TW202102361A

TW202102361A - Copper foil with insulating resin later, laminate body using same, and method for manufacturing laminate body

Info

Publication number: TW202102361A
Application number: TW109109892A
Authority: TW
Inventors: 川下和晃; 中村和宏; 杉本憲明; 平野俊介; 喜多村慎也
Original assignee: 日商三菱瓦斯化學股份有限公司
Priority date: 2019-03-29
Filing date: 2020-03-25
Publication date: 2021-01-16
Also published as: JPWO2020203418A1; JP7479596B2; CN113573887A; KR20210149683A; WO2020203418A1

Abstract

A copper foil with an insulating resin layer comprises a copper foil and an insulating resin layer disposed on top of the copper foil, wherein the insulating resin layer contains a thermosetting resin, a spherical filler, and short glass fibers with a mean fiber length of at least 10 µm but not more than 300 µm, and the degree of orientation (fp) of the short glass fibers along the surface direction of the insulating resin layer is less than 0.60.

Description

附絕緣性樹脂層之銅箔、以及使用其之疊層體及疊層體之製造方法Copper foil with insulating resin layer, laminated body using the same, and manufacturing method of laminated body

本發明關於附絕緣性樹脂層之銅箔、以及使用其之疊層體及疊層體之製造方法。The present invention relates to a copper foil with an insulating resin layer, a laminate using the copper foil, and a method for manufacturing the laminate.

廣泛地使用於電子設備、通信設備及個人電腦等之半導體封裝體的高程度功能化及小型化在近年愈益加速。伴隨如此的技術之發展，而要求半導體封裝體中的印刷配線板及半導體元件搭載用基板的薄型化。The high degree of functionality and miniaturization of semiconductor packages that are widely used in electronic equipment, communication equipment, and personal computers have been accelerating in recent years. With the development of such technologies, there is a demand for thinning of printed wiring boards and semiconductor element mounting substrates in semiconductor packages.

就薄型的印刷配線板及半導體元件搭載用基板之製造方法而言，已揭示例如在不鏽鋼等剛性高且厚的支持基板(載體基板)上形成可在後續步驟中剝離的銅之層而獲得疊層體，再於其上利用圖案鍍敷來形成電路圖案，疊層如環氧樹脂被覆玻璃纖維之類的絕緣性樹脂層並進行加熱及加壓處理，最後將支持基板剝離、去除來製造薄型的印刷配線板之方法(例如參照專利文獻1)。如此般藉由使電路圖案與絕緣材料疊層在剛性高且厚的支持基板上，最後將支持基板剝離、去除，藉此即使以現有的製造裝置仍可製造薄型的印刷配線板及半導體元件搭載用基板。With regard to the manufacturing method of thin printed wiring boards and substrates for mounting semiconductor elements, it has been disclosed, for example, that a layer of copper that can be peeled off in a subsequent step is formed on a rigid and thick support substrate (carrier substrate) such as stainless steel to obtain a laminate. The layered body is then pattern-plated to form a circuit pattern, laminated with an insulating resin layer such as epoxy-coated glass fiber and heated and pressurized, and finally the support substrate is peeled and removed to produce a thin type The method of printed wiring board (for example, refer to Patent Document 1). In this way, by laminating the circuit pattern and the insulating material on a rigid and thick supporting substrate, and finally peeling and removing the supporting substrate, it is possible to manufacture thin printed wiring boards and semiconductor device mounts even with existing manufacturing equipment Use the substrate.

又，多層印刷配線板及半導體元件搭載用基板為了使電子零件之安裝密度改善，導體配線的微細化正興。在形成導體配線時，通常係對絕緣層使用無電解鍍敷及電解鍍敷來形成導體層。關於如此的技術，例如已揭示可用於形成印刷配線板之絕緣層的樹脂組成物(例如參照專利文獻2)。 [先前技術文獻] [專利文獻]In addition, in order to improve the mounting density of electronic components in multilayer printed wiring boards and semiconductor element mounting substrates, the miniaturization of conductor wiring is in progress. When the conductor wiring is formed, electroless plating and electrolytic plating are generally used for the insulating layer to form the conductor layer. Regarding such a technique, for example, a resin composition that can be used to form an insulating layer of a printed wiring board has been disclosed (for example, refer to Patent Document 2). [Prior Technical Literature] [Patent Literature]

[專利文獻1]日本特表昭59-500341號公報 [專利文獻2]日本特開2015-67626號公報[Patent Document 1] Japanese Special Publication No. 59-500341 [Patent Document 2] Japanese Patent Application Publication No. 2015-67626

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

近年，附絕緣性樹脂層之銅箔被使用作為印刷配線板及半導體元件搭載用基板所使用的構件。關於絕緣性樹脂層，例如專利文獻2已揭示：為了提供在薄層化時仍可達成低表面粗糙度與高鍍敷剝離強度，且可達成高溫時之低CTE化之樹脂組成物，而除了含有環氧樹脂等之外，還含有球狀二氧化矽、及玻璃纖維之樹脂組成物。In recent years, copper foil with an insulating resin layer has been used as a member used for printed wiring boards and substrates for mounting semiconductor elements. Regarding the insulating resin layer, for example, Patent Document 2 has disclosed that in order to provide a resin composition that can achieve low surface roughness and high plating peel strength even when the layer is thinned, and can achieve low CTE at high temperatures, in addition to In addition to epoxy resin, it also contains spherical silica and glass fiber resin composition.

但是，如專利文獻2所記載般使用含有玻璃纖維的黏接薄膜來製作多層印刷配線板之絕緣層時，還是會有觀察到絕緣表面之顯著的凹凸之情況。又，將如專利文獻2所記載之絕緣層進行加熱時，有時會有發生翹曲、伸縮的情況。此外，尤其在這些技術中，在相對於形成絕緣性樹脂層時之樹脂組成物的溶液(清漆)之塗佈方向或輸送方向之平行方向、和在相對於上述塗佈方向或輸送方向之垂直方向上，有時會有絕緣層的黏彈性等機械特性、翹曲量、及伸縮率觀察到差異的情況。在此，上述「平行方向」係指相對於塗佈面為平行且和塗佈方向或輸送方向為同方向之含意，以下有時也稱「X方向」。又，上述「垂直方向」係指相對於塗佈面為平行且和X方向垂直相交的方向之含意，有時也稱「Y方向」。如此在絕緣層的平面方向(以下也簡稱「XY方向」)上，X方向與Y方向之間之絕緣層的翹曲或伸縮率之差異較大的話，在製作具備如此的絕緣層之印刷配線板及半導體元件搭載用基板時，也會成為生產性(成品率)降低的原因。However, when an adhesive film containing glass fibers is used to produce an insulating layer of a multilayer printed wiring board as described in Patent Document 2, significant irregularities on the insulating surface may still be observed. In addition, when the insulating layer as described in Patent Document 2 is heated, warpage and expansion and contraction may occur. In addition, especially in these techniques, in the direction parallel to the coating direction or transport direction of the resin composition solution (varnish) when the insulating resin layer is formed, and in the direction perpendicular to the coating direction or transport direction. In the direction, differences may be observed in mechanical properties such as viscoelasticity, warpage, and expansion ratio of the insulating layer. Here, the above-mentioned "parallel direction" refers to the meaning of being parallel to the coating surface and the same direction as the coating direction or the conveying direction, and may also be referred to as the "X direction" below. In addition, the above-mentioned "vertical direction" means a direction parallel to the coated surface and perpendicular to the X direction, and may also be referred to as the "Y direction". In this way, in the planar direction of the insulating layer (hereinafter also referred to as "XY direction"), if the difference in the warpage or expansion ratio of the insulating layer between the X direction and the Y direction is large, it is necessary to produce printed wiring with such an insulating layer In the case of boards and substrates for mounting semiconductor elements, it also becomes a cause of reduced productivity (yield).

本發明目的為提供即使絕緣性樹脂層含有玻璃纖維，在平面方向上之機械特性、翹曲及伸縮偏差仍受到抑制之附絕緣性樹脂層之銅箔、以及使用其之疊層體及疊層體之製造方法。 [解決課題之手段]The object of the present invention is to provide a copper foil with an insulating resin layer in which the mechanical properties, warpage and expansion deviation in the plane direction are suppressed even if the insulating resin layer contains glass fibers, and laminates and laminates using the same Body manufacturing method. [Means to solve the problem]

本發明人們為了解決前述課題反覆深入探討。其結果發現，藉由將絕緣性樹脂層所含的短纖維之配向度設定為未達特定值，可抑制在平面方向上之絕緣性樹脂層的機械特性、翹曲及伸縮偏差，乃至完成本發明。In order to solve the aforementioned problems, the inventors have repeatedly and in-depth research. As a result, it was found that by setting the degree of orientation of the short fibers contained in the insulating resin layer below a specific value, the mechanical properties, warpage, and expansion deviation of the insulating resin layer in the planar direction can be suppressed, and the invention can be achieved. invention.

亦即，本發明如下所述。＜1＞一種附絕緣性樹脂層之銅箔，具備：銅箔，及配置於前述銅箔上之絕緣性樹脂層；前述絕緣性樹脂層含有熱硬化性樹脂、球狀填料、及平均纖維長為10μm以上且300μm以下之玻璃短纖維，前述玻璃短纖維在前述絕緣性樹脂層之平面方向上之配向度(fp)未達0.60。＜2＞如上述附絕緣性樹脂層之銅箔，其中，前述絕緣性樹脂層的厚度為3μm以上且50μm以下。＜3＞如上述附絕緣性樹脂層之銅箔，其中，前述銅箔的厚度為1μm以上且18μm以下。＜4＞如上述附絕緣性樹脂層之銅箔，其中，前述玻璃短纖維的平均纖維徑為3.0μm以上且15μm以下。＜5＞如上述附絕緣性樹脂層之銅箔，其中，前述配向度(fp)為0.40以下。＜6＞如上述附絕緣性樹脂層之銅箔，其中，前述絕緣性樹脂層表面的算術平均粗糙度(Ra)為2μm以下。＜7＞如上述附絕緣性樹脂層之銅箔，其中，前述玻璃短纖維的含量相對於前述絕緣性樹脂層中之樹脂固體成分100質量份，為5質量份以上且450質量份以下。＜8＞如上述附絕緣性樹脂層之銅箔，其中，前述玻璃短纖維為磨碎纖維。＜9＞如上述附絕緣性樹脂層之銅箔，其中，前述球狀填料的含量相對於前述絕緣性樹脂層中之樹脂固體成分100質量份，為50質量份以上且500質量份以下。＜10＞如上述附絕緣性樹脂層之銅箔，其中，前述熱硬化性樹脂包含選自於由環氧樹脂、氰酸酯化合物、馬來醯亞胺化合物、酚醛樹脂、熱硬化改性聚苯醚樹脂、苯并㗁𠯤化合物、有機基改性聚矽氧化合物及具有可聚合之不飽和基的化合物構成之群組中之至少1種。＜11＞如上述附絕緣性樹脂層之銅箔，其係用於印刷配線板或半導體元件搭載用基板之堆疊材料用的無芯基板之製作。＜12＞如上述附絕緣性樹脂層之銅箔，其中，前述無芯基板為3層無芯基板。＜13＞一種疊層體，具有：堆疊層，該堆疊層係由導體層與使用如上述附絕緣性樹脂層之銅箔形成的絕緣層交替疊層而成。＜14＞如上述疊層體，其中，至少1層之前述絕緣層的厚度為4μm以上且未達15μm。＜15＞如上述疊層體，其中，前述堆疊層具有多層之前述導體層與前述絕緣層，且前述導體層配置於各前述絕緣層之間以及前述堆疊層之最外層的表面。＜16＞如上述疊層體，其中，具有3層或4層之前述絕緣層。＜17＞如上述疊層體，其係無芯基板。＜18＞一種疊層體之製造方法，具有下列步驟：使用如上述附絕緣性樹脂層之銅箔在導體層表面形成絕緣層，藉此形成由前述導體層與前述絕緣層交替疊層而成的堆疊層。＜19＞如上述疊層體之製造方法，其中，至少1層之前述絕緣層的厚度為4μm以上且未達15μm。＜20＞如上述疊層體之製造方法，其中，前述堆疊層具有多層之前述導體層與前述絕緣層，且前述導體層配置於各前述絕緣層之間以及前述堆疊層之最外層的表面。＜21＞如上述疊層體之製造方法，其中，前述疊層體具有3層或4層之前述絕緣層。＜22＞如上述疊層體之製造方法，其中，前述疊層體為無芯基板。 [發明之效果]That is, the present invention is as follows. <1> A copper foil with an insulating resin layer, with: Copper foil, and The insulating resin layer arranged on the aforementioned copper foil; The aforementioned insulating resin layer contains thermosetting resin, spherical fillers, and short glass fibers having an average fiber length of 10 μm or more and 300 μm or less, The alignment degree (fp) of the short glass fiber in the plane direction of the insulating resin layer is less than 0.60. <2> The above-mentioned copper foil with an insulating resin layer, wherein the thickness of the insulating resin layer is 3 μm or more and 50 μm or less. <3> The copper foil with an insulating resin layer as described above, wherein the thickness of the copper foil is 1 μm or more and 18 μm or less. <4> The above-mentioned copper foil with an insulating resin layer, wherein the average fiber diameter of the short glass fibers is 3.0 μm or more and 15 μm or less. <5> The above-mentioned copper foil with an insulating resin layer, wherein the degree of alignment (fp) is 0.40 or less. <6> The above-mentioned copper foil with an insulating resin layer, wherein the arithmetic mean roughness (Ra) of the surface of the insulating resin layer is 2 μm or less. <7> The above-mentioned copper foil with an insulating resin layer, wherein the content of the short glass fiber is 5 parts by mass or more and 450 parts by mass or less with respect to 100 parts by mass of the resin solid content in the insulating resin layer. <8> The above-mentioned copper foil with an insulating resin layer, wherein the short glass fibers are ground fibers. <9> The above-mentioned copper foil with an insulating resin layer, wherein the content of the spherical filler is 50 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the resin solid content in the insulating resin layer. <10> The above-mentioned copper foil with an insulating resin layer, wherein the thermosetting resin contains selected from epoxy resin, cyanate ester compound, maleimide compound, phenol resin, thermosetting modified poly At least one of the group consisting of a phenyl ether resin, a benzophenone compound, an organo-modified polysiloxane compound, and a compound having a polymerizable unsaturated group. <11> The above-mentioned copper foil with an insulating resin layer is used for the production of a coreless substrate used as a stacking material for a printed wiring board or a substrate for mounting semiconductor elements. <12> The above-mentioned copper foil with an insulating resin layer, wherein the coreless substrate is a three-layer coreless substrate. <13> A laminated body having: The stacked layer is formed by alternately stacking a conductive layer and an insulating layer formed using the above-mentioned copper foil with an insulating resin layer. <14> The above-mentioned laminate, wherein the thickness of at least one insulating layer is 4 μm or more and less than 15 μm. <15> The laminate described above, wherein the stacked layer has multiple layers of the conductive layer and the insulating layer, and the conductive layer is disposed between the insulating layers and on the surface of the outermost layer of the stacked layer. <16> The above-mentioned laminated body, which has the aforementioned insulating layer of 3 or 4 layers. <17> The laminated body described above is a coreless substrate. <18> A method for manufacturing a laminated body, which has the following steps: The above-mentioned copper foil with an insulating resin layer is used to form an insulating layer on the surface of the conductor layer, thereby forming a stacked layer in which the conductor layer and the insulating layer are alternately laminated. <19> The method for manufacturing a laminate as described above, wherein the thickness of at least one insulating layer is 4 μm or more and less than 15 μm. <20> The manufacturing method of the above-mentioned laminate, wherein the stacked layer has multiple layers of the conductive layer and the insulating layer, and the conductive layer is disposed between the insulating layers and on the surface of the outermost layer of the stacked layer. <21> The method for manufacturing a laminate as described above, wherein the laminate has three or four insulating layers. <22> The method for manufacturing a laminate as described above, wherein the laminate is a coreless substrate. [Effects of Invention]

根據本發明可提供即使絕緣性樹脂層含有玻璃纖維，在平面方向上之機械特性、翹曲及伸縮偏差仍受到抑制之附絕緣性樹脂層之銅箔、以及使用其之疊層體及疊層體之製造方法。According to the present invention, it is possible to provide a copper foil with an insulating resin layer in which the mechanical properties, warpage and expansion deviation in the plane direction are suppressed even if the insulating resin layer contains glass fibers, and laminates and laminates using the same. Body manufacturing method.

以下，因應需要邊參照圖式邊針對用以實施本發明的形態(以下簡稱「本實施形態」)進行詳細地說明，但本發明不限於下列本實施形態。本發明在不悖離其要旨之範圍內可有各種變化。另外，圖式中，相同元件標附相同符號，並省略重複的說明。又，上下左右等位置關係除非有特別說明，否則即根據圖式所示之位置關係。此外，圖式之尺寸比率不限於圖式之比率。本說明書中，疊層體之各層係相互黏接，但其各層也可因應需要為相互可剝離者。Hereinafter, a mode for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail with reference to the drawings as needed, but the present invention is not limited to the following embodiment. Various changes can be made to the present invention within a range that does not deviate from its gist. In addition, in the drawings, the same elements are denoted by the same symbols, and repeated descriptions are omitted. In addition, unless otherwise specified, the positional relationship of up, down, left, and right is based on the positional relationship shown in the diagram. In addition, the size ratio of the drawing is not limited to the ratio of the drawing. In this specification, the layers of the laminate are adhered to each other, but the layers may be peelable from each other as needed.

本實施形態中，「樹脂固體成分」或「絕緣性樹脂層中之樹脂固體成分」除非有特別說明，否則意指絕緣性樹脂層或樹脂組成物所含的樹脂及硬化後構成樹脂的成分。又，「樹脂固體成分100質量份」係指絕緣性樹脂層或樹脂組成物中之樹脂及硬化後構成樹脂的成分之合計為100質量份。In the present embodiment, "resin solid content" or "resin solid content in insulating resin layer" means the resin contained in the insulating resin layer or the resin composition and the components constituting the resin after curing, unless otherwise specified. In addition, "100 parts by mass of resin solid content" means that the total of the resin in the insulating resin layer or the resin composition and the components constituting the resin after curing is 100 parts by mass.

[附絕緣性樹脂層之銅箔] 本實施形態之附絕緣性樹脂層之銅箔(以下有時也簡稱「附樹脂層之銅箔」)係具備銅箔及配置於該銅箔上之絕緣性樹脂層的附絕緣性樹脂層之銅箔，其中，絕緣性樹脂層含有(A)熱硬化性樹脂、(B)球狀填料、及(C)平均纖維長為10μm～300μm之玻璃短纖維，且對於絕緣性樹脂層的平面方向(以下有時也將絕緣性樹脂層的平面方向簡稱「平面方向」)之玻璃短纖維的配向度(fp)(以下有時也簡稱「配向度(fp)」)未達0.6。[Copper foil with insulating resin layer] The copper foil with an insulating resin layer of this embodiment (hereinafter sometimes referred to as "copper foil with a resin layer") is a copper foil and an insulating resin layer with an insulating resin layer arranged on the copper foil. Copper foil, in which the insulating resin layer contains (A) thermosetting resin, (B) spherical fillers, and (C) short glass fibers with an average fiber length of 10 μm to 300 μm. (Hereinafter, the plane direction of the insulating resin layer may also be referred to as "planar direction") The orientation degree (fp) of the short glass fiber (hereinafter sometimes also referred to as “orientation degree (fp)”) is less than 0.6.

