TW202003723A

TW202003723A - Resin varnish, prepreg, laminate, printed wiring board, and semiconductor package

Info

Publication number: TW202003723A
Application number: TW108117253A
Authority: TW
Inventors: 白男川芳克; 合津周治; 串田圭祐; 金子辰德; 清水浩
Original assignee: 日商日立化成股份有限公司
Priority date: 2018-05-21
Filing date: 2019-05-20
Publication date: 2020-01-16
Also published as: JPWO2019225482A1; WO2019225482A1; JP7452417B2

Abstract

Provided is a resin varnish having high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, and low thermal expansion properties, excellent moldability and plating uniformity, and also minimal fluctuation in the amount of dimensional variation. Also provided are a prepreg, a laminate, a printed wiring board, and a semiconductor package obtained using the resin varnish. The resin varnish comprises (A) a maleimide compound, (B) an epoxy resin, and (C) a copolymer resin having structural units derived from an aromatic vinyl compound and structural units derived from maleic anhydride, the maleimide compound (A) being a maleimide compound having an N-substituted maleimide group, obtained by reacting (a1) a maleimide compound having at least two N-substituted maleimide groups, (a2) a monoamine compound, and (a3) a diamine compound, and being obtained by reaction in which the usage ratio [(a2) component/(a3) component] (mole ratio) of the (a2) component to the (a3) component is 0.9-5.0.

Description

樹脂清漆、預浸體、積層板、印刷線路板及半導體封裝體Resin varnish, prepreg, laminate, printed wiring board and semiconductor package

本發明有關一種樹脂清漆、預浸體、積層板、印刷線路板及半導體封裝體。The invention relates to a resin varnish, prepreg, laminate, printed circuit board and semiconductor package.

近年來，在多功能型行動電話終端等的主機板中，隨著高速通訊化、線路的高密度化、印刷線路板的極薄化，印刷線路板的線路寬度(L)與間隔(S)(以下有時將線路寬度與間隔一併表記為[L/S])亦有狹小化的傾向。伴隨這樣的L/S的狹小化，而逐漸難以產率良好且穩定地生產印刷線路板。又，在以往的印刷線路板的設計中，考慮到通訊故障等，而在部分的層中設置有被稱為「跨越層(skip layer)」的不具線路圖案之層。電子機器變得高功能化，線路設計量增加，且印刷線路板的層數逐漸增加，但是由於設置前述跨越層，而產生了主機板的厚度會更進一步增加這樣的問題。作為改善這些問題的方法，使被使用於印刷線路板中的絕緣材料的相對介電常數降低是有效的。藉由降低絕緣材料的相對介電常數，容易進行L/S的控制，因此能夠將L/S穩定生產成近似於現狀設計的形狀，並減少跨越層，藉此能夠減少層數。因此，對於被使用於印刷線路板中的絕緣材料，要求相對介電常數較小的材料特性。In recent years, in motherboards such as multifunctional mobile phone terminals, with the increase in high-speed communication, the increase in density of lines, and the extremely thinning of printed wiring boards, the line width (L) and spacing (S) of printed wiring boards (The line width and the interval are sometimes referred to as [L/S] in the following.) There is also a tendency to become narrower. With such a narrowing of L/S, it is gradually difficult to produce a printed wiring board with good yield and stability. In addition, in the design of conventional printed wiring boards, in consideration of communication failures and the like, a layer without a wiring pattern called a "skip layer" is provided in some layers. Electronic devices have become more functional, the amount of circuit design has increased, and the number of layers of printed wiring boards has gradually increased. However, due to the provision of the aforementioned crossover layers, there is a problem that the thickness of the main board will further increase. As a method for improving these problems, it is effective to reduce the relative dielectric constant of the insulating material used in the printed wiring board. By lowering the relative dielectric constant of the insulating material, it is easy to control the L/S. Therefore, the L/S can be stably produced in a shape similar to the current design, and the number of crossing layers can be reduced, thereby reducing the number of layers. Therefore, for insulating materials used in printed wiring boards, material characteristics with a relatively low relative dielectric constant are required.

除了多功能型行動電話終端以外，例如，在以伺服器、路由器、行動基地台等為代表的通訊系機器中，亦已開始被使用在更高頻帶區域。又，高熔點的無鉛焊料已開始被利用於電子零件的焊接，因此有下述傾向：作為使用於該等機器中的基板的材料，要求一種材料，該材料為低介電常數、高玻璃轉化溫度(高Tg)，並且回焊耐熱性優異。又，使用於多功能型行動電話終端等之中的主機板，伴隨線路密度的增加和圖案寬度的狹小化，在將層間加以連結時，要求藉由小孔徑的雷射通孔(laser via)來進行連接。從連接可靠性的觀點而言，有很多使用填充鍍覆(filled plating)的事例，且在內層銅與鍍覆銅的界面的連接性非常重要，因此有亦要求提升基材的雷射加工性的傾向。In addition to multi-function mobile phone terminals, for example, communication systems such as servers, routers, mobile base stations, etc., have also begun to be used in higher frequency bands. In addition, high-melting point lead-free solders have been used for soldering electronic parts, so there is a tendency that as a substrate material used in such machines, a material is required which has a low dielectric constant and high glass transition Temperature (high Tg), and excellent reflow heat resistance. In addition, motherboards used in multifunctional mobile phone terminals, etc., with the increase in line density and the narrowing of the pattern width, when connecting layers, it is required to use a laser via with a small aperture To connect. From the viewpoint of connection reliability, there are many cases where filled plating is used, and the connectivity of the interface between the inner layer copper and the plated copper is very important. Therefore, laser processing of the substrate is also required to be improved. Sexual orientation.

在基材的雷射加工後，一般是實行去除樹脂的殘渣成分的步驟(去膠渣(desmear)處理步驟)。由於對雷射通孔底面和壁面實行去膠渣處理，因此當由於去膠渣處理而導致基材的樹脂成分大量溶解時，可能由於樹脂溶解而導致雷射通孔形狀明顯地變形，並且可能發生由於壁面的凹凸的偏差而產生鍍覆分佈(throwing power)的不均性等的各種問題。因此，要求由於去膠渣處理而溶解基材的樹脂成分的量也就是去膠渣溶解量為適當值。After the laser processing of the base material, a step of removing resin residue components (desmear treatment step) is generally performed. Since the slag removal treatment is performed on the bottom surface and the wall surface of the laser through hole, when the resin component of the base material is largely dissolved due to the slag removal processing, the shape of the laser through hole may be significantly deformed due to the resin dissolution, and may Various problems such as unevenness of the plating power (throwing power) occur due to the unevenness of the wall surface. Therefore, it is required that the amount of the resin component that dissolves the base material due to the desmear treatment, that is, the amount of the desmear dissolved, is an appropriate value.

又，關於藉由小孔徑的雷射通孔來進行的層間連接，基材的尺寸變化量的偏差小亦被列舉為重要的特性之一。伴隨主機板的薄型化，作為基材的積層方法，需要多階段積層方法，而會對基材施加複數次的熱量和積層時的應力。因此，當基材本身的尺寸變化量的偏差(意指基材的熱收縮量的偏差)較大時，每次進行積層時可能造成連接層間的通孔發生錯位的不良情形。因此，要求將基材的熱收縮量的偏差加以穩定化。In addition, regarding the interlayer connection by a small-diameter laser through hole, the small variation in the dimensional change of the base material is also cited as one of the important characteristics. Along with the thinning of the motherboard, a multi-layer stacking method is required as a stacking method of the base material, and a plurality of heat and stress during the stacking are applied to the base material. Therefore, when the variation in the amount of dimensional change of the substrate itself (meaning the variation in the amount of thermal shrinkage of the substrate) is large, the through-hole between the connection layers may be misaligned each time the layer is deposited. Therefore, it is required to stabilize the variation in the amount of thermal shrinkage of the base material.

到目前為止，對使用於印刷線路板中的絕緣材料要求的各種特性之中，為了縮小相對介電常數的目的，是使用下述方法：含有相對介電常數小之環氧樹脂的方法、導入氰酸基的方法、含有聚伸苯基醚的方法等。已提案例如以下的各種樹脂組成物：一種樹脂組成物，其含有環氧樹脂(參照專利文獻1)；一種樹脂組成物，其含有聚伸苯基醚與雙馬來醯亞胺(參照專利文獻2)；一種樹脂組成物，其含有聚伸苯基醚與氰酸酯樹脂(參照專利文獻3)；一種樹脂組成物，其含有苯乙烯系熱可塑性彈性體等及/或三聚氰酸三烯丙酯等中的至少一種(參照專利文獻4)；一種樹脂組成物，其含有聚丁二烯(參照專利文獻5)；一種樹脂組成物，其是使聚伸苯基醚系樹脂、多官能性馬來醯亞胺及/或多官能性氰酸酯樹脂、以及液狀聚丁二烯進行預反應而成(參照專利文獻6)；一種樹脂組成物，其含有聚伸苯基醚與三聚氰酸三烯丙酯及/或異三聚氰酸三烯丙酯等，該聚伸苯基醚加成或接枝有具有不飽和雙鍵基之化合物(參照專利文獻7)；一種樹脂組成物，其含有聚伸苯基醚與不飽和羧酸或不飽和酸酐之反應生成物、與多官能性馬來醯亞胺等(參照專利文獻8)。 [先前技術文獻] (專利文獻)Among the various characteristics required for insulating materials used in printed wiring boards so far, in order to reduce the relative dielectric constant, the following method has been used: a method containing an epoxy resin with a small relative dielectric constant, introduction The method of cyanate group, the method containing polyphenylene ether, etc. Various resin compositions such as the following have been proposed: a resin composition containing an epoxy resin (refer to Patent Document 1); and a resin composition containing a polyphenylene ether and bismaleimide (refer to Patent Document) 2); a resin composition containing polyphenylene ether and cyanate resin (refer to Patent Document 3); a resin composition containing styrene-based thermoplastic elastomer and/or cyanuric acid tricyanide At least one of allyl esters and the like (refer to Patent Document 4); a resin composition containing polybutadiene (refer to Patent Document 5); a resin composition which is a polyphenylene ether-based resin, many The functional maleimide and/or multifunctional cyanate resin and liquid polybutadiene are pre-reacted (refer to Patent Document 6); a resin composition containing polyphenylene ether and Triallyl cyanurate and/or triallyl isocyanurate, etc., the polyphenylene ether is added or grafted with a compound having an unsaturated double bond group (refer to Patent Document 7); one The resin composition contains a reaction product of polyphenylene ether and unsaturated carboxylic acid or unsaturated acid anhydride, polyfunctional maleimide and the like (see Patent Document 8). [Prior Technical Literature] (Patent Literature)

專利文獻1：日本特開昭58-69046號公報專利文獻2：日本特開昭56-133355號公報專利文獻3：日本特公昭61-18937號公報專利文獻4：日本特開昭61-286130號公報專利文獻5：日本特開昭62-148512號公報專利文獻6：日本特開昭58-164638號公報專利文獻7：日本特開平2-208355號公報專利文獻8：日本特開平6-179734號公報Patent Document 1: Japanese Patent Laid-Open No. 58-69046 Patent Document 2: Japanese Patent Laid-Open No. 56-133355 Patent Document 3: Japanese Patent Publication No. 61-18937 Patent Document 4: Japanese Patent Laid-Open No. 61-286130 Patent Document 5: Japanese Patent Laid-Open No. 62-148512 Patent Document 6: Japanese Patent Laid-Open No. 58-164638 Patent Document 7: Japanese Patent Laid-Open No. 2-208355 Patent Document 8: Japanese Patent Laid-Open No. 6-179734

[發明所欲解決的問題] 如前所述，有對使用於印刷線路板中的絕緣材料要求縮小相對介電常數等各種特性的傾向，雖然含有專利文獻1～8所記載的樹脂組成物而成之預浸體顯示比較良好的相對介電常數，但是近年來無法滿足市場的嚴格要求的事例逐漸變多。又，大多是高耐熱性、高金屬箔黏合性、高玻璃轉化溫度、低熱膨脹性，成形性和鍍覆分佈性(雷射加工性)以及尺寸變化量的偏差的大小的任一者變得不充分的情形，而有進一步改善的餘地。尤其，根據本發明人的研究，已發現含有以往的樹脂組成物而成之預浸體無法充分抑制此尺寸變化量的偏差，因此在這一點有進一步改善的餘地。[Problems to be solved by the invention] As mentioned above, there is a tendency for insulating materials used in printed wiring boards to reduce various characteristics such as relative dielectric constant, although prepregs containing the resin compositions described in Patent Documents 1 to 8 show relatively good The relative dielectric constant, but in recent years has not been able to meet the stringent requirements of the market has gradually increased. In addition, most of the high heat resistance, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability and plating distribution (laser processability), and any of the size of the amount of variation Insufficient situation, but there is room for further improvement. In particular, according to the research of the present inventors, it has been found that a prepreg containing a conventional resin composition cannot sufficiently suppress the variation in the amount of dimensional change, so there is room for further improvement in this point.

因此，本發明所欲解決的問題在於提供一種樹脂清漆，以及提供一種使用該樹脂清漆而獲得的預浸體、積層板、印刷線路板及半導體封裝體，該樹脂清漆具有高耐熱性、低相對介電常數、高金屬箔黏合性、高玻璃轉化溫度、低熱膨脹性，並且成形性和鍍覆分佈性優異，進一步尺寸變化量的偏差小。 [解決問題的技術手段]Therefore, the problem to be solved by the present invention is to provide a resin varnish, and to provide a prepreg, a laminate, a printed wiring board and a semiconductor package obtained using the resin varnish, the resin varnish has high heat resistance, low relative Dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, and excellent formability and plating distribution, further small variation in dimensional change. [Technical means to solve the problem]

本發明人為了解決上述問題而專心研究，結果發現一種樹脂清漆，其含有「(A)馬來醯亞胺化合物」、「(B)環氧樹脂」、「(C)具有特定結構單元之共聚合樹脂」，且藉由將前述(A)馬來醯亞胺化合物設為下述特定的馬來醯亞胺化合物，能夠解決上述問題，從而完成本發明。本發明是基於所述知識見解而完成。In order to solve the above problems, the present inventors concentrated on research and found that a resin varnish containing "(A) maleimide compound", "(B) epoxy resin", "(C) having a specific structural unit "Polymer resin", and by setting the (A) maleimide compound as the following specific maleimide compound, the above problems can be solved, and the present invention has been completed. The present invention is completed based on the knowledge and knowledge.

本發明有關下述[1]～[15]。 [1] 一種樹脂清漆，其是含有下述成分而成： (A)馬來醯亞胺化合物； (B)環氧樹脂；及， (C)共聚合樹脂，其具有源自芳香族乙烯系化合物的結構單元與源自馬來酸酐的結構單元；其中，前述(A)馬來醯亞胺化合物是具有N-取代馬來醯亞胺基之馬來醯亞胺化合物，該馬來醯亞胺化合物是使(a1)具有至少2個N-取代馬來醯亞胺基之馬來醯亞胺化合物、(a2)單胺化合物及(a3)二胺化合物進行反應而獲得，並且，前述(A)馬來醯亞胺化合物是將前述(a2)成分相對於前述(a3)成分的使用比率也就是(a2)成分/(a3)成分，以莫耳比計，設為0.9～5.0來進行反應而獲得。 [2] 如上述[1]所述之樹脂清漆，其中，前述(a2)單胺化合物是由下述通式(a2-1)表示，前述(a3)二胺化合物是由下述通式(a3-1)表示；

通式(a2-1)中，R^A4 表示由羥基、羧基及磺酸基中選出的酸性取代基，R^A5 表示碳數1～5的烷基或鹵素原子，t是1～5的整數，u是0～4的整數，且滿足1≦t＋u≦5，其中，當t為2～5的整數時，複數個R^A4 可相同亦可不同，並且，當u為2～4的整數時，複數個R^A5 可相同亦可不同；

通式(a3-1)中，X^A2 表示碳數1～3的脂肪族烴基或-O-，R^A6 和R^A7 各自獨立地表示碳數1～5的烷基、鹵素原子、羥基、羧基或磺酸基，v和w各自獨立地為0～4的整數。 [3] 如上述[1]或[2]所述之樹脂清漆，其中，前述(a2)成分和前述(a3)成分具有的-NH² 基當量的總和與前述(a1)成分的馬來醯亞胺基當量的關係，滿足下述式子： 0.1≦〔馬來醯亞胺基當量〕／〔-NH² 基當量的總和〕≦10。 [4] 如上述[1]～[3]中任一項所述之樹脂清漆，其中，前述(B)成分是選自由雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、萘型環氧樹脂、蒽型環氧樹脂、聯苯型環氧樹脂、聯苯芳烷基酚醛清漆型環氧樹脂及雙環戊二烯型環氧樹脂所組成之群組中的至少1種。 [5] 如上述[1]～[4]中任一項所述之樹脂清漆，其中，前述(C)成分是一共聚合樹脂，該共聚合樹脂具有由下述通式(C-i)表示的結構單元與由下述式(C-ii)表示的結構單元；

式(C-i)中，R^C1 是氫原子或碳數1～5的烷基，R^C2 是碳數1～5的烷基、碳數2～5的烯基、碳數6～20的芳基、羥基或(甲基)丙烯醯基，x是0～3的整數，其中，當x為2或3時，複數個R^C2 可相同亦可不同。 [6] 如上述[1]～[4]中任一項所述之樹脂清漆，其中，在前述(C)成分中，源自芳香族乙烯系化合物的結構單元與源自馬來酸酐的結構單元的含有比例，也就是源自芳香族乙烯系化合物的結構單元/源自馬來酸酐的結構單元，以莫耳比計，為1～9。 [7] 如上述[1]～[6]中任一項所述之樹脂清漆，其中，相對於前述(A)～(C)成分的總和100質量份，前述(A)～(C)成分的含量是(A)成分為15～65質量份，(B)成分為15～50質量份，(C)成分為10～45質量份。 [8] 如上述[1]～[7]中任一項所述之樹脂清漆，其中，該樹脂清漆是進一步含有(D)無機填充材料而成。 [9] 如上述[1]～[8]中任一項所述之樹脂清漆，其中，該樹脂清漆是進一步含有(E)硬化劑而成。 [10] 如上述[1]～[9]中任一項所述之樹脂清漆，其中，該樹脂清漆是進一步含有(F)難燃劑而成。 [11] 一種預浸體，其是含有上述[1]～[10]中任一項所述之樹脂清漆而成。 [12] 如上述[11]所述之預浸體，其中，依照下述方法來求出的標準偏差σ是0.012%以下，該標準偏差σ的計算方法如下：在1片預浸體的雙面上重疊厚度18μm的銅箔，並以190℃、2.45MPa的條件進行90分鐘的加熱加壓並成形，來製作厚度0.1mm的雙面覆銅積層板，然後在藉由上述方法獲得的雙面覆銅積層板的面內，於第1圖所示的1～8的位置，實施直徑為1.0mm的穿孔，並使用影像測定機來分別測定第1圖所示的經線方向(1-7、2-6、3-5)和緯線方向(1-3、8-4、7-5)的各3點的距離，並將各測定距離設為起始值，然後去除外層銅箔，並利用乾燥機以185℃加熱60分鐘，冷卻後，採用與起始值的測定方法相同之方法，分別測定經線方向(1-7、2-6、3-5)和緯線方向(1-3、8-4、7-5)的各3點的距離，然後根據相對於各測定距離的起始值的變化率來求出這些變化率的平均值，並計算相對於該平均值的標準偏差σ。 [13] 一種積層板，其是含有上述[11]或[12]所述之預浸體與金屬箔而成。 [14] 一種印刷線路板，其是含有上述[11]或[12]所述之預浸體或上述[13]所述之積層板而成。 [15] 一種半導體封裝體，其是在上述[14]所述之印刷線路板上搭載半導體元件而成。 [發明的功效]The present invention relates to the following [1] to [15]. [1] A resin varnish containing the following components: (A) Maleimide compound; (B) Epoxy resin; and, (C) Copolymer resin, which has aromatic vinyl origin The structural unit of the compound and the structural unit derived from maleic anhydride; wherein, the aforementioned (A) maleimide compound is a maleimide compound having an N-substituted maleimide group, the maleimide The amine compound is obtained by reacting (a1) a maleimide compound having at least two N-substituted maleimide groups, (a2) a monoamine compound, and (a3) a diamine compound, and, A) The maleimide compound is obtained by setting the use ratio of the aforementioned (a2) component to the aforementioned (a3) component, that is, (a2) component/(a3) component, in molar ratios to 0.9 to 5.0. Obtained by reaction. [2] The resin varnish described in [1] above, wherein the (a2) monoamine compound is represented by the following general formula (a2-1), and the (a3) diamine compound is represented by the following general formula (a2) a3-1) means;

In the general formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group and a sulfonic acid group, R ^A5 represents a C 1-5 alkyl group or a halogen atom, and t is an integer of 1 to 5, u is an integer from 0 to 4, and satisfies 1≦t+u≦5, wherein when t is an integer from 2 to 5, plural R ^A4 may be the same or different, and when u is an integer from 2 to 4, Plural R ^A5 may be the same or different;

In the general formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or -O-, and R ^A6 and R ^A7 each independently represent an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, or a carboxyl group Or a sulfonic acid group, v and w are each independently an integer of 0 to 4. [3] The resin varnish as described in [1] or [2] above, wherein the sum of the (NH ⁾ group equivalent of the component (a2) and the component (a3) and the maleic amide of the component (a1) The relationship of the imine equivalents satisfies the following formula: 0.1≦[maleimide equivalent]/[total of -NH ² equivalents]≦10. [4] The resin varnish according to any one of the above [1] to [3], wherein the component (B) is selected from the group consisting of bisphenol F type epoxy resin, phenol novolak type epoxy resin, and cresol A group consisting of novolak epoxy resin, naphthalene epoxy resin, anthracene epoxy resin, biphenyl epoxy resin, biphenyl aralkyl novolak epoxy resin and dicyclopentadiene epoxy resin At least 1 species in the group. [5] The resin varnish as described in any one of [1] to [4] above, wherein the component (C) is a mono-copolymerized resin having a structure represented by the following general formula (Ci) Unit and structural unit represented by the following formula (C-ii);

