calculation of the amount of carbon per unit surface area>

將下述之各無機填充材3g分別作為試料使用。將試料與30g之MEK(甲基乙基酮)放入離心分離機之離心管，進行攪拌使固形分懸濁，將500W之超音波於25℃照射5分鐘。然後，藉由離心分離進行固液分離，去除上清液20g。進而，再加20g之MEK，進行攪拌使固形分懸濁，將500W之超音波於25℃照射5分鐘。然後，藉由離心分離進行固液分離，去除上清液26g。將殘留之懸濁液在160℃乾燥30分鐘。將此乾燥試料0.3g於測定用坩堝正確量取，進而於測定用坩堝放入助燃劑(鎢3.0g及錫0.3g)。將測定用坩堝設定在碳分析計((股)堀場製作所製「EMIA-321V2」)，測定碳量。將碳量的測定值藉由以使用之無機填充劑的比表面積除，算出每一單位表面 積之碳量。 3 g of each inorganic filler described below was used as a sample. Put the sample and 30g of MEK (methyl ethyl ketone) into the centrifuge tube of the centrifugal separator, stir to suspend the solids, and irradiate 500W ultrasonic waves at 25°C for 5 minutes. Then, solid-liquid separation was performed by centrifugal separation, and 20 g of the supernatant was removed. Furthermore, 20 g of MEK was added, stirring was performed to suspend the solid content, and 500 W ultrasonic waves were irradiated at 25° C. for 5 minutes. Then, solid-liquid separation was performed by centrifugal separation, and 26 g of the supernatant was removed. The remaining suspension was dried at 160°C for 30 minutes. 0.3 g of this dry sample was accurately measured in a crucible for measurement, and a combustion aid (3.0 g of tungsten and 0.3 g of tin) was put in the crucible for measurement. The crucible for measurement was set in a carbon analyzer ("EMIA-321V2" manufactured by Horiba Manufacturing Co., Ltd.), and the carbon content was measured. Divide the measured value of carbon content by the specific surface area of the inorganic filler used to calculate each unit surface The amount of carbon accumulated.

<使用之無機填充材> <Used inorganic filler>

無機填充材1：相對於球形二氧化矽((股)Admatechs製「SC4500SQ」(以六甲基二矽氮烷表面處理之「SO-C4」)、廠商記載之平均粒徑約1μm)100份，以3,3,3-三氟丙基三甲氧基矽烷(信越化學工業(股)製、KBM-7103)1份表面處理者。每一單位表面積之碳量為0.25mg/m2。 Inorganic filler 1: 100 parts to spherical silica ("SC4500SQ" manufactured by Admatechs ("SO-C4" with hexamethyldisilazane surface treatment), average particle size of about 1μm as stated by the manufacturer) 100 parts of spherical silica , With 3,3,3-trifluoropropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-7103) 1 part surface treatment. The amount of carbon per unit surface area is 0.25 mg/m 2 .

無機填充材2：相對於球形二氧化矽((股)Admatechs製「SC1500SQ」(以六甲基二矽氮烷表面處理之「SO-C1」)、廠商記載平均粒徑約0.3μm)100份，以3,3,3-三氟丙基三甲氧基矽烷(信越化學工業(股)製、KBM-7103)2份表面處理者。每一單位表面積之碳量為0.16mg/m2。 Inorganic filler 2: 100 parts relative to spherical silica ("SC1500SQ" manufactured by Admatechs ("SO-C1" with hexamethyldisilazane surface treatment), average particle size about 0.3μm as stated by the manufacturer) of spherical silica , Surface treated with 2 parts of 3,3,3-trifluoropropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-7103). The amount of carbon per unit surface area is 0.16 mg/m 2 .

無機填充材3：相對於球形氧化鋁(Denka(股)製「DAW-01」、廠商記載平均粒徑約1.5μm)100份，以3,3,3-三氟丙基三甲氧基矽烷(信越化學工業(股)製、KBM-7103)1份表面處理者。每一單位表面積之碳量為0.12mg/m2。 Inorganic filler 3: 3,3,3-trifluoropropyltrimethoxysilane ( Shin-Etsu Chemical Co., Ltd., KBM-7103) 1 part of surface treatment. The amount of carbon per unit surface area is 0.12 mg/m 2 .

無機填充材4：相對於球形二氧化矽((股)Admatechs製「SC4500SQ」(以六甲基二矽氮烷表面處理之「SO-C4」)、廠商記載平均粒徑約1μm)100份，以3-縮水甘油氧基丙基三甲氧基矽烷(信越化學工業(股) 製、「KBM-403」)1份表面處理者。每一單位表面積之碳量為0.31mg/m2。 Inorganic filler 4: Relative to 100 parts of spherical silicon dioxide ("SC4500SQ" manufactured by Admatechs ("SO-C4" surface-treated with hexamethyldisilazane), manufacturer’s average particle size of about 1μm), Surface treated with 1 part of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-403"). The amount of carbon per unit surface area is 0.31 mg/m 2 .

無機填充材5：相對於球形二氧化矽((股)Admatechs製「SC1500SQ」(以六甲基二矽氮烷表面處理之「SO-C1」)、廠商記載平均粒徑約0.3μm)100份，以3-胺基丙基三甲氧基矽烷(信越化學工業(股)製、「KBM-903」)2份表面處理者。每一單位表面積之碳量為0.23mg/m2。 Inorganic filler 5: 100 parts relative to spherical silica (“SC1500SQ” manufactured by Admatechs (“SO-C1” with hexamethyldisilazane surface treatment), average particle diameter of about 0.3μm according to the manufacturer) , Surface treated with 2 parts of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-903"). The amount of carbon per unit surface area is 0.23 mg/m 2 .

無機填充材6：相對於球形氧化鋁(Denka(股)製「DAW-01」、廠商記載平均粒徑約1.5μm)100份，以乙醯烷氧基二異丙醇鋁(味之素精細化工技術(股)製、「PlainactAL-M」)1份表面處理者。每一單位表面積之碳量為0.15mg/m2。 Inorganic filler 6: To 100 parts of spherical alumina (Denka Co., Ltd. "DAW-01", manufacturer’s description of average particle size is about 1.5μm), acetoxy aluminum diisopropoxide (Ajinomoto Fine Chemical Technology (Stock) System, "PlainactAL-M") 1 part of surface treatment. The amount of carbon per unit surface area is 0.15 mg/m 2 .