本說明書中，「玻璃短纖維在絕緣性樹脂層之平面方向上之配向度(fp)」係表示玻璃短纖維在附樹脂層之銅箔的平面方向上之配向狀態之參數。配向度(fp)係以0.00～1.00之數值來表示纖維配向分佈之參數。fp=1.00時意指絕緣性樹脂層中之玻璃短纖維在平面方向上全部配向於單1方向，fp=0.00時意指玻璃短纖維完全隨機地配置。In this specification, "the degree of orientation (fp) of short glass fibers in the plane direction of the insulating resin layer" is a parameter indicating the orientation state of the short glass fibers in the plane direction of the copper foil with the resin layer. The degree of orientation (fp) is a parameter of the fiber orientation distribution with a value ranging from 0.00 to 1.00. When fp=1.00, it means that the short glass fibers in the insulating resin layer are all aligned in a single direction in the plane direction. When fp=0.00, it means that the short glass fibers are arranged completely randomly.

絕緣性樹脂層中之玻璃短纖維的配向度(fp)未達0.60的話，可將在絕緣性樹脂層之平面方向(XY方向)上之黏彈性等機械特性、(尤其附樹脂層之銅箔加熱後之)翹曲量、及伸縮率的差異更為縮小。具體而言，使用本實施形態之附絕緣性樹脂層之銅箔的話，可將在相對於形成絕緣性樹脂層時之樹脂組成物的塗佈方向之平行方向、和在相對於前述塗佈方向之垂直方向上之各物性(機械特性、翹曲及伸縮產生量)的差異縮小。因此，絕緣性樹脂層表面的凹凸會變少。其結果，將本實施形態之附絕緣性樹脂層之銅箔使用作為印刷配線板及半導體元件搭載用基板的堆疊材料時，可製作各層間之黏合力及生產性(成品率)優良的疊層體。又，配向度(fp)未達0.60的話，也可抑制絕緣性樹脂層之翹曲產生量本身。If the orientation degree (fp) of the short glass fiber in the insulating resin layer is less than 0.60, the mechanical properties such as viscoelasticity in the plane direction (XY direction) of the insulating resin layer can be improved (especially the copper foil with the resin layer). After heating, the difference in the amount of warpage and expansion ratio is further reduced. Specifically, when the copper foil with an insulating resin layer of the present embodiment is used, the direction parallel to the coating direction of the resin composition when the insulating resin layer is formed can be adjusted in parallel with respect to the aforementioned coating direction. The difference in physical properties (mechanical properties, warpage and expansion) in the vertical direction is reduced. Therefore, the irregularities on the surface of the insulating resin layer are reduced. As a result, when the copper foil with an insulating resin layer of this embodiment is used as a stack material for printed wiring boards and semiconductor element mounting substrates, a laminate with excellent adhesion between the layers and productivity (yield) can be produced body. In addition, if the degree of alignment (fp) is less than 0.60, the amount of warpage of the insulating resin layer itself can be suppressed.

本實施形態之附絕緣性樹脂層之銅箔例如可將其進行疊層來形成疊層體。得到的疊層體作為製造電子設備、通信設備及個人電腦等所使用的印刷配線板或半導體元件搭載用基板的堆疊材料係為有效。The copper foil with an insulating resin layer of this embodiment can be laminated, for example, to form a laminate. The obtained laminate is effective as a stacking material for manufacturing printed wiring boards or semiconductor element mounting substrates used in electronic equipment, communication equipment, personal computers, and the like.

[銅箔] 本實施形態之銅箔可使用通常的印刷配線板所使用的銅箔或銅薄膜。銅箔之具體例可列舉：電解銅箔、壓延銅箔及銅合金薄膜。銅箔或銅薄膜也可施加例如消光處理、電暈處理、鎳處理及鈷處理等公知的表面處理。本實施形態中的銅箔也可使用市售品，例如可使用如JX金屬(股)製之GHY5(商品名，12μm厚之銅箔)、三井金屬礦業(股)製之3EC-VLP(商品名，12μm厚之銅箔)、3EC-III(商品名，12μm厚之銅箔)及3EC-M2S-VLP(商品名，12μm厚之銅箔)、古河電氣興業(股)製之銅箔GTS-MP(商品名，12μm厚之銅箔)、以及JX金屬(股)製之JXUT-I(商品名，1.5μm厚之銅箔)之類的市售品。[Copper foil] The copper foil of this embodiment can use the copper foil or copper film used for a normal printed wiring board. Specific examples of copper foil include electrolytic copper foil, rolled copper foil, and copper alloy thin film. The copper foil or copper thin film may be subjected to well-known surface treatments such as matting treatment, corona treatment, nickel treatment, and cobalt treatment. The copper foil in this embodiment can also use commercially available products. For example, GHY5 (trade name, 12μm thick copper foil) manufactured by JX Metal Co., Ltd., and 3EC-VLP (commodity product) manufactured by Mitsui Metals Mining Co., Ltd. can be used. Name, 12μm thick copper foil), 3EC-III (trade name, 12μm thick copper foil) and 3EC-M2S-VLP (trade name, 12μm thick copper foil), copper foil GTS manufactured by Furukawa Electric Co., Ltd. -MP (trade name, 12μm thick copper foil), and JXUT-I (trade name, 1.5μm thick copper foil) manufactured by JX Metals.

考慮使銅箔與絕緣性樹脂層之黏合強度改善，且可防止長時間使用時之層剝離的觀點，銅箔表面的算術平均粗糙度(Ra)通常宜為0.05μm以上且2μm以下，為0.08μm以上且1.7μm以下更佳。考慮可獲得銅箔與絕緣性樹脂層之更優良的黏合性之觀點，其算術平均粗糙度(Ra)為0.2μm以上且1.6μm以下特佳。本實施形態中，具備算術平均粗糙度落在上述範圍內之銅箔的附絕緣性樹脂層之銅箔可理想地使用於製造形成有高密度的微細配線之印刷配線板及半導體元件搭載用基板。另外，算術平均粗糙度可使用市售之形狀測定顯微鏡(雷射顯微鏡，例如KEYENCE股份有限公司製VK-X210(商品名))來測定。Considering that the bonding strength between the copper foil and the insulating resin layer is improved, and the layer peeling can be prevented during long-term use, the arithmetic average roughness (Ra) of the copper foil surface is usually 0.05μm or more and 2μm or less, which is 0.08 It is more preferably not less than μm and not more than 1.7 μm. From the viewpoint of obtaining better adhesion between the copper foil and the insulating resin layer, the arithmetic average roughness (Ra) is particularly preferably 0.2 μm or more and 1.6 μm or less. In this embodiment, a copper foil with an insulating resin layer and a copper foil with arithmetic average roughness falling within the above range can be ideally used to manufacture printed wiring boards formed with high-density fine wiring and substrates for mounting semiconductor elements . In addition, the arithmetic average roughness can be measured using a commercially available shape measuring microscope (laser microscope, for example, VK-X210 (trade name) manufactured by KEYENCE Co., Ltd.).

銅箔的厚度只要會發揮本實施形態的效果，則無特別限制，考慮容易進行銅箔表面之粗糙化處理的觀點，宜落在1μm以上且18μm以下之範圍內。考慮可理想地獲得薄型的印刷配線板及半導體元件搭載用基板之情況，其厚度落在2μm以上且15μm以下之範圍內更佳。The thickness of the copper foil is not particularly limited as long as it exhibits the effects of the present embodiment, and considering the ease of roughening the surface of the copper foil, it is preferably within the range of 1 μm or more and 18 μm or less. Considering that a thin printed wiring board and a substrate for mounting a semiconductor element can be ideally obtained, the thickness is preferably within a range of 2 μm or more and 15 μm or less.

[絕緣性樹脂層] 本實施形態中，絕緣性樹脂層含有(A)熱硬化性樹脂、(B)球狀填料、及(C)平均纖維長為10μm以上且300μm以下之玻璃短纖維。本實施形態中的絕緣性樹脂層可使用含有這些成分的樹脂組成物之溶液即清漆來形成。[Insulating resin layer] In this embodiment, the insulating resin layer contains (A) thermosetting resin, (B) spherical filler, and (C) short glass fibers having an average fiber length of 10 μm or more and 300 μm or less. The insulating resin layer in this embodiment can be formed using a varnish which is a solution of a resin composition containing these components.

(A)熱硬化性樹脂考慮耐熱性、絕緣性、及鍍敷黏合性之觀點，絕緣性樹脂層含有熱硬化性樹脂。熱硬化性樹脂若為用於印刷配線板的絕緣層之樹脂，則並無特別限制。(A) Thermosetting resin Considering the viewpoints of heat resistance, insulation, and plating adhesion, the insulating resin layer contains a thermosetting resin. The thermosetting resin is not particularly limited as long as it is a resin used for the insulating layer of a printed wiring board.

熱硬化性樹脂之具體例可列舉：環氧樹脂、氰酸酯化合物、馬來醯亞胺化合物、酚醛樹脂、熱硬化改性聚苯醚樹脂、苯并㗁𠯤化合物、有機基改性聚矽氧化合物及具有可聚合之不飽和基的化合物。這些熱硬化性樹脂可單獨使用1種或將2種以上適當地混合使用。Specific examples of thermosetting resins include epoxy resins, cyanate ester compounds, maleimide compounds, phenolic resins, thermosetting modified polyphenylene ether resins, benzophenone compounds, and organically modified polysilicones. Oxygen compounds and compounds with polymerizable unsaturated groups. These thermosetting resins can be used individually by 1 type or in mixture of 2 or more types suitably.

這些熱硬化性樹脂之中，考慮可獲得具有優良的剝離強度之絕緣性樹脂層的觀點，熱硬化性樹脂宜含有環氧樹脂及酚醛樹脂，含有環氧樹脂及酚醛樹脂而且更含有雙馬來醯亞胺化合物更佳。Among these thermosetting resins, considering that an insulating resin layer with excellent peel strength can be obtained, the thermosetting resin preferably contains epoxy resin and phenolic resin, epoxy resin and phenolic resin, and further contains bismaleic resin. The imine compound is more preferable.

環氧樹脂若為1分子中具有2個以上之環氧基者，則無特別限制，可使用習知之任意的環氧樹脂。考慮使黏接性及可撓性更良好之觀點，環氧樹脂之環氧當量宜為250g/eq以上且850g/eq以下，為250g/eq以上且450g/eq以下更佳。環氧當量可利用常用方法來測定。The epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule, and any conventional epoxy resin can be used. Considering the viewpoint of making the adhesiveness and flexibility better, the epoxy equivalent of the epoxy resin is preferably 250 g/eq or more and 850 g/eq or less, and more preferably 250 g/eq or more and 450 g/eq or less. The epoxy equivalent can be measured by a common method.

環氧樹脂之具體例可列舉：聚氧伸萘基型環氧樹脂、聯苯芳烷基型環氧樹脂、萘4官能型環氧樹脂、二甲苯型環氧樹脂、萘酚芳烷基型環氧樹脂、萘芳烷基型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、3官能苯酚型環氧樹脂、4官能苯酚型環氧樹脂、萘型環氧樹脂、聯苯型環氧樹脂、芳烷基酚醛清漆型環氧樹脂、脂環族環氧樹脂、多元醇型環氧樹脂、環氧丙基胺型環氧樹脂、環氧丙基酯型環氧樹脂、將丁二烯等之雙鍵環氧化而成的化合物、及利用含羥基之聚矽氧樹脂類與環氧氯丙烷之反應而獲得的化合物。它們之中，尤其考慮鍍敷銅附著性與阻燃性之觀點，宜為聚氧伸萘基型環氧樹脂、聯苯芳烷基型環氧樹脂、萘4官能型環氧樹脂、二甲苯型環氧樹脂、萘酚芳烷基型環氧樹脂、及萘芳烷基型環氧樹脂。環氧樹脂可單獨使用1種或將2種以上適當地混合使用。Specific examples of epoxy resins include: polyoxynaphthylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene tetrafunctional epoxy resin, xylene type epoxy resin, naphthol aralkyl type epoxy resin Epoxy resin, naphthalene aralkyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A novolak type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol Type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, aralkyl novolak type epoxy resin, cycloaliphatic epoxy resin, polyol type epoxy resin, epoxypropyl amine type epoxy resin Resins, epoxy propyl ester type epoxy resins, compounds obtained by epoxidizing double bonds such as butadiene, and compounds obtained by the reaction of hydroxyl-containing polysiloxane resins with epichlorohydrin. Among them, especially considering the adhesion and flame retardancy of copper plating, polyoxynaphthylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene tetrafunctional epoxy resin, and xylene are preferred. Type epoxy resin, naphthol aralkyl type epoxy resin, and naphthol aralkyl type epoxy resin. The epoxy resin can be used individually by 1 type or in mixture of 2 or more types suitably.

本實施形態中，環氧樹脂的含量並無特別限制，考慮耐熱性及硬化性之觀點，相對於絕緣性樹脂層中之樹脂固體成分100質量份，宜落在10質量份以上且80質量份以下之範圍內，落在30質量份以上且70質量份以下之範圍內更佳。In this embodiment, the content of epoxy resin is not particularly limited. Considering heat resistance and curability, relative to 100 parts by mass of the resin solid content in the insulating resin layer, it is preferably 10 parts by mass or more and 80 parts by mass. The following range is more preferably within the range of 30 parts by mass or more and 70 parts by mass or less.

氰酸酯化合物具有耐藥品性、黏接性等優良的特性，憑藉其優良的耐藥品性而可形成均勻的粗糙化面。因此，氰酸酯化合物可理想地使用作為本實施形態中的絕緣性樹脂層之成分。The cyanate ester compound has excellent characteristics such as chemical resistance and adhesion, and can form a uniform roughened surface due to its excellent chemical resistance. Therefore, the cyanate ester compound can be suitably used as a component of the insulating resin layer in this embodiment.

氰酸酯化合物之具體例可列舉：下式(1)表示之α-萘酚芳烷基型氰酸酯化合物、下式(2)表示之酚醛清漆型氰酸酯化合物、下式(3)表示之聯苯芳烷基型氰酸酯化合物、1,3-二氰氧基苯、1,4-二氰氧基苯、1,3,5-三氰氧基苯、雙(3,5-二甲基-4-氰氧基苯基)甲烷、1,3-二氰氧基萘、1,4-二氰氧基萘、1,6-二氰氧基萘、1,8-二氰氧基萘、2,6-二氰氧基萘、2,7-二氰氧基萘、1,3,6-三氰氧基萘、4,4’-二氰氧基聯苯、雙(4-氰氧基苯基)甲烷、雙(4-氰氧基苯基)丙烷、雙(4-氰氧基苯基)醚、雙(4-氰氧基苯基)硫醚、雙(4-氰氧基苯基)碸、2,2’-雙(4-氰氧基苯基)丙烷、及雙(3,5-二甲基-4-氰氧基苯基)甲烷。氰酸酯化合物可單獨使用1種或將2種以上適當地混合使用。Specific examples of cyanate ester compounds include: α-naphthol aralkyl type cyanate ester compounds represented by the following formula (1), novolac type cyanate ester compounds represented by the following formula (2), and the following formula (3) Represented biphenyl aralkyl cyanate ester compound, 1,3-dicyanooxybenzene, 1,4-dicyanooxybenzene, 1,3,5-tricyanoxybenzene, bis(3,5 -Dimethyl-4-cyanooxyphenyl)methane, 1,3-dicyanooxynaphthalene, 1,4-dicyanooxynaphthalene, 1,6-dicyanooxynaphthalene, 1,8-di Cyanoxynaphthalene, 2,6-dicyanooxynaphthalene, 2,7-dicyanooxynaphthalene, 1,3,6-tricyanoxynaphthalene, 4,4'-dicyanooxybiphenyl, double (4-cyanooxyphenyl)methane, bis(4-cyanoxyphenyl)propane, bis(4-cyanoxyphenyl)ether, bis(4-cyanoxyphenyl)sulfide, bis( 4-cyanooxyphenyl) sulfide, 2,2'-bis(4-cyanooxyphenyl)propane, and bis(3,5-dimethyl-4-cyanooxyphenyl)methane. A cyanate ester compound can be used individually by 1 type or in mixture of 2 or more types suitably.

它們之中，下式(1)表示之α-萘酚芳烷基型氰酸酯化合物、下式(2)表示之酚醛清漆型氰酸酯化合物、及下式(3)表示之聯苯芳烷基型氰酸酯化合物由於阻燃性優良、硬化性高且硬化物之熱膨脹係數低，故較理想。Among them, the α-naphthol aralkyl type cyanate compound represented by the following formula (1), the novolak type cyanate compound represented by the following formula (2), and the biphenyl aryl compound represented by the following formula (3) Alkyl-type cyanate ester compounds are ideal because they have excellent flame retardancy, high curability, and low thermal expansion coefficient of the cured product.

[化1]

[化1]

式(1)中，R¹ 分別獨立地表示氫原子或甲基，n¹ 表示1以上之整數。n¹ 宜為1～50之整數。In formula (1), R ¹ each independently represents a hydrogen atom or a methyl group, and n ¹ represents an integer of 1 or more. n ^{1 is} preferably an integer of 1-50.

[化2]

[化2]

式(2)中，R² 分別獨立地表示氫原子或甲基，n² 表示1以上之整數。n² 宜為1～50之整數。In formula (2), R ² each independently represents a hydrogen atom or a methyl group, and n ² represents an integer of 1 or more. n ^{2 is} preferably an integer of 1-50.

[化3]

[化3]

式(3)中，R³ 分別獨立地表示氫原子或甲基，n³ 表示1以上之整數。n³ 宜為1～50之整數。In formula (3), R ³ each independently represents a hydrogen atom or a methyl group, and n ³ represents an integer of 1 or more. n ^{3 is} preferably an integer of 1-50.

本實施形態中，氰酸酯化合物的含量並無特別限制，考慮耐熱性、和銅箔之黏合性的觀點，相對於絕緣性樹脂層中之樹脂固體成分100質量份，宜落在15質量份以上且85質量份以下之範圍內，落在25質量份以上且65質量份以下之範圍內更佳。In this embodiment, the content of the cyanate ester compound is not particularly limited. Considering the heat resistance and the adhesion of the copper foil, it is preferably 15 parts by mass or more with respect to 100 parts by mass of the resin solid content in the insulating resin layer. And it is within the range of 85 parts by mass or less, more preferably within the range of 25 parts by mass or more and 65 parts by mass or less.

馬來醯亞胺化合物可使絕緣性樹脂層之吸濕耐熱性改善，故可理想地使用作為本實施形態中的絕緣性樹脂層之成分。馬來醯亞胺化合物若為1分子中具有2個以上之馬來醯亞胺基者，則無特別限制，可使用習知之任意的馬來醯亞胺化合物。The maleimide compound can improve the moisture absorption and heat resistance of the insulating resin layer, so it can be ideally used as a component of the insulating resin layer in this embodiment. As long as the maleimide compound has two or more maleimide groups in one molecule, it is not particularly limited, and any conventionally known maleimide compound can be used.