In formula (Ci), R ^C1 is a hydrogen atom or a C 1-5 alkyl group, R ^C2 is a C 1-5 alkyl group, a C 2-5 alkenyl group, and a C 6-20 aryl group , Hydroxyl or (meth)acryloyl, x is an integer from 0 to 3, wherein when x is 2 or 3, the plurality of R ^C2 may be the same or different. [6] The resin varnish as described in any one of [1] to [4] above, wherein in the component (C), a structural unit derived from an aromatic vinyl compound and a structure derived from maleic anhydride The content ratio of the unit, that is, the structural unit derived from the aromatic vinyl compound/the structural unit derived from maleic anhydride, is 1 to 9 in terms of molar ratio. [7] The resin varnish as described in any one of the above [1] to [6], wherein the components (A) to (C) are relative to 100 parts by mass of the total of the components (A) to (C). The content of (A) component is 15 to 65 parts by mass, (B) component is 15 to 50 parts by mass, and (C) component is 10 to 45 parts by mass. [8] The resin varnish as described in any one of the above [1] to [7], wherein the resin varnish further contains (D) an inorganic filler. [9] The resin varnish as described in any one of [1] to [8] above, wherein the resin varnish further contains (E) a hardener. [10] The resin varnish according to any one of the above [1] to [9], wherein the resin varnish further contains (F) a flame retardant. [11] A prepreg containing the resin varnish described in any one of [1] to [10] above. [12] The prepreg according to the above [11], wherein the standard deviation σ determined according to the following method is 0.012% or less, and the calculation method of the standard deviation σ is as follows: A copper foil with a thickness of 18 μm was laminated on the surface, and heated and pressed at 190° C. and 2.45 MPa for 90 minutes to form a double-sided copper-clad laminate with a thickness of 0.1 mm. In the surface of the copper-clad laminate, at the positions 1 to 8 shown in Fig. 1, a hole with a diameter of 1.0 mm was perforated, and the longitudinal direction shown in Fig. 1 (1- 7, 2-6, 3-5) and the distance between the three points in the latitude direction (1-3, 8-4, 7-5), and set the measured distance to the initial value, and then remove the outer layer of copper foil, And use a dryer to heat at 185 ℃ for 60 minutes. After cooling, use the same method as the initial value measurement method to measure the warp direction (1-7, 2-6, 3-5) and the weft direction (1- 3. The distances of 3 points of 8-4, 7-5), then calculate the average of these rates of change based on the rate of change from the starting value of each measured distance, and calculate the standard relative to the average Deviation σ. [13] A laminate comprising the prepreg described in [11] or [12] and a metal foil. [14] A printed wiring board comprising the prepreg according to [11] or [12] or the laminate according to [13]. [15] A semiconductor package in which a semiconductor element is mounted on the printed wiring board described in [14] above. [Efficacy of invention]

根據本發明，能夠提供一種樹脂清漆，其具有高耐熱性、低相對介電常數、高金屬箔黏合性、高玻璃轉化溫度、低熱膨脹性，並且成形性和鍍覆分佈性優異，進一步尺寸變化量的偏差小。又，能夠提供一種使用該樹脂清漆而獲得的預浸體、積層板、印刷線路板及半導體封裝體。According to the present invention, it is possible to provide a resin varnish having high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, and excellent formability and plating distribution, and further dimensional changes The amount of deviation is small. In addition, it is possible to provide a prepreg, a laminate, a printed wiring board, and a semiconductor package obtained using the resin varnish.

在本說明書中所記載的數值範圍中，該數值範圍的上限値或下限値可置換成實施例中所示的值。又，數值範圍的上限値或下限値，各自能夠與其他數值範圍的上限値或下限値任意地組合。又，只要未特別說明，本說明書中例示的各成分和材料，可使用單獨1種，亦可將2種以上合併使用。在本說明書中，當組成物中存在有複數種符合各成分的物質時，只要未特別說明，組成物中的各成分的含量，意指存在於組成物中的該複數種物質的合計量。將本說明書中的記載事項任意地組合而得的態樣，亦包含在本發明之中。In the numerical range described in this specification, the upper limit value or the lower limit value of the numerical range can be replaced with the values shown in the examples. In addition, the upper limit value or the lower limit value of the numerical range can be arbitrarily combined with the upper limit value or the lower limit value of the other numerical range. Unless otherwise specified, each component and material exemplified in this specification may be used alone or in combination of two or more. In this specification, when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified, the content of each component in the composition means the total amount of the plurality of substances present in the composition. The aspect which combined the matters described in this specification arbitrarily is also included in this invention.

[樹脂清漆] 本發明的樹脂清漆，如以下所述，是含有下述成分而成： (A)馬來醯亞胺化合物； (B)環氧樹脂；及， (C)共聚合樹脂，其具有源自芳香族乙烯系化合物的結構單元與源自馬來酸酐的結構單元；其中，前述(A)馬來醯亞胺化合物是具有N-取代馬來醯亞胺基之馬來醯亞胺化合物，該馬來醯亞胺化合物是使(a1)具有至少2個N-取代馬來醯亞胺基之馬來醯亞胺化合物、(a2)單胺化合物及(a3)二胺化合物進行反應而獲得，並且，前述(A)馬來醯亞胺化合物是將前述(a2)成分相對於前述(a3)成分的使用比率[(a2)成分/(a3)成分](莫耳比)，設為0.9～5.0來進行反應而獲得。[Resin Varnish] The resin varnish of the present invention contains the following components as described below: (A) Maleimide compounds; (B) epoxy resin; and, (C) A copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride; Wherein, the aforementioned (A) maleimide compound is a maleimide compound having an N-substituted maleimide group, and the maleimide compound is such that (a1) has at least 2 N-substitutions The maleimide compound of maleimide group, (a2) monoamine compound and (a3) diamine compound are obtained by reacting, In addition, the (A) maleimide compound is the use ratio of the (a2) component to the (a3) component [(a2) component/(a3) component] (mole ratio), and is set to 0.9 to 5.0 to get the reaction.

首先，詳述樹脂清漆所含有的各成分。＜(A)馬來醯亞胺化合物＞ (A)成分，是以下具有N-取代馬來醯亞胺基之馬來醯亞胺化合物(以下，有時稱為馬來醯亞胺化合物(A))。具體而言，是一種具有N-取代馬來醯亞胺基之馬來醯亞胺化合物，其是使(a1)具有至少2個N-取代馬來醯亞胺基之馬來醯亞胺化合物[以下簡稱為馬來醯亞胺化合物(a1)]、(a2)單胺化合物[以下簡稱為單胺化合物(a2)]及(a3)二胺化合物(以下簡稱為二胺化合物(a3))進行反應而獲得。尤其，該馬來醯亞胺化合物(A)，是以下述特定的使用比率來使前述(a2)成分與前述(a3)成分進行反應而獲得。First, the components contained in the resin varnish will be described in detail. ＜(A) Maleimide Compound＞ The component (A) is a maleimide compound having the following N-substituted maleimide group (hereinafter, sometimes referred to as a maleimide compound (A)). Specifically, it is a maleimide compound having an N-substituted maleimide group, which is (a1) a maleimide compound having at least 2 N-substituted maleimide groups [Hereinafter referred to as maleimide compound (a1)], (a2) monoamine compound [hereinafter referred to as monoamine compound (a2)] and (a3) diamine compound (hereinafter referred to as diamine compound (a3)) Obtained through the reaction. In particular, the maleimide compound (A) is obtained by reacting the aforementioned (a2) component with the aforementioned (a3) component at the following specific use ratio.

馬來醯亞胺化合物的重量平均分子量(Mw)，從對有機溶劑的溶解性的觀點和機械強度的觀點而言，較佳是400～3500，更佳是400～2000，進一步更佳是800～1500。再者，本說明書中的重量平均分子量，是利用凝膠滲透層析(GPC)法(以標準聚苯乙烯換算)所測定的值，該凝膠滲透層析法是使用四氫呋喃作為溶析液，更具體而言，是利用實施例所記載的方法所測定的值。The weight average molecular weight (Mw) of the maleimide compound is preferably 400 to 3500, more preferably 400 to 2000, and even more preferably 800 from the viewpoint of solubility in organic solvents and mechanical strength. ~1500. In addition, the weight average molecular weight in this specification is the value measured by the gel permeation chromatography (GPC) method (in terms of standard polystyrene conversion) which uses tetrahydrofuran as the eluent, More specifically, it is the value measured by the method described in the Examples.

(馬來醯亞胺化合物(a1)) 馬來醯亞胺化合物(a1)，是具有至少2個N-取代馬來醯亞胺基之馬來醯亞胺化合物。作為馬來醯亞胺化合物(a1)，是在複數個馬來醯亞胺基中的任意2個馬來醯亞胺基之間具有脂肪族烴基(但是不存在芳香族烴基)之馬來醯亞胺化合物(以下，稱為含脂肪族烴基馬來醯亞胺)，或者可列舉在複數個馬來醯亞胺基中的任意2個馬來醯亞胺基之間具有芳香族烴基之馬來醯亞胺化合物(以下，稱為含芳香族烴基馬來醯亞胺)。其中，從高耐熱性、低相對介電常數、高金屬箔黏合性、高玻璃轉化溫度、低熱膨脹性、成形性及鍍覆分佈性的觀點而言，較佳是含芳香族烴基馬來醯亞胺。含芳香族烴基馬來醯亞胺，只要在任意選擇的2個馬來醯亞胺基的組合中的任一組合之間含有芳香族烴基即可，並且，亦可具有芳香族烴基以及脂肪族烴基。作為馬來醯亞胺化合物(a1)，從高耐熱性、低相對介電常數、高金屬箔黏合性、高玻璃轉化溫度、低熱膨脹性、成形性及鍍覆分佈性的觀點而言，較佳是一分子中具有2個～5個N-取代馬來醯亞胺基之馬來醯亞胺化合物，更佳是一分子中具有2個N-取代馬來醯亞胺基之馬來醯亞胺化合物。又，作為馬來醯亞胺化合物(a1)，從高耐熱性、低相對介電常數、高金屬箔黏合性、高玻璃轉化溫度、低熱膨脹性、成形性及鍍覆分佈性的觀點而言，更佳是由下述通式(a1-1)～(a1-4)中的任一個表示的含芳香族烴基馬來醯亞胺，進一步更佳是由下述通式(a1-1)、(a1-2)或(a1-4)表示的含芳香族烴基馬來醯亞胺，特佳是由下述通式(a1-2)表示的含芳香族烴基馬來醯亞胺。(Maleimide compound (a1)) The maleimide compound (a1) is a maleimide compound having at least two N-substituted maleimide groups. The maleimide compound (a1) is a maleimide having an aliphatic hydrocarbon group (but no aromatic hydrocarbon group) between any two maleimide groups in the plurality of maleimide groups. An imine compound (hereinafter referred to as an aliphatic hydrocarbon group-containing maleimide), or a horse having an aromatic hydrocarbon group between any two maleimide groups in the plurality of maleimide groups Laimide compounds (hereinafter, referred to as aromatic hydrocarbon group-containing maleimide). Among them, from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating distribution, maleic amide containing aromatic hydrocarbon groups is preferred Imine. The aromatic hydrocarbon group-containing maleimide only needs to contain an aromatic hydrocarbon group between any combination of two arbitrarily selected combinations of maleimide groups, and may also have an aromatic hydrocarbon group and an aliphatic group Hydrocarbyl. As the maleimide compound (a1), from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating distribution, It is preferably a maleimide compound having 2 to 5 N-substituted maleimide groups in one molecule, and more preferably a maleimide compound having 2 N-substituted maleimide groups in one molecule. Imine compounds. Also, as the maleimide compound (a1), from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating distribution , More preferably, the aromatic hydrocarbon group-containing maleimide represented by any one of the following general formulas (a1-1) to (a1-4), and still more preferably, the following general formula (a1-1) , The aromatic hydrocarbon group-containing maleimide represented by (a1-2) or (a1-4), particularly preferably the aromatic hydrocarbon group-containing maleimide represented by the following general formula (a1-2).

上述式中，R^A1 ～R^A3 各自獨立地表示碳數1～5的脂肪族烴基。X^A1 表示碳數1～5的伸烷基、碳數2～5的亞烷基、-O-、-C(=O)-、-S-、-S-S-或磺醯基。p、q及r各自獨立地為0～4的整數。s是0～10的整數。作為R^A1 ～R^A3 所表示的碳數1～5的脂肪族烴基，可列舉例如：甲基、乙基、正丙基、異丙基、正丁基、異丁基、三級丁基、正戊基等。作為該脂肪族烴基，從高耐熱性、低相對介電常數、高金屬箔黏合性、高玻璃轉化溫度、低熱膨脹性、成形性及鍍覆分佈性的觀點而言，較佳是碳數1～3的脂肪族烴基，更佳是甲基、乙基。In the above formula, R ^A1 to R ^A3 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms. X ^A1 represents an alkylene group having 1 to 5 carbon atoms, an alkylene group having 2 to 5 carbon atoms, -O-, -C(=O)-, -S-, -SS-, or sulfonyl group. p, q and r are each independently an integer of 0 to 4. s is an integer of 0-10. Examples of the aliphatic hydrocarbon groups having 1 to 5 carbon atoms represented by R ^A1 to R ^A3 include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, N-pentyl and so on. The aliphatic hydrocarbon group is preferably carbon number 1 from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating distribution. The aliphatic hydrocarbon group of ~3 is more preferably methyl or ethyl.

作為X^A1 所表示的碳數1～5的伸烷基，可列舉例如：亞甲基、1,2-二亞甲基、1,3-三亞甲基、1,4-四亞甲基、1,5-五亞甲基等。作為該伸烷基，從高耐熱性、低相對介電常數、高金屬箔黏合性、高玻璃轉化溫度、低熱膨脹性、成形性及鍍覆分佈性的觀點而言，較佳是碳數1～3的伸烷基，更佳是亞甲基。作為X^A1 所表示的碳數2～5的亞烷基，可列舉例如：亞乙基、亞丙基、亞異丙基、亞丁基、亞異丁基、亞戊基、亞異戊基等。其中，從高耐熱性、低相對介電常數、高金屬箔黏合性、高玻璃轉化溫度、低熱膨脹性、成形性及鍍覆分佈性的觀點而言，較佳是亞異丙基。作為X^A1 ，在上述選項中，較佳是碳數1～5的伸烷基、碳數2～5的亞烷基。更佳的基團如前所述。 p、q及r各自獨立地為0～4的整數，從高耐熱性、低相對介電常數、高金屬箔黏合性、高玻璃轉化溫度、低熱膨脹性、成形性及鍍覆分佈性的觀點而言，p、q及r都是：較佳為0～2的整數，更佳為0或1，進一較佳為0。 s是0～10的整數，從取得容易性的觀點，較佳是0～5，更佳是0～3。尤其，由通式(a1-3)表示的含芳香族烴基馬來醯亞胺，較佳是s為0～3之混合物。Examples of the C 1-5 alkylene group represented by X ^A1 include methylene, 1,2-dimethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,5-pentamethylene etc. The alkylene group preferably has a carbon number of 1 from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating distribution. The alkylene group of ~3 is more preferably methylene. Examples of the C 2-5 alkylene group represented by X ^A1 include ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, and isopentylene. . Among them, from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating distribution, isopropylidene is preferred. As X ^A1 , among the above options, alkylene groups having 1 to 5 carbon atoms and alkylene groups having 2 to 5 carbon atoms are preferred. More preferred groups are as described above. p, q and r are each independently an integer of 0 to 4, from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability and plating distribution In general, p, q, and r are all integers of 0 to 2, preferably 0 or 1, more preferably 0. s is an integer of 0-10, and from the viewpoint of ease of acquisition, it is preferably 0-5, and more preferably 0-3. In particular, the aromatic hydrocarbon group-containing maleimide represented by the general formula (a1-3) is preferably a mixture in which s is 0 to 3.

作為馬來醯亞胺化合物(a1)，具體而言，可列舉例如：N,N’-伸乙基雙馬來醯亞胺、N,N’-六亞甲基雙馬來醯亞胺、雙(4-馬來醯亞胺基環己基)甲烷、1,4-雙(馬來醯亞胺基甲基)環己烷等含脂肪族烴基馬來醯亞胺；N,N’-(1,3-伸苯基)雙馬來醯亞胺、N,N’-[1,3-(2-甲基伸苯基)]雙馬來醯亞胺、N,N’-[1,3-(4-甲基伸苯基)]雙馬來醯亞胺、N,N’-(1,4-伸苯基)雙馬來醯亞胺、雙(4-馬來醯亞胺基苯基)甲烷、雙(3-甲基4-馬來醯亞胺基苯基)甲烷、3,3’-二甲基-5,5’-二乙基-4,4’-二苯基甲烷雙馬來醯亞胺、雙(4-馬來醯亞胺基苯基)醚、雙(4-馬來醯亞胺基苯基) 碸、雙(4-馬來醯亞胺基苯基)硫醚、雙(4-馬來醯亞胺基苯基)酮、1,4-雙(4-馬來醯亞胺基苯基)環己烷、1,4-雙(馬來醯亞胺基甲基)環己烷、1,3-雙(4-馬來醯亞胺基苯氧基)苯、1,3-雙(3-馬來醯亞胺基苯氧基)苯、雙[4-(3-馬來醯亞胺基苯氧基)苯基]甲烷、雙[4-(4-馬來醯亞胺基苯氧基)苯基]甲烷、1,1-雙[4-(3-馬來醯亞胺基苯氧基)苯基]乙烷、1,1-雙[4-(4-馬來醯亞胺基苯氧基)苯基]乙烷、1,2-雙[4-(3-馬來醯亞胺基苯氧基)苯基]乙烷、1,2-雙[4-(4-馬來醯亞胺基苯氧基)苯基]乙烷、2,2-雙[4-(3-馬來醯亞胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-馬來醯亞胺基苯氧基)苯基]丙烷、2,2-雙[4-(3-馬來醯亞胺基苯氧基)苯基]丁烷、2,2-雙[4-(4-馬來醯亞胺基苯氧基)苯基]丁烷、2,2-雙[4-(3-馬來醯亞胺基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷、2,2-雙[4-(4-馬來醯亞胺基苯氧基)苯基] -1,1,1,3,3,3-六氟丙烷、4,4’-雙(3-馬來醯亞胺基苯氧基)聯苯、4,4’-雙(4-馬來醯亞胺基苯氧基)聯苯、雙[4-(3-馬來醯亞胺基苯氧基)苯基]酮、雙[4-(4-馬來醯亞胺基苯氧基)苯基]酮、雙(4-馬來醯亞胺基苯基)二硫醚、雙[4-(3-馬來醯亞胺基苯氧基)苯基]硫醚、雙[4-(4-馬來醯亞胺基苯氧基)苯基]硫醚、雙[4-(3-馬來醯亞胺基苯氧基)苯基]亞碸、雙[4-(4-馬來醯亞胺基苯氧基)苯基]亞碸、雙[4-(3-馬來醯亞胺基苯氧基)苯基]碸、雙[4-(4-馬來醯亞胺基苯氧基)苯基]碸、雙[4-(3-馬來醯亞胺基苯氧基)苯基]醚、雙[4-(4-馬來醯亞胺基苯氧基)苯基]醚、1,4-雙[4-(4-馬來醯亞胺基苯氧基)-α,α-二甲基苯甲基]苯、1,3-雙[4-(4-馬來醯亞胺基苯氧基)-α,α-二甲基苯甲基]苯、1,4-雙[4-(3-馬來醯亞胺基苯氧基)-α,α-二甲基苯甲基]苯、1,3-雙[4-(3-馬來醯亞胺基苯氧基)-α,α-二甲基苯甲基]苯、1,4-雙[4-(4-馬來醯亞胺基苯氧基)-3,5-二甲基-α,α-二甲基苯甲基]苯、1,3-雙[4-(4-馬來醯亞胺基苯氧基)-3,5-二甲基-α,α-二甲基苯甲基]苯、1,4-雙[4-(3-馬來醯亞胺基苯氧基)-3,5-二甲基-α,α-二甲基苯甲基]苯、1,3-雙[4-(3-馬來醯亞胺基苯氧基)-3,5-二甲基-α,α-二甲基苯甲基]苯、聚苯基甲烷馬來醯亞胺等含芳香族烴基馬來醯亞胺。Specific examples of the maleimide compound (a1) include, for example, N,N′-ethylidenebismaleimide, N,N′-hexamethylenebismaleimide, Aliphatic hydrocarbon-containing maleimide such as bis(4-maleimidocyclohexyl)methane, 1,4-bis(maleimidomethyl)cyclohexane; N,N'-( 1,3-Phenylphenyl)bismaleimide, N,N'-[1,3-(2-Methylphenylene)]bismaleimide, N,N'-[1, 3-(4-methylphenylene)] bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4-maleimide) Phenyl)methane, bis(3-methyl4-maleimidophenyl)methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenyl Methane bismaleimide, bis(4-maleimidophenyl) ether, bis(4-maleimidophenyl) benzene, bis(4-maleimidophenyl) ) Sulfide, bis(4-maleimidophenyl) ketone, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4-bis(maleimidophenyl) Aminomethyl)cyclohexane, 1,3-bis(4-maleimidophenoxy)benzene, 1,3-bis(3-maleimidophenoxy)benzene, bis [4-(3-maleimidophenoxy)phenyl]methane, bis[4-(4-maleimidophenoxy)phenyl]methane, 1,1-bis[4 -(3-maleimidophenoxy)phenyl]ethane, 1,1-bis[4-(4-maleimidophenoxy)phenyl]ethane, 1,2 -Bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(4-maleimidophenoxy)phenyl]ethane , 2,2-bis[4-(3-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(4-maleimidophenoxy)phenyl ] Propane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(4-maleimidophenoxy) phenoxy )Phenyl]butane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2, 2-bis[4-(4-maleimidophenoxy)phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4'-bis(3-maleic (Imidophenoxy) biphenyl, 4,4'-bis(4-maleimidophenoxy) biphenyl, bis(4-(3-maleimidophenoxy) Phenyl] ketone, bis[4-(4-maleimidophenoxy)phenyl] ketone, bis(4-maleimidophenyl) disulfide, bis[4-(3 -Maleimidophenoxy)phenyl]sulfide, bis[4-(4-maleimidophenoxy)phenyl]sulfide, bis[4-(3-maleimide) Iminophenoxy)phenyl] sulfonamide, bis[4-(4-maleimidophenoxy)phenyl] sulfonamide, bis[4-(3-maleimidophenoxy) Oxy)phenyl] sulfonamide, bis[4-(4-maleimidophenoxy)phenyl]碸, bis[4-(3-maleimidophenoxy)phenyl] ether, bis[4-(4-maleimidophenoxy)phenyl] ether, 1,4- Bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleimidophenoxy) Group)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene , 1,3-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-maleimide Iminophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleimidophenoxy) -3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-3,5-dimethyl -Α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-bis Methylbenzyl]benzene, polyphenylmethane maleimide and other aromatic hydrocarbon-containing maleimide.

