TW202411338A

TW202411338A - Resin compositions, cured products, resin films, prepregs, laminates, and materials for electronic circuit boards

Info

Publication number: TW202411338A
Application number: TW112128103A
Authority: TW
Inventors: 松岡裕太; 武田圭史
Original assignee: 日商旭化成股份有限公司
Priority date: 2022-08-02
Filing date: 2023-07-27
Publication date: 2024-03-16

Abstract

本發明提供一種可獲得低介電常數及低介電損耗因數、強度特性優異、翹曲較小之硬化物的樹脂組合物。本發明之樹脂組合物含有成分(I)與選自由成分(II)～(IV)所組成之群中之至少一種成分，成分(I)：滿足條件(i)～(iii)之共軛二烯系共聚物，＜條件(i)＞ Mw為3.5萬以上，＜條件(ii)＞乙烯基芳香族單體單元之含量為15質量%以上80質量%以下，＜條件(iii)＞乙烯基鍵量為55%以上；成分(II)：自由基起始劑；成分(III)：極性樹脂(成分(I)除外)；成分(IV)：硬化劑(成分(II)除外)。 The present invention provides a resin composition that can obtain a cured product with low dielectric constant and low dielectric dissipation factor, excellent strength characteristics, and less warping. The resin composition of the present invention contains component (I) and at least one component selected from the group consisting of components (II) to (IV), Component (I): a covalent diene copolymer satisfying conditions (i) to (iii), ＜Condition (i)＞ Mw is 35,000 or more, ＜Condition (ii)＞ The content of vinyl aromatic monomer units is 15% to 80% by mass, ＜Condition (iii)＞ The vinyl bond content is 55% or more; Component (II): a free radical initiator; Component (III): a polar resin (excluding component (I)); Component (IV): a hardener (excluding component (II)).

Description

樹脂組合物、硬化物、樹脂膜、預浸體、積層體、及電子電路基板用之材料Resin composition, cured product, resin film, prepreg, laminate, and material for electronic circuit substrate

本發明關於一種樹脂組合物、硬化物、樹脂膜、預浸體、積層體、及電子電路基板用之材料。The present invention relates to a resin composition, a cured product, a resin film, a prepreg, a laminate, and a material for an electronic circuit substrate.

近年來，隨著資訊網路技術顯著進步、及資訊網路運用業務擴大，對於電子機器要求資訊量之大容量化以及機器之小型化。為了應對該等要求，要求印刷基板或撓性基板等各種基板用材料為介電損失較小、且與銅箔等金屬箔製成積層體時翹曲較小之材料。 In recent years, with the remarkable progress of information network technology and the expansion of information network application business, electronic equipment is required to have larger information capacity and smaller equipment. In order to meet these requirements, various substrate materials such as printed circuit boards or flexible substrates are required to have smaller dielectric loss and less warpage when laminated with metal foils such as copper foil.

迄今為止，為了獲得介電損失較小之材料，業界已研究、揭示有以低介電常數及/或低介電損耗因數、且強度等機械物性優異之環氧樹脂等熱硬化性樹脂或者聚苯醚系樹脂等熱塑性樹脂作為主成分之樹脂硬化物等各種樹脂材料。然而，既往揭示之樹脂材料於低介電常數及低介電損耗因數之方面仍有改善餘地，將該等材料用於印刷基板之情形時，存在資訊量及處理速度受到限制之問題點。 To date, in order to obtain materials with less dielectric loss, the industry has studied and disclosed various resin materials such as resin hardeners with low dielectric constant and/or low dielectric loss factor and excellent mechanical properties such as strength, such as epoxy resins and other thermosetting resins or polyphenylene ether resins. However, the resin materials disclosed in the past still have room for improvement in terms of low dielectric constant and low dielectric loss factor. When these materials are used in printed circuit boards, there is a problem that the amount of information and processing speed are limited.

基於改善該問題點之目的，一直以來，提出有各種橡膠成分作為如上所述之熱硬化性樹脂或熱塑性樹脂之改質劑。例如，於專利文獻1中，作為用以使聚苯醚樹脂低介電損耗因數化及低介電常數化之改質劑，揭示有選自由乙烯基芳香族化合物與烯烴(olefin)系烯烴(alkene)化合物之共聚物及其氫化物、以及乙烯基芳香族化合物之均聚物所組成之群中之至少一種彈性體。又，於專利文獻2中，作為用以使環氧樹脂低介電損耗因數化及低介電常數化之改質劑，揭示有苯乙烯系彈性體。 [先前技術文獻] [專利文獻] In order to improve this problem, various rubber components have been proposed as modifiers for the thermosetting resin or thermoplastic resin as described above. For example, in Patent Document 1, at least one elastomer selected from the group consisting of copolymers of vinyl aromatic compounds and olefin-based alkene compounds and their hydrides, and homopolymers of vinyl aromatic compounds is disclosed as a modifier for lowering the dielectric loss tangent and the dielectric constant of polyphenylene ether resin. In addition, in Patent Document 2, a styrene-based elastomer is disclosed as a modifier for lowering the dielectric loss tangent and the dielectric constant of epoxy resin. [Prior Art Document] [Patent Document]

[專利文獻1]日本專利特開2021-147486號公報 [專利文獻2]日本專利特開2020-15861號公報 [Patent document 1] Japanese Patent Publication No. 2021-147486 [Patent document 2] Japanese Patent Publication No. 2020-15861

[發明所欲解決之問題][The problem the invention is trying to solve]

然而，使用專利文獻1及2所揭示之改質劑之樹脂組合物於低介電常數化、低介電損耗因數化方面仍不充分，又，改質劑之添加致使拉伸強度降低，無法顯示出足夠之強度，另有翹曲易變大之問題點。However, the resin composition using the modifier disclosed in Patent Documents 1 and 2 is still insufficient in terms of lowering the dielectric constant and dielectric loss tangent. Moreover, the addition of the modifier reduces the tensile strength and fails to show sufficient strength. There is also a problem that the warping is easily increased.

因此，本發明之目的在於提供一種可獲得低介電常數及低介電損耗因數、拉伸強度亦優異之硬化物的含有特定共軛二烯系共聚物之樹脂組合物。 [解決問題之技術手段] Therefore, the purpose of the present invention is to provide a resin composition containing a specific covalent diene copolymer that can obtain a cured product having a low dielectric constant and a low dielectric dissipation factor and excellent tensile strength. [Technical means for solving the problem]

本發明者等人為了解決上述先前技術之課題，經過銳意研究，結果發現，包含具有特定結構之共軛二烯系共聚物之樹脂組合物之硬化物具備低介電常數及低介電損耗因數，強度特性亦優異，從而完成本發明。即，本發明如下所述。 In order to solve the above-mentioned problems of the prior art, the inventors of the present invention have conducted intensive research and found that the cured product of the resin composition containing the covalent diene copolymer with a specific structure has a low dielectric constant and a low dielectric dissipation factor, and also has excellent strength properties, thereby completing the present invention. That is, the present invention is as follows.

[1] 一種樹脂組合物，其含有成分(I)與選自由下述成分(II)～(IV)所組成之群中之至少一種成分，成分(I)：共軛二烯系共聚物，該共聚物具有選自由包含乙烯基芳香族單體單元與共軛二烯單體單元之無規聚合物嵌段(C)、以乙烯基芳香族單體單元為主體之聚合物嵌段(A)、及以共軛二烯單體單元為主體之聚合物嵌段(B) 所組成之群中之至少2個聚合物嵌段，且滿足以下之條件(i)、條件(ii)及條件(iii)，＜條件(i)＞上述共軛二烯系共聚物之重量平均分子量為3.5萬以上，＜條件(ii)＞上述共軛二烯系共聚物中之乙烯基芳香族單體單元之含量為15質量%以上80質量%以下，＜條件(iii)＞上述共軛二烯系共聚物之共軛二烯單體單元包含源自1,2-鍵及/或3,4-鍵之單元(a)、與源自1,4-鍵之單元(b)，於將上述共軛二烯單體單元之總含量設為100%之情形時，上述源自1,2-鍵及/或3,4-鍵之單元(a)含量為55%以上；成分(II)：自由基起始劑；成分(III)：極性樹脂(成分(I)除外)；成分(IV)：硬化劑(成分(II)除外)。 [2] 如上述[1]記載之樹脂組合物，其中上述共軛二烯系共聚物之源自共軛二烯單體單元之不飽和鍵之氫化率為5～95%。 [3] 如上述[1]或[2]記載之樹脂組合物，其含有上述成分(III)，上述成分(III)為選自由環氧系樹脂、聚醯亞胺系樹脂、聚苯醚系樹脂、液晶聚酯系樹脂及氟系樹脂所組成之群中之至少一種。 [4] 一種硬化物，其係如上述[1]至[3]中任一項記載之樹脂組合物之硬化物。 [5] 一種樹脂膜，其包含如上述[1]至[3]中任一項記載之樹脂組合物。 [6] 一種預浸體，其係基材、與如上述[1]至[3]中任一項記載之樹脂組合物之複合體。 [7] 如上述[6]記載之預浸體，其中上述基材為玻璃布。 [8] 一種積層體，其具有如上述[5]記載之樹脂膜與金屬箔。 [9] 一種積層體，其具有如上述[6]或[7]記載之預浸體之硬化物與金屬箔。 [10] 一種電子電路基板用之材料，其包含如上述[4]記載之硬化物。 [發明之效果] [1] A resin composition comprising component (I) and at least one component selected from the group consisting of the following components (II) to (IV), Component (I): a covalent diene copolymer having at least two polymer blocks selected from the group consisting of a random polymer block (C) comprising vinyl aromatic monomer units and covalent diene monomer units, a polymer block (A) comprising vinyl aromatic monomer units as the main component, and a polymer block (B) comprising covalent diene monomer units as the main component, and satisfying the following conditions (i), (ii) and (iii), <Condition (i)> the weight average molecular weight of the covalent diene copolymer is 35,000 or more, <Condition (ii)> The content of the vinyl aromatic monomer unit in the above-mentioned covalent diene copolymer is 15 mass % or more and 80 mass % or less, ＜Condition (iii)＞ The covalent diene monomer unit of the above-mentioned covalent diene copolymer comprises a unit (a) derived from a 1,2-bond and/or a 3,4-bond, and a unit (b) derived from a 1,4-bond, and when the total content of the above-mentioned covalent diene monomer unit is set to 100%, the content of the above-mentioned unit (a) derived from a 1,2-bond and/or a 3,4-bond is 55% or more; Component (II): free radical initiator; Component (III): polar resin (excluding component (I)); Component (IV): hardener (excluding component (II)). [2] A resin composition as described in [1] above, wherein the hydrogenation rate of unsaturated bonds derived from the covalent diene monomer units of the covalent diene copolymer is 5 to 95%. [3] A resin composition as described in [1] or [2] above, which contains the component (III), wherein the component (III) is at least one selected from the group consisting of epoxy resins, polyimide resins, polyphenylene ether resins, liquid crystal polyester resins and fluorine resins. [4] A cured product, which is a cured product of the resin composition as described in any one of [1] to [3] above. [5] A resin film, which comprises the resin composition as described in any one of [1] to [3] above. [6] A prepreg comprising a substrate and a composite of a resin composition as described in any one of [1] to [3]. [7] The prepreg as described in [6], wherein the substrate is glass cloth. [8] A laminate comprising a resin film as described in [5] and a metal foil. [9] A laminate comprising a cured product of the prepreg as described in [6] or [7] and a metal foil. [10] A material for an electronic circuit substrate comprising a cured product as described in [4]. [Effect of the invention]

根據本發明，可提供一種獲得低介電常數及低介電損耗因數、強度特性優異、翹曲較小之硬化物的樹脂組合物。According to the present invention, a resin composition can be provided for obtaining a cured product having low dielectric constant and low dielectric dissipation factor, excellent strength characteristics and less warping.

以下，對用以實施本發明之方式(以下稱為「本實施方式」)進行詳細說明。再者，以下之本實施方式為用以說明本發明之例示，並非意在將本發明限定於以下內容，本發明可於其主旨範圍內加以各種變化而實施。 The following is a detailed description of the method for implementing the present invention (hereinafter referred to as "this embodiment") . Furthermore, the following embodiment is an example for illustrating the present invention and is not intended to limit the present invention to the following contents. The present invention can be implemented with various modifications within the scope of its subject matter.

[樹脂組合物] 本實施方式之樹脂組合物係含有成分(I)與選自由下述成分(II)～(IV)所組成之群中之至少一種成分之樹脂組合物，成分(I)：共軛二烯系共聚物，該共聚物具有選自由包含乙烯基芳香族單體單元與共軛二烯單體單元之無規聚合物嵌段(以下有時記為聚合物嵌段(C))、以乙烯基芳香族單體單元為主體之聚合物嵌段(A)(以下有時記為聚合物嵌段(A))、及以共軛二烯單體單元為主體之聚合物嵌段(B)(以下有時記為聚合物嵌段(B)) 所組成之群中之至少2個聚合物嵌段，且滿足以下之條件(i)～(iii)，＜條件(i)＞上述共軛二烯系共聚物之重量平均分子量為3.5萬以上，＜條件(ii)＞上述共軛二烯系共聚物中之乙烯基芳香族單體單元之含量為15質量%以上80質量%以下，＜條件(iii)＞上述共軛二烯系共聚物之共軛二烯單體單元包含源自1,2-鍵及/或3,4-鍵之單元(a)、與源自1,4-鍵之單元(b)，於將上述共軛二烯單體單元之總含量設為100%之情形時，上述源自1,2-鍵及/或3,4-鍵之單元(a)含量為55%以上。 [Resin composition] The resin composition of the present embodiment is a resin composition comprising component (I) and at least one component selected from the group consisting of the following components (II) to (IV), Component (I): a covalent diene copolymer, the copolymer having at least two polymer blocks selected from the group consisting of a random polymer block comprising vinyl aromatic monomer units and covalent diene monomer units (hereinafter sometimes referred to as polymer block (C)), a polymer block (A) mainly comprising vinyl aromatic monomer units (hereinafter sometimes referred to as polymer block (A)), and a polymer block (B) mainly comprising covalent diene monomer units (hereinafter sometimes referred to as polymer block (B)), and satisfying the following conditions (i) to (iii), ＜Condition (i)＞ The weight average molecular weight of the above covalent diene copolymer is 35,000 or more, <Condition (ii)> The content of the vinyl aromatic monomer unit in the above-mentioned covalent diene copolymer is 15 mass % or more and 80 mass % or less, <Condition (iii)> The covalent diene monomer unit of the above-mentioned covalent diene copolymer includes a unit (a) derived from a 1,2-bond and/or a 3,4-bond and a unit (b) derived from a 1,4-bond, and when the total content of the above-mentioned covalent diene monomer unit is set to 100%, the content of the above-mentioned unit (a) derived from a 1,2-bond and/or a 3,4-bond is 55% or more.

根據本實施方式之樹脂組合物，可獲得低介電常數及低介電損耗因數、強度特性優異、且翹曲較小之硬化物。According to the resin composition of this embodiment, a hardened material with low dielectric constant and low dielectric dissipation factor, excellent strength characteristics and less warping can be obtained.

(成分(I)) 本實施方式之樹脂組合物含有具有選自由上述聚合物嵌段(A)～(C)所組成之群中之至少2個聚合物嵌段、且滿足上述條件(i)～(iii)的共軛二烯系共聚物(成分(I))。 (Component (I)) The resin composition of this embodiment contains a covalent diene copolymer (component (I)) having at least two polymer blocks selected from the group consisting of the above-mentioned polymer blocks (A) to (C) and satisfying the above-mentioned conditions (i) to (iii).

所謂共軛二烯單體單元，意指由共軛二烯化合物聚合形成之聚合物中之源自共軛二烯化合物之結構單元。共軛二烯化合物係具有一對共軛雙鍵之二烯烴。作為共軛二烯化合物，例如可例舉但不限定於以下各者：1,3-丁二烯、2-甲基-1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯、1,3-戊二烯、2-甲基-1,3-戊二烯、1,3-己二烯、1,3-環己二烯等。該等之中，較佳為1,3-丁二烯、異戊二烯，更佳為1,3-丁二烯。1,3-丁二烯或異戊二烯使用廣泛且易於獲得，就成本觀點而言亦有利，亦易與後述廣泛用作乙烯基芳香族化合物之苯乙烯進行共聚。該等可單獨使用一種，亦可將兩種以上組合使用。共軛二烯化合物亦可為利用生物技術而成之化合物。 The so-called conjugated diene monomer unit refers to a structural unit derived from a conjugated diene compound in a polymer formed by polymerization of the conjugated diene compound. A conjugated diene compound is a diene having a pair of conjugated double bonds. Examples of conjugated diene compounds include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-cyclohexadiene, and the like. Among them, 1,3-butadiene and isoprene are preferred, and 1,3-butadiene is more preferred. 1,3-Butadiene or isoprene is widely used and easily available, and is also advantageous from a cost point of view. It is also easy to copolymerize with styrene, which is widely used as a vinyl aromatic compound as described later. These can be used alone or in combination of two or more. The covalent diene compound can also be a compound produced by biotechnology.

所謂乙烯基芳香族單體單元，意指由乙烯基芳香族化合物聚合形成之聚合物中之源自乙烯基芳香族化合物之結構單元。作為乙烯基芳香族化合物，例如可例舉但不限定於以下各者：苯乙烯、α-甲基苯乙烯、對甲基苯乙烯、二乙烯苯、1,1-二苯乙烯、N,N-二甲基對胺基乙基苯乙烯、N,N-二乙基對胺基乙基苯乙烯等。該等可單獨使用一種，亦可將兩種以上組合使用。 The so-called vinyl aromatic monomer unit refers to a structural unit derived from a vinyl aromatic compound in a polymer formed by polymerization of a vinyl aromatic compound. Examples of the vinyl aromatic compound include, but are not limited to, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-stilbene, N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, etc. These may be used alone or in combination of two or more.

＜條件(i)＞本實施方式之樹脂組合物中使用之共軛二烯系共聚物其重量平均分子量為3.5萬以上。藉由使重量平均分子量為3.5萬以上，可獲得強度較高之共軛二烯系共聚物，本實施方式之樹脂組合物、及樹脂組合物之硬化物之強度亦提高。就上述觀點而言，共軛二烯系共聚物之重量平均分子量為3.5萬以上，較佳為4.0萬以上，更佳為4.5萬以上，進而較佳為5.0萬以上，進而更佳為5.5萬以上，進而更佳為6.0萬以上，尤佳為6.5萬以上。重量平均分子量之上限並無特別限定，但於本實施方式之樹脂組合物之製造方法中，一般為將各成分溶解於溶劑後進行混合而製作樹脂膜、預浸體之方法，因此，就於溶劑中之溶解性之觀點而言，共軛二烯系共聚物之重量平均分子量較佳為30萬以下，更佳為20萬以下，進而較佳為15萬以下，進而更佳為13萬以下，進而更佳為10萬以下。重量平均分子量可藉由後述實施例中記載之方法測定，其係基於由市售標準聚苯乙烯之測定求出之校準曲線(使用標準聚苯乙烯之峰值分子量製成)，求出利用凝膠滲透層析法(GPC)測得之層析圖之峰值分子量而獲得之重量平均分子量(Mw)。 <Condition (i)> The weight average molecular weight of the covalent diene copolymer used in the resin composition of the present embodiment is 35,000 or more. By setting the weight average molecular weight to 35,000 or more, a covalent diene copolymer with higher strength can be obtained, and the strength of the resin composition of the present embodiment and the cured product of the resin composition is also improved. From the above viewpoints, the weight average molecular weight of the covalent diene copolymer is 35,000 or more, preferably 40,000 or more, more preferably 45,000 or more, further preferably 50,000 or more, further preferably 55,000 or more, further preferably 60,000 or more, and particularly preferably 65,000 or more. The upper limit of the weight average molecular weight is not particularly limited, but in the method for producing the resin composition of the present embodiment, each component is dissolved in a solvent and then mixed to produce a resin film or a prepreg. Therefore, from the viewpoint of solubility in the solvent, the weight average molecular weight of the covalent diene copolymer is preferably 300,000 or less, more preferably 200,000 or less, further preferably 150,000 or less, further preferably 130,000 or less, further preferably 100,000 or less. The weight average molecular weight can be measured by the method described in the embodiments described below, which is based on the calibration curve obtained by measuring commercially available standard polystyrene (prepared using the peak molecular weight of standard polystyrene) and the peak molecular weight of the chromatogram measured by gel permeation chromatography (GPC) to obtain the weight average molecular weight (Mw).

分子量分佈係重量平均分子量(Mw)與重量平均分子量(Mn)之比率。就防止因混入低分子量聚合物導致操作性變差之觀點而言，本實施方式之樹脂組合物中使用之共軛二烯系共聚物藉由GPC測定之單峰分子量分佈較佳為5.0以下，更佳為4.0以下，進而較佳為3.0以下，進而更佳為2.5以下。 The molecular weight distribution is the ratio of the weight average molecular weight (Mw) to the weight average molecular weight (Mn). From the viewpoint of preventing the deterioration of operability due to the mixing of low molecular weight polymers, the single peak molecular weight distribution of the covalent diene copolymer used in the resin composition of the present embodiment measured by GPC is preferably 5.0 or less, more preferably 4.0 or less, further preferably 3.0 or less, and further preferably 2.5 or less.

共軛二烯系共聚物之重量平均分子量、分子量分佈可藉由後述實施例中記載之方法測定，又，藉由調整單體添加量、添加時機、聚合溫度、聚合時間等聚合條件而可控制於上述數值範圍。The weight average molecular weight and molecular weight distribution of the covalent diene copolymer can be measured by the method described in the examples below, and can be controlled within the above numerical range by adjusting polymerization conditions such as the amount of monomer added, the timing of addition, the polymerization temperature, and the polymerization time.

本實施方式之樹脂組合物中使用之共軛二烯系共聚物具有選自由以乙烯基芳香族單體單元為主體之聚合物嵌段(A)、以共軛二烯單體單元為主體之聚合物嵌段(B)、及包含乙烯基芳香族單體單元與共軛二烯單體單元之無規聚合物嵌段(C)所組成之群中之至少2個聚合物嵌段。聚合物嵌段(A)以乙烯基芳香族單體單元作為主體。該「作為主體」意指不有意添加其他單體。聚合物嵌段(B)以共軛二烯單體單元作為主體。該「作為主體」意指不有意添加其他單體。聚合物嵌段(C)包含乙烯基芳香族單體單元與共軛二烯單體單元。聚合物嵌段(C)係有意添加乙烯基芳香族單體單元與共軛二烯單體單元，可明確區別於聚合物嵌段(A)及(B)。為了將共軛二烯系共聚物之極性提高至藉由控制上述乙烯基芳香族單體單元之含量及控制氫化率能夠達到之範圍以上，賦予與後述成分(II)、成分(III)及成分(IV)之相容性及/或反應性及/或與金屬箔之接著性，本實施方式之樹脂組合物中使用之共軛二烯系共聚物(成分(I))亦可於無損本實施方式之樹脂組合物之介電性能之範圍內具有上述聚合物嵌段(A)～(C)以外之使其他化合物與共軛二烯化合物及/或乙烯基芳香族化合物共聚而成之共聚物嵌段(D)。例如於藉由陰離子聚合製造具有共聚物嵌段(D)之共軛二烯系共聚物之情形時，甲基丙烯酸甲酯(MMA)能夠與乙烯基芳香族化合物或共軛二烯化合物進行共聚，可用作構成共聚物嵌段(D)之化合物。藉由含有MMA，儘管有共軛二烯系共聚物之介電常數及/或介電損耗因數劣化之傾向，但存在共軛二烯系共聚物之極性變高，上述相容性及/或反應性及/或與金屬箔之接著性提高之傾向。 The covalent diene copolymer used in the resin composition of the present embodiment has at least two polymer blocks selected from the group consisting of a polymer block (A) mainly composed of vinyl aromatic monomer units, a polymer block (B) mainly composed of covalent diene monomer units, and a random polymer block (C) containing vinyl aromatic monomer units and covalent diene monomer units. Polymer block (A) mainly contains vinyl aromatic monomer units. The "mainly" means that no other monomers are intentionally added. Polymer block (B) mainly contains covalent diene monomer units. The "mainly" means that no other monomers are intentionally added. Polymer block (C) contains vinyl aromatic monomer units and covalent diene monomer units. The polymer block (C) is a block to which vinyl aromatic monomer units and covalent diene monomer units are intentionally added, and can be clearly distinguished from the polymer blocks (A) and (B). In order to increase the polarity of the covalent diene copolymer to a level that can be achieved by controlling the content of the above-mentioned vinyl aromatic monomer units and controlling the hydrogenation rate, and to impart compatibility and/or reactivity with the components (II), (III) and (IV) described later and/or adhesion to the metal foil, the covalent diene copolymer (component (I)) used in the resin composition of the present embodiment may also have a copolymer block (D) formed by copolymerizing other compounds with the covalent diene compound and/or the vinyl aromatic compound in addition to the above-mentioned polymer blocks (A) to (C) within the range that does not impair the dielectric properties of the resin composition of the present embodiment. For example, when a covalent diene copolymer having a copolymer block (D) is produced by anionic polymerization, methyl methacrylate (MMA) can be copolymerized with a vinyl aromatic compound or a covalent diene compound and can be used as a compound constituting the copolymer block (D). By including MMA, although the dielectric constant and/or dielectric dissipation factor of the covalent diene copolymer tends to deteriorate, the polarity of the covalent diene copolymer becomes higher, and the above-mentioned compatibility and/or reactivity and/or adhesion to the metal foil tend to be improved.

＜條件(ii)＞本實施方式之樹脂組合物中使用之共軛二烯系共聚物中之乙烯基芳香族單體單元之含量為15質量%以上80質量%以下。後述成分(II)：自由基起始劑、成分(III)：極性樹脂及成分(IV)：硬化劑具有極性基。就溶解性參數之觀點而言，構成共軛二烯系共聚物之單體單元中之乙烯基芳香族單體單元存在與成分(II)、成分(III)及成分(IV)之相容性優於共軛二烯單體單元之傾向。藉由使上述成分(II)、成分(III)及成分(IV)與共軛二烯系共聚物相容，抑制本實施方式之樹脂組合物及硬化物因外部電場引起之聚合物之移動性降低及/或極化，本實施方式之樹脂組合物及硬化物之介電損耗因數及/或介電常數優化，即，介電常數之絕對值變低而實現低介電常數化。又，亦可獲得強度提高之效果。就上述相容性之觀點而言，共軛二烯系共聚物中之乙烯基芳香族單體單元之量為15質量%以上，較佳為25質量%以上，更佳為30質量%以上，進而較佳為35質量%以上，進而更佳為40質量%以上，進而更佳為45質量%以上。 <Condition (ii)> The content of the vinyl aromatic monomer unit in the covalent diene copolymer used in the resin composition of the present embodiment is 15 mass % or more and 80 mass % or less. The component (II): free radical initiator, component (III): polar resin and component (IV): curing agent described later have polar groups. From the viewpoint of solubility parameters, the vinyl aromatic monomer unit in the monomer units constituting the covalent diene copolymer tends to be more compatible with the components (II), (III) and (IV) than the covalent diene monomer unit. By making the above-mentioned components (II), (III) and (IV) compatible with the covalent diene copolymer, the resin composition and the cured product of the present embodiment are inhibited from reducing the mobility and/or polarization of the polymer due to the external electric field, and the dielectric dissipation factor and/or dielectric constant of the resin composition and the cured product of the present embodiment are optimized, that is, the absolute value of the dielectric constant becomes lower to achieve a low dielectric constant. In addition, the effect of improving strength can also be obtained. From the perspective of the above-mentioned compatibility, the amount of the vinyl aromatic monomer unit in the covalent diene copolymer is 15% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, further preferably 35% by mass or more, further preferably 40% by mass or more, further preferably 45% by mass or more.

