TW201808645A - Method for manufacturing laminate and method for manufacturing wiring board - Google Patents

Abstract

Provided is a method for manufacturing a laminate, which comprises a step of obtaining a laminate by forming a resin composition layer on a base material. The base material contains a glass substrate or a silicon wafer. The resin composition layer is not more than 10 [mu]m thick. The resin composition layer contains: an epoxy resin having structural units derived from alkylene glycol which includes three or more carbon atoms; and a compound containing an ester group.

Description

積層體的製造方法及配線板的製造方法Manufacturing method of laminated body and manufacturing method of wiring board

本發明是有關於一種積層體的製造方法及配線板的製造方法。The present invention relates to a method for manufacturing a laminated body and a method for manufacturing a wiring board.

近年來，電子機器的小型化、輕量化及多功能化進一步發展，大規模積體電路（Large Scale Integrated circuit，LSI）、晶片零件等的高積體化隨之發展。而且，其形態亦向著多引腳化、小型化迅速變化。因此，於配線板中，為了提高電子零件的安裝密度，微細配線化的開發正在發展。In recent years, miniaturization, weight reduction, and multifunctionalization of electronic devices have been further developed, and large scale integrated circuits (LSIs), chip components, and the like have been developed. In addition, its shape is rapidly changing towards multi-pin and miniaturization. Therefore, in wiring boards, in order to increase the mounting density of electronic components, development of fine wiring has been progressing.

作為用以應對微細配線化的要求的方法之一，已知有藉由鍍敷而於樹脂層上形成導體層的方法。例如，作為如專利文獻1中所存在的層疊（bulid up）方式的配線板的電路形成方法，主要使用半加成法（Semi-Additive method）。所述方法為如下方法：於進行無電解鍍敷而形成無電解鍍敷層後，利用電解鍍敷（電氣鍍敷）而僅於必要的部分形成電路，其後將未形成配線圖案的部分所存在的無電解鍍敷層去除。As one of the methods for responding to the demand for fine wiring, a method of forming a conductor layer on a resin layer by plating is known. For example, as a circuit forming method of a wiring board of a bulk up method as described in Patent Document 1, a semi-additive method is mainly used. The method is a method of forming an electroless plating layer by performing electroless plating, and then using electrolytic plating (electrical plating) to form a circuit only at a necessary portion, and thereafter, forming a portion where a wiring pattern is not formed. Existing electroless plating is removed.

所述方法由於要去除的導體層薄，因此較先前而言導體層的蝕刻量少，不易產生電路（配線圖案）細的問題，對於微細配線化有利。所述方法中為如下狀況：藉由因樹脂層的表面粗糙度引起的錨固效果而確保樹脂層與鍍敷層（銅鍍敷層）的接著力；其表面粗糙度Ra大至0.5 μm以上。This method has a thin conductor layer, so the amount of etching of the conductor layer is smaller than before, and the problem of thin circuits (wiring patterns) is less likely to occur, which is advantageous for fine wiring. In the method described above, there is a situation in which the adhesion between the resin layer and the plating layer (copper plating layer) is ensured by an anchor effect due to the surface roughness of the resin layer; and the surface roughness Ra is as large as 0.5 μm or more.

於此種狀況下，於專利文獻2中，為了提高內層電路板與外層電路的密接度，而提出有預先層壓絕緣樹脂層與無電解鍍敷用接著劑層而成的複合層片。另外，於專利文獻3中，提出有與鍍敷銅的接著力優異的加成法配線板用接著劑的組成物。 [現有技術文獻] [專利文獻]Under such circumstances, in Patent Document 2, in order to improve the adhesion between the inner-layer circuit board and the outer-layer circuit, a composite layer sheet in which an insulating resin layer and an adhesive layer for electroless plating are previously laminated is proposed. In addition, Patent Document 3 proposes a composition of an additive for a wiring board with an addition method having excellent adhesion to copper plating. [Prior Art Literature] [Patent Literature]

[專利文獻1]日本專利第3290296號公報 [專利文獻2]日本專利特開平1-99288號公報 [專利文獻3]日本專利特開2001-123137號公報 [專利文獻4]日本專利第4657554號公報[Patent Literature 1] Japanese Patent No. 3290296 [Patent Literature 2] Japanese Patent Laid-Open No. 1-99288 [Patent Literature 3] Japanese Patent Laid-Open No. 2001-123137 [Patent Literature 4] Japanese Patent No. 4565554

[發明所欲解決之課題][Problems to be Solved by the Invention]

先前的層疊方式中，由於無電解鍍敷深入至粗化形狀的深處而難以去除，且為了形成寬度為10 μm以下的微細的電路而樹脂層的表面粗糙度大，故而有時會產生絕緣不良（短路不良）、開路不良等不良狀況。因此，存在無法良率良好地製造配線板的情況。另一方面，若使粗化形狀小（使表面平滑），則對於微細配線形成而言有利，但有時與導體層（無電解鍍敷層等）的接著力下降，而產生電路（線路）剝離等不良情況。因此，要求開發為平滑的表面且對導體層顯示出高接著力的配線板材料（構成配線板的材料）、即具有可兼具與導體層的接著力、及微細配線形成性的樹脂層的配線板材料。In the conventional lamination method, since the electroless plating is difficult to remove as it goes deep into the roughened shape, and in order to form a fine circuit with a width of 10 μm or less, the surface roughness of the resin layer is large, so insulation sometimes occurs. Defective conditions (short circuit failure), open circuit failure, etc. Therefore, there is a case where the wiring board cannot be manufactured with good yield. On the other hand, if the roughened shape is made small (the surface is smoothed), it is advantageous for the formation of fine wiring. However, the bonding force with the conductor layer (electroless plating layer, etc.) may be reduced and a circuit (circuit) may be generated. Defects such as peeling. Therefore, it is required to develop a wiring board material (a material constituting a wiring board) that has a smooth surface and exhibits high adhesion to a conductor layer, that is, a resin layer having a resin layer that can have both adhesion to a conductor layer and fine wiring formability. Wiring board material.

且說，為了配線板的薄型化，理想的是使配線板材料薄型化。就此種觀點而言，認為使配置於基材上的樹脂層的厚度變薄。然而，若使樹脂層的厚度變薄，則存在因基材的凹凸而樹脂層的表面的平滑性下降且微細配線形成性下降的傾向。In addition, in order to reduce the thickness of the wiring board, it is desirable to reduce the thickness of the wiring board material. From such a viewpoint, it is considered that the thickness of the resin layer arranged on the substrate is reduced. However, if the thickness of the resin layer is reduced, the smoothness of the surface of the resin layer is lowered due to the unevenness of the substrate, and the fine wiring formability tends to be lowered.

本發明是鑒於所述情況而成，目的在於提供一種使樹脂層薄層化且微細配線形成性優異，並且樹脂層與導體層的接著性優異的積層體的製造方法。另外，本發明的目的在於提供一種使用藉由所述積層體的製造方法而獲得的積層體而成的配線板的製造方法。 [解決課題之手段]The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a laminated body in which a thin resin layer is formed and fine wiring formation is excellent, and the adhesiveness between the resin layer and the conductor layer is excellent. Another object of the present invention is to provide a method for manufacturing a wiring board using the multilayer body obtained by the method for manufacturing the multilayer body. [Means for solving problems]

本發明者等人為了解決所述課題而進行了研究，結果發現藉由下述本發明可解決所述課題。The present inventors have conducted studies in order to solve the problems, and as a result, have found that the problems can be solved by the present invention described below.

本發明的積層體的製造方法包括在基材上形成樹脂組成物層而獲得積層體的步驟，所述基材包含玻璃基板或矽晶圓，所述樹脂組成物層的厚度為10 μm以下，所述樹脂組成物層含有具有源自碳數3以上的烷二醇的結構單元的環氧樹脂、及含酯基的化合物。The manufacturing method of the laminated body of the present invention includes the step of obtaining a laminated body by forming a resin composition layer on a substrate, the substrate includes a glass substrate or a silicon wafer, and the thickness of the resin composition layer is 10 μm or less, The resin composition layer contains an epoxy resin having a structural unit derived from an alkanediol having 3 or more carbon atoms, and an ester group-containing compound.

根據本發明的積層體的製造方法，可獲得使樹脂層薄層化且微細配線形成性優異，並且樹脂層與導體層（無電解銅鍍敷層等）的接著性優異的積層體。根據本發明的積層體的製造方法，可獲得使樹脂層薄層化且即便表面粗糙度Ra小亦對導體層顯示出高接著性的積層體。根據本發明的積層體的製造方法，可獲得能夠實現配線高密度化的積層體。According to the manufacturing method of the laminated body of this invention, the laminated body which thinned the resin layer and was excellent in the fine wiring formability, and was excellent in adhesiveness of a resin layer and a conductor layer (electroless copper plating layer etc.) can be obtained. According to the manufacturing method of the laminated body of this invention, the laminated body which thinned the resin layer and showed high adhesiveness to a conductor layer even if surface roughness Ra is small can be obtained. According to the manufacturing method of the laminated body of this invention, the laminated body which can achieve high-density wiring can be obtained.

且說，於先前的配線板材料中，由於基材與樹脂層的接著性不足等的情況而存在於焊料回流時產生剝離，且安裝時的耐熱性不充分的情況。例如，於所述專利文獻4中，揭示了使用玻璃基板來製造多層印刷基板的手法。但是，樹脂層與玻璃基板的接著性低，於高溫時因由熱膨脹率差引起的應力而在樹脂層與玻璃基板之間產生剝離，因此回流耐熱性不充分。另一方面，根據本發明的積層體的製造方法，可獲得焊料耐熱性（焊料回流耐熱性）優異的積層體。即，根據本發明的積層體的製造方法，可獲得使樹脂層薄層化且微細配線形成性優異，並且導體層、樹脂層及基材間的接著性優異，焊料耐熱性優異的積層體。In addition, in the conventional wiring board materials, peeling occurs when the solder is reflowed due to insufficient adhesion between the substrate and the resin layer, and heat resistance during mounting may be insufficient. For example, Patent Document 4 discloses a method of manufacturing a multilayer printed circuit board using a glass substrate. However, the adhesiveness between the resin layer and the glass substrate is low, and peeling occurs between the resin layer and the glass substrate due to a stress caused by a difference in thermal expansion coefficient at a high temperature, so the reflow heat resistance is insufficient. On the other hand, according to the manufacturing method of the laminated body of this invention, the laminated body which is excellent in solder heat resistance (solder reflow heat resistance) can be obtained. That is, according to the manufacturing method of the laminated body of this invention, the laminated body which thinned the resin layer and was excellent in the fine wiring formability, was excellent in adhesiveness between a conductor layer, a resin layer, and a base material, and was excellent in heat resistance of solder.

所述碳數3以上的烷二醇較佳為己二醇。相對於所述環氧樹脂的環氧基1當量，所述含酯基的化合物的酯當量較佳為0.3當量～1.5當量。The alkanediol having 3 or more carbon atoms is preferably hexanediol. The ester equivalent of the ester group-containing compound is preferably 0.3 equivalent to 1.5 equivalent with respect to 1 equivalent of the epoxy group of the epoxy resin.

所述玻璃基板的厚度較佳為200 μm以下。The thickness of the glass substrate is preferably 200 μm or less.

本發明的積層體的製造方法較佳為藉由旋塗法而形成所述樹脂組成物層的態樣。It is preferable that the manufacturing method of the laminated body of this invention is a state which forms the said resin composition layer by a spin coating method.

本發明的積層體的製造方法可進而包括將所述樹脂組成物層熱硬化而形成樹脂硬化物層的步驟。本發明的積層體的製造方法亦可進而包括對所述樹脂硬化物層照射紫外線的步驟。本發明的積層體的製造方法較佳為使用最大波長300 nm～450 nm的紫外線燈，於大氣壓環境下照射所述紫外線的態樣。所述樹脂硬化物層的表面粗糙度（Ra）較佳為0.2 μm以下。The manufacturing method of the laminated body of this invention may further include the process of thermally hardening the said resin composition layer, and forming a resin hardened | cured material layer. The manufacturing method of the laminated body of this invention may further include the process of irradiating the said resin hardened | cured material layer with an ultraviolet-ray. In the method for manufacturing the laminated body of the present invention, it is preferable to use an ultraviolet lamp with a maximum wavelength of 300 nm to 450 nm and irradiate the ultraviolet rays in an atmospheric pressure environment. The surface roughness (Ra) of the resin hardened material layer is preferably 0.2 μm or less.

本發明的配線板的製造方法包括藉由本發明的積層體的製造方法而製造積層體的步驟；以及於所述積層體形成導體層的步驟。 [發明的效果]The manufacturing method of the wiring board of this invention includes the process of manufacturing a laminated body by the manufacturing method of the laminated body of this invention, and the process of forming a conductor layer in the said laminated body. [Effect of the invention]

根據本發明，可提供一種使樹脂層薄層化且微細配線形成性優異，並且導體層、樹脂層及基材間的接著性優異，焊料耐熱性優異的積層體的製造方法，以及使用藉由所述積層體的製造方法而獲得的積層體而成的配線板（印刷配線板等）的製造方法。According to the present invention, it is possible to provide a method for manufacturing a laminated body that reduces the thickness of a resin layer and has excellent fine-wire formation properties, excellent adhesion between a conductor layer, a resin layer, and a substrate, and excellent solder heat resistance, and uses The manufacturing method of the wiring board (printed wiring board etc.) which obtained the laminated body obtained by the manufacturing method of the said laminated body.

以下，對本實施方式進行詳細說明。於本說明書中，使用「～」來表示的數值範圍表示包含「～」的前後所記載的數值來分別作為最小值及最大值的範圍。於本說明書中階段性地記載的數值範圍中，某階段的數值範圍的上限值或下限值亦可置換為其他階段的數值範圍的上限值或下限值。於本說明書中記載的數值範圍中，該數值範圍的上限值或下限值亦可置換為實施例中所示的值。所謂「A或B」只要包含A及B的任一者即可，亦可兩者均包含在內。只要無特別說明，則於本說明書中例示的材料可單獨使用一種或者組合使用兩種以上。於本說明書中，於組成物中存在多種相當於各成分的物質的情況下，只要無特別說明，則組成物中的各成分的含量是指組成物中存在的所述多種物質的合計量。Hereinafter, this embodiment will be described in detail. In the present specification, a numerical range expressed using "~" means a range including the numerical value described before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described stepwise in this specification, the upper limit value or lower limit value of the numerical range at one stage may be replaced with the upper limit value or lower limit value of the numerical range at another stage. In the numerical range described in this specification, the upper limit value or lower limit value of the numerical range may be replaced with the value shown in the examples. The "A or B" may include any one of A and B, and may include both. Unless otherwise specified, the materials exemplified in this specification may be used alone or in combination of two or more. In the present specification, when a plurality of substances corresponding to each component are present in the composition, the content of each component in the composition refers to the total amount of the plurality of substances present in the composition unless otherwise specified.

＜積層體的製造方法＞ 本實施方式的積層體的製造方法包括在基材上形成樹脂組成物層（含有樹脂組成物的層）而獲得積層體的積層體形成步驟。於本實施方式中，所述基材包含玻璃基板或矽晶圓，所述樹脂組成物層的厚度為10 μm以下，樹脂組成物層含有具有源自碳數3以上的烷二醇的結構單元的環氧樹脂、及含酯基的化合物。藉由本實施方式的積層體的製造方法而獲得的積層體可用於配線板的製造。樹脂組成物層及基材只要分別為一層以上即可。<The manufacturing method of a laminated body> The manufacturing method of the laminated body of this embodiment includes the laminated body formation process of forming a resin composition layer (layer containing a resin composition) on a base material, and obtaining a laminated body. In this embodiment, the base material includes a glass substrate or a silicon wafer, the resin composition layer has a thickness of 10 μm or less, and the resin composition layer includes a structural unit having an alkanediol having 3 or more carbon atoms. Epoxy resin, and ester-containing compounds. The laminated body obtained by the manufacturing method of the laminated body of this embodiment can be used for manufacture of a wiring board. The resin composition layer and the substrate need only be one or more layers, respectively.

積層體形成步驟亦可包括將所述樹脂組成物層硬化而形成樹脂硬化物層（絕緣樹脂層等）的硬化步驟。硬化步驟例如可為將樹脂組成物層熱硬化而形成樹脂硬化物層的熱硬化步驟。於熱硬化步驟中，例如藉由對樹脂組成物層進行加熱而獲得樹脂硬化物層。於樹脂硬化物層中，例如作為其構成成分的熱硬化性樹脂（環氧樹脂等）完全硬化，或者熱硬化性樹脂的90%以上硬化（例如超過90%的熱硬化性樹脂硬化）。The laminated body forming step may include a hardening step of hardening the resin composition layer to form a hardened resin layer (such as an insulating resin layer). The curing step may be, for example, a thermal curing step of thermally curing the resin composition layer to form a resin cured material layer. In the heat curing step, for example, the resin composition layer is obtained by heating the resin composition layer. In the resin cured material layer, for example, the thermosetting resin (epoxy resin, etc.) as its constituent component is completely cured, or 90% or more of the thermosetting resin is cured (for example, more than 90% of the thermosetting resin is cured).

