TW201736413A - Soluble polyfunctional vinyl aromatic copolymer, method for producing same and curable composition - Google Patents

Soluble polyfunctional vinyl aromatic copolymer, method for producing same and curable composition Download PDF

Info

Publication number
TW201736413A
TW201736413A TW105143267A TW105143267A TW201736413A TW 201736413 A TW201736413 A TW 201736413A TW 105143267 A TW105143267 A TW 105143267A TW 105143267 A TW105143267 A TW 105143267A TW 201736413 A TW201736413 A TW 201736413A
Authority
TW
Taiwan
Prior art keywords
group
formula
copolymer
aromatic compound
mol
Prior art date
Application number
TW105143267A
Other languages
Chinese (zh)
Other versions
TWI706963B (en
Inventor
川辺正直
太田道貴
Original Assignee
新日鐵住金化學股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 新日鐵住金化學股份有限公司 filed Critical 新日鐵住金化學股份有限公司
Publication of TW201736413A publication Critical patent/TW201736413A/en
Application granted granted Critical
Publication of TWI706963B publication Critical patent/TWI706963B/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Abstract

Provided are: a soluble polyfunctional vinyl aromatic copolymer which has improved heat resistance, thermal decomposition resistance, solubility in solvents, processability and compatibility with specific resins; and a curable composition of this soluble polyfunctional vinyl aromatic copolymer . A soluble polyfunctional vinyl aromatic copolymer which contains a repeating structural unit derived from a divinyl aromatic compound (a) and a repeating unit derived from a monovinyl aromatic compound (b), and which is characterized in that, the repeating structural unit derived from a divinyl aromatic compound (a) is a unit having an unsaturated hydrocarbon group, which is a vinyl group-containing unit and/or a vinylene group-containing unit; and the copolymer has, as a terminal group, a vinylene group-containing terminal group that is derived from the divinyl aromatic compound (a) and/or the monovinyl aromatic compound (b). This soluble polyfunctional vinyl aromatic copolymer is also characterized by being polymerizable and by being soluble in a solvent.

Description

可溶性多官能乙烯基芳香族共聚合物、其製造方法、硬化性組成物及其應用Soluble polyfunctional vinyl aromatic copolymer, preparation method thereof, hardening composition and application thereof

本發明是有關於一種耐熱性、相容性、透明性及韌性得到改善的新型可溶性多官能乙烯基芳香族共聚合物、其製造方法及含有該共聚合物的硬化性組成物。進而有關於一種包含該硬化性組成物的膜、進行硬化而獲得的硬化物、包含硬化性組成物與基材的硬化性複合材料、包含硬化物與金屬箔的積層體及帶有樹脂的銅箔。The present invention relates to a novel soluble polyfunctional vinyl aromatic copolymer having improved heat resistance, compatibility, transparency, and toughness, a method for producing the same, and a curable composition containing the copolymer. Further, there is a film comprising the curable composition, a cured product obtained by curing, a curable composite material comprising a curable composition and a substrate, a laminate comprising a cured product and a metal foil, and copper with a resin. Foil.

伴隨近年來的資訊通信量的增加，而積極地進行高頻率帶中的資訊通信，為了更優異的電氣特性，其中為了減少高頻率帶中的傳輸損耗，而正尋求一種具有低介電常數與低介電損耗正切，尤其吸水後的介電特性變化小的電氣絕緣材料。進而，使用該些電氣絕緣材料的印刷基板或電子零件於安裝時暴露在高溫的回流焊中，因此期望一種耐熱性高，即顯示出高玻璃轉移溫度的材料。尤其最近就環境問題的觀點而言，使用熔點高的無鉛的焊料，因此耐熱性更高的電氣絕緣材料的要求提高。針對該些要求，自先前以來提出有使用具有各種化學結構的乙烯基系化合物的硬化樹脂。With the increase in the amount of information traffic in recent years, information communication in the high-frequency band is actively carried out, and in order to improve the electrical characteristics, in order to reduce the transmission loss in the high-frequency band, a low dielectric constant is sought. Low dielectric loss tangent, especially electrical insulation materials with small changes in dielectric properties after water absorption. Further, printed substrates or electronic parts using such electrical insulating materials are exposed to high-temperature reflow at the time of mounting, and therefore, a material which exhibits high heat resistance, that is, a high glass transition temperature, is desired. In particular, from the viewpoint of environmental problems, since a lead-free solder having a high melting point is used, the demand for an electric insulating material having higher heat resistance is increased. In response to these demands, a hardening resin using a vinyl compound having various chemical structures has been proposed from the past.