馬來醯亞胺化合物之具體例可列舉：雙(4-馬來醯亞胺基苯基)甲烷、2,2-雙{4-(4-馬來醯亞胺基苯氧基)苯基}丙烷、雙(3,5-二甲基-4-馬來醯亞胺基苯基)甲烷、雙(3-乙基-5-甲基-4-馬來醯亞胺基苯基)甲烷、雙(3,5-二乙基-4-馬來醯亞胺基苯基)甲烷等雙馬來醯亞胺化合物；及聚苯基甲烷馬來醯亞胺。另外，馬來醯亞胺化合物能以馬來醯亞胺化合物之預聚物、或馬來醯亞胺化合物與胺化合物之預聚物之類的型態摻合到樹脂組成物中。這些馬來醯亞胺化合物可單獨使用1種或將2種以上適當地混合使用。Specific examples of the maleimide compound include: bis(4-maleiminophenyl)methane, 2,2-bis{4-(4-maleiminophenoxy)phenyl } Propane, bis(3,5-dimethyl-4-maleimidphenyl)methane, bis(3-ethyl-5-methyl-4-maleimidphenyl)methane , Bis(3,5-diethyl-4-maleimidphenyl) methane and other bismaleimid compounds; and polyphenylmethane maleimid. In addition, the maleimide compound can be blended into the resin composition in the form of a prepolymer of a maleimine compound, or a prepolymer of a maleimine compound and an amine compound. These maleimide compounds can be used individually by 1 type or in mixture of 2 or more types suitably.

它們之中，考慮耐熱性的觀點，宜為雙馬來醯亞胺化合物，為雙(3-乙基-5-甲基-4-馬來醯亞胺基苯基)甲烷更佳。Among them, from the viewpoint of heat resistance, a bismaleimide compound is preferable, and bis(3-ethyl-5-methyl-4-maleiminophenyl)methane is more preferable.

本實施形態中，馬來醯亞胺化合物的含量並無特別限制，考慮耐熱性與和銅箔之黏合性的觀點，相對於絕緣性樹脂層中之樹脂固體成分100質量份，宜落在5質量份以上且75質量份以下之範圍內，落在5質量份以上且45質量份以下之範圍內更佳。In this embodiment, the content of the maleimide compound is not particularly limited. Considering the heat resistance and adhesion to the copper foil, it is preferably 5 mass parts relative to 100 mass parts of the resin solid content in the insulating resin layer. It is more preferable to fall within the range of 5 parts by mass or more and 45 parts by mass or less.

酚醛樹脂若為1分子中具有2個以上之酚性羥基之樹脂，則無特別限制，可使用習知之任意的酚醛樹脂。酚醛樹脂之具體例可列舉：苯酚酚醛清漆樹脂、烷基苯酚酚醛清漆樹脂、雙酚A酚醛清漆樹脂、雙環戊二烯型酚醛樹脂、苯酚-芳烷基醚(Xylok)型酚醛樹脂、萜烯改性酚醛樹脂、聚乙烯基酚類、芳烷基型酚醛樹脂、聯苯芳烷基型酚醛樹脂等在1分子內鍵結於芳香族性之環的氫原子被2個以上之羥基取代而成的化合物。這些酚醛樹脂可單獨使用1種或將2種以上適當地混合使用。The phenol resin is not particularly limited as long as it has two or more phenolic hydroxyl groups in one molecule, and any conventional phenol resin can be used. Specific examples of phenol resins include: phenol novolak resin, alkylphenol novolak resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, phenol-aralkyl ether (Xylok) type phenol resin, terpene Modified phenolic resins, polyvinyl phenols, aralkyl phenolic resins, biphenyl aralkyl phenolic resins, etc. The hydrogen atoms bonded to the aromatic ring in one molecule are replaced by two or more hydroxyl groups. Into the compound. These phenol resins can be used individually by 1 type or in mixture of 2 or more types suitably.

熱硬化改性聚苯醚樹脂係將熱塑性聚苯醚樹脂與環氧樹脂進行摻合後溶解於甲苯等溶劑中，再添加如2-乙基-4-甲基咪唑之類的觸媒來使其交聯而成的樹脂。熱硬化改性聚苯醚樹脂可單獨使用1種或將2種以上適當地混合使用。The thermosetting modified polyphenylene ether resin is a mixture of thermoplastic polyphenylene ether resin and epoxy resin and then dissolved in a solvent such as toluene, and then a catalyst such as 2-ethyl-4-methylimidazole is added to make The cross-linked resin. The thermosetting modified polyphenylene ether resin can be used individually by 1 type or in mixture of 2 or more types suitably.

苯并㗁𠯤化合物若具有㗁𠯤環作為基本骨架，則無特別限制。又，本實施形態中，苯并㗁𠯤化合物也包含萘并㗁𠯤化合物等具有多環㗁𠯤骨架之化合物。苯并㗁𠯤化合物可單獨使用1種或將2種以上適當地混合使用。If the benzoglyph compound has a 㗁𠯤 ring as a basic skeleton, it is not particularly limited. In addition, in the present embodiment, the benzoglyph compound also includes a compound having a polycyclic glyph skeleton such as a naphthoglyph compound. The benzogamma compound can be used individually by 1 type or in mixture of 2 or more types suitably.

有機基改性聚矽氧化合物並無特別限制，具體例可列舉：二(甲胺基)聚二甲基矽氧烷、二(乙胺基)聚二甲基矽氧烷、二(丙胺基)聚二甲基矽氧烷、二(環氧丙基)聚二甲基矽氧烷、及二(環氧丁基)聚二甲基矽氧烷。有機基改性聚矽氧化合物可單獨使用1種或將2種以上適當地混合使用。The organo-modified polysiloxane compound is not particularly limited, and specific examples include: bis(methylamino)polydimethylsiloxane, bis(ethylamino)polydimethylsiloxane, bis(propylamino) ) Polydimethylsiloxane, di(glycidyl) polydimethylsiloxane, and di(epoxybutyl) polydimethylsiloxane. The organo-modified polysiloxane compound can be used alone or in combination of two or more.

具有可聚合之不飽和基的化合物並無特別限制，例如可列舉：乙烯、丙烯、苯乙烯、二乙烯基苯、二乙烯基聯苯等乙烯系化合物；(甲基)丙烯酸甲酯、(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、聚丙二醇二(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等1元或多元醇的(甲基)丙烯酸酯類；雙酚A型環氧(甲基)丙烯酸酯、雙酚F型環氧(甲基)丙烯酸酯等環氧(甲基)丙烯酸酯類；及苯并環丁烯樹脂。具有可聚合之不飽和基的化合物可單獨使用1種或將2種以上適當地混合使用。另外，「(甲基)丙烯酸酯」係包含甲基丙烯酸酯及丙烯酸酯之概念。The compound having a polymerizable unsaturated group is not particularly limited, and examples include: vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; methyl (meth)acrylate, (formaldehyde) Base)-2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane Mono- or polyhydric alcohol (meth)acrylates such as tri(meth)acrylate, neopentylerythritol tetra(meth)acrylate, dineopentaerythritol hexa(meth)acrylate, etc.; bisphenol A Epoxy (meth)acrylates such as type epoxy (meth)acrylate and bisphenol F type epoxy (meth)acrylate; and benzocyclobutene resin. The compound having a polymerizable unsaturated group can be used singly or as a mixture of two or more types as appropriate. In addition, "(meth)acrylate" includes the concept of methacrylate and acrylate.

(B)球狀填料考慮低熱膨脹率、成形性、填充性及剛性之觀點，本實施形態中的絕緣性樹脂層含有球狀填料。球狀填料若為用於印刷配線板之絕緣層的球狀之填料，則無特別限制。(B) Spherical packing Considering the viewpoints of low thermal expansion coefficient, moldability, filling properties, and rigidity, the insulating resin layer in this embodiment contains spherical fillers. The spherical filler is not particularly limited as long as it is a spherical filler used for the insulating layer of a printed wiring board.

球狀填料並無特別限制，但其平均粒徑(D50)宜落在0.01μm以上且5μm以下之範圍內。另外，D50意指中值粒徑，係將測定之粉體的粒度分佈分成2種時之較大側與較小側成為等量之粒徑，本說明書中為體積基準。球狀填料的D50值一般而言係利用濕式雷射繞射-散射法來測定。The spherical filler is not particularly limited, but its average particle diameter (D50) should preferably fall within the range of 0.01 μm or more and 5 μm or less. In addition, D50 means the median particle size, and when the particle size distribution of the measured powder is divided into two types, the larger side and the smaller side become the same particle size, which is the volume basis in this specification. The D50 value of the spherical filler is generally measured by the wet laser diffraction-scattering method.

球狀填料可列舉例如：氫氧化鎂、氧化鎂、天然二氧化矽、熔融二氧化矽、非晶態二氧化矽、及中空二氧化矽等二氧化矽類；二硫化鉬、氧化鉬、及鉬酸鋅等鉬化合物；氧化鋁；氮化鋁；玻璃；氧化鈦；及氧化鋯。球狀填料可單獨使用1種或將2種以上適當地混合使用。Examples of spherical fillers include: magnesium hydroxide, magnesium oxide, natural silica, fused silica, amorphous silica, and hollow silica and other silicas; molybdenum disulfide, molybdenum oxide, and Molybdenum compounds such as zinc molybdate; aluminum oxide; aluminum nitride; glass; titanium oxide; and zirconium oxide. A spherical filler can be used individually by 1 type or in mixture of 2 or more types suitably.

球狀填料考慮低熱膨脹性之觀點，宜為球狀熔融二氧化矽。市售的球狀熔融二氧化矽可列舉例如：Admatechs(股)製之SC2050-MB、SC2500-SQ、SC4500-SQ、SO-C2、SO-C1、電氣化學工業(股)製之SFP-130MC(均為產品名)。Considering the viewpoint of low thermal expansion, the spherical filler is preferably spherical molten silica. Commercially available spherical fused silica can include, for example, SC2050-MB, SC2500-SQ, SC4500-SQ, SO-C2, SO-C1, and SFP-130MC manufactured by Admatechs (Stock) (All product names).

球狀二氧化矽之類的球狀填料之平均粒徑(D50)並無特別限制，宜落在0.01μm以上且5μm以下之範圍內，落在0.05μm以上且3μm以下之範圍內更佳，落在0.1μm以上且2μm以下之範圍內再更佳，落在0.3μm以上且1.5μm以下之範圍內又更佳。球狀填料之平均粒徑可利用基於米氏(Mie)散射理論之雷射繞射-散射法來測定。具體而言，可利用雷射繞射散射式粒度分佈測定裝置測定球狀填料之粒度，並以體積基準作成其粒度分佈，將該中值粒徑定義為平均粒徑。測定樣本可理想地使用利用超音波使球狀填料分散於水中者。雷射繞射散射式粒度分佈測定裝置例如可使用堀場製作所(股)製之LA-500(產品名)。The average particle size (D50) of spherical fillers such as spherical silica is not particularly limited. It should fall within the range of 0.01 μm or more and 5 μm or less, and more preferably within the range of 0.05 μm or more and 3 μm or less. It is more preferable to fall within the range of 0.1 μm or more and 2 μm or less, and it is still more preferable to fall within the range of 0.3 μm or more and 1.5 μm or less. The average particle size of the spherical filler can be measured by the laser diffraction-scattering method based on the Mie scattering theory. Specifically, the particle size of the spherical filler can be measured by a laser diffraction scattering particle size distribution measuring device, and the particle size distribution can be created on a volume basis, and the median particle size can be defined as the average particle size. The measurement sample can ideally be one that uses ultrasonic waves to disperse the spherical filler in water. For the laser diffraction scattering type particle size distribution measuring device, for example, LA-500 (product name) manufactured by Horiba Manufacturing Co., Ltd. can be used.

本實施形態中，球狀填料的含量並無特別限制，考慮成形性之觀點，相對於絕緣性樹脂層中之樹脂固體成分100質量份，宜落在50質量份以上且500質量份以下之範圍內，落在100質量份以上且400質量份以下之範圍內更佳。In this embodiment, the content of the spherical filler is not particularly limited. From the viewpoint of formability, it is preferable to fall within the range of 50 parts by mass to 500 parts by mass relative to 100 parts by mass of the resin solid content in the insulating resin layer. Within, it is more preferable to fall within the range of 100 parts by mass or more and 400 parts by mass or less.

又，本實施形態之球狀填料也可利用矽烷偶聯劑等進行表面處理。矽烷偶聯劑可使用後述矽烷偶聯劑。In addition, the spherical filler of this embodiment may be surface-treated with a silane coupling agent or the like. As the silane coupling agent, the silane coupling agent described later can be used.

(C)平均纖維長為10μm以上且300μm以下之玻璃短纖維本實施形態中的絕緣性樹脂層為了對銅箔之優良的黏合性、對樹脂組成物賦予韌性、及獲得具有低熱膨脹率之樹脂組成物而含有平均纖維長為10μm以上且300μm以下之玻璃短纖維。本實施形態之玻璃短纖維若為以SiO₂ 、Al₂ O₃ 、CaO、MgO、B₂ O₃ 、Na₂ O及K₂ O作為主成分，且平均纖維長為10μm以上且300μm以下，則無特別限制，可利用常用方法製得也可使用市售品。(C) Short glass fibers with an average fiber length of 10 μm or more and 300 μm or less. The insulating resin layer in this embodiment is used to provide excellent adhesion to copper foil, to impart toughness to the resin composition, and to obtain a resin with a low thermal expansion rate. The composition contains short glass fibers having an average fiber length of 10 μm or more and 300 μm or less. If the short glass fiber of this embodiment has SiO ₂ , Al ₂ O ₃ , CaO, MgO, B ₂ O ₃ , Na ₂ O, and K ₂ O as the main components, and the average fiber length is 10 μm or more and 300 μm or less, There is no particular limitation, and it can be prepared by a common method or a commercially available product can be used.

玻璃短纖維的平均纖維長考慮降低熱膨脹率之觀點，宜為20μm以上，為30μm以上更佳。又，考慮使玻璃短纖維的分散性改善之觀點，宜為250μm以下，為200μm以下更佳，為150μm以下再更佳。The average fiber length of short glass fibers is preferably 20 μm or more, more preferably 30 μm or more in consideration of reducing the thermal expansion rate. Furthermore, in consideration of the viewpoint of improving the dispersibility of short glass fibers, it is preferably 250 μm or less, more preferably 200 μm or less, and even more preferably 150 μm or less.

玻璃短纖維的平均纖維徑並無特別限制，考慮可更為降低熱膨脹率之觀點，宜為3.0μm以上且15μm以下，為3.0μm以上且13μm以下更佳，為3.5μm以上且11μm以下再更佳。The average fiber diameter of short glass fibers is not particularly limited. Considering that the thermal expansion rate can be further reduced, it is preferably 3.0 μm or more and 15 μm or less, more preferably 3.0 μm or more and 13 μm or less, and more preferably 3.5 μm or more and 11 μm or less. good.

玻璃短纖維的平均纖維長及平均纖維徑可使用光學顯微鏡或電子顯微鏡等來測定。The average fiber length and average fiber diameter of short glass fibers can be measured using an optical microscope, an electron microscope, or the like.

玻璃短纖維之具體例可列舉：磨碎纖維(通常稱「milled fiber」)、玻璃絨及微桿(micro-rod)。玻璃短纖維考慮摻合於絕緣性樹脂層時可獲得和銅箔優良的黏合性且為低價之情況，宜為磨碎纖維。這些玻璃短纖維可單獨使用1種或將2種以上適當地混合使用。Specific examples of short glass fiber include: milled fiber (usually called "milled fiber"), glass wool, and micro-rod. Considering that short glass fibers can obtain excellent adhesion with copper foil when blended into the insulating resin layer and are low-priced, they are preferably ground fibers. These short glass fibers can be used individually by 1 type or in mixture of 2 or more types suitably.

本實施形態中，玻璃短纖維的含量並無特別限制，考慮熱膨脹率、韌性的賦予、及成形性之觀點，相對於絕緣性樹脂層中之樹脂固體成分100質量份，宜落在5質量份以上且450質量份以下之範圍內，落在10質量份以上且400質量份以下之範圍內更佳，落在15質量份以上且300質量份以下之範圍內再更佳，落在20質量份以上且200質量份以下之範圍內又更佳，落在20質量份以上且100質量份以下之範圍內特佳。In this embodiment, the content of short glass fibers is not particularly limited. Considering the thermal expansion coefficient, the imparting of toughness, and the formability, it is preferably 5 parts by mass relative to 100 parts by mass of the resin solid content in the insulating resin layer. Within the range of above and 450 parts by mass, it is more preferably within the range of 10 parts by mass or more and 400 parts by mass or less, and more preferably within the range of 15 parts by mass or more and 300 parts by mass or less, and it is more preferably within the range of 20 parts by mass. It is more preferably within the range of the above and 200 parts by mass or less, and is particularly preferably within the range of 20 or more parts by mass and 100 parts by mass or less.

本實施形態中，球狀填料與玻璃短纖維之摻合比並無特別限制，考慮成形性之觀點，球狀填料：玻璃短纖維之質量比宜為1：20～100：1，為1：10～150：1更佳，為1：2～10：1再更佳。In this embodiment, the blending ratio of spherical filler and short glass fiber is not particularly limited. Considering the formability, the mass ratio of spherical filler: short glass fiber is preferably 1:20-100:1, which is 1: 10～150:1 is more preferable, and 1:2～10:1 is even more preferable.

如上所述，絕緣性樹脂層中之玻璃短纖維之平面方向上的配向度(fp)未達0.60。此外，考慮縮小各物性在XY方向上之差異的觀點及使翹曲之產生量本身降低之觀點，配向度(fp)宜為0.40以下，為0.35以下更佳，為0.30以下再更佳。又，配向度(fp)的下限並無特別限制，例如配向度可為0.10以上，也可為0.15以上，亦可為0.20以上。As described above, the degree of alignment (fp) in the plane direction of the short glass fibers in the insulating resin layer does not reach 0.60. In addition, considering the viewpoint of reducing the difference in the XY directions of various physical properties and the viewpoint of reducing the amount of warpage itself, the degree of alignment (fp) is preferably 0.40 or less, more preferably 0.35 or less, and even more preferably 0.30 or less. In addition, the lower limit of the degree of alignment (fp) is not particularly limited. For example, the degree of alignment may be 0.10 or more, 0.15 or more, or 0.20 or more.

附絕緣性樹脂層之銅箔中之平面方向的配向度之測定具體如下所述。首先，將切成長度3cm×寬3cm之附絕緣性樹脂層之銅箔載置於載玻片上，從上方再放置載玻片。將如此獲得之以載玻片挾持的附絕緣性樹脂層之銅箔之試驗片，使用顯微鏡觀察通常之反射光來測定配向度(fp)。另外，測定時，也可因應需要對附絕緣性樹脂層之銅箔施加樹脂包埋等處理。The measurement of the degree of alignment in the plane direction in the copper foil with an insulating resin layer is specifically as follows. First, the copper foil with an insulating resin layer cut into a length of 3 cm × a width of 3 cm is placed on a glass slide, and the glass slide is placed from above. The thus obtained test piece of copper foil with an insulating resin layer sandwiched by a glass slide was used to observe normal reflected light with a microscope to measure the degree of alignment (fp). In addition, during the measurement, the copper foil with an insulating resin layer can also be treated with resin embedding.