於硬化步驟中，較佳為於積層體的製造時不進行加壓。該情況下，可抑制於製造時產生裂紋。再者，本實施方式的積層體可藉由壓製法而製造，亦可藉由於將樹脂組成物塗敷於基材並加以乾燥而獲得樹脂組成物層後利用壓製法進行加熱及加壓並加以硬化而製造積層體。In the hardening step, it is preferable not to pressurize during the production of the laminated body. In this case, the occurrence of cracks during production can be suppressed. In addition, the laminated body of the present embodiment can be produced by a pressing method, or a resin composition layer can be obtained by applying a resin composition to a substrate and drying to obtain a resin composition layer. Laminated by hardening.

積層體形成步驟亦可包括在硬化步驟後對樹脂硬化物層照射紫外線的紫外線照射步驟。於紫外線照射步驟中，可藉由對樹脂硬化物層照射紫外線，而使樹脂硬化物層的表面的官能基改質，並提高接著力。The laminated body forming step may include an ultraviolet irradiation step of irradiating the resin hardened material layer with ultraviolet rays after the hardening step. In the ultraviolet irradiation step, the functional group on the surface of the resin hardened material layer can be modified by irradiating ultraviolet rays to the resin hardened material layer, and the adhesive force can be improved.

（積層體形成步驟） [樹脂組成物層] 樹脂組成物層於成為配線板的層的一部分之前，是以未硬化或半硬化狀態（所謂的B階段（B-Stage）狀態）存在於支持體上、玻璃基板或矽晶圓上等。例如，於樹脂組成物層中，作為樹脂組成物層的構成成分的熱硬化性樹脂（環氧樹脂等）為未硬化或半硬化狀態。熱硬化性樹脂的硬化度可藉由根據示差掃描熱量計測定而得的反應率而測定。所謂「B階段狀態」是指硬化率為5%～90%的狀態。(Laminate Formation Step) [Resin Composition Layer] Before the resin composition layer becomes part of the layer of the wiring board, it exists in the support in an unhardened or semi-hardened state (so-called B-Stage state). On glass substrate or silicon wafer. For example, in the resin composition layer, a thermosetting resin (epoxy resin or the like) as a constituent of the resin composition layer is in an uncured or semi-cured state. The degree of hardening of the thermosetting resin can be measured by a reaction rate measured by a differential scanning calorimeter. The "B-stage state" refers to a state where the hardening rate is 5% to 90%.

本實施方式的樹脂組成物層含有（A）具有源自碳數3以上的烷二醇的結構單元的環氧樹脂（以下，有時稱為「（A）成分」）、以及（B）含酯基的化合物（以下，有時稱為「（B）成分」）。本實施方式的樹脂組成物層亦可進而含有（C）硬化促進劑（以下，有時稱為「（C）成分」）。The resin composition layer of the present embodiment contains (A) an epoxy resin (hereinafter, sometimes referred to as "(A) component") having a structural unit derived from an alkanediol having 3 or more carbon atoms, and (B) containing Ester-based compounds (hereinafter, sometimes referred to as "(B) component"). The resin composition layer of the present embodiment may further contain a (C) curing accelerator (hereinafter, sometimes referred to as “(C) component”).

於積層體形成步驟中，使用樹脂組成物，而於基材上形成至少包含（A）成分及（B）成分的樹脂組成物層。作為樹脂組成物層的形成方法，例如可列舉塗佈方式、層壓方式等。In the laminated body forming step, a resin composition is used to form a resin composition layer containing at least the component (A) and the component (B) on the substrate. Examples of the method for forming the resin composition layer include a coating method and a lamination method.

本實施方式的樹脂組成物的製備方法並無特別限制，可使用先前公知的製備方法。例如，於在溶媒中加入（A）成分、（B）成分及視需要而使用的各種成分後，使用超音波分散方式、高壓衝擊式分散方式、高速旋轉分散方式、珠磨機方式、高速剪切分散方式、自轉公轉式分散方式等各種混合機進行混合、攪拌，藉此可製備成清漆。就塗敷性等優異的觀點而言，所述清漆中除了溶媒以外的固體成分濃度較佳為20質量%～70質量%。The method for producing the resin composition of the present embodiment is not particularly limited, and a conventionally known method can be used. For example, after adding (A) component, (B) component and various components used as needed in the solvent, ultrasonic dispersion method, high-pressure impact dispersion method, high-speed rotation dispersion method, bead mill method, and high-speed shear are used. Various types of mixers, such as cutting dispersion method and rotation revolution dispersion method, can be mixed and stirred to prepare a varnish. From the viewpoint of excellent coating properties and the like, the solid content concentration of the varnish other than the solvent is preferably 20% by mass to 70% by mass.

於藉由塗佈而形成樹脂組成物層的情況下，塗佈方法不受限定。例如可藉由旋塗法、浸漬法、噴塗法、薄霧狀噴塗法（Mist Coat）、流塗法、簾塗法、輥塗法、刀片塗佈法、刮塗法、空氣刮刀塗佈法、棒塗法、網版印刷法、凹版印刷法、平板印刷法、柔版印刷法、刷塗法等而將樹脂組成物塗佈於基材上。就容易使樹脂組成物層的厚度變薄的觀點而言，較佳為旋塗法。When a resin composition layer is formed by coating, the coating method is not limited. For example, a spin coating method, a dipping method, a spray coating method, a mist coating method (Mist Coat), a flow coating method, a curtain coating method, a roll coating method, a blade coating method, a blade coating method, and an air blade coating method can be used. , A bar coating method, a screen printing method, a gravure printing method, a lithographic printing method, a flexographic printing method, a brush coating method, or the like to apply a resin composition to a substrate. From the viewpoint of easily reducing the thickness of the resin composition layer, a spin coating method is preferred.

於藉由塗佈而形成樹脂組成物層的情況下，較佳為於塗佈樹脂組成物後使塗膜乾燥，並使溶媒揮發。根據組成物中的各成分的種類、調配比例、塗膜的厚度等而不同，就提高作業性的觀點而言，若於40℃～180℃下為1分鐘～30分鐘左右，則較佳。When a resin composition layer is formed by coating, it is preferable that the coating film is dried after the resin composition is applied, and the solvent is evaporated. It varies depending on the type of each component in the composition, the blending ratio, the thickness of the coating film, and the like. From the viewpoint of improving workability, it is preferably about 1 minute to 30 minutes at 40 ° C to 180 ° C.

於藉由塗佈而形成樹脂組成物層的情況下，由於於基材上直接形成樹脂組成物層，因此可進一步減少所獲得的樹脂組成物層的厚度。When the resin composition layer is formed by coating, since the resin composition layer is directly formed on the substrate, the thickness of the obtained resin composition layer can be further reduced.

於使用旋塗法而於基材上形成樹脂組成物層的情況下，例如於利用旋塗而於基材上將本實施方式的樹脂組成物（清漆）製膜後，於80℃～180℃左右的溫度下，進行1分鐘～10分鐘左右的乾燥處理，藉此可製作帶有樹脂組成物層的基材。於乾燥處理的溫度為80℃以上且時間為1分鐘以上的情況下，由於可充分進行乾燥，並抑制於樹脂硬化物層內產生空隙，因此較佳。再者，此處，藉由乾燥而清漆中的溶媒為揮發的狀態，且為未進行硬化處理的未硬化的狀態、所謂的未硬化的樹脂組成物層。When a resin composition layer is formed on a base material by a spin coating method, for example, after the resin composition (varnish) of this embodiment is formed on a base material by spin coating, the temperature is 80 ° C to 180 ° C. A substrate with a resin composition layer can be produced by performing a drying process at a temperature of about 1 minute to about 10 minutes. When the temperature of the drying process is 80 ° C. or higher and the time is 1 minute or longer, drying is sufficiently performed and voids are suppressed from occurring in the resin hardened layer, which is preferable. Here, the solvent in the varnish is in a volatilized state by drying, and is an uncured state without a hardening treatment, a so-called uncured resin composition layer.

旋塗裝置只要為具備轉臺及真空流路的一般的裝置，則並無特別限制，所述轉臺支持應當塗佈的基材並進行旋轉，所述真空流路為了可於所述轉臺的上表面吸附並保持基材而形成為槽狀。The spin coating device is not particularly limited as long as it is a general device including a turntable and a vacuum flow path. The turntable supports and rotates a substrate to be coated. The upper surface of the stage is formed in a groove shape by adsorbing and holding the substrate.

藉由旋塗而形成的樹脂組成物層的厚度可藉由調整清漆的黏度而加以調整。作為清漆的黏度，並無特別限制，較佳為1 cP～1000 cP。另外，旋塗的轉速亦無特別限制，較佳為100 rpm～5000 rpm的範圍。The thickness of the resin composition layer formed by spin coating can be adjusted by adjusting the viscosity of the varnish. The viscosity of the varnish is not particularly limited, but is preferably 1 cP to 1000 cP. In addition, the rotation speed of the spin coating is also not particularly limited, but is preferably in the range of 100 rpm to 5000 rpm.

於使用層壓方式而形成樹脂組成物層的情況下，可藉由利用真空層壓、輥層壓等加壓層壓將帶有樹脂的載體膜與基材層壓而製造。可使帶有樹脂的載體膜以樹脂組成物與基材面對面的方式接觸，使用例如真空加壓層壓積層裝置進行層壓，藉此形成樹脂組成物層。When the resin composition layer is formed using a lamination method, it can be produced by laminating a carrier film with a resin and a substrate by pressure lamination such as vacuum lamination and roll lamination. The resin-containing carrier film can be brought into contact with the resin composition and the substrate face-to-face, and laminated using, for example, a vacuum pressure lamination and lamination device, thereby forming a resin composition layer.

於使用真空加壓層壓積層裝置的情況下，較佳為溫度為50℃～170℃左右、壓力為0.2 MPa以上。較佳的壓力值與加熱溫度同樣地，根據基板的厚度、殘存銅率（銅的殘存量）等而變化，較佳為1.0 MPa以下。另外，若真空度為15 hPa以下，則朝內層電路板的埋入性變得更良好。真空度越低者越佳，若考慮裝置的能力、達到規定值的等待時間等對生產性產生的影響，則較佳為5 hPa～10 hPa的範圍。熱壓接時間較佳為10秒～90秒左右。若熱壓接時間為10秒以上，則朝內層電路的樹脂埋入性變得更優異。若熱壓接時間為90秒以下，則生產性變得更良好。更佳的熱壓接時間為20秒～60秒。When using a vacuum pressure lamination and lamination device, the temperature is preferably about 50 ° C to 170 ° C, and the pressure is preferably 0.2 MPa or more. The preferred pressure value varies depending on the thickness of the substrate, the remaining copper ratio (remaining amount of copper), and the like, as well as the heating temperature, and is preferably 1.0 MPa or less. In addition, if the degree of vacuum is 15 hPa or less, the embedding property toward the inner-layer circuit board becomes better. The lower the degree of vacuum is, the better it is. In consideration of the influence of the capacity of the device and the waiting time to reach a predetermined value on productivity, the range of 5 hPa to 10 hPa is preferred. The thermal compression bonding time is preferably about 10 seconds to 90 seconds. When the thermocompression bonding time is 10 seconds or more, the resin embedding property toward the inner layer circuit becomes more excellent. When the thermal compression bonding time is 90 seconds or less, productivity is further improved. A more preferable thermal compression bonding time is 20 seconds to 60 seconds.

為了於樹脂組成物層的形成中使用本實施方式的樹脂組成物，可塗敷於載體膜並以帶有樹脂的載體膜的狀態加以保存。具體而言，將包含本實施方式的樹脂組成物的清漆塗敷於載體膜後，例如於80℃～180℃左右的溫度下進行1分鐘～10分鐘左右的乾燥處理，藉此可獲得帶有樹脂的載體膜。於乾燥處理的溫度為80℃以上且乾燥處理的時間為1分鐘以上的情況下，可充分進行乾燥，並進一步抑制於樹脂內產生空隙。若乾燥處理的溫度為180℃以下且乾燥處理的時間為10分鐘以下，則可進一步抑制乾燥過渡地進行而樹脂流動量降低的情況。In order to use the resin composition of this embodiment for formation of a resin composition layer, it can apply | coat to a carrier film, and can store it in the state of the carrier film with a resin. Specifically, after the varnish containing the resin composition of this embodiment is applied to a carrier film, for example, a drying treatment is performed at a temperature of about 80 ° C. to 180 ° C. for about 1 minute to 10 minutes, thereby obtaining Resin carrier film. When the temperature of the drying process is 80 ° C. or higher and the time of the drying process is 1 minute or longer, the drying can be sufficiently performed and the generation of voids in the resin can be further suppressed. When the temperature of the drying process is 180 ° C. or lower and the time of the drying process is 10 minutes or shorter, it is possible to further suppress the transition of the drying process and reduce the resin flow amount.

作為塗敷裝置，可使用缺角輪塗佈機、棒塗機、吻合式塗佈機、輥塗機、凹版塗佈機、模塗機等本領域技術人員公知的塗敷裝置，較佳為根據製作的樹脂組成物層的厚度而適宜選擇。再者，於所述帶有樹脂的載體膜中，亦可使樹脂半硬化。所述載體膜成為後述的製造樹脂組成物層時的支持體，且為於製造印刷配線板的過程中藉由剝離等而經去除者。As the coating device, a coating device known to those skilled in the art, such as a notch wheel coater, a bar coater, an anastomotic coater, a roll coater, a gravure coater, and a die coater, can be used. It is appropriately selected depending on the thickness of the produced resin composition layer. Furthermore, the resin-containing carrier film may be semi-hardened. The said carrier film becomes a support body at the time of manufacturing the resin composition layer mentioned later, and is removed by peeling etc. in the process of manufacturing a printed wiring board.

作為載體膜，可列舉包含塑膠材料的膜、金屬箔（銅箔、鋁箔等）、脫模紙等，可較佳地使用包含塑膠材料的膜。作為塑膠材料，可列舉：聚對苯二甲酸乙二酯（Polyethylene Terephthalate，PET）、聚萘二甲酸乙二酯（Polyethylene Naphthalate，PEN）等聚酯；聚碳酸酯（Polycarbonate，PC）；聚甲基丙烯酸甲酯（Polymethyl Methacrylate，PMMA）等丙烯酸樹脂；環狀聚烯烴；三乙醯纖維素（Triacetyl Cellulose，TAC）；聚醚碸（Polyether sulfone，PES）；聚醚酮；聚醯亞胺等。其中，較佳為選自由聚對苯二甲酸乙二酯（PET）及聚萘二甲酸乙二酯（PEN）所組成的群組中的一種以上，更佳為廉價的聚對苯二甲酸乙二酯（PET）。Examples of the carrier film include a film containing a plastic material, a metal foil (copper foil, aluminum foil, etc.), a release paper, and the like. A film containing a plastic material is preferably used. Examples of the plastic material include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polycarbonate (PC); and polyethylene terephthalate Polymethyl Methacrylate (PMMA) and other acrylic resins; Cyclic polyolefin; Triacetyl Cellulose (TAC); Polyether sulfone (PES); Polyether ketone; Polyimide . Among them, one or more members selected from the group consisting of polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are preferred, and inexpensive polyethylene terephthalate is more preferred. Diester (PET).

載體膜的厚度並無特別限定，較佳為10 μm～200 μm的範圍，更佳為20 μm～60 μm的範圍，進而佳為20 μm～50 μm的範圍。The thickness of the carrier film is not particularly limited, but is preferably in the range of 10 μm to 200 μm, more preferably in the range of 20 μm to 60 μm, and even more preferably in the range of 20 μm to 50 μm.

作為載體膜，可使用於與樹脂接合的面具有脫膜層的帶有脫膜層的載體膜。作為於帶有脫膜層的載體膜的脫膜層中使用的脫模劑，例如可列舉選自由醇酸樹脂、聚烯烴樹脂、胺基甲酸酯樹脂及矽酮樹脂所組成的群組中的一種以上的脫模劑。As the carrier film, a carrier film with a release layer having a release layer on the surface to be bonded to the resin can be used. Examples of the release agent used in the release layer of a carrier film with a release layer include a group selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin. More than one release agent.

於本實施方式中，帶有脫膜層的載體膜可使用市售品。作為市售品，可列舉琳得科（Lintec）股份有限公司製造的「PET 501010」、「SK-1」、「AL-5」、「AL-7」等。In this embodiment, a commercially available product can be used as the carrier film with a release layer. Examples of commercially available products include "PET 501010", "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation.

就達成薄層化的觀點而言，樹脂組成物層的厚度為10 μm以下。就容易達成薄層化的觀點而言，樹脂組成物層的厚度較佳為未滿10 μm，更佳為5 μm以下，進而佳為3 μm以下。就進一步提高與導體層的接著強度的觀點而言，樹脂組成物層的厚度較佳為0.1 μm以上，更佳為0.5 μm以上，進而佳為1 μm以上。From the viewpoint of achieving a thin layer, the thickness of the resin composition layer is 10 μm or less. From the viewpoint of making thinning easy, the thickness of the resin composition layer is preferably less than 10 μm, more preferably 5 μm or less, and even more preferably 3 μm or less. From the viewpoint of further improving the bonding strength with the conductor layer, the thickness of the resin composition layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more.

以下，對樹脂組成物中的（A）～（C）成分等構成成分進行說明。Hereinafter, constituent components such as (A) to (C) components in the resin composition will be described.

{（A）環氧樹脂} （A）成分為具有源自碳數3以上的烷二醇的結構單元的環氧樹脂。藉由（A）成分具有源自碳數3以上的烷二醇的結構單元，而提高樹脂組成物的柔軟性，容易達成薄層化。{(A) Epoxy resin} The (A) component is an epoxy resin having a structural unit derived from an alkanediol having 3 or more carbon atoms. When the component (A) has a structural unit derived from an alkanediol having 3 or more carbon atoms, the flexibility of the resin composition is improved, and it is easy to achieve a thin layer.