藉由使本實施方式之樹脂組合物中使用之共軛二烯系共聚物中之乙烯基芳香族單體單元之含量為15質量%以上，與後述成分(II)、成分(III)、成分(IV)之相容性變得良好；藉由使該含量為80質量%以下，能夠充分確保對成分(II)、成分(III)之反應性、及共軛二烯系共聚物彼此之反應性，本實施方式之樹脂組合物之硬化物之強度、介電性能及低翹曲性提昇。為了成為具有一定量之源自顯示出自由基反應性之共軛二烯單體之雙鍵者，將共軛二烯系共聚物中之乙烯基芳香族單體單元設為80質量%以下，較佳為85質量%以下，更佳為75質量%以下，進而較佳為70質量%以下。於對後述成分(II)、成分(III)之反應性、及共軛二烯系共聚物彼此之反應性得以充分確保之下進行硬化，藉此，包含本實施方式之樹脂組合物之硬化物之強度、介電性能提高。 By making the content of the vinyl aromatic monomer unit in the covalent diene copolymer used in the resin composition of the present embodiment 15 mass % or more, the compatibility with the components (II), (III) and (IV) described later becomes good; by making the content 80 mass % or less, the reactivity with the components (II) and (III) and the reactivity between the covalent diene copolymers can be fully ensured, and the strength, dielectric properties and low warpage of the cured product of the resin composition of the present embodiment are improved. In order to have a certain amount of double bonds derived from the covalent diene monomers showing free radical reactivity, the vinyl aromatic monomer unit in the covalent diene copolymer is set to 80 mass % or less, preferably 85 mass % or less, more preferably 75 mass % or less, and further preferably 70 mass % or less. Curing is performed while the reactivity of the component (II) and component (III) described later, and the reactivity of the covalent diene copolymers are fully ensured, thereby improving the strength and dielectric properties of the cured product of the resin composition of this embodiment.

本實施方式之樹脂組合物中使用之共軛二烯系共聚物中之乙烯基芳香族單體單元之含量可藉由後述實施例中記載之方法測定。又，藉由調整聚合步驟中之單體添加量、聚合時間而可將乙烯基芳香族單體單元之含量控制於上述數值範圍。 The content of the vinyl aromatic monomer unit in the covalent diene copolymer used in the resin composition of this embodiment can be measured by the method described in the following embodiments. In addition, the content of the vinyl aromatic monomer unit can be controlled within the above numerical range by adjusting the monomer addition amount and polymerization time in the polymerization step.

＜條件(iii)＞共軛二烯系共聚物中之共軛二烯單體單元由源自1,2-鍵及/或3,4-鍵之單元(a)與源自1,4-鍵之單元(b)構成，但已知單元(a)之自由基反應性高於單元(b)。就上述反應性提高之觀點而言，於本實施方式之樹脂組合物所使用之共軛二烯系共聚物中，將共軛二烯單體單元之總含量設為100%之情形時，反應性更高之上述單元(a)之含量(有時亦記為乙烯基鍵量)為55%以上，較佳為57%以上，更佳為60%以上，進而較佳為65%以上，進而更佳為67%以上，進而更佳為70%以上。 <Condition (iii)> The covalent diene monomer units in the covalent diene copolymer are composed of units (a) derived from 1,2-bonds and/or 3,4-bonds and units (b) derived from 1,4-bonds, but it is known that the free radical reactivity of unit (a) is higher than that of unit (b). From the viewpoint of the above-mentioned improvement in reactivity, in the covalent diene copolymer used in the resin composition of the present embodiment, when the total content of the covalent diene monomer units is set to 100%, the content of the above-mentioned unit (a) with higher reactivity (sometimes also recorded as the vinyl bond content) is 55% or more, preferably 57% or more, more preferably 60% or more, further preferably 65% or more, further preferably 67% or more, further preferably 70% or more.

又，於共軛二烯系共聚物與後述成分(II)、成分(III)及成分(IV)相容之狀態下共軛二烯系共聚物彼此交聯，藉此，共軛二烯系共聚物之網狀結構與後述成分(II)、成分(III)及成分(IV)之網狀結構相互交織，銅箔等金屬箔與樹脂組合物之積層體於硬化後之翹曲性變低。就確保共軛二烯系共聚物彼此(亦包括經由成分(II)自由基起始劑、成分(IV)硬化劑而成之鍵結)之反應性、抑制包含硬化物層之積層體之翹曲的觀點而言，將自由基反應性優異之乙烯基鍵量設為55%以上，較佳為57%以上，更佳為60%以上，進而較佳為65%以上，進而較佳為67%以上，進而更佳為70%以上；為了確保與後述成分(II)、成分(III)及成分(IV)之相容性，如上所述，共軛二烯系共聚物中之乙烯基芳香族單體之含量為15質量%以上，較佳為20質量%以上，更佳為25質量%以上，進而較佳為30質量%以上，進而更佳為35質量%以上，進而更佳為40質量%以上，尤佳為45質量%以上。 Furthermore, the covalent diene copolymers are cross-linked with each other when the covalent diene copolymers are compatible with the components (II), (III) and (IV) described later. As a result, the network structure of the covalent diene copolymers is intertwined with the network structure of the components (II), (III) and (IV) described later. The laminate of the metal foil such as copper foil and the resin composition has lower warpage after curing. From the viewpoint of ensuring the reactivity of the covalent diene copolymers (including the bonds formed via the component (II) free radical initiator and the component (IV) curing agent) and suppressing the warping of the laminate including the cured layer, the amount of vinyl bonds having excellent free radical reactivity is set to 55% or more, preferably 57% or more, more preferably 60% or more, further preferably 65% or more, further preferably 67% or more, further preferably 70%. In order to ensure compatibility with the components (II), (III) and (IV) described below, as mentioned above, the content of the vinyl aromatic monomer in the covalent diene copolymer is 15% by mass or more, preferably 20% by mass or more, more preferably 25% by mass or more, further preferably 30% by mass or more, further preferably 35% by mass or more, further preferably 40% by mass or more, and particularly preferably 45% by mass or more.

藉由使本實施方式之樹脂組合物中使用之共軛二烯系共聚物之乙烯基鍵量為55%以上，存在顯示出充分之反應性，後述樹脂組合物之硬化物顯示出良好之強度、介電性能，積層體不易翹曲之傾向。藉由使共軛二烯系共聚物中之乙烯基芳香族單體量為15質量%以上，存在與成分(II)、成分(III)及成分(IV)具有充分之相容性，後述樹脂組合物之強度、介電性能優化，並顯示出低翹曲性之傾向。即，藉由兼備上述條件(ii)及條件(iii)，發揮如下效果：本實施方式之樹脂組合物之硬化物顯示出良好之強度、介電性能，且不易翹曲。 By making the vinyl bond content of the covalent diene copolymer used in the resin composition of the present embodiment 55% or more, there is a sufficient reactivity, and the cured product of the resin composition described below shows good strength and dielectric properties, and the laminate tends to be less likely to warp. By making the vinyl aromatic monomer content in the covalent diene copolymer 15% or more by mass, there is a sufficient compatibility with component (II), component (III) and component (IV), and the strength and dielectric properties of the resin composition described below are optimized, and it tends to have low warping. That is, by combining the above conditions (ii) and (iii), the following effects are achieved: the cured product of the resin composition of the present embodiment shows good strength and dielectric properties, and is less likely to warp.

關於構成本實施方式之樹脂組合物中使用之共軛二烯系共聚物的各單體單元之含量，可將本實施方式之共軛二烯系共聚物作為樣本，藉由使用核磁共振裝置(NMR)之方法(Y. Tanaka, et al., 《橡膠化學與技術(RUBBER CHEMISTRY and TECHNOLOGY)》54, 685(1981)中記載之方法。以下稱為「NMR法」)測定。The content of each monomer unit of the covalent diene copolymer used in the resin composition of the present embodiment can be measured by using the covalent diene copolymer of the present embodiment as a sample by a method using a nuclear magnetic resonance apparatus (NMR) (the method described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981). hereinafter referred to as "NMR method").

上述單元(a)之含量(乙烯基鍵量)可藉由在共軛二烯系共聚物之聚合步驟中使用極性化合物等調整劑而控制於上述數值範圍，可藉由後述實施例中記載之方法算出。作為調整劑，例如可例舉：三級胺化合物、醚化合物。較佳為使用三級胺化合物。三級胺化合物係通式R1R2R3N(其中，R1、R2、R3表示碳數1～20之烴基、或具有三級胺基之烴基)表示之化合物。作為三級胺化合物，例如可例舉但不限定於以下各者：三甲基胺、三乙基胺、三丁基胺、N,N-二甲基苯胺、N-乙基哌啶、N-甲基吡咯啶、N,N,N',N'-四甲基乙二胺、N,N,N',N'-四乙基乙二胺、1,2-二哌啶基乙烷、三甲基胺基乙基哌𠯤、N,N,N',N'',N''-五甲基伸乙基三胺、N,N'-二辛基對苯二胺等。調整劑之添加量相對於後述聚合起始劑1 mol，較佳為0.1 mol以上，更佳為0.5 mol以上，進而較佳為1.0 mol以上。又，於將單元(a)之含量設為80%以上之情形時，調整劑之添加量相對於後述聚合起始劑1 mol，較佳為0.15 mol以上，更佳為0.5 mol以上，進而較佳為1.0 mol以上。 The content (vinyl bond content) of the above-mentioned unit (a) can be controlled within the above-mentioned numerical range by using a modifier such as a polar compound in the polymerization step of the covalent diene copolymer, and can be calculated by the method described in the following examples. As a modifier, for example: tertiary amine compounds and ether compounds can be cited. It is preferred to use a tertiary amine compound. The tertiary amine compound is a compound represented by the general formula R1R2R3N (wherein R1, R2, and R3 represent a carbon number of 1 to 20, or a carbon group having a tertiary amine group). As tertiary amine compounds, for example, but not limited to the following: trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-dipiperidinylethane, trimethylaminoethylpiperidin, N,N,N',N'',N''-pentamethylethylenetriamine, N,N'-dioctyl-p-phenylenediamine, etc. The amount of the modifier added is preferably 0.1 mol or more, more preferably 0.5 mol or more, and further preferably 1.0 mol or more relative to 1 mol of the polymerization initiator described below. Furthermore, when the content of unit (a) is set to 80% or more, the amount of the modifier added is preferably 0.15 mol or more, more preferably 0.5 mol or more, and further preferably 1.0 mol or more relative to 1 mol of the polymerization initiator described below.

＜氫化率＞本實施方式之樹脂組合物中使用之共軛二烯系共聚物較佳為源自共軛二烯單體單元之不飽和鍵之氫化率為5～95%。近年來，隨著各種電子機器之小型化要求，對於印刷基板要求基板之小型化。為了實現印刷基板之小型化，必須進行精密之佈線，此時存在要求印刷配線板用材料具有韌性之傾向。於本實施方式之樹脂組合物中，藉由成分(I)共軛二烯系共聚物與後述成分(III)、成分(IV)之剛直樹脂反應，存在韌性提高之傾向。共軛二烯系共聚物之源自共軛二烯單體之不飽和鍵可被氫化，但就上述反應性之觀點而言，其氫化率較佳為95%以下，更佳為90%以下，進而較佳為85%以下，進而更佳為80%以下，進而更佳為75%以下，尤佳為70%以下。藉由使氫化率為95%以下，存在能夠充分確保上述反應性，韌性優異之傾向。就本實施方式之樹脂組合物於硬化步驟前之組合物(清漆)之保存穩定性之觀點而言，氫化率之下限較佳為5%以上，更佳為10%以上，進而較佳為15%以上，進而更佳為20%以上，進而更佳為25%以上，尤佳為30%以上。藉由使氫化率為5%以上，可獲得優異之保存穩定性。 <Hydrogenation rate> The covalent diene copolymer used in the resin composition of the present embodiment preferably has a hydrogenation rate of 5 to 95% of the unsaturated bonds derived from the covalent diene monomer units. In recent years, with the demand for miniaturization of various electronic devices, the miniaturization of printed circuit boards has been required. In order to achieve the miniaturization of printed circuit boards, precise wiring must be performed, and at this time, there is a tendency to require the materials for printed wiring boards to have toughness. In the resin composition of the present embodiment, the toughness tends to be improved by reacting the covalent diene copolymer of component (I) with the rigid resins of components (III) and (IV) described later. The unsaturated bonds derived from the covalent diene monomers of the covalent diene copolymer can be hydrogenated, but from the viewpoint of the above-mentioned reactivity, the hydrogenation rate is preferably 95% or less, more preferably 90% or less, further preferably 85% or less, further preferably 80% or less, further preferably 75% or less, and particularly preferably 70% or less. By making the hydrogenation rate 95% or less, there is a tendency to be able to fully ensure the above-mentioned reactivity and excellent toughness. From the perspective of the storage stability of the resin composition of this embodiment before the curing step (varnish), the lower limit of the hydrogenation rate is preferably 5% or more, more preferably 10% or more, further preferably 15% or more, further preferably 20% or more, further preferably 25% or more, and particularly preferably 30% or more. By setting the hydrogenation rate to 5% or more, excellent storage stability can be obtained.

作為使共軛二烯系共聚物氫化之方法，並無特別限定，可應用公知方法。氫化反應時可使用公知之氫化觸媒。作為氫化觸媒，例如可例舉：(1)使Ni、Pt、Pd、Ru等金屬擔載於碳、二氧化矽、氧化鋁、矽藻土等上而成之擔載型非均相氫化觸媒；(2)使用Ni、Co、Fe、Cr等之有機酸鹽或乙醯丙酮鹽等過渡金屬鹽與有機鋁等還原劑的所謂齊格勒型氫化觸媒；(3)Ti、Ru、Rh、Zr等之有機金屬化合物等所謂有機金屬錯合物等均相氫化觸媒。作為氫化觸媒，具體而言，可使用日本專利特公昭42-8704號公報、日本專利特公昭43-6636號公報、日本專利特公昭63-4841號公報、日本專利特公平1-37970號公報、日本專利特公平1-53851號公報、日本專利特公平2-9041號公報中記載之氫化觸媒。作為較佳之氫化觸媒，可例舉二茂鈦化合物及/或還原性有機金屬化合物。 The method for hydrogenating the covalent diene copolymer is not particularly limited, and a known method can be applied. A known hydrogenation catalyst can be used for the hydrogenation reaction. Examples of the hydrogenation catalyst include: (1) a supported heterogeneous hydrogenation catalyst in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like; (2) a so-called Ziegler-type hydrogenation catalyst using an organic acid salt of Ni, Co, Fe, or Cr, or a transition metal salt such as acetylacetonate and a reducing agent such as an organic aluminum; (3) a homogeneous hydrogenation catalyst such as an organic metal complex such as an organic metal compound of Ti, Ru, Rh, or Zr, or the like. As the hydrogenation catalyst, specifically, the hydrogenation catalyst described in Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-37970, Japanese Patent Publication No. 1-53851, and Japanese Patent Publication No. 2-9041 can be used. As a preferred hydrogenation catalyst, a titanocene compound and/or a reducing organic metal compound can be cited.

作為二茂鈦化合物，可使用日本專利特開平8-109219號公報中記載之化合物。作為二茂鈦化合物，例如可例舉但不限定於以下各者：二氯化雙環戊二烯基鈦、三氯化單五甲基環戊二烯基鈦等包含至少1個以上具有(取代)環戊二烯基骨架、茚基骨架或茀基骨架之配位基之化合物。二茂鈦化合物可單獨包含一種上述骨架、或組合包含兩種骨架。As the titanocene compound, the compounds described in Japanese Patent Laid-Open No. 8-109219 can be used. Examples of the titanocene compound include, but are not limited to, the following: compounds containing at least one ligand having a (substituted) cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton, such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. The titanocene compound may contain one of the above skeletons alone, or a combination of two skeletons.

作為還原性有機金屬化合物，例如可例舉但不限定於以下各者：有機鋰等有機鹼金屬化合物、有機鎂化合物、有機鋁化合物、有機硼化合物、及有機鋅化合物等。該等可單獨使用一種，亦可將兩種以上組合使用。 Examples of reducing organic metal compounds include, but are not limited to, organic alkali metal compounds such as organic lithium, organic magnesium compounds, organic aluminum compounds, organic boron compounds, and organic zinc compounds. These compounds may be used alone or in combination of two or more.

本實施方式之樹脂組合物中使用之共軛二烯系共聚物之氫化率可藉由適時調整氫化方法中之反應溫度、反應時間、氫供給量、觸媒量等而控制於上述數值範圍。氫化反應時之溫度較佳為55～200℃，更佳為60～170℃，進而較佳為65℃～160℃。又，氫化反應中使用之氫氣之壓力為0.1～15 MPa，較佳為0.2～10 MPa，更佳為0.3～5 MPa。又，氫化反應時間通常為3分鐘～10小時，較佳為10分鐘～5小時。氫化反應可採用分批處理、連續處理、或該等之組合之任意者。 The hydrogenation rate of the covalent diene copolymer used in the resin composition of the present embodiment can be controlled within the above numerical range by appropriately adjusting the reaction temperature, reaction time, hydrogen supply, catalyst amount, etc. in the hydrogenation method. The temperature during the hydrogenation reaction is preferably 55 to 200°C, more preferably 60 to 170°C, and further preferably 65 to 160°C. In addition, the pressure of the hydrogen used in the hydrogenation reaction is 0.1 to 15 MPa, preferably 0.2 to 10 MPa, and more preferably 0.3 to 5 MPa. In addition, the hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours. The hydrogenation reaction can be carried out by batch processing, continuous processing, or any combination thereof.

(共軛二烯系共聚物之製造方法) 本實施方式之樹脂組合物中使用之共軛二烯系共聚物例如可藉由以下方式製造：於烴溶劑中，使用有機鹼金屬化合物等聚合起始劑進行活性陰離子聚合，其後視需要進行氫化反應。 (Method for producing covalent diene copolymers) The covalent diene copolymers used in the resin composition of the present embodiment can be produced, for example, by carrying out living anionic polymerization in a hydrocarbon solvent using a polymerization initiator such as an organic alkali metal compound, and then carrying out a hydrogenation reaction as needed.

作為烴溶劑，例如可例舉但不限定於以下各者：正丁烷、異丁烷、正戊烷、正己烷、正庚烷、正辛烷等脂肪族烴類；環己烷、環庚烷、甲基環庚烷等脂環式烴類；苯、甲苯、二甲苯、乙基苯等芳香族烴等。Examples of hydrocarbon solvents include, but are not limited to, aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; alicyclic hydrocarbons such as cyclohexane, cycloheptane, and methylcycloheptane; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.

作為聚合起始劑，可例舉公知之對共軛二烯化合物及乙烯基芳香族化合物具有陰離子聚合活性之脂肪族烴鹼金屬化合物、芳香族烴鹼金屬化合物、有機胺基鹼金屬化合物等有機鹼金屬化合物。作為鹼金屬，可例舉：鋰、鈉、鉀等。作為有機鹼金屬化合物，例如可例舉碳數1～20之脂肪族及芳香族烴鋰化合物，包括一分子中包含1個鋰之化合物、一分子中包含複數個鋰之二鋰化合物、三鋰化合物、四鋰化合物。 As polymerization initiators, there can be mentioned organic alkali metal compounds such as aliphatic alkali metal compounds, aromatic alkali metal compounds, and organic amine alkali metal compounds that are known to have anionic polymerization activity for conjugated diene compounds and vinyl aromatic compounds. As alkali metals, there can be mentioned lithium, sodium, potassium, etc. As organic alkali metal compounds, there can be mentioned, for example, aliphatic and aromatic alkali lithium compounds with carbon numbers of 1 to 20, including compounds containing one lithium in one molecule, dilithium compounds containing multiple lithium in one molecule, trilithium compounds, and tetralithium compounds.

作為有機鹼金屬化合物，例如可例舉但不限定於以下各者：正丙基鋰、正丁基鋰、第二丁基鋰、第三丁基鋰、正戊基鋰、正己基鋰、苄基鋰、苯基鋰、甲苯基鋰、二異丙烯基苯與第二丁基鋰之反應產物，進而，二乙烯苯、第二丁基鋰及少量1,3-丁二烯之反應產物等。進而，亦可使用美國專利5,708,092號說明書中揭示之1-(第三丁氧基)丙基鋰及為了改善其溶解性而***有一～數分子之異戊二烯單體之鋰化合物、英國專利2,241,239號說明書中揭示之1-(第三丁基二甲基矽烷氧基)己基鋰等含矽烷氧基之烷基鋰、美國專利5,527,753號說明書中揭示之含胺基之烷基鋰、二異丙基醯胺鋰及雙(三甲基矽烷)胺基鋰(lithium hexamethyldisilazide)等胺基鋰類。Examples of the organoalkali metal compound include, but are not limited to, n-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, tolyl lithium, the reaction product of diisopropenylbenzene and sec-butyl lithium, and further, the reaction product of divinylbenzene, sec-butyl lithium and a small amount of 1,3-butadiene. Furthermore, lithium compounds having one to several molecules of isoprene monomers inserted therein to improve their solubility, alkyl lithium containing silaneoxy groups such as 1-(tert-butyldimethylsiloxy)hexyllithium disclosed in U.S. Patent No. 5,708,092, lithium amides such as alkyl lithium containing amine groups disclosed in U.S. Patent No. 5,527,753, lithium diisopropylamide, and lithium bis(trimethylsilyl)amide (lithium hexamethyldisilazide) and the like can also be used.

使用有機鹼金屬化合物作為聚合起始劑使乙烯基芳香族化合物及共軛二烯化合物聚合之方法可應用先前公知之方法。作為聚合方法，例如可為分批聚合、連續聚合、或該等之組合之任意者。為了獲得均勻之聚合物，尤佳為分批聚合。聚合溫度較佳為0℃～180℃，更佳為30℃～150℃。聚合時間視條件而異，通常為48小時以內，較佳為0.1～10小時。又，作為聚合體系之環境，較佳為氮氣等惰性氣體氛圍。聚合壓力並無特別限定，只要設定為能夠於上述溫度範圍內使單體及溶劑維持液相之壓力範圍即可。進而，需留意避免聚合體系內混入如會使觸媒及活性聚合物失去活性之雜質，例如水、氧氣、二氧化碳等。 The method of polymerizing a vinyl aromatic compound and a covalent diene compound using an organic alkali metal compound as a polymerization initiator can be applied to a previously known method. As a polymerization method, for example, it can be batch polymerization, continuous polymerization, or any combination thereof. In order to obtain a uniform polymer, batch polymerization is particularly preferred. The polymerization temperature is preferably 0°C to 180°C, and more preferably 30°C to 150°C. The polymerization time varies depending on the conditions, but is usually within 48 hours, preferably 0.1 to 10 hours. In addition, as an environment of the polymerization system, an inert gas atmosphere such as nitrogen is preferred. The polymerization pressure is not particularly limited, as long as it is set to a pressure range that can keep the monomer and the solvent in the liquid phase within the above temperature range. Furthermore, care must be taken to avoid the incorporation of impurities into the polymer system that may render the catalyst and active polymer inactive, such as water, oxygen, carbon dioxide, etc.

又，亦可於上述聚合步驟結束時添加必要量之二官能以上之偶合劑進行偶合反應，但偶合率較佳為40%以下，更佳為30%以下，進而較佳為20%以下，進而更佳為不含偶合劑。Furthermore, a necessary amount of a bifunctional or higher coupling agent may be added at the end of the above polymerization step to carry out a coupling reaction, but the coupling rate is preferably 40% or less, more preferably 30% or less, further preferably 20% or less, and further preferably no coupling agent is contained.

二官能偶合劑並無特別限定，可應用先前公知者。作為二官能偶合劑，例如可例舉但不限定於以下各者：三甲氧基矽烷、三乙氧基矽烷、四甲氧基矽烷、四乙氧基矽烷、二甲基二甲氧基矽烷、二乙基二甲氧基矽烷、二氯二甲氧基矽烷、二氯二乙氧基矽烷、三氯甲氧基矽烷、三氯乙氧基矽烷等烷氧基矽烷化合物，二氯乙烷、二溴乙烷、二甲基二氯矽烷、二甲基二溴矽烷等二鹵化合物，苯甲酸甲酯、苯甲酸乙酯、苯甲酸苯酯、苯二甲酸酯類等酸酯類等。 The difunctional coupling agent is not particularly limited, and previously known ones can be used. As the difunctional coupling agent, for example, but not limited to, the following can be cited: alkoxysilane compounds such as trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, trichloroethoxysilane, dihalogen compounds such as dichloroethane, dibromoethane, dimethyldichlorosilane, dimethyldibromosilane, methyl benzoate, ethyl benzoate, phenyl benzoate, phthalic acid esters, etc.

又，三官能以上之多官能偶合劑並無特別限定，可應用先前公知者。作為三官能以上之多官能偶合劑，例如可例舉但不限定於以下各者：三元以上之多元醇類、環氧化大豆油、二縮水甘油基雙酚A、1,3-雙(N-N'-二縮水甘油基胺基甲基)環己烷等多元環氧化合物；通式R ₄-nSiX _n(此處，R表示碳數1～20之烴基，X表示鹵素，n表示3～4之整數)表示之鹵化矽化合物，例如三氯化甲基矽烷、三氯化第三丁基矽烷、四氯化矽及該等之溴化物等；通式R ₄-nSnX _n(此處，R表示碳數1～20之烴基，X表示鹵素，n表示3～4之整數)表示之鹵化錫化合物，例如三氯化甲基錫、三氯化第三丁基錫、四氯化錫等多元鹵化合物。又，亦可使用碳酸二甲酯或碳酸二乙酯等。 Furthermore, the trifunctional or higher polyfunctional coupling agent is not particularly limited, and previously known ones can be used. Examples of the trifunctional or higher polyfunctional coupling agent include, but are not limited to, the following: trivalent or higher polyols, epoxidized soybean oil, diglycidyl bisphenol A, 1,3-bis(N-N'-diglycidylaminomethyl)cyclohexane and other polycyclic epoxy compounds; halogenated silicon compounds represented by the general formula _R4 - _nSiXn (wherein R represents a alkyl group having 1 to 20 carbon atoms, X represents a halogen, and n represents an integer of 3 to 4), such as trichloromethylsilane, trichlorotetylsilane, tetrachlorosilane and bromides thereof; and the general formula _R4 - _nSnXn. (Herein, R represents a carbonyl group having 1 to 20 carbon atoms, X represents a halogen, and n represents an integer of 3 to 4) a tin halide compound represented by, for example, methyltin trichloride, tert-butyltin trichloride, tin tetrachloride, or other polyhalogen compounds. Alternatively, dimethyl carbonate or diethyl carbonate may be used.

對共軛二烯系共聚物之氫化反應如上所述可使用公知之氫化觸媒、藉由公知方法進行。As described above, the hydrogenation reaction of the covalent diene copolymer can be carried out by a known method using a known hydrogenation catalyst.

對於藉由如上方式獲得之本實施方式之樹脂組合物中使用之共軛二烯系共聚物之溶液，可視需要去除觸媒殘渣，自溶液分離共軛二烯系共聚物。For the solution of the covalent diene copolymer used in the resin composition of the present embodiment obtained in the above manner, the catalyst residue can be removed as needed to separate the covalent diene copolymer from the solution.

藉由陰離子活性聚合製造共軛二烯系共聚物時之聚合起始劑、氫化反應時之氫化觸媒中之含金屬原子之化合物存在於脫溶劑步驟等中與空氣中之水分等反應生成特定之金屬化合物而殘存於共軛二烯系共聚物中的傾向。若硬化物中含有該等化合物，則存在介電常數及介電損耗因數增大之傾向，進而於電子材料用途中存在易發生離子遷移之傾向。作為殘存之金屬化合物，可例舉聚合起始劑、氫化觸媒中包含之金屬之化合物，例如氧化鈦、非晶性氧化鈦、正鈦酸或偏鈦酸、氫氧化鈦、氫氧化鎳、一氧化鎳、氧化鋰、氫氧化鋰、氧化鈷、氫氧化鈷等各原子之氧化物，鈦酸鋰、鈦酸鋇、鈦酸鍶、鈦酸鎳、鎳・鐵氧化物等各原子與異種金屬之複合氧化物。 When manufacturing covalent diene copolymers by anionic living polymerization, compounds containing metal atoms in the polymerization initiator and the hydrogenation catalyst in the hydrogenation reaction tend to exist in the desolventizing step, etc., and react with moisture in the air to generate specific metal compounds, which remain in the covalent diene copolymers. If the cured product contains these compounds, the dielectric constant and dielectric dissipation factor tend to increase, and further, ion migration tends to occur easily in electronic material applications. Examples of the residual metal compounds include compounds of metals contained in polymerization initiators and hydrogenation catalysts, such as oxides of atoms of titanium oxide, amorphous titanium oxide, orthotitanium acid or metatitanium acid, titanium hydroxide, nickel hydroxide, nickel monoxide, lithium oxide, lithium hydroxide, cobalt oxide, cobalt hydroxide, and composite oxides of atoms of lithium titanate, barium titanate, strontium titanate, nickel titanate, nickel and iron oxides and other metals.

就上述低介電常數化、低介電損耗因數化、及不易發生離子遷移之觀點而言，本實施方式之樹脂組合物所使用之共軛二烯系共聚物中之金屬化合物之殘存量以殘存金屬量計，較佳為150 ppm以下，更佳為130 ppm以下，進而較佳為100 ppm以下，進而更佳為90 ppm以下。作為具體之殘存金屬，一般而言，可例舉：Ti、Ni、Li、Co等。From the viewpoint of the aforementioned low dielectric constant, low dielectric loss factor, and low ion migration, the residual amount of the metal compound in the covalent diene copolymer used in the resin composition of the present embodiment is preferably 150 ppm or less, more preferably 130 ppm or less, further preferably 100 ppm or less, and further preferably 90 ppm or less, in terms of the residual metal amount. Specific residual metals generally include Ti, Ni, Li, Co, and the like.

