TW202015920A - Cured body layer printed wiring board semiconductor device resin sheet method for manufacturing printed wiring board and method for manufacturing resin sheet - Google Patents

Cured body layer printed wiring board semiconductor device resin sheet method for manufacturing printed wiring board and method for manufacturing resin sheet Download PDF

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TW202015920A
TW202015920A TW108118340A TW108118340A TW202015920A TW 202015920 A TW202015920 A TW 202015920A TW 108118340 A TW108118340 A TW 108118340A TW 108118340 A TW108118340 A TW 108118340A TW 202015920 A TW202015920 A TW 202015920A
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body layer
resin composition
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TWI838374B (en
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西村嘉生
岡崎大地
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日商味之素股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4028—Isocyanates; Thioisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/145—Organic substrates, e.g. plastic
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/09—Treatments involving charged particles
    • H05K2203/095—Plasma, e.g. for treating a substrate to improve adhesion with a conductor or for cleaning holes

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Epoxy Resins (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

Provided is a cured body layer which sufficiently ensures smear removal characteristics even when plasma by N2 gas or O2 gas having a low inorganic filler removal capability is used. The cured body layer is based on a cured product of a resin composition containing 40 mass% or more of an inorganic filler arranged on a side of a conductive layer of a substrate, wherein the substrate comprises an outermost layer with the conduct layer on at least part thereof. The cured body layer satisfies an inequation, A(0-1) / A(1-2) > 1.1.

Description

硬化體層、印刷配線板、半導體裝置、樹脂薄片、印刷配線板之製造方法及樹脂薄片之製造方法Method for manufacturing hardened body layer, printed wiring board, semiconductor device, resin sheet, printed wiring board, and resin sheet

本發明係關於硬化體層、印刷配線板、半導體裝置、樹脂薄片、印刷配線板之製造方法及樹脂薄片之製造方法。The present invention relates to a method of manufacturing a cured body layer, a printed wiring board, a semiconductor device, a resin sheet, a printed wiring board, and a resin sheet.

近年來，對於電子機器之小型化、高性能化的推進之多層印刷配線板，積聚層被複層化，配線之微型化及高密度化亦更上一層地進行著。作為導體形成方法，例如已知有以無電解鍍敷與電解鍍敷形成導體層之半添加法等。絕緣層與鍍敷導體層之密著性受到藉由絕緣層之粗化處理所形成的凹凸程度之影響，一般被認為欲提高密著性時，可使絕緣層表面之粗度更大。In recent years, for multi-layer printed wiring boards that are advancing the miniaturization and high performance of electronic devices, the accumulation layer has been multi-layered, and the miniaturization and high-density of wiring have been further advanced. As a conductor forming method, for example, a semi-additive method of forming a conductor layer by electroless plating and electrolytic plating is known. The adhesion between the insulating layer and the plated conductor layer is affected by the degree of unevenness formed by the roughening treatment of the insulating layer. It is generally considered that when the adhesion is to be improved, the surface roughness of the insulating layer can be made larger.

然而，若絕緣層表面的粗度大時，於該表面上所形成的電路間之寬度的限制亦必須變大，對於高密度配線變得不利。因此，欲進行高密度配線化，要求對於絕緣層表面進行粗化處理後的粗度即使小，亦形成密著性優良的導體層之方法。However, if the thickness of the surface of the insulating layer is large, the limitation of the width between the circuits formed on the surface must also become large, which is disadvantageous for high-density wiring. Therefore, in order to achieve high-density wiring, a method of forming a conductive layer having excellent adhesion even if the roughness of the surface of the insulating layer is roughened is required.

於專利文獻1中記載，將於支持薄膜上形成樹脂組成物層的接著薄膜層合於電路基板上，使樹脂組成物層進行熱硬化後使支持薄膜剝離，藉由於絕緣層表面藉由濺射法而形成導體層，即使變得粗度比較小，亦可製造導體層顯示高剝離強度的多層印刷配線板之方法。又，於專利文獻2中記載，欲絕緣層與銅配線之熱膨張率的錯配解消，於樹脂組成物高量添加無機填充材，且即使欲對應高密度化•小型化而使粗度變得比較小，亦可得到高剝離強度。 [先前技術文獻] [專利文獻]It is described in Patent Document 1 that a bonding film formed with a resin composition layer on a support film is laminated on a circuit board, the resin composition layer is thermally hardened, and the support film is peeled off by sputtering on the surface of the insulating layer Method to form a conductor layer, even if the thickness becomes relatively small, a method of manufacturing a multilayer printed wiring board in which the conductor layer shows high peel strength. In addition, it is described in Patent Document 2 that if the thermal expansion ratio mismatch between the insulating layer and the copper wiring is to be eliminated, a high amount of inorganic filler is added to the resin composition, and even if the density is to be increased or miniaturized, the thickness will be changed. If it is relatively small, high peel strength can also be obtained. [Prior Technical Literature] [Patent Literature]

[專利文獻1] 日本特開2007-273615號公報 [專利文獻2] 日本特開2015-150885號公報[Patent Document 1] Japanese Patent Laid-Open No. 2007-273615 [Patent Document 2] Japanese Patent Laid-Open No. 2015-150885

[發明所解決的問題][Problems solved by the invention]

對於添加高量無機填充材之過去絕緣層(硬化體層)而採用乾式粗化步驟時，在使用CF4 氣體等氟系氣體的電漿處理中，雖污跡除去性良好，但要求高價設備投資下，對於人體及環境之影響成為課題。其中另一方面，在使用無機填充材之除去能低的N2 氣體或O2 氣體之電漿處理時，因無機填充材及位置於該無機填充材的下部之樹脂成分無法充分地除去，故無法充分地確保污跡除去性。For the past insulation layer (hardened body layer) to which a high amount of inorganic filler is added and the dry roughening step is adopted, in the plasma treatment using fluorine-based gas such as CF 4 gas, although the stain removal property is good, an expensive equipment investment is required Next, the impact on the human body and the environment becomes a problem. On the other hand, in the plasma treatment using N 2 gas or O 2 gas with low removal ability of the inorganic filler, the inorganic filler and the resin component located under the inorganic filler cannot be sufficiently removed, so The stain removal property cannot be sufficiently ensured.

其中，本發明之課題為提供，對於乾式粗化步驟，即使未使用氟系氣體，藉由以無機填充材的除去能低之N2 氣體或O2 氣體的電漿處理，亦可確保充分良好的污跡除去性之硬化體層；具備前述硬化體層的印刷配線板及其製造方法；具備前述硬化體層的半導體裝置；可得到前述硬化體層之樹脂薄片；及其製造方法。 [解決課題的手段]Among them, the object of the present invention is to provide, even in the dry roughening step, even if a fluorine-based gas is not used, by using an inorganic filler to remove the low energy N 2 gas or O 2 gas plasma treatment can ensure sufficient good A stain-removable hardened body layer; a printed wiring board provided with the above hardened body layer and a manufacturing method thereof; a semiconductor device provided with the above hardened body layer; a resin sheet capable of obtaining the above hardened body layer; and a manufacturing method thereof. [Means to solve the problem]

本發明者們對於上述課題進行詳細檢討結果，發現將對於硬化體層之導體層附近區域中的無機填充材之樹脂成分的量(無機填充材/樹脂成分)抑制至相對低時，可解決上述課題，而完成本發明。The inventors conducted a detailed review of the above-mentioned problems and found that the above-mentioned problems can be solved when the amount of the resin component (inorganic filler/resin component) of the inorganic filler in the vicinity of the conductive layer of the cured body layer is suppressed , And completed the present invention.

即，本發明含有以下內容。That is, the present invention includes the following.

[1] 一種硬化體層，其為設置於在最外層的至少一部分具備導體層的基板之前述導體層側的面上，且以無機填充材含有量為40質量%以上的樹脂組成物之硬化物所形成的硬化體層，對於在前述硬化體層的主表面呈垂直的前述硬化體層之截面，對於自前述導體層的距離而言，將自0μm至1μm為止的區域中之每單位面積的樹脂成分之面積作為A0-1 ，將自1μm至2μm為止的區域中之每單位面積的樹脂成分之面積作為A1-2 時，滿足A0-1 /A1-2 ＞1.1者。 [2] 如[1]所記載的硬化體層，對於前述截面，對於自前述導體層的距離而言，將自0μm至0.5μm為止的區域中之每單位面積的樹脂成分之面積作為A0-0.5 ，將自0.5μm至1μm為止的區域中之每單位面積的樹脂成分之面積作為A0.5-1 時，滿足A0-0.5 /A0.5-1 ＞1.1者。 [3] 如[1]或[2]所記載的硬化體層，對於前述截面，對於自前述導體層的距離而言，將自0.5μm至dμm為止的區域中之每單位面積的樹脂成分之面積作為A0.5-d ，將自dμm至0.5Dμm為止的區域中之每單位面積的樹脂成分之面積作為Ad-0.5D 時，滿足0.9≦A0.5-d /Ad-0.5D ≦1.1(其中，d為滿足0.5＜d＜0.5D的數，D為前述硬化體層的厚度)者。 [4] 前述樹脂組成物含有環氧樹脂之[1]~[3]中任一所記載的硬化體層。 [5] 前述樹脂組成物進一步含有活性酯系硬化劑之[4]所記載的硬化體層。 [6] 前述樹脂組成物進一步含有氰酸酯系硬化劑，該含有量對於前述樹脂組成物中之樹脂成分100質量%而言為15質量%以上之[4]或[5]所記載的硬化體層。 [7] 前述樹脂組成物之氮原子含有量對於前述樹脂組成物中之樹脂成分100質量%而言為1質量%以上之[1]~[6]中任一所記載的硬化體層。 [8] 如[1]~[7]中任一所記載的硬化體層，其中前述硬化體層為，自與前述基板相反側依序具備以下第1硬化體層與第2硬化體層；第1硬化體層係以第1樹脂組成物的硬化物所形成者；第2硬化體層係以具有與前述第1樹脂組成物相異組成之第2樹脂組成物的硬化物所形成者。 [9] 前述第2硬化體層的厚度為未達2μm之[8]所記載的硬化體層。 [10] 前述第2樹脂組成物的無機填充材含有量為未達20質量%之[8]或[9]所記載的硬化體層。 [11] 欲提供於藉由選自含有O2 氣體及N2 氣體所成群的1種以上之氣體的電漿處理之[1]~[10]中任一所記載的硬化體層。[1] A cured body layer, which is a cured product of a resin composition provided on a surface of the substrate provided with a conductive layer on at least a part of the outermost layer on the side of the conductive layer, and containing an inorganic filler content of 40% by mass or more The formed hardened body layer has a cross section of the hardened body layer that is perpendicular to the main surface of the hardened body layer, and the distance from the conductive layer to the resin component per unit area in the area from 0 μm to 1 μm When the area is A 0-1 and the area of the resin component per unit area in the area from 1 μm to 2 μm is A 1-2 , those satisfying A 0-1 /A 1-2 >1.1 are satisfied. [2] The cured body layer as described in [1], with respect to the cross section and the distance from the conductor layer, the area of the resin component per unit area in the area from 0 μm to 0.5 μm is defined as A 0− 0.5 , when the area of the resin component per unit area in the area from 0.5 μm to 1 μm is regarded as A 0.5-1 , A 0-0.5 /A 0.5-1 >1.1 is satisfied. [3] The cured body layer as described in [1] or [2], with respect to the cross-section, the distance from the conductor layer to the area of the resin component per unit area in the area from 0.5 μm to d μm As A 0.5-d , when the area of the resin component per unit area in the region from dμm to 0.5Dμm is taken as A d-0.5D , 0.9≦A 0.5-d /A d-0.5D ≦1.1 (where , D is a number that satisfies 0.5<d<0.5D, and D is the thickness of the hardened body layer). [4] The resin composition contains the cured body layer described in any one of [1] to [3] of the epoxy resin. [5] The resin composition further contains the cured body layer described in [4] of the active ester-based curing agent. [6] The resin composition further contains a cyanate-based curing agent, the content of which is 15% by mass or more with respect to 100% by mass of the resin component in the resin composition. The curing described in [4] or [5] Body layer. [7] The nitrogen atom content of the resin composition is 1% by mass or more of the cured body layer described in any one of [1] to [6] for 100% by mass of the resin component in the resin composition. [8] The hardened body layer according to any one of [1] to [7], wherein the hardened body layer is provided with the following first hardened body layer and second hardened body layer in order from the opposite side of the substrate; the first hardened body layer It is formed by the cured product of the first resin composition; the second cured body layer is formed by the cured product of the second resin composition having a different composition from the aforementioned first resin composition. [9] The thickness of the second cured body layer is the cured body layer described in [8] of less than 2 μm. [10] The cured material layer described in [8] or [9] in which the inorganic filler content of the second resin composition is less than 20% by mass. [11] It is intended to provide the hardened body layer described in any one of [1] to [10] by plasma treatment with one or more gases selected from the group consisting of O 2 gas and N 2 gas.

[12] 具有[1]~[11]中任一所記載的硬化體層，與具備導體層的基板之印刷配線板。 [13] 於前述硬化體層形成頂徑為15μm以下之貫通孔的[12]所記載的印刷配線板。 [14] 含有[1]~[11]中任一所記載的硬化體層之半導體裝置。[12] A printed wiring board having the cured body layer described in any one of [1] to [11] and a substrate provided with a conductor layer. [13] The printed wiring board described in [12] in which a through hole with a top diameter of 15 μm or less is formed in the cured body layer. [14] A semiconductor device including the hardened body layer described in any one of [1] to [11].

[15] 一種樹脂薄片，其為具有支持體，與無機填充材含有量為40質量%以上之樹脂組成物層的樹脂薄片，對於使前述樹脂組成物層進行硬化而形成硬化體層時之在前述硬化體層的主表面呈垂直的前述硬化體層之截面，對於自與前述支持體為相反側之前述硬化體層的主表面之距離而言，將自0μm至1μm為止的區域中之每單位面積的樹脂成分之面積作為A0-1 ，將自1μm至2μm為止的區域中之每單位面積的樹脂成分之面積作為A1-2 時，滿足 A0-1 /A1-2 ＞1.1者。 [16] 如[15]所記載的樹脂薄片，對於前述截面，對自與前述支持體為相反側的前述硬化體層之主表面的距離而言，將自0μm至0.5μm為止的區域中之每單位面積的樹脂成分之面積作為A0-0.5 ，將自0.5μm至1μm為止的區域中之每單位面積的樹脂成分之面積作為A0.5-1 時，滿足A0-0.5 / A0.5-1 ＞1.1者。 [17] 如[15]或[16]所記載的樹脂薄片，對於前述截面，對自與前述支持體為相反側的前述硬化體層之主表面的距離而言，自0.5μm至dμm為止的區域中之每單位面積的樹脂成分之面積作為A0.5-d ，將自dμm至0.5Dμm為止的區域中之每單位面積的樹脂成分之面積作為Ad-0.5D 時，滿足0.9≦A0.5-d /Ad-0.5D ≦1.1(其中，d為滿足0.5＜d＜0.5D的數，D為前述硬化體層的厚度)者。 [18] 前述樹脂組成物層含有環氧樹脂之[15]~[17]中任一所記載的樹脂薄片。 [19] 前述樹脂組成物層進一步含有活性酯系硬化劑之[18]所記載的樹脂薄片。 [20] 前述樹脂組成物層進一步含有氰酸酯系硬化劑，該含有量對於前述樹脂組成物層中之樹脂成分100質量%而言為15質量%以上之[18]或[19]所記載的樹脂薄片。 [21] 前述樹脂組成物層之氮原子含有量對於前述樹脂組成物層中之樹脂成分100質量%而言為1質量%以上之[15]~[20]中任一所記載的樹脂薄片。 [22] 如[15]~[21]中任一所記載的樹脂薄片，其中前述樹脂組成物層為，自前述支持體側依序具備以第1樹脂組成物所形成的第1層，與以具有與前述第1樹脂組成物相異的組成之第2樹脂組成物所形成的第2層者。 [23] 前述第2層的厚度為未達2μm之[22]所記載的樹脂薄片。 [24] 前述第2樹脂組成物之無機填充材含有量為未達20質量%之[22]或[23]所記載的樹脂薄片。 [25] 在使前述樹脂組成物層進行硬化而形成硬化體層後，欲將前述硬化體層提供於藉由選自含有O2 氣體及N2 氣體所成群的1種以上之氣體的電漿處理之[15]~[24]中任一所記載的樹脂薄片。[15] A resin sheet comprising a support and a resin composition layer having an inorganic filler content of 40% by mass or more. When the resin composition layer is cured to form a cured body layer, The main surface of the hardened body layer is perpendicular to the cross section of the hardened body layer. For the distance from the main surface of the hardened body layer opposite to the support, the resin per unit area in the area from 0 μm to 1 μm When the area of the component is A 0-1 and the area of the resin component per unit area in the region from 1 μm to 2 μm is A 1-2 , those satisfying A 0-1 /A 1-2 >1.1 are satisfied. [16] The resin sheet as described in [15], for the cross section, the distance from the main surface of the hardened body layer on the opposite side of the support to the area from 0 μm to 0.5 μm When the area of the resin component per unit area is A 0-0.5 and the area of the resin component per unit area in the area from 0.5 μm to 1 μm is A 0.5-1 , A 0-0.5 / A 0.5-1 is satisfied> 1.1. [17] The resin sheet as described in [15] or [16], with respect to the cross-section, the distance from the main surface of the cured body layer on the opposite side to the support from 0.5 μm to d μm Where the area of the resin component per unit area is A 0.5-d , and the area of the resin component per unit area in the area from dμm to 0.5Dμm is A d-0.5D , satisfying 0.9≦A 0.5-d /A d-0.5D ≦1.1 (where d is a number satisfying 0.5<d<0.5D and D is the thickness of the hardened body layer). [18] The resin composition layer contains the resin sheet according to any one of [15] to [17] of epoxy resin. [19] The resin composition layer further contains the resin sheet described in [18] of an active ester hardener. [20] The resin composition layer further contains a cyanate-based hardener, and the content thereof is as described in [18] or [19] of 15% by mass or more for 100% by mass of the resin component in the resin composition layer Resin sheet. [21] The nitrogen atom content of the resin composition layer is the resin sheet described in any one of [15] to [20] to 100% by mass of the resin component in the resin composition layer to be 1% by mass or more. [22] The resin sheet according to any one of [15] to [21], wherein the resin composition layer is provided with a first layer formed of the first resin composition in order from the support side, and The second layer is formed of a second resin composition having a composition different from that of the first resin composition. [23] The thickness of the second layer is the resin sheet described in [22] of less than 2 μm. [24] The resin sheet according to [22] or [23] in which the inorganic filler content of the second resin composition is less than 20% by mass. [25] After the resin composition layer is cured to form a cured body layer, the cured body layer is intended to be subjected to plasma treatment by one or more gases selected from the group consisting of O 2 gas and N 2 gas The resin sheet described in any of [15] to [24].