作為（A）成分的環氧樹脂例如於一分子中具有兩個以上的環氧基。（A）成分亦可於主鏈具有源自碳數3以上的烷二醇的結構單元。另外，就提高柔軟性的觀點而言，源自碳數3以上的烷二醇的結構單元較佳為兩個以上連續重複。就進一步提高耐熱性的觀點而言，（A）成分較佳為芳香族環氧樹脂。The epoxy resin as the component (A) has, for example, two or more epoxy groups in one molecule. The component (A) may have a structural unit derived from an alkanediol having 3 or more carbon atoms in the main chain. In addition, from the viewpoint of improving the flexibility, it is preferable that the structural unit derived from an alkanediol having 3 or more carbon atoms is continuously repeated in two or more. From the viewpoint of further improving heat resistance, the (A) component is preferably an aromatic epoxy resin.

作為（A）成分，可列舉：甲酚酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂、萘酚酚醛清漆型環氧樹脂、芳烷基酚醛清漆型環氧樹脂、聯苯基酚醛清漆型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚T型環氧樹脂、雙酚Z型環氧樹脂、四溴雙酚A型環氧樹脂、聯苯基型環氧樹脂、四甲基聯苯基型環氧樹脂、三苯基型環氧樹脂、四苯基型環氧樹脂、萘酚芳烷基型環氧樹脂、萘二醇芳烷基型環氧樹脂、萘酚芳烷基型環氧樹脂、茀型環氧樹脂、具有二環戊二烯骨架的環氧樹脂、骨架中具有乙烯性不飽和基的環氧樹脂、脂環式型環氧樹脂等。（A）成分可單獨使用一種，就絕緣可靠性及耐熱性更優異的觀點而言，可組合使用兩種以上。Examples of the component (A) include cresol novolac epoxy resin, phenol novolac epoxy resin, naphthol novolac epoxy resin, aralkyl novolac epoxy resin, and biphenyl novolac Type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol T type epoxy resin, bisphenol Z type epoxy resin, tetrabromobisphenol A Epoxy resin, biphenyl epoxy resin, tetramethylbiphenyl epoxy resin, triphenyl epoxy resin, tetraphenyl epoxy resin, naphthol aralkyl epoxy resin, Naphthalene glycol aralkyl epoxy resin, naphthol aralkyl epoxy resin, fluorene epoxy resin, epoxy resin having a dicyclopentadiene skeleton, epoxy resin having an ethylenically unsaturated group in the skeleton Resin, alicyclic epoxy resin, etc. (A) A component can be used individually by 1 type, and can use 2 or more types in combination from a viewpoint of being more excellent in insulation reliability and heat resistance.

作為（A）成分，具體而言可列舉雙酚A型環氧樹脂（三菱化學股份有限公司製造的「jER 828EL」、「YL980」等）、雙酚F型環氧樹脂（三菱化學股份有限公司製造的「jER 806H」、「YL983U」等）等。Specific examples of the component (A) include bisphenol A epoxy resin ("jER 828EL" and "YL980" manufactured by Mitsubishi Chemical Corporation), and bisphenol F epoxy resin (Mitsubishi Chemical Corporation) "JER 806H", "YL983U", etc.).

就進一步提高柔軟性的觀點而言，（A）成分的烷二醇的碳數較佳為4以上，更佳為5以上，進而佳為6以上。就操作性優異的觀點而言，（A）成分的烷二醇的碳數較佳為15以下，更佳為10以下，進而佳為8以下。就該些觀點而言，作為（A）成分的烷二醇，較佳為碳數3～15的烷二醇，更佳為碳數3～10的烷二醇，進而佳為碳數4～8的烷二醇，尤佳為己二醇。作為（A）成分，例如較佳為於主鏈具有源自己二醇的結構單元的雙酚A型環氧樹脂。源自己二醇的結構單元例如可使用1,6-己二醇二***而獲得。From the viewpoint of further improving flexibility, the carbon number of the alkanediol of the (A) component is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. From the viewpoint of excellent workability, the carbon number of the alkanediol of the (A) component is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less. From these viewpoints, the alkanediol as the component (A) is preferably an alkanediol having 3 to 15 carbon atoms, more preferably an alkanediol having 3 to 10 carbon atoms, and even more preferably 4 to 4 carbon atoms. Alkanediol of 8 is particularly preferably hexanediol. As (A) component, the bisphenol A epoxy resin which has a structural unit derived from a diol in a main chain is preferable, for example. The structural unit derived from a diol can be obtained using 1,6-hexanediol diethyl ether, for example.

作為於主鏈具有源自碳數3以上的烷二醇的結構單元的（A）成分的具體例，例如可列舉具有選自由下述通式（I）所表示的結構單元及下述通式（II）所表示的結構單元所組成的群組中的至少一種的環氧樹脂。作為具有式（I）所表示的結構單元及式（II）所表示的結構單元的環氧樹脂，例如可列舉下述通式（III）所表示的環氧樹脂。Specific examples of the (A) component having a structural unit derived from an alkanediol having 3 or more carbon atoms in the main chain include, for example, a component having a structural unit selected from the following general formula (I) and the following general formula An epoxy resin of at least one of the group consisting of the structural unit represented by (II). As an epoxy resin which has the structural unit represented by Formula (I) and the structural unit represented by Formula (II), the epoxy resin represented by following General formula (III) is mentioned, for example.

[化1][化2][通式（I）中，（-O-R₁ -O-）表示源自碳數3以上的烷二醇的結構單元，較佳為如上所述。通式（II）中，R₂ 表示碳數1～10的脂肪族烴基或單鍵，較佳為碳數1～5的脂肪族烴基]。[Chemical 1] [Chemical 2] [In general formula (I), (-OR ₁ -O-) represents a structural unit derived from an alkanediol having 3 or more carbon atoms, and is preferably as described above. In the general formula (II), R ₂ represents an aliphatic hydrocarbon group or a single bond having 1 to 10 carbon atoms, and preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms].

[化3][式（III）中，（-R₃ -O-）表示源自碳數3以上的烷二醇的結構單元，較佳為如上所述。R₄ 表示碳數1～10的脂肪族烴基，較佳為碳數1～5的脂肪族烴基。另外，n表示1～15，較佳為2～10]。[Chemical 3] [In formula (III), (-R ₃ -O-) represents a structural unit derived from an alkanediol having 3 or more carbon atoms, and is preferably as described above. R ₄ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms. In addition, n represents 1 to 15, preferably 2 to 10].

於利用層壓方式形成樹脂組成物層的情況下，就作業性優異的觀點而言，作為（A）成分，較佳為於層壓時的溫度以下熔融者。例如於使用真空層壓機或輥層壓機進行層壓的情況下，樹脂組成物中的（A）成分較佳為熔點為170℃以下者。When the resin composition layer is formed by a lamination method, from the viewpoint of excellent workability, the component (A) is preferably one that melts at a temperature below the temperature at the time of lamination. For example, when laminating using a vacuum laminator or a roll laminator, the component (A) in the resin composition is preferably one having a melting point of 170 ° C or lower.

（A）成分的環氧當量不受限定，較佳為50～3000，更佳為80～2000，進而佳為100～1000。再者，環氧當量可根據日本工業標準（Japanese Industrial Standards，JIS）K7236而測定，表示每1當量的環氧基的環氧樹脂的質量。(A) The epoxy equivalent of a component is not limited, Preferably it is 50-3000, More preferably, it is 80-2000, More preferably, it is 100-1000. The epoxy equivalent can be measured in accordance with Japanese Industrial Standards (JIS) K7236, and represents the mass of epoxy resin per epoxy equivalent.

（A）成分的含量並無特別限定，就進一步提高樹脂層（樹脂組成物層或樹脂硬化物層）與玻璃基板或矽晶圓的密接性的觀點而言，以樹脂組成物的總質量（總固體成分）為基準，較佳為10質量%以上，更佳為15質量%以上，進而佳為20質量%以上，尤佳為30質量%以上，極佳為40質量%以上。另外，以樹脂組成物的總質量（總固體成分）為基準，（A）成分的含量較佳為80質量%以下，更佳為75質量%以下，進而佳為70質量%以下。The content of the component (A) is not particularly limited. From the viewpoint of further improving the adhesion between the resin layer (resin composition layer or resin hardened layer) and the glass substrate or silicon wafer, the total mass of the resin composition ( The total solid content) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, even more preferably 30% by mass or more, and most preferably 40% by mass or more. In addition, based on the total mass (total solid content) of the resin composition, the content of the component (A) is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.

{（B）含酯基的化合物} 作為（B）成分的含酯基的化合物為含有酯基的化合物。（B）成分可用作（A）成分的硬化劑。作為（B）成分，例如可列舉於一分子中包含一個以上的酯基且可使環氧樹脂硬化的化合物，亦可為於一分子中具有一個以上的酯基的樹脂。{(B) ester group-containing compound} The ester group-containing compound as the component (B) is an ester group-containing compound. The component (B) can be used as a hardener for the component (A). Examples of the component (B) include a compound which contains one or more ester groups in one molecule and can harden an epoxy resin, and a resin having one or more ester groups in one molecule.

（B）成分較佳為具有選自由脂肪族鏈及芳香族環所組成的群組中的至少一種。作為（B）成分，例如可列舉由脂肪族或芳香族羧酸、與脂肪族或芳香族羥基化合物而獲得的酯化合物。該些中，由脂肪族羧酸與脂肪族羥基化合物而獲得的酯化合物藉由包含脂肪族鏈，可提高對有機溶媒的可溶性及與環氧樹脂的相容性。由芳香族羧酸與芳香族羥基化合物而獲得的酯化合物藉由具有芳香族環，可進一步提高耐熱性。The component (B) preferably has at least one selected from the group consisting of an aliphatic chain and an aromatic ring. Examples of the component (B) include an ester compound obtained from an aliphatic or aromatic carboxylic acid and an aliphatic or aromatic hydroxy compound. Among these, an ester compound obtained from an aliphatic carboxylic acid and an aliphatic hydroxy compound can improve solubility in an organic solvent and compatibility with an epoxy resin by including an aliphatic chain. The ester compound obtained from an aromatic carboxylic acid and an aromatic hydroxy compound can further improve heat resistance by having an aromatic ring.

作為（B）成分，亦可使用含活性型酯基的化合物。作為含活性型酯基的化合物，可列舉含紫外線活性型酯基的化合物等。含紫外線活性型酯基的化合物為含有藉由紫外線的照射而經活性化的酯基的化合物。As the component (B), a compound containing an active ester group may also be used. Examples of the compound containing an active ester group include compounds containing an ultraviolet-active ester group. The compound containing an ultraviolet-active type ester group is a compound containing an ester group activated by irradiation with ultraviolet rays.

關於作為（B）成分而較佳地使用的化合物，例如可列舉如下芳香族酯，所述芳香族酯是將芳香族化合物（苯、萘、聯苯基、二苯基丙烷、二苯基甲烷、二苯基醚、二苯基磺酸、二苯甲酮等）的2個～4個氫原子經羧基取代而成的芳香族羧酸、與所述芳香族化合物的1個氫原子經羥基取代而成的一元酚系化合物或者所述芳香族化合物的2個～4個氫原子經羥基取代而成的多元酚系化合物的混合物作為原材料，藉由芳香族羧酸與酚性羥基的縮合反應而獲得。Examples of the compound that is preferably used as the component (B) include aromatic esters made of aromatic compounds (benzene, naphthalene, biphenyl, diphenylpropane, and diphenylmethane). , Diphenyl ether, diphenylsulfonic acid, benzophenone, etc.) An aromatic carboxylic acid in which two to four hydrogen atoms are substituted by a carboxyl group, and one hydrogen atom of the aromatic compound is substituted by a hydroxyl group A substituted monohydric phenol compound or a mixture of a polyhydric phenol compound in which two to four hydrogen atoms of the aromatic compound are substituted with a hydroxyl group is used as a raw material, and a condensation reaction between an aromatic carboxylic acid and a phenolic hydroxyl group is performed. And get.

作為一元酚系化合物，可列舉：苯酚、各種甲酚、α-萘酚、β-萘酚等。作為多元酚系化合物，可列舉：對苯二酚、間苯二酚、鄰苯二酚、4,4'-聯苯酚、4,4'-二羥基二苯基醚、雙酚A、雙酚F、雙酚S、雙酚Z、溴化雙酚A、溴化雙酚F、溴化雙酚S、甲基化雙酚S、各種二羥基萘、各種二羥基二苯甲酮、各種三羥基二苯甲酮、各種四羥基二苯甲酮、間苯三酚（phloroglucin）等。作為芳香族羧酸，可列舉：鄰苯二甲酸、間苯二甲酸、對苯二甲酸、苯三羧酸等。Examples of the monohydric phenol compound include phenol, various cresols, α-naphthol, and β-naphthol. Examples of polyhydric phenol compounds include hydroquinone, resorcinol, catechol, 4,4'-biphenol, 4,4'-dihydroxydiphenyl ether, bisphenol A, and bisphenol F, bisphenol S, bisphenol Z, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, methylated bisphenol S, various dihydroxynaphthalenes, various dihydroxybenzophenones, various three Hydroxybenzophenone, various tetrahydroxybenzophenone, phloroglucin, etc. Examples of the aromatic carboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, and trimellitic acid.

作為（B）成分的市售品，可列舉：DIC股份有限公司製造的「EXB-9451」、「EXB-9460」、「EXB-9460S」、「EXB-9470」、「EXB-9480」、「EXB-9420」、三井化學股份有限公司製造的「BPN80」等。Examples of commercially available components of (B) include "EXB-9451", "EXB-9460", "EXB-9460S", "EXB-9470", "EXB-9480", "EXB-9480", " EXB-9420 "," BPN80 "manufactured by Mitsui Chemicals Co., Ltd., etc.

（B）成分可單獨使用一種，亦可組合使用兩種以上。(B) A component may be used individually by 1 type, and may use 2 or more types together.

相對於（A）成分的環氧基1當量，（B）成分的酯當量（酯基當量、活性酯當量）較佳為下述範圍。就黏性及硬化性變得更充分的觀點而言，（B）成分的酯當量較佳為0.3當量以上，更佳為0.4當量以上，進而佳為0.5當量以上。就可獲得更充分的硬化性、耐熱性及耐化學品性的觀點而言，（B）成分的酯當量較佳為1.5當量以下，更佳為1.25當量以下，進而佳為0.9當量以下，尤佳為0.6當量以下。就該些觀點而言，（B）成分的酯當量較佳為0.3當量～1.5當量，更佳為0.3當量～1.25當量，進而佳為0.4當量～1.25當量，尤佳為0.5當量～0.9當量，極佳為0.5當量～0.6當量。The ester equivalent (ester group equivalent, active ester equivalent) of the (B) component is preferably within the following range with respect to 1 equivalent of the epoxy group of the component (A). From the viewpoint that the viscosity and hardenability become more sufficient, the ester equivalent of the component (B) is preferably 0.3 equivalent or more, more preferably 0.4 equivalent or more, and even more preferably 0.5 equivalent or more. From the viewpoint of obtaining more sufficient hardenability, heat resistance, and chemical resistance, the ester equivalent of the component (B) is preferably 1.5 equivalents or less, more preferably 1.25 equivalents or less, and still more preferably 0.9 equivalent or less, particularly It is preferably 0.6 equivalents or less. From these viewpoints, the ester equivalent of the component (B) is preferably 0.3 to 1.5 equivalents, more preferably 0.3 to 1.25 equivalents, still more preferably 0.4 to 1.25 equivalents, and even more preferably 0.5 to 0.9 equivalents. Excellent is 0.5 to 0.6 equivalents.

{（C）硬化促進劑} 本實施方式的樹脂組成物可進而含有作為（C）成分的硬化促進劑。（C）成分例如為環氧樹脂硬化促進劑，可使用環氧樹脂的硬化中所使用的一般的硬化促進劑。再者，將可相當於（B）成分及（C）成分兩者的化合物設為屬於（B）成分。（C）成分可單獨使用一種，亦可組合使用兩種以上。{(C) Hardening Accelerator} The resin composition of the present embodiment may further contain a hardening accelerator as a component (C). (C) A component is an epoxy resin hardening accelerator, for example, the general hardening accelerator used for hardening of an epoxy resin can be used. In addition, the compound which can correspond to both (B) component and (C) component is made into the (B) component. (C) A component may be used individually by 1 type, and may use 2 or more types together.

作為（C）成分，例如可使用咪唑系化合物；有機膦系化合物；有機亞磷酸鹽系化合物；鏻鹽化合物；胺系化合物；與1,8-二氮雜雙環(5,4,0)-7-十一烯等的鹽；四級銨鹽化合物等。As component (C), for example, an imidazole-based compound; an organic phosphine-based compound; an organic phosphite-based compound; a phosphonium salt compound; an amine-based compound; and 1,8-diazabicyclo (5,4,0)- 7-undecene and the like; quaternary ammonium salts and the like.