作為減少共軛二烯系共聚物中之殘存金屬量之方法，可應用公知方法，並無特別限定。例如可採用如下方法：於共軛二烯系共聚物之氫化反應後添加水及二氧化碳而中和氫化觸媒殘渣；除水、二氧化碳以外亦添加酸而中和氫化觸媒殘渣。具體而言可應用日本專利特願2014-557427號說明書中記載之方法。即便採用該等金屬去除方法，由於共軛二烯系共聚物之脫溶劑步驟中會混入含有金屬化合物之氫氧化物之水，故一般亦包含1～15 ppm左右。因此，較佳為去除相對於共軛二烯系共聚物中之金屬添加量之20%以上，更佳為去除30%以上，進而較佳為去除40%以上，進而更佳為去除50%以上，進而更佳為去除60%以上。As a method for reducing the amount of residual metal in the conjugated diene copolymer, a known method can be applied without particular limitation. For example, the following method can be adopted: after the hydrogenation reaction of the conjugated diene copolymer, water and carbon dioxide are added to neutralize the hydrogenation catalyst residue; in addition to water and carbon dioxide, an acid is also added to neutralize the hydrogenation catalyst residue. Specifically, the method described in the specification of Japanese Patent Application No. 2014-557427 can be applied. Even if such metal removal methods are adopted, since water containing hydroxides of metal compounds will be mixed in the desolventizing step of the conjugated diene copolymer, it generally contains about 1 to 15 ppm. Therefore, it is preferred to remove more than 20% of the amount of metal added to the covalent diene copolymer, more preferably more than 30%, further preferably more than 40%, further preferably more than 50%, further preferably more than 60%.

又，藉由減少本身所添加之聚合起始劑及氫化觸媒之量，亦能夠減少本實施方式之樹脂組合物所使用之共軛二烯系共聚物中之殘存金屬量，但若減少聚合起始劑之量，則存在共軛二烯系共聚物之分子量變高，後述樹脂組合物之溶劑溶解性變差、或該樹脂組合物溶液之高黏度化導致操作性變差之傾向。又，進行氫化反應時，若減少氫化反應觸媒之量，則存在引起氫化反應時間之長時間化、氫化反應溫度之高溫化，生產性明顯降低之傾向。Furthermore, by reducing the amount of the polymerization initiator and hydrogenation catalyst added, the amount of residual metal in the covalent diene copolymer used in the resin composition of the present embodiment can also be reduced. However, if the amount of the polymerization initiator is reduced, the molecular weight of the covalent diene copolymer becomes higher, the solvent solubility of the resin composition described later becomes worse, or the viscosity of the resin composition solution becomes higher, resulting in poor operability. Furthermore, when the hydrogenation reaction is carried out, if the amount of the hydrogenation catalyst is reduced, the hydrogenation reaction time is prolonged, the hydrogenation reaction temperature is increased, and the productivity tends to be significantly reduced.

作為提取共軛二烯系共聚物時之溶劑之分離方法，例如可例舉：於氫化後之反應液中添加丙酮或醇等對氫化共軛二烯系共聚物而言為不良溶劑之極性溶劑以使氫化共軛二烯系共聚物沈澱而回收之方法；一面攪拌一面將反應液投入至沸水中，藉由蒸汽汽提去除溶劑而回收之方法；直接對共聚物溶液進行加熱而蒸餾去除溶劑之方法等。As a method for separating the solvent when extracting the conjugated diene copolymer, for example, there can be cited: a method of adding a polar solvent such as acetone or alcohol, which is a poor solvent for the hydrogenated conjugated diene copolymer, to the reaction liquid after hydrogenation to precipitate and recover the hydrogenated conjugated diene copolymer; a method of adding the reaction liquid into boiling water while stirring and recovering the solvent by steam stripping; a method of directly heating the copolymer solution and distilling to remove the solvent, etc.

再者，可於本實施方式之樹脂組合物所使用之共軛二烯系共聚物中添加各種酚系穩定劑、磷系穩定劑、硫系穩定劑、胺系穩定劑等穩定劑。於本實施方式之樹脂組合物所使用之共軛二烯系共聚物之製造步驟中，可在無損本實施方式之樹脂組合物之介電性能之範圍內實施形成「極性基」之步驟。 Furthermore, various stabilizers such as phenol stabilizers, phosphorus stabilizers, sulfur stabilizers, and amine stabilizers may be added to the covalent diene copolymer used in the resin composition of the present embodiment. In the manufacturing step of the covalent diene copolymer used in the resin composition of the present embodiment, the step of forming a "polar group" may be performed within the range of not damaging the dielectric properties of the resin composition of the present embodiment.

極性基例如可例舉但不限定於以下各者：含有至少一種選自由羥基、羧基、羰基、硫羰基、醯鹵化物基、酸酐基、羧酸基、硫羧酸基、醛基、硫醛基、羧酸酯基、醯胺基、磺酸基、磺酸酯基、磷酸基、磷酸酯基、胺基、亞胺基、腈基、吡啶基、喹啉基、環氧基、硫代環氧基、硫基(sulfide)、異氰酸基、異硫氰酸基、鹵化矽基、矽烷醇基、烷氧基矽基、鹵化錫基、硼酸基、含硼基、硼酸鹽基、烷氧基錫基及苯基錫基等所組成之群中之官能基的原子團。Examples of polar groups include, but are not limited to, the following: an atomic group containing at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acyl halide group, an acid anhydride group, a carboxylic acid group, a thiocarboxylic acid group, an aldehyde group, a thialdehyde group, a carboxylate group, an amide group, a sulfonic acid group, a sulfonate group, a phosphoric acid group, a phosphoric acid ester group, an amine group, an imino group, a nitrile group, a pyridyl group, a quinolyl group, an epoxy group, a thioepoxy group, a sulfide group, an isocyanate group, an isothiocyanate group, a silyl halide group, a silanol group, an alkoxysilyl group, a tin halide group, a boric acid group, a boron-containing group, a borate group, an alkoxytin group, and a phenyltin group.

極性基可藉由使共軛二烯系共聚物與改性劑反應而形成。作為改性劑，例如可例舉但不限定於不以下各者：四縮水甘油基間二甲苯二胺、四縮水甘油基-1,3-雙胺基甲基環己烷、ε-己內酯、δ-戊內酯、4-甲氧基二苯甲酮、γ-縮水甘油氧基乙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基二甲基苯氧基矽烷、雙(γ-縮水甘油氧基丙基)甲基丙氧基矽烷、1,3-二甲基-2-咪唑啶酮、1,3-二乙基-2-咪唑啶酮、N,N'-二甲基伸丙基脲、N-甲基吡咯啶酮、順丁烯二酸、順丁烯二酸酐、順丁烯二酸酐醯亞胺、反丁烯二酸、伊康酸、丙烯酸、甲基丙烯酸、甲基丙烯酸縮水甘油酯、丁烯酸等。 The polar group can be formed by reacting a covalent diene copolymer with a modifier. Examples of the modifier include, but are not limited to, tetraglycidyl-m-xylene diamine, tetraglycidyl-1,3-diaminomethylcyclohexane, ε-caprolactone, δ-valerolactone, 4-methoxybenzophenone, γ-glycidyloxyethyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyldimethylphenoxysilane, bis(2-hydroxy-1-methyl-2-phenyl-2-yl)-1-nitropropene, 1- ... (γ-Glyceryloxypropyl)methylpropoxysilane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropylurea, N-methylpyrrolidone, maleic acid, maleic anhydride, maleic anhydride imide, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, glycidyl methacrylate, butenoic acid, etc.

作為形成極性基之方法，並無特別限定，可應用公知方法。例如可例舉：熔融混練方法、或者使各成分溶解或分散混合於溶劑等中進行反應之方法等。又，除上述使用改性劑之方法以外，亦可應用如下方法：藉由陰離子活性聚合，使用含有官能基之聚合起始劑或含有官能基之不飽和單體進行聚合。進而，亦可例舉：藉由使活性末端與形成或含有官能基之改性劑發生加成反應而進行改性之方法；使共聚物與有機鋰化合物等有機鹼金屬化合物反應(金屬化反應)後，使加成了有機鹼金屬之聚合物與含有官能基之改性劑發生加成反應之方法。 There is no particular limitation on the method for forming the polar group, and a known method can be applied. For example, a melt kneading method or a method of dissolving or dispersing and mixing the components in a solvent or the like and reacting the components can be cited. In addition, in addition to the above-mentioned method using a modifier, the following method can also be applied: polymerization by anion living polymerization using a polymerization initiator containing a functional group or an unsaturated monomer containing a functional group. Furthermore, a method of modifying the active terminal by an addition reaction with a modifier that forms or contains a functional group can also be cited; a method of reacting a copolymer with an organic alkali metal compound such as an organic lithium compound (metallization reaction), and then causing an addition reaction of the polymer to which the organic alkali metal is added with a modifier containing a functional group.

(構成樹脂組合物之成分) 如上所述，本實施方式之樹脂組合物含有共軛二烯系共聚物(成分(I))與選自由下述成分(II)～(IV)所組成之群中之至少一種成分。成分(II)：自由基起始劑成分(III)：極性樹脂(成分(I)除外) 成分(IV)：硬化劑(成分(II)除外) 就本實施方式之樹脂組合物及其硬化物之低介電常數化、低介電損耗因數化、及柔軟性之觀點而言，本實施方式之樹脂組合物較佳為含有成分(I)：共軛二烯系共聚物與成分(II)：自由基起始劑。 (Components constituting the resin composition) As described above, the resin composition of the present embodiment contains a covalent diene copolymer (component (I)) and at least one component selected from the group consisting of the following components (II) to (IV). Component (II): free radical initiator Component (III): polar resin (excluding component (I)) Component (IV): curing agent (excluding component (II)) From the viewpoint of lowering the dielectric constant, lowering the dielectric dissipation factor, and flexibility of the resin composition of the present embodiment and its cured product, the resin composition of the present embodiment preferably contains component (I): covalent diene copolymer and component (II): free radical initiator.

(成分(II)：自由基起始劑) 作為自由基起始劑，可使用先前公知者，例如可例舉熱自由基起始劑。作為熱自由基起始劑，例如可例舉但不限定於以下各者：二異丙基苯過氧化氫(Percumyl P)、異丙苯過氧化氫(Percumyl H)、第三丁基過氧化氫(Perbutyl H)等過氧化氫類；或α,α-雙(第三丁基過氧基間異丙基)苯(Perbutyl P)、過氧化二異丙苯(Percumyl D)、2,5-二甲基-2,5-雙(第三丁基過氧基)己烷(Perhexa 25B)、過氧化第三丁基異丙苯(Perbutyl C)、過氧化二第三丁基(Perbutyl D)、2,5-二甲基-2,5-雙(第三丁基過氧基)己炔-3(Perhexyne 25B)、過氧化(2-乙基己酸)第三丁酯(Perbutyl O)等二烷基過氧化物類；或過氧化酮類；或4,4-二-(第三丁基過氧基)戊酸正丁酯(Perhexa V)等過氧縮酮等；或二醯基過氧化物類；或過氧化二碳酸酯類；或過氧酯等有機過氧化物；或2,2-偶氮二異丁腈、1,1'-(環己烷-1-1-甲腈)、2,2'-偶氮雙(2-環丙基丙腈)、2,2'-偶氮雙(2,4-二甲基戊腈)等偶氮化合物等。該等可單獨使用一種，亦可使用兩種以上。 (Component (II): free radical initiator) As the free radical initiator, a previously known one can be used, for example, a thermal free radical initiator can be cited. As the thermal free radical initiator, for example, but not limited to the following: hydrogen peroxides such as diisopropylbenzene hydroperoxide (Percumyl P), isopropylbenzene hydroperoxide (Percumyl H), and tert-butyl hydroperoxide (Perbutyl H); or α,α-bis(tert-butylperoxy-m-isopropyl)benzene (Perbutyl P), diisopropylbenzene peroxide (Percumyl D), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (Perhexa 25B), tert-butyl isopropyl peroxide (Perbutyl C), di-tert-butyl peroxide (Perbutyl D), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3 (Perhexyne 25B), tert-butyl peroxide (2-ethylhexanoate) (Perbutyl O) and other dialkyl peroxides; or ketone peroxides; or peroxyketal such as 4,4-di-(tert-butylperoxy) valerate (Perhexa V); or diacyl peroxides; or peroxydicarbonates; or organic peroxides such as peroxyesters; or azo compounds such as 2,2-azobisisobutyronitrile, 1,1'-(cyclohexane-1-1-carbonitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), etc. These may be used alone or in combination of two or more.

(成分(III)：極性樹脂) 就於無損硬化物之介電性能之範圍內賦予與特定基板之接著性等性能之觀點而言，本實施方式之樹脂組合物較佳為含有成分(III)：極性樹脂(成分(I)除外)。藉由含有極性樹脂，本實施方式之樹脂組合物存在與特定基板之接著性優異之傾向。於成分(III)為具有自由基反應性之極性樹脂之情形時，可根據反應性，任意地適當調整上述成分(II)自由基起始劑之量、或不添加成分(II)。 (Component (III): Polar resin) From the perspective of imparting properties such as adhesion to a specific substrate within the range of dielectric properties of the cured product without damaging it, the resin composition of the present embodiment preferably contains component (III): polar resin (excluding component (I)). By containing the polar resin, the resin composition of the present embodiment tends to have excellent adhesion to a specific substrate. When component (III) is a polar resin having free radical reactivity, the amount of the free radical initiator of component (II) can be appropriately adjusted according to the reactivity, or component (II) can be omitted.

作為成分(III)之所謂具有自由基反應性之極性樹脂，例如可例舉：聚合物中含有至少一個乙烯基及/或鹵元素之化合物之均聚物、或者上述含有乙烯基及/或鹵元素之化合物與任意其他化合物之共聚物。就本實施方式之樹脂組合物之介電性能之觀點而言，極性樹脂較佳為含有乙烯基之聚合物。The so-called free radical reactive polar resin as component (III) may be, for example, a homopolymer of a compound containing at least one vinyl group and/or a halogen element, or a copolymer of the above-mentioned compound containing a vinyl group and/or a halogen element and any other compound. From the perspective of the dielectric properties of the resin composition of the present embodiment, the polar resin is preferably a polymer containing a vinyl group.

上述所謂含有乙烯基之聚合物，可為含有包含乙烯基之重複單元之聚合物，亦可為與含有乙烯基及極性基之化合物之聚合物，亦可為藉由使含有極性基之化合物之各極性基反應而獲得之含有乙烯基之聚合物。作為含有乙烯基及極性基之化合物，例如可例舉但不限定於以下各者：(甲基)丙烯酸(於本發明中，「(甲基)丙烯酸意指甲基丙烯酸或丙烯酸」)、順丁烯二酸、順丁烯二酸單烷基酯、反丁烯二酸等含羧基之乙烯基單體，乙烯基磺酸、(甲基)烯丙基磺酸、甲基乙烯基磺酸、苯乙烯磺酸等含碸基之乙烯基單體，羥基苯乙烯、N-羥甲基(甲基)丙烯醯胺、(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯等含羥基之乙烯基單體，(甲基)丙烯醯基磷酸2-羥基乙酯、2-丙烯醯氧基乙基磷酸苯酯、2-丙烯醯氧基乙基膦酸等含磷酸基之乙烯基單體，羥基苯乙烯、N-羥甲基(甲基)丙烯醯胺、(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、聚乙二醇(甲基)丙烯酸酯、1-丁烯-3-醇等含羥基之乙烯基單體，(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二乙基胺基乙酯等含胺基之乙烯基單體，(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-丁基丙烯醯胺等含醯胺基之乙烯基單體，(甲基)丙烯腈、氰基苯乙烯、氰基丙烯酸酯等含腈基之乙烯基單體，甲基丙烯酸縮水甘油酯、(甲基)丙烯酸四氫糠酯、對乙烯基苯基苯基氧化物等含環氧基之乙烯基單體。作為含有鹵元素之化合物，例如可例舉但不限定於以下各者：氯乙烯、溴乙烯、偏二氯乙烯、烯丙基氯、氯苯乙烯、溴苯乙烯、二氯苯乙烯、氯甲基苯乙烯、四氟苯乙烯、氯丁二烯等。 The above-mentioned vinyl group-containing polymer may be a polymer containing a repeating unit containing a vinyl group, a polymer containing a compound containing a vinyl group and a polar group, or a vinyl group-containing polymer obtained by reacting the polar groups of a compound containing a polar group. Examples of compounds containing a vinyl group and a polar group include, but are not limited to, the following: (meth)acrylic acid (in the present invention, "(meth)acrylic acid means methacrylic acid or acrylic acid"), maleic acid, maleic acid monoalkyl esters, fumaric acid and other vinyl monomers containing a carboxyl group; vinyl sulfonic acid, (meth)allyl sulfonic acid, methylvinyl sulfonic acid, styrene sulfonic acid and other vinyl monomers containing a sulfonyl group; hydroxystyrene, N-hydroxymethyl (meth)acrylamide, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate and other vinyl monomers containing a hydroxyl group; vinyl monomers containing a phosphate group such as 2-hydroxyethyl (meth)acryloyl phosphate, 2-acryloyloxyethylphenyl phosphate, 2-acryloyloxyethylphosphonic acid and other vinyl monomers containing a phosphate group; Hydroxyl group-containing vinyl monomers such as hydroxystyrene, N-hydroxymethyl (meth)acrylamide, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, polyethylene glycol (meth)acrylate, 1-butene-3-ol, aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, amide-containing vinyl monomers such as (meth)acrylamide, N-methyl (meth)acrylamide, N-butylacrylamide, nitrile-containing vinyl monomers such as (meth)acrylonitrile, cyanostyrene, cyanoacrylate, epoxy group-containing vinyl monomers such as glycidyl methacrylate, tetrahydrofurfuryl (meth)acrylate, p-vinylphenyl phenyl oxide, etc. Examples of compounds containing halogen elements include, but are not limited to, the following: vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene, etc.

(成分(IV)：硬化劑) 於上述成分(III)之自由基反應性較低之情形時，就反應性之觀點而言，本實施方式之樹脂組合物較佳為含有成分(IV)：硬化劑(成分(II)除外)。成分(IV)硬化劑通常具有與成分(III)：極性樹脂反應而使樹脂組合物硬化之功能。所謂成分(III)與成分(IV)「反應」，意指各成分之極性基彼此具有共價鍵結性。極性基彼此反應時，例如若羧基之OH脫離，則原本之極性基發生改變或消失，但藉此形成共價鍵，此種情形屬於極性基彼此顯示「反應性」之定義範疇。就硬化功能之觀點而言，成分(IV)：硬化劑較佳為一分子鏈中含有至少2個以上能夠與成分(III)：極性樹脂之官能基反應之極性基。成分(IV)可單獨使用一種，亦可併用兩種以上。 (Component (IV): Hardener) In the case where the free radical reactivity of the above-mentioned component (III) is relatively low, from the viewpoint of reactivity, the resin composition of the present embodiment preferably contains component (IV): hardener (excluding component (II)). Component (IV) hardener generally has the function of reacting with component (III): polar resin to harden the resin composition. The so-called "reaction" between component (III) and component (IV) means that the polar groups of each component have covalent bonding properties. When polar groups react with each other, for example, if the OH of the carboxyl group is detached, the original polar group changes or disappears, but a covalent bond is formed thereby. This situation belongs to the definition category of polar groups showing "reactivity" with each other. From the perspective of curing function, component (IV): curing agent preferably has at least two polar groups in one molecular chain that can react with the functional groups of component (III): polar resin. Component (IV) can be used alone or in combination of two or more.

成分(III)及成分(IV)所含有之極性基之種類並無特別限定，例如可例舉：環氧基與羧基、羰基、酯基、咪唑基、羥基、胺基、硫醇基、苯并㗁𠯤基、碳二醯亞胺基、酚系羥基；胺基與選自由羧基、羰基、羥基、酸酐基、磺酸及醛基所組成之群中之任意者的組合；異氰酸基與選自由羥基、羧酸及酚系羥基所組成之群中之任意者的組合；酸酐基與羥基之組合；矽烷醇基與選自由羥基及羧酸基所組成之群中之任意者的組合；鹵基與選自由羧酸基、羧酸酯基、胺基、苯酚基及硫醇基所組成之群中之任意者的組合；烷氧基與選自由羥基、烷氧化物基及胺基所組成之群中之任意者的組合；順丁烯二醯亞胺基與氰酸基之組合等。至於該等極性基之鍵是成分(III)還是成分(IV)，可任意地選擇。 The types of polar groups contained in component (III) and component (IV) are not particularly limited, and examples thereof include: An epoxy group and a carboxyl group, a carbonyl group, an ester group, an imidazole group, a hydroxyl group, an amine group, a thiol group, a benzophenone group, a carbodiimide group, and a phenolic hydroxyl group; An amine group and any one selected from the group consisting of a carboxyl group, a carbonyl group, a hydroxyl group, an anhydride group, a sulfonic acid group, and an aldehyde group; An isocyanate group and any one selected from the group consisting of a hydroxyl group, a carboxylic acid group, and a phenolic hydroxyl group; An anhydride group and a hydroxyl group; A silanol group and any one selected from the group consisting of a hydroxyl group and a carboxylic acid group; A halogen group and any one selected from the group consisting of a carboxylic acid group, a carboxylate group, an amine group, a phenol group, and a thiol group; A combination of an alkoxy group and any one selected from the group consisting of a hydroxyl group, an alkoxide group, and an amino group; A combination of a succinimidyl group and a cyanate group, etc. As for whether the bond of the polar group is component (III) or component (IV), it can be selected arbitrarily.

又，於成分(III)之極性基與成分(IV)之極性基不直接反應之情形時，藉由添加觸媒等硬化促進劑而能夠反應，此種情形亦屬於顯示「反應性」之定義範疇。例如於成分(III)為含有環氧基之極性樹脂、成分(IV)為含有酸酐基之硬化劑之情形時，環氧基與酸酐基之反應性通常非常低，但藉由添加含有胺基之化合物作為硬化促進劑，從而成分(III)之環氧基與胺基反應，成分(III)之一部分或全部環氧基變成羥基。該羥基與成分(IV)硬化劑之酸酐基發生反應，藉此樹脂組合物硬化。 Furthermore, when the polar groups of component (III) and component (IV) do not react directly, they can react by adding a curing accelerator such as a catalyst, and this situation also falls within the definition of "reactivity". For example, when component (III) is a polar resin containing an epoxy group and component (IV) is a curing agent containing an acid anhydride group, the reactivity between the epoxy group and the acid anhydride group is usually very low, but by adding a compound containing an amino group as a curing accelerator, the epoxy group of component (III) reacts with the amino group, and part or all of the epoxy groups of component (III) become hydroxyl groups. The hydroxyl group reacts with the acid anhydride group of the curing agent of component (IV), thereby curing the resin composition.

就反應性之觀點而言，成分(III)極性樹脂與成分(IV)硬化劑之量比以極性基之莫耳(mol)比率計，成分(III)之極性基：成分(IV)之極性基較佳為1：0.01～1：20，更佳為1：0.05～1：15，進而較佳為1：0.1～1：10。From the viewpoint of reactivity, the amount ratio of the polar resin of component (III) to the hardener of component (IV) is preferably 1:0.01 to 1:20, more preferably 1:0.05 to 1:15, and even more preferably 1:0.1 to 1:10, based on the molar ratio of the polar groups.

作為成分(IV)：作為硬化劑的含有酯基之硬化劑例如可例舉但不限定於以下各者：DIC公司製造之EXB9451、EXB9460、EXB、9460S、HPC8000-65T、HPC8000H-65TM、EXB8000L-65TM、EXB8150-65T、EXB9416-70BK；Mitsubishi Chemical公司製造之YLH1026、DC808、YLH1026、YLH1030、YLH1048。As component (IV): Examples of hardeners containing an ester group as hardeners include, but are not limited to, the following: EXB9451, EXB9460, EXB, 9460S, HPC8000-65T, HPC8000H-65TM, EXB8000L-65TM, EXB8150-65T, EXB9416-70BK manufactured by DIC Corporation; YLH1026, DC808, YLH1026, YLH1030, YLH1048 manufactured by Mitsubishi Chemical Corporation.

作為成分(IV)：作為硬化劑的含有羥基之硬化劑例如可例舉但不限定於以下各者：MEH-7700、MEH-7810、MEH-7851；日本化藥公司製造之NHN、CBN、GPH；新日鐵住金化學公司製造之SN170、SN170、SN180、SN190、SN475、SN485、SN495、SN-495V、SN375；DIC公司製造之TD-2090、LA-7052、LA-7054、LA-1356、LA-3018-50P、EXB-9500等。As component (IV): Examples of hydroxyl-containing hardeners as hardeners include, but are not limited to, the following: MEH-7700, MEH-7810, MEH-7851; NHN, CBN, GPH manufactured by Nippon Kayaku Co., Ltd.; SN170, SN170, SN180, SN190, SN475, SN485, SN495, SN-495V, SN375 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; TD-2090, LA-7052, LA-7054, LA-1356, LA-3018-50P, EXB-9500 manufactured by DIC Corporation.

作為成分(IV)：作為硬化劑的含有苯并㗁𠯤基之硬化劑例如可例舉但不限定於以下各者：JFE Chemical公司製造之ODA-BOZ；昭和高分子公司製造之HFB2006M；四國化成工業公司製造之P-d、F-a。As component (IV): The curing agent containing a benzophenone group may be exemplified by, but not limited to, the following: ODA-BOZ manufactured by JFE Chemical Co., Ltd.; HFB2006M manufactured by Showa High Polymer Co., Ltd.; P-d and F-a manufactured by Shikoku Chemical Industries Co., Ltd.

作為成分(IV)：作為硬化劑的含有異氰酸基之硬化劑例如可例舉但不限定於以下各者：雙酚A二氰酸酯、聚苯酚氰酸酯、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-氰酸基)苯基丙烷、1,1-雙(4-氰酸基苯基甲烷)、雙(4-氰酸基-3,5-二甲基苯基)甲烷、1,3-雙(4-氰酸基苯基-1-(甲基亞乙基))苯、雙(4-氰酸基苯基)硫醚、及雙(4-氰酸基苯基)醚等二官能氰酸酯樹脂；自苯酚酚醛清漆及甲酚酚醛清漆等衍生之多官能氰酸酯樹脂；該等氰酸酯樹脂經部分三𠯤化而成之預聚物等。作為市售品，可例舉：Lonza Japan公司製造之PT30、PT60、ULL-950S、BA230、BA230S75等。As component (IV): the curing agent containing an isocyanate group may be exemplified by, but not limited to, the following: bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanato)phenylpropane, 1, Difunctional cyanate resins such as 1-bis(4-cyanatophenylmethane), bis(4-cyanato-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)sulfide, and bis(4-cyanatophenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; prepolymers of these cyanate resins partially tri-hydrated, etc. Examples of commercially available products include PT30, PT60, ULL-950S, BA230, and BA230S75 manufactured by Lonza Japan.

作為成分(IV)：作為硬化劑的含有碳二醯亞胺基之硬化劑例如可例舉但不限定於以下各者：Nisshinbo Chemical公司製造之V-03、V-07。Component (IV): The carbodiimide group-containing curing agent as a curing agent may be exemplified by, but not limited to, the following: V-03 and V-07 manufactured by Nisshinbo Chemical Co., Ltd.

作為成分(IV)：作為硬化劑的含有胺基之硬化劑例如可例舉但不限定於以下各者：4,4'-亞甲基雙(2,6-二甲基苯胺)、二苯基二胺基碸、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。作為市售品，可例舉：日本化藥公司製造之KAYABOND C-200S、KAYABOND C-100，Kayahard A-A、Kayahard A-B、Kayahard A-S；Mitsubishi Chemical公司製造之EPI-CURE W等。As component (IV): The amine-containing curing agent as a curing agent may be exemplified by, but not limited to, the following: 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfonate, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfonate, 3,3'-diaminodiphenylsulfonate, 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-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfonate, bis(4-(3-aminophenoxy)phenyl)sulfonate, etc. Examples of commercially available products include KAYABOND C-200S, KAYABOND C-100, Kayahard A-A, Kayahard A-B, and Kayahard A-S manufactured by Nippon Kayaku Co., Ltd. and EPI-CURE W manufactured by Mitsubishi Chemical Co., Ltd.

