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TW202419503A - Resin composition - Google Patents

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TW202419503A
TW202419503A TW112134888A TW112134888A TW202419503A TW 202419503 A TW202419503 A TW 202419503A TW 112134888 A TW112134888 A TW 112134888A TW 112134888 A TW112134888 A TW 112134888A TW 202419503 A TW202419503 A TW 202419503A
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resin composition
resin
mass
inorganic filler
manufactured
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渡邊真俊
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日商味之素股份有限公司
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    • C08L101/00—Compositions of unspecified macromolecular compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
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    • C—CHEMISTRY; METALLURGY
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    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
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    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

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Abstract

本發明提供可形成衝擊性優異的絕緣層的樹脂組成物。一種樹脂組成物，其是包含(A)硬化性樹脂和(B)無機填充材料的樹脂組成物，將樹脂組成物硬化而得到的硬化物的比重為1.6g/cm 3以下，將樹脂組成物硬化而得到的硬化物的熱膨脹係數為40ppm/℃以下。 The present invention provides a resin composition capable of forming an insulating layer with excellent impact resistance. A resin composition comprising (A) a curable resin and (B) an inorganic filler, wherein the specific gravity of the cured product obtained by curing the resin composition is 1.6 g/cm 3 or less, and the thermal expansion coefficient of the cured product obtained by curing the resin composition is 40 ppm/°C or less.

Description

樹脂組成物Resin composition

本發明係關於樹脂組成物。The present invention relates to a resin composition.

作為印刷配線板的製造技術，已知基於將絕緣層和導體層交替堆積的積層(build-up)方式的製造方法。在基於積層方式的製造方法中，通常，絕緣層由使樹脂組成物硬化而成的硬化物形成(專利文獻1)。 [先前技術文獻] [專利文獻] As a manufacturing technology for printed wiring boards, a manufacturing method based on a build-up method in which insulating layers and conductive layers are alternately stacked is known. In a manufacturing method based on a build-up method, the insulating layer is usually formed of a cured product obtained by curing a resin composition (Patent Document 1). [Prior Technical Document] [Patent Document]

專利文獻1：日本特開2020-23714號公報。Patent document 1: Japanese Patent Application Publication No. 2020-23714.

[發明欲解決之課題][Problems to be solved by the invention]

在設置有印刷配線板的半導體裝置中，包括智慧型手機等行動裝置。這些行動裝置經常受到衝擊。例如，行動裝置在使用時有時會意外地掉落，因此，有時會受到由落下引起的衝擊。當受到衝擊時，在印刷配線板中，有可能絕緣層與導電層剝離，或者在絕緣層上形成裂紋。因此，要求開發可形成耐衝擊性優異的絕緣層的樹脂組成物。Among semiconductor devices equipped with printed wiring boards, there are mobile devices such as smartphones. These mobile devices are often subjected to shocks. For example, mobile devices may accidentally fall while in use, and therefore may be subjected to shocks caused by the fall. When subjected to shocks, in the printed wiring board, there is a possibility that the insulating layer and the conductive layer may be separated, or cracks may be formed on the insulating layer. Therefore, it is required to develop a resin composition that can form an insulating layer with excellent shock resistance.

本發明是鑒於上述課題而提出的發明，其目的在於提供：可形成耐衝擊性優異的絕緣層的樹脂組成物；該樹脂組成物的硬化物；含有該樹脂組成物的片狀層合材料；具有由該樹脂組成物形成的樹脂組成物層的樹脂片；具備包含該樹脂組成物的硬化物的絕緣層的印刷配線板；以及具備該印刷配線板的半導體裝置。 [用以解決課題之手段] The present invention is proposed in view of the above-mentioned problems, and its purpose is to provide: a resin composition capable of forming an insulating layer with excellent impact resistance; a cured product of the resin composition; a sheet-like laminate containing the resin composition; a resin sheet having a resin composition layer formed of the resin composition; a printed wiring board having an insulating layer containing a cured product of the resin composition; and a semiconductor device having the printed wiring board. [Means for Solving the Problem]

本發明人為了解決上述的課題而進行了深入研究。其結果，本發明人發現：通過適當地調整包含(A)硬化性樹脂和(B)無機填充材料的樹脂組成物的組成，可解決上述的課題，從而完成了本發明。 即，本發明包含以下的內容。 The inventors of the present invention have conducted in-depth research to solve the above-mentioned problems. As a result, the inventors of the present invention have found that the above-mentioned problems can be solved by appropriately adjusting the composition of the resin composition containing (A) a hardening resin and (B) an inorganic filler, thereby completing the present invention. That is, the present invention includes the following contents.

[1] 一種樹脂組成物，其是包含(A)硬化性樹脂和(B)無機填充材料的樹脂組成物， 將樹脂組成物硬化而得到的硬化物的比重為1.6g/cm 3以下， 將樹脂組成物硬化而得到的硬化物的熱膨脹係數為40ppm/℃以下。 [2] [1]之樹脂組成物，其中，(B)無機填充材料的平均粒徑為0.01μm以上且5μm以下。 [3] [1]或[2]之樹脂組成物，其中，(B)無機填充材料的BET比表面積為1m 2/g以上且100m 2/g以下。 [4] [1]～[3]中任一項之樹脂組成物，其中，(B)無機填充材料包含內部具有空孔的(B-1)中空無機填充材料。 [5] [4]之樹脂組成物，其中，(B-1)中空無機填充材料具有10體積%以上的空孔率。 [6] [1]～[5]中任一項之樹脂組成物，其進一步包含(C)有機粒子。 [7] [6]之樹脂組成物，其中，相對於100質量%樹脂組成物的非揮發成分，(C)有機粒子的量為2質量%以上。 [8] [6]或[7]之樹脂組成物，其中，(C)有機粒子具備：殼部和形成於殼部內的內置部， 內置部包含橡膠成分、或為中空部。 [9] [1]～[8]中任一項之樹脂組成物，其中，(A)硬化性樹脂選自熱硬化性樹脂和光硬化性樹脂。 [10] [9]之樹脂組成物，其中，熱硬化性樹脂包含選自下述的至少一種：環氧樹脂、酚醛樹脂、活性酯樹脂、氰酸酯樹脂和自由基聚合性樹脂。 [11] [9]或[10]之樹脂組成物，其中，光硬化性樹脂包含自由基聚合性樹脂。 [12] 一種樹脂組成物，其是包含(A)硬化性樹脂、(B)無機填充材料和(C)有機粒子的樹脂組成物， (B)無機填充材料包含內部具有空孔的(B-1)中空無機填充材料， (B-1)中空無機填充材料具有10體積%以上的空孔率， 相對於100體積%樹脂組成物的非揮發成分，(B)無機填充材料的量為40體積%以上， 相對於100體積%樹脂組成物的非揮發成分，(B-1)中空無機填充材料的量為10體積%以上。 [13] [1]～[12]中任一項之樹脂組成物，其用於形成絕緣層。 [14] 一種[1]～[13]中任一項之樹脂組成物的硬化物。 [15] 一種片狀層合材料，其含有[1]～[13]中任一項之樹脂組成物。 [16] 一種樹脂片，其具有：支撐體和在該支撐體上由[1]～[13]中任一項之樹脂組成物形成的樹脂組成物層。 [17] 一種印刷配線板，其具備絕緣層，所述絕緣層包含[1]～[13]中任一項之樹脂組成物的硬化物。 [18] 一種半導體裝置，其具備[17]之印刷配線板。 [發明之效果] [1] A resin composition comprising (A) a curable resin and (B) an inorganic filler, wherein the specific gravity of a cured product obtained by curing the resin composition is 1.6 g/cm 3 or less, and the thermal expansion coefficient of the cured product obtained by curing the resin composition is 40 ppm/°C or less. [2] The resin composition of [1], wherein the average particle size of the inorganic filler (B) is 0.01 μm or more and 5 μm or less. [3] The resin composition of [1] or [2], wherein the BET specific surface area of the inorganic filler (B) is 1 m 2 /g or more and 100 m 2 /g or less. [4] The resin composition of any one of [1] to [3], wherein the inorganic filler (B) comprises a hollow inorganic filler (B-1) having pores therein. [5] The resin composition of [4], wherein the (B-1) hollow inorganic filler has a porosity of 10 volume % or more. [6] The resin composition of any one of [1] to [5], further comprising (C) organic particles. [7] The resin composition of [6], wherein the amount of (C) organic particles is 2 mass % or more relative to 100 mass % of the non-volatile components of the resin composition. [8] The resin composition of [6] or [7], wherein the (C) organic particles have: a shell and an inner portion formed in the shell, the inner portion containing a rubber component or being a hollow portion. [9] The resin composition of any one of [1] to [8], wherein the (A) curable resin is selected from a thermosetting resin and a photocurable resin. [10] The resin composition of [9], wherein the thermosetting resin comprises at least one selected from the group consisting of epoxy resin, phenolic resin, active ester resin, cyanate resin and free radical polymerizable resin. [11] The resin composition of [9] or [10], wherein the photocurable resin comprises a free radical polymerizable resin. [12] A resin composition comprising (A) a curable resin, (B) an inorganic filler and (C) organic particles, wherein the (B) inorganic filler comprises a (B-1) hollow inorganic filler having pores therein, the (B-1) hollow inorganic filler having a porosity of 10% by volume or more, the amount of the (B) inorganic filler relative to 100% by volume of the non-volatile components of the resin composition is 40% by volume or more, and the amount of the (B-1) hollow inorganic filler relative to 100% by volume of the non-volatile components of the resin composition is 10% by volume or more. [13] The resin composition of any one of [1] to [12], which is used to form an insulating layer. [14] A cured product of a resin composition of any one of [1] to [13]. [15] A sheet-like laminate material comprising a resin composition of any one of [1] to [13]. [16] A resin sheet comprising: a support and a resin composition layer formed on the support from a resin composition of any one of [1] to [13]. [17] A printed wiring board having an insulating layer, wherein the insulating layer comprises a cured product of a resin composition of any one of [1] to [13]. [18] A semiconductor device having the printed wiring board of [17]. [Effect of the Invention]

根據本發明，可提供：可形成耐衝擊性優異的絕緣層的樹脂組成物；該樹脂組成物的硬化物；含有該樹脂組成物的片狀層合材料；具有由該樹脂組成物形成的樹脂組成物層的樹脂片；具備包含該樹脂組成物的硬化物的絕緣層的印刷配線板；以及具備該印刷配線板的半導體裝置。According to the present invention, there can be provided: a resin composition capable of forming an insulating layer having excellent impact resistance; a cured product of the resin composition; a sheet-like laminate material containing the resin composition; a resin sheet having a resin composition layer formed of the resin composition; a printed wiring board having an insulating layer including a cured product of the resin composition; and a semiconductor device having the printed wiring board.

以下，給出實施方式和例示物對本發明進行說明。然而，本發明不限定於下述所示的實施方式和例示物，可在不超出申請專利範圍及其等同範圍的範圍內任意地進行變更來實施。The present invention is described below by way of embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and can be implemented with modifications as desired within the scope of the claims and their equivalents.

在以下的說明中，術語「(甲基)丙烯酸」包括丙烯酸、甲基丙烯酸及其組合。另外，術語「(甲基)丙烯酸酯」包括丙烯酸酯、甲基丙烯酸酯及其組合。而且，術語「(甲基)丙烯腈」包括丙烯腈、甲基丙烯腈及其組合。In the following description, the term "(meth)acrylic acid" includes acrylic acid, methacrylic acid, and combinations thereof. In addition, the term "(meth)acrylate" includes acrylate, methacrylate, and combinations thereof. Furthermore, the term "(meth)acrylonitrile" includes acrylonitrile, methacrylonitrile, and combinations thereof.

[1. 第一實施方式所涉及的樹脂組成物的概要] 對於本發明的第一實施方式所涉及的樹脂組成物而言，組合地包含(A)硬化性樹脂和(B)無機填充材料。另外，將該樹脂組成物硬化而得到的硬化物具有特定範圍的比重。而且，將該樹脂組成物硬化而得到的硬化物具有特定範圍的熱膨脹係數。根據滿足這樣的要件的樹脂組成物，可形成耐衝擊性優異的絕緣層。因此，包含本發明的第一實施方式所涉及的樹脂組成物的硬化物的絕緣層在受到衝擊時，可抑制絕緣層與導電層的剝離，而且可抑制在絕緣層上形成裂紋。在以下的說明中，有時將在受到衝擊時可抑制絕緣層與導電層的剝離的性質稱為「抗衝擊剝離性」，另外，有時將在受到衝擊時可抑制裂紋的性質稱為「抗衝擊裂紋性」。 [1. Overview of the resin composition involved in the first embodiment] The resin composition involved in the first embodiment of the present invention includes (A) a curable resin and (B) an inorganic filler in combination. In addition, the cured product obtained by curing the resin composition has a specific gravity within a specific range. Moreover, the cured product obtained by curing the resin composition has a thermal expansion coefficient within a specific range. According to the resin composition that meets such requirements, an insulating layer with excellent impact resistance can be formed. Therefore, when the insulating layer of the cured product including the resin composition involved in the first embodiment of the present invention is subjected to an impact, the separation of the insulating layer and the conductive layer can be suppressed, and the formation of cracks on the insulating layer can be suppressed. In the following description, the property of suppressing the separation of the insulating layer and the conductive layer when subjected to impact is sometimes referred to as "anti-shock peeling property", and the property of suppressing cracking when subjected to impact is sometimes referred to as "anti-shock cracking property".

對於本發明的第一實施方式所涉及的樹脂組成物而言，優選與(A)硬化性樹脂和(B)無機填充材料組合地包含(C)有機粒子。另外，本發明的第一實施方式所涉及的樹脂組成物可進一步包含任選成分。The resin composition according to the first embodiment of the present invention preferably contains (C) organic particles in combination with (A) the curable resin and (B) the inorganic filler. In addition, the resin composition according to the first embodiment of the present invention may further contain optional components.

本發明人對通過本發明的第一實施方式所涉及的樹脂組成物可得到如上所述優異的耐衝擊性的機制進行如下推測。然而，本發明的技術範圍不受下述所說明的機制的限制。The inventors of the present invention have speculated as follows on the mechanism by which the resin composition according to the first embodiment of the present invention can obtain the above-mentioned excellent impact resistance. However, the technical scope of the present invention is not limited to the mechanism described below.

通常，(A)硬化性樹脂的熱膨脹係數大，(B)無機填充材料的熱膨脹係數小。因此，為了得到具有特定的小範圍的熱膨脹係數的硬化物，要求樹脂組成物包含大量的(B)無機填充材料。因此，如果樹脂組成物的硬化物具有特定的小範圍的熱膨脹係數，則表示樹脂組成物中所含的(B)無機填充材料的量多。如此，在(B)無機填充材料的量多的情況下，(B)無機填充材料在硬化物中作為骨料發揮功能，可提高硬化物的剛性。而且，由於硬化物的剛性高，可提高該硬化物對衝擊的抗性。Generally, the thermal expansion coefficient of the (A) curable resin is large, and the thermal expansion coefficient of the (B) inorganic filler is small. Therefore, in order to obtain a cured product with a specific small range of thermal expansion coefficient, the resin composition is required to contain a large amount of (B) inorganic filler. Therefore, if the cured product of the resin composition has a specific small range of thermal expansion coefficient, it means that the amount of (B) inorganic filler contained in the resin composition is large. In this way, when the amount of (B) inorganic filler is large, the (B) inorganic filler functions as an aggregate in the cured product and can improve the rigidity of the cured product. Moreover, due to the high rigidity of the cured product, the impact resistance of the cured product can be improved.

另外，通常，由於無機材料的比重大於樹脂的比重，所以在無機填充材料的量多的情況下，硬化物的比重有增大的傾向。因此，在本發明的第一實施方式所涉及的樹脂組成物中，為了大量使用(B)無機填充材料並將硬化物的比重限制在特定的小範圍，而控制(B)無機填充材料的種類和量。例如，通過以適當的量使用內部具有空孔的(B-1)中空無機填充材料，使硬化物能夠具有特定的小範圍的比重。對於包含硬化性樹脂和無機填充材料的以往的樹脂組成物的硬化物，通常，在無機填充材料的量多的情況下，硬化物的脆性有提高的傾向。相對於此，如果對(B)無機填充材料進行研究而使硬化物的比重處於特定的小範圍，則出乎意料地，可抑制硬化物的脆性，提高對衝擊的抗性。根據本發明人的研究，特別是在(B)無機填充材料包含(B-1)中空無機填充材料的情況下，認為通過(B-1)中空無機填充材料內的空孔，衝擊的能量得以緩和，耐衝擊性提高。而且，在樹脂組成物包含(C)有機粒子的情況下，認為通過該(C)有機粒子的作用，衝擊的能量也被協同地緩和，可實現耐衝擊性的有效改善。In addition, generally, since the specific gravity of inorganic materials is greater than that of resins, the specific gravity of the cured product tends to increase when the amount of inorganic filler is large. Therefore, in the resin composition involved in the first embodiment of the present invention, the type and amount of (B) inorganic filler are controlled in order to use a large amount of (B) inorganic filler and limit the specific gravity of the cured product to a specific small range. For example, by using (B-1) hollow inorganic filler having pores inside in an appropriate amount, the cured product can have a specific gravity within a specific small range. For the cured product of the conventional resin composition including a curable resin and an inorganic filler, generally, when the amount of inorganic filler is large, the brittleness of the cured product tends to increase. In contrast, if the (B) inorganic filler is studied so that the specific gravity of the cured product is within a specific small range, the brittleness of the cured product can be unexpectedly suppressed and the impact resistance can be improved. According to the research of the inventors, especially when the (B) inorganic filler includes the (B-1) hollow inorganic filler, it is believed that the energy of the impact is mitigated by the pores in the (B-1) hollow inorganic filler, and the impact resistance is improved. Moreover, when the resin composition includes the (C) organic particles, it is believed that the energy of the impact is also synergistically mitigated by the action of the (C) organic particles, and an effective improvement in the impact resistance can be achieved.

[2. (A)硬化性樹脂] 本發明的第一實施方式所涉及的樹脂組成物包含作為(A)成分的(A)硬化性樹脂。(A)硬化性樹脂可選自熱硬化性樹脂和光硬化性樹脂。因此，作為(A)硬化性樹脂，可以僅使用熱硬化性樹脂，也可以僅使用光硬化性樹脂，還可以組合使用熱硬化性樹脂和光硬化性樹脂。另外，硬化性樹脂可單獨使用1種，也可將2種以上組合使用。 [2. (A) Curable resin] The resin composition according to the first embodiment of the present invention includes (A) curable resin as component (A). The (A) curable resin can be selected from thermosetting resins and photocurable resins. Therefore, as the (A) curable resin, only thermosetting resins can be used, only photocurable resins can be used, or a combination of thermosetting resins and photocurable resins can be used. In addition, the curable resins can be used alone or in combination of two or more.

作為熱硬化性樹脂，可使用在加熱時能夠硬化的樹脂。作為熱硬化性樹脂的例子，可舉出：環氧樹脂、酚醛樹脂、活性酯樹脂、氰酸酯樹脂、碳二亞胺樹脂、酸酐樹脂、胺樹脂、苯並噁嗪樹脂、硫醇樹脂和自由基聚合性樹脂等。熱硬化性樹脂可單獨使用1種，也可將2種以上組合使用。其中，熱硬化性樹脂優選包含選自下述的至少一種：環氧樹脂、酚醛樹脂、活性酯樹脂、氰酸酯樹脂和自由基聚合性樹脂。As the thermosetting resin, a resin that can be cured when heated can be used. Examples of thermosetting resins include epoxy resins, phenolic resins, active ester resins, cyanate resins, carbodiimide resins, acid anhydride resins, amine resins, benzoxazine resins, thiol resins, and free radical polymerizable resins. The thermosetting resin can be used alone or in combination of two or more. Among them, the thermosetting resin preferably includes at least one selected from the following: epoxy resins, phenolic resins, active ester resins, cyanate resins, and free radical polymerizable resins.

特別是，從可顯著地得到本發明效果的觀點出發，優選將環氧樹脂和可與該環氧樹脂反應而使樹脂組成物硬化的樹脂組合使用。以下有時將可與環氧樹脂反應而使樹脂組成物硬化的樹脂稱為「硬化劑」。作為硬化劑，例如可舉出：酚醛樹脂、活性酯樹脂、氰酸酯樹脂、碳二亞胺樹脂、酸酐樹脂、胺樹脂、苯並噁嗪樹脂、硫醇樹脂等。其中，優選酚醛樹脂、活性酯樹脂、氰酸酯樹脂和碳二亞胺樹脂，更優選酚醛樹脂、活性酯樹脂和氰酸酯樹脂。另外，硬化劑可單獨使用1種，也可將2種以上組合使用。In particular, from the viewpoint of significantly obtaining the effect of the present invention, it is preferred to use an epoxy resin in combination with a resin that can react with the epoxy resin to harden the resin composition. Hereinafter, the resin that can react with the epoxy resin to harden the resin composition is sometimes referred to as a "hardener". Examples of hardeners include phenolic resins, active ester resins, cyanate resins, carbodiimide resins, acid anhydride resins, amine resins, benzoxazine resins, and thiol resins. Among them, phenolic resins, active ester resins, cyanate resins, and carbodiimide resins are preferred, and phenolic resins, active ester resins, and cyanate resins are more preferred. In addition, the hardener may be used alone or in combination of two or more.

環氧樹脂是具有環氧基的硬化性樹脂。作為環氧樹脂，例如可舉出：聯二甲酚(bixylenol)型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚AF型環氧樹脂、雙環戊二烯型環氧樹脂、三酚型環氧樹脂、萘酚酚醛清漆(naphthol novolac)型環氧樹脂、苯酚酚醛清漆(phenol novolac)型環氧樹脂、叔丁基-鄰苯二酚型環氧樹脂、萘型環氧樹脂、萘酚型環氧樹脂、蒽型環氧樹脂、縮水甘油基胺型環氧樹脂、縮水甘油基酯型環氧樹脂、甲酚酚醛清漆(cresol novolac)型環氧樹脂、苯酚芳烷基型環氧樹脂、聯苯型環氧樹脂、線狀脂肪族環氧樹脂、具有丁二烯結構的環氧樹脂、脂環式環氧樹脂、雜環式環氧樹脂、含有螺環的環氧樹脂、環己烷型環氧樹脂、環己烷二甲醇型環氧樹脂、伸萘基醚(naphthylene ether)型環氧樹脂、三羥甲基型環氧樹脂、四苯基乙烷型環氧樹脂、異氰脲酸酯型環氧樹脂、苯酚苄甲內醯胺(phenol phthalimidine)型環氧樹脂等。環氧樹脂可單獨使用1種，也可將2種以上組合使用。Epoxy resins are curable resins having epoxy groups. Examples of epoxy resins include bixylenol epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bisphenol AF epoxy resins, dicyclopentadiene epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, phenol novolac epoxy resins, and bisphenol A epoxy resins. novolac) type epoxy resin, tert-butyl-ophthalic acid type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac (cresol Novolac) type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spirocyclic epoxy resin, oxalic acid type epoxy resin, oxalic acid dimethanol type epoxy resin, naphthylene ether type epoxy resin, trihydroxymethyl type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenol phthalimidine type epoxy resin, etc. Epoxy resins may be used alone or in combination of two or more.

從得到耐熱性優異的硬化物的觀點考慮，環氧樹脂優選包含含有芳香族結構的環氧樹脂。芳香族結構是指通常定義為芳香族的化學結構，也包括多環芳香族和芳香族雜環。作為含有芳香族結構的環氧樹脂，例如可舉出：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚AF型環氧樹脂、雙環戊二烯型環氧樹脂、三酚型環氧樹脂、萘酚酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂、叔丁基-鄰苯二酚型環氧樹脂、萘型環氧樹脂、萘酚型環氧樹脂、蒽型環氧樹脂、聯二甲酚型環氧樹脂、具有芳香族結構的縮水甘油基胺型環氧樹脂、具有芳香族結構的縮水甘油基酯型環氧樹脂、甲酚酚醛清漆型環氧樹脂、聯苯型環氧樹脂、具有芳香族結構的線狀脂肪族環氧樹脂、具有芳香族結構的具有丁二烯結構的環氧樹脂、具有芳香族結構的脂環式環氧樹脂、雜環式環氧樹脂、具有芳香族結構的含有螺環的環氧樹脂、具有芳香族結構的環己烷二甲醇型環氧樹脂、伸萘基醚型環氧樹脂、具有芳香族結構的三羥甲基型環氧樹脂、具有芳香族結構的四苯基乙烷型環氧樹脂等。From the viewpoint of obtaining a cured product having excellent heat resistance, the epoxy resin preferably includes an epoxy resin containing an aromatic structure. The aromatic structure refers to a chemical structure generally defined as an aromatic structure, and also includes polycyclic aromatics and aromatic heterocyclics. Examples of the epoxy resin containing an aromatic structure include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-ophthalic acid type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, dimethylphenol type epoxy resin, glycidylamine type epoxy resin having an aromatic structure, glycidylamine type epoxy resin having an aromatic structure, and Oil-based ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having an aromatic structure, butadiene structure epoxy resin having an aromatic structure, alicyclic epoxy resin having an aromatic structure, heterocyclic epoxy resin, spirocyclic epoxy resin having an aromatic structure, cyclohexanedimethanol type epoxy resin having an aromatic structure, naphthyl ether type epoxy resin, trihydroxymethyl type epoxy resin having an aromatic structure, tetraphenylethane type epoxy resin having an aromatic structure, etc.

對於(A)硬化性樹脂而言，作為環氧樹脂，優選包含1分子中具有2個以上環氧基的環氧樹脂。相對於100質量%環氧樹脂的非揮發成分，1分子中具有2個以上環氧基的環氧樹脂的比例優選為50質量%以上、更優選為60質量%以上、特別優選為70質量%以上。The (A) curable resin preferably includes an epoxy resin having two or more epoxy groups in one molecule as the epoxy resin. The proportion of the epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the non-volatile component of the epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

環氧樹脂包括在溫度20℃下為液態的環氧樹脂(以下有時稱為「液態環氧樹脂」)和在溫度20℃下為固態的環氧樹脂(以下有時稱為「固態環氧樹脂」)。對於樹脂組成物而言，作為環氧樹脂，可以僅包含液態環氧樹脂，或者也可以僅包含固態環氧樹脂，或者還可以組合地包含液態環氧樹脂和固態環氧樹脂。Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may contain only liquid epoxy resins, only solid epoxy resins, or a combination of liquid epoxy resins and solid epoxy resins as epoxy resins.

作為液態環氧樹脂，優選1分子中具有2個以上環氧基的液態環氧樹脂。As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

作為液態環氧樹脂，優選雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AF型環氧樹脂、萘型環氧樹脂、縮水甘油基酯型環氧樹脂、縮水甘油基胺型環氧樹脂、苯酚酚醛清漆型環氧樹脂、具有酯骨架的脂環式環氧樹脂、環己烷型環氧樹脂、環己烷二甲醇型環氧樹脂和具有丁二烯結構的環氧樹脂。As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin and epoxy resin having a butadiene structure are preferred.

作為液態環氧樹脂的具體例，可舉出：DIC公司製造的「HP4032」、「HP4032D」、「HP4032SS」(萘型環氧樹脂)；三菱化學公司製造的「828US」、「828EL」、「jER828EL」、「825」、「EPIKOTE 828EL」(雙酚A型環氧樹脂)；三菱化學公司製造的「jER807」、「1750」(雙酚F型環氧樹脂)；三菱化學公司製造的「jER152」(苯酚酚醛清漆型環氧樹脂)；三菱化學公司製造的「630」、「630LSD」、「604」(縮水甘油基胺型環氧樹脂)；ADEKA公司製造的「ED-523T」(甘草醇(Glycyrol)型環氧樹脂)；ADEKA公司製造的「EP-3950L」、「EP-3980S」(縮水甘油基胺型環氧樹脂)；ADEKA公司製造的「EP-4088S」(雙環戊二烯型環氧樹脂)；日鐵化學材料化學公司製造的「ZX1059」(雙酚A型環氧樹脂與雙酚F型環氧樹脂的混合品)；Nagase ChemteX公司製造的「EX-721」(縮水甘油基酯型環氧樹脂)；大賽璐公司製造的「Celloxide 2021P」(具有酯骨架的脂環式環氧樹脂)；大賽璐公司製造的「PB-3600」、日本曹達公司製造的「JP-100」、「JP-200」(具有丁二烯結構的環氧樹脂)；日鐵化學材料製造的「ZX1658」、「ZX1658GS」(液態1,4-縮水甘油基環己烷型環氧樹脂)等。它們可單獨使用1種，也可將2種以上組合使用。Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-based epoxy resins) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", and "EPIKOTE" manufactured by Mitsubishi Chemical Corporation. "828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical; "630", "630LSD", and "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical; "ED-523T" (glycerylamine type epoxy resin) manufactured by ADEKA Glycyrol type epoxy resin); "EP-3950L" and "EP-3980S" manufactured by ADEKA (glycidylamine type epoxy resin); "EP-4088S" manufactured by ADEKA (dicyclopentadiene type epoxy resin); "ZX1059" manufactured by Nippon Steel Chemical Materials Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase "EX-721" manufactured by ChemteX (glycidyl ester type epoxy resin); "Celloxide 2021P" manufactured by Daicell (lipid epoxy resin with ester skeleton); "PB-3600" manufactured by Daicell, "JP-100" and "JP-200" manufactured by Nippon Soda (epoxy resin with butadiene structure); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel Chemical Materials (liquid 1,4-glycidyl cyclohexane type epoxy resin), etc. They can be used alone or in combination of two or more.

作為固態環氧樹脂，優選1分子中具有3個以上環氧基的固態環氧樹脂，更優選1分子中具有3個以上環氧基的芳香族系的固態環氧樹脂。As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred.

作為固態環氧樹脂，優選聯二甲酚型環氧樹脂、萘型環氧樹脂、萘型四官能環氧樹脂、萘酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙環戊二烯型環氧樹脂、三酚型環氧樹脂、萘酚型環氧樹脂、聯苯型環氧樹脂、伸萘基醚型環氧樹脂、蒽型環氧樹脂、雙酚A型環氧樹脂、雙酚AF型環氧樹脂、苯酚芳烷基型環氧樹脂、四苯基乙烷型環氧樹脂、苯酚苄甲內醯胺型環氧樹脂。As the solid epoxy resin, preferred are bixylene type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, and phenol benzyl formamide type epoxy resin.

作為固態環氧樹脂的具體例，可舉出：DIC公司製造的「HP4032H」(萘型環氧樹脂)；DIC公司製造的「HP-4700」、「HP-4710」(萘型四官能環氧樹脂)；DIC公司製造的「N-690」(甲酚酚醛清漆型環氧樹脂)；DIC公司製造的「N-695」(甲酚酚醛清漆型環氧樹脂)；DIC公司製造的「HP-7200」、「HP-7200HH」、「HP-7200H」、「HP-7200L」(雙環戊二烯型環氧樹脂)；DIC公司製造的「EXA-7311」、「EXA-7311-G3」、「EXA-7311-G4」、「EXA-7311-G4S」、「HP6000」(伸萘基醚型環氧樹脂)；日本化藥公司製造的「EPPN-502H」(三酚型環氧樹脂)；日本化藥公司製造的「NC7000L」(萘酚酚醛清漆型環氧樹脂)；日本化藥公司製造的「NC3000H」、「NC3000」、「NC3000L」、「NC3000FH」、「NC3100」(聯苯型環氧樹脂)；日鐵化學材料公司製造的「ESN475V」、「ESN4100V」(萘型環氧樹脂)；日鐵化學材料公司製造的「ESN485」(萘酚型環氧樹脂)；日鐵化學材料公司製造的「ESN375」(二羥基萘型環氧樹脂)；三菱化學公司製造的「YX4000H」、「YX4000」、「YX4000HK」、「YL7890」(聯二甲酚型環氧樹脂)；三菱化學公司製造的「YL6121」(聯苯型環氧樹脂)；三菱化學公司製造的「YX8800」(蒽型環氧樹脂)；三菱化學公司製造的「YX7700」(苯酚芳烷基型環氧樹脂)；大阪燃氣化學公司製造的「PG-100」、「CG-500」；三菱化學公司製造的「YX7760」(雙酚AF型環氧樹脂)；三菱化學公司製造的「YL7800」(芴型環氧樹脂)；三菱化學公司製造的「jER1010」(雙酚A型環氧樹脂)；三菱化學公司製造的「jER1031S」(四苯基乙烷型環氧樹脂)；日本化藥公司製造的「WHR991S」(苯酚苄甲內醯胺型環氧樹脂)等。它們可單獨使用1種，也可將2種以上組合使用。Specific examples of solid epoxy resins include: "HP4032H" manufactured by DIC Corporation (naphthalene-based epoxy resin); "HP-4700" and "HP-4710" manufactured by DIC Corporation (naphthalene-based tetrafunctional epoxy resin); "N-690" manufactured by DIC Corporation (cresol novolac-based epoxy resin); "N-695" manufactured by DIC Corporation (cresol novolac-based epoxy resin); "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" manufactured by DIC Corporation (dicyclopentadiene-based epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V", "ESN4100V" (naphthalene type epoxy resin) manufactured by Japan Materials Corporation; "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical Materials Corporation; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical Materials Corporation; "YX4000H", "YX4000", "YX4000HK", "YL7890" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenol aralkyl type epoxy resin) manufactured by Mitsubishi Chemical; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YX7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical; "WHR991S" (phenol benzyl formamide type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., etc. These can be used alone or in combination.

作為環氧樹脂，在組合使用液態環氧樹脂和固態環氧樹脂的情況下，它們的質量比(液態環氧樹脂：固態環氧樹脂)優選為20：1～1：20、更優選為10：1～1：10、特別優選為7：1～1：7。When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the mass ratio of them (liquid epoxy resin: solid epoxy resin) is preferably 20:1 to 1:20, more preferably 10:1 to 1:10, and particularly preferably 7:1 to 1:7.

環氧樹脂的環氧當量優選為50g/eq.～5,000g/eq.、更優選為60g/eq.～3,000g/eq.、進一步優選為80g/eq.～2,000g/eq.、特別優選為110g/eq.～1,000g/eq.。環氧當量表示每1當量環氧基的樹脂的質量。該環氧當量可按照JIS K7236進行測定。The epoxy equivalent of the epoxy resin is preferably 50 g/eq. to 5,000 g/eq., more preferably 60 g/eq. to 3,000 g/eq., further preferably 80 g/eq. to 2,000 g/eq., and particularly preferably 110 g/eq. to 1,000 g/eq. The epoxy equivalent means the mass of the resin per 1 equivalent of epoxy groups. The epoxy equivalent can be measured in accordance with JIS K7236.

環氧樹脂的重量平均分子量(Mw)優選為100～5,000、更優選為250～3,000、進一步優選為400～1,500。樹脂的重量平均分子量可利用凝膠滲透層析(GPC)法、作為聚苯乙烯換算值來測定。The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and further preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

在將樹脂組成物中的非揮發成分設為100質量%的情況下，樹脂組成物中的環氧樹脂的量優選為1質量%以上、更優選為2質量%以上、特別優選為5質量%以上，優選為50質量%以下、更優選為40質量%以下、特別優選為35質量%以下。在環氧樹脂的量處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。When the non-volatile components in the resin composition are set to 100 mass %, the amount of the epoxy resin in the resin composition is preferably 1 mass % or more, more preferably 2 mass % or more, particularly preferably 5 mass % or more, and preferably 50 mass % or less, more preferably 40 mass % or less, particularly preferably 35 mass % or less. When the amount of the epoxy resin is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved.