本實施形態係利用光學顯微鏡觀察以載玻片挾持的附絕緣性樹脂之銅箔的絕緣性樹脂層側之面。光學顯微鏡可使用奧林巴斯(股)製之倒立顯微鏡、或KEYENCE(股)製之顯微鏡。調整光學顯微鏡的倍率使其可辨認單纖絲，利用反射光，或合併使用反射光與透射光，觀察絕緣性樹脂層中的玻璃短纖維。本實施形態中，例如可從100倍、300倍、600倍、及800倍中選擇上述倍率，例如理想可設定為100倍。藉此，觀察其中一側之面中之任意地選擇之連續的1.5mm² 之測定區域，並測定存在該測定區域中之可辨認之全部玻璃短纖維(令纖維數為m條)的配向角度θ_i 。然後，針對存在上述測定區域中之於觀察圖像中可辨認之全部玻璃短纖維，以後述方法測定相對於已設定之基準線的角度θ_i (i=1～m)。配向角度θ_i 係測定相對於基準線為順時鐘方向之角度，故為0°以上且未達180°之角度。使用圖1針對玻璃短纖維與基準線之關係進行說明。圖1中(a)係從向著其平面方向的方向觀察絕緣性樹脂層之示意俯視圖，(b)係用以說明玻璃短纖維的配向角度θ之示意圖。如圖1(a)所示，絕緣性樹脂層1中分散有大量的玻璃短纖維2。圖1(a)中，箭頭X表示在俯視圖中，形成絕緣性樹脂層時的塗佈方向或輸送方向，箭頭Y表示相對於箭頭X之垂直方向。又，直線P表示基準線。如圖1(b)所示，基準線P與各玻璃短纖維2A～2C(i=1～3)所成的角度即為各個配向角度θ₁ ～θ₃ 。各配向角度係如圖中箭頭所示，為順時鐘方向之角度。In this embodiment, the surface of the insulating resin layer side of the copper foil with insulating resin pinched by a glass slide is observed with an optical microscope. The optical microscope can be an inverted microscope made by Olympus (stock) or a microscope made by KEYENCE (stock). Adjust the magnification of the optical microscope so that single filaments can be recognized, and observe the short glass fibers in the insulating resin layer by using reflected light or a combination of reflected light and transmitted light. In this embodiment, the above-mentioned magnification can be selected from, for example, 100 times, 300 times, 600 times, and 800 times, and for example, it can be set to 100 times ideally. By this, observe the arbitrarily selected continuous ^{measurement area of 1.5 mm 2} in one of the surfaces, and measure the alignment angle of all the identifiable short glass fibers (let the number of fibers be m) existing in the measurement area θ _i . Then, for all the short glass fibers that are recognizable in the observation image existing in the above-mentioned measurement area, the angle θ _i (i=1 to m) relative to the set reference line is measured by the method described later. The alignment angle θ _i is an angle measured in the clockwise direction relative to the reference line, so it is an angle above 0° and less than 180°. The relationship between the short glass fiber and the reference line will be described using FIG. 1. In FIG. 1, (a) is a schematic plan view of the insulating resin layer viewed from a direction toward the plane direction thereof, and (b) is a schematic diagram for explaining the alignment angle θ of short glass fibers. As shown in Fig. 1(a), a large amount of short glass fibers 2 are dispersed in the insulating resin layer 1. In FIG. 1(a), the arrow X indicates the coating direction or the conveying direction when the insulating resin layer is formed in a plan view, and the arrow Y indicates the direction perpendicular to the arrow X. In addition, the straight line P represents a reference line. As shown in Fig. 1(b), the angle formed by the reference line P and each short glass fiber 2A-2C (i=1 to 3) is the respective alignment angle θ ₁ ˜θ ₃ . The alignment angles are shown by the arrows in the figure, which are angles in the clockwise direction.

測定角度θ_i 後，從短纖維相對於已設定之基準線的角度θ_i ，使用下式(2)算出平面方向的配向度(fp)。 fp=2×Σ(cos² θ_i /m)-1…(2)After the measurement angle θ _i, the short fibers with respect to the reference line has been set angle θ _i, using (2) the degree of orientation of the plane direction was calculated by the following formula (fp). fp=2×Σ(cos ² θ _i /m)-1…(2)

測定平面方向的配向度時之基準線可利用下述方法來決定。首先，在決定基準線時，選擇第1暫時基準線p，測定存在測定區域內之可辨認的全部m條玻璃短纖維m條的角度。此時，第1暫時基準線p和各纖維的角度以α(p)_i (i=1～m)表示。使用下式計算使用第1暫時基準線p時的配向度(fp(p))。式中，角度α(p)_i ，和配向角度θ_i 同樣地係相對於第1暫時基準線p為順時鐘方向之角度，為0°以上且未達180°之角度。 fp(p)=2×Σ(cos² α(p)_i /m)-1 (i=1、2、3、…、m)The reference line when measuring the alignment in the plane direction can be determined by the following method. First, when determining the reference line, the first temporary reference line p is selected, and the angles of all m recognizable short glass fibers in the measurement area are measured. At this time, the angle between the first temporary reference line p and each fiber is represented by α(p) _i (i=1 to m). The degree of alignment (fp(p)) when the first temporary reference line p is used is calculated using the following formula. In the formula, the angle α(p) _{i is} , like the alignment angle θ _i , an angle in the clockwise direction with respect to the first temporary reference line p, and is an angle of 0° or more and less than 180°. fp(p)=2×Σ(cos ² α(p) _i /m)-1 (i=1, 2, 3,..., m)

然後，取得從第1暫時基準線p起以順時鐘逐次旋轉±1°直至±90°為止之多條暫時基準線(p+z、p-z(z=1～90))。暫時基準線p+z係從第1暫時基準線p起以順時鐘逐次旋轉1°直至90°為止者，例如從暫時基準線p起以順時鐘旋轉1°者為暫時基準線p+1，順時鐘旋轉2°者為暫時基準線p+2，順時鐘旋轉90°者為暫時基準線p+90。又，暫時基準線p-z係從第1暫時基準線p起以逆時鐘逐次旋轉1°直至90°為止者，例如從暫時基準線p起以逆時鐘旋轉1°者為暫時基準線p-1，逆時鐘旋轉2°者為暫時基準線p-2，逆時鐘旋轉90°者為暫時基準線p-90。然後，分別計算暫時基準線p+z及暫時基準線p-z和m條短纖維的角度。此時的角度以α(p+z)_i 、及α(p-z)_i (i=1～m)表示。旋轉後的暫時基準線(p+z、p-z(z=1～90))和短纖維的配向度(fp(p±z))使用下式進行計算。 fp(p±z)=2×Σ(cos² α(p±z)_i /m)-1 (i=1、2、3、…、m) 將以此方式設成得到的fp(p)值及fp(p±z)值之中可獲得最大值時之暫時基準線定為基準線P。Then, a plurality of temporary reference lines (p+z, pz (z=1 to 90)) that are sequentially rotated by ±1° clockwise to ±90° from the first temporary reference line p are obtained. The temporary reference line p+z is one rotated 1° clockwise to 90° from the first temporary reference line p, for example, the temporary reference line p+1 is rotated 1° clockwise from the temporary reference line p, A clockwise rotation of 2° is the temporary reference line p+2, and a clockwise rotation of 90° is the temporary reference line p+90. In addition, the temporary reference line pz is one that is rotated 1° counterclockwise from the first temporary reference line p to 90° successively, for example, the temporary reference line p-1 is the one that is rotated 1° counterclockwise from the temporary reference line p. A counterclockwise rotation of 2° is the temporary reference line p-2, and a counterclockwise rotation of 90° is the temporary reference line p-90. Then, the temporary reference line p+z and the temporary reference line pz and the angles of m short fibers are respectively calculated. The angle at this time is represented by α(p+z) _i and α(pz) _i (i=1 to m). The rotated temporary reference line (p+z, pz (z=1 to 90)) and the degree of alignment of the short fiber (fp(p±z)) are calculated using the following formula. fp(p±z)=2×Σ(cos ² α(p±z) _i /m)-1 (i=1, 2, 3,..., m) Set the fp(p) obtained in this way The temporary reference line when the maximum value is obtained among the values of fp(p±z) and fp(p±z) is set as the reference line P.

將由如上般決定的基準線P所算出之配向度定為平面方向的配向度(fp)。The degree of alignment calculated from the reference line P determined as above is defined as the degree of alignment (fp) in the plane direction.

另外，例如絕緣性樹脂層的厚度為1μm以上且18μm以下時，玻璃短纖維的長度會影響配向偏差，且玻璃短纖維相對於絕緣性樹脂層之厚度方向的配向偏差小。因此，本實施形態中，例如絕緣性樹脂層的厚度為1μm以上且18μm以下時，玻璃短纖維相對於絕緣性樹脂層之厚度方向的配向度對絕緣性樹脂層之物性造成的影響較少。In addition, for example, when the thickness of the insulating resin layer is 1 μm or more and 18 μm or less, the length of the short glass fibers affects the alignment deviation, and the alignment deviation of the short glass fibers with respect to the thickness direction of the insulating resin layer is small. Therefore, in the present embodiment, for example, when the thickness of the insulating resin layer is 1 μm or more and 18 μm or less, the degree of alignment of the short glass fibers with respect to the thickness direction of the insulating resin layer has less influence on the physical properties of the insulating resin layer.

(其它成分) 本實施形態中的絕緣性樹脂層除了含有(A)熱硬化性樹脂、(B)球狀填料及(C)玻璃短纖維之外，也可含有其它1種或2種以上之成分。就其它成分而言，例如為了改善本實施形態相關之絕緣性樹脂層的吸濕耐熱性，本實施形態中的絕緣性樹脂層也可含有矽烷偶聯劑。矽烷偶聯劑若為通常使用於無機物之表面處理的矽烷偶聯劑，則無特別限制。其具體例可列舉：胺基矽烷系矽烷偶聯劑(例如γ-胺基丙基三乙氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基三甲氧基矽烷)、環氧矽烷系矽烷偶聯劑(例如γ-環氧丙氧基丙基三甲氧基矽烷)、乙烯基矽烷系矽烷偶聯劑(例如γ-甲基丙烯醯氧基丙基三甲氧基矽烷)、陽離子性矽烷系矽烷偶聯劑(例如N-β-(N-乙烯基苄基胺基乙基)-γ-胺基丙基三甲氧基矽烷鹽酸鹽)、及苯基矽烷系矽烷偶聯劑。矽烷偶聯劑可單獨使用1種或將2種以上適當地混合使用。(Other ingredients) In addition to containing (A) thermosetting resin, (B) spherical filler, and (C) short glass fiber, the insulating resin layer in this embodiment may contain one or more other components. Regarding other components, for example, in order to improve the moisture absorption and heat resistance of the insulating resin layer in this embodiment, the insulating resin layer in this embodiment may also contain a silane coupling agent. The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for the surface treatment of inorganic substances. Specific examples include: aminosilane coupling agents (for example, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane) , Silicone oxide coupling agent (e.g. γ-glycidoxypropyltrimethoxysilane), vinyl silane coupling agent (e.g. γ-methacryloxypropyltrimethoxysilane) ), cationic silane coupling agent (such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyl trimethoxysilane hydrochloride), and phenylsilane series silane Coupling agent. A silane coupling agent can be used individually by 1 type or in mixture of 2 or more types suitably.

本實施形態中，矽烷偶聯劑的含量並無特別限制，考慮改善吸濕耐熱性之觀點，相對於球狀填料100質量份，宜落在0.05質量份以上且5質量份以下之範圍內，落在0.1質量份以上且3質量份以下之範圍內更佳。另外，合併使用2種以上之矽烷偶聯劑時，它們的合計量宜符合上述範圍。In this embodiment, the content of the silane coupling agent is not particularly limited. In view of improving the moisture absorption and heat resistance, it should preferably fall within the range of 0.05 parts by mass to 5 parts by mass relative to 100 parts by mass of the spherical filler. It is more preferable to fall within the range of 0.1 parts by mass or more and 3 parts by mass or less. In addition, when two or more silane coupling agents are used in combination, their total amount should fall within the above range.

本實施形態中的絕緣性樹脂層為了改善絕緣性樹脂層之製造性等，也可含有濕潤分散劑。濕潤分散劑若為通常使用於塗料等之濕潤分散劑，則無特別限制。其市售品可列舉例如：BYK(股)製之Disperbyk(註冊商標)-110、Disperbyk-111、Disperbyk-180、Disperbyk-161、BYK(註冊商標)-W996、BYK-W9010、BYK-W903。濕潤分散劑可單獨使用1種或將2種以上適當地混合使用。In order to improve the manufacturability of the insulating resin layer, etc., the insulating resin layer in this embodiment may contain a wetting and dispersing agent. The wetting and dispersing agent is not particularly limited as long as it is a wetting and dispersing agent generally used for paints and the like. Examples of commercially available products include: Disperbyk (registered trademark)-110, Disperbyk-111, Disperbyk-180, Disperbyk-161, BYK (registered trademark)-W996, BYK-W9010, BYK-W903 manufactured by BYK (Stock). A wetting and dispersing agent can be used individually by 1 type or in mixture of 2 or more types suitably.

本實施形態中，濕潤分散劑的含量並無特別限制，考慮改善絕緣性樹脂層之製造性的觀點，相對於球狀填料100質量份，宜落在0.1質量份以上且5質量份以下之範圍內，落在0.5質量份以上且3質量份以下之範圍內更佳。另外，合併使用2種以上之濕潤分散劑時，它們的合計量宜符合上述範圍。In this embodiment, the content of the wetting and dispersing agent is not particularly limited. In view of improving the manufacturability of the insulating resin layer, it should preferably fall within the range of 0.1 parts by mass to 5 parts by mass relative to 100 parts by mass of the spherical filler. Within, it is more preferable to fall within the range of 0.5 parts by mass or more and 3 parts by mass or less. In addition, when two or more types of wetting and dispersing agents are used in combination, their total amount should fall within the above-mentioned range.

本實施形態中的絕緣性樹脂層為了調整硬化速度等目的，也可含有硬化促進劑。硬化促進劑若為使用於環氧樹脂或氰酸酯化合物等之硬化促進劑等通常使用者，則無特別限制。其具體例可列舉：含有銅、鋅、鈷、鎳、錳等金屬之有機金屬鹽類(例如辛酸鋅、環烷酸鈷、辛酸鎳、辛酸錳)、咪唑類及其衍生物(例如2-乙基-4-甲基咪唑、1-苄基-2-苯基咪唑、2,4,5-三苯基咪唑)、三級胺(例如三乙胺、三丁胺)。這些硬化促進劑可單獨使用1種或將2種以上適當地混合使用。The insulating resin layer in this embodiment may contain a curing accelerator for the purpose of adjusting the curing speed and the like. The hardening accelerator is not particularly limited if it is a hardening accelerator used for epoxy resins, cyanate ester compounds, and the like for ordinary users. Specific examples include: organometallic salts containing metals such as copper, zinc, cobalt, nickel, and manganese (such as zinc octoate, cobalt naphthenate, nickel octoate, and manganese octoate), imidazoles and their derivatives (such as 2- Ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4,5-triphenylimidazole), tertiary amine (for example, triethylamine, tributylamine). These hardening accelerators can be used individually by 1 type or in mixture of 2 or more types suitably.

本實施形態中，硬化促進劑的含量並無特別限制，考慮獲得高玻璃轉移溫度之觀點，相對於絕緣性樹脂層中之樹脂固體成分100質量份，宜落在0.001質量份以上且5質量份以下之範圍內，落在0.01質量份以上且3質量份以下之範圍內更佳。另外，合併使用2種以上之硬化促進劑時，它們的合計量宜符合上述範圍。In this embodiment, the content of the hardening accelerator is not particularly limited. In consideration of obtaining a high glass transition temperature, relative to 100 parts by mass of the resin solid content in the insulating resin layer, it is preferably 0.001 parts by mass or more and 5 parts by mass. The following ranges are more preferably within the range of 0.01 parts by mass or more and 3 parts by mass or less. In addition, when two or more hardening accelerators are used in combination, the total amount of them should fall within the above-mentioned range.

本實施形態中的絕緣性樹脂層也可含有其它各種高分子化合物及/或阻燃性化合物等。高分子化合物及阻燃性化合物若為通常使用者，則無特別限制。The insulating resin layer in this embodiment may contain other various polymer compounds and/or flame-retardant compounds. The polymer compound and the flame-retardant compound are not particularly limited as long as they are general users.

就高分子化合物而言，可列舉(A)熱硬化性樹脂以外之各種熱塑性樹脂以及其寡聚物、及彈性體類。其具體例可列舉：聚醯亞胺、聚醯胺醯亞胺、聚苯乙烯、聚烯烴、苯乙烯-丁二烯橡膠(SBR)、異戊二烯橡膠(IR)、丁二烯橡膠(BR)、丙烯腈丁二烯橡膠(NBR)、聚胺甲酸酯、聚丙烯、(甲基)丙烯酸系寡聚物、(甲基)丙烯酸系聚合物及聚矽氧樹脂。它們之中，考慮相容性之觀點，高分子化合物宜為丙烯腈丁二烯橡膠或苯乙烯丁二烯橡膠。另外，「(甲基)丙烯酸」係包含甲基丙烯酸及丙烯酸之概念。Examples of the polymer compound include (A) various thermoplastic resins other than thermosetting resins, and oligomers and elastomers thereof. Specific examples thereof include: polyimide, polyimide, polystyrene, polyolefin, styrene-butadiene rubber (SBR), isoprene rubber (IR), butadiene rubber ( BR), acrylonitrile butadiene rubber (NBR), polyurethane, polypropylene, (meth)acrylic oligomer, (meth)acrylic polymer and silicone resin. Among them, considering compatibility, the polymer compound is preferably acrylonitrile butadiene rubber or styrene butadiene rubber. In addition, "(meth)acrylic acid" includes the concepts of methacrylic acid and acrylic acid.

就阻燃性化合物之具體例而言，可列舉(B)球狀填料及(C)玻璃短纖維以外之含磷之化合物(例如磷酸酯、磷酸三聚氰胺、含磷之環氧樹脂)、含氮之化合物(例如三聚氰胺、苯并胍胺)、含㗁𠯤環之化合物、聚矽氧系化合物。這些高分子化合物及阻燃性化合物分別可單獨使用1種或將2種以上適當地混合使用。Specific examples of flame retardant compounds include (B) spherical fillers and (C) phosphorus-containing compounds other than short glass fibers (for example, phosphoric acid ester, melamine phosphate, phosphorus-containing epoxy resin), nitrogen-containing Compounds (such as melamine, benzoguanamine), compounds containing 㗁𠯤 ring, polysiloxane compounds. These polymer compounds and flame-retardant compounds can be used individually by 1 type or in mixture of 2 or more types suitably.