無機填充材7：相對於球形二氧化矽((股)Admatechs製「SC4500SQ」、廠商記載平均粒徑約1μm)100份，以苯基三甲氧基矽烷(信越化學工業(股)製、KBM-103)1份表面處理者。每一單位表面積之碳量為0.30mg/m2。 Inorganic filler 7: 100 parts of phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM- 103) 1 part of surface treatment. The amount of carbon per unit surface area is 0.30 mg/m 2 .

[樹脂薄片的製作] [Production of resin sheet]

使用藉由以下之順序所調製之樹脂清漆(樹脂組成物)，製作實施例及比較例之樹脂薄片。 Using the resin varnish (resin composition) prepared by the following procedure, the resin sheet of the Example and the comparative example was produced.

<樹脂清漆1的調製> <Preparation of resin varnish 1>

將雙酚型環氧樹脂(新日鐵住金化學(股)製「ZX1059」、環氧當量約169、雙酚A型與雙酚F型之1：1混合品)4份、二羥基二甲苯(Bixylenol)型環氧樹脂(三菱化學(股)製「YX4000HK」、環氧當量約185)6份、聯苯型環氧樹脂(日本化藥(股)製「NC3000L」、環氧當量約272)20份，邊於溶劑石腦油15份及環己酮10份的混合溶劑攪拌邊使其加熱溶解。冷卻至室溫後，對其混合含有三嗪骨架之甲酚酚醛清漆系硬化劑(DIC(股)製「LA-3018-50P」、羥基當量約151、固形分50%之2-甲氧基丙醇溶液)8份、含有三嗪骨架之酚酚醛清漆系硬化劑(DIC(股)製「LA-7054」、羥基當量約125、固形分60%之MEK溶液)4份、萘酚系硬化劑(新日鐵住金化學(股)製「SN-495V」、羥基當量約231、固形分60%之MEK溶液)10份、胺系硬化促進劑(4-二甲基胺基吡啶(DMAP)、固形分5質量%之MEK溶液)1份、橡膠粒子(陶氏化學日本(股)製、EXL2655)2份、無機填充材1之190份，以高速回轉攪拌機均勻分散後，再以筒式過濾器(ROKITECHNO製「SHP050」)過濾，調製樹脂清漆1。 4 parts of bisphenol epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169, 1:1 mixture of bisphenol A type and bisphenol F type), dihydroxyxylene (Bixylenol) type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent approximately 185) 6 parts, biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent approximately 272 ) 20 parts, heated and dissolved while stirring in a mixed solvent of 15 parts of solvent naphtha and 10 parts of cyclohexanone. After cooling to room temperature, mix it with a cresol novolac hardener containing a triazine skeleton (LA-3018-50P made by DIC), a hydroxyl equivalent of about 151, and a solid content of 50% 2-methoxy Propanol solution) 8 parts, phenolic novolac hardener containing triazine skeleton (LA-7054 made by DIC, a MEK solution with a hydroxyl equivalent of about 125 and a solid content of 60%) 4 parts, naphthol hardening Agent (Nippon Steel & Sumikin Chemical Co., Ltd. "SN-495V", a MEK solution with a hydroxyl equivalent of about 231 and a solid content of 60%) 10 parts, amine hardening accelerator (4-dimethylaminopyridine (DMAP)) , Solid content 5 mass% MEK solution) 1 part, rubber particles (made by Dow Chemical Japan Co., Ltd., EXL2655) 2 parts, inorganic filler 1 190 parts, uniformly dispersed by a high-speed rotary mixer, and then in a cylinder Filter ("SHP050" manufactured by ROKITECHNO) to prepare resin varnish 1.

<樹脂清漆2的調製> <Preparation of resin varnish 2>

將環己烷二甲醇型液狀環氧樹脂(新日鐵住金化學(股)製「ZX1658GS」、環氧當量約135)4份、雙酚AF型環氧樹脂(三菱化學(股)製「YL7760」、環氧當 量約238)15份、萘型環氧樹脂(新日鐵住金化學(股)製「ESN475V」、環氧當量約330)15份、及苯氧基樹脂(三菱化學(股)製「YX7553BH30」、固形分30質量%之環己酮：甲基乙基酮(MEK)之1：1溶液)10份，邊於溶劑石腦油15份及環己酮5份的混合溶劑攪拌邊使其加熱溶解。冷卻至室溫後，對其混合含有三嗪骨架之甲酚酚醛清漆系硬化劑(DIC(股)製「LA-3018-50P」、羥基當量約151、固形分50%之2-甲氧基丙醇溶液)8份、活性酯系硬化劑(DIC(股)製「EXB-8000L-65M」、活性基當量約220、不揮發成分65質量%之MEK溶液)12份、胺系硬化促進劑(4-二甲基胺基吡啶(DMAP)、固形分5質量%之MEK溶液)1.5份、無機填充材2之125份，以高速回轉攪拌機均勻分散，再以筒式過濾器(ROKITECHNO製「SHP030」)過濾，調製樹脂清漆2。 4 parts of cyclohexanedimethanol type liquid epoxy resin ("ZX1658GS" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent approximately 135), and 4 parts of bisphenol AF type epoxy resin (made by Mitsubishi Chemical Co., Ltd.) YL7760", epoxy resin About 238) 15 parts, naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent: about 330) 15 parts, and phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd.) , 30% solid content of cyclohexanone: methyl ethyl ketone (MEK) 1:1 solution) 10 parts, heated while stirring in a mixed solvent of 15 parts of solvent naphtha and 5 parts of cyclohexanone Dissolve. After cooling to room temperature, mix it with a cresol novolac hardener containing a triazine skeleton ("LA-3018-50P" made by DIC Co., Ltd., a hydroxyl equivalent of about 151, and a solid content of 50% 2-methoxy Propanol solution) 8 parts, active ester curing agent (DIC (stock) "EXB-8000L-65M", active group equivalent of about 220, non-volatile content 65% by mass MEK solution) 12 parts, amine curing accelerator (4-Dimethylaminopyridine (DMAP), MEK solution with a solid content of 5 mass%) 1.5 parts, 125 parts of inorganic filler 2 are uniformly dispersed with a high-speed rotary mixer, and then a cartridge filter (manufactured by ROKITECHNO" SHP030”) filter to prepare resin varnish 2.

