TW201635877A - Method for producing resin sheet - Google Patents

Method for producing resin sheet Download PDF

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Publication number
TW201635877A
TW201635877A TW104144250A TW104144250A TW201635877A TW 201635877 A TW201635877 A TW 201635877A TW 104144250 A TW104144250 A TW 104144250A TW 104144250 A TW104144250 A TW 104144250A TW 201635877 A TW201635877 A TW 201635877A
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Taiwan
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resin
resin composition
layer
varnish
composition layer
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TW104144250A
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Chinese (zh)
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TWI702891B (en
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Hiroshi Akimoto
Shigeo Nakamura
Hirohisa Narahashi
Yukinori Edo
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Ajinomoto Kk
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Publication of TWI702891B publication Critical patent/TWI702891B/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/22—Making multilayered or multicoloured articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Provided is a method for producing a resin sheet in which it is possible to suppress delamination and actualize an insulating layer having high stability in terms of roughness and peel strength. A method for producing a resin sheet having a support, a first resin composition layer comprising a first resin composition provided on the support, and a second resin composition layer comprising a second resin composition provided on the first resin composition layer, the resin sheet also having a mixed layer that is a mixture of the first resin composition and second resin composition between the first resin composition layer and the second resin composition layer, wherein: the method for producing a resin sheet includes a step for applying a first resin varnish, obtained by dissolving the first resin composition, on the support, applying a second resin varnish, obtained by dissolving the second resin composition, on the first resin varnish, and drying; the viscosity of the first resin varnish is 100 mPa.s or higher; and the viscosity of the second resin varnish is 100 mPa.s or higher.

Description

樹脂薄片之製造方法 Method for producing resin sheet

本發明係關於樹脂薄片之製造方法。進而係關於樹脂薄片、印刷配線板之製造方法、印刷配線板、及半導體裝置。 The present invention relates to a method of producing a resin sheet. Further, the present invention relates to a resin sheet, a method of producing a printed wiring board, a printed wiring board, and a semiconductor device.

作為印刷配線板之製造技術，被廣泛使用在交替堆疊經電路形成之導體層與絕緣層之積聚方式。積聚方式中，絕緣層一般而言係將包含樹脂組成物層之樹脂薄片層合於內層基板，使樹脂組成物層硬化而形成。 As a manufacturing technique of a printed wiring board, it is widely used in an accumulation manner in which a conductor layer formed by a circuit and an insulating layer are alternately stacked. In the accumulation method, the insulating layer is generally formed by laminating a resin sheet including a resin composition layer on an inner layer substrate and curing the resin composition layer.

近年來，雖已知增多樹脂組成物層中之無機填充材的含量，會降低絕緣層之熱膨脹率，但無機填充材的含量多時，所得之絕緣層與導體層的密著強度(剝離強度)易降低。因此，例如於專利文獻1，揭示有一種樹脂薄片，其係包含複數樹脂組成物層之樹脂薄片，作為成為與導體層接合之樹脂組成物層，包含樹脂成分之比例多之層。 In recent years, although it is known that the content of the inorganic filler in the resin composition layer is increased, the thermal expansion coefficient of the insulating layer is lowered, but when the content of the inorganic filler is large, the adhesion strength between the obtained insulating layer and the conductor layer (peel strength) ) Easy to lower. For example, Patent Document 1 discloses a resin sheet comprising a resin sheet having a plurality of resin composition layers, and a resin composition layer bonded to the conductor layer, which has a layer containing a large proportion of the resin component.

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

[專利文獻1]日本特開2014-17301號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2014-17301

本發明者們，發現在使用包含複數樹脂組成物層之樹脂薄片所形成之絕緣層中，曝露於回流時等之高溫環境下時有產生層間剝離(Delamination)的情況。本發明者們又發現在包含複數樹脂組成物層之樹脂薄片，各層之厚度的調控困難，有返回粗糙度或剝離強度之安定性不良之絕緣層的情況。 The present inventors have found that in an insulating layer formed using a resin sheet including a plurality of resin composition layers, interlayer peeling occurs when exposed to a high temperature environment such as reflow. The present inventors have found that in the resin sheet including the plurality of resin composition layers, it is difficult to adjust the thickness of each layer, and there is a case where the insulating layer having poor returning roughness or peel strength is poor in stability.

本發明係以提供一種抑制層間剝離，可實現粗糙度或剝離強度之安定性高的絕緣層的樹脂薄片之製造方法作為課題。 The present invention has been made in an effort to provide a method for producing a resin sheet which can suppress the peeling between layers and which can realize an insulating layer having high roughness or peel strength.

本發明者們，對於上述課題經努力研究的結果，發現製造包含複數樹脂組成物層之樹脂薄片時，於樹脂組成物層彼此接觸的區域，藉由新設置混在各樹脂組成物層之成分之層，可解決上述課題，而終至完成本發明。 As a result of intensive studies on the above-mentioned problems, the present inventors have found that when a resin sheet containing a plurality of resin composition layers is produced, a component which is mixed in each resin composition layer is newly provided in a region where the resin composition layers are in contact with each other. The layer can solve the above problems, and finally complete 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]一種樹脂薄片之製造方法，其係具有由支持體、與於支持體上所設置之第1樹脂組成物所成之第1樹脂組成物層、與由第1樹脂組成物層上所設置之第2樹脂組成 物所成之第2樹脂組成物層，於第1樹脂組成物層與第2樹脂組成物層之間具有混在第1樹脂組成物及第2樹脂組成物之混合層的樹脂薄片之製造方法，其係包含於支持體上塗佈溶解第1樹脂組成物之第1樹脂清漆，於第1樹脂清漆上塗佈溶解第2樹脂組成物之第2樹脂清漆，再進行乾燥之步驟，第1樹脂清漆的黏度為100mPa．s以上，第2樹脂清漆的黏度為100mPa．s以上。 [1] A method for producing a resin sheet, comprising: a first resin composition layer formed of a support, a first resin composition provided on the support, and a layer composed of the first resin composition Set the second resin composition The second resin composition layer formed of the material has a method of producing a resin sheet mixed with the mixed layer of the first resin composition and the second resin composition between the first resin composition layer and the second resin composition layer. The first resin varnish in which the first resin composition is dissolved and coated on the support, and the second resin varnish in which the second resin composition is dissolved is applied onto the first resin varnish, followed by drying, the first resin The varnish has a viscosity of 100mPa. Above s, the viscosity of the second resin varnish is 100 mPa. s above.

[2]如[1]之樹脂薄片之製造方法，其係包含與於支持體上塗佈第1樹脂清漆同時於第1樹脂清漆上塗佈第2樹脂清漆，然後進行乾燥之步驟、或包含於支持體上塗佈第1樹脂清漆，使其預備乾燥後，再於第1樹脂清漆上塗佈第2樹脂清漆，然後進行乾燥之步驟。 [2] The method for producing a resin sheet according to [1], comprising the step of applying a second resin varnish to the first resin varnish while applying the first resin varnish to the support, and then drying the step, or comprising After the first resin varnish is applied onto the support and preliminarily dried, the second resin varnish is applied onto the first resin varnish, and then dried.

[3]如[2]之樹脂薄片之製造方法，其中，使其預備乾燥後之第1樹脂清漆中之殘留溶劑量，將第1樹脂清漆中所包含之不揮發成分的合計定為100質量%時，為15質量%~70質量%。 [3] The method for producing a resin sheet according to [2], wherein the total amount of the solvent contained in the first resin varnish after preliminary drying is set to 100 masses of the total nonvolatile components contained in the first resin varnish. When it is %, it is 15 mass% - 70 mass%.

[4]如[1]或[2]之樹脂薄片之製造方法，其係包含與於支持體上塗佈第1樹脂清漆同時於第1樹脂清漆上塗佈第2樹脂清漆，然後進行乾燥之步驟。 [4] The method for producing a resin sheet according to [1] or [2], comprising applying a second resin varnish to the first resin varnish while applying the first resin varnish to the support, and then drying the resin varnish. step.

[5]如[1]~[4]中任一項之樹脂薄片之製造方法，其中，第1樹脂組成物層的厚度為0.3μm~15μm，第2樹脂組成物層的厚度為3μm~200μm，混合層的厚度為0.4μm以上且為第1樹脂組成物層的厚度之2倍以下。 [5] The method for producing a resin sheet according to any one of [1] to [4] wherein the thickness of the first resin composition layer is 0.3 μm to 15 μm, and the thickness of the second resin composition layer is 3 μm to 200 μm. The thickness of the mixed layer is 0.4 μm or more and is twice or less the thickness of the first resin composition layer.

[6]如[1]~[5]中任一項之樹脂薄片之製造方法，其中，支持體為附脫膜層之支持體。 [6] The method for producing a resin sheet according to any one of [1] to [5] wherein the support is a support having a release layer.

[7]如[1]~[6]中任一項之樹脂薄片之製造方法，其中，第1樹脂組成物層之最低熔融黏度為3000poise以上，第2樹脂組成物層之最低熔融黏度為10000poise以下。 [7] The method for producing a resin sheet according to any one of [1] to [6] wherein the first resin composition layer has a minimum melt viscosity of 3,000 poise or more, and the second resin composition layer has a lowest melt viscosity of 10,000 poise. the following.

[8]如[1]~[7]中任一項之樹脂薄片之製造方法，其中，第1樹脂清漆的黏度為100mPa．s~3000mPa．s，第2樹脂清漆的黏度為100mPa．s~6000mPa．s。 [8] The method for producing a resin sheet according to any one of [1] to [7] wherein the viscosity of the first resin varnish is 100 mPa. s~3000mPa. s, the viscosity of the second resin varnish is 100mPa. s~6000mPa. s.

[9]如[1]~[8]中任一項之樹脂薄片之製造方法，其中，在同一塗佈線上，塗佈第1樹脂清漆與第2樹脂清漆。 [9] The method for producing a resin sheet according to any one of [1] to [8] wherein the first resin varnish and the second resin varnish are applied on the same coating line.

[10]一種印刷配線板之製造方法，其係將藉由如[1]~[9]中任一項之方法所製造之樹脂薄片層合於內層基板上，使其熱硬化後再去除支持體。 [10] A method of producing a printed wiring board, which is obtained by laminating a resin sheet produced by the method according to any one of [1] to [9] on an inner layer substrate, thermally hardening, and then removing Support body.

[11]一種樹脂薄片，其係具有由支持體、與於支持體上所設置之第1樹脂組成物所成之第1樹脂組成物層、與由第1樹脂組成物層上所設置之第2樹脂組成物所成之第2樹脂組成物層，並於第1樹脂組成物層與第2樹脂組成物層之間具有混在第1樹脂組成物及第2樹脂組成物之混合層，混合層的厚度為0.4μm以上。 [11] A resin sheet comprising a first resin composition layer formed of a support and a first resin composition provided on a support, and a first resin composition layer provided on the first resin composition layer (2) The second resin composition layer formed of the resin composition, and a mixed layer of the first resin composition and the second resin composition, and a mixed layer, between the first resin composition layer and the second resin composition layer The thickness is 0.4 μm or more.

[12]如[11]之樹脂薄片，其中，第1樹脂組成物層的厚度為0.3μm~15μm，第2樹脂組成物層的厚度為3μm~200μm，混合層的厚度為0.4μm以上且為第1樹脂組成物 層的厚度之2倍以下。 [12] The resin sheet according to [11], wherein the thickness of the first resin composition layer is 0.3 μm to 15 μm, the thickness of the second resin composition layer is 3 μm to 200 μm, and the thickness of the mixed layer is 0.4 μm or more. First resin composition The thickness of the layer is less than 2 times.

[13]如[11]或[12]之樹脂薄片，其中，第1樹脂組成物層之最低熔融黏度為3000poise以上。 [13] The resin sheet according to [11] or [12] wherein the first resin composition layer has a minimum melt viscosity of 3,000 poise or more.

[14]如[11]~[13]中任一項之樹脂薄片，其中，第2樹脂組成物層之最低熔融黏度為10000poise以下。 [14] The resin sheet according to any one of [11] to [13] wherein the second resin composition layer has a minimum melt viscosity of 10,000 poise or less.

[15]一種印刷配線板，其係包含使用如[11]~[14]中任一項之樹脂薄片所形成之絕緣層。 [15] A printed wiring board comprising an insulating layer formed using the resin sheet of any one of [11] to [14].

[16]一種半導體裝置，其係包含如[15]之印刷配線板。 [16] A semiconductor device comprising the printed wiring board of [15].

根據本發明，使得提供一種抑制層間剝離，可實現粗糙度或剝離強度之安定性高的絕緣層的樹脂薄片之製造方法變可能。 According to the present invention, it is possible to provide a method for producing a resin sheet which can suppress the peeling between layers and which can realize an insulating layer having high roughness or peel strength.

1‧‧‧樹脂薄片 1‧‧‧resin sheet

11‧‧‧支持體 11‧‧‧Support

12‧‧‧第1樹脂組成物層 12‧‧‧1st resin composition layer

13‧‧‧混合層 13‧‧‧ mixed layer

14‧‧‧第2樹脂組成物層 14‧‧‧Second resin composition layer

100‧‧‧樹脂薄片之製造裝置 100‧‧‧Manufacturer of resin sheet

101‧‧‧塗佈裝置 101‧‧‧ Coating device

102‧‧‧乾燥裝置 102‧‧‧Drying device

200‧‧‧樹脂薄片之製造裝置 200‧‧‧Manufacturer of resin sheet

201‧‧‧第1塗佈裝置 201‧‧‧1st coating device

202‧‧‧預備乾燥裝置 202‧‧‧Preparation drying unit

203‧‧‧第2塗佈裝置 203‧‧‧2nd coating device

204‧‧‧乾燥裝置 204‧‧‧Drying device

[圖1]圖1係表示本發明之樹脂薄片之一例的模式截面圖。 Fig. 1 is a schematic cross-sectional view showing an example of a resin sheet of the present invention.

[圖2]圖2係表示本發明之樹脂薄片之製造方法之一例的模式圖。 Fig. 2 is a schematic view showing an example of a method for producing a resin sheet of the present invention.

[圖3]圖3係表示本發明之樹脂薄片之製造方法之另一例的模式圖。 Fig. 3 is a schematic view showing another example of the method for producing a resin sheet of the present invention.

以下針對本發明進行詳細說明。 The invention is described in detail below.

[樹脂薄片] [resin sheet]

本發明之樹脂薄片，其特徵為具有由支持體、與於支持體上所設置之第1樹脂組成物所成之第1樹脂組成物層、與由第1樹脂組成物層上所設置之第2樹脂組成物所成之第2樹脂組成物層，於第1樹脂組成物層與第2樹脂組成物層之間，具有混在第1樹脂組成物及第2樹脂組成物之混合層，混合層的厚度為0.4μm以上。 The resin sheet of the present invention is characterized in that it has a first resin composition layer formed of a support and a first resin composition provided on the support, and a first resin composition layer provided on the first resin composition layer. The second resin composition layer formed of the resin composition has a mixed layer of the first resin composition and the second resin composition interposed between the first resin composition layer and the second resin composition layer, and the mixed layer The thickness is 0.4 μm or more.

如先述，本發明者們發現在使用包含複數樹脂組成物層之樹脂薄片所形成之絕緣層，曝露於回流時等之高溫環境下時，有產生層間剝離(Delamination)的情況。使用包含複數樹脂組成物層之樹脂薄片形成絕緣層時，在所得之絕緣層，形成源自各樹脂組成物層之複數硬化物層。此等之硬化物層起因於組成之異同，在高溫環境下有展示不同膨脹率的情況。該情況推測是因為集中應力於層間，易產生層間剝離者。此點，本發明之樹脂薄片係於第1及第2樹脂組成物層之間具有混在形成第1及第2樹脂組成物層之各樹脂組成物的混合層。在使用本發明之樹脂薄片所形成之絕緣層，於源自第1樹脂組成物層之第1硬化物層、與源自第2樹脂組成物層之第2硬化物層之間，形成源自混合層之硬化物層。源自混合層之硬化物層由於緩和起因於第1硬化物層與第2硬化物層之膨脹率的 異同之應力的集中，可抑制回流時等在高溫環境下之層間剝離。尚，即使在使用包含複數樹脂組成物層之以往樹脂薄片以形成絕緣層的情況下，有因各樹脂組成物層之組成或熱硬化條件而導致形成應力緩和層的情況。然而，所形成之應力緩和層的厚度消除在高溫環境下之層間剝離的問題並不夠充分。對此，藉由使用具有特定厚度之混合層之本發明之樹脂薄片，無論各樹脂組成物層之組成或熱硬化條件，亦可輕易實現層間剝離所抑制之絕緣層。 As described above, the present inventors have found that when an insulating layer formed using a resin sheet including a plurality of resin composition layers is exposed to a high temperature environment such as a reflow, there is a case where interlayer peeling occurs. When an insulating layer is formed using a resin sheet containing a plurality of resin composition layers, a plurality of cured layers derived from the respective resin composition layers are formed in the obtained insulating layer. These hardened layers are caused by the similarities and differences of composition, and exhibit different expansion ratios in a high temperature environment. This situation is presumed to be due to the concentration of stress between the layers, which tends to cause interlayer peeling. In this regard, the resin sheet of the present invention has a mixed layer in which the respective resin compositions forming the first and second resin composition layers are mixed between the first and second resin composition layers. The insulating layer formed using the resin sheet of the present invention is formed between the first cured material layer derived from the first resin composition layer and the second cured material layer derived from the second resin composition layer. The hardened layer of the mixed layer. The cured layer derived from the mixed layer is attenuated due to the expansion ratio of the first cured layer and the second cured layer. The concentration of the similarities and differences can suppress the peeling between layers in a high temperature environment such as during reflow. In the case where a conventional resin sheet containing a plurality of resin composition layers is used to form an insulating layer, a stress relaxation layer may be formed due to the composition of each resin composition layer or the heat curing condition. However, the problem that the thickness of the stress relieving layer formed eliminates the peeling between layers in a high temperature environment is not sufficient. On the other hand, by using the resin sheet of the present invention having a mixed layer having a specific thickness, the insulating layer suppressed by the interlayer peeling can be easily realized regardless of the composition of each resin composition layer or the heat curing condition.

圖1係表示本發明之樹脂薄片之一例的模式截面圖。在圖1所示之樹脂薄片1，依支持體11、第1樹脂組成物層12、混合層13、及第2樹脂組成物層14順序層合。 Fig. 1 is a schematic cross-sectional view showing an example of a resin sheet of the present invention. In the resin sheet 1 shown in FIG. 1, the support 11, the first resin composition layer 12, the mixed layer 13, and the second resin composition layer 14 are sequentially laminated.

以下針對構成本發明之樹脂薄片之各層進行詳細說明。 Hereinafter, each layer constituting the resin sheet of the present invention will be described in detail.

<支持體> <Support>

本發明之樹脂薄片係具有支持體。作為在本發明之支持體，例如可列舉由塑膠材料所成之薄膜、金屬箔、脫膜紙，較佳為由塑膠材料所成之薄膜、金屬箔。 The resin sheet of the present invention has a support. Examples of the support of the present invention include a film made of a plastic material, a metal foil, and a release paper, and a film or a metal foil made of a plastic material is preferable.

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, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter, Polyester, polycarbonate (hereinafter sometimes abbreviated as "PC"), polyacrylic acid methyl ester (PMMA), etc. Polyolefin, triethylenesulfonyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimine, and the like. Among them, polyethylene terephthalate or polyethylene naphthalate is preferred, and 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 a metal foil is used as the support, examples of the metal foil include a copper foil, an aluminum foil, and the like, and a copper foil is preferable. As the copper foil, a foil made of a single metal of copper or a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, hafnium, titanium, or the like) may be used.

支持體可於與第1樹脂組成物層接合的面實施磨砂處理、電暈處理。 The support can be subjected to a sanding treatment or a corona treatment on the surface joined to the first resin composition layer.

又，作為支持體，可使用於與第1樹脂組成物層接合的面具有脫膜層之附脫膜層之支持體。作為附脫膜層之支持體的脫膜層所使用之脫膜劑，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種以上的脫膜劑。附脫膜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膜劑作為主成分之脫膜層之PET薄膜即Lintec(股)製之「SK-1」、「AL-5」、「AL-7」、東麗(股)製「LumirrorT6AM」等。 Further, as the support, a support for the release layer of the release layer can be provided on the surface to be bonded to the first resin composition layer. The release agent used for the release layer of the support of the release film layer is, for example, selected from the group consisting of an acid alcohol resin, a polyolefin resin, a urethane resin, and a oxime resin. One or more kinds of release agents. For the support of the release layer, a commercially available product can be used. For example, a PET film having a release layer containing an acid alcohol resin-based release agent as a main component, that is, "SK-1" and "AL" manufactured by Lintec Co., Ltd. -5", "AL-7", Toray (share) system "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，使用附脫膜層之支持體的情況下，較佳為附脫膜層之支持體全體的厚度為上述範圍。 The thickness of the support is not particularly limited, but 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 having a release layer, it is preferable that the thickness of the entire support of the release layer is in the above range.