又，就反應性之觀點而言，作為胺基，較佳為一級胺及/或二級胺，更佳為一級胺。Furthermore, from the viewpoint of reactivity, the amine group is preferably a primary amine and/or a diamine, and more preferably a primary amine.

作為成分(IV)：作為硬化劑的含有酸酐基之硬化劑例如可例舉但不限定於以下各者：鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、甲基耐地酸酐、氫化甲基耐地酸酐、三烷基四氫鄰苯二甲酸酐、十二烯基琥珀酸酐、5-(2,5-二側氧四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、偏苯三甲酸酐、均苯四甲酸二酐、二苯甲酮四羧酸二酐、聯苯四羧酸二酐、萘四羧酸二酐、氧二鄰苯二甲酸二酐、3,3',4,4'-二苯基碸四羧酸二酐、1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二側氧-3-呋喃基)-萘并[1,2-C]呋喃-1,3-二酮、乙二醇雙(脫水偏苯三酸酯)、苯乙烯與順丁烯二酸共聚而成之苯乙烯-順丁烯二酸樹脂等聚合物型酸酐等。As component (IV): Examples of curing agents containing an acid anhydride group as curing agents include, but are not limited to, the following: phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnalidic anhydride, hydrogenated methylnalidic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxytetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride , pyromellitic acid dianhydride, benzophenone 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-dioxy-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(dehydrated trimellitate), styrene-maleic acid resin obtained by copolymerization of styrene and maleic acid, and other polymer-type acid anhydrides.

又，含有至少2個上述具有自由基反應性之結構之化合物亦具有與成分(III)反應而使樹脂組合物硬化之功能。該化合物亦可用作成分(IV)之硬化劑。作為含有至少2個具有自由基反應性之結構之化合物，例如可例舉但不限定於以下各者：異氰尿酸三烯丙酯(Mitsubishi Chemical公司製造，TAIC)、異三聚氰酸三(2-羥基乙基)酯，反丁烯二酸二烯丙酯、己二酸二烯丙酯、檸檬酸三烯丙酯、六氫鄰苯二甲酸二烯丙酯等烯丙基單體等。 Furthermore, the compound containing at least two structures having free radical reactivity also has the function of reacting with component (III) to cure the resin composition. The compound can also be used as a curing agent for component (IV). As the compound containing at least two structures having free radical reactivity, for example, but not limited to, the following can be cited: triallyl isocyanurate (manufactured by Mitsubishi Chemical Co., Ltd., TAIC), tris(2-hydroxyethyl)isocyanurate, diallyl fumarate, diallyl adipate, triallyl citrate, diallyl hexahydrophthalate and other allyl monomers, etc.

(較佳之成分(III)之材料) 於本實施方式之樹脂組合物含有成分(III)之情形時，作為成分(III)極性樹脂，就接著性之觀點而言，較佳為選自由環氧系樹脂、聚醯亞胺系樹脂、聚苯醚系樹脂、液晶聚酯系樹脂、及氟系樹脂所組成之群中之至少一種以上。更佳為選自由環氧系樹脂、聚醯亞胺系樹脂、聚苯醚系樹脂所組成之群中之至少一種以上。 (Preferred materials for component (III)) When the resin composition of the present embodiment contains component (III), the polar resin of component (III) is preferably at least one selected from the group consisting of epoxy resins, polyimide resins, polyphenylene ether resins, liquid crystal polyester resins, and fluorine resins from the viewpoint of adhesion. More preferably, it is at least one selected from the group consisting of epoxy resins, polyimide resins, and polyphenylene ether resins.

作為聚醯亞胺系樹脂，只要為重複單元中含有醯亞胺鍵、且屬於稱作聚醯亞胺樹脂之範疇者即可。例如可例舉使四羧酸或其二酐與二胺進行縮聚(醯亞胺鍵)而獲得之一般性之聚醯亞胺結構。就硬化性之觀點而言，較佳為於上述聚醯亞胺結構之末端具有不飽和基。作為末端具有不飽和基之聚醯亞胺樹脂，例如可例舉：順丁烯二醯亞胺型聚醯亞胺樹脂、耐地醯亞胺(nadiimide)型聚醯亞胺樹脂、烯丙基耐地醯亞胺型聚醯亞胺樹脂等。作為四羧酸或其二酐，例如可例舉但不限定於以下各者：芳香族四羧酸二酐、脂環式四羧酸二酐、脂肪族四羧酸二酐等。該等可單獨使用一種，亦可併用兩種以上。作為二胺，並無特別限定，例如可例舉通常用於合成聚醯亞胺之芳香族二胺類、脂環式二胺類、脂肪族二胺類等。該等可單獨使用一種，亦可併用兩種以上。 As a polyimide resin, any resin that contains an imide bond in the repeating unit and belongs to the category of polyimide resins can be used. For example, a general polyimide structure obtained by condensing tetracarboxylic acid or its dianhydride with diamine (imide bond) can be cited. From the perspective of curability, it is preferred that the terminal of the above polyimide structure has an unsaturated group. As polyimide resins having an unsaturated group at the terminal, for example, cis-butylene diimide type polyimide resins, nadiimide type polyimide resins, allyl nadiimide type polyimide resins, etc. can be cited. As tetracarboxylic acid or its dianhydride, for example, but not limited to the following: aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, etc. These can be used alone or in combination of two or more. As diamine, there is no particular limitation, for example, aromatic diamines, alicyclic diamines, aliphatic diamines, etc., which are commonly used in the synthesis of polyimide, can be cited. These can be used alone or in combination of two or more.

又，就低介電常數化及低介電損耗因數化之觀點而言，上述四羧酸或其二酐、二胺之至少一者可含有1個或複數個選自由氟基、三氟甲基、羥基、碸基、羰基、雜環、長鏈烷基、烯丙基等所組成之群中之至少一種官能基。Furthermore, from the viewpoint of lowering the dielectric constant and the dielectric dissipation factor, at least one of the above-mentioned tetracarboxylic acids or their dianhydrides or diamines may contain one or more functional groups selected from the group consisting of fluoro, trifluoromethyl, hydroxyl, sulfonyl, carbonyl, heterocyclic, long-chain alkyl, allyl, etc.

又，作為聚醯亞胺系樹脂，亦可使用市售之聚醯亞胺系樹脂，例如可例舉但不限定於以下各者：Neopulim(註冊商標)C-3650(Mitsubishi Gas Chemical股份有限公司製造，商品名)、Neopulim C-3G30(Mitsubishi Gas Chemical股份有限公司製造，商品名)、Neopulim C-3450(Mitsubishi Gas Chemical股份有限公司製造，商品名)、Neopulim P500(Mitsubishi Gas Chemical股份有限公司製造，商品名)；BT(雙順丁烯二醯亞胺-三𠯤)系列(Mitsubishi Gas Chemical股份有限公司製造)；JL-20(新日本理化製造，商品名)(該等聚醯亞胺樹脂之清漆中可含有二氧化矽)，新日本理化公司製造之Liquacoat SN20、Liquacoat PN20；I.S.T公司製造之Pyre-ML；宇部興產公司製造之UPIA-AT、UPIA-ST、UPIA-NF、UPIA-LB；日立化成公司製造之PIX-1400、PIX-3400、PI2525、PI2610、HD-3000、AS-2600；昭和電工股份有限公司製造之HPC-5000、HPC-5012、HPC-1000、HPC-5020、HPC-3010、HPC-6000、HPC-9000、HCI-7000、HCI-1000S、HCI-1200E、HCI-1300；大和化成工業股份有限公司製造之BMI-2300；新日本化藥股份有限公司製造之MIR-3000。In addition, as the polyimide resin, commercially available polyimide resins may be used, for example, but not limited to the following: Neopulim (registered trademark) C-3650 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), Neopulim C-3G30 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), Neopulim C-3450 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), Neopulim P500 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name); BT (bis(butylene)diimide-tris(imide)) series (manufactured by Mitsubishi Gas Chemical Co., Ltd.); JL-20 (manufactured by Shin Nippon Rika Co., Ltd., trade name) (the varnish of these polyimide resins may contain silicon dioxide), Liquacoat 900 (manufactured by Shin Nippon Rika Co., Ltd.); SN20, Liquacoat PN20; Pyre-ML manufactured by I.S.T.; UPIA-AT, UPIA-ST, UPIA-NF, UPIA-LB manufactured by Ube Industries; PIX-1400, PIX-3400, PI2525, PI2610, HD-3000, AS-2600 manufactured by Hitachi Chemical; HPC-5000, HPC-5012, HPC-1000, HPC-5020, HPC-3010, HPC-6000, HPC-9000, HCI-7000, HCI-1000S, HCI-1200E, HCI-1300 manufactured by Showa Denko Co., Ltd.; BMI-2300 manufactured by Yamato Chemical Industries Co., Ltd.; MIR-3000 manufactured by Shin Nippon Kayaku Co., Ltd.

作為成分(III)之聚苯醚系樹脂，只要為屬於稱作聚苯醚樹脂之範疇者即可，包含苯醚單元作為重複結構單元。又，亦可包含苯醚單元以外之其他結構單元。The polyphenylene ether resin as component (III) may be any resin that falls within the category of polyphenylene ether resins and contains phenylene ether units as repeating structural units. Furthermore, it may contain structural units other than phenylene ether units.

作為包含苯醚單元之均聚物，伸苯基單元中之伸苯基是否具有取代基並無特別限制。作為取代基，例如可例舉：乙基、丙基、異丙基、丁基、異丁基、第三丁基等丙烯醯基；環己基等環狀烷基；乙烯基、烯丙基、異丙烯基、1-丁烯基、1-戊烯基、對乙烯基苯基、對異丙烯基苯基、間乙烯基苯基、間異丙烯基苯基、鄰乙烯基苯基、鄰異丙烯基苯基、對乙烯基苄基、對異丙烯基苄基、間乙烯基苄基、間異丙烯基苄基、鄰乙烯基苄基、鄰異丙烯基苄基、對乙烯基苯基乙烯基、對乙烯基苯基丙烯基、對乙烯基苯基丁烯基、間乙烯基苯基乙烯基、間乙烯基苯基丙烯基、間乙烯基苯基丁烯基、鄰乙烯基苯基乙烯基、鄰乙烯基苯基丙烯基、鄰乙烯基苯基丁烯基、甲基丙烯醯基、丙烯醯基、2-乙基丙烯醯基、2-羥基甲基丙烯醯基等含不飽和鍵之取代基；羥基、羧基、羰基、硫羰基、醯鹵化物基、酸酐基、羧酸基、硫羧酸基、醛基、硫醛基、羧酸酯基、醯胺基、磺酸基、磺酸酯基、磷酸基、磷酸酯基、胺基、亞胺基、腈基、吡啶基、喹啉基、環氧基、硫代環氧基、硫基(sulfide)、異氰酸基、異硫氰酸基、鹵化矽基、矽烷醇基、烷氧基矽基、鹵化錫基、硼酸基、含硼基、硼酸鹽基、烷氧基錫基及苯基錫基等含官能基之取代基。就硬化性之觀點而言，為了具有自由基反應性及/或與成分(IV)硬化劑之反應性，較佳為具有任意之極性基。As a homopolymer containing a phenylene ether unit, whether the phenylene group in the phenylene group unit has a substituent is not particularly limited. Examples of the substituent include: ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and other acryl groups; cycloalkyl groups such as cyclohexyl; vinyl, allyl, isopropenyl, 1-butenyl, 1-pentenyl, p-vinylphenyl, p-isopropenylphenyl, m-vinylphenyl, m-isopropenylphenyl, o-vinylphenyl, o-isopropenylphenyl, p-vinylbenzyl, p-isopropenylbenzyl, m-vinylbenzyl, m-isopropenylbenzyl, o-vinylbenzyl, o-isopropenylbenzyl, p-vinylphenylvinyl, p-vinylphenylpropenyl, p-vinylphenylbutenyl, m-vinylphenylvinyl, m-vinylphenylpropenyl, m-vinylphenylbutenyl, o-vinylphenylvinyl, Substituents containing unsaturated bonds such as o-vinylphenylpropenyl, o-vinylphenylbutenyl, methacryl, acryl, 2-ethylacryl, 2-hydroxymethacryl, etc.; hydroxyl, carboxyl, carbonyl, thiocarbonyl, acyl halide, anhydride, carboxylic acid, thiocarboxylic acid, aldehyde, thialdehyde, carboxylate, amide, sulfonic acid, sulfonic acid Substituents containing functional groups such as ester groups, phosphate groups, phosphate ester groups, amino groups, imine groups, nitrile groups, pyridyl groups, quinol groups, epoxy groups, thioepoxy groups, sulfide groups, isocyanate groups, isothiocyanate groups, silyl halides, silanol groups, alkoxysilyl groups, tin halides, boric acid groups, boron-containing groups, borate groups, alkoxytin groups, and phenyltin groups. From the viewpoint of curability, in order to have free radical reactivity and/or reactivity with the component (IV) curing agent, it is preferred to have any polar group.

就本實施方式之樹脂組合物之硬化性之觀點而言，作為成分(III)之聚苯醚系樹脂之分子量較佳為100000以下，更佳為50000以下，進而較佳為10000以下。又，聚苯醚系樹脂可為直鏈狀結構，亦可為交聯或分支結構。From the viewpoint of curability of the resin composition of the present embodiment, the molecular weight of the polyphenylene ether resin as component (III) is preferably 100,000 or less, more preferably 50,000 or less, and further preferably 10,000 or less. The polyphenylene ether resin may have a linear structure, or a cross-linked or branched structure.

作為成分(III)之液晶聚酯系樹脂只要為形成各向異性熔融相之聚酯、且屬於稱作液晶聚酯樹脂之範疇者即可。例如可例舉：Eastman Kodak公司製造之「X7G」、Dartco公司製造之「Xyday」、住友化學公司製造之「Ekonol」、Celanese公司製造之「Vectra」等。 The liquid crystal polyester resin as component (III) can be any polyester that forms an anisotropic melt phase and belongs to the category of liquid crystal polyester resins. For example, "X7G" manufactured by Eastman Kodak, "Xyday" manufactured by Dartco, "Ekonol" manufactured by Sumitomo Chemical, "Vectra" manufactured by Celanese, etc.

作為成分(III)之氟系樹脂只要為屬於稱作氟樹脂之範疇者即可，為含有氟基之烯烴系聚合物。作為該氟系樹脂，例如可例舉但不限定於以下各者：聚四氟乙烯、全氟烷氧基烷烴、乙烯-四氟乙烯共聚物、全氟乙烯-丙烯共聚物、聚偏二氟乙烯、聚氯三氟乙烯、乙烯-氯三氟乙烯共聚物等。 The fluorine-based resin as component (III) can be any fluorine-based resin, which is an olefin polymer containing a fluorine group. Examples of the fluorine-based resin include, but are not limited to, polytetrafluoroethylene, perfluoroalkoxyalkane, ethylene-tetrafluoroethylene copolymer, perfluoroethylene-propylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer, etc.

作為成分(III)之環氧系樹脂只要為屬於稱作環氧樹脂之範疇者即可，就強度觀點而言，較佳為一分子中含有2個以上之環氧基。環氧樹脂可單獨使用一種，亦可將兩種以上組合使用。作為環氧樹脂，例如可例舉但不限定於以下各者：聯二甲苯酚型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚AF型環氧樹脂、二環戊二烯型環氧樹脂、三苯酚型環氧樹脂、萘酚酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂、第三丁基-兒茶酚型環氧樹脂、萘型環氧樹脂、萘酚型環氧樹脂、蒽型環氧樹脂、縮水甘油胺型環氧樹脂、縮水甘油酯型環氧樹脂、甲酚酚醛清漆型環氧樹脂、聯苯型環氧樹脂、脂環式環氧樹脂、雜環式環氧樹脂、含螺環之環氧樹脂、環己烷型環氧樹脂、環己烷二甲醇型環氧樹脂、伸萘基醚型環氧樹脂、三羥甲基型環氧樹脂、四苯基乙烷型環氧樹脂等。 The epoxy resin as component (III) may be any one that falls within the category of epoxy resins, and preferably contains two or more epoxy groups in one molecule from the viewpoint of strength. The epoxy resin may be used alone or in combination of two or more. Examples of epoxy resins include, but are not limited to, 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, tert-butyl-catechol epoxy resins, naphthalene epoxy resins, Naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spirocyclic epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthyl ether type epoxy resin, trihydroxymethyl type epoxy resin, tetraphenylethane type epoxy resin, etc.

又，就反應性之觀點而言，於使用環氧樹脂作為成分(III)之情形時，較佳為一併含有成分(IV)硬化劑。此時，作為成分(IV)硬化劑所含有之極性基，例如可例舉：羧基、咪唑基、羥基、胺基、硫醇基、苯并㗁𠯤基、碳二醯亞胺基，就反應性之觀點而言，較佳為羧基、咪唑基、羥基、苯并㗁𠯤基、碳二醯亞胺基；就本實施方式之樹脂組合物之介電性能之觀點而言，更佳為羥基、羧基、咪唑基、苯并㗁𠯤基、碳二醯亞胺基，進而較佳為羥基、羧基、碳二醯亞胺基。Furthermore, from the viewpoint of reactivity, when an epoxy resin is used as component (III), it is preferably contained together with component (IV) of the curing agent. In this case, the polar group contained in the component (IV) of the curing agent may include, for example, a carboxyl group, an imidazole group, a hydroxyl group, an amino group, a thiol group, a benzothiol group, and a carbodiimide group. From the viewpoint of reactivity, a carboxyl group, an imidazole group, a hydroxyl group, a benzothiol group, and a carbodiimide group are preferred. From the viewpoint of the dielectric properties of the resin composition of the present embodiment, a hydroxyl group, a carboxyl group, an imidazole group, a benzothiol group, and a carbodiimide group are more preferred, and a hydroxyl group, a carboxyl group, and a carbodiimide group are further preferred.

又，於使用自由基反應性不同之2種以上之極性樹脂作為成分(III)之情形時，就硬化性之觀點而言，較佳為併用成分(II)：自由基起始劑與成分(IV)：硬化劑。例如於使用自由基反應性優異之順丁烯二醯亞胺型聚醯亞胺樹脂及不具有自由基反應性之雙酚A環氧樹脂作為成分(III)之情形時，就硬化性之觀點而言，較佳為添加上述成分(II)自由基起始劑與上述成分(IV)硬化劑。Furthermore, when two or more polar resins with different free radical reactivity are used as component (III), it is preferred to use component (II): free radical initiator and component (IV): curing agent in combination from the viewpoint of curability. For example, when a succinimidyl polyimide resin with excellent free radical reactivity and a bisphenol A epoxy resin without free radical reactivity are used as component (III), it is preferred to add the free radical initiator of component (II) and the curing agent of component (IV) from the viewpoint of curability.

又，於使用高熔點及高剛性之極性樹脂作為成分(III)：極性樹脂之情形時，本實施方式之樹脂組合物亦可不含成分(IV)。作為成分(III)之高熔點及高剛性之極性樹脂例如可例舉：液晶聚酯系樹脂、聚四氟乙烯等氟系樹脂。藉由使成分(III)為高熔點及高剛性，存在即便於不含成分(IV)之情形時亦能夠具有實用所需強度之傾向。 Furthermore, when a polar resin with a high melting point and high rigidity is used as component (III): polar resin, the resin composition of the present embodiment may not contain component (IV). Examples of polar resins with a high melting point and high rigidity as component (III) include liquid crystal polyester resins, fluorine resins such as polytetrafluoroethylene, etc. By making component (III) high melting point and high rigidity, there is a tendency to have the strength required for practical use even when component (IV) is not contained.

(成分(I)～(IV)之含量) 本實施方式之樹脂組合物含有共軛二烯系共聚物(成分(I))與選自由上述成分(II)～(IV)所組成之群中之至少一種成分。於將成分(I)設為100質量份時，含量較佳為下述數值範圍。成分(II)：較佳為0.01質量份～200質量份，更佳為0.05質量份～150質量份，進而較佳為0.10質量份～100質量份。成分(III)：較佳為5質量份～2000質量份，更佳為10質量份～1000質量份，進而較佳為30質量份～500質量份。成分(IV)：較佳為5質量份～2000質量份，更佳為10質量份～1000質量份，進而較佳為30質量份～500質量份。 (Content of components (I) to (IV)) The resin composition of the present embodiment contains a covalent diene copolymer (component (I)) and at least one component selected from the group consisting of the above-mentioned components (II) to (IV). When component (I) is set to 100 parts by mass, the content is preferably in the following numerical range. Component (II): preferably 0.01 parts by mass to 200 parts by mass, more preferably 0.05 parts by mass to 150 parts by mass, and further preferably 0.10 parts by mass to 100 parts by mass. Component (III): preferably 5 parts by mass to 2000 parts by mass, more preferably 10 parts by mass to 1000 parts by mass, and further preferably 30 parts by mass to 500 parts by mass. Component (IV): preferably 5 to 2000 parts by mass, more preferably 10 to 1000 parts by mass, and even more preferably 30 to 500 parts by mass.

(成分(V)：添加劑) 本實施方式之樹脂組合物可進而含有硬化促進劑、填料、阻燃劑等各種添加劑作為成分(V)。又，作為成分(I)氫化共軛二烯系共聚物之添加劑所含有者亦與上述樹脂組合物之成分(V)同義。 (Component (V): additive) The resin composition of this embodiment may further contain various additives such as a curing accelerator, a filler, a flame retardant, etc. as component (V). In addition, the additive contained in the hydrogenated covalent diene copolymer as component (I) is also synonymous with the component (V) of the above-mentioned resin composition.

硬化促進劑係基於促進上述各成分間之反應性之目的而添加，可使用先前公知者。例如可例舉：磷系硬化促進劑、胺系硬化促進劑、咪唑系硬化促進劑、胍系硬化促進劑、金屬系硬化促進劑等。硬化促進劑可單獨使用一種，亦可將兩種以上組合使用。 The hardening accelerator is added for the purpose of promoting the reactivity between the above-mentioned components, and previously known ones can be used. For example, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, metal-based hardening accelerators, etc. The hardening accelerator can be used alone or in combination of two or more.

作為磷系硬化促進劑，例如可例舉但不限定於以下各者：三苯基膦、鏻硼酸鹽化合物、四苯基鏻四苯基硼酸鹽、正丁基鏻四苯基硼酸鹽、四丁基鏻癸酸鹽、(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，較佳為三苯基膦、四丁基鏻癸酸鹽。Examples of phosphorus-based hardening accelerators include, but are not limited to, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., preferably triphenylphosphine and tetrabutylphosphonium decanoate.

作為胺系硬化促進劑，例如可例舉但不限定於以下各者：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)-十一烯等，較佳為4-二甲基胺基吡啶、1,8-二氮雜雙環(5,4,0)-十一烯。Examples of the amine-based curing accelerator include, but are not limited to, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, preferably 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene.

作為咪唑系硬化促進劑，例如可例舉但不限定於以下各者：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酸鹽、1-氰基乙基-2-苯基咪唑鎓偏苯三酸鹽、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基對稱三𠯤、2,4-二胺基-6-[2'-十一烷基咪唑基-(1')]-乙基對稱三𠯤、2,4-二胺基-6-[2'-乙基-4'-甲基咪唑基-(1')]-乙基對稱三𠯤、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基對稱三𠯤異三聚氰酸加成物、2-苯基咪唑異三聚氰酸加成物、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-吡咯并[1,2-a]苯并咪唑、1-十二烷基-2-甲基-3-苄基咪唑鎓氯化物、2-甲基咪唑啉、2-苯基咪唑啉等咪唑化合物、及咪唑化合物與環氧樹脂之加成物，較佳為2-乙基-4-甲基咪唑、1-苄基-2-苯基咪唑。作為咪唑系硬化促進劑，亦可使用市售品，例如可例舉Mitsubishi Chemical公司製造之P200-H50等。 Examples of imidazole-based hardening accelerators include, but are not limited to, 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 trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl symmetric tris( ... 4-Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl symmetric tris(iodine), 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl symmetric tris(iodine), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl symmetric tris(iodine) isocyanuric acid adduct, 2-phenylimidazolyl isocyanuric acid adduct, 2-phenyl-4,5-dihydroxy Imidazole compounds such as 2-ethyl-4-methylimidazole, 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 and epoxy resins are preferred, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole. As imidazole-based hardening accelerators, commercially available products may also be used, such as P200-H50 manufactured by Mitsubishi Chemical Co., Ltd.

作為胍系硬化促進劑，例如可例舉但不限定於以下各者：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，較佳為雙氰胺、1,5,7-三氮雜雙環[4.4.0]癸-5-烯。Examples of guanidine-based hardening accelerators include, but are not limited to, dicyandiamide, 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, 1-(o-tolyl)biguanidine, etc., preferably dicyanamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

作為金屬系硬化促進劑，例如可例舉但不限定於以下各者：鈷、銅、鋅、鐵、鎳、錳、錫等金屬之有機金屬錯合物或有機金屬鹽。作為有機金屬錯合物之具體例，可例舉：乙醯丙酮酸鈷(II)、乙醯丙酮酸鈷(III)等有機鈷錯合物，乙醯丙酮酸銅(II)等有機銅錯合物，乙醯丙酮酸鋅(II)等有機鋅錯合物，乙醯丙酮酸鐵(III)等有機鐵錯合物，乙醯丙酮酸鎳(II)等有機鎳錯合物，乙醯丙酮酸錳(II)等有機錳錯合物等。作為有機金屬鹽，例如可例舉：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 but are not limited to the following: organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include 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. As the organic metal salt, for example, zinc octylate, tin octylate, zinc cycloalkanoate, cobalt cycloalkanoate, tin stearate, zinc stearate, and the like.

作為填料，例如可例舉但不限定於以下各者：二氧化矽、碳酸鈣、碳酸鎂、氫氧化鎂、氫氧化鋁、硫酸鈣、硫酸鋇、碳黑、玻璃纖維、玻璃珠、玻璃氣球、玻璃鱗片、石墨、氧化鈦、鈦酸鉀鬚晶、碳纖維、氧化鋁、高嶺黏土、矽酸、矽酸鈣、石英、雲母、滑石、黏土、氧化鋯、鈦酸鉀、氧化鋁、金屬粒子等無機填充劑；木製碎片、木製粉末、紙漿、纖維素奈米纖維等有機填料。該等可單獨使用一種，或將複數種組合使用。作為該等填料之形狀，可為鱗片狀、球狀、粒狀、粉體、不定形狀等任意者，並無特別限制。本實施方式之樹脂組合物或硬化物於成形時等多會暴露於高溫下，為了防止因該溫度變化引起之收縮、成形體變形，填料之線膨脹係數宜較小。就降低線膨脹係數之觀點而言，填料較佳為二氧化矽，作為二氧化矽，例如可例舉：非晶質二氧化矽、熔融二氧化矽、晶性二氧化矽、合成二氧化矽、中空二氧化矽等。 As fillers, for example, but not limited to the following, there can be cited: inorganic fillers such as silicon dioxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, calcium sulfate, barium sulfate, carbon black, glass fiber, glass beads, glass balloons, glass scales, graphite, titanium oxide, potassium titanium oxide whiskers, carbon fiber, aluminum oxide, kaolin clay, silicic acid, calcium silicate, quartz, mica, talc, clay, zirconium oxide, potassium titanium oxide, aluminum oxide, metal particles, etc.; organic fillers such as wood chips, wood powder, pulp, cellulose nanofibers, etc. These can be used alone or in combination. The shapes of the fillers may be any of scales, spheres, particles, powders, and irregular shapes, without particular limitation. The resin composition or cured product of the present embodiment is often exposed to high temperatures during molding, and in order to prevent shrinkage and deformation of the molded body caused by the temperature change, the linear expansion coefficient of the filler should be smaller. From the perspective of reducing the linear expansion coefficient, the filler is preferably silica, and examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica.

作為阻燃劑，例如可例舉但不限定於以下各者：溴化合物等鹵素系阻燃劑、芳香族化合物等磷系阻燃劑、金屬氫氧化物、烷基磺酸鹽、三氧化銻、氫氧化鋁、氫氧化鎂、硼酸鋅、六溴苯、十溴二苯基乙烷、4,4-二溴聯苯、伸乙基雙四溴鄰苯二甲醯亞胺等包含芳香族溴化合物之阻燃劑等。該等阻燃劑可單獨使用一種或將兩種以上組合使用。上述阻燃劑之中，亦包括其本身所表現出之阻燃性效果較低，但藉由與其他阻燃劑併用而相輔相成地發揮更優異效果之所謂阻燃助劑。 As flame retardants, for example, but not limited to the following: halogen flame retardants such as bromine compounds, phosphorus flame retardants such as aromatic compounds, metal hydroxides, alkyl sulfonates, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, hexabromobenzene, decabromodiphenylethane, 4,4-dibromobiphenyl, ethylenediamine, etc., flame retardants containing aromatic bromine compounds, etc. These flame retardants can be used alone or in combination of two or more. Among the above flame retardants, there are also so-called flame retardant additives that have a lower flame retardant effect by themselves, but can play a better effect by complementing other flame retardants.