在將樹脂組成物中的樹脂成分設為100質量%的情況下，樹脂組成物中的環氧樹脂的量優選為5質量%以上、更優選為10質量%以上、特別優選為20質量%以上，優選為80質量%以下、更優選為70質量%以下、特別優選為65質量%以下。除非另外說明，樹脂組成物的樹脂成分表示樹脂組成物的非揮發成分中去除(B)無機填充材料後的成分。在環氧樹脂的量處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。When the resin component in the resin composition is set to 100 mass%, the amount of the epoxy resin in the resin composition is preferably 5 mass% or more, more preferably 10 mass% or more, particularly preferably 20 mass% or more, preferably 80 mass% or less, more preferably 70 mass% or less, particularly preferably 65 mass% or less. Unless otherwise specified, the resin component of the resin composition means the component after removing the (B) inorganic filler from the non-volatile components of the resin composition. When the amount of the epoxy resin is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved.

作為酚醛樹脂，可使用1分子中具有1個以上、優選2個以上鍵結於苯環、萘環等芳香環的羥基的化合物。由於酚醛樹脂在與環氧樹脂組合時可與環氧樹脂反應而使樹脂組成物硬化，所以有時稱為「酚系硬化劑」。從耐熱性和耐水性的觀點出發，優選具有酚醛清漆結構的酚醛樹脂。另外，從密合性的觀點出發，優選含氮酚醛樹脂，更優選含有三嗪骨架的酚醛樹脂。其中，從高度地滿足耐熱性、耐水性和密合性的觀點出發，優選含有三嗪骨架的苯酚酚醛清漆樹脂。作為酚醛樹脂的具體例，例如可舉出：明和化成公司製造的「MEH-7700」、「MEH-7810」、「MEH-7851」；日本化藥公司製造的「NHN」、「CBN」、「GPH」；日鐵化學材料公司製造的「SN-170」、「SN-180」、「SN-190」、「SN-475」、「SN-485」、「SN-495」、「SN-375」、「SN-395」；DIC公司製造的「LA-7052」、「LA-7054」、「LA-3018」、「LA-3018-50P」、「LA-1356」、「TD2090」、「TD-2090-60M」等。As the phenolic resin, a compound having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring in one molecule can be used. Since the phenolic resin can react with the epoxy resin to harden the resin composition when combined with the epoxy resin, it is sometimes called a "phenolic hardener". From the viewpoint of heat resistance and water resistance, a phenolic resin having a novolac structure is preferred. In addition, from the viewpoint of adhesion, a nitrogen-containing phenolic resin is preferred, and a phenolic resin containing a triazine skeleton is more preferred. Among them, from the viewpoint of highly satisfying heat resistance, water resistance and adhesion, a phenol novolac resin containing a triazine skeleton is preferred. Specific examples of phenolic resins include: "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemicals; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", and "SN-395" manufactured by Nippon Steel Chemicals; and "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", and "TD-2090-60M" manufactured by DIC Corporation.

作為活性酯樹脂，通常，優選使用酚酯類、硫酚酯類、N-羥基胺酯類、雜環羥基化合物的酯類等的1分子中具有2個以上反應活性高的酯基的化合物。活性酯樹脂由於在與環氧樹脂組合時可與環氧樹脂反應而使樹脂組成物硬化，所以有時稱為「活性酯系硬化劑」。該活性酯樹脂優選通過羧酸化合物和/或硫代羧酸化合物與羥基化合物和/或硫醇化合物的縮合反應而得到。特別是，從提高耐熱性的觀點出發，優選由羧酸化合物與羥基化合物得到的活性酯樹脂，更優選由羧酸化合物與苯酚化合物和/或萘酚化合物得到的活性酯樹脂。作為羧酸化合物，例如可舉出：苯甲酸、乙酸、琥珀酸、馬來酸、衣康酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、均苯四甲酸等。作為苯酚化合物或萘酚化合物，例如可舉出：對苯二酚、間苯二酚、雙酚A、雙酚F、雙酚S、酚酞啉、甲基化雙酚A、甲基化雙酚F、甲基化雙酚S、苯酚、鄰甲酚、間甲酚、對甲酚、鄰苯二酚、α-萘酚、β-萘酚、1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯甲酮、三羥基二苯甲酮、四羥基二苯甲酮、間苯三酚、苯三酚(benzenetriol)、雙環戊二烯型二苯酚化合物、苯酚酚醛清漆等。在此，「雙環戊二烯型二苯酚化合物」是指2分子苯酚與1分子雙環戊二烯縮合而得到的二苯酚化合物。As the active ester resin, it is usually preferred to use a compound having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds. The active ester resin is sometimes referred to as an "active ester curing agent" because it can react with an epoxy resin to cure the resin composition when combined with an epoxy resin. The active ester resin is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxyl compound is preferred, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, o-cresol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

具體而言，作為活性酯樹脂，優選雙環戊二烯型活性酯樹脂、包含萘結構的萘型活性酯樹脂、包含苯酚酚醛清漆的乙醯化物的活性酯樹脂、包含苯酚酚醛清漆的苯甲醯化物的活性酯樹脂，其中，更優選選自雙環戊二烯型活性酯樹脂和萘型活性酯樹脂的至少一種。作為雙環戊二烯型活性酯樹脂，優選包含雙環戊二烯型二苯酚結構的活性酯樹脂。Specifically, as the active ester resin, dicyclopentadiene type active ester resin, naphthalene type active ester resin containing a naphthalene structure, active ester resin containing acetylated phenol novolac, active ester resin containing benzoylated phenol novolac is preferred, and among them, at least one selected from dicyclopentadiene type active ester resin and naphthalene type active ester resin is more preferred. As the dicyclopentadiene type active ester resin, an active ester resin containing a dicyclopentadiene type diphenol structure is preferred.

作為活性酯樹脂的市售品，例如，作為包含雙環戊二烯型二苯酚結構的活性酯樹脂，可舉出「EXB9451」、「EXB9460」、「EXB9460S」、「EXB-8000L」、「EXB-8000L-65M」、「EXB-8000L-65TM」、「HPC-8000L-65TM」、「HPC-8000」、「HPC-8000-65T」、「HPC-8000H」、「HPC-8000H-65TM」(DIC公司製造)；作為包含萘結構的活性酯樹脂，可舉出「HPB-8151-62T」、「EXB-8100L-65T」、「EXB-8150-60T」、「EXB-8150-62T」、「EXB-9416-70BK」、「HPC-8150-60T」、「HPC-8150-62T」、「EXB-8」(DIC公司製造)；作為含有磷的活性酯樹脂，可舉出「EXB9401」(DIC公司製造)；關於作為苯酚酚醛清漆的乙醯化物的活性酯樹脂，可舉出「DC808」(三菱化學公司製造)；關於作為苯酚酚醛清漆的苯甲醯化物的活性酯樹脂，可舉出「YLH1026」、「YLH1030」、「YLH1048」(三菱化學公司製造)；作為包含苯乙烯基和萘結構的活性酯樹脂，可舉出「PC1300-02-65MA」(AIR WATER公司製造)等。Examples of commercially available active ester resins include "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65T", and "EXB-8000L-65T". M", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC Corporation); as active ester resins containing a naphthalene structure, "HPB-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); as active ester resins containing phosphorus, "EXB9401" (manufactured by DIC Corporation) can be cited; regarding active ester resins that are acetylated products of phenol novolac As for active ester resins, "DC808" (manufactured by Mitsubishi Chemical Corporation) can be cited; as for active ester resins which are benzoyl compounds of phenol novolac, "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) can be cited; as for active ester resins containing styrene and naphthalene structures, "PC1300-02-65MA" (manufactured by Air Water Corporation) can be cited.

作為氰酸酯樹脂，可使用在1分子內具有1個以上、優選2個以上氰酸酯基的化合物。氰酸酯樹脂由於在與環氧樹脂組合時可與環氧樹脂反應而使樹脂組成物硬化，所以有時稱為「氰酸酯系硬化劑」。作為氰酸酯樹脂，例如可舉出：雙酚A二氰酸酯、多酚氰酸酯(低聚(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-氰酸酯基)苯基丙烷、1,1-雙(4-氰酸酯基苯基甲烷)、雙(4-氰酸酯基-3,5-二甲基苯基)甲烷、1,3-雙(4-氰酸酯基苯基-1-(甲基亞乙基))苯、雙(4-氰酸酯基苯基)硫醚和雙(4-氰酸酯基苯基)醚等2官能氰酸酯樹脂、由苯酚酚醛清漆和甲酚酚醛清漆等衍生的多官能氰酸酯樹脂、這些氰酸酯樹脂進行部分三嗪化而成的預聚物等。作為氰酸酯樹脂的具體例，可舉出：Lonza Japan公司製造的「PT30」和「PT60」(均為苯酚酚醛清漆型多官能氰酸酯樹脂)、「BA230」、「BA230S75」(雙酚A二氰酸酯的一部分或全部進行三嗪化而成為三聚體的預聚物)等。As the cyanate resin, a compound having one or more, preferably two or more, cyanate groups in one molecule can be used. Since the cyanate resin can react with the epoxy resin when combined with the epoxy resin to cure the resin composition, it is sometimes called a "cyanate curing agent". Examples of the cyanate resin include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane) , bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)sulfide and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolac and cresol novolac, prepolymers of these cyanate resins partially triazinated, etc. Specific examples of cyanate resins include "PT30" and "PT60" manufactured by Lonza Japan (both are phenol novolac type polyfunctional cyanate resins), "BA230", "BA230S75" (prepolymers of bisphenol A dicyanate partially or completely triazinated to form a trimer), etc.

作為碳二亞胺樹脂，可使用在1分子內具有1個以上、優選2個以上碳二亞胺結構的化合物。碳二亞胺樹脂由於在與環氧樹脂組合時可與環氧樹脂反應而使樹脂組成物硬化，所以有時稱為「碳二亞胺系硬化劑」。作為碳二亞胺樹脂的具體例，可舉出：四亞甲基-雙(叔丁基碳二亞胺)、環己烷雙(亞甲基-叔丁基碳二亞胺)等脂肪族雙碳二亞胺；伸苯基-雙(二甲苯基碳二亞胺)等芳香族雙碳二亞胺等的雙碳二亞胺；聚六亞甲基碳二亞胺、聚三甲基六亞甲基碳二亞胺、聚伸環己基碳二亞胺、聚(亞甲基雙伸環己基碳二亞胺)、聚(異佛爾酮碳二亞胺)等脂肪族聚碳二亞胺；聚(伸苯基碳二亞胺)、聚(伸萘基碳二亞胺)、聚(伸甲苯基碳二亞胺)、聚(甲基二異丙基伸苯基碳二亞胺)、聚(三乙基伸苯基碳二亞胺)、聚(二乙基伸苯基碳二亞胺)、聚(三異丙基伸苯基碳二亞胺)、聚(二異丙基伸苯基碳二亞胺)、聚(伸二甲苯基碳二亞胺)、聚(四甲基伸二甲苯基碳二亞胺)、聚(亞甲基二伸苯基碳二亞胺)、聚[亞甲基雙(甲基伸苯基)碳二亞胺]等芳香族聚碳二亞胺等的聚碳二亞胺。作為碳二亞胺樹脂的市售品，例如可舉出：日清紡化學公司製造的「CARBODILITE V-02B」、「CARBODILITE V-03」、「CARBODILITE V-04K」、「CARBODILITE V-07」和「CARBODILITE V-09」；Rhein Chemie公司製造的「Stabaxol P」、「Stabaxol P400」、「Hycasyl 510」等。As the carbodiimide resin, a compound having one or more, preferably two or more carbodiimide structures in one molecule can be used. When combined with an epoxy resin, the carbodiimide resin can react with the epoxy resin to cure the resin composition, so it is sometimes called a "carbodiimide-based curing agent." Specific examples of carbodiimide resins include aliphatic biscarbodiimides such as tetramethylene-bis(tert-butylcarbodiimide) and cyclohexanebis(methylene-tert-butylcarbodiimide); aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide); poly(phenylenecarbodiimide), poly(xylylenecarbodiimide); Polycarbodiimides such as aromatic polycarbodiimides such as poly(tolylcarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenebisphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide] are also included. Examples of commercially available carbodiimide resins include "CARBODILITE V-02B", "CARBODILITE V-03", "CARBODILITE V-04K", "CARBODILITE V-07" and "CARBODILITE V-09" manufactured by Nisshinbo Chemical Co., Ltd.; and "Stabaxol P", "Stabaxol P400" and "Hycasyl 510" manufactured by Rhein Chemie.

作為酸酐樹脂，可使用在1分子內具有1個以上、優選2個以上酸酐基的化合物。酸酐樹脂由於在與環氧樹脂組合時可與環氧樹脂反應而使樹脂組成物硬化，所以有時稱為「酸酐系硬化劑」。作為酸酐樹脂的具體例，可舉出：鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、甲基納迪克酸酐、氫化甲基納迪克酸酐、三烷基四氫鄰苯二甲酸酐、十二碳烯基琥珀酸酐、5-(2,5-二氧代四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二甲酸酐、偏苯三甲酸酐、均苯四甲酸酐、二苯甲酮四甲酸二酐、聯苯四甲酸二酐、萘四甲酸二酐、氧基二鄰苯二甲酸二酐、3,3’-4,4’-二苯基碸四甲酸二酐、1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二氧代-3-呋喃基)-萘並[1,2-C]呋喃-1,3-二酮、乙二醇雙(偏苯三甲酸酐酯)、苯乙烯與馬來酸進行共聚而成的苯乙烯-馬來酸樹脂等聚合物型的酸酐等。作為酸酐樹脂的市售品，例如可舉出：新日本理化公司製造的「HNA-100」、「MH-700」、「MTA-15」、「DDSA」、「OSA」；三菱化學公司製造的「YH-306」、「YH-307」；日立化成公司製造的「HN-2200」、「HN-5500」；Cray Valley公司製造的「EF-30」、「EF-40」、「EF-60」、「EF-80」等。As the acid anhydride resin, a compound having one or more, preferably two or more, acid anhydride groups in one molecule can be used. When combined with an epoxy resin, the acid anhydride resin can react with the epoxy resin to cure the resin composition, so it is sometimes called an "acid anhydride curing agent". Specific examples of the acid anhydride resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, diphenyl Acid anhydrides of polymer type such as ketone tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid dianhydride, naphthalene tetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'-diphenylsulfonate tetracarboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride ester), styrene-maleic acid resin obtained by copolymerization of styrene and maleic acid, etc. Examples of commercially available acid anhydride resins include "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by Shin Nippon Chemical Co., Ltd.; "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Co., Ltd.; "HN-2200" and "HN-5500" manufactured by Hitachi Chemical Co., Ltd.; and "EF-30", "EF-40", "EF-60", and "EF-80" manufactured by Cray Valley Co., Ltd.

作為胺樹脂，可使用在1分子內具有1個以上、優選2個以上胺基的化合物。胺樹脂由於在與環氧樹脂組合時可與環氧樹脂反應而使樹脂組成物硬化，所以有時稱為「胺系硬化劑」。作為胺樹脂，例如可舉出：脂肪族胺類、聚醚胺類、脂環式胺類、芳香族胺類等，其中，優選芳香族胺類。胺樹脂優選伯胺或仲胺，更優選伯胺。作為胺樹脂的具體例，可舉出：4,4’-亞甲基雙(2,6-二甲基苯胺)、4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基碸、3,3’-二胺基二苯基碸、間苯二胺、間苯二甲胺、二乙基甲苯二胺、4,4’-二胺基二苯基醚、3,3’-二甲基-4,4’-二胺基聯苯、2,2’-二甲基-4,4’-二胺基聯苯、3,3’-二羥基聯苯胺、2,2-雙(3-胺基-4-羥基苯基)丙烷、3,3-二甲基-5,5-二乙基-4,4-二苯基甲烷二胺、2,2-雙(4-胺基苯基)丙烷、2,2-雙(4-(4-胺基苯氧基)苯基)丙烷、1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、4,4’-雙(4-胺基苯氧基)聯苯、雙(4-(4-胺基苯氧基)苯基)碸、雙(4-(3-胺基苯氧基)苯基)碸等。作為胺樹脂的市售品，例如可舉出：SEIKA公司製造的「SEIKACURE-S」；日本化藥公司製造的「KAYABOND C-200S」、「KAYABOND C-100」、「KAYAHARD A-A」、「KAYAHARD A-B」、「KAYAHARD A-S」；三菱化學公司製造的「EPICURE W」；住友精化公司製造的「DTDA」等。As the amine resin, a compound having one or more, preferably two or more, amine groups in one molecule can be used. When combined with an epoxy resin, the amine resin can react with the epoxy resin to cure the resin composition, so it is sometimes called an "amine-based curing agent". Examples of the amine resin include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, aromatic amines are preferred. The amine resin is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine resin include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, metaphenylenediamine, metaphenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxybenzene) bis(4-aminophenoxy)phenyl)sulfone, bis(4-(4-aminophenoxy)phenyl)sulfone, and the like. Examples of commercially available amine resins include "SEIKACURE-S" manufactured by SEIKA Corporation; "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", and "KAYAHARD A-S" manufactured by Nippon Kayaku Co., Ltd.; "EPICURE W" manufactured by Mitsubishi Chemical Corporation; and "DTDA" manufactured by Sumitomo Seika Chemicals Co., Ltd.

苯並噁嗪樹脂由於在與環氧樹脂組合時可與環氧樹脂反應而使樹脂組成物硬化，所以有時稱為「苯並噁嗪系硬化劑」。作為苯並噁嗪樹脂的具體例，可舉出：JFE化學公司製造的「JBZ-OP100D」、「ODA-BOZ」；昭和高分子公司製造的「HFB2006M」；四國化成工業公司製造的「P-d」、「F-a」等。Benzoxazine resins are sometimes referred to as "benzoxazine-based hardeners" because they react with epoxy resins to harden the resin composition when combined with epoxy resins. Specific examples of benzoxazine resins include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemicals, "HFB2006M" manufactured by Showa High Polymer, and "P-d" and "F-a" manufactured by Shikoku Chemicals.

硫醇樹脂由於在與環氧樹脂組合時可與環氧樹脂反應而使樹脂組成物硬化，所以有時稱為「硫醇系硬化劑」。作為硫醇樹脂，例如可舉出：三羥甲基丙烷三(3-巰基丙酸酯)、季戊四醇四(3-巰基丁酸酯)、三(3-巰基丙基)異氰脲酸酯等。When combined with an epoxy resin, a thiol resin can react with an epoxy resin to cure the resin composition, so it is sometimes called a "thiol-based hardener." Examples of thiol resins include trihydroxymethylpropane tris(3-butylpropionate), pentaerythritol tetra(3-butylbutyrate), and tris(3-butylpropyl)isocyanurate.

硬化劑的活性基當量優選為50g/eq.～3000g/ eq.、更優選為100g/eq.～1000g/eq.、進一步優選為100g/ eq.～500g/eq.、特別優選為100g/eq.～300g/eq.。活性基當量是每1當量活性基的硬化劑的質量。The active group equivalent of the hardener is preferably 50 g/eq. to 3000 g/eq., more preferably 100 g/eq. to 1000 g/eq., further preferably 100 g/eq. to 500 g/eq., and particularly preferably 100 g/eq. to 300 g/eq. The active group equivalent is the mass of the hardener per 1 equivalent of active groups.

在將環氧樹脂的環氧基數設為1的情況下，硬化劑的活性基數優選為0.1以上、更優選為0.2以上、進一步優選為0.5以上，優選為5.0以下、更優選為4.0以下、特別優選為3.0以下。「環氧樹脂的環氧基數」表示將在樹脂組成物中存在的環氧樹脂的非揮發成分的質量除以環氧當量而得的值全部相加後的值。另外，「硬化劑的活性基數」表示將在樹脂組成物中存在的硬化劑的非揮發成分的質量除以活性基當量而得的值全部相加後的值。When the number of epoxy groups of the epoxy resin is 1, the number of active groups of the hardener is preferably 0.1 or more, more preferably 0.2 or more, and further preferably 0.5 or more, and preferably 5.0 or less, more preferably 4.0 or less, and particularly preferably 3.0 or less. The "number of epoxy groups of the epoxy resin" means the sum of all values obtained by dividing the mass of the non-volatile components of the epoxy resin present in the resin composition by the epoxy equivalent. In addition, the "active group number of the hardener" means the sum of all values obtained by dividing the mass of the non-volatile components of the hardener present in the resin composition by the active group equivalent.

在將樹脂組成物中的非揮發成分設為100質量%的情況下，樹脂組成物中的硬化劑的量優選為1質量%以上、更優選為2質量%以上、特別優選為5質量%以上，優選為50質量%以下、更優選為40質量%以下、特別優選為30質量%以下。在硬化劑的量處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。When the non-volatile components in the resin composition are set to 100 mass %, the amount of the hardener in the resin composition is preferably 1 mass % or more, more preferably 2 mass % or more, particularly preferably 5 mass % or more, and preferably 50 mass % or less, more preferably 40 mass % or less, particularly preferably 30 mass % or less. When the amount of the hardener is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the hardened material containing the resin composition can be effectively improved.

在將樹脂組成物中的樹脂成分設為100質量%的情況下，樹脂組成物中的硬化劑的量優選為5質量%以上、更優選為10質量%以上、特別優選為20質量%以上，優選為80質量%以下、更優選為70質量%以下、特別優選為60質量%以下。在硬化劑的量處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。When the resin component in the resin composition is 100 mass %, the amount of the hardener in the resin composition is preferably 5 mass % or more, more preferably 10 mass % or more, particularly preferably 20 mass % or more, and preferably 80 mass % or less, more preferably 70 mass % or less, particularly preferably 60 mass % or less. When the amount of the hardener is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the hardened material including the resin composition can be effectively improved.

作為自由基聚合性樹脂，可使用具有乙烯性不飽和鍵的化合物。因此，自由基聚合性樹脂可具有包含乙烯性不飽和鍵的自由基聚合性基。作為自由基聚合性基，例如可舉出：乙烯基、烯丙基、3-環己烯基、3-環戊烯基、2-乙烯基苯基、3-乙烯基苯基、4-乙烯基苯基等不飽和烴基；丙烯醯基、甲基丙烯醯基、馬來醯亞胺基(2,5-二氫-2,5-二氧代-1H-吡咯-1-基)等的α,β-不飽和羰基等。自由基聚合性樹脂在1分子內包含的自由基聚合性基的數目可以是1個，但優選2個以上。自由基聚合性樹脂可單獨使用1種，也可將2種以上組合使用。As a free radical polymerizable resin, a compound having an ethylenic unsaturated bond can be used. Therefore, the free radical polymerizable resin may have a free radical polymerizable group containing an ethylenic unsaturated bond. As free radical polymerizable groups, for example, unsaturated alkyl groups such as vinyl, allyl, 3-cyclohexenyl, 3-cyclopentenyl, 2-vinylphenyl, 3-vinylphenyl, 4-vinylphenyl, etc.; α,β-unsaturated carbonyl groups such as acryl, methacryl, maleimide (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl), etc. can be cited. The number of free radical polymerizable groups contained in one molecule of the free radical polymerizable resin may be one, but preferably two or more. The free radical polymerizable resin may be used alone or in combination of two or more.

作為優選的自由基聚合性樹脂，例如可舉出：苯乙烯系自由基聚合性樹脂。苯乙烯系自由基聚合性樹脂可以是具有與芳香族碳原子直接鍵結的1個以上、優選2個以上乙烯基的化合物。作為苯乙烯系自由基聚合性樹脂，例如可舉出：二乙烯基苯、2,4-二乙烯基甲苯、2,6-二乙烯基萘、1,4-二乙烯基萘、4,4’-二乙烯基聯苯、1,2-雙(4-乙烯基苯基)乙烷、2,2-雙(4-乙烯基苯基)丙烷、雙(4-乙烯基苯基)醚等低分子量(分子量小於1000)的苯乙烯系化合物；乙烯基苄基改性聚苯醚樹脂、苯乙烯-二乙烯基苯共聚物等高分子量(分子量1000以上)的苯乙烯系化合物等。As a preferred free radical polymerizable resin, for example, styrene-based free radical polymerizable resins can be cited. The styrene-based free radical polymerizable resin can be a compound having one or more, preferably two or more vinyl groups directly bonded to an aromatic carbon atom. As styrene-based free radical polymerizable resins, for example, low molecular weight (molecular weight less than 1000) styrene-based compounds such as divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl)ether; high molecular weight (molecular weight 1000 or more) styrene-based compounds such as vinylbenzyl-modified polyphenylene ether resins and styrene-divinylbenzene copolymers can be cited.

作為苯乙烯系自由基聚合性樹脂，優選具有乙烯基苯基的改性聚苯醚樹脂。乙烯基苯基可包含2-乙烯基苯基、3-乙烯基苯基、4-乙烯基苯基、或它們的芳香族碳原子進一步被1個以上烷基取代的基。其中，作為苯乙烯系自由基聚合性樹脂，特別優選下述式(A-1)所表示的樹脂。As the styrene-based free radical polymerizable resin, a modified polyphenylene ether resin having a vinylphenyl group is preferred. The vinylphenyl group may include 2-vinylphenyl, 3-vinylphenyl, 4-vinylphenyl, or a group in which the aromatic carbon atoms thereof are further substituted with one or more alkyl groups. Among them, as the styrene-based free radical polymerizable resin, a resin represented by the following formula (A-1) is particularly preferred.

(式(A-1)中， R 11和R 12各自獨立地表示烷基； R 13、R 14、R 21、R 22、R 23和R 24各自獨立地表示氫原子或烷基； R 31和R 32各自獨立地表示乙烯基苯基； Y 1表示單鍵、-C(R y) 2-、-O-、-CO-、-S-、-SO-或   -SO 2-； R y各自獨立地表示氫原子或烷基； Y 2表示單鍵或伸烷基； p表示0或1； q和r各自獨立地表示1以上的整數。) q單元和r單元中，各自的每單元可相同也可不同。 (In formula (A-1), R 11 and R 12 each independently represent an alkyl group; R 13 , R 14 , R 21 , R 22 , R 23 and R 24 each independently represent a hydrogen atom or an alkyl group; R 31 and R 32 each independently represent a vinylphenyl group; Y 1 represents a single bond, -C(R y ) 2 -, -O-, -CO-, -S-, -SO- or -SO 2 -; R y each independently represents a hydrogen atom or an alkyl group; Y 2 represents a single bond or an alkylene group; p represents 0 or 1; q and r each independently represent an integer greater than 1.) In the q unit and the r unit, each unit may be the same or different.

式(A-1)中，R 11和R 12各自獨立地表示烷基，優選為甲基。 In formula (A-1), R 11 and R 12 each independently represent an alkyl group, preferably a methyl group.

式(A-1)中，R 13和R 14各自獨立地表示氫原子或烷基，優選為氫原子。 In formula (A-1), R 13 and R 14 each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom.

式(A-1)中，R 21和R 22各自獨立地表示氫原子或烷基，優選為氫原子或甲基，更優選為甲基。 In formula (A-1), R 21 and R 22 each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, more preferably a methyl group.

式(A-1)中，R 23和R 24各自獨立地表示氫原子或烷基，優選為氫原子或甲基。 In formula (A-1), R 23 and R 24 each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.

式(A-1)中，R 31和R 32各自獨立地表示乙烯基苯基。 In formula (A-1), R 31 and R 32 each independently represent a vinylphenyl group.

式(A-1)中，Y 2表示單鍵或伸烷基。伸烷基是指直鏈、支鏈和/或環狀的二價脂肪族飽和烴基。伸烷基優選為碳原子數1～14的伸烷基、更優選為碳原子數1～10的伸烷基、特別優選為碳原子數1～6的伸烷基。作為伸烷基，例如可舉出：-CH 2-、-CH 2-CH 2-、-CH(CH 3)-、   -CH 2-CH 2-CH 2-、-CH 2-CH(CH 3)-、-CH(CH 3)-CH 2-、    -C(CH 3) 2-等。優選Y 2為伸烷基(特別優選為-CH 2-)。 In formula (A-1), Y2 represents a single bond or an alkylene group. The alkylene group refers to a linear, branched and/or cyclic divalent aliphatic saturated hydrocarbon group. The alkylene group is preferably an alkylene group having 1 to 14 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and particularly preferably an alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group include -CH2- , -CH2 - CH2- , -CH ( CH3 )-, -CH2 - CH2 - CH2- , -CH2 - CH( CH3 )-, -CH(CH3) -CH2- , -C( CH3 ) 2- , and the like. Y2 is preferably an alkylene group (particularly preferably -CH2- ).

式(A-1)中，Y 1表示單鍵、-C(R y) 2-、-O-、  -CO-、-S-、-SO-或-SO 2-，優選為單鍵、-C(R y) 2-或-O-，特別優選為單鍵。R y各自獨立地表示氫原子或烷基，優選為氫原子或甲基。 In formula (A-1), Y1 represents a single bond, -C( Ry ) 2- , -O-, -CO-, -S-, -SO- or -SO2- , preferably a single bond, -C( Ry ) 2- or -O-, particularly preferably a single bond. Ry each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.

式(A-1)中，p表示0或1，優選為1。In formula (A-1), p represents 0 or 1, and preferably 1.

式(A-1)中，q和r各自獨立地表示1以上的整數，優選為1～200的整數，更優選為1～100的整數。In formula (A-1), q and r each independently represent an integer greater than or equal to 1, preferably an integer of 1 to 200, and more preferably an integer of 1 to 100.

作為式(A-1)所表示的樹脂的具體例，例如可舉出下述式(A-1-1)所表示的樹脂。作為式(A-1-1)所表示的樹脂，例如可舉出：三菱瓦斯化學公司製造的「OPE-2St 1200」、「OPE-2St 2200」(乙烯基苄基改性聚苯醚樹脂)。Specific examples of the resin represented by formula (A-1) include resins represented by the following formula (A-1-1). Examples of the resin represented by formula (A-1-1) include "OPE-2St 1200" and "OPE-2St 2200" (vinyl benzyl-modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Co., Ltd.

作為另一優選的自由基聚合性樹脂，例如可舉出：馬來醯亞胺系自由基聚合性樹脂。馬來醯亞胺系自由基聚合性樹脂可以是具有1個以上、優選2個以上馬來醯亞胺基的化合物。馬來醯亞胺系自由基聚合性樹脂可以是包含脂肪族胺骨架的脂肪族馬來醯亞胺化合物，也可以是包含芳香族胺骨架的芳香族馬來醯亞胺化合物。其中，作為馬來醯亞胺系自由基聚合性樹脂，特別優選下述式(A-2)所表示的樹脂。As another preferred free radical polymerizable resin, for example, maleimide-based free radical polymerizable resin can be cited. Maleimide-based free radical polymerizable resin can be a compound having one or more, preferably two or more maleimide groups. Maleimide-based free radical polymerizable resin can be an aliphatic maleimide compound containing an aliphatic amine skeleton, or an aromatic maleimide compound containing an aromatic amine skeleton. Among them, as the maleimide-based free radical polymerizable resin, the resin represented by the following formula (A-2) is particularly preferred.

(式(A-2)中， R a各自獨立地表示氫原子或烷基； 環E、環F和環G各自獨立地表示可具有取代基的芳香環； Z各自獨立地表示單鍵、-C(R z) 2-、-O-、-CO-、-S-、 -SO-、-SO 2-、-CONH-或-NHCO-； R z各自獨立地表示氫原子或烷基； s表示1以上的整數； t各自獨立地表示0或1； u各自獨立地表示0、1、2或3。) s單元、t單元和u單元中，各自的每單元可相同也可不同。 (In formula (A-2), Ra each independently represents a hydrogen atom or an alkyl group; Ring E, Ring F and Ring G each independently represent an aromatic ring which may have a substituent; Z each independently represents a single bond, -C( Rz ) 2- , -O-, -CO-, -S-, -SO-, -SO2- , -CONH- or -NHCO-; Rz each independently represents a hydrogen atom or an alkyl group; s represents an integer greater than 1; t each independently represents 0 or 1; u each independently represents 0, 1, 2 or 3.) In the s unit, t unit and u unit, each unit may be the same or different.

式(A-2)中，R a各自獨立地表示氫原子或烷基，優選為氫原子或甲基，更優選為氫原子。 In formula (A-2), Ra each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

式(A-2)中，環E、環F和環G各自獨立地表示可具有取代基的芳香環，優選為可具有取代基的苯環，更優選為可被選自烷基和芳基的基取代的苯環，特別優選為無取代的苯環。In formula (A-2), ring E, ring F and ring G each independently represent an aromatic ring which may have a substituent, preferably a benzene ring which may have a substituent, more preferably a benzene ring which may be substituted with a group selected from an alkyl group and an aryl group, and particularly preferably an unsubstituted benzene ring.

式(A-2)中，Z各自獨立地表示單鍵、     -C(R z) 2-、-O-、-CO-、-S-、-SO-、-SO 2-、-CONH-或    -NHCO-，優選為單鍵、-C(R z) 2-或-O-，更優選為單鍵或 -C(R z) 2-，特別優選為單鍵。R z各自獨立地表示氫原子或烷基，優選為氫原子或甲基。 In formula (A-2), Z each independently represents a single bond, -C( Rz ) 2- , -O-, -CO-, -S-, -SO-, -SO2- , -CONH- or -NHCO-, preferably a single bond, -C( Rz ) 2- or -O-, more preferably a single bond or -C( Rz ) 2- , particularly preferably a single bond. Rz each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.

式(A-2)中，s表示1以上的整數，優選為1～10的整數。In formula (A-2), s represents an integer of 1 or more, and preferably an integer of 1-10.

式(A-2)中，t各自獨立地表示0或1，優選為1。In formula (A-2), t each independently represents 0 or 1, and is preferably 1.

式(A-2)中，u各自獨立地表示0、1、2或3，優選為0、1或2，更優選為0或1，特別優選為1。In formula (A-2), u each independently represents 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 1.

作為式(A-2)所表示的樹脂的具體例，例如可舉出下述式(A-2-1)所表示的樹脂。作為式(A-2-1)所表示的樹脂，例如可舉出日本化藥公司製造的「MIR-3000-70MT」等。Specific examples of the resin represented by formula (A-2) include resins represented by the following formula (A-2-1). Examples of the resin represented by formula (A-2-1) include "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.