<第1樹脂組成物層> <First resin composition layer>

本發明之樹脂薄片係具有由第1樹脂組成物所成之第1樹脂組成物層。第1樹脂組成物層已與支持體接合，於印刷配線板之製造時，於其上形成設置導體層之絕緣層之表面附近的區域。第1樹脂組成物並未特別限定，若其硬化物為具有充分之硬度與絕緣性者即可。作為該樹脂組成物，例如可列舉包含硬化性樹脂與其硬化劑之組成物。作為硬化性樹脂，可使用形成印刷配線板之絕緣層時所使用之以往周知的硬化性樹脂，其中較佳為環氧樹脂。據此，在一實施形態，第1樹脂組成物係包含(a)環氧樹脂及(b)硬化劑。第1樹脂組成物如有必要可進一步包含(c)無機填充材、(d)熱塑性樹脂、(e)硬化促進劑、(f)阻燃劑及(g)有機填充材等之添加劑。 The resin sheet of the present invention has a first resin composition layer made of the first resin composition. The first resin composition layer is bonded to the support, and a region in the vicinity of the surface of the insulating layer on which the conductor layer is provided is formed on the printed wiring board. The first resin composition is not particularly limited, and the cured product may have sufficient hardness and insulation properties. As the resin composition, for example, a composition containing a curable resin and a curing agent thereof can be mentioned. As the curable resin, a conventionally known curable resin used in forming an insulating layer of a printed wiring board can be used, and among them, an epoxy resin is preferable. Accordingly, in one embodiment, the first resin composition includes (a) an epoxy resin and (b) a curing agent. The first resin composition may further contain an additive such as (c) an inorganic filler, (d) a thermoplastic resin, (e) a curing accelerator, (f) a flame retardant, and (g) an organic filler.

以下，針對可作為第1樹脂組成物之材料使用之環氧樹脂、硬化劑、及添加劑進行說明。 Hereinafter, an epoxy resin, a curing agent, and an additive which can be used as a material of the first resin composition will be described.

-(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、奈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、奈酚型環氧樹脂、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、萘醚型環氧樹脂及三羥甲基型環氧樹脂等。環氧樹脂可1種單獨使用、或亦可併用2種以上。 Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, dicyclopentadiene epoxy resin, and ginseng. Phenolic epoxy resin, naphthol novolak epoxy resin, phenol novolak epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphth 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 epoxy resin, naphthyl ether Type epoxy resin and trishydroxymethyl epoxy resin. Epoxy resins may be used alone or in combination of two or more.

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，較佳為於1分子中包含具有2個以上(較佳為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」)。環氧樹脂又可由於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」)。在第1樹脂組成物，環氧樹脂中之固體狀環氧樹脂的含量將環氧樹脂全體之不揮發成分定為100質量%時，較佳為30質量%以上，更佳為40質量%以上，再更佳為50質量%以上、60質量%以上、70質量%以上、80質量%以上、或90質量%以上。該固體狀環氧樹脂的含量之上限並未特別限定，可為100質量%。 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 100% by mass, it is preferably at least 50% by mass or more of an epoxy resin having two or more epoxy groups in one molecule. Among them, an epoxy resin (hereinafter referred to as "solid epoxy resin") having two or more (preferably three or more) epoxy groups and having a solid content at a temperature of 20 ° C is preferably contained in one molecule. The epoxy resin may be an epoxy resin (hereinafter referred to as "liquid epoxy resin") having a liquidity at 20 ° C in a molecule of two or more epoxy groups. In the first resin composition, the content of the solid epoxy resin in the epoxy resin is preferably 30% by mass or more, and more preferably 40% by mass or more, when the nonvolatile content of the entire epoxy resin is 100% by mass. More preferably, it is 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, or 90 mass% or more. The upper limit of the content of the solid epoxy resin is not particularly limited and may be 100% by mass.

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、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、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、具有丁二烯構造之環氧樹脂、酚酚醛清漆型環氧樹脂、及萘型環氧樹脂，更佳為雙酚A型環氧樹脂、雙 酚F型環氧樹脂、雙酚AF型環氧樹脂、及萘型環氧樹脂，再更佳為雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AF型環氧樹脂。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「jER828EL」(雙酚A型環氧樹脂)、「jER807」(雙酚F型環氧樹脂)、「YL7223」、「YL7723」(雙酚AF型環氧樹脂)、「jER152」(酚酚醛清漆型環氧樹脂)、新日鐵住金化學(股)製之「ZX1059」(雙酚A型環氧樹脂與雙酚F型環氧樹脂之混合品)、Nagase ChemteX(股)製之「EX-721」(縮水甘油酯型環氧樹脂)。此等可1種單獨使用、或亦可併用2種以上。 The liquid epoxy resin is preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol AF epoxy resin, a glycidyl ester epoxy resin, or a glycidylamine epoxy resin. An alicyclic epoxy resin having an ester skeleton, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, an epoxy resin having a butadiene structure, a phenol novolak type epoxy resin, and a naphthalene type Epoxy resin, more preferably bisphenol A epoxy resin, double Phenol F type epoxy resin, bisphenol AF type epoxy resin, and naphthalene type epoxy resin, and more preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene epoxy resin) manufactured by DIC Co., Ltd., and "jER828EL" (bisphenol) manufactured by Mitsubishi Chemical Corporation. A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "YL7223", "YL7723" (bisphenol AF type epoxy resin), "jER152" (phenol novolak type epoxy resin), "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Co., Ltd., and "EX-721" (glycidyl ester) manufactured by Nagase ChemteX Co., Ltd. Type epoxy resin). These may be used alone or in combination of two or more.

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、奈酚型環氧樹脂、聯苯型環氧樹脂、奈酚酚醛清漆型環氧樹脂、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、及四苯基乙烷型環氧樹脂，更佳為萘型4官能環氧樹脂、聯苯型環氧樹脂、或萘醚型環氧樹脂，再更佳為萘型4官能環氧樹脂、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「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)、「EXA7311」、「EXA7311- G3」、「EXA7311-G4」、「EXA7311-G4S」、「HP6000」(萘醚型環氧樹脂)、日本化藥(股)製之「EPPN-502H」(參酚環氧樹脂)、「NC7000L」(奈酚酚醛清漆環氧樹脂)、「NC3000H」、「NC3000」、「NC3000L」、「NC3100」(聯苯型環氧樹脂)、新日鐵住金化學(股)製之「ESN475V」(奈酚酚醛清漆型環氧樹脂)、「ESN485V」(奈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」(聯二甲酚型環氧樹脂)、大阪瓦斯化學(股)製之「PG-100」、「CG-500」、三菱化學(股)製之「YL7800」(茀型環氧樹脂)、「YL7760」(雙酚AF型環氧樹脂)等。 As the solid epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a phenol type epoxy resin, a naphthol type epoxy resin, or the like is preferable. Biphenyl type epoxy resin, naphthol novolak type epoxy resin, biphenyl type epoxy resin, naphthalene ether type epoxy resin, onion type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane The epoxy resin is more preferably a naphthalene type tetrafunctional epoxy resin, a biphenyl type epoxy resin or a naphthene ether type epoxy resin, and more preferably a naphthalene type tetrafunctional epoxy resin or a biphenyl type epoxy resin. Specific examples of the solid epoxy resin include "HP-4700" manufactured by DIC Co., Ltd., "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N-690" (cresol novolac type). Epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "EXA7311", "EXA7311- G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (naphthyl ether type epoxy resin), "EPPN-502H" manufactured by Nippon Kayaku Co., Ltd. (phenol epoxy resin), "NC7000L" "Nylon novolac varnish epoxy resin", "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. "Phenolic novolak type epoxy resin", "ESN485V" (naphthol novolak type epoxy resin), "YX4000H" made by Mitsubishi Chemical Corporation, "YL6121" (biphenyl type epoxy resin), "YX4000HK" ( "Dylenol type epoxy resin", "PG-100" made by Osaka Gas Chemical Co., Ltd., "CG-500", "YL7800" (茀 type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YL7760" (Bisphenol AF type epoxy resin), etc.

第1樹脂組成物中之環氧樹脂的含量較佳為5質量%以上，更佳為10質量%以上，再更佳為20質量%以上或30質量%以上。環氧樹脂的含量之上限雖並未特別限定，但較佳為50質量%以下，更佳為45質量%以下，又再更佳為40質量%以下。 The content of the epoxy resin in the first resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more or 30% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited, but is preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less.

尚，在本發明，構成樹脂組成物之各成分的含量除非另有說明，係指將樹脂組成物中之不揮發成分的合計定為100質量%時之值。 In the present invention, the content of each component constituting the resin composition is a value obtained by setting the total of the nonvolatile components in the resin composition to 100% by mass unless otherwise specified.

環氧樹脂之環氧當量較佳為50~3000，更佳為80~2000，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之表面粗糙度小的絕緣層。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 from 50 to 3,000, more preferably from 80 to 2,000, still more preferably from 110 to 1,000. By setting it as such a range, it is possible to provide an insulating layer having a small surface roughness with a sufficient crosslinking density of the cured product. However, the epoxy equivalent can be determined according to JIS K7236, which contains 1 equivalent of epoxy group. The quality of the resin.

環氧樹脂之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，環氧樹脂之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之重量平均分子量。 The weight average molecular weight of the epoxy resin is preferably from 100 to 5,000, more preferably from 250 to 3,000, still more preferably from 400 to 1,500. Here, the weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) 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、奈酚系硬化劑、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。 The curing agent is not particularly limited as long as it has a function of curing the epoxy resin, and examples thereof include a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, and a cyanate ester system. A hardener, a carbodiimide-based hardener, and the like. The curing agent may be used alone or in combination of two or more.

作為酚系硬化劑及奈酚系硬化劑，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奈酚系硬化劑。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(剝離強度)的觀點來看，較佳為含有三嗪骨架之酚酚醛清漆硬化劑。 The phenolic curing agent and the naphthol curing agent are preferably a phenolic curing agent having a novolac structure or a naphthol curing agent having a novolac structure from the viewpoint of heat resistance and water resistance. Moreover, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferred, and a phenol-based curing agent containing a triazine skeleton is more preferred. Among them, from the viewpoint of satisfying heat resistance, water resistance, and adhesion to the conductor layer (peeling strength), a phenol novolak curing agent containing a triazine skeleton is preferred.

作為酚系硬化劑及奈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「LA-7052」、「LA-7054」、「LA-3018」、「EXB-9500」等。 Specific examples of the phenolic curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851", and Nippon Chemical Co., Ltd., manufactured by Megumi Kasei Co., Ltd. "NSN", "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395", DIC (share) system "LA-7052", "LA-7054", "LA-3018", "EXB-9500", etc.

作為含有三嗪骨架之酚酚醛清漆硬化劑之具體例，例如可列舉「LA-3018-50P」等。 Specific examples of the phenol novolak curing agent containing a triazine skeleton include "LA-3018-50P" and the like.

從於粗糙化處理後得到表面粗糙度小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/或奈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。作為酚化合物或奈酚化合物，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-奈酚、β-奈酚、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 having a small surface roughness after roughening treatment, an active ester-based hardener is also preferable. The active ester-based curing agent is not particularly limited, but is generally preferably a phenolic ester having two or more compounds in one molecule, a thiophenol ester, an N-hydroxyamine ester, or a heterocyclic hydroxy compound. An ester group having a high reactivity such as an ester. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is more preferred, and an active ester system obtained 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 the phenol compound or the naphthol compound include hydroquinone, resorcin, 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 Diphenol compound, phenolic phenol Aldehyde varnish, etc. Here, the "dicyclopentadiene type diphenol compound" means a diphenol compound obtained by condensing a phenol 2 molecule with a 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 comprising a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetal of a phenol novolac, and benzamidine containing a phenol novolac. The active ester compound of the base compound is more preferably an active ester compound containing a naphthalene structure or an active ester compound containing a dicyclopentadiene type diphenol structure. The "dicyclopentadiene type diphenol structure" is a divalent structural unit formed of a phenyl-bicyclopentyl-phenylene group.

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」(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)等。 As a commercial product of the active ester-based curing agent, examples of the active ester compound containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" (DIC ( In the case of the active ester compound containing a naphthalene structure, "EXB9416-70BK" (manufactured by DIC Co., Ltd.) is used, and as an active ester compound containing an acetophenone of a phenol novolak, "DC808" (Mitsubishi) In the chemical (manufactured by the Mitsubishi Chemical Co., Ltd.), etc., the active ester compound of the benzamidine-based phenol phenol aldehyde varnish is exemplified.

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 the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industries 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」(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。 Examples of the cyanate-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylenecyanate), and 4,4'- Methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl Di- dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), double ( 4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanic acid) Polyfunctional cyanate resins derived from bifunctional cyanate resins, phenol novolacs, cresol novolacs, etc., such as ester phenyl) sulfides and bis(4-cyanate phenyl) ethers, etc. The cyanate resin is subjected to a part of a triazine-formed prepolymer or the like. Specific examples of the cyanate-based curing agent include "PT30" and "PT60" (all phenol novolac type polyfunctional cyanate resins) manufactured by Lonza Japan Co., Ltd., and "BA230" (becoming bisphenol A II) a prepolymer of a partially or fully triazineated trimer of a cyanate ester or the like.

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 curing agent include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

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1：0.2~1：2的範圍，更佳為1：0.3~1：1.5，再更佳為1：0.4~1：1.2。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 the epoxy resin to the hardener is in the range of [the total number of epoxy groups of the epoxy resin]: [the total number of the reactive groups of the hardener], preferably in the range of 1:0.2 to 1:2, Good is 1:0.3~1:1.5, and even better is 1:0.4~1:1.2. Here, the reactive group of the curing agent means an active hydroxyl group, an active ester group, or the like, and is different depending on the type of the curing agent. In addition, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the solid content of each epoxy resin by the value of the epoxy equivalent for all the epoxy resins, and the total of the reactive groups of the curing agent. The number refers to the value obtained by dividing the solid content of each hardener by the value of the reactive base equivalent, and totaling all the hardeners. By setting the amount ratio of the epoxy resin to the hardener to be in this range, the heat resistance of the cured product of the resin composition can be further improved.

在一實施形態，第1樹脂組成物係包含上述 之(a)環氧樹脂及(b)硬化劑。第1樹脂組成物較佳為分別包含：作為(a)環氧樹脂之包含固體狀環氧樹脂之環氧樹脂(環氧樹脂中之固體狀環氧樹脂的含量較佳為30質量%以上，更佳為40質量%以上，再更佳為50質量%以上、60質量%以上、70質量%以上、80質量%以上、或90質量%以上)，作為(b)硬化劑之選自由酚系硬化劑、奈酚系硬化劑、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、奈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 first resin composition includes the above (a) epoxy resin and (b) hardener. The first resin composition preferably contains, as the (a) epoxy resin, an epoxy resin containing a solid epoxy resin (the content of the solid epoxy resin in the epoxy resin is preferably 30% by mass or more, More preferably, it is 40 mass% or more, more preferably 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, or 90 mass% or more, and it is selected from the phenol type as (b) hardening agent. One or more selected from the group consisting of a curing agent, a naphthol curing agent, an active ester curing agent, and a cyanate curing agent (preferably selected from the group consisting of a phenolic curing agent, a naphthol curing agent, and an active ester) One or more of the group consisting of hardeners).

第1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3質量%以上。 The content of the curing agent in the first resin composition is not particularly limited, but 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. %the following. Further, the lower limit is not particularly limited, but is preferably 3% by mass or more.

-(c)無機填充材- - (c) inorganic filler -

第1樹脂組成物可進一步包含無機填充材。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，尤其適合無定形二氧化矽、熔融二氧化矽、結晶二氧化矽、合成二 氧化矽、中空二氧化矽等之二氧化矽。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。 The first resin composition may further contain an inorganic filler. The material of the inorganic filler is not particularly limited, and examples thereof include cerium oxide, aluminum oxide, glass, cordierite, cerium oxide, barium sulfate, cerium carbonate, talc, clay, mica powder, zinc oxide, and hydrotalcite. Boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, barium carbonate, barium titanate, calcium titanate, titanic acid Magnesium, barium titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate, and the like. Among these, it is especially suitable for amorphous cerium oxide, molten cerium oxide, crystalline cerium oxide, and synthetic two. Cerium oxide such as cerium oxide or hollow cerium oxide. Further, as the cerium oxide, spherical cerium oxide is preferred. The inorganic filler may be used singly or in combination of two or more.

第1樹脂組成物所使用之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的觀點來看，較佳為600nm以下，更佳為300nm以下，再更佳為200nm以下，又再更佳為150nm以下，100nm以下，90nm以下，80nm以下，70nm以下，60nm以下或50nm以下。該平均粒徑的下限雖並未特別限定，但通常為5nm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」。 The average particle diameter of the inorganic filler used in the first resin composition is not particularly limited, but from the viewpoint of obtaining an insulating layer having a small surface roughness, it is preferably 600 nm or less, more preferably 300 nm or less. It is preferably 200 nm or less, more preferably 150 nm or less, 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less, or 50 nm or less. The lower limit of the average particle diameter is not particularly limited, but is usually 5 nm or more. For example, "YC100C", "YA050C", "YA050C-MJE", "YA010C", and "UFP-30" made by the Chemical Industry Co., Ltd., manufactured by Admatechs, may be mentioned as a commercial product of the inorganic filler having such an average particle diameter. "Sifil NSS-3N", "Sifil NSS-4N" and "Sifil NSS-5N" made by Tokuyama.

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、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 determined by laser diffraction or scattering according to the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis by a laser diffraction scattering type particle size distribution measuring apparatus, and can be measured by using the median diameter as an average particle diameter. It is preferable to use a sample in which the inorganic filler is dispersed in water by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring apparatus, "LA-500" manufactured by Horiba, Ltd., or the like can be used.

無機填充材從提高耐濕性及分散性的觀點來看，較佳為以胺基矽烷系偶合劑、環氧矽烷系偶合劑、巰基矽烷系偶合劑、矽烷系偶合劑、有機矽氮烷化合物、鈦 酸酯系偶合劑等之1種以上之表面處理劑進行處理。作為表面處理劑之市售品，例如可列舉信越化學工業(股)製「KBM403」(3-環氧甘油氧基丙基三甲氧基矽烷)、信越化學工業(股)製「KBM803」(3-巰基丙基三甲氧基矽烷)、信越化學工業(股)製「KBE903」(3-胺基丙基三乙氧基矽烷)、信越化學工業(股)製「KBM573」(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「KBM103」(苯基三甲氧基矽烷)等。 The inorganic filler is preferably an amine decane coupling agent, an epoxy decane coupling agent, a mercapto decane coupling agent, a decane coupling agent, or an organic decazane compound from the viewpoint of improving moisture resistance and dispersibility. ,titanium One or more surface treatment agents such as an acid ester coupling agent are treated. As a commercial product of the surface treatment agent, "KBM403" (3-epoxyglyceryl propyl trimethoxy decane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" manufactured by Shin-Etsu Chemical Co., Ltd. (3) "Methyl propyl trimethoxy decane", "KBE903" (3-aminopropyltriethoxy decane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-based) manufactured by Shin-Etsu Chemical Co., Ltd. "3-Aminopropyltrimethoxydecane", "SZ-31" (hexamethylguanidinium) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (Phenyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd. )Wait.

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0.02mg/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。 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 is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and still more preferably 0.2 from the viewpoint of improving the dispersibility of the inorganic filler. Mg/m 2 or more. In addition, from the viewpoint of preventing the melt viscosity of the resin varnish or the increase in the melt viscosity in the form of a sheet, it is preferably 1 mg/m 2 or less, more preferably 0.8 mg/m 2 or less, still more preferably 0.5 mg/m 2 or less. .

每一無機填充材之單位表面積的碳量，可將表面處理後之無機填充材藉由溶劑(例如甲基乙基酮(MEK))洗淨處理後來測定。具體而言，作為溶劑除了將充分量之MEK以表面處理劑進行表面處理之無機填充材之外，並於25℃進行5分鐘超音波洗淨。去除上清液，使固形分乾燥後，可使用碳分析計測定每一無機填充材之單位表面積之碳量。作為碳分析計可使用(股)堀場製作所製 「EMIA-320V」等。 The amount of carbon per unit surface area of each inorganic filler can be determined by washing the surface-treated inorganic filler with a solvent such as methyl ethyl ketone (MEK). Specifically, ultrasonic cleaning was carried out for 5 minutes at 25 ° C as a solvent in addition to an inorganic filler which had a sufficient amount of MEK surface-treated with a surface treatment agent. After the supernatant is removed and the solid fraction is dried, the amount of carbon per unit surface area of each inorganic filler can be determined using a carbon analyzer. As a carbon analyzer, it can be used by the market. "EMIA-320V" and so on.