填料、阻燃劑亦可使用預先利用矽烷偶合劑等表面處理劑進行表面處理之類型。作為表面處理劑，例如可例舉：含氟矽烷偶合劑、胺基矽烷系偶合劑、環氧矽烷系偶合劑、巰基矽烷系偶合劑、矽烷系偶合劑、烷氧基矽烷、有機矽氮烷化合物、鈦酸酯系偶合劑等。該等可單獨使用一種或將複數種組合使用。 Fillers and flame retardants can also be used in the type that is pre-surface treated with a surface treatment agent such as a silane coupling agent. As surface treatment agents, for example: 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, titanium ester-based coupling agents, etc. These can be used alone or in combination.

作為其他添加劑，只要為樹脂組合物及/或硬化物之調配中常用者，則無特別限制。作為其他添加劑，例如可例舉但不限定於以下各者：碳黑、氧化鈦等顏料及/或著色劑；硬脂酸、山萮酸、硬脂酸鋅、硬脂酸鈣、硬脂酸鎂、伸乙基雙硬脂醯胺等潤滑劑；離型劑；有機聚矽氧烷、苯二甲酸酯系或己二酸酯化合物、壬二酸酯化合物等脂肪酸酯系、礦物油等塑化劑；受阻酚系、磷系熱穩定劑等抗氧化劑；受阻胺系光穩定劑；苯并***系紫外線吸收劑；抗靜電劑；有機填充劑；增黏劑；消泡劑；調平劑；密著性賦予劑等樹脂添加劑；其他添加劑或該等之混合物等。就上述低介電常數及低介電損耗因數化之觀點而言，本實施方式之樹脂組合物存在較佳為不含顏料、著色劑、潤滑劑、離型劑、抗靜電劑之傾向。 As other additives, there are no particular restrictions as long as they are commonly used in the formulation of resin compositions and/or cured products. As other additives, for example, but not limited to the following: pigments and/or coloring agents such as carbon black and titanium oxide; lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, and ethyl distearate; release agents; organic polysiloxanes, phthalate or adipic acid compounds, azelaic acid esters, Fatty acid esters such as compounds, plasticizers such as mineral oils; antioxidants such as hindered phenols and phosphorus heat stabilizers; hindered amine light stabilizers; benzotriazole ultraviolet absorbers; antistatic agents; organic fillers; thickeners; defoamers; leveling agents; adhesion agents and other resin additives; other additives or mixtures thereof. From the perspective of the above-mentioned low dielectric constant and low dielectric loss factor, the resin composition of this embodiment has a tendency to be preferably free of pigments, colorants, lubricants, release agents, and antistatic agents.

本實施方式中之所謂樹脂組合物，可為將各成分熔融混練而成者，亦可為使各成分溶解於能夠溶解各成分之溶劑並進行攪拌而成者(以下稱為「清漆」)，就操作性之觀點而言，較佳為清漆。作為構成清漆之溶劑，例如可例舉：丙酮、甲基乙基酮(MEK)、環己酮、γ-丁內酯等酮類；乙酸乙酯、乙酸丁酯、乙酸溶纖劑、丙二醇單甲醚乙酸酯、卡必醇乙酸酯及二乙二醇單乙酸酯等乙酸酯類；溶纖劑及丁基卡必醇等卡必醇類；甲苯及二甲苯等芳香族烴類；二甲基甲醯胺、二甲基乙醯胺(DMAc)及N-甲基吡咯啶酮等醯胺系溶劑等。有機溶劑可單獨使用一種，亦可將兩種以上組合使用。 The resin composition in the present embodiment may be obtained by melting and kneading the components, or by dissolving the components in a solvent capable of dissolving the components and stirring (hereinafter referred to as "varnish"). From the viewpoint of operability, varnish is preferred. As the solvent constituting the varnish, for example, ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, and γ-butyrolactone; acetates such as ethyl acetate, butyl acetate, acetic acid solvent, propylene glycol monomethyl ether acetate, carbitol acetate, and diethylene glycol monoacetate; carbitols such as solvent and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone, etc. Organic solvents can be used alone or in combination of two or more.

(樹脂組合物之製造方法) 本實施方式之樹脂組合物之製造方法並無特別限制，可利用公知方法。例如可例舉：使用班布里混合機、單螺桿擠出機、雙螺桿擠出機、雙向捏合機、多螺桿擠出機等一般之混合機將各成分熔融混練之方法；將各成分溶解或分散混合後加熱去除溶劑之方法等；就製成後述預浸體、片材等適宜用作電子電路基板用材料之成形體之加工性之觀點而言，較佳為將各成分溶解或分散混合後加熱去除溶劑之方法。 (Manufacturing method of resin composition) The manufacturing method of the resin composition of the present embodiment is not particularly limited, and a known method can be used. For example, there can be cited: a method of melting and kneading the components using a general mixer such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a bidirectional kneader, a multi-screw extruder, etc.; a method of heating and removing the solvent after dissolving or dispersing and mixing the components, etc.; from the perspective of processability of forming a molded body suitable for use as a material for an electronic circuit substrate such as a prepreg or sheet described later, a method of heating and removing the solvent after dissolving or dispersing and mixing the components is preferred.

[硬化物] 本實施方式之硬化物為上述本實施方式之樹脂組合物之硬化物，含有上述成分(I)之共軛二烯系共聚物。又，本實施方式之硬化物藉由使本實施方式之樹脂組合物於任意溫度下進行任意時間之硬化反應而獲得。除了完全硬化之形態，僅使一部分樹脂組合物硬化而包含未硬化成分之形態(半硬化)亦包含於概念內。於後述積層體之製造過程中，亦可實施使硬化物進一步硬化之步驟。本實施方式之硬化物之硬化步驟之反應溫度較佳為80℃以上，更佳為100℃以上，進而較佳為120℃以上。作為反應時間，較佳為10～240分鐘，更佳為20～230分鐘，進而較佳為30～220分鐘。於本實施方式之樹脂組合物為清漆之情形時，較佳為去除溶劑後進行硬化反應。作為乾燥方法，可藉由加熱、吹送熱風等先前公知之方法實施，較佳為於比硬化反應溫度低之溫度下進行，較佳為乾燥至樹脂組合物中之溶劑量變為10質量%以下、更佳為5質量%以下。 [Cured product] The cured product of the present embodiment is a cured product of the resin composition of the present embodiment, and contains the covalent diene copolymer of the above-mentioned component (I). Furthermore, the cured product of the present embodiment is obtained by subjecting the resin composition of the present embodiment to a curing reaction at an arbitrary temperature and for an arbitrary time. In addition to the completely cured form, a form (semi-cured) in which only a part of the resin composition is cured and contains uncured components is also included in the concept. In the manufacturing process of the laminate described later, a step of further curing the cured product may also be implemented. The reaction temperature of the curing step of the cured product of the present embodiment is preferably 80°C or more, more preferably 100°C or more, and further preferably 120°C or more. The reaction time is preferably 10 to 240 minutes, more preferably 20 to 230 minutes, and further preferably 30 to 220 minutes. When the resin composition of the present embodiment is a varnish, it is preferred to remove the solvent before performing the curing reaction. The drying method can be implemented by heating, blowing hot air, and other previously known methods, preferably at a temperature lower than the curing reaction temperature, and preferably drying until the amount of solvent in the resin composition becomes less than 10% by mass, more preferably less than 5% by mass.

[樹脂膜] 本實施方式之樹脂膜包含本實施方式之樹脂組合物。本實施方式之樹脂膜例如藉由使包含上述本實施方式之樹脂組合物之清漆於特定支持體上延展成均勻薄膜狀，進行乾燥處理去除溶劑而獲得。可以將該樹脂膜捲取成卷狀加以保管。本實施方式之樹脂膜可採用積層有特定保護膜之構成，於該情形時，將保護膜剝離而可使用。 [Resin film] The resin film of the present embodiment includes the resin composition of the present embodiment. The resin film of the present embodiment is obtained, for example, by extending a varnish including the resin composition of the present embodiment into a uniform film on a specific support, and drying the film to remove the solvent. The resin film can be rolled up and stored. The resin film of the present embodiment can be laminated with a specific protective film. In this case, the protective film can be peeled off and used.

[預浸體] 本實施方式之預浸體包含基材與含浸或塗佈於該基材之本實施方式之樹脂組合物。即，本實施方式之預浸體為本實施方式之樹脂組合物與基材之複合體。預浸體例如藉由將玻璃布等基材含浸於作為上述本實施方式之樹脂組合物的清漆中後，利用上述乾燥方法去除溶劑而獲得。作為基材，例如可例舉：紗束布(roving cloth)、布、短切氈(chopped mat)、表面氈等各種玻璃布，石綿布、金屬纖維布、及其他合成或天然之無機纖維布，由全芳香族聚醯胺纖維、全芳香族聚酯纖維、聚苯并㗁唑纖維等液晶纖維製成之織布或不織布，棉布、麻布、毛氈等天然纖維布，碳纖維布、牛皮紙、棉紙(cotton paper)、由紙-玻璃混纖紗製成之布等天然纖維素系基材，聚四氟乙烯多孔質膜等；就介電性能之觀點而言，較佳為玻璃布。該等基材可單獨使用一種或將兩種以上組合使用。預浸體中之包含本實施方式之樹脂組合物之固形物成分之比率較佳為30～80質量%，更佳為40～70質量%。藉由使包含樹脂組合物之固形物成分之比率為30質量%以上，預浸體用於電子基板等用途之情形時存在絕緣可靠性更優異之傾向。藉由為80質量%以下，用於電子基板等用途之情形時存在剛性等機械特性更優異之傾向。 [Prepreg] The prepreg of the present embodiment includes a substrate and the resin composition of the present embodiment impregnated or coated on the substrate. That is, the prepreg of the present embodiment is a composite of the resin composition of the present embodiment and the substrate. The prepreg is obtained by, for example, impregnating a substrate such as glass cloth in a varnish which is the resin composition of the present embodiment, and then removing the solvent by the above-mentioned drying method. As the substrate, for example, various glass cloths such as roving cloth, cloth, chopped mat, and surface felt, stone wool cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloths, woven or non-woven cloths made of liquid crystal fibers such as wholly aromatic polyamide fiber, wholly aromatic polyester fiber, and polybenzoxazole fiber, natural fiber cloths such as cotton cloth, linen, and felt, natural fiber-based substrates such as carbon fiber cloth, kraft paper, cotton paper, and cloth made of paper-glass mixed yarn, and polytetrafluoroethylene porous membranes can be cited; from the perspective of dielectric properties, glass cloth is preferred. These substrates can be used alone or in combination of two or more. The ratio of the solid content of the resin composition of the present embodiment in the prepreg is preferably 30 to 80% by mass, and more preferably 40 to 70% by mass. When the ratio of the solid content of the resin composition is 30% by mass or more, the insulation reliability of the prepreg tends to be better when used for electronic substrates, etc. When it is 80% by mass or less, the mechanical properties such as rigidity tend to be better when used for electronic substrates, etc.

[積層體] 本實施方式之積層體具有上述樹脂膜與金屬箔。又，本實施方式之積層體亦可設為具有上述預浸體之硬化物與金屬箔之構成。本實施方式之積層體例如可藉由如下等步驟製造：步驟(a)，於基材上積層包含本實施方式之樹脂組合物之樹脂膜而形成樹脂層，獲得預浸體；步驟(b)，對上述樹脂層進行加熱、加壓使其平坦化，獲得預浸體之硬化物；及步驟(c)，進而於上述樹脂層上形成包含金屬箔之特定配線層。 [Laminate] The laminate of the present embodiment has the resin film and the metal foil. Furthermore, the laminate of the present embodiment may also be configured to have a cured product of the prepreg and a metal foil. The laminate of the present embodiment may be manufactured, for example, by the following steps: step (a), laminating a resin film comprising the resin composition of the present embodiment on a substrate to form a resin layer to obtain a prepreg; step (b), heating and pressurizing the resin layer to flatten it to obtain a cured product of the prepreg; and step (c), further forming a specific wiring layer comprising a metal foil on the resin layer.

於步驟(a)中，在基材上積層樹脂膜之方法並無特別限定，例如可例舉採用多段加壓、真空加壓、常壓貼合機、真空下加熱加壓之貼合機進行積層之方法等，較佳為使用真空下加熱加壓之貼合機之方法。藉由該使用貼合機之方法，即便目標電子電路基板之表面具有微細配線電路，亦能夠向電路間無空隙地嵌埋樹脂。又，層壓可為分批式，亦可為使用輥等之連續式。作為基材，例如可例舉但不限定於以下各者：玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、聚苯醚系基板、氟樹脂基板等。基材之待積層樹脂層之面可預先經過粗化處理，基材層數並無限定。 In step (a), the method of laminating the resin film on the substrate is not particularly limited. For example, there can be cited a method of laminating using a multi-stage pressurization, vacuum pressurization, a normal pressure laminating machine, a laminating machine with heating and pressurization under vacuum, etc., and preferably a method using a laminating machine with heating and pressurization under vacuum. By using the method using the laminating machine, even if the surface of the target electronic circuit substrate has a fine wiring circuit, the resin can be embedded in the circuit without gaps. In addition, the lamination can be batch-type or continuous using a roller, etc. As the substrate, for example, but not limited to the following: glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, polyphenylene ether substrate, fluororesin substrate, etc. The surface of the substrate on which the resin layer is to be deposited can be roughened in advance, and the number of substrate layers is not limited.

於上述步驟(b)中，將上述步驟(a)中積層之樹脂膜與基材於加熱下加壓而使其平坦化。條件可根據基材之種類或樹脂膜之組成而任意調整，例如較佳為如下範圍：溫度100～300℃、壓力0.2～20 MPa、時間30～180分鐘。In the above step (b), the resin film and the substrate layered in the above step (a) are flattened by applying pressure under heating. The conditions can be adjusted arbitrarily according to the type of substrate or the composition of the resin film, for example, preferably in the following range: temperature 100-300°C, pressure 0.2-20 MPa, time 30-180 minutes.

於上述步驟(c)中，在樹脂膜與基材經過加熱下加壓而製作之樹脂層上進而形成包含金屬箔之特定配線層。作為形成方法，並無特別限定，可例舉先前公知之方法，例如可例舉：減成法等蝕刻法、半加成法等。減成法係如下方法：於金屬層之上形成與所需圖案形狀對應之形狀的蝕刻抗蝕層，其後藉由顯影處理，利用藥液將抗蝕層經去除部分之金屬層溶解去除，藉此形成所需配線。半加成法係如下方法：藉由無電解鍍覆法於樹脂層之表面形成金屬覆膜，於金屬覆膜上形成與所需圖案對應之形狀的鍍覆抗蝕層，繼而藉由電解鍍覆法形成金屬層後，利用藥液等去除不需要之無電解鍍覆層而形成所需配線層。 In the above step (c), a specific wiring layer including a metal foil is further formed on the resin layer produced by heating and pressurizing the resin film and the substrate. The formation method is not particularly limited, and previously known methods can be cited, such as etching methods such as subtractive methods, semi-additive methods, etc. The subtractive method is a method in which an etching resist layer of a shape corresponding to the desired pattern shape is formed on the metal layer, and then the metal layer of the removed portion of the resist layer is dissolved and removed by a chemical solution through a development process, thereby forming the desired wiring. The semi-additive method is a method in which a metal coating is formed on the surface of a resin layer by electroless plating, a coating anti-corrosion layer of a shape corresponding to the desired pattern is formed on the metal coating, and then a metal layer is formed by electrolytic plating, and then the unnecessary electroless plating layer is removed using a chemical solution to form the desired wiring layer.

又，視需要可於樹脂層形成導孔等孔洞，孔洞之形成方法並無特別限定，可使用先前公知之方法。作為孔洞之形成方法，例如可使用NC鑽孔器、二氧化碳雷射、UV雷射、YAG雷射、電漿等。Furthermore, if necessary, holes such as vias can be formed in the resin layer. The method for forming the holes is not particularly limited, and a previously known method can be used. For example, an NC drill, a carbon dioxide laser, a UV laser, a YAG laser, plasma, etc. can be used as the method for forming the holes.

[金屬箔積層板] 上述本實施方式之積層體可為板狀，亦可為具有可撓性之撓性積層體。本實施方式之積層體可為金屬箔積層板。金屬箔積層板藉由將本實施方式之樹脂組合物或本實施方式之預浸體與金屬箔進行積層，使之硬化而獲得，將上述金屬箔之一部分去除。金屬箔積層板較佳為具有預浸體之硬化物(亦稱為「硬化物複合體」)與金屬箔積層並密接之形態，適宜用作電子電路基板用之材料。作為金屬箔，例如可例舉鋁箔及銅箔，其中，銅箔因電阻較低而較佳。與金屬箔組合之預浸體之硬化物可為一張亦可為複數張，根據用途而於硬化物之單面或雙面重疊金屬箔而加工成金屬箔積層板。作為上述金屬箔積層板之製造方法，例如可例舉如下方法：形成由本實施方式之樹脂組合物與基材構成之預浸體，將其與金屬箔重疊後，使樹脂組合物硬化，藉此獲得積層有預浸體硬化物與金屬箔之金屬箔積層板。上述金屬箔積層板之尤佳用途之一為印刷配線板。印刷配線板較佳為自金屬箔積層板去除金屬箔之至少一部分。上述印刷配線板可藉由使用上述本實施方式之預浸體進行加壓加熱成型之方法製作。作為基材，可使用與上述預浸體之相關說明相同者。上述印刷配線板藉由包含本實施方式之樹脂組合物，具有優異之強度及電氣特性(低介電常數及低介電損耗因數)，進而能夠抑制隨環境變化產生之電氣特性之變化，具有優異之絕緣可靠性及機械特性。 [Metal foil laminate] The laminate of the present embodiment described above may be in the form of a plate or a flexible laminate having flexibility. The laminate of the present embodiment may be a metal foil laminate. The metal foil laminate is obtained by laminating the resin composition of the present embodiment or the prepreg of the present embodiment with metal foil, hardening the laminate, and removing a portion of the metal foil. The metal foil laminate is preferably in a form in which a hardened prepreg (also referred to as a "hardened composite") and a metal foil are laminated and closely connected, and is suitable for use as a material for electronic circuit substrates. As metal foil, for example, aluminum foil and copper foil can be cited, among which copper foil is preferred because of its lower electrical resistance. The cured product of the prepreg combined with the metal foil can be one sheet or multiple sheets, and the metal foil is stacked on one or both sides of the cured product according to the application to form a metal foil laminate. As a method for manufacturing the above-mentioned metal foil laminate, for example, the following method can be cited: a prepreg composed of the resin composition of the present embodiment and a substrate is formed, and after stacking it with a metal foil, the resin composition is cured to obtain a metal foil laminate laminated with the cured prepreg and the metal foil. One of the particularly preferred uses of the above-mentioned metal foil laminate is a printed wiring board. The printed wiring board is preferably a metal foil laminate with at least a portion of the metal foil removed. The printed wiring board can be produced by a method of pressurizing and heating the prepreg of the present embodiment. As a substrate, the same as the relevant description of the prepreg can be used. The printed wiring board has excellent strength and electrical properties (low dielectric constant and low dielectric dissipation factor) by including the resin composition of the present embodiment, and can suppress the change of electrical properties caused by environmental changes, and has excellent insulation reliability and mechanical properties.

[電子電路基板用之材料] 本實施方式之電子電路基板之材料包含本實施方式之樹脂組合物之硬化物。本實施方式之電子電路基板用之材料可使用上述本實施方式之樹脂組合物及/或清漆進行製作。本實施方式之電子電路基板用之材料包括選自由上述樹脂組合物之硬化物、包含本實施方式之樹脂組合物或其硬化物之樹脂膜、及作為基材與樹脂組合物之複合體的預浸體所組成之群中之至少任一者。本實施方式之電子電路基板用之材料可用作具備帶樹脂金屬箔之印刷配線板。 [實施例] [Material for electronic circuit substrate] The material for electronic circuit substrate of the present embodiment includes a cured product of the resin composition of the present embodiment. The material for electronic circuit substrate of the present embodiment can be produced using the resin composition and/or varnish of the present embodiment described above. The material for electronic circuit substrate of the present embodiment includes at least one selected from the group consisting of a cured product of the above-mentioned resin composition, a resin film containing the resin composition of the present embodiment or its cured product, and a prepreg as a composite of a substrate and a resin composition. The material for electronic circuit substrate of the present embodiment can be used as a printed wiring board having a metal foil with a resin. [Example]

以下，例舉具體之實施例及比較例，對本實施方式進行具體說明，但本發明不受下述實施例及比較例之任何限定。Hereinafter, the present embodiment will be specifically described with reference to specific embodiments and comparative examples, but the present invention is not limited to the following embodiments and comparative examples.

以下揭示下述實施例及比較例之氫化共軛二烯系共聚物或未氫化之共軛二烯系共聚物(成分(I))(以下有時記為共軛二烯系共聚物)之結構之鑑定及物性之測定方法。The following describes methods for identifying the structure and measuring the physical properties of the hydrogenated covalent diene copolymer or the unhydrogenated covalent diene copolymer (component (I)) (hereinafter sometimes referred to as the covalent diene copolymer) of the following Examples and Comparative Examples.

[共軛二烯系共聚物之結構之鑑定及物性之測定方法] ((1)共軛二烯系共聚物之乙烯基芳香族單體單元之含量) 使用氫化前之共軛二烯系共聚物，使用紫外分光光度計(島津製作所製造，UV-2450)，測定共聚物中之乙烯基芳香族單體單元之含量。 [Methods for identification of the structure and determination of physical properties of covalent diene copolymers] ((1) Content of vinyl aromatic monomer units in covalent diene copolymers) The covalent diene copolymers before hydrogenation were used to determine the content of vinyl aromatic monomer units in the copolymers using an ultraviolet spectrophotometer (manufactured by Shimadzu Corporation, UV-2450).

((2)共軛二烯系共聚物之乙烯基鍵量) 使用氫化前之共軛二烯系共聚物，使用紅外分光光度計(日本分光公司製造，FT/IR-230)，測定乙烯基鍵量。藉由漢普頓(Hampton)法算出共軛二烯系共聚物之乙烯基鍵量。 ((2) Vinyl bond content of covalent diene copolymer) The vinyl bond content of the covalent diene copolymer before hydrogenation was measured using an infrared spectrophotometer (manufactured by JASCO Corporation, FT/IR-230). The vinyl bond content of the covalent diene copolymer was calculated by the Hampton method.

((3)共軛二烯系共聚物之分子量及分子量分佈) 藉由GPC[裝置：LC-10(島津製作所製造)，管柱：TSKgelGMHXL(4.6 mm×30 cm)]測定改性前且氫化前之成分(I)共軛二烯系共聚物之分子量。溶劑使用四氫呋喃。測定條件：於溫度35℃下進行。分子量係使用由市售標準聚苯乙烯之測定求出之校準曲線(使用標準聚苯乙烯之峰值分子量製成)，求出層析圖之峰值分子量而獲得之重量平均分子量。再者，層析圖中存在複數個波峰時之分子量採用根據各波峰之分子量與各波峰之組成比(由層析圖之各波峰之面積比求出)而求出之平均分子量。 ((3) Molecular weight and molecular weight distribution of covalent diene copolymer) The molecular weight of the covalent diene copolymer of component (I) before modification and hydrogenation was measured by GPC [apparatus: LC-10 (manufactured by Shimadzu Corporation), column: TSKgelGMHXL (4.6 mm×30 cm)]. The solvent used was tetrahydrofuran. The measurement conditions were: temperature 35°C. The molecular weight was obtained by calculating the peak molecular weight of the chromatogram using a calibration curve obtained by measuring commercial standard polystyrene (prepared using the peak molecular weight of standard polystyrene). In addition, when there are multiple peaks in the chromatogram, the molecular weight is the average molecular weight obtained by calculating the molecular weight of each peak and the composition ratio of each peak (calculated from the area ratio of each peak in the chromatogram).

((4)共軛二烯系共聚物之共軛二烯單體單元之雙鍵之氫化率) 使用氫化後之成分(I)：氫化共軛二烯系共聚物，使用核磁共振裝置(BRUKER公司製造之DPX-400)，測定共軛二烯單體單元之雙鍵之氫化率。 ((4) Hydrogenation rate of double bonds of covalent diene monomer units in covalent diene copolymers) Using hydrogenated component (I): hydrogenated covalent diene copolymers, the hydrogenation rate of double bonds of covalent diene monomer units was measured using a nuclear magnetic resonance device (DPX-400 manufactured by BRUKER).

[氫化或非氫化之共軛二烯系共聚物(有時統稱為共軛二烯系共聚物)、樹脂組合物之材料] (氫化觸媒之製備) 於後述製造例及比較製造例中，藉由下述方法製備製作氫化共軛二烯系共聚物時使用之氫化觸媒。預先對具備攪拌裝置之反應容器進行氮氣置換，於其中添加經過乾燥、精製之環己烷1升。其次，添加二氯化雙(η5-環戊二烯基)鈦100毫莫耳。一面充分攪拌一面添加包含三甲基鋁200毫莫耳之正己烷溶液，於室溫下反應約3天。藉此獲得氫化觸媒。 [Materials for hydrogenated or non-hydrogenated covalent diene copolymers (sometimes collectively referred to as covalent diene copolymers) and resin compositions] (Preparation of hydrogenated catalyst) In the production examples and comparative production examples described below, the hydrogenated catalyst used in the production of hydrogenated covalent diene copolymers was prepared by the following method. A reaction vessel equipped with a stirring device was replaced with nitrogen in advance, and 1 liter of dried and purified cyclohexane was added thereto. Next, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added. While stirring thoroughly, an n-hexane solution containing 200 mmol of trimethylaluminum was added, and the mixture was reacted at room temperature for about 3 days. A hydrogenated catalyst was obtained in this way.

(成分(I)：共軛二烯系共聚物) 藉由如下方式製備乙烯基芳香族化合物與共軛二烯化合物之共軛二烯系共聚物。將各共軛二烯系共聚物之結構及物性值示於表1、2。表1及表2之「結構」中，A表示以乙烯基芳香族單體單元為主體之聚合物嵌段(A)，B表示以共軛二烯單體單元為主體之聚合物嵌段(B)，C表示包含乙烯基芳香族單體單元與共軛二烯單體單元之無規聚合物嵌段(C)。 (Component (I): Copolymer of Diene) Copolymer of a vinyl aromatic compound and a copolymer of a diene compound was prepared as follows. The structure and physical property values of each copolymer of a diene compound are shown in Tables 1 and 2. In "Structure" in Tables 1 and 2, A represents a polymer block (A) mainly composed of a vinyl aromatic monomer unit, B represents a polymer block (B) mainly composed of a copolymer of a diene monomer unit, and C represents a random polymer block (C) containing a vinyl aromatic monomer unit and a copolymer of a diene monomer unit.

＜(製造例1)：氫化共軛二烯系共聚物(1)＞使用具備攪拌裝置與夾套之槽型反應器(內容積10 L)進行分批聚合。首先，投入包含苯乙烯10質量份之環己烷溶液(濃度20質量%)。其次，添加相對於全部單體100質量份為0.17質量份之正丁基鋰、及相對於正丁基鋰1 mol為1.0 mоl之四甲基乙二胺(TMEDA)，於70℃下進行10分鐘聚合。其次，添加包含丁二烯80質量份之環己烷溶液(濃度20質量%)，於70℃下進行40分鐘聚合。其次，添加包含苯乙烯10質量份之環己烷溶液(濃度20質量%)，於70℃下進行10分鐘聚合。其後添加甲醇使聚合反應停止，獲得共軛二烯系共聚物。按照如上方式獲得之共軛二烯系嵌段共聚物(1)之苯乙烯含量20質量%、重量平均分子量6.0×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)60%。使用所獲得之共軛二烯系共聚物，進而相對於共軛二烯系共聚物每100質量份，添加以Ti基準計90 ppm之按照如上方式製備之氫化觸媒，於氫氣壓力0.7 MPa、溫度80℃下進行約0.5小時之氫化反應，獲得氫化共軛二烯系共聚物(1)。所獲得之氫化共軛二烯共聚物之氫化率為45%。＜(Production Example 1): Hydrogenated covalent diene copolymer (1)＞ Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 10 parts by mass of styrene (concentration 20 mass%) was added. Next, 0.17 parts by mass of n-butyl lithium relative to 100 parts by mass of all monomers and 1.0 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyl lithium were added, and polymerization was carried out at 70°C for 10 minutes. Next, a cyclohexane solution containing 80 parts by mass of butadiene (concentration 20 mass%) was added, and polymerization was carried out at 70°C for 40 minutes. Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration 20 mass%) was added, and polymerization was carried out at 70°C for 10 minutes. Methanol was then added to stop the polymerization reaction, and a covalent diene copolymer was obtained. The covalent diene block copolymer (1) obtained in the above manner had a styrene content of 20% by mass, a weight average molecular weight of 6.0×10 ⁴ , and a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond amount: unit (a)/butadiene) of 60%. The covalent diene copolymer obtained was used, and a hydrogenation catalyst prepared in the above manner was further added in an amount of 90 ppm based on Ti per 100 parts by mass of the covalent diene copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80°C for about 0.5 hours to obtain a hydrogenated covalent diene copolymer (1). The hydrogenation rate of the obtained hydrogenated covalent diene copolymer is 45%.