本實施形態中的絕緣性樹脂層依各種目的也可含有其它各種添加劑。添加劑之具體例可列舉：紫外線吸收劑、抗氧化劑、光聚合起始劑、螢光增白劑、光敏劑、染料、顏料、增黏劑、潤滑劑、消泡劑、分散劑、整平劑及亮光劑。這些添加劑可單獨使用1種或將2種以上適當地混合使用。The insulating resin layer in this embodiment may contain other various additives according to various purposes. Specific examples of additives include: ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, tackifiers, lubricants, defoamers, dispersants, leveling agents And brightener. These additives can be used individually by 1 type or in mixture of 2 or more types suitably.

(樹脂組成物) 本實施形態中的絕緣性樹脂層可使用樹脂組成物來形成。樹脂組成物係藉由將(A)熱硬化性樹脂、(B)球狀填料、及(C)平均纖維長為10μm以上且300μm以下之玻璃短纖維、以及因應需要之其它成分進行混合來製得。又，樹脂組成物也可因應需要製成使這些成分溶解於有機溶劑而成的溶液之形態。如此的樹脂組成物之溶液可理想地使用作為製作後述本實施形態之附絕緣性樹脂層之銅箔時的清漆。(Resin composition) The insulating resin layer in this embodiment can be formed using a resin composition. The resin composition is made by mixing (A) thermosetting resin, (B) spherical filler, and (C) short glass fibers with an average fiber length of 10 μm or more and 300 μm or less, and other components as needed. Got. In addition, the resin composition may be in the form of a solution in which these components are dissolved in an organic solvent, if necessary. The solution of such a resin composition can be used ideally as a varnish when manufacturing the copper foil with an insulating resin layer of this embodiment mentioned later.

有機溶劑只要可使各成分各別適當地溶解或分散，且發揮本實施形態中的絕緣性樹脂層之效果，即無特別限制。有機溶劑之具體例可列舉：醇類(例如甲醇、乙醇及丙醇)、酮類(例如丙酮、甲乙酮及甲基異丁基酮)、醯胺類(例如二甲基乙醯胺及二甲基甲醯胺)、及芳香族烴類(例如甲苯及二甲苯)。這些有機溶劑可單獨使用1種或將2種以上適當地混合使用。The organic solvent is not particularly limited as long as it can appropriately dissolve or disperse each component individually and exhibit the effect of the insulating resin layer in this embodiment. Specific examples of organic solvents include alcohols (such as methanol, ethanol, and propanol), ketones (such as acetone, methyl ethyl ketone, and methyl isobutyl ketone), amides (such as dimethyl acetamide and dimethyl acetamide). Methyl methamide), and aromatic hydrocarbons (such as toluene and xylene). These organic solvents can be used individually by 1 type or in mixture of 2 or more types suitably.

樹脂組成物之溶液中的有機溶劑之含量考量獲得期望的黏度之觀點等而適當地決定即可，並無特別限制。其含量例如相對於樹脂組成物溶液100質量份，可為20質量份以上且500質量份以下，也可為30質量份以上且300質量份以下。The content of the organic solvent in the solution of the resin composition may be appropriately determined considering the viewpoint of obtaining the desired viscosity, etc., and is not particularly limited. The content thereof may be 20 parts by mass or more and 500 parts by mass or less, or 30 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the resin composition solution, for example.

(絕緣性樹脂層) 本實施形態中的絕緣性樹脂層可如上述般由樹脂組成物獲得。絕緣性樹脂層的厚度並無特別限制，考慮平滑性及玻璃短纖維的配向之觀點，宜落在3μm以上且50μm以下之範圍內。又，絕緣性樹脂層的厚度考慮可進一步獲得良好的成形性之觀點，宜為6μm以上且45μm以下，考慮可進一步獲得良好的銅箔與絕緣性樹脂層之黏合性的觀點，為8μm以上且40μm以下更佳。(Insulating resin layer) The insulating resin layer in this embodiment can be obtained from the resin composition as described above. The thickness of the insulating resin layer is not particularly limited, but considering the smoothness and the orientation of short glass fibers, it is preferably within the range of 3 μm or more and 50 μm or less. In addition, the thickness of the insulating resin layer is preferably 6 μm or more and 45 μm or less from the viewpoint of further obtaining good moldability, and from the viewpoint of further obtaining good adhesion between the copper foil and the insulating resin layer, it is 8 μm or more and 40μm or less is more preferable.

絕緣性樹脂層表面的算術平均粗糙度(Ra)宜為2μm以下，為0.1μm以上且1μm以下更佳，為0.15μm以上且0.5μm以下再更佳。其算術平均粗糙度(Ra)藉由落在上述範圍內，可改善銅箔與絕緣性樹脂層之黏合強度、或絕緣性樹脂層彼此之黏合強度，且可更有效地防止長時間使用時的層剝離。就絕緣性樹脂層的表面而言，各面可因應目的各別成為和銅箔相接觸的面、及和銅箔以外(例如其它絕緣性樹脂層)相接觸的面，為任一面其算術平均粗糙度(Ra)皆宜落在上述範圍內。絕緣性樹脂層表面的算術平均粗糙度可使用市售之形狀測定顯微鏡(雷射顯微鏡，例如KEYENCE股份有限公司製之VK-X210(產品名))來測定。The arithmetic average roughness (Ra) of the surface of the insulating resin layer is preferably 2 μm or less, more preferably 0.1 μm or more and 1 μm or less, and even more preferably 0.15 μm or more and 0.5 μm or less. The arithmetic average roughness (Ra) falls within the above range to improve the bonding strength between the copper foil and the insulating resin layer, or the bonding strength between the insulating resin layers, and it can more effectively prevent long-term use. Layer peeling. Regarding the surface of the insulating resin layer, each surface can be the surface in contact with the copper foil and the surface in contact with other than the copper foil (for example, other insulating resin layers) according to the purpose. The arithmetic average roughness of either surface (Ra) should fall within the above range. The arithmetic average roughness of the surface of the insulating resin layer can be measured using a commercially available shape measuring microscope (laser microscope, for example, VK-X210 (product name) manufactured by KEYENCE Co., Ltd.).

絕緣性樹脂層表面的算術平均粗糙度(Ra)可藉由調整有機溶劑的含量、或適當地選擇塗佈方式等來控制在上述範圍內。The arithmetic average roughness (Ra) of the surface of the insulating resin layer can be controlled within the above-mentioned range by adjusting the content of the organic solvent or appropriately selecting the coating method.

(附絕緣性樹脂層之銅箔之製造方法) 本實施形態中的附絕緣性樹脂層之銅箔之製造方法若為具有於銅箔上疊層由上述樹脂組成物構成的絕緣性樹脂層之步驟的方法，則無特別限制。疊層步驟可列舉例如將使樹脂組成物溶解或分散於有機溶劑而成的溶液(清漆)塗佈於銅箔的表面，並於加熱及/或減壓下進行乾燥，將溶劑去除而使樹脂組成物固化來形成絕緣性樹脂層之步驟。乾燥條件並無特別限制，以有機溶劑相對於絕緣性樹脂層之含有比率係相對於絕緣性樹脂層100質量份成為10質量份以下的方式使其乾燥較理想，以成為5質量份以下的方式使其乾燥更佳。達成乾燥的條件取決於清漆中之有機溶劑量而有所不同，例如為含有相對於清漆100質量份為30質量份以上且60質量份以下之有機溶劑的清漆時，以50℃以上且160℃以下之加熱條件下使其乾燥約3～10分鐘即可。(Method of manufacturing copper foil with insulating resin layer) The manufacturing method of the copper foil with an insulating resin layer in this embodiment will not be specifically limited if it has the process of laminating|stacking the insulating resin layer which consists of the said resin composition on copper foil. The laminating step includes, for example, applying a solution (varnish) prepared by dissolving or dispersing the resin composition in an organic solvent on the surface of the copper foil, and then drying under heating and/or reduced pressure to remove the solvent to make the resin The step of curing the composition to form an insulating resin layer. The drying conditions are not particularly limited. It is preferable to dry the organic solvent so that the content ratio of the organic solvent to the insulating resin layer is 10 parts by mass or less with respect to 100 parts by mass of the insulating resin layer, and it is preferably 5 parts by mass or less. Make it dry better. The conditions for achieving drying vary depending on the amount of organic solvent in the varnish. For example, for a varnish containing 30 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the varnish, use 50°C or more and 160°C Allow it to dry for about 3-10 minutes under the following heating conditions.

針對將樹脂組成物塗佈於銅箔上之方法亦無特別限制，例如可使用塗佈棒塗佈、氣刀塗佈、凹版塗佈、反向凹版塗佈、微凹版塗佈、微反向凹版塗佈機塗佈、模塗機塗佈、浸漬塗佈、旋塗塗佈、噴霧塗佈之類的公知之塗佈法。另外，為了將玻璃短纖維的配向度控制在較低，例如凹版塗佈等般在1次的塗覆中，玻璃短纖維不易沿單一方向進行配向之方法較理想。又，如塗佈棒塗佈般在1次的塗覆中，玻璃短纖維容易沿單一方向進行配向之塗佈方法時，宜變更塗佈方向並進行2次以上塗覆(例如第2次塗覆時，將塗佈方向變換成垂直方向等)。此時，變更的塗佈方向宜為在平面方向中相互垂直相交之方向。又，相同的塗佈方法中，欲降低平面方向的配向度，例如將玻璃纖維的平均纖維長縮短即可。There is no particular limitation on the method of coating the resin composition on the copper foil. For example, coating bar coating, air knife coating, gravure coating, reverse gravure coating, micro gravure coating, and micro reverse gravure coating can be used. Well-known coating methods such as gravure coater coating, die coater coating, dip coating, spin coating, and spray coating. In addition, in order to control the degree of alignment of the short glass fibers at a low level, for example, gravure coating is generally used in one coating, and the method in which the short glass fibers are not easily aligned in a single direction is preferable. In addition, in a coating method in which short glass fibers are easily aligned in a single direction in a single coating like coating bar coating, it is advisable to change the coating direction and apply more than two coatings (e.g., the second coating). When covering, change the coating direction to a vertical direction, etc.). At this time, the changed coating direction is preferably a direction that intersects each other perpendicularly in the plane direction. In addition, in the same coating method, to reduce the degree of alignment in the plane direction, for example, the average fiber length of the glass fiber may be shortened.

＜本實施形態之疊層體及其製造方法＞使用有本實施形態之附絕緣性樹脂層之銅箔的疊層體(以下有時簡稱「疊層體」)，例如可用於印刷配線板或半導體元件搭載用基板之堆疊材料用的無芯基板之製作。本實施形態之疊層體例如為具有由導體層與使用本實施形態之附絕緣性樹脂層之銅箔形成的絕緣層交替疊層而成的堆疊層之疊層體。另外，疊層體中的絕緣層可為絕緣性樹脂層本身，也可為絕緣性樹脂層硬化而成者。疊層體分別具有1個或2個以上之導體層及絕緣層。在此，絕緣層例如係將本實施形態之附絕緣性樹脂層之銅箔進行疊層來形成絕緣層時，若為2層結構的情況，係將本實施形態之附絕緣性樹脂層之銅箔以絕緣性樹脂層彼此相接觸的方式進行疊層。又，使用3層以上之附絕緣性樹脂層之銅箔的情況，可因應需要從附絕緣性樹脂層之銅箔將銅箔去除，並將各絕緣性樹脂層進行疊層來形成絕緣層。又，本實施形態之附絕緣性樹脂層之銅箔中的銅箔可擔任上述導體層的角色，也可再新疊層和其不同的導體(銅箔等)來形成導體層。本實施形態之疊層體之製造方法若為具有使用本實施形態之附絕緣性樹脂層之銅箔在導體層表面形成絕緣層，藉此形成由導體層與絕緣層交替疊層而成的堆疊層之步驟者，則無特別限制。<Laminated body of this embodiment and its manufacturing method> A laminate using the copper foil with an insulating resin layer of this embodiment (hereinafter sometimes referred to as "laminate"), for example, a coreless substrate that can be used as a stack material for printed wiring boards or substrates for mounting semiconductor elements The production. The laminated body of this embodiment is a laminated body which has the laminated body which laminated|stacked alternately the conductor layer and the insulating layer formed using the copper foil with an insulating resin layer of this embodiment, for example. In addition, the insulating layer in the laminated body may be the insulating resin layer itself, or the insulating resin layer may be cured. The laminated body has one or more conductor layers and insulating layers, respectively. Here, the insulating layer is formed by laminating the copper foil with an insulating resin layer of this embodiment to form an insulating layer. In the case of a two-layer structure, it is the copper foil with an insulating resin layer of this embodiment. The foil is laminated so that the insulating resin layers are in contact with each other. In addition, when using copper foil with insulating resin layers with three or more layers, the copper foil can be removed from the copper foil with insulating resin layer as needed, and the insulating resin layers can be laminated to form an insulating layer. In addition, the copper foil in the copper foil with an insulating resin layer of the present embodiment may play the role of the above-mentioned conductor layer, or it may be newly laminated with a different conductor (copper foil, etc.) to form the conductor layer. If the method of manufacturing the laminate of this embodiment is to use the copper foil with an insulating resin layer of this embodiment to form an insulating layer on the surface of the conductor layer, thereby forming a stack in which the conductor layer and the insulating layer are alternately laminated There are no special restrictions on the steps of the layers.

本實施形態之疊層體具有堆疊層時，例如該堆疊層具有多層之導體層與絕緣層，且導體層配置於各絕緣層之間以及堆疊層之最外層的表面。此時，絕緣層的數量並無特別限制，例如可製成3層或4層。又，可使用本實施形態之疊層體來製作無芯基板。無芯基板可列舉例如2層以上之無芯基板，也可為3層無芯基板。針對無芯基板的結構如後所述。When the laminated body of this embodiment has a stacked layer, for example, the stacked layer has a plurality of conductive layers and insulating layers, and the conductive layer is disposed between the insulating layers and on the surface of the outermost layer of the stacked layer. At this time, the number of insulating layers is not particularly limited, and for example, it can be made into 3 layers or 4 layers. In addition, the laminate of this embodiment can be used to produce a coreless substrate. The coreless substrate may be, for example, a coreless substrate with two or more layers, or a three-layer coreless substrate. The structure of the coreless substrate will be described later.

本實施形態之疊層體中，考慮實現薄膜化的要求之觀點，至少1層之絕緣層的厚度宜為4μm以上且未達15μm。該絕緣層的厚度取決於各種疊層體用途而有所不同，例如為6μm以上且14μm以下更佳，為8μm以上且12μm以下再更佳。In the laminate of this embodiment, considering the requirements for achieving thinning, the thickness of at least one insulating layer is preferably 4 μm or more and less than 15 μm. The thickness of the insulating layer varies depending on the use of the various laminates. For example, it is 6 μm or more and 14 μm or less, and more preferably 8 μm or more and 12 μm or less.

[印刷配線板] 本實施形態之疊層體可使用作為印刷配線板。在此，印刷配線板可藉由對被稱為芯基材之絕緣性樹脂層經完全硬化而成的覆金屬箔疊層板，使用得自本實施形態之附絕緣性樹脂層之銅箔的疊層體作為堆疊材料而獲得。使用本實施形態之附絕緣性樹脂層之銅箔及得自於其之疊層體的話，例如可在不使用厚的支持基板(載體基板)的情況下來製造薄型的印刷配線板。又，使用本實施形態之附絕緣性樹脂層之銅箔而獲得的印刷配線板，其各層間的黏合力、生產性(成品率)更優良。[Printed Wiring Board] The laminated body of this embodiment can be used as a printed wiring board. Here, the printed wiring board can be a metal-clad laminate formed by completely hardening an insulating resin layer called a core base material, and a copper foil with an insulating resin layer obtained from this embodiment can be used. The laminate is obtained as a stacked material. If the copper foil with an insulating resin layer of this embodiment and the laminate derived therefrom are used, for example, a thin printed wiring board can be manufactured without using a thick support substrate (carrier substrate). In addition, the printed wiring board obtained by using the copper foil with an insulating resin layer of the present embodiment has more excellent adhesion between the layers and productivity (yield rate).

覆金屬箔疊層板的表面會利用通常使用的覆金屬箔疊層板之金屬箔及/或將金屬箔剝離後進行鍍敷等而獲得之導體層來形成導體電路。又，覆金屬箔疊層板的基材並無特別限制，例如主要為玻璃環氧樹脂基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板及熱硬化型聚苯醚基板。On the surface of the metal-clad laminate, a conductor circuit is formed by using the metal foil of a commonly used metal-clad laminate and/or the conductor layer obtained by plating the metal foil after peeling off the metal foil. In addition, the base material of the metal foil-clad laminate is not particularly limited. For example, it is mainly a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate.

本實施形態中，「堆疊」係指對覆金屬箔疊層板之表面的金屬箔及/或對導體層疊層本實施形態之附絕緣性樹脂層之銅箔中的絕緣性樹脂層。In this embodiment, "stack" refers to the insulating resin layer in the metal foil on the surface of the metal foil-clad laminate and/or the conductor laminated layer in the insulating resin layer of the copper foil of this embodiment.

通常，使用黏接薄膜等作為堆疊材料而在覆金屬箔疊層板疊層絕緣性樹脂層(樹脂組成物層)時，得到的印刷配線板在其單面或雙面具有硬化後之絕緣性樹脂層亦即絕緣層。再對該絕緣層形成導體層，但絕緣層的表面粗糙度低。因此，通常會利用包含除膠渣處理之粗糙化處理使絕緣層形成凹凸，其後再使用無電解鍍敷及/或電解鍍敷來形成導體層。但是，施以粗糙化處理之絕緣層的表面會有絕緣層中的玻璃短纖維等無機物露出(例如突出)，其表面粗糙。又，亦有無機物從絕緣層脫落導致絕緣層形成大的凹陷孔等問題。因此，不易在如此的絕緣層之表面形成高密度的微細配線。又，還有形成導孔及/或通孔等導通孔時，玻璃短纖維等無機物容易殘留在絕緣層，並對可靠性造成影響之問題。Generally, when an insulating resin layer (resin composition layer) is laminated on a metal foil laminate using an adhesive film or the like as a stacking material, the resulting printed wiring board has cured insulation on one or both sides The resin layer is also the insulating layer. A conductive layer is formed on the insulating layer, but the surface roughness of the insulating layer is low. Therefore, a roughening treatment including desmear treatment is generally used to form unevenness on the insulating layer, and then electroless plating and/or electrolytic plating are used to form a conductor layer. However, on the surface of the insulating layer subjected to the roughening treatment, inorganic substances such as short glass fibers in the insulating layer are exposed (for example, protruding), and the surface is rough. In addition, there are also problems such as the separation of inorganic substances from the insulating layer and the formation of large recessed holes in the insulating layer. Therefore, it is difficult to form high-density fine wiring on the surface of such an insulating layer. In addition, there is a problem that when via holes such as via holes and/or via holes are formed, inorganic substances such as short glass fibers are likely to remain in the insulating layer and affect reliability.