作為又一優選的自由基聚合性樹脂，例如可舉出：(甲基)丙烯酸系自由基聚合性樹脂。(甲基)丙烯酸系自由基聚合性樹脂可以是具有1個以上、優選2個以上丙烯醯基和/或甲基丙烯醯基的化合物。作為(甲基)丙烯酸系自由基聚合性樹脂，例如可舉出：環己烷-1,4-二甲醇二(甲基)丙烯酸酯、環己烷-1,3-二甲醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,8-辛二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯等低分子量(分子量小於1000)的脂肪族(甲基)丙烯酸酯化合物；二噁烷二醇二(甲基)丙烯酸酯、3,6-二氧雜-1,8-辛二醇二(甲基)丙烯酸酯、3,6,9-三氧雜十一烷-1,11-二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、9,9-雙[4-(2-丙烯醯氧基乙氧基)苯基]芴、乙氧基化雙酚A二(甲基)丙烯酸酯、丙氧基化雙酚A二(甲基)丙烯酸酯等低分子量(分子量小於1000)的含醚(甲基)丙烯酸酯化合物；三(3-羥丙基)異氰脲酸酯基三(甲基)丙烯酸酯、三(2-羥乙基)異氰脲酸酯基三(甲基)丙烯酸酯、乙氧基化異氰脲酸三(甲基)丙烯酸酯等低分子量(分子量小於1000)的含異氰脲酸酯基的(甲基)丙烯酸酯化合物；(甲基)丙烯酸改性聚苯醚樹脂等高分子量(分子量1000以上)的丙烯酸酯化合物等。作為(甲基)丙烯酸系自由基聚合性樹脂的市售品，例如可舉出：新中村化學工業公司製造的「A-DOG」(二噁烷二醇二丙烯酸酯)、共榮社化學公司製造的「DCP-A」(三環癸烷二甲醇二丙烯酸酯)、「DCP」 (三環癸烷二甲醇二甲基丙烯酸酯)、日本化藥株式會社的「KAYARAD R-684」(三環癸烷二甲醇二丙烯酸酯)、「KAYARAD R-604」(二噁烷二醇二丙烯酸酯)、SABIC Innovative Plastics公司製造的「SA9000」、「SA9000-111」(甲基丙烯酸改性聚苯醚)等。As another preferred free radical polymerizable resin, for example, (meth)acrylic free radical polymerizable resin can be mentioned. The (meth)acrylic free radical polymerizable resin can be a compound having one or more, preferably two or more acryl groups and/or methacrylic groups. As the (meth)acrylic free radical polymerizable resin, for example, cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1 ,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate and other low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylate compounds; dioxanediol di(meth)acrylate, 3,6-dioxa-1,8-octane Ether (methyl) acrylates containing low molecular weight (molecular weight less than 1000) such as glycol di(meth)acrylate, 3,6,9-trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, etc. ) acrylate compounds; low molecular weight (molecular weight less than 1000) isocyanurate group-containing (meth)acrylate compounds such as tri(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and ethoxylated isocyanuric acid tri(meth)acrylate; high molecular weight (molecular weight of 1000 or more) acrylate compounds such as (meth)acrylic acid-modified polyphenylene ether resin, etc. Examples of commercially available (meth)acrylic radical polymerizable resins include "A-DOG" (dioxanediol diacrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "DCP-A" (tricyclodecanedimethanol diacrylate) and "DCP" (tricyclodecanedimethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., "KAYARAD R-684" (tricyclodecanedimethanol diacrylate) and "KAYARAD R-604" (dioxanediol diacrylate) manufactured by Nippon Kayaku Co., Ltd., and "SA9000" and "SA9000-111" (methacrylic acid-modified polyphenylene ether) manufactured by SABIC Innovative Plastics Co., Ltd.

作為又一優選的自由基聚合性樹脂，例如可舉出：烯丙基系自由基聚合性樹脂。烯丙基系自由基聚合性樹脂可以是具有1個以上、優選2個以上烯丙基的化合物。作為烯丙基系自由基聚合性樹脂，例如可舉出：聯苯二甲酸二烯丙酯、偏苯三酸三烯丙酯、鄰苯二甲酸二烯丙酯、間苯二甲酸二烯丙酯、對苯二甲酸二烯丙酯、2,6-萘二甲酸二烯丙酯、2,3-萘甲酸二烯丙酯等芳香族羧酸烯丙酯化合物；1,3,5-三烯丙基異氰脲酸酯、1,3-二烯丙基-5-縮水甘油基異氰脲酸酯等異氰脲酸烯丙酯化合物；2,2-雙[3-烯丙基-4-(縮水甘油氧基)苯基]丙烷等含有環氧基的芳香族烯丙基化合物；雙[3-烯丙基-4-(3,4-二氫-2H-1,3-苯並噁嗪-3-基)苯基]甲烷等含有苯並噁嗪的芳香族烯丙基化合物；1,3,5-三烯丙基醚苯等含醚芳香族烯丙基化合物；二烯丙基二苯基矽烷等的烯丙基矽烷化合物等。作為烯丙基系自由基聚合性樹脂的市售品，例如可舉出：日本化成公司製造的「TAIC」 (1,3,5-三烯丙基異氰脲酸酯)、日觸Techno Fine Chemical公司製造的「DAD」(聯苯二甲酸二烯丙酯)、和光純藥工業公司製造的「TRIAM-705」(偏苯三酸三烯丙酯)、日本蒸餾工業公司製造的商品名「DAND」(2,3-萘甲酸二烯丙酯)、四國化成工業公司製造的「ALP-d」(雙[3-烯丙基-4-(3,4-二氫-2H-1,3-苯並噁嗪-3-基)苯基]甲烷)、日本化藥公司製造的「RE-810NM」(2,2-雙[3-烯丙基-4-(縮水甘油氧基)苯基]丙烷)、四國化成公司製造的「DA-MGIC」(1,3-二烯丙基-5-縮水甘油基異氰脲酸酯)等。As another preferred free radical polymerizable resin, for example, there can be mentioned: allyl-based free radical polymerizable resin. The allyl-based free radical polymerizable resin can be a compound having one or more, preferably two or more allyl groups. As the allyl-based free radical polymerizable resin, for example, there can be mentioned: aromatic carboxylic acid allyl ester compounds such as diallyl diphenyl dicarboxylate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalene dicarboxylate, and diallyl 2,3-naphthalene dicarboxylate; aromatic carboxylic acid allyl ester compounds such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; Ester compounds; aromatic allyl compounds containing an epoxy group such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; aromatic allyl compounds containing benzoxazine such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane; ether-containing aromatic allyl compounds such as 1,3,5-triallyl ether benzene; allyl silane compounds such as diallyldiphenylsilane, etc. Commercially available products of allyl-based free radical polymerizable resins include, for example, "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Chemical Industry Co., Ltd., and Nichikatsu Techno Fine "DAD" (diallyl diphenyl dicarboxylate) manufactured by Chemical Co., Ltd., "TRIAM-705" (triallyl trimellitate) manufactured by Wako Junyaku Industries Co., Ltd., "DAND" (diallyl 2,3-naphthoate) manufactured by Nippon Distillery Industries Co., Ltd., "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) manufactured by Shikoku Chemical Co., Ltd., "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane) manufactured by Nippon Kayaku Co., Ltd., "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Chemical Co., Ltd., etc.

另外，作為自由基聚合性樹脂，可使用在光硬化性樹脂的項目中說明的樹脂。As the radical polymerizable resin, the resins described in the section of the photocurable resin can be used.

自由基聚合性樹脂的乙烯性不飽和鍵當量優選為20g/eq.～3000g/eq.、更優選為50g/eq.～2500g/eq.、進一步優選為70g/eq.～2000g/eq.、特別優選為90g/eq.～1500g/eq.。乙烯性不飽和鍵當量表示每1當量乙烯性不飽和鍵的自由基聚合性樹脂的質量。The ethylenic unsaturated bond equivalent of the radical polymerizable resin is preferably 20 g/eq. to 3000 g/eq., more preferably 50 g/eq. to 2500 g/eq., further preferably 70 g/eq. to 2000 g/eq., and particularly preferably 90 g/eq. to 1500 g/eq. The ethylenic unsaturated bond equivalent indicates the mass of the radical polymerizable resin per 1 equivalent of ethylenic unsaturated bonds.

自由基聚合性樹脂的重量平均分子量(Mw)優選為40000以下、更優選為10000以下、進一步優選為5000以下、特別優選為3000以下。對下限沒有特別限定，例如可以是150以上。The weight average molecular weight (Mw) of the radical polymerizable resin is preferably 40,000 or less, more preferably 10,000 or less, further preferably 5,000 or less, and particularly preferably 3,000 or less. The lower limit is not particularly limited, and may be, for example, 150 or more.

在將樹脂組成物中的非揮發成分設為100質量%的情況下，樹脂組成物中的自由基聚合性樹脂的量優選為0.1質量%以上、更優選為0.5質量%以上、特別優選為1.0質量%以上，優選為10質量%以下、更優選為5.0質量%以下、特別優選為3.0質量%以下。在自由基聚合性樹脂的量處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。When the non-volatile components in the resin composition are set to 100% by mass, the amount of the radical polymerizable resin in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 1.0% by mass or more, and preferably 10% by mass or less, more preferably 5.0% by mass or less, particularly preferably 3.0% by mass or less. When the amount of the radical polymerizable resin is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved.

在將樹脂組成物中的樹脂成分設為100質量%的情況下，樹脂組成物中的自由基聚合性樹脂的量優選為0.1質量%以上、更優選為1.0質量%以上、特別優選為2.0質量%以上，優選為15質量%以下、更優選為10質量%以下、特別優選為8.0質量%以下。在自由基聚合性樹脂的量處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。When the resin component in the resin composition is 100 mass %, the amount of the radical polymerizable resin in the resin composition is preferably 0.1 mass % or more, more preferably 1.0 mass % or more, particularly preferably 2.0 mass % or more, and preferably 15 mass % or less, more preferably 10 mass % or less, particularly preferably 8.0 mass % or less. When the amount of the radical polymerizable resin is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved.

作為光硬化性樹脂，可使用在曝光時能夠硬化的樹脂。作為光硬化性樹脂的例子，可舉出自由基聚合性樹脂。光硬化性樹脂可單獨使用1種，也可將2種以上組合使用。As the photocurable resin, a resin that can be cured when exposed to light can be used. As an example of the photocurable resin, a radical polymerizable resin can be cited. The photocurable resin can be used alone or in combination of two or more.

關於作為光硬化性樹脂的自由基聚合性樹脂，可使用在熱硬化性樹脂的項目中說明的樹脂。另外，從能夠利用鹼性顯影液進行顯影的觀點出發，關於作為光硬化性樹脂的自由基聚合性樹脂，優選具有乙烯性不飽和鍵和羧基的樹脂。As the radical polymerizable resin as the photocurable resin, the resins described in the section of the thermosetting resin can be used. In addition, from the viewpoint of being able to be developed using an alkaline developer, the radical polymerizable resin as the photocurable resin is preferably a resin having an ethylenic unsaturated bond and a carboxyl group.

關於具有乙烯性不飽和鍵和羧基的樹脂，可組合具有包含乙烯性不飽和鍵的自由基聚合性基和羧基。作為自由基聚合性基的例子，可舉出上述的基。其中，優選(甲基)丙烯醯基。術語「(甲基)丙烯醯基」包括丙烯醯基、甲基丙烯醯基及其組合。每1分子樹脂的自由基聚合性基的數目可以是1個，也可以是2個以上。在每1分子樹脂包含2個以上自由基聚合性基的情況下，這些自由基聚合性基可相同也可不同。另外，每1分子樹脂的羧基的數目可以是1個，也可以是2個以上。Regarding the resin having ethylenic unsaturated bonds and carboxyl groups, a free radical polymerizable group containing ethylenic unsaturated bonds and a carboxyl group can be combined. As examples of free radical polymerizable groups, the above-mentioned groups can be cited. Among them, (meth)acryl group is preferred. The term "(meth)acryl group" includes acryl group, methacryl group and a combination thereof. The number of free radical polymerizable groups per 1 molecule of resin can be 1 or more than 2. When each molecule of resin contains more than 2 free radical polymerizable groups, these free radical polymerizable groups can be the same or different. In addition, the number of carboxyl groups per 1 molecule of resin can be 1 or more than 2.

具有乙烯性不飽和鍵和羧基的樹脂優選含有萘骨架。具有乙烯性不飽和鍵和羧基的樹脂在1分子中可包含1個萘骨架、也可包含2個以上的萘骨架。另外，具有乙烯性不飽和鍵和羧基的樹脂優選每1個萘骨架具有2個以下的自由基聚合性基。而且，自由基聚合性基優選包含在萘骨架的取代基中。另外，具有乙烯性不飽和鍵和羧基的樹脂優選每1個萘骨架具有2個以下的羧基。而且，羧基優選包含在萘骨架的取代基中。The resin having an ethylenic unsaturated bond and a carboxyl group preferably contains a naphthalene skeleton. The resin having an ethylenic unsaturated bond and a carboxyl group may contain one naphthalene skeleton or two or more naphthalene skeletons in one molecule. In addition, the resin having an ethylenic unsaturated bond and a carboxyl group preferably has two or less free radical polymerizable groups per one naphthalene skeleton. Moreover, the free radical polymerizable group is preferably contained in a substituent of the naphthalene skeleton. In addition, the resin having an ethylenic unsaturated bond and a carboxyl group preferably has two or less carboxyl groups per one naphthalene skeleton. Moreover, the carboxyl group is preferably contained in a substituent of the naphthalene skeleton.

作為具有乙烯性不飽和鍵和羧基的優選樹脂，可舉出含有下述式(A-3)所表示的結構的樹脂。具有乙烯性不飽和鍵和羧基的樹脂可僅具有1個下述式(A-3)所表示的結構、也可具有多個。具有乙烯性不飽和鍵和羧基的每1分子樹脂的式(A-3)所表示的結構的數目優選為1～10個、更優選為1～6個。式(A-3)中，R 1可以與萘骨架中所含的碳原子中的、任何可鍵結的碳原子鍵結。因此，R 1相對於末端結合鍵，可與相同苯環的碳原子鍵結，也可與不同苯環的碳原子鍵結。上述的末端結合鍵表示在與萘環鍵結的鍵結鍵中的、除與R 1鍵結的鍵結鍵和與OR 0鍵結的鍵結鍵以外的鍵結鍵，具體而言，表示描繪於式(A-3)的左端的鍵結鍵。例如，萘骨架中的末端鍵結鍵和與R 1鍵結的鍵結鍵的位置的組合可以是1,2位、1,3位、1,4位、1,5位、1,6位、1,7位、1,8位、2,3位、2,6位和2,7位。 As a preferred resin having an ethylenic unsaturated bond and a carboxyl group, a resin containing a structure represented by the following formula (A-3) can be cited. The resin having an ethylenic unsaturated bond and a carboxyl group may have only one structure represented by the following formula (A-3) or may have multiple structures. The number of structures represented by the formula (A-3) per molecule of the resin having an ethylenic unsaturated bond and a carboxyl group is preferably 1 to 10, more preferably 1 to 6. In formula (A-3), R1 can bond to any bondable carbon atom among the carbon atoms contained in the naphthalene skeleton. Therefore, R1 can bond to a carbon atom of the same benzene ring or to a carbon atom of a different benzene ring with respect to the terminal bonding bond. The terminal bond mentioned above refers to a bond other than the bond to R1 and the bond to OR0 among the bonds to the naphthalene ring, and specifically refers to the bond depicted on the left side of formula (A-3). For example, the combination of the position of the terminal bond in the naphthalene skeleton and the bond to R1 can be 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 2,3, 2,6 and 2,7.

式(A-3)中，R 1和R 2各自獨立地表示可具有取代基的伸烷基。R 1和R 2的碳原子數通常為1～20、優選為1～10、更優選為1～6。另外，伸烷基可以是直鏈狀、也可以是支鏈狀。作為伸烷基，例如可舉出：亞甲基、伸乙基、伸丙基、伸丁基等，優選為亞甲基。關於R 1和R 2可具有的取代基，例如可舉出：鹵原子、烷基、烷氧基、芳基、芳基烷基、矽基、醯基、醯氧基、羧基、磺基、氰基、硝基、羥基、巰基、氧代基等。 In formula (A-3), R1 and R2 each independently represent an alkylene group which may have a substituent. The number of carbon atoms of R1 and R2 is usually 1 to 20, preferably 1 to 10, and more preferably 1 to 6. In addition, the alkylene group may be linear or branched. Examples of the alkylene group include methylene, ethyl, propyl, butyl, and the like, preferably methylene. Examples of the substituents which R1 and R2 may have include halogen atoms, alkyl, alkoxy, aryl, arylalkyl, silyl, acyl, acyloxy, carboxyl, sulfo, cyano, nitro, hydroxyl, hydroxyl, oxo, and the like.

式(A-3)中，X表示可具有取代基的伸芳基。X的碳原子數通常為6～30、優選為6～20、更優選為6～10。伸芳基例如可舉出：伸苯基、伸蒽基、伸菲基、伸聯苯基，優選為伸苯基。X可具有的取代基例如可舉出：與R 1和R 2可具有的取代基相同的例子。 In formula (A-3), X represents an arylene group which may have a substituent. The number of carbon atoms of X is usually 6 to 30, preferably 6 to 20, and more preferably 6 to 10. Examples of the arylene group include phenylene, anthracenyl, phenanthrenyl, and biphenylene, preferably phenylene. Examples of the substituent that X may have include the same examples as the substituent that R 1 and R 2 may have.

式(A-3)中，a表示0或1，優選為1。在此，a為基X的數目。In formula (A-3), a represents 0 or 1, preferably 1. Here, a is the number of the base X.

式(A-3)中，b表示0或1。另外，式(A-3)中，c表示0或1。在此，b和c分別是基R 1和基R 2的數目。然而，b和c是b+c不等於0。b和c均優選為1。 In formula (A-3), b represents 0 or 1. In formula (A-3), c represents 0 or 1. Here, b and c are the number of groups R1 and R2 , respectively. However, b and c are such that b+c is not equal to 0. Both b and c are preferably 1.

式(A-3)中，OR 0表示萘骨架上的取代基。R 0各自獨立地表示包含自由基聚合性基和羧基的有機基。該R 0優選表示下述式(A-4)所示的基。 In formula (A-3), OR 0 represents a substituent on the naphthalene skeleton. R 0 each independently represents an organic group including a radical polymerizable group and a carboxyl group. The R 0 preferably represents a group represented by the following formula (A-4).

式(A-4)中，R 3表示三價基。R 3優選表示可具有取代基的三價烴基(其中，雜原子可介於碳-碳鍵(C-C鍵)之間)。其中，R 3優選可具有取代基的三價脂肪族烴基。關於R 3可具有的取代基，例如可舉出：與R 1和R 2可具有的取代基相同的例子。 In formula (A-4), R3 represents a trivalent group. R3 preferably represents a trivalent hydrocarbon group which may have a substituent (wherein a heteroatom may be present between carbon-carbon bonds (CC bonds)). Among them, R3 is preferably a trivalent aliphatic hydrocarbon group which may have a substituent. Regarding the substituent that R3 may have, for example, the same examples as the substituents that R1 and R2 may have can be cited.

式(A-4)中，R 4表示包含自由基聚合性基的有機基。作為包含自由基聚合性基的有機基的優選例子，可舉出(甲基)丙烯醯氧基。「(甲基)丙烯醯氧基」包括丙烯醯氧基、甲基丙烯醯氧基和它們的組合。 In formula (A-4), R4 represents an organic group containing a radical polymerizable group. As a preferred example of an organic group containing a radical polymerizable group, a (meth)acryloyloxy group can be cited. "(Meth)acryloyloxy group" includes an acryloxy group, a methacryloyloxy group, and a combination thereof.

式(A-4)中，R 5表示包含羧基的有機基。包含羧基的有機基的例子，可舉出-OCO-R 6-COOH。在此，R 6表示二價基。作為R 6，優選可具有取代基的二價烴基。R 6的碳原子數通常為1～30、優選為1～20、更優選為1～6。作為二價烴基，例如可舉出：亞甲基、伸乙基、伸丙基、伸丁基等直鏈狀或支鏈狀的非環式伸烷基；飽和或不飽和的二價脂環式烴基；伸苯基、伸萘基等的伸芳基等。其中，優選二價脂環式烴基和伸芳基，特別優選4-伸環己烯基和伸苯基。另外，關於R 6可具有的取代基，例如可舉出：與R 1和R 2可具有的取代基相同的例子。-OCO-R 6-COOH中的-CO-R 6-COOH可以是羧酸酐的殘基。作為羧酸酐的例子，可舉出：馬來酸酐、琥珀酸酐、衣康酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、偏苯三酸酐、均苯四酸酐、二苯甲酮四甲酸二酐。 In formula (A-4), R 5 represents an organic group containing a carboxyl group. Examples of organic groups containing a carboxyl group include -OCO-R 6 -COOH. Here, R 6 represents a divalent group. As R 6 , a divalent alkyl group which may have a substituent is preferred. The number of carbon atoms of R 6 is usually 1 to 30, preferably 1 to 20, and more preferably 1 to 6. Examples of the divalent alkyl group include: linear or branched non-cyclic alkyl groups such as methylene, ethyl, propyl, and butyl; saturated or unsaturated divalent alicyclic alkyl groups; aryl groups such as phenyl and naphthyl. Among them, divalent alicyclic alkyl groups and aryl groups are preferred, and 4-cyclohexenyl and phenyl are particularly preferred. In addition, as for the substituent which R 6 may have, for example, the same examples as the substituent which R 1 and R 2 may have can be cited. -CO-R 6 -COOH in -OCO-R 6 -COOH may be a residue of a carboxylic anhydride. Examples of carboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic anhydride.

式(A-3)中，d通常表示1～6、優選為1～3、更優選為1～2的整數。在此，d表示基OR 0的數目。 In formula (A-3), d is an integer of usually 1 to 6, preferably 1 to 3, and more preferably 1 to 2. Here, d represents a number in the radical OR 0 .

從成膜性的觀點出發，具有乙烯性不飽和鍵和羧基的樹脂的重量平均分子量優選為500以上、更優選為1000以上、進一步優選為1500以上、更進一步優選為2000以上。作為上限，從顯影性的觀點出發，優選為10000以下、更優選為8000以下、進一步優選為7500以下。From the viewpoint of film-forming property, the weight average molecular weight of the resin having an ethylenically unsaturated bond and a carboxyl group is preferably 500 or more, more preferably 1000 or more, further preferably 1500 or more, further preferably 2000 or more. From the viewpoint of developing property, the upper limit is preferably 10000 or less, more preferably 8000 or less, further preferably 7500 or less.

從使對鹼性顯影液的溶解性限制在適當範圍的觀點出發，具有乙烯性不飽和鍵和羧基的樹脂的酸價優選為0.1mgKOH/g以上、更優選為0.5mgKOH/g以上、特別優選為1mgKOH/g以上，優選為150mgKOH/g以下、更優選為120mgKOH/g以下、特別優選為100mgKOH/g以下。From the viewpoint of limiting the solubility in alkaline developer to an appropriate range, the acid value of the resin having ethylenically unsaturated bonds and carboxyl groups is preferably 0.1 mgKOH/g or more, more preferably 0.5 mgKOH/g or more, particularly preferably 1 mgKOH/g or more, and preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, particularly preferably 100 mgKOH/g or less.

酸價可通過以下方法來測定。首先，精密稱量約1g的測定樹脂溶液之後，向該樹脂溶液中添加30g的丙酮，使樹脂溶液均勻地溶解。然後，向該溶液中適量添加作為指示劑的酚酞，使用0.1N的乙醇性KOH溶液進行滴定。而且，通過下述式(X1)算出酸價。 The acid value can be measured by the following method. First, after accurately weighing about 1 g of the test resin solution, 30 g of acetone is added to the resin solution to uniformly dissolve the resin solution. Then, an appropriate amount of phenolphthalein is added to the solution as an indicator, and titration is performed using a 0.1 N ethanolic KOH solution. Then, the acid value is calculated by the following formula (X1).

需要說明的是，上述式(X1)中，A表示酸價[mgKOH/g]，Vf表示KOH溶液的滴定量[mL]，Wp表示測定樹脂溶液的質量[g]，I表示測定樹脂溶液的非揮發成分的比例[質量%]。It should be noted that in the above formula (X1), A represents the acid value [mgKOH/g], Vf represents the titration amount of the KOH solution [mL], Wp represents the mass of the measured resin solution [g], and I represents the ratio of the non-volatile components of the measured resin solution [mass %].

在將樹脂組成物中的非揮發成分設為100質量%的情況下，作為光硬化性樹脂的自由基聚合性樹脂的量優選為5質量%以上、更優選為10質量%以上、進一步優選為20質量%以上，優選為50質量%以下、更優選為40質量%以下、進一步優選為30質量%以下。在自由基聚合性樹脂的量處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。When the non-volatile components in the resin composition are 100% by mass, the amount of the radical polymerizable resin as the photocurable resin is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less. When the amount of the radical polymerizable resin is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product including the resin composition can be effectively improved.

在將樹脂組成物中的樹脂成分設為100質量%的情況下，作為光硬化性樹脂的自由基聚合性樹脂的量優選為20質量%以上、更優選為30質量%以上、特別優選為40質量%以上，優選為80質量%以下、更優選為70質量%以下、特別優選為65質量%以下。在自由基聚合性樹脂的量處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。When the resin component in the resin composition is 100 mass %, the amount of the radical polymerizable resin as the photocurable resin is preferably 20 mass % or more, more preferably 30 mass % or more, particularly preferably 40 mass % or more, and preferably 80 mass % or less, more preferably 70 mass % or less, particularly preferably 65 mass % or less. When the amount of the radical polymerizable resin is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product including the resin composition can be effectively improved.

在將樹脂組成物中的非揮發成分設為100質量%的情況下，樹脂組成物中的(A)硬化性樹脂的量優選為10質量%以上、更優選為20質量%以上、特別優選為30質量%以上，優選為70質量%以下、更優選為60質量%以下、特別優選為50質量%以下。在(A)硬化性樹脂的量處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。When the non-volatile components in the resin composition are set to 100 mass %, the amount of the (A) curable resin in the resin composition is preferably 10 mass % or more, more preferably 20 mass % or more, particularly preferably 30 mass % or more, and preferably 70 mass % or less, more preferably 60 mass % or less, particularly preferably 50 mass % or less. When the amount of the (A) curable resin is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved.

在將樹脂組成物中的樹脂成分設為100質量%的情況下，樹脂組成物中的(A)硬化性樹脂的量優選為60質量%以上、更優選為70質量%以上、特別優選為80質量%以上，優選為97質量%以下、更優選為95質量%以下、特別優選為90質量%以下。在(A)硬化性樹脂的量處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。When the resin component in the resin composition is 100 mass %, the amount of the (A) curable resin in the resin composition is preferably 60 mass % or more, more preferably 70 mass % or more, particularly preferably 80 mass % or more, and preferably 97 mass % or less, more preferably 95 mass % or less, particularly preferably 90 mass % or less. When the amount of the (A) curable resin is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved.

[3. (B)無機填充材料] 本發明的第一實施方式所涉及的樹脂組成物包含作為(B)成分的(B)無機填充材料。(B)無機填充材料通常以粒子的狀態包含在樹脂組成物中。 [3. (B) Inorganic filler] The resin composition according to the first embodiment of the present invention contains (B) inorganic filler as component (B). The (B) inorganic filler is usually contained in the resin composition in the form of particles.

作為(B)無機填充材料的材料，可使用無機化合物。作為(B)無機填充材料的材料，例如可舉出：二氧化矽、氧化鋁、玻璃、堇青石、矽氧化物、硫酸鋇、碳酸鋇、滑石、黏土、雲母粉、氧化鋅、水滑石、勃姆石、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、氧化鎂、氮化硼、氮化鋁、氮化錳、硼酸鋁、碳酸鍶、鈦酸鍶、鈦酸鈣、鈦酸鎂、鈦酸鉍、氧化鈦、氧化鋯、鈦酸鋇、鈦酸鋯酸鋇、鋯酸鋇、鋯酸鈣、磷酸鋯和磷酸鎢酸鋯等。As the material of the (B) inorganic filler, an inorganic compound can be used. Examples of the material of the (B) inorganic filler include silicon dioxide, aluminum oxide, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate.

另外，作為(B)無機填充材料的材料，可使用無機複合氧化物。無機複合氧化物表示包含選自金屬原子和類金屬原子的2種以上原子的氧化物。作為這樣的無機複合氧化物，優選包含矽與矽以外的選自金屬原子和類金屬原子的1種以上原子的組合的氧化物。作為與矽組合的金屬原子，可舉出：鋁、鉛、鎳、鈷、銅、鋅、鋯、鐵、鋰、鎂、鋇、鉀、鈣、鈦、硼、鈉等，其中特別優選鋁。因此，作為無機複合氧化物，優選包含矽和鋁的氧化物，特別優選矽鋁酸鹽。In addition, as the material of (B) inorganic filler, an inorganic composite oxide can be used. The inorganic composite oxide means an oxide containing two or more atoms selected from metal atoms and metalloid atoms. As such an inorganic composite oxide, an oxide containing a combination of silicon and one or more atoms selected from metal atoms and metalloid atoms other than silicon is preferred. As metal atoms combined with silicon, there can be cited: aluminum, lead, nickel, cobalt, copper, zinc, zirconium, iron, lithium, magnesium, barium, potassium, calcium, titanium, boron, sodium, etc., among which aluminum is particularly preferred. Therefore, as an inorganic composite oxide, an oxide containing silicon and aluminum is preferred, and aluminosilicate is particularly preferred.

這些(B)無機填充材料的材料之中，適合的是二氧化矽、氧化鋁和矽鋁酸鹽，特別適合的是二氧化矽。(B)無機填充材料可單獨使用1種，也可將2種以上組合使用。Among these (B) inorganic fillers, silicon dioxide, aluminum oxide and aluminosilicate are suitable, and silicon dioxide is particularly suitable. The (B) inorganic filler may be used alone or in combination of two or more.

(B)無機填充材料可分類為：內部具有空孔的(B-1)中空無機填充材料和內部不具有空孔的(B-2)實心無機填充材料。(B)無機填充材料優選包含(B-1)中空無機填充材料。(B-1)中空無機填充材料由於在該(B-1)中空無機填充材料的粒子的內部具有空孔，所以通常可具有小於(B-2)實心無機填充材料的比重。因此，在(B)無機填充材料包含(B-1)中空無機填充材料的情況下，可減小樹脂組成物的硬化物的比重。另外，在使用(B-1)中空無機填充材料的情況下，通常可降低樹脂組成物的硬化物的相對介電常數。(B) Inorganic fillers can be classified into (B-1) hollow inorganic fillers having pores inside and (B-2) solid inorganic fillers not having pores inside. (B) Inorganic fillers preferably include (B-1) hollow inorganic fillers. Since (B-1) hollow inorganic fillers have pores inside the particles of the (B-1) hollow inorganic fillers, they generally have a specific gravity smaller than that of (B-2) solid inorganic fillers. Therefore, when (B) Inorganic fillers include (B-1) hollow inorganic fillers, the specific gravity of the cured resin composition can be reduced. In addition, when (B-1) hollow inorganic fillers are used, the relative dielectric constant of the cured resin composition can generally be reduced.

(B-1)中空無機填充材料可以是在粒子內部僅具有1個空孔的單中空粒子，也可以是在粒子內部具有2個以上空孔的多中空粒子，還可以是單中空粒子與多中空粒子的組合。The (B-1) hollow inorganic filler may be a single hollow particle having only one hole inside the particle, may be a multi-hollow particle having two or more holes inside the particle, or may be a combination of a single hollow particle and a multi-hollow particle.

(B-1)中空無機填充材料由於具有空孔，所以通常具有大於0體積%的空孔率。從有效地改善包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性的觀點出發，(B-1)中空無機填充材料的空孔率優選為10體積%以上、更優選為15體積%以上、特別優選為20體積%以上。另外，從樹脂組成物的硬化物的機械強度的觀點出發，(B-1)中空無機填充材料的空孔率優選為95體積%以下、更優選為90體積%以下、特別優選為85體積%以下。Since the hollow inorganic filler (B-1) has pores, it usually has a porosity greater than 0 volume %. From the viewpoint of effectively improving the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition, the porosity of the hollow inorganic filler (B-1) is preferably 10 volume % or more, more preferably 15 volume % or more, and particularly preferably 20 volume % or more. In addition, from the viewpoint of the mechanical strength of the cured product of the resin composition, the porosity of the hollow inorganic filler (B-1) is preferably 95 volume % or less, more preferably 90 volume % or less, and particularly preferably 85 volume % or less.

粒子的空孔率P(體積%)被定義為：在粒子內部存在1個或2個以上的空孔的總體積相對於以粒子的外表面為基準的粒子整體的體積的體積基準比例(空孔的總體積/粒子的體積)。該空孔率P可使用粒子的實際密度的測定值D M(g/cm 3)和形成粒子的材料的物質密度的理論值D T(g/cm 3)，通過下述式(X2)算出。 The porosity P (volume %) of a particle is defined as the volume ratio of the total volume of one or more pores existing inside the particle to the volume of the entire particle based on the outer surface of the particle (total volume of pores/volume of particle). The porosity P can be calculated by the following formula (X2) using the measured value DM (g/ cm3 ) of the actual density of the particle and the theoretical value DT (g/ cm3 ) of the material density of the material forming the particle.

(B)中空無機粒子通常具有在該粒子內形成的空孔和包圍該空孔的由無機材料形成的外殼部。通常，空孔通過外殼部而與粒子外部區分開。此時，希望空孔不與粒子外部連通。因此，希望外殼部為不具有將空孔與粒子外部連通的孔的無氣孔的殼。外殼部為無氣孔的情況可通過用透射型電子顯微鏡(TEM)觀察來確認。(B) Hollow inorganic particles usually have pores formed in the particles and a shell formed of an inorganic material surrounding the pores. Usually, the pores are separated from the outside of the particles by the shell. In this case, it is desirable that the pores are not connected to the outside of the particles. Therefore, it is desirable that the shell is a non-porous shell without holes connecting the pores to the outside of the particles. Whether the shell is non-porous can be confirmed by observation with a transmission electron microscope (TEM).

(B-1)中空無機填充材料的平均粒徑優選為0.01μm以上、更優選為0.1μm以上、特別優選為0.3μm以上，優選為5μm以下、更優選為4μm以下、特別優選為3μm以下。在(B-1)中空無機填充材料的平均粒徑處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。The average particle size of the hollow inorganic filler (B-1) is preferably 0.01 μm or more, more preferably 0.1 μm or more, particularly preferably 0.3 μm or more, and preferably 5 μm or less, more preferably 4 μm or less, particularly preferably 3 μm or less. When the average particle size of the hollow inorganic filler (B-1) is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved.

粒子的平均粒徑可通過基於米氏(Mie)散射理論的雷射繞射/散射法進行測定。具體而言，可通過雷射繞射散射式粒徑分佈測定裝置，以體積基準製作粒子的粒徑分佈，將其中值粒徑作為平均粒徑來進行測定。無機填充材料的測定樣品可使用將100mg無機填充材料、10g甲基乙基酮稱量至管形瓶中並通過超音波分散10分鐘而得的樣品。對於測定樣品，使用雷射繞射式粒徑分佈測定裝置，將使用光源波長設為藍色和紅色，以流動池(flow cell)方式測定無機填充材料的體積基準的粒徑分佈，根據所得的粒徑分佈可算出作為中值粒徑的平均粒徑。作為雷射繞射式粒徑分佈測定裝置，例如可舉出：堀場製作所公司製造的「LA-960」等。The average particle size of particles can be measured by the laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of particles can be prepared on a volume basis using a laser diffraction scattering particle size distribution measuring device, and the median particle size can be used as the average particle size for measurement. The measurement sample of the inorganic filler can be a sample obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing it by ultrasonic waves for 10 minutes. For the sample to be measured, a laser diffraction particle size distribution measuring device is used, and the wavelength of the light source used is set to blue and red. The particle size distribution of the inorganic filler based on the volume is measured by a flow cell method, and the average particle size as the median particle size is calculated from the obtained particle size distribution. Examples of laser diffraction particle size distribution measuring devices include "LA-960" manufactured by Horiba, Ltd.