＜(製造例2)：氫化共軛二烯系共聚物(2)＞添加相對於正丁基鋰1 mol為1.2 mol之TMEDA，將各聚合時間延長5分鐘，除此以外，進行與製造例1相同之操作。按照如上方式獲得之共軛二烯系共聚物(2)之苯乙烯含量20質量%、重量平均分子量6.0×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)70%、氫化率45%。 <(Production Example 2): Hydrogenated covalent diene copolymer (2)> The same operation as in Production Example 1 was performed except that 1.2 mol of TMEDA was added relative to 1 mol of n-butyl lithium and each polymerization time was extended by 5 minutes. The covalent diene copolymer (2) obtained in the above manner had a styrene content of 20% by mass, a weight average molecular weight of 6.0×10 ⁴ , a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 70%, and a hydrogenation rate of 45%.

＜(製造例3)：共軛二烯系共聚物(3)＞使用具備攪拌裝置與夾套之槽型反應器(內容積10 L)進行分批聚合。首先，投入包含苯乙烯30質量份之環己烷溶液(濃度20質量%)。其次，添加相對於全部單體100質量份為0.13質量份之正丁基鋰、及相對於正丁基鋰1 mol為1.1 mоl之四甲基乙二胺(TMEDA)，於60℃下進行20分鐘聚合。其次，添加包含丁二烯40質量份之環己烷溶液(濃度20質量%)，於60℃下進行25分鐘聚合。其次，添加包含苯乙烯30質量份之環己烷溶液(濃度20質量%)，於60℃下進行20分鐘聚合。其後添加甲醇使聚合反應停止，獲得共軛二烯系共聚物。按照如上方式獲得之共軛二烯系共聚物(3)之苯乙烯含量60質量%、重量平均分子量6.0×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)71%。＜(Production Example 3): Copolymerized diene copolymer (3)＞ Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 30 parts by mass of styrene (concentration 20 mass%) was added. Next, 0.13 parts by mass of n-butyl lithium relative to 100 parts by mass of all monomers and 1.1 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyl lithium were added, and polymerization was carried out at 60°C for 20 minutes. Next, a cyclohexane solution containing 40 parts by mass of butadiene (concentration 20 mass%) was added, and polymerization was carried out at 60°C for 25 minutes. Next, a cyclohexane solution containing 30 parts by mass of styrene (concentration 20 mass%) was added, and polymerization was carried out at 60°C for 20 minutes. Methanol was then added to terminate the polymerization reaction, and a covalent diene copolymer was obtained. The covalent diene copolymer (3) obtained in the above manner had a styrene content of 60% by mass, a weight average molecular weight of 6.0×10 ⁴ , and a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 71%.

＜(製造例4)：氫化共軛二烯系共聚物(4)＞進行與製造例3相同之操作，獲得共軛二烯系共聚物溶液，進而於與製造例1相同之條件下進行氫化反應。所獲得之氫化共軛二烯系共聚物(4)之苯乙烯含量60質量%、重量平均分子量6.0×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)71%、氫化率45%。 <(Preparation Example 4): Hydrogenated covalent diene copolymer (4)> The same operation as in Preparation Example 3 was carried out to obtain a covalent diene copolymer solution, and then a hydrogenation reaction was carried out under the same conditions as in Preparation Example 1. The obtained hydrogenated covalent diene copolymer (4) had a styrene content of 60% by mass, a weight average molecular weight of 6.0×10 ⁴ , a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 71%, and a hydrogenation rate of 45%.

＜(製造例5)：氫化共軛二烯系共聚物(5)＞將氫化反應時間設為0.75小時，除此以外，進行與製造例4相同之操作。所獲得之氫化共軛二烯系共聚物(5)之苯乙烯含量60質量%、重量平均分子量6.0×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)70%、氫化率84%。 <(Production Example 5): Hydrogenated covalent diene copolymer (5)> The same operation as in Production Example 4 was carried out except that the hydrogenation reaction time was changed to 0.75 hours. The obtained hydrogenated covalent diene copolymer (5) had a styrene content of 60% by mass, a weight average molecular weight of 6.0×10 ⁴ , a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 70%, and a hydrogenation rate of 84%.

＜(製造例6)：氫化共軛二烯系共聚物(6)＞將氫化反應時間設為1.00小時，除此以外，進行與製造例4相同之操作。所獲得之氫化共軛二烯系共聚物(6)之苯乙烯含量60質量%、重量平均分子量6.1×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)70%、氫化率99%。 <(Production Example 6): Hydrogenated covalent diene copolymer (6)> The same operation as in Production Example 4 was performed except that the hydrogenation reaction time was 1.00 hour. The obtained hydrogenated covalent diene copolymer (6) had a styrene content of 60% by mass, a weight average molecular weight of 6.1×10 ⁴ , a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 70%, and a hydrogenation rate of 99%.

＜(製造例7)：氫化共軛二烯系共聚物(7)＞添加相對於全部單體100質量份為0.078質量份之正丁基鋰，除此以外，進行與氫化共軛二烯系共聚物(4)相同之操作。所獲得之氫化共軛二烯系共聚物(7)之苯乙烯含量60質量%、重量平均分子量10.0×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)70%、氫化率45%。 <(Production Example 7): Hydrogenated covalent diene copolymer (7)> The same operation as in the hydrogenated covalent diene copolymer (4) was performed except that 0.078 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers. The obtained hydrogenated covalent diene copolymer (7) had a styrene content of 60% by mass, a weight average molecular weight of 10.0×10 ⁴ , a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: units (a)/butadiene) of 70%, and a hydrogenation rate of 45%.

＜(製造例8)：氫化共軛二烯系共聚物(8)＞添加相對於全部單體100質量份為0.19質量份之正丁基鋰，除此以外，進行與氫化共軛二烯系共聚物(4)相同之操作。所獲得之氫化共軛二烯系共聚物(8)之苯乙烯含量60質量%、重量平均分子量4.1×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)71%、氫化率46%。 <(Production Example 8): Hydrogenated conjugated diene copolymer (8)> The same operation as in the hydrogenated conjugated diene copolymer (4) was performed except that 0.19 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers. The obtained hydrogenated conjugated diene copolymer (8) had a styrene content of 60% by mass, a weight average molecular weight of 4.1×10 ⁴ , a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: units (a)/butadiene) of 71%, and a hydrogenation rate of 46%.

＜(製造例9)：氫化共軛二烯系共聚物(9)＞使用具備攪拌裝置與夾套之槽型反應器(內容積10 L)進行分批聚合。首先，投入包含苯乙烯37.5質量份之環己烷溶液(濃度20質量%)。其次，添加相對於全部單體100質量份為0.12質量份之正丁基鋰、及相對於正丁基鋰1 mol為1.1 mоl之四甲基乙二胺(TMEDA)，於60℃下進行25分鐘聚合。其次，添加包含丁二烯25質量份之環己烷溶液(濃度20質量%)，於60℃下進行15分鐘聚合。其次，添加包含苯乙烯37.5質量份之環己烷溶液(濃度20質量%)，於60℃下進行25分鐘聚合。其後，添加甲醇使聚合反應停止。按照如上方式獲得之共軛二烯系共聚物(9)之苯乙烯含量75質量%、重量平均分子量5.9×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)70%。使用所獲得之共軛二烯系共聚物，進而相對於共軛二烯系共聚物每100質量份，添加以Ti基準計90 ppm之按照如上方式製備之氫化觸媒，於氫氣壓力0.7 MPa、溫度80℃下進行約0.25小時之氫化反應，獲得氫化共軛二烯系共聚物(9)。所獲得之氫化共軛二烯系共聚物之氫化率為44%。＜(Production Example 9): Hydrogenated covalent diene copolymer (9)＞ Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 37.5 parts by mass of styrene (concentration 20 mass%) was added. Next, 0.12 parts by mass of n-butyl lithium relative to 100 parts by mass of all monomers and 1.1 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyl lithium were added, and polymerization was carried out at 60°C for 25 minutes. Next, a cyclohexane solution containing 25 parts by mass of butadiene (concentration 20 mass%) was added, and polymerization was carried out at 60°C for 15 minutes. Next, a cyclohexane solution containing 37.5 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 60°C for 25 minutes. Thereafter, methanol was added to terminate the polymerization reaction. The covalent diene copolymer (9) obtained in the above manner had a styrene content of 75% by mass, a weight average molecular weight of 5.9×10 ⁴ , and a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 70%. The obtained covalent diene copolymer was used, and a hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by weight of the covalent diene copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80°C for about 0.25 hours to obtain a hydrogenated covalent diene copolymer (9). The hydrogenation rate of the obtained hydrogenated covalent diene copolymer was 44%.

＜(製造例10)：氫化共軛二烯系共聚物(10)＞使用具備攪拌裝置與夾套之槽型反應器(內容積10 L)進行分批聚合。首先，投入包含苯乙烯5質量份之環己烷溶液(濃度20質量%)。其次，添加相對於全部單體100質量份為0.064質量份之正丁基鋰、及相對於正丁基鋰1 mol為1.2 mоl之四甲基乙二胺(TMEDA)，於60℃下進行7分鐘聚合。其次，添加包含丁二烯70質量份、苯乙烯20質量份之環己烷溶液(濃度20質量%)，於60℃下進行40分鐘聚合。其次，添加包含苯乙烯5質量份之環己烷溶液(濃度20質量%)，於60℃下進行7分鐘聚合。其後，添加甲醇使聚合反應停止。按照如上方式獲得之共軛二烯系共聚物(10)之苯乙烯含量30質量%、重量平均分子量15.1×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)69%。使用所獲得之共軛二烯系共聚物，進而相對於共軛二烯系共聚物每100質量份，添加以Ti基準計90 ppm之按照如上方式製備之氫化觸媒，於氫氣壓力0.7 MPa、溫度80℃下進行約1.00小時之氫化反應，獲得氫化共軛二烯系共聚物(10)。所獲得之氫化共軛二烯系共聚物之氫化率為98%。＜(Production Example 10): Hydrogenated covalent diene copolymer (10)＞ Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 5 parts by mass of styrene (concentration 20 mass%) was added. Next, 0.064 parts by mass of n-butyl lithium relative to 100 parts by mass of all monomers and 1.2 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyl lithium were added, and polymerization was carried out at 60°C for 7 minutes. Next, a cyclohexane solution containing 70 parts by mass of butadiene and 20 parts by mass of styrene (concentration 20 mass%) was added, and polymerization was carried out at 60°C for 40 minutes. Next, a cyclohexane solution containing 5 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 60°C for 7 minutes. Methanol was then added to terminate the polymerization reaction. The covalent diene copolymer (10) obtained in the above manner had a styrene content of 30% by mass, a weight average molecular weight of 15.1×10 ⁴ , and a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 69%. The obtained covalent diene copolymer was used, and a hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by weight of the covalent diene copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80°C for about 1 hour to obtain a hydrogenated covalent diene copolymer (10). The hydrogenation rate of the obtained hydrogenated covalent diene copolymer was 98%.

＜(製造例11)：氫化共軛二烯系共聚物(11)＞使用具備攪拌裝置與夾套之槽型反應器(內容積10 L)進行分批聚合。首先，投入包含苯乙烯15質量份之環己烷溶液(濃度20質量%)。其次，添加相對於全部單體100質量份為0.065質量份之正丁基鋰、及相對於正丁基鋰1 mol為1.1 mоl之四甲基乙二胺(TMEDA)，於70℃下進行15分鐘聚合。其次，添加包含丁二烯70質量份之環己烷溶液(濃度20質量%)，於60℃下進行30分鐘聚合。其次，添加包含苯乙烯15質量份之環己烷溶液(濃度20質量%)，於60℃下進行15分鐘聚合。其後，添加甲醇使聚合反應停止。按照如上方式獲得之共軛二烯系共聚物(11)之苯乙烯含量30質量%、重量平均分子量15.0×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)69%。使用所獲得之共軛二烯系共聚物，進而相對於共軛二烯系共聚物每100質量份，添加以Ti基準計90 ppm之按照如上方式製備之氫化觸媒，於氫氣壓力0.7 MPa、溫度80℃下進行約1.00小時之氫化反應，獲得氫化共軛二烯系共聚物(11)。所獲得之氫化共軛二烯系共聚物(11)之氫化率為99%。＜(Production Example 11): Hydrogenated covalent diene copolymer (11)＞ Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 15 parts by mass of styrene (concentration 20 mass%) was added. Next, 0.065 parts by mass of n-butyl lithium relative to 100 parts by mass of all monomers and 1.1 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyl lithium were added, and polymerization was carried out at 70°C for 15 minutes. Next, a cyclohexane solution containing 70 parts by mass of butadiene (concentration 20 mass%) was added, and polymerization was carried out at 60°C for 30 minutes. Next, a cyclohexane solution containing 15 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 60°C for 15 minutes. Thereafter, methanol was added to terminate the polymerization reaction. The covalent diene copolymer (11) obtained in the above manner had a styrene content of 30% by mass, a weight average molecular weight of 15.0×10 ⁴ , and a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 69%. The obtained covalent diene copolymer was used, and a hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by mass of the covalent diene copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80°C for about 1.00 hour to obtain a hydrogenated covalent diene copolymer (11). The hydrogenation rate of the obtained hydrogenated covalent diene copolymer (11) was 99%.

＜(製造例12)：氫化共軛二烯系共聚物(12)＞將氫化反應時間設為0.15小時，除此以外，進行與製造例10相同之操作。按照如上方式獲得之氫化共軛二烯系共聚物(12)之苯乙烯含量30質量%、重量平均分子量15.0×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)70%、氫化率為7%。 <(Production Example 12): Hydrogenated covalent diene copolymer (12)> The same operation as in Production Example 10 was performed except that the hydrogenation reaction time was changed to 0.15 hours. The hydrogenated covalent diene copolymer (12) obtained in the above manner had a styrene content of 30% by mass, a weight average molecular weight of 15.0×10 ⁴ , a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 70%, and a hydrogenation rate of 7%.

＜(製造例13)：氫化共軛二烯系共聚物(13)＞將氫化反應時間設為0.90小時，除此以外，進行與製造例10相同之操作。按照如上方式獲得之氫化共軛二烯系共聚物(13)之苯乙烯含量30質量%、重量平均分子量15.0×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)70%、氫化率91%。 <(Production Example 13): Hydrogenated covalent diene copolymer (13)> The same operation as in Production Example 10 was performed except that the hydrogenation reaction time was changed to 0.90 hours. The hydrogenated covalent diene copolymer (13) obtained in the above manner had a styrene content of 30% by mass, a weight average molecular weight of 15.0×10 ⁴ , a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 70%, and a hydrogenation rate of 91%.

＜(製造例14)：共軛二烯系共聚物(14)＞使用具備攪拌裝置與夾套之槽型反應器(內容積10 L)進行分批聚合。首先，投入包含丁二烯15質量份之環己烷溶液(濃度20質量%)。其次，添加相對於全部單體100質量份為0.13質量份之正丁基鋰、及相對於正丁基鋰1 mol為1.0 mоl之四甲基乙二胺(TMEDA)，於70℃下進行15分鐘聚合。其次，添加包含丁二烯20質量份、苯乙烯50質量份之環己烷溶液(濃度20質量%)，於70℃下進行30分鐘聚合。其次，投入包含丁二烯15質量份之環己烷溶液(濃度20質量%)，於60℃下進行15分鐘聚合。其後，添加甲醇使聚合反應停止。按照如上方式獲得之共軛二烯系共聚物(14)之乙烯基芳香族單體量80質量%、重量平均分子量6.5×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)60%。使用所獲得之共軛二烯系共聚物(14)，相對於共軛二烯系共聚物每100質量份，添加以Ti基準計90 ppm之按照如上方式製備之氫化觸媒，於氫氣壓力0.7 MPa、溫度80℃下進行約0.3小時之氫化反應，獲得氫化共軛二烯系共聚物(14)。氫化率為30%。＜(Production Example 14): Copolymerized diene copolymer (14)＞ Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 15 parts by mass of butadiene (concentration 20 mass%) was added. Next, 0.13 parts by mass of n-butyl lithium relative to 100 parts by mass of all monomers and 1.0 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyl lithium were added, and polymerization was carried out at 70°C for 15 minutes. Next, a cyclohexane solution containing 20 parts by mass of butadiene and 50 parts by mass of styrene (concentration 20 mass%) was added, and polymerization was carried out at 70°C for 30 minutes. Next, a cyclohexane solution (concentration 20% by mass) containing 15 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 15 minutes. Methanol was then added to terminate the polymerization reaction. The covalent diene copolymer (14) obtained in the above manner had a vinyl aromatic monomer content of 80% by mass, a weight average molecular weight of 6.5×10 ⁴ , and a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 60%. The obtained covalent diene copolymer (14) was used to add 90 ppm of a hydrogenation catalyst prepared as described above based on Ti per 100 parts by weight of the covalent diene copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80°C for about 0.3 hours to obtain a hydrogenated covalent diene copolymer (14). The hydrogenation rate was 30%.

＜(製造例15)：氫化共軛二烯系共聚物(15)＞將正丁基鋰設為相對於全部單體100質量份為0.12質量份、將TMEDA設為相對於正丁基鋰1 mol為1.3 mоl，將聚合溫度設為55℃、將氫化反應時間設為0.5小時，除此以外，進行與製造例11相同之操作。所獲得之氫化共軛二烯系共聚物(15)之苯乙烯含量30質量%、重量平均分子量8.1×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)81%、氫化率為74%。 <(Production Example 15): Hydrogenated covalent diene copolymer (15)> The same operation as in Production Example 11 was carried out except that the amount of n-butyl lithium was 0.12 parts by mass relative to 100 parts by mass of all monomers, the amount of TMEDA was 1.3 mol relative to 1 mol of n-butyl lithium, the polymerization temperature was 55°C, and the hydrogenation reaction time was 0.5 hours. The obtained hydrogenated covalent diene copolymer (15) had a styrene content of 30% by mass, a weight average molecular weight of 8.1×10 ⁴ , a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond amount: unit (a)/butadiene) of 81%, and a hydrogenation rate of 74%.

＜(比較製造例1)：氫化共軛二烯系共聚物(16)＞使用具備攪拌裝置與夾套之槽型反應器(內容積10 L)進行分批聚合。首先，投入包含苯乙烯5質量份之環己烷溶液(濃度20質量%)。其次，添加相對於全部單體100質量份為0.18質量份之正丁基鋰、及相對於正丁基鋰1 mol為0.65 mоl之四甲基乙二胺(TMEDA)，於70℃下進行10分鐘聚合。其次，添加包含丁二烯90質量份之環己烷溶液(濃度20質量%)，於60℃下進行45分鐘聚合。其次，添加包含苯乙烯5質量份之環己烷溶液(濃度20質量%)，於60℃下進行5分鐘聚合。其後，添加甲醇使聚合反應停止。按照如上方式獲得之共軛二烯系共聚物(16)之苯乙烯含量10質量%、重量平均分子量6.0×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)60%。使用所獲得之共軛二烯系共聚物，進而相對於共軛二烯系共聚物每100質量份，添加以Ti基準計90 ppm之按照如上方式製備之氫化觸媒，於氫氣壓力0.7 MPa、溫度80℃下進行約1.00小時之氫化反應，獲得氫化共軛二烯系共聚物(16)。所獲得之氫化共軛二烯系共聚物(16)之氫化率為44%。＜(Comparative Production Example 1): Hydrogenated covalent diene copolymer (16)＞ Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 5 parts by mass of styrene (concentration 20 mass%) was added. Next, 0.18 parts by mass of n-butyl lithium relative to 100 parts by mass of all monomers and 0.65 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyl lithium were added, and polymerization was carried out at 70°C for 10 minutes. Next, a cyclohexane solution containing 90 parts by mass of butadiene (concentration 20 mass%) was added, and polymerization was carried out at 60°C for 45 minutes. Next, a cyclohexane solution containing 5 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 60°C for 5 minutes. Thereafter, methanol was added to terminate the polymerization reaction. The covalent diene copolymer (16) obtained in the above manner had a styrene content of 10% by mass, a weight average molecular weight of 6.0×10 ⁴ , and a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 60%. The obtained covalent diene copolymer was used, and a hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by weight of the covalent diene copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80°C for about 1 hour to obtain a hydrogenated covalent diene copolymer (16). The hydrogenation rate of the obtained hydrogenated covalent diene copolymer (16) was 44%.

＜(比較製造例2)：氫化共軛二烯系共聚物(17)＞添加相對於全部單體100質量份為0.068質量份之正丁基鋰、及相對於正丁基鋰1 mol為1.2 mol之TMEDA，將各反應時間延長5分鐘，除此以外，進行與比較製造例1相同之操作。所獲得之氫化共軛二烯系共聚物(17)之苯乙烯含量10質量%、重量平均分子量15.9×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)69%、氫化率為99%。 <(Comparative Production Example 2): Hydrogenated covalent diene copolymer (17)> The same operation as in Comparative Production Example 1 was performed except that 0.068 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers and 1.2 mol of TMEDA was added relative to 1 mol of n-butyl lithium, and each reaction time was extended by 5 minutes. The obtained hydrogenated covalent diene copolymer (17) had a styrene content of 10% by mass, a weight average molecular weight of 15.9×10 ⁴ , a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 69%, and a hydrogenation rate of 99%.

＜(比較製造例3)：氫化共軛二烯系共聚物(18)＞添加相對於正丁基鋰1 mol為0.45 mol之TMEDA，除此以外，進行與製造例(4)相同之操作。所獲得之氫化共軛二烯系共聚物(18)之苯乙烯含量60質量%、重量平均分子量6.0×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)50%、氫化率45%。 <(Comparative Production Example 3): Hydrogenated covalent diene copolymer (18)> The same operation as in Production Example (4) was performed except that 0.45 mol of TMEDA was added relative to 1 mol of n-butyl lithium. The obtained hydrogenated covalent diene copolymer (18) had a styrene content of 60% by mass, a weight average molecular weight of 6.0×10 ⁴ , a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 50%, and a hydrogenation rate of 45%.

＜(比較製造例4)：氫化共軛二烯系共聚物(19)＞添加相對於全部單體100質量份為0.27質量份之正丁基鋰，除此以外，進行與製造例4相同之操作。所獲得之氫化共軛二烯系共聚物(19)之苯乙烯含量60質量%、重量平均分子量3.0×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)70%、氫化率為45%。 <(Comparative Production Example 4): Hydrogenated covalent diene copolymer (19)> The same operation as in Production Example 4 was performed except that 0.27 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers. The obtained hydrogenated covalent diene copolymer (19) had a styrene content of 60% by mass, a weight average molecular weight of 3.0×10 ⁴ , a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: units (a)/butadiene) of 70%, and a hydrogenation rate of 45%.

＜(比較製造例5)：氫化共軛二烯系共聚物(20)＞添加相對於正丁基鋰1 mol為0.54 mоl之TMEDA，除此以外，進行與製造例10相同之操作。所獲得之氫化共軛二烯系共聚物(20)之苯乙烯含量30質量%、重量平均分子量15.0×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)49%、氫化率為98%。 <(Comparative Production Example 5): Hydrogenated covalent diene copolymer (20)> The same operation as in Production Example 10 was performed except that 0.54 mol of TMEDA was added relative to 1 mol of n-butyl lithium. The obtained hydrogenated covalent diene copolymer (20) had a styrene content of 30% by mass, a weight average molecular weight of 15.0×10 ⁴ , a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 49%, and a hydrogenation rate of 98%.

＜(比較製造例6)：氫化共軛二烯系共聚物(21)＞添加相對於全部單體100質量份為0.15質量份之正丁基鋰、及相對於正丁基鋰1 mol為0.28 mоl之TMEDA，除此以外，進行與製造例11相同之操作。所獲得之氫化共軛二烯系共聚物(21)之苯乙烯含量30質量%、重量平均分子量7.5×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)41%、氫化率為98%。 <(Comparative Production Example 6): Hydrogenated covalent diene copolymer (21)> The same operation as in Production Example 11 was performed except that 0.15 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers, and 0.28 mol of TMEDA was added relative to 1 mol of n-butyl lithium. The obtained hydrogenated covalent diene copolymer (21) had a styrene content of 30% by mass, a weight average molecular weight of 7.5×10 ⁴ , a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: units (a)/butadiene) of 41%, and a hydrogenation rate of 98%.

＜(比較製造例7)：氫化共軛二烯系共聚物(22)＞添加相對於全部單體100質量份為0.12質量份之正丁基鋰、及相對於正丁基鋰1 mol為0.23 mоl之TMEDA，除此以外，進行與製造例11相同之操作。所獲得之氫化共軛二烯系共聚物(22)之苯乙烯含量30質量%、重量平均分子量8.1×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)35%、氫化率為99%。 <(Comparative Production Example 7): Hydrogenated covalent diene copolymer (22)> The same operation as in Production Example 11 was performed except that 0.12 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers, and 0.23 mol of TMEDA was added relative to 1 mol of n-butyl lithium. The obtained hydrogenated covalent diene copolymer (22) had a styrene content of 30% by mass, a weight average molecular weight of 8.1×10 ⁴ , a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 35%, and a hydrogenation rate of 99%.

＜(比較製造例8)：氫化共軛二烯系共聚物(23)＞添加相對於全部單體100質量份為0.15質量份之正丁基鋰、及相對於正丁基鋰1 mol為0.23 mоl之TMEDA，除此以外，進行與製造例11相同之操作。所獲得之氫化共軛二烯系共聚物(23)之苯乙烯含量30質量%、重量平均分子量6.5×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)35%、氫化率為99%。 <(Comparative Production Example 8): Hydrogenated covalent diene copolymer (23)> The same operation as in Production Example 11 was performed except that 0.15 parts by mass of n-butyl lithium was added to 100 parts by mass of all monomers and 0.23 mol of TMEDA was added to 1 mol of n-butyl lithium. The obtained hydrogenated covalent diene copolymer (23) had a styrene content of 30% by mass, a weight average molecular weight of 6.5×10 ⁴ , a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 35%, and a hydrogenation rate of 99%.

＜(比較製造例9)：氫化共軛二烯系共聚物(24)＞使用具備攪拌裝置與夾套之槽型反應器(內容積10 L)進行分批聚合。首先，投入包含苯乙烯20質量份之環己烷溶液(濃度20質量%)。其次，添加相對於全部單體100質量份為0.12質量份之正丁基鋰、及相對於正丁基鋰1 mol為0.22 mоl之四甲基乙二胺(TMEDA)，於70℃下進行15分鐘聚合。其次，添加包含丁二烯60質量份之環己烷溶液(濃度20質量%)，於70℃下進行30分鐘聚合。其次，添加包含苯乙烯20質量份之環己烷溶液(濃度20質量%)，於70℃下進行15分鐘聚合。其後，添加甲醇使聚合反應停止。按照如上方式獲得之共軛二烯系共聚物(24)之苯乙烯含量40質量%、重量平均分子量7.5×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)35%。使用所獲得之共軛二烯系共聚物，進而相對於共軛二烯系共聚物每100質量份，添加以Ti基準計90 ppm之按照如上方式製備之氫化觸媒，於氫氣壓力0.7 MPa、溫度80℃下進行約1.00小時之氫化反應，獲得氫化共軛二烯系共聚物(24)。所獲得之氫化共軛二烯系嵌段共聚物之氫化率為98%。＜(Comparative Production Example 9): Hydrogenated covalent diene copolymer (24)＞ Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 20 parts by mass of styrene (concentration 20 mass%) was added. Next, 0.12 parts by mass of n-butyl lithium relative to 100 parts by mass of all monomers and 0.22 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyl lithium were added, and polymerization was carried out at 70°C for 15 minutes. Next, a cyclohexane solution containing 60 parts by mass of butadiene (concentration 20 mass%) was added, and polymerization was carried out at 70°C for 30 minutes. Next, a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 15 minutes. Thereafter, methanol was added to terminate the polymerization reaction. The covalent diene copolymer (24) obtained in the above manner had a styrene content of 40% by mass, a weight average molecular weight of 7.5×10 ⁴ , and a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 35%. The obtained covalent diene copolymer was used, and a hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by weight of the covalent diene copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80°C for about 1 hour to obtain a hydrogenated covalent diene copolymer (24). The hydrogenation rate of the obtained hydrogenated covalent diene block copolymer was 98%.