但是，使作為堆疊材料之本實施形態之附絕緣性樹脂層之銅箔疊層於覆金屬箔疊層板的話，得到的印刷配線板之單面或雙面已具有銅箔。因此，即使不施以鍍敷處理也可對銅箔直接形成電路圖案，且可形成高密度的微細配線。又，製造印刷配線板或半導體元件搭載用基板時，在將銅箔蝕刻後施以鍍敷處理時，銅箔面亦會轉印到絕緣性樹脂層，故絕緣層與鍍敷之間的黏合性會改善。However, when the copper foil with an insulating resin layer of this embodiment as a stacked material is laminated on a metal foil-clad laminate, one or both sides of the obtained printed wiring board already have copper foil. Therefore, it is possible to directly form a circuit pattern on the copper foil even without applying a plating process, and it is possible to form high-density fine wiring. In addition, when manufacturing a printed wiring board or a substrate for mounting semiconductor elements, when the copper foil is etched and then plated, the surface of the copper foil is also transferred to the insulating resin layer, so the adhesion between the insulating layer and the plating Sex will improve.

印刷配線板的製造係因應需要為了將各導體層予以電性連接而實施導孔及/或通孔等孔洞加工。實施該孔洞加工的情況，會在其後實施包含除膠渣處理之粗糙化處理。本實施形態中，印刷配線板的表面受到和絕緣層之黏合性優良的銅箔保護，故即使實施粗糙化處理，仍可抑制印刷配線板的表面粗糙。In the manufacture of printed wiring boards, hole processing such as vias and/or through holes is implemented in order to electrically connect the conductor layers as needed. In the case of performing the hole processing, a roughening treatment including desmear treatment will be performed thereafter. In this embodiment, the surface of the printed wiring board is protected by copper foil having excellent adhesion to the insulating layer, so even if the roughening treatment is performed, the surface roughness of the printed wiring board can be suppressed.

孔洞加工通常使用機械鑽孔機、二氧化碳雷射、UV雷射及YAG雷射等來實施。本實施形態中，印刷配線板的表面受到銅箔保護，故可將這些鑽孔機或雷射的能量加強。因此，根據本實施形態，在孔洞加工時可理想地去除從孔洞之表面露出的玻璃纖維等無機物。Hole processing is usually carried out using mechanical drilling machines, carbon dioxide lasers, UV lasers and YAG lasers. In this embodiment, the surface of the printed wiring board is protected by copper foil, so the energy of these drills or lasers can be enhanced. Therefore, according to this embodiment, it is possible to ideally remove inorganic substances such as glass fibers exposed from the surface of the hole during hole processing.

另外，通常粗糙化處理係由膨潤步驟、表面粗糙化及膠渣溶解步驟、以及中和步驟構成。In addition, the roughening treatment usually consists of a swelling step, a surface roughening and scum dissolution step, and a neutralization step.

膨潤步驟係使用膨潤劑使絕緣層的表面膨潤。膨潤劑若為可改善絕緣層之表面的潤濕性，並可使絕緣層之表面膨潤到在後續表面粗糙化及膠渣溶解步驟中會促進氧化分解的程度者，則無特別限制。其例可列舉鹼溶液及界面活性劑溶液。The swelling step uses a swelling agent to swell the surface of the insulating layer. The swelling agent is not particularly limited if it can improve the wettability of the surface of the insulating layer and can swell the surface of the insulating layer to the extent that it will promote oxidative decomposition in the subsequent surface roughening and scum dissolving steps. Examples thereof include alkaline solutions and surfactant solutions.

表面粗糙化及膠渣溶解步驟係使用氧化劑使絕緣層之表面粗糙化，同時將膠渣溶解。氧化劑可列舉例如鹼性之過錳酸鹽溶液，理想之具體例可列舉過錳酸鉀水溶液、及過錳酸鈉水溶液。該氧化劑處理稱為濕式除膠渣，除了實施該濕式除膠渣之外，也可適當地組合利用電漿處理、UV處理所為之乾式除膠渣、利用拋光輪等所為之機械研磨、噴砂等其它公知的粗糙化處理。The surface roughening and scum dissolving step uses an oxidizing agent to roughen the surface of the insulating layer while dissolving the scum. Examples of the oxidizing agent include alkaline permanganate solutions, and desirable specific examples include potassium permanganate aqueous solutions and sodium permanganate aqueous solutions. This oxidant treatment is called wet desmear. In addition to the wet desmear, plasma treatment, dry desmear by UV treatment, mechanical grinding by polishing wheels, etc. can also be appropriately combined. Other well-known roughening treatments such as sandblasting.

中和步驟係以還原劑中和前步驟所使用的氧化劑。還原劑可列舉例如胺系還原劑。其理想之具體例可列舉例如：硫酸羥胺水溶液、乙二胺四乙酸水溶液、氮基三乙酸水溶液等酸性水溶液。The neutralization step is to neutralize the oxidizing agent used in the previous step with a reducing agent. Examples of the reducing agent include amine-based reducing agents. Preferred specific examples thereof include acidic aqueous solutions such as hydroxylamine sulfate aqueous solution, ethylenediaminetetraacetic acid aqueous solution, and nitrotriacetic acid aqueous solution.

本實施形態中，在設置導孔及/或通孔後、或對導孔及/或通孔內進行除膠渣處理後，為了將各導體層予以電性連接，宜進行金屬鍍敷處理。本實施形態中，施以金屬鍍敷處理時，銅箔面亦會轉印到絕緣層，故絕緣層與金屬鍍敷之間的黏合性會改善。In this embodiment, after the vias and/or vias are provided, or after the vias and/or vias are desmeared, in order to electrically connect the conductor layers, metal plating is preferably performed. In this embodiment, when metal plating is applied, the copper foil surface is also transferred to the insulating layer, so the adhesion between the insulating layer and the metal plating is improved.

金屬鍍敷處理的方法並無特別限制，可適當地使用通常製造多層印刷配線板時的金屬鍍敷處理之方法。金屬鍍敷處理之方法及鍍敷所使用的藥液之種類並無特別限制，可適當地使用通常製造多層印刷配線板時的金屬鍍敷處理之方法及藥液。金屬鍍敷處理所使用的藥液也可為市售品。金屬鍍敷處理方法並無特別限制，可列舉例如：利用脫脂液所為之處理、利用微蝕刻(softetching)液所為之處理、酸清洗、利用預浸液所為之處理、利用催化液(catalyst)所為之處理、利用促進液(accelerator)所為之處理、利用化學銅液所為之處理、酸清洗及浸漬於硫酸銅液並流通電流之處理。The method of the metal plating treatment is not particularly limited, and the method of the metal plating treatment at the time of manufacturing a multilayer printed wiring board can be suitably used. The method of the metal plating treatment and the type of the chemical solution used for plating are not particularly limited, and the method and the chemical solution of the metal plating treatment generally used in the manufacture of a multilayer printed wiring board can be suitably used. The chemical solution used for the metal plating treatment may also be a commercially available product. The metal plating treatment method is not particularly limited. Examples include: treatment with a degreasing solution, treatment with a softetching solution, acid cleaning, treatment with a prepreg solution, and treatment with a catalyst solution. Treatment, treatment by accelerator, treatment by chemical copper solution, acid cleaning and treatment by immersion in copper sulfate solution and current flow.

又，使用半硬化狀態之附絕緣性樹脂層之銅箔來進行堆疊時，通常可藉由對半硬化狀態之絕緣性樹脂層施以熱處理等來使其完全硬化而獲得印刷配線板。本實施形態中，也可對得到的印刷配線板進一步疊層另外的附絕緣性樹脂層之銅箔。In addition, when stacking copper foil with an insulating resin layer in a semi-cured state, it is usually possible to obtain a printed wiring board by subjecting the insulating resin layer in a semi-cured state to heat treatment or the like to completely harden it. In this embodiment, another copper foil with an insulating resin layer may be further laminated on the obtained printed wiring board.

利用堆疊法所為之疊層(層合)方法並無特別限制，可適當地使用真空加壓式層合機。此時，也可對覆金屬箔疊層板介隔橡膠等彈性體而疊層本實施形態之附絕緣性樹脂層之銅箔。層合條件若為通常在疊層印刷配線板時使用的條件，則無特別限制，可列舉例如：70℃以上且140℃以下之溫度、1kgf/cm² 以上且11kgf/cm² 以下之範圍的接觸壓力、以及20hPa以下之環境減壓下。層合之後也可藉由利用金屬板所為之熱壓製來實施經疊層之絕緣性樹脂層的平滑化。層合及平滑化可利用市售之真空加壓式層合機連續地實施。層合之後或平滑化之後，可藉由對絕緣性樹脂層進行加熱來使其熱硬化而完全地硬化。熱硬化條件取決於樹脂組成物所含的成分之種類等而有所不同，通常硬化溫度為170℃以上且190℃以下，硬化時間為15分鐘～60分鐘。The method of lamination (laminating) by the stacking method is not particularly limited, and a vacuum pressure laminator can be suitably used. At this time, the copper foil with an insulating resin layer of this embodiment may be laminated on the metal foil-clad laminate through an elastic body such as rubber. The lamination conditions are not particularly limited as long as they are generally used when laminating printed wiring boards. Examples include: 70°C or more and 140°C or less, and 1kgf/cm ² or more and 11kgf/cm ² or less. The contact pressure and the reduced pressure of the environment below 20hPa. After lamination, the laminated insulating resin layer can be smoothed by hot pressing using a metal plate. Laminating and smoothing can be performed continuously using a commercially available vacuum press laminator. After lamination or smoothing, the insulating resin layer can be thermally cured by heating it to be completely cured. The thermosetting conditions vary depending on the types of components contained in the resin composition, etc. Generally, the curing temperature is 170° C. or more and 190° C. or less, and the curing time is 15 minutes to 60 minutes.

對本實施形態中的印刷配線板之單面或雙面的銅箔或導體層形成電路圖案之方法可列舉：半加成(Semi-additive)法、全加成(full-additive)法、及減去(subtractive)法。其中，考慮形成微細配線圖案之觀點，宜為半加成法。The method of forming a circuit pattern on the copper foil or conductor layer on one or both sides of the printed wiring board in this embodiment can include the semi-additive method, the full-additive method, and the subtractive method. The subtractive method. Among them, considering the viewpoint of forming a fine wiring pattern, a semi-additive method is preferable.

以半加成法形成電路圖案之方法的例子可列舉：使用鍍敷阻劑選擇性地施以電解鍍敷(圖案鍍敷)，其後將鍍敷阻劑剝離，並對整體進行適量蝕刻來形成配線圖案之方法。利用半加成法所為之電路圖案形成係組合實施無電解鍍敷與電解鍍敷，此時宜分別在無電解鍍敷之後及電解鍍敷之後實施乾燥。無電解鍍敷後的乾燥並無特別限制，例如宜於80℃以上且180℃以下實施10分鐘～120分鐘。電解鍍敷後的乾燥並無特別限制，例如宜於130℃以上且220℃以下實施10分鐘～120分鐘。鍍敷宜為銅鍍敷。An example of a method of forming a circuit pattern by a semi-additive method includes: using a plating resist to selectively apply electrolytic plating (pattern plating), then peeling the plating resist, and etching the entire Method of forming wiring patterns. The circuit pattern formation system by the semi-additive method is combined to perform electroless plating and electrolytic plating. In this case, it is preferable to perform drying after electroless plating and after electrolytic plating, respectively. The drying after electroless plating is not particularly limited. For example, it is preferable to perform the drying at 80°C or higher and 180°C or lower for 10 minutes to 120 minutes. The drying after electrolytic plating is not particularly limited. For example, it is preferable to perform the drying at 130°C or higher and 220°C or lower for 10 minutes to 120 minutes. The plating should be copper plating.

以減去法形成電路圖案之方法的例子可列舉：使用蝕刻阻劑選擇性地去除導體層，並藉此形成電路圖案之方法。具體而言，例如以下述方式形成電路圖案。於銅箔的全面以溫度110±10℃、壓力0.50±0.02MPa疊層貼附(層合)乾式薄膜阻劑(例如日立化成製RD-1225(商品名))。然後，沿著電路圖案進行曝光並實施遮蔽。其後，利用1%碳酸鈉水溶液對乾式薄膜阻劑進行顯影處理，最後利用胺系之阻劑剝離液將乾式薄膜阻劑剝離。藉此可在銅箔上形成電路圖案。An example of the method of forming the circuit pattern by the subtractive method may include a method of selectively removing the conductor layer using an etching resist to form the circuit pattern. Specifically, for example, the circuit pattern is formed in the following manner. A dry film resist (for example, RD-1225 (trade name) manufactured by Hitachi Chemical Co., Ltd.) is laminated (laminated) on the entire surface of the copper foil at a temperature of 110±10°C and a pressure of 0.50±0.02 MPa. Then, exposure is performed along the circuit pattern and masking is performed. After that, the dry film resist was developed with a 1% sodium carbonate aqueous solution, and finally the dry film resist was peeled off with an amine-based resist stripping solution. Thereby, a circuit pattern can be formed on the copper foil.

本實施形態也可在印刷配線板上進一步疊層絕緣層及/或導體層，並獲得多層印刷配線板。多層印刷配線板之內層也可具有電路基板。本實施形態之附絕緣性樹脂層之銅箔中的絕緣性樹脂層係構成多層印刷配線板之絕緣層及導體層中之一種。In this embodiment, an insulating layer and/or a conductor layer may be further laminated on the printed wiring board to obtain a multilayer printed wiring board. The inner layer of the multilayer printed wiring board may also have a circuit board. The insulating resin layer in the copper foil with an insulating resin layer of this embodiment constitutes one of the insulating layer and the conductor layer of the multilayer printed wiring board.

疊層的方法並無特別限制，可使用通常在疊層成形印刷配線板時一般使用的方法。疊層方法可列舉例如：多層壓製、多層真空壓製、層合機、真空層合機、及高溫高壓(autoclave)成形機。疊層時的溫度並無特別限制，例如為100℃以上且300℃以下。疊層時的壓力並無特別限制，例如為0.1kgf/cm² 以上且100kgf/cm² 以下(約9.8kPa以上且約9.8MPa以下)。疊層時的加熱時間並無特別限制，例如為30秒～5小時。又，也可因應需要例如於150～300℃之溫度範圍實施後硬化，並調整硬化度。The method of lamination is not particularly limited, and a method generally used for lamination and molding of printed wiring boards can be used. Examples of the lamination method include multi-layer lamination, multi-layer vacuum pressing, laminators, vacuum laminators, and autoclave molding machines. The temperature at the time of lamination is not particularly limited, and is, for example, 100°C or more and 300°C or less. The pressure at the time of lamination is not particularly limited, and is, for example, 0.1 kgf/cm ² or more and 100 kgf/cm ² or less (about 9.8 kPa or more and about 9.8 MPa or less). The heating time at the time of lamination is not particularly limited, and is, for example, 30 seconds to 5 hours. In addition, it is also possible to perform post-curing in the temperature range of 150 to 300°C according to needs, and adjust the degree of curing.

[半導體元件搭載用基板] 如上所述，本實施形態之疊層體可使用作為半導體元件搭載用基板。半導體元件搭載用基板例如藉由在覆金屬箔疊層板疊層本實施形態之附絕緣性樹脂層之銅箔，對得到的疊層體之表面或單面的銅箔進行遮蔽及圖案化來形成電路圖案而製得。遮蔽及圖案化可使用製造印刷配線板時實施的公知之遮蔽及圖案化，並無特別限制，宜利用前述減去法來形成電路圖案。電路圖案可僅在疊層體之單面形成，也可在雙面形成。[Substrate for mounting semiconductor elements] As described above, the laminate of this embodiment can be used as a substrate for mounting semiconductor elements. The substrate for mounting a semiconductor element is, for example, by laminating the copper foil with an insulating resin layer of this embodiment on a metal foil-clad laminate, and masking and patterning the surface or single-sided copper foil of the obtained laminate Manufactured by forming a circuit pattern. For the masking and patterning, known masking and patterning performed during the manufacture of a printed wiring board can be used, and there is no particular limitation, and it is preferable to use the aforementioned subtractive method to form a circuit pattern. The circuit pattern may be formed only on one side of the laminate, or may be formed on both sides.

[多層無芯基板(多層印刷配線板)] 本實施形態之疊層體可製成無芯基板。無芯基板之一例可列舉多層無芯基板。多層無芯基板例如具有由第1絕緣層與疊層於第1絕緣層之單面側之1層或多層之第2絕緣層構成的多層絕緣層、以及由配置於多層絕緣層之各層之間的第1導體層與配置於多層絕緣層之最外層的表面之第2導體層構成的多層導體層，且第1絕緣層及第2絕緣層分別具有本實施形態之附絕緣性樹脂層之銅箔中的絕緣性樹脂層之硬化物。針對多層無芯基板之具體例使用圖2進行說明。圖2係顯示本實施形態中之多層無芯基板的一例之示意圖。圖2所示之多層無芯基板10含有第1絕緣層11、疊層於第1絕緣層11之單面方向(圖式底面方向)之2層第2絕緣層12，第1絕緣層11及2層之第2絕緣層12分別使用1層本實施形態之附絕緣性樹脂層之銅箔中之絕緣性樹脂層來形成。又，圖2所示之多層無芯基板10具有由配置於多層絕緣層(絕緣層11及12)之各層之間的第1導體層13、以及配置於這些多層絕緣層(絕緣層11及12)之最外層的第2導體層13構成之多層導體層。 [實施例][Multilayer coreless substrate (multilayer printed wiring board)] The laminated body of this embodiment can be made into a coreless substrate. An example of a coreless substrate can be a multilayer coreless substrate. The multilayer coreless substrate has, for example, a multilayer insulating layer composed of a first insulating layer and one or more second insulating layers laminated on a single side of the first insulating layer, and a multilayer insulating layer arranged between the layers of the multilayer insulating layer. The first conductor layer and the second conductor layer arranged on the surface of the outermost layer of the multilayer insulating layer are composed of a multilayer conductor layer, and the first insulating layer and the second insulating layer respectively have the copper with insulating resin layer of this embodiment The hardened material of the insulating resin layer in the foil. A specific example of a multilayer coreless substrate will be described with reference to FIG. 2. FIG. 2 is a schematic diagram showing an example of the multilayer coreless substrate in this embodiment. The multilayer coreless substrate 10 shown in FIG. 2 includes a first insulating layer 11, two layers of a second insulating layer 12 laminated on a single side of the first insulating layer 11 (the bottom direction of the drawing), a first insulating layer 11 and The two second insulating layers 12 are each formed using one insulating resin layer in the copper foil with an insulating resin layer of this embodiment. In addition, the multilayer coreless substrate 10 shown in FIG. 2 has a first conductor layer 13 arranged between the layers of the multilayer insulating layers (insulating layers 11 and 12), and a first conductor layer 13 arranged on these multilayer insulating layers (insulating layers 11 and 12). ) Is a multilayer conductor layer composed of the second conductor layer 13 at the outermost layer. [Example]

以下使用實施例及比較例更具體地說明本發明，但本發明不受這些實施例任何限制。The following examples and comparative examples are used to explain the present invention more specifically, but the present invention is not limited by these examples at all.