(B-1)中空無機填充材料的BET比表面積優選為1m 2/g以上、更優選為2m 2/g以上、特別優選為5m 2/g以上，優選為100m 2/g以下、更優選為50m 2/g以下、特別優選為30m 2/g以下。在(B-1)中空無機填充材料的BET比表面積處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。粒子的BET比表面積可通過下述方式進行測定：按照BET法，使用比表面積測定裝置(Mountech公司製造的Macsorb HM-1210)，使氮氣吸附於試樣表面，利用BET多點法算出比表面積。 The BET specific surface area of the hollow inorganic filler (B-1) is preferably 1 m 2 /g or more, more preferably 2 m 2 /g or more, particularly preferably 5 m 2 /g or more, and is preferably 100 m 2 /g or less, more preferably 50 m 2 /g or less, particularly preferably 30 m 2 /g or less. When the BET specific surface area of the hollow inorganic filler (B-1) is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved. The BET specific surface area of the particles can be measured in the following manner: According to the BET method, a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) is used to adsorb nitrogen gas on the sample surface and the specific surface area is calculated using the BET multipoint method.

(B-1)中空無機填充材料可使用市售品。作為市售的(B-1)中空無機填充材料，可舉出：太平洋水泥公司製造的「CellSpheres」和「MGH-005」；日揮觸媒化成公司製造的「ESPHERIQUE」和「BA-1」等。另外，(B-1)中空無機填充材料可使用通過常規方法製造的材料。舉具體例子來說，作為(B-1)中空無機填充材料的一個例子的中空二氧化矽粒子可通過包括下述步驟的方法製造：準備包含可形成空孔的物質和鹼性化合物的水溶液的步驟；將上述水溶液與烷氧基矽烷混合並攪拌，使二氧化矽粒子析出的步驟；從二氧化矽粒子中去除可形成空孔的物質，得到中空二氧化矽前驅物的步驟；以及燒成中空二氧化矽前驅物的步驟。(B-1) Hollow inorganic filler materials may be commercially available. Examples of commercially available (B-1) hollow inorganic filler materials include "CellSpheres" and "MGH-005" manufactured by Pacific Cement Co., Ltd., and "ESPHERIQUE" and "BA-1" manufactured by Nichia Catalyst Chemicals Co., Ltd. In addition, (B-1) hollow inorganic filler materials may be materials produced by conventional methods. To give a specific example, hollow silica particles as an example of the hollow inorganic filler (B-1) can be produced by a method comprising the following steps: a step of preparing an aqueous solution containing a substance capable of forming pores and an alkaline compound; a step of mixing and stirring the aqueous solution with alkoxysilane to precipitate silica particles; a step of removing the substance capable of forming pores from the silica particles to obtain a hollow silica precursor; and a step of calcining the hollow silica precursor.

從提高耐濕性和分散性的觀點出發，(B-1)中空無機填充材料優選用表面處理劑進行處理。作為表面處理劑，例如可舉出：含氟矽烷偶合劑、胺基矽烷系偶合劑、環氧基矽烷系偶合劑、巰基矽烷系偶合劑、矽烷系偶合劑、烷氧基矽烷、有機矽氮烷化合物、鈦酸酯系偶合劑等。表面處理劑可單獨使用1種，也可將2種以上任意地組合使用。From the viewpoint of improving moisture resistance and dispersibility, the (B-1) hollow inorganic filler material is preferably treated with a surface treatment agent. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, butylsilane-based coupling agents, silane-based coupling agents, alkoxysilanes, organic silazane compounds, and titanium ester-based coupling agents. The surface treatment agent may be used alone or in any combination of two or more.

作為表面處理劑的市售品，例如可舉出：信越化學工業公司製造的「KBM403」(3-環氧丙氧基丙基三甲氧基矽烷)、信越化學工業公司製造的「KBM803」(3-巰基丙基三甲氧基矽烷)、信越化學工業公司製造的「KBE903」(3-胺基丙基三乙氧基矽烷)、信越化學工業公司製造的「KBM573」(N-苯基-3-胺基丙基三甲氧基矽烷)、信越化學工業公司製造的「SZ-31」(六甲基二矽氮烷)、信越化學工業公司製造的「KBM103」(苯基三甲氧基矽烷)、信越化學工業公司製造的「KBM-4803」(長鏈環氧型矽烷偶合劑)、信越化學工業公司製造的「KBM-7103」(3,3,3-三氟丙基三甲氧基矽烷)等。Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical, "KBM803" (3-butylpropyltrimethoxysilane) manufactured by Shin-Etsu Chemical, "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical, and "KBM573" (N-phenyl -3-aminopropyltrimethoxysilane), "SZ-31" manufactured by Shin-Etsu Chemical Co., Ltd. (hexamethyldisilazane), "KBM103" manufactured by Shin-Etsu Chemical Co., Ltd. (phenyltrimethoxysilane), "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy-type silane coupling agent), "KBM-7103" manufactured by Shin-Etsu Chemical Co., Ltd. (3,3,3-trifluoropropyltrimethoxysilane), etc.

從分散性提高的觀點出發，通過表面處理劑進行的表面處理的程度優選限制在特定的範圍。具體而言，100質量%的無機填充材料優選通過0.2質量%～8質量%的表面處理劑進行表面處理，更優選通過0.2質量%～5質量%的表面處理劑進行表面處理，進一步優選通過0.3質量%～3質量%的表面處理劑進行表面處理。From the viewpoint of improving dispersibility, the degree of surface treatment by the surface treatment agent is preferably limited to a specific range. Specifically, 100% by mass of the inorganic filler is preferably surface treated with 0.2% by mass to 8% by mass of the surface treatment agent, more preferably 0.2% by mass to 5% by mass of the surface treatment agent, and further preferably 0.3% by mass to 3% by mass of the surface treatment agent.

通過表面處理劑進行的表面處理的程度可通過無機填充材料的每單位表面積的碳量進行評價。從無機填充材料的分散性提高的觀點出發，無機填充材料的每單位表面積的碳量優選0.02mg/m 2以上、更優選0.1mg/m 2以上、進一步優選0.2mg/m 2以上。另一方面，從防止樹脂組成物的熔融黏度的上升的觀點出發，優選1.0mg/m 2以下、更優選0.8mg/m 2以下、進一步優選0.5mg/m 2以下。 The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/ m2 or more, more preferably 0.1 mg/ m2 or more, and further preferably 0.2 mg/ m2 or more. On the other hand, from the viewpoint of preventing the increase in the melt viscosity of the resin composition, it is preferably 1.0 mg/ m2 or less, more preferably 0.8 mg/ m2 or less, and further preferably 0.5 mg/ m2 or less.

可在用溶劑(例如，甲基乙基酮(MEK))對表面處理後的無機填充材料進行洗滌處理之後，測定無機填充材料的每單位表面積的碳量。具體而言，將作為溶劑的足夠量的MEK加入到用表面處理劑進行了表面處理的無機填充材料中，在25℃下進行5分鐘的超音波洗滌。去除上清液，使固體成分乾燥後，使用碳分析儀，可測定無機填充材料的每單位表面積的碳量。作為碳分析儀，可使用堀場製作所公司製造的「EMIA-320V」等。The amount of carbon per unit surface area of the inorganic filler can be measured after washing the surface-treated inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic washing is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid components, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

在將樹脂組成物中的非揮發成分設為100質量%的情況下，樹脂組成物中的(B-1)中空無機填充材料的量(質量%)優選為5質量%以上、更優選為10質量%以上、特別優選為15質量%以上，優選為80質量%以下、更優選為70質量%以下、特別優選為60質量%以下。在(B-1)中空無機填充材料的量處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。When the non-volatile components in the resin composition are set to 100 mass %, the amount (mass %) of the hollow inorganic filler (B-1) in the resin composition is preferably 5 mass % or more, more preferably 10 mass % or more, particularly preferably 15 mass % or more, and preferably 80 mass % or less, more preferably 70 mass % or less, particularly preferably 60 mass % or less. When the amount of the hollow inorganic filler (B-1) is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved.

在將樹脂組成物中的非揮發成分設為100質量%的情況下，樹脂組成物中的(B-1)中空無機填充材料的量(體積%)優選為5體積%以上、更優選為10體積%以上、特別優選為15體積%以上，優選為80體積%以下、更優選為70體積%以下、特別優選為60體積%以下。在(B-1)中空無機填充材料的量處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。When the non-volatile components in the resin composition are set to 100% by mass, the amount (volume %) of the hollow inorganic filler (B-1) in the resin composition is preferably 5% by volume or more, more preferably 10% by volume or more, particularly preferably 15% by volume or more, and preferably 80% by volume or less, more preferably 70% by volume or less, particularly preferably 60% by volume or less. When the amount of the hollow inorganic filler (B-1) is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved.

(B)無機填充材料可包含(B-2)實心無機填充材料。作為(B-2)實心無機填充材料的市售品，例如可舉出：日鐵化學材料公司製造的「SP60-05」、「SP507-05」；Admatechs公司製造的「YC100C」、「YA050C」、「YA050C-MJE」、「YA010C」、「SC2500SQ」、「SO-C4」、「SO-C2」、「SO-C1」；DENKA公司製造的「UFP-30」、「DAW-03」、「FB-105FD」；Tokuyama公司製造的「SILFIL NSS-3N」、「SILFIL NSS-4N」、「SILFIL NSS-5N」等。(B) The inorganic filler may include (B-2) a solid inorganic filler. Examples of commercially available solid inorganic fillers (B-2) include: "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs; "UFP-30", "DAW-03", and "FB-105FD" manufactured by DENKA; and "SILFIL NSS-3N", "SILFIL NSS-4N", and "SILFIL NSS-5N" manufactured by Tokuyama Co., Ltd.

(B-2)實心無機填充材料的平均粒徑優選為0.01μm以上、更優選為0.1μm以上、特別優選為0.3μm以上，優選為10μm以下、更優選為5μm以下、特別優選為3μm以下。The average particle size of the solid inorganic filler (B-2) is preferably 0.01 μm or more, more preferably 0.1 μm or more, particularly preferably 0.3 μm or more, and is preferably 10 μm or less, more preferably 5 μm or less, particularly preferably 3 μm or less.

(B-2)實心無機填充材料的BET比表面積優選為0.1m 2/g以上、更優選為0.5m 2/g以上、特別優選為1m 2/g以上，優選為100m 2/g以下、更優選為70m 2/g以下、特別優選為40m 2/g以下。 The BET specific surface area of the (B-2) solid inorganic filler is preferably 0.1 m 2 /g or more, more preferably 0.5 m 2 /g or more, particularly preferably 1 m 2 /g or more, and is preferably 100 m 2 /g or less, more preferably 70 m 2 /g or less, particularly preferably 40 m 2 /g or less.

(B-2)實心無機填充材料與(B-1)中空無機填充材料相同，優選用表面處理劑進行處理。The solid inorganic filler (B-2) is similar to the hollow inorganic filler (B-1) and is preferably treated with a surface treatment agent.

在將樹脂組成物中的非揮發成分設為100質量%的情況下，樹脂組成物中的(B-2)實心無機填充材料的量(質量%)可以是0質量%、也可以多於0質量%、優選為10質量%以上、更優選為20質量%以上、特別優選為30質量%以上，優選為50質量%以下、更優選為45質量%以下、特別優選為40質量%以下。When the non-volatile components in the resin composition are taken as 100 mass %, the amount (mass %) of the solid inorganic filler (B-2) in the resin composition may be 0 mass %, may be more than 0 mass %, is preferably 10 mass % or more, is more preferably 20 mass % or more, is particularly preferably 30 mass % or more, is preferably 50 mass % or less, is more preferably 45 mass % or less, is particularly preferably 40 mass % or less.

在將樹脂組成物中的非揮發成分設為100體積%的情況下，樹脂組成物中的(B-2)實心無機填充材料的量(體積%)可以是0體積%、也可以多於0體積%、優選為5體積%以上、更優選為10體積%以上、特別優選為20體積%以上，優選為50體積%以下、更優選為40體積%以下、特別優選為30體積%以下。When the non-volatile component in the resin composition is set to 100 volume %, the amount (volume %) of the solid inorganic filler (B-2) in the resin composition can be 0 volume %, or more than 0 volume %, preferably 5 volume % or more, more preferably 10 volume % or more, particularly preferably 20 volume % or more, preferably 50 volume % or less, more preferably 40 volume % or less, and particularly preferably 30 volume % or less.

包含(B-1)中空無機填充材料和(B-2)實心無機填充材料這兩者的(B)無機填充材料整體中所含的空孔的比例，以(B)無機填充材料的空孔率(體積%)的形式求出。(B)無機填充材料的空孔率(體積%)是以體積基準表示空孔占(B)無機填充材料的體積的比例的代表值，以「空孔的總體積/(B)無機填充材料的總體積」表示。(B)無機填充材料的空孔率的具體範圍優選為10體積%以上、更優選為15體積%以上、特別優選為20體積%以上，優選為80體積%以下、更優選為70體積%以下、特別優選為60體積%以下。The ratio of pores contained in the whole (B) inorganic filler material including both (B-1) hollow inorganic filler material and (B-2) solid inorganic filler material is obtained as the porosity (volume %) of the (B) inorganic filler material. The porosity (volume %) of the (B) inorganic filler material is a representative value expressing the ratio of pores to the volume of the (B) inorganic filler material on a volume basis, and is expressed as "total volume of pores/total volume of (B) inorganic filler material". The specific range of the porosity of the (B) inorganic filler material is preferably 10 volume % or more, more preferably 15 volume % or more, particularly preferably 20 volume % or more, preferably 80 volume % or less, more preferably 70 volume % or less, and particularly preferably 60 volume % or less.

包含(B-1)中空無機填充材料和(B-2)實心無機填充材料這兩者的(B)無機填充材料整體的平均粒徑優選為0.01μm以上、更優選為0.1μm以上、特別優選為0.3μm以上，優選為5μm以下、更優選為4μm以下、特別優選為3μm以下。在(B)無機填充材料的平均粒徑處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。The average particle size of the (B) inorganic filler material as a whole, which includes both the (B-1) hollow inorganic filler material and the (B-2) solid inorganic filler material, is preferably 0.01 μm or more, more preferably 0.1 μm or more, particularly preferably 0.3 μm or more, and is preferably 5 μm or less, more preferably 4 μm or less, particularly preferably 3 μm or less. When the average particle size of the (B) inorganic filler material is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product including the resin composition can be effectively improved.

包含(B-1)中空無機填充材料和(B-2)實心無機填充材料這兩者的(B)無機填充材料整體的BET比表面積優選為1m 2/g以上、更優選為2m 2/g以上、特別優選為5m 2/g以上，優選為100m 2/g以下、更優選為50m 2/g以下、特別優選為30m 2/g以下。在(B)無機填充材料的BET比表面積處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。 The BET specific surface area of the (B) inorganic filler material as a whole, which includes both the (B-1) hollow inorganic filler material and the (B-2) solid inorganic filler material, is preferably 1 m 2 /g or more, more preferably 2 m 2 /g or more, particularly preferably 5 m 2 /g or more, and is preferably 100 m 2 /g or less, more preferably 50 m 2 /g or less, particularly preferably 30 m 2 /g or less. When the BET specific surface area of the (B) inorganic filler material is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product including the resin composition can be effectively improved.

在將樹脂組成物中的非揮發成分設為100質量%的情況下，樹脂組成物中的(B)無機填充材料的量(質量%)優選為20質量%以上、更優選為30質量%以上、特別優選為40質量%以上，優選為80質量%以下、更優選為70質量%以下、特別優選為60質量%以下。在(B)無機填充材料的量處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。When the non-volatile components in the resin composition are set to 100 mass %, the amount (mass %) of the (B) inorganic filler in the resin composition is preferably 20 mass % or more, more preferably 30 mass % or more, particularly preferably 40 mass % or more, and preferably 80 mass % or less, more preferably 70 mass % or less, particularly preferably 60 mass % or less. When the amount of the (B) inorganic filler is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved.

在將樹脂組成物中的非揮發成分設為100體積%的情況下，樹脂組成物中的(B)無機填充材料的量(體積%)優選為20體積%以上、更優選為30體積%以上、特別優選為40體積%以上，優選為80體積%以下、更優選為75體積%以下、特別優選為70體積%以下。在(B)無機填充材料的量處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。When the non-volatile components in the resin composition are set to 100 volume %, the amount (volume %) of the (B) inorganic filler in the resin composition is preferably 20 volume % or more, more preferably 30 volume % or more, particularly preferably 40 volume % or more, and preferably 80 volume % or less, more preferably 75 volume % or less, particularly preferably 70 volume % or less. When the amount of the (B) inorganic filler is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved.

[4. (C)有機粒子] 對於本發明的第一實施方式所涉及的樹脂組成物而言，優選與(A)硬化性樹脂和(B)無機填充材料組合地包含作為(C)成分的(C)有機粒子。(C)有機粒子以粒子狀的形態存在於樹脂組成物中，通常在維持該粒子狀的形態下包含在硬化物中。 [4. (C) Organic particles] The resin composition according to the first embodiment of the present invention preferably contains (C) organic particles as the (C) component in combination with (A) the curable resin and (B) the inorganic filler. The (C) organic particles exist in the resin composition in the form of particles and are usually contained in the cured product while maintaining the particle form.

(C)有機粒子由於包含有機材料，所以通常熱膨脹係數大於(B)無機填充材料，而且比重小於(B)無機填充材料。因此，通過使用(C)有機粒子，可調整樹脂組成物的硬化物的熱膨脹係數和比重。另外，由於通常(C)有機粒子比(B)無機填充材料具有更高的柔軟性的傾向，所以根據(C)有機粒子，可提高樹脂組成物的硬化物對應力的抗性。Since (C) organic particles contain organic materials, they generally have a greater thermal expansion coefficient than (B) inorganic fillers and a smaller specific gravity than (B) inorganic fillers. Therefore, by using (C) organic particles, the thermal expansion coefficient and specific gravity of the cured product of the resin composition can be adjusted. In addition, since (C) organic particles generally tend to have higher flexibility than (B) inorganic fillers, the (C) organic particles can improve the resistance of the cured product of the resin composition to the stress.

作為(C)有機粒子，可使用粒子整體具有均勻組成的粒子，也可使用具有不均勻組成的粒子。例如，優選具有殼部和形成於該殼部內的內置部的多層粒子。另外，多層粒子也可包含殼部和內置部以外的部分。例如，多層粒子可在內置部內進一步包含任選部分。另外，例如多層粒子可在殼部與內置部之間包含任選的層。通常，由於內置部被殼部覆蓋，所以多層粒子可不依賴於內置部的組成而高度地分散在樹脂組成物中，因此，可提高內置部的組成的自由度。因此，由於可採用具有適合於絕緣層的組成的內置部，所以可使絕緣層的特性良好。在此所說的多層粒子並不一定僅指殼部和內置部能夠明確區分的粒子，也包含殼部與內置部的邊界不清楚的粒子，內置部也可不被殼部完全地包覆。As (C) organic particles, particles having a uniform composition as a whole can be used, and particles having a non-uniform composition can also be used. For example, multilayer particles having a shell and an internal part formed in the shell are preferred. In addition, the multilayer particles may also include parts other than the shell and the internal part. For example, the multilayer particles may further include an optional part in the internal part. In addition, for example, the multilayer particles may include an optional layer between the shell and the internal part. Usually, since the internal part is covered by the shell, the multilayer particles can be highly dispersed in the resin composition without relying on the composition of the internal part, and therefore, the degree of freedom of the composition of the internal part can be increased. Therefore, since the internal part having a composition suitable for the insulating layer can be adopted, the characteristics of the insulating layer can be made good. The multi-layer particles mentioned here do not necessarily refer to particles whose shell and interior can be clearly distinguished, but also include particles whose boundaries between the shell and interior are unclear, and the interior may not be completely covered by the shell.

多層粒子的殼部通常由聚合物形成。形成殼部的聚合物可以是作為1種單體的聚合物的均聚物，也可以是作為2種以上單體的共聚物的共聚物。對於形成殼部的聚合物及其單體的種類，優選選擇抑制(C)有機粒子的凝集而能夠良好地分散在樹脂組成物中的那些。具體的種類可依賴於(A)硬化性樹脂的組成，但作為單體的優選例，可舉出：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸縮水甘油酯等(甲基)丙烯酸酯；(甲基)丙烯酸；N-甲基馬來醯亞胺、N-苯基馬來醯亞胺等N-取代馬來醯亞胺；馬來醯亞胺；馬來酸、衣康酸等α,β-不飽和羧酸；苯乙烯、4-乙烯基甲苯、α-甲基苯乙烯等芳香族乙烯基化合物；(甲基)丙烯腈等。這些單體可單獨使用1種，也可將2種以上組合使用。The shell of the multilayer particle is usually formed of a polymer. The polymer forming the shell may be a homopolymer of a single monomer or a copolymer of two or more monomers. The type of the polymer forming the shell and its monomer are preferably selected from those that can suppress the aggregation of the (C) organic particles and can be well dispersed in the resin composition. The specific type depends on the composition of the (A) curable resin, but preferred examples of the monomer include: (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, and glycidyl (meth)acrylate; (meth)acrylic acid; N-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; maleimide; α,β-unsaturated carboxylic acids such as maleic acid and itaconic acid; aromatic vinyl compounds such as styrene, 4-vinyltoluene, and α-methylstyrene; (meth)acrylonitrile, etc. These monomers may be used alone or in combination of two or more.

多層粒子的內置部優選包含與殼部中所含的有機材料不同的有機材料。如此，由於具備包含有機材料的內置部的多層粒子可具備相當於內置部的芯部和覆蓋該芯部的殼部，所以有時稱為「芯殼粒子」。其中，內置部優選包含橡膠成分。在(C)有機粒子包含在內置部含有橡膠成分的多層粒子的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。作為橡膠成分，例如，在依據日本工業規格(JIS K7161)以溫度25℃、濕度40%RH進行拉伸試驗的情況下，可使用顯示1GPa以下的彈性模數的樹脂。另外，作為橡膠成分，例如，可使用具有優選為0℃以下、更優選為-10℃以下、進一步優選為-20℃以下、特別優選為-30℃以下的玻璃轉移溫度的樹脂。玻璃轉移溫度可通過DSC(差示掃描量熱測定)以10℃/分鐘的升溫速度進行測定。這些橡膠成分例如可作為在分子內具有選自下述的1種以上結構的樹脂來準備：聚丁二烯結構、聚矽氧烷結構、聚(甲基)丙烯酸酯結構、聚伸烷基結構、聚伸烷基氧基結構、聚異戊二烯結構、聚異丁烯結構和聚碳酸酯結構。The internal part of the multilayer particle preferably contains an organic material different from the organic material contained in the shell. In this way, since the multilayer particle having an internal part containing an organic material can have a core part corresponding to the internal part and a shell part covering the core part, it is sometimes called a "core-shell particle". Among them, the internal part preferably contains a rubber component. In the case where (C) the organic particle is included in the multilayer particle containing a rubber component in the internal part, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved. As the rubber component, for example, a resin showing an elastic modulus of 1 GPa or less in a tensile test at a temperature of 25°C and a humidity of 40% RH in accordance with Japanese Industrial Standards (JIS K7161) can be used. In addition, as the rubber component, for example, a resin having a glass transition temperature of preferably 0°C or less, more preferably -10°C or less, further preferably -20°C or less, and particularly preferably -30°C or less can be used. The glass transition temperature can be measured by DSC (differential scanning calorimetry) at a heating rate of 10°C/min. These rubber components can be prepared as resins having, for example, one or more structures selected from the group consisting of a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule.

作為橡膠成分的具體例，可舉出：聚二甲基矽氧烷等聚矽氧系彈性體；聚丁二烯、聚異戊二烯、聚氯丁二烯、乙烯-乙酸乙烯酯共聚物、苯乙烯-丁二烯共聚物、苯乙烯-異戊二烯共聚物、苯乙烯-異丁烯共聚物、丙烯腈-丁二烯共聚物、異戊二烯-異丁烯共聚物、異丁烯-丁二烯共聚物、乙烯-丙烯-二烯三元共聚物、乙烯-丙烯-丁烯三元共聚物等烯烴系熱塑性彈性體；聚(甲基)丙烯酸丙酯、聚(甲基)丙烯酸丁酯、聚(甲基)丙烯酸環己酯、聚(甲基)丙烯酸辛酯等丙烯酸系熱塑性彈性體等的熱塑性彈性體等。而且，在橡膠成分中可混合聚有機矽氧烷橡膠等聚矽氧系橡膠。Specific examples of the rubber component include silicone-based elastomers such as polydimethylsiloxane; olefin-based thermoplastic elastomers such as polybutadiene, polyisoprene, polychloroprene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutylene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, isobutylene-butadiene copolymer, ethylene-propylene-diene terpolymer, ethylene-propylene-butylene terpolymer; and thermoplastic elastomers such as acrylic-based thermoplastic elastomers such as polypropyl (meth)acrylate, polybutyl (meth)acrylate, polycyclohexyl (meth)acrylate, and polyoctyl (meth)acrylate. Furthermore, a polysilicone-based rubber such as polyorganosiloxane rubber may be mixed into the rubber component.

在包含橡膠成分的多層粒子中，橡膠成分的量優選為40質量%以上、更優選為50質量%以上、特別優選為60質量%以上。對上限沒有特別限制，從用殼部充分地包覆內置部的觀點出發，例如可以是95質量%以下、90質量%等。In the multilayer particles containing the rubber component, the amount of the rubber component is preferably 40% by mass or more, more preferably 50% by mass or more, and particularly preferably 60% by mass or more. There is no particular upper limit, but from the perspective of fully covering the inner part with the shell, it can be, for example, 95% by mass or less, 90% by mass, etc.

具備包含橡膠成分的內置部的多層粒子例如可通過包括下述步驟的製造方法來製造：準備包含橡膠成分的芯粒子的步驟；使可與芯粒子所含的橡膠成分共聚的單體成分接枝共聚而形成殼部的步驟。另外，具備包含橡膠成分的內置部的多層粒子可使用市售品。作為市售品，例如可舉出：Cheil Industries公司製造的「CHT」；UMGABS公司製造的「B602」；Dow Chemical日本公司製造的「Polaraoid EXL-2602」、「Polaraoid EXL-2603」、「Polaraoid EXL-2655」、「Polaraoid EXL-2311」、「Polaraoid -EXL2313」、「Polaraoid EXL-2315」、「Polaraoid KM-330」、「Polaraoid KM-336P」、「Polaraoid KCZ-201」；三菱麗陽公司製造的「METABLEN C-223A」、「METABLEN E-901」、「METABLEN S-2001」、「METABLEN W-450A」「METABLEN SRK-200」；Kaneka公司製造的「KaneAce M-511」、「KaneAce M-600」、「KaneAce M-400」、「KaneAce M-580」、「KaneAce MR-01」；愛克工業公司製造的Staphyloid 「AC3832」、「AC3816N」等。The multilayer particles having an internal part containing a rubber component can be produced, for example, by a production method comprising the steps of: preparing a core particle containing a rubber component; and graft-copolymerizing a monomer component copolymerizable with the rubber component contained in the core particle to form a shell part. In addition, the multilayer particles having an internal part containing a rubber component can use commercially available products. Examples of commercially available products include: "CHT" manufactured by Cheil Industries; "B602" manufactured by UMGABS; "Polaraoid EXL-2602", "Polaraoid EXL-2603", "Polaraoid EXL-2655", "Polaraoid EXL-2311", "Polaraoid -EXL2313", "Polaraoid EXL-2315", "Polaraoid KM-330", "Polaraoid KM-336P", "Polaraoid KCZ-201" manufactured by Dow Chemical Japan; "METABLEN C-223A", "METABLEN E-901", "METABLEN S-2001", "METABLEN W-450A", "METABLEN SRK-200" manufactured by Mitsubishi Rayon Corporation; "KaneAce M-511", "KaneAce M-600", "KaneAce M-400", "KaneAce M-580", "KaneAce MR-01"; Staphyloid "AC3832", "AC3816N" manufactured by AICA Industries, etc.

多層粒子的內置部也優選成為中空部。即，多層粒子也優選具有作為被殼部包圍的空孔的中空部。有時將這樣具備中空部作為內置部的多層粒子稱為「中空有機粒子」。在(C)有機粒子包含含有中空部作為內置部的多層粒子的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。The inner part of the multilayer particle is preferably a hollow part. That is, the multilayer particle preferably has a hollow part as a hole surrounded by the shell. Multilayer particles having a hollow part as an inner part are sometimes referred to as "hollow organic particles". When (C) the organic particles include multilayer particles having a hollow part as an inner part, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product including the resin composition can be effectively improved.

包含中空部的多層粒子通常具有大於0體積%的空孔率。從有效地改善包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性的觀點出發，多層粒子的空孔率優選為10體積%以上、更優選為15體積%以上、特別優選為20體積%以上。另外，從樹脂組成物的硬化物的機械強度的觀點出發，多層粒子的空孔率優選為90體積%以下、更優選為90體積%以下、特別優選為80體積%以下。The multilayer particles including the hollow part usually have a porosity greater than 0 volume %. From the viewpoint of effectively improving the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product including the resin composition, the porosity of the multilayer particles is preferably 10 volume % or more, more preferably 15 volume % or more, and particularly preferably 20 volume % or more. In addition, from the viewpoint of the mechanical strength of the cured product of the resin composition, the porosity of the multilayer particles is preferably 90 volume % or less, more preferably 90 volume % or less, and particularly preferably 80 volume % or less.

包含中空部的多層粒子例如可通過日本特開2006-265394號公報、日本特開2007-238792號公報、國際公開第2011/040376號、日本特開2016-190980號公報、國際公開第2018/051794號、日本特開2020-189978號公報等文獻中記載的方法來製造。另外，包含中空部的多層粒子可使用市售品。作為市售品，例如可舉出：積水化成品工業公司製造的「XX-5598Z」。The multilayer particles including the hollow part can be produced by the methods described in Japanese Patent Publication No. 2006-265394, Japanese Patent Publication No. 2007-238792, International Publication No. 2011/040376, Japanese Patent Publication No. 2016-190980, International Publication No. 2018/051794, Japanese Patent Publication No. 2020-189978, etc. In addition, the multilayer particles including the hollow part can use commercial products. As a commercial product, for example, "XX-5598Z" manufactured by Sekisui Chemicals Co., Ltd. can be cited.

(C)有機粒子可單獨使用1種，也可將2種以上組合使用。(C) The organic particles may be used alone or in combination of two or more.

(C)有機粒子也可用表面處理劑進行處理。作為用於(C)有機粒子的表面處理劑，例如可舉出：鹽酸、硝酸、硫酸等無機酸；乙酸、丙酸、丁酸、丙烯酸等羧酸，對甲苯磺酸、乙基磺酸、十二烷基苯磺酸等磺酸，聚氧乙烯烷基醚磷酸等磷酸，膦酸、次膦酸等有機酸；四乙氧基矽烷、甲基三甲氧基矽烷、苯基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、8-(甲基)丙烯醯氧基辛基三甲氧基矽烷等矽烷偶合劑；乙基異氰酸酯等異氰酸酯系化合物等。(C) Organic particles may also be treated with a surface treatment agent. Examples of the surface treatment agent for (C) organic particles include: inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid; carboxylic acids such as acetic acid, propionic acid, butyric acid, and acrylic acid; sulfonic acids such as p-toluenesulfonic acid, ethylsulfonic acid, and dodecylbenzenesulfonic acid; phosphoric acids such as polyoxyethylene alkyl ether phosphoric acid; organic acids such as phosphonic acid and phosphinic acid; silane coupling agents such as tetraethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, and 8-(meth)acryloyloxyoctyltrimethoxysilane; isocyanate compounds such as ethyl isocyanate, etc.

優選(C)有機粒子的平均粒徑小於(B-1)中空無機填充材料的平均粒徑。(C)有機粒子的具體平均粒徑優選為0.01μm以上、更優選為0.05μm以上、進一步優選為0.10μm以上，優選為5μm以下、更優選為2μm以下、進一步優選為1μm以下。(C)有機粒子的平均粒徑可使用Zeta電位粒度分佈測定裝置進行測定。The average particle size of the organic particles (C) is preferably smaller than the average particle size of the hollow inorganic filler (B-1). The specific average particle size of the organic particles (C) is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.10 μm or more, and preferably 5 μm or less, more preferably 2 μm or less, further preferably 1 μm or less. The average particle size of the organic particles (C) can be measured using a zeta potential particle size distribution measuring device.

在將樹脂組成物中的非揮發成分設為100質量%的情況下，樹脂組成物中的(C)有機粒子的量(質量%)優選為0.5質量%以上、更優選為1.5質量%以上、特別優選為2質量%以上，優選為20質量%以下、更優選為15質量%以下、特別優選為10質量%以下。在(C)有機填充材料的量處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。When the non-volatile components in the resin composition are set to 100 mass %, the amount (mass %) of the (C) organic particles in the resin composition is preferably 0.5 mass % or more, more preferably 1.5 mass % or more, particularly preferably 2 mass % or more, and preferably 20 mass % or less, more preferably 15 mass % or less, particularly preferably 10 mass % or less. When the amount of the (C) organic filler is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved.

在將樹脂組成物中的非揮發成分設為100體積%的情況下，樹脂組成物中的(C)有機粒子的量(體積%)優選為0.5體積%以上、更優選為1.5體積%以上、特別優選為2.0體積%以上，優選為20體積%以下、更優選為15體積%以下、特別優選為10體積%以下。在(C)有機填充材料的量處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。When the non-volatile components in the resin composition are set to 100 volume %, the amount (volume %) of the (C) organic particles in the resin composition is preferably 0.5 volume % or more, more preferably 1.5 volume % or more, particularly preferably 2.0 volume % or more, and preferably 20 volume % or less, more preferably 15 volume % or less, particularly preferably 10 volume % or less. When the amount of the (C) organic filler is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved.

在將樹脂組成物中的樹脂成分設為100質量%的情況下，樹脂組成物中的(C)有機粒子的量(質量%)優選為1.0質量%以上、更優選為1.5質量%以上、特別優選為2.0質量%以上，優選為30質量%以下、更優選為20質量%以下、特別優選為15質量%以下。在(C)有機填充材料的量處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。When the resin component in the resin composition is 100 mass %, the amount (mass %) of the (C) organic particles in the resin composition is preferably 1.0 mass % or more, more preferably 1.5 mass % or more, particularly preferably 2.0 mass % or more, and preferably 30 mass % or less, more preferably 20 mass % or less, particularly preferably 15 mass % or less. When the amount of the (C) organic filler is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved.

樹脂組成物中的(C)有機粒子與(B-1)中空無機填充材料的質量比((C)有機粒子/(B-1)中空無機填充材料)優選為0.01以上、更優選為0.02以上、特別優選為0.03以上，優選為0.50以下、更優選為0.40以下、特別優選為0.30以下。在質量比((C)有機粒子/(B-1)中空無機填充材料)處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。The mass ratio of the (C) organic particles to the (B-1) hollow inorganic filler in the resin composition ((C) organic particles/(B-1) hollow inorganic filler) is preferably 0.01 or more, more preferably 0.02 or more, particularly preferably 0.03 or more, and is preferably 0.50 or less, more preferably 0.40 or less, particularly preferably 0.30 or less. When the mass ratio ((C) organic particles/(B-1) hollow inorganic filler) is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved.

樹脂組成物中的(C)有機粒子與(B-1)中空無機填充材料的體積比((C)有機粒子/(B-1)中空無機填充材料)優選為0.01以上、更優選為0.03以上、特別優選為0.05以上，優選為0.50以下、更優選為0.30以下、特別優選為0.20以下。在體積比((C)有機粒子/(B-1)中空無機填充材料)處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。The volume ratio of the (C) organic particles to the (B-1) hollow inorganic filler in the resin composition ((C) organic particles/(B-1) hollow inorganic filler) is preferably 0.01 or more, more preferably 0.03 or more, particularly preferably 0.05 or more, and is preferably 0.50 or less, more preferably 0.30 or less, particularly preferably 0.20 or less. When the volume ratio ((C) organic particles/(B-1) hollow inorganic filler) is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved.