第1樹脂組成物中之無機填充材的含量並未特別限定，較佳為60質量%以下，更佳為55質量%以下，再更佳為50質量%以下，又再更佳為48質量%以下，46質量%以下，44質量%以下，42質量%以下，或40質量%以下。第1樹脂組成物中之無機填充材的含量的下限並未特別限定可為0質量%。 The content of the inorganic filler in the first resin composition is not particularly limited, but is preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less, and still more preferably 48% by mass. Hereinafter, it is 46% by mass or less, 44% by mass or less, 42% by mass or less, or 40% by mass or less. The lower limit of the content of the inorganic filler in the first resin composition is not particularly limited to 0% by mass.

-(d)熱塑性樹脂- - (d) thermoplastic resin -

第1樹脂組成物可進一步包含熱塑性樹脂。作為熱塑性樹脂，例如可列舉苯氧基樹脂、聚乙烯縮醛樹脂、丙烯酸樹脂、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、聚醚碸樹脂、聚醚醯亞胺樹脂、聚碳酸酯樹脂、聚醚醚酮樹脂、聚酯樹脂、聚苯醚樹脂及聚碸樹脂等。熱塑性樹脂可1種單獨使用、或亦可併用2種以上。 The first resin composition may further contain a thermoplastic resin. Examples of the thermoplastic resin include a phenoxy resin, a polyvinyl acetal resin, an acrylic resin, a polyolefin resin, a polybutadiene resin, a polyimide resin, a polyamidimide resin, a polyether oxime resin, and the like. A polyether phthalimide resin, a polycarbonate resin, a polyether ether ketone resin, a polyester resin, a polyphenylene ether resin, a polyfluorene resin, and the like. One type of the thermoplastic resin may be used alone or two or more types may be used in combination.

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 polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, still more preferably in the range of 20,000 to 60,000. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight of the thermoplastic resin in terms of polystyrene is determined by using LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P/K-804L manufactured by Showa Denko Co., Ltd. /K-804L as a column, using chloroform as the mobile equal, in the column The temperature is measured at 40 ° C and can be calculated using a 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、或亦可併用2種以上。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「YX6954」(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「YX7553BH30」、「YL7769BH30」、「YL6794」、「YL7213」、「YL7290」及「YL7482」等。 The phenoxy resin may, for example, be selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolak skeleton, a biphenyl skeleton, an anthracene skeleton, and a dicyclopentadiene skeleton. A phenoxy resin having one or more kinds of skeletons in the group consisting of a norbornene skeleton, a naphthalene skeleton, an onion skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be a functional group of any one of a phenolic hydroxyl group and an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both phenoxy resins containing a bisphenol A skeleton) and "YX8100" (including a bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation. "Phenoxy resin" and "YX6954" (phenoxy resin containing bisphenol acetophenone skeleton), among others, "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., Mitsubishi "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482" made by the chemical company.

作為丙烯酸樹脂，較佳為含有官能基之丙烯酸樹脂，更佳為含有環氧基之丙烯酸樹脂，再更佳為含有環氧基之丙烯酸酯共聚物樹脂。作為丙烯酸樹脂使用含有官能基之丙烯酸樹脂的情況下，其官能基當量較佳為1000~50000，更佳為2500~30000。 The acrylic resin is preferably an acrylic resin containing a functional group, more preferably an epoxy group-containing acrylic resin, and still more preferably an epoxy group-containing acrylate copolymer resin. When an acrylic resin containing a functional group is used as the acrylic resin, the functional group equivalent is preferably from 1,000 to 50,000, more preferably from 2,500 to 30,000.

作為丙烯酸樹脂之具體例，可列舉Nagase Chemte X(股)製之「SG-80H」、「SG-P3」(含有環氧基之丙烯酸酯共聚物樹脂)。 Specific examples of the acrylic resin include "SG-80H" and "SG-P3" (epoxy group-containing acrylate copolymer resin) manufactured by Nagase Chemte X.

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、5000-A、6000-C、6000-EP、積水化學工業(股)製之S-LEC BH系列、BX系列、KS系列(具體為「KS-1」等)、BL系列、BM系列等。 Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include electroless butyral 4000-2, 5000-A, 6000-C, 6000-EP, and S-made by the Sekisui Chemical Industry Co., Ltd. LEC BH series, BX series, KS series (specifically "KS-1", etc.), BL series, BM series, etc.

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)、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)等之改質聚醯亞胺。 Specific examples of the polyimine resin include "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Nippon Chemical and Chemical Co., Ltd. In addition, as a specific example of the polyimine resin, a linear polyimine obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (Japanese Patent Laid-Open No. 2006-37083) The modified polyimine, such as a polyfluorene-containing polyamine, which is a polyfluorene skeleton (Japanese Patent Laid-Open Publication No. 2002-12667, JP-A-2000-319386, etc.).

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)製之含有聚矽氧烷骨架之聚醯胺醯亞胺「KS9100」、「KS9300」等之改質聚醯胺醯亞胺。 Specific examples of the polyamidoximine resin include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamidoximine resin include modified polyamines such as polyacrylamide skeletons "KS9100" and "KS9300" which are manufactured by Hitachi Chemical Co., Ltd. Yttrium.

作為聚醚碸樹脂之具體例，可列舉住友化學(股)製之「PES5003P」等。 Specific examples of the polyether oxime resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

作為聚碸樹脂之具體例，可列舉Solvay Advanced Polymers(股)製之聚碸「P1700」、「P3500」等。 Specific examples of the polybenzazole resin include polydiprene "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd.

第1樹脂組成物中之熱塑性樹脂的含量雖並未特別限定，但較佳為0.1質量%以上，更佳為1質量%以上，再更佳為3質量%以上、5質量%以上或7質量%以上。熱塑性樹脂的含量之上限雖並未特別限定，但較佳為30質量%以下，更佳為20質量%以下，再更佳為10質量%以下。 The content of the thermoplastic resin in the first resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, 5% by mass or more, or 7% by mass. %the above. The upper limit of the content of the thermoplastic resin is not particularly limited, but is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less.

-(e)硬化促進劑- - (e) hardening accelerator -

第1樹脂組成物可進一步包含硬化促進劑。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，更佳為胺系硬化促進劑、咪唑系硬化促進劑。硬化促進劑可1種單獨使用，亦可組合2種以上使用。 The first resin composition may further contain a curing accelerator. Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, an lanthanum-based curing accelerator, and a metal-based curing accelerator. Preferred examples are a phosphorus-based curing accelerator and an amine-based curing agent. The hardening accelerator and the imidazole-based hardening accelerator are more preferably an amine-based hardening accelerator or an imidazole-based hardening accelerator. The curing accelerator may be used alone or in combination of two or more.

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 the phosphorus-based hardening accelerator include triphenylphosphine, bismuth borate compound, tetraphenylphosphonium tetraphenyl borate, n-butyl phosphotetraphenyl borate, and tetrabutyl decanoic acid. a salt, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., preferably triphenylphosphine, tetrabutyl Sulfate.

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、1,8-二氮雜二環(5,4,0)-十一碳烯等，較佳為4-二甲基胺基吡啶、1,8-二氮雜二環(5,4,0)-十一碳烯。 Examples of the amine-based curing accelerator include a trialkylamine such as triethylamine or tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, and a ginseng. (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 the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl group. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4- Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium benzene Triester, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2' -undecyl imidazolyl-(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]benzimidazole, 1-dodecyl An imidazole compound of 2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline or the like, and an adduct of an imidazole compound and an epoxy resin, preferably 2-B 4-methylimidazole, 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。 A commercially available product can be used as the imidazole-based hardening accelerator, and examples thereof 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。 Examples of the oxime-based hardening accelerator include dicyandiamide, 1-methyl hydrazine, 1-ethyl hydrazine, 1-cyclohexyl hydrazine, 1-phenyl fluorene, 1-(o-methylphenyl) fluorene, and dimethyl Base, diphenyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, pentamethyl hydrazine, 1,5,7-triazabicyclo[4.4.0]non-5-ene, 7-methyl-1 ,5,7- Triazabicyclo[4.4.0]non-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-di Methyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenylbiguanide, 1-(o-methylphenyl)biguanide, etc., preferably dicyandiamide, 1,5,7-triazabicyclo[4.4.0]non-5-ene.

又，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。 Moreover, examples of the metal-based curing accelerator include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include cobalt (II) acetoacetate, an organic cobalt complex such as cobalt (III) acetoacetate, and copper (II) acetoacetate. Organic copper complex, organic zinc complex such as zinc (II) acetamidine pyruvate, organic iron complex such as iron (III) acetoacetate, nickel (II) acetoacetate, etc. An organic manganese complex such as an organic nickel complex or manganese (II) acetoacetate or the like. Examples of the organic metal salt include zinc octoate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

第1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，以0.05質量%~3質量%的範圍使用。 The content of the curing accelerator in the first resin composition is not particularly limited, but is preferably 0.05% by mass to 3% by mass when the total amount of the non-volatile components of the epoxy resin and the curing agent is 100% by mass. The scope of use.

-(f)阻燃劑- - (f) flame retardant -

第1樹脂組成物可進一步包含阻燃劑。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、矽氧系阻燃劑、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。 The first resin composition may further contain a flame retardant. Examples of the flame retardant include an organic phosphorus-based flame retardant, a phosphorus compound containing an organic nitrogen, a nitrogen compound, a rhodium-based flame retardant, and a metal hydroxide. Flame retardant can be 1 These may be used alone or in combination of two or more.

作為阻燃劑可使用市售品，例如可列舉三光公司製之「HCA-HQ」等。 A commercially available product can be used as the flame retardant, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd., and the like.

第1樹脂組成物層中之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1質量%~15質量%，再更佳為1.5質量%~10質量%更佳。 The content of the flame retardant in the first resin composition layer is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, still more preferably 1.5% by mass. ~10% by mass is better.

-(g)有機填充材- - (g) organic filler -

第1樹脂組成物可進一步包含有機填充材。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，較佳為橡膠粒子。作為橡膠粒子可使用市售品，例如可列舉Aica工業(股)製之「AC3816N」等。 The first resin composition may further contain an organic filler. As the organic filler, any organic filler which can be used in forming the insulating layer of the printed wiring board can be used, and examples thereof include rubber particles, polyamide fine particles, and xenon particles, and rubber particles are preferable. Commercially available products can be used as the rubber particles, and examples thereof include "AC3816N" manufactured by Aica Industries Co., Ltd., and the like.

第1樹脂組成物中之有機填充材的含量較佳為1質量%~20質量%，更佳為2質量%~10質量%。 The content of the organic filler in the first resin composition is preferably from 1% by mass to 20% by mass, and more preferably from 2% by mass to 10% by mass.

-其他成分- -Other ingredients -

第1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、以及有機填料、增黏劑、消泡劑、均染劑、密著性賦予劑、及著色劑等之樹脂添加劑等。 The first resin composition may contain other additives as necessary, and examples of the other additives include organometallic compounds such as an organic copper compound, an organic zinc compound, and an organic cobalt compound, and an organic filler, a tackifier, and an antifoaming agent. A resin additive such as a leveling agent, a tackifier, and a coloring agent.

作為第1樹脂組成物層的厚度，從得到粗糙度或剝離強度之安定性高的絕緣層的觀點來看，較佳為 0.3μm~15μm。第1樹脂組成物層的厚度的下限，更佳為0.5μm以上，再更佳為1μm以上、1.5μm以上、2μm以上、2.5μm以上、或3μm以上。尤其是藉由將第1樹脂組成物層的厚度定為1μm以上，可更提高粗糙度或剝離強度之安定性。第1樹脂組成物層的厚度之上限更佳為12μm以下，再更佳為10μm以下，9μm以下，或8μm以下。尚，第1樹脂組成物層的厚度較佳為較第2樹脂組成物層的厚度更薄。 The thickness of the first resin composition layer is preferably from the viewpoint of obtaining an insulating layer having high roughness or peel strength stability. 0.3μm~15μm. The lower limit of the thickness of the first resin composition layer is more preferably 0.5 μm or more, still more preferably 1 μm or more, 1.5 μm or more, 2 μm or more, 2.5 μm or more, or 3 μm or more. In particular, by setting the thickness of the first resin composition layer to 1 μm or more, the stability of the roughness or the peel strength can be further improved. The upper limit of the thickness of the first resin composition layer is more preferably 12 μm or less, still more preferably 10 μm or less, 9 μm or less, or 8 μm or less. Further, the thickness of the first resin composition layer is preferably thinner than the thickness of the second resin composition layer.

第1樹脂組成物層的厚度可依後述之(樹脂薄片之各層的厚度的測定)的順序來測定。 The thickness of the first resin composition layer can be measured in the order described later (measurement of the thickness of each layer of the resin sheet).

作為第1樹脂組成物層之最低熔融黏度，從對內層基板的層合時易維持所期望的厚度，最終可達成粗糙度或剝離強度之安定性高的絕緣層的觀點來看，較佳為3000poise(300Pa．s)以上，更佳為5000poise(500Pa．s)以上，再更佳為10000poise(1000Pa．s)以上。尤其是該最低熔融黏度為5000poise以上的情況下，得到顯示顯著良好回流耐性之絕緣層。對於第1樹脂組成物層之最低熔融黏度之上限雖並未特別限制，但較佳為100000poise(10000Pa．s)以下，更佳為80000poise(8000Pa．s)以下，再更佳為50000poise(5000Pa．s)以下。 The lowest melt viscosity of the first resin composition layer is preferably from the viewpoint of easily maintaining a desired thickness when laminating the inner layer substrate, and finally achieving an insulating layer having high roughness or peel strength stability. It is 3000 poise (300 Pa.s) or more, more preferably 5000 poise (500 Pa.s) or more, and even more preferably 10000 poise (1000 Pa.s) or more. In particular, in the case where the minimum melt viscosity is 5,000 poise or more, an insulating layer exhibiting remarkably good reflow resistance is obtained. The upper limit of the minimum melt viscosity of the first resin composition layer is not particularly limited, but is preferably 100,000 poise (10000 Pa.s) or less, more preferably 80,000 poise (8000 Pa.s) or less, and even more preferably 50,000 poise (5000 Pa.). s) below.

所謂第1樹脂組成物層之最低熔融黏度，係指熔融第1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第1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。第1樹脂組成物層之最低熔融黏度，例如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℃，可在測定溫度間隔2.5℃、振動數1Hz、扭曲1deg的測定條件來測定。第2樹脂組成物層之最低熔融黏度的定義及測定法亦相同。 The lowest melt viscosity of the first resin composition layer means that the resin composition layer exhibits the lowest viscosity when the resin of the first resin composition layer is melted. Specifically, when the first resin composition layer is heated at a constant temperature increase rate to melt the resin, the initial stage melt viscosity is accompanied by a temperature rise. And drop, and then when the temperature exceeds a certain degree, the melt viscosity is increased together with the temperature rise. The lowest melt viscosity refers to the melt viscosity of the minimum point. For the lowest melt viscosity of the first resin composition layer, for example, a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM) is used, and a parallel plate having a diameter of 18 mm is used for the sample resin composition 1 g at a temperature rising rate of 5 ° C / The temperature was raised from the starting temperature of 60 ° C to 200 ° C, and the measurement was carried out under the measurement conditions of a measurement temperature interval of 2.5 ° C, a vibration number of 1 Hz, and a twist of 1 deg. The definition and measurement method of the lowest melt viscosity of the second resin composition layer are also the same.

<第2樹脂組成物層> <Second resin composition layer>

本發明之樹脂薄片係具有由第2樹脂組成物所成之第2樹脂組成物層。第2樹脂組成物層對所得之絕緣層的整體特性帶來影響。 The resin sheet of the present invention has a second resin composition layer made of the second resin composition. The second resin composition layer affects the overall characteristics of the obtained insulating layer.

從使所得之絕緣層之熱膨脹率降低，防止因絕緣層與導體層的熱膨脹之差異導致裂痕或電路歪斜的發生的觀點來看，較佳為第2樹脂組成物包含無機填充材。第2樹脂組成物中之無機填充材的含量，從使所得之絕緣層之熱膨脹率降低的觀點來看，較佳為50質量%以上，更佳為55質量%以上，再更佳為60質量%以上、62質量%以上、64質量%以上、66質量%以上、68質量%以上或70質量%以上。第2樹脂組成物中之無機填充材的含量之上限，從所得之絕緣層之機械強度的觀點來看，較佳為96質量%以下，更佳為95質量%以下，再更佳為90質量%以下或85質量%以下。 From the viewpoint of reducing the thermal expansion coefficient of the obtained insulating layer and preventing the occurrence of cracks or circuit skew due to the difference in thermal expansion between the insulating layer and the conductor layer, it is preferred that the second resin composition contains an inorganic filler. The content of the inorganic filler in the second resin composition is preferably 50% by mass or more, more preferably 55% by mass or more, and still more preferably 60%, from the viewpoint of lowering the thermal expansion coefficient of the obtained insulating layer. % or more, 62% by mass or more, 64% by mass or more, 66% by mass or more, 68% by mass or more, or 70% by mass or more. The upper limit of the content of the inorganic filler in the second resin composition is preferably 96% by mass or less, more preferably 95% by mass or less, still more preferably 90%, from the viewpoint of mechanical strength of the obtained insulating layer. % or less or 85% by mass or less.

在合適之一實施形態，第2樹脂組成物中之無機填充材的含量較第1樹脂組成物中之無機填充材的含量更高。將第1樹脂組成物中之無機填充材的含量定為A1(質量%)，將第2樹脂組成物中之無機填充材的含量定為A2(質量%)時，A1及A2的差異(A2-A1)，較佳為10質量%以上，更佳為15質量%以上，再更佳為20質量%以上、25質量%以上、或30質量%以上。差異(A2-A1)之上限雖並未特別限定，但通常可成為90質量%以下，80質量%以下等。關於以往之樹脂薄片，本發明者們發現增加差異(A2-A1)時，曝露於回流時等之高溫環境下時，於絕緣層易產生層間剝離。對此，使用具有混合層之本發明之樹脂薄片所形成之絕緣層，即使於差異(A2-A1)之值較大的情況下，亦可抑制層間剝離。據此，於本發明，各層之組成的設計自由度高，可有利於賦予各層所期待功能。又，如此A1與A2為不同的情況下，後述之混在層之掌握變更為容易。 In a preferred embodiment, the content of the inorganic filler in the second resin composition is higher than the content of the inorganic filler in the first resin composition. When the content of the inorganic filler in the first resin composition is A1 (% by mass), and the content of the inorganic filler in the second resin composition is A2 (% by mass), the difference between A1 and A2 (A2) -A1) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, 25% by mass or more, or 30% by mass or more. The upper limit of the difference (A2-A1) is not particularly limited, but is usually 90% by mass or less, 80% by mass or less, or the like. In the conventional resin sheet, the inventors have found that when the difference (A2-A1) is increased, when exposed to a high-temperature environment such as reflow, interlayer peeling easily occurs in the insulating layer. On the other hand, when the insulating layer formed of the resin sheet of the present invention having a mixed layer is used, even when the value of the difference (A2-A1) is large, interlayer peeling can be suppressed. Accordingly, in the present invention, the design freedom of the composition of each layer is high, which is advantageous for imparting desired functions to the respective layers. Moreover, when A1 and A2 are different, the grasp of the layer to be described later is changed to be easy.

作為無機填充材，例如可列舉針對第1樹脂組成物所說明之無機填充材，其中較佳為二氧化矽，更佳為球狀二氧化矽。第2樹脂組成物所包含之無機填充材的平均粒徑，從提高第2樹脂組成物層之流動性實現充分之電路嵌入性的觀點來看，較佳為0.01μm~5μm的範圍，更佳為0.05μm~2μm的範圍，再更佳為0.1μm~1μm的範圍，又再更佳為0.2μm~0.8μm。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 「SOC4」、「SOC2」、「SOC1」。 The inorganic filler is, for example, an inorganic filler described for the first resin composition. Among them, cerium oxide is preferred, and spherical cerium oxide is more preferred. The average particle diameter of the inorganic filler contained in the second resin composition is preferably in the range of 0.01 μm to 5 μm from the viewpoint of improving the fluidity of the second resin composition layer to achieve sufficient circuit embedding property. It is in the range of 0.05 μm to 2 μm, more preferably in the range of 0.1 μm to 1 μm, still more preferably 0.2 μm to 0.8 μm. As a commercial item of the inorganic filler which has such an average particle diameter, the product of Admatechs is mentioned, for example. "SOC4", "SOC2", and "SOC1".