[實施例1] 摻合聯苯芳烷基型酚醛樹脂(產品名：KAYAHARD GPH-103，羥基當量：231g/eq.，日本化藥(股)製)36質量份、聯苯芳烷基型環氧樹脂(產品名：NC-3000-FH，日本化藥(股)製，環氧當量：320g/eq.)39質量份、萘芳烷基型環氧樹脂(產品名：HP-9900，環氧當量：274g/eq.，DIC(股)製)7質量份、雙(3-乙基-5-甲基-4-馬來醯亞胺基苯基)甲烷(產品名：BMI-70，K･I化成(股)製)18質量份、作為球狀填料之漿體二氧化矽1(產品名：SC2050-MB，平均粒徑0.7μm，Admatechs(股)製)200質量份、作為高分子化合物之聚矽氧複合粉末(產品名：KMP-600，日信化學(股)製)20質量份、作為玻璃短纖維之E玻璃磨碎纖維(產品名：EFDE50-31，Central Glass(股)製)40質量份、苯乙烯丁二烯橡膠(產品名：JSR TR2003，JSR(股)製)5質量份、濕潤分散劑1(產品名：DISPERBYK-161，BYK(股)製)1質量份、濕潤分散劑2(產品名：DISPERBYK-111，BYK(股)製)2質量份、矽烷偶聯劑(產品名：KBM-403，信越化學(股)製)1質量份、2,4,5-三苯基咪唑(東京化成工業(股)製)0.5質量份並進行混合，其後利用甲乙酮稀釋獲得樹脂組成物之溶液即清漆。[Example 1] Blended with biphenyl aralkyl type phenolic resin (product name: Kayahard GPH-103, hydroxyl equivalent: 231g/eq., manufactured by Nippon Kayaku Co., Ltd.) 36 parts by mass, biphenyl aralkyl type epoxy resin (product Name: NC-3000-FH, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 320g/eq.) 39 parts by mass, naphthalene aralkyl type epoxy resin (product name: HP-9900, epoxy equivalent: 274g /eq., manufactured by DIC (Stock) 7 parts by mass, bis(3-ethyl-5-methyl-4-maleiminophenyl)methane (product name: BMI-70, K･I Chemical (Stock) system) 18 parts by mass, as spherical filler, slurry silica 1 (product name: SC2050-MB, average particle size 0.7μm, made by Admatechs (stock)) 200 parts by mass, as a polymer compound Silica composite powder (product name: KMP-600, manufactured by Nissin Chemical Co., Ltd.) 20 parts by mass, E glass ground fiber as short glass fiber (product name: EFDE50-31, manufactured by Central Glass Co., Ltd.) 40 Parts by mass, styrene butadiene rubber (product name: JSR TR2003, manufactured by JSR (Stock)) 5 parts by mass, wetting and dispersing agent 1 (product name: DISPERBYK-161, manufactured by BYK (Stock)) 1 part by mass, wetting and dispersing Agent 2 (product name: DISPERBYK-111, manufactured by BYK Co., Ltd.) 2 parts by mass, silane coupling agent (product name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 mass part, 2,4,5-tri 0.5 parts by mass of phenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and then diluted with methyl ethyl ketone to obtain a varnish as a solution of the resin composition.

將該清漆利用甲乙酮以有機溶劑相對於清漆100質量份之含量成為130質量份的方式進一步稀釋後，藉由凹版塗佈機塗佈於600mm寬、12μm厚之銅箔(產品名：3EC-VLP，三井金屬礦業(股)製)的消光面側來獲得塗佈膜。然後，將塗佈膜於130℃加熱乾燥5分鐘，藉此獲得絕緣性樹脂層的厚度為20μm之附絕緣性樹脂層之銅箔。如下述般測得的玻璃短纖維之平均纖維長為55μm，平均纖維徑為6.13μm。又，如下述般測得的絕緣性樹脂層表面之算術平均粗糙度(Ra)為0.3μm。The varnish was further diluted with methyl ethyl ketone so that the content of the organic solvent relative to 100 parts by mass of the varnish became 130 parts by mass, and then coated with a gravure coater on a 600mm wide and 12μm thick copper foil (product name: 3EC-VLP , Mitsui Metals Mining Co., Ltd.) matte side to obtain a coating film. Then, the coating film was heated and dried at 130° C. for 5 minutes, thereby obtaining a copper foil with an insulating resin layer having an insulating resin layer with a thickness of 20 μm. The average fiber length of the short glass fiber measured as described below was 55 μm, and the average fiber diameter was 6.13 μm. In addition, the arithmetic average roughness (Ra) of the surface of the insulating resin layer measured as follows was 0.3 μm.

[平均纖維長之測定] 玻璃短纖維的平均纖維長如下述般進行測定。使用奧林巴斯公司製之倒立顯微鏡，放大100倍以反射光觀察玻璃短纖維，任意地選擇100條玻璃短纖維並測定各別的纖維長，求出其算術平均值作為平均纖維長。[Measurement of average fiber length] The average fiber length of short glass fibers is measured as follows. Using an inverted microscope manufactured by Olympus Corporation, the glass short fibers were observed with reflected light at a magnification of 100 times, and 100 short glass fibers were arbitrarily selected and the respective fiber lengths were measured.

[平均纖維徑之測定] 玻璃短纖維的平均纖維徑如下述般進行測定。使用電子顯微鏡(KEYENCE股份有限公司製，產品名「VE-7800」)，以倍率1000倍任意地選擇50條玻璃短纖維並測定各別的纖維徑，求出其算術平均值作為平均纖維徑。[Measurement of average fiber diameter] The average fiber diameter of short glass fibers is measured as follows. Using an electron microscope (manufactured by KEYENCE Co., Ltd., product name "VE-7800"), 50 short glass fibers were arbitrarily selected at a magnification of 1000 times, and the respective fiber diameters were measured, and the arithmetic average was determined as the average fiber diameter.

[算術平均粗糙度(Ra)之測定] 使用形狀測定顯微鏡(雷射顯微鏡，KEYENCE股份有限公司製，產品名「VK-X210」)，以物鏡倍率150倍(15吋顯示器上倍率：3000倍)拍攝絕緣性樹脂層表面。然後，於拍攝的圖像之中，利用圖像處理求出任意地選擇之長度90μm的直線區域內之高度分佈，並算出算術平均粗糙度(Ra)。[Measurement of Arithmetic Average Roughness (Ra)] A shape measuring microscope (laser microscope, manufactured by KEYENCE Co., Ltd., product name "VK-X210") was used to photograph the surface of the insulating resin layer at an objective lens magnification of 150 times (magnification on a 15-inch monitor: 3000 times). Then, among the captured images, image processing is used to obtain the height distribution in an arbitrarily selected linear region with a length of 90 μm, and the arithmetic average roughness (Ra) is calculated.

[實施例2] 將和實施例1同樣地獲得之清漆利用甲乙酮以有機溶劑相對於清漆100質量份之含量成為130質量份的方式進一步稀釋後，藉由塗佈棒塗佈於350mm×250mm×12μm厚之銅箔(產品名：3EC-VLP，三井金屬礦業(股)製)的消光面側來獲得1次塗佈膜(第1次塗佈)。然後，將1次塗佈膜風乾，並沿平面方向從相對於第1次塗佈方向為90°之方向，再次將上述清漆藉由塗佈棒塗佈於1次塗佈膜上來獲得2次塗佈膜(第2次塗佈)。將得到的2次塗佈膜於130℃加熱乾燥5分鐘，藉此獲得絕緣性樹脂層的厚度為20μm之附絕緣性樹脂層之銅箔。如上述般測得的玻璃短纖維之平均纖維長為55μm，平均纖維徑為6.13μm。又，如上述般測得的絕緣性樹脂層表面之算術平均粗糙度(Ra)為0.5μm。[Example 2] The varnish obtained in the same manner as in Example 1 was further diluted with methyl ethyl ketone so that the content of the organic solvent relative to 100 parts by mass of the varnish became 130 parts by mass, and then coated on a 350mm×250mm×12μm thick copper foil with a coating bar. (Product name: 3EC-VLP, manufactured by Mitsui Metals & Mining Co., Ltd.) to obtain a primary coating film (primary coating). Then, the first coating film is air-dried, and the above-mentioned varnish is applied to the first coating film with a coating bar from a direction of 90° in the plane direction from the first coating direction to obtain the second time Coated film (second coating). The obtained secondary coating film was heated and dried at 130° C. for 5 minutes, thereby obtaining a copper foil with an insulating resin layer having an insulating resin layer with a thickness of 20 μm. The average fiber length of the short glass fiber measured as described above was 55 μm, and the average fiber diameter was 6.13 μm. In addition, the arithmetic average roughness (Ra) of the surface of the insulating resin layer measured as described above was 0.5 μm.

[比較例1] 將和實施例1同樣地獲得之清漆利用甲乙酮以有機溶劑相對於清漆100質量份之含量成為130質量份的方式進一步稀釋後，藉由塗佈棒塗佈於350mm×250mm×12μm厚之銅箔(產品名：3EC-VLP，三井金屬礦業(股)製)的消光面側來獲得塗佈膜。然後，將塗佈膜於130℃加熱乾燥5分鐘，藉此獲得絕緣性樹脂層的厚度為20μm之附絕緣性樹脂層之銅箔。如上述般測得的玻璃短纖維之平均纖維長為55μm，平均纖維徑為6.13μm。又，如上述般測得的絕緣性樹脂層表面之算術平均粗糙度(Ra)為0.4μm。[Comparative Example 1] The varnish obtained in the same manner as in Example 1 was further diluted with methyl ethyl ketone so that the content of the organic solvent relative to 100 parts by mass of the varnish became 130 parts by mass, and then coated on a 350mm×250mm×12μm thick copper foil with a coating bar. (Product name: 3EC-VLP, manufactured by Mitsui Metals & Mining Co., Ltd.) to obtain a coating film on the matte side. Then, the coating film was heated and dried at 130° C. for 5 minutes, thereby obtaining a copper foil with an insulating resin layer having an insulating resin layer with a thickness of 20 μm. The average fiber length of the short glass fiber measured as described above was 55 μm, and the average fiber diameter was 6.13 μm. In addition, the arithmetic average roughness (Ra) of the surface of the insulating resin layer measured as described above was 0.4 μm.

＜物性測定評價＞使用各實施例及比較例得到的附絕緣性樹脂層之銅箔，利用下列各項目所示之程序製作物性測定評價用之樣本，並測定評價機械特性(40℃時的儲藏彈性模量)、翹曲量、及伸縮率。＜Measurement and evaluation of physical properties＞ Using the copper foil with an insulating resin layer obtained in each of the Examples and Comparative Examples, a sample for physical property measurement and evaluation was prepared using the procedures shown in the following items, and the mechanical properties (storage elastic modulus at 40°C) were measured and evaluated. The amount of warpage and expansion ratio.

[機械特性：彈性模量] 將各實施例及比較例得到的附絕緣性樹脂層之銅箔2片以絕緣性樹脂層成為內側的方式進行重疊配置，於壓力30kgf/cm² 、溫度220℃實施120分鐘的疊層成形(熱硬化)，獲得具有絕緣層與銅箔之覆銅箔疊層板。得到的覆銅箔疊層板之絕緣層的厚度為40μm。將得到的覆銅箔疊層板以切片鋸裁切成尺寸5.0mm×20mm後，利用蝕刻去除表面的銅箔，獲得測定用樣本。使用得到的測定用樣本，依據JIS C 6481：1996以動態黏彈性分析裝置(TA Instruments公司製)並利用DMA法測定機械特性(40℃時的儲藏彈性模量E’)。該測定係針對相對於塗佈方向之平行方向(表1中之X)、與相對於塗佈方向之垂直方向(表1中之Y)來實施，將分別測定3次(n=3)時的平均值定為測定值。結果如表1所示。[Mechanical properties: modulus of elasticity] Two pieces of copper foil with an insulating resin layer obtained in each of the examples and comparative examples were superimposed so that the insulating resin layer became the inner side. The pressure was 30kgf/cm ² and the temperature was 220°C. The laminate molding (thermosetting) was performed for 120 minutes to obtain a copper-clad laminate having an insulating layer and copper foil. The thickness of the insulating layer of the obtained copper-clad laminated board was 40 μm. The obtained copper-clad laminate was cut into a size of 5.0 mm×20 mm with a dicing saw, and then the copper foil on the surface was removed by etching to obtain a measurement sample. Using the obtained measurement sample, the mechanical properties (storage elastic modulus E'at 40° C.) were measured by a dynamic viscoelasticity analyzer (manufactured by TA Instruments) in accordance with JIS C 6481:1996 and the DMA method. The measurement is carried out for the direction parallel to the coating direction (X in Table 1) and the perpendicular direction to the coating direction (Y in Table 1). When measuring 3 times (n=3) respectively The average value of is determined as the measured value. The results are shown in Table 1.

[翹曲量：貼合(bimetal)法] 將各實施例及比較例得到的附絕緣性樹脂層之銅箔2片以絕緣性樹脂層成為內側的方式進行重疊配置，於壓力30kgf/cm² 、溫度220℃實施120分鐘的疊層成形(熱硬化)，獲得覆銅箔疊層板。覆銅箔疊層板中之絕緣層的厚度為40μm。然後，利用蝕刻從得到的覆銅箔疊層板之雙面去除銅箔。然後，將各實施例及比較例得到的附絕緣性樹脂層之銅箔1片以樹脂層彼此相接觸的方式再配置於已去除銅箔之疊層體的單面(以下稱「第2片地進行疊層之附絕緣性樹脂層之銅箔」)，再於其上下雙面配置銅箔(產品名：3EC-VLP，厚度12μm)，以壓力30kgf/cm² 、溫度220℃實施120分鐘的疊層成形(熱硬化)，再次獲得覆銅箔疊層板。再從得到的覆銅箔疊層板利用蝕刻去除銅箔(和第2片地進行疊層之附絕緣性樹脂層之銅箔為相反側之面的銅箔)，獲得疊層體。然後，從得到的疊層體分別以20mm×200mm之條狀板的形式切出長邊成為相對於清漆的塗佈方向為平行方向之樣本(表1中之X)、及長邊成為相對於該塗佈方向為垂直方向之樣本(表1中之Y)。針對各樣本，將第2片地進行疊層之附絕緣性樹脂層之銅箔的面朝上，利用角尺測定縱向兩端之翹曲量的最大值，將其平均值定為利用貼合法所為之「翹曲量」。結果如表1所示。[Warpage amount: bimetal method] The two copper foils with insulating resin layers obtained in each of the examples and comparative examples were stacked so that the insulating resin layer became the inner side, and the pressure was 30kgf/cm ² , The temperature is 220°C for 120 minutes of lamination molding (thermal curing) to obtain a copper-clad laminate. The thickness of the insulating layer in the copper clad laminate is 40 μm. Then, the copper foil is removed from both sides of the obtained copper-clad laminated board by etching. Then, one sheet of the copper foil with insulating resin layer obtained in each of the Examples and Comparative Examples was re-arranged on one side of the laminate from which the copper foil was removed so that the resin layers were in contact with each other (hereinafter referred to as "Second Sheet Laminated copper foil with insulating resin layer"), and then arrange copper foils (product name: 3EC-VLP, thickness 12μm) on the upper and lower sides of it, and apply it at a pressure of 30kgf/cm ² and a temperature of 220°C for 120 minutes The laminated molding (thermal hardening) of, the copper clad laminated board is obtained again. Furthermore, the copper foil was removed by etching from the obtained copper-clad laminate (the copper foil with the insulating resin layer laminated on the second sheet is the copper foil on the opposite side) to obtain a laminate. Then, from the obtained laminates, cut out samples in the form of strips of 20mm×200mm with long sides parallel to the coating direction of the varnish (X in Table 1), and the long sides became relative to the coating direction of the varnish. The coating direction is the vertical direction of the sample (Y in Table 1). For each sample, the second layer of copper foil with an insulating resin layer was laminated, and the maximum value of the warpage at both ends in the longitudinal direction was measured with a square, and the average value was determined by the laminating method. The "warpage amount". The results are shown in Table 1.

[伸縮率] 將各實施例及比較例得到的附絕緣性樹脂層之銅箔2片以絕緣性樹脂層成為內側的方式進行重疊配置，於壓力30kgf/cm² 、溫度220℃實施120分鐘的疊層成形(同時熱硬化)，獲得覆銅箔疊層板。然後，從得到的覆銅箔疊層板切出150mm×150mm之正方形狀板，利用開孔加工機以100mm間隔形成4處φ1mm之孔洞。對於得到的孔洞利用座標測定器，針對相對於塗佈方向為平行方向的2孔洞間(表1中之X)、及相對於塗佈方向為垂直方向之2孔洞間(表1中之Y)測定各別之2孔洞間距離。測定後，從這些覆銅箔疊層板之雙面利用蝕刻去除銅箔。其後，再次利用座標測定器測定各孔洞間距離，將蝕刻前後之孔洞間距離的比定為「伸縮率」。結果如表1所示。[Expansion rate] Two pieces of copper foil with an insulating resin layer obtained in each of the examples and comparative examples were superimposed so that the insulating resin layer became the inner side, and the pressure was 30kgf/cm ² and the temperature was 220°C for 120 minutes. Laminate forming (simultaneous thermal hardening) to obtain a copper clad laminate. Then, a 150mm×150mm square-shaped board was cut out from the obtained copper-clad laminated board, and 4 holes of φ1mm were formed at 100mm intervals using a drilling machine. For the obtained holes, use a coordinate measuring device for the space between 2 holes that are parallel to the coating direction (X in Table 1) and the space between 2 holes that are perpendicular to the coating direction (Y in Table 1) Measure the distance between the 2 holes respectively. After the measurement, the copper foil was removed by etching from both sides of these copper-clad laminate boards. After that, the distance between the holes was measured again with the coordinate measuring device, and the ratio of the distance between the holes before and after the etching was defined as the "stretch rate". The results are shown in Table 1.