在將樹脂組成物中的非揮發成分設為100質量%的情況下，樹脂組成物中的(C)有機粒子和(B-1)中空無機填充材料的總計質量優選為5質量%以上、更優選為10質量%以上、特別優選為15質量%以上，優選為80質量%以下、更優選為75質量%以下、特別優選為70質量%以下。在(C)有機粒子和(B-1)中空無機填充材料的總計質量處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。When the non-volatile components in the resin composition are set to 100 mass %, the total mass of the (C) organic particles and the (B-1) hollow inorganic filler in the resin composition is preferably 5 mass % or more, more preferably 10 mass % or more, particularly preferably 15 mass % or more, and preferably 80 mass % or less, more preferably 75 mass % or less, particularly preferably 70 mass % or less. When the total mass of the (C) organic particles and the (B-1) hollow inorganic filler is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved.

在將樹脂組成物中的非揮發成分設為100體積%的情況下，樹脂組成物中的(C)有機粒子和(B-1)中空無機填充材料的總體積優選為10體積%以上、更優選為15體積%以上、特別優選為20體積%以上，優選為85體積%以下、更優選為80體積%以下、特別優選為75體積%以下。在(C)有機粒子和(B-1)中空無機填充材料的總體積處於上述範圍的情況下，能夠有效地使包含樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。When the non-volatile components in the resin composition are set to 100 volume %, the total volume of the (C) organic particles and the (B-1) hollow inorganic filler in the resin composition is preferably 10 volume % or more, more preferably 15 volume % or more, particularly preferably 20 volume % or more, and preferably 85 volume % or less, more preferably 80 volume % or less, particularly preferably 75 volume % or less. When the total volume of the (C) organic particles and the (B-1) hollow inorganic filler is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer of the cured product containing the resin composition can be effectively improved.

[5. (D)硬化促進劑] 對於本發明的第一實施方式所涉及的樹脂組成物而言，可與上述的(A)～(C)成分組合，進一步包含(D)硬化促進劑作為任選成分。在作為該(D)成分的(D)硬化促進劑中，不包含相當於上述的(A)～(C)成分的物質。(D)硬化促進劑具有作為促進(A)硬化性樹脂硬化的硬化觸媒的功能。 [5. (D) Hardening accelerator] The resin composition according to the first embodiment of the present invention may be combined with the above-mentioned (A) to (C) components and further include a (D) hardening accelerator as an optional component. The (D) hardening accelerator as the (D) component does not include a substance equivalent to the above-mentioned (A) to (C) components. The (D) hardening accelerator has a function as a hardening catalyst that accelerates the hardening of the (A) hardening resin.

作為(D)硬化促進劑，可根據(A)硬化性樹脂的種類使用適當的硬化促進劑。例如，在(A)硬化性樹脂包含環氧樹脂的情況下，作為可促進該環氧樹脂的硬化的(D)硬化促進劑，例如可舉出：磷系硬化促進劑、脲系硬化促進劑、胍系硬化促進劑、咪唑系硬化促進劑、金屬系硬化促進劑、胺系硬化促進劑等。(D)硬化促進劑可單獨使用1種，也可將2種以上組合使用。As the (D) hardening accelerator, an appropriate hardening accelerator may be used depending on the type of the (A) hardening resin. For example, when the (A) hardening resin includes an epoxy resin, examples of the (D) hardening accelerator that can accelerate the hardening of the epoxy resin include phosphorus-based hardening accelerators, urea-based hardening accelerators, guanidine-based hardening accelerators, imidazole-based hardening accelerators, metal-based hardening accelerators, and amine-based hardening accelerators. The (D) hardening accelerator may be used alone or in combination of two or more.

作為磷系硬化促進劑，例如可舉出：溴化四丁基鏻、氯化四丁基鏻、四丁基鏻乙酸鹽、四丁基鏻癸酸鹽、四丁基鏻月桂酸鹽、雙(四丁基鏻)均苯四甲酸鹽、四丁基鏻六氫鄰苯二甲酸氫鹽、四丁基鏻2,6-雙[(2-羥基-5-甲基苯基)甲基]-4-甲基苯酚鹽、二叔丁基二甲基鏻四苯基硼酸鹽等脂肪族鏻鹽；溴化甲基三苯基鏻、溴化乙基三苯基鏻、溴化丙基三苯基鏻、溴化丁基三苯基鏻、氯化苄基三苯基鏻、溴化四苯基鏻、對甲苯基三苯基鏻四對甲苯基硼酸鹽、四苯基鏻四苯基硼酸鹽、四苯基鏻四對甲苯基硼酸鹽、三苯基乙基鏻四苯基硼酸鹽、三(3-甲基苯基)乙基鏻四苯基硼酸鹽、三(2-甲氧基苯基)乙基鏻四苯基硼酸鹽、(4-甲基苯基)三苯基鏻硫氰酸鹽、四苯基鏻硫氰酸鹽、丁基三苯基鏻硫氰酸鹽等芳香族鏻鹽；三苯基膦-三苯基硼烷等芳香族膦-硼烷複合物；三苯基膦-對苯醌加成反應物等芳香族膦-醌加成反應物；三丁基膦、三叔丁基膦、三辛基膦、二叔丁基(2-丁烯基)膦、二叔丁基(3-甲基-2-丁烯基)膦、三環己基膦等脂肪族膦；二丁基苯基膦、二叔丁基苯基膦、甲基二苯基膦、乙基二苯基膦、丁基二苯基膦、二苯基環己基膦、三苯基膦、三鄰甲苯基膦、三間甲苯基膦、三對甲苯基膦、三(4-乙基苯基)膦、三(4-丙基苯基)膦、三(4-異丙基苯基)膦、三(4-丁基苯基)膦、三(4-叔丁基苯基)膦、三(2,4-二甲基苯基)膦、三(2,5-二甲基苯基)膦、三(2,6-二甲基苯基)膦、三(3,5-二甲基苯基)膦、三(2,4,6-三甲基苯基)膦、三(2,6-二甲基-4-乙氧基苯基)膦、三(2-甲氧基苯基)膦、三(4-甲氧基苯基)膦、三(4-乙氧基苯基)膦、三(4-叔丁氧基苯基)膦、二苯基-2-吡啶基膦、1,2-雙(二苯基膦基)乙烷、1,3-雙(二苯基膦基)丙烷、1,4-雙(二苯基膦基)丁烷、1,2-雙(二苯基膦基)乙炔、2,2’-雙(二苯基膦基)二苯基醚等芳香族膦等。Examples of the phosphorus-based hardening accelerator include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitic acid salt, tetrabutylphosphonium hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butyldimethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, and p-tolyltriphenylphosphonium. Aromatic phosphonium salts such as tetra-p-tolyl borate, tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium tetra-p-tolyl borate, triphenylethylphosphonium tetraphenyl borate, tris(3-methylphenyl)ethylphosphonium tetraphenyl borate, tris(2-methoxyphenyl)ethylphosphonium tetraphenyl borate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2- aliphatic phosphines such as dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(4-tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,5-dimethylphenyl)phosphine, tri(2,6-dimethylphenyl)phosphine, tri(2,6-dimethylphenyl)phosphine, tri(2,7-dimethylphenyl)phosphine, tri(2,8-dimethylphenyl)phosphine, tri(2,9-dimethylphenyl)phosphine, tri(3-methyl-2-butenyl)phosphine, tri-tert-butyl(3-methyl-2-butenyl)phosphine, tri-tert-butyl(3-methyl-2-butenyl)phosphine, tri-tert-butyl(3-methyl-2-butenyl)phosphine, tri-tert-butyl(3-methyl-2-butenyl)phosphine, tri-tert-butyl Aromatic phosphines such as tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether may be used.

作為脲系硬化促進劑，例如可舉出：1,1-二甲基脲；1,1,3-三甲基脲、3-乙基-1,1-二甲基脲、3-環己基-1,1-二甲基脲、3-環辛基-1,1-二甲基脲等脂肪族二甲基脲；3-苯基-1,1-二甲基脲、3-(4-氯苯基)-1,1-二甲基脲、3-(3,4-二氯苯基)-1,1-二甲基脲、3-(3-氯-4-甲基苯基)-1,1-二甲基脲、3-(2-甲基苯基)-1,1-二甲基脲、3-(4-甲基苯基)-1,1-二甲基脲、3-(3,4-二甲基苯基)-1,1-二甲基脲、3-(4-異丙基苯基)-1,1-二甲基脲、3-(4-甲氧基苯基)-1,1-二甲基脲、3-(4-硝基苯基)-1,1-二甲基脲、3-[4-(4-甲氧基苯氧基)苯基]-1,1-二甲基脲、3-[4-(4-氯苯氧基)苯基]-1,1-二甲基脲、3-[3-(三氟甲基)苯基]-1,1-二甲基脲、N,N-(1,4-伸苯基)雙(N’,N’-二甲基脲)、N,N-(4-甲基-1,3-伸苯基)雙(N’,N’-二甲基脲)[甲苯雙二甲基脲]等芳香族二甲基脲等。Examples of the urea-based curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1, Aromatic dimethylureas such as 1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea], and the like.

作為胍系硬化促進劑，例如可舉出：雙氰胺、1-甲基胍、1-乙基胍、1-環己基胍、1-苯基胍、1-(鄰甲苯基)胍、二甲基胍、二苯基胍、三甲基胍、四甲基胍、五甲基胍、1,5,7-三氮雜雙環[4.4.0]癸-5-烯、7-甲基-1,5,7-三氮雜雙環[4.4.0]癸-5-烯、1-甲基雙胍、1-乙基雙胍、1-正丁基雙胍、1-正十八烷基雙胍、1,1-二甲基雙胍、1,1-二乙基雙胍、1-環己基雙胍、1-烯丙基雙胍、1-苯基雙胍、1-(鄰甲苯基)雙胍等。Examples of the guanidine-based hardening accelerator include cyanamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine.

作為咪唑系硬化促進劑，例如可舉出：2-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-十一烷基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-十一烷基咪唑鎓偏苯三甲酸鹽、1-氰基乙基-2-苯基咪唑鎓偏苯三甲酸鹽、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-均三嗪、2,4-二胺基-6-[2’-十一烷基咪唑基-(1’)]-乙基-均三嗪、2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-均三嗪、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-均三嗪異氰脲酸加成物、2-苯基咪唑異氰脲酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2,3-二氫-1H-吡咯並[1,2-a]苯並咪唑、1-十二烷基-2-甲基-3-苄基咪唑鎓氯化物、2-甲基咪唑啉、2-苯基咪唑啉等咪唑化合物、及咪唑化合物與環氧樹脂的加合物。作為咪唑系硬化促進劑的市售品，例如可舉出：四國化成工業公司製造的「1B2PZ」、「2E4MZ」、「2MZA-PW」、「2MZ-OK」、「2MA-OK」、「2MA-OK-PW」、「2PHZ」、「2PHZ-PW」、「C11Z」、「C11Z-CN」、「C11Z-CNS」、「C11Z-A」，三菱化學公司製造的「P200-H50」等。Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1' )]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, isocyanuric acid adduct of 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2-phenylimidazole Imidazole compounds such as isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins. Examples of commercially available imidazole curing accelerators include "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2PHZ", "2PHZ-PW", "C11Z", "C11Z-CN", "C11Z-CNS", and "C11Z-A" manufactured by Shikoku Chemical Industries, Ltd. and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

作為金屬系硬化促進劑，例如可舉出：鈷、銅、鋅、鐵、鎳、錳、錫等金屬的有機金屬錯合物或有機金屬鹽。作為有機金屬錯合物的具體例，可舉出：乙醯丙酮鈷(II)、乙醯丙酮鈷(III)等有機鈷錯合物、乙醯丙酮銅(II)等有機銅錯合物、乙醯丙酮鋅(II)等有機鋅錯合物、乙醯丙酮鐵(III)等有機鐵錯合物、乙醯丙酮鎳(II)等有機鎳錯合物、乙醯丙酮錳(II)等有機錳錯合物等。作為有機金屬鹽，例如可舉出：辛酸鋅、辛酸錫、環烷酸鋅、環烷酸鈷、硬脂酸錫、硬脂酸鋅等。Examples of metal hardening accelerators include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organic metal complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc cycloalkanoate, cobalt cycloalkanoate, tin stearate, zinc stearate, and the like.

作為胺系硬化促進劑，例如可舉出：三乙基胺、三丁基胺等三烷基胺、4-二甲基胺基吡啶、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)-十一碳烯等。作為胺系硬化促進劑，可使用市售品，例如可舉出：味之素Fine-techno公司製造的「MY-25」等。Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene. A commercially available amine-based hardening accelerator may be used, and examples thereof include "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd.

在將樹脂組成物中的非揮發成分設為100質量%的情況下，樹脂組成物中的(D)硬化促進劑的量可以是0質量%、也可以大於0質量%、優選為0.01質量%以上、更優選為0.02質量%以上、特別優選為0.05質量%以上，優選為1.0質量%以下、更優選為0.5質量%以下、特別優選為0.2質量%以下。When the non-volatile component in the resin composition is 100 mass %, the amount of the hardening accelerator (D) in the resin composition may be 0 mass %, or may be greater than 0 mass %, preferably 0.01 mass % or more, more preferably 0.02 mass % or more, particularly preferably 0.05 mass % or more, and preferably 1.0 mass % or less, more preferably 0.5 mass % or less, particularly preferably 0.2 mass % or less.

在將樹脂組成物中的樹脂成分設為100質量%的情況下，樹脂組成物中的(D)硬化促進劑的量可以是0質量%、也可以大於0質量%、優選為0.01質量%以上、更優選為0.05質量%以上、特別優選為0.10質量%以上，優選為2.0質量%以下、更優選為1.0質量%以下、特別優選為0.5質量%以下。When the resin component in the resin composition is 100 mass%, the amount of the (D) hardening accelerator in the resin composition may be 0 mass%, or may be greater than 0 mass%, preferably 0.01 mass% or more, more preferably 0.05 mass% or more, particularly preferably 0.10 mass% or more, and preferably 2.0 mass% or less, more preferably 1.0 mass% or less, particularly preferably 0.5 mass% or less.

[6. (E)聚合起始劑] 對於本發明的第一實施方式所涉及的樹脂組成物而言，可與上述的(A)～(D)成分組合，進一步包含(E)聚合起始劑作為任選成分。在作為該(E)成分的(E)聚合起始劑中不包含相當於上述的(A)～(D)成分的物質。(E)聚合起始劑可單獨使用1種，也可將2種以上組合使用。 [6. (E) Polymerization initiator] The resin composition according to the first embodiment of the present invention may be combined with the above-mentioned components (A) to (D) and further include an (E) polymerization initiator as an optional component. The (E) polymerization initiator as the (E) component does not include a substance equivalent to the above-mentioned components (A) to (D). The (E) polymerization initiator may be used alone or in combination of two or more.

(E)聚合起始劑的種類可根據(A)硬化性樹脂的種類進行選擇。例如，在(A)硬化性樹脂包含作為光硬化性樹脂的自由基聚合性樹脂的情況下，作為(E)聚合起始劑，優選使用光聚合起始劑。The type of the polymerization initiator (E) can be selected according to the type of the curable resin (A). For example, when the curable resin (A) contains a radical polymerizable resin which is a photocurable resin, it is preferable to use a photopolymerization initiator as the polymerization initiator (E).

作為(E)聚合起始劑，例如可舉出：2-苄基-2-二甲基胺基-1-(4-嗎啉代基苯基)-1-丁酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-[4-(4-嗎啉基)苯基]-1-丁酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代基丙烷-1-酮等α-胺基烷基苯酮系聚合起始劑；1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-乙酮-1-(O-乙醯肟)等肟酯系聚合起始劑；二苯甲酮、甲基二苯甲酮、鄰苯甲醯苯甲酸、苯甲醯基乙醚、2,2-二乙氧基苯乙酮、2,4-二乙基噻噸酮、二苯基-(2,4,6-三甲基苯甲醯基)氧化膦、(2,4,6-三甲基苯甲醯基)苯基次膦酸乙酯、4,4’-雙(二乙基胺基)二苯甲酮、1-羥基-環己基-苯基甲酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦等，另外，也可使用鋶鹽系光聚合起始劑。Examples of the polymerization initiator (E) include α-aminoalkylphenone-based polymerization initiators such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-[4-(4-morpholino)phenyl]-1-butanone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one; oxime ester-based polymerization initiators such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyl oxime); benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2,2-dimethylbenzoyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyl oxime); -diethoxyacetophenone, 2,4-diethylthiothione, diphenyl-(2,4,6-trimethylbenzyl)phosphine oxide, (2,4,6-trimethylbenzyl)phenylphosphinate ethyl ester, 4,4'-bis(diethylamino)benzophenone, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, etc., and coronium salt-based photopolymerization initiators can also be used.

作為(E)聚合起始劑的市售品的例子，可舉出：IGM公司製造的「Omnirad 907」、「Omnirad 369」、「Omnirad 379」、「Omnirad 819」、「Omnirad TPO」、BASF公司製造的「Irgacure TPO」、「Irgacure OXE-01」、「Irgacure OXE-02」、ADEKA公司製造的「N-1919」等。Examples of commercially available products of the (E) polymerization initiator include "Omnirad 907", "Omnirad 369", "Omnirad 379", "Omnirad 819", and "Omnirad TPO" manufactured by IGM, "Irgacure TPO", "Irgacure OXE-01", and "Irgacure OXE-02" manufactured by BASF, and "N-1919" manufactured by ADEKA.

在將樹脂組成物中的非揮發成分設為100質量%的情況下，樹脂組成物中的(E)聚合起始劑的量可以是0質量%、也可以大於0質量%、優選為0.01質量%以上、更優選為0.1質量%以上、特別優選為1質量%以上，優選為10質量%以下、更優選為7質量%以下、特別優選為5質量%以下。When the non-volatile components in the resin composition are taken as 100% by mass, the amount of the polymerization initiator (E) in the resin composition may be 0% by mass, or may be greater than 0% by mass, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 1% by mass or more, and preferably 10% by mass or less, more preferably 7% by mass or less, particularly preferably 5% by mass or less.

在將樹脂組成物中的樹脂成分設為100質量%的情況下，樹脂組成物中的(E)聚合起始劑的量可以是0質量%、也可以大於0質量%、優選為0.01質量%以上、更優選為0.1質量%以上、特別優選為1質量%以上，優選為20質量%以下、更優選為15質量%以下、特別優選為10質量%以下。When the resin component in the resin composition is 100 mass%, the amount of the polymerization initiator (E) in the resin composition may be 0 mass%, or may be greater than 0 mass%, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, particularly preferably 1 mass% or more, and preferably 20 mass% or less, more preferably 15 mass% or less, particularly preferably 10 mass% or less.

[7. (F)熱塑性樹脂] 對於本發明的第一實施方式所涉及的樹脂組成物而言，可與上述的(A)～(E)成分組合，進一步包含(F)熱塑性樹脂作為任選成分。在作為該(F)成分的(F)熱塑性樹脂中，不包含相當於上述的(A)～(E)成分的物質。 [7. (F) Thermoplastic resin] The resin composition according to the first embodiment of the present invention may be combined with the above-mentioned components (A) to (E) to further include a (F) thermoplastic resin as an optional component. The (F) thermoplastic resin as the (F) component does not include substances equivalent to the above-mentioned components (A) to (E).

作為(F)熱塑性樹脂，例如可舉出：苯氧樹脂、聚醯亞胺樹脂、聚乙烯醇縮醛樹脂、聚烯烴樹脂、聚丁二烯樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞胺樹脂、聚碸樹脂、聚醚碸樹脂、聚苯醚樹脂、聚碳酸酯樹脂、聚醚醚酮樹脂、聚酯樹脂等。(F)熱塑性樹脂可單獨使用1種，或者也可將2種以上組合使用。Examples of the (F) thermoplastic resin include phenoxy resins, polyimide resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamide imide resins, polyether imide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, polyester resins, etc. The (F) thermoplastic resin may be used alone or in combination of two or more.

作為苯氧樹脂，例如可舉出具有選自下述的1種以上骨架的苯氧樹脂：雙酚A骨架、雙酚F骨架、雙酚S骨架、雙酚苯乙酮骨架、酚醛清漆骨架、聯苯骨架、芴骨架、雙環戊二烯骨架、降冰片烯骨架、萘骨架、蒽骨架、金剛烷骨架、萜烯骨架和三甲基環己烷骨架。苯氧樹脂的末端可以是酚性羥基、環氧基等中的任意的官能基。作為苯氧樹脂的具體例，可舉出：三菱化學公司製造的「1256」和「4250」(均為含有雙酚A骨架的苯氧樹脂)；三菱化學公司製造的「YX8100」(含有雙酚S骨架的苯氧樹脂)；三菱化學公司製造的「YX6954」(含有雙酚苯乙酮骨架的苯氧樹脂)；新日鐵住金化學公司製造的「FX280」和「FX293」；三菱化學公司製造的「YL7500BH30」、「YX6954BH30」、「YX7553」、「YX7553BH30」、「YL7769BH30」、「YL6794」、「YL7213」、「YL7290」、「YL7482」和「YL7891BH30」等。Examples of the phenoxy resin include phenoxy resins having one or more skeletons selected from the following: bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group. Specific examples of phenoxy resins include: "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (a phenoxy resin containing a bisphenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (a phenoxy resin containing a bisphenol acetophenone skeleton); "F X280" and "FX293"; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation.

作為聚醯亞胺樹脂的具體例，可舉出：信越化學工業公司製造的「SLK-6100」、新日本理化公司製造的「RIKACOAT SN20」和「RIKACOAT PN20」等。Specific examples of polyimide resins include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Shin Nippon Chemical Co., Ltd., and the like.

作為聚乙烯醇縮醛樹脂，例如可舉出：聚乙烯醇縮甲醛樹脂、聚乙烯醇縮丁醛樹脂，優選聚乙烯醇縮丁醛樹脂。作為聚乙烯醇縮醛樹脂的具體例，可舉出：電氣化學工業公司製造的「Denka Butyral 4000-2」、「Denka Butyral 5000-A」、「Denka Butyral 6000-C」、「Denka Butyral 6000-EP」；積水化學工業公司製造的S-LEC BH系列、BX系列(例如BX-5Z)、KS系列(例如KS-1)、BL系列、BM系列等。Examples of the polyvinyl acetal resin include polyvinyl formaldehyde resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", and "Denka Butyral 6000-EP" manufactured by Denki Kagaku Kogyo Co., Ltd.; and S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemical Industries, Ltd.

作為聚烯烴樹脂，例如可舉出：低密度聚乙烯、超低密度聚乙烯、高密度聚乙烯、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸甲酯共聚物等乙烯系共聚樹脂；聚丙烯、乙烯-丙烯嵌段共聚物等聚烯烴系聚合物等。Examples of the polyolefin resin include ethylene copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; and polyolefin polymers such as polypropylene and ethylene-propylene block copolymer.

作為聚丁二烯樹脂，例如可舉出：含有氫化聚丁二烯骨架的樹脂、含有羥基的聚丁二烯樹脂、含有酚性羥基的聚丁二烯樹脂、含有羧基的聚丁二烯樹脂、含有酸酐基的聚丁二烯樹脂、含有環氧基的聚丁二烯樹脂、含有異氰酸酯基的聚丁二烯樹脂、含有胺基甲酸酯基的聚丁二烯樹脂、聚苯醚-聚丁二烯樹脂等。Examples of the polybutadiene resin include a resin containing a hydrogenated polybutadiene skeleton, a polybutadiene resin containing a hydroxyl group, a polybutadiene resin containing a phenolic hydroxyl group, a polybutadiene resin containing a carboxyl group, a polybutadiene resin containing an acid anhydride group, a polybutadiene resin containing an epoxy group, a polybutadiene resin containing an isocyanate group, a polybutadiene resin containing a urethane group, and a polyphenylene ether-polybutadiene resin.

作為聚醯胺醯亞胺樹脂的具體例，可舉出：東洋紡公司製造的「VYLOMAX HR11NN」和「VYLOMAX HR16NN」。作為聚醯胺醯亞胺樹脂的具體例，還可舉出：日立化成公司製造的「KS9100」、「KS9300」(含有聚矽氧烷骨架的聚醯胺醯亞胺)等改性聚醯胺醯亞胺。Specific examples of polyamide-imide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide-imide resins include modified polyamide-imides such as "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd.

作為聚醚碸樹脂的具體例，可舉出：住友化學公司製造的「PES5003P」等。Specific examples of polyether sulphate resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

作為聚碸樹脂的具體例，可舉出：Solvay Advanced Polymers公司製造的聚碸「P1700」、「P3500」等。Specific examples of polyol resins include polyol "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

作為聚苯醚樹脂的具體例，可舉出：SABIC製造的「NORYL SA90」等。作為聚醚醯亞胺樹脂的具體例，可舉出：GE公司製造的「ULTEM」等。Specific examples of polyphenylene ether resins include "NORYL SA90" manufactured by SABIC, etc. Specific examples of polyetherimide resins include "ULTEM" manufactured by GE, etc.

作為聚碳酸酯樹脂，例如可舉出：含有羥基的碳酸酯樹脂、含有酚性羥基的碳酸酯樹脂、含有羧基的碳酸酯樹脂、含有酸酐基的碳酸酯樹脂、含有異氰酸酯基的碳酸酯樹脂、含有胺基甲酸酯基的碳酸酯樹脂等。作為聚碳酸酯樹脂的具體例，可舉出三菱瓦斯化學公司製造的「FPC0220」、旭化成化學公司製造的「T6002」、「T6001」(聚碳酸酯二醇)、可樂麗公司製造的「C-1090」、「C-2090」、「C-3090」(聚碳酸酯二醇)等。作為聚醚醚酮樹脂的具體例，可舉出：住友化學公司製造的「SUMIPLOY K」等。Examples of the polycarbonate resin include hydroxyl-containing carbonate resins, phenolic hydroxyl-containing carbonate resins, carboxyl-containing carbonate resins, anhydride-containing carbonate resins, isocyanate-containing carbonate resins, and urethane-containing carbonate resins. Specific examples of the polycarbonate resin include "FPC0220" manufactured by Mitsubishi Gas Chemicals, "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Chemicals, and "C-1090", "C-2090", and "C-3090" (polycarbonate diols) manufactured by Kuraray. Specific examples of polyetheretherketone resins include "SUMIPLOY K" manufactured by Sumitomo Chemical Co., Ltd.

作為聚酯樹脂，例如可舉出：聚對苯二甲酸乙二醇酯樹脂、聚萘二甲酸乙二醇酯樹脂、聚對苯二甲酸丁二醇酯樹脂、聚萘二甲酸丁二醇酯樹脂、聚對苯二甲酸丙二醇酯樹脂、聚萘二甲酸丙二醇酯樹脂、聚對苯二甲酸環己烷二甲醇酯樹脂等。Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexanedimethylene terephthalate resin.

(F)熱塑性樹脂的重量平均分子量(Mw)優選大於5,000、更優選為8,000以上、進一步優選為10,000以上、特別優選為20,000以上，優選為100,000以下、更優選為70,000以下、進一步優選為60,000以下、特別優選為50,000以下。(F) The weight average molecular weight (Mw) of the thermoplastic resin is preferably greater than 5,000, more preferably 8,000 or more, further preferably 10,000 or more, particularly preferably 20,000 or more, and is preferably 100,000 or less, more preferably 70,000 or less, further preferably 60,000 or less, particularly preferably 50,000 or less.

在將樹脂組成物中的非揮發成分設為100質量%的情況下，樹脂組成物中的(F)熱塑性樹脂的量可以是0質量%、也可以大於0質量%、優選為0.01質量%以上、更優選為0.1質量%以上、特別優選為1質量%以上，優選為20質量%以下、更優選為10質量%以下、特別優選為5質量%以下。When the non-volatile components in the resin composition are taken as 100% by mass, the amount of the (F) thermoplastic resin in the resin composition may be 0% by mass, or may be greater than 0% by mass, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 1% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

在將樹脂組成物中的樹脂成分設為100質量%的情況下，樹脂組成物中的(F)熱塑性樹脂的量可以是0質量%、也可以大於0質量%、優選為0.1質量%以上、更優選為1質量%以上、特別優選為2質量%以上，優選為30質量%以下、更優選為20質量%以下、特別優選為10質量%以下。When the resin component in the resin composition is 100 mass%, the amount of the (F) thermoplastic resin in the resin composition may be 0 mass%, or may be greater than 0 mass%, preferably 0.1 mass% or more, more preferably 1 mass% or more, particularly preferably 2 mass% or more, and preferably 30 mass% or less, more preferably 20 mass% or less, particularly preferably 10 mass% or less.

[8. (G)任選的添加劑] 對於本發明的第一實施方式所涉及的樹脂組成物而言，可與上述的(A)～(F)成分組合，進一步包含(G)任選的添加劑作為任選的非揮發成分。作為(G)任選的添加劑，例如可舉出：有機銅化合物、有機鋅化合物、有機鈷化合物等有機金屬化合物；酞菁藍、酞菁綠、碘綠、重氮黃、結晶紫、氧化鈦、炭黑等著色劑；對苯二酚、鄰苯二酚、連苯三酚、吩噻嗪等阻聚劑；聚矽氧系調平劑、丙烯酸聚合物系調平劑等調平劑；Benton、蒙脫石等增稠劑；聚矽氧系消泡劑、丙烯酸系消泡劑、氟系消泡劑、乙烯基樹脂系消泡劑等消泡劑；苯並三唑系紫外線吸收劑等紫外線吸收劑；脲矽烷等黏接性提高劑；三唑系密合性賦予劑、四唑系密合性賦予劑、三嗪系密合性賦予劑等密合性賦予劑；受阻酚系抗氧化劑等抗氧化劑；芪類衍生物等螢光增白劑；氟系界面活性劑、聚矽氧系界面活性劑等界面活性劑；磷系阻燃劑(例如磷酸酯化合物、膦腈化合物、次膦酸化合物、紅磷)、氮系阻燃劑(例如硫酸三聚氰胺)、鹵素系阻燃劑、無機系阻燃劑(例如三氧化銻)等阻燃劑；磷酸酯系分散劑、聚氧化烯系分散劑、乙炔系分散劑、聚矽氧系分散劑、陰離子性分散劑、陽離子性分散劑等分散劑；硼酸酯系穩定劑、鈦酸酯系穩定劑、鋁酸酯系穩定劑、鋯酸酯系穩定劑、異氰酸酯系穩定劑、羧酸系穩定劑、羧酸酐系穩定劑等穩定劑；叔胺類等光聚合引發助劑；吡唑啉類、蒽類、香豆素類、氧雜蒽酮類、噻噸酮類等光敏劑。(G)任選的添加劑可單獨使用1種，也可將2種以上組合使用。 [8. (G) Optional additives] The resin composition involved in the first embodiment of the present invention can be combined with the above-mentioned (A) to (F) components to further include (G) optional additives as optional non-volatile components. Examples of (G) optional additives include: organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; inhibitors such as hydroquinone, o-catechin, pyrogallol, and phenothiazine; leveling agents such as polysilicone-based leveling agents and acrylic polymer-based leveling agents; Benton , montmorillonite and other thickeners; silicone defoamers, acrylic defoamers, fluorine defoamers, vinyl resin defoamers and other defoamers; benzotriazole UV absorbers and other UV absorbers; urea silane and other adhesion enhancers; triazole adhesion enhancers, tetrazole adhesion enhancers, triazine adhesion enhancers and other adhesion enhancers; hindered phenol antioxidants and other antioxidants; stilbene derivatives Biological and other fluorescent whitening agents; fluorine-based surfactants, polysilicone-based surfactants and other surfactants; phosphorus-based flame retardants (such as phosphate compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (such as melamine sulfate), halogen-based flame retardants, inorganic flame retardants (such as antimony trioxide) and other flame retardants; phosphate-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants; Dispersants such as dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanium-based stabilizers, aluminum-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers; photopolymerization initiators such as tertiary amines; and photosensitizers such as pyrazoline, anthracene, coumarin, oxanthrone, and thioxanthine. (G) The optional additives may be used alone or in combination of two or more.

[9. (I)溶劑] 對於本發明的第一實施方式所涉及的樹脂組成物而言，可與上述的(A)～(G)成分這樣的非揮發成分組合，進一步包含(I)溶劑作為任選的揮發性成分。作為(I)溶劑，通常使用有機溶劑。作為有機溶劑，例如可舉出：丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮系溶劑；乙酸甲酯、乙酸乙酯、乙酸丁酯、乙酸異丁酯、乙酸異戊酯、丙酸甲酯、丙酸乙酯、γ-丁內酯等酯系溶劑；四氫吡喃、四氫呋喃、1,4-二噁烷、二乙醚、二異丙基醚、二丁基醚、二苯基醚、苯甲醚等醚系溶劑；甲醇、乙醇、丙醇、丁醇、乙二醇等醇系溶劑；乙酸2-乙氧基乙酯、丙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、乙基二甘醇乙酸酯(ethyl diglycol acetate)、γ-丁內酯、甲氧基丙酸甲酯等醚酯系溶劑；乳酸甲酯、乳酸乙酯、2-羥基異丁酸甲酯等酯醇系溶劑；2-甲氧基丙醇、2-甲氧基乙醇、2-乙氧基乙醇、丙二醇單甲基醚、二乙二醇單丁基醚(丁基卡必醇)等醚醇系溶劑；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮等醯胺系溶劑；二甲基亞碸等亞碸系溶劑；乙腈、丙腈等腈系溶劑；己烷、環戊烷、環己烷、甲基環己烷等脂肪族烴系溶劑；苯、甲苯、二甲苯、乙基苯、三甲基苯等芳香族烴系溶劑等。(I)溶劑可單獨使用1種，也可將2種以上組合使用。 [9. (I) Solvent] The resin composition according to the first embodiment of the present invention may be combined with the non-volatile components such as the above-mentioned components (A) to (G) and further contain a (I) solvent as an optional volatile component. As the (I) solvent, an organic solvent is generally used. Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and ethyl diglycol acetate. Ether ester solvents such as acetate), γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene, etc. (I) Solvents may be used alone or in combination of two or more.

對(I)溶劑的量沒有特別限定，在將樹脂組成物中的全部成分設為100質量%的情況下，例如可以是60質量%以下、40質量%以下、30質量%以下、20質量%以下、15質量%以下、10質量%以下等，也可以是0質量%。The amount of the solvent (I) is not particularly limited, and when all components in the resin composition are set to 100 mass %, for example, it can be 60 mass % or less, 40 mass % or less, 30 mass % or less, 20 mass % or less, 15 mass % or less, 10 mass % or less, etc., or it can be 0 mass %.

[10. 樹脂組成物的硬化物的比重] 將本發明的第一實施方式所涉及的樹脂組成物硬化而得到的硬化物具有特定範圍的比重。硬化物的比重的具體範圍通常為1.6g/cm 3以下、優選為1.58g/cm 3以下、更優選為1.56g/cm 3以下。硬化物的比重的下限優選為1.0g/cm 3以上、更優選為1.02g/cm 3以上、特別優選為1.05g/cm 3以上。可得到具有上述範圍的比重的硬化物的樹脂組成物，能夠使包含該樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。 [10. Specific gravity of cured product of resin composition] The cured product obtained by curing the resin composition involved in the first embodiment of the present invention has a specific gravity within a specific range. The specific range of the cured product is usually 1.6 g/cm 3 or less, preferably 1.58 g/cm 3 or less, and more preferably 1.56 g/cm 3 or less. The lower limit of the specific gravity of the cured product is preferably 1.0 g/cm 3 or more, more preferably 1.02 g/cm 3 or more, and particularly preferably 1.05 g/cm 3 or more. The resin composition that can obtain a cured product having a specific gravity within the above range can make the insulation layer of the cured product containing the resin composition have good impact peeling resistance and impact cracking resistance.