其中，從反應率高且能夠更高耐熱性化的觀點而言，較佳是雙(4-馬來醯亞胺基苯基)甲烷、雙(4-馬來醯亞胺基苯基)碸、雙(4-馬來醯亞胺基苯基)硫醚、雙(4-馬來醯亞胺基苯基)二硫醚、N,N’-(1,3-伸苯基)雙馬來醯亞胺、2,2-雙[4-(4-馬來醯亞胺苯氧基)苯基]丙烷；從廉價這樣的觀點，較佳是雙(4-馬來醯亞胺基苯基)甲烷、N,N’-(1,3-伸苯基)雙馬來醯亞胺；從對有機溶劑的溶解性的觀點而言，特佳是雙(4-馬來醯亞胺基苯基)甲烷。馬來醯亞胺化合物(a1)，可單獨使用1種，亦可將2種以上合併使用。Among them, bis(4-maleimidophenyl)methane and bis(4-maleimidophenyl)methane are preferred from the viewpoint of high reaction rate and higher heat resistance. , Bis(4-maleimidophenyl) sulfide, bis(4-maleimidophenyl) disulfide, N,N'-(1,3-phenylene)bisma Laimide, 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane; from the viewpoint of cheapness, bis(4-maleimidephenyl) is preferred Group) methane, N,N'-(1,3-phenylene)bismaleimide; from the viewpoint of solubility in organic solvents, particularly preferably is bis(4-maleimide group Phenyl)methane. The maleimide compound (a1) may be used alone or in combination of two or more.

(單胺化合物(a2)) 單胺化合物(a2)，只要是具有1個胺基之化合物，並無特別限制，從高耐熱性、低相對介電常數、高金屬箔黏合性、高玻璃轉化溫度、低熱膨脹性、成形性、鍍覆分佈性及尺寸變化量的偏差的觀點而言，較佳是具有酸性取代基之單胺化合物，較佳是由下述通式(a2-1)表示的單胺化合物。

(Monoamine compound (a2)) The monoamine compound (a2) is not particularly limited as long as it has one amine group, from high heat resistance, low relative dielectric constant, high metal foil adhesion, and high glass transition From the viewpoints of variation in temperature, low thermal expansion, formability, plating distribution, and dimensional change, it is preferably a monoamine compound having an acidic substituent, preferably represented by the following general formula (a2-1) Of monoamine compounds.

上述通式(a2-1)中，R^A4 表示由羥基、羧基及磺酸基中選出的酸性取代基。R^A5 表示碳數1～5的烷基或鹵素原子。t是1～5的整數，u是0～4的整數，且滿足1≦t＋u≦5。其中，當t為2～5的整數時，複數個R^A4 可相同亦可不同。又，當u為2～4的整數時，複數個R^A5 可相同亦可不同。作為R^A4 所表示的酸性取代基，從溶解性和反應性的觀點而言，較佳是羥基、羧基；如果也考慮到耐熱性，更佳是羥基。 t是1～5的整數，從高耐熱性、低相對介電常數、高金屬黏合性、高玻璃轉化溫度、低熱膨脹性、成形性、鍍覆分佈性及尺寸變化量的偏差的觀點而言，較佳是1～3的整數，更佳是1或2，進一步更佳是1。作為R^A5 所表示的碳數1～5的烷基，可列舉例如：甲基、乙基、正丙基、異丙基、正丁基、異丁基、三級丁基、正戊基等。作為該烷基，較佳是碳數1～3的烷基。作為R^A5 所表示的鹵素原子，可列舉：氟原子、氯原子、溴原子、碘原子等。 u是0～4的整數，從高耐熱性、低相對介電常數、高金屬黏合性、高玻璃轉化溫度、低熱膨脹性、成形性、鍍覆分佈性及尺寸變化量的偏差的觀點而言，較佳是0～3的整數，更佳是0～2的整數，進一步更佳是0或1，特佳是0。作為單胺化合物(a2)，從高耐熱性、低相對介電常數、高金屬黏合性、高玻璃轉化溫度、低熱膨脹性、成形性、鍍覆分佈性及尺寸變化量的偏差的觀點而言，更佳是由下述通式(a2-2)或(a2-3)表示的單胺化合物，進一步更佳是由下述通式(a2-2)表示的單胺化合物。其中，通式(a2-2)和(a2-3)中的R^A4 、R^A5 及u，與通式(a2-1)中相同，較佳的R^A4 、R^A5 及u亦相同。In the above general formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group and a sulfonic acid group. R ^A5 represents a C 1-5 alkyl group or a halogen atom. t is an integer of 1 to 5, u is an integer of 0 to 4, and satisfies 1≦t+u≦5. However, when t is an integer of 2 to 5, a plurality of R ^A4 may be the same or different. In addition, when u is an integer of 2 to 4, plural R ^A5s may be the same or different. The acidic substituent represented by R ^A4 is preferably a hydroxyl group or a carboxyl group from the viewpoints of solubility and reactivity; if heat resistance is also taken into consideration, a hydroxyl group is more preferable. t is an integer of 1 to 5, from the viewpoints of high heat resistance, low relative dielectric constant, high metal adhesion, high glass transition temperature, low thermal expansion, formability, plating distribution and variation in dimensional change , Is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1. Examples of the C 1-5 alkyl represented by R ^A5 include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, and n-pentyl. . The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. Examples of the halogen atom represented by R ^A5 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. u is an integer of 0 to 4, from the viewpoints of high heat resistance, low relative dielectric constant, high metal adhesion, high glass transition temperature, low thermal expansion, formability, plating distribution and variation in dimensional change Is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably 0 or 1, particularly preferably 0. As the monoamine compound (a2), from the viewpoints of high heat resistance, low relative dielectric constant, high metal adhesion, high glass transition temperature, low thermal expansion, moldability, plating distribution and variation in dimensional change It is more preferably a monoamine compound represented by the following general formula (a2-2) or (a2-3), and still more preferably a monoamine compound represented by the following general formula (a2-2). Among them, R ^A4 , R ^A5 and u in the general formulas (a2-2) and (a2-3) are the same as in the general formula (a2-1), and the preferred R ^A4 , R ^A5 and u are also the same.

作為單胺化合物(a2)，可列舉例如下述具有酸性取代基之單胺化合物：鄰胺基苯酚、間胺基苯酚、對胺基苯酚、鄰胺基苯甲酸、間胺基苯甲酸、對胺基苯甲酸、鄰胺基苯磺酸、間胺基苯磺酸、對胺基苯磺酸、3,5-二羥基苯胺、3,5-二羧基苯胺等。其中，從溶解性和反應性的觀點而言，較佳是間胺基苯酚、對胺基苯酚、對胺基苯甲酸、3,5-二羥基苯胺；從耐熱性的觀點而言，較佳是鄰胺基苯酚、間胺基苯酚、對胺基苯酚；如果也考慮到介電特性、低熱膨脹性及製造成本，更佳是對胺基苯酚。單胺化合物(a2)，可單獨使用1種，亦可將2種以上合併使用。Examples of the monoamine compound (a2) include the following monoamine compounds having an acidic substituent: o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p Aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, etc. Among them, from the viewpoint of solubility and reactivity, m-aminophenol, p-aminophenol, p-aminobenzoic acid, and 3,5-dihydroxyaniline are preferred; from the viewpoint of heat resistance, preferred It is o-aminophenol, m-aminophenol, and p-aminophenol; if dielectric properties, low thermal expansion, and manufacturing costs are also considered, p-aminophenol is more preferred. The monoamine compound (a2) may be used alone or in combination of two or more.

(二胺化合物(a3)) 二胺化合物(a3)，只要是具有2個胺基之化合物，並無特別限制，從高耐熱性、低相對介電常數、高金屬箔黏合性、高玻璃轉化溫度、低熱膨脹性、成形性、鍍覆分佈性及尺寸變化量的偏差的觀點而言，較佳是由下述通式(a3-1)表示的二胺化合物。

式(a3-1)中，X^A2 表示碳數1～3的脂肪族烴基或-O-。R^A6 和R^A7 各自獨立地表示碳數1～5的烷基、鹵素原子、羥基、羧基或磺酸基。v和w各自獨立地為0～4的整數。(Diamine compound (a3)) The diamine compound (a3) is not particularly limited as long as it has two amine groups, from high heat resistance, low relative dielectric constant, high metal foil adhesion, and high glass transition From the viewpoint of variations in temperature, low thermal expansion, formability, plating distribution, and dimensional change, a diamine compound represented by the following general formula (a3-1) is preferred.

In formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or -O-. R ^A6 and R ^A7 each independently represent a C 1-5 alkyl group, a halogen atom, a hydroxyl group, a carboxyl group or a sulfonic acid group. v and w are each independently an integer of 0 to 4.

作為X^A2 所表示的碳數1～3的脂肪族烴基，可列舉例如：亞甲基、伸乙基、伸丙基、亞丙基等。作為X^A2 ，較佳是碳數1～3的脂肪族烴基，更佳是亞甲基。作為R^A6 和R^A7 所表示的碳數1～5的烷基，可列舉例如：甲基、乙基、正丙基、異丙基、正丁基、異丁基、三級丁基、正戊基等。作為該烷基，較佳是碳數1～3的烷基。 v和w，較佳是0～2的整數，更佳是0或1，進一步更佳是0。Examples of the C 1-3 aliphatic hydrocarbon group represented by X ^A2 include methylene, ethylidene, propylidene, and propylene groups. As X ^A2 , an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, and methylene is more preferred. Examples of the C 1-5 alkyl groups represented by R ^A6 and R ^A7 include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, and n Amyl and so on. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. v and w are preferably integers from 0 to 2, more preferably 0 or 1, and even more preferably 0.

作為二胺化合物(a3)，較佳是由下述通式(a3-1’)表示的二胺化合物。

式(a3-1’)中，X^A2 、R^A6 、R^A7 、v及w與前述通式(a3-1)中的相同，較佳態樣亦相同。As the diamine compound (a3), a diamine compound represented by the following general formula (a3-1') is preferred.

In formula (a3-1'), X ^A2 , R ^A6 , R ^A7 , v and w are the same as those in the aforementioned general formula (a3-1), and the preferred aspects are also the same.

作為二胺化合物(a3)，具體而言，可列舉例如：4,4’-二胺基苯基甲烷、4,4’-二胺基苯基乙烷、4,4’-二胺基苯基丙烷、2,2’-雙(4,4’-二胺基苯基)丙烷、3,3’-二甲基-4,4’-二胺基苯基甲烷、3,3’-二乙基-4,4’-二胺基苯基甲烷、3,3’-二甲基-4,4’-二胺基苯基乙烷、3,3’-二乙基-4,4’-二胺基苯基乙烷、4,4’-二胺基苯基醚、4,4’-二胺基苯基硫醚、3,3’-二羥基-4,4’-二胺基苯基甲烷、2,2’,6,6’-四甲基-4,4’-二胺基苯基甲烷、3,3’-二氯-4,4’-二胺基苯基甲烷、3,3’-二溴-4,4’-二胺基苯基甲烷、2,2’,6,6’-四氯-4,4’-二胺基苯基甲烷、2,2’,6,6’-四溴-4,4’-二胺基苯基甲烷等。其中，從廉價這樣的觀點而言，較佳是4,4’-二胺基苯基甲烷、3,3’-二乙基-4,4’-二胺基苯基甲烷；從對溶劑的溶解性的觀點而言，更佳是4,4’-二胺基苯基甲烷。Specific examples of the diamine compound (a3) include: 4,4'-diaminophenylmethane, 4,4'-diaminophenylethane, and 4,4'-diaminobenzene Propane, 2,2'-bis(4,4'-diaminophenyl)propane, 3,3'-dimethyl-4,4'-diaminophenylmethane, 3,3'-di Ethyl-4,4'-diaminophenylmethane, 3,3'-dimethyl-4,4'-diaminophenylethane, 3,3'-diethyl-4,4' -Diaminophenylethane, 4,4'-diaminophenyl ether, 4,4'-diaminophenyl sulfide, 3,3'-dihydroxy-4,4'-diamino Phenylmethane, 2,2',6,6'-tetramethyl-4,4'-diaminophenylmethane, 3,3'-dichloro-4,4'-diaminophenylmethane, 3,3'-dibromo-4,4'-diaminophenylmethane, 2,2',6,6'-tetrachloro-4,4'-diaminophenylmethane, 2,2', 6,6'-tetrabromo-4,4'-diaminophenylmethane, etc. Among them, from the viewpoint of cheapness, 4,4'-diaminophenylmethane and 3,3'-diethyl-4,4'-diaminophenylmethane are preferred; From the viewpoint of solubility, 4,4'-diaminophenylmethane is more preferable.

馬來醯亞胺化合物(a1)、單胺化合物(a2)及二胺化合物(a3)的反應，較佳是藉由下述方式實施：在有機溶劑的存在下，於反應溫度70～200℃使其反應0.1～10小時。反應溫度，更佳是70～160℃，進一步更佳是70～130℃，特佳是80～120℃。反應時間，更佳是1～6小時，進一步更佳是1～4小時。The reaction of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3) is preferably carried out in the following manner: in the presence of an organic solvent at a reaction temperature of 70 to 200°C Let it react for 0.1 to 10 hours. The reaction temperature is more preferably 70 to 160°C, still more preferably 70 to 130°C, and particularly preferably 80 to 120°C. The reaction time is more preferably 1 to 6 hours, and still more preferably 1 to 4 hours.

(馬來醯亞胺化合物(a1)、單胺化合物(a2)及二胺化合物(a3)的使用量) 又，在馬來醯亞胺化合物(a1)、單胺化合物(a2)及二胺化合物(a3)的反應中，三者的使用量，較佳是：單胺化合物(a2)和二胺化合物(a3)所具有的-NH₂ 基當量(一級胺基當量)的總和與馬來醯亞胺化合物(a1)的馬來醯亞胺基當量的關係，滿足下述式子。 0.1≦〔馬來醯亞胺基當量〕／〔-NH₂ 基當量的總和〕≦10 如此一來，藉由將〔馬來醯亞胺基當量〕／〔-NH₂ 基當量的總和〕設為0.1以上，不會膠化且耐熱性不會下降，並且，藉由設為10以下，對有機溶劑的溶解性、金屬箔黏合性及耐熱性不會下降，因此較佳。從相同的觀點而言，更佳是滿足1≦〔馬來醯亞胺基當量〕／〔-NH₂ 基當量的總和〕≦9，更佳是滿足2≦〔馬來醯亞胺基當量〕／〔-NH₂ 基當量的總和〕≦8。(Use amount of maleimide compound (a1), monoamine compound (a2) and diamine compound (a3)) In addition, in maleimide compound (a1), monoamine compound (a2) and diamine In the reaction of the compound (a3), the usage amount of the three is preferably: the sum of the -NH ₂ group equivalent (primary amine group equivalent) of the monoamine compound (a2) and the diamine compound (a3) and Malay The relationship of the maleimide equivalent of the imidate compound (a1) satisfies the following formula. 0.1≦[maleimide equivalent]/[total equivalent of -NH ₂ groups]≦10 In this way, by setting [maleimide equivalent]/[total of -NH ₂ equivalents] If it is 0.1 or more, it does not gel and the heat resistance does not decrease, and by setting it to 10 or less, the solubility in organic solvents, the adhesion of the metal foil, and the heat resistance do not decrease, which is preferable. From the same viewpoint, it is more preferable to satisfy 1≦[maleimide equivalent]/[total of -NH ₂ equivalent]≦9, and it is more preferable to satisfy 2≦[maleimide equivalent] / [Total of -NH ₂ radical equivalents]≦8.

(單胺化合物(a2)與二胺化合物(a3)的使用比率) 本發明中，藉由前述(A)馬來醯亞胺化合物是將前述單胺化合物(a2)成分相對於前述二胺化合物(a3)成分的使用比率[(a2)成分/(a3)成分](莫耳比)，設為0.9～5.0來進行反應而獲得，能夠顯著地減少尺寸變化量的偏差。顯現該效果的機制尚不明確。無論該使用比率低於0.9還是超過5.0，尺寸變化量的偏差都會變大。從相同的觀點而言，該使用比率，較佳是1.0～4.5，更佳是1.0～4.0，亦可以是1.5～3.5，亦可以是1.5～3.0，亦可以是1.5～2.5。藉由以如上所述的使用比率來進行反應，(A)成分中的源自單胺化合物(a2)的結構單元與源自二胺化合物(a3)的結構單元的比率(莫耳比)成為0.9～5.0，較佳是成為1.0～4.5，更佳是成為1.0～4.0，亦能夠設為1.5～3.5，亦能夠設為1.5～3.0。(Usage ratio of monoamine compound (a2) to diamine compound (a3)) In the present invention, the (A) maleimide compound is the use ratio of the monoamine compound (a2) component to the diamine compound (a3) component [(a2) component/(a3) component] (Molar ratio) is obtained by performing the reaction at 0.9 to 5.0, and can significantly reduce the variation in the amount of dimensional change. The mechanism for showing this effect is not yet clear. Regardless of whether the usage ratio is less than 0.9 or exceeds 5.0, the variation in the amount of dimensional change will increase. From the same viewpoint, the use ratio is preferably 1.0 to 4.5, more preferably 1.0 to 4.0, 1.5 to 3.5, 1.5 to 3.0, or 1.5 to 2.5. By performing the reaction at the use ratio as described above, the ratio (mol ratio) of the structural unit derived from the monoamine compound (a2) to the structural unit derived from the diamine compound (a3) in the component (A) becomes 0.9 to 5.0, preferably 1.0 to 4.5, more preferably 1.0 to 4.0, 1.5 to 3.5, and 1.5 to 3.0.

(有機溶劑) 馬來醯亞胺化合物(a1)、單胺化合物(a2)及二胺化合物(a3)的反應，較佳是在有機溶劑中實行。作為有機溶劑，只要不對該反應造成不良影響，並無特別限制。可列舉例如：乙醇、丙醇、丁醇、甲基賽珞蘇、丁基賽珞蘇、丙二醇單甲基醚等醇系溶劑；丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮系溶劑；四氫呋喃等醚系溶劑；甲苯、二甲苯、均三甲苯(mesitylene)等芳香族系溶劑；含氮原子之溶劑，其包括二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮等醯胺系溶劑；含硫原子之溶劑，其包括二甲基亞碸等亞碸系溶劑；乙酸乙酯、γ-丁內酯等酯系溶劑等。其中，從溶解性的觀點而言，較佳是醇系溶劑、酮系溶劑、酯系溶劑；從低毒性這樣的觀點而言，更佳是環己酮、丙二醇單甲基醚、甲基賽珞蘇、γ-丁內酯；如果也考慮到揮發性高，在製造預浸體時不易作為殘留溶劑殘留，進一步更佳是環己酮、丙二醇單甲基醚、二甲基乙醯胺，特佳是二甲基乙醯胺。有機溶劑，可單獨使用1種，亦可將2種以上合併使用。有機溶劑的使用量並無特別限制，從溶解性和反應效率的觀點而言，相對於馬來醯亞胺化合物(a1)、單胺化合物(a2)及二胺化合物(a3)的合計100質量份，只要使該有機溶劑的使用量成為下述量即可：較佳是25～1000質量份，更佳是40～700質量份，進一步更佳是60～250質量份。相對於馬來醯亞胺化合物(a1)、單胺化合物(a2)及二胺化合物(a3)的合計100質量份，藉由將該有機溶劑的使用量設為25質量份以上，有易於確保溶解性的傾向；藉由設為1000質量份以下，有易於抑制反應效率大幅下降的傾向。本發明的樹脂清漆中可包含該有機溶劑。(Organic solvents) The reaction of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3) is preferably carried out in an organic solvent. The organic solvent is not particularly limited as long as it does not adversely affect the reaction. Examples include alcohol solvents such as ethanol, propanol, butanol, methylcellulose, butylcellulose, and propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclic Ketone solvents such as hexanone; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; solvents containing nitrogen atoms, including dimethylformamide and dimethylacetamide Amine-based solvents such as amines and N-methylpyrrolidone; solvents containing sulfur atoms, including sulfonated solvents such as dimethyl sulfoxide; ester-based solvents such as ethyl acetate and γ-butyrolactone. Among them, from the viewpoint of solubility, alcohol solvents, ketone solvents, and ester solvents are preferred; from the viewpoint of low toxicity, cyclohexanone, propylene glycol monomethyl ether, and methylcellulose are more preferred. Luosu, γ-butyrolactone; if high volatility is also considered, it is not easy to remain as a residual solvent when manufacturing prepregs, further preferably cyclohexanone, propylene glycol monomethyl ether, dimethylacetamide, Particularly preferred is dimethylacetamide. Organic solvents may be used alone or in combination of two or more. The amount of the organic solvent used is not particularly limited, and from the viewpoint of solubility and reaction efficiency, it is 100 masses relative to the total of the maleimide compound (a1), the monoamine compound (a2), and the diamine compound (a3). Parts, as long as the amount of the organic solvent used is as follows: preferably 25 to 1000 parts by mass, more preferably 40 to 700 parts by mass, still more preferably 60 to 250 parts by mass. The amount of the organic solvent used is set to 25 parts by mass or more relative to 100 parts by mass of the total amount of maleimide compound (a1), monoamine compound (a2) and diamine compound (a3), so it is easy to ensure Tendency to solubility; by setting it to 1000 parts by mass or less, there is a tendency to easily suppress a significant decrease in reaction efficiency. The organic solvent may be included in the resin varnish of the present invention.