第2樹脂組成物所包含之無機填充材，較佳為以表面處理劑進行處理。表面處理劑之種類及表面處理的程度係如在<第1樹脂組成物層>欄所說明。 The inorganic filler contained in the second resin composition is preferably treated with a surface treatment agent. The type of the surface treatment agent and the degree of surface treatment are as described in the column of <First Resin Composition Layer>.

作為第2樹脂組成物所包含之其他材料，例如可列舉在<第1樹脂組成物層>欄所說明，初次將(a)環氧樹脂作為硬化性樹脂、及(b)硬化劑。據此，在一實施形態，第2樹脂組成物係包含(a)環氧樹脂、(b)硬化劑及(c)無機填充材。各成分適合之例雖如在<第1樹脂組成物層>欄所說明，但其中，第2樹脂組成物較佳為分別包含：作為(a)環氧樹脂之包含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1：0.1~1：4的範圍，更佳為1：0.3~1：3.5的範圍，再更佳為1：0.6~1：3的範圍，特佳為1：0.8~1：2.5的範圍)，作為(b)硬化劑之選自由酚系硬化劑、奈酚系硬化劑、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、奈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)，作為(c)無機填充材之二氧化矽。 The other material contained in the second resin composition is, for example, as described in the column of <First Resin Composition Layer>, and (a) the epoxy resin is used as the curable resin and (b) the curing agent. Accordingly, in one embodiment, the second resin composition includes (a) an epoxy resin, (b) a curing agent, and (c) an inorganic filler. In the case of the <first resin composition layer>, the second resin composition preferably includes, as the (a) epoxy resin, a liquid epoxy resin and a solid. Mixture of epoxy resin (liquid epoxy resin: the quality of the solid epoxy resin is preferably in the range of 1:0.1 to 1:4, more preferably in the range of 1:0.3 to 1:3.5, and even more preferably a range of 1:0.6 to 1:3, particularly preferably in the range of 1:0.8 to 1:2.5), and the (b) curing agent is selected from the group consisting of a phenolic curing agent, a naphthol curing agent, and an active ester curing agent. One or more of the group consisting of a cyanate-based curing agent (preferably one or more selected from the group consisting of a phenolic curing agent, a naphthol curing agent, and an active ester curing agent), As the (c) inorganic filler, cerium oxide.

第2樹脂組成物中之(a)環氧樹脂的含量雖並未特別限定，但較佳為3質量%~50質量%，更佳為5質量%~45質量%，再更佳為5質量%~40質量%，又再更佳為7質量%~35質量%。 The content of the (a) epoxy resin in the second resin composition is not particularly limited, but is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 45% by mass, even more preferably 5 mass%. %~40% by mass, and more preferably 7% by mass to 35% by mass.

在第2樹脂組成物之(a)環氧樹脂與(b)硬化劑 的量比可與在<第1樹脂組成物層>欄所說明者相同。 (a) epoxy resin and (b) hardener in the second resin composition The amount ratio can be the same as that described in the <First Resin Composition Layer> column.

第2樹脂組成物中之(b)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，10質量%以下。又，下限雖並未特別限制，但較佳為3質量%以上。 The content of the (b) curing agent in the second resin composition is not particularly limited, but 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. It is 15% by mass or less and 10% by mass or less. Further, the lower limit is not particularly limited, but is preferably 3% by mass or more.

第2樹脂組成物可進一步包含選自由(d)熱塑性樹脂、(e)硬化促進劑、(f)阻燃劑及(g)有機填充材所構成之群組中之1種以上的成分。此等(d)至(g)成分之適合例係如在<第1樹脂組成物層>欄所說明。 The second resin composition may further contain one or more components selected from the group consisting of (d) a thermoplastic resin, (e) a curing accelerator, (f) a flame retardant, and (g) an organic filler. Suitable examples of the components (d) to (g) are as described in the <First Resin Composition Layer> column.

第2樹脂組成物中之(d)熱塑性樹脂的含量雖並未特別限定，但較佳為0.1質量%~20質量%，更佳為0.5質量%~10質量%。 The content of the (d) thermoplastic resin in the second resin composition is not particularly limited, but is preferably 0.1% by mass to 20% by mass, and more preferably 0.5% by mass to 10% by mass.

第2樹脂組成物中之(e)硬化促進劑的含量將(a)環氧樹脂與(b)硬化劑之不揮發成分合計量定為100質量%時，較佳為0.05質量%~3質量%。 (e) The content of the (e) curing accelerator in the second resin composition is preferably 0.05% by mass to 3 mass when the total amount of the non-volatile components of the (a) epoxy resin and the (b) curing agent is 100% by mass. %.

第2樹脂組成物中之(f)阻燃劑的含量雖並未特別限定，但較佳為0.5質量%~10質量%，更佳為1質量%~9質量%，又再更佳為1.5質量%~8質量%。 The content of the (f) flame retardant in the second resin composition is not particularly limited, but is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 9% by mass, still more preferably 1.5% by mass. Mass%~8 mass%.

第2樹脂組成物中之(g)有機填充材的含量雖並未特別限定，但較佳為1質量%~10質量%，更佳為2質量%~5質量%。 The content of the (g) organic filler in the second resin composition is not particularly limited, but is preferably 1% by mass to 10% by mass, and more preferably 2% by mass to 5% by mass.

第2樹脂組成物如有必要可包含其他添加劑，作為該等之其他添加劑，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、以及有機填料、增黏劑、消泡劑、均染劑、密著性賦予劑、及著色劑等之樹脂添加劑等。 The second resin composition may contain other additives as necessary, and examples of the other additives include organic copper compounds. An organometallic compound such as an organic zinc compound or an organic cobalt compound, and an organic filler, a tackifier, an antifoaming agent, a leveling agent, a tackifier, and a resin additive such as a coloring agent.

作為第2樹脂組成物層的厚度，只要能得到所期望厚度之絕緣層雖並未特別限定，但較佳為3μm~200μm。第2樹脂組成物層的厚度的下限更佳為5μm以上，再更佳為10μm以上、或15μm以上。第2樹脂組成物層的厚度之上限，更佳為180μm以下，再更佳為160μm以下，150μm以下，140μm以下，120μm以下，或100μm以下。 The thickness of the second resin composition layer is not particularly limited as long as the desired thickness can be obtained, but is preferably 3 μm to 200 μm. The lower limit of the thickness of the second resin composition layer is more preferably 5 μm or more, still more preferably 10 μm or more, or 15 μm or more. The upper limit of the thickness of the second resin composition layer is more preferably 180 μm or less, still more preferably 160 μm or less, 150 μm or less, 140 μm or less, 120 μm or less, or 100 μm or less.

第2樹脂組成物層的厚度可依後述之(樹脂薄片之各層的厚度的測定)順序來測定。 The thickness of the second resin composition layer can be measured in the order described below (measurement of the thickness of each layer of the resin sheet).

作為第2樹脂組成物層之最低熔融黏度，從得到良好之電路嵌入性的觀點來看，較佳為10000poise(1000Pa．s)以下，更佳為8000poise(800Pa．s)以下，再更佳為5000poise(500Pa．s)以下。對於下限雖並未特別限制，但較佳為500poise(50Pa．s)以上，更佳為800poise(80Pa．s)以上，再更佳為1000poise(100Pa．s)以上。 The lowest melt viscosity of the second resin composition layer is preferably 10,000 poise (1000 Pa.s) or less, more preferably 8000 poise (800 Pa.s) or less, and more preferably from the viewpoint of obtaining good circuit embedding property. Below 5000poise (500Pa.s). The lower limit is not particularly limited, but is preferably 500 poise (50 Pa.s) or more, more preferably 800 poise (80 Pa.s) or more, still more preferably 1000 poise (100 Pa.s) or more.

<混合層> <mixed layer>

本發明之樹脂薄片係於第1樹脂組成物層與第2樹脂組成物層之間具有混在第1樹脂組成物及第2樹脂組成物之混合層。 The resin sheet of the present invention has a mixed layer of the first resin composition and the second resin composition interposed between the first resin composition layer and the second resin composition layer.

混合層的厚度從在回流時等之高溫環境下得到層間剝離之經抑制之絕緣層的觀點來看，為0.4μm以上，較佳為0.5μm以上，更佳為1.0μm以上。對於混合層的厚度之上限雖並未特別限制，但較佳為第1樹脂組成物層的厚度之2倍以下。例如將第1樹脂組成物層的厚度定為t(μm)時，混合層的厚度較佳為2t以下，更佳為1.5t以下，再更佳為t以下，0.9t以下，0.8t以下，或0.7t以下。混合層的厚度只要是在2t以下，更佳為10μm以下，再更佳為5μm以下，特佳為3μm以下。 The thickness of the mixed layer is 0.4 μm or more, preferably 0.5 μm or more, and more preferably 1.0 μm or more from the viewpoint of obtaining an insulating layer which is suppressed by interlayer peeling in a high-temperature environment such as reflow. The upper limit of the thickness of the mixed layer is not particularly limited, but is preferably twice or less the thickness of the first resin composition layer. For example, when the thickness of the first resin composition layer is t (μm), the thickness of the mixed layer is preferably 2 t or less, more preferably 1.5 t or less, still more preferably t or less, 0.9 t or less, and 0.8 t or less. Or below 0.7t. The thickness of the mixed layer is preferably 2 t or less, more preferably 10 μm or less, still more preferably 5 μm or less, and particularly preferably 3 μm or less.

混合層的厚度可依後述之(樹脂薄片之各層的厚度的測定)順序來測定。尚，混合層可作為具有與第1樹脂組成物層或第2樹脂組成物層不同組成之區域來掌握。例如，第1樹脂組成物層中之無機填充材的含量A1與第2樹脂組成物層中之無機填充材的含量A2滿足A1<A2的關係時，在樹脂薄片之剖面SEM觀察，混合層可如以下來掌握。亦即，在樹脂薄片之剖面，於從與支持體之接合界面的距離為0至t1為止的區域，無機填充材/樹脂成分比為一定，於從與支持體之接合界面的距離為t1至t2為止的區域，無機填充材/樹脂成分比慢慢提高，於從與支持體之接合界面的距離為t2至t3為止的區域，無機填充材/樹脂成分比為一定。尚，從與支持體之接合界面的距離t3之位置係與支持體相反側之樹脂組成物層的表面位置。該情況下，從與支持體之接合界面的距離為0至t1為止的區域為第1樹脂組成物層，該距離為從t1至t2為止的區 域為混合層，該距離為從t2至t3為止的區域為第2樹脂組成物層。或者又，第1樹脂組成物層中之無機填充材的粒徑、與第2樹脂組成物層中之無機填充材的粒徑不同的情況下，從無機填充材之粒徑變化的觀點來看，亦可掌握混合層。 The thickness of the mixed layer can be measured in the order described later (measurement of the thickness of each layer of the resin sheet). Further, the mixed layer can be grasped as a region having a composition different from that of the first resin composition layer or the second resin composition layer. For example, when the content A1 of the inorganic filler in the first resin composition layer and the content A2 of the inorganic filler in the second resin composition layer satisfy the relationship of A1 < A2, the mixed layer can be observed in the cross section of the resin sheet. Take the following to grasp. That is, in the cross section of the resin sheet, the ratio of the inorganic filler/resin component is constant in the region from the bonding interface with the support from 0 to t1, and the distance from the bonding interface with the support is t1 to In the region from t2, the ratio of the inorganic filler/resin component is gradually increased, and the ratio of the inorganic filler/resin component is constant in a region from the bonding interface with the support from t2 to t3. Further, the position from the distance t3 of the joint interface with the support is the surface position of the resin composition layer on the side opposite to the support. In this case, the region from the bonding interface with the support from 0 to t1 is the first resin composition layer, and the distance is the region from t1 to t2. The domain is a mixed layer, and the distance from t2 to t3 is the second resin composition layer. In addition, when the particle diameter of the inorganic filler in the first resin composition layer is different from the particle diameter of the inorganic filler in the second resin composition layer, the particle diameter of the inorganic filler changes. You can also master the mixed layer.

本發明之樹脂薄片可進一步於第2樹脂組成物層之表面包含保護薄膜。保護薄膜有助於對第2樹脂組成物層之表面的垃圾等之附著或傷痕的防止。作為保護薄膜之材料可使用與針對支持體所說明之材料相同者。保護薄膜的厚度雖並非被特別限定者，但例如為1μm~40μm。附支持體之樹脂薄片係於製造印刷配線板時，藉由剝離保護薄膜而變成可使用。 The resin sheet of the present invention may further comprise a protective film on the surface of the second resin composition layer. The protective film contributes to the prevention of adhesion or scratches on the surface of the second resin composition layer. As the material of the protective film, the same material as that described for the support can be used. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. The resin sheet with a support can be used by peeling off a protective film when manufacturing a printed wiring board.

本發明之樹脂薄片可使用在用以形成金屬包層層合板之絕緣層(金屬包層層合板之絕緣層用)、用以形成印刷配線板之絕緣層(印刷配線板之絕緣層用)。其中，在藉由積聚方式之印刷配線板的製造，可適合使用在用以形成絕緣層(印刷配線板之積聚絕緣層用)，進而可適合使用在藉由鍍敷用以形成導體層(藉由鍍敷形成導體層之印刷配線板的積聚絕緣層用)。 The resin sheet of the present invention can be used for forming an insulating layer (for an insulating layer of a metal clad laminate) for forming a metal clad laminate, and an insulating layer for forming a printed wiring board (for an insulating layer of a printed wiring board). Among them, in the production of a printed wiring board by an accumulation method, it can be suitably used for forming an insulating layer (for an accumulated insulating layer of a printed wiring board), and can be suitably used for forming a conductor layer by plating. It is used for accumulating an insulating layer of a printed wiring board in which a conductor layer is formed by plating.

-其他實施形態- -Other implementations -

於本發明，在包含複數樹脂組成物層之樹脂薄片，於樹脂組成物層彼此接觸的區域，設置混在各樹脂組成物層的成分之層。藉此，本發明係實現在高溫環境下之層間剝 離經抑制之絕緣層。在上述，雖針對包含2個樹脂組成物層之實施形態進行說明，但使用該本發明之概念，可得到包含更多層之樹脂組成物層的樹脂薄片。例如可得到包含第1樹脂組成物層、第2樹脂組成物層及追加之樹脂組成物層(第3樹脂組成物層)的3個樹脂組成物層之樹脂薄片。該情況於第1樹脂組成物層與第3樹脂組成物層之間、及於第2樹脂組成物層與第3樹脂組成物層之間分別設置混合層即可。即使在包含3層以上樹脂組成物層之樹脂薄片，與支持體接合之第1樹脂組成物層的適合組成或厚度係如在上述之<第1樹脂組成物層>所述。又，成為與內層基板接合之樹脂組成物層的適合組成係如在上述之<第2樹脂組成物層>所述。詳細而言係可得到具有支持體\第1樹脂組成物層\第1混合層\追加之樹脂組成物層(第3樹脂組成物層)\第2混合層\第2樹脂組成物層之層構成的樹脂薄片。在該樹脂薄片，追加之樹脂組成物層的組成或厚度可因應所期望之印刷配線板的設計而適當決定即可。即使在設置呈現與第1及第2樹脂組成物層大為不同之膨脹特性的追加之樹脂組成物層的情況下，根據設置混合層之本發明，可將具有所期望功能之絕緣層有利達成無在高溫環境下之層間剝離。作為追加之樹脂組成物層，例如為了對樹脂薄片賦予新的功能，可為包含玻璃纖維等之樹脂組成物層。 In the present invention, in the resin sheet including the plurality of resin composition layers, a layer of components mixed in the respective resin composition layers is provided in a region where the resin composition layers are in contact with each other. Thereby, the invention realizes the peeling between layers in a high temperature environment Insulating insulation. In the above description, an embodiment including two resin composition layers will be described. However, the resin sheet including a plurality of resin composition layers can be obtained by using the concept of the present invention. For example, a resin sheet including three resin composition layers of the first resin composition layer, the second resin composition layer, and the additional resin composition layer (third resin composition layer) can be obtained. In this case, a mixed layer may be provided between the first resin composition layer and the third resin composition layer, and between the second resin composition layer and the third resin composition layer. Even in the resin sheet containing three or more resin composition layers, a suitable composition or thickness of the first resin composition layer bonded to the support is as described above in the <first resin composition layer>. Further, a suitable composition of the resin composition layer to be bonded to the inner layer substrate is as described in the above-mentioned <second resin composition layer>. Specifically, a layer having a support, a first resin composition layer, a first mixed layer, an additional resin composition layer (third resin composition layer), a second mixed layer, and a second resin composition layer can be obtained. A resin sheet composed. In the resin sheet, the composition or thickness of the additional resin composition layer may be appropriately determined depending on the desired design of the printed wiring board. Even when an additional resin composition layer exhibiting expansion characteristics different from those of the first and second resin composition layers is provided, the insulating layer having a desired function can be advantageously obtained according to the present invention in which the mixed layer is provided. There is no peeling between layers in a high temperature environment. The resin composition layer to be added may be a resin composition layer containing glass fibers or the like, for example, in order to impart a new function to the resin sheet.

[樹脂薄片之製造方法] [Method for Producing Resin Sheet]

本發明之樹脂薄片係如先述，係具有由支持體、與支持體上所形成之第1樹脂組成物所成之第1樹脂組成物層、與由第1樹脂組成物層上所形成之第2樹脂組成物所成之第2樹脂組成物層，於第1樹脂組成物層與第2樹脂組成物層之間，具有混在第1樹脂組成物及第2樹脂組成物之混合層。該樹脂薄片之製造方法，其特徵為包含於支持體上塗佈溶解第1樹脂組成物之第1樹脂清漆，再於第1樹脂清漆上塗佈溶解第2樹脂組成物之第2樹脂清漆，並進行乾燥之步驟，第1樹脂清漆的黏度為100mPa．s以上，第2樹脂清漆的黏度為100mPa．s以上。 The resin sheet of the present invention has a first resin composition layer formed of a support and a first resin composition formed on the support, and a first resin composition layer formed on the first resin composition layer. The second resin composition layer formed of the resin composition has a mixed layer of the first resin composition and the second resin composition interposed between the first resin composition layer and the second resin composition layer. In the method of producing a resin sheet, the first resin varnish in which the first resin composition is dissolved is applied onto the support, and the second resin varnish in which the second resin composition is dissolved is applied onto the first resin varnish. And the drying step, the viscosity of the first resin varnish is 100 mPa. Above s, the viscosity of the second resin varnish is 100 mPa. s above.

以往，例如日本特開2014-17301號公報所記載之樹脂薄片係於支持體上塗佈溶解第1樹脂組成物之第1樹脂清漆，形成第1樹脂組成物層之後，再於第1樹脂組成物層上塗佈溶解第2樹脂組成物之第2樹脂清漆，形成第2樹脂組成物層(以下亦稱為「2度塗佈法」)。 In the resin sheet described in Japanese Laid-Open Patent Publication No. 2014-17301, the first resin varnish in which the first resin composition is dissolved is applied onto the support to form the first resin composition layer, and then the first resin composition is formed. The second resin varnish in which the second resin composition is dissolved is applied to the layer to form a second resin composition layer (hereinafter also referred to as "two-degree coating method").

於本發明，係於同一塗佈線上塗佈第1樹脂清漆與第2樹脂清漆。詳細而言，並非將第2樹脂清漆塗佈於第1樹脂組成物層，而且塗佈於第1樹脂清漆上。亦即，於形成第1樹脂組成物層之前塗佈第2樹脂清漆。藉此，於第1樹脂組成物層與第2樹脂組成物層之間，可形成混在第1樹脂清漆所包含之第1樹脂組成物、與第2樹脂清漆所包含之第2樹脂組成物的混合層。 In the present invention, the first resin varnish and the second resin varnish are applied to the same coating line. Specifically, the second resin varnish is not applied to the first resin composition layer, and is applied to the first resin varnish. That is, the second resin varnish is applied before the formation of the first resin composition layer. Thereby, between the first resin composition layer and the second resin composition layer, the first resin composition contained in the first resin varnish and the second resin composition included in the second resin varnish can be formed. Mixed layer.

本發明之樹脂薄片之製造方法只要是可於第1樹脂清漆上塗佈第2樹脂清漆，形成所期望混合層則並未 特別限制。在合適之一實施形態，本發明之樹脂薄片之製造方法係包含與於支持體上塗佈第1樹脂清漆同時於第1樹脂清漆上塗佈第2樹脂清漆，然後進行乾燥之步驟、或 In the method for producing a resin sheet of the present invention, the second resin varnish can be applied to the first resin varnish to form a desired mixed layer. Special restrictions. In a preferred embodiment, the method for producing a resin sheet of the present invention comprises the steps of applying a second resin varnish to the first resin varnish while applying the first resin varnish to the support, followed by drying, or

包含於支持體上塗佈第1樹脂清漆，使其預備乾燥後，再於第1樹脂清漆上塗佈第2樹脂清漆，然後進行乾燥之步驟。 After the first resin varnish is applied onto the support and dried, the second resin varnish is applied to the first resin varnish, and then dried.