在樹脂組成物是通過加熱可硬化的熱硬化性樹脂組成物的情況下，評價比重的上述硬化物是使樹脂組成物在180℃、90分鐘的條件下硬化而得到的。另外，在樹脂組成物是通過曝光可硬化的光硬化性樹脂組成物的情況下，評價比重的上述硬化物是通過對樹脂組成物進行1J/cm 2的活性光線的照射之後、在180℃下加熱90分鐘而得到的。用於得到硬化物的具體方法可採用後述的實施例中說明的方法。另外，硬化物的比重的測定方法可採用後述的實施例中說明的方法。 When the resin composition is a thermosetting resin composition that can be cured by heating, the above-mentioned cured product for evaluating specific gravity is obtained by curing the resin composition at 180°C for 90 minutes. In addition, when the resin composition is a photocurable resin composition that can be cured by exposure, the above-mentioned cured product for evaluating specific gravity is obtained by irradiating the resin composition with 1 J/ cm2 of active light and then heating it at 180°C for 90 minutes. The specific method for obtaining the cured product can adopt the method described in the examples described below. In addition, the method for measuring the specific gravity of the cured product can adopt the method described in the examples described below.

樹脂組成物的硬化物的比重可根據樹脂組成物的組成來調整。例如，根據增多(B)無機填充材料的量的方法，可增大比重。另外，例如，根據採用具有大空孔率的材料作為(B-1)中空無機填充材料、或者增多(B-1)中空無機填充材料的量的方法，可減小硬化物的比重。而且，通過調整(A)硬化性樹脂的種類和量的方法，也可調整硬化物的比重。The specific gravity of the cured product of the resin composition can be adjusted according to the composition of the resin composition. For example, by increasing the amount of (B) the inorganic filler, the specific gravity can be increased. In addition, for example, by using a material with a large porosity as (B-1) the hollow inorganic filler, or by increasing the amount of (B-1) the hollow inorganic filler, the specific gravity of the cured product can be reduced. Furthermore, the specific gravity of the cured product can also be adjusted by adjusting the type and amount of (A) the curable resin.

[11. 樹脂組成物的硬化物的熱膨脹係數] 將本發明的第一實施方式所涉及的樹脂組成物硬化而得到的硬化物具有特定範圍的熱膨脹係數。硬化物的熱膨脹係數的具體範圍通常為40ppm/℃以下、優選為30ppm/℃以下、更優選為25ppm/℃以下。硬化物的熱膨脹係數的下限優選為5ppm/℃以上、更優選為10ppm/℃以上、特別優選為15ppm/℃以上。可得到具有上述範圍的熱膨脹係數的硬化物的樹脂組成物，能夠使包含該樹脂組成物的硬化物的絕緣層的抗衝擊剝離性和抗衝擊裂紋性良好。 [11. Thermal expansion coefficient of cured resin composition] The cured product obtained by curing the resin composition involved in the first embodiment of the present invention has a thermal expansion coefficient within a specific range. The specific range of the thermal expansion coefficient of the cured product is usually 40ppm/℃ or less, preferably 30ppm/℃ or less, and more preferably 25ppm/℃ or less. The lower limit of the thermal expansion coefficient of the cured product is preferably 5ppm/℃ or more, more preferably 10ppm/℃ or more, and particularly preferably 15ppm/℃ or more. The resin composition that can obtain a cured product having a thermal expansion coefficient within the above range can make the insulation layer of the cured product containing the resin composition have good impact peeling resistance and impact cracking resistance.

在樹脂組成物是通過加熱可硬化的熱硬化性樹脂組成物的情況下，評價熱膨脹係數的上述硬化物是使樹脂組成物在180℃、90分鐘的條件下硬化而得到的。另外，在樹脂組成物是通過曝光可硬化的光硬化性樹脂組成物的情況下，評價熱膨脹係數的上述硬化物是對樹脂組成物進行1J/cm 2的活性光線的照射之後、在180℃下加熱90分鐘而得到的。用於得到硬化物的具體方法可採用後述的實施例中說明的方法。另外，硬化物的熱膨脹係數是25℃至150℃的溫度範圍的平均線熱膨脹率，可通過基於在負載1g、升溫速度5℃/分鐘的測定條件下的拉伸負重法的熱機械分析來測定。硬化物的熱膨脹係數的具體測定方法可採用後述的實施例中說明的方法。 When the resin composition is a thermosetting resin composition that can be cured by heating, the above-mentioned cured product for evaluating the thermal expansion coefficient is obtained by curing the resin composition at 180°C for 90 minutes. In addition, when the resin composition is a photocurable resin composition that can be cured by exposure, the above-mentioned cured product for evaluating the thermal expansion coefficient is obtained by irradiating the resin composition with 1 J/ cm2 of active light and then heating it at 180°C for 90 minutes. The specific method for obtaining the cured product can adopt the method described in the examples described later. The thermal expansion coefficient of the cured product is the average linear thermal expansion rate in the temperature range of 25°C to 150°C, and can be measured by thermomechanical analysis based on the tensile weight method under the measurement conditions of a load of 1 g and a heating rate of 5°C/min. The specific measurement method of the thermal expansion coefficient of the cured product can be the method described in the examples described below.

樹脂組成物的硬化物的熱膨脹係數可根據樹脂組成物的組成來調整。例如，根據增多(B)無機填充材料的量的方法，可減小熱膨脹係數。另外，根據增多樹脂成分的方法，可增大熱膨脹係數。而且，調整無機填充材料和樹脂成分的種類，也可改變熱膨脹係數。The thermal expansion coefficient of the cured product of the resin composition can be adjusted according to the composition of the resin composition. For example, by increasing the amount of (B) inorganic filler, the thermal expansion coefficient can be reduced. Alternatively, by increasing the resin component, the thermal expansion coefficient can be increased. Furthermore, by adjusting the types of inorganic filler and resin component, the thermal expansion coefficient can also be changed.

[12. 第二實施方式所涉及的樹脂組成物] 本發明的第二實施方式所涉及的樹脂組成物如下：(i)樹脂組成物包含(C)有機粒子；(ii) (B)無機填充材料包含(B-1)中空無機填充材料；(iii) (B-1)中空無機填充材料具有特定範圍的空孔率；(iv)相對於100體積%樹脂組成物的非揮發成分，(B)無機填充材料的量處於特定的範圍；(v)相對於100體積%樹脂組成物的非揮發成分，(B-1)中空無機填充材料的量處於特定的範圍；(vi)將樹脂組成物硬化而得到的硬化物的比重和熱膨脹係數可不處於特定的範圍；除此以外，與本發明的第一實施方式所涉及的樹脂組成物相同。 [12. Resin composition according to the second embodiment] The resin composition according to the second embodiment of the present invention is as follows: (i) the resin composition includes (C) organic particles; (ii) the (B) inorganic filler includes (B-1) hollow inorganic filler; (iii) the (B-1) hollow inorganic filler has a porosity within a specific range; (iv) the amount of the (B) inorganic filler relative to 100% by volume of the non-volatile components of the resin composition is within a specific range; (v) the amount of the (B-1) hollow inorganic filler relative to 100% by volume of the non-volatile components of the resin composition is within a specific range; (vi) the specific gravity and thermal expansion coefficient of the cured product obtained by curing the resin composition may not be within the specific range; except for this, it is the same as the resin composition according to the first embodiment of the present invention.

本發明的第二實施方式所涉及的樹脂組成物的(B-1)中空無機填充材料的空孔率的範圍通常為10體積%以上，優選與第一實施方式所涉及的樹脂組成物的(B-1)中空無機填充材料的空孔率處於相同的範圍。 另外，本發明的第二實施方式所涉及的樹脂組成物中的(B)無機填充材料的量，相對於100體積%樹脂組成物的非揮發成分，通常為40體積%以上，優選與第一實施方式所涉及的樹脂組成物的(B)無機填充材料的量處於相同的範圍。 而且，本發明的第二實施方式所涉及的樹脂組成物中的(B-1)中空無機填充材料的量，相對於100體積%樹脂組成物的非揮發成分，通常為10體積%以上，優選與第一實施方式所涉及的樹脂組成物的(B-1)中空無機填充材料的量處於相同的範圍。 另外，將本發明的第二實施方式所涉及的樹脂組成物硬化而得到的硬化物的比重和熱膨脹係數可與第一實施方式所涉及的樹脂組成物的硬化物的比重和熱膨脹係數處於不同的範圍，但優選處於相同的範圍。第二實施方式所涉及的樹脂組成物的硬化物的比重和熱膨脹係數可通過與第一實施方式所涉及的樹脂組成物的硬化物的比重和熱膨脹係數相同的方法來測定和調整。 The porosity of the hollow inorganic filler (B-1) in the resin composition of the second embodiment of the present invention is usually 10% by volume or more, preferably in the same range as the porosity of the hollow inorganic filler (B-1) in the resin composition of the first embodiment. In addition, the amount of the inorganic filler (B) in the resin composition of the second embodiment of the present invention is usually 40% by volume or more relative to 100% by volume of the non-volatile components of the resin composition, preferably in the same range as the amount of the inorganic filler (B) in the resin composition of the first embodiment. Moreover, the amount of the hollow inorganic filler (B-1) in the resin composition of the second embodiment of the present invention is usually 10% by volume or more relative to 100% by volume of the non-volatile components of the resin composition, and is preferably in the same range as the amount of the hollow inorganic filler (B-1) in the resin composition of the first embodiment. In addition, the specific gravity and thermal expansion coefficient of the cured product obtained by curing the resin composition of the second embodiment of the present invention may be in a different range from the specific gravity and thermal expansion coefficient of the cured product of the resin composition of the first embodiment, but are preferably in the same range. The specific gravity and thermal expansion coefficient of the cured product of the resin composition of the second embodiment can be measured and adjusted by the same method as the specific gravity and thermal expansion coefficient of the cured product of the resin composition of the first embodiment.

根據本發明的第二實施方式所涉及的樹脂組成物，可得到與第一實施方式所涉及的樹脂組成物相同的優點。According to the resin composition involved in the second embodiment of the present invention, the same advantages as the resin composition involved in the first embodiment can be obtained.

[13. 樹脂組成物的製造方法] 在以下的說明中，除非另外說明，「樹脂組成物」是指，包括上述的第一實施方式所涉及的樹脂組成物和第二實施方式所涉及的樹脂組成物這兩者。樹脂組成物例如可通過混合可包含在樹脂組成物中的成分來製造。上述的成分可將一部分或全部同時混合，也可依次混合。在混合各成分的過程中，可適當設定溫度，因此可暫時地或持續地進行加熱和/或冷卻。另外，在混合各成分的過程中，可進行攪拌或振盪。 [13. Method for producing resin composition] In the following description, unless otherwise specified, "resin composition" refers to both the resin composition involved in the first embodiment and the resin composition involved in the second embodiment. The resin composition can be produced, for example, by mixing components that can be contained in the resin composition. The above components can be mixed partially or all at the same time or sequentially. During the process of mixing the components, the temperature can be appropriately set, so that heating and/or cooling can be performed temporarily or continuously. In addition, during the process of mixing the components, stirring or shaking can be performed.

[14. 樹脂組成物的物性] 第一實施方式所涉及的樹脂組成物和第二實施方式所涉及的樹脂組成物的硬化物，耐衝擊性優異。因此，通過這些樹脂組成物的硬化物，可形成耐衝擊性優異的絕緣層。詳細而言，由上述的樹脂組成物的硬化物形成的絕緣層可具有優異的抗衝擊剝離性和抗衝擊裂紋性。 [14. Physical properties of resin composition] The resin composition involved in the first embodiment and the resin composition involved in the second embodiment have excellent impact resistance. Therefore, an insulating layer with excellent impact resistance can be formed by the cured product of these resin compositions. Specifically, the insulating layer formed by the cured product of the above-mentioned resin composition can have excellent resistance to impact peeling and impact cracking.

具體而言，在由樹脂組成物的硬化物在導體層上形成絕緣層的情況下，該絕緣層可抑制由衝擊引起的從導體層的剝離。此時，作為導體層，例如可使用銅箔。另外，絕緣層可在導體層上設置包含樹脂組成物的樹脂組成物層，使樹脂組成物硬化而形成。在樹脂組成物為熱硬化性的情況下，樹脂組成物的硬化可通過在180℃、90分鐘的條件下的加熱來進行。另外，在樹脂組成物為光硬化性的情況下，樹脂組成物的硬化可通過進行1J/cm 2的紫外線照射，然後在180℃、90分鐘的條件下的加熱來進行。 Specifically, when an insulating layer is formed on a conductive layer by a cured product of a resin composition, the insulating layer can suppress peeling from the conductive layer due to impact. In this case, for example, copper foil can be used as the conductive layer. Alternatively, the insulating layer can be formed by providing a resin composition layer containing a resin composition on the conductive layer and curing the resin composition. When the resin composition is thermosetting, the curing of the resin composition can be performed by heating at 180°C for 90 minutes. In addition, when the resin composition is photocurable, the curing of the resin composition can be performed by irradiating it with ultraviolet rays at 1 J/cm 2 and then heating it at 180°C for 90 minutes.

在一個例子中，具備導體層和在該導體層上由樹脂組成物的硬化物形成的絕緣層的樣品，在通過後述的落下試驗施加衝擊的情況下，可抑制絕緣層從導體層的剝離。具體而言，在對5個樣品進行落下試驗的情況下，產生絕緣層從導體層剝離的樣品的數目可優選為1個以下，可更優選為零個。In one example, when a sample having a conductive layer and an insulating layer formed of a cured product of a resin composition on the conductive layer is subjected to an impact in a drop test described below, the insulating layer can be prevented from peeling off from the conductive layer. Specifically, when the drop test is performed on 5 samples, the number of samples in which the insulating layer peels off from the conductive layer is preferably 1 or less, and more preferably zero.

另外，在由樹脂組成物的硬化物形成絕緣層的情況下，該絕緣層可抑制由衝擊引起的裂紋和缺損的形成。此時，絕緣層可通過準備包含樹脂組成物的樹脂組成物層，使樹脂組成物硬化而形成。在樹脂組成物為熱硬化性的情況下，樹脂組成物的硬化可通過在180℃、90分鐘的條件下的加熱來進行。另外，在樹脂組成物為光硬化性的情況下，樹脂組成物的硬化可通過進行1J/cm 2的紫外線照射，然後在180℃、90分鐘的條件下的加熱來進行。 In addition, when the insulating layer is formed by a cured product of a resin composition, the insulating layer can suppress the formation of cracks and defects caused by impact. In this case, the insulating layer can be formed by preparing a resin composition layer containing a resin composition and curing the resin composition. In the case where the resin composition is thermosetting, the curing of the resin composition can be performed by heating at 180°C for 90 minutes. In addition, in the case where the resin composition is photocurable, the curing of the resin composition can be performed by irradiating ultraviolet rays at 1 J/ cm2 and then heating at 180°C for 90 minutes.

在一個例子中，具備由樹脂組成物的硬化物形成的絕緣層的樣品，在通過後述的落下試驗施加衝擊的情況下，可抑制絕緣層的裂紋和缺損。具體而言，在對5個樣品進行落下試驗的情況下，產生絕緣層的裂紋或缺損的樣品的數目可優選為1個以下，可更優選為零個。In one example, when a sample having an insulating layer formed of a cured product of a resin composition is subjected to an impact in a drop test described below, cracks and defects in the insulating layer can be suppressed. Specifically, when a drop test is performed on five samples, the number of samples in which cracks or defects in the insulating layer occur is preferably one or less, and more preferably zero.

落下試驗可通過下述方法進行。圖1是示意性地表示為了評價耐衝擊性而進行的落下試驗的情形的正視圖。如圖1所示，使用膠帶(未圖示)，將樣品11固定在重量200g的圓筒形的錘12的底部，以準備試驗體13。使試驗體13從1.5m的高度H以樣品11朝下的方式，3次自由落下到厚度20mm、直徑200mm的SS400製造的鋼鐵圓板14上。當所落下的試驗體13與鋼鐵圓板14碰撞時，自錘12對樣品11施加衝擊。因此，通過上述的落下試驗，可評價樣品11中所含的絕緣層的耐衝擊性。The drop test can be performed by the following method. FIG. 1 is a front view schematically showing a drop test performed to evaluate impact resistance. As shown in FIG. 1 , a sample 11 is fixed to the bottom of a cylindrical hammer 12 weighing 200 g using an adhesive tape (not shown) to prepare a test body 13. The test body 13 is made to fall freely three times from a height H of 1.5 m onto a steel circular plate 14 made of SS400 with a thickness of 20 mm and a diameter of 200 mm with the sample 11 facing downward. When the dropped test body 13 collides with the steel circular plate 14, the hammer 12 applies an impact to the sample 11. Therefore, through the above-mentioned drop test, the impact resistance of the insulating layer contained in the sample 11 can be evaluated.

上述的耐衝擊性的評價方法的具體操作可採用後述的實施例中說明的方法。The specific operation of the above-mentioned impact resistance evaluation method can adopt the method described in the embodiment described later.

第一實施方式所涉及的樹脂組成物和第二實施方式所涉及的樹脂組成物的硬化物可具有低的相對介電常數。因此，通過這些樹脂組成物的硬化物，可形成相對介電常數低的絕緣層。在一個例子中，硬化物的相對介電常數優選為3.1以下、更優選為3.0以下、特別優選為2.9以下。對下限沒有特別限制，例如可以是1.5以上、2.0以上等。The resin composition involved in the first embodiment and the resin composition involved in the second embodiment can have a low relative dielectric constant when cured. Therefore, an insulating layer with a low relative dielectric constant can be formed by the cured product of these resin compositions. In one example, the relative dielectric constant of the cured product is preferably 3.1 or less, more preferably 3.0 or less, and particularly preferably 2.9 or less. There is no particular limitation on the lower limit, and it can be, for example, 1.5 or more, 2.0 or more, etc.

第一實施方式所涉及的樹脂組成物和第二實施方式所涉及的樹脂組成物的硬化物可具有低的介電損耗角正切。因此，通過這些樹脂組成物的硬化物，可形成介電損耗角正切低的絕緣層。在一個例子中，硬化物的介電損耗角正切優選為0.020以下、更優選為0.018以下、特別優選為0.016以下。對下限沒有特別限制，例如可以是0.001以上、0.002以上等。The resin composition involved in the first embodiment and the resin composition involved in the second embodiment can have a low dielectric loss tangent when cured. Therefore, an insulating layer with a low dielectric loss tangent can be formed by the cured product of these resin compositions. In one example, the dielectric loss tangent of the cured product is preferably 0.020 or less, more preferably 0.018 or less, and particularly preferably 0.016 or less. There is no particular limitation on the lower limit, and for example, it can be 0.001 or more, 0.002 or more, etc.

在樹脂組成物為熱硬化性的情況下，上述的相對介電常數和介電損耗角正切例如可使用使樹脂組成物在180℃、90分鐘的條件下熱硬化而得到的硬化物來測定。另外，在樹脂組成物為光硬化性的情況下，上述的相對介電常數和介電損耗角正切可使用在進行樹脂組成物1J/cm 2的紫外線照射之後，在180℃、90分鐘的條件下加熱而得到的硬化物來測定。硬化物的相對介電常數和介電損耗角正切的測定可通過空腔共振擾動法在測定頻率5.8GHz、測定溫度23℃的條件下來進行。相對介電常數和介電損耗角正切的測定方法的具體操作可採用後述的實施例中說明的方法。 When the resin composition is thermosetting, the relative dielectric constant and dielectric loss tangent can be measured using, for example, a cured product obtained by thermally curing the resin composition at 180°C for 90 minutes. In addition, when the resin composition is photocurable, the relative dielectric constant and dielectric loss tangent can be measured using a cured product obtained by irradiating the resin composition with ultraviolet light at 1 J/ cm2 and then heating the cured product at 180°C for 90 minutes. The relative dielectric constant and dielectric loss tangent of the cured product can be measured by a cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. The specific operation of the method for measuring the relative dielectric constant and the dielectric loss tangent can adopt the method described in the embodiments described later.

第一實施方式所涉及的樹脂組成物和第二實施方式所涉及的樹脂組成物的硬化物可具有大的斷裂伸長率。因此，通過這些樹脂組成物的硬化物，可形成斷裂伸長率大的絕緣層。在一個例子中，硬化物的斷裂伸長率優選為0.5%以上、更優選為1.0%以上、特別優選為1.2%以上。對上限沒有特別限制，例如可以是10%以下、5.0%以下等。The resin composition involved in the first embodiment and the resin composition involved in the second embodiment can have a large elongation at break when cured. Therefore, an insulating layer with a large elongation at break can be formed by the cured product of these resin compositions. In one example, the elongation at break of the cured product is preferably 0.5% or more, more preferably 1.0% or more, and particularly preferably 1.2% or more. There is no particular limitation on the upper limit, and it can be, for example, 10% or less, 5.0% or less, etc.

在樹脂組成物為熱硬化性的情況下，上述的斷裂伸長率例如可使用使樹脂組成物在180℃、90分鐘的條件下熱硬化而得到的硬化物來測定。另外，在樹脂組成物為光硬化性的情況下，上述的斷裂伸長率可使用在進行樹脂組成物1J/cm 2的紫外線照射之後，在180℃、90分鐘的條件下加熱而得到的硬化物來測定。斷裂伸長率可在溫度25℃(室溫)、拉伸速度50mm/分鐘下進行拉伸試驗，作為斷裂時刻的伸長率進行測定。斷裂伸長率的測定方法的具體操作可採用後述的實施例中說明的方法。 When the resin composition is thermosetting, the elongation at break can be measured, for example, using a cured product obtained by thermally curing the resin composition at 180°C for 90 minutes. In addition, when the resin composition is photocurable, the elongation at break can be measured using a cured product obtained by irradiating the resin composition with ultraviolet light at 1 J/ cm2 and then heating it at 180°C for 90 minutes. The elongation at break can be measured as the elongation at the moment of fracture by conducting a tensile test at a temperature of 25°C (room temperature) and a tensile speed of 50 mm/min. The specific operation of the method for measuring the elongation at break can be the method described in the embodiments described later.

[15. 樹脂組成物的用途] 上述的樹脂組成物可用作絕緣用途的樹脂組成物，特別是可適合用作用於形成絕緣層的樹脂組成物(絕緣層形成用的樹脂組成物)。例如，上述的樹脂組成物可用作用於形成印刷配線板的絕緣層的樹脂組成物，可適合用作用於形成層間絕緣層的樹脂組成物(層間絕緣用途的樹脂組成物)。 [15. Use of resin composition] The above-mentioned resin composition can be used as a resin composition for insulating purposes, and in particular, can be suitably used as a resin composition for forming an insulating layer (resin composition for forming an insulating layer). For example, the above-mentioned resin composition can be used as a resin composition for forming an insulating layer of a printed wiring board, and can be suitably used as a resin composition for forming an interlayer insulating layer (resin composition for interlayer insulation).

另外，上述的樹脂組成物也可用作用於形成再配線形成層的樹脂組成物(再配線形成層形成用的樹脂組成物)。再配線形成層表示用於形成再配線層的絕緣層。另外，再配線層表示在作為絕緣層的再配線形成層上形成的導體層。例如，在經過以下的(1)～(6)步驟來製造半導體晶片封裝的情況下，上述的樹脂組成物也可用作用於形成再配線形成層的樹脂組成物。另外，在通過下述的(1)～(6)步驟來製造半導體晶片封裝時，可在密封層上進一步形成再配線層。 (1) 在基材上層合臨時固定膜的步驟； (2) 將半導體晶片臨時固定在臨時固定膜上的步驟； (3) 在半導體晶片上形成密封層的步驟； (4) 將基材和臨時固定膜從半導體晶片上剝離的步驟； (5) 在半導體晶片的剝離了基材和臨時固定膜的面上，形成作為絕緣層的再配線形成層的步驟；以及 (6) 在再配線形成層上形成作為導體層的再配線層的步驟。 In addition, the above-mentioned resin composition can also be used as a resin composition for forming a redistribution formation layer (resin composition for forming a redistribution formation layer). The redistribution formation layer refers to an insulating layer for forming a redistribution layer. In addition, the redistribution layer refers to a conductive layer formed on the redistribution formation layer as an insulating layer. For example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the above-mentioned resin composition can also be used as a resin composition for forming a redistribution formation layer. In addition, when a semiconductor chip package is manufactured through the following steps (1) to (6), a redistribution layer can be further formed on the sealing layer. (1) a step of laminating a temporary fixing film on a substrate; (2) a step of temporarily fixing a semiconductor chip on the temporary fixing film; (3) a step of forming a sealing layer on the semiconductor chip; (4) a step of peeling the substrate and the temporary fixing film from the semiconductor chip; (5) a step of forming a redistribution layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film are peeled; and (6) a step of forming a redistribution layer as a conductive layer on the redistribution layer.

而且，上述的樹脂組成物可在例如樹脂片、預浸料等片狀層合材料、阻焊劑、底部填充材料、黏晶材料、半導體密封材料、填孔樹脂、部件埋入樹脂等可使用樹脂組成物的用途中廣泛地使用。Moreover, the above-mentioned resin composition can be widely used in applications where the resin composition can be used, such as resin sheets, prepreg and other sheet-shaped laminate materials, solder resists, bottom filling materials, die bonding materials, semiconductor sealing materials, hole filling resins, component embedding resins, etc.

[16. 片狀層合材料] 上述的樹脂組成物可以以清漆狀態進行塗布而使用，但在工業上，適合以含有該樹脂組成物的片狀層合材料的形態使用。 [16. Sheet-like laminate] The above-mentioned resin composition can be applied in a varnish state and used, but in industry, it is suitable to be used in the form of a sheet-like laminate containing the resin composition.

作為片狀層合材料，優選以下所示的樹脂片、預浸料。As the sheet-like laminate material, the resin sheets and prepregs shown below are preferred.

在一個實施方式中，樹脂片包含支撐體和設置在該支撐體上的樹脂組成物層。樹脂組成物層由上述的樹脂組成物形成。因此，樹脂組成物層通常包含樹脂組成物，優選僅包含樹脂組成物。In one embodiment, the resin sheet comprises a support and a resin composition layer disposed on the support. The resin composition layer is formed by the above-mentioned resin composition. Therefore, the resin composition layer usually comprises a resin composition, preferably only comprises a resin composition.

對於樹脂組成物層的厚度而言，從印刷配線板的薄型化以及即使該樹脂組成物的硬化物為薄膜也可提供絕緣性優異的硬化物的觀點出發，優選為50μm以下、更優選為40μm以下。對樹脂組成物層的厚度的下限沒有特別限定，可以是5μm以上、10μm以上等。The thickness of the resin composition layer is preferably 50 μm or less, and more preferably 40 μm or less, from the viewpoint of thinning the printed wiring board and providing a cured product having excellent insulation even if the cured product of the resin composition is a thin film. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be 5 μm or more, 10 μm or more, etc.

作為支撐體，例如可舉出：由塑膠材料構成的膜、金屬箔、脫模紙，優選由塑膠材料構成的膜、金屬箔。Examples of the support include a film made of a plastic material, a metal foil, and a release paper, preferably a film made of a plastic material or a metal foil.

在使用由塑膠材料構成的膜作為支撐體的情況下，作為塑膠材料，例如可舉出：聚對苯二甲酸乙二醇酯(以下有時簡稱「PET」)、聚萘二甲酸乙二醇酯(以下有時簡稱為「PEN」)等聚酯、聚碳酸酯(以下有時簡稱為「PC」)、聚甲基丙烯酸甲酯(PMMA)等丙烯酸、環狀聚烯烴、三乙醯纖維素(TAC)、聚醚硫化物(PES)、聚醚酮、聚醯亞胺等。其中，優選聚對苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯，特別優選廉價的聚對苯二甲酸乙二醇酯。When a film made of a plastic material is used as a support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate (hereinafter sometimes referred to as "PEN"), polycarbonate (hereinafter sometimes referred to as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

在使用金屬箔作為支撐體的情況下，作為金屬箔，例如可舉出：銅箔、鋁箔等，優選銅箔。作為銅箔，可使用由銅的單金屬構成的箔，也可使用由銅與其它金屬(例如，錫、鉻、銀、鎂、鎳、鋯、矽、鈦等)的合金構成的箔。When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferred. The copper foil may be a foil made of copper alone or an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

可對支撐體的與樹脂組成物層接合的面實施消光處理、電暈處理、防靜電處理。The surface of the support body that is bonded to the resin composition layer may be subjected to matte treatment, corona treatment, and anti-static treatment.

作為支撐體，可使用在與樹脂組成物層接合的面具有脫模層的帶脫模層的支撐體。作為用於帶脫模層的支撐體的脫模層的脫模劑，例如可舉出：選自醇酸樹脂、聚烯烴樹脂、胺基甲酸酯樹脂和聚矽氧樹脂的1種以上的脫模劑。帶脫模層的支撐體可使用市售品，例如可舉出：作為具有以醇酸樹脂系脫模劑為主要成分的脫模層的PET膜的、LINTEC公司製造的「SK-1」、「AL-5」、「AL-7」、東麗公司製造的「Lumirror T60」、帝人公司製造的「Purex」、UNITIKA公司製造的「Unipeel」等。As the support, a support with a release layer having a release layer on the surface bonded to the resin composition layer can be used. Examples of release agents used for the release layer of the support with a release layer include at least one release agent selected from alkyd resins, polyolefin resins, urethane resins, and silicone resins. The support body with a release layer can use commercially available products, for example: PET film having a release layer with an alkyd resin-based release agent as a main component, "SK-1", "AL-5", "AL-7" manufactured by LINTEC, "Lumirror T60" manufactured by Toray, "Purex" manufactured by Teijin, "Unipeel" manufactured by UNITIKA, etc.

對支撐體的厚度沒有特別限定，優選5μm～75μm的範圍、更優選10μm～60μm的範圍。需要說明的是，在使用帶脫模層的支撐體的情況下，優選帶脫模層的支撐體整體的厚度為上述範圍。The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

在一個實施方式中，根據需要，樹脂片可進一步包含任選的層。作為所述任選的層，例如可舉出：設置於樹脂組成物層的不與支撐體接合的面(即，與支撐體相反一側的面)上的、按照支撐體而選用的保護膜等。對保護膜的厚度沒有特別限定，例如為1μm～40μm。通過層合保護膜，可抑制灰塵附著於樹脂組成物層的表面或對樹脂組成物層的表面造成損傷。In one embodiment, the resin sheet may further include an optional layer as needed. Examples of the optional layer include a protective film selected according to the support and disposed on the surface of the resin composition layer that is not bonded to the support (i.e., the surface on the opposite side of the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, dust can be prevented from adhering to the surface of the resin composition layer or causing damage to the surface of the resin composition layer.

樹脂片例如可通過以下方式來製造：使用模塗機等塗布裝置，將液態(清漆狀)的樹脂組成物直接塗布於支撐體上，或者將樹脂組成物溶解於溶劑而調製液態(清漆狀)的樹脂組成物並將其塗布於支撐體上，進一步進行乾燥，形成樹脂組成物層。The resin sheet can be manufactured, for example, by directly applying a liquid (varnish-like) resin composition to a support using a coating device such as a die coater, or by dissolving the resin composition in a solvent to prepare a liquid (varnish-like) resin composition and applying it to a support, followed by drying to form a resin composition layer.

作為溶劑，可舉出：與作為樹脂組成物的成分而說明的溶劑相同的溶劑。溶劑可單獨使用1種，也可將2種以上組合使用。Examples of the solvent include the same solvents as those described as components of the resin composition. The solvent may be used alone or in combination of two or more.

乾燥可通過加熱、吹熱風等方法來實施。對乾燥條件沒有特別限定，使樹脂組成物層中的溶劑的含量達到通常為10質量%以下、優選為5質量%以下的方式進行乾燥。雖然根據樹脂組成物中的溶劑的沸點而不同，但例如在使用包含30質量%～60質量%溶劑的樹脂組成物的情況下，通過在50℃～150℃下乾燥3分鐘～10分鐘，可形成樹脂組成物層。Drying can be carried out by heating, blowing hot air, etc. There is no particular limitation on the drying conditions, and drying is performed so that the content of the solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the solvent in the resin composition, for example, when a resin composition containing 30% by mass to 60% by mass of the solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

樹脂片可捲繞成卷狀而進行保存。在樹脂片具有保護膜的情況下，通常可通過剝離保護膜來使用。The resin sheet can be stored in a roll. If the resin sheet has a protective film, it can usually be used by peeling off the protective film.

在一個實施方式中，預浸料是通過在片狀纖維基材中浸漬上述的樹脂組成物而形成的。In one embodiment, the prepreg is formed by impregnating the above-mentioned resin composition into a sheet-like fiber base material.

用於預浸料的片狀纖維基材例如可使用：玻璃布、芳香族聚醯胺不織布、液晶聚合物不織布等通常用作預浸料用基材的片狀纖維基材。從印刷配線板的薄型化的觀點出發，片狀纖維基材的厚度優選為50μm以下、更優選為40μm以下、進一步優選為30μm以下、特別優選為20μm以下。對片狀纖維基材的厚度的下限沒有特別限定，通常為10μm以上。The sheet-like fiber substrate used for the prepreg can be, for example, glass cloth, aromatic polyamide non-woven fabric, liquid crystal polymer non-woven fabric, etc., which are generally used as sheet-like fiber substrates for prepreg substrates. From the perspective of thinning the printed wiring board, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, and particularly preferably 20 μm or less. There is no particular lower limit to the thickness of the sheet-like fiber substrate, but it is usually 10 μm or more.

預浸料可通過熱熔法、溶劑法等方法來製造。Prepreg can be manufactured by hot melt method, solvent method and other methods.

預浸料的厚度可以是與上述的樹脂片中的樹脂組成物層同樣的範圍。The thickness of the prepreg can be in the same range as that of the resin composition layer in the above-mentioned resin sheet.

片狀層合材料可適合用於形成印刷配線板的絕緣層(用於印刷配線板的絕緣層)，可更適合用於形成印刷配線板的層間絕緣層(用於印刷配線板的層間絕緣層)。The sheet-shaped laminate material can be suitably used for forming an insulating layer of a printed wiring board (insulating layer for a printed wiring board), and can be more suitably used for forming an interlayer insulating layer of a printed wiring board (interlayer insulating layer for a printed wiring board).

[17. 印刷配線板] 本發明的一實施方式所涉及的印刷配線板具備包含將上述的將樹脂組成物硬化而得到的硬化物的絕緣層。該印刷配線板例如可通過使用上述的樹脂片，利用包括下述(I)和(II)的步驟的方法來製造。 (I) 以樹脂片的樹脂組成物層與內層基板接合的方式，在內層基板上層合樹脂片的步驟； (II) 將樹脂組成物層硬化以形成絕緣層的步驟。 [17. Printed wiring board] A printed wiring board according to one embodiment of the present invention comprises an insulating layer comprising a cured product obtained by curing the above-mentioned resin composition. The printed wiring board can be manufactured, for example, by using the above-mentioned resin sheet and utilizing a method comprising the following steps (I) and (II). (I) a step of laminating the resin sheet on the inner substrate in such a manner that the resin composition layer of the resin sheet is bonded to the inner substrate; (II) a step of curing the resin composition layer to form an insulating layer.