<樹脂清漆3的調製> <Preparation of Resin Varnish 3>

將如下述般調製之(i)成分50份、萘醚型環氧樹脂(DIC(股)製「EXA-7311-G4」、環氧當量約213)2份、雙酚AF型環氧樹脂(三菱化學(股)製「YL7760」、環氧當量約238)4份、及阻燃劑(大八化學工業(股)製「PX-200」)2份，於溶劑石腦油10份及環己酮5份之混合溶劑邊攪拌邊使其加熱溶解。對其混合活性酯系硬化劑(DIC(股)製「EXB-8000L-65M」、 活性基當量約220、不揮發成分65質量%之MEK溶液)2份、咪唑系硬化促進劑(四國化成工業(股)製「1B2PZ」1-苄基-2-苯基咪唑、固形分5%之MEK溶液)1份、及無機填充材3之125份，以高速回轉攪拌機均勻分散，再以筒式過濾器(ROKITECHNO製「SHP030」)過濾，調製樹脂清漆3。 50 parts of component (i) prepared as follows, 2 parts of naphthyl ether type epoxy resin ("EXA-7311-G4" manufactured by DIC Co., Ltd., epoxy equivalent of about 213), and bisphenol AF type epoxy resin ( 4 parts of "YL7760" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 238), and 2 parts of flame retardant ("PX-200" manufactured by Dahachi Chemical Industry Co., Ltd.), in 10 parts of solvent naphtha and ring The mixed solvent of 5 parts of hexanone is heated and dissolved while stirring. It is mixed with an active ester-based hardener (DIC Co., Ltd. product "EXB-8000L-65M", 2 parts of MEK solution with active group equivalent of about 220 and 65% by mass of non-volatile content), imidazole-based hardening accelerator (Shikoku Chemical Industry Co., Ltd. "1B2PZ" 1-benzyl-2-phenylimidazole, solid content 5 % MEK solution) and 125 parts of inorganic filler 3 are uniformly dispersed with a high-speed rotary mixer, and then filtered with a cartridge filter ("SHP030" manufactured by ROKITECHNO) to prepare resin varnish 3.

((i)成分的調製) ((i) Modulation of component)

於反應容器混合G-3000(2官能性羥基末端聚丁二烯、數平均分子量=5047(GPC法)、羥基當量=1798g/eq.、固形分100質量%、日本曹達(股)製)50g、與溶劑石腦油(芳香族烴系混合溶劑：出光石油化學(股)製「Ipsol150」)23.5g、月桂酸二丁錫0.005g使其均勻溶解。成為均勻時昇溫至50℃，進而邊攪拌邊添加甲苯-2,4-二異氰酸酯(異氰酸酯基當量=87.08g/eq.)4.8g，進行約3小時反應。其次，將此反應物冷卻至室溫後，於此添加二苯甲酮四羧酸二酐(酸酐當量=161.1g/eq.)8.96g、與三乙烯二胺0.07g、與乙基二甘醇乙酸酯((股)Daicel製)40.4g，邊攪拌邊昇溫至130℃，進行約4小時反應。由FT-IR進行2250cm-1之NCO峰值消失的確認。具有NCO峰值消失的確認視為反應的終點，將反應物降溫至室溫後，以100篩目之濾布過濾，而得到具有醯亞胺骨架、胺基甲酸乙酯骨架、丁二烯骨架之高分子樹脂((i)成分)。此高分子樹脂((i)成 分)之分析結果係如以下。 G-3000 (2-functional hydroxyl-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl equivalent = 1798 g/eq., solid content 100% by mass, manufactured by Nippon Soda Co., Ltd.) 50g in the reaction vessel , Solvent naphtha (aromatic hydrocarbon-based mixed solvent: "Ipsol150" manufactured by Idemitsu Petrochemical Co., Ltd.) 23.5g, and dibutyltin laurate 0.005g to make it uniformly dissolved. When it became uniform, the temperature was raised to 50°C, and 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g/eq.) was added while stirring, and the reaction was performed for about 3 hours. Next, after cooling the reactant to room temperature, 8.96 g of benzophenone tetracarboxylic dianhydride (anhydride equivalent = 161.1 g/eq.), 0.07 g of triethylene diamine, and ethyl diglycerol were added here. 40.4 g of alcohol acetate (manufactured by Daicel) was heated to 130°C while stirring, and the reaction was carried out for about 4 hours. It was confirmed by FT-IR that the NCO peak at 2250 cm -1 disappeared. The confirmation of the disappearance of the NCO peak is regarded as the end of the reaction. After the reactant is cooled to room temperature, it is filtered with a 100-mesh filter cloth to obtain an imide skeleton, an ethyl urethane skeleton, and a butadiene skeleton. Polymer resin (component (i)). The analysis results of this polymer resin (component (i)) are as follows.

黏度：7.5Pa．s(25℃、E型黏度計) Viscosity: 7.5Pa. s(25℃, E-type viscometer)

酸價：16.9mgKOH/g Acid value: 16.9mgKOH/g

固形分：50質量% Solid content: 50% by mass

數平均分子量：13723 Number average molecular weight: 13723

玻璃轉移溫度：-10℃ Glass transition temperature: -10℃

聚丁二烯構造部分之含有率：50/(50+4.8+8.96)×100=78.4質量% The content of polybutadiene structural part: 50/(50+4.8+8.96)×100=78.4% by mass

<樹脂清漆4的調製> <Preparation of Resin Varnish 4>

除了在樹脂清漆1的調製，將無機填充材1 190份變更為無機填充材4 190份，且將溶劑石腦油15份變更為20份。以上之事項以外其他與樹脂清漆1的調製同樣進行，來調製樹脂清漆4。 Except for the preparation of resin varnish 1, 1 190 parts of inorganic filler was changed to 4 190 parts of inorganic filler, and 15 parts of solvent naphtha was changed to 20 parts. Other than the above matters, the resin varnish 4 was prepared in the same manner as the preparation of the resin varnish 1.