作為此種硬化樹脂，例如於專利文獻1中揭示了藉由於磺酸酯陰離子或過氯酸陰離子的存在下使二乙烯基芳香族化合物聚合而可獲得於主鏈包含苯基與雙鍵、即具有由本申請案的式（a2）（以下，簡稱為「式（a2）」）所表示的結構的、溶劑可溶性的聚二乙烯基苯。而且，於專利文獻1中，作為為了專門合成具有由式（a2）所表示的結構的聚二乙烯基苯而於聚合時可使用的溶媒所例示者為如苯等般的芳香族化合物、正己烷等般的飽和脂肪族烴、環己烷、甲基環己烷般的飽和脂環式烴、或者氯仿、三氯乙烷等的鹵化物。而且，關於溶媒的極性，揭示了較佳為無極性或極性低者，且較佳為將單體濃度設為20 vol%以下。進而，記載了當使用極性高的溶媒時，容易引起交聯反應而欠佳。 因此，於專利文獻1中，關於藉由可使單乙烯基芳香族化合物與二乙烯基芳香族化合物共聚合且使單乙烯基芳香族化合物共聚合而獲得的共聚合物具有何種有用的特性，並未進行任何揭示。另外，雖然有於聚合時藉由併用極性化合物而生成於側鏈具有乙烯基的聚合物的可能性的記載，但揭示了容易引起交聯反應而欠佳。 因此，基於專利文獻1的揭示技術，若使用使單乙烯基芳香族化合物與二乙烯基芳香族化合物共聚合而成的溶劑可溶性的共聚合物作為要求高度的耐熱性的絕緣材料用硬化樹脂，則導致伴隨耐熱性下降、硬化反應性下降的成形加工性的惡化，從而不適合於工業性實施。As such a hardening resin, for example, Patent Document 1 discloses that a divinyl aromatic compound can be polymerized in the presence of a sulfonate anion or a perchloric acid anion to obtain a phenyl group and a double bond in the main chain, that is, The solvent-soluble polydivinylbenzene having the structure represented by the formula (a2) (hereinafter, abbreviated as "formula (a2)") of the present application. In addition, in the case of the solvent which can be used for the polymerization of the polydivinylbenzene having the structure represented by the formula (a2), it is exemplified by an aromatic compound such as benzene or the like. A saturated aliphatic hydrocarbon such as an alkane, a saturated alicyclic hydrocarbon such as cyclohexane or methylcyclohexane, or a halide such as chloroform or trichloroethane. Further, regarding the polarity of the solvent, it is revealed that the polarity is not high or the polarity is low, and it is preferable to set the monomer concentration to 20 vol% or less. Further, it is described that when a solvent having a high polarity is used, a crosslinking reaction is likely to occur, which is not preferable. Therefore, in Patent Document 1, what kind of useful properties are obtained by copolymerizing a monovinyl aromatic compound with a divinyl aromatic compound and copolymerizing a monovinyl aromatic compound , did not reveal anything. In addition, there is a description of the possibility that a polymer having a vinyl group in a side chain is formed by using a polar compound in combination at the time of polymerization, but it is revealed that the crosslinking reaction is likely to be caused, which is not preferable. Therefore, according to the technique disclosed in Patent Document 1, a solvent-soluble copolymer obtained by copolymerizing a monovinyl aromatic compound and a divinyl aromatic compound is used as a hardening resin for an insulating material which requires high heat resistance. This causes deterioration in moldability due to a decrease in heat resistance and a decrease in hardening reactivity, and is not suitable for industrial implementation.