(反應觸媒) 馬來醯亞胺化合物(a1)、單胺化合物(a2)及二胺化合物(a3)的反應，可根據需要而在反應觸媒的存在下實施。作為反應觸媒，可列舉例如：三乙胺、吡啶、三丁胺等胺系觸媒；甲基咪唑、苯基咪唑等咪唑系觸媒；三苯基膦等磷系觸媒等。反應觸媒，可單獨使用1種，亦可將2種以上合併使用。反應觸媒的使用並無特別限制，相對於馬來醯亞胺化合物(a1)與單胺化合物(a2)的質量總和100質量份，較佳是0.001～5質量份。(Reaction catalyst) The reaction of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3) can be carried out in the presence of a reaction catalyst as needed. Examples of the reaction catalyst include amine catalysts such as triethylamine, pyridine, and tributylamine; imidazole catalysts such as methylimidazole and phenylimidazole; phosphorus catalysts such as triphenylphosphine. One type of reaction catalyst may be used alone, or two or more types may be used in combination. The use of the reaction catalyst is not particularly limited, and it is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total mass of the maleimide compound (a1) and the monoamine compound (a2).

＜(B)環氧樹脂＞ (B)成分，是環氧樹脂(以下，有時稱為(B)環氧樹脂)，較佳是一分子中具有至少2個環氧基之環氧樹脂。作為一分子中具有至少2個環氧基之環氧樹脂，可列舉：縮水甘油基醚型環氧樹脂、縮水甘油基胺型環氧樹脂、縮水甘油酯型環氧樹脂等。其中，較佳是縮水甘油基醚型環氧樹脂。 (B)環氧樹脂，根據主骨架的不同而被分類成各種環氧樹脂，在上述各型的環氧樹脂中，進一步分類成以下環氧樹脂：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂等雙酚型環氧樹脂；聯苯芳烷基酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂、烷基苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、萘酚烷基苯酚共聚合酚醛清漆型環氧樹脂、萘酚烷基甲酚共聚合酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、雙酚F酚醛清漆型環氧樹脂等酚醛清漆型環氧樹脂；二苯乙烯型環氧樹脂；含三嗪骨架之環氧樹脂；含茀骨架之環氧樹脂；萘型環氧樹脂；蒽型環氧樹脂；三酚甲烷型環氧樹脂；聯苯型環氧樹脂；伸苯二甲基(xylylene)型環氧樹脂；雙環戊二烯型環氧樹脂等脂環式環氧樹脂等。＜(B) epoxy resin＞ The component (B) is an epoxy resin (hereinafter sometimes referred to as (B) epoxy resin), preferably an epoxy resin having at least two epoxy groups in one molecule. Examples of the epoxy resin having at least two epoxy groups in one molecule include glycidyl ether epoxy resin, glycidyl amine epoxy resin, and glycidyl ester epoxy resin. Among them, glycidyl ether type epoxy resins are preferred. (B) Epoxy resins are classified into various epoxy resins according to the main skeleton. Among the above-mentioned various types of epoxy resins, they are further classified into the following epoxy resins: bisphenol A epoxy resin, bisphenol F Type epoxy resin, bisphenol S type epoxy resin and other bisphenol type epoxy resin; biphenyl aralkyl novolak type epoxy resin, phenol novolak type epoxy resin, alkyl phenol novolak type epoxy resin, Cresol novolac epoxy resin, naphthol alkyl phenol copolymer novolac epoxy resin, naphthol alkyl cresol copolymer novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resins such as novolac epoxy resins; stilbene epoxy resins; epoxy resins containing triazine skeletons; epoxy resins containing stilbene skeletons; naphthalene epoxy resins; anthracene epoxy resins Resin; triphenol methane epoxy resin; biphenyl epoxy resin; xylylene epoxy resin; alicyclic epoxy resin such as dicyclopentadiene epoxy resin.

其中，從高耐熱性、低相對介電常數、高金屬黏合性、高玻璃轉化溫度、低熱膨脹性、成形性及鍍覆分佈性的觀點而言，較佳是選自由雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、萘型環氧樹脂、蒽型環氧樹脂、聯苯型環氧樹脂、聯苯芳烷基酚醛清漆型環氧樹脂及雙環戊二烯型環氧樹脂所組成之群組中的至少1種；從低熱膨脹性和高玻璃轉化溫度的觀點而言，更佳是選自由甲酚酚醛清漆型環氧樹脂、萘型環氧樹脂、蒽型環氧樹脂、聯苯型環氧樹脂、聯苯芳烷基酚醛清漆型環氧樹脂及苯酚酚醛清漆型環氧樹脂所組成之群組中的至少1種，進一步更佳是甲酚酚醛清漆型環氧樹脂。 (B)環氧樹脂，可單獨使用1種，亦可將2種以上合併使用。Among them, from the viewpoint of high heat resistance, low relative dielectric constant, high metal adhesion, high glass transition temperature, low thermal expansion, moldability, and plating distribution, it is preferably selected from bisphenol F-type epoxy Resin, phenol novolac epoxy resin, cresol novolac epoxy resin, naphthalene epoxy resin, anthracene epoxy resin, biphenyl epoxy resin, biphenyl aralkyl novolac epoxy resin and At least one of the group consisting of dicyclopentadiene-type epoxy resin; from the viewpoint of low thermal expansion and high glass transition temperature, it is more preferably selected from the group consisting of cresol novolac-type epoxy resin and naphthalene-type ring At least one of the group consisting of oxygen resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl novolak type epoxy resin and phenol novolak type epoxy resin, further preferably Cresol novolac epoxy resin. (B) One type of epoxy resin may be used alone, or two or more types may be used in combination.

(B)環氧樹脂的環氧當量，較佳是100～500g/eq，更佳是120～400g/eq，進一步更佳是140～300g/eq，特佳是170～240g/eq。此處，環氧當量，是每個環氧基的樹脂質量(g/eq)，可依照日本工業標準(JIS) K 7236(2001年)所規定的方法來進行測定。具體而言，是藉由下述方式求出該環氧當量：使用三菱Chemical Analytech股份有限公司製造的自動滴定裝置「GT-200型」，將2g環氧樹脂秤量至200ml燒杯中，並滴入90ml甲基乙基酮，利用超音波清洗器加以溶解後，添加10ml冰醋酸和1.5g溴化十六烷基三甲基銨，並以0.1mol/L的過氯酸/乙酸溶液進行滴定。作為(B)環氧樹脂的市售品，可列舉：甲酚酚醛清漆型環氧樹脂「EPICLON(註冊商標) N-673」(DIC故份有限公司製造，環氧當量：205～215g/eq)、萘型環氧樹脂「HP-4032」(三菱化學股份有限公司製造，環氧當量：152g/eq)、聯苯型環氧樹脂「YX-4000」(三菱化學股份有限公司製造，環氧當量：186g/eq)、雙環戊二烯型環氧樹脂「HP-7200H」(DIC股份有限公司製造，環氧當量：280g/eq)等。再者，環氧當量，是該商品的製造公司的型錄所記載的值。(B) The epoxy equivalent of the epoxy resin is preferably 100 to 500 g/eq, more preferably 120 to 400 g/eq, even more preferably 140 to 300 g/eq, and particularly preferably 170 to 240 g/eq. Here, the epoxy equivalent is the resin mass (g/eq) per epoxy group, and can be measured in accordance with the method specified in Japanese Industrial Standards (JIS) K 7236 (2001). Specifically, the epoxy equivalent is determined by the following method: using an automatic titration device "GT-200" manufactured by Mitsubishi Chemical Analytech Co., Ltd., weighing 2 g of epoxy resin into a 200 ml beaker and dropping After 90 ml of methyl ethyl ketone was dissolved in an ultrasonic cleaner, 10 ml of glacial acetic acid and 1.5 g of cetyltrimethylammonium bromide were added, and titration was performed with a 0.1 mol/L perchloric acid/acetic acid solution. As a commercially available product of (B) epoxy resin, a cresol novolac epoxy resin "EPICLON (registered trademark) N-673" (manufactured by DIC Kokube Co., Ltd., epoxy equivalent: 205 to 215 g/eq ), naphthalene type epoxy resin "HP-4032" (Mitsubishi Chemical Co., Ltd., epoxy equivalent: 152g/eq), biphenyl type epoxy resin "YX-4000" (Mitsubishi Chemical Co., Ltd., epoxy Equivalent: 186g/eq), dicyclopentadiene epoxy resin "HP-7200H" (manufactured by DIC Corporation, epoxy equivalent: 280g/eq), etc. In addition, the epoxy equivalent is the value described in the catalog of the manufacturer of the product.

＜(C)特定共聚合樹脂＞ (C)成分，是具有源自取代乙烯系化合物的結構單元與源自馬來酸酐的結構單元之共聚合樹脂(以下，有時稱為(C)共聚合樹脂)。作為取代乙烯系化合物，可列舉例如：芳香族乙烯系化合物、脂肪族乙烯系化合物、官能基取代乙烯系化合物等。作為芳香族乙烯系化合物，可列舉例如：苯乙烯、1-甲基苯乙烯、乙烯基甲苯、二甲基苯乙烯等。其中，較佳是苯乙烯。作為脂肪族乙烯系化合物，可列舉例如：丙烯、丁二烯、異丁烯等。作為官能基取代乙烯系化合物，可列舉例如：丙烯腈；丙烯酸甲酯、甲基丙烯酸甲酯等具有(甲基)丙烯醯基之化合物等。其中，作為取代乙烯系化合物，較佳是芳香族乙烯系化合物，更佳是苯乙烯。作為(C)成分，較佳是具有由下述通式(C-i)表示的結構單元與由下述通式(C-ii)表示的結構單元之共聚合樹脂。＜(C) Specific copolymerization resin＞ The component (C) is a copolymer resin having a structural unit derived from a substituted vinyl compound and a structural unit derived from maleic anhydride (hereinafter, sometimes referred to as (C) copolymer resin). Examples of the substituted vinyl compounds include aromatic vinyl compounds, aliphatic vinyl compounds, and functional group-substituted vinyl compounds. Examples of the aromatic vinyl compound include styrene, 1-methylstyrene, vinyltoluene, and dimethylstyrene. Among them, styrene is preferred. Examples of aliphatic vinyl compounds include propylene, butadiene, and isobutene. Examples of the functional group-substituted vinyl compounds include acrylonitrile; compounds having a (meth)acryloyl group such as methyl acrylate and methyl methacrylate. Among them, the substituted vinyl compound is preferably an aromatic vinyl compound, and more preferably styrene. The component (C) is preferably a copolymerized resin having a structural unit represented by the following general formula (C-i) and a structural unit represented by the following general formula (C-ii).

式(C-i)中，R^C1 是氫原子或碳數1～5的烷基，R^C2 是碳數1～5的烷基、碳數2～5的烯基、碳數6～20的芳基、羥基或(甲基)丙烯醯基。x是0～3的整數。其中，當x為2或3時，複數個R^C2 可相同亦可不同。

In formula (Ci), R ^C1 is a hydrogen atom or a C 1-5 alkyl group, R ^C2 is a C 1-5 alkyl group, a C 2-5 alkenyl group, and a C 6-20 aryl group , Hydroxy or (meth) acryl. x is an integer from 0 to 3. Wherein, when x is 2 or 3, the plurality of R ^C2 may be the same or different.

作為R^C1 和R^C2 所表示的碳數1～5的烷基，可列舉例如：甲基、乙基、正丙基、異丙基、正丁基、異丁基、三級丁基、正戊基等。作為該烷基，較佳是碳數1～3的烷基。作為R^C2 所表示的碳數2～5的烯基，可列舉例如：烯丙基、巴豆基(crotyl)等。作為該烯基，較佳是碳數3～5的烯基，更佳是碳數3或4的烯基。作為R^C2 所表示的碳數6～20的芳基，可列舉例如：苯基、萘基、蒽基、聯苯基等。作為該芳基，較佳是碳數6～12的芳基，更佳是碳數6～10的芳基。 x，較佳是0或1，更佳是0。在由通式(C-i)表示的結構單元中，較佳是：R^C1 是氫原子且x為0之由下述通式(C-i-1)表示的結構單元也就是源自苯乙烯的結構單元。

Examples of the C 1-5 alkyl represented by R ^C1 and R ^C2 include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, and n Amyl and so on. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. Examples of the C 2-5 alkenyl groups represented by R ^C2 include allyl groups and crotyl groups. The alkenyl group is preferably an alkenyl group having 3 to 5 carbon atoms, and more preferably an alkenyl group having 3 or 4 carbon atoms. Examples of the C 6-20 aryl group represented by R ^C2 include phenyl, naphthyl, anthracenyl, and biphenyl. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. x, preferably 0 or 1, more preferably 0. Among the structural units represented by the general formula (Ci), it is preferable that the structural unit represented by the following general formula (Ci-1) where R ^C1 is a hydrogen atom and x is 0 is a structural unit derived from styrene .

(C)共聚合樹脂中的源自取代乙烯系化合物的結構單元與源自馬來酸酐的結構單元的含有比例[源自取代乙烯系化合物的結構單元／源自馬來酸酐的結構單元]，以莫耳比計，較佳是1～9，更佳是2～9，進一步更佳是3～8，特佳是3～7。又，前述由(C-i)表示的結構單元相對於前述由(C-ii)表示的結構單元的含有比例[(C-i)／(C-ii)]，以莫耳比計，亦同樣地，較佳是1～9，更佳是2～9，進一步更佳是3～8，特佳是3～7。若這些莫耳比為1以上，較佳是2以上，則有改善介電特性的功效充分的傾向，若是9以下，則有使互溶性良好的傾向。 (C)共聚合樹脂中的源自取代乙烯系化合物的結構單元與源自馬來酸酐的結構單元的合計含量、及由通式(C-i)表示的結構單元與由式(C-ii)表示的結構單元的合計含量，分別較佳是50質量%以上，更佳是70質量%以上，進一步更佳是90質量%以上，特佳是實質上100質量%。 (C)共聚合樹脂的重量平均分子量(Mw)，較佳是4500～18000，更佳是5000～18000，更佳是6000～17000，進一步更佳是8000～16000，特佳是8000～15000，最佳是9000～13000。(C) The content ratio of the structural unit derived from the substituted vinyl compound and the structural unit derived from maleic anhydride in the copolymer resin [structural unit derived from the substituted vinyl compound/structural unit derived from maleic anhydride], In terms of molar ratio, it is preferably 1-9, more preferably 2-9, still more preferably 3-8, and particularly preferably 3-7. In addition, the content ratio of the structural unit represented by (Ci) to the structural unit represented by (C-ii) [(Ci)/(C-ii)], in molar ratio, is similarly It is preferably 1-9, more preferably 2-9, even more preferably 3-8, and particularly preferably 3-7. If these molar ratios are 1 or more, preferably 2 or more, the effect of improving the dielectric properties tends to be sufficient, and if it is 9 or less, the mutual solubility tends to be good. (C) The total content of the structural unit derived from the substituted vinyl compound and the structural unit derived from maleic anhydride in the copolymer resin, and the structural unit represented by the general formula (Ci) and represented by the formula (C-ii) The total content of the structural units is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably 100% by mass. (C) The weight average molecular weight (Mw) of the copolymerized resin is preferably 4500 to 18000, more preferably 5000 to 18000, more preferably 6000 to 17000, still more preferably 8000 to 16000, and particularly preferably 8000 to 15000, The best is 9000 ~ 13000.

再者，藉由使用苯乙烯與馬來酸酐的共聚合樹脂來使環氧樹脂低介電常數化的方法，如果應用於印刷線路板用材料，則會使對基材的含浸性和銅箔剝離強度不足，因此一般而言有避免該方法的傾向。因此，雖然一般而言有避免使用前述(C)共聚合樹脂的傾向，但是本發明藉由使用前述(C)共聚合樹脂，並且含有前述(A)成分、前述(B)成分及前述(D)成分，從而成為一種優異的樹脂清漆，該樹脂清漆具有高耐熱性、低相對介電常數、高金屬黏合性、高玻璃轉化溫度及低熱膨脹性，並且成形性、鍍覆分佈性優異及尺寸變化量的偏差小。Furthermore, the method of reducing the dielectric constant of epoxy resin by using a copolymer resin of styrene and maleic anhydride, if applied to materials for printed wiring boards, will impregnate the substrate and peel off the copper foil The strength is insufficient, so in general there is a tendency to avoid this method. Therefore, although there is a general tendency to avoid the use of the (C) copolymerized resin, the present invention contains the (A) component, the (B) component, and the (D) by using the (C) copolymerized resin ) Component, thus becoming an excellent resin varnish with high heat resistance, low relative dielectric constant, high metal adhesion, high glass transition temperature and low thermal expansion, and excellent formability, plating distribution and size The deviation of the amount of change is small.

((C)共聚合樹脂的製造方法) 可藉由使取代乙烯系化合物與馬來酸酐進行共聚合，來製造(C)共聚合樹脂。取代乙烯系化合物，如前所述。取代乙烯系化合物，可單獨使用1種，亦可將2種以上合併使用。進一步，除了前述取代乙烯系化合物和前述馬來酸酐以外，亦可使各種能夠聚合的成分進行共聚合。又，可透過夫里得-夸夫特反應(Friedel-Crafts reaction)或使用鋰等金屬觸媒之反應，來對該取代乙烯系化合物、尤其是芳香族乙烯系化合物導入烯丙基、甲基丙烯醯基、丙烯醯基、羥基等取代基。((C) Manufacturing method of copolymer resin) The copolymerized resin (C) can be produced by copolymerizing the substituted vinyl compound and maleic anhydride. The substitution of vinyl compounds is as described above. Instead of vinyl compounds, one type may be used alone, or two or more types may be used in combination. Furthermore, in addition to the substituted vinyl compound and the maleic anhydride, various polymerizable components may be copolymerized. In addition, allyl and methyl groups can be introduced into the substituted vinyl compound, especially the aromatic vinyl compound through the Friedel-Crafts reaction or the reaction using metal catalysts such as lithium Propylene acetyl, propylene acetyl, hydroxy and other substituents.

作為(C)共聚合樹脂，可使用市售品。作為市售品，可列舉例如：「SMA(註冊商標)1000」(苯乙烯／馬來酸酐＝1、Mw＝5000)、「SMA(註冊商標)EF30」(苯乙烯／馬來酸酐＝3、Mw＝9500)、「SMA(註冊商標)EF40」(苯乙烯／馬來酸酐＝4、Mw＝11000)、「SMA(註冊商標)EF60」(苯乙烯／馬來酸酐＝6、Mw＝11500)、「SMA(註冊商標)EF80」(苯乙烯／馬來酸酐＝8、Mw＝14400)(以上為CRAY VALLEY公司製造)等。As the (C) copolymer resin, a commercially available product can be used. Examples of commercially available products include "SMA (registered trademark) 1000" (styrene/maleic anhydride=1, Mw=5000), "SMA (registered trademark) EF30" (styrene/maleic anhydride=3, Mw = 9500), "SMA (registered trademark) EF40" (styrene/maleic anhydride = 4, Mw = 11000), "SMA (registered trademark) EF60" (styrene/maleic anhydride = 6, Mw = 11500) , "SMA (registered trademark) EF80" (styrene/maleic anhydride = 8, Mw = 14400) (above manufactured by Cray Valley), etc.