<樹脂清漆5之調製> <Preparation of Resin Varnish 5>

除了在樹脂清漆2的調製，將無機填充材2 125份變更為無機填充材5 125份，且將溶劑石腦油15份變更為20份。以上之事項以外其他與樹脂清漆2的調製同樣進行，來調製樹脂清漆5。 Except for the preparation of resin varnish 2, 125 parts of inorganic fillers were changed to 5 125 parts of inorganic fillers, and 15 parts of solvent naphtha were changed to 20 parts. Other than the above items, the resin varnish 2 was prepared in the same manner as the resin varnish 2 to prepare the resin varnish 5.

<樹脂清漆6之調製> <Preparation of resin varnish 6>

除了在樹脂清漆3的調製，將無機填充材3 125份變更為無機填充材6 125份。以上之事項以外其他與樹脂清 漆3的調製同樣進行，來調製樹脂清漆6。 Except for the preparation of resin varnish 3, 3 125 parts of inorganic filler was changed to 6 125 parts of inorganic filler. Other than the above items and resin clear The preparation of the lacquer 3 was carried out in the same manner, and the resin varnish 6 was prepared.

<樹脂清漆7的調製> <Preparation of resin varnish 7>

除了在樹脂清漆1的調製，將無機填充材1 190份變更為無機填充材7 190份。以上之事項以外其他與樹脂清漆1的調製同樣進行，來調製樹脂清漆7。 Except for the preparation of resin varnish 1, 1 190 parts of inorganic filler was changed to 7 190 parts of inorganic filler. Other than the above matters, the resin varnish 7 was prepared in the same manner as the preparation of the resin varnish 1.

將各樹脂清漆的製作所使用之材料與其摻合量(不揮發成分之質量份)示於下述表。液狀環氧樹脂與(C)無機填充材之不揮發成分中的含量(質量%)亦一併表示。 The materials used in the production of each resin varnish and their blending amounts (mass parts of non-volatile components) are shown in the following table. The content (mass%) of the non-volatile components of the liquid epoxy resin and (C) inorganic filler is also shown together.

Figure 105137480-A0202-12-0055-1
Figure 105137480-A0202-12-0055-1

<實施例1~3及比較例1~4：樹脂薄片的製作> <Examples 1 to 3 and Comparative Examples 1 to 4: Production of Resin Sheets>

作為支持體，準備以酸醇樹脂系脫模劑(Lintec(股)製「AL-5」)脫模處理之PET薄膜(東麗(股)製「Lumirror T6AM」、厚度38μm、軟化點130℃、「脫模PET」)。 As a support, prepare a PET film ("Lumirror T6AM" made by Toray Co., Ltd., with a thickness of 38μm, and a softening point of 130°C. , "Release PET").

將各樹脂清漆於脫模PET上，以乾燥後之樹脂組成物層的厚度成為25μm的方式在模塗佈機進行塗佈，藉由在80℃~110℃乾燥4分鐘，於脫模PET上得到樹脂組成物層。其次，於未與樹脂組成物層之脫模PET接合的面，作為保護薄膜，將聚丙烯薄膜(王子特殊紙(股)製「ALPHAN MA-430」、厚度20μm)以與樹脂組成物層接合的方式層合。藉此，得到由脫模PET、樹脂組成物層、及保護薄膜的順序所構成之順樹脂薄片。 Put each resin varnish on the release PET, apply it on the die coater so that the thickness of the resin composition layer after drying becomes 25μm, and dry it at 80℃~110℃ for 4 minutes, and then apply it on the release PET The resin composition layer is obtained. Next, on the surface that is not bonded with the release PET of the resin composition layer, as a protective film, a polypropylene film ("ALPHAN MA-430" manufactured by Oji Special Paper Co., Ltd., thickness 20μm) is bonded to the resin composition layer Way to laminate. Thereby, a smooth resin sheet composed of the release PET, the resin composition layer, and the protective film in this order is obtained.

<樹脂組成物層之最低熔融黏度的測定> <Measurement of the lowest melt viscosity of the resin composition layer>

藉由僅從脫模PET剝離樹脂組成物層，以模具進行壓縮，來製作測定用顆粒(直徑18mm、1.2g~1.3g)。使用測定用顆粒，使用動態黏彈性測定裝置((股)UBM製「Rheosol-G3000」)，針對試料樹脂組成物1g，使用直徑18mm之平行板，在昇溫速度5℃/分鐘從開始溫度60℃昇溫至200℃，在測定溫度間隔2.5℃、振動數1Hz、扭曲1deg的測定條件測定動態黏彈性率，算出最低熔融黏度(poise)，將結果示於下述表。 The resin composition layer was peeled only from the mold-releasing PET and compressed with a mold to produce measurement pellets (diameter 18 mm, 1.2 g to 1.3 g). Using measurement pellets, using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM (stock)), and using a parallel plate with a diameter of 18 mm for 1 g of the sample resin composition, at a heating rate of 5°C/min from the starting temperature of 60°C The temperature was raised to 200°C, the dynamic viscoelasticity was measured under the measurement conditions of a measurement temperature interval of 2.5°C, a number of vibrations of 1 Hz, and a twist of 1 deg, and the lowest melt viscosity (poise) was calculated. The results are shown in the following table.

<零件嵌入性之評估> <Evaluation of part embedding>

使用於實施例及比較例製作之樹脂薄片，沿著以下之順序，製作暫時配附零件之電路基板評估零件嵌入性。 Using the resin sheets produced in the Examples and Comparative Examples, the following procedures were followed to produce a circuit board with temporarily attached parts to evaluate the insertability of the parts.