於專利文獻2中揭示了二乙烯基芳香族化合物與作為單乙烯基芳香族化合物的具有低級烷基、鹵化烷基、醯基、醯氧基、羥基或鹵素原子的苯乙烯類共聚合。但是，關於按照專利文獻2中揭示的技術而合成的共聚合物，於主鏈包含苯基與雙鍵的、具有由式（a2）所表示的結構的聚二乙烯基苯成為構成主鏈的主骨架，苯乙烯類作為加成於末端的末端基而被導入。因此，於專利文獻2中揭示了為了一邊維持溶劑可溶性一邊提高共聚合物的產率，較佳為將苯乙烯類與二乙烯基苯的莫耳比設為5～0.01的範圍。實際上若觀察專利文獻2的實施例，則揭示了作為觸媒，使用過氯酸乙醯酯或三氟甲烷磺酸作為觸媒，使用苯作為溶媒，以苯乙烯類與二乙烯基苯的莫耳比為二乙烯基苯/苯乙烯類=0.33～3的範圍進行，藉此乙烯基消失，末端經苯乙烯類密封的寡聚物被回收。 但是，基於專利文獻2的揭示技術，若使用使苯乙烯類與二乙烯基苯共聚合而成的溶劑可溶性的共聚合物作為要求高度的耐熱性與電氣特性的絕緣材料用硬化樹脂，則導致伴隨耐熱性下降、硬化反應性下降的成形加工性的惡化，從而不適合於工業性實施。Patent Document 2 discloses copolymerization of a divinyl aromatic compound with a styrene having a lower alkyl group, a halogenated alkyl group, a decyl group, a decyloxy group, a hydroxyl group or a halogen atom as a monovinyl aromatic compound. However, with respect to the copolymer synthesized according to the technique disclosed in Patent Document 2, the polydivinylbenzene having a structure represented by the formula (a2) containing a phenyl group and a double bond in the main chain becomes a main chain. The main skeleton, styrene, is introduced as a terminal group added to the terminal. Therefore, in Patent Document 2, in order to increase the yield of the copolymer while maintaining solvent solubility, it is preferred to set the molar ratio of styrene to divinylbenzene to be in the range of 5 to 0.01. Actually, if the example of Patent Document 2 is observed, it is disclosed that as a catalyst, ethyl perchlorate or trifluoromethanesulfonic acid is used as a catalyst, benzene is used as a solvent, and styrene and divinylbenzene are used. The molar ratio is in the range of divinylbenzene/styrene = 0.33 to 3, whereby the vinyl group disappears, and the terminal-terminated styrene-terminated oligomer is recovered. However, according to the technique disclosed in Patent Document 2, when a solvent-soluble copolymer obtained by copolymerizing styrene and divinylbenzene is used as a curing resin for insulating materials requiring high heat resistance and electrical properties, The deterioration of the moldability due to a decrease in heat resistance and a decrease in hardening reactivity is not suitable for industrial implementation.

於專利文獻3中揭示有一種可溶性多官能乙烯基芳香族共聚合物，其藉由在路易斯酸觸媒及1-氯乙基苯、1-溴乙基苯及雙(1-氯-1-甲基乙基)苯等特定結構的起始劑的存在下，使二乙烯基芳香族化合物與單乙烯基芳香族化合物於有機溶媒中以20℃～100℃的溫度進行聚合而獲得。另外，於專利文獻4中揭示有一種可溶性多官能乙烯基芳香族共聚合物的製造方法，其是於四級銨鹽的存在下，藉由路易斯酸觸媒及特定結構的起始劑，使含有二乙烯基芳香族化合物20莫耳%～100莫耳%而成的單量體成分以20℃～120℃的溫度進行陽離子聚合，藉此具有得到控制的分子量分佈的可溶性多官能乙烯基芳香族共聚合物的製造方法。藉由所述2個專利文獻中揭示的技術所獲得的可溶性多官能乙烯基芳香族共聚合物的溶劑可溶性及加工性優異，藉由使用該可溶性多官能乙烯基芳香族共聚合物，可獲得玻璃轉移溫度高且耐熱性優異的硬化物。Patent Document 3 discloses a soluble polyfunctional vinyl aromatic copolymer by Lewis acid catalyst and 1-chloroethylbenzene, 1-bromoethylbenzene and bis(1-chloro-1- The divinyl aromatic compound and the monovinyl aromatic compound are polymerized in an organic solvent at a temperature of from 20 ° C to 100 ° C in the presence of a specific initiator such as methyl ethyl benzene. Further, Patent Document 4 discloses a process for producing a soluble polyfunctional vinyl aromatic copolymer which is obtained by using a Lewis acid catalyst and a specific structure initiator in the presence of a quaternary ammonium salt. The monomer component containing 20% by mole of the divinyl aromatic compound in an amount of from 100% by mole to 100% by weight is subjected to cationic polymerization at a temperature of from 20 ° C to 120 ° C to thereby obtain a soluble polyfunctional vinyl aromatic having a controlled molecular weight distribution. A method of producing a co-polymer. The soluble polyfunctional vinyl aromatic copolymer obtained by the techniques disclosed in the above two patent documents is excellent in solvent solubility and processability, and can be obtained by using the soluble polyfunctional vinyl aromatic copolymer. A cured product having a high glass transition temperature and excellent heat resistance.