作為（C）成分的具體例，可列舉：2-甲基咪唑、2-乙基-4-甲基咪唑、1-苄基-2-甲基咪唑、2-十七烷基咪唑、2-十一烷基咪唑、1-氰基乙基-2-苯基咪唑鎓偏苯三酸酯等咪唑系化合物；三苯基膦、三丁基膦等有機膦系化合物；三甲基亞磷酸鹽、三乙基亞磷酸鹽等有機亞磷酸鹽系化合物；乙基三苯基溴化鏻、四苯基鏻四苯基硼酸鹽等鏻鹽化合物；三烷基胺（例如三乙基胺及三丁基胺）、4-二甲基胺基吡啶、苄基二甲基胺、2,4,6-三(二甲基胺基甲基)苯酚、1,8-二氮雜雙環(5.4.0)-7-十一烯（1,8-Diazabicyclo[5.4.0]undec-7-ene，DBU）、二胺基二苯基甲烷、二胺基二苯基碸、二胺基二苯基醚、對苯二胺、間苯二胺、鄰苯二胺、1,5-二胺基萘、間二甲苯二胺等胺系化合物；DBU與對苯二甲酸、2,6-萘二羧酸等的鹽；四乙基氯化銨、四丙基氯化銨、四丁基氯化銨、四丁基溴化銨、四己基溴化銨、苄基三甲基氯化銨等四級銨鹽化合物等。該些可單獨使用一種，亦可組合使用兩種以上。Specific examples of the component (C) include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2- Imidazole compounds such as undecyl imidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate; organic phosphine compounds such as triphenylphosphine and tributylphosphine; trimethylphosphite Organophosphite compounds such as triethyl phosphite; phosphonium salt compounds such as ethyltriphenylphosphonium bromide and tetraphenylphosphonium tetraphenylborate; trialkylamines (such as triethylamine and triethylphosphonium) Butylamine), 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5.4. 0) -7-undecene (1,8-Diazabicyclo [5.4.0] undec-7-ene, DBU), diaminodiphenylmethane, diaminodiphenylphosphonium, diaminodiphenyl Ethers, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,5-diaminonaphthalene, m-xylenediamine and other amine compounds; DBU and terephthalic acid, 2,6-naphthalenedicarboxylic acid Salts of acids, etc .; tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrahexyl bromide Quaternary ammonium salts such as ammonium chloride, benzyltrimethylammonium chloride, and the like. These may be used alone or in combination of two or more.

相對於（A）成分100質量份，（C）成分的含量較佳為下述範圍。就環氧樹脂的硬化變得更充分且耐熱性變得更良好的觀點而言，（C）成分的含量較佳為0.02質量份以上，更佳為0.1質量份以上，進而佳為0.2質量份以上，尤佳為0.3質量份以上。就樹脂組成物的保存穩定性及樹脂組成物層的操作性存在進一步提高的傾向的觀點而言，（C）成分的含量較佳為1.5質量份以下，更佳為1.3質量份以下，進而佳為1質量份以下，尤佳為0.5質量份以下。就該些觀點而言，（C）成分的含量較佳為0.02質量份～1.5質量份，更佳為0.1質量份～1.5質量份，進而佳為0.2質量份～1.5質量份，尤佳為0.3質量份～1.3質量份，極佳為0.3質量份～1質量份，非常佳為0.3質量份～0.5質量份。The content of the (C) component is preferably within the following range with respect to 100 parts by mass of the (A) component. From the viewpoint that the curing of the epoxy resin becomes more sufficient and the heat resistance becomes better, the content of the (C) component is preferably 0.02 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 0.2 parts by mass. The above is particularly preferably 0.3 parts by mass or more. From the viewpoint that the storage stability of the resin composition and the handleability of the resin composition layer tend to be further improved, the content of the (C) component is preferably 1.5 parts by mass or less, more preferably 1.3 parts by mass or less, and further preferably It is 1 part by mass or less, and particularly preferably 0.5 part by mass or less. From these viewpoints, the content of the component (C) is preferably 0.02 to 1.5 parts by mass, more preferably 0.1 to 1.5 parts by mass, still more preferably 0.2 to 1.5 parts by mass, and even more preferably 0.3. Part by mass to 1.3 parts by mass, 0.3 to 1 part by mass is very preferable, and 0.3 to 0.5 part by mass is very preferable.

{其他成分} [（A）成分以外的環氧樹脂] 本實施方式的樹脂組成物亦可含有（A）成分以外的環氧樹脂。作為（A）成分以外的環氧樹脂，就耐熱性更優異的觀點而言，較佳為具有聯苯基結構的芳烷基酚醛清漆型環氧樹脂。所謂具有聯苯基結構的芳烷基酚醛清漆型環氧樹脂是指於分子中含有聯苯基衍生物的芳香族環的芳烷基酚醛清漆型的環氧樹脂，例如可列舉具有下述式（i）所表示的結構單元的環氧樹脂。作為具有式（i）所表示的結構單元的環氧樹脂，例如可列舉下述通式（ii）所表示的環氧樹脂。{Other components} [Epoxy resin other than (A) component] The resin composition of the present embodiment may contain an epoxy resin other than the (A) component. As the epoxy resin other than the component (A), an aralkyl novolak-type epoxy resin having a biphenyl structure is preferred from the viewpoint of more excellent heat resistance. The aralkyl novolak type epoxy resin having a biphenyl structure refers to an aralkyl novolak type epoxy resin containing an aromatic ring of a biphenyl derivative in a molecule, and examples thereof include the following formulas (I) The epoxy resin of the structural unit shown. As an epoxy resin which has a structural unit represented by Formula (i), the epoxy resin represented by following General formula (ii) is mentioned, for example.

[化4] [Chemical 4]

[化5][式（ii）中，p表示1～5]。[Chemical 5] [In formula (ii), p represents 1 to 5].

作為具有式（i）所表示的結構單元的環氧樹脂的市售品，可列舉日本化藥股份有限公司製造的商品名「NC-3000」（p=1.7）、「NC-3000H」（p=2.8）等。Examples of commercially available epoxy resins having a structural unit represented by formula (i) include trade names "NC-3000" (p = 1.7) and "NC-3000H" (p = 2.8) and so on.

[硬化劑] 本實施方式的樹脂組成物中，可與（B）成分一同併用具有將環氧樹脂硬化的功能的公知的硬化劑（除了（B）成分以外）。作為此種硬化劑，例如可列舉：酚系硬化劑、氰酸酯（cyanate ester）系硬化劑及酸酐系硬化劑。[Hardener] In the resin composition of the present embodiment, a known hardener (other than the (B) component) having a function of curing an epoxy resin can be used together with the component (B). Examples of such a hardener include a phenol-based hardener, a cyanate ester-based hardener, and an acid anhydride-based hardener.

作為酚系硬化劑，並無特別限制，較佳為選自由甲酚酚醛清漆型硬化劑、聯苯基型硬化劑、苯酚酚醛清漆型硬化劑、伸萘基醚型硬化劑及含三嗪骨架的酚系硬化劑所組成的群組中的一種以上。酚系硬化劑可單獨使用一種，亦可組合使用兩種以上。The phenol-based hardener is not particularly limited, but is preferably selected from the group consisting of a cresol novolac hardener, a biphenyl hardener, a phenol novolac hardener, a naphthyl ether-based hardener, and a triazine-containing skeleton. One or more of the group consisting of phenolic hardeners. A phenolic hardener may be used individually by 1 type, and may use 2 or more types together.

作為酚系硬化劑的市售品，可列舉：KA-1160、KA-1163、KA-1165（均為DIC股份有限公司製造，商品名）等甲酚酚醛清漆型硬化劑（甲酚酚醛清漆型苯酚樹脂）；MEH-7700、MEH-7810、MEH-7851（均為明和化成股份有限公司製造，商品名）等聯苯基型硬化劑；TD2090（DIC股份有限公司製造，商品名）等苯酚酚醛清漆型硬化劑；EXB-6000（DIC股份有限公司製造，商品名）等伸萘基醚型硬化劑；LA3018、LA7052、LA7054、LA1356（均為DIC股份有限公司製造，商品名）等含三嗪骨架的酚系硬化劑等。Examples of commercially available phenolic hardeners include cresol novolac type hardeners such as KA-1160, KA-1163, and KA-1165 (all manufactured by DIC Corporation, trade names) (cresol novolac type) Phenol resin); MEH-7700, MEH-7810, MEH-7851 (all manufactured by Meiwa Chemical Co., Ltd., etc.) biphenyl type hardener; TD2090 (made by DIC Corporation, trade name), etc. Varnish type hardener; EXB-6000 (manufactured by DIC Corporation, trade name) and other naphthyl ether type hardener; LA3018, LA7052, LA7054, LA1356 (both manufactured by DIC Corporation, trade name) and other triazines A phenolic hardener such as a skeleton.

作為氰酸酯系硬化劑，並無特別限制，可列舉雙酚A二氰酸酯、聚酚氰酸酯（寡(3-亞甲基-1,5-伸苯基氰酸酯)、4,4'-亞甲基雙(2,6-二甲基苯基氰酸酯)、4,4'-亞乙基二苯基二氰酸酯、六氟雙酚A二氰酸酯、2,2-雙(4-氰酸酯)苯基丙烷、1,1-雙(4-氰酸酯苯基甲烷)、雙(4-氰酸酯-3,5-二甲基苯基)甲烷、1,3-雙(4-氰酸酯苯基-1-(甲基亞乙基))苯、雙(4-氰酸酯苯基)硫醚、雙(4-氰酸酯苯基)醚等。作為酸酐系硬化劑，並無特別限制，可列舉鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、甲基耐地酸酐、氫化甲基耐地酸酐、三烷基四氫鄰苯二甲酸酐、十二烯基丁二酸酐、5-(2,5-二氧代四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、偏苯三甲酸酐、均苯四甲酸酐等。The cyanate-based curing agent is not particularly limited, and examples thereof include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4 , 4'-methylenebis (2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane , 1,3-bis (4-cyanatephenyl-1- (methylethylene)) benzene, bis (4-cyanatephenyl) sulfide, bis (4-cyanatephenyl) Ether, etc. The acid anhydride-based hardener is not particularly limited, and examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methyl Hexahydrophthalic anhydride, methyl dianhydride, hydrogenated methyl dianhydride, trialkyltetrahydrophthalic anhydride, dodecylsuccinic anhydride, 5- (2,5-dioxo Tetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride and the like.

本實施方式的樹脂組成物可於不損及本發明的目的的範圍內視需要進而含有溶媒、無機填料、各種添加成分（例如，調平劑、抗氧化劑、阻燃劑、觸變性賦予劑、增黏劑）等。The resin composition according to the present embodiment may further contain a solvent, an inorganic filler, and various additional components (for example, a leveling agent, an antioxidant, a flame retardant, a thixotropy imparting agent, and the like) as long as the object of the present invention is not impaired. Tackifier) and so on.

[溶媒] 本實施方式的樹脂組成物亦可含有溶媒。作為溶媒，可列舉：甲基乙基酮、二甲苯、甲苯、丙酮、乙二醇單***、環己酮、乙基乙氧基丙酸酯、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、丙二醇單甲醚等。溶媒可單獨使用一種，亦可混合使用兩種以上。溶媒相對於所述樹脂組成物的使用比例可為先前使用的比例，亦可根據目標樹脂組成物層的塗膜形成的設備來調整使用量。[Solvent] The resin composition of the present embodiment may contain a solvent. Examples of the solvent include methyl ethyl ketone, xylene, toluene, acetone, ethylene glycol monoethyl ether, cyclohexanone, ethyl ethoxypropionate, N, N-dimethylformamide, and N , N-dimethylacetamide, propylene glycol monomethyl ether and the like. The solvents may be used singly or in combination of two or more. The usage ratio of the solvent with respect to the resin composition may be the ratio used previously, and the usage amount may be adjusted according to equipment for forming a coating film of the target resin composition layer.

[無機填料] 就熱膨脹率的抑制及塗膜強度的提高的觀點而言，本實施方式的樹脂組成物亦可含有無機填料。作為無機填料，例如可使用二氧化矽（例如熔融二氧化矽及熔融二氧化矽以外的二氧化矽）、滑石、氧化鋁、氫氧化鋁、硫酸鋇、氫氧化鈣、氣相二氧化矽、碳酸鈣等無機填料，就介電特性優異的觀點及低熱膨脹的觀點而言，較佳為使用二氧化矽。無機填料可單獨使用一種，亦可組合使用兩種以上。[Inorganic Filler] The resin composition of the present embodiment may contain an inorganic filler from the viewpoint of suppression of thermal expansion coefficient and improvement of coating film strength. As the inorganic filler, for example, silicon dioxide (such as fused silica and fused silica other than fused silica), talc, alumina, aluminum hydroxide, barium sulfate, calcium hydroxide, fumed silica, From the viewpoint of excellent dielectric properties and low thermal expansion, inorganic fillers such as calcium carbonate are preferably silicon dioxide. The inorganic fillers may be used singly or in combination of two or more kinds.

無機填料的含量不受限定，較佳為相對於除了溶媒以外的樹脂組成物的固體成分總量而為下述範圍。就可抑制熱膨脹係數與介電損失的增大的觀點而言，無機填料的含量較佳為1質量%以上，更佳為3質量%以上，進而佳為5質量%以上。就於內層電路形成絕緣樹脂時的必要流動變得充分而難以產生未填充部位的觀點而言，無機填料的含量較佳為60質量%以下，更佳為50質量%以下，進而佳為40質量%以下。就該些觀點而言，無機填料的含量較佳為1質量%～60質量%，更佳為3質量%～50質量%，進而佳為5質量%～40質量%。該些無機填料出於提高分散性的目的，可利用偶合劑進行處理，亦可藉由利用捏合機、球磨機、珠磨機、三輥磨等已知的方法進行的混煉而均質地分散於樹脂組成物中。The content of the inorganic filler is not limited, but is preferably within the following range with respect to the total solid content of the resin composition other than the solvent. From the viewpoint of suppressing an increase in the thermal expansion coefficient and the dielectric loss, the content of the inorganic filler is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The content of the inorganic filler is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% from the viewpoint that the necessary flow when the insulating resin is formed in the inner layer circuit is sufficient to make it impossible to generate unfilled portions. Mass% or less. From these viewpoints, the content of the inorganic filler is preferably 1% by mass to 60% by mass, more preferably 3% by mass to 50% by mass, and still more preferably 5% by mass to 40% by mass. These inorganic fillers can be treated with a coupling agent for the purpose of improving dispersibility, or they can be homogeneously dispersed in a kneading machine, a ball mill, a bead mill, a three-roll mill, or other known methods. In the resin composition.

出於提高無機填料的分散性的目的，較佳為使用偶合劑對無機填料進行表面處理。作為偶合劑，可列舉：矽烷系偶合劑、鈦酸鹽系偶合劑、鋁系偶合劑等。其中，較佳為矽烷系偶合劑。作為矽烷系偶合劑，可列舉：N-苯基-γ-胺基丙基三甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-(2-胺基乙基)胺基丙基三甲氧基矽烷、γ-(2-胺基乙基)胺基丙基三乙氧基矽烷、γ-苯胺丙基三甲氧基矽烷、γ-苯胺丙基三乙氧基矽烷、N-β-(N-乙烯基苄基胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-β-(N-乙烯基苄基胺基乙基)-γ-胺基丙基三乙氧基矽烷等胺基矽烷化合物；γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基三乙氧基矽烷、β-(3,4-環氧基環己基)乙基三甲氧基矽烷等環氧基矽烷化合物；γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基乙烯基乙氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-巰基丙基三乙氧基矽烷、γ-脲基丙基三甲氧基矽烷、γ-脲基丙基三乙氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷等化合物等。For the purpose of improving the dispersibility of the inorganic filler, it is preferable to surface-treat the inorganic filler using a coupling agent. Examples of the coupling agent include a silane-based coupling agent, a titanate-based coupling agent, and an aluminum-based coupling agent. Among these, a silane-based coupling agent is preferred. Examples of the silane-based coupling agent include N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ- (2-Aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ-anilinepropyltrimethoxysilane, γ-aniline Propyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) ) -Amino-silane compounds such as γ-aminopropyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane and other epoxysilane compounds; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylvinylethoxysilane , Γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-methacryl Compounds such as methoxypropyltrimethoxysilane and the like.

[玻璃基板] 作為玻璃基板的原料，例如可使用矽酸鹼系玻璃、無鹼玻璃、石英玻璃等玻璃，就低熱膨脹性的觀點而言，較佳為矽酸鹼系玻璃。另外，作為玻璃基板的原料，就低熱膨脹性的觀點而言，較佳為矽成分比率高的玻璃。玻璃基板的厚度並無特別限定，較佳為下述範圍。就積層體的薄型化及加工性優異的觀點而言，玻璃基板的厚度較佳為200 μm以下，更佳為150 μm以下，進而佳為120 μm以下，尤佳為100 μm以下。就操作的容易性優異的觀點而言，玻璃基板的厚度較佳為30 μm以上，更佳為50 μm以上。就積層體的薄型化及加工性優異的觀點而言，例如玻璃基板的厚度較佳為200 μm以下，更佳為30 μm～200 μm。就操作容易性優異的觀點而言，玻璃基板的厚度進而佳為50 μm～150 μm。另外，就積層體的薄型化的觀點而言，玻璃基板的厚度較佳為30 μm～120 μm，更佳為30 μm～100 μm。[Glass substrate] As a raw material of the glass substrate, for example, glass such as alkali-silicate glass, alkali-free glass, and quartz glass can be used. From the viewpoint of low thermal expansion, alkali-silicate glass is preferred. Moreover, as a raw material of a glass substrate, the glass with a high silicon component ratio is preferable from a viewpoint of low thermal expansion. The thickness of the glass substrate is not particularly limited, but is preferably in the following range. From the standpoint of thinning the laminate and excellent processability, the thickness of the glass substrate is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 120 μm or less, and even more preferably 100 μm or less. From the viewpoint of excellent ease of handling, the thickness of the glass substrate is preferably 30 μm or more, and more preferably 50 μm or more. From the standpoint of the thickness reduction and processability of the laminated body, for example, the thickness of the glass substrate is preferably 200 μm or less, and more preferably 30 μm to 200 μm. From the viewpoint of excellent ease of handling, the thickness of the glass substrate is more preferably 50 μm to 150 μm. From the viewpoint of reducing the thickness of the laminated body, the thickness of the glass substrate is preferably 30 μm to 120 μm, and more preferably 30 μm to 100 μm.