(1)暫時配附零件之電路基板(孔洞基板)之準備 (1) Preparation of the circuit board (hole board) for temporarily attaching parts

於玻璃布基材BT樹脂兩面銅包層層合板(銅箔之厚度18μm、基板厚度0.15mm、三菱瓦斯化學(股)製「HL832NSF LCA」)255mm×340mm尺寸的全面，將0.7mm×1.1mm之孔洞以3mm間距形成。其次，將兩面在微蝕刻劑(MEC(股)製「CZ8100」)進行1μm蝕刻，進行銅表面的粗糙化處理，進而實施防鏽處理(MEC(股)製「CL8300」)，於180℃乾燥30分鐘。 BT resin copper clad laminate on both sides of the glass cloth substrate (the thickness of copper foil is 18μm, the thickness of the substrate is 0.15mm, Mitsubishi Gas Chemical Co., Ltd. "HL832NSF LCA") 255mm×340mm, the overall size is 0.7mm×1.1mm The holes are formed at a pitch of 3mm. Next, both sides are etched with a micro-etching agent ("CZ8100" made by MEC (Stock)) for 1μm, the copper surface is roughened, and then anti-rust treatment ("CL8300" made by MEC (Stock)) is performed, and dried at 180°C. 30 minutes.

(2)暫時配附零件之電路基板的製作 (2) Production of circuit board with temporarily attached parts

於(1)所得之基板的單面，將25μm厚之附黏著劑之聚醯亞胺薄膜(聚醯亞胺38μm厚、(股)有澤製作所製、「PFDKE-1525TT」)使用批次式真空加壓層合機(Nichigo-Morton(股)製2階段積聚層合機「CVP700」)，以黏著劑與基板接合的方式配置，層合在單面。層合係進行30秒減壓將氣壓降為13hPa以下後，藉由在80℃、壓力0.74MPa使其壓著30秒來實施。其次，將層合陶瓷電容器零件(1005=1×0.5mm尺寸、厚度0.14mm)一個一個暫時配附在孔洞內，製作暫時配附 零件之電路基板(孔洞基板)。 On one side of the substrate obtained in (1), a 25μm thick polyimide film with adhesive (polyimide 38μm thick, manufactured by Arisawa Manufacturing Co., Ltd., "PFDKE-1525TT") was used in batch vacuum The pressure laminator (Nichigo-Morton Co., Ltd. two-stage accumulation laminator "CVP700") is arranged so that the adhesive is bonded to the substrate and laminated on one side. After the lamination system was depressurized for 30 seconds to reduce the air pressure to 13 hPa or less, it was carried out by pressing it at 80°C and 0.74 MPa for 30 seconds. Secondly, the laminated ceramic capacitor parts (1005=1×0.5mm size, thickness 0.14mm) are temporarily fitted into the holes one by one to make temporary fittings The circuit board of the component (hole board).

(3)零件嵌入性之評估試驗 (3) Evaluation test of part embedding

使用批次式真空加壓層合機(Nichigo-Morton(股)製2階段積聚層合機「CVP700」)，以接合從於實施例及比較例製作之樹脂薄片剝離保護薄膜而露出之樹脂組成物層、與和於(2)製作之暫時配附零件之電路基板(孔洞基板)之附黏著劑之聚醯亞胺薄膜配置面相反側的面的方式層合。層合係進行30秒減壓將氣壓降為13hPa以下後，藉由在120℃、壓力0.74MPa使其壓著30秒來實施。其次，將經層合之樹脂薄片在大氣壓下、120℃、壓力0.5MPa進行60秒熱沖壓而平滑化。藉由從冷卻至室溫之暫時配附零件之電路基板剝離附黏著劑之聚醯亞胺薄膜，來製作評估用基板A。從剝離評估用基板A之聚醯亞胺薄膜的面，將孔洞內之樹脂流動以光學顯微鏡(150倍)觀察(針對10個孔洞進行)，藉由下述基準評估零件嵌入性，將結果示於下述表。 A batch-type vacuum pressure laminator (two-stage accumulation laminator "CVP700" manufactured by Nichigo-Morton Co., Ltd.) was used to join the resin composition exposed by peeling the protective film from the resin sheet produced in the Examples and Comparative Examples The material layer is laminated with the surface on the opposite side of the polyimide film arrangement surface of the adhesive-attached circuit substrate (hole substrate) of the temporarily attached parts produced in (2). After the lamination system was depressurized for 30 seconds to reduce the air pressure to 13 hPa or less, it was carried out by pressing it at 120° C. and a pressure of 0.74 MPa for 30 seconds. Next, the laminated resin sheet was smoothed by hot stamping for 60 seconds under atmospheric pressure, 120° C., and pressure 0.5 MPa. The evaluation substrate A was prepared by peeling off the polyimide film with the adhesive from the circuit board of the temporarily attached part that was cooled to room temperature. From the surface of the polyimide film peeling off the evaluation substrate A, the resin flow in the hole was observed with an optical microscope (150 times) (for 10 holes), the insertability of the part was evaluated by the following criteria, and the results were shown In the following table.

(評估基準) (Assessment criteria)

判斷為 Judged as

○：在全部孔洞，層合陶瓷電容器零件之外周邊以樹脂被覆。 ○: All the holes and the outer periphery of the laminated ceramic capacitor parts are coated with resin.

×：即使一個孔洞，發生孔隙(Void)或於層合陶瓷電容器零件之外周邊未嵌入樹脂者。 ×: Even if there is a hole, a void occurs or the resin is not embedded in the outer periphery of the laminated ceramic capacitor part.

<鍍敷導體層之剝離強度(剝離強度)、粗糙度(算術平均粗糙度(Ra)、均方根粗糙度(Rq))、及鍍敷潛入深度的評估> <Evaluation of the peel strength (peel strength), roughness (arithmetic mean roughness (Ra), root mean square roughness (Rq)), and plating penetration depth of the plated conductor layer>

使用於實施例及比較例製作之樹脂薄片，沿著以下之順序製作測定用基板B、C，評估剝離強度、粗糙度及鍍敷潛入深度。 Using the resin sheets produced in the Examples and Comparative Examples, measurement substrates B and C were produced in the following procedures, and the peel strength, roughness, and plating penetration depth were evaluated.