＜(D)無機填充材料＞從低熱膨脹性的觀點而言，本發明的樹脂清漆，較佳是包含無機填充材料作為(D)成分。作為前述無機填充材料，可列舉例如：二氧化矽、氧化鋁、硫酸鋇、滑石、黏土、雲母粉、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、氧化鎂、氮化硼、硼酸鋁、鈦酸鋇、鈦酸鍶、鈦酸鈣、鈦酸鉍、氧化鈦、鋯酸鋇、鋯酸鈣等。這些無機填充材料，可使用單獨1種，亦可將2種以上合併使用。其中，從降低熱膨脹係數的觀點而言，較佳是二氧化矽。作為前述二氧化矽，可列舉例如：沉澱二氧化矽，其是以濕式法製造且含水率高；及，乾式二氧化矽，其是以乾式法製造且幾乎不含結合水。作為乾式二氧化矽，進一步根據製造方法的不同，可列舉：破碎二氧化矽、氣相二氧化矽(fumed silica)、熔融二氧化矽(熔融球狀二氧化矽)。從低熱膨脹性和對樹脂進行填充時的高流動性的觀點而言，二氧化矽較佳是熔融二氧化矽。<(D) inorganic filler> From the viewpoint of low thermal expansion, the resin varnish of the present invention preferably contains an inorganic filler as the (D) component. Examples of the inorganic filler include silicon dioxide, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, and aluminum borate. , Barium titanate, strontium titanate, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, etc. These inorganic fillers can be used alone or in combination of two or more. Among them, from the viewpoint of reducing the thermal expansion coefficient, silicon dioxide is preferred. Examples of the aforementioned silica include precipitated silica, which is produced by a wet method and has a high water content; and dry silica, which is produced by a dry method and contains almost no bound water. Examples of dry silica include crushed silica, fumed silica, and fumed silica (fused spherical silica) depending on the manufacturing method. From the viewpoint of low thermal expansion and high fluidity when the resin is filled, the silica is preferably fused silica.

作為無機填充材料的平均粒徑、尤其是二氧化矽的平均粒徑，並無特別限制，較佳是0.1～10μm，更佳是0.1～6μm，進一步更佳是0.1～3μm，特佳是1～3μm。藉由將無機填充材料、尤其是二氧化矽的平均粒徑設為0.1μm以上，能夠良好地保持高度填充時的流動性，並且，藉由設為10μm以下，能夠減少混入粗大粒子的機率，抑制產生由粗大粒子所引起的不良。此處，平均粒徑，是指當將粒子的總體積設為100%來求出基於粒徑的累積次數分佈曲線時，相當於正好體積50%的點的粒徑，能以使用了雷射繞射散射法的粒度分佈測定裝置等來進行測定。又，無機填充材料的比表面積、尤其是二氧化矽的比表面積，較佳是4cm² /g以上，更佳是4～9cm² /g，進一步更佳是5～7cm² /g。The average particle size of the inorganic filler, especially the average particle size of silica, is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.1 to 6 μm, even more preferably 0.1 to 3 μm, and particularly preferably 1 ~3μm. By setting the average particle diameter of the inorganic filler, especially silica, to 0.1 μm or more, the fluidity at the time of high filling can be maintained well, and by setting it to 10 μm or less, the probability of mixing coarse particles can be reduced, Suppression of defects caused by coarse particles. Here, the average particle size refers to the particle size corresponding to the point of exactly 50% of the volume when the cumulative volume distribution curve based on the particle size is obtained by setting the total volume of the particles to 100%, and the laser can be used The measurement is performed by a particle size distribution measuring device of the diffraction scattering method. In addition, the specific surface area of the inorganic filler, especially the specific surface area of silicon dioxide, is preferably 4 cm ² /g or more, more preferably 4 to 9 cm ² /g, and still more preferably 5 to 7 cm ² /g.

再者，無機填充材料中，尤其只要是經表面處理後的無機填充材料，除了能夠提升低熱膨脹性這樣的效果以外，還能夠提升與前述(A)～(C)成分的密合性，藉此抑制無機填充材料本身脫落，因此有能夠獲得下述效果的傾向：抑制由於過度去膠渣而導致的雷射通孔變形等。此外，有能夠提升鍍覆分佈性且尺寸變化量的偏差變小的傾向，因此無機填充材料更佳是經表面處理後的無機填充材料。藉由將無機填充材料製成經表面處理後的無機填充材料，能夠提升鍍覆分佈性，推測其原因在於，去膠渣溶解量變大，有成為雷射孔壁面的凹凸和玻璃布的突出較大之孔形狀的傾向。Furthermore, among the inorganic fillers, in particular, as long as they are surface-treated inorganic fillers, in addition to the effect of improving low thermal expansion, they can also improve the adhesion to the aforementioned components (A) to (C). This suppresses the inorganic filler itself from falling off, so there is a tendency that the following effects can be obtained: the deformation of the laser through hole due to excessive degumming is suppressed. In addition, there is a tendency to improve the plating distribution and the variation in the amount of dimensional change becomes smaller. Therefore, the inorganic filler is more preferably an inorganic filler after surface treatment. By making the inorganic filler into a surface-treated inorganic filler, the plating distribution can be improved, presumably because the dissolving amount of the degumming slag becomes larger, and there are irregularities on the wall surface of the laser hole and the protrusion of the glass cloth. The tendency of large hole shape.

作為能夠用來對無機填充材料進行表面處理的表面處理劑，可列舉例如：胺基矽烷系偶合劑、環氧基矽烷系偶合劑、苯基矽烷系偶合劑、烷基矽烷系偶合劑、烯基矽烷系偶合劑、炔基矽烷系偶合劑、鹵烷基矽烷系偶合劑、矽氧烷系偶合劑、氫矽烷系偶合劑、矽氮烷系偶合劑、烷氧基矽烷系偶合劑、氯矽烷系偶合劑、(甲基)丙烯醯基矽烷系偶合劑、異氰脲酸基矽烷系偶合劑、脲基矽烷系偶合劑、巰基矽烷系偶合劑、硫醚基矽烷系偶合劑或異氰酸基矽烷系偶合劑等。表面處理劑，可使用單獨1種，亦可將2種以上合併使用。從提升與前述(A)～(C)成分的密合性的效果的觀點、以及提升鍍覆分佈性和尺寸變化量的偏差變小這樣的觀點而言，作為表面處理劑，較佳是胺基矽烷系偶合劑。也就是說，作為(D)成分，較佳是經以胺基矽烷系偶合劑進行處理後的無機填充材料。作為該胺基矽烷系偶合劑，較佳是具有由下述通式(D-1)表示的含矽基與胺基之矽烷系偶合劑。

式(D-1)中，R^D1 是碳數1～3的烷基或碳數2～4的醯基。y是0～3的整數。Examples of surface treatment agents that can be used for surface treatment of inorganic fillers include aminosilane-based coupling agents, epoxysilane-based coupling agents, phenylsilane-based coupling agents, alkylsilane-based coupling agents, alkene Silane-based coupling agent, alkynyl silane-based coupling agent, haloalkyl silane-based coupling agent, siloxane-based coupling agent, hydrogen silane-based coupling agent, silazane-based coupling agent, alkoxysilane-based coupling agent, chlorine Silane-based coupling agent, (meth)acryloyl silane-based coupling agent, isocyanuric acid-based silane-based coupling agent, urea-based silane-based coupling agent, mercaptosilane-based coupling agent, thioether-based silane-based coupling agent or isocyanide Acid-based silane-based coupling agent, etc. As the surface treatment agent, one kind may be used alone, or two or more kinds may be used in combination. The surface treatment agent is preferably an amine from the viewpoint of improving the effect of adhesion with the aforementioned components (A) to (C), and from the viewpoint of improving the variation in plating distribution and dimensional change to be small. Silane-based coupling agent. That is, the component (D) is preferably an inorganic filler treated with an aminosilane-based coupling agent. As the amine-based silane-based coupling agent, a silane-based coupling agent having a silane group and an amine group containing the following general formula (D-1) is preferable.

In the formula (D-1), R ^D1 is a C 1-3 alkyl group or a C 2 -C 4 acetyl group. y is an integer from 0 to 3.

作為R^D1 所表示的碳數1～3的烷基，可列舉：甲基、乙基、正丙基、異丙基。其中，較佳是甲基。作為R^D1 所表示的碳數2～4的醯基，可列舉：乙醯基、丙醯基、丙烯醯基。其中，較佳是乙醯基。Examples of the C 1-3 alkyl represented by R ^D1 include methyl, ethyl, n-propyl, and isopropyl. Among them, methyl is preferred. Examples of the C 2-4 acyl group represented by R ^D1 include acetyl group, propyl group, and propenyl group. Among them, acetyl is preferred.

胺基矽烷系偶合劑，可具有1個胺基，亦可具有2個胺基，亦可具有3個以上的胺基，但通常是具有1個或2個胺基。作為具有1個胺基之胺基矽烷系偶合劑，可列舉例如：3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、N-苯基3-胺基丙基三甲氧基矽烷、3-三乙氧基矽基-N-(1,3-二甲基-亞丁基)丙基胺、2-丙醯基[3-(三甲氧基矽基)丙基]胺基甲酸酯等；但不受限於這些胺基矽烷系偶合劑。作為具有2個胺基之胺基矽烷系偶合劑，可列舉例如：N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、1-[3-(三甲氧基矽基)丙基]脲、1-[3-(三乙氧基矽基)丙基]脲等；但不受限於這些胺基矽烷系偶合劑。The aminosilane-based coupling agent may have 1 amine group, 2 amine groups, or 3 or more amine groups, but usually has 1 or 2 amine groups. Examples of the aminosilane-based coupling agent having one amine group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl 3-aminopropyl Trimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, 2-propionyl[3-(trimethoxysilyl)propyl ] Carbamates, etc.; but not limited to these aminosilane-based coupling agents. Examples of the aminosilane-based coupling agent having two amine groups include N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane and N-(2-amino group Ethyl)-3-aminopropyltrimethoxysilane, 1-[3-(trimethoxysilyl)propyl]urea, 1-[3-(triethoxysilyl)propyl]urea, etc. ; But not limited to these amine silane coupling agents.

又，可合併使用經表面處理後的無機填充材料與未進行表面處理的無機填充材料。此時，並無特別限制，相對於經表面處理後的無機填充材料100質量份，未進行表面處理的無機填充材料的含量，較佳是50質量份以下，更佳是30質量份以下，進一步更佳是15質量份以下，特佳是10質量份以下，最佳是5質量份以下。In addition, the inorganic filler after surface treatment and the inorganic filler without surface treatment can be used in combination. At this time, there is no particular limitation, and the content of the inorganic filler that has not been surface-treated is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, relative to 100 parts by mass of the surface-treated inorganic filler. It is more preferably 15 parts by mass or less, particularly preferably 10 parts by mass or less, and most preferably 5 parts by mass or less.

＜(E)硬化劑＞樹脂清漆，可進一步含有作為(E)成分的硬化劑(以下，有時稱為(E)硬化劑)。作為(E)硬化劑，可列舉：二氰二胺(dicyandiamide)；乙二胺、二乙三胺、三乙四胺、四乙五胺、六亞甲基二胺、二乙基胺基丙基胺、四甲基胍、三乙醇胺等的除了二氰二胺以外的鏈狀脂肪族胺；異佛爾酮二胺、二胺基二環己基甲烷、雙(胺基甲基)環己烷、雙(4-胺基-3-甲基二環己基)甲烷、N-胺基乙基哌嗪、3,9-雙(3-胺基丙基)-2,4,8,10-四氧雜螺[5.5]十一烷等環狀脂肪族胺；苯二甲胺、苯二胺、二胺基二苯基甲烷、二胺基二苯基碸等芳香族胺等。其中，從金屬箔黏合性和低熱膨脹性的觀點而言，較佳是二氰二胺。該二氰二胺，是由H₂ N-C(=NH)-NH-CN表示，其熔點通常是205～215℃，純度更高的二氰二胺則是207～212℃。二氰二胺，是結晶性物質，可以是斜方晶，亦可以是片狀晶。二氰二胺，較佳是純度98%以上，更佳是純度99%以上，進一步更佳是99.4%以上。作為二氰二胺，可使用市售品，可使用例如下述公司製造的市售品：日本電石工業股份有限公司製造、東京化成工業股份有限公司製造、KISHIDA化學股份有限公司製造、NACALAI TESQUE股份有限公司製造等。<(E) Hardener> The resin varnish may further contain a hardener as a component (E) (hereinafter, sometimes referred to as (E) hardener). Examples of (E) hardeners include: dicyandiamide (dicyandiamide); ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, diethylaminopropylene Chain aliphatic amines other than dicyandiamine such as diamine, tetramethylguanidine, triethanolamine; isophoronediamine, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane , Bis(4-amino-3-methyldicyclohexyl)methane, N-aminoethylpiperazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetra Cycloaliphatic amines such as oxaspiro[5.5]undecane; aromatic amines such as xylylenediamine, phenylenediamine, diaminodiphenylmethane, and diaminodiphenylbenzene. Among them, dicyandiamide is preferred from the viewpoint of metal foil adhesion and low thermal expansion. The dicyandiamide is represented by H ₂ NC(=NH)-NH-CN, its melting point is usually 205 to 215°C, and the higher purity dicyandiamide is 207 to 212°C. Dicyandiamide is a crystalline substance that can be orthorhombic or lamellar. The dicyandiamide preferably has a purity of 98% or higher, more preferably a purity of 99% or higher, and even more preferably 99.4% or higher. As dicyandiamide, commercially available products can be used, for example, commercially available products manufactured by the following companies: Japan Calcium Carbide Industry Co., Ltd., Tokyo Chemical Industry Co., Ltd., KISHIDA Chemical Co., Ltd., NACALAI TESQUE Co., Ltd. Manufacturing, etc.

＜(F)難燃劑＞樹脂清漆，可進一步含有作為(F)成分的難燃劑(以下，有時稱為(F) 難燃劑)。此處，前述硬化劑中的二氰二胺等亦具有作為難燃劑的功效，但在本發明中，能夠作為硬化劑發揮功能的成分是分類為硬化劑，不包括在(F)成分中。作為難燃劑，可列舉例如：含有溴、氯等之含鹵素系難燃劑；磷系難燃劑；胺磺酸胍(guanidine sulfamate)、硫酸三聚氰胺、聚磷酸三聚氰胺、三聚氰酸三聚氰胺等氮系難燃劑；環偶磷氮(cyclophosphazene)、聚偶磷氮(polyphosphazene)等偶磷氮(phosphazene)系難燃劑；三氧化二銻等無機系難燃劑等。其中，較佳是磷系難燃劑。作為磷系難燃劑，有無機系磷系難燃劑與有機系磷系難燃劑。作為無機系磷系難燃劑，可列舉例如：紅磷；磷酸一銨、磷酸二銨、磷酸三銨、聚磷酸銨等磷酸銨；磷醯胺等無機系含氮之磷化合物；磷酸；膦氧化物(phosphine oxide)等。作為有機系磷系難燃劑，可列舉例如：芳香族磷酸酯、1取代膦酸二酯、2取代膦酸酯、2取代膦酸的金屬鹽、有機系含氮之磷化合物、環狀有機磷化合物、含磷之酚樹脂等。其中，較佳是芳香族磷酸酯、2取代膦酸的金屬鹽。此處，作為金屬鹽，較佳是鋰鹽、鈉鹽、鉀鹽、鈣鹽、鎂鹽、鋁鹽、鈦鹽、鋅鹽中的任一種，較佳是鋁鹽。又，在有機系磷系難燃劑中，較佳是芳香族磷酸酯。＜(F) flame retardant＞ The resin varnish may further contain a flame retardant as component (F) (hereinafter, sometimes referred to as (F) flame retardant). Here, the dicyandiamide and the like in the aforementioned hardener also have the effect as a flame retardant, but in the present invention, the component that can function as a hardener is classified as a hardener and is not included in the (F) component . Examples of flame retardants include halogen-containing flame retardants containing bromine, chlorine, etc.; phosphorus flame retardants; guanidine sulfamate, melamine sulfate, melamine polyphosphate, melamine cyanurate, etc. Nitrogen-based flame retardants; phosphazene-based flame retardants such as cyclophosphazene and polyphosphazene; inorganic-based flame retardants such as antimony trioxide. Among them, the phosphorus-based flame retardant is preferred. As phosphorus-based flame retardants, there are inorganic phosphorus-based flame retardants and organic phosphorus-based flame retardants. Examples of inorganic phosphorus-based flame retardants include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphamide; phosphoric acid; phosphine Oxide (phosphine oxide), etc. Examples of the organic phosphorus-based flame retardant include aromatic phosphates, 1-substituted phosphonic acid diesters, 2-substituted phosphonates, metal salts of 2-substituted phosphonic acids, organic nitrogen-containing phosphorus compounds, and cyclic organic compounds. Phosphorus compounds, phosphorus-containing phenol resins, etc. Among them, metal salts of aromatic phosphates and 2-substituted phosphonic acids are preferred. Here, as the metal salt, any one of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt, and zinc salt is preferred, and aluminum salt is preferred. In addition, among the organic phosphorus-based flame retardants, aromatic phosphates are preferred.

作為芳香族磷酸酯，可列舉例如：磷酸三苯酯、磷酸三甲苯酯、磷酸三(二甲苯)酯、磷酸甲苯二苯酯、磷酸甲苯二-2,6-二甲苯酯、間苯二酚雙(二苯基磷酸酯)、1,3-伸苯基雙(二--2,6-二甲苯基磷酸酯)、雙酚A-雙(二苯基磷酸酯)、1,3-伸苯基雙(二苯基磷酸酯)等。作為1取代膦酸二酯，可列舉例如：苯基膦酸二乙烯酯、苯基膦酸二烯丙酯、苯基膦酸雙(1-丁烯)酯等。作為2取代膦酸酯，可列舉例如：二苯基膦酸苯酯、二苯基膦酸甲酯等。作為2取代膦酸的金屬鹽，可列舉例如：二苯基膦酸的金屬鹽、二烯丙基膦酸的金屬鹽、二乙烯基膦酸的金屬鹽、二芳基膦酸的金屬鹽等。這些金屬鹽，如前所述，較佳是鋰鹽、鈉鹽、鉀鹽、鈣鹽、鎂鹽、鋁鹽、鈦鹽、鋅鹽中的任一種。作為有機系含氮之磷化合物，可列舉例如：雙(2-烯丙基苯氧基)偶磷氮；磷酸三聚氰胺、焦磷酸三聚氰胺、聚磷酸三聚氰胺、聚磷酸蜜白胺(melam polyphosphate)等。作為環狀有機磷化合物，可列舉例如：9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、10-(2,5-二羥基苯基)- 9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物等。其中，較佳是選自芳香族磷酸酯、2取代膦酸的金屬鹽及環狀有機磷化合物中的至少一種，更佳是芳香族磷酸酯。Examples of the aromatic phosphate ester include triphenyl phosphate, tricresyl phosphate, tricresyl phosphate, toluene diphenyl phosphate, toluene di-2,6-xylyl phosphate, and resorcinol. Bis(diphenyl phosphate), 1,3-pylene bis(di-2,6-xylyl phosphate), bisphenol A-bis(diphenyl phosphate), 1,3-extenyl Phenyl bis (diphenyl phosphate), etc. Examples of the mono-substituted phosphonic acid diesters include phenylphosphonic acid divinyl ester, phenylphosphonic acid diallyl ester, and phenylphosphonic acid bis(1-butene) ester. Examples of 2-substituted phosphonates include phenyl diphenylphosphonate and methyl diphenylphosphonate. Examples of metal salts of 2-substituted phosphonic acids include metal salts of diphenylphosphonic acid, metal salts of diallylphosphonic acid, metal salts of divinylphosphonic acid, and metal salts of diarylphosphonic acid. . As mentioned above, these metal salts are preferably any of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt, and zinc salt. Examples of the organic nitrogen-containing phosphorus compound include bis(2-allylphenoxy)azophosphine; melamine phosphate, melamine pyrophosphate, melamine polyphosphate, and melam polyphosphate. Examples of the cyclic organic phosphorus compound include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc. Among them, at least one selected from an aromatic phosphate, a metal salt of a 2-substituted phosphonic acid, and a cyclic organic phosphorus compound is preferable, and an aromatic phosphate is more preferable.

又，前述芳香族磷酸酯，較佳是由下述通式(F-1)或(F-2)表示的芳香族磷酸酯，更佳是由下述通式(F-1)表示的芳香族磷酸酯。前述2取代膦酸的金屬鹽，較佳是由下述通式(F-3)表示的2取代膦酸的金屬鹽。

In addition, the aromatic phosphoric acid ester is preferably an aromatic phosphoric acid ester represented by the following general formula (F-1) or (F-2), and more preferably an aromatic phosphoric acid ester represented by the following general formula (F-1) Group phosphates. The metal salt of 2-substituted phosphonic acid is preferably a metal salt of 2-substituted phosphonic acid represented by the following general formula (F-3).

式(F-1)～(F-3)中，R^F1 ～R^F5 各自獨立地為碳數1～5的烷基或鹵素原子。e和f各自獨立地為0～5的整數，g、h及i各自獨立地為0～4的整數。 R^F6 和R^F7 各自獨立地為碳數1～5的烷基或碳數6～14的芳基。M是鋰原子、鈉原子、鉀原子、鈣原子、鎂原子、鋁原子、鈦原子、鋅原子。j是1～4的整數。In formulas (F-1) to (F-3), R ^F1 to R ^F5 are each independently a C 1-5 alkyl group or a halogen atom. e and f are each independently an integer of 0 to 5, and g, h, and i are each independently an integer of 0 to 4. R ^F6 and R ^F7 are each independently a C 1-5 alkyl group or a C 6-14 aryl group. M is a lithium atom, sodium atom, potassium atom, calcium atom, magnesium atom, aluminum atom, titanium atom, zinc atom. j is an integer of 1-4.