作為玻璃基板，藉由使用與矽晶片為相同程度的低熱膨脹率且高彈性係數者，則變得容易抑制翹曲，且難以產生龜裂。尤其，此種積層體藉由具有耐熱性高的玻璃基板，而自100℃至未滿樹脂硬化物的Tg的溫度區域內顯著地具有低熱膨脹性。另外，藉由樹脂硬化物層含有無機填充材，樹脂硬化物層成為低熱膨脹性且高彈性者，包含所述樹脂硬化物層的積層體進而成為低熱膨脹性且高彈係數者。As a glass substrate, by using a low thermal expansion coefficient and a high coefficient of elasticity similar to those of a silicon wafer, it becomes easy to suppress warping and it is difficult to generate cracks. In particular, such a laminated body has a glass substrate having high heat resistance, and has a significantly low thermal expansion property in a temperature range from 100 ° C. to a Tg of a resin hardened material. In addition, when the resin hardened material layer contains an inorganic filler, the resin hardened material layer has low thermal expansion and high elasticity, and the laminated body including the resin hardened material layer further has low thermal expansion and high elastic coefficient.

就抑制積層體的翹曲的觀點而言，玻璃基板的熱膨脹係數較佳為8 ppm/℃以下，更佳為6 ppm/℃以下，進而佳為4 ppm/℃以下。另外，所述熱膨脹係數的下限並無特別限定，若為1 ppm/℃以上，則較佳。From the viewpoint of suppressing the warpage of the laminated body, the thermal expansion coefficient of the glass substrate is preferably 8 ppm / ° C or lower, more preferably 6 ppm / ° C or lower, and even more preferably 4 ppm / ° C or lower. In addition, the lower limit of the thermal expansion coefficient is not particularly limited, but is preferably 1 ppm / ° C or higher.

玻璃基板的40℃下的動態貯存彈性係數越大越佳，較佳為20 GPa以上，更佳為25 GPa以上，進而佳為30 GPa以上。The larger the dynamic storage elastic coefficient of the glass substrate at 40 ° C., the better, preferably 20 GPa or more, more preferably 25 GPa or more, and even more preferably 30 GPa or more.

[矽晶圓] 作為基材，可應用矽晶圓。晶圓的直徑例如為50 mm～300 mm。另外，若考量製造步驟中的操作的容易性、簡便性等實用性，則矽晶圓的厚度較佳為0.5 mm～1 mm左右。[Silicon wafer] As a substrate, a silicon wafer can be applied. The diameter of the wafer is, for example, 50 mm to 300 mm. In addition, considering practicality such as ease of operation and simplicity in manufacturing steps, the thickness of the silicon wafer is preferably about 0.5 mm to 1 mm.

（硬化步驟） 於硬化步驟中，例如可藉由將樹脂組成物熱硬化而獲得樹脂組成物的硬化物。熱硬化處理可以考慮之後的鍍敷處理、電路層的退火處理等的溫度及時間適宜進行。就可獲得於之後的鍍敷處理時與電路層的接著性變得更良好、鍍敷處理時的對鹼性處理液的侵蝕得到進一步抑制般的硬化度的樹脂硬化物層的觀點而言，熱硬化的條件較佳為下述範圍。加熱溫度較佳為150℃以上，更佳為160℃以上。加熱溫度較佳為220℃以下，更佳為200℃以下。加熱時間較佳為20分鐘以上，更佳為30分鐘以上。加熱時間較佳為120分鐘以下，更佳為90分鐘以下，進而佳為80分鐘以下。熱硬化的條件可為於150℃～220℃下為20分鐘～80分鐘，亦可為於160℃～200℃下為30分鐘～120分鐘。於使用實施了脫模處理的支持體膜的情況下，可於進行加熱硬化後剝離支持體膜。(Hardening step) In the hardening step, for example, a hardened product of the resin composition can be obtained by thermally hardening the resin composition. The heat hardening treatment can be appropriately performed in consideration of the temperature and time of the subsequent plating treatment, the annealing treatment of the circuit layer, and the like. From the standpoint of obtaining a resin hardened material layer having better adhesion to the circuit layer during the subsequent plating process and a degree of hardening such that the erosion of the alkaline treatment solution during the plating process is further suppressed, The conditions for thermal curing are preferably within the following ranges. The heating temperature is preferably 150 ° C or higher, and more preferably 160 ° C or higher. The heating temperature is preferably 220 ° C or lower, and more preferably 200 ° C or lower. The heating time is preferably 20 minutes or more, and more preferably 30 minutes or more. The heating time is preferably 120 minutes or shorter, more preferably 90 minutes or shorter, and even more preferably 80 minutes or shorter. The conditions for heat curing may be 20 minutes to 80 minutes at 150 ° C to 220 ° C, or 30 minutes to 120 minutes at 160 ° C to 200 ° C. In the case of using a support film that has been subjected to a release treatment, the support film can be peeled off after being subjected to heat curing.

（紫外線照射步驟） 於所述硬化步驟後，亦可對樹脂組成物的硬化物（樹脂硬化物層）進行紫外線照射處理。作為紫外線照射條件，並無特別限定。就步驟容易的觀點而言，較佳為使用最大波長300 nm～450 nm的紫外線燈（於最大波長300 nm～450 nm的範圍內放射紫外線的紫外線燈），於大氣壓環境下照射紫外線，更佳為使用最大波長300 nm～450 nm的紫外線燈，於大氣壓環境下以光量成為1000 mJ/cm² ～5000 mJ/cm² 的範圍的方式照射紫外線。所述光量（mJ/cm² ）以「照度（mW/cm² ）×照射時間（秒）」表示。紫外線照射時的樹脂硬化物層的溫度較佳為50℃～80℃左右，更佳為60℃～70℃。(Ultraviolet irradiation step) After the said hardening step, the hardened | cured material (resin hardened | cured material layer) of a resin composition may also be subjected to an ultraviolet irradiation process. The ultraviolet irradiation conditions are not particularly limited. From the viewpoint of easy steps, it is preferable to use an ultraviolet lamp with a maximum wavelength of 300 nm to 450 nm (an ultraviolet lamp that emits ultraviolet rays in a range of a maximum wavelength of 300 nm to 450 nm), and it is more preferable to irradiate ultraviolet rays in an atmospheric pressure environment. In order to use an ultraviolet lamp having a maximum wavelength of 300 nm to 450 nm, the ultraviolet light is irradiated in a range of 1000 mJ / cm ² to 5000 mJ / cm ² under an atmospheric pressure environment. The light amount (mJ / cm ² ) is expressed by “illumination (mW / cm ² ) × irradiation time (second)”. The temperature of the cured resin layer at the time of ultraviolet irradiation is preferably about 50 ° C to 80 ° C, and more preferably 60 ° C to 70 ° C.

用以照射紫外線的方法根據紫外線裝置而不同，因此並無特別限定，若考慮生產性，則較佳為傳送式的紫外線照射方式。紫外線燈之中，作為具有最大波長300 nm～450 nm的範圍的燈，可列舉水銀短弧燈、高壓水銀燈、毛細管型超高壓燈、高壓燈、金屬鹵化物燈等。該些燈中，較佳為紫外線的波長寬的金屬鹵化物燈。The method for irradiating ultraviolet rays is not particularly limited depending on the ultraviolet device, and in consideration of productivity, a transmission-type ultraviolet irradiation method is preferred. Among the ultraviolet lamps, lamps having a maximum wavelength in the range of 300 nm to 450 nm include mercury short-arc lamps, high-pressure mercury lamps, capillary ultrahigh-pressure lamps, high-pressure lamps, and metal halide lamps. Among these lamps, a metal halide lamp having a wide wavelength of ultraviolet rays is preferred.

使用紫外線的最大波長具有300 nm～450 nm的範圍的紫外線燈的目的在於常用性與紫外線的波長域。即，這是因為最大波長顯示300 nm～450 nm的紫外線燈作為傳送式型的紫外線照射裝置（例如阻焊劑的後曝光裝置）而通常使用。進而，金屬鹵化物型的傳送照射裝置的紫外線波長區域寬，不需要特別的裝置即可代替該些裝置，從而可發揮本發明的效果。若紫外線的光量為1000 mJ/cm² 以上，則即便不利用氧化性粗化液對樹脂硬化物層進行處理，與鍍敷導體的接著力亦充分，另一方面，若紫外線的光量為5000 mJ/cm² 以下，則所述接著力可良好地表現出來，於經濟方面而言亦有利。光量更佳為2000 mJ/cm² ～4000 mJ/cm² ，進而佳為3000 mJ/cm² ～4000 mJ/cm² 。The purpose of using an ultraviolet lamp having a maximum wavelength of ultraviolet rays in a range of 300 nm to 450 nm is in the general purpose and wavelength range of ultraviolet rays. That is, this is because an ultraviolet lamp having a maximum wavelength of 300 nm to 450 nm is generally used as a transmission type ultraviolet irradiation device (for example, a post-exposure device for a solder resist). Furthermore, the metal halide-type transmission and irradiation device has a wide ultraviolet wavelength range, and no special device is required to replace these devices, so that the effects of the present invention can be exhibited. If the amount of ultraviolet light is 1000 mJ / cm ² or more, the adhesion to the plated conductor is sufficient even if the resin hardened layer is not treated with the oxidizing roughening solution. On the other hand, if the amount of ultraviolet light is 5000 mJ / cm ² or less, the adhesive force can be expressed well, and it is also economically advantageous. The light amount is more preferably 2000 mJ / cm ² to 4000 mJ / cm ² , and further preferably 3000 mJ / cm ² to 4000 mJ / cm ² .

如此，藉由對樹脂組成物層進行熱硬化處理後進行紫外線照射處理，樹脂硬化物層即便不使用先前所使用的過錳酸鈉系等的粗化液而形成凹凸形狀，亦可對導體層表現出高接著力，因此可抑制配線形成的良率下降。進而，可不進行使用粗化液而進行的水洗處理及廢液處理，對於成本而言亦有利。In this way, by subjecting the resin composition layer to a thermosetting treatment and then performing an ultraviolet irradiation treatment, the resin hardened material layer can be formed into a concave-convex shape without using a roughening solution such as a sodium permanganate-based roughening solution previously used. Since a high bonding force is exhibited, a decrease in the yield of wiring formation can be suppressed. Furthermore, it is possible to perform a water washing treatment and a waste liquid treatment without using a roughening solution, which is also advantageous in terms of cost.

另外，於本實施方式中，為了去除通孔（via hole）底的膠渣（smear），即便利用過錳酸鈉系等的粗化液進行處理，凹凸形狀亦小，且可容易確保對導體層的高接著力。In addition, in this embodiment, in order to remove smear at the bottom of a via hole, even if it is processed with a roughening solution such as sodium permanganate, the uneven shape is small, and the conductor can be easily secured. High adhesion of the layers.

樹脂硬化物層的厚度並無特別限定，就相對地基材（玻璃基板等）的厚度變大等而可容易達成積層體的低熱膨脹係數化及高彈性係數化的觀點而言，較佳為10 μm以下，更佳為未滿10 μm，進而佳為5 μm以下，尤佳為3 μm以下。就進一步提高剝離強度（peel strength）的觀點而言，樹脂硬化物層的厚度較佳為0.1 μm以上，更佳為0.5 μm以上，進而佳為1 μm以上，進而更佳為2 μm以上。The thickness of the hardened resin layer is not particularly limited, and it is preferable that the thickness of the base material (glass substrate, etc.) is relatively large, and it is easy to achieve a low thermal expansion coefficient and a high elastic coefficient of the laminate. 10 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, and even more preferably 3 μm or less. From the viewpoint of further improving peel strength, the thickness of the resin hardened material layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, still more preferably 1 μm or more, and even more preferably 2 μm or more.

就配線的微細化容易的觀點而言，樹脂硬化物層的形成有導體層（電路層等）的一側的表面（和與載體膜將相接或已相接的面為相反側的表面）的表面粗糙度Ra較佳為0.2 μm以下，更佳為0.15 μm以下，進而佳為0.1 μm以下，尤佳為0.05 μm以下。表面粗糙度Ra的下限並無特別限定，就進一步提高剝離強度的觀點而言，較佳為0.001 μm。樹脂硬化物層的所述表面粗糙度Ra例如可使用基恩斯（Keyencec）股份有限公司製造的超深度形狀測定顯微鏡「VK-8500型」而測定。From the viewpoint of ease of miniaturization of the wiring, the surface of the resin hardened material layer on the side where the conductor layer (circuit layer, etc.) is formed (the surface on the opposite side to the surface to be in contact with or to the carrier film) The surface roughness Ra is preferably 0.2 μm or less, more preferably 0.15 μm or less, even more preferably 0.1 μm or less, and even more preferably 0.05 μm or less. The lower limit of the surface roughness Ra is not particularly limited, but from the viewpoint of further improving the peel strength, it is preferably 0.001 μm. The surface roughness Ra of the resin hardened material layer can be measured using, for example, an ultra-depth shape measuring microscope "VK-8500" manufactured by Keyencec Co., Ltd.

關於本實施方式中所形成的樹脂硬化物層，儘管樹脂硬化物層的表面的凹凸形狀小，但仍容易對導體層表現出高接著力。其機構未必明確，但於對樹脂硬化物層照射紫外線的情況下，推測藉由照射紫外線，作為（B）成分的含酯基的化合物的酯基分解，於樹脂硬化物層的表面形成含氧的基，所述含氧的基有助於對導體層的高接著力。再者，形成於樹脂硬化物層的表面的含氧的基的氧原子量可藉由X射線光電子分光法而測定。Regarding the resin hardened material layer formed in this embodiment, although the uneven shape of the surface of the resin hardened material layer is small, it is easy to show a high adhesive force to the conductor layer. The mechanism is not necessarily clear, but when the resin hardened material layer is irradiated with ultraviolet rays, it is speculated that by irradiating ultraviolet rays, the ester group of the ester group-containing compound as component (B) is decomposed to form oxygen containing on the surface of the resin hardened material layer The oxygen-containing group contributes to high adhesion to the conductor layer. The amount of oxygen atoms of the oxygen-containing group formed on the surface of the resin hardened material layer can be measured by an X-ray photoelectron spectroscopy method.

本實施方式中所形成的樹脂硬化物層不僅可較高地維持樹脂硬化物層與導體層的接著力，而且亦可較高地維持凹凸小的玻璃基板與樹脂硬化物層的接著力。藉此，可實現迄今為止無法實現的於玻璃基板上形成微細電路。The resin hardened material layer formed in this embodiment can not only maintain high adhesion between the resin hardened material layer and the conductor layer, but also maintain high adhesion between the glass substrate with small unevenness and the resin hardened material layer. This makes it possible to form a fine circuit on a glass substrate, which has not been possible so far.

具體而言，例如可較佳地用於形成線與空間（L/S）為10 μm/10 μm以下的配線，尤其可進一步較佳地用於形成5 μm/5 μm以下、進而3 μm/3 μm以下的配線。Specifically, for example, it can be preferably used to form a wiring having a line and space (L / S) of 10 μm / 10 μm or less, and can be particularly preferably used to form 5 μm / 5 μm or less, and further 3 μm / 3 μm or less wiring.

本實施方式的積層體的40℃下的貯存彈性係數較佳為1 GPa～80 GPa。若貯存彈性係數為1 GPa以上，則基材（玻璃基板等）得到保護，積層體的龜裂得到進一步抑制。若貯存彈性係數為80 GPa以下，則由基材（玻璃基板等）與樹脂硬化物層的熱膨脹率的差引起的應力得到抑制，積層體的翹曲及龜裂得到進一步抑制。就該些觀點而言，樹脂硬化物層的貯存彈性係數更佳為3 GPa～70 GPa，進而佳為5 GPa～60 GPa。The storage elastic coefficient of the laminated body of this embodiment at 40 ° C. is preferably 1 GPa to 80 GPa. When the storage elastic coefficient is 1 GPa or more, the base material (glass substrate, etc.) is protected, and cracking of the laminated body is further suppressed. When the storage elastic coefficient is 80 GPa or less, the stress caused by the difference in thermal expansion coefficient between the substrate (glass substrate, etc.) and the resin hardened material layer is suppressed, and warpage and cracking of the laminated body are further suppressed. From these viewpoints, the storage elastic coefficient of the resin hardened material layer is more preferably 3 GPa to 70 GPa, and even more preferably 5 GPa to 60 GPa.

本實施方式的積層體可為於單面或兩面具有銅、鋁等金屬箔的帶有金屬箔的積層體。金屬箔只要為於電氣絕緣材料用途中使用者，則並無特別限制。The laminated body of this embodiment can be a laminated body with a metal foil which has metal foils, such as copper and aluminum, on one or both surfaces. The metal foil is not particularly limited as long as it is used for electrical insulation materials.