(1)層合板的基底處理 (1) Substrate treatment of laminates

將玻璃布基材環氧樹脂兩面銅包層層合板(銅箔的厚度18μm、基板厚度0.3mm、松下電工(股)製R5715ES)的兩面藉由MEC(股)製粗糙化處理劑(CZ8100)，將兩面在微蝕刻劑(MEC(股)製「CZ8100」)蝕刻1μm，進行銅表面的粗糙化處理。 The glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18μm, substrate thickness 0.3mm, Matsushita Electric Works Co., Ltd. R5715ES) is applied to both sides of the MEC (stock) roughening treatment agent (CZ8100) , Both sides were etched with a micro-etchant ("CZ8100" manufactured by MEC (Stock)) for 1 μm, and the copper surface was roughened.

(2)樹脂薄片的層合 (2) Laminating of resin flakes

從於實施例及比較例製作之樹脂薄片剝離保護薄膜，將經露出之樹脂組成物層使用批次式真空加壓層合機((股)Nichigo-Morton製2階段積聚層合機「CVP700」)，以樹脂組成物層與基板接合的方式層合於基板兩面。層合係藉由將進行30秒減壓之氣壓成為13hPa以下後，在110℃、壓力0.74MPa進行30秒壓著來實施。其次，將經層合之樹脂薄片在大氣壓下、120℃、壓力0.5MPa進行60秒熱沖壓而平滑化。 The protective film was peeled off from the resin sheet produced in the Examples and Comparative Examples, and the exposed resin composition layer was used a batch-type vacuum pressure laminator ((stock) Nichigo-Morton two-stage accumulation laminator "CVP700" ), laminated on both sides of the substrate such that the resin composition layer is bonded to the substrate. The lamination is carried out by reducing the pressure for 30 seconds to 13 hPa or less, and then pressing at 110°C and 0.74 MPa for 30 seconds. Next, the laminated resin sheet was smoothed by hot stamping for 60 seconds under atmospheric pressure, 120° C., and pressure 0.5 MPa.

(3)樹脂組成物層之熱硬化 (3) Thermal curing of resin composition layer

樹脂薄片的層合後，使樹脂組成物層熱硬化(於100℃ 30分鐘，其次於175℃ 30分鐘)，於基板的兩面形成絕緣層。此時，關於實施例1、2及比較例1、2、4，以附支持體即脫模PET的狀態，使樹脂組成物層熱硬化。關於實施例3及比較例3，剝離支持體即脫模PET後，使樹脂組成物熱硬化。 After the lamination of the resin sheets, the resin composition layer is thermally cured (at 100°C for 30 minutes, followed by 175°C for 30 minutes) to form insulating layers on both sides of the substrate. At this time, regarding Examples 1, 2 and Comparative Examples 1, 2, and 4, the resin composition layer was thermally cured in a state of mold-releasing PET with a support. Regarding Example 3 and Comparative Example 3, after peeling off the mold release PET that is the support, the resin composition was thermally cured.

(4)粗糙化處理 (4) Roughening treatment

將形成絕緣層之層合板浸漬於膨潤液之含有Atotech Japan(股)之二乙二醇單丁基醚的Swelling Dip Securiganth P(甘醇醚類、氫氧化鈉之水溶液)，以60℃浸漬5分鐘。其次作為粗糙化液，於Atotech Japan(股)之Concentrate Compact P(KMnO4：60g/L、NaOH：40g/L之水溶液)以80℃浸漬15分鐘(實施例2、比較例2係於80℃浸漬20分鐘)。最後作為中和液，於Atotech Japan(股)之Reduction solution Securiganth P(硫酸之水溶液)以40℃浸漬5分鐘。以80℃乾燥30分鐘後，將此基板稱為「評估用基板B」。 The laminated board forming the insulating layer is immersed in the swelling liquid Swelling Dip Securiganth P (aqueous solution of glycol ethers and sodium hydroxide) containing Atotech Japan's diethylene glycol monobutyl ether, and immersed at 60°C for 5 minute. Next, as a roughening solution, immerse in Concentrate Compact P (KMnO 4 : 60g/L, NaOH: 40g/L aqueous solution) of Atotech Japan (stock) at 80°C for 15 minutes (Example 2 and Comparative Example 2 are at 80°C Dipping for 20 minutes). Finally, as a neutralization solution, it was immersed in Reduction solution Securiganth P (aqueous solution of sulfuric acid) of Atotech Japan (stock) at 40°C for 5 minutes. After drying at 80°C for 30 minutes, this substrate is referred to as "evaluation substrate B".

(5)藉由半加成工法之鍍敷 (5) Plating by semi-additive method

將於(4)製得之評估用基板B於包含PdCl2之無電解鍍敷液，以40℃浸漬5分鐘，其次於無電解銅鍍敷液 以25℃浸漬20分鐘。在150℃加熱30分鐘，進行退火處理後，形成蝕刻光阻劑，藉由蝕刻之圖型形成後，進行硫酸銅電解鍍敷，形成30μm厚度之導體層。其次，在190℃進行60分鐘退火處理，將所得之基板訂為評估用基板C。 The evaluation substrate B prepared in (4) 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. After heating at 150°C for 30 minutes and performing annealing treatment, an etching photoresist is formed. After pattern formation by etching, copper sulfate electrolytic plating is performed to form a conductor layer with a thickness of 30 μm. Next, an annealing treatment was performed at 190°C for 60 minutes, and the obtained substrate was designated as the evaluation substrate C.

(算術平均粗糙度(Ra)、均方根粗糙度(Rq)的測定) (Measurement of Arithmetic Average Roughness (Ra), Root Mean Square Roughness (Rq))

針對評估用基板B，使用非接觸型表面粗糙度計(威科儀器公司製「WYKO NT3300」)，藉由VSI接觸模式、50倍鏡頭，將測定範圍定為121μm×92μm來測定，藉由所得之數值求得Ra值、Rq值。分別算出10點之平均值。將結果示於下述表。 For evaluation substrate B, use a non-contact surface roughness meter (WYKO NT3300 manufactured by Waco Instruments), use VSI contact mode, 50 times lens, and set the measurement range to 121μm×92μm. Calculate the value of Ra and Rq. Calculate the average of 10 points respectively. The results are shown in the following table.