＜(比較製造例10)：氫化共軛二烯系共聚物(25)＞使用具備攪拌裝置與夾套之槽型反應器(內容積10 L)進行分批聚合。首先，投入包含苯乙烯22.5質量份之環己烷溶液(濃度20質量%)。其次，添加相對於全部單體100質量份為0.15質量份之正丁基鋰、及相對於正丁基鋰1 mol為0.11 mоl之四甲基乙二胺(TMEDA)，於70℃下進行20分鐘聚合。其次，添加包含丁二烯55質量份之環己烷溶液(濃度20質量%)，於70℃下進行30分鐘聚合。其次，添加包含苯乙烯22.5質量份之環己烷溶液(濃度20質量%)，於70℃下進行15分鐘聚合。其後，添加甲醇使聚合反應停止。按照如上方式獲得之共軛二烯系共聚物(25)之苯乙烯含量45質量%、重量平均分子量6.0×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)21%。使用所獲得之共軛二烯系共聚物，進而相對於共軛二烯系共聚物每100質量份，添加以Ti基準計90 ppm之按照如上方式製備之氫化觸媒，於氫氣壓力0.7 MPa、溫度80℃下進行約0.25小時之氫化反應，獲得氫化共軛二烯系共聚物(25)。所獲得之氫化共軛二烯系共聚物之氫化率為35%。＜(Comparative Production Example 10): Hydrogenated covalent diene copolymer (25)＞ Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 22.5 parts by mass of styrene (concentration 20 mass%) was added. Next, 0.15 parts by mass of n-butyl lithium relative to 100 parts by mass of all monomers and 0.11 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyl lithium were added, and polymerization was carried out at 70°C for 20 minutes. Next, a cyclohexane solution containing 55 parts by mass of butadiene (concentration 20 mass%) was added, and polymerization was carried out at 70°C for 30 minutes. Next, a cyclohexane solution containing 22.5 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 15 minutes. Thereafter, methanol was added to terminate the polymerization reaction. The covalent diene copolymer (25) obtained in the above manner had a styrene content of 45% by mass, a weight average molecular weight of 6.0×10 ⁴ , and a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 21%. The obtained covalent diene copolymer was used, and a hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by weight of the covalent diene copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80°C for about 0.25 hours to obtain a hydrogenated covalent diene copolymer (25). The hydrogenation rate of the obtained hydrogenated covalent diene copolymer was 35%.

＜(比較製造例11)：氫化共軛二烯系共聚物(26)＞添加相對於全部單體100質量份為0.081質量份之正丁基鋰、及相對於正丁基鋰1 mol為0.25 mоl之TMEDA，除此以外，進行與製造例6相同之操作。所獲得之氫化共軛二烯系共聚物(26)之苯乙烯含量60質量%、重量平均分子量9.9×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)35%、氫化率為99%。 <(Comparative Production Example 11): Hydrogenated covalent diene copolymer (26)> The same operation as in Production Example 6 was performed except that 0.081 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers, and 0.25 mol of TMEDA was added relative to 1 mol of n-butyl lithium. The obtained hydrogenated covalent diene copolymer (26) had a styrene content of 60% by mass, a weight average molecular weight of 9.9×10 ⁴ , a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 35%, and a hydrogenation rate of 99%.

＜(比較製造例12)：氫化共軛二烯系共聚物(27)＞使用具備攪拌裝置與夾套之槽型反應器(內容積10 L)進行分批聚合。首先，投入包含苯乙烯32.5質量份之環己烷溶液(濃度20質量%)。其次，添加相對於全部單體100質量份為0.14質量份之正丁基鋰、及相對於正丁基鋰1 mol為0.29 mоl之四甲基乙二胺(TMEDA)，於70℃下進行25分鐘聚合。其次，添加包含丁二烯35質量份之環己烷溶液(濃度20質量%)，於70℃下進行20分鐘聚合。其次，添加包含苯乙烯32.5質量份之環己烷溶液(濃度20質量%)，於70℃下進行25分鐘聚合。其後，添加甲醇使聚合反應停止。按照如上方式獲得之共軛二烯系共聚物(27)之苯乙烯含量65質量%、重量平均分子量5.5×10 ⁴、源自1,2-鍵及/或3,4-鍵之單元(a)之含量(乙烯基鍵量：單元(a)/丁二烯)41%。使用所獲得之共軛二烯系共聚物，進而相對於共軛二烯系共聚物每100質量份，添加以Ti基準計90 ppm之按照如上方式製備之氫化觸媒，於氫氣壓力0.7 MPa、溫度80℃下進行約1.00小時之氫化反應，獲得氫化共軛二烯系共聚物(27)。所獲得之氫化共軛二烯系共聚物(27)之氫化率為99%。＜(Comparative Production Example 12): Hydrogenated covalent diene copolymer (27)＞ Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 32.5 parts by mass of styrene (concentration 20 mass%) was added. Next, 0.14 parts by mass of n-butyl lithium relative to 100 parts by mass of all monomers and 0.29 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyl lithium were added, and polymerization was carried out at 70°C for 25 minutes. Next, a cyclohexane solution containing 35 parts by mass of butadiene (concentration 20 mass%) was added, and polymerization was carried out at 70°C for 20 minutes. Next, a cyclohexane solution containing 32.5 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 25 minutes. Methanol was then added to terminate the polymerization reaction. The covalent diene copolymer (27) obtained in the above manner had a styrene content of 65% by mass, a weight average molecular weight of 5.5×10 ⁴ , and a content of units (a) derived from 1,2-bonds and/or 3,4-bonds (vinyl bond content: unit (a)/butadiene) of 41%. The obtained covalent diene copolymer was used, and a hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by mass of the covalent diene copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80°C for about 1.00 hour to obtain a hydrogenated covalent diene copolymer (27). The hydrogenation rate of the obtained hydrogenated covalent diene copolymer (27) was 99%.

(成分(II)：自由基起始劑) Perbutyl P(日油股份有限公司製造) Percumyl D(日油股份有限公司製造) (Component (II): free radical initiator) Perbutyl P (manufactured by NOF Corporation) Percumyl D (manufactured by NOF Corporation)

(成分(III)：極性樹脂) ＜環氧樹脂＞雙酚A型環氧樹脂EXA-850CRP(DIC股份有限公司製造) (Component (III): Polar resin) ＜Epoxy resin＞ Bisphenol A type epoxy resin EXA-850CRP (manufactured by DIC Corporation)

＜聚醯亞胺系樹脂＞雙(3-乙基-5-甲基-4-順丁烯二醯亞胺苯基)甲烷(BMI-70)(K-I Chemical Industry股份有限公司製造) 4,4'-雙順丁烯二醯亞胺二苯基甲烷(BMI-H)(K-I Chemical Industry股份有限公司製造) ＜Polyimide resin＞ Bis(3-ethyl-5-methyl-4-cis-butylenediimidephenyl)methane (BMI-70) (manufactured by K-I Chemical Industry Co., Ltd.) 4,4'-Bis(cis-butylenediimidephenyl)methane (BMI-H) (manufactured by K-I Chemical Industry Co., Ltd.)

＜聚苯醚系樹脂(PPE樹脂)＞藉由如下方式聚合形成PPE樹脂。向於反應器底部具備用以導入含氧氣體之噴布器、攪拌渦輪翼及擋板、於反應器上部之排氣管線具備回流冷卻器之1.5升附夾套之反應器內，添加氯化銅二水合物0.2512 g、35%鹽酸1.1062 g、二正丁基胺3.6179 g、N,N,N',N'-四甲基丙二胺9.5937 g、甲醇211.63 g、正丁醇493.80 g、及包含5莫耳%之2,2-雙(3,5-二甲基-4-羥基苯基)丙烷之2,6-二甲基苯酚180.0 g。使用溶劑之組成質量比為正丁醇：甲醇＝70：30。繼而，一面劇烈攪拌一面經由噴布器以180 mL/min之速度向反應器內開始導入氧氣，與此同時，向夾套內通入熱媒調節聚合溫度以使其保持於40℃。聚合液逐漸呈現漿料狀態。待聚苯醚達到所需數量平均分子量時停止通入含氧氣體，將所獲得之聚合混合物加溫至50℃。繼而，逐次少量添加對苯二酚(和光純藥公司製造之試劑)，並繼續保持於50℃，直至漿料狀之聚苯醚變成白色。繼而，添加包含6.5質量%之36%鹽酸之甲醇溶液720 g，進行過濾，再用甲醇重複清洗，獲得濕潤之聚苯醚。繼而，於100℃下真空乾燥，獲得乾燥之聚苯醚。ηsp/c為0.103 dl/g、產率為97%。測定ηsp/c時，將上述聚苯醚製成0.5 g/dl之氯仿溶液，使用烏氏黏度計，求出30℃下之還原黏度(ηsp/c)。單元為dl/g。藉由如下方式對所獲得之聚苯醚進行改性。將聚苯醚152.5 g及甲苯152.5 g進行混合，加熱至約85℃。繼而，添加二甲基胺基吡啶2.1 g。待固體完全溶解時，緩慢添加甲基丙烯酸酐18.28 g。一面連續混合所獲得之溶液一面於85℃下維持3小時。繼而，將溶液冷卻至室溫，獲得甲基丙烯酸酯封端聚苯醚之甲苯溶液。將所獲得之甲苯溶液一面攪拌一面加入具備均質機之圓筒狀3升SUS容器內，逐次少量滴加10℃之甲醇1000 mL。對所獲得之粉體進行過濾，用甲醇洗浄，於85℃氮氣下乾燥18小時。 <Polyphenylene ether resin (PPE resin)> The PPE resin was polymerized as follows. Into a 1.5-liter jacketed reactor equipped with a sparger for introducing oxygen-containing gas, a stirring turbine blade and a baffle at the bottom of the reactor, and a reflux cooler at the exhaust line at the top of the reactor, 0.2512 g of cupric chloride dihydrate, 1.1062 g of 35% hydrochloric acid, 3.6179 g of di-n-butylamine, 9.5937 g of N,N,N',N'-tetramethylpropylenediamine, 211.63 g of methanol, 493.80 g of n-butanol, and 180.0 g of 2,6-dimethylphenol containing 5 mol% of 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane were added. The mass ratio of the solvent used is n-butanol: methanol = 70:30. Then, while stirring vigorously, oxygen is introduced into the reactor through a sprayer at a rate of 180 mL/min. At the same time, a heat medium is introduced into the jacket to adjust the polymerization temperature so that it is maintained at 40°C. The polymerization liquid gradually presents a slurry state. When the polyphenylene ether reaches the required average molecular weight, the introduction of oxygen-containing gas is stopped, and the obtained polymerization mixture is heated to 50°C. Then, hydroquinone (a reagent manufactured by Wako Junyaku Co., Ltd.) is added in small amounts gradually, and the temperature is maintained at 50°C until the slurry-like polyphenylene ether turns white. Next, 720 g of a methanol solution containing 6.5 mass % of 36% hydrochloric acid was added, filtered, and repeatedly washed with methanol to obtain a wet polyphenylene ether. Next, vacuum drying was performed at 100°C to obtain a dry polyphenylene ether. ηsp/c was 0.103 dl/g and the yield was 97%. When measuring ηsp/c, the above polyphenylene ether was made into a 0.5 g/dl chloroform solution, and the reduced viscosity (ηsp/c) at 30°C was determined using an Oobleck viscometer. The unit is dl/g. The obtained polyphenylene ether was modified as follows. 152.5 g of polyphenylene ether and 152.5 g of toluene were mixed and heated to about 85°C. Next, 2.1 g of dimethylaminopyridine was added. When the solid is completely dissolved, slowly add 18.28 g of methacrylic anhydride. While continuously mixing the obtained solution, maintain it at 85°C for 3 hours. Then, cool the solution to room temperature to obtain a toluene solution of methacrylate-terminated polyphenylene ether. Add the obtained toluene solution into a cylindrical 3-liter SUS container equipped with a homogenizer while stirring, and gradually add 1000 mL of 10°C methanol in small amounts. Filter the obtained powder, wash with methanol, and dry it at 85°C under nitrogen for 18 hours.

＜苯氧基樹脂＞ YP-50S(Nippon Steel Chemicals公司製造) <Phenoxy resin> YP-50S (manufactured by Nippon Steel Chemicals)

(成分(IV)：硬化劑) 氰酸酯系硬化劑2,2-雙(4-氰酸基苯基)丙烷(東京化成股份有限公司製造) 二胺系硬化劑4,4'-二胺基二苯基甲烷(東京化成股份有限公司製造) 1-苄基-2-苯基咪唑(東京化成工業股份有限公司製造) 酚系硬化劑KA-1163(DIC股份有限公司製造) 異氰尿酸三烯丙酯(TAIC ^TM)(Mitsubishi Chemical公司製造) (Component (IV): Hardener) Cyanate hardener 2,2-bis(4-cyanatophenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd.) Diamine hardener 4,4'-diaminodiphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.) 1-Benzyl-2-phenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) Phenol hardener KA-1163 (manufactured by DIC Corporation) Triallyl isocyanurate (TAIC ^™ ) (manufactured by Mitsubishi Chemical Co., Ltd.)

[樹脂組合物之物性之測定方法] ((1)介電損耗因數及介電常數) 藉由空腔共振法測定10 GHz下之介電損耗因數及介電常數。作為測定裝置，使用網路分析儀(N5230A，AgilentTechnologies公司製造)、及關東電子應用開發公司製造之空腔共振器(Cavity Resornator CP系列)。作為測定樣品，自後述硬化物膜切出寬2.6 mm×長80 mm之試驗片作為測定樣品。使用上述測得之介電損耗因數及介電常數，按照以下之基準評價下述實施例及比較例。 [Measurement method of physical properties of resin composition] ((1) Dielectric dissipation factor and dielectric constant) The dielectric dissipation factor and dielectric constant at 10 GHz were measured by the cavity resonance method. As the measurement apparatus, a network analyzer (N5230A, manufactured by Agilent Technologies) and a cavity resonator (Cavity Resornator CP series) manufactured by Kanto Electronics Application Development Co., Ltd. were used. As the measurement sample, a test piece of 2.6 mm wide × 80 mm long was cut out from the cured film described later. Using the dielectric dissipation factor and dielectric constant measured above, the following examples and comparative examples were evaluated according to the following criteria.

＜(實施例1～17)及(比較例1～13)中之評價基準＞基於不含共軛二烯系共聚物之比較例1與各實施例或比較例之介電損耗因數及介電常數之差(比較例1－各實施例或比較例)進行評價。介電損耗因數 ◎：0.025以上 ○：0.020以上且未達0.025 △：0.015以上且未達0.020 ×：未達0.015(亦包括差值為0及差值為負數) 介電常數 ◎：0.30以上 ○：0.20以上且未達0.25 △：0.15以上且未達0.20 ×：未達0.15(亦包括差值為0及差值為負數) <Evaluation criteria in (Examples 1 to 17) and (Comparative Examples 1 to 13)> Evaluation was performed based on the difference in dielectric dissipation factor and dielectric constant between Comparative Example 1, which does not contain a covalent diene copolymer, and each Example or Comparative Example (Comparative Example 1 - each Example or Comparative Example). Dielectric dissipation factor ◎: 0.025 or more ○: 0.020 or more but less than 0.025 △: 0.015 or more but less than 0.020 ×: less than 0.015 (including the difference of 0 and the difference of negative number) Dielectric constant ◎: 0.30 or more ○: 0.20 or more but less than 0.25 △: 0.15 or more but less than 0.20 ×: less than 0.15 (including the difference of 0 and the difference of negative number)

＜(實施例18～25)及(比較例14～30)中之評價基準＞基於不含共軛二烯系共聚物之比較例14與各實施例或比較例之介電損耗因數及介電常數之差(比較例14－各實施例或比較例)進行評價。介電損耗因數 ◎：0.00090以上 ○：0.00080以上且未達0.00090 △：0.00070以上且未達0.00080 ×：未達0.00070(亦包括差值為0及差值為負數) 介電常數 ◎：0.25以上 ○：0.20以上且未達0.25 △：0.15以上且未達0.20 ×：未達0.15(亦包括差值為0及差值為負數) <Evaluation criteria in (Examples 18 to 25) and (Comparative Examples 14 to 30)> Evaluation was performed based on the difference in dielectric loss factor and dielectric constant between Comparative Example 14, which does not contain a covalent diene copolymer, and each of the Examples or Comparative Examples (Comparative Example 14 - each of the Examples or Comparative Examples). Dielectric dissipation factor ◎: 0.00090 or more ○: 0.00080 or more but less than 0.00090 △: 0.00070 or more but less than 0.00080 ×: less than 0.00070 (including the difference of 0 and the difference of negative number) Dielectric constant ◎: 0.25 or more ○: 0.20 or more but less than 0.25 △: 0.15 or more but less than 0.20 ×: less than 0.15 (including the difference of 0 and the difference of negative number)

＜(實施例26～40)及(比較例31～43)中之評價基準＞基於不含共軛二烯系共聚物之比較例31與各實施例或比較例之介電損耗因數及介電常數之差(比較例31－各實施例或比較例)進行評價。介電損耗因數 ◎：0.00070以上 ○：0.00060以上且未達0.00070 △：0.00050以上且未達0.00060 ×：未達0.00050(亦包括差值為0及差值為負數) 介電常數 ◎：0.10以上 ○：0.08以上且未達0.10 △：0.05以上且未達0.08 ×：未達0.05(亦包括差值為0及差值為負數) <Evaluation criteria in (Examples 26 to 40) and (Comparative Examples 31 to 43)> Evaluation was performed based on the difference in dielectric dissipation factor and dielectric constant between Comparative Example 31, which does not contain a covalent diene copolymer, and each of the Examples or Comparative Examples (Comparative Example 31 - each of the Examples or Comparative Examples). Dielectric dissipation factor ◎: 0.00070 or more ○: 0.00060 or more and less than 0.00070 △: 0.00050 or more and less than 0.00060 ×: less than 0.00050 (including the difference of 0 and the difference of negative number) Dielectric constant ◎: 0.10 or more ○: 0.08 or more and less than 0.10 △: 0.05 or more and less than 0.08 ×: less than 0.05 (including the difference of 0 and the difference of negative number)

((2)強度(拉伸強度)) 將包含後述樹脂組合物之硬化物之片材沖裁成JIS1號啞鈴，於常溫下以拉伸速度1 mm/min進行拉伸試驗，算出拉伸強度(MPa)。使用上述測得之拉伸強度，按照以下之基準評價下述實施例及比較例。 ((2) Strength (tensile strength)) A sheet containing the cured product of the resin composition described below was punched into a JIS No. 1 dumbbell and subjected to a tensile test at room temperature at a tensile speed of 1 mm/min to calculate the tensile strength (MPa). The following examples and comparative examples were evaluated according to the following criteria using the tensile strength measured above.

＜(實施例1～17)及(比較例1～13)中之評價基準＞基於不含共軛二烯系共聚物之比較例1與各實施例或比較例之拉伸強度之差(比較例1－各實施例或比較例)進行評價。拉伸強度 ◎：0.7倍以上 ○：0.5倍以上且未達0.7倍 △：0.3倍以上且未達0.5倍 ×：未達0.3倍 <Evaluation criteria in (Examples 1 to 17) and (Comparative Examples 1 to 13)> Evaluation was performed based on the difference in tensile strength between Comparative Example 1, which does not contain a covalent diene copolymer, and each Example or Comparative Example (Comparative Example 1 - each Example or Comparative Example). Tensile strength ◎: 0.7 times or more ○: 0.5 times or more and less than 0.7 times △: 0.3 times or more and less than 0.5 times ×: less than 0.3 times

＜(實施例18～25)及(比較例14～30)中之評價基準＞基於不含共軛二烯系共聚物之比較例14與各實施例或比較例之拉伸強度之差(比較例14－各實施例或比較例)進行評價。拉伸強度 ◎：0.7倍以上 ○：0.5倍以上且未達0.7倍 △：0.3倍以上且未達0.5倍 ×：未達0.3倍 <Evaluation criteria in (Examples 18 to 25) and (Comparative Examples 14 to 30)> Evaluation was performed based on the difference in tensile strength between Comparative Example 14, which does not contain a covalent diene copolymer, and each Example or Comparative Example (Comparative Example 14 - Each Example or Comparative Example). Tensile strength ◎: 0.7 times or more ○: 0.5 times or more and less than 0.7 times △: 0.3 times or more and less than 0.5 times ×: less than 0.3 times

＜(實施例26～40)及(比較例31～43)中之評價基準＞基於不含共軛二烯系共聚物之比較例31與各實施例或比較例之拉伸強度之差(比較例31－各實施例或比較例)進行評價。拉伸強度 ◎：0.7倍以上 ○：0.5倍以上且未達0.7倍 △：0.3倍以上且未達0.5倍 ×：未達0.3倍 <Evaluation criteria in (Examples 26 to 40) and (Comparative Examples 31 to 43)> Evaluation was performed based on the difference in tensile strength between Comparative Example 31 not containing a covalent diene copolymer and each Example or Comparative Example (Comparative Example 31 - Each Example or Comparative Example). Tensile strength ◎: 0.7 times or more ○: 0.5 times or more and less than 0.7 times △: 0.3 times or more and less than 0.5 times ×: less than 0.3 times

(3)低翹曲性於聚醯亞胺膜塗佈後述各樹脂組合物，乾燥去除溶劑後，重疊厚度35 μm之銅箔，於100℃、1 MPa下加熱壓接2分鐘，藉此層壓銅箔，製作包含聚醯亞胺膜-樹脂組合物-銅箔之積層體。將上述積層體以樹脂組合物層成為上面之方式置於厚1 mm之SUS板上，用聚醯亞胺膠帶固定四角後，於180℃下加熱1小時，藉此使樹脂組合物硬化。硬化後，將上述4個聚醯亞胺膠帶中之3個剝離，放置10分鐘。10分鐘後，取上述積層體之銅箔部分與SUS板之距離中之最高值作為翹曲值。又，按照以下之基準評價上述翹曲值。 ○：翹曲之大小未達2 cm △：翹曲之大小為2 cm以上且未達4 cm ×：翹曲之大小為4 cm以上 (3) Low warp property The resin compositions described later were coated on the polyimide film, dried to remove the solvent, and then a copper foil with a thickness of 35 μm was superimposed and heated and pressed at 100°C and 1 MPa for 2 minutes to produce a laminate comprising polyimide film-resin composition-copper foil. The laminate was placed on a 1 mm thick SUS plate with the resin composition layer on top, and the four corners were fixed with polyimide tapes. The resin composition was heated at 180°C for 1 hour to cure. After curing, three of the four polyimide tapes were peeled off and left for 10 minutes. After 10 minutes, the maximum value of the distance between the copper foil part of the laminate and the SUS plate was taken as the warp value. In addition, the warp value was evaluated according to the following criteria. ○: The warp size is less than 2 cm △: The warp size is more than 2 cm and less than 4 cm ×: The warp size is more than 4 cm

[樹脂組合物之製作] (實施例1～17)、(比較例1～13) 將成分比及物性示於下述表3～4。首先，將除酚系硬化劑、苯氧基樹脂以外者添加至甲苯中，進行攪拌使之溶解，製備濃度20質量%～50質量%之清漆。酚系硬化劑係以甲基乙基酮(直接使用和光純藥股份有限公司製造之特級品)作為溶劑，製備濃度50質量%之酚系硬化劑溶液，添加至上述清漆中，進行攪拌製備清漆。苯氧基樹脂係以環己酮(直接使用和光純藥股份有限公司製造之特級品)作為溶劑，製備濃度25質量%之苯氧基樹脂溶液，添加至上述清漆中，進行攪拌製備清漆。將清漆以30 mm/秒之速度塗佈於經離型處理之Kapton膜上，其後，於氮氣流下利用風乾機於100℃下乾燥30分鐘，獲得膜。於氮氣流下利用風乾機使所獲得之膜於200℃下進行90分鐘之硬化反應，獲得硬化物膜。將硬化物膜供於評價樣品。 [Preparation of resin composition] (Examples 1 to 17), (Comparative Examples 1 to 13) The component ratios and physical properties are shown in Tables 3 to 4 below. First, the components other than the phenolic hardener and the phenoxy resin are added to toluene and stirred to dissolve to prepare a varnish having a concentration of 20% to 50% by mass. The phenolic hardener is prepared by using methyl ethyl ketone (a special grade product manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent, and a phenolic hardener solution having a concentration of 50% by mass is prepared and added to the above-mentioned varnish and stirred to prepare the varnish. The phenoxy resin was prepared with cyclohexanone (special grade product manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent, and a phenoxy resin solution with a concentration of 25 mass% was added to the above varnish and stirred to prepare the varnish. The varnish was applied to the release treated Kapton film at a speed of 30 mm/sec, and then dried at 100°C for 30 minutes in a wind dryer under a nitrogen flow to obtain a film. The obtained film was cured at 200°C for 90 minutes in a wind dryer under a nitrogen flow to obtain a cured film. The cured film was provided as an evaluation sample.

(實施例18～25)、(比較例14～30) 首先，使作為極性樹脂之聚醯亞胺系樹脂與氰酸酯系硬化劑及/或二胺系硬化劑按照下述表5、6之調配比率於160℃下溶解，一面攪拌一面反應6小時，獲得雙順丁烯二醯亞胺-三𠯤樹脂低聚物。使所獲得之雙順丁烯二醯亞胺-三𠯤樹脂低聚物溶解於甲苯，添加剩餘成分，進行攪拌使之溶解，製備濃度20質量%～50質量%之清漆。將上述清漆以30 mm/秒之速度塗佈於經離型處理之Kapton膜上，其後，於氮氣流下利用風乾機於100℃下乾燥30分鐘，獲得膜。於氮氣流下利用風乾機使膜於200℃下進行最長90分鐘之硬化反應，獲得硬化物膜。將硬化物膜供於評價樣品。 (Examples 18 to 25), (Comparative Examples 14 to 30) First, a polyimide resin as a polar resin and a cyanate hardener and/or a diamine hardener are dissolved at 160°C according to the mixing ratios in Tables 5 and 6 below, and reacted for 6 hours while stirring to obtain a dibutylene diimide-trisin resin oligomer. The obtained dibutylene diimide-trisin resin oligomer is dissolved in toluene, and the remaining components are added and stirred to dissolve, thereby preparing a varnish with a concentration of 20% to 50% by mass. The above varnish was applied to the release treated Kapton film at a speed of 30 mm/sec, and then dried at 100°C for 30 minutes in a wind dryer under a nitrogen flow to obtain a film. The film was cured at 200°C for up to 90 minutes in a wind dryer under a nitrogen flow to obtain a cured film. The cured film was provided as an evaluation sample.

(實施例26～40)、(比較例31～43) 將成分比及物性示於下述表7、8。首先，將各成分添加至甲苯(直接使用和光純藥股份有限公司製造之特級品)中，進行攪拌使之溶解，製備濃度20質量%～50質量%之清漆。將清漆以30 mm/秒之速度塗佈於經離型處理之Kapton膜上，其後，於氮氣流下利用風乾機於100℃下乾燥30分鐘，獲得膜。於氮氣流下利用風乾機使所獲得之膜於200℃下進行90分鐘之硬化反應，獲得硬化物膜。將硬化物膜供於評價樣品。 (Examples 26 to 40), (Comparative Examples 31 to 43) The component ratios and physical properties are shown in Tables 7 and 8 below. First, each component was added to toluene (special grade product manufactured by Wako Pure Chemical Industries, Ltd. was used directly), stirred to dissolve, and a varnish with a concentration of 20% to 50% by mass was prepared. The varnish was applied to a release-treated Kapton film at a speed of 30 mm/sec, and then dried at 100°C for 30 minutes in a blow dryer under a nitrogen flow to obtain a film. The obtained film was subjected to a curing reaction at 200°C for 90 minutes in a blow dryer under a nitrogen flow to obtain a cured film. The cured film was provided as an evaluation sample.

顯而易見，實施例之使用氫化共軛二烯系共聚物之硬化物於介電性能與強度之均衡性上優異。從而可知本發明之硬化物適宜用於使用玻璃布、金屬積層板之印刷配線板。Obviously, the cured product of the hydrogenated covalent diene copolymer of the embodiment has an excellent balance between dielectric properties and strength. It can be seen that the cured product of the present invention is suitable for use in printed wiring boards using glass cloth and metal laminates.