步驟(I)中使用的「內層基板」是指成為印刷配線板的基板的構件，例如可舉出：玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚苯醚基板等。另外，該基板可在其一面或雙面具有導體層，該導體層也可進行圖案加工。有時將在基板的一面或雙面形成有導體層(電路)的內層基板稱為「內層電路基板」。另外，在製造印刷配線板時，待進一步形成絕緣層和/或導體層的中間製造物也包括在上述的「內層基板」中。在印刷配線板為部件內置電路板的情況下，也可使用內置有部件的內層基板。The "inner layer substrate" used in step (I) refers to a component that becomes the substrate of a printed wiring board, and examples thereof include: glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate, etc. In addition, the substrate may have a conductive layer on one or both sides thereof, and the conductive layer may also be patterned. An inner layer substrate having a conductive layer (circuit) formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit substrate". In addition, when manufacturing a printed wiring board, an intermediate product to be further formed with an insulating layer and/or a conductive layer is also included in the above-mentioned "inner layer substrate". In the case where the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components can also be used.

內層基板與樹脂片的層合例如可通過從支撐體側將樹脂片向內層基板加熱壓接來進行。作為將樹脂片加熱壓接於內層基板的構件(以下，也稱為「加熱壓接構件」)，例如可舉出：經加熱的金屬板(SUS端板等)或金屬輥(SUS輥等)。需要說明的是，優選並非將加熱壓接構件向樹脂片直接壓製，而是隔著耐熱橡膠等彈性材料進行壓製，以使樹脂片充分地追隨內層基板的表面凹凸。The inner substrate and the resin sheet can be laminated, for example, by heat-pressing the resin sheet to the inner substrate from the support body side. As a component for heat-pressing the resin sheet to the inner substrate (hereinafter, also referred to as a "heat-pressing component"), for example, a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller, etc.) can be cited. It should be noted that it is preferred not to press the heat-pressing component directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet can fully follow the surface unevenness of the inner substrate.

內層基板與樹脂片的層合可通過真空層壓法來實施。真空層壓法中，加熱壓接溫度優選為60℃～160℃、更優選為80℃～140℃的範圍，加熱壓接壓力優選為0.098MPa～1.77MPa、更優選為0.29MPa～1.47MPa的範圍，加熱壓接時間優選為20秒～400秒、更優選為30秒～300秒的範圍。層合優選在壓力為26.7hPa以下的減壓條件下實施。The lamination of the inner substrate and the resin sheet can be performed by vacuum lamination. In the vacuum lamination, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heating and pressing pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7hPa or less.

層合可利用市售的真空層壓機來進行。作為市售的真空層壓機，例如可舉出：名機製作所公司製造的真空加壓式層壓機、Nikko-Materials公司製造的真空敷料器(vacuum applicator)、批次式真空加壓層壓機等。Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum press laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko-Materials Co., Ltd., and a batch vacuum press laminator.

在層合之後，也可通過在常壓下(大氣壓下)、例如從支撐體側對加熱壓接構件進行壓製，從而對層合後的樹脂片進行平滑化處理。平滑化處理的壓製條件可設為與上述層合的加熱壓接條件同樣的條件。平滑化處理可利用市售的層壓機來進行。需要說明的是，層合與平滑化處理可使用上述的市售的真空層壓機連續地進行。After lamination, the laminated resin sheet may be smoothed by pressing the heat-pressed member under normal pressure (atmospheric pressure), for example, from the side of the support body. The pressing conditions for the smoothing treatment may be the same as the heat-pressed conditions for the lamination described above. The smoothing treatment may be performed using a commercially available laminating press. It should be noted that the lamination and smoothing treatment may be performed continuously using the commercially available vacuum laminating press described above.

支撐體可在步驟(I)與步驟(II)之間去除，也可在步驟(II)之後去除。The support may be removed between step (I) and step (II), or after step (II).

步驟(II)中，將樹脂組成物層硬化，形成由樹脂組成物的硬化物構成的絕緣層。樹脂組成物層的硬化可利用適合於樹脂組成物的方法來進行，如熱硬化、光硬化等。樹脂組成物層的具體硬化條件可使用在形成印刷配線板的絕緣層時通常採用的條件。In step (II), the resin composition layer is cured to form an insulating layer composed of a cured product of the resin composition. The resin composition layer can be cured by a method suitable for the resin composition, such as heat curing, light curing, etc. The specific curing conditions of the resin composition layer can be the conditions generally used when forming an insulating layer of a printed wiring board.

在使用熱硬化性的樹脂組成物的情況下，樹脂組成物的硬化可作為熱硬化進行。因此，在這種情況下，步驟(II)可包括使樹脂組成物層熱硬化。樹脂組成物層的熱硬化條件可根據樹脂組成物的種類而不同。例如，硬化溫度優選為120℃～240℃、更優選為150℃～220℃、進一步優選為170℃～210℃。另外，硬化時間可以是優選5分鐘～120分鐘、更優選10分鐘～100分鐘、進一步優選15分鐘～100分鐘。In the case of using a thermosetting resin composition, the curing of the resin composition can be performed as thermal curing. Therefore, in this case, step (II) may include thermally curing the resin composition layer. The thermal curing conditions of the resin composition layer may differ depending on the type of the resin composition. For example, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and further preferably 170°C to 210°C. In addition, the curing time may be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and further preferably 15 minutes to 100 minutes.

另外，在使樹脂組成物層熱硬化的情況下，印刷配線板的製造方法優選包括：在該熱硬化之前，在低於硬化溫度的溫度下對樹脂組成物層進行預加熱。例如，可在使樹脂組成物層熱硬化之前，在通常50℃～150℃、優選60℃～140℃、更優選70℃～130℃的溫度下，對樹脂組成物層進行通常5分鐘以上、優選5分鐘～150分鐘、更優選15分鐘～120分鐘、進一步優選15分鐘～100分鐘預加熱。In addition, when the resin composition layer is heat-cured, the method for manufacturing a printed wiring board preferably includes: preheating the resin composition layer at a temperature lower than the curing temperature before the heat-curing. For example, before the resin composition layer is heat-cured, the resin composition layer may be preheated at a temperature of usually 50°C to 150°C, preferably 60°C to 140°C, and more preferably 70°C to 130°C for usually 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and further preferably 15 minutes to 100 minutes.

另一方面，在使用光硬化性的樹脂組成物的情況下，樹脂組成物的硬化可作為光硬化進行。因此，在這種情況下，步驟(II)可包括使樹脂組成物層光硬化。樹脂組成物的光硬化條件可根據樹脂組成物的種類而不同。例如，通過對樹脂組成物層照射活性光線的曝光處理，可使照射部的樹脂組成物層光硬化。作為活性光線，例如可舉出：紫外線、可見光線、電子射線、X射線等，特別優選紫外線。紫外線的照射量例如為10mJ/cm 2～1000mJ/ cm 2。在使用具備支撐體的樹脂片的情況下，可穿過支撐體進行曝光，也可在剝離支撐體之後進行曝光。 On the other hand, when a photocurable resin composition is used, the curing of the resin composition can be performed as photocuring. Therefore, in this case, step (II) may include photocuring the resin composition layer. The photocuring conditions of the resin composition may differ depending on the type of the resin composition. For example, by exposing the resin composition layer to active light, the resin composition layer in the irradiated portion can be photocured. Examples of active light include ultraviolet light, visible light, electron rays, X-rays, etc., with ultraviolet light being particularly preferred. The irradiation amount of ultraviolet light is, for example, 10 mJ/ cm2 to 1000 mJ/ cm2 . When a resin sheet with a support is used, exposure can be performed through the support or after the support is peeled off.

在曝光處理中，可穿過形成有圖案的遮罩對樹脂組成物層照射活性光線。在使用遮罩的曝光方法中，有使遮罩與工件接觸而進行曝光的接觸曝光法和不接觸而使用平行光線進行曝光的非接觸曝光法，使用任一種均可。In the exposure process, the resin composition layer can be irradiated with active light through a mask formed with a pattern. Among the exposure methods using a mask, there are contact exposure methods in which the mask is brought into contact with the workpiece for exposure and non-contact exposure methods in which parallel light is used for exposure without contact. Either method can be used.

步驟(II)可包括在曝光處理之後進行顯影處理。根據顯影處理，去除未光硬化的部分(未曝光部)，可在硬化體層形成圖案。顯影通常通過濕式顯影來進行。在濕式顯影中，作為顯影液，例如可使用：鹼性水溶液、水系顯影液、有機溶劑等安全且穩定、且操作性良好的顯影液。其中，優選基於鹼水溶液的顯影步驟。作為顯影方法，例如可採用：噴霧、搖動浸漬、刷洗、刮塗等方法。Step (II) may include performing a developing process after the exposure process. According to the developing process, the un-photocured portion (unexposed portion) is removed, and a pattern can be formed on the cured layer. The developing is usually performed by wet developing. In the wet developing, as the developer, for example, an alkaline aqueous solution, an aqueous developer, an organic solvent, etc., which are safe, stable, and easy to operate, can be used. Among them, the developing step based on the alkaline aqueous solution is preferred. As the developing method, for example, a spraying, agitation dipping, brushing, scraping, etc. can be used.

而且，在使樹脂組成物層光硬化的情況下，根據必要，可在光硬化和顯影之後，進行後烘烤處理。作為後烘烤處理，例如可舉出：基於高壓汞燈的紫外線照射處理、使用潔淨烘箱的加熱處理等。紫外線照射處理例如可在0.05J/cm 2～10J/cm 2左右的照射量下進行。另外，加熱處理例如優選可在150℃～250℃下進行20分鐘～180分鐘的範圍、更優選可在160℃～230℃下進行30分鐘～120分鐘的範圍。 Furthermore, when the resin composition layer is photocured, a post-baking treatment may be performed after the photocuring and development, if necessary. Examples of the post-baking treatment include ultraviolet irradiation treatment using a high-pressure mercury lamp and heat treatment using a clean oven. The ultraviolet irradiation treatment may be performed at an irradiation dose of about 0.05 J/cm 2 to 10 J/cm 2. The heat treatment may be performed at, for example, 150°C to 250°C for 20 minutes to 180 minutes, and more preferably at 160°C to 230°C for 30 minutes to 120 minutes.

在製造印刷配線板時，可進一步實施(III)在絕緣層上開孔的步驟、(IV)對絕緣層進行粗化處理的步驟、(V)形成導體層的步驟。這些步驟(III)至步驟(V)可按照用於製造印刷配線板的、本發明所屬技術領域中具有通常知識者公知的各種方法來實施。需要說明的是，在步驟(II)之後去除支撐體的情況下，該支撐體的去除可在步驟(II)與步驟(III)之間、步驟(III)與步驟(IV)之間、或步驟(IV)與步驟(V)之間實施。另外，根據必要，也可反覆實施步驟(I)～步驟(V)的絕緣層和導體層的形成，從而形成多層配線板。When manufacturing a printed wiring board, (III) a step of opening holes in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductive layer may be further performed. These steps (III) to (V) may be performed according to various methods known to those skilled in the art for manufacturing printed wiring boards. It should be noted that, when the support is removed after step (II), the removal of the support may be performed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). Furthermore, if necessary, the formation of the insulating layer and the conductive layer in steps (I) to (V) may be repeated to form a multi-layer wiring board.

在其它實施方式中，印刷配線板可使用上述的預浸料來製造。製造方法基本上可與使用樹脂片的情況同樣。In other embodiments, a printed wiring board can be manufactured using the above-mentioned prepreg. The manufacturing method can be basically the same as that of the case of using a resin sheet.

步驟(III)是在絕緣層上開孔的步驟，由此，可在絕緣層上形成通孔、貫穿孔(through hole)等孔。對於步驟(III)而言，根據用於形成絕緣層的樹脂組成物的組成等，例如可使用鑽頭、雷射、電漿等來實施。孔的尺寸和形狀可根據印刷配線板的設計適當確定。Step (III) is a step of opening holes in the insulating layer, thereby forming holes such as through holes and through holes in the insulating layer. Step (III) can be performed using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The size and shape of the hole can be appropriately determined according to the design of the printed wiring board.

步驟(IV)是對絕緣層進行粗化處理的步驟。通常，在該步驟(IV)中，也進行膠渣的去除。對粗化處理的步驟、條件沒有特別限定，可採用在形成印刷配線板的絕緣層時通常使用的公知的步驟、條件。例如，可依次實施基於膨潤液的膨潤處理、基於氧化劑的粗化處理、基於中和液的中和處理，以對絕緣層進行粗化處理。Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), the scum is also removed. There is no particular limitation on the steps and conditions of the roughening treatment, and the known steps and conditions commonly used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by sequentially performing swelling treatment based on swelling liquid, roughening treatment based on oxidizing agent, and neutralization treatment based on neutralizing liquid.

作為用於粗化處理的膨潤液，例如可舉出：鹼溶液、界面活性劑溶液等，優選為鹼溶液。作為該鹼溶液，更優選氫氧化鈉溶液、氫氧化鉀溶液。作為市售的膨潤液，例如可舉出：Atotech Japan公司製造的「Swelling Dip Securiganth P」、「Swelling Dip Securiganth SBU」等。基於膨潤液的膨潤處理例如可通過將絕緣層在30℃～90℃的膨潤液中浸漬1分鐘～20分鐘來進行。從將絕緣層的樹脂的膨潤抑制在適度的水平的觀點出發，優選將絕緣層在40℃～80℃的膨潤液中浸漬5分鐘～15分鐘。As the swelling liquid used for the roughening treatment, for example, alkaline solution, surfactant solution, etc. can be cited, and alkaline solution is preferred. As the alkaline solution, sodium hydroxide solution and potassium hydroxide solution are more preferred. As commercially available swelling liquid, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan can be cited. The swelling treatment based on the swelling liquid can be performed, for example, by immersing the insulating layer in the swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferred to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 to 15 minutes.

作為用於粗化處理的氧化劑，例如可舉出：在氫氧化鈉的水溶液中溶解過錳酸鉀或過錳酸鈉而得的鹼性過錳酸溶液。基於鹼性過錳酸溶液等氧化劑的粗化處理優選通過將絕緣層在加熱至60℃～100℃的氧化劑溶液中浸漬10分鐘～30分鐘來進行。另外，鹼性過錳酸溶液中的過錳酸鹽的濃度優選5質量%～10質量%。作為市售的氧化劑，例如可舉出：Atotech Japan公司製造的「Concentrate Compact CP」、「Dosing Solution Securiganth P」等鹼性過錳酸溶液。As an oxidizing agent used for the roughening treatment, for example, an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be cited. The roughening treatment based on an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. As a commercially available oxidizing agent, for example, alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan can be cited.

作為用於粗化處理的中和液，優選酸性的水溶液，作為市售品，例如可舉出：Atotech Japan公司製造的「Reduction Solution Securiganth P」。基於中和液的處理可通過使進行了基於氧化劑的粗化處理的處理面在30℃～80℃的中和液中浸漬5分鐘～30分鐘來進行。從操作性等方面考慮，優選將進行了基於氧化劑的粗化處理的對象物在40℃～70℃的中和液中浸漬5分鐘～20分鐘的方法。As the neutralizing solution used for the roughening treatment, an acidic aqueous solution is preferred, and as a commercially available product, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan Co., Ltd. can be cited. The treatment based on the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment based on the oxidant in the neutralizing solution at 30°C to 80°C for 5 minutes to 30 minutes. From the perspective of operability, etc., it is preferred to immerse the object subjected to the roughening treatment based on the oxidant in the neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes.

步驟(V)是形成導體層的步驟，在絕緣層上形成導體層。對用於導體層的導體材料沒有特別限定。在適合的實施方式中，導體層包含選自金、白金、鈀、銀、銅、鋁、鈷、鉻、鋅、鎳、鈦、鎢、鐵、錫和銦的1種以上的金屬。導體層可以是單金屬層也可以是合金層，作為合金層，例如可舉出：由選自上述的2種以上的金屬的合金(例如，鎳-鉻合金、銅-鎳合金和銅-鈦合金)形成的層。其中，從導體層形成的通用性、成本、圖案化的容易性等觀點出發，優選鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅的單金屬層、或者鎳-鉻合金、銅-鎳合金、銅-鈦合金的合金層，更優選鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅的單金屬層、或者鎳-鉻合金的合金層，進一步優選銅的單金屬層。Step (V) is a step of forming a conductive layer, and the conductive layer is formed on the insulating layer. There is no particular limitation on the conductive material used for the conductive layer. In a suitable embodiment, the conductive layer contains one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductive layer can be a single metal layer or an alloy layer. As an example of the alloy layer, there can be cited: a layer formed of an alloy of two or more metals selected from the above (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among them, from the viewpoints of versatility, cost, and ease of patterning of the conductive layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferred; a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferred; and a single metal layer of copper is further preferred.

導體層可以是單層結構，也可以是由不同種類的金屬或合金構成的單金屬層或合金層層合2層以上而得的多層結構。在導體層為多層結構的情況下，優選與絕緣層相接的層為鉻、鋅或鈦的單金屬層、或者為鎳-鉻合金的合金層。The conductive layer may be a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers composed of different types of metals or alloys are laminated. When the conductive layer is a multilayer structure, it is preferred that the layer in contact with the insulating layer is a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

導體層的厚度取決於所期望的印刷配線板的設計，但通常為3μm～35μm、優選為5μm～30μm。The thickness of the conductor layer depends on the desired design of the printed wiring board, but is usually 3 μm to 35 μm, preferably 5 μm to 30 μm.

在一個實施方式中，導體層可通過鍍敷形成。例如，可利用半加成法、全加成法等以往公知的技術對絕緣層的表面進行鍍敷，形成具有所期望的配線圖案的導體層。從製造的簡便性的觀點出發，優選半加成法。以下，示出通過半加成法形成導體層的例子。In one embodiment, the conductive layer can be formed by plating. For example, the surface of the insulating layer can be plated using a conventionally known technique such as a semi-additive method or a full-additive method to form a conductive layer having a desired wiring pattern. From the perspective of simplicity of manufacturing, the semi-additive method is preferred. The following is an example of forming a conductive layer by a semi-additive method.

首先，在絕緣層的表面上，通過無電解鍍敷形成鍍敷晶種層。然後，在所形成的鍍敷晶種層上，形成對應於所期望的配線圖案而使鍍敷晶種層的一部分暴露的遮罩圖案。通過電解鍍敷在暴露的鍍敷晶種層上形成金屬層之後，去除遮罩圖案。之後，通過蝕刻等去除不需要的鍍敷晶種層，可形成具有所期望的配線圖案的導體層。First, a coating seed layer is formed on the surface of the insulating layer by electroless plating. Then, a mask pattern is formed on the formed coating seed layer to expose a portion of the coating seed layer corresponding to the desired wiring pattern. After a metal layer is formed on the exposed coating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, the unnecessary coating seed layer is removed by etching or the like, and a conductive layer having a desired wiring pattern can be formed.

在其它實施方式中，導體層可使用金屬箔來形成。在使用金屬箔形成導體層的情況下，步驟(V)適合在步驟(I)與步驟(II)之間實施。例如，在步驟(I)之後，去除支撐體，在暴露的樹脂組成物層的表面上層合金屬箔。樹脂組成物層與金屬箔的層合可通過真空層壓法來實施。層合的條件可與關於步驟(I)而說明的條件同樣。然後，實施步驟(II)，以形成絕緣層。之後，利用絕緣層上的金屬箔，通過減成法、改良的半加成法等以往公知的技術，可形成具有所期望的配線圖案的導體層。In other embodiments, the conductive layer may be formed using a metal foil. In the case where the conductive layer is formed using a metal foil, step (V) is suitably performed between step (I) and step (II). For example, after step (I), the support is removed, and the metal foil is layered on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil may be performed by vacuum lamination. The lamination conditions may be the same as those described with respect to step (I). Then, step (II) is performed to form an insulating layer. Thereafter, a conductive layer having a desired wiring pattern can be formed by utilizing the metal foil on the insulating layer through conventionally known techniques such as a subtractive process and an improved semi-additive process.

金屬箔例如可通過電解法、壓延法等公知的方法來製造。作為金屬箔的市售品，例如可舉出：JX金屬公司製造的HLP箔、JXUT-III箔，三井金屬礦業公司製造的3EC-III箔、TP-III箔等。The metal foil can be produced by a known method such as electrolysis or rolling. Examples of commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Metals, and 3EC-III foil and TP-III foil manufactured by Mitsui Metals and Mining Co., Ltd.

[18. 半導體裝置] 本發明的一實施方式所涉及的半導體裝置包含上述的印刷配線板。半導體裝置可使用印刷配線板來製造。 [18. Semiconductor device] A semiconductor device according to one embodiment of the present invention includes the above-mentioned printed wiring board. The semiconductor device can be manufactured using the printed wiring board.

作為半導體裝置，可舉出：用於電氣製品(例如，電腦、行動電話、數位相機和電視等)和交通工具(例如，摩托車、汽車、電車、船舶和飛機等)等的各種半導體裝置。 [實施例] As semiconductor devices, there can be cited: various semiconductor devices used in electrical products (e.g., computers, mobile phones, digital cameras, and televisions, etc.) and transportation vehicles (e.g., motorcycles, cars, trains, ships, and airplanes, etc.). [Examples]

以下，示出實施例具體地說明本發明。然而，本發明不限定於這些實施例。以下的說明中，只要沒有另行明確說明，表示量的「份」和「%」分別是指「質量份」和「質量%」。另外，在沒有特別指定溫度的情況下的溫度條件和壓力條件為室溫(25℃)和大氣壓(1atm)。The present invention is specifically described below by way of examples. However, the present invention is not limited to these examples. In the following description, unless otherwise clearly stated, "parts" and "%" indicating quantities refer to "parts by mass" and "% by mass", respectively. In addition, the temperature conditions and pressure conditions when no particular temperature is specified are room temperature (25°C) and atmospheric pressure (1 atm).

[合成例1：含有乙烯性不飽和鍵和羧基的樹脂(a1)的合成] 準備了以下的式(1)所示的萘酚芳烷基型環氧樹脂(新日鐵住金化學公司製造的「ESN-475V」、環氧當量約325g/eq.)。 [Synthesis Example 1: Synthesis of Resin (a1) Containing Ethylenically Unsaturated Bonds and Carboxyl Groups] A naphthol aralkyl type epoxy resin represented by the following formula (1) ("ESN-475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent weight of about 325 g/eq.) was prepared.

式(1)中，Z為縮水甘油基(Gl)或碳原子數1～8的烴基(R6)，R6/Gl的比率為0.05～2.0。另外，n作為平均值表示1～6的數。In formula (1), Z is a glycidyl group (G1) or a alkyl group (R6) having 1 to 8 carbon atoms, and the ratio of R6/G1 is 0.05 to 2.0. In addition, n represents a number of 1 to 6 as an average value.

將325份該萘酚芳烷基型環氧樹脂(新日鐵住金化學公司製造的「ESN-475V」、環氧當量約325g/eq.)裝入具備氣體導入管、攪拌裝置、冷卻管和溫度計的燒瓶中，加入340份卡必醇乙酸酯，加熱溶解，加入0.46份對苯二酚和1份三苯基膦。將該混合物加熱至95℃～105℃，緩慢地滴加72份丙烯酸，反應16小時。將該反應產物冷卻至80℃～90℃，加入80份四氫鄰苯二甲酸酐，反應8小時，使其冷卻。如此進行操作，得到了固體物質的酸價為60mgKOH/g的樹脂溶液(非揮發成分70%、以下有時簡稱為「樹脂(a1)溶液」)。確認到：該樹脂(a1)溶液至少包含含有下述式(2)所示結構的樹脂(a1)。325 parts of the naphthol aralkyl epoxy resin ("ESN-475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent of about 325 g/eq.) were placed in a flask equipped with a gas inlet tube, a stirrer, a cooling tube and a thermometer, 340 parts of carbitol acetate were added, heated to dissolve, 0.46 parts of hydroquinone and 1 part of triphenylphosphine were added. The mixture was heated to 95°C to 105°C, 72 parts of acrylic acid were slowly added dropwise, and the reaction was carried out for 16 hours. The reaction product was cooled to 80°C to 90°C, 80 parts of tetrahydrophthalic anhydride were added, the reaction was carried out for 8 hours, and the mixture was cooled. In this way, a resin solution having a solid acid value of 60 mgKOH/g (70% non-volatile matter, hereinafter sometimes referred to as "resin (a1) solution") was obtained. It was confirmed that the resin (a1) solution contained at least a resin (a1) having a structure represented by the following formula (2).

[實施例1] 在10份雙酚A型環氧樹脂(三菱化學公司製造的「828EL」、環氧當量約180g/eq.)、25份聯苯型環氧樹脂(日本化藥公司製造的「NC3000L」、環氧當量約269g/eq.)中加入50份甲基乙基酮，邊攪拌邊加熱溶解。將其冷卻至室溫，調製了環氧樹脂溶解組成物。在該環氧樹脂溶解組成物中混合10份含有三嗪骨架的酚系硬化劑(DIC公司製造的「LA-3018-50P」、活性基當量約151g/eq.、非揮發成分率50%的2-甲氧基丙醇溶液)、10份萘酚型硬化劑(日鐵化學材料公司製造的「SN-485」、羥基當量約205g/eq.)、15份苯氧樹脂(三菱化學公司製造的「YX7553BH30」、非揮發成分30質量%的MEK與環己酮的1：1溶液)、50份用矽烷偶合劑(信越化學工業公司製造的「KBM-573」)進行表面處理的作為實心無機填充材料的球形二氧化矽(Admatechs公司製造的「SO-C2」、平均粒徑0.5μm、BET比表面積5.8m 2/g)、25份用矽烷偶合劑(信越化學工業公司製造的「KBM-573」)進行表面處理的中空二氧化矽粒子1(平均粒徑1.6μm、BET比表面積12m 2/g、空孔率50體積%)、3份橡膠粒子(Dow Chemical日本公司製造的「PARALOID EXL2655」；具備由丁二烯(比重0.91)的聚合物形成的芯部、以及由苯乙烯(比重1.06)和甲基丙烯酸甲酯(比重1.18)的共聚物形成的殼部的芯殼粒子；平均粒徑0.2μm)、4份胺系硬化促進劑(4-二甲基胺基吡啶(DMAP)、固體成分5質量%的MEK溶液)，用高速旋轉混合器均勻地分散，調製了樹脂清漆。該樹脂清漆中所含的無機填充材料的平均粒徑為1.1μm、BET比表面積為9.0m 2/g。 [Example 1] 50 parts of methyl ethyl ketone were added to 10 parts of bisphenol A type epoxy resin ("828EL" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 180 g/eq.) and 25 parts of biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.), and heated and dissolved while stirring. The mixture was cooled to room temperature to prepare an epoxy resin solution composition. The epoxy resin solution composition was mixed with 10 parts of a phenolic hardener containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation, an active group equivalent of about 151 g/eq., a 2-methoxypropanol solution with a non-volatile content of 50%), 10 parts of a naphthol hardener ("SN-485" manufactured by Nippon Steel Chemical Materials Co., Ltd., a hydroxyl equivalent of about 205 g/eq.), and 15 parts of a phenoxy resin (Mitsubishi Chemical Co., Ltd., 50 parts of spherical silica (SO-C2 manufactured by Admatechs, average particle size 0.5 μm, BET specific surface area 5.8 m2) surface treated with a silane coupling agent (KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.) as a solid inorganic filler 2 /g), 25 parts of hollow silica particles 1 (average particle size 1.6 μm, BET specific surface area 12 m 2 /g, porosity 50 volume %) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts of rubber particles ("PARALOID EXL2655" manufactured by Dow Chemical Japan Co., Ltd.; core-shell particles having a core formed of a polymer of butadiene (specific gravity 0.91) and a shell formed of a copolymer of styrene (specific gravity 1.06) and methyl methacrylate (specific gravity 1.18); average particle size 0.2 μm), and 4 parts of an amine-based curing accelerator (4-dimethylaminopyridine (DMAP), a MEK solution having a solid content of 5 mass %) were uniformly dispersed using a high-speed rotary mixer to prepare a resin varnish. The inorganic filler contained in the resin varnish had an average particle size of 1.1 μm and a BET specific surface area of 9.0 m 2 /g.

然後，在作為支撐體的帶脫模處理的聚對苯二甲酸乙二醇酯膜(LINTEC公司製造的「AL5」、厚度38μm)的脫模面上，均勻地塗布樹脂清漆，使樹脂組成物層的厚度為40μm，在80℃～120℃(平均100℃)下乾燥5分鐘，製作了樹脂片。Then, a resin varnish was evenly applied on the release surface of a release-treated polyethylene terephthalate film ("AL5" manufactured by LINTEC, thickness 38 μm) serving as a support so that the thickness of the resin composition layer was 40 μm, and dried at 80°C to 120°C (average 100°C) for 5 minutes to produce a resin sheet.

[實施例2] 不使用由矽烷偶合劑(信越化學工業公司製造的「KBM-573」)進行表面處理的球形二氧化矽(Admatechs公司製造的「SO-C2」)。 另外，將中空二氧化矽粒子1(平均粒徑1.6μm、BET比表面積12m 2/g、空孔率50體積%)的量由25份變更為50份。 而且，在樹脂清漆中追加了3份聯苯芳烷基酚醛清漆型馬來醯亞胺(日本化藥公司製造的「MIR-3000-70MT」、非揮發成分率70%的MEK/甲苯混合溶液)。 除了以上事項以外，通過與實施例1相同的方法，製造了樹脂清漆和樹脂片。樹脂清漆中所含的無機填充材料的平均粒徑為1.6μm、BET比表面積為12m 2/g。 [Example 2] Spherical silica ("SO-C2" manufactured by Admatechs) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) was not used. In addition, the amount of hollow silica particles 1 (average particle size 1.6 μm, BET specific surface area 12 m 2 /g, porosity 50 volume %) was changed from 25 parts to 50 parts. Furthermore, 3 parts of biphenyl aralkylphenol formaldehyde varnish type maleimide ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., MEK/toluene mixed solution with a non-volatile content of 70%) were added to the resin varnish. Except for the above matters, the resin varnish and the resin sheet were manufactured by the same method as in Example 1. The average particle size of the inorganic filler contained in the resin varnish was 1.6 μm, and the BET specific surface area was 12 m 2 /g.

[實施例3] 不使用由矽烷偶合劑(信越化學工業公司製造的「KBM-573」)進行表面處理的球形二氧化矽(Admatechs公司製造的「SO-C2」)。 另外，代替25份中空二氧化矽粒子1(平均粒徑1.6μm、BET比表面積12m 2/g、空孔率50體積%)，使用了80份用矽烷偶合劑(信越化學工業公司製造的「KBM-573」)進行表面處理的中空二氧化矽粒子2(平均粒徑2.0μm、BET比表面積3.8m 2/g、空孔率20體積%)。 而且，代替3份橡膠粒子(Dow Chemical日本公司製造的「PARALOID EXL2655」)，使用了3份中空丙烯酸粒子(積水化成品工業公司製造的「XX-5598Z」；具備由苯乙烯(比重1.06)和甲基丙烯酸甲酯(比重1.18)的共聚物形成的殼部和在該殼部內形成的中空部的中空粒子；平均粒徑0.5μm、空孔率35體積%)。 另外，在樹脂清漆中追加了5份乙烯基苄基改性聚苯醚(三菱瓦斯化學公司製造的「OPE-2St 2200」、非揮發成分率65%的甲苯溶液)。 除了以上事項以外，通過與實施例1相同的方法，製造了樹脂清漆和樹脂片。樹脂清漆中所含的無機填充材料的平均粒徑為2.0μm、BET比表面積為3.8m 2/g。 [Example 3] Spherical silica ("SO-C2" manufactured by Admatechs) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) was not used. In addition, 80 parts of hollow silica particles 2 (average particle size 2.0 μm, BET specific surface area 3.8 m 2 /g, porosity 20% by volume) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) were used instead of 25 parts of hollow silica particles 1 (average particle size 1.6 μm, BET specific surface area 12 m 2 /g, porosity 50% by volume). Furthermore, instead of 3 parts of rubber particles ("PARALOID EXL2655" manufactured by Dow Chemical Japan Co., Ltd.), 3 parts of hollow acrylic particles ("XX-5598Z" manufactured by Sekisui Chemicals Co., Ltd.; hollow particles having a shell formed of a copolymer of styrene (specific gravity 1.06) and methyl methacrylate (specific gravity 1.18) and a hollow portion formed in the shell; average particle size 0.5 μm, porosity 35 volume %) were used. In addition, 5 parts of vinyl benzyl-modified polyphenylene ether ("OPE-2St 2200" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution having a non-volatile content of 65%) were added to the resin varnish. Except for the above matters, the resin varnish and the resin sheet were manufactured by the same method as Example 1. The average particle size of the inorganic filler contained in the resin varnish was 2.0 μm, and the BET specific surface area was 3.8 m 2 /g.

[實施例4] 代替25份聯苯型環氧樹脂(日本化藥公司製造的「NC3000L」)，使用了25份伸萘基醚型環氧樹脂(環氧當量約250g/eq.、DIC公司製造、「HP6000」)。 另外，代替25份中空二氧化矽粒子1(平均粒徑1.6μm、BET比表面積12m 2/g、空孔率50體積%)，使用了22份用矽烷偶合劑(信越化學工業公司製造的「KBM-573」)進行表面處理的中空氧化鋁硼矽酸玻璃粒子(太平洋水泥公司製造的「MG-005」、平均粒徑1.6μm、BET比表面積6.5m 2/g、空孔率80體積%)。 而且，將橡膠粒子(Dow Chemical日本公司製造的「PARALOID EXL2655」)的量由3份變更為5份。 除了以上事項以外，通過與實施例1相同的方法，製造了樹脂清漆和樹脂片。樹脂清漆中所含的無機填充材料的平均粒徑為1.1μm、BET比表面積為6.2m 2/g。 [Example 4] 25 parts of naphthyl ether epoxy resin (epoxy equivalent about 250 g/eq., DIC Corporation, “HP6000”) were used in place of 25 parts of biphenyl epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd.). Also, 22 parts of hollow alumina borosilicate glass particles (“MG-005” manufactured by Pacific Cement Co., Ltd., average particle size 1.6 μm, BET specific surface area 6.5 m 2 /g, porosity 80 vol%) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) were used in place of 25 parts of hollow silica particles 1 (average particle size 1.6 μm, BET specific surface area 12 m 2 /g, porosity 50 vol%). Furthermore, the amount of rubber particles ("PARALOID EXL2655" manufactured by Dow Chemical Japan) was changed from 3 parts to 5 parts. Except for the above, a resin varnish and a resin sheet were prepared in the same manner as in Example 1. The average particle size of the inorganic filler contained in the resin varnish was 1.1 μm, and the BET specific surface area was 6.2 m 2 /g.