(剝離強度的測定) (Measurement of peel strength)

於評估用基板C之導體層，放入寬度10mm、長度100mm部分的切片，剝離此一端並以挾具((股)TSE、Autocom型試驗機AC-50C-SL)挾住，在室溫(25℃)以50mm/分鐘之速度測定往垂直方向剝離35mm時之荷重(kgf/cm(N/cm))，將結果示於下述表。 Place a section with a width of 10mm and a length of 100mm on the conductor layer of the evaluation substrate C, peel off this end and hold it with a clamp ((strand) TSE, Autocom type tester AC-50C-SL), and at room temperature ( 25°C) The load (kgf/cm(N/cm)) when peeling 35mm in the vertical direction was measured at a speed of 50mm/min, and the results are shown in the following table.

(鍍敷潛入深度的測定) (Measurement of plating penetration depth)

針對評估用基板C，使用FIB-SEM複合裝置(SII奈米技術(股)製「SMI3050SE」)進行剖面觀察。詳細而 言，將在與評估用基板C的表面垂直之方向的剖面藉由FIB(集束離子束)削出，取得鍍敷與粗糙化硬化體(絕緣層)的界面附近之剖面SEM圖像(觀察寬度7.5μm、觀察倍率×36000)。對於各樣品，取得隨機選定10處的剖面SEM圖像，測定銅鍍敷深度之最大值(μm)。 For evaluation substrate C, cross-sectional observation was performed using a FIB-SEM composite device (SII Nano Technology Co., Ltd. "SMI3050SE"). Detailed and In other words, the cross section in the direction perpendicular to the surface of the evaluation substrate C was cut out by FIB (Clustered Ion Beam), and a cross-sectional SEM image (observation width) near the interface between the plating and the roughened hardened body (insulating layer) 7.5μm, observation magnification×36000). For each sample, randomly selected 10 cross-sectional SEM images were obtained, and the maximum copper plating depth (μm) was measured.

<阻燃性的評估> <Evaluation of Flame Retardancy>

(1)樹脂薄片的層合 (1) Laminating of resin flakes

將從於實施例及比較例製作之樹脂薄片剝離保護薄膜而露出之樹脂組成物層，使用批次式真空加壓層合機(Nichigo-Morton(股)製2階段積聚層合機「CVP700」)，以樹脂組成物層與層合板(無銅箔，基板厚度0.2mm、日立化成(股)製679FG)接合的方式層合在層合板兩面。層合係藉由將進行30秒減壓之氣壓成為13hPa以下後，在100℃、壓力0.74MPa進行30秒壓著來實施。其次，將經層合之樹脂薄片在大氣壓下、120℃、壓力0.5MPa進行60秒熱沖壓而平滑化。 The resin composition layer exposed by peeling the protective film from the resin sheet produced in the Examples and Comparative Examples was performed using a batch-type vacuum pressure laminator (Nichigo-Morton Co., Ltd. two-stage accumulation laminator "CVP700" ), the resin composition layer and the laminate (no copper foil, substrate thickness 0.2mm, Hitachi Chemical Co., Ltd. 679FG) were bonded on both sides of the laminate. The lamination is carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 100° C. and a pressure of 0.74 MPa for 30 seconds. Next, the laminated resin sheet was smoothed by hot stamping for 60 seconds under atmospheric pressure, 120° C., and pressure 0.5 MPa.

(2)樹脂組成物層的硬化 (2) Hardening of the resin composition layer

樹脂薄片之層合後，剝離支持體之脫模PET，使樹脂組成物層熱硬化(於190℃ 90分鐘)，於層合板的兩面形成硬化物。 After the lamination of the resin sheet, the release PET of the support is peeled off, and the resin composition layer is thermally cured (90 minutes at 190°C) to form a cured product on both sides of the laminate.

(3)阻燃試驗 (3) Flame retardant test

依UL-94V之規格實施。將所得之層合體(厚度約380μm)切成12.7mm×127mm的大小，以邊緣成為1.27mm的方式切斷，於70±1℃烤箱中處理168小時後，再於乾燥器放冷4小時以上，而得到試驗片。 Implemented in accordance with UL-94V specifications. Cut the resulting laminate (thickness about 380μm) into a size of 12.7mm×127mm, cut it so that the edge becomes 1.27mm, and treat it in an oven at 70±1°C for 168 hours, and then cool it in a desiccator for more than 4 hours , And get the test piece.

使火爐於所得之試驗片正下方移動，將火焰與試驗片之下端中央接觸火焰10秒，計測之後的燃燒時間。再次接觸火焰10秒，計測之後的燃燒時間。將此重複5次，根據以下之基準評估。 The furnace was moved directly below the obtained test piece, and the flame was brought into contact with the flame at the center of the lower end of the test piece for 10 seconds, and the burning time after that was measured. Expose the flame again for 10 seconds, and measure the burning time after that. Repeat this 5 times and evaluate according to the following benchmarks.

(評估基準) (Assessment criteria)

V-0：燃燒物的落下無試驗片的全燒，試驗片之燃燒時間為50秒以下 V-0: The falling of the burning material does not burn the test piece completely, and the burning time of the test piece is less than 50 seconds

V-1：燃燒物的落下無試驗片的全燒，試驗片之燃燒時間為超過50秒且250秒以下 V-1: The falling of the burning material does not burn the test piece completely, and the burning time of the test piece is more than 50 seconds and less than 250 seconds

Not：燃燒物的落下，試驗片的全燒、或試驗片的燃燒時間超過250秒 Not: Falling of the burning material, full burning of the test piece, or burning time of the test piece more than 250 seconds

Figure 105137480-A0202-12-0064-2
Figure 105137480-A0202-12-0064-2

使用包含(C)成分之樹脂組成物的實施例1~3，瞭解到零件嵌入性、算術平均粗糙度(Ra)、均方根粗糙度(Rq)、剝離強度、鍍敷潛入深度、及阻燃性優異。 Using the examples 1 to 3 of the resin composition containing the component (C), it is understood that the part embedding property, arithmetic mean roughness (Ra), root mean square roughness (Rq), peel strength, plating penetration depth, and resistance Excellent flammability.