[26] 一種印刷配線板之製造方法，其為含有以下(A)~(D)的步驟者； (A)欲使含有無機填充材含有量為40質量%以上的樹脂組成物層之樹脂薄片，於最外層的至少一部分具備導體層的基板上，前述樹脂組成物層接合於前述基板的前述導體層側之面的層合步驟； (B)使前述樹脂組成物層進行硬化而形成硬化體層的步驟； (C)於前述硬化體層形成貫通孔之步驟； (D)對於前述硬化體層，進行藉由選自含有O2 氣體及N2 氣體所成群的1種以上的氣體之電漿處理的步驟； 對於在前述硬化體層的主表面呈垂直的前述硬化體層之截面，對於自前述導體層的距離而言，將自0μm至1μm為止的區域中之每單位面積的樹脂成分之面積作為A0-1 ，將自1μm至2μm為止的區域中之每單位面積的樹脂成分之面積作為A1-2 時，滿足A0-1 /A1-2 ＞1.1者。 [27] 如[26]所記載的印刷配線板之製造方法，對於前述截面，對於自前述導體層的距離而言，將自0μm至0.5μm為止的區域中之每單位面積的樹脂成分之面積作為A0-0.5 ，將自0.5μm至1μm為止的區域中之每單位面積的樹脂成分之面積作為A0.5-1 時，滿足A0-0.5 /A0.5-1 ＞1.1者。 [28] 如[26]或[27]所記載的印刷配線板之製造方法，對於前述截面，對於自前述導體層的距離而言，將自0.5μm至dμm為止的區域中之每單位面積的樹脂成分之面積作為A0.5-d ，將自dμm至0.5Dμm為止的區域中之每單位面積的樹脂成分之面積作為Ad-0.5D 時，滿足0.9≦A0.5-d / Ad-0.5D ≦1.1(其中，d為滿足0.5＜d＜0.5D的數，D為前述硬化體層的厚度)者。 [29] 前述樹脂組成物層含有環氧樹脂之[26]~[28]中任一所記載的印刷配線板之製造方法。 [30] 前述樹脂組成物層進一步含有活性酯系硬化劑之[29]所記載的印刷配線板之製造方法。 [31] 前述樹脂組成物層進一步含有氰酸酯系硬化劑，該含有量對於樹脂組成物中之樹脂成分100質量%而言為15質量%以上之[29]或[30]所記載的印刷配線板之製造方法。 [32] 前述樹脂組成物層之氮原子含有量對於樹脂組成物中之樹脂成分100質量%而言為1質量%以上之[26]~ [31]中任一所記載的印刷配線板之製造方法。 [33] 前述樹脂組成物層為具備以第1樹脂組成物所形成的第1層，與以具有與前述第1樹脂組成物相異的組成之第2樹脂組成物所形成的第2層之[26]~[32]中任一所記載的印刷配線板之製造方法。 [34] 前述第2層之厚度為未達2μm，前述第2層與前述基板接合之[33]所記載的印刷配線板之製造方法。 [35] 前述第2樹脂組成物之無機填充材含有量為未達20質量%之[33]或[34]所記載的印刷配線板之製造方法。 [36] (A)步驟含有將具有支持體，與形成於前述支持體上的前述樹脂組成物層之樹脂薄片，使前述樹脂組成物層接合於前述基板的前述導體層側之面的層合之[26]~[35]中任一所記載的印刷配線板之製造方法。 [37] 前述貫通孔的頂徑為15μm以下之[26]~[36]中任一所記載的印刷配線板之製造方法。 [38] (D)步驟為藉由O2 氣體進行電漿處理之步驟的[26]~[37]中任一所記載的印刷配線板之製造方法。 [39] 一種樹脂薄片之製造方法，其為具有支持體，與無機填充材含有量為40質量%以上之樹脂組成物層的樹脂薄片之製造方法，含有以下(α)之步驟； (α)於在前述支持體上所形成的第1樹脂組成物而形成的第1層上，形成以具有與前述第1樹脂組成物相異的組成之第2樹脂組成物所形成的第2層，得到樹脂組成物層之步驟； 對於使前述樹脂組成物層進行硬化而形成硬化體層時之在前述硬化體層的主表面呈垂直的前述硬化體層之截面，對於自與前述支持體為相反側之前述硬化體層的主表面之距離而言，將自0μm至1μm為止的區域中之每單位面積的樹脂成分之面積作為A0-1 ，將自1μm至2μm為止的區域中之每單位面積的樹脂成分之面積作為A1-2 時，滿足A0-1 / A1-2 ＞1.1者。 [40] 對於前述截面，對自與前述支持體為相反側的前述硬化體層之主表面的距離而言，將自0μm至0.5μm為止的區域中之每單位面積的樹脂成分之面積作為A0-0.5 ，將自0.5μm至1μm為止的區域中之每單位面積的樹脂成分之面積作為A0.5-1 時，滿足A0-0.5 /A0.5-1 ＞1.1之[39]所記載的樹脂薄片之製造方法。 [41] 對於前述截面，對自與前述支持體為相反側的前述硬化體層之主表面的距離而言，自0.5μm至dμm為止的區域中之每單位面積的樹脂成分之面積作為A0.5-d ，將自dμm至0.5Dμm為止的區域中之每單位面積的樹脂成分之面積作為Ad-0.5D 時，滿足0.9≦A0.5-d /Ad-0.5D ≦1.1(其中，d為滿足0.5＜d＜0.5D的數，D為前述硬化體層的厚度)之[39]或[40]所記載的樹脂薄片之製造方法。 [42] 前述樹脂組成物層含有環氧樹脂之[39]~[41]中任一所記載的樹脂薄片之製造方法。 [43] 前述樹脂組成物層進一步含有活性酯系硬化劑之[42]所記載的樹脂薄片之製造方法。 [44] 前述第2層的厚度為未達2μm之[39]~[43]中任一所記載的樹脂薄片之製造方法。 [45] 前述第2樹脂組成物之無機填充材含有量為未達20質量%之[39]~[44]中任一所記載的樹脂薄片之製造方法。 [46] 如[39]~[45]中任一所記載的樹脂薄片之製造方法，其中(α)步驟為含有： (α1)準備含有支持體，與於前述支持體上所形成的前述第1樹脂組成物所成的第1層之附有支持體的臨時樹脂薄片之步驟，及 (α2)於前述第1層上，塗布含有前述第2樹脂組成物之塗層液，經乾燥而形成第2層之步驟。 [47] 如[39]~[46]中任一所記載的樹脂薄片之製造方法，其中樹脂薄片為，於將前述樹脂組成物層進行硬化而形成硬化體層後，欲將前述硬化體層提供於藉由選自含有O2 氣體及N2 氣體所群的1種以上之氣體的電漿處理者。 [發明之效果][26] A method of manufacturing a printed wiring board, which includes the following steps (A) to (D); (A) a resin sheet containing a resin composition layer containing an inorganic filler content of 40% by mass or more , On a substrate provided with a conductor layer on at least a part of the outermost layer, a lamination step in which the resin composition layer is bonded to the surface of the substrate on the conductor layer side; (B) curing the resin composition layer to form a cured body layer Steps; (C) Steps for forming through holes in the hardened body layer; (D) Plasma treatment of the hardened body layer with one or more gases selected from the group consisting of O 2 gas and N 2 gas Steps: For the cross section of the hardened body layer that is perpendicular to the main surface of the hardened body layer, for the distance from the conductive layer, the area of the resin component per unit area in the area from 0 μm to 1 μm is taken as A 0-1 , when the area of the resin component per unit area in the area from 1 μm to 2 μm is regarded as A 1-2 , those satisfying A 0-1 /A 1-2 >1.1 are satisfied. [27] The method for manufacturing a printed wiring board according to [26], wherein the cross-section and the distance from the conductor layer are the areas of the resin component per unit area in the area from 0 μm to 0.5 μm As A 0-0.5 , when the area of the resin component per unit area in the region from 0.5 μm to 1 μm is taken as A 0.5-1 , A 0-0.5 /A 0.5-1 >1.1 is satisfied. [28] The method for manufacturing a printed wiring board as described in [26] or [27], for the cross section, the distance from the conductor layer to the unit area per unit area in the area from 0.5 μm to d μm The area of the resin component is A 0.5-d , and the area of the resin component per unit area in the area from dμm to 0.5Dμm is A d-0.5D , satisfying 0.9≦A 0.5-d / A d-0.5D ≦1.1 (where d is a number satisfying 0.5<d<0.5D, and D is the thickness of the hardened body layer). [29] The method for producing a printed wiring board according to any one of [26] to [28] in which the resin composition layer contains an epoxy resin. [30] The method for producing a printed wiring board described in [29] in which the resin composition layer further contains an active ester hardener. [31] The resin composition layer further contains a cyanate-based curing agent, the content of which is 15% by mass or more for the printing of the resin composition in the resin composition according to [29] or [30] Manufacturing method of wiring board. [32] The manufacture of the printed wiring board according to any one of [26] to [31] in which the nitrogen atom content of the resin composition layer is 1% by mass or more for 100% by mass of the resin component in the resin composition method. [33] The resin composition layer includes a first layer formed with a first resin composition and a second layer formed with a second resin composition having a composition different from that of the first resin composition [26] ~ [32] Any one of the methods of manufacturing printed wiring boards. [34] The thickness of the second layer is less than 2 μm, and the method of manufacturing the printed wiring board described in [33] where the second layer is bonded to the substrate. [35] The method for producing a printed wiring board according to [33] or [34] in which the content of the inorganic filler of the second resin composition is less than 20% by mass. [36] Step (A) includes laminating a resin sheet having a support and the resin composition layer formed on the support, and bonding the resin composition layer to the surface of the substrate on the side of the conductor layer The manufacturing method of printed wiring board described in any of [26]~[35]. [37] The method for manufacturing a printed wiring board according to any one of [26] to [36] whose top diameter of the through-hole is 15 μm or less. [38] Step (D) is a method of manufacturing a printed wiring board described in any one of [26] to [37] of the step of plasma treatment with O 2 gas. [39] A method of manufacturing a resin sheet, which is a method of manufacturing a resin sheet having a support and a resin composition layer having an inorganic filler content of 40% by mass or more, including the following steps (α); (α) Forming a second layer formed of a second resin composition having a composition different from the first resin composition on the first layer formed by the first resin composition formed on the support, to obtain A step of the resin composition layer; for the cross section of the hardened body layer that is perpendicular to the main surface of the hardened body layer when the hardened body layer is formed by hardening the resin composition layer, and for the hardening from the opposite side to the support For the distance of the main surface of the body layer, the area of the resin component per unit area in the area from 0 μm to 1 μm is regarded as A 0-1 , and the area of the resin component per unit area in the area from 1 μm to 2 μm When the area is A 1-2 , A 0-1 / A 1-2 > 1.1 is satisfied. [40] For the cross section, the distance from the main surface of the hardened body layer on the opposite side to the support is the area of the resin component per unit area in the area from 0 μm to 0.5 μm as A 0 -0.5 , when the area of the resin component per unit area in the area from 0.5 μm to 1 μm is regarded as A 0.5-1 , the resin sheet described in [39] of A 0-0.5 /A 0.5-1 >1.1 is satisfied Of manufacturing methods. [41] For the cross section, the distance from the main surface of the hardened body layer on the opposite side to the support is the area of the resin component per unit area in the area from 0.5 μm to d μm as A 0.5- d , when the area of the resin component per unit area in the area from dμm to 0.5Dμm is taken as A d-0.5D , satisfy 0.9≦A 0.5-d /A d-0.5D ≦1.1 (where d is 0.5<d<0.5D, D is the thickness of the hardened body layer) [39] or [40] The method for producing the resin sheet. [42] The method for producing a resin sheet according to any one of [39] to [41] in which the resin composition layer contains an epoxy resin. [43] The method for producing a resin sheet described in [42] in which the resin composition layer further contains an active ester hardener. [44] The method for producing a resin sheet according to any one of [39] to [43] in which the thickness of the second layer is less than 2 μm. [45] The method for producing a resin sheet according to any one of [39] to [44] in which the content of the inorganic filler of the second resin composition is less than 20% by mass. [46] The method for producing a resin sheet as described in any one of [39] to [45], wherein the step (α) includes: (α1) preparing to contain a support, and the above-mentioned first formed on the support 1 The step of forming a temporary resin sheet with a support in the first layer of the resin composition, and (α2) applying the coating liquid containing the second resin composition on the first layer and drying to form Steps for layer 2. [47] The method of manufacturing a resin sheet as described in any one of [39] to [46], wherein the resin sheet is to provide the hardened body layer after hardening the resin composition layer to form a hardened body layer A plasma processor selected from one or more gases selected from the group consisting of O 2 gas and N 2 gas. [Effect of invention]

依據本發明提供：對於除污跡處理，即使使用無機填充材的除去能為低之藉由N2 氣體或O2 氣體的電漿，亦可充分地確保污跡除去性之硬化體層；具備前述硬化體層的印刷配線板及其製造方法；具備前述硬化體層的半導體裝置；可得到前述硬化體層之樹脂薄片及其製造方法。According to the present invention, it is provided that, for the stain removal treatment, even if the removal energy of the inorganic filler is low, the plasma with N 2 gas or O 2 gas can sufficiently ensure the stain removal hardened body layer; The printed wiring board of the hardened body layer and the manufacturing method thereof; the semiconductor device provided with the hardened body layer; the resin sheet capable of obtaining the hardened body layer and the manufacturing method thereof.

[實施發明的型態][Type of implementation of invention]

以下將本發明以該適當的實施型態進行詳細說明。但，本發明並非限定於下述實施型態及例示物者，未脫離本發明之申請專利範圍及其均等範圍的範圍下可任意地變更而實施。Hereinafter, the present invention will be described in detail in this appropriate embodiment. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily changed and implemented without departing from the scope of the patent application of the present invention and its equivalent range.

＜硬化體層之概要＞ 圖1表示以模型方式表示本發明之一實施型態中之硬化體層100的截面之截面圖。於圖1所示的硬化體層100可設置於具備導體層210之基板200的前述導體層210側之面210U上。其中，圖1中不僅表示硬化體層100，亦表示具備導體層210之基板200。<Summary of hardened body layer> FIG. 1 shows a cross-sectional view showing in a model manner the cross-section of a hardened body layer 100 in an embodiment of the present invention. The hardened body layer 100 shown in FIG. 1 may be provided on the surface 210U of the substrate 200 provided with the conductor layer 210 on the conductor layer 210 side. In FIG. 1, not only the hardened body layer 100 but also the substrate 200 provided with the conductor layer 210 are shown.

於圖1所示本發明之一實施型態中的硬化體層100為，以無機填充材含有量為40質量%以上之樹脂組成物的硬化物所形成。該硬化體層100為，設置在具備導體層210之基板200的導體層210側之面210U上。又，導體層210係以作為基板200之最外層的至少一部分而設置。因此，硬化體層100的至少一部分設置於導體層210上。The cured body layer 100 in one embodiment of the present invention shown in FIG. 1 is formed of a cured product of a resin composition having an inorganic filler content of 40% by mass or more. The hardened body layer 100 is provided on the surface 210U of the substrate 200 provided with the conductor layer 210 on the conductor layer 210 side. In addition, the conductor layer 210 is provided as at least a part of the outermost layer of the substrate 200. Therefore, at least a part of the hardened body layer 100 is provided on the conductor layer 210.

對於在硬化體層100之主表面(於此為硬化體層100的導體層210側之面)100D上呈垂直的硬化體層100之截面，對自導體層210的距離而言，將自0μm至1μm為止的區域110中之每單位面積的樹脂成分之面積作為A0-1 。又，對於在硬化體層100的主表面100D上呈垂直的硬化體層100之截面，對自導體層210的距離而言，將自1μm至2μm為止的區域120中之每單位面積的樹脂成分之面積作為A1-2 。此時，硬化體層100為滿足A0-1 /A1-2 ＞1.1(以下亦稱為「條件(1)」)。For the cross section of the hardened body layer 100 that is perpendicular to the main surface of the hardened body layer 100 (here, the surface of the hardened body layer 100 on the conductor layer 210 side) 100D, the distance from the conductive layer 210 will be from 0 μm to 1 μm The area of the resin component per unit area in the area 110 is regarded as A 0-1 . In addition, the cross section of the cured body layer 100 perpendicular to the main surface 100D of the cured body layer 100 is the area of the resin component per unit area in the region 120 from 1 μm to 2 μm in terms of the distance from the conductor layer 210 As A 1-2 . At this time, the hardened body layer 100 satisfies A 0-1 /A 1-2 &gt; 1.1 (hereinafter also referred to as "condition (1)").

對於本說明書，所謂「樹脂成分」表示構成樹脂組成物之成分中，除去無機填充材之成分。所謂「每單位面積之樹脂成分的面積」表示在硬化體層100之截面的每單位面積中之樹脂成分所佔面積。For the purpose of this specification, the "resin component" means a component excluding the inorganic filler among the components constituting the resin composition. The “area of the resin component per unit area” means the area occupied by the resin component per unit area of the cross section of the cured body layer 100.

條件(1)表示：對自導體層210的距離而言，自0μm至1μm為止的區域110，與自1μm至2μm為止的區域120相比較，樹脂成分之面積較大，且無機填充材的量較少者。The condition (1) indicates that the distance from the conductor layer 210 to the area 110 from 0 μm to 1 μm is larger than the area 120 from 1 μm to 2 μm, the area of the resin component is larger, and the amount of the inorganic filler Less.

條件(1)由可充分地確保污跡除去性之觀點來看，以A0-1 /A1-2 ＞1.13者為佳，以A0-1 /A1-2 ＞1.15者為較佳，以A0-1 /A1-2 ＞1.2者為更佳。The condition (1) is from the viewpoint of sufficiently ensuring the stain removability, preferably A 0-1 /A 1-2 >1.13, preferably A 0-1 /A 1-2 >1.15 , A 0-1 /A 1-2 >1.2 is better.

且，對於在硬化體層100的主表面100D上呈垂直的硬化體層100之截面，對自導體層210的距離而言，將自0μm至0.5μm為止的區域130中之每單位面積的樹脂成分之面積作為A0-0.5 。又，對於在硬化體層100的主表面100D上呈垂直的硬化體層100之截面，對自導體層210的距離而言，將自0.5μm至1μm為止的區域140中之每單位面積之樹脂成分的面積作為A0.5-1 。此時，硬化體層100為滿足A0-0.5 /A0.5-1 ＞1.1(以下亦稱為「條件(2)」)者為佳。In addition, with regard to the cross section of the cured body layer 100 that is perpendicular to the main surface 100D of the cured body layer 100, the distance from the conductor layer 210 is the resin component per unit area in the region 130 from 0 μm to 0.5 μm The area is referred to as A 0-0.5 . In addition, for the cross section of the cured body layer 100 that is perpendicular to the main surface 100D of the cured body layer 100, the distance from the conductor layer 210 is the resin component per unit area in the region 140 from 0.5 μm to 1 μm. The area is referred to as A 0.5-1 . At this time, it is preferable that the cured body layer 100 satisfies A 0-0.5 /A 0.5-1 &gt; 1.1 (hereinafter also referred to as "condition (2)").

條件(2)表示：對離導體層210的距離而言，自0μm至0.5μm為止的區域130，與自0.5μm至1μm為止的區域140相比較，樹脂成分之面積較大，且無機填充材之量較少。Condition (2) indicates that the area 130 from 0 μm to 0.5 μm has a larger area of the resin component than the area 140 from 0.5 μm to 1 μm, and the inorganic filler The amount is less.

條件(2)由可充分地確保污跡除去性的觀點來看，以A0-0.5 /A0.5-1 ＞1.13者為佳，以A0-0.5 /A0.5-1 ＞1.15為較佳，以A0-0.5 /A0.5-1 ＞1.2者為更佳。The condition (2) is preferably A 0-0.5 /A 0.5-1 &gt; 1.13, and preferably A 0-0.5 /A 0.5-1 &gt; 1.15, from the viewpoint of sufficiently ensuring the stain removability. A 0-0.5 /A 0.5-1 >1.2 is better.

圖2表示以模型方式表示本發明之一實施型態中之硬化體層100的截面之截面圖。該圖2中表示於硬化體層100形成貫通孔300後，進行除污跡處理之前的狀態。FIG. 2 shows a cross-sectional view showing in a model manner the cross-section of the hardened body layer 100 in an embodiment of the present invention. FIG. 2 shows a state before the through-hole 300 is formed after the through-hole 300 is formed in the cured body layer 100.

如圖2所示，若於硬化體層100形成貫通孔300時，於該貫通孔300之側面300S上會產生污跡310。貫通孔300之徑，一般為越接近導體層210越小。藉此，假如於接近導體層210的貫通孔300之底部320上有污跡310殘留時，貫通孔300會塞住，可能成為導通不良之原因。藉此，如此貫通孔300之底部320的污跡310藉由除污跡處理而除去為佳。但若污跡310含有大量無機填充材時，作為使用如N2 氣體及O2 氣體的未含氟之氣體的電漿處理之除污跡處理中，難充分地去除污跡310。As shown in FIG. 2, when a through hole 300 is formed in the hardened body layer 100, a stain 310 will be generated on the side surface 300S of the through hole 300. The diameter of the through hole 300 generally decreases as it approaches the conductor layer 210. In this way, if the stain 310 remains on the bottom 320 of the through hole 300 close to the conductor layer 210, the through hole 300 may be plugged, which may be a cause of poor conduction. Therefore, it is preferable that the stain 310 of the bottom 320 of the through hole 300 is removed by the stain removal process. However, if the stain 310 contains a large amount of inorganic filler, it is difficult to sufficiently remove the stain 310 in the stain removal process of plasma treatment using a non-fluorine-containing gas such as N 2 gas and O 2 gas.

相對於此，有關本實施型態之硬化體層100，因滿足條件(1)或除滿足條件(1)外亦滿足條件(2)，故在導體層210之附近區域中，無機填充材的量為相對性地少，依據自導體層210的距離，隨著連續或階段性梯度，無機填充材之比例上升。因此，在形成於硬化體層100的貫通孔300內，形成於底部320的污跡310所含的無機填充材之量為少。因此，即使在使用作為絕緣層的添加高量無機填充材之硬化體層100之情況下，亦可將產生於貫通孔300的污跡310，經由無機填充材之除去能低的藉由N2 氣體或O2 氣體的電漿而有效果地除去。因此，即使不使用氟系氣體，亦可達成良好污跡除去性。In contrast, in the hardened body layer 100 of the present embodiment, the condition (1) is satisfied or the condition (2) is satisfied in addition to the condition (1). Therefore, in the vicinity of the conductor layer 210, the amount of the inorganic filler To be relatively small, according to the distance from the conductor layer 210, the proportion of the inorganic filler increases with a continuous or stepwise gradient. Therefore, in the through hole 300 formed in the hardened body layer 100, the amount of the inorganic filler contained in the stain 310 formed in the bottom 320 is small. Therefore, even in the case where the hardened body layer 100 added with a high amount of inorganic filler as an insulating layer is used, the stain 310 generated in the through-hole 300 can be removed through the inorganic filler by N 2 gas with low energy Or the plasma of O 2 gas is effectively removed. Therefore, even if a fluorine-based gas is not used, good stain removal can be achieved.

圖3係將作為本發明之一實施型態的硬化體層100之截面以模型方式表示的截面圖。如圖3所示，對於在硬化體層100之主表面100D呈垂直的硬化體層100之截面，對自導體層210的距離而言，將自0.5μm至dμm為止的區域150中之每單位面積的樹脂成分之面積作為A0.5-d 。又，對於在硬化體層100的主表面100D呈垂直的硬化體層100之截面，對自導體層210的距離而言，將自dμm至0.5Dμm為止的區域160中之每單位面積的樹脂成分之面積作為Ad-0.5D 。此時，滿足0.9≦A0.5-d /Ad-0.5D ≦1.1(以下亦稱為「條件(3)」)者為佳。其中，d為滿足0.5＜d＜0.5D的數，D為硬化體層100之厚度。FIG. 3 is a cross-sectional view showing a modeled cross-section of a hardened body layer 100 which is one embodiment of the present invention. As shown in FIG. 3, for the cross section of the hardened body layer 100 that is perpendicular to the main surface 100D of the hardened body layer 100, the distance per unit area in the region 150 from 0.5 μm to d μm for the distance from the conductor layer 210 The area of the resin component is A 0.5-d . In addition, the cross-section of the cured body layer 100 perpendicular to the main surface 100D of the cured body layer 100 is the area of the resin component per unit area in the area 160 from d μm to 0.5 D μm in terms of the distance from the conductor layer 210 As Ad-0.5D . In this case, it is preferable to satisfy 0.9≦A 0.5-d /A d-0.5D ≦1.1 (hereinafter also referred to as “condition (3)”). Here, d is a number that satisfies 0.5<d<0.5D, and D is the thickness of the hardened body layer 100.

條件(3)表示：對離導體層100的一定距離以上時，無機填充材與樹脂成分之量比的變化會消失，成為具有相對性均勻的組成之相。Condition (3) indicates that when the distance from the conductor layer 100 is greater than a certain distance, the change in the ratio of the amount of the inorganic filler to the resin component disappears, and it becomes a phase having a relatively uniform composition.

條件(3)係以0.92≦A0.5-d /Ad-0.5D ≦1.08者為佳，以0.95≦A0.5-d /Ad-0.5D ≦1.05者為較佳，以0.98≦A0.5-d /Ad-0.5D ≦1.02者為更佳。Condition (3) is preferably 0.92≦A 0.5-d /A d-0.5D ≦1.08, preferably 0.95≦A 0.5-d /A d-0.5D ≦1.05, preferably 0.98≦A 0.5- d /A d-0.5D ≦1.02 is better.

藉由滿足條件(3)，因在導體層210附近之有限區域中具有急激的組成梯度，不僅可確保高剝離強度，亦可確保充分的污跡除去性。By satisfying the condition (3), since there is a sharp composition gradient in a limited area near the conductor layer 210, not only can a high peel strength be ensured, but also sufficient stain removability can be ensured.

硬化體層100的厚度D，由即使印刷配線板的薄型化，及該樹脂組成物之硬化物為薄膜，亦可提供絕緣性優良的硬化物之觀點來看，以50μm以下為佳，較佳為40μm以下。硬化體層100之厚度D的下限雖無特別限定，通常為5μm以上等。The thickness D of the cured body layer 100 is preferably 50 μm or less from the viewpoint of providing a cured product with excellent insulation even if the printed wiring board is thinned and the cured product of the resin composition is a thin film. Below 40μm. Although the lower limit of the thickness D of the cured body layer 100 is not particularly limited, it is usually 5 μm or more.

如前述，硬化體層100為顯示藉由使用N2 氣體或O2 氣體的電漿處理之污跡除去性優良的特性。前述污跡除去性可藉由最大污跡長度進行評估。作為最大污跡長度，以未達5μm者為佳，以未達3μm者為較佳，以未達2μm者為更佳。所謂「最大污跡長度」表示自貫通孔的底面圓周至圓中心的污跡之最大長度。前述最大污跡長度的評估可依據後述實施例所記載的方法而進行測定。As described above, the hardened body layer 100 exhibits excellent stain removal properties by plasma treatment using N 2 gas or O 2 gas. The aforementioned stain removability can be evaluated by the maximum stain length. The maximum smear length is preferably less than 5 μm, preferably less than 3 μm, and more preferably less than 2 μm. The so-called "maximum stain length" means the maximum length of the stain from the circumference of the bottom surface of the through hole to the center of the circle. The evaluation of the aforementioned maximum stain length can be measured according to the method described in the examples described later.

又，硬化體層100為顯示與導體層210之間的剝離強度在高水準下獲得之特性者。作為剝離強度，雖非無特別限定者，以0.40 kgf/cm以上為佳，較佳為0.50 kgf/cm以上，更佳為0.55 kgf/cm以上。另一方面，上限值可為5 kgf/cm以下等。剝離強度可依據後述實施例所記載的方法進行測定。In addition, the hardened body layer 100 exhibits characteristics obtained at a high level in peel strength with the conductor layer 210. Although the peel strength is not particularly limited, it is preferably 0.40 kgf/cm or more, preferably 0.50 kgf/cm or more, and more preferably 0.55 kgf/cm or more. On the other hand, the upper limit may be 5 kgf/cm or less. The peel strength can be measured according to the method described in the examples described below.

在某實施型態中，硬化體層為藉由自與前述基板相反側依序具備以第1樹脂組成物的硬化物所形成的第1硬化體層，與以第2樹脂組成物的硬化物所形成的第2硬化體層而滿足條件(1)(以下亦稱為「層狀梯度型」)。此時，將形成與具備導體層的基板接合的側之第2硬化體層的第2樹脂組成物之無機填充材含有量，設定成比第1樹脂組成物之無機填充材含有量低時，可提高導體層附近區域之樹脂成分的面積。第2硬化體層的厚度雖僅可得到本發明之所望效果即可而未限定，但以未達2μm為佳，較佳為未達1.5μm，更佳為1μm，特佳為0.8μm。對於在該實施型態中之第2樹脂組成物的無機填充材含有量，在以下詳述。在該實施型態中，硬化體層並未限定於含有第1硬化體層與第2硬化體層所成的2層型態，亦可為3層以上的硬化體層。因此，硬化體層亦可進一步具備，以具有與第1及2樹脂組成物相異的組成之樹脂組成物的硬化物所形成的硬化體層。In a certain embodiment, the hardened body layer is formed by sequentially including a first hardened body layer formed of a hardened body of the first resin composition and a hardened body of the second resin composition from the opposite side of the substrate The second hardened body layer satisfies the condition (1) (hereinafter also referred to as "layered gradient type"). In this case, when the content of the inorganic filler of the second resin composition forming the second cured body layer on the side joined to the substrate provided with the conductor layer is set to be lower than the content of the inorganic filler of the first resin composition, Increase the area of the resin component in the vicinity of the conductor layer. Although the thickness of the second hardened body layer is not limited as long as the desired effect of the present invention is obtained, it is preferably less than 2 μm, preferably less than 1.5 μm, more preferably 1 μm, and particularly preferably 0.8 μm. The content of the inorganic filler in the second resin composition in this embodiment will be described in detail below. In this embodiment mode, the hardened body layer is not limited to the two-layer type formed by the first hardened body layer and the second hardened body layer, and may be a hardened body layer of three or more layers. Therefore, the cured body layer may be further provided with a cured body layer formed of a cured product of a resin composition having a composition different from that of the first and second resin compositions.

在其他實施型態中，硬化體層為在具備導體層的基板上使組成均質的樹脂組成物進行硬化而得之硬化體層，藉由在導體層附近區域具有不均勻組成而滿足條件(1)之硬化體層(以下亦稱為「導體層附近梯度型」)。盡可能滿足條件(1)而非特別限定者，但例如藉由於樹脂組成物中含有一定量氰酸酯系硬化劑等含有氮之成分時，可得到導體層附近梯度型之硬化體層。對於氰酸酯系硬化劑之具體例子或含有量等，在以下詳述。在該實施型態中，硬化體層可為一層，亦可為複數層。即，亦可為組合層狀梯度型與導體層附近梯度型之型態。In other embodiments, the hardened body layer is a hardened body layer obtained by hardening a homogeneous resin composition on a substrate provided with a conductor layer, and the condition (1) is satisfied by having an uneven composition in the vicinity of the conductor layer Hardened body layer (hereinafter also referred to as "gradient type near conductor layer"). The condition (1) is satisfied as much as possible without being particularly limited, but, for example, when a certain amount of a nitrogen-containing component such as a cyanate-based hardener is contained in the resin composition, a gradient-type hardened body layer near the conductor layer can be obtained. Specific examples and content of the cyanate ester hardener will be described in detail below. In this embodiment, the hardened body layer may be one layer or a plurality of layers. In other words, a layered gradient type and a gradient type near the conductor layer may be combined.