以下，亦可將包含前者之步驟的方法稱為「同時塗佈法」，將包含後者之步驟的方法稱為「串聯塗佈法」。尚，同時塗佈法、串聯塗佈法皆與以往之2度塗佈法不同，其特徵為在同一塗佈線上，塗佈第1樹脂清漆與第2樹脂清漆。 Hereinafter, the method including the former step may be referred to as "simultaneous coating method", and the method including the latter step may be referred to as "series coating method". In addition, both the coating method and the tandem coating method are different from the conventional two-degree coating method, and are characterized in that the first resin varnish and the second resin varnish are applied on the same coating line.

以下，參照圖2及圖3，針對本發明之樹脂薄片之製造方法之適合實施形態即同時塗佈法與串聯塗佈法進行說明。 Hereinafter, a simultaneous coating method and a tandem coating method, which are suitable embodiments of the method for producing a resin sheet of the present invention, will be described with reference to FIGS. 2 and 3.

<同時塗佈法> <simultaneous coating method>

於圖2表示在同時塗佈法之樹脂薄片之製造裝置之一例。圖2所示之樹脂薄片之製造裝置100係包含塗佈裝置101及乾燥裝置102。在該裝置100，支持體11供給於塗佈裝置101。塗佈裝置101係與於支持體11上塗佈第1樹脂清漆同時於第1樹脂清漆上塗佈第2樹脂清漆。塗佈第1及第2樹脂清漆之支持體供給於乾燥裝置102。乾燥裝置102係乾燥塗佈於支持體上之第1及第2樹脂清漆。如有必要將樹脂薄片捲成輥狀。藉此，於支持體上形成源 自第1樹脂清漆之第1樹脂組成物層與源自第2樹脂清漆之第2樹脂組成物層，並於第1樹脂組成物層與第2樹脂組成物層之間，形成混合第1樹脂清漆與第2樹脂清漆所得之混合層。 An example of a manufacturing apparatus of a resin sheet by a simultaneous coating method is shown in Fig. 2 . The resin sheet manufacturing apparatus 100 shown in FIG. 2 includes a coating apparatus 101 and a drying apparatus 102. In the device 100, the support 11 is supplied to the coating device 101. In the coating device 101, the second resin varnish is applied onto the first resin varnish while applying the first resin varnish to the support 11. The support to which the first and second resin varnishes are applied is supplied to the drying device 102. The drying device 102 dries the first and second resin varnishes applied to the support. If necessary, roll the resin sheet into a roll. Thereby forming a source on the support The first resin composition layer of the first resin varnish and the second resin composition layer derived from the second resin varnish form a first resin mixed between the first resin composition layer and the second resin composition layer A mixed layer of the varnish and the second resin varnish.

在同時塗佈法，可抑制在樹脂薄片之製造之熱履歴，又，可抑制支持體之熱收縮。藉此，藉由同時塗佈法所形成之樹脂薄片，可提供粗糙度或剝離強度之安定性優異之絕緣層。又，在同時塗佈法，藉由同時塗佈第1及第2樹脂清漆，易將混合層的厚度形成較厚。據此，藉由同時塗佈法所製造之樹脂薄片可提供較回流耐性更優異之絕緣層。 In the simultaneous coating method, heat stagnation in the production of the resin sheet can be suppressed, and heat shrinkage of the support can be suppressed. Thereby, the resin sheet formed by the simultaneous coating method can provide an insulating layer excellent in stability of roughness or peel strength. Further, in the simultaneous coating method, the thickness of the mixed layer is easily formed by simultaneously applying the first and second resin varnishes. According to this, the resin sheet produced by the simultaneous coating method can provide an insulating layer which is more excellent in reflow resistance.

在同時塗佈法，第1及第2樹脂清漆可使用與塗佈第1樹脂清漆同時於第1樹脂清漆上塗佈第2樹脂清漆之周知塗佈裝置來進行塗佈。例如，可使用具備用以塗佈第1樹脂清漆之裂縫與用以塗佈第2樹脂清漆之裂縫的多裂縫型模塗佈機等之周知多層塗佈系統來進行塗佈。 In the simultaneous coating method, the first and second resin varnishes can be applied by using a known coating device that applies the second resin varnish to the first resin varnish simultaneously with the application of the first resin varnish. For example, coating can be carried out using a well-known multilayer coating system including a crack for applying the first resin varnish and a multi-crack die coater for applying a crack of the second resin varnish.

第1及第2樹脂清漆可分別將第1及第2樹脂組成物溶解於溶劑來調製。作為樹脂清漆的調製所用之溶劑，雖並未特別限制但較佳為有機溶劑。作為有機溶劑，例如可列舉丙酮、甲基乙基酮及環己酮等之酮類、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、二甲基乙醯胺及N-甲基吡咯啶酮等之醯胺系溶劑或 溶劑油等。有機溶劑可1種單獨使用、或亦可併用2種以上。 The first and second resin varnishes can be prepared by dissolving the first and second resin compositions in a solvent, respectively. The solvent used for the preparation of the resin varnish is not particularly limited, but is preferably an organic solvent. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol. Acetate such as acetate, cellosolve, carbitol such as butyl carbitol, aromatic hydrocarbon such as toluene and xylene, dimethylformamide, dimethylacetamide, and a guanamine solvent such as N-methylpyrrolidone or Solvent oil, etc. The organic solvent may be used alone or in combination of two or more.

又，溶解第1樹脂組成物之溶劑、與溶解第2樹脂組成物之溶劑可為相同或相異。 Further, the solvent for dissolving the first resin composition may be the same as or different from the solvent for dissolving the second resin composition.

第1及第2樹脂清漆中所含之溶劑將樹脂清漆中所含之不揮發成分的合計定為100質量%時，以較佳成為75質量%以下，更佳成為65質量%以下，再更佳成為55質量%以下，特佳成為45質量%以下的方式來調整。下限從促進混合層之形成的觀點來看，較佳為15質量%以上，更佳為20質量%以上。 When the total amount of the non-volatile components contained in the resin varnish is 100% by mass, the solvent contained in the first and second resin varnish is preferably 75% by mass or less, more preferably 65% by mass or less, and more preferably It is adjusted to be 55 mass% or less, and particularly preferably 45 mass% or less. The lower limit is preferably 15% by mass or more, and more preferably 20% by mass or more from the viewpoint of promoting formation of the mixed layer.

第1樹脂清漆的黏度從可輕易調控第1樹脂組成物層的厚度的觀點來看，提昇與支持體的親和性，從未產生排斥或條紋等可塗佈第1樹脂清漆的觀點來看，為100mPa．s以上，較佳為200mPa．s以上，更佳為300mPa．s以上。對於第1樹脂清漆的黏度之上限雖並未特別限制，但從易調控第1樹脂組成物層的厚度薄膜化容易的觀點來看，較佳為3000mPa．s以下，更佳為2000mPa．s以下，再更佳為1000mPa．s以下。 The viscosity of the first resin varnish is improved from the viewpoint of the thickness of the first resin composition layer, and the affinity with the support is improved, and the first resin varnish can be applied without repulsion or streaking. It is 100mPa. Above s, preferably 200 mPa. Above s, more preferably 300mPa. s above. The upper limit of the viscosity of the first resin varnish is not particularly limited, but is preferably 3000 mPa from the viewpoint of easy control of the thickness of the first resin composition layer. Below s, more preferably 2000mPa. Below s, more preferably 1000mPa. s below.

第2樹脂清漆的黏度從可輕易調控第2樹脂組成物層的厚度的觀點來看，為100mPa．s以上，較佳為200mPa．s以上，更佳為300mPa．s以上。對於第2樹脂清漆的黏度之上限雖並未特別限制，但從易調控第2樹脂組成物層的厚度薄膜化容易的觀點來看，較佳為6000mPa．s以下，更佳為3000mPa．s以下，再更佳為1000mPa．s以 下。 The viscosity of the second resin varnish is 100 mPa from the viewpoint of easily adjusting the thickness of the second resin composition layer. Above s, preferably 200 mPa. Above s, more preferably 300mPa. s above. The upper limit of the viscosity of the second resin varnish is not particularly limited, but is preferably 6000 mPa from the viewpoint of easy control of the thickness of the second resin composition layer. Below s, more preferably 3000mPa. Below s, more preferably 1000mPa. s under.

第1及第2樹脂清漆的黏度，例如可使用旋轉式(E型)黏度計測定。作為該旋轉式(E型)黏度計，例如可列舉東機產業(股)「RE-80U」。 The viscosity of the first and second resin varnishes can be measured, for example, by a rotary (E type) viscometer. As the rotary type (E type) viscometer, for example, the "E-sports" "RE-80U" can be cited.

第1及第2樹脂清漆的乾燥可藉由加熱、熱風吹送等之周知的乾燥方法實施。乾燥條件雖並未特別限定，但乾燥後之樹脂薄片中之殘留溶劑量，將第1樹脂組成物層、混合層及第2樹脂組成物層中所含之不揮發成分的合計定為100質量%時，以較佳成為10質量%以下，更佳成為5質量%以下的方式來乾燥。殘留溶劑量的下限雖並未特別限定，但通常可成為0.1質量%以上、0.5質量%以上等。雖因第1及第2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%之有機溶劑之第1及第2樹脂清漆時，藉由使其於50℃~150℃乾燥3分鐘~10分鐘，可製造本發明之樹脂薄片。 The drying of the first and second resin varnishes can be carried out by a known drying method such as heating or hot air blowing. The drying condition is not particularly limited, but the total amount of the solvent in the resin sheet after drying is set to 100 masses in total of the non-volatile components contained in the first resin composition layer, the mixed layer, and the second resin composition layer. In the case of %, it is preferably dried to 10% by mass or less, more preferably 5% by mass or less. The lower limit of the amount of the residual solvent is not particularly limited, but may be usually 0.1% by mass or more and 0.5% by mass or more. The first and second resin varnishes containing 30% by mass to 60% by mass of the organic solvent are used, for example, at 50 ° C, depending on the boiling point of the organic solvent in the first and second resin varnishes. The resin sheet of the present invention can be produced by drying at 150 ° C for 3 minutes to 10 minutes.

<串聯塗佈法> <Series coating method>

於圖3表示在串聯塗佈法之樹脂薄片之製造裝置之一例。圖3所示之樹脂薄片之製造裝置200係包含第1塗佈裝置201、預備乾燥裝置202、第2塗佈裝置203、及乾燥裝置204。在該製造裝置200，支持體11供給於第1塗佈裝置201。第1塗佈裝置201係於支持體11上塗佈第1樹脂清漆。塗佈第1樹脂清漆之支持體係供給於預備乾燥裝置202。預備乾燥裝置202預備乾燥第1樹脂清漆。第 1樹脂清漆之預備乾燥後，支持體供給於第2塗佈裝置203。第2塗佈裝置203係於第1樹脂清漆上塗佈第2樹脂清漆。然後，塗佈第1及第2樹脂清漆之支持體供給於乾燥裝置204。乾燥裝置204係乾燥塗佈於支持體上之第1及第2樹脂清漆。如有必要將樹脂薄片捲成輥狀。藉此，於支持體上形成源自第1樹脂清漆之第1樹脂組成物層與源自第2樹脂清漆之第2樹脂組成物層，並於第1樹脂組成物層與第2樹脂組成物層之間，形成混合第1樹脂清漆與第2樹脂清漆所得之混合層。 An example of a manufacturing apparatus of a resin sheet in a tandem coating method is shown in Fig. 3 . The resin sheet manufacturing apparatus 200 shown in FIG. 3 includes a first coating apparatus 201, a preliminary drying apparatus 202, a second coating apparatus 203, and a drying apparatus 204. In the manufacturing apparatus 200, the support 11 is supplied to the first coating apparatus 201. The first coating device 201 applies a first resin varnish to the support 11 . The support system to which the first resin varnish is applied is supplied to the preliminary drying device 202. The preliminary drying device 202 prepares to dry the first resin varnish. First After the resin varnish is preliminarily dried, the support is supplied to the second coating device 203. The second coating device 203 applies a second resin varnish to the first resin varnish. Then, the support for applying the first and second resin varnishes is supplied to the drying device 204. The drying device 204 dries the first and second resin varnishes applied to the support. If necessary, roll the resin sheet into a roll. Thereby, the first resin composition layer derived from the first resin varnish and the second resin composition layer derived from the second resin varnish are formed on the support, and the first resin composition layer and the second resin composition are formed on the support. A mixed layer obtained by mixing the first resin varnish and the second resin varnish is formed between the layers.

在串聯塗佈法，藉由使第1樹脂清漆預備乾燥，可提昇第1樹脂組成物層之厚度的精度。 In the tandem coating method, the thickness of the thickness of the first resin composition layer can be improved by preliminarily drying the first resin varnish.

在串聯塗佈法，預備乾燥只要在不阻礙藉由第1樹脂清漆與第2樹脂清漆的混合之混合層的形成，並未特別限制，可藉由加熱、熱風吹送等之周知的乾燥方法實施。預備乾燥條件雖並未特別限定，但乾燥後之第1樹脂清漆中之殘留溶劑量，將第1樹脂清漆中所含之不揮發成分的合計定為100質量%時，以較佳成為70質量%以下，更佳成為60質量%以下，再更佳成為50質量%以下，特佳成為40質量%以下的方式來進行預備乾燥。殘留溶劑量的下限從促進混合層之形成的觀點來看，較佳為15質量%以上，更佳為20質量%以上，再更佳為25質量%以上。雖因第1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%之有機溶劑之第1樹脂清漆時，較佳為使其於50℃~150℃乾燥0.1分鐘~3 分鐘(更佳為於60℃~130℃乾燥0.2分鐘~2分鐘，再更佳為於70℃~120℃乾燥0.3分鐘~1.5分鐘)。 In the tandem coating method, the preliminary drying is not particularly limited as long as it does not inhibit the formation of the mixed layer by the mixing of the first resin varnish and the second resin varnish, and can be carried out by a known drying method such as heating or hot air blowing. . The pre-drying condition is not particularly limited, and the amount of the residual solvent in the first resin varnish after drying is preferably 70% by mass when the total amount of the non-volatile components contained in the first resin varnish is 100% by mass. More preferably, it is 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less. The lower limit of the amount of the residual solvent is preferably 15% by mass or more, more preferably 20% by mass or more, and still more preferably 25% by mass or more from the viewpoint of promoting formation of the mixed layer. Although it is different in the boiling point of the organic solvent in the first resin varnish, for example, when the first resin varnish containing 30% by mass to 60% by mass of the organic solvent is used, it is preferably dried at 50 ° C to 150 ° C for 0.1 minute. ~3 Minutes (more preferably from 60 ° C to 130 ° C for 0.2 minutes to 2 minutes, and more preferably from 70 ° C to 120 ° C for 0.3 minutes to 1.5 minutes).

第1及第2樹脂清漆(黏度、溶劑的種類等)對於同時塗佈法係如說明。又，塗佈第2樹脂清漆後之乾燥可與在同時塗佈法之乾燥以相同之條件實施。 The first and second resin varnishes (viscosity, type of solvent, etc.) are described for the simultaneous coating method. Further, the drying after the application of the second resin varnish can be carried out under the same conditions as the drying by the simultaneous coating method.

本發明之樹脂薄片之製造方法可進一步包含於第2樹脂組成物層之表面(與支持體側相反側的面)層合保護薄膜之步驟。保護薄膜的細節係如先述。 The method for producing a resin sheet of the present invention may further comprise the step of laminating a protective film on the surface (surface opposite to the support side) of the second resin composition layer. The details of the protective film are as described above.

[印刷配線板及其製造方法] [Printed wiring board and its manufacturing method]

使用藉由本發明之方法所製造之樹脂薄片，可製造印刷配線板。例如將藉由本發明之方法所製造之樹脂薄片層合於內層基板上，於使其熱硬化後藉由去除支持體，可製造印刷配線板。據此，本發明之印刷配線板，其特徵為包含使用本發明之樹脂薄片所形成之絕緣層。 A printed wiring board can be produced by using the resin sheet produced by the method of the present invention. For example, a resin sheet produced by the method of the present invention is laminated on an inner layer substrate, and after being thermally cured, the printed wiring board can be manufactured by removing the support. Accordingly, the printed wiring board of the present invention is characterized by comprising an insulating layer formed using the resin sheet of the present invention.

詳細而言，本發明之印刷配線板係使用本發明之樹脂薄片，可藉由包含下述步驟(I)~(III)之方法製造。 Specifically, the printed wiring board of the present invention can be produced by the method comprising the following steps (I) to (III) by using the resin sheet of the present invention.

(I)將本發明之樹脂薄片以第2樹脂組成物層與內層基板接合的方式，層合於內層基板之步驟 (I) a step of laminating the resin sheet of the present invention to the inner layer substrate by bonding the second resin composition layer to the inner layer substrate

(II)熱硬化樹脂薄片形成絕緣層之步驟 (II) Step of forming a heat insulating resin sheet to form an insulating layer

(III)去除支持體之步驟 (III) Steps of removing the support

在步驟(I)，將本發明之樹脂薄片以第2樹脂組成物層與內層基板接合的方式，層合於內層基板。 In the step (I), the resin sheet of the present invention is laminated on the inner layer substrate such that the second resin composition layer is bonded to the inner layer substrate.

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」。 The "inner substrate" used in the step (I) mainly refers to a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, or a thermosetting polyphenylene ether substrate. Or forming a circuit substrate patterned on one or both of the conductor layers (circuits) of the substrate. Further, when a printed wiring board is manufactured, an inner layer circuit board in which an intermediate layer of an insulating layer and/or a conductor layer is formed is also included in the "inner substrate" of the present invention.

在步驟(I)之樹脂薄片與內層基板的層合雖可用以往周知之任意方法實施，但較佳為以輥壓著或沖壓壓著等，使第2樹脂組成物層與內層基板接合的方式來進行層合處理。 The lamination of the resin sheet and the inner layer substrate in the step (I) may be carried out by any conventionally known method. However, it is preferable to bond the second resin composition layer to the inner layer substrate by roll pressing or press pressing. The way to do the lamination process.

層合處理較佳為以輥壓著或沖壓壓著等來進行層合處理。其中，更佳為於減壓下進行層合之真空層合法。層合的方法可為批次式亦可為連續式。 The lamination treatment is preferably carried out by lamination or press pressing or the like. Among them, it is more preferable to carry out lamination vacuum lamination under reduced pressure. The lamination method can be batch or continuous.

層合處理，一般而言較佳為將壓著壓力定為1kgf/cm2~11kgf/cm2(9.8×104N/m2~107.9×104N/m2)的範圍，將壓著溫度定為70℃~120℃的範圍，將壓著時間定為5秒~180秒的範圍，以空氣壓為20mmHg(26.7hPa)以下之減壓下實施。 For the lamination treatment, it is generally preferred to set the pressing pressure to a range of 1 kgf/cm 2 to 11 kgf/cm 2 (9.8×10 4 N/m 2 to 107.9×10 4 N/m 2 ), which will be pressed. The temperature is set to a range of 70 ° C to 120 ° C, and the pressing time is set to a range of 5 seconds to 180 seconds, and the air pressure is 20 mmHg (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 carried out using a commercially available vacuum laminator. For example, a vacuum press laminator manufactured by Nippon Machine Co., Ltd., a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., or the like can be used.

尚，較佳為於內層基板之表面凹凸(例如內層電路基 板之表面電路的凹凸)以樹脂薄片充分追隨的方式，透過耐熱橡膠等之彈性材來進行層合處理。 Preferably, the surface of the inner substrate is uneven (for example, an inner circuit substrate) The unevenness of the surface circuit of the board is performed by laminating the elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows.

在步驟(I)，樹脂薄片可層合於內層基板之單面，亦可層合於內層基板之兩面。 In the step (I), the resin sheet may be laminated on one side of the inner substrate or may be laminated on both sides of the inner substrate.

步驟(I)之後，可將層合於內層基板之樹脂薄片進行加熱及加壓，實施平滑化之處理。平滑化處理一般係於常壓(大氣壓)下藉由經加熱之金屬板或金屬輥，藉由加熱及加壓樹脂薄片來實施。加熱及加壓的條件可使用與上述層合處理之條件相同之條件。尚，層合處理與平滑化處理可使用市售之真空層合機連續性實施。 After the step (I), the resin sheet laminated on the inner layer substrate may be heated and pressurized to perform a smoothing treatment. The smoothing treatment is generally carried out by heating and pressing a resin sheet under a normal pressure (atmospheric pressure) by a heated metal plate or a metal roll. The conditions of heating and pressurization can be the same as those of the above lamination treatment. Further, the laminating treatment and the smoothing treatment can be carried out continuously using a commercially available vacuum laminator.