[表1] (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) 結構 - A-B-A A-B-A A-B-A A-B-A A-B-A A-B-A A-B-A A-B-A A-B-A A-C-A A-B-A A-C-A A-C-A 乙烯基芳香族單體量質量% 20 20 60 60 60 60 60 60 75 30 30 30 30 乙烯基鍵量 % 60 70 71 71 70 70 70 71 70 69 69 70 70 重量平均分子量萬 6.0 6.0 6.0 6.0 6.0 6.1 10.0 4.1 5.9 15.1 15.0 15.0 15.0 氫化率 % 45 45 0 45 84 99 45 46 44 98 99 7 91 [Table 1] (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) Structure - ABA ABA ABA ABA ABA ABA ABA ABA ABA ACA ABA ACA ACA Vinyl aromatic monomer content Quality% 20 20 60 60 60 60 60 60 75 30 30 30 30 Vinyl Key % 60 70 71 71 70 70 70 71 70 69 69 70 70 Weight average molecular weight ten thousand 6.0 6.0 6.0 6.0 6.0 6.1 10.0 4.1 5.9 15.1 15.0 15.0 15.0 Hydrogenation rate % 45 45 0 45 84 99 45 46 44 98 99 7 91

[表2] (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) (25) (26) (27) 結構 - B-C-B A-B-A A-B-A A-B-A A-B-A A-B-A A-C-A A-B-A A-B-A A-B-A A-B-A A-B-A A-B-A A-B-A 乙烯基芳香族單體量質量% 80 30 10 10 60 60 30 30 30 30 40 45 60 65 乙烯基鍵量 % 60 81 60 69 50 70 49 41 35 35 35 21 35 41 重量平均分子量萬 6.5 8.1 6.0 15.9 6.0 3.0 15.0 7.5 8.1 6.5 7.5 6.0 9.9 5.5 氫化率 % 30 74 44 99 45 45 98 98 99 99 98 35 99 99 [Table 2] (14) (15) (16) (17) (18) (19) (20) (twenty one) (twenty two) (twenty three) (twenty four) (25) (26) (27) Structure - BCB ABA ABA ABA ABA ABA ACA ABA ABA ABA ABA ABA ABA ABA Vinyl aromatic monomer content Quality% 80 30 10 10 60 60 30 30 30 30 40 45 60 65 Vinyl Key % 60 81 60 69 50 70 49 41 35 35 35 twenty one 35 41 Weight average molecular weight ten thousand 6.5 8.1 6.0 15.9 6.0 3.0 15.0 7.5 8.1 6.5 7.5 6.0 9.9 5.5 Hydrogenation rate % 30 74 44 99 45 45 98 98 99 99 98 35 99 99

[表3] 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 實施例11 實施例12 實施例13 實施例14 實施例15 實施例16 實施例17 成分(I) (1) 份 10 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 (2) 份 0 10 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 (3) 份 0 0 10 0 0 0 0 0 0 0 0 0 0 0 0 0 0 (4) 份 0 0 0 10 0 0 0 0 0 0 0 0 0 0 0 0 0 (5) 份 0 0 0 0 10 0 0 0 0 0 0 0 0 0 0 0 0 (6) 份 0 0 0 0 0 10 0 0 0 0 0 0 0 0 0 0 0 (7) 份 0 0 0 0 0 0 10 0 0 0 0 0 0 0 0 0 0 (8) 份 0 0 0 0 0 0 0 10 0 0 0 0 0 0 0 0 0 (9) 份 0 0 0 0 0 0 0 0 10 0 0 0 0 0 0 0 0 (10) 份 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0 10 0 (11) 份 0 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0 10 (12) 份 0 0 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0 (13) 份 0 0 0 0 0 0 0 0 0 0 0 0 10 0 0 0 0 (14) 份 0 0 0 0 0 0 0 0 0 0 0 0 0 10 0 0 0 (15) 份 0 0 0 0 0 0 0 0 0 0 0 0 0 0 10 0 0 成分(II) Perbutyl P 份 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0 0 成分(III) EXA-850CRP 份 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 YP-50S 份 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 成分(IV) 1-苄基-2-苯基咪唑份 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 KA-1163 份 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 拉伸強度 - ○ ◎ ◎ ◎ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ ○ ◎ ◎ ◎ ◎ 介電損耗因數 - ◎ ◎ ○ ◎ ◎ ◎ ○ ◎ ○ ◎ ◎ ○ ◎ ○ ○ ◎ ◎ 介電常數 - ◎ ◎ ○ ◎ ◎ ◎ ○ ◎ ○ ◎ ◎ ○ ◎ ○ ○ ◎ ◎ 低翹曲性 - △ △ ○ ○ ○ △ ○ ○ ○ △ △ △ △ △ △ △ △ [table 3] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17 Ingredient (I) (1) share 10 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 (2) share 0 10 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 (3) share 0 0 10 0 0 0 0 0 0 0 0 0 0 0 0 0 0 (4) share 0 0 0 10 0 0 0 0 0 0 0 0 0 0 0 0 0 (5) share 0 0 0 0 10 0 0 0 0 0 0 0 0 0 0 0 0 (6) share 0 0 0 0 0 10 0 0 0 0 0 0 0 0 0 0 0 (7) share 0 0 0 0 0 0 10 0 0 0 0 0 0 0 0 0 0 (8) share 0 0 0 0 0 0 0 10 0 0 0 0 0 0 0 0 0 (9) share 0 0 0 0 0 0 0 0 10 0 0 0 0 0 0 0 0 (10) share 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0 10 0 (11) share 0 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0 10 (12) share 0 0 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0 (13) share 0 0 0 0 0 0 0 0 0 0 0 0 10 0 0 0 0 (14) share 0 0 0 0 0 0 0 0 0 0 0 0 0 10 0 0 0 (15) share 0 0 0 0 0 0 0 0 0 0 0 0 0 0 10 0 0 Component (II) Perbutyl P share 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0 0 Component (III) EXA-850CRP share 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 YP-50S share 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 Component (IV) 1-Benzyl-2-phenylimidazole share 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 KA-1163 share 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Tensile strength - ○ ◎ ◎ ◎ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ ○ ◎ ◎ ◎ ◎ Dielectric dissipation factor - ◎ ◎ ○ ◎ ◎ ◎ ○ ◎ ○ ◎ ◎ ○ ◎ ○ ○ ◎ ◎ Dielectric constant - ◎ ◎ ○ ◎ ◎ ◎ ○ ◎ ○ ◎ ◎ ○ ◎ ○ ○ ◎ ◎ Low curvature - △ △ ○ ○ ○ △ ○ ○ ○ △ △ △ △ △ △ △ △

[表4] 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 比較例7 比較例8 比較例9 比較例10 比較例11 比較例12 比較例13 成分(I) (16) 份 0 10 0 0 0 0 0 0 0 0 0 0 0 (17) 份 0 0 10 0 0 0 0 0 0 0 0 0 0 (18) 份 0 0 0 10 0 0 0 0 0 0 0 0 0 (19) 份 0 0 0 0 10 0 0 0 0 0 0 0 0 (20) 份 0 0 0 0 0 10 0 0 0 0 0 0 0 (21) 份 0 0 0 0 0 0 10 0 0 0 0 0 0 (22) 份 0 0 0 0 0 0 0 10 0 0 0 0 0 (23) 份 0 0 0 0 0 0 0 0 10 0 0 0 0 (24) 份 0 0 0 0 0 0 0 0 0 10 0 0 0 (25) 份 0 0 0 0 0 0 0 0 0 0 10 0 0 (26) 份 0 0 0 0 0 0 0 0 0 0 0 10 0 (27) 份 0 0 0 0 0 0 0 0 0 0 0 0 10 成分(II) Perbutyl P 份 1 1 1 1 1 1 1 1 1 1 1 1 1 成分(III) EXA-850CRP 份 40 35 35 35 35 35 35 35 35 35 35 35 35 YP-50S 份 40 35 35 35 35 35 35 35 35 35 35 35 35 成分(IV) 1-苄基-2-苯基咪唑份 0.1 5 5 5 5 5 5 5 5 5 5 5 5 KA-1163 份 20 20 20 20 20 20 20 20 20 20 20 20 20 TAIC 份 10 0 0 0 0 10 10 10 10 10 10 10 10 拉伸強度 - - × × × △ × × × × × × × × 介電損耗因數 - - △ △ △ ○ × × × × × △ △ △ 介電常數 - - △ △ △ ○ × × × × × △ △ △ 低翹曲性 - ○ × × △ × × × × × △ × △ △ [Table 4] Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 Comparison Example 5 Comparative Example 6 Comparison Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Ingredient (I) (16) share 0 10 0 0 0 0 0 0 0 0 0 0 0 (17) share 0 0 10 0 0 0 0 0 0 0 0 0 0 (18) share 0 0 0 10 0 0 0 0 0 0 0 0 0 (19) share 0 0 0 0 10 0 0 0 0 0 0 0 0 (20) share 0 0 0 0 0 10 0 0 0 0 0 0 0 (twenty one) share 0 0 0 0 0 0 10 0 0 0 0 0 0 (twenty two) share 0 0 0 0 0 0 0 10 0 0 0 0 0 (twenty three) share 0 0 0 0 0 0 0 0 10 0 0 0 0 (twenty four) share 0 0 0 0 0 0 0 0 0 10 0 0 0 (25) share 0 0 0 0 0 0 0 0 0 0 10 0 0 (26) share 0 0 0 0 0 0 0 0 0 0 0 10 0 (27) share 0 0 0 0 0 0 0 0 0 0 0 0 10 Component (II) Perbutyl P share 1 1 1 1 1 1 1 1 1 1 1 1 1 Component (III) EXA-850CRP share 40 35 35 35 35 35 35 35 35 35 35 35 35 YP-50S share 40 35 35 35 35 35 35 35 35 35 35 35 35 Component (IV) 1-Benzyl-2-phenylimidazole share 0.1 5 5 5 5 5 5 5 5 5 5 5 5 KA-1163 share 20 20 20 20 20 20 20 20 20 20 20 20 20 TAIC share 10 0 0 0 0 10 10 10 10 10 10 10 10 Tensile strength - - × × × △ × × × × × × × × Dielectric dissipation factor - - △ △ △ ○ × × × × × △ △ △ Dielectric constant - - △ △ △ ○ × × × × × △ △ △ Low curvature - ○ × × △ × × × × × △ × △ △

[表5] 實施例18 實施例19 實施例20 實施例21 實施例22 實施例23 實施例24 實施例25 成分(I) (2) 份 10 0 0 0 10 0 0 0 (4) 份 0 10 0 0 0 10 0 0 (8) 份 0 0 10 0 0 0 10 0 (10) 份 0 0 0 10 0 0 0 10 成分(II) Percumyl D 份 1 1 1 1 1 1 1 1 成分(III) BMI-70 份 27.5 27.5 27.5 27.5 0 0 0 0 BMI-H 份 5 5 5 5 75 75 75 75 成分(IV) 氰酸酯系硬化劑份 72.5 72.5 72.5 72.5 0 0 0 0 4,4'-二胺基二苯基甲烷份 0 0 0 0 25 25 25 25 拉伸強度 - ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 介電損耗因數 - ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 介電常數 - ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 低翹曲性 - △ ○ ○ △ △ ○ ○ △ [table 5] Embodiment 18 Embodiment 19 Embodiment 20 Embodiment 21 Embodiment 22 Embodiment 23 Embodiment 24 Embodiment 25 Ingredient (I) (2) share 10 0 0 0 10 0 0 0 (4) share 0 10 0 0 0 10 0 0 (8) share 0 0 10 0 0 0 10 0 (10) share 0 0 0 10 0 0 0 10 Component (II) Percumyl D share 1 1 1 1 1 1 1 1 Component (III) BMI-70 share 27.5 27.5 27.5 27.5 0 0 0 0 BMI-H share 5 5 5 5 75 75 75 75 Component (IV) Cyanate ester hardener share 72.5 72.5 72.5 72.5 0 0 0 0 4,4'-Diaminodiphenylmethane share 0 0 0 0 25 25 25 25 Tensile strength - ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Dielectric dissipation factor - ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Dielectric constant - ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Low curvature - △ ○ ○ △ △ ○ ○ △

[表6] 比較例14 比較例15 比較例16 比較例17 比較例18 比較例19 比較例20 比較例21 比較例22 比較例23 比較例24 比較例25 比較例26 比較例27 比較例28 比較例29 比較例30 成分(I) (16) 份 0 0 10 0 0 0 0 0 0 0 0 0 0 0 10 0 0 (17) 份 0 0 0 10 0 0 0 0 0 0 0 0 0 0 0 0 0 (18) 份 0 0 0 0 10 0 0 0 0 0 0 0 0 0 0 0 0 (19) 份 0 0 0 0 0 10 0 0 0 0 0 0 0 0 0 10 0 (20) 份 0 0 0 0 0 0 10 0 0 0 0 0 0 0 0 0 10 (21) 份 0 0 0 0 0 0 0 10 0 0 0 0 0 0 0 0 0 (22) 份 0 0 0 0 0 0 0 0 10 0 0 0 0 0 0 0 0 (23) 份 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0 0 0 (24) 份 0 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0 0 (25) 份 0 0 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0 (26) 份 0 0 0 0 0 0 0 0 0 0 0 0 10 0 0 0 0 (27) 份 0 0 0 0 0 0 0 0 0 0 0 0 0 10 0 0 0 成分(II) Percumyl D 份 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 成分(III) BMI-70 份 25 0 25 25 25 25 25 25 25 25 25 25 25 25 0 0 0 BMI-H 份 5 75 5 5 5 5 5 5 5 5 5 5 5 5 75 75 75 成分(IV) 氰酸酯系硬化劑份 70 0 70 70 70 70 70 70 70 70 70 70 70 70 0 0 0 4,4'-二胺基二苯基甲烷份 0 25 0 0 0 0 0 0 0 0 0 0 0 0 25 25 25 拉伸強度 - - ○ × × × △ × × × × × × × × × △ × 介電損耗因數 - - × △ △ △ ○ × × × × × △ △ △ △ ○ × 介電常數 - - × △ △ △ ○ × × × × × △ △ △ △ ○ × 低翹曲性 - ○ ○ × × △ × × × × × △ × △ △ × × × [Table 6] Comparative Example 14 Comparative Example 15 Comparative Example 16 Comparative Example 17 Comparative Example 18 Comparative Example 19 Comparative Example 20 Comparative Example 21 Comparative Example 22 Comparative Example 23 Comparative Example 24 Comparative Example 25 Comparative Example 26 Comparative Example 27 Comparative Example 28 Comparative Example 29 Comparative Example 30 Ingredient (I) (16) share 0 0 10 0 0 0 0 0 0 0 0 0 0 0 10 0 0 (17) share 0 0 0 10 0 0 0 0 0 0 0 0 0 0 0 0 0 (18) share 0 0 0 0 10 0 0 0 0 0 0 0 0 0 0 0 0 (19) share 0 0 0 0 0 10 0 0 0 0 0 0 0 0 0 10 0 (20) share 0 0 0 0 0 0 10 0 0 0 0 0 0 0 0 0 10 (twenty one) share 0 0 0 0 0 0 0 10 0 0 0 0 0 0 0 0 0 (twenty two) share 0 0 0 0 0 0 0 0 10 0 0 0 0 0 0 0 0 (twenty three) share 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0 0 0 (twenty four) share 0 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0 0 (25) share 0 0 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0 (26) share 0 0 0 0 0 0 0 0 0 0 0 0 10 0 0 0 0 (27) share 0 0 0 0 0 0 0 0 0 0 0 0 0 10 0 0 0 Component (II) Percumyl D share 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Component (III) BMI-70 share 25 0 25 25 25 25 25 25 25 25 25 25 25 25 0 0 0 BMI-H share 5 75 5 5 5 5 5 5 5 5 5 5 5 5 75 75 75 Component (IV) Cyanate ester hardener share 70 0 70 70 70 70 70 70 70 70 70 70 70 70 0 0 0 4,4'-Diaminodiphenylmethane share 0 25 0 0 0 0 0 0 0 0 0 0 0 0 25 25 25 Tensile strength - - ○ × × × △ × × × × × × × × × △ × Dielectric dissipation factor - - × △ △ △ ○ × × × × × △ △ △ △ ○ × Dielectric constant - - × △ △ △ ○ × × × × × △ △ △ △ ○ × Low curvature - ○ ○ × × △ × × × × × △ × △ △ × × ×

[表7] 實施例26 實施例27 實施例28 實施例29 實施例30 實施例31 實施例32 實施例33 實施例34 實施例35 實施例36 實施例37 實施例38 實施例39 實施例40 成分(I) (1) 份 30 0 0 0 0 0 0 0 0 0 0 0 0 0 0 (2) 份 0 30 0 0 0 0 0 0 0 0 0 0 0 0 0 (3) 份 0 0 30 0 0 0 0 0 0 0 0 0 0 0 0 (4) 份 0 0 0 30 0 0 0 0 0 0 0 0 0 0 0 (5) 份 0 0 0 0 30 0 0 0 0 0 0 0 0 0 0 (6) 份 0 0 0 0 0 30 0 0 0 0 0 0 0 0 0 (7) 份 0 0 0 0 0 0 30 0 0 0 0 0 0 0 0 (8) 份 0 0 0 0 0 0 0 30 0 0 0 0 0 0 0 (9) 份 0 0 0 0 0 0 0 0 30 0 0 0 0 0 0 (10) 份 0 0 0 0 0 0 0 0 0 30 0 0 0 0 0 (11) 份 0 0 0 0 0 0 0 0 0 0 30 0 0 0 0 (12) 份 0 0 0 0 0 0 0 0 0 0 0 30 0 0 0 (13) 份 0 0 0 0 0 0 0 0 0 0 0 0 30 0 0 (14) 份 0 0 0 0 0 0 0 0 0 0 0 0 0 30 0 (15) 份 0 0 0 0 0 0 0 0 0 0 0 0 0 0 30 成分(II) Perbutyl P 份 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 成分(III) PPE 份 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 成分(IV) TAIC 份 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 拉伸強度 - ○ ◎ ◎ ◎ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ ○ ◎ ◎ 介電損耗因數 - ◎ ◎ ○ ◎ ◎ ◎ ○ ◎ ○ ◎ ◎ ○ ◎ ○ ○ 介電常數 - ◎ ◎ ○ ◎ ◎ ◎ ○ ◎ ○ ◎ ◎ ○ ◎ ○ ○ 低翹曲性 - △ △ ○ ○ ○ △ ○ ○ ○ △ △ △ △ △ △ [Table 7] Embodiment 26 Embodiment 27 Embodiment 28 Embodiment 29 Embodiment 30 Embodiment 31 Embodiment 32 Embodiment 33 Embodiment 34 Embodiment 35 Embodiment 36 Embodiment 37 Embodiment 38 Embodiment 39 Embodiment 40 Ingredient (I) (1) share 30 0 0 0 0 0 0 0 0 0 0 0 0 0 0 (2) share 0 30 0 0 0 0 0 0 0 0 0 0 0 0 0 (3) share 0 0 30 0 0 0 0 0 0 0 0 0 0 0 0 (4) share 0 0 0 30 0 0 0 0 0 0 0 0 0 0 0 (5) share 0 0 0 0 30 0 0 0 0 0 0 0 0 0 0 (6) share 0 0 0 0 0 30 0 0 0 0 0 0 0 0 0 (7) share 0 0 0 0 0 0 30 0 0 0 0 0 0 0 0 (8) share 0 0 0 0 0 0 0 30 0 0 0 0 0 0 0 (9) share 0 0 0 0 0 0 0 0 30 0 0 0 0 0 0 (10) share 0 0 0 0 0 0 0 0 0 30 0 0 0 0 0 (11) share 0 0 0 0 0 0 0 0 0 0 30 0 0 0 0 (12) share 0 0 0 0 0 0 0 0 0 0 0 30 0 0 0 (13) share 0 0 0 0 0 0 0 0 0 0 0 0 30 0 0 (14) share 0 0 0 0 0 0 0 0 0 0 0 0 0 30 0 (15) share 0 0 0 0 0 0 0 0 0 0 0 0 0 0 30 Component (II) Perbutyl P share 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Component (III) PPE share 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 Component (IV) TAIC share 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Tensile strength - ○ ◎ ◎ ◎ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ ○ ◎ ◎ Dielectric dissipation factor - ◎ ◎ ○ ◎ ◎ ◎ ○ ◎ ○ ◎ ◎ ○ ◎ ○ ○ Dielectric constant - ◎ ◎ ○ ◎ ◎ ◎ ○ ◎ ○ ◎ ◎ ○ ◎ ○ ○ Low curvature - △ △ ○ ○ ○ △ ○ ○ ○ △ △ △ △ △ △

[表8] 比較例31 比較例32 比較例33 比較例34 比較例35 比較例36 比較例37 比較例38 比較例39 比較例40 比較例41 比較例42 比較例43 成分(I) (16) 份 0 30 0 0 0 0 0 0 0 0 0 0 0 (17) 份 0 0 30 0 0 0 0 0 0 0 0 0 0 (18) 份 0 0 0 30 0 0 0 0 0 0 0 0 0 (19) 份 0 0 0 0 30 0 0 0 0 0 0 0 0 (20) 份 0 0 0 0 0 30 0 0 0 0 0 0 0 (21) 份 0 0 0 0 0 0 30 0 0 0 0 0 0 (22) 份 0 0 0 0 0 0 0 30 0 0 0 0 0 (23) 份 0 0 0 0 0 0 0 0 30 0 0 0 0 (24) 份 0 0 0 0 0 0 0 0 0 30 0 0 0 (25) 份 0 0 0 0 0 0 0 0 0 0 30 0 0 (26) 份 0 0 0 0 0 0 0 0 0 0 0 30 0 (27) 份 0 0 0 0 0 0 0 0 0 0 0 0 30 成分(II) Perbutyl P 份 2 2 2 2 2 2 2 2 2 2 2 2 2 成分(III) PPE 份 100 70 70 70 70 70 70 70 70 70 70 70 70 成分(IV) TAIC 份 10 10 10 10 10 10 10 10 10 10 10 10 10 拉伸強度 - - × × × △ × × × × × × × × 介電損耗因數 - - △ △ △ ○ × × × × × △ △ △ 介電常數 - - △ △ △ ○ × × × × × △ △ △ 低翹曲性 - ○ × × △ × × × × × △ × △ △ [產業上之可利用性] [Table 8] Comparative Example 31 Comparative Example 32 Comparative Example 33 Comparative Example 34 Comparative Example 35 Comparative Example 36 Comparative Example 37 Comparative Example 38 Comparative Example 39 Comparative Example 40 Comparative Example 41 Comparative Example 42 Comparative Example 43 Ingredient (I) (16) share 0 30 0 0 0 0 0 0 0 0 0 0 0 (17) share 0 0 30 0 0 0 0 0 0 0 0 0 0 (18) share 0 0 0 30 0 0 0 0 0 0 0 0 0 (19) share 0 0 0 0 30 0 0 0 0 0 0 0 0 (20) share 0 0 0 0 0 30 0 0 0 0 0 0 0 (twenty one) share 0 0 0 0 0 0 30 0 0 0 0 0 0 (twenty two) share 0 0 0 0 0 0 0 30 0 0 0 0 0 (twenty three) share 0 0 0 0 0 0 0 0 30 0 0 0 0 (twenty four) share 0 0 0 0 0 0 0 0 0 30 0 0 0 (25) share 0 0 0 0 0 0 0 0 0 0 30 0 0 (26) share 0 0 0 0 0 0 0 0 0 0 0 30 0 (27) share 0 0 0 0 0 0 0 0 0 0 0 0 30 Component (II) Perbutyl P share 2 2 2 2 2 2 2 2 2 2 2 2 2 Component (III) PPE share 100 70 70 70 70 70 70 70 70 70 70 70 70 Component (IV) TAIC share 10 10 10 10 10 10 10 10 10 10 10 10 10 Tensile strength - - × × × △ × × × × × × × × Dielectric dissipation factor - - △ △ △ ○ × × × × × △ △ △ Dielectric constant - - △ △ △ ○ × × × × × △ △ △ Low curvature - ○ × × △ × × × × × △ × △ △ [Industrial Availability]

本發明之樹脂組合物及硬化物作為膜、預浸體、電子電路基板、新一代通信用基板之材料，具有產業上之可利用性。The resin composition and cured product of the present invention are industrially applicable as materials for films, prepregs, electronic circuit substrates, and next-generation communication substrates.

Claims

一種樹脂組合物，其含有成分(I)與選自由下述成分(II)～(IV)所組成之群中之至少一種成分，成分(I)：共軛二烯系共聚物，該共聚物具有選自由包含乙烯基芳香族單體單元與共軛二烯單體單元之無規聚合物嵌段(C)、以乙烯基芳香族單體單元為主體之聚合物嵌段(A)、及以共軛二烯單體單元為主體之聚合物嵌段(B) 所組成之群中之至少2個聚合物嵌段，且滿足以下之條件(i)、條件(ii)及條件(iii)，＜條件(i)＞上述共軛二烯系共聚物之重量平均分子量為3.5萬以上，＜條件(ii)＞上述共軛二烯系共聚物中之乙烯基芳香族單體單元之含量為15質量%以上80質量%以下，＜條件(iii)＞上述共軛二烯系共聚物之共軛二烯單體單元包含源自1,2-鍵及/或3,4-鍵之單元(a)、與源自1,4-鍵之單元(b)，於將上述共軛二烯單體單元之總含量設為100%之情形時，上述源自1,2-鍵及/或3,4-鍵之單元(a)含量為55%以上；成分(II)：自由基起始劑；成分(III)：極性樹脂(成分(I)除外)；成分(IV)：硬化劑(成分(II)除外)。 A resin composition comprising component (I) and at least one component selected from the group consisting of the following components (II) to (IV), Component (I): a covalent diene copolymer, the copolymer having at least two polymer blocks selected from the group consisting of a random polymer block (C) comprising vinyl aromatic monomer units and covalent diene monomer units, a polymer block (A) mainly comprising vinyl aromatic monomer units, and a polymer block (B) mainly comprising covalent diene monomer units, and satisfying the following conditions (i), (ii) and (iii), ＜Condition (i)＞ The weight average molecular weight of the covalent diene copolymer is 35,000 or more, ＜Condition (ii)＞ The content of the vinyl aromatic monomer unit in the above-mentioned covalent diene copolymer is 15 mass % or more and 80 mass % or less, ＜Condition (iii)＞ The covalent diene monomer unit of the above-mentioned covalent diene copolymer comprises a unit (a) derived from a 1,2-bond and/or a 3,4-bond, and a unit (b) derived from a 1,4-bond, and when the total content of the above-mentioned covalent diene monomer unit is set to 100%, the content of the above-mentioned unit (a) derived from a 1,2-bond and/or a 3,4-bond is 55% or more; Component (II): free radical initiator; Component (III): polar resin (excluding component (I)); Component (IV): hardener (excluding component (II)).

如請求項1之樹脂組合物，其中上述共軛二烯系共聚物之源自共軛二烯單體單元之不飽和鍵之氫化率為5～95%。The resin composition of claim 1, wherein the hydrogenation rate of unsaturated bonds derived from the covalent diene monomer units of the covalent diene copolymer is 5 to 95%.

如請求項1或2之樹脂組合物，其含有上述成分(III)，上述成分(III)為選自由環氧系樹脂、聚醯亞胺系樹脂、聚苯醚系樹脂、液晶聚酯系樹脂及氟系樹脂所組成之群中之至少一種。 The resin composition of claim 1 or 2 contains the above-mentioned component (III), The above-mentioned component (III) is at least one selected from the group consisting of epoxy resin, polyimide resin, polyphenylene ether resin, liquid crystal polyester resin and fluorine resin.

一種硬化物，其係如請求項1至3中任一項之樹脂組合物之硬化物。A cured product, which is a cured product of the resin composition according to any one of claims 1 to 3.

一種樹脂膜，其包含如請求項1至3中任一項之樹脂組合物。A resin film comprising the resin composition according to any one of claims 1 to 3.

一種預浸體，其係基材、與如請求項1至3中任一項之樹脂組合物之複合體。 A prepreg, which is a composite of a substrate and a resin composition as described in any one of claims 1 to 3.

如請求項6之預浸體，其中上述基材為玻璃布。The prepreg as claimed in claim 6, wherein the substrate is glass cloth.

一種積層體，其具有如請求項5之樹脂膜與金屬箔。A laminate having a resin film and a metal foil as claimed in claim 5.

一種積層體，其具有如請求項6之預浸體之硬化物與金屬箔。A laminate comprising a cured product of the prepreg of claim 6 and a metal foil.

一種電子電路基板用之材料，其包含如請求項4之硬化物。A material for an electronic circuit substrate, comprising the hardened material as claimed in claim 4.