藉由該些技術所獲得的可溶性多官能乙烯基芳香族共聚合物因其本身具有聚合性的雙鍵，故藉由使其硬化，可提供具有高玻璃轉移溫度的硬化物。因此，該硬化物或可溶性多官能乙烯基芳香族共聚合物可以說是耐熱性優異的聚合物或其前驅物。而且，該可溶性多官能乙烯基芳香族共聚合物與其他自由基聚合性單體進行共聚合而提供硬化物，該硬化物亦成為耐熱性優異的聚合物。The soluble polyfunctional vinyl aromatic copolymer obtained by these techniques has a polymerizable double bond, so that by hardening it, a cured product having a high glass transition temperature can be provided. Therefore, the cured product or the soluble polyfunctional vinyl aromatic copolymer can be said to be a polymer excellent in heat resistance or a precursor thereof. Further, the soluble polyfunctional vinyl aromatic copolymer is copolymerized with another radically polymerizable monomer to provide a cured product, and the cured product is also a polymer excellent in heat resistance.

但是，若自專利文獻3及專利文獻4中揭示的可溶性多官能乙烯基芳香族共聚合物與其他硬化性樹脂的相容性、或硬化後的耐熱變色性這一觀點來看，與極性高的環氧化合物或酚樹脂之間的相容性或溶解性並不充分，另外對於高製程溫度的耐熱分解性亦不充分。因此，因環氧化合物或酚樹脂的種類而提供不均勻的組成物的情況多，難以製作環氧化合物或酚樹脂與可溶性多官能乙烯基芳香族共聚合物的均勻的硬化物。因此，除產生調配配方設計的自由度小、硬化物的韌性低這一缺點以外，存在因280℃～300℃附近的高熱歷程而產生膨脹或剝離等不良的情況。However, the compatibility of the soluble polyfunctional vinyl aromatic copolymer disclosed in Patent Document 3 and Patent Document 4 with other curable resins or heat discoloration resistance after curing is high. The compatibility or solubility between the epoxy compound or the phenol resin is not sufficient, and the heat decomposition resistance to a high process temperature is also insufficient. Therefore, there are many cases in which a non-uniform composition is provided depending on the kind of the epoxy compound or the phenol resin, and it is difficult to produce a uniform cured product of the epoxy compound or the phenol resin and the soluble polyfunctional vinyl aromatic copolymer. Therefore, in addition to the disadvantage that the degree of freedom in designing the formulation is small and the toughness of the cured product is low, there are cases in which expansion or peeling occurs due to a high heat history in the vicinity of 280 ° C to 300 ° C.