改變(C)成分使用環氧矽烷系偶合劑(KBM-403)之比較例1，與實施例1~3相比較，瞭解到易凝聚，其結果藉由提高最低熔融黏度，而使零件嵌入性劣化，又，算術平均粗糙度(Ra)、均方根粗糙度(Rq)、鍍敷潛入深度、及阻燃性亦劣化。 Compared with Examples 1 to 3 in Comparative Example 1 using a siloxane-based coupling agent (KBM-403) by changing the component (C), it was found that it is easy to agglomerate. As a result, the lowest melt viscosity was increased to improve the embedding of parts. Deterioration, arithmetic average roughness (Ra), root mean square roughness (Rq), plating penetration depth, and flame retardancy are also degraded.

改變(C)成分使用胺基矽烷系偶合劑(KBM-903)之比較例2，瞭解到藉由胺基與(A)成分等之樹脂偶合，雖降低鍍敷潛入深度，但由於提高最低熔融黏度，零件嵌入性劣化。又，瞭解到與實施例1~3相比較，阻燃性亦劣化。 In Comparative Example 2 using an aminosilane coupling agent (KBM-903) for component (C), it is understood that the resin coupling of the amine group with component (A) reduces the plating penetration depth, but it increases the minimum melting point. Viscosity, the embedding of parts deteriorates. In addition, it is understood that the flame retardancy is also deteriorated compared with Examples 1 to 3.

改變(C)成分使用鋁系偶合劑(Plainact AL-M)之比較例3，瞭解到由於最低熔融黏度較低，雖零件嵌入性良好，但算術平均粗糙度(Ra)、均方根粗糙度(Rq)、鍍敷潛入深度、及阻燃性劣化。 In Comparative Example 3 using aluminum coupling agent (Plainact AL-M) by changing the component (C), it was learned that the arithmetic mean roughness (Ra) and root mean square roughness of the parts are good although the minimum melt viscosity is low. (Rq), plating penetration depth, and deterioration of flame retardancy.

針對改變(C)成分使用矽烷化合物(KBM-103)之比較例4，瞭解到矽烷化合物由於不具有反應基，無法與(A)成分等之樹脂偶合，提高鍍敷潛入深度。又，瞭解到與實施例1~3相比較，算術平均粗糙度(Ra)、均方根粗糙度(Rq)、鍍敷潛入深度、及阻燃性亦劣化。 For Comparative Example 4 where the component (C) is changed and the silane compound (KBM-103) is used, it is understood that the silane compound cannot be coupled with the resin such as the component (A) because it does not have a reactive group, thereby increasing the plating penetration depth. In addition, it is understood that compared with Examples 1 to 3, the arithmetic average roughness (Ra), root mean square roughness (Rq), plating penetration depth, and flame retardancy are also deteriorated.

Claims (15)

一種樹脂組成物，其係含有(A)由液狀環氧樹脂與固體狀環氧樹脂組成之環氧樹脂、(B)硬化劑、(C)含有氟原子之烷氧基矽烷化合物、及(D)無機填充材，前述液狀環氧樹脂與前述固體狀環氧樹脂之質量比為1：0.1~1：15。 A resin composition containing (A) an epoxy resin composed of a liquid epoxy resin and a solid epoxy resin, (B) a hardener, (C) an alkoxysilane compound containing fluorine atoms, and ( D) Inorganic filler, the mass ratio of the liquid epoxy resin to the solid epoxy resin is 1:0.1 to 1:15. 如請求項1之樹脂組成物，其中，將樹脂組成物中之不揮發成分定為100質量%時，(D)成分的含量為60質量%以上。 The resin composition of claim 1, wherein, when the non-volatile content in the resin composition is 100% by mass, the content of the component (D) is 60% by mass or more. 如請求項1之樹脂組成物，其中，(D)成分之平均粒徑為0.01μm~2μm。 The resin composition of claim 1, wherein the average particle size of the component (D) is 0.01 μm to 2 μm. 如請求項1之樹脂組成物，其中，(D)成分為二氧化矽或氧化鋁。 Such as the resin composition of claim 1, wherein the component (D) is silica or alumina. 如請求項1之樹脂組成物，其中，(C)成分1分子中之氟原子的數目為1~10。 Such as the resin composition of claim 1, wherein the number of fluorine atoms in one molecule of component (C) is 1-10. 如請求項1之樹脂組成物，其中，(C)成分1分子中之烷氧基的數目為1~5。 Such as the resin composition of claim 1, wherein the number of alkoxy groups in one molecule of component (C) is 1 to 5. 如請求項1之樹脂組成物，其中，(C)成分為3,3,3-三氟丙基三甲氧基矽烷。 The resin composition of claim 1, wherein the component (C) is 3,3,3-trifluoropropyltrimethoxysilane. 如請求項1之樹脂組成物，其中，(D)成分係以(C)成分表面處理。 The resin composition of claim 1, wherein the component (D) is surface-treated with the component (C). 如請求項1之樹脂組成物，其係印刷配線板之絕緣層形成用。 Such as the resin composition of claim 1, which is used for forming an insulating layer of a printed wiring board. 如請求項1之樹脂組成物，其係印刷配線板之積聚層用。 Such as the resin composition of claim 1, which is used for the accumulation layer of a printed wiring board. 一種薄片狀層合材料，其係包含如請求項1~10中任一項之樹脂組成物。 A sheet-like laminate material, which contains the resin composition according to any one of claims 1 to 10. 一種薄片狀層合材料，其係包含以如請求項1~10中任一項之樹脂組成物形成之樹脂組成物層。 A sheet-like laminate material comprising a resin composition layer formed of the resin composition according to any one of claims 1 to 10. 如請求項12之薄片狀層合材料，其中，樹脂組成物層的厚度為10μm以下。 The sheet-like laminated material of claim 12, wherein the thickness of the resin composition layer is 10 μm or less. 一種印刷配線板，其係包含藉由如請求項1~10中任一項之樹脂組成物的硬化物所形成之絕緣層。 A printed wiring board comprising an insulating layer formed by a cured product of a resin composition as claimed in any one of claims 1 to 10. 一種半導體裝置，其係包含如請求項14之印刷配線板。 A semiconductor device including the printed wiring board as claimed in claim 14.
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