＜每單位面積的樹脂成分之面積＞ 每單位面積的樹脂成分之面積，可藉由後述[樹脂面積比之測定]所記載的方法而測定及算出。具體而言，可藉由(1)欲使於硬化體層的主表面上露出垂直截面而進行截面露出，製作出截面試料，及(2)將截面試料以掃描電子顯微鏡(SEM)觀察，對於所得之SEM像進行圖像解析後求得樹脂面積而測定。<area of resin component per unit area> The area of the resin component per unit area can be measured and calculated by the method described in [Measurement of Resin Area Ratio] described later. Specifically, a cross-sectional sample can be prepared by (1) exposing a vertical cross-section on the main surface of the hardened body layer to produce a cross-sectional sample, and (2) observing the cross-sectional sample with a scanning electron microscope (SEM). The SEM image was subjected to image analysis to determine and measure the resin area.

在圖像解析中，將樹脂成分部分與無機填充材部分進行二進制化，將樹脂成分部分的像素數作為樹脂面積使用。又，對於樹脂面積之測定，將測定區域的寬度(例如，於硬化體層主表面的平行方向中之測定距離)設定為相等。In image analysis, the resin component portion and the inorganic filler portion are binarized, and the number of pixels of the resin component portion is used as the resin area. In addition, for the measurement of the resin area, the width of the measurement area (for example, the measurement distance in the parallel direction of the main surface of the cured body layer) is set to be equal.

雖為理所當然，但在測定樹脂面積之比時，必須擔保圖像解析之精度而進行條件之校正(calibration)。該校正為可藉由設定二進制化閾值而使(無機填充材部分之像素數)/(截面試料之截面的全像素數)×100之值與截面試料之無機填充材的體積%值成為實質上一致而實施。Although it is a matter of course, when measuring the ratio of the resin area, it is necessary to ensure the accuracy of image analysis and calibration of the conditions. The correction is such that by setting the binarization threshold, the value of (the number of pixels of the inorganic filler part)/(the total number of pixels of the cross section of the cross-sectional sample) × 100 and the volume% value of the inorganic filler of the cross-sectional sample become substantially Implement in unison.

＜樹脂組成物＞ 樹脂組成物為含有樹脂成分及(A)無機填充材。樹脂組成物以含有作為樹脂成分之(B)環氧樹脂者為佳。樹脂組成物除(A)成分及(B)成分以外，亦可進一步含有任意成分。作為任意成分，例如可舉出(C)硬化劑、(D)熱可塑性樹脂、(E)有機填充材、(F)難燃劑、(G)硬化促進劑、(H)其他添加劑等。以下對於含於樹脂組成物的各成分做詳細說明。<Resin composition> The resin composition contains a resin component and (A) an inorganic filler. The resin composition preferably contains (B) epoxy resin as a resin component. The resin composition may contain arbitrary components other than (A) component and (B) component. Examples of optional components include (C) hardeners, (D) thermoplastic resins, (E) organic fillers, (F) flame retardants, (G) hardening accelerators, (H) other additives, and the like. Hereinafter, each component contained in the resin composition will be described in detail.

＜(A)無機填充材＞ 樹脂組成物為，對於樹脂組成物中之不揮發成分100質量%，含有(A)成分40質量%以上。對於樹脂組成物中之(A)成分，不僅在樹脂組成物全體中使其均勻含有，對於樹脂組成物全體而言亦使其中含有(A)成分40質量%以上。<(A) inorganic filler> The resin composition contains 100% by mass of the non-volatile component in the resin composition and contains 40% by mass or more of the component (A). The component (A) in the resin composition is not only contained uniformly in the entire resin composition, but also contained in the entire resin composition (A) component in an amount of 40% by mass or more.

(A)無機填充材的材料雖無特別限定，例如可舉出二氧化矽、氧化鋁、玻璃、堇青石、矽酸化物、硫酸鋇、碳酸鋇、滑石、黏土、雲母粉、氧化鋅、水滑石、勃姆石、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，以二氧化矽為特佳。作為二氧化矽，例如可舉出無定形二氧化矽、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。又，作為二氧化矽以球形二氧化矽為佳。無機填充材單獨使用1種，亦可組合2種以上後使用。(A) The material of the inorganic filler is not particularly limited, and examples thereof include silica, alumina, glass, cordierite, silicate, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, and water. Talc, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, titanium Magnesium acid, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc., especially silicon dioxide. Examples of silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, hollow silicon dioxide, and the like. Furthermore, spherical silica is preferred as silica. One type of inorganic filler is used alone, or two or more types may be used in combination.

作為(A)無機填充材之販賣品，例如可舉出電化化學工業公司製之「UFP-30」；新日鐵住金Materials公司製之「SP60-05」、「SP507-05」；Admatechs公司製之「YC100C」、「YA050C」、「YA050C-MJE」、「YA010C」；Denka公司製之「UFP-30」；Tokuyama公司製之「SilfirNSS-3N」、「SilfirNSS-4N」、「SilfirNSS-5N」；Admatechs公司製之「SC2500SQ」、「SO-C4」、「SO-C2」、「SO-C1」等。Examples of (A) sales of inorganic fillers include "UFP-30" manufactured by Denka Chemical Industry Corporation; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Materials Corporation; manufactured by Admatechs Corporation "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" made by Denka; "SilfirNSS-3N", "SilfirNSS-4N", "SilfirNSS-5N" made by Tokuyama ; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", etc. manufactured by Admatechs.

無機填充材之平均粒徑以4μm以下為佳，較佳為3μm以下，更佳為2.5μm以下，更較佳為2μm以下，特佳為1μm以下，0.7μm以下。無機填充材的平均粒徑之下限，以0.01μm以上為佳，較佳為0.03μm以上，更佳為0.05μm以上、0.07μm以上或0.1μm以上。無機填充材之平均粒徑可藉由依據米氏(Mie)散射理論的雷射衍射•散射法而測定。具體而言，藉由雷射衍射散射式粒徑分布測定裝置，將無機填充材的粒徑分布以體積做基準而作成，將該中位直徑作為平均粒徑而可測定。測定試樣為使用將無機填充材100mg、甲基乙基酮10g秤取於樣品瓶中以超音波進行10分鐘分散者。將測定試樣，使用雷射衍射式粒徑分布測定裝置，將使用的光源波長設定為藍色及紅色，以流動池方式測定無機填充材之體積基準的粒徑分布，由所得之粒徑分布算出作為中位直徑的平均粒徑。作為雷射衍射式粒徑分布測定裝置，例如可舉出堀場製作所公司製「LA-960」等。The average particle diameter of the inorganic filler is preferably 4 μm or less, preferably 3 μm or less, more preferably 2.5 μm or less, more preferably 2 μm or less, particularly preferably 1 μm or less, 0.7 μm or less. The lower limit of the average particle diameter of the inorganic filler is preferably 0.01 μm or more, preferably 0.03 μm or more, more preferably 0.05 μm or more, 0.07 μm or more, or 0.1 μm or more. The average particle diameter of the inorganic filler can be determined by the laser diffraction/scattering method according to the Mie scattering theory. Specifically, with a laser diffraction scattering type particle size distribution measuring device, the particle size distribution of the inorganic filler is made on a volume basis, and the median diameter can be measured as the average particle size. The measurement sample was obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a sample bottle and dispersing it with ultrasound for 10 minutes. The measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelength of the light source used is set to blue and red, and the volume-based particle size distribution of the inorganic filler is measured by a flow cell method. The average particle diameter as the median diameter was calculated. As a laser diffraction type particle size distribution measuring apparatus, for example, "LA-960" manufactured by HORIBA, Ltd. can be cited.

作為無機填充材，由提高耐濕性及分散性之觀點來看，以藉由胺基矽烷系偶合劑、環氧矽烷系偶合劑、巰基矽烷系偶合劑、烷氧基矽烷化合物、有機矽氮烷化合物、鈦酸鹽系偶合劑等1種以上的表面處理劑進行處理者為佳。作為表面處理劑的販賣品，例如可舉出信越化學工業公司製「KBM403」(3-環氧丙氧基丙基三甲氧基矽烷)、信越化學工業公司製「KBM803」(3-巰基丙基三甲氧基矽烷)、信越化學工業公司製「KBE903」(3-胺基丙基三乙氧基矽烷)、信越化學工業公司製「KBM573」(N-苯基-3-胺基丙基三甲氧基矽烷)、信越化學工業公司製「SZ-31」(六甲基二矽氮烷)、信越化學工業公司製「KBM103」(苯基三甲氧基矽烷)、信越化學工業公司製「KBM-4803」(長鏈環氧型矽烷偶合劑)、信越化學工業公司製「KBM-7103」(3,3,3-三氟丙基三甲氧基矽烷)等。As an inorganic filler, from the viewpoint of improving moisture resistance and dispersibility, by means of an aminosilane coupling agent, epoxy silane coupling agent, mercaptosilane coupling agent, alkoxysilane compound, organic silicon nitrogen One or more surface treatment agents such as alkane compounds and titanate-based coupling agents are preferred. Examples of sales of surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-mercaptopropyl) manufactured by Shin-Etsu Chemical Co., Ltd. (Trimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyl trimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803 "(Long-chain epoxy type silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

藉由表面處理劑的表面處理之程度，由無機填充材之分散性提高的觀點來看，控制在所定範圍者為佳。具體而言，無機填充材100質量份以0.2質量份~5質量份的表面處理劑進行表面處理者為佳，以0.2質量份~3質量份進行表面處理者為佳，以0.3質量份~2質量份進行表面處理者為佳。From the viewpoint of improving the dispersibility of the inorganic filler by the degree of surface treatment by the surface treatment agent, it is preferably controlled within a predetermined range. Specifically, it is preferred that 100 parts by mass of the inorganic filler be subjected to surface treatment with a surface treatment agent of 0.2 parts by mass to 5 parts by mass, and those subject to surface treatment with 0.2 parts by mass to 3 parts by mass, preferably 0.3 parts by mass to 2 It is better if the surface is treated by mass.

藉由表面處理劑的表面處理之程度，可藉由無機填充材之每單位表面積的碳量進行評估。無機填充材的美單位表面積之碳量，由無機填充材之分散性提高的觀點來看，以0.02 mg/m2 以上為佳，以0.1 mg/m2 以上為較佳，以0.2 mg/m2 以上為更佳。另一方面，由防止樹脂塗漆的熔融黏度或在薄片型態的熔融黏度提高的觀點來看，以1 mg/m2 以下為佳，以0.8 mg/m2 以下為較佳，以0.5 mg/m2 以下為更佳。The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, preferably 0.1 mg/m 2 or more, and 0.2 mg/m from the viewpoint of improving the dispersibility of the inorganic filler. 2 or more is better. On the other hand, from the viewpoint of preventing the increase of the melt viscosity of the resin coating or the melt viscosity in the form of a sheet, it is preferably 1 mg/m 2 or less, preferably 0.8 mg/m 2 or less, and 0.5 mg /m 2 or less is better.

無機填充材的每單位表面積之碳量為，將表面處理後的無機填充材藉由溶劑(例如，甲基乙基酮(MEK))進行洗淨處理後測定。具體而言，將充分量的作為溶劑之MEK加入於以表面處理劑進行表面處理的無機填充材，在25℃進行5分鐘超音波洗淨。除去上清液，乾燥固體成分後，使用碳分析計可測定出無機填充材的每單位表面積之碳量。作為碳分析計，可使用堀場製作所公司製「EMIA-320V」等。The amount of carbon per unit surface area of the inorganic filler is measured by washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic washing is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. can be used.

(A)無機填充材的比表面積，由可進一步提高本發明之效果的觀點來看，以1 m2 /g以上為佳，較佳為1.5 m2 /g以上，特佳為2 m2 /g以上。上限雖無特別限制，以50 m2 /g以下、45 m2 /g以下或40 m2 /g以下為佳。無機填充材的比表面積，依據BET法，使用比表面積測定裝置(Mountech公司製Macsorb HM-1210)，於試料表面使氮氣吸附，使用BET多點法而算出比表面積而得到。(A) From the viewpoint of further improving the effect of the present invention, the specific surface area of the inorganic filler is preferably 1 m 2 /g or more, preferably 1.5 m 2 /g or more, and particularly preferably 2 m 2 / g or more. Although the upper limit is not particularly limited, it is preferably 50 m 2 /g or less, 45 m 2 /g or less, or 40 m 2 /g or less. The specific surface area of the inorganic filler is obtained by using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, adsorbing nitrogen gas on the surface of the sample, and calculating the specific surface area using the BET multipoint method.

對於樹脂組成物全體的(A)無機填充材之含有量，當樹脂組成物中之不揮發成分作為100質量%時，由得到線熱膨張係數及介電損耗正切低之硬化物的觀點來看，以45質量%以上為佳，較佳為50質量%以上，55質量%以上。該上限由所得的硬化物之機械強度的觀點來看，以90質量%以下為佳，較佳為85質量%以下，更佳為80質量%以下。Regarding the content of the (A) inorganic filler in the entire resin composition, when the non-volatile content in the resin composition is 100% by mass, from the viewpoint of obtaining a hardened product having a low linear thermal expansion coefficient and a low dielectric loss tangent It is preferably 45% by mass or more, preferably 50% by mass or more, and 55% by mass or more. From the viewpoint of the mechanical strength of the obtained cured product, the upper limit is preferably 90% by mass or less, preferably 85% by mass or less, and more preferably 80% by mass or less.

硬化體層為含有第1硬化體層與第2硬化體層的2層所成層狀梯度型時，樹脂組成物全體之(A)無機填充材的含有量F可藉由以下式子計算出。 F(質量%)=(F1 L1 +F2 L2 )/(L1 +L2 ) (式中，F1 表示第1樹脂組成物的無機填充材之含有量(質量%)，F2 表示第2樹脂組成物的無機填充材之含有量(質量%)，L1 表示硬化前的第1樹脂組成物之厚度，L2 表示硬化前的第2樹脂組成物之厚度)When the cured body layer is a layered gradient type composed of two layers including the first cured body layer and the second cured body layer, the content F of the (A) inorganic filler in the entire resin composition can be calculated by the following formula. F (mass %)=(F 1 L 1 +F 2 L 2 )/(L 1 +L 2 ) (where F 1 represents the content (mass %) of the inorganic filler of the first resin composition, F 2 represents the content (% by mass) of the inorganic filler of the second resin composition, L 1 represents the thickness of the first resin composition before curing, and L 2 represents the thickness of the second resin composition before curing)

欲得到層狀梯度型之硬化體層，使用第1樹脂組成物與第2樹脂組成物時，形成與具備導體層的基板接合的側之第2硬化體層的第2樹脂組成物(第2層)之無機填充材含有量，只要滿足條件(1)便可無須特別限定，但將樹脂組成物中之不揮發成分作為100質量%時，以未達20質量%為佳，較佳為10質量%，更佳為5質量%，特佳為0質量%。此時，形成與第2硬化體層為相反的側，即具有支持體時，形成與支持體接合的側之第1硬化體層的第1樹脂組成物(第1層)之無機填充材含有量，只要滿足樹脂組成物全體之(A)無機填充材的含有量之條件，並無特別限定，但將樹脂組成物中之不揮發成分作為100質量%時，由可得到線熱膨張係數及介電損耗正切較低的硬化物之觀點來看，以50質量%以上為佳，較佳為55質量%以上，60質量%以上。該上限，由所得之硬化物的機械強度之觀點來看，以90質量%以下為佳，較佳為85質量%以下，更佳為80質量%以下。To obtain a layered gradient type cured body layer, when using the first resin composition and the second resin composition, the second resin composition (second layer) forming the second cured body layer on the side bonded to the substrate provided with the conductor layer The content of the inorganic filler is not particularly limited as long as the condition (1) is satisfied, but when the non-volatile content in the resin composition is 100% by mass, it is preferably less than 20% by mass, preferably 10% by mass , More preferably 5% by mass, and particularly preferably 0% by mass. In this case, the inorganic filler content of the first resin composition (first layer) forming the first cured body layer on the side where the support is bonded to the support is formed on the side opposite to the second cured body layer, that is, with a support, There is no particular limitation as long as the condition of the content of (A) inorganic filler in the entire resin composition is satisfied, but when the non-volatile component in the resin composition is taken as 100% by mass, the linear thermal expansion coefficient and dielectric From the viewpoint of the hardened product having a low loss tangent, it is preferably 50% by mass or more, preferably 55% by mass or more, and 60% by mass or more. From the viewpoint of the mechanical strength of the obtained hardened product, the upper limit is preferably 90% by mass or less, preferably 85% by mass or less, and more preferably 80% by mass or less.

＜(B)環氧樹脂＞ 樹脂組成物可任意地含有(B)環氧樹脂。＜(B) epoxy resin＞ The resin composition may optionally contain (B) epoxy resin.

作為(B)環氧樹脂，例如可舉出雙二甲酚型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚AF型環氧樹脂、二環戊二烯型環氧樹脂、參酚型環氧樹脂、萘酚酚醛清漆型環氧樹脂、酚酚醛清漆型環氧樹脂、tert-丁基-鄰苯二酚型環氧樹脂、萘型環氧樹脂、萘酚型環氧樹脂、蒽型環氧樹脂、縮水甘油基胺型環氧樹脂、縮水甘油基酯型環氧樹脂、甲酚酚醛清漆型環氧樹脂、聯苯基型環氧樹脂、線狀脂肪族環氧樹脂、具有丁二烯結構的環氧樹脂、脂環式環氧樹脂、雜環式環氧樹脂、含有螺環的環氧樹脂、環己烷型環氧樹脂、環己烷二甲醇型環氧樹脂、亞萘基醚型環氧樹脂、三羥甲基型環氧樹脂、四苯基乙烷型環氧樹脂等。環氧樹脂可單獨使用1種類，亦可組合2種類以上而使用。Examples of the (B) epoxy resin include bis-cresol epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and bisphenol AF ring. Oxygen resin, dicyclopentadiene epoxy resin, phenolic epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin , Naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin, cresol novolac 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 type ring Oxygen resin, cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. One type of epoxy resin may be used alone, or two or more types may be used in combination.

樹脂組成物中，作為(B)環氧樹脂，含有於1分子中具有2個以上環氧基之環氧樹脂者為佳。由可顯著本發明之所望效果的觀點來看，對於(B)環氧樹脂之不揮發成分100質量%而言，於1分子中具有2個以上環氧基之環氧樹脂的比例，以50質量%以上為佳，較佳為60質量%以上，特佳為70質量%以上。In the resin composition, as the (B) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule is preferable. From the viewpoint of achieving the desired effect of the present invention, for the (B) 100% by mass of the non-volatile component of the epoxy resin, the ratio of epoxy resins having two or more epoxy groups in one molecule is 50 It is preferably at least 100% by mass, preferably at least 60% by mass, and particularly preferably at least 70% by mass.

環氧樹脂中有在溫度20℃下為液狀的環氧樹脂(以下有時稱為「液狀環氧樹脂」)，與在溫度20℃下為固體狀的環氧樹脂(以下有時稱為「固體狀環氧樹脂」)。樹脂組成物中，作為(B)環氧樹脂，可僅含有液狀環氧樹脂，或亦可僅含有固體狀環氧樹脂，以組合液狀環氧樹脂與固體狀環氧樹脂而含有者為佳。Among epoxy resins, there are epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as “liquid epoxy resins”), and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as “liquid epoxy resins”) It is "solid epoxy resin"). In the resin composition, as the (B) epoxy resin, only a liquid epoxy resin may be contained, or only a solid epoxy resin may be contained. The combination of the liquid epoxy resin and the solid epoxy resin is: good.

作為液狀環氧樹脂，以於1分子中具有2個以上的環氧基之液狀環氧樹脂為佳。The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

作為液狀環氧樹脂，以雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AF型環氧樹脂、萘型環氧樹脂、縮水甘油基酯型環氧樹脂、縮水甘油基胺型環氧樹脂、酚酚醛清漆型環氧樹脂、具有酯骨架的脂環式環氧樹脂、環己烷型環氧樹脂、環己烷二甲醇型環氧樹脂、縮水甘油基胺型環氧樹脂，及具有丁二烯結構的環氧樹脂為佳，以雙酚A型環氧樹脂、雙酚F型環氧樹脂為較佳。As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl group Amine epoxy resin, phenol novolac epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane epoxy resin, cyclohexane dimethanol epoxy resin, glycidylamine epoxy resin The resin and the epoxy resin having a butadiene structure are preferred, and bisphenol A epoxy resin and bisphenol F epoxy resin are preferred.

作為液狀環氧樹脂的具體例子，可舉出DIC公司製的「HP4032」、「HP4032D」、「HP4032SS」(萘型環氧樹脂)；三菱化學公司製的「828US」、「jER828EL」、「825」、「EPICOAT828EL」(雙酚A型環氧樹脂)；三菱化學公司製的「jER807」、「1750」(雙酚F型環氧樹脂)；三菱化學公司製的「jER152」(酚酚醛清漆型環氧樹脂)；三菱化學公司製的「630」、「630LSD」(縮水甘油基胺型環氧樹脂)；新日鐵住金化學公司製的「ZX1059」(雙酚A型環氧樹脂與雙酚F型環氧樹脂的混合品)；Nagase Chemtex公司製的「EX-721」(縮水甘油基酯型環氧樹脂)；Daicel Chemical Industries, Ltd.製的「CELLOXIDE2021P」(具有酯骨架的脂環式環氧樹脂)；Daicel Chemical Industries, Ltd.製的「PB-3600」(具有丁二烯結構的環氧樹脂)；新日鐵住金化學公司製的「ZX1658」、「ZX1658GS」(液狀1,4-縮水甘油基環己烷型環氧樹脂)等。這些可單獨使用1種類，亦可組合2種類以上而使用。Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC; "828US", "jER828EL" and "" manufactured by Mitsubishi Chemical Corporation. "825", "EPICOAT828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolak) manufactured by Mitsubishi Chemical Corporation Type epoxy resin); "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (bisphenol A type epoxy resin and double (Phenol F-type epoxy resin mixed product); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex; "CELLOXIDE2021P" (alicyclic ring with ester skeleton) manufactured by Daicel Chemical Industries, Ltd. Epoxy resin); "PB-3600" (epoxy resin with butadiene structure) manufactured by Daicel Chemical Industries, Ltd.; "ZX1658" and "ZX1658GS" (liquid 1) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. , 4-glycidyl cyclohexane epoxy resin), etc. One of these may be used alone, or two or more types may be used in combination.

作為固體狀環氧樹脂，以於1分子中具有3個以上環氧基之固體狀環氧樹脂為佳，以於1分子中具有3個以上環氧基的芳香族系之固體狀環氧樹脂為較佳。The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule. Is better.

作為固體狀環氧樹脂，以雙二甲酚型環氧樹脂、萘型環氧樹脂、萘型4官能環氧樹脂、甲酚酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、參酚型環氧樹脂、萘酚型環氧樹脂、聯苯基型環氧樹脂、亞萘基醚型環氧樹脂、蒽型環氧樹脂、雙酚A型環氧樹脂、雙酚AF型環氧樹脂、四苯基乙烷型環氧樹脂為佳，以萘型環氧樹脂為較佳。As the solid epoxy resin, bis-cresol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type 4-functional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, Phenol epoxy resin, naphthol epoxy resin, biphenyl epoxy resin, naphthylene ether epoxy resin, anthracene epoxy resin, bisphenol A epoxy resin, bisphenol AF ring Oxygen resin and tetraphenylethane type epoxy resin are preferred, and naphthalene type epoxy resin is preferred.