在步驟(II)，熱硬化樹脂薄片而形成絕緣層。詳細而言，係熱硬化經層合之樹脂薄片之第1樹脂組成物層、混合層、及第2樹脂組成物層而形成絕緣層。 In the step (II), the resin sheet is thermally cured to form an insulating layer. Specifically, the first resin composition layer, the mixed layer, and the second resin composition layer of the laminated resin sheet are thermally cured to form an insulating layer.

熱硬化之條件並未特別限定，可使用形成印刷配線板之絕緣層時通常所採用之條件。 The conditions of the thermosetting are not particularly limited, and the conditions generally employed in forming the insulating layer of the printed wiring board can be used.

例如，樹脂薄片之熱硬化條件，雖因構成第1及第2樹脂組成物層之樹脂組成物的組成而不同，但硬化溫度可成為120℃~240℃的範圍(較佳為150℃~210℃的範圍，更佳為170℃~190℃的範圍)，硬化時間可成為5分鐘~90分鐘的範圍(較佳為10分鐘~75分鐘，更佳為15分鐘~60分鐘)。 For example, the thermosetting condition of the resin sheet differs depending on the composition of the resin composition constituting the first and second resin composition layers, but the curing temperature may be in the range of 120 ° C to 240 ° C (preferably 150 ° C to 210 ° C) The range of °C, more preferably in the range of 170 ° C to 190 ° C), the hardening time may be in the range of 5 minutes to 90 minutes (preferably 10 minutes to 75 minutes, more preferably 15 minutes to 60 minutes).

熱硬化樹脂薄片之前，可將各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，在熱硬化樹脂薄片之前，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，將各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)。 Prior to thermally hardening the resin sheet, each of the resin composition layers may be preheated at a temperature lower than the hardening temperature. For example, before the thermosetting resin sheet, it may be 50 ° C or more and less than 120 ° C (preferably 60 ° C The resin composition layer is preheated for 5 minutes or longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes) at a temperature of 110 ° C or lower, more preferably 70 ° C or higher and 100 ° C or lower.

在步驟(III)，去除支持體。藉此，露出絕緣層之表面。支持體的去除可手動進行，亦可使用自動剝離裝置等機械性進行。又，作為支持體，使用金屬箔的情況下，可使用化學藥品去除。 In step (III), the support is removed. Thereby, the surface of the insulating layer is exposed. The removal of the support can be carried out manually or mechanically using an automatic peeling device or the like. Further, when a metal foil is used as the support, it can be removed by using a chemical.

製造印刷配線板時，可進一步實施(IV)鑽孔於絕緣層之步驟、(V)粗糙化處理絕緣層之步驟、(VI)於絕緣層表面形成導體層之步驟。此等之步驟(IV)至(VI)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，支持體的去除，可於步驟(II)與步驟(IV)之間、步驟(IV)與步驟(V)之間、或步驟(V)與步驟(VI)之間來實施。 When the printed wiring board is manufactured, (IV) the step of drilling the insulating layer, (V) the step of roughening the insulating layer, and (VI) the step of forming the conductor layer on the surface of the insulating layer may be further performed. These steps (IV) to (VI) can be used in the manufacture of printed wiring boards, and the various fields of the art are well known in the art. Further, the removal of the support may be carried out between step (II) and step (IV), between step (IV) and step (V), or between step (V) and step (VI).

步驟(IV)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，例如使用鑽孔機、雷射(碳酸氣體雷射、YAG雷射等)、電漿等可於絕緣層形成孔。 Step (IV) is a step of drilling a hole in the insulating layer, thereby forming a hole such as a through hole or a through hole in the insulating layer, for example, using a drill, a laser (carbon gas laser, YAG laser, etc.), A plasma or the like can form a hole in the insulating layer.

步驟(V)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。作為氧化劑雖並未特別限定，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、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。 Step (V) is a step of roughening the insulating layer. The order and conditions of the roughening treatment are not particularly limited, and a well-known sequence and conditions which are generally used when forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened by the swelling treatment by the swelling liquid, the roughening treatment by the oxidizing agent, and the neutralization treatment by the neutralization liquid. The swelling solution is not particularly limited, but may be exemplified by an alkali solution or a surfactant. The liquid or the like is preferably an alkali solution, and more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of the commercially available swelling liquid include Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, and the like manufactured by Atotech Japan Co., Ltd. The swelling treatment by the swelling liquid is not particularly limited, and may be carried out, for example, by immersing the insulating layer at 30 ° C to 90 ° C for 1 minute to 20 minutes. The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the oxidizing agent solution heated to 60 to 80 ° C for 10 minutes to 30 minutes. Further, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of the commercially available oxidizing agent include an alkaline permanganic acid solution such as Concentrate Compact CP manufactured by Atotech Japan Co., Ltd., and Dozing Solusion Securiganth P. In addition, as a neutralizing liquid, an acidic aqueous solution is preferable, and as a commercial item, the reduction solution Securiganth P by Atotech Japan Co., Ltd. is mentioned, for example. The treatment with the neutralizing solution can be carried out by immersing the surface of the treatment with the roughening treatment of the oxidizing agent solution at 30 ° C to 80 ° C for 5 minutes to 30 minutes.

在一實施形態，粗糙化處理後之絕緣層表面之算術平均粗糙度Ra，較佳為400nm以下，更佳為350nm以下，再更佳為300nm以下，250nm以下，200nm以下，150nm以下，或100nm以下。使用本發明之樹脂薄片所形成之絕緣層，如此，即使於Ra小的情況，亦對導體層呈現優異之剝離強度。Ra值的下限雖並未特別限 定，但通常可成為0.5nm以上、1nm以上等。尚，粗糙化處理後之絕緣層表面的Ra有變異的情況下，以Ra的最大值(Ramax)為上述的範圍較佳。 In one embodiment, the arithmetic mean roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, still more preferably 300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less, or 100 nm. the following. The insulating layer formed by using the resin sheet of the present invention exhibits excellent peel strength to the conductor layer even when Ra is small. Although the lower limit of the Ra value is not particularly limited, it is usually 0.5 nm or more and 1 nm or more. Ra lower surface of the insulating layer after the still, there are variations in the roughening treatment, the maximum value of Ra (Ra max) of the above-described preferred range.

又，在本發明，於粗糙化處理後可形成表面粗糙度的變異少，且粗糙度之安定性高的絕緣層。在一實施形態，粗糙化處理後之絕緣層表面之算術平均粗糙度的最大值(Ramax)與最小值(Ramin)的差異Ramax-Ramin，較佳為150nm以下，更佳為100nm以下，再更佳為80nm以下，60nm以下，40nm以下或30nm以下。差異Ramax-Ramin的下限較佳為低，雖可為0nm，但通常可成為0.1nm以上、0.5nm以上等。 Further, in the present invention, after the roughening treatment, an insulating layer having less variation in surface roughness and high stability of roughness can be formed. In one embodiment, the arithmetic difference between the surface of the insulating layer after the roughening treatment the maximum average roughness (Ra max) and the minimum value (Ra min) to Ra max -Ra min, preferably 150nm or less, more preferably 100nm More preferably, it is 80 nm or less, 60 nm or less, 40 nm or less, or 30 nm or less. The lower limit of the difference Ra max -Ra min is preferably low, and may be 0 nm, but usually 0.1 nm or more and 0.5 nm or more.

絕緣層表面之算術平均粗糙度Ra可使用非接觸型表面粗糙度計測定。作為非接觸型表面粗糙度計之具體例，可列舉威科儀器製之「WYKO NT3300」。 The arithmetic mean roughness Ra of the surface of the insulating layer can be measured using a non-contact type surface roughness meter. As a specific example of the non-contact type surface roughness meter, "WYKO NT3300" manufactured by Waco Instruments can be cited.

步驟(VI)係於絕緣層表面形成導體層之步驟。 Step (VI) is a step of forming a conductor layer on the surface of the insulating 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．鉻合金、銅．鎳合金及銅．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．鉻合金、銅． 鎳合金、銅．鈦合金之合金層，更佳為鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅之單金屬層、或鎳．鉻合金之合金層，再更佳為銅之單金屬層。 The conductor material used for the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer comprises 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 may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys of two or more metals selected from the group (for example, nickel, chromium alloy, copper, nickel alloy, copper, titanium). The layer formed by the alloy). Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper is preferred from the viewpoints of versatility, cost, and ease of pattern formation of the conductor layer. Or nickel. Chrome alloy, copper. Nickel alloy, copper. The alloy layer of titanium alloy is more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel. The alloy layer of chrome alloy 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．鉻合金之合金層。 The conductor layer may have a single layer structure, or may be a single metal layer formed of different kinds of metals or alloys or a laminated structure of two or more alloy layers laminated. When the conductor layer is a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or nickel. Alloy layer of chrome 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, preferably 5 μm to 30 μm.

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。 The conductor layer can be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a conventional technique such as a semi-additive method or a full additive method. Hereinafter, an example in which the conductor layer is formed by a semi-additive method will be described.

首先，於絕緣層之表面，藉由無電解鍍敷形成鍍敷薄片層。其次，於所形成之鍍敷薄片層上，對應所期望之配線圖型，形成使鍍敷薄片層之一部分露出之遮罩圖型。於露出之鍍敷薄片層上，藉由電解鍍敷形成金屬層後，去除遮罩圖型。然後，將不要之鍍敷薄片層藉由蝕刻等去除，可形成具有所期望配線圖型之導體層。 First, a plating sheet layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating sheet layer, a mask pattern for exposing a portion of the plating sheet layer is formed corresponding to the desired wiring pattern. On the exposed plating layer, a metal layer is formed by electrolytic plating, and the mask pattern is removed. Then, the unnecessary plating layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

在一實施形態，粗糙化處理後之絕緣層與導體層的剝離強度，較佳為0.4kgf/cm以上，更佳為0.45kgf/cm以上，再更佳為0.50kgf/cm以上。另外，剝離強度之上限值雖並未特別限定，但成為1.2kgf/cm以下，0.9kgf/cm以下等。在本發明，即便粗糙化處理後之絕緣 層之表面粗糙度Ra小，由於可形成呈現如此高之剝離強度的絕緣層，係顯著有助於印刷配線板之微細配線化者。尚，絕緣層與導體層的剝離強度有變異的情況，以剝離強度之最小值(Smin)為上述的範圍較佳。 In one embodiment, the peeling strength between the insulating layer and the conductor layer after the roughening treatment is preferably 0.4 kgf/cm or more, more preferably 0.45 kgf/cm or more, still more preferably 0.50 kgf/cm or more. In addition, the upper limit of the peeling strength is not particularly limited, but is 1.2 kgf/cm or less and 0.9 kgf/cm or less. In the present invention, even if the surface roughness Ra of the insulating layer after the roughening treatment is small, an insulating layer exhibiting such a high peeling strength can be formed, which contributes significantly to the fine wiring of the printed wiring board. Further, in the case where the peeling strength of the insulating layer and the conductor layer is varied, the minimum value (S min ) of the peeling strength is preferably in the above range.

又，在本發明，可形成絕緣層與導體層的剝離強度的變異少，且剝離強度之安定性高的絕緣層。在一實施形態，絕緣層與導體層的剝離強度的最大值(Smax)與最小值(Smin)的差異Smax-Smin，較佳為0.15kgf/cm以下，更佳為0.1kgf/cm以下。差異Smax-Smin的下限較佳為低，雖可為0kgf/cm，但通常可成為0.01kgf/cm以上、0.05kgf/cm以上等。 Moreover, in the present invention, it is possible to form an insulating layer having a small variation in peel strength between the insulating layer and the conductor layer and having high peel strength. A maximum peel strength in the embodiment, the insulating layer and the conductor layer (S max) and the minimum value (S min) of the difference S max -S min, preferably 0.15kgf / cm or less, more preferably 0.1kgf / Below cm. The lower limit of the difference S max -S min is preferably low, and although it can be 0 kgf/cm, it can be usually 0.01 kgf/cm or more, 0.05 kgf/cm or more.

尚，在本發明，所謂絕緣層與導體層的剝離強度，係指將導體層對於絕緣層以垂直方向(90度方向)剝離時之剝離強度(90度剝離強度)，可藉由將導體層對於絕緣層以垂直方向(90度方向)剝離時之剝離強度以拉伸試驗機測定求得。作為拉伸試驗機，例如可列舉(股)TSE製之「AC-50C-SL」等。 Further, in the present invention, the peeling strength between the insulating layer and the conductor layer means the peeling strength (90-degree peeling strength) when the conductor layer is peeled off in the vertical direction (90-degree direction) from the insulating layer, and the conductor layer can be formed by The peel strength at the time when the insulating layer was peeled in the vertical direction (90-degree direction) was determined by a tensile tester. Examples of the tensile tester include "AC-50C-SL" manufactured by TSE.

[半導體裝置] [semiconductor device]

本發明之半導體裝置其特徵為包含本發明之印刷配線板，使用本發明之印刷配線板，可製造半導體裝置。藉由使用本發明之印刷配線板，即使在採用高焊接回流溫度之實裝步驟，亦可有利抑制絕緣層之層間剝離，即便絕緣層與導體層的剝離強度之安定性高度，亦可實現高回流信賴 性。 The semiconductor device of the present invention is characterized by comprising the printed wiring board of the present invention, and a semiconductor device can be manufactured by using the printed wiring board of the present invention. By using the printed wiring board of the present invention, even in the mounting step using a high solder reflow temperature, it is possible to suppress the interlayer peeling of the insulating layer, and the height of the peeling strength of the insulating layer and the conductor layer can be high. Backflow trust Sex.

作為該半導體裝置，可列舉供於電氣製品(例如電腦、手機、數位相機及電視等)及乘物(例如自動二輪車、汽車、電車、船舶及飛機等)等之各種半導體裝置。 Examples of the semiconductor device include various semiconductor devices such as electric products (for example, computers, mobile phones, digital cameras, and televisions) and multi-functions (for example, motorcycles, automobiles, electric cars, ships, airplanes, etc.).

本發明之半導體裝置可於印刷配線板之導通地點，藉由實裝零件(半導體晶片)來製造。所謂「導通地點」，係指「傳遞在印刷配線板之電氣信號的地點」，其地點可為表面，可為嵌入地點皆無妨。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 fabricated by mounting components (semiconductor wafers) at the conduction points of the printed wiring board. The term "conducting place" means "the place where the electrical signal is transmitted on the printed wiring board". The location may be the surface and may be the embedded location. Further, the semiconductor wafer is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material.

製造本發明之半導體裝置時之半導體晶片的實裝方法，只要是半導體晶片為有效功能，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之凹部，連接半導體晶片與印刷配線板上之配線的實裝方法」。 The method of mounting the semiconductor wafer in the manufacture of the semiconductor device of the present invention is not particularly limited as long as it is an effective function of the semiconductor wafer, and specifically, a wire bonding mounting method, a flip chip mounting method, and a borrowing method are exemplified. The mounting method by the non-convex accumulation layer (BBUL), the mounting method by the anisotropic conductive film (ACF), the mounting method by the non-conductive film (NCF), and the like. Here, the "mounting method of the non-convex accumulation layer (BBUL)" refers to a method of mounting "a semiconductor wafer directly embedded in a concave portion of a printed wiring board and connecting wirings on a semiconductor wafer and a printed wiring board".

[實施例] [Examples]

以下，雖將本發明藉由實施例具體進行說明，但本發明並非被限定於此等之實施例者。尚，在以下之記載，「份」及「%」除非另有說明，不然分別意味著「質量份」及「質量%」。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. In the following, "parts" and "%" mean "parts by mass" and "% by mass" unless otherwise stated.

(樹脂清漆1的調製) (Modulation of Resin Varnish 1)

將萘醚型環氧樹脂(DIC(股)製「EXA-7311-G4S」、環氧當量186)10份、聯二甲酚型環氧樹脂(三菱化學(股)製「YX4000HK」、環氧當量約185)10份、聯苯型環氧樹脂(日本化藥(股)製「NC3000H」、環氧當量288)20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)25份，於溶劑油15份及環己酮5份之混合溶劑邊進行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酚酚醛清漆系硬化劑(羥基當量125、DIC(股)製「LA-7054」、固形分60%之MEK溶液)12份、奈酚系硬化劑(新日鐵住金化學(股)製「SN485」、羥基當量215、固形分60%之MEK溶液)15份、聚乙烯縮丁醛樹脂(玻璃轉移溫度105℃、積水化學工業(股)製「KS-1」)之固形分15%之乙醇與甲苯之1：1的混合溶液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、咪唑系硬化促進劑(三菱化學(股)製「P200-H50」、固形分50質量%之丙二醇單甲基醚溶液)2份、將橡膠粒子(Aica工業(股)製、AC3816N)4份於MEK20份以室溫使其膨潤12小時者、以胺基矽烷系偶合劑(信越化學工業(股)製「KBM573」)表面處理之球狀二氧化矽((股)Admatechs製「SOC2」、平均粒徑0.5μm、每一單位表面積之碳量0.38mg/m2)50份，再以高速旋轉攪拌機均 勻分散後，以濾芯過濾器(ROKITECHNO製「SHP050」)過濾，來調製樹脂清漆1。 10 parts of a naphthalene ether type epoxy resin ("EXA-7311-G4S" manufactured by DIC Co., Ltd., epoxy equivalent 186), a bisphenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy resin) Equivalent: 185) 10 parts, biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288) 20 parts, and phenoxy resin ("XX7553BH30" manufactured by Mitsubishi Chemical Corporation), solid form 25 parts by mass of cyclohexanone: a 1:1 solution of methyl ethyl ketone (MEK), 25 parts, and heated and dissolved while stirring in a solvent mixture of 15 parts of a solvent oil and 5 parts of cyclohexanone. After cooling to room temperature, 12 parts of a phenol novolak-based curing agent (hydroxy equivalent of 125, DIC ("LA-7054", 60% solid MEK solution) containing a triazine skeleton, and a naphthol system were mixed. Hardening agent (Nippon Steel Chemical Co., Ltd. "SN485", hydroxyl equivalent 215, 60% solid MEK solution) 15 parts, polyvinyl butyral resin (glass transition temperature 105 ° C, Sekisui Chemical Industry Co., Ltd.) 10 parts of a solid solution of "KS-1"), 10 parts of a mixed solution of 15% ethanol and toluene, and an amine-based hardening accelerator (4-dimethylaminopyridine (DMAP), solid content of 5% by mass) One part of the MEK solution, an imidazole-based hardening accelerator ("P200-H50" manufactured by Mitsubishi Chemical Co., Ltd., and a propylene glycol monomethyl ether solution of 50% by mass in solid content), and rubber particles (Aica Industrial Co., Ltd.) , AC3816N) 4 parts of MEK 20 parts of the spheroidal cerium oxide (()) Ltd. "SOC2", average particle diameter of 0.5 m, the carbon amount per unit surface area of 0.38mg / m 2) 50 parts of the stirrer rotating at high speed and then uniformly dispersed in the filter cartridge (ROKI Filtered by TECHNO "SHP050") to prepare resin varnish 1.

(樹脂清漆2的調製) (modulation of resin varnish 2)

將雙酚AF型環氧樹脂(三菱化學(股)製「YL7760」、環氧當量238)10份、聯二甲酚型環氧樹脂(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「NC3000H」、環氧當量288)30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)5份、苯氧基樹脂(三菱化學(股)製「YL7769BH30」、固形分30質量%之環己酮：甲基乙基酮(MEK)之1：1溶液)20份，於MEK20份及環己酮5份之混合溶劑邊進行攪拌邊使其加熱溶解。冷卻至室溫後，對其混合活性酯系硬化劑(DIC(股)製「HPC8000-65T」、活性基當量約223、不揮發成分65質量%之甲苯溶液)20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)4份、咪唑系硬化促進劑(1-苄基-2-苯基咪唑(1B2PZ)、固形分5質量%之MEK溶液)3份、以苯基三甲氧基矽烷(信越化學工業(股)製「KBM103」)表面處理之球狀二氧化矽(電氣化學工業(股)製「UFP-30」、平均粒徑0.1μm、每一單位表面積之碳量0.22mg/m2)45份，再以高速旋轉攪拌機均勻分散後，再以濾芯過濾器(ROKITECHNO製「SHP030」)過濾，來調製樹脂清漆2。 Bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 238) 10 parts, bisphenol type epoxy resin ("XX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent) 185) 6 parts, biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288), 30 parts, and phenoxy resin ("XX7553BH30" manufactured by Mitsubishi Chemical Corporation), solid content 30 Mass % of cyclohexanone: 1:1 solution of methyl ethyl ketone (MEK)) 5 parts, phenoxy resin (Mitsubishi Chemical Co., Ltd. "YL7769BH30", solid content 30% by mass of cyclohexanone: A 20 parts of a 1:1 solution of a base ethyl ketone (MEK) was dissolved in a mixed solvent of 20 parts of MEK and 5 parts of cyclohexanone while stirring. After cooling to room temperature, an active ester-based curing agent ("HPC8000-65T" manufactured by DIC Co., Ltd., a toluene solution having a reactive base equivalent of about 223 and a nonvolatile content of 65 mass%) was mixed with 20 parts of an amine-based hardening accelerator. (4-dimethylaminopyridine (DMAP), solid content 5% by mass MEK solution) 4 parts, imidazole-based hardening accelerator (1-benzyl-2-phenylimidazole (1B2PZ), solid content 5 mass% 3 parts of spheroidal cerium oxide (UFP-30, manufactured by Shin-Etsu Chemical Co., Ltd.), which is surface-treated with phenyltrimethoxy decane ("KBM103" manufactured by Shin-Etsu Chemical Co., Ltd.) The resin varnish 2 was prepared by a filter having a diameter of 0.12 mg/m 2 and 45 parts per unit surface area, and then uniformly dispersing it in a high-speed rotary mixer, followed by filtration through a filter cartridge ("SHP030" manufactured by ROKITECHNO).