作為R^F1 ～R^F5 所表示的碳數1～5的烷基，可列舉例如：甲基、乙基、正丙基、異丙基、正丁基、異丁基、三級丁基、正戊基等。作為該烷基，較佳是碳數1～3的烷基。作為R^F1 ～R^F5 所表示的鹵素原子，可列舉氟原子等。 e和f，較佳是0～2的整數，更佳是2。g、h及i，較佳是0～2的整數，更佳是0或1，進一步更佳是0。作為R^F6 和R^F7 所表示的碳數1～5的烷基，可列舉與R^F1 ～R^F5 的情況相同的烷基。作為R^F6 和R^F7 所表示的碳數6～14的芳基，可列舉例如：苯基、萘基、聯苯基、蒽基等。作為該芳香族烴基，較佳是碳數6～10的芳基。 j，與金屬原子的價數相同，也就是對應於M的種類且在1～4的範圍內變化。作為M，較佳是鋁原子。再者，當M為鋁原子時，j為3。Examples of the C 1-5 alkyl groups represented by R ^F1 to R ^F5 include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, and n Amyl and so on. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. Examples of the halogen atom represented by R ^F1 to R ^F5 include a fluorine atom and the like. e and f are preferably integers from 0 to 2, and more preferably 2. g, h and i are preferably integers from 0 to 2, more preferably 0 or 1, and even more preferably 0. Examples of the C 1-5 alkyl groups represented by R ^F6 and R ^F7 include the same alkyl groups as in the case of R ^F1 to R ^F5 . Examples of the C 6-14 aryl groups represented by R ^F6 and R ^F7 include phenyl, naphthyl, biphenyl, and anthracenyl. The aromatic hydrocarbon group is preferably an aryl group having 6 to 10 carbon atoms. j is the same as the valence of the metal atom, that is, it corresponds to the type of M and varies within a range of 1 to 4. As M, an aluminum atom is preferred. Furthermore, when M is an aluminum atom, j is 3.

(樹脂清漆的各成分的含量) 樹脂清漆中，(A)～(C)成分的含量，並無特別限制，相對於(A)～(C)成分的總和100質量份，較佳是：(A)成分為15～65質量份，(B)成分為15～50質量份，(C)成分為10～45質量份。又，樹脂清漆(其中，此處(D)成分除外)中，(A)～(C)成分的合計含量，較佳是80質量%以上，更佳是90質量%以上，進一步更佳是95質量%以上。相對於(A)～(C)成分的總和100質量份，藉由使(A)成分為15質量份以上，有下述傾向：高耐熱性、低相對介電常數、高玻璃轉化溫度及低熱膨脹性優異，進一步尺寸變化量的偏差變小。另一方面，藉由使(A)成分為65質量份以下，有使樹脂清漆的流動性和成形性良好的傾向。從相同的觀點而言，相對於(A)～(C)成分的總和100質量份，(A)成分的含量可設為25～65質量份。相對於(A)～(C)成分的總和100質量份，藉由使(B)成分為15質量份以上，有能夠獲得高耐熱性、高玻璃轉化溫度及低熱膨脹性的傾向。另一方面，藉由使(B)成分為50質量份以下，有成為高耐熱性、低相對介電常數、高玻璃轉化溫度及低熱膨脹性的傾向。從相同的觀點而言，相對於(A)～(C)成分的總和100質量份，(B)成分的含量可設為20～45質量份。相對於(A)～(C)成分的總和100質量份，藉由使(C)成分為10質量份以上，有能夠獲得高耐熱性和低相對介電常數的傾向。另一方面，藉由使(C)成分為45質量份以下，有能夠獲得高耐熱性、高金屬箔黏合性及低熱膨脹性的傾向。相對於(A)～(C)成分的總和100質量份，(C)成分的含量可以是10～30質量份，或亦可以是20～45質量份。進一步，並無特別限制，當本發明的樹脂清漆含有(D)成分時，相對於(A)～(C)成分的總和100質量份，該(D)成分的含量較佳是30～70質量份。藉由使(D)成分為30質量份以上，有能夠獲得優異的低熱膨脹性的傾向，另一方面，藉由使(D)成分為70質量份以下，有能夠獲得耐熱性並且使樹脂清漆的流動性和成形性良好的傾向。從相同的觀點而言，相對於(A)～(C)成分的總和100質量份，(D)成分的含量可設為40～60質量份。(Content of each component of resin varnish) In the resin varnish, the content of the components (A) to (C) is not particularly limited, and it is preferably 15 to 65 parts by mass relative to the total of 100 parts by mass of the components (A) to (C). The component (B) is 15 to 50 parts by mass, and the component (C) is 10 to 45 parts by mass. Moreover, in the resin varnish (excluding (D) component here), the total content of the components (A) to (C) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95 Mass% or more. With respect to 100 parts by mass of the total of (A) to (C) components, by making the (A) component 15 parts by mass or more, there is a tendency to have high heat resistance, low relative dielectric constant, high glass transition temperature and low The thermal expansion is excellent, and the variation in the amount of dimensional change becomes smaller. On the other hand, when the component (A) is 65 parts by mass or less, the fluidity and moldability of the resin varnish tend to be good. From the same viewpoint, the content of the component (A) can be set to 25 to 65 parts by mass relative to 100 parts by mass of the total of the components (A) to (C). With respect to 100 parts by mass of the total of the components (A) to (C), by making the component (B) 15 parts by mass or more, there is a tendency that high heat resistance, high glass transition temperature, and low thermal expansion can be obtained. On the other hand, by setting the (B) component to 50 parts by mass or less, there is a tendency to have high heat resistance, low relative dielectric constant, high glass transition temperature, and low thermal expansion. From the same viewpoint, the content of the component (B) can be 20 to 45 parts by mass relative to 100 parts by mass of the total of the components (A) to (C). With respect to 100 parts by mass of the total of the components (A) to (C), by setting the (C) component to 10 parts by mass or more, there is a tendency that high heat resistance and low relative dielectric constant can be obtained. On the other hand, by setting the component (C) to 45 parts by mass or less, there is a tendency that high heat resistance, high metal foil adhesion, and low thermal expansion can be obtained. The content of the (C) component may be 10 to 30 parts by mass, or may be 20 to 45 parts by mass relative to 100 parts by mass of the total of the components (A) to (C). Furthermore, there is no particular limitation. When the resin varnish of the present invention contains the component (D), the content of the component (D) is preferably 30 to 70 parts by mass relative to 100 parts by mass of the total of the components (A) to (C). Copies. By setting the (D) component to 30 parts by mass or more, there is a tendency to obtain excellent low thermal expansion. On the other hand, by setting the (D) component to 70 parts by mass or less, it is possible to obtain heat resistance and make the resin varnish The flowability and formability tend to be good. From the same viewpoint, the content of the component (D) can be 40 to 60 parts by mass relative to 100 parts by mass of the total of the components (A) to (C).

又，當使樹脂清漆含有(E)成分時，相對於(A)～(C)成分的總和100質量份，該(E)成分的含量較佳是0.5～6質量份。相對於(A)～(C)成分的總和100質量份，藉由使(E)成分為0.5質量份以上，有能夠獲得高金屬箔黏合性和優異的低熱膨脹性的傾向。另一方面，藉由使(E)成分為6質量份以下，有能夠獲得高耐熱性的傾向。In addition, when the resin varnish contains the component (E), the content of the component (E) is preferably 0.5 to 6 parts by mass relative to 100 parts by mass of the total of the components (A) to (C). With respect to 100 parts by mass of the total of the components (A) to (C), by making the component (E) 0.5 parts by mass or more, there is a tendency that high metal foil adhesion and excellent low thermal expansion properties can be obtained. On the other hand, by setting the (E) component to 6 parts by mass or less, high heat resistance tends to be obtained.

又，當使樹脂清漆含有(F)成分時，從難燃性的觀點而言，相對於(A)～(C)成分的總和100質量份，該(F)成分的含量較佳是0.1～20質量份，更佳是0.5～10質量份。尤其，當使用磷系難燃劑作為(F)成分時，從難燃性的觀點而言，相對於(A)～(C)成分的總和100質量份，較佳是磷原子的含率成為0.1～3質量份的量，更佳是成為0.2～3質量份的量，進一步更佳是成為0.5～3質量份的量。In addition, when the resin varnish contains the component (F), from the viewpoint of flame retardancy, the content of the component (F) is preferably 0.1 to 100 parts by mass relative to the total of the components (A) to (C). 20 parts by mass, more preferably 0.5 to 10 parts by mass. In particular, when a phosphorus-based flame retardant is used as the (F) component, from the viewpoint of flame retardancy, it is preferable that the content of the phosphorus atom is 100 parts by mass relative to the total of the components (A) to (C). The amount of 0.1 to 3 parts by mass is more preferably 0.2 to 3 parts by mass, and even more preferably 0.5 to 3 parts by mass.

(其他成分) 在不損及本發明的功效的範圍內，可根據需要而使樹脂清漆含有添加劑等其他成分。這些成分，可單獨含有1種，亦可含有2種以上。(Other ingredients) The resin varnish may contain other components such as additives within the range that does not impair the efficacy of the present invention. These components may contain one kind alone or two or more kinds.

(添加劑) 作為添加劑，可列舉例如：硬化促進劑、著色劑、抗氧化劑、還原劑、紫外線吸收劑、螢光增白劑、密合性提升劑、有機填充材料等。這些添加劑，可單獨使用1種，亦可將2種以上合併使用。(additive) Examples of the additives include curing accelerators, colorants, antioxidants, reducing agents, ultraviolet absorbers, fluorescent whitening agents, adhesion promoters, organic fillers, and the like. These additives may be used alone or in combination of two or more.

(有機溶劑) 從使操作較容易這樣的觀點和易於製造後述預浸體的觀點而言，樹脂清漆，含有有機溶劑。作為該有機溶劑，並無特別限制，可列舉例如：甲醇、乙醇、乙二醇、乙二醇單甲基醚、乙二醇單乙基醚、二乙二醇、三乙二醇單甲基醚、三乙二醇單乙基醚、三乙二醇、丙二醇單甲基醚、二丙二醇單甲基醚、丙二醇單丙基醚、二丙二醇單丙基醚等醇系溶劑；丙酮、甲基乙基酮、甲基異丁基酮、丁酮、環己酮等酮系溶劑；四氫呋喃等醚系溶劑；甲苯、二甲苯、均三甲苯等芳香族系溶劑；含氮原子之溶劑，其包括甲醯胺、N-甲基甲醯胺、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺及N-甲基吡咯啶酮等醯胺系溶劑；含硫原子之溶劑，其包括二甲基亞碸等亞碸系溶劑；乙酸甲氧基乙酯、乙酸乙氧基乙酯、乙酸丁氧基乙酯、丙二醇單甲基醚乙酸酯、乙酸乙酯等酯系溶劑等。其中，從溶解性的觀點而言，較佳是醇系溶劑、酮系溶劑、含氮原子之溶劑，更佳是甲基乙基酮、甲基異丁基酮、環己酮、甲基賽珞蘇、丙二醇單甲基醚，進一步更佳是甲基乙基酮、甲基異丁基酮，特佳是甲基乙基酮。有機溶劑，可單獨使用1種，亦可將2種以上合併使用。(Organic solvents) The resin varnish contains an organic solvent from the viewpoint of making the operation easier and the viewpoint of easy production of the prepreg described later. The organic solvent is not particularly limited, and examples thereof include methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, and triethylene glycol monomethyl. Alcohol solvents such as ether, triethylene glycol monoethyl ether, triethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether; acetone, methyl Ketone solvents such as ethyl ketone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; solvents containing nitrogen atoms, including Acetamide-based solvents such as methylamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; containing sulfur atoms The solvents include sulfonate solvents such as dimethyl sulfoxide; methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, etc. Ester solvents, etc. Among them, from the viewpoint of solubility, alcohol-based solvents, ketone-based solvents, and nitrogen atom-containing solvents are preferred, and methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and methylcellulose are more preferred. Luosu and propylene glycol monomethyl ether, further preferably methyl ethyl ketone and methyl isobutyl ketone, particularly preferably methyl ethyl ketone. Organic solvents may be used alone or in combination of two or more.

樹脂清漆中的有機溶劑的含量，只要適當調整成樹脂清漆容易操作的程度即可，並且，只要是在使樹脂清漆的塗佈性良好的範圍內，並無特別限制，較佳是調整成非揮發成分濃度(除了有機溶劑以外的成分的濃度)成為下述濃度：較佳是30～90質量%，更佳是40～80質量%，進一步更佳是50～80質量%。The content of the organic solvent in the resin varnish may be adjusted as long as the resin varnish is easy to handle, and it is not particularly limited as long as the resin varnish has good coatability. The volatile component concentration (the concentration of components other than the organic solvent) becomes the following concentration: preferably 30 to 90% by mass, more preferably 40 to 80% by mass, still more preferably 50 to 80% by mass.

[預浸體] 本發明的預浸體，是含有本發明的樹脂清漆而成，其製造方法並無特別限制，例如，可對片狀補強基材含浸或塗佈樹脂清漆，並且由加熱等使其半硬化(B階段化)來進行製造。作為預浸體的片狀補強基材，可使用習知的片狀補強基材，該片狀補強基材用於各種電絕緣材料用積層板。作為片狀補強基材的材質，可列舉例如：像紙、棉絨這樣的天然纖維；玻璃纖維和石綿等無機纖維；芳香族聚醯胺(aramid)、聚醯亞胺、聚乙烯醇、聚酯、四氟乙烯及壓克力等有機纖維；這些纖維的混合物等。其中，從難燃性的觀點而言，較佳是玻璃纖維。作為玻璃纖維基材，可列舉：玻璃布，其是將使用E玻璃(E-glass)、C玻璃(C-glass)、D玻璃(D-glass)、S玻璃(S-glass)等而成之織布或短纖維，以有機黏結劑來黏合而成；由玻璃纖維與纖維素纖維混紡而成之基材等。更佳是使用E玻璃之玻璃布。這些片狀補強基材，具有下述形狀：織布、不織布、粗紗(roving)、切股氈(chopped strand mat)或表面氈(surfacing mat)等。再者，材質和形狀，是根據目標之成形物的用途和性能來選擇，可單獨使用1種，亦可根據需要而將2種以上的材質和形狀加以組合。從成形性和能夠進行高密度配線的觀點而言，本發明的預浸體的厚度，較佳是0.01～0.5mm，更佳是0.02～0.3mm，進一步更佳是0.05～0.2mm。[Prepreg] The prepreg of the present invention is formed by containing the resin varnish of the present invention, and its production method is not particularly limited. For example, the sheet-shaped reinforcing substrate can be impregnated or coated with the resin varnish, and semi-hardened by heating or the like ( B stage) to manufacture. As the sheet-like reinforcing base material of the prepreg, a conventional sheet-like reinforcing base material can be used, and the sheet-like reinforcing base material is used for a laminate for various electrical insulating materials. Examples of the material of the sheet-like reinforcing substrate include: natural fibers such as paper and cotton wool; inorganic fibers such as glass fiber and asbestos; aromatic aramid, polyimide, polyvinyl alcohol, and poly Organic fibers such as esters, tetrafluoroethylene and acrylic; mixtures of these fibers. Among them, from the viewpoint of flame retardancy, glass fiber is preferable. Examples of the glass fiber substrate include glass cloth, which is formed by using E glass (E-glass), C glass (C-glass), D glass (D-glass), S glass (S-glass), etc. The woven fabric or short fiber is made of organic binder; the base material is made of glass fiber and cellulose fiber. It is better to use E-glass cloth. These sheet-like reinforcing substrates have the following shapes: woven fabric, non-woven fabric, roving, chopped strand mat, surfacing mat, or the like. In addition, the material and shape are selected according to the intended use and performance of the molded product, and one type may be used alone, or two or more types of materials and shapes may be combined as needed. The thickness of the prepreg of the present invention is preferably 0.01 to 0.5 mm, more preferably 0.02 to 0.3 mm, and still more preferably 0.05 to 0.2 mm from the viewpoint of formability and high-density wiring.

在藉由上述方法獲得的本發明的預浸體，其依照下述方法來求出標準偏差σ能夠達到0.012%以下。此代表尺寸變化量的偏差小。 (標準偏差σ的計算方法) 在1片預浸體的雙面上重疊厚度18μm的銅箔，並以190℃、2.45MPa的條件進行90分鐘的加熱加壓並成形，來製作厚度0.1mm的雙面覆銅積層板。在藉由上述方法獲得的雙面覆銅積層板的面內，於第1圖所示的1～8的位置，實施直徑為1.0mm的穿孔。使用影像測定機來分別測定第1圖所示的經線方向(1-7、2-6、3-5)和緯線方向(1-3、8-4、7-5)的各3點的距離，並將各測定距離設為起始值。然後，去除外層銅箔，並利用乾燥機以185℃加熱60分鐘。冷卻後，採用與起始值的測定方法相同之方法，分別測定經線方向(1-7、2-6、3-5)和緯線方向(1-3、8-4、7-5)的各3點的距離。根據相對於各測定距離的起始值的變化率來求出這些變化率的平均值，並計算相對於該平均值的標準偏差σ。前述影像測定機並無特別限制，能夠使用例如「QV-A808P1L-D」(三豐公司製造)。In the prepreg of the present invention obtained by the above method, the standard deviation σ obtained by the following method can be 0.012% or less. This represents a small deviation in the amount of dimensional change. (Calculation method of standard deviation σ) A copper foil with a thickness of 18 μm was laminated on both sides of one prepreg, and heated and pressed at 190° C. and 2.45 MPa for 90 minutes to form a double-sided copper-clad laminate with a thickness of 0.1 mm. In the surface of the double-sided copper-clad laminate obtained by the above method, a hole with a diameter of 1.0 mm was punched at the positions 1 to 8 shown in FIG. 1. Use an image measuring machine to measure the three points of the warp direction (1-7, 2-6, 3-5) and the weft direction (1-3, 8-4, 7-5) shown in Figure 1 respectively. Distance, and set each measured distance as the initial value. Then, the outer layer copper foil was removed, and it heated at 185 degreeC for 60 minutes by the dryer. After cooling, use the same method as the initial value measurement method to measure the warp direction (1-7, 2-6, 3-5) and weft direction (1-3, 8-4, 7-5) 3 points each. The average of these rates of change is obtained from the rate of change with respect to the initial value of each measured distance, and the standard deviation σ relative to the average is calculated. The aforementioned image measuring machine is not particularly limited, and for example, "QV-A808P1L-D" (manufactured by Mitutoyo Corporation) can be used.

前述標準偏差σ，較佳是0.011%以下，更佳是0.010%以下，進一步更佳是0.009%以下。標準偏差σ的下限值並無特別限制，通常是0.003%以上，亦可以是0.005%以上，亦可以是0.006%以上，亦可以是0.007%以上。The aforementioned standard deviation σ is preferably 0.011% or less, more preferably 0.010% or less, and still more preferably 0.009% or less. The lower limit of the standard deviation σ is not particularly limited, and it is usually 0.003% or more, 0.005% or more, 0.006% or more, or 0.007% or more.

[積層板] 本發明的積層板，是含有前述預浸體與金屬箔而成。可藉由以例如下述構成(較佳是進行加熱)進行積層成形來製造：使用1片前述預浸體或根據需要將2～20片前述預浸體重疊，並在其單面或雙面配置金屬箔而成之構成。再者，有時將配置有金屬箔之積層板稱為覆金屬積層板。作為金屬箔的金屬，只要是用於電絕緣材料用途的金屬，並無特別限制，從導電性的觀點，較佳是銅、金、銀、鎳、鉑、鉬、釕、鋁、鎢、鐵、鈦、鉻、或包含這些金屬元素中的至少一種之合金，更佳是銅、鋁，進一步較佳是銅。作為積層板的成形條件，可應用電絕緣材料用積層板和多層板的公知的成形方法，例如，可使用多段壓製、多段真空壓製、連續成形、熱壓釜成形機等，在溫度100～250℃、壓力0.2～10MPa、加熱時間0.1～5小時的條件下進行成形。又，亦可將本發明的預浸體與內層用印刷線路板加以組合，並進行積層成形，來製造多層板。金屬箔的厚度並無特別限制，可根據印刷線路板的用途等來適當選擇。金屬箔的厚度，較佳是0.5～150μm，更佳是1～100μm，進一步較佳是5～50μm，特佳是5～30μm。[Laminate] The laminate of the present invention is formed by containing the prepreg and metal foil. It can be manufactured by lamination molding with the following configuration (preferably heated), for example: using one piece of the prepreg or stacking 2 to 20 pieces of the prepreg as needed, on one side or both sides It is made of metal foil. In addition, the laminate with metal foil is sometimes referred to as a metal-clad laminate. The metal of the metal foil is not particularly limited as long as it is used for electrical insulation materials, and from the viewpoint of conductivity, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, and iron are preferred , Titanium, chromium, or alloys containing at least one of these metal elements, more preferably copper and aluminum, and even more preferably copper. As the molding conditions of the laminate, the well-known molding methods of the laminate for electrical insulating materials and the multilayer board can be applied. For example, multi-stage pressing, multi-stage vacuum pressing, continuous molding, autoclave forming machine, etc., at a temperature of 100 to 250 Molding is carried out under the conditions of ℃, pressure of 0.2-10MPa and heating time of 0.1-5 hours. In addition, the prepreg of the present invention may be combined with a printed wiring board for an inner layer and layered to form a multilayer board. The thickness of the metal foil is not particularly limited, and can be appropriately selected according to the application of the printed wiring board and the like. The thickness of the metal foil is preferably 0.5 to 150 μm, more preferably 1 to 100 μm, still more preferably 5 to 50 μm, and particularly preferably 5 to 30 μm.