＜配向度(fp值)之測定＞將各實施例及比較例得到的附絕緣性樹脂層之銅箔以成為3cm×3cm的方式切出製成試驗片。然後，以載玻片挾持試驗片，並利用光學顯微鏡觀察該試驗片之絕緣性樹脂層側的面。光學顯微鏡使用奧林巴斯公司製之倒立顯微鏡，放大100倍以反射光於1.5mm² 之測定區域內觀察玻璃短纖維。然後，針對存在上述測定區域中之在觀察圖像中可辨認的全部玻璃短纖維(纖維數為m條)，測定相對於以後述方法進行設定之基準線的角度θ_i (i=1～m)。就配向角度θ_i 而言，測定相對於基準線為順時鐘方向之角度，為0°以上且未達180°之角度。測定角度θ_i 後，從短纖維相對於已設定之基準線的角度θ_i ，使用下式(2)算出平面方向的配向度(fp)。結果如表1所示。 fp=2×Σ(cos² θ_i /m)-1…(2)<Measurement of the degree of orientation (fp value)> The copper foil with an insulating resin layer obtained in each of the Examples and Comparative Examples was cut out so as to be 3 cm×3 cm to prepare a test piece. Then, the test piece was pinched by a slide glass, and the surface of the insulating resin layer side of the test piece was observed with an optical microscope. The optical microscope uses an inverted microscope made by Olympus, magnified 100 times to observe the short glass fibers ^{in a 1.5mm 2 measurement area with reflected light.} Then, for all short glass fibers (the number of fibers is m) that are recognizable in the observation image in the above-mentioned measurement area, the angle θ _i (i=1～m) relative to the reference line set by the method described later is measured. ). Regarding the alignment angle θ _i , the angle measured in the clockwise direction relative to the reference line is an angle above 0° and less than 180°. After the measurement angle θ _i, the short fibers with respect to the reference line has been set angle θ _i, using (2) the degree of orientation of the plane direction was calculated by the following formula (fp). The results are shown in Table 1. fp=2×Σ(cos ² θ _i /m)-1…(2)

[基準線之設定方法] 基準線利用下述方法來決定。首先，在決定基準線時，選擇第1暫時基準線p，測定存在測定區域內之可辨認的全部m條玻璃短纖維的角度。第1暫時基準線p和各纖維的角度以α(p)_i (i=1～m)表示(該式中，角度α(p)_i ，係和配向角度θ_i 同樣係相對於第1暫時基準線p為順時鐘方向之角度，為0°以上且未達180°之角度)。使用第1暫時基準線p時的配向度(fp(p))使用下式進行計算。 fp(p)=2×Σ(cos² α(p)_i /m)-1 (i=1、2、3、…、m)[How to set the reference line] The reference line is determined by the following method. First, when determining the reference line, the first temporary reference line p is selected, and the angles of all m short glass fibers that can be identified in the measurement area are measured. The first temporary reference line p and each fiber angle _{α (p) i (i =} 1 ~ m) represents (in this formula, the angle α (p) _i, lines and with the same system with respect to an angle θ _i of the first temporary The reference line p is an angle in the clockwise direction, which is an angle above 0° and less than 180°). The degree of alignment (fp(p)) when the first temporary reference line p is used is calculated using the following formula. fp(p)=2×Σ(cos ² α(p) _i /m)-1 (i=1, 2, 3,..., m)

然後，取得從第1暫時基準線p起以順時鐘逐次旋轉±1°直至±90°為止之多條暫時基準線(p+z、p-z(z=1～90))，並分別計算暫時基準線p+z及暫時基準線p-z和m條短纖維的角度。此時的角度以α(p+z)_i 、及α(p-z)_i (i=1～m)表示。旋轉後的暫時基準線(p+z、p-z(z=1～90))和短纖維的配向度(fp(p±z))此用下式進行計算。 fp(p±z)=2×Σ(cos² α(p±z)_i /m)-1 (i=1、2、3、…、m) 將以此方式設定成得到的fp(p)值及fp(p±z)值之中可獲得最大值時之暫時基準線定為基準線P。Then, obtain a number of temporary reference lines (p+z, pz (z=1 to 90)) that are rotated by ±1° clockwise to ±90° from the first temporary reference line p, and calculate the temporary reference lines respectively The angle between the line p+z and the temporary reference line pz and m short fibers. The angle at this time is represented by α(p+z) _i and α(pz) _i (i=1 to m). The rotated temporary reference line (p+z, pz (z=1 to 90)) and the degree of alignment of the short fiber (fp(p±z)) are calculated using the following formula. fp(p±z)=2×Σ(cos ² α(p±z) _i /m)-1 (i=1, 2, 3,...,m) will be set in this way to the obtained fp(p) The temporary reference line when the maximum value is obtained among the values of fp(p±z) and fp(p±z) is set as the reference line P.

[表1] 實施例1 實施例2 比較例1 配向度(fp) 0.26 0.41 0.71 彈性模量 X(GPa) 9.9 10 10.1 Y(GPa) 9.8 9.9 9.8 翹曲量 (mm) X 0.25 0.5 1.5 Y 0.25 0.5 0.5 伸縮率 X(ppm) 1295 1302 927 Y(ppm) 1726 1691 3923 [Table 1] Example 1 Example 2 Comparative example 1 Orientation degree (fp) 0.26 0.41 0.71 Elastic Modulus X(GPa) 9.9 10 10.1 Y(GPa) 9.8 9.9 9.8 Warpage (mm) X 0.25 0.5 1.5 Y 0.25 0.5 0.5 Expansion rate X(ppm) 1295 1302 927 Y(ppm) 1726 1691 3923

如表1所示之結果可知，配向度(fp)未達0.60之實施例的樣本對比於配向度(fp)0.60以上之比較例，前者在XY方向上之各評價結果的差異較小。又，可知在實施例之樣本中，在平面方向上之翹曲量(實施例2係在X方向上之翹曲量)比起比較例1更受到抑制。As can be seen from the results shown in Table 1, the samples of the examples with an orientation degree (fp) of less than 0.60 are compared with the comparative examples with an orientation degree (fp) of 0.60 or more, and the difference of the evaluation results in the XY directions of the former is smaller. In addition, it can be seen that in the samples of the examples, the amount of warpage in the plane direction (the amount of warpage in the X direction of Example 2) is more suppressed than that of Comparative Example 1.

[多層無芯基板] 依循圖3所示之步驟，使用各實施例及比較例製得的附絕緣性樹脂層之銅箔來製作多層無芯基板，並測定翹曲量。圖3係顯示實施例中之多層無芯基板的製作步驟的流程之概略圖。首先，如圖3(A)所示，將附載體之極薄銅箔b1(產品名：MT18Ex，三井金屬礦業(股)製，厚度：5μm)的載體銅箔面朝向預浸體側配置於作為支持體a之預浸體(產品名：GHPL-830NS SF70，三菱瓦斯化學股份有限公司製，厚度：20μm)的雙面。然後，因應各樣本將實施例1、實施例2或比較例1得到的附絕緣性樹脂層之銅箔(絕緣性樹脂層以「c1」表示，銅箔以「d」表示)，以絕緣性樹脂層c1和附載體之極薄銅箔b1相接觸的方式配置於各附載體之極薄銅箔b1上。然後，於壓力30kgf/cm² 、溫度220℃實施120分鐘的疊層成形，獲得如圖3(B)所示之覆銅箔疊層板。[Multilayer coreless substrate] Following the steps shown in FIG. 3, the copper foil with insulating resin layer prepared in each of the Examples and Comparative Examples was used to produce a multilayer coreless substrate, and the amount of warpage was measured. FIG. 3 is a schematic diagram showing the flow of the manufacturing steps of the multilayer coreless substrate in the embodiment. First, as shown in Figure 3(A), the ultra-thin copper foil b1 with carrier (product name: MT18Ex, manufactured by Mitsui Mining Co., Ltd., thickness: 5μm) is placed on the prepreg side with the carrier copper foil surface facing A prepreg (product name: GHPL-830NS SF70, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness: 20 μm) as a support a on both sides. Then, according to each sample, the copper foil with an insulating resin layer obtained in Example 1, Example 2 or Comparative Example 1 (the insulating resin layer is represented by "c1", and the copper foil is represented by "d"), with insulating properties The resin layer c1 and the ultra-thin copper foil b1 with a carrier are arrange|positioned on each ultra-thin copper foil b1 with a carrier so that it may contact. Then, lamination molding was performed at a pressure of 30 kgf/cm ² and a temperature of 220° C. for 120 minutes to obtain a copper-clad laminate as shown in Fig. 3(B).

然後，對得到的覆銅箔疊層板上之銅箔d，如圖3(C)所示般蝕刻成預定的配線圖案，形成導體層d’。然後，如圖3(D)所示般將因應各樣本將實施例1、實施例2或比較例1中的銅箔(3EC-VLP)變更為銅箔(產品名：MT18Ex，三井金屬礦業(股)，5μm)而成的附絕緣性樹脂層之銅箔(樹脂層以「c2」表示，銅箔以「b2」表示)，以銅箔b2朝向外側的方式配置於形成有導體層(d’)之疊層板的雙面，於壓力30kgf/cm² 、溫度230℃實施120分鐘的疊層成形，獲得如圖3(E)所示之覆銅箔疊層板。Then, the copper foil d on the obtained copper-clad laminated board is etched into a predetermined wiring pattern as shown in FIG. 3(C) to form a conductor layer d'. Then, as shown in Figure 3(D), the copper foil (3EC-VLP) in Example 1, Example 2 or Comparative Example 1 was changed to copper foil (product name: MT18Ex, Mitsui Metal Mining Co., Ltd.) according to each sample. Strand), 5μm) of copper foil with an insulating resin layer (resin layer is represented by "c2", copper foil is represented by "b2"), and the copper foil b2 is arranged on the outside where the conductor layer (d On both sides of the laminated board of'), laminate forming was performed at a pressure of 30kgf/cm ² and a temperature of 230°C for 120 minutes to obtain a copper clad laminated board as shown in Fig. 3(E).

針對得到的覆銅箔疊層板，如圖3(F)所示般將配置於支持體a(已硬化之支持體用預浸體)的附載體之極薄銅箔b1的載體銅箔和極薄銅箔剝離，從支持體a剝離2片疊層板。分別測定得到的各疊層板之邊角部4處、各邊之中心4處的翹曲量，並將平均值定為無芯基板的翹曲量。其結果，使用實施例1之附絕緣性樹脂層之銅箔時的翹曲量為0.4mm，使用實施例2之附絕緣性樹脂層之銅箔時的翹曲量為1.2mm，使用比較例1之附絕緣性樹脂層之銅箔時的翹曲量為2.1mm。由這些結果可知，使用有實施例之附絕緣性樹脂層之銅箔的無芯基板，比起使用有比較例之附絕緣性樹脂層之銅箔的無芯基板，前者翹曲量的產生較少。For the obtained copper clad laminate, as shown in FIG. 3(F), the carrier copper foil of the ultra-thin copper foil b1 with the carrier placed on the support a (hardened support prepreg) and The ultra-thin copper foil was peeled off, and two laminates were peeled off from the support a. The warpage at 4 corners and 4 at the center of each side of each laminated board thus obtained was measured, and the average value was determined as the warpage of the coreless substrate. As a result, the amount of warpage when the copper foil with an insulating resin layer of Example 1 was used was 0.4 mm, and the amount of warpage when using the copper foil with an insulating resin layer of Example 2 was 1.2 mm, and the comparative example was used The amount of warpage of the copper foil with insulating resin layer in 1 is 2.1mm. From these results, it can be seen that the coreless substrate using the copper foil with the insulating resin layer of the example has a greater amount of warpage than the coreless substrate using the copper foil with the insulating resin layer of the comparative example. less.

1:絕緣性樹脂層 2,2A,2B,2C:玻璃短纖維 10:多層無芯基板 11:第1絕緣層 12:第2絕緣層 13:導體層 a:支持體 b1:附載體之極薄銅箔 c1,c2:樹脂層 d,b2:銅箔 d’:圖案 P:基準線 X:平行方向 Y:垂直方向 θ₁ ,θ₂ ,θ₃ :配向角度1: Insulating resin layer 2, 2A, 2B, 2C: short glass fiber 10: multilayer coreless substrate 11: first insulating layer 12: second insulating layer 13: conductor layer a: support b1: extremely thin with carrier Copper foil c1, c2: resin layer d, b2: copper foil d': pattern P: reference line X: parallel direction Y: vertical direction θ ₁ , θ ₂ , θ ₃ : alignment angle

[圖1](a)係從附絕緣性樹脂之銅箔中的絕緣性樹脂層之向著其平面方向的方向進行觀察之示意俯視圖，(b)係用以說明玻璃短纖維的配向角度θ之示意圖。 [圖2]係顯示本實施形態中之多層無芯基板的一例之示意圖。 [圖3](A)～(F)係顯示實施例中之多層無芯基板的製作步驟的流程之概略圖。[Figure 1] (a) is a schematic plan view viewed from the direction of the insulating resin layer in the copper foil with insulating resin toward its plane direction, and (b) is used to illustrate the orientation angle θ of short glass fibers Schematic. [Fig. 2] is a schematic diagram showing an example of the multilayer coreless substrate in this embodiment. [Fig. 3] (A) to (F) are schematic diagrams showing the flow of the manufacturing steps of the multilayer coreless substrate in the embodiment.

Claims

一種附絕緣性樹脂層之銅箔，具備：銅箔，及配置於該銅箔上之絕緣性樹脂層；該絕緣性樹脂層含有熱硬化性樹脂、球狀填料、及平均纖維長為10μm以上且300μm以下之玻璃短纖維，該玻璃短纖維在該絕緣性樹脂層之平面方向上之配向度(fp)未達0.60。A copper foil with an insulating resin layer, which has: Copper foil, and An insulating resin layer arranged on the copper foil; The insulating resin layer contains thermosetting resin, spherical fillers, and short glass fibers with an average fiber length of 10 μm or more and 300 μm or less, The alignment degree (fp) of the short glass fiber in the plane direction of the insulating resin layer does not reach 0.60.

如請求項1之附絕緣性樹脂層之銅箔，其中，該絕緣性樹脂層的厚度為3μm以上且50μm以下。The copper foil with an insulating resin layer of claim 1, wherein the thickness of the insulating resin layer is 3 μm or more and 50 μm or less.

如請求項1或2之附絕緣性樹脂層之銅箔，其中，該銅箔的厚度為1μm以上且18μm以下。The copper foil with an insulating resin layer of claim 1 or 2, wherein the thickness of the copper foil is 1 μm or more and 18 μm or less.

如請求項1或2之附絕緣性樹脂層之銅箔，其中，該玻璃短纖維的平均纖維徑為3.0μm以上且15μm以下。The copper foil with an insulating resin layer of claim 1 or 2, wherein the average fiber diameter of the short glass fibers is 3.0 μm or more and 15 μm or less.

如請求項1或2之附絕緣性樹脂層之銅箔，其中，該配向度(fp)為0.40以下。The copper foil with an insulating resin layer of claim 1 or 2, wherein the degree of alignment (fp) is 0.40 or less.

如請求項1或2之附絕緣性樹脂層之銅箔，其中，該絕緣性樹脂層表面的算術平均粗糙度(Ra)為2μm以下。The copper foil with an insulating resin layer of claim 1 or 2, wherein the arithmetic average roughness (Ra) of the surface of the insulating resin layer is 2 μm or less.

如請求項1或2之附絕緣性樹脂層之銅箔，其中，該玻璃短纖維的含量相對於該絕緣性樹脂層中之樹脂固體成分100質量份，為5質量份以上且450質量份以下。The copper foil with an insulating resin layer of claim 1 or 2, wherein the content of the short glass fiber is 5 parts by mass or more and 450 parts by mass or less relative to 100 parts by mass of the resin solid content in the insulating resin layer .

如請求項1或2之附絕緣性樹脂層之銅箔，其中，該玻璃短纖維為磨碎纖維。According to claim 1 or 2, the copper foil with an insulating resin layer, wherein the short glass fibers are ground fibers.

如請求項1或2之附絕緣性樹脂層之銅箔，其中，該球狀填料的含量相對於該絕緣性樹脂層中之樹脂固體成分100質量份，為50質量份以上且500質量份以下。The copper foil with an insulating resin layer of claim 1 or 2, wherein the content of the spherical filler is 50 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the resin solid content in the insulating resin layer .

如請求項1或2之附絕緣性樹脂層之銅箔，其中，該熱硬化性樹脂包含選自於由環氧樹脂、氰酸酯化合物、馬來醯亞胺化合物、酚醛樹脂、熱硬化改性聚苯醚樹脂、苯并㗁𠯤化合物、有機基改性聚矽氧化合物及具有可聚合之不飽和基的化合物構成之群組中之至少1種。According to claim 1 or 2, the copper foil with an insulating resin layer, wherein the thermosetting resin is selected from epoxy resins, cyanate ester compounds, maleimide compounds, phenolic resins, and thermosetting resins. At least one of the group consisting of a polyphenylene ether resin, a benzophenone compound, an organo-modified polysiloxane compound, and a compound having a polymerizable unsaturated group.

如請求項1或2之附絕緣性樹脂層之銅箔，其係用於印刷配線板或半導體元件搭載用基板之堆疊材料用的無芯基板之製作。For example, the copper foil with insulating resin layer of claim 1 or 2, which is used for the production of coreless substrates for stacking materials of printed wiring boards or substrates for mounting semiconductor elements.

如請求項11之附絕緣性樹脂層之銅箔，其中，該無芯基板為3層無芯基板。Such as the copper foil with insulating resin layer of claim 11, wherein the coreless substrate is a three-layer coreless substrate.

一種疊層體，具有：堆疊層，該堆疊層係由導體層與使用如請求項1～12中任一項之附絕緣性樹脂層之銅箔形成的絕緣層交替疊層而成。A laminated body having: The stacked layer is formed by alternately stacking a conductive layer and an insulating layer formed using a copper foil with an insulating resin layer according to any one of claims 1 to 12.

如請求項13之疊層體，其中，至少1層之該絕緣層的厚度為4μm以上且未達15μm。The laminate according to claim 13, wherein at least one layer of the insulating layer has a thickness of 4 μm or more and less than 15 μm.

如請求項13或14之疊層體，其中，該堆疊層具有多層之該導體層與該絕緣層，且該導體層配置於各該絕緣層之間以及該堆疊層之最外層的表面。The laminated body of claim 13 or 14, wherein the laminated layer has multiple layers of the conductor layer and the insulating layer, and the conductor layer is arranged between the insulating layers and on the surface of the outermost layer of the laminated layer.

如請求項13或14之疊層體，其中，具有3層或4層之該絕緣層。Such as the laminate of claim 13 or 14, wherein the insulating layer has 3 or 4 layers.

如請求項13或14之疊層體，其係無芯基板。Such as the laminate of claim 13 or 14, which is a coreless substrate.

一種疊層體之製造方法，具有下列步驟：使用如請求項1～12中任一項之附絕緣性樹脂層之銅箔在導體層表面形成絕緣層，藉此形成由該導體層與該絕緣層交替疊層而成的堆疊層。A manufacturing method of a laminated body has the following steps: An insulating layer is formed on the surface of the conductor layer using the copper foil with an insulating resin layer according to any one of claims 1 to 12, thereby forming a stacked layer formed by alternately laminating the conductor layer and the insulating layer.

如請求項18之疊層體之製造方法，其中，至少1層之該絕緣層的厚度為4μm以上且未達15μm。The method for manufacturing a laminate according to claim 18, wherein the thickness of at least one insulating layer is 4 μm or more and less than 15 μm.

如請求項18或19之疊層體之製造方法，其中，該堆疊層具有多層之該導體層與該絕緣層，且該導體層配置於各該絕緣層之間以及該堆疊層之最外層的表面。The method for manufacturing a laminate of claim 18 or 19, wherein the stacked layer has multiple layers of the conductor layer and the insulating layer, and the conductor layer is disposed between the insulating layers and the outermost layer of the stacked layer surface.

如請求項18或19之疊層體之製造方法，其中，該疊層體具有3層或4層之該絕緣層。The method for manufacturing a laminated body of claim 18 or 19, wherein the laminated body has the insulating layer of 3 or 4 layers.

如請求項18或19之疊層體之製造方法，其中，該疊層體為無芯基板。The method for manufacturing a laminate according to claim 18 or 19, wherein the laminate is a coreless substrate.