所述帶有金屬箔的積層體的製造方法並無特別限制。例如，藉由使用金屬箔作為支持體膜，可製造帶有金屬箔的積層體。另外，亦可將已述的藉由層壓或塗敷而獲得的積層體重疊1枚或多枚（例如，2枚～20枚），以於其單面或兩面配置金屬箔的構成積層成形，藉此製造帶有金屬箔的積層體。The manufacturing method of the said metal foil laminated body is not specifically limited. For example, by using a metal foil as a support film, a laminated body with a metal foil can be manufactured. In addition, one or more layers (for example, 2 to 20 pieces) of the layered body obtained by lamination or coating described above may be stacked to form a layered structure in which metal foils are arranged on one or both sides. Thus, a laminated body with a metal foil is manufactured.

成形條件可應用電氣絕緣材料用積層體或多層板的手法，例如可使用多層壓製、多層真空壓製、連續成形機、高壓釜成形機等，以溫度100℃～250℃左右、壓力2 MPa～100 MPa左右及加熱時間0.1小時～5小時左右的範圍成形。The forming conditions can be applied to laminated bodies or multilayer boards for electrical insulation materials. For example, multilayer pressing, multilayer vacuum pressing, continuous forming machines, autoclave forming machines, etc. can be used, at a temperature of about 100 ° C to 250 ° C and a pressure of 2 MPa to 100 Molding is performed in a range of about MPa and a heating time of about 0.1 to 5 hours.

（其他步驟） 於進行熱硬化處理或紫外線照射步驟後，視需要亦可進行於樹脂硬化物層及/或基材（玻璃基板等）形成過孔（via）的步驟。藉此，可於樹脂硬化物層等形成通孔、穿孔（through hole）等。通孔是為了實現層間的電連接而設，可考慮樹脂硬化物層的特性而藉由使用鑽、雷射、電漿等的公知的方法而形成。例如，於存在載體膜的情況下，可自載體膜上照射雷射光而於樹脂硬化物層形成通孔。(Other steps) After performing the heat curing treatment or the ultraviolet irradiation step, if necessary, a step of forming a via in the resin hardened material layer and / or the substrate (such as a glass substrate) may be performed. Thereby, a through hole, a through hole, etc. can be formed in a resin hardened | cured material layer etc. The through holes are provided for achieving electrical connection between the layers, and can be formed by a known method using a drill, a laser, a plasma, or the like in consideration of the characteristics of the resin hardened layer. For example, when a carrier film is present, laser light may be radiated from the carrier film to form a through hole in the resin hardened material layer.

作為雷射光源，可列舉：碳酸氣體雷射、釔鋁石榴石（Yttrium aluminium garnet，YAG）雷射、紫外線（Ultra Violet，UV）雷射、準分子雷射等。其中，就加工速度及成本優異的觀點而言，較佳為碳酸氣體雷射。Examples of the laser light source include a carbon dioxide gas laser, a yttrium aluminum garnet (YAG) laser, an ultraviolet (Ultra Violet) laser, and an excimer laser. Among them, a carbon dioxide gas laser is preferred from the viewpoint of excellent processing speed and cost.

沖孔加工可使用市售的雷射裝置而實施。作為市售的碳酸氣體雷射裝置，例如可列舉：維亞機械（Via Mechanics）股份有限公司製造的LC-2E21B/1C、三菱電機股份有限公司製造的ML605GTWII及松下（Panasonic）熔接系統股份有限公司製造的基板沖孔雷射加工機。The punching process can be performed using a commercially available laser device. Examples of commercially available carbon dioxide gas laser devices include LC-2E21B / 1C manufactured by Via Mechanics Co., Ltd., ML605GTWII manufactured by Mitsubishi Electric Corporation, and Panasonic Welding System Co., Ltd. Manufacturing of substrate punching laser processing machines.

於形成所述過孔的步驟後，視需要可使用氧化劑進行處理（除膠渣（desmear）處理步驟）。於除膠渣處理步驟中，例如過孔底部產生的膠渣得以去除。作為氧化劑，較佳為過錳酸鹽（過錳酸鉀、過錳酸鈉等）、重鉻酸鹽、臭氧、過氧化氫/硫酸、硝酸等，更佳為過錳酸鉀、過錳酸鈉等氫氧化鈉水溶液（鹼性過錳酸水溶液）。After the step of forming the via hole, an oxidizing agent may be used for processing (desmear processing step) if necessary. In the slag removal treatment step, for example, the slag generated at the bottom of the via hole is removed. As the oxidizing agent, permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, etc. are preferred, and potassium permanganate and permanganate are more preferred. An aqueous solution of sodium hydroxide such as sodium (aqueous solution of alkaline permanganic acid).

作為氧化劑，可使用氧化性粗化液。作為氧化性粗化液，可使用鉻/硫酸粗化液、鹼性過錳酸粗化液（過錳酸鈉粗化液等）、氟化鈉/鉻/硫酸粗化液、硼氟酸粗化液等。另外，於利用氧化性粗化液進行處理時，亦可於浸漬於溶媒或鹼液、或者該些的混合溶液（通常而言為膨潤液或預浸液）中後，利用氧化性粗化液進行處理。作為所述溶媒，可使用醇系溶媒（二乙二醇單甲醚、二乙二醇單丁醚、異丙基醇等）。另外，鹼液只要為於溶解於水時顯示鹼性的溶液即可，並無特別限制，可使用氫氧化鈉溶液、氫氧化鉀溶液等。進而，亦可將溶媒或鹼液混合，例如可使用包含氫氧化鈉及二乙二醇單丁醚的組成（例如，氫氧化鈉為3 g/L與二乙二醇單丁醚為300 mL/L的組成）者。As the oxidizing agent, an oxidizing roughening solution can be used. As the oxidizing roughening solution, chromium / sulfuric acid roughening solution, alkaline permanganic acid roughening solution (sodium permanganate roughening solution, etc.), sodium fluoride / chromium / sulfuric acid roughening solution, boron fluoride crude Chemical fluid, etc. In addition, when processing with an oxidizing roughening solution, the oxidizing roughening solution may be used after being immersed in a solvent, an alkali solution, or a mixed solution of these (usually a swelling solution or a prepreg solution). For processing. As the solvent, an alcohol-based solvent (diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, isopropyl alcohol, or the like) can be used. The lye is not particularly limited as long as it is a solution that shows alkalinity when dissolved in water, and a sodium hydroxide solution, a potassium hydroxide solution, or the like can be used. Furthermore, a solvent or an alkaline solution may be mixed, for example, a composition containing sodium hydroxide and diethylene glycol monobutyl ether (for example, 3 g / L of sodium hydroxide and 300 mL of diethylene glycol monobutyl ether) may be used. / L 的 组合） 者.

所述除膠渣處理步驟可於硬化步驟及紫外線照射步驟之間進行，亦可於紫外線照射步驟及導體層形成步驟（後述）之間進行。The dross removing treatment step may be performed between the hardening step and the ultraviolet irradiation step, or may be performed between the ultraviolet irradiation step and the conductor layer forming step (described later).

再者，於進行所述除膠渣處理步驟時，可為於樹脂硬化物層帶有載體膜的狀態。若為帶有載體膜的狀態，則可防止藉由粗化液而樹脂硬化物層的表面的凹凸變大，於樹脂硬化物層中可實現配線的進一步的微細化。即，若為藉由不進行除膠渣處理步驟、或者於樹脂硬化物層的表面帶有載體膜的狀態下進行除膠渣處理步驟等方法而使樹脂硬化物層的表面與粗化液不接觸的實施方式，則可容易防止樹脂硬化物層的表面的凹凸變大。In addition, when performing the said desmearing process, it can be in the state which carried the carrier film on the resin hardened | cured material layer. In the state with a carrier film, it is possible to prevent the unevenness of the surface of the resin hardened material layer from being increased by the roughening solution, and further refine the wiring in the resin hardened material layer. That is, the surface of the resin hardened material layer and the roughened solution are not changed by a method such as not performing a desmearing treatment step or performing a desizing treatment step with a carrier film on the surface of the resin hardened material layer. In the contact embodiment, it is possible to easily prevent the unevenness on the surface of the resin hardened material layer from increasing.

本實施方式的積層體亦可為包含多個積層體的多層積層體。所述多層積層體的製造方法並無特別限制。例如，可經由自已述的接著膜將支持體膜及保護膜去除而得的接著劑來將本實施方式的積層體積層多層而進行多層化。The laminated body of this embodiment may be a multilayer laminated body including a plurality of laminated bodies. The manufacturing method of the said multilayer laminated body is not specifically limited. For example, the laminated volume layer of this embodiment can be multilayered by using an adhesive obtained by removing the support film and the protective film from the adhesive film described above.

另外，亦可藉由將積層體重疊多枚（例如，2枚～20枚）並進行積層成形而製造多層積層體。具體而言，可使用多層壓製、多層真空壓製、連續成形機、高壓釜成形機等，以溫度100℃～250℃左右、壓力2 MPa～100 MPa左右及加熱時間0.1小時～5小時左右的範圍成形。In addition, a multilayered body can also be manufactured by stacking a plurality of laminated bodies (for example, 2 to 20 pieces) and forming a laminated body. Specifically, a multilayer press, a multilayer vacuum press, a continuous forming machine, an autoclave forming machine, and the like can be used at a temperature of about 100 ° C to 250 ° C, a pressure of about 2 MPa to 100 MPa, and a heating time of about 0.1 to 5 hours. Forming.

＜配線板的製造方法＞ 本實施方式的配線板（印刷配線板等）是於本實施方式的積層體的至少一面設置導體層（配線等）而成。本實施方式的配線板例如是於使用本實施方式的樹脂組成物而在基材上形成未硬化樹脂層後將其熱硬化，繼而照射紫外線並於所獲得的絕緣硬化樹脂層上利用鍍敷形成導體層而成。本實施方式的配線板亦可為包含多個積層體的構成（多層印刷配線板等）。<The manufacturing method of a wiring board> The wiring board (printed wiring board, etc.) of this embodiment is a thing provided with the conductor layer (wiring etc.) on at least one surface of the laminated body of this embodiment. The wiring board of the present embodiment is formed by, for example, using the resin composition of the present embodiment to form an uncured resin layer on a substrate, heat curing the uncured resin layer, and then irradiating ultraviolet rays to the obtained insulating hardened resin layer by plating. Conductor layer. The wiring board according to the present embodiment may have a configuration including a plurality of laminated bodies (multilayer printed wiring board, etc.).

其次，對本實施方式的配線板的製造方法進行說明。Next, the manufacturing method of the wiring board of this embodiment is demonstrated.

本實施方式的配線板的製造方法包括：（a）藉由本實施方式的積層體的製造方法而製造積層體的積層體形成步驟（使用至少包含（A）成分及（B）成分的樹脂組成物，於包含玻璃基板或矽晶圓的基材上形成樹脂組成物層而獲得積層體的步驟）；以及（b）於所述積層體（積層體的樹脂硬化物層上）形成導體層的導體層形成步驟。The manufacturing method of the wiring board of this embodiment includes (a) a laminated body forming step of manufacturing a laminated body by the laminated body manufacturing method of this embodiment (using a resin composition containing at least (A) component and (B) component A step of forming a laminated body by forming a resin composition layer on a substrate including a glass substrate or a silicon wafer; and (b) forming a conductor of the conductive layer on the laminated body (on the resin hardened layer of the laminated body) Layer formation step.

積層體形成步驟例如可包括：將樹脂組成物層熱硬化而形成樹脂硬化物層的熱硬化步驟；以及對樹脂硬化物層照射紫外線的紫外線照射步驟。導體層形成步驟例如包括：藉由無電解鍍敷而於樹脂硬化物層上形成作為第1導體層的鍍敷種子層的無電解鍍敷步驟；以及藉由電解鍍敷形成第2導體層而獲得電路層（包含第1導體層及第2導體層的層）的電解鍍敷步驟。The laminated body forming step may include, for example, a thermal curing step of thermally curing the resin composition layer to form a resin cured layer; and an ultraviolet irradiation step of irradiating the resin cured layer with ultraviolet rays. The conductor layer forming step includes, for example, an electroless plating step of forming a plating seed layer as a first conductor layer on a resin hardened layer by electroless plating, and forming a second conductor layer by electrolytic plating. An electrolytic plating step of obtaining a circuit layer (a layer including a first conductor layer and a second conductor layer).

電路層例如可藉由對樹脂硬化物層實施無電解鍍敷，其後實施電解鍍敷而獲得。該情況下，電路層包括藉由無電解鍍敷而獲得的鍍敷種子層（第1導體層）、以及藉由電解鍍敷而獲得的導體層（第2導體層）。鍍敷種子層與導體層（第2導體層）經一體化。The circuit layer can be obtained, for example, by performing electroless plating on the resin hardened material layer and then performing electrolytic plating. In this case, the circuit layer includes a plating seed layer (first conductor layer) obtained by electroless plating and a conductor layer (second conductor layer) obtained by electrolytic plating. The plating seed layer and the conductor layer (second conductor layer) are integrated.

電路層中使用的導體材料並無特別限定。例如電路層包含選自由金、鉑、鈀、銀、銅、鋁、鈷、鉻、鋅、鎳、鈦、鎢、鐵、錫及銦所組成的群組中的一種以上的金屬。電路層可為單金屬層，亦可為合金層。作為合金層，例如可列舉由選自由所述群組中的兩種以上的金屬的合金（例如鎳·鉻合金、銅·鎳合金及銅·鈦合金）而形成的層。The conductive material used in the circuit layer is not particularly limited. For example, the circuit layer includes one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The circuit layer may be a single metal layer or an alloy layer. Examples of the alloy layer include a layer formed of an alloy (for example, nickel · chrome alloy, copper · nickel alloy, and copper · titanium alloy) of two or more metals selected from the group.

電路層的厚度根據所需的配線板的設計而不同，通常較佳為3 μm～35 μm，更佳為5 μm～30 μm。The thickness of the circuit layer varies depending on the design of the required wiring board, and is generally preferably 3 μm to 35 μm, and more preferably 5 μm to 30 μm.

電路層可藉由鍍敷而形成。例如，可藉由減除法（subtractive method）、半加成法、全加成法（fully-additive method）等先前公知的技術於樹脂硬化物層的表面進行鍍敷而形成。The circuit layer may be formed by plating. For example, it can be formed by plating on the surface of a resin hardened | cured material layer by the conventionally well-known technique, such as a subtractive method, a semi-additive method, and a fully-additive method.

於在本實施方式的積層體的樹脂硬化物層上藉由鍍敷法進行電路加工的情況下，首先可進行粗化處理。作為該情況下的粗化液，可使用鉻/硫酸粗化液、鹼性過錳酸粗化液、氟化鈉/鉻/硫酸粗化液、硼氟酸粗化液等氧化性粗化液。作為粗化處理，例如首先，作為膨潤液，將包含二乙二醇單丁醚與NaOH的水溶液加溫為70℃並對積層體進行5分鐘浸漬處理。其次，作為粗化液，將KMnO₄ 與NaOH的水溶液加溫為80℃並進行10分鐘浸漬處理。繼而，於中和液（例如氯化亞錫（SnCl₂ ）的鹽酸水溶液）中在室溫下進行5分鐘浸漬處理並中和。When performing circuit processing by the plating method on the resin hardened | cured material layer of the laminated body of this embodiment, a roughening process can be performed first. As the roughening solution in this case, an oxidizing roughening solution such as a chromium / sulfuric acid roughening solution, an alkaline permanganic acid roughening solution, a sodium fluoride / chromium / sulfuric acid roughening solution, and a boron fluoride acid roughening solution can be used. . As the roughening treatment, for example, first, as the swelling liquid, an aqueous solution containing diethylene glycol monobutyl ether and NaOH is heated to 70 ° C., and the laminated body is immersed for 5 minutes. Next, as a roughening solution, an aqueous solution of KMnO ₄ and NaOH was heated to 80 ° C. and subjected to an immersion treatment for 10 minutes. Then, a neutralization solution (such as an aqueous solution of stannous chloride (SnCl ₂ ) in hydrochloric acid) is immersed at room temperature for 5 minutes and neutralized.

粗化處理後進行使鈀附著的鍍敷觸媒賦予處理。鍍敷觸媒賦予處理是藉由浸漬於氯化鈀系的鍍敷觸媒液中而進行。其次，藉由浸漬於無電解鍍敷液中，而進行使厚度0.3 μm～1.5 μm左右的無電解鍍敷層（導體層、鍍敷種子層）於鍍敷製程用樹脂硬化物層的整個表面析出的無電解鍍敷處理。無電解鍍敷處理中使用的無電解鍍敷液可使用公知的無電解鍍敷液，並無特別限制。無電解鍍敷較佳為無電解銅鍍敷。After the roughening treatment, a plating catalyst applying treatment for adhering palladium is performed. The plating catalyst applying treatment is performed by immersing in a palladium chloride-based plating catalyst liquid. Next, by immersing in an electroless plating solution, an electroless plating layer (conductor layer, plating seed layer) having a thickness of about 0.3 μm to 1.5 μm is performed on the entire surface of the resin hardened layer for the plating process. Precipitated electroless plating. The electroless plating solution used in the electroless plating treatment can be a known electroless plating solution, and is not particularly limited. The electroless plating is preferably electroless copper plating.