再者，亦較佳是藉由對金屬箔進行鍍覆來形成鍍覆層。鍍覆層的金屬，只要是能夠使用於鍍覆的金屬，並無特別限制。鍍覆層的金屬，較佳是選自下述中的金屬：銅、金、銀、鎳、鉑、鉬、釕、鋁、鎢、鐵、鈦、鉻、及包含這些金屬元素中的至少一種之合金。作為鍍覆方法，可無特別限制地利用公知的方法，例如電鍍法、無電鍍覆法。Furthermore, it is also preferable to form a plating layer by plating a metal foil. The metal of the plating layer is not particularly limited as long as it can be used for plating. The metal of the plating layer is preferably a metal selected from the group consisting of copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and at least one of these metal elements Of the alloy. As the plating method, known methods such as an electroplating method and an electroless plating method can be used without particular limitation.

[印刷線路板] 本發明亦提供一種印刷線路板，其是含有前述預浸體或前述積層板而成。本發明的印刷線路板，可藉由下述方式製造：對於覆金屬積層板的金屬箔，實施電路加工。電路加工，可藉由例如下述方式實行：在金屬箔表面形成阻劑圖案後，利用蝕刻去除不需要的部分的金屬箔，並剝離阻劑圖案後，利用鑽孔器來形成需要的貫通孔(through hole)，並再次形成阻劑圖案後，對貫通孔實施用以導通的鍍覆，最後剝離阻劑圖案。可在藉由上述方法獲得的印刷線路板的表面上，以與前述相同的條件進一步積層上述覆金屬積層板，進一步，與上述同樣地進行，並進行電路加工，來作成多層印刷線路板。此時，不一定需要形成貫通孔，可形成介層孔(via hole)，亦可形成兩者。這樣的多層化，是依所需要的片數實行。[Printed Circuit Board] The present invention also provides a printed wiring board comprising the prepreg or the laminate. The printed wiring board of the present invention can be manufactured by performing circuit processing on the metal foil of the metal-clad laminate. Circuit processing can be performed by, for example, forming a resist pattern on the surface of the metal foil, removing unnecessary portions of the metal foil by etching, and peeling off the resist pattern, and then using a drill to form the required through holes (through hole), and after forming the resist pattern again, the through-hole is plated for conduction, and finally the resist pattern is peeled off. The surface of the printed wiring board obtained by the above method can be further laminated on the surface of the metal-clad laminate under the same conditions as described above. Further, the circuit can be processed in the same manner as described above to produce a multilayer printed wiring board. At this time, it is not necessary to form a through hole, a via hole may be formed, or both may be formed. Such multi-layering is implemented according to the required number of slices.

[半導體封裝體] 本發明的半導體封裝體，是在本發明的印刷線路板上搭載半導體而成。本發明的半導體封裝體，能夠在本發明的印刷線路板的規定位置上搭載半導體晶片、記憶體等來製造。 [實施例][Semiconductor package] The semiconductor package of the present invention is formed by mounting semiconductors on the printed wiring board of the present invention. The semiconductor package of the present invention can be manufactured by mounting a semiconductor wafer, a memory, etc. on a predetermined position of the printed wiring board of the present invention. [Example]

繼而，藉由下述實施例進一步詳細地說明本發明，但無論在任何意義上本發明並不限於這些實施例。使用本發明的熱硬化性樹脂組成物，來製作樹脂清漆、使用該樹脂清漆所製作之預浸體，進一步製作覆銅積層板，並依照下述方法來實行各評估。Next, the present invention will be described in further detail by the following examples, but the present invention is not limited to these examples in any sense. Using the thermosetting resin composition of the present invention, a resin varnish, a prepreg produced using the resin varnish, and a copper-clad laminate were further produced, and each evaluation was carried out according to the following method.

[評估方法] ＜1.耐熱性(回焊耐熱性)＞使用各例所製作的4層覆銅積層板，並將最高到達溫度設為266℃，在260℃以上的恆溫槽環境下花費30秒使4層覆銅積層板通動，將此步驟設為1個循環，並求出至能夠以目視確認到基板膨脹為止的循環數。循環數越多，耐熱性越優異，若是10個循環以上，則可以說是具有充分的耐熱性。[assessment method] ＜1. Heat resistance (Reflow resistance heat resistance)＞ Use the four-layer copper-clad laminates produced in each example, and set the maximum reach temperature to 266°C. It takes 30 seconds in a constant-temperature bath environment above 260°C to activate the four-layer copper-clad laminates. Set this step to 1 cycle, and the number of cycles until the expansion of the substrate can be visually confirmed. The greater the number of cycles, the better the heat resistance. If it is 10 cycles or more, it can be said to have sufficient heat resistance.

＜2.相對介電常數(Dk)＞使用網路分析器「87722C」(惠普公司製造)，根據三板結構直線線路共振器法，在1GHz時實施雙面覆銅積層板的相對介電常數的測定。試驗片尺寸，是200mm×50mm×厚度0.8mm，利用蝕刻在1片雙面覆銅積層板的單面的中心形成寬度1.0mm的直線線路(線長200mm)，並在背面的整個面上殘留銅來製成地線層。對於另1片雙面覆銅積層板，對其單面的整個面進行蝕刻，並將背面製成地線層。將地線層朝外側，並重疊此2片雙面覆銅積層板，來製成帶狀線路(stripline)。測定是25℃實行。相對介電常數越小越佳。＜2. Relative dielectric constant (Dk)＞ Using a network analyzer "87722C" (manufactured by Hewlett-Packard Co., Ltd.), the relative dielectric constant of the double-sided copper clad laminate was measured at 1 GHz according to the three-plate structure linear line resonator method. The size of the test piece is 200 mm × 50 mm × thickness 0.8 mm. A linear line with a width of 1.0 mm (line length of 200 mm) is formed on the center of one side of a double-sided copper clad laminate by etching, and remains on the entire surface of the back surface Copper to make the ground layer. For the other double-sided copper-clad laminate, the entire surface of one side was etched, and the back surface was made into a ground layer. Place the ground wire layer to the outside and overlap the two double-sided copper clad laminates to make a stripline. The measurement is carried out at 25°C. The smaller the relative dielectric constant, the better.

＜3.金屬箔黏合性(銅箔剝離強度)＞金屬箔黏合性，是根據銅箔剝離強度來評估。將各例所製作的雙面覆銅積層板浸泡於銅蝕刻液「過硫酸銨(APS)」(ADEKA股份有限公司製造)中，藉此形成3mm寬的銅箔來製作評估基板，並使用自動立體測圖儀(autograph)「AG-100C」(島津製作所股份有限公司製造)來測定銅箔的剝離強度。數值越大，表示金屬箔黏合性越優異。＜3. Metal foil adhesion (copper foil peel strength)＞ The adhesion of the metal foil is evaluated based on the peel strength of the copper foil. The double-sided copper-clad laminates produced in each example were immersed in a copper etching solution "ammonium persulfate (APS)" (made by ADEKA Corporation) to form a 3mm-wide copper foil to prepare an evaluation substrate, and use automatic An autograph "AG-100C" (made by Shimadzu Corporation) was used to measure the peel strength of the copper foil. The larger the value, the better the adhesion of the metal foil.

＜4.玻璃轉化溫度(Tg)＞將各例所製作的雙面覆銅積層板浸泡於銅蝕刻液「過硫酸銨(APS)」(ADEKA股份有限公司製造)中，藉此製作除去銅箔後之5mm見方的評估基板，然後使用熱機械分析(TMA)試驗裝置「Q400EM」(TA儀器公司製造)，來觀察評估基板的面方向(Z方向)在30～260℃時的熱膨脹特性，並將膨脹量的反曲點設為玻璃轉化溫度。＜4. Glass transition temperature (Tg)＞ The double-sided copper-clad laminate produced in each example was immersed in a copper etching solution "Ammonium Persulfate (APS)" (made by ADEKA Co., Ltd.) to prepare a 5 mm square evaluation substrate after removing the copper foil, and then used Thermomechanical analysis (TMA) test device "Q400EM" (manufactured by TA Instruments) to observe and evaluate the thermal expansion characteristics of the substrate in the plane direction (Z direction) at 30 to 260°C, and set the inflection point of the expansion amount to glass Conversion temperature.

＜5.低熱膨脹性＞將各例所製作的雙面覆銅積層板浸泡於銅蝕刻液「過硫酸銨(APS)」(ADEKA股份有限公司製造)中，藉此製作除去銅箔後之5mm見方的評估基板，然後使用熱機械分析(TMA)試驗裝置「Q400EM」(TA儀器公司製造)，來測定評估基板的面方向的熱膨脹率(線膨脹率)。再者，為了去除試樣所具有熱應變的影響，重複2次升溫-冷卻循環，然後測定第2次循環的溫度變位圖的30℃～260℃時的熱膨脹率[ppm/℃]，並設為低熱膨脹性的指標。數值越小，低熱膨脹性越優異。再者，表中是分成小於Tg(標記為「＜Tg」)時的熱膨脹率與超過Tg(標記為「＞Tg」)時的熱膨脹率來記載。測定條件第1行程：室溫→210℃(升溫速度10℃/min) 第2行程：0℃→270℃(升溫速度10℃/min) 覆銅積層板，期望進一步薄型化，此外也正在研究用以構成覆銅積層板的預浸體。經薄型化後的預浸體，變得易於翹曲，因此期望在熱處理時預浸體的翹曲較小。為了縮小翹曲，使基材的面方向的熱膨脹率小是有效的。<5. Low thermal expansion> The double-sided copper-clad laminate produced in each example was immersed in a copper etching solution "Ammonium Persulfate (APS)" (made by ADEKA Co., Ltd.) to prepare a 5 mm square evaluation substrate after removing the copper foil, and then used A thermomechanical analysis (TMA) test device "Q400EM" (manufactured by TA Instruments) was used to measure the thermal expansion coefficient (linear expansion coefficient) of the evaluation substrate in the plane direction. In addition, in order to remove the influence of the thermal strain of the sample, the temperature-cooling cycle is repeated twice, and then the thermal expansion rate [ppm/°C] at 30°C-260°C of the temperature displacement map of the second cycle is measured, and Set as an index of low thermal expansion. The smaller the value, the better the low thermal expansion. In addition, in the table, the thermal expansion coefficient when it is less than Tg (marked as "<Tg") and the thermal expansion coefficient when it exceeds Tg (marked as ">Tg") are described. Measurement conditions 1st stroke: room temperature → 210°C (heating rate 10°C/min) Second stroke: 0℃→270℃ (heating rate 10℃/min) Copper-clad laminates are expected to be thinner, and prepregs for forming copper-clad laminates are also being studied. The thinned prepreg becomes susceptible to warpage, so it is desirable that the prepreg warp less during heat treatment. In order to reduce warpage, it is effective to reduce the thermal expansion rate in the plane direction of the base material.

＜6.鍍覆分佈性(雷射加工性)＞對於各例所製作的4層覆銅積層板，使用雷射加工機(laser machine)「LC-2F21B/2C」(日立比亞機械股份有限公司製造)，並根據目標孔徑80μm、高斯光束(Gaussian beam)、循環模式，實行銅直接法(銅箔直接加工法)、脈衝寬度15μs×1次、7μs×4次，來實施雷射穿孔。關於所獲得的雷射穿孔基板，以70℃、5分鐘的條件使用膨潤液「Swelling Dip Securiganth P」(日本阿托科股份有限公司製造)，以70℃、9分鐘的條件使用粗糙化液「Dosing Securiganth P500J」(日本阿托科股份有限公司製造)，以40℃、5分鐘的條件使用中和液「Reduction Conditioner Securiganth P500」(日本阿托科股份有限公司製造)，來實施去膠渣處理。之後，以無電鍍覆液「Printganth MSK-DK」(日本阿托科股份有限公司製造)在30℃實施20分鐘，以電鍍液「Cupracid HL」(日本阿托科股份有限公司製造)在24℃、2A/dm² 的條件下實施2小時，來對雷射加工基板施加鍍覆。實施所獲得的基板的剖面觀察，來確認鍍覆分佈性。作為鍍覆分佈性的評估方法，雷射孔上部的鍍覆厚度與雷射孔底部的鍍覆厚度的差值，在雷射孔上部的鍍覆厚度的10%以內，就鍍覆分佈性而言為較佳，由此求出100孔中的包含於此範圍內的孔的存在比例(%)。<6. Plating distribution (laser workability)> For the 4-layer copper-clad laminates produced in each example, use a laser machine (LC-2F21B/2C) (Hitachi Biya Co., Ltd. Manufactured by the company), and according to the target aperture 80μm, Gaussian beam (Gaussian beam), circulation mode, the copper direct method (copper foil direct processing method), pulse width 15μs × 1 time, 7μs × 4 times, to perform laser perforation. Regarding the obtained laser perforated substrate, the swelling liquid "Swelling Dip Securiganth P" (manufactured by Japan Atoko Co., Ltd.) was used at 70°C for 5 minutes, and the roughening liquid was used at 70°C for 9 minutes. "Dosing Securiganth P500J" (manufactured by Japan Atoko Co., Ltd.), using the neutralization solution "Reduction Conditioner Securiganth P500" (manufactured by Japan Atoko Co., Ltd.) at 40°C for 5 minutes to carry out the slag removal treatment . After that, the electroless plating solution "Printganth MSK-DK" (manufactured by Japan Atoko Co., Ltd.) was carried out at 30°C for 20 minutes, and the plating solution "Cupracid HL" (manufactured by Japan Atoko Co., Ltd.) at 24°C. And 2A/dm ² for 2 hours to apply plating to the laser processed substrate. The cross-sectional observation of the obtained substrate was carried out to confirm the plating distribution. As a method for evaluating the plating distribution, the difference between the plating thickness at the upper part of the laser hole and the plating thickness at the bottom of the laser hole is within 10% of the plating thickness at the upper part of the laser hole. It is better to say that the ratio (%) of the holes included in this range out of 100 holes is obtained.

＜7.成形性＞對於各例所製作的4層覆銅積層板，在去除外層銅後，作為樹脂的填埋性，是利用目視確認340mm×500mm的面內有無孔隙(void)和模糊(blur)，並設為成形性的指標。當沒有孔隙和模糊時，表示為「良好」；當存在孔隙和模糊時，表示該異常情況。當沒有孔隙和模糊時，可以說是成形性良好。＜7. Formability＞ For the four-layer copper-clad laminates produced in each example, after removing the outer layer of copper, as the resin's embeddability, visually confirm whether there are voids and blurs in the 340 mm × 500 mm plane, and set Index of formability. When there is no porosity and blur, it is expressed as "good"; when there is porosity and blur, it indicates the abnormal condition. When there is no porosity and blur, it can be said that the moldability is good.

＜8.尺寸變化量的偏差的評估＞在藉由各例所製作的雙面覆銅積層板的面內，如第1圖所示，實施直徑為1.0mm的穿孔。如第1圖所示，使用影像測定機「QV-A808P1L-D」(三豐公司製造)來分別測定玻璃布的經線方向(1-7、2-6、3-5)和緯線方向(1-3、8-4、7-5)的各3點的距離，並將各測定距離設為起始值。然後，去除外層銅箔，並利用乾燥機以185℃加熱60分鐘。冷卻後，採用與起始值的測定方法相同之方法，分別測定經線方向(1-7、2-6、3-5)和緯線方向(1-3、8-4、7-5)的各3點的距離。由相對於各測定距離的起始值的變化率[(測定值－起始值) ×100／起始值]求出這些變化率的平均值，並計算相對於該平均值的標準偏差σ，並將該標準偏差σ設為尺寸變化量的偏差的指標。標準偏差σ越小，表示尺寸變化量的偏差越小且越佳。<8. Evaluation of deviations in dimensional change> On the surface of the double-sided copper-clad laminate produced in each example, as shown in Fig. 1, a hole with a diameter of 1.0 mm was punched. As shown in Figure 1, use the image measuring machine "QV-A808P1L-D" (manufactured by Mitutoyo Corporation) to measure the warp direction (1-7, 2-6, 3-5) and weft direction of the glass cloth ( 1-3, 8-4, 7-5) the distance of each 3 points, and set each measured distance as the initial value. Then, the outer layer copper foil was removed, and it heated at 185 degreeC for 60 minutes by the dryer. After cooling, use the same method as the initial value measurement method to measure the warp direction (1-7, 2-6, 3-5) and weft direction (1-3, 8-4, 7-5) 3 points each. Find the average of these rates of change from the rate of change relative to the starting value of each measured distance [(measured value-starting value) × 100/starting value], and calculate the standard deviation σ relative to the average value, The standard deviation σ is used as an index of the deviation of the dimensional change. The smaller the standard deviation σ, the smaller and better the deviation of the dimensional change.

以下，說明實施例和比較例所使用的各成分。Hereinafter, each component used in Examples and Comparative Examples will be described.

(A)成分：使用下述製造例A-1～A-5所製造的馬來醯亞胺化合物(A-1)～(A-5)的溶液。 [製造例A-1] 在具備溫度計、攪拌裝置及附有回流冷卻管之水分定量器之容積1L的反應容器中，加入12.1g 4,4’-二胺基二苯基甲烷、174.4g雙(4-馬來醯亞胺基苯基)甲烷、13.3g對胺基苯酚、及330.0g二甲基乙醯胺，並在100℃使其反應2小時，來獲得具有酸性取代基與N-取代馬來醯亞胺基之馬來醯亞胺化合物(A-1)(Mw＝965)的二甲基乙醯胺溶液，並將其作為(A-1)成分使用。(A) Component: The solutions of the maleimide compounds (A-1) to (A-5) manufactured by the following manufacturing examples A-1 to A-5 were used. [Production Example A-1] Into a 1L reaction vessel equipped with a thermometer, a stirring device and a moisture meter with a reflux cooling tube, add 12.1g of 4,4'-diaminodiphenylmethane and 174.4g of bis(4-maleimide Aminophenyl)methane, 13.3g of p-aminophenol, and 330.0g of dimethylacetamide, and reacted at 100°C for 2 hours to obtain an acidic substituent and an N-substituted maleimide group A solution of maleimide compound (A-1) (Mw=965) in dimethylacetamide and used as the component (A-1).

[製造例A-2] 在具備溫度計、攪拌裝置及附有回流冷卻管之水分定量器之容積1L的反應容器中，加入22.8g 4,4’-二胺基二苯基甲烷、164.5g雙(4-馬來醯亞胺基苯基)甲烷、12.5g對胺基苯酚、及330.0g二甲基乙醯胺，並在100℃使其反應2小時，來獲得具有酸性取代基與N-取代馬來醯亞胺基之馬來醯亞胺化合物(A-2)(Mw＝1021)的二甲基乙醯胺溶液，並將其作為(A-2)成分使用。[Production Example A-2] Into a 1L reaction vessel equipped with a thermometer, a stirring device and a moisture meter with a reflux cooling tube, add 22.8g 4,4'-diaminodiphenylmethane and 164.5g bis(4-maleimide Aminophenyl)methane, 12.5g of p-aminophenol, and 330.0g of dimethylacetamide, and reacted at 100°C for 2 hours to obtain an acidic substituent and an N-substituted maleimide group A solution of the maleimide compound (A-2) (Mw=1021) in dimethylacetamide and used as the (A-2) component.

[製造例A-3] 在具備溫度計、攪拌裝置及附有回流冷卻管之水分定量器之容積1L的反應容器中，加入6.2g 4,4’-二胺基二苯基甲烷、179.8g雙(4-馬來醯亞胺基苯基)甲烷、13.7g對胺基苯酚、及330.0g二甲基乙醯胺，並在100℃使其反應2小時，來獲得具有酸性取代基與N-取代馬來醯亞胺基之馬來醯亞胺化合物(A-3)(Mw＝908)的二甲基乙醯胺溶液，並將其作為(A-3)成分使用。[Production Example A-3] Into a 1 L reaction vessel equipped with a thermometer, a stirring device, and a moisture meter with a reflux cooling tube, add 6.2 g of 4,4'-diaminodiphenylmethane and 179.8 g of bis(4-maleimide Aminophenyl)methane, 13.7g of p-aminophenol, and 330.0g of dimethylacetamide, and reacted at 100°C for 2 hours to obtain an acidic substituent and an N-substituted maleimide group A solution of the maleimide compound (A-3) (Mw=908) in dimethylacetamide and used as the (A-3) component.

[製造例A-4] 在具備溫度計、攪拌裝置及附有回流冷卻管之水分定量器之容積1L的反應容器中，加入18.2g 4,4’-二胺基二苯基甲烷、174.9g雙(4-馬來醯亞胺基苯基)甲烷、6.7g對胺基苯酚、及330.0g二甲基乙醯胺，並在100℃使其反應2小時，來獲得具有酸性取代基與N-取代馬來醯亞胺基之馬來醯亞胺化合物(A-4)(Mw＝1034)的二甲基乙醯胺溶液，並將其作為(A-4)成分使用。[Production Example A-4] Into a 1L reaction vessel equipped with a thermometer, a stirring device and a moisture meter with a reflux cooling tube, add 18.2g of 4,4'-diaminodiphenylmethane and 174.9g of bis(4-maleimide Aminophenyl)methane, 6.7g of p-aminophenol, and 330.0g of dimethylacetamide, and reacted at 100°C for 2 hours to obtain an acidic substituent and an N-substituted maleimide group A solution of the maleimide compound (A-4) (Mw = 1034) in dimethylacetamide and used as the (A-4) component.

[製造例A-5] 在具備溫度計、攪拌裝置及附有回流冷卻管之水分定量器之容積1L的反應容器中，加入4.9g 4,4’-二胺基二苯基甲烷、178.5g雙(4-馬來醯亞胺基苯基)甲烷、16.3g對胺基苯酚、及330.0g二甲基乙醯胺，並在100℃使其反應2小時，來獲得具有酸性取代基與N-取代馬來醯亞胺基之馬來醯亞胺化合物(A-5)(Mw＝911)的二甲基乙醯胺溶液，並將其作為(A-5)成分使用。[Production Example A-5] In a 1 L reaction vessel equipped with a thermometer, a stirring device and a moisture meter with a reflux cooling tube, add 4.9 g of 4,4'-diaminodiphenylmethane and 178.5 g of bis(4-maleimide Aminophenyl)methane, 16.3g of p-aminophenol, and 330.0g of dimethylacetamide, and reacted at 100°C for 2 hours to obtain an acidic substituent and an N-substituted maleimide group A solution of the maleimide compound (A-5) (Mw=911) in dimethylacetamide and used as the (A-5) component.