另一方面，揭示了於專利文獻3及專利文獻4中揭示的可溶性多官能乙烯基芳香族共聚合物中可導入於主鏈包含苯基與雙鍵的、即由式（a2）所表示的結構，但實際上於專利文獻3及專利文獻4的實施例中揭示的共聚合物中，相對於式（a1）與式（a2）的合計，由式（a1）所表示的結構單元的莫耳分率為0.98～0.99，而由式（a2）所表示的結構只能以非常有限的量存在。On the other hand, in the soluble polyfunctional vinyl aromatic copolymer disclosed in Patent Document 3 and Patent Document 4, it is disclosed that the main chain includes a phenyl group and a double bond, that is, represented by the formula (a2). In the copolymer disclosed in the examples of Patent Document 3 and Patent Document 4, the structural unit represented by the formula (a1) is the same as the total of the formula (a1) and the formula (a2). The ear fraction is 0.98 to 0.99, and the structure represented by the formula (a2) can only exist in a very limited amount.

於專利文獻5中揭示有一種可溶性多官能乙烯基芳香族共聚合物，其是使二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）進行共聚合所獲得的共聚合物，於其末端基的一部分具有介隔醚鍵或硫醚鍵的鏈狀烴基或芳香族烴基。 但是，該可溶性多官能乙烯基芳香族共聚合物的韌性不足，因此於其硬化性組成物的硬化物中，無法獲得充分的力學性質，故於複合體硬化物中，存在層間剝離強度不足、可靠性下降等課題。另外，雖然記載有可使用酯化合物作為促進劑，但作為可使用的酯化合物而具體例示者為乙酸乙酯、丙酸甲酯等不具有向可溶性多官能乙烯基芳香族共聚合物的末端導入官能基的功能的酯化合物。因此，專利文獻5中揭示的可溶性多官能乙烯基芳香族共聚合物的末端基是含有源自具有醇性羥基的鏈狀烴化合物及芳香族烴化合物、以及具有硫醇性巰基的鏈狀烴化合物及芳香族烴化合物的介隔醚鍵或硫醚鍵的任一者的鏈狀烴基或芳香族烴基者。Patent Document 5 discloses a soluble polyfunctional vinyl aromatic copolymer which is a copolymer obtained by copolymerizing a divinyl aromatic compound (a) and a monovinyl aromatic compound (b). A part of the terminal group has a chain hydrocarbon group or an aromatic hydrocarbon group interposing an ether bond or a thioether bond. However, since the solubility of the soluble polyfunctional vinyl aromatic copolymer is insufficient, sufficient mechanical properties cannot be obtained in the cured product of the curable composition, so that the interlaminar peel strength is insufficient in the cured product of the composite. Problems such as reduced reliability. Further, although an ester compound can be used as an accelerator, as an ester compound which can be used, specifically, ethyl acetate, methyl propionate or the like is not introduced into the terminal end of the soluble polyfunctional vinyl aromatic copolymer. Functional ester compound of a functional group. Therefore, the terminal group of the soluble polyfunctional vinyl aromatic copolymer disclosed in Patent Document 5 contains a chain hydrocarbon compound derived from an alcoholic hydroxyl group and an aromatic hydrocarbon compound, and a chain hydrocarbon having a mercaptan thiol group. A chain hydrocarbon group or an aromatic hydrocarbon group in which any of an ether bond or a thioether bond is interposed between a compound and an aromatic hydrocarbon compound.

另外，揭示了於專利文獻5中揭示的可溶性多官能乙烯基芳香族共聚合物中可導入於主鏈包含苯基與雙鍵的、由式（a2）所表示的結構，但實際上於專利文獻5的實施例中揭示的共聚合物中，相對於式（a1）與式（a2）的合計，由式（a1）所表示的結構單元的莫耳分率為0.98～0.99，而由式（a2）所表示的結構只能以非常有限的量存在。Further, it is disclosed that the soluble polyfunctional vinyl aromatic copolymer disclosed in Patent Document 5 can be introduced into a structure represented by the formula (a2) in which a main chain includes a phenyl group and a double bond, but is actually a patent. In the copolymer disclosed in the examples of the literature 5, the molar fraction of the structural unit represented by the formula (a1) is 0.98 to 0.99 with respect to the total of the formula (a1) and the formula (a2). The structure represented by (a2) can only exist in a very limited amount.