鍍敷種子層中使用的導體材料並無特別限定。例如，可列舉與可較佳地用於所述電路層的導體材料相同者。另外，鍍敷種子層的厚度亦無限定。鍍敷種子層的厚度例如可設為0.1 μm～2 μm。The conductive material used for the plating seed layer is not particularly limited. For example, the same thing as the conductor material which can be preferably used for the said circuit layer is mentioned. The thickness of the plating seed layer is also not limited. The thickness of the plating seed layer can be, for example, 0.1 μm to 2 μm.

其次，進行電解鍍敷處理而於所需部位形成所需厚度的電路。電解鍍敷處理可藉由公知的方法而進行，並無特別限制。電解鍍敷較佳為銅鍍敷。電路層例如可藉由半加成法、全加成法等先前公知的技術於樹脂硬化物層的表面進行鍍敷而形成。以下，示出藉由半加成法而形成電路層的例子。Next, an electrolytic plating process is performed to form a circuit of a desired thickness at a desired location. The electrolytic plating treatment can be performed by a known method, and is not particularly limited. The electrolytic plating is preferably copper plating. The circuit layer can be formed by, for example, plating the surface of the resin hardened material layer by a conventionally known technique such as a semi-additive method and a full-additive method. An example of forming a circuit layer by a semi-additive method is shown below.

於藉由無電解鍍敷步驟中進行的無電解鍍敷而形成於樹脂硬化物層的表面的鍍敷種子層上，形成與所需配線圖案對應且使鍍敷種子層的一部分露出的鍍敷抗蝕劑（遮罩圖案）。於露出的鍍敷種子層上藉由電解鍍敷而形成導體層後，去除鍍敷抗蝕劑。其後，可藉由蝕刻等去除不需要的鍍敷種子層而形成電路層。作為鍍敷抗蝕劑，可使用公知的鍍敷抗蝕劑，並無特別限制。於本實施方式的配線板的製造方法中，可形成表面平滑性優異的樹脂硬化物層，因此可藉由微細的配線圖案而於樹脂硬化物層上形成電路層。On the plating seed layer formed on the surface of the resin hardened layer by electroless plating in the electroless plating step, a plating corresponding to a desired wiring pattern and exposing a part of the plating seed layer is formed. Resist (mask pattern). After forming a conductor layer by electrolytic plating on the exposed plating seed layer, the plating resist is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a circuit layer. As a plating resist, a well-known plating resist can be used, and it does not specifically limit. In the method for manufacturing a wiring board according to this embodiment, since a resin hardened material layer having excellent surface smoothness can be formed, a circuit layer can be formed on the resin hardened layer by a fine wiring pattern.

亦可重複該些手法而製作多層配線板。為了製造多層配線板，可經由已述的接著劑來將所述形成導體層（配線圖案等）的多個積層體積層而進行多層化。其後，亦可進行利用鑽加工或者雷射加工的穿孔或盲通孔（blind via hole）的形成、以及利用鍍敷或導電性糊的層間配線的形成。如此，可製造多層印刷配線板。These methods may be repeated to produce a multilayer wiring board. In order to manufacture a multilayer wiring board, the plurality of laminated volume layers forming the conductor layer (wiring pattern, etc.) may be multilayered through the aforementioned adhesive. Thereafter, formation of perforations or blind via holes by drilling or laser processing, and formation of interlayer wiring by plating or conductive paste may be performed. In this way, a multilayer printed wiring board can be manufactured.

電路層與樹脂硬化物層的接著強度並無特別限定，較佳為0.6 kN/m以上，更佳為0.7 kN/m以上，進而佳為0.8 kN/m以上。接著強度的上限不受限定，例如可為10 kN/m以下。再者，接著強度為寬度10 mm、長度100 mm的片狀的樹脂硬化物層在垂直方向剝下約50 mm時的荷重的大小。The bonding strength of the circuit layer and the resin hardened material layer is not particularly limited, but is preferably 0.6 kN / m or more, more preferably 0.7 kN / m or more, and even more preferably 0.8 kN / m or more. The upper limit of the subsequent strength is not limited, and may be, for example, 10 kN / m or less. Further, the magnitude of the load when the sheet-like resin hardened material layer having a strength of 10 mm in width and 100 mm in length was peeled off approximately 50 mm in the vertical direction.

以上，對本發明的實施方式進行了說明，但該些為用以對本發明進行說明的例示，主旨並非為將本發明的範圍僅限定於該些實施方式。本發明可於不脫離其主旨的範圍內以與所述實施方式不同的各種態樣來實施。 [實施例]As mentioned above, although embodiment of this invention was described, these are illustrations for demonstrating this invention, It is not the intention to limit the scope of this invention to only these embodiment. The present invention can be implemented in various aspects different from the embodiment described above without departing from the spirit thereof. [Example]

其次，藉由實施例對本發明進行更詳細地說明，但本發明並不受該些例子的任何限定。Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples at all.

＜實施例1＞ （1）環氧樹脂（（A）成分）的製作 於安裝有溫度計及攪拌機的燒瓶中，裝入雙酚A 228 g（1.00莫耳）及1,6-己二醇二乙烯醚170 g（1.00莫耳），花1小時升溫至120℃後，於120℃下反應6小時而獲得398 g的透明半固體的改質多元酚類。<Example 1> (1) Preparation of epoxy resin (component (A)) A flask equipped with a thermometer and a stirrer was charged with 228 g (1.00 mol) of bisphenol A and 1,6-hexanediol di 170 g (1.00 mol) of vinyl ether was heated to 120 ° C for 1 hour, and then reacted at 120 ° C for 6 hours to obtain 398 g of a transparent semi-solid modified polyphenol.

其次，於安裝有溫度計、滴液漏斗、冷卻管及攪拌機的燒瓶中，裝入所述改質多元酚類398 g、表氯醇925 g（10莫耳）及正丁醇185 g並加以溶解。其後，一邊實施氮氣吹洗，一邊升溫至65℃後，減壓至進行共沸的壓力為止，花費5小時滴加49質量%氫氧化鈉水溶液122 g（1.5莫耳）。繼而，於該條件下繼續攪拌0.5小時。該期間，利用迪安-斯脫克分水器（Dean-Stark trap）將利用共沸而蒸餾出的蒸餾成分分離，去除水相，一邊使有機相返回至反應系統內一邊進行反應。其後，對未反應的表氯醇進行減壓蒸餾並蒸餾去除。於所獲得的粗糙環氧樹脂中加入甲基異丁基酮1000 g與正丁醇100 g並加以溶解。進而，於該溶液中添加10質量%氫氧化鈉水溶液20 g並於80℃下反應2小時後，重複進行3次水洗。繼而，藉由共沸將系統內脫水，經過精密過濾後，於減壓下將溶媒蒸餾去除，而獲得透明液體的環氧樹脂425 g。環氧當量為403。Next, a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer was charged with 398 g of the modified polyphenols, 925 g of epichlorohydrin (10 mol), and 185 g of n-butanol and dissolved. . Thereafter, the temperature was raised to 65 ° C. while purging with nitrogen, and the pressure was reduced to azeotropic pressure, and 122 g (1.5 mol) of a 49% by mass sodium hydroxide aqueous solution was added dropwise over 5 hours. Then, stirring was continued for 0.5 hours under these conditions. During this period, a Dean-Stark trap was used to separate the distillation component distilled by azeotropy, the water phase was removed, and the reaction was performed while returning the organic phase to the reaction system. Thereafter, the unreacted epichlorohydrin was distilled under reduced pressure and distilled off. 1000 g of methyl isobutyl ketone and 100 g of n-butanol were added to the obtained rough epoxy resin and dissolved. Further, 20 g of a 10% by mass sodium hydroxide aqueous solution was added to the solution, and the mixture was reacted at 80 ° C. for 2 hours, and then washed with water three times. Then, the inside of the system was dehydrated by azeotropy, and after precision filtration, the solvent was distilled off under reduced pressure to obtain 425 g of a transparent liquid epoxy resin. The epoxy equivalent was 403.

（2）樹脂組成物的製備 將所述（1）中製作的環氧樹脂（（A）成分）49質量份、含活性型酯基的樹脂「EXB-9460」（（B）成分，DIC股份有限公司製造，商品名，酯當量：223）14質量份及1-氰基乙基-2-苯基咪唑鎓偏苯三酸酯（（C）成分，四國化成工業股份有限公司製造，商品名「2PZ-CNS」）0.15質量份溶解於甲基乙基酮（MEK（Methyl Ethyl Ketone），溶媒）95質量份中而獲得樹脂組成物（清漆）。(2) Preparation of resin composition 49 parts by mass of the epoxy resin ((A) component) produced in the above (1), and active ester group-containing resin "EXB-9460" ((B) component, DIC Corporation) Co., Ltd. product name, ester equivalent: 223) 14 parts by mass and 1-cyanoethyl-2-phenylimidazolium trimellitic acid ester ((C) component, manufactured by Shikoku Chemical Industry Co., Ltd. The name "2PZ-CNS") was dissolved in 0.15 parts by mass of 95 parts by mass of methyl ethyl ketone (MEK (Methyl Ethyl Ketone), solvent) to obtain a resin composition (varnish).

（3）B階段樹脂層的形成、熱硬化及紫外線照射處理 利用押鐘有限公司製造的旋轉器「SC-308S」將所述（2）中獲得的樹脂組成物（清漆）塗敷（旋塗）於日本電器硝子股份有限公司製造的極薄玻璃基板「OA-10G」（商品名，厚度100 μm）（旋塗條件，1st：500 rpm-30秒，2nd：600 rpm-10秒）。藉由於100℃下進行10分鐘乾燥處理，而製作具有厚度4 μm的樹脂組成物層（B階段樹脂層）的帶有樹脂的玻璃基板。於170℃、60分鐘的硬化條件下對樹脂層進行熱硬化處理，繼而，使用傳送式紫外線照射裝置，利用金屬鹵化物燈（最大波長：350 nm～380 nm），以光量成為3000 mJ/cm² 的方式照射紫外線而獲得絕緣樹脂層。(3) Formation, thermal hardening, and ultraviolet irradiation treatment of the B-stage resin layer The resin composition (varnish) obtained in the above (2) was applied (spin-coated) using a spinner "SC-308S" manufactured by Oshika Corporation ) Very thin glass substrate "OA-10G" (trade name, thickness 100 μm) manufactured by Nippon Electric Glass Co., Ltd. (spin coating conditions, 1st: 500 rpm-30 seconds, 2nd: 600 rpm-10 seconds). The resin-containing glass substrate having a resin composition layer (B-stage resin layer) having a thickness of 4 μm was prepared by drying at 100 ° C. for 10 minutes. The resin layer was thermally cured at 170 ° C for 60 minutes. Then, a transmission type ultraviolet irradiation device was used, and a metal halide lamp (maximum wavelength: 350 nm to 380 nm) was used to achieve a light intensity of 3000 mJ / cm. The method of ² irradiates ultraviolet rays to obtain an insulating resin layer.

（4）無電解鍍敷處理及電解鍍敷處理 作為無電解鍍敷的前處理，將包含二乙二醇單丁醚：200 mL/L及NaOH：5 g/L的水溶液（膨潤液）加溫為80℃後，將所述（3）中所獲得的帶有絕緣樹脂層的基板於所述水溶液中進行5分鐘浸漬處理。其次，於60℃下將帶有絕緣樹脂層的基板於調理液「CLC-601」（日立化成股份有限公司製造，商品名）中浸漬5分鐘後，進行水洗，並於室溫下於預浸液「預浸新甘特（pre-dip Neogant）B」（日本安美特（Atotech）股份有限公司製造，商品名）中浸漬2分鐘。其次，於35℃下將帶有絕緣樹脂層的基板於作為無電解鍍敷用觸媒的「Activator Neogant 834」（日本安美特（Atotech）股份有限公司製造，商品名，鹼種（alkali seeder））中進行5分鐘浸漬處理後，進行水洗。繼而，於35℃下將帶有絕緣樹脂層的基板於作為無電解銅鍍敷液的「PrintGant MSK-DK鍍敷液」（日本安美特（Atotech）股份有限公司製造，商品名）中浸漬15分鐘，進而進行硫酸銅電解鍍敷。其後，於170℃下進行30分鐘的退火處理，於絕緣樹脂層的表面上形成厚度20 μm的鍍敷導體層。(4) Electroless plating treatment and electrolytic plating treatment As a pretreatment of electroless plating, an aqueous solution (swelling solution) containing diethylene glycol monobutyl ether: 200 mL / L and NaOH: 5 g / L is added. After the temperature was 80 ° C., the substrate with an insulating resin layer obtained in (3) was immersed in the aqueous solution for 5 minutes. Next, the substrate with an insulating resin layer was immersed in a conditioning liquid "CLC-601" (manufactured by Hitachi Chemical Co., Ltd., trade name) at 60 ° C for 5 minutes, then washed with water, and pre-dipped at room temperature. "Pre-dip Neogant B" (manufactured by Atotech Co., Ltd., trade name) in a liquid for 2 minutes. Next, the substrate with an insulating resin layer was applied to "Activator Neogant 834" (manufactured by Atotech Japan, trade name, alkali seeder) as a catalyst for electroless plating at 35 ° C. ) For 5 minutes, and then washed with water. Next, the substrate with an insulating resin layer was immersed in a "PrintGant MSK-DK plating solution" (manufactured by Japan Atotech Co., Ltd., trade name) as an electroless copper plating solution at 35 ° C. After that, copper sulfate electrolytic plating was performed. Thereafter, an annealing treatment was performed at 170 ° C. for 30 minutes to form a plated conductor layer having a thickness of 20 μm on the surface of the insulating resin layer.

（5）電路層的形成 為了對鍍敷導體層的不需要的部位進行蝕刻去除，首先利用#600的清輥器（buff roll）研磨將銅表面的氧化被膜去除。繼而，於形成蝕刻用抗蝕劑膜後進行蝕刻處理，其後，將蝕刻用抗蝕劑膜去除，藉此形成電路層。進而，為了進行多層化，將電路層的表面於包含亞氯酸鈉：50 g/L、NaOH：20 g/L及磷酸三鈉：10 g/L的水溶液中於85℃下浸漬20分鐘後，進行水洗，於80℃下進行20分鐘乾燥，而於電路層的表面上形成氧化銅的凹凸。(5) Formation of circuit layer In order to etch and remove unnecessary parts of the plated conductor layer, first, the oxide film on the copper surface was removed by buff roll grinding with # 600. Then, an etching process is performed after the etching resist film is formed, and thereafter, the etching resist film is removed to form a circuit layer. Furthermore, for the purpose of multilayering, the surface of the circuit layer was immersed in an aqueous solution containing sodium chlorite: 50 g / L, NaOH: 20 g / L, and trisodium phosphate: 10 g / L at 85 ° C for 20 minutes. , Washed with water, and dried at 80 ° C. for 20 minutes, thereby forming unevenness of copper oxide on the surface of the circuit layer.

（6）多層配線板的製作 重複所述（3）～（5）的步驟，而製作三層的多層配線板。再者，將形成於最外側的電路層稱為外層電路層（第3電路層）。(6) Production of multilayer wiring board Repeat the steps (3) to (5) to produce a three-layer multilayer wiring board. The circuit layer formed on the outermost side is referred to as an outer circuit layer (third circuit layer).

＜實施例2～實施例7、實施例11、實施例13及實施例14＞ 如表1及表2所示般變更樹脂組成物的組成，除此以外，與實施例1進行相同的操作，而製作各種多層配線板。<Example 2 to Example 7, Example 11, Example 13 and Example 14> Except that the composition of the resin composition was changed as shown in Tables 1 and 2, the same operation was performed as in Example 1, Various multilayer wiring boards are produced.

＜實施例8＞ 如表2所示般，使用加入作為無機填料的平均粒徑0.5 μm的球狀二氧化矽「SO-25R」（亞都瑪科技（Admatechs）股份有限公司製造，商品名）的樹脂組成物，將溶媒的量變更為151質量份，除此以外，與實施例1進行相同的操作，而製作多層配線板。<Example 8> As shown in Table 2, spherical silica "SO-25R" (manufactured by Admatechs Co., Ltd., trade name) with an average particle diameter of 0.5 μm as an inorganic filler was used. Except for changing the amount of the solvent to 151 parts by mass of the resin composition, the same operation as in Example 1 was performed to produce a multilayer wiring board.

＜實施例9＞ 使用與實施例1相同的樹脂組成物，利用與實施例1相同的方法，進行自B階段樹脂層的形成至熱硬化為止。其次，於所述帶有絕緣樹脂層的基板藉由日立維亞機械（Hitachi Via Mechanics）製造的CO₂ 雷射加工機「LCO-1B21型」，於光束直徑80 μm、頻率500 Hz、脈衝寬度5 μsec、發射數7的條件下對層間連接用通孔進行加工。其後，使用燈為金屬鹵化物燈的傳送式紫外線照射裝置（最大波長：350 nm～380 nm），以光量成為3000 mJ/cm² 的方式對帶有絕緣樹脂層的基板進行紫外線照射。<Example 9> The same resin composition as in Example 1 was used to perform the process from the formation of the B-stage resin layer to the thermosetting by the same method as in Example 1. Next, on the substrate with an insulating resin layer, a CO ₂ laser processing machine "LCO-1B21" manufactured by Hitachi Via Mechanics was used, with a beam diameter of 80 μm, a frequency of 500 Hz, and a pulse width. The through-hole for interlayer connection was processed under the conditions of 5 μsec and the number of shots of 7. Thereafter, the substrate with an insulating resin layer was irradiated with ultraviolet rays using a transmission type ultraviolet irradiation device (maximum wavelength: 350 nm to 380 nm) whose lamp was a metal halide lamp so that the light amount became 3000 mJ / cm ² .