再者，上述製造例中獲得的馬來醯亞胺化合物的重量平均分子量(Mw)，是利用凝膠滲透層析(GPC)，由使用標準聚苯乙烯而得的校準曲線所換算而得。校準曲線，是使用標準聚苯乙烯：TSKstandard POLYSTYRENE(型號：A-2500、A-5000、F-1、F-2、F-4、F-10、F-20、F-40)[東曹股份有限公司製造]，並利用3次式進行近似而得。GPC的條件，如下所示。裝置：泵浦L-6200型[日立先端科技股份有限公司製造]、偵測器L-3300型RI[日立先端科技股份有限公司製造]、管柱烘箱L-655A-52[日立先端科技股份有限公司製造] 管柱：TSKgel SuperHZ2000＋TSKgel SuperHZ2300(皆為東曹股份有限公司製造) 管柱尺寸：6.0mm×40mm(保護管柱)、7.8mm×300mm(管柱) 溶析液：四氫呋喃試樣濃度：20mg/5mL 注入量：10μL 流量：0.5mL/分鐘測定溫度：40℃In addition, the weight average molecular weight (Mw) of the maleimide compound obtained in the above production example was converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). Calibration curve, using standard polystyrene: TSKstandard POLYSTYRENE (Models: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [TOSO Co., Ltd.], and approximated using the third degree. The conditions of GPC are as follows. Device: Pump L-6200 [manufactured by Hitachi Advanced Technology Co., Ltd.], detector L-3300 RI [manufactured by Hitachi Advanced Technology Co., Ltd.], column oven L-655A-52 [Hitachi Advanced Technology Co., Ltd. limited Company manufacturing] Column: TSKgel SuperHZ2000 + TSKgel SuperHZ2300 (all made by Tosoh Corporation) Column size: 6.0mm×40mm (protection column), 7.8mm×300mm (pipe column) Eluent: Tetrahydrofuran Sample concentration: 20mg/5mL Injection volume: 10μL Flow rate: 0.5mL/min Measuring temperature: 40℃

(B)成分：甲酚酚醛清漆型環氧樹脂「EPICLON(註冊商標)N-673」(DIC股份有限公司製造) (C-1)成分：「SMA(註冊商標)EF40」(苯乙烯/馬來酸酐＝4，Mw＝11000，CRAY VALLEY公司製造) (C-2)成分：「SMA(註冊商標)3000」(苯乙烯/馬來酸酐＝2，Mw＝7500，CRAY VALLEY公司製造) (C-3)成分：「SMA(註冊商標)EF80」(苯乙烯/馬來酸酐＝8，Mw＝14400，CRAY VALLEY公司製造) (C-4)成分：「SMA(註冊商標)1000」(苯乙烯/馬來酸酐＝1，Mw＝5000，CRAY VALLEY公司製造)(B) Ingredient: Cresol novolac epoxy resin "EPICLON (registered trademark) N-673" (made by DIC Corporation) (C-1) Ingredient: "SMA (registered trademark) EF40" (styrene/maleic anhydride = 4, Mw = 11000, manufactured by Cray Valley) (C-2) Ingredient: "SMA (registered trademark) 3000" (styrene/maleic anhydride=2, Mw=7500, manufactured by Cray Valley) (C-3) Ingredient: "SMA (registered trademark) EF80" (styrene/maleic anhydride=8, Mw=14400, manufactured by Cray Valley) (C-4) Ingredient: "SMA (registered trademark) 1000" (styrene/maleic anhydride=1, Mw=5000, manufactured by Cray Valley)

(D)成分：經以胺基矽烷系偶合劑進行表面處理後之熔融二氧化矽(平均粒徑：1.9μm，比表面積5.8m² /g)(D) Component: Molten silica after surface treatment with aminosilane coupling agent (average particle diameter: 1.9 μm, specific surface area 5.8 m ² /g)

(E)成分：二氰二胺 (F)成分：芳香族磷酸酯(參照下述結構式)

(E) component: dicyandiamide (F) component: aromatic phosphate (refer to the following structural formula)

[實施例1～15、比較例1～2] 如下述表1～4所示，摻合上述所示的各成分(其中，在溶液的情況下表示固體成分換算量)，進一步以溶液的非揮發成分成為67質量%的方式追加甲基乙基酮，來製備樹脂清漆。使國際電子工業聯接協會(IPC)規格#3313的玻璃布(0.1mm)含浸所獲得的各樹脂清漆，並在160℃進行乾燥4分鐘，來獲得預浸體。[Examples 1 to 15, Comparative Examples 1 to 2] As shown in Tables 1 to 4 below, each of the above-mentioned components (wherein, in the case of a solution represents a solid content conversion amount) is blended, and methyl ethyl is added so that the non-volatile content of the solution becomes 67% by mass Ketones to prepare resin varnishes. Each resin varnish obtained was impregnated with a glass cloth (0.1 mm) of International Electronics Industry Connection Association (IPC) specification #3313, and dried at 160°C for 4 minutes to obtain a prepreg.

(雙面覆銅積層板的製作和性能評估) 將8片前述預浸體重疊後，在其雙面上重疊厚度18μm的銅箔「3EC-VLP-18」(三井金屬股份有限公司製造)，並以溫度190℃、壓力25kgf/cm² (2.45MPa)的條件進行90分鐘的加熱加壓並成形，來製作厚度0.8mm(8片預浸體的量)的雙面覆銅積層板，然後使用該覆銅積層板，依照前述方法，來測定和評估相對介電常數、金屬箔黏合性、玻璃轉化溫度(Tg)及低熱膨脹性。又，在1片預浸體的雙面上重疊厚度18μm的銅箔「3EC-VLP-18」(三井金屬股份有限公司製造)，並以溫度190℃、壓力25kgf/cm² (2.45MPa)的條件進行90分鐘的加熱加壓並成形，來製作厚度0.1mm(1片預浸體的量)的雙面覆銅積層板，然後使用該雙面覆銅積層板，依照前述方法，來測定和評估尺寸變化量的偏差。(Fabrication and performance evaluation of double-sided copper-clad laminates) After stacking 8 pieces of the above prepreg, 18 μm thick copper foil "3EC-VLP-18" (made by Mitsui Metals Co., Ltd.) was laminated on both sides. Then, it was heated and pressed at a temperature of 190°C and a pressure of 25 kgf/cm ² (2.45 MPa) for 90 minutes to form a double-sided copper-clad laminate with a thickness of 0.8 mm (amount of 8 prepregs). Using this copper-clad laminate, the relative dielectric constant, metal foil adhesion, glass transition temperature (Tg), and low thermal expansion were measured and evaluated in accordance with the aforementioned method. In addition, a copper foil "3EC-VLP-18" (manufactured by Mitsui Metals Co., Ltd.) with a thickness of 18 μm was laminated on both sides of one prepreg at a temperature of 190°C and a pressure of 25 kgf/cm ² (2.45 MPa). Conditioning was performed by heating and pressing for 90 minutes and forming to produce a double-sided copper-clad laminate with a thickness of 0.1 mm (the amount of one prepreg), and then using this double-sided copper-clad laminate to measure and Evaluate the deviation of the dimensional change.

(4層覆銅積層板的製作和性能評估) 另一方面，使用1片前述預浸體，在其雙面上重疊厚度18μm的銅箔「YGP-18」(日本電解股份有限公司製造)，並以溫度190℃、壓力25kgf/cm² (2.45MPa)的條件進行90分鐘的加熱加壓並成形，來製作厚度0.1mm(1片預浸體的量)的雙面覆銅積層板後，對兩銅箔面施加內層密合處理(使用「BF處理液」(日立化成股份有限公司製造))，並重疊各1片厚度0.05mm的預浸體，然後在其雙面上重疊厚度18μm的銅箔「YGP-18」(日本電解股份有限公司製造)，並以溫度190℃、壓力25kgf/cm² (2.45MPa)的條件進行90分鐘的加熱加壓並成形，來製作4層覆銅積層板。使用該4層覆銅積層板，依照前述方法，來實施耐熱性、鍍覆分佈性及成形性的評估。將結果表示於表1～4中。(Fabrication and performance evaluation of a 4-layer copper-clad laminate) On the other hand, using one piece of the aforementioned prepreg, a copper foil "YGP-18" (manufactured by Nippon Electrolytic Co., Ltd.) with a thickness of 18 μm was laminated on both sides, After heating and pressurizing at a temperature of 190°C and a pressure of 25 kgf/cm ² (2.45 MPa) for 90 minutes and forming, a double-sided copper-clad laminate with a thickness of 0.1 mm (a prepreg) was produced. Apply the inner layer adhesion treatment (using "BF treatment liquid" (manufactured by Hitachi Chemical Co., Ltd.)) to the two copper foil surfaces, overlay one prepreg with a thickness of 0.05 mm, and overlay the thickness of 18 μm on both sides Copper foil "YGP-18" (manufactured by Nippon Electrolytic Co., Ltd.), and heated and pressed at a temperature of 190°C and a pressure of 25 kgf/cm ² (2.45 MPa) for 90 minutes to form a 4-layer copper clad Laminates. Using this four-layer copper-clad laminate, the heat resistance, plating distribution, and formability were evaluated in accordance with the aforementioned method. The results are shown in Tables 1 to 4.

[表1]

*1：磷原子換算量[Table 1]

*1: Conversion amount of phosphorus atom

[表2]

*1：磷原子換算量[Table 2]

*1: Conversion amount of phosphorus atom

[表3]

*1：磷原子換算量[table 3]

*1: Conversion amount of phosphorus atom

[表4]

*1：磷原子換算量[Table 4]

*1: Conversion amount of phosphorus atom

由以上結果可知以下內容。在實施例1～15中，回焊耐熱性達成耐熱要求等級以上也就是10個循環以上，並能夠獲得低相對介電常數、高金屬箔黏合性及高玻璃轉化溫度，且顯示低熱膨脹性。又，由於自壁面突出適度的玻璃布以及具有適度的粗糙化形狀等，因此確認到具有良好的鍍覆分佈性。在成形性方面，樹脂的填埋性良好，未確認到模糊和孔隙等異常。進一步，在實施例1～15中，標準偏差σ變小，因而充分地抑制尺寸變化量的偏差。另一方面，在比較例1～2中，標準偏差σ超過0.012%，因而尺寸變化量的偏差變大。 [產業上之可利用性]From the above results, the following can be seen. In Examples 1 to 15, the reflow heat resistance reached a heat-resistance level or higher, that is, 10 cycles or more, and a low relative dielectric constant, high metal foil adhesion, and high glass transition temperature were obtained, and low thermal expansion was exhibited. In addition, since the glass cloth protruding moderately from the wall surface and having a moderately roughened shape, etc., it was confirmed that it had good plating distribution. In terms of formability, the resin has good landfill properties, and no abnormalities such as blurring and porosity have been confirmed. Further, in Examples 1 to 15, the standard deviation σ becomes small, so that the variation in the amount of dimensional change is sufficiently suppressed. On the other hand, in Comparative Examples 1 to 2, the standard deviation σ exceeds 0.012%, so the variation in the amount of dimensional change becomes larger. [Industry availability]

藉由本發明所獲得的樹脂清漆、含有該樹脂清漆而成之預浸體及含有該預浸體而成之積層板，具有高耐熱性、低相對介電常數、高金屬箔黏合性、高玻璃轉化溫度、低熱膨脹性，並且成形性和鍍覆分佈性優異，進一步尺寸變化量的偏差小，因此作為電子機器用的印刷線路板和半導體封裝體是有用的。The resin varnish obtained by the present invention, a prepreg containing the resin varnish, and a laminate containing the prepreg have high heat resistance, low relative dielectric constant, high metal foil adhesion, and high glass The conversion temperature and low thermal expansion are excellent in formability and plating distribution, and the variation in the amount of further dimensional change is small. Therefore, it is useful as a printed wiring board and a semiconductor package for electronic equipment.

無no

第1圖是實施例中的用於測定尺寸變化量的偏差的評估基板之概略圖。FIG. 1 is a schematic diagram of an evaluation board for measuring the deviation of the dimensional change in the embodiment.

國內寄存資訊 (請依寄存機構、日期、號碼順序註記) 無Domestic storage information (please note in order of storage institution, date, number) no

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Claims

一種樹脂清漆，其是含有下述成分而成： (A)馬來醯亞胺化合物； (B)環氧樹脂；及， (C)共聚合樹脂，其具有源自芳香族乙烯系化合物的結構單元與源自馬來酸酐的結構單元；其中，前述(A)馬來醯亞胺化合物是具有N-取代馬來醯亞胺基之馬來醯亞胺化合物，該馬來醯亞胺化合物是使(a1)具有至少2個N-取代馬來醯亞胺基之馬來醯亞胺化合物、(a2)單胺化合物及(a3)二胺化合物進行反應而獲得，並且，前述(A)馬來醯亞胺化合物是將前述(a2)成分相對於前述(a3)成分的使用比率也就是(a2)成分/(a3)成分，以莫耳比計，設為0.9～5.0來進行反應而獲得。A resin varnish containing the following components: (A) Maleimide compounds; (B) epoxy resin; and, (C) A copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride; Wherein, the aforementioned (A) maleimide compound is a maleimide compound having an N-substituted maleimide group, and the maleimide compound is such that (a1) has at least 2 N-substitutions The maleimide compound of maleimide group, (a2) monoamine compound and (a3) diamine compound are obtained by reacting, In addition, the (A) maleimide compound is obtained by using the ratio of the (a2) component relative to the (a3) component, that is, (a2) component/(a3) component, in molar ratio, to 0.9 ~5.0 to obtain the reaction.

如請求項1所述之樹脂清漆，其中，前述(a2)單胺化合物是由下述通式(a2-1)表示，前述(a3)二胺化合物是由下述通式(a3-1)表示；

通式(a3-1)中，X^A2 表示碳數1～3的脂肪族烴基或-O-，R^A6 和R^A7 各自獨立地表示碳數1～5的烷基、鹵素原子、羥基、羧基或磺酸基，v和w各自獨立地為0～4的整數。The resin varnish according to claim 1, wherein the (a2) monoamine compound is represented by the following general formula (a2-1), and the (a3) diamine compound is represented by the following general formula (a3-1) Express

In the general formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or -O-, and R ^A6 and R ^A7 each independently represent an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, or a carboxyl group Or a sulfonic acid group, v and w are each independently an integer of 0 to 4.

如請求項1或2所述之樹脂清漆，其中，前述(a2)成分和前述(a3)成分具有的-NH₂ 基當量的總和與前述(a1)成分的馬來醯亞胺基當量的關係，滿足下述式子： 0.1≦〔馬來醯亞胺基當量〕／〔-NH₂ 基當量的總和〕≦10。The resin varnish according to claim 1 or 2, wherein the relationship between the sum of the -NH ₂ group equivalents of the component (a2) and the component (a3) and the equivalent of the maleimide group of the component (a1) , Which satisfies the following formula: 0.1≦[maleimide equivalent]/[total of -NH ₂ equivalent]≦10.

如請求項1～3中任一項所述之樹脂清漆，其中，前述(B)成分是選自由雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、萘型環氧樹脂、蒽型環氧樹脂、聯苯型環氧樹脂、聯苯芳烷基酚醛清漆型環氧樹脂及雙環戊二烯型環氧樹脂所組成之群組中的至少1種。The resin varnish according to any one of claims 1 to 3, wherein the component (B) is selected from the group consisting of bisphenol F type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin , Naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl novolac type epoxy resin and dicyclopentadiene type epoxy resin at least one group .

如請求項1～4中任一項所述之樹脂清漆，其中，前述(C)成分是一共聚合樹脂，該共聚合樹脂具有由下述通式(C-i)表示的結構單元與由下述式(C-ii)表示的結構單元；

式(C-i)中，R^C1 是氫原子或碳數1～5的烷基，R^C2 是碳數1～5的烷基、碳數2～5的烯基、碳數6～20的芳基、羥基或(甲基)丙烯醯基，x是0～3的整數，其中，當x為2或3時，複數個R^C2 可相同亦可不同。The resin varnish according to any one of claims 1 to 4, wherein the component (C) is a copolymerized resin having a structural unit represented by the following general formula (Ci) and a formula The structural unit represented by (C-ii);

In formula (Ci), R ^C1 is a hydrogen atom or a C 1-5 alkyl group, R ^C2 is a C 1-5 alkyl group, a C 2-5 alkenyl group, and a C 6-20 aryl group , Hydroxyl or (meth)acryloyl, x is an integer from 0 to 3, wherein when x is 2 or 3, the plurality of R ^C2 may be the same or different.

如請求項1～4中任一項所述之樹脂清漆，其中，在前述(C)成分中，源自芳香族乙烯系化合物的結構單元與源自馬來酸酐的結構單元的含有比例，也就是源自芳香族乙烯系化合物的結構單元/源自馬來酸酐的結構單元，以莫耳比計，為1～9。The resin varnish according to any one of claims 1 to 4, wherein in the component (C), the content ratio of the structural unit derived from the aromatic vinyl compound to the structural unit derived from maleic anhydride is also It is the structural unit derived from the aromatic vinyl compound/the structural unit derived from maleic anhydride, and it is 1 to 9 in terms of molar ratio.

如請求項1～6中任一項所述之樹脂清漆，其中，相對於前述(A)～(C)成分的總和100質量份，前述(A)～(C)成分的含量是(A)成分為15～65質量份，(B)成分為15～50質量份，(C)成分為10～45質量份。The resin varnish according to any one of claims 1 to 6, wherein the content of the components (A) to (C) is (A) relative to 100 parts by mass of the total of the components (A) to (C). The component is 15 to 65 parts by mass, (B) the component is 15 to 50 parts by mass, and (C) the component is 10 to 45 parts by mass.

如請求項1～7中任一項所述之樹脂清漆，其中，該樹脂清漆是進一步含有(D)無機填充材料而成。The resin varnish according to any one of claims 1 to 7, wherein the resin varnish further contains (D) an inorganic filler.

如請求項1～8中任一項所述之樹脂清漆，其中，該樹脂清漆是進一步含有(E)硬化劑而成。The resin varnish according to any one of claims 1 to 8, wherein the resin varnish further contains (E) a hardener.

如請求項1～9中任一項所述之樹脂清漆，其中，該樹脂清漆是進一步含有(F)難燃劑而成。The resin varnish according to any one of claims 1 to 9, wherein the resin varnish further contains (F) a flame retardant.

一種預浸體，其是含有請求項1～10中任一項所述之樹脂清漆而成。A prepreg made of the resin varnish described in any one of claims 1 to 10.

如請求項11所述之預浸體，其中，依照下述方法來求出的標準偏差σ是0.012%以下，該標準偏差σ的計算方法如下：在1片預浸體的雙面上重疊厚度18μm的銅箔，並以190℃、2.45MPa的條件進行90分鐘的加熱加壓並成形，來製作厚度0.1mm的雙面覆銅積層板，然後在藉由上述方法獲得的雙面覆銅積層板的面內，於第1圖所示的1～8的位置，實施直徑為1.0mm的穿孔，並使用影像測定機來分別測定第1圖所示的經線方向(1-7、2-6、3-5)和緯線方向(1-3、8-4、7-5)的各3點的距離，並將各測定距離設為起始值，然後去除外層銅箔，並利用乾燥機以185℃加熱60分鐘，冷卻後，採用與起始值的測定方法相同之方法，分別測定經線方向(1-7、2-6、3-5)和緯線方向(1-3、8-4、7-5)的各3點的距離，然後根據相對於各測定距離的起始值的變化率來求出這些變化率的平均值，並計算相對於該平均值的標準偏差σ。The prepreg according to claim 11, wherein the standard deviation σ determined according to the following method is 0.012% or less, and the standard deviation σ is calculated as follows: A copper foil with a thickness of 18 μm was laminated on both sides of one prepreg, and heated and pressed at 190° C. and 2.45 MPa for 90 minutes to form a double-sided copper-clad laminate with a thickness of 0.1 mm. In the plane of the double-sided copper-clad laminate obtained by the above method, perforations with a diameter of 1.0 mm were carried out at the positions 1 to 8 shown in FIG. 1, and the image measuring machine was used to measure the positions shown in FIG. 1 respectively. The distances of the three points in the meridian direction (1-7, 2-6, 3-5) and the weft direction (1-3, 8-4, 7-5) are shown, and each measured distance is set as the starting point Value, and then remove the outer layer of copper foil, and use a dryer to heat at 185 ℃ for 60 minutes, after cooling, use the same method as the initial value measurement method to measure the warp direction (1-7, 2-6, 3- 5) The distance from each of the three points in the latitude direction (1-3, 8-4, 7-5), and then the average value of these rates of change is calculated from the rate of change relative to the initial value of each measured distance, and The standard deviation σ relative to this average value is calculated.

一種積層板，其是含有請求項11或12所述之預浸體與金屬箔而成。A laminate comprising the prepreg described in claim 11 or 12 and metal foil.

一種印刷線路板，其是含有請求項11或12所述之預浸體或請求項13所述之積層板而成。A printed wiring board comprising the prepreg according to claim 11 or 12 or the laminate according to claim 13

一種半導體封裝體，其是在請求項14所述之印刷線路板上搭載半導體元件而成。A semiconductor package formed by mounting semiconductor elements on a printed wiring board according to claim 14.