於專利文獻6及專利文獻7中揭示有一種具有源自芳香族系醚化合物的末端基的多官能乙烯基芳香族共聚合物、及具有源自硫代(甲基)丙烯酸酯系化合物的末端基的可溶性多官能乙烯基芳香族共聚合物。但是，該些專利文獻6、專利文獻7中揭示的可溶性多官能乙烯基芳香族共聚合物雖然韌性得到改善，但存在如下的問題點：不具有伴隨近年來的資訊通信量的增加的高頻率帶中的低介電特性，無法應用於如尖端電氣·電子領域般的要求高功能且高度的電氣特性、熱特性·機械特性的領域。另外，於濕熱歷程後，該些可溶性多官能乙烯基芳香族共聚合物與玻璃布的界面的密接性下降，因此存在無法用於要求高度的可靠性的領域的基板材料這一缺點。 另外，並未揭示於專利文獻6、專利文獻7中揭示的可溶性多官能乙烯基芳香族共聚合物中可導入於主鏈包含苯基與雙鍵的、由式（a2）所表示的結構。Patent Document 6 and Patent Document 7 disclose a polyfunctional vinyl aromatic copolymer having a terminal group derived from an aromatic ether compound, and an end derived from a thio(meth)acrylate compound. a soluble polyfunctional vinyl aromatic copolymer. However, although the toughness of the soluble polyfunctional vinyl aromatic copolymer disclosed in Patent Document 6 and Patent Document 7 is improved, there is a problem that it does not have a high frequency accompanying an increase in information traffic in recent years. The low dielectric properties in the tape cannot be applied to fields requiring high functionality and high electrical, thermal, and mechanical properties such as in the field of advanced electrical and electronic fields. Further, after the wet heat history, the adhesion between the soluble polyfunctional vinyl aromatic copolymer and the interface of the glass cloth is lowered, so that there is a disadvantage that it cannot be used for a substrate material in a field requiring high reliability. Further, the soluble polyfunctional vinyl aromatic copolymer disclosed in Patent Document 6 and Patent Document 7 is not disclosed in the structure represented by the formula (a2) which can be introduced into the main chain and includes a phenyl group and a double bond.

於專利文獻8中揭示有一種硬化性樹脂組成物，其包括於兩末端具有乙烯基的聚苯醚寡聚物、與具有源自包含二乙烯基芳香族化合物及乙基乙烯基芳香族化合物的單量體的結構單元的多官能乙烯基芳香族共聚合物。但是，該使用可溶性多官能乙烯基芳香族共聚合物的硬化性樹脂組成物因層間剝離強度、鍍層剝離強度與濕熱歷程後的介電特性不足，故存在無法用作尖端電子機器領域中的基板材料這一缺點。Patent Document 8 discloses a curable resin composition comprising a polyphenylene ether oligomer having a vinyl group at both terminals, and having a divinyl aromatic compound and an ethyl vinyl aromatic compound derived therefrom. A monofunctional structural unit of a polyfunctional vinyl aromatic copolymer. However, the curable resin composition using the soluble polyfunctional vinyl aromatic copolymer is insufficient in dielectric properties after interlayer peel strength, plating peel strength, and wet heat history, and thus cannot be used as a substrate in the field of sophisticated electronic equipment. This shortcoming of materials.

於專利文獻9中揭示有一種硬化性樹脂組成物，其包括具有源自包含二乙烯基芳香族化合物及乙基乙烯基芳香族化合物的單量體的結構單元的多官能乙烯基芳香族共聚合物，與含有選自由環氧基、氰酸酯基、乙烯基、乙炔基、異氰酸酯基及羥基所組成的群組中的一種以上的官能基的熱硬化性樹脂。但是，該使用可溶性多官能乙烯基芳香族共聚合物的硬化性樹脂組成物因鍍敷性不足，故存在無法應用於要求高度的微細化的高功能的尖端技術領域這一問題點。 [現有技術文獻] [專利文獻]Patent Document 9 discloses a curable resin composition comprising a polyfunctional vinyl aromatic copolymer having a structural unit derived from a monomeric body comprising a divinyl aromatic compound and an ethyl vinyl aromatic compound. And a thermosetting resin containing one or more functional groups selected from the group consisting of an epoxy group, a cyanate group, a vinyl group, an ethynyl group, an isocyanate group, and a hydroxyl group. However, since the curable resin composition using the soluble polyfunctional vinyl aromatic copolymer is insufficient in plating property, there is a problem that it cannot be applied to a highly functional advanced technology field requiring a high degree of refinement. [Prior Art Document] [Patent Literature]