作為固體狀環氧樹脂的具體例子，可舉出DIC公司製的「HP4032H」(萘型環氧樹脂)；DIC公司製的「HP-4700」、「HP-4710」(萘型4官能環氧樹脂)；DIC公司製的「N-690」(甲酚酚醛清漆型環氧樹脂)；DIC公司製的「N-695」(甲酚酚醛清漆型環氧樹脂)；DIC公司製的「HP-7200」、「HP-7200HH」、「HP-7200H」(二環戊二烯型環氧樹脂)；DIC公司製的「EXA-7311」、「EXA-7311-G3」、「EXA-7311-G4」、「EXA-7311-G4S」、「HP6000」(亞萘基醚型環氧樹脂)；日本化藥公司製的「EPPN-502H」(參酚型環氧樹脂)；日本化藥公司製的「NC7000L」(萘酚酚醛清漆型環氧樹脂)；日本化藥公司製的「NC3000H」、「NC3000」、「NC3000L」、「NC3100」(聯苯基型環氧樹脂)；新日鐵住金化學公司製的「ESN475V」(萘酚型環氧樹脂)；新日鐵住金化學公司製的「ESN485」(萘酚酚醛清漆型環氧樹脂)；三菱化學公司製的「YX4000H」、「YX4000」、「YL6121」(聯苯基型環氧樹脂)；三菱化學公司製的「YX4000HK」(雙二甲酚型環氧樹脂)；三菱化學公司製的「YX8800」(蒽型環氧樹脂)；大阪氣體化學公司製的「PG-100」、「CG-500」；三菱化學公司製的「YL7760」(雙酚AF型環氧樹脂)；三菱化學公司製的「YL7800」(芴型環氧樹脂)；三菱化學公司製的「jER1010」(固體狀雙酚A型環氧樹脂)；三菱化學公司製的「jER1031S」(四苯基乙烷型環氧樹脂)等。這些可單獨使用1種類，亦可組合2種類以上而使用。Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type 4-functional epoxy manufactured by DIC). Resin); "N-690" (cresol novolac epoxy resin) made by DIC; "N-695" (cresol novolac epoxy resin) made by DIC; "HP-" made by DIC "7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" manufactured by DIC Corporation ", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (Shenphenol type epoxy resin) manufactured by Nippon Kayaku; manufactured by Nippon Kayaku "NC7000L" (naphthol novolac epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl epoxy resin) manufactured by Nippon Kayaku; Nippon Steel & Sumitomo Chemical "ESN475V" (naphthol epoxy resin) manufactured by the company; "ESN485" (naphthol novolac epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; "YX4000H" and "YX4000" manufactured by Mitsubishi Chemical Corporation, "YL6121" (biphenyl type epoxy resin); "YX4000HK" (bis-xylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Osaka Gas "PG-100" and "CG-500" manufactured by Chemical Company; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "JER1010" (solid bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. One of these may be used alone, or two or more types may be used in combination.

作為(B)環氧樹脂，組合液狀環氧樹脂與固體狀環氧樹脂而使用時，這些量比(液狀環氧樹脂：固體狀環氧樹脂)以質量比表示時，以1：1~1：20為佳，較佳為1：1~1：10，特佳為1：1~1：5。藉由將液狀環氧樹脂與固體狀環氧樹脂的量比設定在此範圍時，可顯著地得到本發明之所望效果。When (B) an epoxy resin is used in combination with a liquid epoxy resin and a solid epoxy resin, when these quantity ratios (liquid epoxy resin: solid epoxy resin) are expressed in terms of mass ratio, 1:1 ~1:20 is better, preferably 1:1~1:10, and particularly preferably 1:1~1:5. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within this range, the desired effect of the present invention can be remarkably obtained.

(B)環氧樹脂之環氧當量，以50 g/eq~5000 g/eq為佳，較佳為50 g/eq~3000 g/eq，更佳為80 g/eq~2000 g/eq，更較佳為110 g/eq~1000 g/eq。藉由設定為該範圍，可使樹脂組成物層的硬化物之交聯密度變得充分，可達成具有表面粗度小的絕緣層。環氧當量為含有1當量之環氧基的環氧樹脂之質量。該環氧當量可依據JIS K7236而測定。(B) The epoxy equivalent of epoxy resin is preferably 50 g/eq~5000 g/eq, preferably 50 g/eq~3000 g/eq, more preferably 80 g/eq~2000 g/eq, More preferably, it is 110 g/eq to 1000 g/eq. By setting to this range, the cross-linking density of the cured product of the resin composition layer can be sufficient, and an insulating layer having a small surface roughness can be achieved. Epoxy equivalent is the mass of epoxy resin containing 1 equivalent of epoxy group. The epoxy equivalent can be measured in accordance with JIS K7236.

(B)環氧樹脂之重量平均分子量(Mw)由顯著得到本發明之所望效果的觀點來看，以100~5000為佳，較佳為250~3000，更佳為400~1500。樹脂之重量平均分子量為藉由凝膠滲透層析法(GPC)法，可測定出聚苯乙烯換算之值。(B) The weight average molecular weight (Mw) of the epoxy resin is preferably from 100 to 5000, preferably from 250 to 3000, and more preferably from 400 to 1500 from the viewpoint of remarkably obtaining the desired effect of the present invention. The weight average molecular weight of the resin is a value in terms of polystyrene that can be measured by gel permeation chromatography (GPC) method.

樹脂組成物為含有(B)環氧樹脂時，(B)環氧樹脂的含有量雖非特別限定者，當使樹脂組成物中之樹脂成分作為100質量%時，由顯著地得到本發明之所望效果的觀點來看，以20質量%以上為佳，較佳為30質量%以上，更佳為40質量%以上，特佳為45質量%以上。該上限由顯著得到本發明之所望效果的觀點來看，以80質量%以下為佳，較佳為70質量%以下，更佳為65質量%以下，特佳為60質量%以下。對於樹脂組成物中，(B)成分並非僅要均勻地含於樹脂組成物全體，於此所謂的(B)成分之含有量為表示對於樹脂組成物全體而言之含有量。When the resin composition contains (B) epoxy resin, although the content of (B) epoxy resin is not particularly limited, when the resin component in the resin composition is taken as 100% by mass, the present invention is remarkably obtained From the viewpoint of the desired effect, it is preferably 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 45% by mass or more. From the viewpoint of remarkably obtaining the desired effect of the present invention, the upper limit is preferably 80% by mass or less, preferably 70% by mass or less, more preferably 65% by mass or less, and particularly preferably 60% by mass or less. In the resin composition, the component (B) is not necessarily uniformly contained in the entire resin composition, and the content of the component (B) here means the content for the entire resin composition.

＜(C)硬化劑＞ 樹脂組成物為任意地含有(C)硬化劑。＜(C) Hardener＞ The resin composition contains (C) hardener arbitrarily.

作為(C)硬化劑，只要具有使環氧樹脂硬化的功能者即可，並無特別限定，例如可舉出酚系硬化劑、萘酚系硬化劑、酸酐系硬化劑、活性酯系硬化劑、苯並噁嗪系硬化劑、氰酸酯系硬化劑及碳二亞胺系硬化劑。硬化劑可單獨使用1種，亦可組合2種以上而使用。The (C) curing agent is not particularly limited as long as it has the function of curing the epoxy resin, and examples thereof include phenol-based curing agents, naphthol-based curing agents, anhydride-based curing agents, and active ester-based curing agents. , Benzoxazine hardener, cyanate ester hardener and carbodiimide hardener. One kind of hardener may be used alone, or two or more kinds may be used in combination.

作為酚系硬化劑及萘酚系硬化劑，由耐熱性及耐水性的觀點來看，以具有酚醛清漆結構的酚系硬化劑，或具有酚醛清漆結構的萘酚系硬化劑為佳。又，由對於被著體的密著性之觀點來看，以含氮酚系硬化劑或含氮萘酚系硬化劑為佳，以含有三嗪骨架的酚系硬化劑或含有三嗪骨架的萘酚系硬化劑為較佳。其中亦由可使耐熱性、耐水性及密著性高度令人滿足之觀點來看，以含有三嗪骨架的酚酚醛清漆樹脂為佳。作為酚系硬化劑及萘酚系硬化劑之具體例子，例如可舉出明和化成公司製的「MEH-7700」、「MEH-7810」、「MEH-7851」、日本化藥公司製的「NHN」、「CBN」、「GPH」、新日鐵住金化學公司製的「SN-170」、「SN-180」、「SN-190」、「SN-475」、「SN-485」、「SN-495」、「SN-375」、「SN-395」、DIC公司製的「LA-7052」、「LA-7054」、「LA-3018」、「LA-3018-50P」、「LA-1356」、「TD2090」等。As the phenol-based hardener and the naphthol-based hardener, from the viewpoint of heat resistance and water resistance, a phenol-based hardener having a novolak structure or a naphthol-based hardener having a novolak structure is preferred. In addition, from the viewpoint of adhesion to the object, a nitrogen-containing phenol-based hardener or a nitrogen-containing naphthol-based hardener is preferred, and a phenol-based hardener containing a triazine skeleton or a triazine skeleton-containing one Naphthol-based hardeners are preferred. Among them, a phenol novolak resin containing a triazine skeleton is preferred from the viewpoint that heat resistance, water resistance, and adhesion are highly satisfactory. Specific examples of the phenol-based hardener and naphthol-based hardener include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Chemicals, and "NHN" manufactured by Nippon Kayaku Co., Ltd., for example. ", "CBN", "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. -495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356" manufactured by DIC Corporation ", "TD2090", etc.

作為酸酐系硬化劑，可舉出於1分子內中具有1個以上酸酐基之硬化劑。作為酸酐系硬化劑的具體例子，可舉出鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、甲基納迪克酸酐、氫化甲基納迪克酸酐、三烷基四氫鄰苯二甲酸酐、十二烯基琥珀酸酐、5-(2,5-二氧代四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、偏苯三酸酐、苯四酸酐、二苯甲酮四羧酸二酐、聯苯基四羧酸二酐、萘四羧酸二酐、氧代二鄰苯二甲酸二酐、3,3’-4,4’-二苯基碸四羧酸二酐、1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二氧代-3-呋喃基)-萘並[1,2-C]呋喃-1,3-二酮、乙二醇雙(脫氫偏苯三酸酯)、苯乙烯與馬來酸經共聚合之苯乙烯•馬來酸樹脂等聚合物型的酸酐等。Examples of the acid anhydride hardener include hardeners having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride hardener include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic acid. Dicarboxylic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3- (Furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalene tetra Carboxylic dianhydride, oxodiphthalic dianhydride, 3,3'-4,4'-diphenylbenzene tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro- 5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(dehydro trimellitate) ), Polymeric anhydrides such as styrene and maleic acid copolymerized with styrene and maleic acid.

作為活性酯系硬化劑，雖無特別限制，一般使用酚酯類、硫代酚酯類、N-羥基胺酯類、雜環羥基化合物之酯類等在1分子中具有2個以上反應活性高之酯基的化合物為佳。該活性酯系硬化劑以藉由羧酸化合物及/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而得者為佳。特別由耐熱性提高之觀點來看，以由羧酸化合物與羥基化合物所得之活性酯系硬化劑為佳，以由羧酸化合物與酚化合物及/或萘酚化合物所得之活性酯系硬化劑為較佳。作為羧酸化合物，例如可舉出安息香酸、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、苯四酸等。作為酚化合物或萘酚化合物，例如可舉出氫醌、間苯二酚、雙酚A、雙酚F、雙酚S、酚酞嗪、甲基化雙酚A、甲基化雙酚F、甲基化雙酚S、酚、o-甲酚、m-甲酚、p-甲酚、鄰苯二酚、α-萘酚、β-萘酚、1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯甲酮、三羥基二苯甲酮、四羥基二苯甲酮、間苯三酚、苯三醇、二環戊二烯型二酚化合物、酚酚醛清漆等。其中，所謂「二環戊二烯型二酚化合物」表示於二環戊二烯1分子使酚2分子縮合而得之二酚化合物。As the active ester hardener, although not particularly limited, phenolic esters, thiophenolic esters, N-hydroxylamine esters, esters of heterocyclic hydroxy compounds, etc. are generally used. They have more than two reactive molecules per molecule. The ester-based compounds are preferred. The active ester-based hardener is preferably obtained by condensation reaction of a carboxylic acid compound and/or thiocarboxylic acid compound with a hydroxyl compound and/or thiol compound. In particular, from the viewpoint of improving heat resistance, the active ester hardener obtained from the carboxylic acid compound and the hydroxy compound is preferred, and the active ester hardener obtained from the carboxylic acid compound and the phenol compound and/or naphthol compound is Better. 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 naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalazine, methylated bisphenol A, methylated bisphenol F, methyl alcohol 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, pyrogallol, dicyclopentadiene diphenol Compounds, phenolic novolac, etc. Among them, the so-called "dicyclopentadiene type diphenol compound" means a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

具體而言，以含有二環戊二烯型二酚結構之活性酯化合物、含有萘結構之活性酯化合物、含有酚酚醛清漆之乙醯化物的活性酯化合物、含有酚酚醛清漆之苯甲醯基化物的活性酯化合物為佳，其中亦以含有萘結構的活性酯化合物、含有二環戊二烯型二酚結構的活性酯化合物為較佳。所謂「二環戊二烯型二酚結構」表示含有伸苯基-二環環戊二烯-伸苯基所成的2價結構單位。Specifically, an active ester compound containing a dicyclopentadiene diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetal compound containing phenol novolac, and a benzoyl group containing a phenol novolac The active ester compound of the compound is preferable, and the active ester compound containing a naphthalene structure and the active ester compound containing a dicyclopentadiene type diphenol structure are also preferable. The so-called "dicyclopentadiene type diphenol structure" means a divalent structural unit containing phenylene-dicyclocyclopentadiene-phenylene.

作為活性酯系硬化劑之販賣品中，作為含有二環戊二烯型二酚結構之活性酯化合物可舉出「EXB9451」、「EXB9460」、「EXB9460S」、「HPC-8000」、「HPC-8000H」、「HPC-8000-65T」、「HPC-8000H-65TM」、「EXB-8000L」、「EXB-8000L-65TM」(DIC公司製)；作為含有萘結構之活性酯化合物可舉出「EXB9416-70BK」、「EXB-8150-65T」(DIC公司製)；作為含有酚酚醛清漆的乙醯化物之活性酯化合物可舉出「DC808」(三菱化學公司製)；作為含有酚酚醛清漆的苯甲醯基化物之活性酯化合物可舉出「YLH1026」(三菱化學公司製)；作為酚酚醛清漆的乙醯化物之活性酯系硬化劑可舉出「DC808」(三菱化學公司製)；作為酚酚醛清漆之苯甲醯基化物的活性酯系硬化劑可舉出「YLH1026」(三菱化學公司製)、「YLH1030」(三菱化學公司製)、「YLH1048」(三菱化學公司製)等。As the active ester-based hardener sales products, examples of the active ester compounds containing a dicyclopentadiene diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", and "HPC- "8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65TM" (manufactured by DIC); examples of active ester compounds containing naphthalene structure include " "EXB9416-70BK", "EXB-8150-65T" (manufactured by DIC); as the active ester compound of phenol novolak-containing acetonitrile, "DC808" (manufactured by Mitsubishi Chemical Corporation); as the one containing phenol novolak The active ester compound of the benzoyl compound can be exemplified by "YLH1026" (manufactured by Mitsubishi Chemical Corporation); the active ester-based hardener of the phenol novolak acetyl compound can be exemplified by "DC808" (manufactured by Mitsubishi Chemical Corporation); Examples of the active ester-based hardeners of benzoyl phenol novolacs include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

作為苯並噁嗪系硬化劑之具體例子，可舉出JFE化學公司製的「JBZ-OP100D」、「ODA-BOZ」；昭和高分子公司製的「HFB2006M」、四國化成工業公司製的「P-d」、「F-a」等。Specific examples of benzoxazine-based hardeners include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemicals; "HFB2006M" manufactured by Showa Polymer Co., Ltd. and ""manufactured by Shikoku Chemical Industry Co., Ltd." "Pd", "Fa", etc.

作為氰酸酯系硬化劑，例如可舉出雙酚A二氰酸酯、聚酚氰酸酯(寡(3-伸甲基-1,5-伸苯基氰酸酯))、4,4’-伸甲基雙(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)硫代醚，及由雙(4-氰酸酯苯基)醚等2官能氰酸酯樹脂、酚酚醛清漆及甲酚酚醛清漆等所衍生的多官能氰酸酯樹脂，這些氰酸酯樹脂的一部分經三嗪化的預聚物等。作為氰酸酯系硬化劑之具體例子，可舉出Lonza Japan公司製的「PT30」及「PT60」(皆為酚酚醛清漆型多官能氰酸酯樹脂)、「BA230」、「BA230S75」(雙酚A二氰酸酯的一部分或全部經三嗪化而成為三聚物的預聚物)等。Examples of the cyanate-based hardener include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylidene-1,5-phenylenecyanate)), 4,4 '-Extended methyl bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2 -Bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1 ,3-bis(4-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl) thioether, and by bis(4-cyanate phenyl ) Polyfunctional cyanate resins derived from bifunctional cyanate resins such as ethers, phenol novolacs, cresol novolacs, etc., and a part of these cyanate resins are triazineized prepolymers. Specific examples of the cyanate ester hardener include "PT30" and "PT60" (both are phenolic novolak type polyfunctional cyanate resins), "BA230", "BA230S75" (double Part or all of phenol A dicyanate is triazineated to form a prepolymer of terpolymer) and the like.

作為碳二亞胺系硬化劑之具體例子，可舉出日清紡化學公司製的「V-03」、「V-07」等。Specific examples of the carbodiimide-based hardener include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

含有硬化劑時，環氧樹脂與硬化劑之量比，以[環氧樹脂的環氧基之合計數]：[硬化劑的反應基之合計數]之比率表示時，以1：0.2~1：2的範圍為佳，以1：0.3~1：1.5為較佳，以1：0.4~1：1.2為更佳。於此，所謂硬化劑的反應基表示活性羥基、活性酯基等，依硬化劑之種類而相異。又，所謂環氧樹脂的環氧基之合計數，表示對於所有環氧樹脂，將各環氧樹脂之不揮發成分質量除以環氧當量的值之合計值，所謂硬化劑之反應基的合計數，表示對於所有硬化劑，將各硬化劑之不揮發成分質量除以反應基當量的值之合計值。藉由將環氧樹脂與硬化劑之量比設定在該範圍時，可使所得之硬化物的耐熱性更提高。When the hardener is included, the ratio of epoxy resin to hardener is expressed as a ratio of [total epoxy resin epoxy resin]: [total reactive resin hardener]: 1:0.2~1 The range of 2:2 is better, preferably 1:0.3~1:1.5, more preferably 1:0.4~1:1.2. Here, the reactive group of the hardener means an active hydroxyl group, an active ester group, etc., which differs depending on the type of hardener. In addition, the total number of epoxy groups of epoxy resins means the total value of the values of the non-volatile components of each epoxy resin divided by the epoxy equivalent for all epoxy resins, and the total of reactive groups of so-called hardeners. The number indicates the total value of the mass of the non-volatile components of each hardener divided by the equivalent of the reaction base for all hardeners. By setting the amount ratio of epoxy resin to hardener within this range, the heat resistance of the resulting hardened product can be further improved.

樹脂組成物含有(C)硬化劑時，(C)硬化劑之含有量雖非特別限定者，但將樹脂組成物中之樹脂成分作為100質量%時，由可顯著地得到本發明之所望效果的觀點來看，以1質量%以上為佳，較佳為10質量%以上，更佳為20質量%以上，特佳為30質量%以上。該上限由可顯著地得到本發明之所望效果的觀點來看，以60質量%以下為佳，較佳為55質量%以下，更佳為50質量%以下，特佳為45質量%以下。對於樹脂組成物中，(C)成分不僅要均勻地含於樹脂組成物全體，於此所謂(C)成分之含有量表示對於樹脂組成物全體之含有量。When the resin composition contains (C) hardener, although the content of (C) hardener is not particularly limited, when the resin component in the resin composition is 100% by mass, the desired effect of the present invention can be obtained remarkably From the viewpoint of 1% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more. The upper limit is preferably 60% by mass or less, preferably 55% by mass or less, more preferably 50% by mass or less, and particularly preferably 45% by mass or less from the viewpoint of remarkably obtaining the desired effect of the present invention. In the resin composition, the component (C) must not only be uniformly contained in the entire resin composition, but the content of the component (C) here means the content in the entire resin composition.

樹脂組成物以含有活性酯系硬化劑者為佳。含有活性酯系硬化劑時，活性酯系硬化劑之含有量雖非特別限定者，但將樹脂組成物中之樹脂成分作為100質量%時，由可顯著地得到本發明之所望效果的觀點來看，以1質量%以上為佳，較佳為5質量%以上，更佳為10質量%以上，特佳為12質量%以上。該上限由可顯著地得到本發明之所望效果的觀點來看，以50質量%以下為佳，較佳為40質量%以下，更佳為35質量%以下，特佳為30質量%以下。The resin composition is preferably one containing an active ester-based hardener. When the active ester-based hardener is contained, although the content of the active ester-based hardener is not particularly limited, when the resin component in the resin composition is taken as 100% by mass, from the viewpoint that the desired effect of the present invention can be remarkably obtained In view of this, it is preferably 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 12% by mass or more. The upper limit is preferably 50% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less, and particularly preferably 30% by mass or less from the viewpoint that the desired effect of the present invention can be remarkably obtained.

在特定較佳實施型態，以含有氰酸酯系硬化劑者為佳。在該實施型態中，可有效果地得到組合導體層附近梯度型之硬化體層，或層狀梯度型與導體層附近梯度型之硬化體層。In certain preferred embodiments, those containing a cyanate hardener are preferred. In this embodiment, a gradient type hardened body layer near the conductor layer or a layered gradient type and a gradient type hardened body layer near the conductor layer can be effectively obtained.

藉由於樹脂組成物含有氰酸酯系硬化劑，即使組成為使用均質樹脂組成物，因於硬化時在導體層附近區域的無機填充材之比例會降低，故對於貫通孔產生的污跡，即使使用無機填充材之除去能低的藉由N2 氣體或O2 氣體之電漿亦可有效果地除去。Since the resin composition contains a cyanate-based hardener, even if the composition is a homogeneous resin composition, the ratio of the inorganic filler in the vicinity of the conductor layer during curing will be reduced, so the stains generated by the through holes, even Plasma using N 2 gas or O 2 gas with low removal energy using an inorganic filler can also be effectively removed.

對於該實施型態，氰酸酯系硬化劑之含有量，將樹脂組成物中之樹脂成分作為100質量%時，由可充分確保污跡除去性之觀點來看，以15質量%以上為佳，較佳為20質量%以上，更佳為25質量%以上。該上限由可顯著地得到本發明之所望效果的觀點來看，以60質量%以下為佳，較佳為50質量%以下，更佳為40質量%以下，特佳為30質量%以下。For this embodiment mode, when the content of the cyanate ester hardener is 100% by mass of the resin component in the resin composition, from the viewpoint of sufficiently ensuring stain removal, it is preferably 15% by mass or more. It is preferably 20% by mass or more, and more preferably 25% by mass or more. The upper limit is preferably 60% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less from the viewpoint that the desired effect of the present invention can be remarkably obtained.

＜(D)熱可塑性樹脂＞ 樹脂組成物依據所需可含有(D)熱可塑性樹脂。＜(D) thermoplastic resin＞ The resin composition may contain (D) a thermoplastic resin as needed.

作為(D)成分之熱可塑性樹脂，例如可舉出苯氧基樹脂、聚乙烯縮醛樹脂、聚烯烴樹脂、聚丁二烯樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞胺樹脂、聚碸樹脂、聚醚碸樹脂、聚伸苯基醚樹脂、聚碳酸酯樹脂、聚醚醚酮樹脂、聚酯樹脂等。其中亦由顯著地得到本發明之所望效果的觀點，以及由得到表面粗度小且與導體層的密著性特優之絕緣層的觀點來看，以苯氧基樹脂為佳。又，熱可塑性樹脂可單獨使用1種類，或亦可組合2種類以上而使用。As the thermoplastic resin of the component (D), for example, phenoxy resin, polyethylene acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyimide amide imide resin, poly Etherimide resin, polyphenol resin, polyether resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. Among them, from the viewpoint of remarkably obtaining the desired effect of the present invention, and from the viewpoint of obtaining an insulating layer having a small surface roughness and excellent adhesion to the conductor layer, a phenoxy resin is preferred. In addition, one type of thermoplastic resin may be used alone, or two or more types may be used in combination.

作為苯氧基樹脂，例如可舉出具有選自含有雙酚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、聯苯基骨架、芴骨架、二環戊二烯骨架、降冰片烯骨架、萘骨架、蒽骨架、金剛烷骨架、萜烯骨架及三甲基環己烷骨架所成群的1種類以上骨架之苯氧基樹脂。苯氧基樹脂之末端亦可為酚性羥基、環氧基等中任一種官能基。Examples of the phenoxy resin include a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, and a bicyclic ring. A phenoxy resin of at least one type of skeleton consisting of a pentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as phenolic hydroxyl group and epoxy group.

作為苯氧基樹脂之具體例子，可舉出三菱化學公司製的「1256」及「4250」(皆為含有雙酚A骨架之苯氧基樹脂)；三菱化學公司製的「YX8100」(含有雙酚S骨架之苯氧基樹脂)；三菱化學公司製的「YX6954」(含有雙酚苯乙酮骨架之苯氧基樹脂)；新日鐵住金化學公司製的「FX280」及「FX293」；三菱化學公司製的「YL7500BH30」、「YX6954BH30」、「YX7553」、「YX7553BH30」、「YL7769BH30」、「YL6794」、「YL7213」、「YL7290」及「YL7482」等。Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (including double Phenoxy resin with phenol S skeleton); "YX6954" (phenoxy resin with bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation; "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Chemical Corporation; Mitsubishi "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482" manufactured by the Chemical Company.