(樹脂清漆3的調製) (Modulation of Resin Varnish 3)

在樹脂清漆2的調製，除了將胺系硬化促進劑(4-二甲基胺基吡啶(DMAP)、固形分5質量%之MEK溶液)的摻合量從4份變更為2份，將咪唑系硬化促進劑(1-苄基-2-苯基咪唑(1B2PZ)、固形分5質量%之MEK溶液)的摻合量從3份變更為1份之外，其他與樹脂清漆2同樣進行調製樹脂清漆3。 In the preparation of the resin varnish 2, the amount of the amine-based hardening accelerator (4-dimethylaminopyridine (DMAP), a solid content of 5% by mass in a MEK solution) was changed from 4 parts to 2 parts, and imidazole was used. The amount of the curing accelerator (1-benzyl-2-phenylimidazole (1B2PZ), a solid content of 5% by mass of MEK solution) was changed from 3 parts to 1 part, and the other was prepared in the same manner as the resin varnish 2 Resin varnish 3.

(樹脂清漆4的調製) (Modulation of Resin Varnish 4)

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)5份、萘型環氧樹脂(DIC(股)製「HP4032SS」、環氧當量約144)5份、萘型環氧樹脂(DIC(股)製「HP-4710」、環氧當量約170)5份、聯二甲酚型環氧樹脂(三菱化學(股)製「YX4000HK」、環氧當量約185)5份、聯苯型環氧樹脂(日本化藥(股)製「NC3000H」、環氧當量288)12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，於溶劑油20份及環己酮10份之混合溶劑邊進行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酚酚醛清漆系硬化劑(羥基當量125、DIC(股)製「LA7054」、固形分60%之MEK溶液)12份、奈酚系硬化劑(DIC(股)製「EXB- 9500」、羥基當量190、固形分50%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份、阻燃劑(三光(股)製「HCA-HQ」、10-(2,5-二羥基苯基)-10-氫-9-氧雜-10-磷菲(Phosphaphenanthrene)-10-氧化物、平均粒徑2μm)2份、將橡膠粒子(Aica工業(股)製「AC3816N」)2份於MEK10份以室溫使其膨潤12小時者、以胺基矽烷系偶合劑(信越化學工業(股)製「KBM573」)表面處理之球狀二氧化矽((股)Admatechs製「SOC4」、平均粒徑1μm、每一單位表面積之碳量0.31mg/m2)200份，再以高速旋轉攪拌機均勻分散後，以濾芯過濾器(ROKITECHNO製「SHP050」)過濾，來調製樹脂清漆4。 Bisphenol type epoxy resin (ZX1059, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., 1:1 epoxy equivalent, 1:1 mixture of bisphenol A and bisphenol F), naphthalene epoxy 5 parts of resin ("HP4032SS" manufactured by DIC Co., Ltd., epoxy equivalent: 144), 5 parts of naphthalene type epoxy resin ("HP-4710" manufactured by DIC Co., Ltd., epoxy equivalent: about 170), bisxylenol Type epoxy resin (YX4000HK, manufactured by Mitsubishi Chemical Corporation), epoxy resin equivalent of 185 parts, and biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288), 12 parts. And phenoxy resin (Mitsubishi Chemical Co., Ltd. "YX7553BH30", solid content 30% by weight of cyclohexanone: methyl ethyl ketone (MEK) 1:1 solution) 10 parts, 20 parts in solvent oil and ring The mixed solvent of 10 parts of hexanone was heated and dissolved while stirring. After cooling to room temperature, 12 parts of a phenol novolac-based curing agent (hydroxy equivalent of 125, DIC (LA7054), 60% solid MEK solution) containing a triazine skeleton, and a naf-based hardener were mixed. (DIC (EXB-9500), hydroxy equivalent 190, 50% solid MEK solution) 12 parts, amine-based hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5% by mass 1 part of MEK solution, flame retardant ("HCA-HQ", 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphanthene (Phosphaphenanthrene) 2 parts of -10 oxides and an average particle diameter of 2 μm), and 2 parts of rubber particles ("AC3816N" manufactured by Aica Co., Ltd.) were immersed in 10 parts of MEK at room temperature for 12 hours, and an amine decane-based couple was used. A mixture of spheroidal cerium oxide ("SK4" manufactured by Shin-Etsu Chemical Co., Ltd.), "SOC4" manufactured by Admatechs, an average particle diameter of 1 μm, and a carbon content per unit surface area of 0.31 mg/m 2 ) The mixture was uniformly dispersed by a high-speed rotary mixer, and then filtered through a filter cartridge ("SHP050" manufactured by ROKITECHNO) to prepare a resin varnish 4.

(樹脂清漆5的調製) (modulation of resin varnish 5)

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)5份、雙酚AF型環氧樹脂(三菱化學(股)製「YL7760」、環氧當量238)10份、聯二甲酚型環氧樹脂(三菱化學(股)製「YX4000HK」、環氧當量約185)5份、萘型環氧樹脂(新日鐵住金化學(股)製「ESN475V」、環氧當量330)20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、溶劑油30份及環己酮5份之混合溶劑邊進行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(羥基當量151、DIC(股)製「LA-3018-50P」、固形分50%之2-甲氧基丙醇溶液)12份、活性酯系硬化劑(DIC(股)製「HPC-8000-65T」、活性基當量約223、不揮發成分65質量%之甲苯溶液)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、咪唑系硬化促進劑(1-苄基-2-苯基咪唑(1B2PZ)、固形分5質量%之MEK溶液)1份、阻燃劑(三光(股)製「HCA-HQ」、10-(2,5-二羥基苯基)-10-氫-9-氧雜-10-磷菲-10-氧化物、平均粒徑2μm)2份、以胺基矽烷系偶合劑(信越化學工業(股)製「KBM573」)表面處理之球狀二氧化矽((股)Admatechs製「SOC1」、平均粒徑0.25μm、每一單位表面積之碳量0.36mg/m2)160份，再以高速旋轉攪拌機均勻分散後，以濾芯過濾器(ROKITECHNO製「SHP030」)過濾，來調製樹脂清漆5。 Bisphenol type epoxy resin (ZX1059 made by Nippon Steel & Sumitomo Chemical Co., Ltd., 1:1 epoxy equivalent, 1:1 mixture of bisphenol A and bisphenol F), bisphenol AF type 10 parts of epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Co., Ltd., epoxide equivalent 238), 5 parts of dixylenol type epoxy resin ("XX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 185), Naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent 330) 20 parts, and phenoxy resin ("XX7553BH30" manufactured by Mitsubishi Chemical Corporation, 30% by mass of solid content) A mixture solvent of 10 parts of methyl ketone (MEK), 10 parts of solvent oil, and 5 parts of cyclohexanone was heated and dissolved while stirring. After cooling to room temperature, a cresol novolak-based hardener containing a triazine skeleton (hydroxyl equivalent 151, DIC (LA-3018-50P), solid 50% 2-methoxypropane) was mixed. 12 parts of an alcohol solution, an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Co., Ltd., a toluene solution having a reactive base equivalent of about 223, and a nonvolatile content of 65 mass%), 12 parts, and an amine-based hardening accelerator ( 4-dimethylaminopyridine (DMAP), 5% by mass of MEK solution) 1.5 parts, imidazole-based hardening accelerator (1-benzyl-2-phenylimidazole (1B2PZ), solid content: 5% by mass MEK solution) 1 part, flame retardant (HCA-HQ), 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphaphene-10- Oxidized cerium oxide (manufactured by Shin-Etsu Chemical Co., Ltd. "KBM573") spherical cerium oxide ("SOC1" manufactured by Shin-Etsu Chemical Co., Ltd.), "average particle size", average particle size: 2 μm) A resin having a diameter of 0.25 μm and a carbon content of 0.36 mg/m 2 per unit surface area was added, and the mixture was uniformly dispersed by a high-speed rotary mixer, and then filtered through a filter cartridge ("SHP030" manufactured by ROKITECHNO) to prepare a resin varnish 5.

(樹脂清漆6的調製) (modulation of resin varnish 6)

在樹脂清漆1的調製，除了取代溶劑油15份及環己酮5份之混合溶劑，改使用溶劑油15份、MEK15份及環己酮15份之混合溶劑之外，其他與樹脂清漆1同樣進行來調製樹脂清漆6 In the preparation of the resin varnish 1, the same solvent as the resin varnish 1 was used except that a solvent mixture of 15 parts of solvent oil and 5 parts of cyclohexanone was used instead of a solvent mixture of 15 parts of solvent oil, 15 parts of MEK and 15 parts of cyclohexanone. To modulate resin varnish 6

(樹脂清漆的黏度測定) (Measurement of viscosity of resin varnish)

使用安裝半徑24mm、角度1.34°之錐板之旋轉式(E 型)黏度計(東機產業(股)「RE-80U」)測定黏度。於使25℃之溫調水進行夾套(Jacket)循環之試料台，以試料樹脂組成清漆1.2g不進入氣泡的方式採取，靜置2分鐘溫調之後，將以20rpm之旋轉數旋轉2分鐘時之值作為黏度。 Use a rotating plate with a cone plate with a radius of 24mm and an angle of 1.34° (E Type) Viscosity meter (Dongye Industry Co., Ltd. "RE-80U") measures viscosity. The sample stage for the jacketing cycle of the temperature-adjusted water at 25 ° C was taken in such a manner that the sample resin composition varnish 1.2 g did not enter the bubble, and after standing for 2 minutes, the number of rotations at 20 rpm was rotated for 2 minutes. The value of time is used as the viscosity.

(實施例1：樹脂薄片1的製作) (Example 1: Production of Resin Sheet 1)

作為支持體，準備以酸醇樹脂系脫膜劑(Lintec(股)製「AL-5」)脫膜處理之PET薄膜(東麗(股)製「Lumirror T6AM」、厚度38μm、軟化點130℃)。 As a support, a PET film ("Lumirror T6AM" manufactured by Toray Co., Ltd.) having a thickness of 38 μm and a softening point of 130 ° C was prepared by a release film of an acid alcohol resin-based release agent ("AL-5" manufactured by Lintec Co., Ltd.). ).

藉由同時塗佈法，在以下之順序製作樹脂薄片1。於塗佈機設置輥形態之PET薄膜，逐步展開，與於該支持體之脫膜面使用2層裂縫模塗佈機塗佈樹脂清漆1同時於樹脂清漆1上塗佈樹脂清漆4。以樹脂清漆1之塗佈、乾燥後之目標厚度成為5μm的方式進行塗佈(塗佈)，以樹脂清漆4之塗佈、乾燥後之目標厚度成為20μm的方式進行塗佈。在70℃~110℃(平均95℃)乾燥4.5分鐘，形成各樹脂組成物層。其次，於未與樹脂組成物層之支持體接合的面，作為保護薄膜，將聚丙烯薄膜(王子特殊紙(股)製「ALPHAN MA-411」、厚度15μm)，該保護薄膜之粗面以與第2樹脂組成物層接合的方式層合。藉此，得到由支持體、第1樹脂組成物層(源自樹脂清漆1)、混合層、第2樹脂組成物層(源自樹脂清漆4)、及保護薄膜的順序所成之樹脂薄片1。尚，所謂樹脂清漆之塗佈、乾燥後之目標厚度，係指塗佈樹脂清漆，直接使其乾燥時的厚度。 The resin sheet 1 was produced in the following order by the simultaneous coating method. The PET film in the form of a roll was placed on the coater, and the resin varnish 4 was applied onto the resin varnish 1 while applying the resin varnish 1 to the release surface of the support using a two-layer slit die coater. The coating (coating) was carried out so that the target thickness after application and drying of the resin varnish 1 was 5 μm, and the coating was applied so that the target thickness after application and drying of the resin varnish 4 was 20 μm. The resin composition layer was formed by drying at 70 ° C to 110 ° C (average 95 ° C) for 4.5 minutes. Next, as a protective film, a polypropylene film ("ALPHAN MA-411" manufactured by Oji Paper Co., Ltd., thickness: 15 μm) was used as a protective film on the surface which was not bonded to the support of the resin composition layer, and the rough surface of the protective film was The layer is bonded to the second resin composition layer. Thereby, the resin sheet 1 obtained by the order of the support, the first resin composition layer (from the resin varnish 1), the mixed layer, the second resin composition layer (from the resin varnish 4), and the protective film is obtained. . Further, the target thickness after application and drying of the resin varnish refers to the thickness when the resin varnish is applied and dried directly.

(實施例2：樹脂薄片2的製作) (Example 2: Production of Resin Sheet 2)

除了取代同時塗佈法改使用串聯塗佈法之外，其他與實施例1同樣進行製作樹脂薄片2。詳細而言，除了使用模塗佈機，以樹脂清漆1成為3μm之塗佈、乾燥後之目標厚度的方式進行塗佈，於90℃預備乾燥0.8分鐘後(殘留溶劑量約30質量%)，使用模塗佈機，於樹脂清漆1上將樹脂清漆4以成為22μm之塗佈、乾燥後之目標厚度的方式進行塗佈，在80℃~110℃(平均100℃)乾燥4分鐘之外其他與實施例1同樣進行，而得到樹脂薄片2。 The resin sheet 2 was produced in the same manner as in Example 1 except that the tandem coating method was used instead of the simultaneous coating method. Specifically, the resin varnish 1 was applied so as to have a target thickness of 3 μm after coating and drying, and was dried at 90 ° C for 0.8 minutes (the amount of residual solvent was about 30% by mass). The resin varnish 4 was applied to the resin varnish 1 so as to have a target thickness of 22 μm after coating and drying, and dried at 80 ° C to 110 ° C (average 100 ° C) for 4 minutes, using a die coater. The resin sheet 2 was obtained in the same manner as in Example 1.

(實施例3：樹脂薄片3的製作) (Example 3: Production of Resin Sheet 3)

除了在實施例1，取代樹脂清漆1改使用樹脂清漆2，同時取代樹脂清漆4改使用樹脂清漆5之外，其他與實施例1同樣進行，而得到樹脂薄片3。 In the same manner as in Example 1, except that the resin varnish 2 was used instead of the resin varnish 1 and the resin varnish 5 was used instead of the resin varnish 1 in the first embodiment, the resin sheet 3 was obtained.

(實施例4：樹脂薄片4的製作) (Example 4: Production of Resin Sheet 4)

除了在實施例1，1)取代樹脂清漆1改使用樹脂清漆3，將樹脂清漆之塗佈、乾燥後之目標厚度從5μm變更為8μm這點、2)取代樹脂清漆4改使用樹脂清漆5，將樹脂清漆之塗佈、乾燥後之目標厚度從20μm變更為17μm這點之外，其他與實施例1同樣進行，而得到樹脂薄片4。 In addition to the resin varnish 3 in the first embodiment, the resin varnish 1 was replaced with the resin varnish 3, the target thickness after application and drying of the resin varnish was changed from 5 μm to 8 μm, and 2) the resin varnish 5 was used instead of the resin varnish 5, The resin sheet 4 was obtained in the same manner as in Example 1 except that the target thickness after application and drying of the resin varnish was changed from 20 μm to 17 μm.

(比較例1：樹脂薄片5的製作) (Comparative Example 1: Production of Resin Sheet 5)

作為支持體，準備以酸醇樹脂系脫膜劑(Lintec(股)製「AL-5」)脫膜處理之PET薄膜(東麗(股)製「Lumirror T6AM」、厚度38μm、軟化點130℃)。 As a support, a PET film ("Lumirror T6AM" manufactured by Toray Co., Ltd.) having a thickness of 38 μm and a softening point of 130 ° C was prepared by a release film of an acid alcohol resin-based release agent ("AL-5" manufactured by Lintec Co., Ltd.). ).

藉由2度塗佈法，在以下的順序製作樹脂薄片5。於支持體上使用模塗佈機，以樹脂清漆1之塗佈、乾燥後之目標厚度成為3μm的方式進行塗佈，在70℃~110℃(平均95℃)乾燥4.5分鐘，形成第1樹脂組成物層。其次，於第1樹脂組成物層上使用模塗佈機，以樹脂清漆4之塗佈、乾燥後之目標厚度成為22μm的方式進行塗佈，在70℃~110℃(平均95℃)乾燥4.5分鐘，形成第2樹脂組成物層，而得到樹脂薄片5。 The resin sheet 5 was produced in the following procedure by a two-degree coating method. The coating was applied to the support by a die coater, and the target resin having a thickness of 3 μm after application and drying of the resin varnish 1 was applied, and dried at 70 ° C to 110 ° C (average 95 ° C) for 4.5 minutes to form a first resin. Composition layer. Then, the coating was applied to the first resin composition layer by a die coater, and the target thickness after application and drying of the resin varnish 4 was 22 μm, and dried at 70 ° C to 110 ° C (average 95 ° C). In a minute, the second resin composition layer was formed, and the resin sheet 5 was obtained.

(比較例2：樹脂薄片6的製作) (Comparative Example 2: Production of Resin Sheet 6)

除了在實施例1，1)取代樹脂清漆1改使用樹脂清漆6，將樹脂清漆之塗佈、乾燥後之目標厚度從5μm變更為3μm這點、2)將樹脂清漆4之塗佈、乾燥後之目標厚度從20μm變更為22μm這點之外，其他與實施例1同樣進行，而得到樹脂薄片6。 In addition to the resin varnish 6, the resin varnish 6 was replaced with the resin varnish 1, and the target thickness after application and drying of the resin varnish was changed from 5 μm to 3 μm, and 2) the resin varnish 4 was applied and dried. The resin sheet 6 was obtained in the same manner as in Example 1 except that the target thickness was changed from 20 μm to 22 μm.

(最低熔融黏度的測定) (Measurement of the lowest melt viscosity)

在與各實施例及各比較例相同條件，於PET薄膜上將第1或第2樹脂組成物層以單層塗佈，準備測定樣品。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，測定最低熔融黏度(poise)。 The first or second resin composition layer was applied as a single layer on the PET film under the same conditions as in the respective examples and the comparative examples to prepare a measurement sample. Using dynamic viscoelasticity measuring device ("share" UBM system "Rheosol- G3000"), using a parallel plate having a diameter of 18 mm for a sample resin composition of 1 g, and raising the temperature from a starting temperature of 60 ° C to 200 ° C at a temperature increase rate of 5 ° C / min, and measuring a temperature interval of 2.5 ° C, a vibration number of 1 Hz, and a twist of 1 deg. The dynamic viscoelasticity rate was determined and the lowest melt viscosity was determined.

(樹脂薄片之各層的厚度的測定) (Measurement of Thickness of Each Layer of Resin Sheet)

從於各實施例及各比較例製作之樹脂薄片(200mm平方)剝離保護薄膜。將第2樹脂組成物層作為上面，將樹脂薄片設置於255mm×255mm尺寸之玻璃布基材環氧樹脂兩面銅包層層合板(0.7mm厚、松下電工(股)製「R5715ES」)上，將樹脂薄片之四邊以聚醯亞胺接著膠帶(寬度10mm)固定，於100℃(投入100℃之烤箱後)30分鐘，其次於175℃(轉移至175℃之烤箱後)30分鐘使其熱硬化。然後，將基板於室溫環境下取出。 The protective film was peeled off from the resin sheet (200 mm square) produced in each of the examples and the comparative examples. The second resin composition layer was used as the upper surface, and the resin sheet was placed on a 256 mm × 255 mm glass cloth substrate epoxy resin double-sided copper clad laminate (0.7 mm thick, "R5715ES" manufactured by Matsushita Electric Works Co., Ltd.). The four sides of the resin sheet were fixed with polyimine followed by a tape (width 10 mm), at 100 ° C (after putting the oven at 100 ° C) for 30 minutes, followed by 175 ° C (after transfer to the oven at 175 ° C) for 30 minutes to make it hot. hardening. Then, the substrate was taken out at room temperature.