[專利文獻1]日本專利特開昭56-62808號公報 [專利文獻2]日本專利特開昭58-76411號公報 [專利文獻3]日本專利特開2004-123873號公報 [專利文獻4]日本專利特開2005-213443號公報 [專利文獻5]日本專利特開2007-332273號公報 [專利文獻6]日本專利特開2010-229263號公報 [專利文獻7]日本專利特開2010-209279號公報 [專利文獻8]WO2005/73264號公報 [專利文獻9]日本專利特開2006-274169號公報[Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. 2010-229273 (Patent Document 6) Japanese Patent Laid-Open No. 2010-229263 (Patent Document 7) Japanese Patent Laid-Open Publication No. 2010-209279 [Patent Document 8] WO2005/73264 (Patent Document 9) Japanese Patent Laid-Open Publication No. 2006-274169

考慮此種背景技術，本發明的目的在於提供一種具備伴隨近年來的資訊通信量的增加的高頻率帶中的低介電特性，可應用於要求高功能的電氣特性、熱特性·機械特性的尖端電氣·電子領域領域的材料、尤其是於作為電氣絕緣材料的積層體用途中有用的材料。 就該觀點而言，本發明的目的在於提供一種耐熱性、相容性、透明性及韌性得到改善的新型可溶性多官能乙烯基芳香族共聚合物、其製造方法及含有該共聚合物的硬化性組成物，進而目的在於提供一種包含該硬化性組成物的膜、進行硬化而獲得的硬化物、包含硬化性組成物與基材的硬化性複合材料、包含硬化物與金屬箔的積層體及帶有樹脂的銅箔。In view of such a background art, it is an object of the present invention to provide a low dielectric property in a high frequency band which is accompanied by an increase in the amount of information communication in recent years, and can be applied to electrical characteristics, thermal characteristics, and mechanical characteristics requiring high functions. Materials used in the field of cutting-edge electrical and electronic fields, especially materials useful as laminates for electrical insulating materials. In view of the above, an object of the present invention is to provide a novel soluble polyfunctional vinyl aromatic copolymer having improved heat resistance, compatibility, transparency and toughness, a process for producing the same, and hardening containing the same. Further, the object of the present invention is to provide a film comprising the curable composition, a cured product obtained by curing, a curable composite material comprising a curable composition and a substrate, a laminate comprising a cured product and a metal foil, and Copper foil with resin.

本發明者等人反覆努力研究的結果，發現使路易斯鹼性化合物與二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）一併於選擇性地生成伸乙烯基的含氧酸觸媒中調配並加以聚合，藉此一邊進行反應過程中生成乙烯基（伸乙烯基）的1,2-加成聚合，一邊藉由β-氫脫離反應而生成含有伸乙烯基的單元或含有伸乙烯基的末端基，可不使用鏈轉移劑地控制分子量，此種藉由聚合而獲得的共聚合物可解決所述課題，從而完成本發明。As a result of repeated efforts by the inventors of the present invention, it has been found that the Lewis basic compound is selectively combined with the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) to form an oxygen-containing vinyl group. By compounding and polymerizing in an acid catalyst, a 1,2-addition polymerization of a vinyl group (vinyl group) is formed during the reaction, and a unit containing a vinyl group is formed by a β-hydrogen detachment reaction or The terminal group containing a vinyl group can control the molecular weight without using a chain transfer agent, and such a copolymer obtained by polymerization can solve the above problems, thereby completing the present invention.