作為聚乙烯縮醛樹脂，例如可舉出聚乙烯甲醛樹脂、聚乙烯縮丁醛樹脂，以聚乙烯縮丁醛樹脂為佳。作為聚乙烯縮醛樹脂之具體例子，可舉出電氣化學工業公司製的「電化縮丁醛4000-2」、「電化縮丁醛5000-A」、「電化縮丁醛6000-C」、「電化縮丁醛6000-EP」；積水化學工業公司製的S-LECBH系列、BX系列(例如BX-5Z)、KS系列(例如KS-1)、BL系列、BM系列等。Examples of polyvinyl acetal resins include polyethylene formaldehyde resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. As specific examples of the polyvinyl acetal resin, "electrochemical butyral 4000-2", "electrochemical butyral 5000-A", "electrochemical butyral 6000-C", "" Electrochemical butyral 6000-EP"; S-LECBH series, BX series (eg BX-5Z), KS series (eg KS-1), BL series, BM series, etc. manufactured by Sekisui Chemical Industry Co., Ltd.

作為聚醯亞胺樹脂之具體例子，可舉出新日本理化公司製的「RIKACOATSN20」及「RIKACOATPN20」。作為聚醯亞胺樹脂之具體例子，又可舉出使2官能性羥基末端聚丁二烯、二異氰酸酯化合物及四元酸酐進行反應而得之線狀聚醯亞胺(日本特開2006-37083號公報記載之聚醯亞胺)、含有聚矽氧烷骨架的聚醯亞胺(日本特開2002-12667號公報及日本特開2000-319386號公報等所記載的聚醯亞胺)等改性聚醯亞胺。As specific examples of the polyimide resin, "RIKACOATSN20" and "RIKACOATPN20" manufactured by New Japan Physical and Chemical Corporation can be cited. As a specific example of the polyimide resin, a linear polyimide obtained by reacting a 2-functional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (Japanese Patent Laid-Open No. 2006-37083) (Polyimide described in Japanese Patent Publication), polyimide containing a polysiloxane skeleton (polyimide described in Japanese Patent Application Publication No. 2002-12667 and Japanese Patent Application Publication No. 2000-319386, etc.) Polyimide.

作為聚醯胺醯亞胺樹脂之具體例子，可舉出東洋紡公司製的「VylomaxHR11NN」及「VylomaxHR16NN」。作為聚醯胺醯亞胺樹脂之具體例子，又可舉出日立化成公司製的「KS9100」、「KS9300」(含有聚矽氧烷骨架的聚醯胺醯亞胺)等改性聚醯胺醯亞胺。Specific examples of the polyimide amide imine resin include "VylomaxHR11NN" and "VylomaxHR16NN" manufactured by Toyobo. As specific examples of the polyimide amide imine resin, modified polyamide amides such as "KS9100" and "KS9300" (polyamide amide imide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd. can also be mentioned. Imine.

作為聚醚碸樹脂之具體例子，可舉出住友化學公司製的「PES5003P」等。As a specific example of the polyether resin, "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., etc. may be mentioned.

作為聚伸苯基醚樹脂之具體例子，可舉出三菱瓦斯化學公司製的寡伸苯基醚•苯乙烯樹脂「OPE-2St 1200」等。Specific examples of polyphenylene ether resins include oligophenylene styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd. and the like.

作為聚碸樹脂之具體例子，可舉出Solvay Advanced Polymers公司製的聚碸「P1700」、「P3500」等。As specific examples of the polyphenol resin, there can be mentioned polyphenol "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

(D)熱可塑性樹脂之重量平均分子量(Mw)由可顯著地得到本發明之所望效果的觀點來看，以8,000以上為佳，較佳為10,000以上，特佳為20,000以上，以70,000以下為佳，較佳為60,000以下，特佳為50,000以下。(D) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 8,000 or more, preferably 10,000 or more, particularly preferably 20,000 or more, and 70,000 or less from the viewpoint that the desired effect of the present invention can be remarkably obtained. Preferably, it is preferably 60,000 or less, and particularly preferably 50,000 or less.

樹脂組成物為含有(D)熱可塑性樹脂時，(D)熱可塑性樹脂之含有量雖非特別限定者，將樹脂組成物中之樹脂成分作為100質量%時，由可顯著地得到本發明之所望效果的觀點來看，以0.1質量%以上為佳，較佳為1質量%以上，更佳為2質量%以上。該上限以40質量%以下為佳，較佳為30質量%以下，更佳為20質量%以下。對於樹脂組成物中，(D)成分不僅要均勻地含於樹脂組成物全體，於此所謂(D)成分的含有量表示對於樹脂組成物全體之含有量。When the resin composition contains (D) thermoplastic resin, although the content of (D) thermoplastic resin is not particularly limited, when the resin component in the resin composition is taken as 100% by mass, the present invention can be remarkably obtained From the viewpoint of the desired effect, it is preferably 0.1% by mass or more, preferably 1% by mass or more, and more preferably 2% by mass or more. The upper limit is preferably 40% by mass or less, preferably 30% by mass or less, and more preferably 20% by mass or less. In the resin composition, the component (D) must not only be uniformly contained in the entire resin composition, but the content of the component (D) here means the content in the entire resin composition.

＜(E)有機填充材＞ 樹脂組成物依據所需可含有(E)有機填充材。＜(E) Organic fillers＞ The resin composition may contain (E) an organic filler as needed.

作為(E)有機填充材，可使用在密封電子零件之情況等時所使用的任意有機填充材，例如可舉出橡膠粒子、聚醯胺微粒子、聚矽氧粒子等，以橡膠粒子為佳。As the (E) organic filler, any organic filler used when sealing electronic parts or the like can be used, and examples thereof include rubber particles, polyamide fine particles, polysiloxane particles, etc., and rubber particles are preferred.

作為橡膠粒子，只要為對於顯示橡膠彈性的樹脂施予化學交聯處理，於有機溶劑中不溶且不熔的樹脂之微粒子體，即未特別限定，例如可舉出丙烯腈丁二烯橡膠粒子、丁二烯橡膠粒子、丙烯酸橡膠粒子等。作為橡膠粒子，具體可舉出XER-91(日本合成橡膠公司製)、StaphyloidAC3355、AC3816、AC3816N、AC3832、AC4030、AC3364、IM101(以上為Aika industry公司製)、PARALOID EXL2655、EXL2602(以上為陶氏化學公司製)等。The rubber particles are not particularly limited as long as they are chemically cross-linked resins that exhibit rubber elasticity and are insoluble and infusible in organic solvents. For example, acrylonitrile butadiene rubber particles, Butadiene rubber particles, acrylic rubber particles, etc. Specific examples of the rubber particles include XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Staphyloid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (above manufactured by Aika Industries), PARALOID EXL2655, and EXL2602 (above Dow). Manufactured by the chemical company).

(E)有機填充材之平均粒徑，以0.005μm~1μm之範圍為佳，較佳為0.2μm~0.6μm之範圍。(E)有機填充材之平均粒徑可使用動態光散射法而測定。例如於適當有機溶劑中將有機填充材藉由超音波等進行均勻分散，使用濃厚系粒徑分析儀(大塚電子公司製「FPAR-1000」)，將有機填充材的粒度分布以質量基準下作成，將該中位直徑作為平均粒子徑而可測定。(E) The average particle size of the organic filler is preferably in the range of 0.005 μm to 1 μm, preferably in the range of 0.2 μm to 0.6 μm. (E) The average particle diameter of the organic filler can be measured using the dynamic light scattering method. For example, the organic filler is uniformly dispersed by ultrasonic waves in an appropriate organic solvent. Using a thick particle size analyzer ("FPAR-1000" manufactured by Otsuka Electronics Co., Ltd.), the particle size distribution of the organic filler is made on the basis of mass The median diameter can be measured as the average particle diameter.

樹脂組成物為含有(E)有機填充材時，(E)有機填充材之含有量雖非特別限定者，但將樹脂組成物中之樹脂成分作為100質量%時，由可顯著地得到本發明之所望效果的觀點來看，以0.1質量%以上為佳，較佳為1質量%以上，更佳為3質量%以上。該上限以30質量%以下為佳，較佳為20質量%以下，更佳為10質量%以下。對於樹脂組成物中，(E)成分不僅要均勻地含於樹脂組成物全體，於此所謂(E)成分之含有量表示對於樹脂組成物全體之含有量。When the resin composition contains (E) an organic filler, although the content of (E) organic filler is not particularly limited, when the resin component in the resin composition is 100% by mass, the present invention can be obtained remarkably From the viewpoint of the desired effect, it is preferably 0.1% by mass or more, preferably 1% by mass or more, and more preferably 3% by mass or more. The upper limit is preferably 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less. In the resin composition, the component (E) must not only be uniformly contained in the entire resin composition, but the content of the component (E) here means the content in the entire resin composition.

＜(F)難燃劑＞ 樹脂組成物依據所需可含有(F)難燃劑。＜(F) flame retardant＞ The resin composition may contain (F) flame retardant as required.

作為(F)難燃劑，例如可舉出有機磷系難燃劑、有機系含氮的磷化合物、氮化合物、聚矽氧系難燃劑、金屬氫氧化物等。難燃劑可單獨使用1種，或亦可併用2種以上。Examples of the (F) flame retardant include organic phosphorus-based flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, polysiloxane-based flame retardants, metal hydroxides, and the like. One type of flame retardant may be used alone, or two or more types may be used in combination.

作為(F)難燃劑，可使用販賣品，例如可舉出大塚化學公司製的「SPS-100」；三光公司製的「HCA-HQ-HST」、「HCA-HQ」等。As the (F) flame retardant, commercial products can be used, and examples thereof include "SPS-100" manufactured by Otsuka Chemical Co., Ltd.; "HCA-HQ-HST" and "HCA-HQ" manufactured by Sanko Corporation.

樹脂組成物為含有(F)難燃劑時，(F)難燃劑的含有量雖非特別限定者，在將樹脂組成物中之樹脂成分作為100質量%時，由可顯著地得到本發明之所望效果的觀點來看，以0.1質量%以上為佳，較佳為1質量%以上，更佳為3質量%以上。該上限以30質量%以下為佳，較佳為20質量%以下，更佳為10質量%以下。對樹脂組成物中，(F)成分不僅要均勻地含於樹脂組成物全體，於此，所謂(F)成分的含有量表示對於樹脂組成物全體之含有量。When the resin composition contains (F) flame retardant, although the content of (F) flame retardant is not particularly limited, when the resin component in the resin composition is 100% by mass, the present invention can be obtained remarkably From the viewpoint of the desired effect, it is preferably 0.1% by mass or more, preferably 1% by mass or more, and more preferably 3% by mass or more. The upper limit is preferably 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less. In the resin composition, the component (F) must not only be uniformly contained in the entire resin composition. Here, the content of the component (F) means the content in the entire resin composition.

＜(G)硬化促進劑＞ 樹脂組成物依據所需可含有(G)硬化促進劑。＜(G) hardening accelerator＞ The resin composition may contain (G) a hardening accelerator as needed.

作為(G)硬化促進劑，例如可舉出磷系硬化促進劑、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。其中亦以磷系硬化促進劑、胺系硬化促進劑、咪唑系硬化促進劑、金屬系硬化促進劑為佳，以胺系硬化促進劑、咪唑系硬化促進劑、金屬系硬化促進劑為較佳。硬化促進劑可單獨使用1種類，亦可組合2種類以上而使用。Examples of (G) hardening accelerators include phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, and metal-based hardening accelerators. Among them, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are preferred, and amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are preferred . One type of hardening accelerator may be used alone, or two or more types may be used in combination.

作為磷系硬化促進劑，例如可舉出三苯基膦、鏻硼酸鹽化合物、四苯基鏻四苯基硼酸鹽、n-丁基鏻四苯基硼酸鹽、四丁基鏻癸烷酸鹽、(4-甲基苯基)三苯基鏻硫代氰酸酯、四苯基鏻硫代氰酸酯、丁基三苯基鏻硫代氰酸酯等，以三苯基膦、四丁基鏻癸烷酸鹽為佳。Examples of phosphorus-based hardening accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, and tetrabutylphosphonium decanate. , (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, etc., with triphenylphosphine, tetrabutyl The phosphonium decanoate is preferred.

作為胺系硬化促進劑，例如可舉出三乙基胺、三丁基胺等三烷基胺、4-二甲基胺基吡啶(DMAP)、苯甲基二甲基胺、2,4,6,-參(二甲基胺基甲基)酚、1,8-二氮雜雙環(5,4,0)-十一碳烯等，以4-二甲基胺基吡啶、1,8-二氮雜雙環(5,4,0)-十一碳烯為佳。Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4, 6,-ginseng (dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., with 4-dimethylaminopyridine, 1,8 -Diazabicyclo(5,4,0)-undecene is preferred.

作為咪唑系硬化促進劑，例如可舉出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-苯甲基-2-甲基咪唑、1-苯甲基-2-苯基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-十一烷基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-十一烷基咪唑鎓偏苯三酸酯、1-氰基乙基-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-吡咯並[1,2-a]苯並咪唑、1-十二烷基-2-甲基-3-苯甲基咪唑鎓氯化物、2-甲基咪唑啉、2-苯基咪唑啉等咪唑化合物及咪唑化合物與環氧樹脂之加成體，以2-乙基-4-甲基咪唑、1-苯甲基-2-苯基咪唑為佳。Examples of the imidazole hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 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 trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4- Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4' -Methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s- Triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2 -Methylimidazoline, 2-phenylimidazoline and other imidazole compounds and adducts of imidazole compounds and epoxy resin, with 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole Better.

作為咪唑系硬化促進劑，亦可使用販賣品，例如可舉出三菱化學公司製的「P200-H50」等。As the imidazole-based hardening accelerator, commercial products can also be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

作為胍系硬化促進劑，例如可舉出二氰二胺、1-甲基胍、1-乙基胍、1-環己基胍、1-苯基胍、1-(鄰甲苯基)胍、二甲基胍、二苯基胍、三甲基胍、四甲基胍、五甲基胍、1,5,7-三氮雜聯環[4.4.0]癸-5-烯、7-甲基-1,5,7-三氮雜聯環[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-(鄰甲苯基)雙胍等，以二氰二胺、1,5,7-三氮雜聯環[4.4.0]癸-5-烯為佳。Examples of the guanidine hardening accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, diacetyl Methylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl -1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecane Biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc., Dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

作為金屬系硬化促進劑，例如可舉出鈷、銅、鋅、鐵、鎳、錳、錫等金屬之有機金屬錯體或有機金屬鹽。作為有機金屬錯體之具體例子，可舉出鈷(II)乙醯丙酮酸酯、鈷(III)乙醯丙酮酸酯等有機鈷錯體、銅(II)乙醯丙酮酸酯等有機銅錯體、鋅(II)乙醯丙酮酸酯等有機鋅錯體、鐵(III)乙醯丙酮酸酯等有機鐵錯體、鎳(II)乙醯丙酮酸酯等有機鎳錯體、錳(II)乙醯丙酮酸酯等有機錳錯體等。作為有機金屬鹽，例如可舉出辛基酸鋅、辛基酸錫、環烷烴酸鋅、環烷烴酸鈷、硬脂酸錫、硬脂酸鋅等。Examples of the metal-based hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetopyruvate and cobalt (III) acetopyruvate, and organic copper complexes such as copper (II) acetopyruvate Body, organic zinc complexes such as zinc (II) acetonate, organic iron complexes such as iron (III) acetonate, organic nickel complexes such as nickel (II) acetonate, and manganese (II ) Organic manganese complexes such as acetopyruvate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

樹脂組成物為含有(G)硬化促進劑時，(G)硬化促進劑之含有量雖非特別限定者，在將樹脂組成物中之樹脂成分作為100質量%時，由可顯著地得到本發明之所望效果的觀點來看，以0.001質量%以上為佳，較佳為0.01質量%以上，更佳為0.05質量%以上。該上限，以5質量%以下為佳，較佳為1質量%以下，更佳為0.5質量%以下。對於脂組成物中，(G)硬化促進劑不僅要均勻地含於樹脂組成物全體，於此所謂(G)硬化促進劑的含有量表示對於樹脂組成物全體之含有量。When the resin composition contains (G) a hardening accelerator, although the content of the (G) hardening accelerator is not particularly limited, when the resin component in the resin composition is 100% by mass, the present invention can be obtained remarkably From the viewpoint of the desired effect, it is preferably 0.001% by mass or more, preferably 0.01% by mass or more, and more preferably 0.05% by mass or more. The upper limit is preferably 5% by mass or less, preferably 1% by mass or less, and more preferably 0.5% by mass or less. For the fat composition, the (G) hardening accelerator should not only be uniformly contained in the entire resin composition, but the content of the (G) hardening accelerator here means the content for the entire resin composition.

＜(H)其他添加劑＞ 樹脂組成物中除上述成分以外，亦可進一步含有作為任意成分的其他添加劑。作為如此添加劑，例如可舉出增黏劑、消泡劑、塗平劑、密著性賦予劑等樹脂添加劑；聚合起始劑等。這些添加劑可單獨使用1種類，亦可組合2種類以上而使用。各含有量可由斯業者做適宜設定。＜(H)Other additives＞ In addition to the above-mentioned components, the resin composition may further contain other additives as optional components. Examples of such additives include resin additives such as tackifiers, defoamers, leveling agents, and adhesion-imparting agents; and polymerization initiators. One type of these additives may be used alone, or two or more types may be used in combination. Each content can be appropriately set by the industry.

在某實施型態中，樹脂組成物之氮原子含有量對於樹脂組成物中之樹脂成分100質量%而言，以1質量%以上者為佳。樹脂組成物之氮原子含有量(質量%)為換算為百分率之數值，該百分率為，於胺系硬化促進劑、氰酸酯系硬化劑等分子內所含的氮原子之質量，除以樹脂成分的總質量之百分率。在該實施型態，可有效果地得到組合導體層附近梯度型之硬化體層，或層狀梯度型與導體層附近梯度型之硬化體層。In a certain embodiment, the nitrogen atom content of the resin composition is preferably 1% by mass or more for 100% by mass of the resin component in the resin composition. The nitrogen atom content (mass %) of the resin composition is a value converted into a percentage, which is the mass of nitrogen atoms contained in the molecule such as an amine-based curing accelerator, a cyanate-based curing agent, etc., divided by the resin The percentage of the total mass of the ingredient. In this embodiment, the gradient-type hardened body layer near the conductor layer or the layered-gradient type and the gradient-type hardened body layer near the conductor layer can be effectively obtained.

藉由使氮原子含有量設定在對樹脂成分為1質量%以上，即使使用組成為均質的樹脂組成物，因在硬化時的導體層附近區域無機填充材的比例會降低，可將於貫通孔所生成的污跡，使用無機填充材的除去能低的藉由N2 氣體或O2 氣體的電漿而有效果地除去。其中，導體層附近區域的無機填充材之比例降低，可推測為含有氮原子之分子往導體層移動而造成。By setting the nitrogen atom content to 1% by mass or more with respect to the resin component, even if a homogeneous resin composition is used, the ratio of the inorganic filler in the vicinity of the conductor layer during curing will decrease, and the through-hole The generated stains are effectively removed by plasma using N 2 gas or O 2 gas with low removal energy using an inorganic filler. Among them, the ratio of the inorganic filler in the area near the conductor layer is reduced, which is presumably caused by the movement of molecules containing nitrogen atoms to the conductor layer.

對於該實施型態，樹脂組成物之氮原子含有量對於樹脂組成物中之樹脂成分100質量%而言，由可充分地確保污跡除去性的觀點來看，較佳為1.5質量%以上，更佳為1.8質量%以上，特佳為2質量%以上。該上限並非特別限定者，但可設定為10質量%等。In this embodiment, the nitrogen atom content of the resin composition is preferably 1.5% by mass or more from the viewpoint of sufficiently ensuring the stain removal property with respect to 100% by mass of the resin component in the resin composition. It is more preferably 1.8% by mass or more, and particularly preferably 2% by mass or more. The upper limit is not particularly limited, but can be set to 10% by mass or the like.

＜樹脂薄片＞ 樹脂組成物雖亦可在塗漆狀態下進行塗布而使用，但在工業上，一般以在含有該樹脂組成物的樹脂薄片之型態下使用者為佳。<Resin sheet> Although the resin composition can also be applied by being applied in a painted state, in industry, it is generally preferred to the user in the form of a resin sheet containing the resin composition.

對於較佳實施型態，樹脂薄片具有支持體，與形成於支持體上的樹脂組成物層。圖4表示將具有本發明之一實施型態中之支持體500與樹脂組成物層400之樹脂薄片600的截面以模型方式表示的截面圖。樹脂組成物層400之無機填充材含有量為40質量%以上。該樹脂組成物層400設置於支持體500上。For a preferred embodiment, the resin sheet has a support and a resin composition layer formed on the support. FIG. 4 shows a cross-sectional view of the resin sheet 600 having the support 500 and the resin composition layer 400 in one embodiment of the present invention in a model manner. The content of the inorganic filler in the resin composition layer 400 is 40% by mass or more. The resin composition layer 400 is provided on the support 500.

圖5表示將使圖4的樹脂組成物層400進行硬化而形成硬化體層100的情況中之支持體500與硬化體層100之截面以模型方式表示的截面圖。對於使樹脂組成物層400進行硬化而形成硬化體層100時的硬化體層100之主表面(此為與硬化體層100之支持體500的相反側之面)100D上呈垂直的硬化體層100之截面，對於自與支持體500為相反側的硬化體層100之主表面100D的距離而言，將自0μm至1μm為止的區域110’中之每單位面積的樹脂成分之面積作為A0-1 。又，對於自主表面100D的距離而言，將自1μm至2μm為止的區域120’中之每單位面積的樹脂成分之面積作為A1-2 。該情況下，硬化體層100滿足上述條件(1)。FIG. 5 shows a cross-sectional view of the cross section of the support 500 and the cured body layer 100 modeled when the resin composition layer 400 of FIG. 4 is cured to form the cured body layer 100. When the resin composition layer 400 is cured to form the cured body layer 100, the main surface of the cured body layer 100 (this is the surface opposite to the support 500 of the cured body layer 100) 100D is a vertical cross-section of the cured body layer 100, For the distance from the main surface 100D of the hardened body layer 100 on the opposite side to the support 500, the area of the resin component per unit area in the region 110' from 0 μm to 1 μm is defined as A 0-1 . In addition, regarding the distance of the main surface 100D, the area of the resin component per unit area in the region 120′ from 1 μm to 2 μm is defined as A 1-2 . In this case, the hardened body layer 100 satisfies the above condition (1).

進一步對於使樹脂組成物層400進行硬化而形成硬化體層100的情況中之硬化體層100的主表面100D上呈垂直的硬化體層100之截面，對於自與支持體500為相反側的硬化體層100之主表面100D的距離而言，將自0μm至0.5μm為止的區域130’中之每單位面積的樹脂成分之面積作為A0-0.5 。又，對於在硬化體層100之主表面100D上呈垂直的硬化體層100之截面，對於自主表面100D的距離而言，將自0.5μm至1μm為止的區域140’中之每單位面積的樹脂成分之面積作為A0.5-1 。此時，硬化體層100以滿足上述條件(2)者為佳。Further, in the case where the resin composition layer 400 is cured to form the cured body layer 100, the cross-section of the vertical cured body layer 100 on the main surface 100D of the cured body layer 100, and from the cured body layer 100 on the opposite side to the support 500 For the distance of the main surface 100D, the area of the resin component per unit area in the region 130' from 0 μm to 0.5 μm is defined as A 0-0.5 . In addition, for the cross section of the hardened body layer 100 that is perpendicular to the main surface 100D of the hardened body layer 100, the distance from the main surface 100D is the resin component per unit area in the region 140' from 0.5 μm to 1 μm. The area is referred to as A 0.5-1 . At this time, it is preferable that the hardened body layer 100 satisfy the above condition (2).

圖6表示將使圖4的樹脂組成物層400進行硬化而形成硬化體層100的情況中之支持體500與硬化體層100的截面以模型方式表示的截面圖。如圖6所示，對於將樹脂組成物層400進行硬化而形成硬化體層100的情況中之硬化體層100的主表面100D上呈垂直的硬化體層100之截面，對於自與支持體500為相反側的硬化體層100之主表面100D的距離而言，將自0.5μm至dμm為止的區域150’中之每單位面積的樹脂成分之面積作為A0.5-d 。又，對於在硬化體層100的主表面100D上呈垂直的硬化體層100之截面，對於自主表面100D的距離而言，將自dμm至0.5Dμm為止的區域160’中之每單位面積的樹脂成分之面積作為Ad-0.5D 。此時，硬化體層100以滿足上述條件(3)者為佳。FIG. 6 shows a cross-sectional view of the support 500 and the cured body layer 100 in a model form when the resin composition layer 400 of FIG. 4 is cured to form the cured body layer 100. As shown in FIG. 6, in the case where the resin composition layer 400 is cured to form the cured body layer 100, the cross-section of the vertical cured body layer 100 on the main surface 100D of the cured body layer 100 is opposite to the support 500. For the distance of the main surface 100D of the cured body layer 100, the area of the resin component per unit area in the region 150' from 0.5 μm to d μm is defined as A 0.5-d . In addition, for the cross section of the hardened body layer 100 that is perpendicular to the main surface 100D of the hardened body layer 100, for the distance from the main surface 100D, the resin component per unit area in the region 160' from dμm to 0.5Dμm The area is referred to as Ad-0.5D . At this time, the hardened body layer 100 preferably satisfies the above condition (3).