其次，為了對絕緣樹脂層進行化學粗化，將包含二乙二醇單丁醚：200 mL/L及NaOH：5 g/L的水溶液（膨潤液）加溫為80℃後，於其中對帶有絕緣樹脂層的基板進行5分鐘浸漬處理。其次，將包含KMnO₄ ：60 g/L及NaOH：40 g/L的水溶液（粗化液）加溫為80℃並於所述水溶液中對帶有絕緣樹脂層的基板進行10分鐘浸漬處理。繼而，於室溫下於作為中和液（SnCl₂ ：30 g/L，濃度98質量%的H₂ SO₄ ：300 mL/L）的水溶液中對帶有絕緣樹脂層的基板進行5分鐘浸漬處理並中和。其後，與實施例1進行相同的操作而製作多層配線板。Next, in order to chemically roughen the insulating resin layer, an aqueous solution (swelling solution) containing diethylene glycol monobutyl ether: 200 mL / L and NaOH: 5 g / L was heated to 80 ° C, and then the tape was applied thereto. The substrate with the insulating resin layer was immersed for 5 minutes. Next, an aqueous solution (roughened solution) containing KMnO ₄ : 60 g / L and NaOH: 40 g / L was heated to 80 ° C., and the substrate with an insulating resin layer was immersed in the aqueous solution for 10 minutes. Then, the substrate with an insulating resin layer was immersed in an aqueous solution as a neutralizing solution (SnCl ₂ : 30 g / L, H ₂ SO ₄ : 98 mL / L concentration: 300 mL / L) at room temperature for 5 minutes. Process and neutralize. Thereafter, the same operation as in Example 1 was performed to produce a multilayer wiring board.

＜實施例10＞ 將紫外線照射燈變更為高壓水銀燈的傳送式紫外線照射裝置（最大波長：310 nm～370 nm），除此以外，與實施例1進行相同的操作而製作多層配線板。再者，紫外線的照射是與實施例1同樣地，以光量成為3000 mJ/cm² 的方式進行。<Example 10> A multilayer wiring board was produced in the same manner as in Example 1 except that the transmission type ultraviolet irradiation device (maximum wavelength: 310 nm to 370 nm) was changed to a high-pressure mercury lamp. Incidentally, the irradiation of ultraviolet rays was performed in the same manner as in Example 1 so that the light amount became 3000 mJ / cm ² .

＜實施例12＞ 利用溶媒對實施例1的樹脂組成物進而進行稀釋而製作清漆。其次，利用押鐘（有）製造的旋轉器「SC-308S」將清漆塗敷（旋塗）於日本電器硝子股份有限公司製造的極薄玻璃基板「OA-10G」（商品名，厚度100 μm）（旋塗條件，1st：1000 rpm-10秒，2nd：1600 rpm-20秒，3rd：1800 rpm-5秒）。藉由於100℃下進行10分鐘乾燥處理，而製作具有厚度1 μm的樹脂組成物層（B階段樹脂層）的帶有樹脂的玻璃基板。除此以外，與實施1進行相同的操作，而製作多層配線板。<Example 12> The resin composition of Example 1 was further diluted with a solvent to prepare a varnish. Next, the varnish was applied (spin-coated) to the ultra-thin glass substrate "OA-10G" (trade name, thickness 100 μm) manufactured by Nippon Electric Glass Co., Ltd. using a spinner "SC-308S" manufactured by Awaji (with). ) (Spin coating conditions, 1st: 1000 rpm-10 seconds, 2nd: 1600 rpm-20 seconds, 3rd: 1800 rpm-5 seconds). The resin-containing glass substrate having a resin composition layer (B-stage resin layer) having a thickness of 1 μm was prepared by drying at 100 ° C. for 10 minutes. Other than that, the same operation as in Example 1 was performed to produce a multilayer wiring board.

＜比較例1＞ 將樹脂組成物的組成變更為表3的組成（不使用含活性型酯基的化合物的組成），除此以外，與實施例1進行相同的操作，而製作多層配線板。<Comparative Example 1> A multilayer wiring board was produced in the same manner as in Example 1 except that the composition of the resin composition was changed to the composition in Table 3 (a composition in which an active ester group-containing compound was not used).

＜比較例2＞ 將樹脂組成物的組成變更為表3的組成（使用作為不具有源自烷二醇的結構單元的環氧樹脂的苯酚酚醛清漆環氧樹脂（「N-770」，DIC股份有限公司製造，商品名，羥基當量：190）來作為（A）成分的組成），除此以外，與實施例1進行相同的操作，而製作多層配線板。<Comparative Example 2> The composition of the resin composition was changed to the composition of Table 3 (a phenol novolak epoxy resin ("N-770", DIC Corporation) was used as the epoxy resin having no structural unit derived from an alkanediol. Co., Ltd., trade name, hydroxyl equivalent weight: 190) as the composition of the component (A)), except that the same operation as in Example 1 was performed to produce a multilayer wiring board.

＜比較例3＞ 將樹脂組成物的組成變更為表3的組成（不使用含活性型酯基的化合物而使用苯酚酚醛清漆型樹脂（「TD-2131」，DIC股份有限公司製造，商品名，羥基當量：105）來作為（B）成分的組成），除此以外，與實施例1進行相同的操作，而製作多層配線板。<Comparative Example 3> The composition of the resin composition was changed to the composition of Table 3 (a phenol novolac resin was used instead of a compound containing an active ester group ("TD-2131", manufactured by DIC Corporation, trade name, A hydroxyl equivalent: 105) was used as the composition of the component (B)), and the same operation as in Example 1 was performed to prepare a multilayer wiring board.

＜比較例4＞ 使用玻璃布質地環氧樹脂兩面敷銅積層板（不含玻璃基板的基材，日立化成股份有限公司製造，商品名「MCL-E679F」）來代替極薄玻璃基板，除此以外，與實施例12進行相同的操作，而製作多層配線板。〈Comparative example 4〉 Instead of an ultra-thin glass substrate, a glass cloth-based epoxy double-sided copper-clad laminate (a substrate without a glass substrate, manufactured by Hitachi Chemical Co., Ltd. under the trade name "MCL-E679F") was used. Other than that, the same operation as in Example 12 was performed to produce a multilayer wiring board.

＜評價方法＞ 各實施例及比較例的評價是藉由以下所示的方法來進行。<Evaluation method> Evaluation of each Example and a comparative example was performed by the method shown below.

（1）與外層電路層的接著強度（90度剝離，單位：kN/m） 於外層電路層的一部分形成寬度10 mm、長度100 mm的部分，將其一端剝下並利用夾具夾住，於室溫中，於垂直方向剝下約50 mm，測定此時的荷重。(1) Adhesion to the outer circuit layer (90 ° peel, unit: kN / m) A part of the outer circuit layer is formed with a width of 10 mm and a length of 100 mm. One end is peeled off and clamped with a clamp. At room temperature, peel off about 50 mm in the vertical direction, and measure the load at this time.

（2）鍍敷銅蝕刻去除面的絕緣樹脂層粗糙度（表面平均粗糙度，單位：μm） 製作對外層電路層進行蝕刻處理而去除銅的試驗片。將所述試驗片切斷為2 mm見方左右，使用基恩斯（Keyencec）股份有限公司製造的超深度形狀測定顯微鏡「VK-8500型」，於測定長度149 μm、倍率2000倍、分解能力0.05 μm的條件下，對試驗片中的不同的三個部位進行測定，將自測定長度149 μm中的粗糙度最大的部位減去最小的部位所得的值設為絕緣樹脂層的表面粗糙度（Ra），並算出三個部位的平均值。(2) Roughness of the insulating resin layer (surface average roughness, unit: μm) on the surface where copper plating is removed by etching. A test piece was prepared by etching the outer circuit layer to remove copper. The test piece was cut to a size of about 2 mm square, and an ultra-depth shape measuring microscope "VK-8500" manufactured by Keyencec Co., Ltd. was used to measure a length of 149 μm, a magnification of 2000 times, and a resolution of 0.05 μm. Under the conditions, the three different parts of the test piece were measured, and the value obtained by subtracting the smallest part from the most rough part in the measurement length of 149 μm was set as the surface roughness (Ra) of the insulating resin layer. And calculate the average of the three parts.

（3）焊料耐熱性 將多層配線板切斷為25 mm見方，之後立刻將其漂浮於調整為288℃±2℃的焊料浴中，調查直至產生氣泡的時間（單位：秒）。(3) Solder heat resistance After cutting the multilayer wiring board to 25 mm square, immediately float it in a solder bath adjusted to 288 ° C ± 2 ° C and investigate the time (unit: second) until the generation of air bubbles.

將樹脂組成物的組成、樹脂組成物層的厚度及評價結果示於表1～表3中。於比較例4中，產生塗敷不均，表面粗糙度相較於實施例及其他比較例而言亦顯著大。Table 1 to Table 3 show the composition of the resin composition, the thickness of the resin composition layer, and the evaluation results. In Comparative Example 4, coating unevenness occurred, and the surface roughness was also significantly larger than that of the examples and other comparative examples.

表中的各成分的詳情如下所述。 A1：於骨架中具有己二醇的環氧樹脂（利用實施例1（1）製作。具有源自己二醇的結構單元的環氧樹脂。具有式（I）所表示的結構單元及式（II）所表示的結構單元的環氧樹脂） A2：苯酚酚醛清漆型環氧樹脂，「N-770」（DIC股份有限公司製造，商品名，比較成分） B1：含活性型酯基的化合物，「EXB-9460」（DIC股份有限公司製造，商品名，酯當量：223） C1：硬化促進劑、咪唑衍生物化合物、1-氰基乙基-2-苯基咪唑鎓偏苯三酸酯（四國化成工業股份有限公司製造，商品名「2PZ-CNS」） C2：硬化促進劑（三苯基膦） D1：甲酚酚醛清漆型苯酚樹脂，「KA-1165」（DIC股份有限公司製造，商品名，比較成分） D2：苯酚酚醛清漆型樹脂，「TD-2131」（DIC股份有限公司製造，商品名，比較成分） E1：甲基乙基酮（MEK） F1：無機填料，平均粒徑0.5 μm的球狀二氧化矽，「SO-25R」（亞都瑪科技（Admatechs）股份有限公司製造，商品名） F2：無機填料，二氧化矽填料，「AEROSIL R972」（日本艾羅西爾（Aerosil）股份有限公司製造，商品名，比表面積：110±20 m² /g）The details of each component in the table are as follows. A1: An epoxy resin having hexanediol in the skeleton (made by Example 1 (1). An epoxy resin having a structural unit derived from its own diol. It has a structural unit represented by formula (I) and formula (II) Epoxy resin of the structural unit represented by A) A2: Phenolic novolac epoxy resin, "N-770" (manufactured by DIC Corporation, trade name, comparative component) B1: compound containing active ester group, " EXB-9460 "(manufactured by DIC Corporation, trade name, ester equivalent: 223) C1: hardening accelerator, imidazole derivative compound, 1-cyanoethyl-2-phenylimidazolium trimellitate (four Manufactured by National Chemical Industry Co., Ltd., trade name "2PZ-CNS") C2: Hardening accelerator (triphenylphosphine) D1: Cresol novolac phenol resin, "KA-1165" (manufactured by DIC Corporation, product (Name, comparative component) D2: phenol novolac resin, "TD-2131" (manufactured by DIC Corporation, trade name, comparative component) E1: methyl ethyl ketone (MEK) F1: inorganic filler, average particle size 0.5 μm spherical silica, "SO-25R (Made by Admatechs Co., Ltd., trade name) F2: inorganic filler, silica filler, "AEROSIL R972" (manufactured by Japan Aerosil Co., Ltd., trade name, specific surface area: 110 ± 20 m ² / g)

[表1] [Table 1]

[表2] [Table 2]

[表3] [table 3]

根據表1及表2可知，於實施例的配線板中，即便絕緣樹脂層的表面粗糙度為小的狀態，與外層銅的接著強度亦良好，適合於微細配線化。另外，即便於1 μm的薄膜品（實施例12）中，亦可將絕緣樹脂層製膜。另外，可知288℃下的焊料耐熱性亦優異，無鉛焊料安裝亦優異。 [產業上之可利用性]As can be seen from Tables 1 and 2, in the wiring boards of the examples, even if the surface roughness of the insulating resin layer is small, the bonding strength with the outer layer copper is good, which is suitable for fine wiring. In addition, even in a 1 μm thin film product (Example 12), an insulating resin layer can be formed into a film. In addition, it is found that the solder has excellent heat resistance at 288 ° C, and it is also excellent in lead-free solder mounting. [Industrial availability]

根據本發明，即便為絕緣樹脂層的表面的凹凸形狀小的狀態，亦可表現出對導體層的高接著力，而且即便為了去除通孔底的膠渣而利用過錳酸鈉系等的粗化液進行處理，絕緣樹脂層的表面的粗化凹凸形狀亦小，且可確保對導體層的高接著力。另外，即便於1 μm的薄膜品中亦可製膜。According to the present invention, even in a state where the uneven shape of the surface of the insulating resin layer is small, a high adhesion force to the conductor layer can be exhibited. In addition, even in order to remove the slag at the bottom of the through hole, a rough material such as sodium permanganate is used The treatment with the chemical solution can also reduce the rough unevenness of the surface of the insulating resin layer, and can ensure high adhesion to the conductor layer. In addition, it is possible to form a film even in a thin film product of 1 μm.

使用本發明的樹脂組成物而製作的配線板與導體層的接著強度良好，且焊料耐熱性亦優異。The bonding strength between the wiring board and the conductor layer produced using the resin composition of the present invention is good, and the solder heat resistance is also excellent.

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Claims (10)

一種積層體的製造方法，包括在基材上形成樹脂組成物層而獲得積層體的步驟， 所述基材包含玻璃基板或矽晶圓， 所述樹脂組成物層的厚度為10 μm以下， 所述樹脂組成物層含有具有源自碳數3以上的烷二醇的結構單元的環氧樹脂、及含酯基的化合物。A method for manufacturing a laminated body includes the step of obtaining a laminated body by forming a resin composition layer on a substrate, the substrate includes a glass substrate or a silicon wafer, and the thickness of the resin composition layer is 10 μm or less. The resin composition layer contains an epoxy resin having a structural unit derived from an alkanediol having 3 or more carbon atoms, and an ester group-containing compound. 如申請專利範圍第1項所述的積層體的製造方法，其中所述碳數3以上的烷二醇為己二醇。The method for producing a laminated body according to item 1 of the scope of patent application, wherein the alkanediol having a carbon number of 3 or more is hexanediol. 如申請專利範圍第1項或第2項所述的積層體的製造方法，其中相對於所述環氧樹脂的環氧基1當量，所述含酯基的化合物的酯當量為0.3當量～1.5當量。The method for manufacturing a laminated body according to item 1 or item 2 of the patent application scope, wherein the ester equivalent of the ester group-containing compound is 0.3 equivalent to 1.5 with respect to 1 equivalent of the epoxy group of the epoxy resin. equivalent. 如申請專利範圍第1項至第3項中任一項所述的積層體的製造方法，其中所述玻璃基板的厚度為200 μm以下。The method for manufacturing a laminated body according to any one of claims 1 to 3, wherein the thickness of the glass substrate is 200 μm or less. 如申請專利範圍第1項至第4項中任一項所述的積層體的製造方法，其中藉由旋塗法而形成所述樹脂組成物層。The method for manufacturing a laminated body according to any one of claims 1 to 4 of the scope of patent application, wherein the resin composition layer is formed by a spin coating method. 如申請專利範圍第1項至第5項中任一項所述的積層體的製造方法，其進而包括將所述樹脂組成物層熱硬化而形成樹脂硬化物層的步驟。The method for manufacturing a laminated body according to any one of claims 1 to 5, further comprising a step of thermally curing the resin composition layer to form a resin cured material layer. 如申請專利範圍第6項所述的積層體的製造方法，其進而包括對所述樹脂硬化物層照射紫外線的步驟。The method for manufacturing a laminated body according to item 6 of the scope of patent application, further comprising the step of irradiating the resin hardened material layer with ultraviolet rays. 如申請專利範圍第7項所述的積層體的製造方法，其中使用最大波長300 nm～450 nm的紫外線燈，於大氣壓環境下照射所述紫外線。The method for manufacturing a laminated body according to item 7 of the scope of application for a patent, wherein an ultraviolet lamp with a maximum wavelength of 300 nm to 450 nm is used, and the ultraviolet rays are irradiated in an atmospheric pressure environment. 如申請專利範圍第6項至第8項中任一項所述的積層體的製造方法，其中所述樹脂硬化物層的表面粗糙度（Ra）為0.2 μm以下。The method for manufacturing a laminated body according to any one of claims 6 to 8 in the scope of the patent application, wherein the surface roughness (Ra) of the resin hardened material layer is 0.2 μm or less. 一種配線板的製造方法，包括： 藉由如申請專利範圍第6項至第9項中任一項所述的積層體的製造方法而製造積層體的步驟；以及 於所述積層體形成導體層的步驟。A manufacturing method of a wiring board, comprising: a step of manufacturing a laminated body by the manufacturing method of a laminated body according to any one of claims 6 to 9 of a patent application scope; and forming a conductor layer on the laminated body A step of.