[實施例5] 將5份橡膠粒子(Dow Chemical日本公司製造的「PARALOID EXL2655」)變更為5份橡膠粒子(愛克工業公司製造的「Staphyloid AC3816N」；具備由丙烯酸丁酯(比重1.09)的聚合物形成的芯部和由甲基丙烯酸甲酯(比重1.18)的聚合物形成的殼部的芯殼粒子；平均粒徑0.5μm)。 除了以上事項以外，通過與實施例4相同的方法，製造了樹脂清漆和樹脂片。樹脂清漆中所含的無機填充材料的平均粒徑為1.1μm、BET比表面積為6.2m 2/g。 [Example 5] 5 parts of rubber particles ("PARALOID EXL2655" manufactured by Dow Chemical Japan) were replaced with 5 parts of rubber particles ("Staphyloid AC3816N" manufactured by AICA Industries; core-shell particles having a core formed of a polymer of butyl acrylate (specific gravity 1.09) and a shell formed of a polymer of methyl methacrylate (specific gravity 1.18); average particle size 0.5 μm). Except for the above matters, a resin varnish and a resin sheet were prepared by the same method as in Example 4. The average particle size of the inorganic filler contained in the resin varnish was 1.1 μm, and the BET specific surface area was 6.2 m 2 /g.

[實施例6] 在10份萘型環氧樹脂(DIC公司製造的「HP-4032-SS」、環氧當量約144g/eq.)中加入50份甲基乙基酮，邊攪拌邊加熱，進行均勻化。將其冷卻至室溫，調製了環氧樹脂溶解組成物。在該環氧樹脂溶解組成物中混合30份活性酯化合物(DIC公司製造的「HPC-8000-65T」、活性酯基當量約223g/eq.、非揮發成分率65%的甲苯溶液)、2份含有三嗪骨架的酚系硬化劑(DIC公司製造的「LA-3018-50P」、活性基當量約151g/eq.、非揮發成分率50%的2-甲氧基丙醇溶液)、5份碳二亞胺系硬化劑(日清紡化學公司製造的「V-03」、活性基當量約216g/eq.、非揮發成分率50%的甲苯溶液)、45份用矽烷偶合劑(信越化學工業公司製造的「KBM-573」)進行表面處理的中空二氧化矽粒子1 (平均粒徑1.6μm、BET比表面積12m 2/g、空孔率50體積%)、5份橡膠粒子(Dow Chemical日本公司製造的「PARALOID EXL2655」)、0.1份咪唑系硬化促進劑(四國化成工業公司製造的「1B2PZ」、1-苄基-2-苯基咪唑)，用高速旋轉混合器均勻地分散，調製了樹脂清漆。樹脂清漆中所含的無機填充材料的平均粒徑為1.6μm、BET比表面積為12m 2/g。 [Example 6] 50 parts of methyl ethyl ketone were added to 10 parts of naphthalene epoxy resin ("HP-4032-SS" manufactured by DIC Corporation, epoxy equivalent of about 144 g/eq.), and the mixture was heated while stirring to be homogenized. The mixture was cooled to room temperature to prepare an epoxy resin solution composition. The epoxy resin solution composition was mixed with 30 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, an active ester group equivalent of about 223 g/eq., a toluene solution with a non-volatile content of 65%), 2 parts of a phenolic curing agent containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation, an active group equivalent of about 151 g/eq., a 2-methoxypropanol solution with a non-volatile content of 50%), 5 parts of a carbodiimide curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., an active group equivalent of about 216 g/eq., a toluene solution with a non-volatile content of 50%), and 45 parts of hollow silica particles 1 surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.). (average particle size 1.6μm, BET specific surface area 12m2 /g, porosity 50% by volume), 5 parts of rubber particles ("PARALOID EXL2655" manufactured by Dow Chemical Japan Co., Ltd.), and 0.1 parts of imidazole-based curing accelerator ("1B2PZ" manufactured by Shikoku Chemical Industries, Ltd., 1-benzyl-2-phenylimidazole) were uniformly dispersed using a high-speed rotary mixer to prepare a resin varnish. The average particle size of the inorganic filler contained in the resin varnish is 1.6μm and the BET specific surface area is 12m2 /g.

然後，在作為支撐體的帶脫模處理的聚對苯二甲酸乙二醇酯膜(LINTEC公司製造的「AL5」、厚度38μm)的脫模面上，均勻地塗布樹脂清漆，使樹脂組成物層的厚度為40μm，在80℃～120℃(平均100℃)下乾燥5分鐘，製作了樹脂片。Then, a resin varnish was evenly applied on the release surface of a release-treated polyethylene terephthalate film ("AL5" manufactured by LINTEC, thickness 38μm) serving as a support so that the thickness of the resin composition layer was 40μm, and dried at 80°C to 120°C (average 100°C) for 5 minutes to produce a resin sheet.

[實施例7] 在10份萘型環氧樹脂(DIC公司製造的「HP-4032-SS」、環氧當量約144g/eq.)中加入10份雙酚A型環氧樹脂(三菱化學公司製造的「828EL」、環氧當量約180g/eq.)、15份伸萘基醚型環氧樹脂(DIC公司製造的「HP6000」、環氧當量約250g/eq.)和50份甲基乙基酮，邊攪拌邊加熱溶解。將其冷卻至室溫，調製了環氧樹脂溶解組成物。在該環氧樹脂溶解組成物中混合15份活性酯化合物(DIC公司製造的「HPC-8000-65T」、活性酯基當量約223g/eq.、非揮發成分率65%的甲苯溶液)、20份雙酚A二氰酸酯的預聚物(Lonza Japan公司製造的「BA230S75」、氰酸酯當量約232g/eq.、非揮發成分75質量%的MEK溶液)、60份用矽烷偶合劑(信越化學工業公司製造的「KBM-573」)進行表面處理的作為實心無機填充材料的球形二氧化矽(Admatechs公司製造的「SO-C2」、BET比表面積5.8m 2/g、平均粒徑0.5μm)、30份用矽烷偶合劑(信越化學工業公司製造的「KBM-573」)進行表面處理的中空二氧化矽粒子1 (平均粒徑1.6μm、BET比表面積12m 2/g、空孔率50體積%)、5份橡膠粒子(Dow Chemical日本公司製造的「PARALOID EXL2655」)、4份胺系硬化促進劑(4-二甲基胺基吡啶(DMAP)、固體成分5質量%的MEK溶液)、1份乙醯丙酮鈷(III)(東京化成公司製造)的1質量%的MEK溶液和8份苯氧樹脂(三菱化學公司製造的「YX7553BH30」、非揮發成分30質量%的MEK與環己酮的1：1溶液)，用高速旋轉混合器均勻地分散，調製了樹脂清漆。樹脂清漆中所含的無機填充材料的平均粒徑為1.1μm、BET比表面積為9.0m 2/g。 [Example 7] 10 parts of bisphenol A type epoxy resin ("828EL" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 180 g/eq.), 15 parts of naphthyl ether type epoxy resin ("HP6000" manufactured by DIC Corporation, epoxy equivalent of about 250 g/eq.) and 50 parts of methyl ethyl ketone were added to 10 parts of naphthalene type epoxy resin ("HP-4032-SS" manufactured by DIC Corporation, epoxy equivalent of about 144 g/eq.), and heated and dissolved while stirring. The mixture was cooled to room temperature to prepare an epoxy resin solution composition. The epoxy resin solution composition was mixed with 15 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, an active ester equivalent of about 223 g/eq., a toluene solution with a non-volatile content of 65%), 20 parts of a prepolymer of bisphenol A dicyanate ("BA230S75" manufactured by Lonza Japan Corporation, a MEK solution with a cyanate equivalent of about 232 g/eq., a non-volatile content of 75% by mass), and 60 parts of spherical silica ("SO-C2" manufactured by Admatechs Corporation, a BET specific surface area of 5.8 m2) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) as a solid inorganic filler. /g, average particle size 0.5μm), 30 parts of hollow silica particles 1 (average particle size 1.6μm, BET specific surface area 12m2 /g, porosity 50 volume %) surface treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.), 5 parts of rubber particles ("PARALOID EXL2655"), 4 parts of an amine curing accelerator (4-dimethylaminopyridine (DMAP), a 5% by mass MEK solution of solid content), 1 part of a 1% by mass MEK solution of cobalt (III) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 8 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a non-volatile content of 30% by mass) were uniformly dispersed using a high-speed rotary mixer to prepare a resin varnish. The average particle size of the inorganic filler contained in the resin varnish was 1.1μm, and the BET specific surface area was 9.0m2 /g.

然後，在作為支撐體的帶脫模處理的聚對苯二甲酸乙二醇酯膜(LINTEC公司製造的「AL5」、厚度38μm)的脫模面上，均勻地塗布樹脂清漆，使樹脂組成物層的厚度為40μm，在80℃～120℃ (平均100℃)下乾燥5分鐘，製作了樹脂片。Then, a resin varnish was evenly applied on the release surface of a release-treated polyethylene terephthalate film ("AL5" manufactured by LINTEC, thickness 38 μm) serving as a support so that the thickness of the resin composition layer was 40 μm, and dried at 80°C to 120°C (average 100°C) for 5 minutes to produce a resin sheet.

[實施例8] 在5份萘型環氧樹脂(DIC公司製造的「HP-4032-SS」、環氧當量約144)中加入10份聯苯型環氧樹脂(日本化藥公司製造的「NC3000L」、環氧當量約269g/eq.)、7份聯苯芳烷基酚醛清漆型馬來醯亞胺(日本化藥公司製造的「MIR-3000-70MT」、非揮發成分率70%的MEK/甲苯混合溶液)、10份甲基乙基酮和10份二乙二醇單乙醚乙酸酯，邊攪拌邊加熱溶解。將其冷卻至室溫，調製了環氧樹脂溶解組成物。在該環氧樹脂溶解組成物中混合56份用矽烷偶合劑(信越化學工業公司製造的「KBM-573」)進行表面處理的作為實心無機填充材料的球形二氧化矽(Admatechs公司製造的「SO-C2」、BET比表面積5.8m 2/g、平均粒徑0.5μm)、28份用矽烷偶合劑(信越化學工業公司製造的「KBM-573」)進行表面處理的中空二氧化矽粒子1、0.02份咪唑系硬化促進劑(四國化成工業公司製造的「1B2PZ」、1-苄基-2-苯基咪唑)、5份橡膠粒子(Dow Chemical日本公司製造的「PARALOID EXL2655」)，用高速旋轉混合器均勻地分散。接下來，加入50份合成例1中製造的樹脂(a1)溶液和5份光聚合起始劑(BASF公司製造的「Irgacure TPO」、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦)，在室溫下攪拌至均勻，調製了樹脂清漆。樹脂清漆中所含的無機填充材料的平均粒徑為1.1μm、BET比表面積為9.0m 2/g。 [Example 8] To 5 parts of a naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC Corporation, epoxy equivalent of about 144), 10 parts of a biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.), 7 parts of a biphenyl aralkylphenol novolac-type maleimide ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., a MEK/toluene mixed solution with a non-volatile content of 70%), 10 parts of methyl ethyl ketone and 10 parts of diethylene glycol monoethyl ether acetate were added, and the mixture was heated and dissolved while stirring. The mixture was cooled to room temperature to prepare an epoxy resin dissolving composition. In the epoxy resin solution composition, 56 parts of spherical silica ("SO-C2" manufactured by Admatechs, BET specific surface area 5.8 m2 /g, average particle size 0.5 μm) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) as a solid inorganic filler, 28 parts of hollow silica particles 1 surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.), 0.02 parts of an imidazole-based curing accelerator ("1B2PZ" manufactured by Shikoku Chemical Industries, Ltd., 1-benzyl-2-phenylimidazole), and 5 parts of rubber particles ("PARALOID EXL2655" manufactured by Dow Chemical Japan Co., Ltd.) were mixed and uniformly dispersed using a high-speed rotary mixer. Next, 50 parts of the resin (a1) solution prepared in Synthesis Example 1 and 5 parts of a photopolymerization initiator ("Irgacure TPO" manufactured by BASF, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide) were added and stirred at room temperature until uniform to prepare a resin varnish. The average particle size of the inorganic filler contained in the resin varnish was 1.1 μm, and the BET specific surface area was 9.0 m 2 /g.

然後，在作為支撐體的帶脫模處理的聚對苯二甲酸乙二醇酯膜(LINTEC公司製造的「AL5」、厚度38μm)的脫模面上，均勻地塗布樹脂清漆，使樹脂組成物層的厚度為40μm，在80℃～120℃ (平均100℃)下乾燥5分鐘，製作了樹脂片。Then, a resin varnish was evenly applied on the release surface of a release-treated polyethylene terephthalate film ("AL5" manufactured by LINTEC, thickness 38 μm) serving as a support so that the thickness of the resin composition layer was 40 μm, and dried at 80°C to 120°C (average 100°C) for 5 minutes to produce a resin sheet.

[比較例1] 將用矽烷偶合劑(信越化學工業公司製造的「KBM-573」)進行表面處理的球形二氧化矽(Admatechs公司製造的「SO-C2」、平均粒徑0.5μm)的量由50份變更為100份。 另外，不使用中空二氧化矽粒子1 (平均粒徑1.6μm、BET比表面積12m 2/g、空孔率50體積%)。 而且，將橡膠粒子(Dow Chemical日本公司製造的「PARALOID EXL2655」)的量由3份變更為5份。 除了以上事項以外，通過與實施例1相同的方法，製造了樹脂清漆和樹脂片。 [Comparative Example 1] The amount of spherical silica ("SO-C2" manufactured by Admatechs, average particle size 0.5 μm) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 50 parts to 100 parts. In addition, hollow silica particles 1 (average particle size 1.6 μm, BET specific surface area 12 m 2 /g, porosity 50 volume %) were not used. In addition, the amount of rubber particles ("PARALOID EXL2655" manufactured by Dow Chemical Japan Co., Ltd.) was changed from 3 parts to 5 parts. Except for the above matters, a resin varnish and a resin sheet were produced by the same method as in Example 1.

[比較例2] 不使用用矽烷偶合劑(信越化學工業公司製造的「KBM-573」)進行表面處理的球形二氧化矽(Admatechs公司製造的「SO-C2」、平均粒徑0.5μm)和橡膠粒子(Dow Chemical日本公司製造的「PARALOID EXL2655」)。 另外，代替25份中空二氧化矽粒子1(平均粒徑1.6μm、BET比表面積12m 2/g、空孔率50體積%)，使用了80份用矽烷偶合劑(信越化學工業公司製造的「KBM-573」)進行表面處理的中空二氧化矽粒子2(平均粒徑2.0μm、BET比表面積3.8m 2/g、空孔率20體積%)。 除了以上事項以外，通過與實施例1相同的方法，製造了樹脂清漆和樹脂片。 [Comparative Example 2] Spherical silica ("SO-C2" manufactured by Admatechs, average particle size 0.5 μm) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) and rubber particles ("PARALOID EXL2655" manufactured by Dow Chemical Japan Co., Ltd.) were not used. In addition, 80 parts of hollow silica particles 2 (average particle size 2.0 μm, BET specific surface area 3.8 m 2 /g, porosity 20 volume %) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) were used instead of 25 parts of hollow silica particles 1 (average particle size 1.6 μm, BET specific surface area 12 m 2 /g, porosity 50 volume %). Except for the above matters, a resin varnish and a resin sheet were produced by the same method as in Example 1.

[介電損耗角正切的測定] (1-1) 評價用硬化物的製作(實施例1～7、比較例1、2)： 準備了具有實施脫模劑處理的面(脫模劑處理面)和未實施脫模劑處理的面(脫模劑未處理面)的PET膜(LINTEC公司製造的「501010」、厚度50μm、240mm見方)。在該PET膜的脫模劑未處理面上重疊玻璃布基材環氧樹脂雙面覆銅層合板(Panasonic公司製造的「R5715ES」、厚度0.7mm、255mm見方)，四邊用聚醯亞胺膠帶(寬度10mm)固定。以下有時將這樣固定在玻璃布基材環氧樹脂雙面覆銅層合板的PET膜稱為「固定PET膜」。 [Determination of dielectric loss tangent] (1-1) Preparation of hardened materials for evaluation (Examples 1 to 7, Comparative Examples 1 and 2): A PET film ("501010" manufactured by LINTEC, thickness 50μm, 240mm square) having a surface treated with a release agent (release agent treated surface) and a surface not treated with a release agent (release agent untreated surface) was prepared. A glass cloth-based epoxy resin double-sided copper-clad laminate ("R5715ES" manufactured by Panasonic, thickness 0.7mm, 255mm square) was stacked on the release agent untreated surface of the PET film and fixed on all four sides with polyimide tape (width 10mm). In the following, the PET film fixed on the glass cloth-based epoxy double-sided copper-clad laminate is sometimes referred to as "fixed PET film".

利用模塗機，將實施例1～7和比較例1、2中製作的樹脂清漆塗布在固定PET膜的脫模處理面上，使乾燥後的樹脂組成物層的厚度為40μm，在80℃～120℃ (平均100℃)下乾燥10分鐘，形成了樹脂組成物層。然後，投入180℃的烘箱中，加熱90分鐘，使樹脂組成物層熱硬化。熱硬化後，剝離聚醯亞胺膠帶，取下玻璃布基材環氧樹脂雙面覆銅層合板，進而還剝離PET膜(LINTEC公司製造的「501010」)，得到了片狀的硬化物。有時將所得的硬化物稱為「評價用硬化物」。The resin varnish prepared in Examples 1 to 7 and Comparative Examples 1 and 2 was applied to the release-treated surface of the fixed PET film using a die coater, so that the thickness of the dried resin composition layer was 40 μm, and dried at 80°C to 120°C (average 100°C) for 10 minutes to form a resin composition layer. Then, it was placed in an oven at 180°C and heated for 90 minutes to thermally cure the resin composition layer. After thermal curing, the polyimide tape was peeled off, and the glass cloth-based epoxy resin double-sided copper-coated laminate was removed, and the PET film ("501010" manufactured by LINTEC) was also peeled off to obtain a sheet-like cured product. The resulting cured product is sometimes referred to as an "evaluation cured product."

(1-2) 評價用硬化物的製作(實施例8)： 利用模塗機，將實施例8中製作的樹脂清漆塗布在固定PET膜的脫模處理面上，使乾燥後的樹脂組成物層的厚度為40μm，在80℃～120℃ (平均100℃)下乾燥10分鐘，形成了樹脂組成物層。然後，進行1J/cm 2的紫外線照射之後，投入180℃的烘箱中，加熱90分鐘，使樹脂組成物層硬化。硬化後，剝離聚醯亞胺膠帶，取下玻璃布基材環氧樹脂雙面覆銅層合板，進而還剝離PET膜(LINTEC公司製造的「501010」)，得到了片狀的硬化物。有時將所得的硬化物稱為「評價用硬化物」。 (1-2) Preparation of hardened material for evaluation (Example 8): The resin varnish prepared in Example 8 was applied to the release-treated surface of the fixed PET film using a die coater to a resin composition layer thickness of 40 μm after drying, and dried at 80°C to 120°C (average 100°C) for 10 minutes to form a resin composition layer. Then, after irradiation with ultraviolet light at 1 J/ cm2 , the resin composition layer was placed in an oven at 180°C and heated for 90 minutes to cure the resin composition layer. After curing, the polyimide tape was peeled off, and the glass cloth-based epoxy resin double-sided copper-clad laminate was removed, and the PET film ("501010" manufactured by LINTEC) was further peeled off to obtain a sheet-shaped cured product. The obtained cured product is sometimes called "cured product for evaluation".

(2) 相對介電常數和介電損耗角正切的測定： 將評價用硬化物切成長度80mm、寬度2mm，得到了評價樣品。對於該評價樣品，通過使用安捷倫科技(Agilent Technologies)公司製造的HP8362B裝置的空腔共振擾動法，在測定頻率5.8GHz、測定溫度23℃下測定了相對介電常數和介電損耗角正切。對2個試驗片進行測定，算出平均值。 (2) Measurement of relative dielectric constant and dielectric loss tangent: The evaluation hardened material was cut into pieces with a length of 80 mm and a width of 2 mm to obtain evaluation samples. The relative dielectric constant and dielectric loss tangent of the evaluation sample were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C using the cavity resonance perturbation method using the HP8362B device manufactured by Agilent Technologies. The measurements were performed on two test pieces and the average value was calculated.

[硬化物的線熱膨脹係數的評價] 將評價用硬化物切成長度約15mm、寬度約5mm，得到了試驗片。使用熱機械分析裝置(RIGAKU公司製造的「Thermo plus TMA8310」)，用拉伸負重法進行了試驗片的熱機械分析。具體而言，將試驗片安裝在上述裝置上之後，在負載1g、升溫速度5℃/分鐘的測定條件下連續測定2次。在第2次測定中，算出玻璃轉移溫度和從25℃到150℃的溫度範圍的平均線熱膨脹率(熱膨脹係數)。 [Evaluation of the linear thermal expansion coefficient of the cured product] The cured product for evaluation was cut into pieces with a length of about 15 mm and a width of about 5 mm to obtain a test piece. The test piece was subjected to a thermomechanical analysis by the tensile load method using a thermomechanical analysis device ("Thermo plus TMA8310" manufactured by RIGAKU). Specifically, after the test piece was mounted on the above device, it was continuously measured twice under the measurement conditions of a load of 1 g and a heating rate of 5°C/min. In the second measurement, the average linear thermal expansion coefficient (thermal expansion coefficient) in the glass transition temperature and the temperature range from 25°C to 150°C was calculated.

[硬化物的比重的測定] 將評價用硬化物切成長度約3cm、寬度約3cm，得到了試驗片。使用METTLER TOLEDO公司製造的分析天平「XP105」(使用比重測定套件)，測定了試驗片的比重。對5個試驗片進行測定，算出平均值。 [Measurement of specific gravity of cured product] The cured product for evaluation was cut into pieces with a length of about 3 cm and a width of about 3 cm to obtain test pieces. The specific gravity of the test pieces was measured using an analytical balance "XP105" manufactured by METTLER TOLEDO (using a specific gravity measurement kit). Five test pieces were measured and the average value was calculated.

[硬化物的斷裂伸長率的測定] 關於評價用硬化物，依據日本工業規格(JIS K7161)，在溫度25℃(室溫)、拉伸速度50mm/分鐘下，使用Tensilon萬能試驗機(A&D公司製造)進行拉伸試驗，測定了斷裂時刻的伸長率(斷裂伸長率)。 [Determination of elongation at break of cured product] For the cured product for evaluation, a tensile test was performed at 25°C (room temperature) and a tensile speed of 50 mm/min using a Tensilon universal testing machine (manufactured by A&D) in accordance with Japanese Industrial Standards (JIS K7161), and the elongation at break (elongation at break) was measured.

[抗衝擊剝離性和抗衝擊裂紋性的評價] (1) 內層基板的準備： 使用微蝕刻劑(MEC公司製造的「CZ8101」)，對玻璃布基材環氧樹脂雙面覆銅層合板(銅箔的厚度18μm、基板的厚度0.8mm、Panasonic公司製造的「R1515A」)的雙面蝕刻1μm，進行銅表面的粗化處理，得到了內層基板。 [Evaluation of impact peeling resistance and impact cracking resistance] (1) Preparation of inner substrate: Using a microetchant ("CZ8101" manufactured by MEC), a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18μm, substrate thickness 0.8mm, "R1515A" manufactured by Panasonic) was etched 1μm on both sides to roughen the copper surface, thus obtaining an inner substrate.

(2) 樹脂片的層壓： 使用批次式真空加壓層壓機(Nikko-Materials公司製造、2階段積層層壓機「CVP700」)，將實施例和比較例中得到的樹脂片以樹脂組成物層與內層基板相接的方式層壓在內層基板的雙面上。層壓是通過減壓30秒以將氣壓調整為13hPa以下之後，在100℃、壓力0.74MPa下壓接30秒來實施的。然後，在100℃、壓力0.5MPa下進行60秒的熱壓製，得到了具有支撐體/樹脂組成物層/內層基板/樹脂組成物層/支撐體的層結構的中間基板。 (2) Lamination of resin sheets: Using a batch vacuum pressure laminating press (manufactured by Nikko-Materials, two-stage laminating press "CVP700"), the resin sheets obtained in the embodiment and comparative example were laminated on both sides of the inner substrate in such a manner that the resin composition layer was in contact with the inner substrate. Lamination was performed by reducing the pressure for 30 seconds to adjust the air pressure to less than 13 hPa, and then laminating at 100°C and a pressure of 0.74 MPa for 30 seconds. Then, hot pressing was performed at 100°C and a pressure of 0.5 MPa for 60 seconds to obtain an intermediate substrate having a layered structure of support body/resin composition layer/inner substrate/resin composition layer/support body.

(3-1) 樹脂組成物層的硬化(實施例1～7、比較例1、2)： 在180℃、90分鐘的熱硬化條件下將樹脂組成物層硬化，形成了絕緣層。之後，將支撐體剝離，得到了具有絕緣層/內層基板/絕緣層的層結構的評價用基板。 (3-1) Curing of the resin composition layer (Examples 1 to 7, Comparative Examples 1 and 2): The resin composition layer was cured under heat curing conditions of 180°C for 90 minutes to form an insulating layer. Thereafter, the support was peeled off to obtain an evaluation substrate having a layered structure of insulating layer/inner substrate/insulating layer.

(3-2) 樹脂組成物層的硬化(實施例8)： 對樹脂組成物層進行1J/cm 2的紫外線照射，然後在180℃下加熱90分鐘，將樹脂組成物層硬化，形成了絕緣層。之後，將支撐體剝離，得到了具有絕緣層/內層基板/絕緣層的層結構的評價用基板。 (3-2) Curing of the resin composition layer (Example 8): The resin composition layer was irradiated with ultraviolet light at 1 J/ cm2 and then heated at 180°C for 90 minutes to cure the resin composition layer and form an insulating layer. Thereafter, the support was peeled off to obtain an evaluation substrate having a layered structure of insulating layer/inner substrate/insulating layer.

(4) 落下試驗： 將評價用基板切成10mm×10mm，得到了多個基板片。如圖1所示，使用膠帶(未圖示)，將作為樣品11的基板片固定在重量200g的圓筒形的錘12的底部，準備了5個試驗體13。使試驗體13分別從1.5m的高度H以作為樣品11的基板片朝下的方式，3次自由落下到厚度20mm、直徑200mm的SS400製造的鋼鐵圓板14上。 (4) Drop test: The evaluation substrate was cut into 10 mm × 10 mm pieces to obtain a plurality of substrate pieces. As shown in FIG1 , the substrate piece as sample 11 was fixed to the bottom of a cylindrical hammer 12 weighing 200 g using tape (not shown) to prepare five test bodies 13. The test body 13 was made to freely fall three times from a height H of 1.5 m with the substrate piece as sample 11 facing downward onto a steel circular plate 14 made of SS400 with a thickness of 20 mm and a diameter of 200 mm.

(5) 抗衝擊剝離性的評價： 觀察上述的落下試驗後的基板片，根據下述的基準，判定了基板片的抗衝擊剝離性。抗衝擊剝離性優異表示：即使落下而施加衝擊，也難以產生絕緣層的剝離。因此，抗衝擊剝離性優異表示：絕緣層對由衝擊引起的剝離具有高的抗性。 「優」：落下試驗後的5個基板片均未觀察到剝離； 「可」：落下試驗後的5個基板片中，只有1個樣品觀察到剝離； 「不可」：落下試驗後的5個基板片中，有2個樣品以上觀察到剝離。 (5) Evaluation of shock peeling resistance: The substrate pieces after the above drop test were observed, and the shock peeling resistance of the substrate pieces was determined according to the following criteria. Excellent shock peeling resistance means that even if the substrate piece is dropped and subjected to impact, it is difficult for the insulating layer to peel off. Therefore, excellent shock peeling resistance means that the insulating layer has high resistance to peeling caused by impact. "Excellent": No peeling was observed in any of the 5 substrate pieces after the drop test; "Acceptable": Only one sample out of the 5 substrate pieces after the drop test was observed to peel off; "Unacceptable": Peeling was observed in two or more samples out of the 5 substrate pieces after the drop test.

(6) 抗衝擊裂紋性的評價： 觀察上述的落下試驗後的基板片，根據下述的基準，判定了基板片的抗衝擊裂紋性。抗衝擊裂紋性優異表示：即使落下而施加衝擊，絕緣層也難以產生裂紋。因此，抗衝擊裂紋性優異表示：絕緣層對由衝擊引起的裂紋的產生具有高的抗性。 「優」：落下試驗後的5個基板片均未觀察到裂紋和缺損； 「可」：落下試驗後的5個基板片中，只有1個樣品觀察到裂紋或缺損； 「不可」：落下試驗後的5個基板片中，有2個樣品以上觀察到裂紋或缺損。 (6) Evaluation of impact crack resistance: The substrate pieces after the above drop test were observed, and the impact crack resistance of the substrate pieces was determined according to the following criteria. Excellent impact crack resistance means that even if an impact is applied by falling, cracks are difficult to form in the insulating layer. Therefore, excellent impact crack resistance means that the insulating layer has high resistance to the formation of cracks caused by impact. "Excellent": No cracks or defects were observed in any of the 5 substrate pieces after the drop test; "Acceptable": Only one sample among the 5 substrate pieces after the drop test was observed to have cracks or defects; "Unacceptable": Cracks or defects were observed in 2 or more samples among the 5 substrate pieces after the drop test.

[結果] 實施例和比較例中的樹脂組成物的組成和評價結果見下表。表3的「抗衝擊剝離性」的欄中，與評價結果一併顯示的數值表示：5個基板片中觀察到剝離的基板片的數目。另外，表3的「抗衝擊裂紋性」的欄中，與評價結果一併顯示的數值表示：5個基板片中觀察到裂紋或缺損的基板片的數目。 下述的表中，簡稱的含義如下所述。 a1：合成例1中製造的樹脂(a1)。 中空玻璃粒子：中空氧化鋁硼矽酸玻璃粒子。 [Results] The composition and evaluation results of the resin compositions in the examples and comparative examples are shown in the table below. In the column "Impact peeling resistance" of Table 3, the numerical values shown together with the evaluation results indicate the number of substrate sheets observed to peel off among 5 substrate sheets. In addition, in the column "Impact cracking resistance" of Table 3, the numerical values shown together with the evaluation results indicate the number of substrate sheets observed to have cracks or defects among 5 substrate sheets. In the following table, the meanings of the abbreviations are as follows. a1: Resin (a1) produced in Synthesis Example 1. Hollow glass particles: hollow alumina borosilicate glass particles.

11:樣品 12:錘 13:試驗體 14:鋼鐵圓板 11: Sample 12: Hammer 13: Test body 14: Steel round plate

[圖1] 圖1是示意性地表示為了評價耐衝擊性而進行的落下試驗的情形的正視圖。[Fig. 1] Fig. 1 is a front view schematically showing a drop test performed to evaluate impact resistance.

Claims (18)

一種樹脂組成物，其是包含(A)硬化性樹脂和(B)無機填充材料的樹脂組成物， 將樹脂組成物硬化而得到的硬化物的比重為1.6g/cm 3以下， 將樹脂組成物硬化而得到的硬化物的熱膨脹係數為40ppm/℃以下。 A resin composition comprising (A) a curable resin and (B) an inorganic filler, wherein the specific gravity of a cured product obtained by curing the resin composition is 1.6 g/cm 3 or less, and the thermal expansion coefficient of the cured product obtained by curing the resin composition is 40 ppm/°C or less. 如請求項1之樹脂組成物，其中，(B)無機填充材料的平均粒徑為0.01μm以上且5μm以下。The resin composition of claim 1, wherein the average particle size of the inorganic filler (B) is not less than 0.01 μm and not more than 5 μm. 如請求項1之樹脂組成物，其中，(B)無機填充材料的BET比表面積為1m 2/g以上且100m 2/g以下。 The resin composition of claim 1, wherein the BET specific surface area of the (B) inorganic filler is 1 m 2 /g or more and 100 m 2 /g or less. 如請求項1之樹脂組成物，其中，(B)無機填充材料包含內部具有空孔的(B-1)中空無機填充材料。The resin composition of claim 1, wherein the (B) inorganic filler comprises a (B-1) hollow inorganic filler having pores therein. 如請求項4之樹脂組成物，其中，(B-1)中空無機填充材料具有10體積%以上的空孔率。The resin composition of claim 4, wherein the hollow inorganic filler (B-1) has a porosity of 10 volume % or more. 如請求項1之樹脂組成物，其進一步包含(C)有機粒子。The resin composition of claim 1 further comprises (C) organic particles. 如請求項6之樹脂組成物，其中，相對於100質量%樹脂組成物的非揮發成分，(C)有機粒子的量為2質量%以上。The resin composition of claim 6, wherein the amount of (C) organic particles is 2 mass % or more relative to 100 mass % of non-volatile components in the resin composition. 如請求項6之樹脂組成物，其中，(C)有機粒子具備：殼部和形成於殼部內的內置部， 內置部包含橡膠成分、或為中空部。 The resin composition of claim 6, wherein (C) the organic particles have: a shell and an inner portion formed in the shell, and the inner portion contains a rubber component or is a hollow portion. 如請求項1之樹脂組成物，其中，(A)硬化性樹脂選自熱硬化性樹脂和光硬化性樹脂。The resin composition of claim 1, wherein (A) the curable resin is selected from thermosetting resins and photocurable resins. 如請求項9之樹脂組成物，其中，熱硬化性樹脂包含選自下述的至少一種：環氧樹脂、酚醛樹脂、活性酯樹脂、氰酸酯樹脂和自由基聚合性樹脂。A resin composition as claimed in claim 9, wherein the thermosetting resin comprises at least one selected from the following: epoxy resin, phenolic resin, active ester resin, cyanate resin and free radical polymerizable resin. 如請求項9之樹脂組成物，其中，光硬化性樹脂包含自由基聚合性樹脂。The resin composition of claim 9, wherein the photocurable resin comprises a free radical polymerizable resin. 一種樹脂組成物，其是包含(A)硬化性樹脂、(B)無機填充材料和(C)有機粒子的樹脂組成物， (B)無機填充材料包含內部具有空孔的(B-1)中空無機填充材料， (B-1)中空無機填充材料具有10體積%以上的空孔率， 相對於100體積%樹脂組成物的非揮發成分，(B)無機填充材料的量為40體積%以上， 相對於100體積%樹脂組成物的非揮發成分，(B-1)中空無機填充材料的量為10體積%以上。 A resin composition comprising (A) a curable resin, (B) an inorganic filler and (C) organic particles, wherein the (B) inorganic filler comprises a (B-1) hollow inorganic filler having pores therein, the (B-1) hollow inorganic filler having a porosity of 10% by volume or more, the amount of the (B) inorganic filler relative to 100% by volume of the non-volatile components of the resin composition is 40% by volume or more, and the amount of the (B-1) hollow inorganic filler relative to 100% by volume of the non-volatile components of the resin composition is 10% by volume or more. 如請求項1之樹脂組成物，其用於形成絕緣層。The resin composition of claim 1 is used to form an insulating layer. 一種如請求項1～13中任一項之樹脂組成物的硬化物。A cured product of the resin composition according to any one of claims 1 to 13. 一種片狀層合材料，其含有如請求項1～13中任一項之樹脂組成物。A sheet-like laminate material comprising the resin composition as claimed in any one of claims 1 to 13. 一種樹脂片，其具有：支撐體和在該支撐體上由如請求項1～13中任一項之樹脂組成物形成的樹脂組成物層。A resin sheet comprising: a support body and a resin composition layer formed on the support body from the resin composition of any one of claims 1 to 13. 一種印刷配線板，其具備絕緣層，所述絕緣層包含如請求項1～13中任一項之樹脂組成物的硬化物。A printed wiring board comprising an insulating layer, wherein the insulating layer comprises a cured product of the resin composition according to any one of claims 1 to 13. 一種半導體裝置，其具備如請求項17之印刷配線板。A semiconductor device comprising a printed wiring board as claimed in claim 17.
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