樹脂組成物層之厚度，由即使印刷配線板的薄型化，及該樹脂組成物之硬化物為薄膜，亦可提高絕緣性優良的硬化物之觀點來看，以50μm以下為佳，較佳為40μm以下。樹脂組成物層之厚度的下限，雖無特別限定，通常可設定為5μm以上等。The thickness of the resin composition layer is preferably 50 μm or less from the viewpoint that the thickness of the printed wiring board is reduced and the cured product of the resin composition is a thin film, and the cured product with excellent insulation can be improved. Below 40μm. The lower limit of the thickness of the resin composition layer is not particularly limited, but can generally be set to 5 μm or more.

使具備以第1樹脂組成物所形成的第1層，與以第2樹脂組成物所形成的第2層之樹脂組成物層進行硬化，得到層狀梯度型之硬化體層時，與基板接合的第2層之厚度雖只要可得到本發明之所望效果者即可，而無須限定，以未達2μm為佳，較佳為1.5μm，更佳為1μm，特佳為0.8μm。When the first layer formed with the first resin composition and the resin composition layer with the second layer formed with the second resin composition are cured to obtain a layered gradient type cured body layer, the The thickness of the second layer is not limited as long as it can obtain the desired effect of the present invention. It is preferably less than 2 μm, preferably 1.5 μm, more preferably 1 μm, and particularly preferably 0.8 μm.

作為支持體，例如可舉出含有塑質材料的薄膜、金屬箔、脫模紙，含有塑質材料的薄膜、金屬箔為佳。Examples of the support include films containing plastic materials, metal foils, and release papers. Films containing plastic materials, metal foils are preferred.

作為支持體使用含有塑質材料的薄膜時，作為塑質材料，例如可舉出聚乙烯對苯二甲酸酯(以下有時簡稱為「PET」)、聚乙烯萘二甲酸酯(以下有時簡稱為「PEN」)等聚酯、聚碳酸酯(以下有時簡稱為「PC」)、聚甲基丙烯酸甲酯(PMMA)等丙烯酸、環狀聚烯烴、三乙醯纖維素(TAC)、聚醚硫化物(PES)、聚醚酮、聚醯亞胺等。其中亦以聚乙烯對苯二甲酸酯、聚乙烯萘二甲酸酯為佳，以便宜的聚乙烯對苯二甲酸酯為特佳。When a film containing a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes simply referred to as "PET") and polyethylene naphthalate (hereinafter referred to as Acrylic, cyclic polyolefin, triacetyl cellulose (TAC) such as polyester, polycarbonate (hereinafter sometimes referred to as "PC"), polymethyl methacrylate (PMMA), etc. , Polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are also preferred, and inexpensive polyethylene terephthalate is particularly preferred.

作為支持體使用金屬箔時，作為金屬箔，例如可舉出銅箔、鋁箔等，以銅箔為佳。作為銅箔，亦可使用含有銅之單金屬的箔，亦可使用含有銅與其他金屬(例如錫、鉻、銀、鎂、鎳、鋯、矽、鈦等)的合金之箔。When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferred. As the copper foil, a foil containing a single metal of copper, or an alloy containing copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may also be used.

支持體中，與樹脂組成物層進行接合的面，亦可施予消光處理、電暈處理、帶電防止處理。In the support, the surface bonded to the resin composition layer may be subjected to matting treatment, corona treatment, and charge prevention treatment.

又，作為支持體，可使用於與樹脂組成物層接合的面上具有脫模層的附有脫模層的支持體。作為使用於附有脫模層的支持體之脫模層的脫模劑，例如可舉出選自含有醇酸樹脂、聚烯烴樹脂、胺基甲酸酯樹脂及聚矽氧樹脂所成群的1種以上之脫模劑。附有脫模層的支持體亦可使用販賣品，例如可舉出具有將醇酸樹脂系脫模劑作為主成分的脫模層之PET薄膜的Lintec公司製的「SK-1」、「AL-5」、「AL-7」、Toray公司製的「Lumirror T60」、帝人公司製的「Purex」、Unitika公司製的「Unipeel」等。In addition, as the support, a support with a release layer having a release layer for bonding to the resin composition layer may be used. Examples of the mold release agent used in the mold release layer of the support with a mold release layer include, for example, those selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and polysiloxane resins. More than one release agent. The support with a release layer can also be used as a commercial product. For example, "SK-1" and "AL" manufactured by Lintec, which have a PET film with a release layer containing an alkyd resin-based release agent as a main component, can be cited. -5", "AL-7", "Lumirror T60" manufactured by Toray, "Purex" manufactured by Teijin, "Unipeel" manufactured by Unitika, etc.

支持體之厚度雖無特別限定，以5μm~75μm的範圍為佳，以10μm~60μm的範圍為較佳。且，使用附有脫模層的支持體時，以附有脫模層的支持體全體之厚度在上述範圍者為佳。Although the thickness of the support is not particularly limited, the range of 5 μm to 75 μm is preferred, and the range of 10 μm to 60 μm is preferred. Moreover, when using the support body with a mold release layer, it is preferable that the thickness of the whole support body with a mold release layer is in the said range.

對於一實施型態，樹脂薄片中視必要可含有任意層。作為該任意層，例如可舉出設置於未與樹脂組成物層的支持體進行接合的面(即，與支持體為相反側的面)之以支持體為準的保護薄膜等。保護薄膜之厚度，雖非特定限定者，例如1μm~40μm。藉由層合保護薄膜，可抑制對樹脂組成物層的表面之垃圾等附著或傷痕。For one embodiment, the resin sheet may contain any layer as necessary. Examples of the optional layer include a protective film based on the support provided on the surface that is not bonded to the support of the resin composition layer (that is, the surface opposite to the support). Although the thickness of the protective film is not specifically limited, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion or scratching of the garbage and the like on the surface of the resin composition layer.

樹脂薄片例如可藉由調製出於有機溶劑溶解樹脂組成物的樹脂塗漆(即含有樹脂組成物的塗層液)，將該塗層液使用模具塗布等塗布於支持體上，進一步進行乾燥形成樹脂組成物層而製造。The resin sheet can be formed by, for example, preparing a resin varnish (that is, a coating solution containing a resin composition) in which an organic solvent dissolves the resin composition, applying the coating solution to the support using a die coating method, and further drying the resin sheet The resin composition layer is manufactured.

欲得到層狀梯度型之硬化體層，使用第1樹脂組成物與第2樹脂組成物時，樹脂組成物層可藉由以下步驟(α)而製造。 (α)藉由於支持體上使用模具塗布等將含有第1樹脂組成物的塗層液進行塗布並乾燥而形成以第1樹脂組成物所形成的第1層，準備含有支持體與第1層之臨時樹脂薄片的步驟(以下亦稱為步驟(α1))，及於在支持體上接合的第1層上，使以第2樹脂組成物所形成的第2層進行接合或形成的步驟(以下亦稱為步驟(α’))。To obtain a layered gradient type cured body layer, when the first resin composition and the second resin composition are used, the resin composition layer can be produced by the following step (α). (α) The coating layer containing the first resin composition is applied and dried on the support to form the first layer formed with the first resin composition by using a die coating method, etc., and the support and the first layer are prepared. The step of temporary resin sheet (hereinafter also referred to as step (α1)), and the step of bonding or forming the second layer formed with the second resin composition on the first layer bonded on the support ( Hereinafter also referred to as step (α')).

在某實施型態中，步驟(α’)較佳為在(α2)第1層上，使用模具塗布等，將含有第2樹脂組成物的塗層液進行塗布並乾燥而形成第2層的步驟。In a certain embodiment, the step (α′) is preferably to coat and dry the coating liquid containing the second resin composition on the first layer of (α2) using a die, etc. to form the second layer step.

在其他實施型態中，步驟(α’)較佳為，於與形成(α2’)第1層的支持體相異的其他第2支持體上，使用模具塗布等，使含有第2樹脂組成物的塗層液進行塗布並乾燥後形成以第2樹脂組成物所形成的第2層，藉由此，準備含有第2支持體與第2層的臨時樹脂薄片之步驟，及(α2”)使含有第1層的臨時樹脂薄片與含有第2層的臨時樹脂薄片進行接合的步驟。In other embodiments, the step (α′) is preferably such that a second resin support that is different from the support forming the (α2′) first layer is coated with a mold or the like to contain the second resin composition The coating liquid of the substance is applied and dried to form a second layer formed with the second resin composition, and thereby, a step of preparing a temporary resin sheet containing the second support and the second layer, and (α2”) The step of joining the temporary resin sheet containing the first layer and the temporary resin sheet containing the second layer.

作為有機溶劑，例如可舉出丙酮、甲基乙基酮(MEK)及環己酮等酮類；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乙酸酯類；溶纖劑及丁基卡必醇等卡必醇類；甲苯及二甲苯等芳香族烴類；二甲基甲醯胺、二甲基乙醯胺(DMAc)及N-甲基吡咯啶酮等醯胺系溶劑等。有機溶劑可單獨使用1種，亦可組合2種以上而使用。Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and Acetates such as carbitol acetate; cellosolve and carbitols such as butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide ( DMAc) and N-methylpyrrolidone and other amide-based solvents. One organic solvent may be used alone, or two or more organic solvents may be used in combination.

乾燥可藉由加熱、吹熱風等的公知方法而實施。乾燥條件並無特別限定，但樹脂組成物層中之有機溶劑的含有量為乾燥至10質量%以下，較佳為乾燥至5質量%以下。雖依樹脂塗漆中之有機溶劑的沸點而相異，但例如使用含有30質量%~60質量%的有機溶劑之樹脂塗漆時，藉由在50℃~150℃進行3分鐘~10分鐘乾燥，可形成樹脂組成物層。Drying can be carried out by known methods such as heating and hot air blowing. The drying conditions are not particularly limited, but the content of the organic solvent in the resin composition layer is dried to 10% by mass or less, preferably dried to 5% by mass or less. Although it varies according to the boiling point of the organic solvent in the resin coating, for example, when using a resin coating containing an organic solvent of 30% by mass to 60% by mass, drying is performed at 50°C to 150°C for 3 minutes to 10 minutes , A resin composition layer can be formed.

樹脂薄片可捲成滾筒狀而保存。樹脂薄片為具有保護薄膜時，藉由剝離保護薄膜而成為可使用。The resin sheet can be rolled and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

樹脂薄片可適用於形成印刷配線板之絕緣層時(印刷配線板之絕緣層用)，更適合使用於形成印刷配線板之層間絕緣層時(印刷配線板之層間絕緣層用)。樹脂薄片特別適合於適用於藉由選自含有O2 氣體及N2 氣體所成群的1種以上氣體的電漿處理之絕緣層用途上。The resin sheet is suitable for forming the insulating layer of the printed wiring board (for the insulating layer of the printed wiring board), and more preferably for forming the interlayer insulating layer of the printed wiring board (for the interlayer insulating layer of the printed wiring board). The resin sheet is particularly suitable for the application of the insulating layer by plasma treatment selected from one or more kinds of gases containing O 2 gas and N 2 gas.

＜印刷配線板＞ 印刷配線板為具備作為絕緣層的上述硬化體層，且於最外層的至少一部分具有具備導體層之基板。硬化體層通常設置於基板之導體層側面上。<Printed wiring board> The printed wiring board is provided with the above-mentioned hardened body layer as an insulating layer, and has a substrate with a conductor layer on at least a part of the outermost layer. The hardened body layer is usually provided on the side of the conductor layer of the substrate.

印刷配線板例如使用上述樹脂薄片，可藉由含有下述(A)至(D)的步驟之方法而製造： (A)將含有無機填充材含有量40質量%以上之樹脂組成物層的樹脂薄片，在於最外層的至少一部分具備導體層之基板上，層合成使樹脂組成物層接合於基板之導體層側面之步驟； (B)使樹脂組成物層進行硬化而形成硬化體層之步驟； (C)於硬化體層形成貫通孔的步驟； (D)於硬化體層，進行藉由選自含有O2 氣體及N2 氣體所成群的1種以上氣體的電漿處理之步驟。The printed wiring board uses the above-mentioned resin sheet, for example, and can be manufactured by a method including the following steps (A) to (D): (A) A resin containing a resin composition layer containing an inorganic filler content of 40% by mass or more A sheet, on a substrate having a conductor layer on at least a part of the outermost layer, a step of laminating a resin composition layer to the side of the conductor layer of the substrate; (B) a step of curing the resin composition layer to form a cured body layer; ( C) A step of forming a through hole in the hardened body layer; (D) A step of performing plasma treatment with one or more gases selected from the group consisting of O 2 gas and N 2 gas in the hardened body layer.

在製造印刷配線板時，亦可進一步實施形成(E)導體層之步驟。When manufacturing a printed wiring board, the step of forming (E) a conductor layer may be further implemented.

這些步驟(A)至步驟(E)亦可依據使用於印刷配線板的製造中之斯業者所公知的各種方法而實施。且，可將支持體的除去在步驟(A)與步驟(B)之間、步驟(B)與步驟(C)之間、步驟(C)與步驟(D)之間，或步驟(D)與步驟(E)之間實施。又，視必要亦可重複實施步驟(B)~步驟(E)之硬化體層及導體層的形成而形成多層配線板。These steps (A) to (E) can also be implemented in accordance with various methods known to those used in the manufacture of printed wiring boards. Furthermore, the support can be removed between step (A) and step (B), between step (B) and step (C), between step (C) and step (D), or step (D) And step (E). Furthermore, if necessary, the formation of the hardened body layer and the conductor layer of steps (B) to (E) may be repeated to form a multilayer wiring board.

步驟(A)為將樹脂薄片於基板上，層合成樹脂組成物層接合於基板之導體層側面上的層合步驟。因此，步驟(A)為含有將具有支持體，與形成於支持體上的樹脂組成物層之樹脂薄片，層合成使樹脂組成物層接合於基板的導體層側面上。Step (A) is a lamination step of bonding a resin sheet on the substrate and bonding a synthetic resin composition layer on the side of the conductor layer of the substrate. Therefore, in step (A), a resin sheet having a support and a resin composition layer formed on the support is laminated to join the resin composition layer on the side of the conductor layer of the substrate.

所謂本說明書中之基板，其為由印刷配線板之基板所成的構件，例如可舉出玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚伸苯基醚基板等。The substrate in this specification is a member made of a substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polymer. Stretching phenyl ether substrate, etc.

又，基板為於單面或雙面上具備導體層，該導體層亦可經由圖型加工。於基板的單面或雙面上形成有導體層(電路)之基板有時稱為「內層電路基板」。又，製造印刷配線板時，必須形成硬化體層及/或導體層的中間製造物亦進一步含於本發明所謂的「內層電路基板」。印刷配線板為零件內藏電路板時，可使用內藏零件的內層電路基板。In addition, the substrate is provided with a conductor layer on one side or both sides, and this conductor layer may also be processed by patterning. A substrate in which a conductor layer (circuit) is formed on one side or both sides of the substrate is sometimes called an "inner layer circuit substrate." In addition, when manufacturing a printed wiring board, an intermediate product in which a hardened body layer and/or a conductor layer must be formed is further included in the so-called "inner layer circuit board" of the present invention. When the printed wiring board is a circuit board with built-in parts, an inner circuit board with built-in parts can be used.

具備基板的導體層之導體材料並無特別限定。在較佳實施型態中，導體層含有選自含有金、鉑、鈀、銀、銅、鋁、鈷、鉻、鋅、鎳、鈦、鎢、鐵、錫及銦所成群的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，例如可舉出由選自含有上述群的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)所形成的層。其中，由導體層形成的汎用性、成本、製圖之容易性等觀點來看，以鉻、鎳、鈦、鋁、鋅、金、鈀、銀或者銅的單金屬層，或鎳•鉻合金、銅•鎳合金、銅•鈦合金的合金層為佳，以鉻、鎳、鈦、鋁、鋅、金、鈀、銀或者銅的單金屬層，或鎳•鉻合金的合金層為較佳，以銅的單金屬層為更佳。The conductor material of the conductor layer provided with the substrate is not particularly limited. In a preferred embodiment, the conductor layer contains one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium Metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy selected from the group consisting of two or more metals (for example, nickel, chromium alloy, copper, nickel alloy, and copper Titanium alloy). Among them, from the viewpoint of versatility, cost, and ease of patterning formed by a conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or a nickel-chromium alloy, The alloy layer of copper•nickel alloy and copper•titanium alloy is preferred. A single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel•chromium alloy is preferred. A single metal layer of copper is preferred.

基板所具備的導體層可為單層結構，亦可為由含有相異種類的金屬或者合金所成的單金屬層或合金層以2層以上進行層合的複層結構。導體層為複層結構時，與硬化體層接觸的層以鉻、鋅或者鈦的單金屬層，或鎳•鉻合金的合金層者為佳。The conductor layer included in the substrate may have a single-layer structure, or may have a multi-layer structure in which a single metal layer or alloy layer composed of different kinds of metals or alloys is laminated in two or more layers. When the conductor layer has a multi-layer structure, the layer in contact with the hardened body layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

基板所具備的導體層之厚度雖依所望印刷配線板的設計而相異，但一般為1μm~35μm，較佳為5μm~ 30μm。Although the thickness of the conductor layer provided on the substrate varies depending on the design of the desired printed wiring board, it is generally 1 μm to 35 μm, preferably 5 μm to 30 μm.

內層電路基板與樹脂薄片的層合，例如可藉由自支持體側將樹脂薄片於內層電路基板施予加熱壓著而進行。作為將樹脂薄片於內層電路基板進行加熱壓著的構件(以下亦稱為「加熱壓著構件」)，例如可舉出施予加熱的金屬板(SUS鏡板等)或金屬輥(SUS輥)等。且，並非使加熱壓著構件於樹脂薄片施予直接加壓，而為欲使樹脂薄片可充分地追隨內層電路基板的表面凹凸，以藉由耐熱橡膠等彈性材進行加壓為佳。The lamination of the inner layer circuit board and the resin sheet can be performed, for example, by applying heat and pressure to the inner layer circuit board from the support side. As a member that heat-presses the resin sheet on the inner-layer circuit board (hereinafter also referred to as "heat-pressing member"), for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roll) Wait. Furthermore, instead of applying direct pressure to the resin sheet by the heating and pressing member, it is preferable to apply pressure with an elastic material such as heat-resistant rubber in order to allow the resin sheet to sufficiently follow the surface irregularities of the inner layer circuit board.

內層電路基板與樹脂薄片的層合可藉由真空層合法實施。對於真空層合法，加熱壓著溫度以60℃~160℃為佳，較佳為80℃~140℃之範圍，加熱壓著壓力係以0.098MPa~1.77MPa為佳，較佳為0.29MPa~1.47MPa的範圍，加熱壓著時間以20秒~400秒為佳，較佳為30秒~300秒的範圍。層合較佳在壓力26.7hPa以下的減壓條件下實施。The lamination of the inner circuit board and the resin sheet can be performed by vacuum lamination. For the vacuum lamination method, the heating and pressing temperature is preferably 60°C to 160°C, preferably 80°C to 140°C, and the heating and pressing pressure is 0.098MPa to 1.77MPa, preferably 0.29MPa to 1.47 In the range of MPa, the heating and pressing time is preferably 20 seconds to 400 seconds, preferably 30 seconds to 300 seconds. The lamination is preferably carried out under a reduced pressure of 26.7 hPa or less.

層合可藉由販賣的真空層合體進行。作為販賣之真空層合體，例如可舉出名機製作所公司製的真空加壓式層合體、Nikko•Materials公司製的真空施放器、分批式真空加壓層合體等。The lamination can be carried out by a vacuum laminate that is sold. Examples of the commercially available vacuum laminates include vacuum pressurized laminates manufactured by Meiji Machine Manufacturing Co., Ltd., vacuum applicators manufactured by Nikko Materials, and batch vacuum pressurized laminates.

於層合後，藉由常壓下(大氣壓下)，例如可藉由將加熱壓著構件自支持體側施予加壓，進行經層合的樹脂薄片之平滑化處理。平滑化處理之加壓條件可設定為與上述層合的加熱壓著條件之相同條件。平滑化處理可藉由販賣之層合體進行。且，層合與平滑化處理亦可使用上述販賣的真空層合體以連續方式進行。After lamination, under normal pressure (at atmospheric pressure), for example, by applying pressure from the support side of the heating and pressing member, the laminated resin sheet can be smoothed. The pressurization conditions of the smoothing treatment can be set to the same conditions as the above-mentioned lamination heat-pressing conditions. The smoothing treatment can be carried out by the laminated product sold. Furthermore, the lamination and smoothing treatment can also be performed in a continuous manner using the above-mentioned commercially available vacuum laminate.

步驟(B)為使樹脂組成物層進行硬化(例如熱硬化)而形成硬化體層的步驟。樹脂組成物層之硬化條件並無特別限定，在形成印刷配線板之硬化體層時，可使用通常所採用的條件。Step (B) is a step of curing (for example, thermally curing) the resin composition layer to form a cured body layer. The curing conditions of the resin composition layer are not particularly limited, and when forming the cured body layer of the printed wiring board, generally used conditions can be used.

例如樹脂組成物層之熱硬化條件雖依樹脂組成物的種類等而相異，但硬化溫度以120℃~240℃為佳，較佳為150℃~220℃，更佳為170℃~210℃。硬化時間以5分鐘~120分鐘為佳，較佳為10分鐘~100分鐘，更佳為15分鐘~100分鐘。For example, although the thermal curing conditions of the resin composition layer vary depending on the type of the resin composition, etc., the curing temperature is preferably 120°C to 240°C, preferably 150°C to 220°C, and more preferably 170°C to 210°C . The hardening time is preferably 5 minutes to 120 minutes, preferably 10 minutes to 100 minutes, and more preferably 15 minutes to 100 minutes.

於熱硬化樹脂組成物層之前，可將樹脂組成物層在比硬化溫度低的溫度下進行預備加熱。例如預先使樹脂組成物層進行熱硬化，可在50℃以上未達120℃，較佳為在60℃以上未達115℃，更佳為在70℃以上未達110℃之溫度下，可將樹脂組成物層進行5分鐘以上，較佳為5分鐘~150分鐘，更佳為15分鐘~120分鐘，特佳為15分鐘~100分鐘的預備加熱。Before the thermosetting resin composition layer, the resin composition layer may be preliminarily heated at a temperature lower than the curing temperature. For example, the resin composition layer is thermally hardened in advance, but it may not reach 120°C above 50°C, preferably 115°C above 60°C, and more preferably 110°C above 70°C. The resin composition layer is subjected to preliminary heating for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and particularly preferably 15 minutes to 100 minutes.

步驟(C)為於硬化體層形成貫通孔的步驟。步驟(C)之貫通孔形成，例如可使用雷射等實施。孔的尺寸或形狀可配合印刷配線板之設計而適宜地做決定。若使用本發明之硬化體層，貫通孔的頂徑，例如可適用15μm以下。貫通孔之最小頂徑雖無特別限定，以15μm以下者為佳，以13μm以下者為較佳，以11μm以下者為更佳。Step (C) is a step of forming a through hole in the hardened body layer. The formation of the through-hole in step (C) can be carried out using a laser, for example. The size or shape of the hole can be appropriately determined in accordance with the design of the printed wiring board. If the hardened body layer of the present invention is used, the top diameter of the through hole can be applied, for example, 15 μm or less. Although the minimum top diameter of the through-hole is not particularly limited, it is preferably 15 μm or less, preferably 13 μm or less, and more preferably 11 μm or less.

步驟(D)為，對硬化體層進行藉由選自含有O2 氣體及N2 氣體所成群的1種以上的氣體進行電漿處理之步驟。使用於電漿處理的氣體以O2 氣體者為佳。對於該步驟(D)，進行污跡除去。電漿處理之程序、條件並無特別限定，可採用形成印刷配線板之硬化體層時通常使用的公知程序、條件。Step (D) is a step of performing plasma treatment on the hardened body layer with one or more kinds of gas selected from the group consisting of O 2 gas and N 2 gas. The gas used for plasma treatment is preferably O 2 gas. For this step (D), stain removal is performed. The procedures and conditions of the plasma treatment are not particularly limited, and known procedures and conditions generally used when forming the hardened body layer of the printed wiring board can be adopted.