將經熱硬化之樹脂薄片使用FIB-SEM複合裝置(SIINanotechnology(股)製「SMI3050SE」)，進行剖面觀察。詳細而言，將在與樹脂薄片的表面垂直之方向之剖面藉由FIB(集束離子束)削出，取得剖面SEM圖像(觀察寬度30μm、觀察倍率9,000倍)。對於各樣品，取得隨機選擇了5處之剖面SEM圖像，將各層的厚度以平均值表示，將此值作為各層的厚度。 The thermosetting resin sheet was subjected to cross-sectional observation using a FIB-SEM composite apparatus ("SMI3050SE" manufactured by SIINanotechnology Co., Ltd.). Specifically, the cross section perpendicular to the surface of the resin sheet was cut by FIB (bundled ion beam) to obtain a cross-sectional SEM image (observation width: 30 μm, observation magnification: 9,000 times). For each sample, a cross-sectional SEM image of five locations was randomly selected, and the thickness of each layer was represented by an average value, and this value was made into the thickness of each layer.

(印刷配線板之製作及評估) (production and evaluation of printed wiring boards)

使用各實施例及各比較例之樹脂薄片，沿著以下之順 序分別製作印刷配線板。 Using the resin sheets of the respective examples and comparative examples, along the following The printed wiring board is separately prepared.

<印刷配線板之製作> <Production of Printed Wiring Board>

(1)電路基板之基底處理 (1) Substrate processing of circuit substrate

於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、日立化成工業(股)製「679FGR」)形成IPC MULTI-PURPOSE TEST BOARD NO.IPC B-25之圖型(線/空間=175/175μm之梳齒圖型(殘銅率50%))，將兩面在微蝕刻劑(MEC(股)製「CZ8100」)進行1μm蝕刻，以進行銅表面之粗糙化處理。 IPC MULTI-PURPOSE TEST BOARD NO.IPC B-25 is formed on the glass cloth substrate epoxy resin double-sided copper clad laminate (18 μm copper foil thickness, substrate thickness 0.3 mm, and "679FGR" manufactured by Hitachi Chemical Co., Ltd.). The pattern (line/space = 175/175 μm comb pattern (50% residual copper)), and the two surfaces are etched by a microetching agent ("CZ8100" manufactured by MEC) to perform copper surface treatment. Roughening treatment.

(2)樹脂薄片的層合 (2) Lamination of resin sheets

從於實施例及比較例製作之樹脂薄片剝離保護薄膜。將樹脂薄片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」)，以第2樹脂組成物層與電路基板接合的方式層合於電路基板之兩面。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、110℃、壓力0.5MPa進行60秒熱沖壓而平滑化。 The protective film was peeled off from the resin sheets produced in the examples and the comparative examples. The resin sheet is laminated on the circuit board so that the second resin composition layer is bonded to the circuit board by using a batch type vacuum pressure laminator (a two-stage accumulation laminator "CVP700" manufactured by Nichigo-Morton). Both sides. The lamination system was carried out by pressing at a pressure of 30 hPa for 30 seconds, and then pressing at 110 ° C and a pressure of 0.74 MPa for 30 seconds. Next, the laminated resin sheet was subjected to hot stamping at 110 ° C and a pressure of 0.5 MPa for 60 seconds to be smoothed.

(3)樹脂組成物層之硬化 (3) Hardening of the resin composition layer

樹脂薄片的層合後，以附支持體的狀態，於100℃(投入100℃之烤箱後)30分鐘，其次於175℃(轉移至175℃ 之烤箱後)30分鐘之條件進行熱硬化，於電路基板之兩面形成絕緣層。然後，將基板從室溫環境下取出。 After lamination of the resin sheet, in the state of the support, at 100 ° C (after putting the oven at 100 ° C) for 30 minutes, followed by 175 ° C (transfer to 175 ° C) After the oven, it was thermally cured under conditions of 30 minutes to form an insulating layer on both sides of the circuit board. Then, the substrate was taken out from the room temperature environment.

(4)粗糙化處理 (4) roughening treatment

將剝離支持體之基板於膨潤液(含有Atotech Japan(股)製「Swelling Dip Securiganth P」、二乙二醇單丁基醚及氫氧化鈉之水溶液)，以60℃浸漬5分鐘(實施例1、2及比較例1、2)或浸漬10分鐘(實施例3、4)，於氧化劑(Atotech Japan(股)製「Concentrate Compact CP」、KMnO4：60g/L、NaOH：40g/L之水溶液)以80℃浸漬20分鐘、最後於中和液(Atotech Japan(股)製「Reduction solution Securiganth P」、硫酸水溶液)以40℃浸漬5分鐘後，以80℃乾燥30分鐘。將所得之基板稱為「評估基板A」。 The substrate of the release support was immersed in a swelling solution (aqueous solution containing "Swelling Dip Securiganth P" manufactured by Atotech Japan Co., Ltd., diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C for 5 minutes (Example 1) 2, and Comparative Examples 1 and 2) or immersed for 10 minutes (Examples 3 and 4), in an oxidizing agent (Acentech Japan Co., Ltd. "Concentrate Compact CP", KMnO 4 : 60 g / L, NaOH: 40 g / L aqueous solution The mixture was immersed at 80 ° C for 20 minutes, and finally immersed in a neutralizing solution ("Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd., aqueous sulfuric acid solution) at 40 ° C for 5 minutes, and then dried at 80 ° C for 30 minutes. The obtained substrate is referred to as "evaluation substrate A".

(5)藉由半加成工法之導體層之形成 (5) Formation of a conductor layer by a semi-additive method

將評估基板A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。將所得之基板在150℃加熱30分鐘，進行退火處理後，進行硫酸銅電解鍍敷，全面形成厚度30μm之導體層。其次，在190℃加熱60分鐘，進行退火處理。將所得之基板稱為「評估基板B」。 The substrate A was evaluated in an electroless plating solution containing PdCl 2 and immersed at 40 ° C for 5 minutes, followed by an electroless copper plating solution at 25 ° C for 20 minutes. The obtained substrate was heated at 150 ° C for 30 minutes, and after annealing treatment, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 30 μm. Next, it was heated at 190 ° C for 60 minutes and annealed. The obtained substrate is referred to as "evaluation substrate B".

<評估> <evaluation>

(1)算術平均粗糙度(Ra) (1) Arithmetic mean roughness (Ra)

絕緣層表面之算術平均粗糙度(Ra)在下述之順序測定以進行評估。針對各評估基板A，將線/空間=175/175μm之梳齒圖型(殘銅率50%)上之絕緣層表面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。對於隨機選擇了10點求得Ra值。而且關於Ra值的最大值與最小值的差異(最大值-最小值)之值，用以下的基準評估。 The arithmetic mean roughness (Ra) of the surface of the insulating layer was measured in the order described below for evaluation. For each evaluation substrate A, a non-contact surface roughness meter (WYKO NT3300) manufactured by Wyco Instruments Co., Ltd. was used for the surface of the insulating layer on the wire/space = 175/175 μm comb pattern (50% residual copper ratio). The measurement range was determined to be 121 μm × 92 μm by a VSI contact mode and a 50-fold lens, and the Ra value was obtained from the obtained value. For the random selection of 10 points, the Ra value is obtained. Further, the value of the difference (maximum-minimum value) between the maximum value and the minimum value of the Ra value is evaluated by the following criteria.

[評估基準] [Evaluation Benchmark]

○：差異為150nm以下 ○: The difference is 150 nm or less

×：差異超過150nm ×: the difference exceeds 150 nm

(2)剝離強度 (2) Peel strength

絕緣層與導體層的剝離強度在下述的順序測定以進行評估。對於各評估基板B，於線/空間=175/175μm之梳齒圖型(殘銅率50%)上之導體層，放入寬度10mm、長度100mm之部分切割，剝離此一端並以夾具(TSE股份有限公司、Auto com型試驗機「AC-50C-SL」)抓住，在室溫中以50mm/分鐘之速度於垂直方向，測定剝離35mm時之荷重(kgf/cm)。而且關於剝離強度的最大值與最小值的差異(最大值-最小值)之值，用以下的基準評估。 The peel strength of the insulating layer and the conductor layer was measured in the following order for evaluation. For each evaluation substrate B, a conductor layer on a wire/space = 175/175 μm comb pattern (50% residual copper ratio) was cut into a portion having a width of 10 mm and a length of 100 mm, and the end was peeled off and clamped (TSE). Co., Ltd., Auto com type test machine "AC-50C-SL") grasped, and measured the load (kgf/cm) when peeling 35 mm in the vertical direction at a temperature of 50 mm/min at room temperature. Further, the value of the difference (maximum-minimum value) between the maximum value and the minimum value of the peel strength was evaluated by the following criteria.

[評估基準] [Evaluation Benchmark]

○：差異為0.15kgf/cm以下 ○: The difference is 0.15 kgf/cm or less

×：差異超過0.15kgf/cm ×: the difference exceeds 0.15 kgf/cm

(3)回流耐性 (3) Reflow resistance

將評估基板B切出45mm平方之個片後(n=3)，在60℃、60%相對濕度之環境中放置48小時。然後，通過再現峰值溫度260℃之焊接回流溫度之回流裝置(日本ANTOM(股)製「HAS-6116」)(回流溫度檔案依據IPC/JEDEC J-STD-020C)。進行13次回流步驟，關於在絕緣層之層間剝離或絕緣層與導體層的剝離等之剝離異常的有無、剝離異常之產生時機，用以下的基準評估。 The evaluation substrate B was cut out of a sheet of 45 mm square (n=3), and left in an environment of 60 ° C and 60% relative humidity for 48 hours. Then, a reflow device ("HAS-6116" manufactured by ANTOM Co., Ltd., Japan) of a solder reflow temperature having a peak temperature of 260 ° C was reproduced (reflow temperature profile according to IPC/JEDEC J-STD-020C). The reflowing step was performed 13 times, and the timing of peeling abnormality such as peeling of the insulating layer or peeling of the insulating layer and the conductor layer, and the timing of occurrence of peeling abnormality were evaluated by the following criteria.

[評估基準] [Evaluation Benchmark]

◎：13次為止無剝離異常者 ◎: No peeling abnormalities up to 13 times

○：在7次~12次，發生有1片剝離異常者 ○: In 7 to 12 times, one peeling abnormality occurred.

×：至6次為止發生有1片剝離異常者 ×: One peeling abnormality occurred up to 6 times

從上述表，瞭解到實施例1~4係粗糙度或剝離強度之安定性高，即使曝露於回流時之高溫環境下時亦抑制層間剝離且回流耐性優異。瞭解到混合層的厚度為1.0μm以上之實施例1及實施例3之樹脂薄片，與混合層的厚度為0.7μm之實施例2之樹脂薄片進行比較，提供回流耐性更為優異之絕緣層。又，瞭解到第1樹脂組成物層之最低熔融黏度為5000poise以上之實施例1及實施例3之樹脂薄片，與第1樹脂組成物層之最低熔融黏度為3900poise之實施例4之樹脂薄片進行比較，提供回流耐性更為優異之絕緣層。 From the above table, it was found that the stability of the roughness and the peel strength of Examples 1 to 4 was high, and the interlayer peeling was suppressed even when exposed to a high temperature environment at the time of reflow, and the backflow resistance was excellent. The resin sheets of Example 1 and Example 3 in which the thickness of the mixed layer was 1.0 μm or more were compared with the resin sheet of Example 2 in which the thickness of the mixed layer was 0.7 μm, and an insulating layer having more excellent reflow resistance was provided. Further, it was found that the resin sheets of Examples 1 and 3 having the lowest melt viscosity of the first resin composition layer of 5000 poise or more were subjected to the resin sheet of Example 4 having the lowest melt viscosity of the first resin composition layer of 3900 poise. In comparison, an insulating layer having superior reflow resistance is provided.

另外，瞭解到藉由2度塗佈法製作之比較例1之樹脂薄片，混合層的厚度為薄，使用該樹脂薄片所形成之絕緣層，在回流時之高溫環境下易發生層間剝離，回流耐性不良。 Further, the resin sheet of Comparative Example 1 produced by the two-degree coating method was found, and the thickness of the mixed layer was thin, and the insulating layer formed using the resin sheet was liable to cause interlayer peeling and reflow under a high temperature environment at the time of reflow. Poor tolerance.

又，瞭解到於使用黏度為80mPa．s之樹脂清漆製作第1樹脂組成物層之比較例2，起因於支持體上之樹脂清漆的排斥等，所得之絕緣層之表面缺陷增多，粗糙度、剝離強度之安定性不良。於比較例2，又瞭解到起因於低黏度之樹脂清漆，即便樹脂清漆彼此的混合變過度之第1樹脂組成物層的厚度薄，粗糙度、剝離強度之安定性亦變劣化。剝離強度低之處，由於亦產生絕緣層與導體層的剝離，故回流耐性顯著劣化。 Also, I learned that the viscosity is 80mPa. In Comparative Example 2 in which the first resin composition layer was produced from the resin varnish of s, the surface defects of the obtained insulating layer were increased due to the repulsion of the resin varnish on the support, and the stability of the roughness and the peel strength was poor. In the case of the resin varnish having a low viscosity, the thickness of the first resin composition layer which is excessively mixed with the resin varnish is thin, and the stability of the roughness and the peel strength is also deteriorated. When the peeling strength is low, peeling of the insulating layer and the conductor layer occurs, so that the reflow resistance is remarkably deteriorated.

1‧‧‧樹脂薄片 1‧‧‧resin sheet

11‧‧‧支持體 11‧‧‧Support

12‧‧‧第1樹脂組成物層 12‧‧‧1st resin composition layer

13‧‧‧混合層 13‧‧‧ mixed layer

14‧‧‧第2樹脂組成物層 14‧‧‧Second resin composition layer

Claims (16)

一種樹脂薄片之製造方法，其係具有由支持體、與於支持體上所設置之第1樹脂組成物所成之第1樹脂組成物層、與於第1樹脂組成物層上所設置之第2樹脂組成物所成之第2樹脂組成物層，並於第1樹脂組成物層與第2樹脂組成物層之間具有混在第1樹脂組成物及第2樹脂組成物之混合層的樹脂薄片之製造方法，其係包含於支持體上塗佈溶解第1樹脂組成物之第1樹脂清漆，於第1樹脂清漆上塗佈溶解第2樹脂組成物之第2樹脂清漆，再進行乾燥之步驟，第1樹脂清漆的黏度為100mPa．s以上，第2樹脂清漆的黏度為100mPa．s以上。 A method for producing a resin sheet, comprising: a first resin composition layer formed of a support and a first resin composition provided on a support; and a first resin composition layer provided on the first resin composition layer a second resin composition layer formed of the resin composition, and a resin sheet mixed with the mixed layer of the first resin composition and the second resin composition between the first resin composition layer and the second resin composition layer A method for producing a first resin varnish in which a first resin composition is dissolved on a support, a second resin varnish in which the second resin composition is dissolved, and drying is applied to the first resin varnish The viscosity of the first resin varnish is 100mPa. Above s, the viscosity of the second resin varnish is 100 mPa. s above. 如請求項1之樹脂薄片之製造方法，其係包含與於支持體上塗佈第1樹脂清漆同時於第1樹脂清漆上塗佈第2樹脂清漆，然後進行乾燥之步驟、或包含於支持體上塗佈第1樹脂清漆，使其預備乾燥後，再於第1樹脂清漆上塗佈第2樹脂清漆，然後進行乾燥之步驟。 The method for producing a resin sheet according to claim 1, which comprises the step of applying a second resin varnish to the first resin varnish while applying the first resin varnish to the support, and then drying the film, or comprising the support. After the first resin varnish is applied and dried, the second resin varnish is applied to the first resin varnish, and then dried. 如請求項2之樹脂薄片之製造方法，其中，使其預備乾燥後之第1樹脂清漆中之殘留溶劑量，將第1樹脂清漆中所包含之不揮發成分的合計定為100質量%時，為15質量%~70質量%。 The method of producing a resin sheet according to claim 2, wherein the total amount of the solvent in the first resin varnish after the preliminary drying is set to 100% by mass based on the total amount of the nonvolatile components contained in the first resin varnish. It is 15% by mass to 70% by mass. 如請求項1之樹脂薄片之製造方法，其係包含與於支持體上塗佈第1樹脂清漆同時於第1樹脂清漆上塗佈第2樹脂清漆，然後進行乾燥之步驟。 The method for producing a resin sheet according to claim 1, further comprising the step of applying a second resin varnish to the first resin varnish while applying the first resin varnish to the support, followed by drying. 如請求項1之樹脂薄片之製造方法，其中，第1樹脂組成物層的厚度為0.3μm~15μm，第2樹脂組成物層的厚度為3μm~200μm，混合層的厚度為0.4μm以上且為第1樹脂組成物層的厚度之2倍以下。 The method for producing a resin sheet according to claim 1, wherein the thickness of the first resin composition layer is 0.3 μm to 15 μm, the thickness of the second resin composition layer is 3 μm to 200 μm, and the thickness of the mixed layer is 0.4 μm or more. The thickness of the first resin composition layer is twice or less. 如請求項1之樹脂薄片之製造方法，其中，支持體為附脫膜層之支持體。 The method for producing a resin sheet according to claim 1, wherein the support is a support having a release layer. 如請求項1之樹脂薄片之製造方法，其中，第1樹脂組成物層之最低熔融黏度為3000poise以上，第2樹脂組成物層之最低熔融黏度為10000poise以下。 The method for producing a resin sheet according to claim 1, wherein the first resin composition layer has a minimum melt viscosity of 3,000 poise or more, and the second resin composition layer has a lowest melt viscosity of 10,000 poise or less. 如請求項1之樹脂薄片之製造方法，其中，第1樹脂清漆的黏度為100mPa．s~3000mPa．s，第2樹脂清漆的黏度為100mPa．s~6000mPa．s。 The method for producing a resin sheet according to claim 1, wherein the viscosity of the first resin varnish is 100 mPa. s~3000mPa. s, the viscosity of the second resin varnish is 100mPa. s~6000mPa. s. 如請求項1之樹脂薄片之製造方法，其中，在同一塗佈線上，塗佈第1樹脂清漆與第2樹脂清漆。 The method for producing a resin sheet according to claim 1, wherein the first resin varnish and the second resin varnish are applied on the same coating line. 一種印刷配線板之製造方法，其係將藉由如請求項1至9中任一項之方法所製造之樹脂薄片層合於內層基板上，使其熱硬化後再去除支持體。 A method of producing a printed wiring board, which is obtained by laminating a resin sheet produced by the method according to any one of claims 1 to 9 on an inner layer substrate, thermally hardening, and then removing the support. 一種樹脂薄片，其係具有由支持體、與於支持體上所設置之第1樹脂組成物所成之第1樹脂組成物層、與由第1樹脂組成物層上所設置之第2樹脂組成物所成之第2樹脂組成物層，並於第1樹脂組成物層與第2樹脂組成物層之間具有混在第1樹脂組成物及第2樹脂組成物之混合層，混合層的厚度為0.4μm以上。 A resin sheet comprising a support, a first resin composition layer formed of a first resin composition provided on a support, and a second resin provided on the first resin composition layer The second resin composition layer formed of the material has a mixed layer of the first resin composition and the second resin composition between the first resin composition layer and the second resin composition layer, and the thickness of the mixed layer is 0.4 μm or more. 如請求項11之樹脂薄片，其中，第1樹脂組成 物層的厚度為0.3μm~15μm，第2樹脂組成物層的厚度為3μm~200μm，混合層的厚度為0.4μm以上且為第1樹脂組成物層的厚度之2倍以下。 The resin sheet of claim 11, wherein the first resin is composed The thickness of the layer is 0.3 μm to 15 μm, the thickness of the second resin composition layer is 3 μm to 200 μm, and the thickness of the mixed layer is 0.4 μm or more and twice or less the thickness of the first resin composition layer. 如請求項11之樹脂薄片，其中，第1樹脂組成物層之最低熔融黏度為3000poise以上。 The resin sheet of claim 11, wherein the first resin composition layer has a minimum melt viscosity of 3,000 poise or more. 如請求項11之樹脂薄片，其中，第2樹脂組成物層之最低熔融黏度為10000poise以下。 The resin sheet of claim 11, wherein the second resin composition layer has a minimum melt viscosity of 10,000 poise or less. 一種印刷配線板，其係包含使用如請求項11至14中任一項之樹脂薄片所形成之絕緣層。 A printed wiring board comprising an insulating layer formed using the resin sheet of any one of claims 11 to 14. 一種半導體裝置，其係包含如請求項15之印刷配線板。 A semiconductor device comprising the printed wiring board of claim 15.
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