對於一實施型態，電漿處理後之硬化體層表面的算術平均粗度(Ra)以400nm以下為佳，較佳為350nm以下，更佳為300nm以下。對於下限並無特別限定，但以0.5nm以上為佳，較佳為1nm以上等。又，電漿處理後之硬化體層表面的均方根粗度(Rq)以400nm以下為佳，較佳為350nm以下，更佳為300nm以下。對於下限並無特別限定，但以0.5nm以上為佳，較佳為1nm以上等。硬化體層表面之算術平均粗度(Ra)及均方根粗度(Rq)可使用非接觸型表面粗度計而測定。For one embodiment, the arithmetic average roughness (Ra) of the surface of the hardened body layer after plasma treatment is preferably 400 nm or less, preferably 350 nm or less, and more preferably 300 nm or less. The lower limit is not particularly limited, but it is preferably 0.5 nm or more, preferably 1 nm or more. Further, the root mean square roughness (Rq) of the surface of the hardened body layer after plasma treatment is preferably 400 nm or less, preferably 350 nm or less, and more preferably 300 nm or less. The lower limit is not particularly limited, but it is preferably 0.5 nm or more, preferably 1 nm or more. The arithmetic average roughness (Ra) and root mean square roughness (Rq) of the surface of the hardened body layer can be measured using a non-contact surface roughness meter.

步驟(E)為形成導體層之步驟，於硬化體層上形成導體層。對於使用於在步驟(E)所形成的導體層之導體材料、型態、厚度等，與具備基板之導體層相同。Step (E) is a step of forming a conductor layer, and a conductor layer is formed on the hardened body layer. The conductor material, type, thickness, etc. used for the conductor layer formed in step (E) are the same as the conductor layer provided with the substrate.

對於一實施型態，導體層可藉由鍍敷而形成。例如藉由半添加法、全添加法等過去公知技術，於導體層的表面進行鍍敷，可形成具有所望配線圖型之導體層，由製造的簡便性之觀點來看以藉由半添加法而形成者為佳。以下例示出導體層藉由半添加法而形成的例子。For one embodiment, the conductor layer can be formed by plating. For example, by semi-additive method, full-additive method, and other well-known technologies in the past, plating on the surface of the conductor layer can form a conductor layer having the desired wiring pattern, from the viewpoint of simplicity of manufacturing, by the semi-additive method The shaper is better. The following illustrates an example in which the conductor layer is formed by the semi-additive method.

首先，於導體層之表面上，藉由無電解鍍敷而形成鍍敷種層。其次，於所形成的鍍敷種層上，對應所望的配線圖而形成露出鍍敷種層一部分的光罩圖型。於露出的鍍敷種層上，藉由電解鍍敷而形成金屬層後，除去光罩圖型。其後，將不要的鍍敷種層藉由蝕刻等而除去，可行持具有所望的配線圖型之導體層。First, a plating seed layer is formed on the surface of the conductor layer by electroless plating. Next, on the formed plating seed layer, a mask pattern exposing a part of the plating seed layer is formed corresponding to the desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like, and it is possible to maintain a conductor layer having a desired wiring pattern.

對於其他實施型態，導體層可使用金屬箔而形成。For other embodiments, the conductor layer can be formed using metal foil.

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

作為半導體裝置，可舉出提供於電氣製品(例如電腦、手機、數位照相機及電視等)及車輛(例如摩托車、汽車、電車、船及飛機等)等之各種半導體裝置。Examples of semiconductor devices include various semiconductor devices provided in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trams, ships, and airplanes).

本發明之半導體裝置可藉由於印刷配線板之導通處實裝零件(半導體晶片)而製造。所謂「導通處」為「傳達於印刷配線板中之電訊息的場所」，該場所可為表面上，亦可在嵌入位置。又，半導體晶片若為將半導體作為材料的電路元件即可並無特別限定。The semiconductor device of the present invention can be manufactured by mounting parts (semiconductor wafers) on the vias of the printed wiring board. The so-called "conducting place" is "the place of electrical information conveyed in the printed wiring board", which can be on the surface or in the embedded position. In addition, the semiconductor wafer is not particularly limited as long as it is a circuit element made of a semiconductor.

製造半導體裝置時的半導體晶片之實裝方法，僅為可有效地發揮半導體晶片之功能者即可，並無特別限定，但具體可舉出引線鍵合實裝方法、倒裝晶片實裝方法、藉由無顛簸的積聚層(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。其中，所謂「藉由無顛簸的積聚層(BBUL)之實裝方法」表示「將半導體晶片直接嵌入於印刷配線板之凹部，連接半導體晶片與印刷配線板上的配線之實裝方法」。 [實施例]The method of mounting a semiconductor wafer when manufacturing a semiconductor device is only required to effectively exert the function of the semiconductor wafer, and is not particularly limited, but specific examples include a wire bonding method, a flip chip mounting method, The mounting method by bumpless accumulation layer (BBUL), the mounting method by anisotropic conductive film (ACF), the mounting method by non-conductive film (NCF), etc. Among them, the so-called "mounting method by bumpless accumulation layer (BBUL)" means "the mounting method of directly embedding the semiconductor wafer in the concave portion of the printed wiring board to connect the semiconductor wafer and the wiring on the printed wiring board". [Example]

以下使用實施例更詳細說明本發明，但本發明並未限定於此等實施例者。且對於以下記載，若無另外記載，「份」及「%」各表示「質量份」及「質量%」。The present invention will be described in more detail using examples below, but the present invention is not limited to those examples. And for the following descriptions, if there is no other description, "parts" and "%" indicate "mass parts" and "mass %", respectively.

＜測定•評估方法＞ 首先，對於在本說明書的物性評估中之測定•評估方法進行說明。<Measurement and evaluation method> First, the measurement and evaluation methods in the physical property evaluation of this specification will be described.

[測定•評估用基板之調製] (1)內層電路基板之基底處理 作為內層電路基板，準備形成電路的玻璃布基材環氧樹脂雙面貼銅層合板(銅箔之厚度3μm、基板厚度0.15mm、三菱瓦斯化學公司製「HL832NSF LCA」、255×340mm尺寸)。將該內層電路基板之雙面以MEC公司製「FlatBOND-FT」的進行銅表面之有機被膜處理。[Modulation of substrate for measurement and evaluation] (1) Base treatment of inner layer circuit board As an inner layer circuit board, prepare a glass cloth substrate epoxy double-sided copper-clad laminate that forms a circuit (thickness of copper foil 3 μm, substrate thickness 0.15 mm, “HL832NSF LCA” manufactured by Mitsubishi Gas Chemical Co., 255×340 mm size) . The both surfaces of the inner layer circuit board were treated with an organic coating on the copper surface by "FlatBOND-FT" manufactured by MEC Corporation.

(2)樹脂薄片之層合 從在下述各實施例及比較例所製作的樹脂薄片1~5剝離保護薄膜。將樹脂組成物層之露出的樹脂薄片，使用分批式真空加壓層合體(Nichigo-Morton公司製2階段積聚層合體「CVP700」)，層合於內層電路基板的雙面，使樹脂組成物層與內層電路基板接合。層合為30秒減壓使氣壓至13hPa以下後，藉由100℃且壓力0.74MPa進行30秒壓著而實施。其次，將經層合的樹脂薄片在大氣壓下，100℃且壓力0.5MPa進行60秒熱壓施予平滑化。(2) Lamination of resin sheets The protective film was peeled from the resin sheets 1 to 5 produced in the following examples and comparative examples. The exposed resin sheet of the resin composition layer was laminated on both sides of the inner circuit board using a batch-type vacuum press laminate (Nichigo-Morton Corporation 2-stage accumulation laminate "CVP700") to make up the resin composition The object layer is bonded to the inner layer circuit board. Lamination was carried out by depressurizing for 30 seconds to reduce the air pressure to 13 hPa or less, and pressing was performed at 100° C. and a pressure of 0.74 MPa for 30 seconds. Next, the laminated resin sheet was hot-pressed under atmospheric pressure at 100° C. and a pressure of 0.5 MPa for 60 seconds for smoothing.

(3)樹脂組成物層之硬化 樹脂薄片經層合後，使樹脂組成物層進行熱硬化，於內層電路基板之雙面形成硬化體層。此時，在附有支持體之狀態下使樹脂組成物層進行熱硬化。(3) Hardening of the resin composition layer After the resin sheets are laminated, the resin composition layer is thermally cured to form a cured body layer on both sides of the inner circuit board. At this time, the resin composition layer is thermally cured with the support attached.

樹脂組成物層的熱硬化為，在130℃(投入於130℃的烤箱後)進行30分鐘熱硬化，然後在175℃(轉移至175℃的烤箱後)進行30分鐘熱硬化。其後，將基板在室溫環境下取出，並剝離支持體。將該基板作為評估基板A。於評估基板A中之硬化體層的厚度為10μm。The thermosetting of the resin composition layer was performed at 130°C (after being put in an oven at 130°C) for 30 minutes, and then at 175°C (after transferring to an oven at 175°C) for 30 minutes. Thereafter, the substrate is taken out in a room temperature environment, and the support is peeled off. Let this board be evaluation board A. The thickness of the hardened body layer in the evaluation substrate A was 10 μm.

(4)藉由UV-YAG雷射之貫通孔的形成 使用UV-YAG雷射加工機(通過力學股份有限公司製「LU-2L212/M50L」)，在下述條件下於硬化體層形成小徑的貫通孔。 能源0.08W，射擊數25，目標最大直徑10μm(4) Through the formation of UV-YAG laser through holes Using a UV-YAG laser processing machine ("LU-2L212/M50L" manufactured by MECHANICS Co., Ltd.), a small-diameter through hole was formed in the hardened body layer under the following conditions. Energy 0.08W, number of shots 25, target maximum diameter 10μm

(5)除污跡處理 在貫通孔形成後，將形成硬化體層的內層電路基板，使用真空電漿蝕刻裝置(Tepla公司製100-E PLASMA SYSTEM)，在O2 氣體100%且真空度100Pa之條件下，進行5分鐘處理。將該基板作為評估基板B。(5) After the through-holes are formed in the decontamination process, the inner circuit board on which the hardened body layer is formed is vacuum plasma etched (100-E PLASMA SYSTEM manufactured by Tepla Corporation) using 100% O 2 gas and a vacuum of 100 Pa Under the conditions, the treatment is carried out for 5 minutes. Let this board be the evaluation board B.

(6)導體層之形成 於硬化體層的露出表面上形成導體層。對於評估基板B，使用濺射裝置(Canon Anerva公司製「E-400S」)，形成鈦層(厚度30nm)，再形成銅層(厚度300nm)。將所得之基板在150℃進行30分鐘加熱並進行退火處理後，依據半添加法，形成蝕刻阻劑，藉由曝光•顯像進行圖型形成後，進行硫酸銅電解鍍敷，形成25μm厚度的導體層。導體圖型形成後，在200℃進行60分鐘加熱並退火處理。將所得之印刷配線板稱為評估基板C。(6) Formation of conductor layer A conductor layer is formed on the exposed surface of the hardened body layer. For the evaluation substrate B, a sputtering device ("E-400S" manufactured by Canon Anerva) was used to form a titanium layer (thickness 30 nm) and then a copper layer (thickness 300 nm). After the obtained substrate was heated at 150° C. for 30 minutes and annealed, an etching resist was formed according to the semi-additive method. After patterning by exposure and development, copper sulfate electrolytic plating was performed to form a 25 μm thick Conductor layer. After the conductor pattern is formed, it is heated and annealed at 200°C for 60 minutes. The obtained printed wiring board is referred to as evaluation board C.

[樹脂面積比之測定] 對於評估基板A，進行截面露出使於支持體表面呈垂直方向的硬化體層之截面露出，將該截面的掃描電子顯微鏡(SEM)觀察，使用集束離子束/掃描離子顯微鏡(II納米技術公司製「SMI3050SE」)而實施，將SEM觀察像作為圖像而保存。使用圖像解析軟體(美國立衛生研究所製「ImageJ」)，對於自在測定區域的寬度7.5μm中之支持體與硬化體層之境界的一定距離a(μm)~b(μm)之區域與b(μm) ~c(μm)之區域，將樹脂部分設定為黑色，將樹脂以外的無機填充材部分設定為白色，進行白黑二進制化，對於各區域，各導出作為黑色部分之像素數的樹脂部分之面積A’a-b 與A’b-c ，將各對應條件(1)~條件(3)的每單位面積之樹脂成分的面積Aa-b /Ab-c 依據下述式算出。 Aa-b /Ab-c =k(A’a-b /A’b-c )[Measurement of resin area ratio] For the evaluation substrate A, the cross section was exposed to expose the cross section of the hardened body layer perpendicular to the surface of the support, and the cross section was observed with a scanning electron microscope (SEM) using a cluster ion beam/scanning ion microscope ("SMI3050SE" manufactured by II Nanotechnology Co., Ltd.) was implemented, and the SEM observation image was saved as an image. Using image analysis software ("ImageJ" manufactured by the American Institute of Hygiene), the area and b of a certain distance a (μm) to b (μm) between the support and the hardened layer in the width of the free measurement area of 7.5 μm In the area from (μm) to c (μm), the resin part is set to black, and the inorganic filler material other than resin is set to white, and the white and black binarization is performed. For each region, the resin that is the number of pixels in the black part is derived The areas A'ab and A'bc of each part are calculated according to the following formula for the area A ab /A bc of the resin component per unit area corresponding to the conditions (1) to (3). A ab /A bc =k(A' ab /A' bc )

於此，k表示滿足k=|c-b|/|b-a|之係數。在條件(1)A0-1 /A1-2 中，a=0、b=1、c=2，在條件(2)A0-0.5 /A0.5-1 中，a=0、b=0.5、c=1。對於條件(3)A0.5-d /Ad-0.5D ，d設定為1(μm)。且，評估基板A之硬化層的厚度D為10(μm)。因此，在條件(3)A0.5-d /Ad-0.5D 中，a=0.5、b=1、c=5。Here, k represents a coefficient that satisfies k=|cb|/|ba|. In condition (1) A 0-1 /A 1-2 , a=0, b=1, c=2, in condition (2) A 0-0.5 /A 0.5-1 , a=0, b= 0.5, c=1. For condition (3) A 0.5-d /A d-0.5D , d is set to 1 (μm). Furthermore, the thickness D of the hardened layer of the evaluation substrate A was 10 (μm). Therefore, in the condition (3) A 0.5-d /A d-0.5D , a=0.5, b=1, c=5.

且，進行樹脂面積比之測定時，設定二進制化閾值使(無機填充材部分之像素數)/(截面試料之截面的全像素數)×100之值成為截面試料之無機填充材的體積%值±3之範圍，校正條件。In addition, when measuring the resin area ratio, set the binarization threshold so that (the number of pixels of the inorganic filler)/(the total number of pixels of the cross section of the cross-sectional sample) × 100 becomes the volume% value of the inorganic filler of the cross-sectional sample ±3 range, calibration conditions.

[污跡除去性之評估] 將評估基板B之貫通孔底部的周圍以SEM觀察，從所得之圖像測定自貫通孔底部之壁面的最大污跡長。污跡除去性為依據以下基準進行評估。 評估基準： ○：最大污跡長未達2μm ×：最大污跡長為2μm以上[Evaluation of stain removal properties] The circumference of the bottom of the through hole of the evaluation substrate B was observed with SEM, and the maximum stain length of the wall surface from the bottom of the through hole was measured from the obtained image. The stain removal property was evaluated based on the following criteria. Evaluation criteria: ○: The maximum stain length is less than 2μm ×: The maximum stain length is more than 2μm

[硬化體層與導體層之密著強度(剝離強度)的測定] 硬化體層與導體層之剝離強度的測定，對於評估基板C為依據JIS C6481進行。具體而言，對於評估基板C之導體層，切出寬度10mm、長度100mm之部分，剝開該一端並以夾具包住，在室溫中，測定以50mm/分的速度之於垂直方向拉剝35mm時的負載，求得剝離強度(kgf/cm)。測定為使用拉伸試驗機(TSE公司製「AC-50C-SL」)。[Measurement of Adhesion Strength (Peel Strength) of Hardened Body Layer and Conductor Layer] The peel strength of the cured body layer and the conductor layer was measured in accordance with JIS C6481 for the evaluation substrate C. Specifically, for the conductor layer of the evaluation substrate C, a portion with a width of 10 mm and a length of 100 mm was cut, the end was peeled off and wrapped with a jig, and the peeling in the vertical direction at a speed of 50 mm/min was measured at room temperature The load at 35 mm was used to determine the peel strength (kgf/cm). The measurement was performed using a tensile tester ("AC-50C-SL" manufactured by TSE).

在下述實施例及比較例所使用的樹脂組成物1~4之塗漆依據下述調製。The paints of the resin compositions 1 to 4 used in the following examples and comparative examples were prepared according to the following.

[樹脂組成物1之塗漆的調製] 將雙酚A型環氧樹脂(三菱化學公司製「828US」、環氧當量約180)10份、雙二甲酚型環氧樹脂(三菱化學公司製「YX4000H」、環氧當量約190)20份，及聯苯基型環氧樹脂(日本化藥公司製「NC3000L」、環氧當量約269)10份、磷腈樹脂(大塚化學公司製「SPS-100」)2份、苯氧基樹脂(三菱化學公司製「YX7553BH30」、固體成分30質量%之MEK與環己酮之1：1溶液)10份，於MEK60份、甲苯20份中一邊攪拌，一邊使其加熱溶解。冷卻至室溫後，將活性酯系硬化劑(DIC公司製「HPC-8000-65T」、活性基當量約223、固體成分65質量%之甲苯溶液)30份、酚系硬化劑(DIC公司製「LA-3018-50P」、活性基當量約151、固體成分50%之2-甲氧基丙醇溶液)8份、苯並噁嗪化合物(JFE化學公司製「ODA-BOZ」之固體成分50質量%之MEK溶液)6份、硬化促進劑(4-二甲基胺基吡啶(DMAP)、固體成分5質量%之MEK溶液)4份、球狀二氧化矽(Denka公司製「UFP-30」、平均粒徑0.3μm、比表面積30.9m2 )110份進行混合，以高速轉動攪拌機進行均勻分散後，以筒式過濾器(ROKITECHNO公司製「SHP020」)進行過濾，調製出樹脂組成物1之塗漆。[Preparation of paint for resin composition 1] 10 parts of bisphenol A epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 180), and bis-cresol epoxy resin (manufactured by Mitsubishi Chemical Corporation) "YX4000H", epoxy equivalent of about 190) 20 parts, and biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269) 10 parts, phosphazene resin (Otsuka Chemical Co., Ltd. "SPS"-100") 2 parts, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) 10 parts, stirring in 60 parts of MEK and 20 parts of toluene , While heating to dissolve. After cooling to room temperature, 30 parts of active ester-based hardener ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223, solid content 65% by mass in toluene solution), phenol-based hardener (manufactured by DIC Corporation) "LA-3018-50P", active group equivalent of approximately 151, 2-methoxypropanol solution with a solid content of 50%) 8 parts, benzoxazine compound (solid content of "ODA-BOZ" manufactured by JFE Chemical Corporation 50 6 parts by mass of MEK solution), 4 parts of hardening accelerator (4-dimethylaminopyridine (DMAP), 5% by mass of MEK solution with solid content), spherical silica (Denka company "UFP-30" ”, average particle diameter 0.3 μm, specific surface area 30.9 m 2 ) 110 parts were mixed, and evenly dispersed by a high-speed rotating mixer, then filtered with a cartridge filter (“SHP020” manufactured by ROKITECHNO) to prepare a resin composition 1 Painted.

[樹脂組成物2之塗漆的調製] 將雙酚A型環氧樹脂(三菱化學公司製「828US」、環氧當量約180)10份、雙二甲酚型環氧樹脂(三菱化學公司製「YX4000H」、環氧當量約190)20份，及聯苯基型環氧樹脂(日本化藥公司製「NC3000L」、環氧當量約269)10份、苯氧基樹脂(三菱化學公司製「YX7553BH30」、固體成分30質量%之MEK與環己酮之1：1溶液)50份於MEK60份、甲苯20份中一邊攪拌，一邊使其加熱溶解。冷卻至室溫後，將活性酯系硬化劑(DIC公司製「HPC-8000-65T」、活性基當量約223、固體成分65質量%之甲苯溶液)30份、酚系硬化劑(DIC公司製「LA-3018-50P」、活性基當量約151、固體成分50%之2-甲氧基丙醇溶液)8份、苯並噁嗪化合物(JFE化學公司製「ODA-BOZ」之固體成分50質量%之MEK溶液)6份、硬化促進劑(4-二甲基胺基吡啶(DMAP)、固體成分5質量%之MEK溶液)4份進行混合後，調製出樹脂組成物2之塗漆。[Preparation of paint of resin composition 2] 10 parts of bisphenol A epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of approximately 180), and bis-cresol epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical Corporation, approximately 190 epoxy equivalent) 20 Parts, and 10 parts of biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd. with an epoxy equivalent of about 269), phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, and 30% by mass of MEK and solids) (1:1 solution of cyclohexanone) 50 parts were dissolved in 60 parts of MEK and 20 parts of toluene while stirring and heating. After cooling to room temperature, 30 parts of active ester-based hardener ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223, solid content 65% by mass in toluene solution), phenol-based hardener (manufactured by DIC Corporation) "LA-3018-50P", active group equivalent of approximately 151, 2-methoxypropanol solution with a solid content of 50%) 8 parts, benzoxazine compound (solid content of "ODA-BOZ" manufactured by JFE Chemical Corporation 50 After mixing 6 parts of a mass% MEK solution) and 4 parts of a hardening accelerator (4-dimethylaminopyridine (DMAP) and a solid content 5% by mass MEK solution), the resin composition 2 paint was prepared.

[樹脂組成物3之塗漆的調製] 將亞萘基醚型環氧樹脂(DIC公司製「HP6000」、環氧當量約250)10份、液狀萘型環氧樹脂(DIC公司製「HP4032SS」、環氧當量約144)10份，與雙二甲酚型環氧樹脂(三菱化學公司製「YX4000H」、環氧當量約185)10份於MEK10份、環己酮10份、溶劑石腦油40份中一邊攪拌，一邊使其加熱溶解。冷卻至室溫後，於此將雙酚A二氰酸酯之預聚物(Lonza Japan公司製「BA230S75」、氰酸酯當量約232、不揮發分75質量%之MEK溶液)16份、酚酚醛清漆型多官能氰酸酯樹脂(Lonza Japan公司製「PT30」、氰酸酯當量約124、不揮發分80質量%之MEK溶液)6份進行共同攪拌混合，進一步混合活性酯硬化劑(DIC公司製「HPC-8000-65T」、活性基當量約223、固體成分65質量%之甲苯溶液)12份、作為硬化促進劑之4-二甲基胺基吡啶(DMAP)的1質量%之MEK溶液2份、鈷(III)乙醯丙酮酸酯(東京化成公司製)之1質量%的MEK溶液4.5份，及球形二氧化矽(將Admatechs公司製「SOC2」以胺基矽烷進行表面處理者，平均粒子徑0.5μm，比表面積5.9m2 )140份、作為難燃劑之(三光公司製「HCA-HQ-HST」、10-(2,5-二羥基苯基)-10-氫-9-氧雜-10-磷菲-10-氧化物)4份、作為橡膠粒子之Staphyloid(Gantz Kasei公司製之AC3816N)2份，以高速轉動攪拌機進行均勻分散後，以筒式過濾器(ROKITECHNO公司製「SHP050」)進行過濾後，調製出樹脂組成物3之塗漆。樹脂組成物3之氮原子含有量為2.02質量%。[Preparation of paint for resin composition 3] 10 parts of naphthalene ether type epoxy resin ("HP6000" manufactured by DIC Corporation, epoxy equivalent of about 250) and liquid naphthalene type epoxy resin ("HP4032SS manufactured by DIC Corporation") ", epoxy equivalent of about 144) 10 parts, and bis-xylenol type epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) 10 parts in MEK 10 parts, cyclohexanone 10 parts, solvent naphtha In 40 parts of oil, it was heated and dissolved while stirring. After cooling to room temperature, 16 parts of bisphenol A dicyanate prepolymer ("BA230S75" manufactured by Lonza Japan Co., Ltd., MEK solution having a cyanate equivalent weight of approximately 232 and a nonvolatile content of 75% by mass) were added to this part. 6 parts of novolac-type multifunctional cyanate resin ("PT30" manufactured by Lonza Japan Co., Ltd., MEK solution having a cyanate equivalent weight of about 124 and a nonvolatile content of 80% by mass) are stirred and mixed together, and further mixed with an active ester hardener (DIC "HPC-8000-65T" manufactured by the company, active group equivalent of about 223, solid content 65% by mass in toluene solution) 12 parts, 1% by mass of MEK as 4-dimethylaminopyridine (DMAP) as a hardening accelerator 2 parts of the solution, 4.5 parts of a 1% by mass MEK solution of cobalt (III) acetopyruvate (manufactured by Tokyo Chemical Industry Co., Ltd.), and spherical silica (when surface treatment of "SOC2" made by Admatechs with aminosilane) , Average particle diameter 0.5μm, specific surface area 5.9m 2 ) 140 parts, as a flame retardant ("HCA-HQ-HST" manufactured by Sanko Company, 10-(2,5-dihydroxyphenyl)-10-hydrogen- 4 parts of 9-oxa-10-phosphaphenanthrene-10-oxide) and 2 parts of Staphyloid (AC3816N manufactured by Gantz Kasei) as rubber particles, after uniformly dispersed by a high-speed rotating mixer, use a cartridge filter (ROKITECHNO "SHP050" manufactured by the company) was filtered to prepare a paint for resin composition 3. The nitrogen atom content of the resin composition 3 is 2.02% by mass.

[樹脂組成物4之塗漆的調製] 對於樹脂組成物3，將雙酚A二氰酸酯之預聚物(Lonza Japan公司製「BA230S75」、氰酸酯當量約232、不揮發分75質量%之MEK溶液)16份改為8份，將酚酚醛清漆型多官能氰酸酯樹脂(Lonza Japan公司製「PT30」、氰酸酯當量約124、不揮發分80質量%之MEK溶液)6份改為1份以外，與樹脂組成物3同樣地調製出樹脂組成物4之塗漆。樹脂組成物3之氮原子含有量為0.88質量%。[Preparation of paint for resin composition 4] For resin composition 3, 16 parts of a prepolymer of bisphenol A dicyanate ("BA230S75" manufactured by Lonza Japan, a MEK solution with a cyanate equivalent of approximately 232, and a nonvolatile content of 75% by mass) were changed to 8 parts , 6 parts of phenol novolac type multifunctional cyanate resin ("PT30" manufactured by Lonza Japan company, MEK solution with a cyanate equivalent of about 124, and 80% by mass nonvolatile content) were changed to 1 part, and the resin composition 3 The paint of the resin composition 4 was prepared in the same manner. The nitrogen atom content of the resin composition 3 was 0.88% by mass.

＜實施例1：樹脂薄片1之製作＞ 作為支持體，準備厚度38μm之PET薄膜(Lintec公司製「AL5」)。於該支持體上將樹脂組成物1之塗漆使用模具塗布進行均勻塗布，將塗布膜在80~120℃(平均100℃)進行3分鐘乾燥，於該支持體上形成以樹脂組成物1形成的第1層(厚度9.5μm)。其次，欲使乾燥後的樹脂組成物層之總厚度成為10μm，於第1層上將樹脂組成物2之塗漆以模具塗布進行均勻塗布，將塗布膜在80℃進行1分鐘乾燥後，於樹脂面使厚度15μm之聚丙烯覆蓋薄膜(Prince F-Tex公司製「AlphanMA-411」)的平滑面側進行貼合，製作出稱為支持體(38μmPET薄膜)/樹脂組成物層1/樹脂組成物層2/保護薄膜(MA-411)之構成的樹脂薄片1。<Example 1: Production of resin sheet 1> As a support, a PET film ("AL5" manufactured by Lintec) with a thickness of 38 μm was prepared. The varnish of the resin composition 1 is uniformly coated on the support using a die coating, and the coating film is dried at 80 to 120°C (average 100°C) for 3 minutes to form the resin composition 1 on the support The first layer (thickness 9.5μm). Next, in order to make the total thickness of the dried resin composition layer 10 μm, the varnish of the resin composition 2 is uniformly coated on the first layer by die coating, and the coating film is dried at 80° C. for 1 minute, then The resin surface was bonded to the smooth side of a polypropylene cover film ("AlphanMA-411" manufactured by Prince F-Tex Co., Ltd.) with a thickness of 15 μm to produce a support (38 μm PET film)/resin composition layer 1/resin composition Resin sheet 1 composed of the object layer 2/protective film (MA-411).

＜實施例2：樹脂薄片2之製作＞ 作為支持體，準備厚度38μm之PET薄膜(Lintec公司製「AL5」)。於該支持體上將樹脂組成物1的塗漆以模具塗布進行均勻塗布，將塗布膜以80~120℃(平均100℃)進行3分鐘乾燥，作成具備樹脂組成物1之層(厚度9.5μm)的樹脂薄片d。其次準備厚度25μm之PET薄膜(Lintec公司製「AL5」)的支持體，將樹脂組成物2之塗漆以模具塗布進行均勻塗布，將塗布膜以80℃進行1分鐘乾燥，製作出具備樹脂組成物2之層(厚度0.5μm)的樹脂薄片e。其次，使用熱輥，欲成為支持體(38μmPET薄膜)/樹脂組成物層1/樹脂組成物層2/支持體(25μm脫模PET：作為保護薄膜，於層合前剝離)之構成，重疊樹脂薄片d與樹脂薄片e而製作樹脂薄片2。<Example 2: Production of resin sheet 2> As a support, a PET film ("AL5" manufactured by Lintec) with a thickness of 38 μm was prepared. On this support, the paint of the resin composition 1 was uniformly coated by die coating, and the coating film was dried at 80 to 120°C (average 100°C) for 3 minutes to prepare a layer (thickness 9.5 μm) with the resin composition 1 )'S resin sheet d. Next, a support of a PET film ("AL5" manufactured by Lintec) with a thickness of 25 μm was prepared, the paint of the resin composition 2 was uniformly coated by die coating, and the coating film was dried at 80° C. for 1 minute to produce a resin composition. Resin sheet e of layer 2 (thickness 0.5 μm). Next, using a hot roller, the resin is laminated to the support (38 μm PET film)/resin composition layer 1/resin composition layer 2/support (25 μm release PET: peeled off as a protective film before lamination), and the resin is overlaid The resin sheet 2 is produced by the sheet d and the resin sheet e.

＜實施例3：樹脂薄片3之製作＞ 作為支持體，準備厚度38μm之PET薄膜(Lintec公司製「AL5」)。於該支持體上將樹脂組成物3之塗漆使用模具塗布進行均勻塗布，將塗布膜以80~120℃(平均100℃)進行3分鐘乾燥，於樹脂面貼合厚度15μm的聚丙烯覆蓋薄膜(Prince F-Tex公司製「AlphanMA-411」)之平滑面側，製作出稱為支持體(38μmPET薄膜)/樹脂組成物層3(厚度10μm)/保護薄膜(MA-411)之構成的樹脂薄片3。<Example 3: Production of resin sheet 3> As a support, a PET film ("AL5" manufactured by Lintec) with a thickness of 38 μm was prepared. On this support, the paint of the resin composition 3 was uniformly coated using a die coater, the coating film was dried at 80 to 120°C (average 100°C) for 3 minutes, and a polypropylene cover film with a thickness of 15 μm was attached to the resin surface (The "AlphanMA-411" manufactured by Prince F-Tex Corporation) on the smooth surface side, a resin composed of a support (38 μm PET film)/resin composition layer 3 (thickness 10 μm)/protective film (MA-411) was fabricated片3。 Thin 3.

＜比較例1：樹脂薄片4之製作＞ 對於樹脂薄片3之製作，將塗漆改為樹脂組成物1以外，與樹脂薄片3同樣地製作出樹脂薄片4。<Comparative Example 1: Production of resin sheet 4> For the production of the resin sheet 3, the resin sheet 4 was produced in the same manner as the resin sheet 3 except that the paint was changed to the resin composition 1.

＜比較例2：樹脂薄片5之製作＞ 對於樹脂薄片3之製作，將塗漆改為樹脂組成物4以外，與樹脂薄片3同樣地製作出樹脂薄片5。<Comparative Example 2: Production of resin sheet 5> For the production of the resin sheet 3, the resin sheet 5 was produced in the same manner as the resin sheet 3 except that the paint was changed to the resin composition 4.

實施例及比較例之各評估結果如表1所示。The evaluation results of Examples and Comparative Examples are shown in Table 1.

Figure 02_image001
Figure 02_image001

由以上結果得知，條件(1)~條件(3)滿足所定範圍的硬化體層，不僅可維持高剝離強度，藉由使用N2 氣體或O2 氣體之電漿處理的污跡除去性亦優良。From the above results, it can be seen that the hardened body layer satisfying the conditions (1) to (3) not only maintains high peel strength, but also has excellent stain removal properties by plasma treatment using N 2 gas or O 2 gas. .

100:硬化體層 100D:硬化體層之主表面 110:對於自導體層的距離而言，自0μm至1μm為止的區域 110’:對於自與支持體為相反側的硬化體層之主表面的距離而言，自0μm至1μm為止的區域 120:對於自導體層的距離而言，自1μm至2μm為止的區域 120’:對於自與支持體為相反側的硬化體層之主表面的距離而言，自1μm至2μm為止的區域 130:對於自導體層的距離而言，自0μm至0.5μm為止的區域 130’:對於自與支持體為相反側的硬化體層之主表面的距離而言，自0μm至0.5μm為止的區域 140:對於自導體層的距離而言，自0.5μm至1μm為止的區域 140’:對於自與支持體為相反側的硬化體層之主表面的距離而言，自0.5μm至1μm為止的區域 150:對於自導體層的距離而言，自0.5μm至dμm為止的區域 150’:對於自與支持體為相反側的硬化體層之主表面的距離而言，自0.5μm至dμm為止的區域 160:對於自導體層的距離而言，自dμm至0.5Dμm為止的區域 160’:對於自與支持體為相反側的硬化體層之主表面的距離而言，自dμm至0.5Dμm為止的區域 200:基板 210:導體層 210U:基板之導體層側的面 300:貫通孔 300S:貫通孔之側面 310:污跡 320:貫通孔之底部 400:樹脂組成物層 500:支持體 600:樹脂薄片100: hardened body 100D: the main surface of the hardened body 110: For the distance from the conductor layer, the area from 0 μm to 1 μm 110’: For the distance from the main surface of the hardened body layer on the opposite side to the support, the area from 0 μm to 1 μm 120: For the distance from the conductor layer, the area from 1 μm to 2 μm 120’: For the distance from the main surface of the hardened body layer on the opposite side to the support, the area from 1 μm to 2 μm 130: For the distance from the conductor layer, the area from 0 μm to 0.5 μm 130’: For the distance from the main surface of the hardened body layer on the opposite side to the support, the area from 0 μm to 0.5 μm 140: For the distance from the conductor layer, the area from 0.5 μm to 1 μm 140’: For the distance from the main surface of the hardened body layer on the opposite side to the support, the area from 0.5 μm to 1 μm 150: For the distance from the conductor layer, the area from 0.5 μm to d μm 150’: For the distance from the main surface of the hardened body layer on the opposite side to the support, the area from 0.5 μm to d μm 160: For the distance from the conductor layer, the area from dμm to 0.5Dμm 160’: For the distance from the main surface of the hardened body layer on the opposite side to the support, the area from dμm to 0.5Dμm 200: substrate 210: conductor layer 210U: the surface of the substrate on the conductor layer side 300: through hole 300S: the side of the through hole 310: smudge 320: the bottom of the through hole 400: resin composition layer 500: support 600: resin sheet

[圖1] 圖1表示以模型方式表示本發明之一實施型態中之硬化體層的截面之截面圖。 [圖2] 圖2表示以模型方式表示本發明之一實施型態中之形成貫通孔的硬化體層之截面的截面圖。 [圖3] 圖3表示以模型方式表示本發明之一實施型態中之硬化體層的截面之截面圖。 [圖4] 圖4表示以模型方式表示本發明之一實施型態中之具有支持體與樹脂組成物層之樹脂薄片的截面之截面圖。 [圖5] 圖5表示以模型方式表示本發明之一實施型態中之將樹脂薄片的樹脂組成物層進行硬化而形成硬化體層時的支持體與硬化體層之截面的截面圖。 [圖6] 圖6表示以模型方式表示本發明之一實施型態中之將樹脂薄片的樹脂組成物層進行硬化而形成硬化體層時的支持體與硬化體層之截面的截面圖。[FIG. 1] FIG. 1 is a cross-sectional view showing in a model manner a cross-section of a hardened body layer in an embodiment of the present invention. [FIG. 2] FIG. 2 is a cross-sectional view showing in model form a cross-section of a through-hole formed hardened body layer in an embodiment of the present invention. [Fig. 3] Fig. 3 shows a cross-sectional view showing in a model manner the cross-section of a hardened body layer in an embodiment of the present invention. [FIG. 4] FIG. 4 is a cross-sectional view showing in model form a cross section of a resin sheet having a support and a resin composition layer in an embodiment of the present invention. [FIG. 5] FIG. 5 is a cross-sectional view showing in model form a cross section of a support and a cured body layer when a resin composition layer of a resin sheet is cured to form a cured body layer in one embodiment of the present invention. [Fig. 6] Fig. 6 is a cross-sectional view showing in model form a cross section of a support and a cured body layer when a resin composition layer of a resin sheet is cured to form a cured body layer in one embodiment of the present invention.

100:硬化體層 100: hardened body

100D:硬化體層之主表面 100D: the main surface of the hardened body

110:對於自導體層的距離而言，自0μm至1μm為止的區域 110: For the distance from the conductor layer, the area from 0 μm to 1 μm

120:對於自導體層的距離而言，自1μm至2μm為止的區域 120: For the distance from the conductor layer, the area from 1 μm to 2 μm

130:對於自導體層的距離而言，自0μm至0.5μm為止的區域 130: For the distance from the conductor layer, the area from 0 μm to 0.5 μm

140:對於自導體層的距離而言，自0.5μm至1μm為止的區域 140: For the distance from the conductor layer, the area from 0.5 μm to 1 μm

200:基板 200: substrate

210:導體層 210: conductor layer

210U:基板之導體層側的面 210U: the surface of the substrate on the conductor layer side

300:貫通孔 300: through hole

300S:貫通孔之側面 300S: the side of the through hole

310:污跡 310: smudge

320:貫通孔之底部 320: the bottom of the through hole

Claims (21)

一種硬化體層，其為設置於在最外層的至少一部分具備導體層的基板之前述導體層側的面上，且以無機填充材含有量為40質量%以上的樹脂組成物之硬化物所形成者，其特徵為對於在前述硬化體層的主表面呈垂直之前述硬化體層的截面，對於自前述導體層的距離而言，將自0μm至1μm為止的區域中之每單位面積的樹脂成分之面積作為 A0-1 ，將自1μm至2μm為止的區域中之每單位面積的樹脂成分之面積作為A1-2 時，滿足A0-1 /A1-2 ＞1.1者。A hardened body layer formed of a hardened product of a resin composition having an inorganic filler content of 40% by mass or more and provided on the surface of the substrate on the conductor layer side of a substrate having a conductor layer on at least a part of the outermost layer , Characterized in that the cross-section of the hardened body layer perpendicular to the main surface of the hardened body layer, and the distance from the conductive layer, the area of the resin component per unit area in the area from 0 μm to 1 μm is taken as A 0-1 , when the area of the resin component per unit area in the area from 1 μm to 2 μm is regarded as A 1-2 , A 0-1 /A 1-2 >1.1 is satisfied. 如請求項1之硬化體層，其中對於前述截面，對於自前述導體層的距離而言，將自0μm至0.5μm為止的區域中之每單位面積的樹脂成分之面積作為A0-0.5 ，將自0.5μm至1μm為止的區域中之每單位面積的樹脂成分之面積作為A0.5-1 時，滿足A0-0.5 /A0.5-1 ＞1.1者。The hardened body layer according to claim 1, wherein the cross section and the distance from the conductor layer are the area of the resin component per unit area in the area from 0 μm to 0.5 μm as A 0-0.5 , and When the area of the resin component per unit area in the area from 0.5 μm to 1 μm is A 0.5-1 , A 0-0.5 /A 0.5-1 >1.1 is satisfied. 如請求項1或2之硬化體層，其中對於前述截面，對於自前述導體層的距離而言，將自0.5μm至dμm為止的區域中之每單位面積的樹脂成分之面積作為A0.5-d ，將自dμm至0.5Dμm為止的區域中之每單位面積的樹脂成分之面積作為Ad-0.5D 時，滿足0.9≦A0.5-d /Ad-0.5D ≦1.1(其中，d為滿足0.5＜d＜0.5D的數，D為前述硬化體層的厚度)者。The hardened body layer according to claim 1 or 2, wherein the cross section and the distance from the conductor layer are the area of the resin component per unit area in the area from 0.5 μm to d μm as A 0.5-d , When the area of the resin component per unit area in the area from dμm to 0.5Dμm is taken as A d-0.5D , 0.9≦A 0.5-d /A d-0.5D ≦1.1 (where d is 0.5≦ d<0.5D, D is the thickness of the hardened body layer). 如請求項1之硬化體層，其中前述樹脂組成物含有環氧樹脂。The hardened body layer according to claim 1, wherein the aforementioned resin composition contains an epoxy resin. 如請求項4之硬化體層，其中前述樹脂組成物進一步含有活性酯系硬化劑。The hardened body layer according to claim 4, wherein the aforementioned resin composition further contains an active ester-based hardener. 如請求項4或5之硬化體層，其中前述樹脂組成物進一步含有氰酸酯系硬化劑，該含有量在將前述樹脂組成物中之樹脂成分作為100質量%時為15質量%以上。The cured body layer according to claim 4 or 5, wherein the resin composition further contains a cyanate-based curing agent, and the content is 15% by mass or more when the resin component in the resin composition is taken as 100% by mass. 如請求項1之硬化體層，其中前述樹脂組成物之氮原子含有量在將前述樹脂組成物中之樹脂成分作為100質量%時為1質量%以上。The hardened body layer according to claim 1, wherein the nitrogen atom content of the resin composition is 1% by mass or more when the resin component in the resin composition is taken as 100% by mass. 如請求項1之硬化體層，其中前述硬化體層為，自與前述基板的相反側依序具備以下第1硬化體層與第2硬化體層；第1硬化體層係以第1樹脂組成物的硬化物所形成者；第2硬化體層係以具有與前述第1樹脂組成物相異組成之第2樹脂組成物的硬化物所形成者。The cured body layer according to claim 1, wherein the cured body layer is provided with the following first cured body layer and second cured body layer in sequence from the opposite side of the substrate; the first cured body layer is formed by the cured body of the first resin composition Former; the second cured body layer is formed of a cured product having a second resin composition different from the first resin composition. 如請求項8之硬化體層，其中前述第2硬化體層的厚度為未達2μm。The hardened body layer according to claim 8, wherein the thickness of the second hardened body layer is less than 2 μm. 如請求項8或9之硬化體層，其中前述第2樹脂組成物的無機填充材含有量為未達20質量%。The hardened body layer according to claim 8 or 9, wherein the content of the inorganic filler in the second resin composition is less than 20% by mass. 如請求項1之硬化體層，其為欲提供於電漿處理者，該電漿處理係藉由選自含有O2 氣體及N2 氣體所成群的1種以上的氣體者。The hardened body layer according to claim 1, which is to be provided to a plasma treatment, which is selected from one or more gases selected from the group consisting of O 2 gas and N 2 gas. 一種印刷配線板，其特徵為具有如請求項1之硬化體層，與具備導體層之基板。A printed wiring board characterized by having a hardened body layer as in claim 1, and a substrate provided with a conductor layer. 如請求項12之印刷配線板，其為於前述硬化體層，形成頂徑為15μm以下的貫通孔。The printed wiring board according to claim 12, which is formed in the hardened body layer and has a through hole with a top diameter of 15 μm or less. 一種半導體裝置，其特徵為含有如請求項1之硬化體層。A semiconductor device characterized by comprising a hardened body layer as in claim 1. 一種樹脂薄片，其為具有支持體，與無機填充材之含有量為40質量%以上的樹脂組成物層者，其特徵為對於 使前述樹脂組成物層進行硬化而形成硬化體層時於前述硬化體層的主表面呈垂直的前述硬化體層之截面，對於自與前述支持體為相反側的前述硬化體層之主表面的距離而言，將自0μm至1μm為止的區域中之每單位面積的樹脂成分之面積作為A0-1 ，將自1μm至2μm為止的區域中之每單位面積的樹脂成分之面積作為A1-2 時，滿足A0-1 /A1-2 ＞1.1者。A resin sheet having a support and a resin composition layer with an inorganic filler content of 40% by mass or more, characterized in that the resin composition layer is hardened to form the cured body layer when the cured body layer is formed The main surface of the vertical cross section of the hardened body layer is the distance from the main surface of the hardened body layer on the opposite side to the support, the resin component per unit area in the area from 0 μm to 1 μm When the area is A 0-1 and the area of the resin component per unit area in the area from 1 μm to 2 μm is A 1-2 , those satisfying A 0-1 /A 1-2 >1.1 are satisfied. 如請求項15之樹脂薄片，其為在使前述樹脂組成物層進行硬化而形成硬化體層後，欲使前述硬化體層提供於藉由選自含有O2 氣體及N2 氣體所成群的1種以上的氣體之電漿處理者。The resin sheet according to claim 15, which is formed by hardening the resin composition layer to form a hardened body layer, and the hardened body layer is to be provided to one kind selected from the group consisting of O 2 gas and N 2 gas Plasma handler for the above gas. 一種印刷配線板之製造方法，其為含有以下(A)~(D)的步驟者； (A)將含有無機填充材含有量為40質量%以上的樹脂組成物層之樹脂薄片，於最外層的至少一部分具備導體層的基板上，使前述樹脂組成物層接合於前述基板的前述導體層側之面的層合步驟； (B)使前述樹脂組成物層進行硬化而形成硬化體層的步驟； (C)於前述硬化體層形成貫通孔之步驟； (D)對於前述硬化體層進行藉由選自含有O2 氣體及N2 氣體所成群的1種以上的氣體之電漿處理的步驟； 對於在前述硬化體層的主表面呈垂直的前述硬化體層之截面，對於自前述導體層的距離而言，將自0μm至1μm為止的區域中之每單位面積的樹脂成分之面積作為A0-1 ，將自1μm至2μm為止的區域中之每單位面積的樹脂成分之面積作為A1-2 時，滿足A0-1 /A1-2 ＞1.1者。A method for manufacturing a printed wiring board, which includes the following steps (A) to (D); (A) A resin sheet containing a resin composition layer having an inorganic filler content of 40% by mass or more on the outermost layer A step of laminating at least a portion of the substrate provided with a conductor layer, the resin composition layer bonded to the surface of the substrate on the conductor layer side; (B) the step of curing the resin composition layer to form a cured body layer; (C) a step of forming a through hole in the hardened body layer; (D) a step of performing plasma treatment of the hardened body layer by one or more gases selected from the group consisting of O 2 gas and N 2 gas; The cross-section of the hardened body layer whose main surface of the hardened body layer is perpendicular to the distance from the conductor layer is defined as the area of the resin component per unit area in the area from 0 μm to 1 μm, A 0-1 , When the area of the resin component per unit area in the area from 1 μm to 2 μm is defined as A 1-2 , those satisfying A 0-1 /A 1-2 >1.1 are satisfied. 如請求項17之印刷配線板的製造方法，其中前述貫通孔之頂徑為15μm以下。The method for manufacturing a printed wiring board according to claim 17, wherein the top diameter of the through hole is 15 μm or less. 如請求項17或18之印刷配線板的製造方法，其中(D)步驟為藉由O2 氣體進行電漿處理的步驟。The method for manufacturing a printed wiring board according to claim 17 or 18, wherein step (D) is a step of performing plasma treatment with O 2 gas. 一種樹脂薄片之製造方法，其為具有支持體，與無機填充材含有量為40質量%以上之樹脂組成物層的樹脂薄片之製造方法，其特徵為含有以下(α)之步驟； (α)於在前述支持體上所形成的第1樹脂組成物而形成的第1層上，形成以具有與前述第1樹脂組成物相異的組成之第2樹脂組成物所形成的第2層，得到樹脂組成物層之步驟； 對於使前述樹脂組成物層進行硬化而形成硬化體層時之在前述硬化體層的主表面呈垂直的前述硬化體層之截面，對於自與前述支持體為相反側之前述硬化體層的主表面之距離而言，將自0μm至1μm為止的區域中之每單位面積的樹脂成分之面積作為A0-1 ，將自1μm至2μm為止的區域中之每單位面積的樹脂成分之面積作為A1-2 時，滿足A0-1 / A1-2 ＞1.1者。A method of manufacturing a resin sheet, which is a method of manufacturing a resin sheet having a support and a resin composition layer having an inorganic filler content of 40% by mass or more, characterized by including the following steps (α); (α) Forming a second layer formed of a second resin composition having a composition different from the first resin composition on the first layer formed by the first resin composition formed on the support, to obtain A step of the resin composition layer; for the cross section of the hardened body layer that is perpendicular to the main surface of the hardened body layer when the hardened body layer is formed by hardening the resin composition layer, and for the hardening from the opposite side to the support For the distance of the main surface of the body layer, the area of the resin component per unit area in the area from 0 μm to 1 μm is regarded as A 0-1 , and the area of the resin component per unit area in the area from 1 μm to 2 μm When the area is A 1-2 , A 0-1 / A 1-2 > 1.1 is satisfied. 如請求項20之樹脂薄片的製造方法，其中樹脂薄片為在使前述樹脂組成物層進行硬化而形成硬化體層後，欲使前述硬化體層提供於藉由選自含有O2 氣體及N2 氣體所成群的1種以上的氣體之電漿處理者。The method of manufacturing a resin sheet according to claim 20, wherein the resin sheet is formed by hardening the resin composition layer to form a hardened body layer, and the hardened body layer is provided by a gas selected from the group consisting of O 2 gas and N 2 gas Plasma processors of more than one gas in groups.
TW108118340A 2018-06-19 2019-05-28 Hardened layer, printed wiring board, semiconductor device, resin sheet, method for producing printed wiring board, and method for producing resin sheet TWI838374B (en)

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