本發明是一種可溶性多官能乙烯基芳香族共聚合物，其是含有源自二乙烯基芳香族化合物（a）的結構單元及源自單乙烯基芳香族化合物（b）的結構單元的多官能乙烯基芳香族共聚合物，且特徵在於：源自二乙烯基芳香族化合物（a）的結構單元具有由下述式（a1）所表示的含有乙烯基的單元、由下述式（a2）所表示的含有伸乙烯基的單元及由下述式（a3）所表示的交聯結構單元以及由下述式（ta1）所表示的含有伸乙烯基的末端單元，且源自單乙烯基芳香族化合物（b）的結構單元具有由下述式（b1）所表示的結構單元及由下述式（tb1）所表示的含有伸乙烯基的末端單元，並且為溶劑可溶性、且具有聚合性；（式中，R1 表示碳數6～30的芳香族烴基）（式中，R1 的含義與式（a1）相同）（式中，R1 的含義與式（a1）相同）（式中，R1 的含義與式（a1）相同）（式中，R2 表示碳數6～30的芳香族烴基，R3 表示氫或碳數1～12的烴基）（式中，R2 、R3 的含義與式（b1）相同）。The present invention is a soluble polyfunctional vinyl aromatic copolymer which is a polyfunctional group containing a structural unit derived from a divinyl aromatic compound (a) and a structural unit derived from a monovinyl aromatic compound (b) a vinyl aromatic copolymer, characterized in that the structural unit derived from the divinyl aromatic compound (a) has a vinyl group-containing unit represented by the following formula (a1), and is represented by the following formula (a2) The unit containing a vinyl group and a crosslinked structural unit represented by the following formula (a3) and a terminal unit containing a vinyl group represented by the following formula (ta1), and derived from a monovinyl aromatic The structural unit of the group compound (b) has a structural unit represented by the following formula (b1) and a terminal group containing a vinyl group represented by the following formula (tb1), and is solvent-soluble and polymerizable; (wherein R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms) (wherein, R 1 has the same meaning as in formula (a1)) (wherein, R 1 has the same meaning as in formula (a1)) (wherein, R 1 has the same meaning as in formula (a1)) (wherein R 2 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms; and R 3 represents hydrogen or a hydrocarbon group having 1 to 12 carbon atoms) (wherein, R 2 and R 3 have the same meanings as in the formula (b1)).

本發明較佳為如申請專利範圍第1項所述的可溶性多官能乙烯基芳香族共聚合物，其含有源自二乙烯基芳香族化合物（a）的結構單元20莫耳%～95莫耳%，且由所述式（a1）、式（a2）、式（a3）、式（ta1）、式（b1）及式（tb1）所表示的結構單元的莫耳分率滿足下述式（1）及下述式（2），   0.2≦[（a1）+（a3）+（ta1）]/[（a1）+（a2）+（a3）+（b1）+（ta1）+（tb1）]≦0.9 ···（1） （ta1）/[（ta1）+（tb1）]＞0.2 ···（2）   數量平均分子量Mn為300～100,000，分子量分佈（Mw/Mn）為100.0以下，且可溶於甲苯、二甲苯、四氫呋喃、二氯乙烷或氯仿。The present invention is preferably a soluble polyfunctional vinyl aromatic copolymer according to claim 1, which comprises a structural unit derived from the divinyl aromatic compound (a) 20 mol% to 95 mol. %, and the molar fraction of the structural unit represented by the formula (a1), the formula (a2), the formula (a3), the formula (ta1), the formula (b1), and the formula (tb1) satisfies the following formula ( 1) and the following formula (2), 0.2≦[(a1)+(a3)+(ta1)]/[(a1)+(a2)+(a3)+(b1)+(ta1)+(tb1) ≦0.9 ···(1) (ta1)/[(ta1)+(tb1)]>0.2 (2) The number average molecular weight Mn is 300 to 100,000, and the molecular weight distribution (Mw/Mn) is 100.0 or less. It is soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.

本發明是一種可溶性多官能乙烯基芳香族共聚合物，其是於作為促進劑成分的路易斯鹼性化合物（c）的存在下，使用選自由無機酸、有機磺酸及過氯酸系化合物所組成的群組中的一種以上的觸媒（d），使二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）聚合而製造多官能乙烯基芳香族共聚合物的方法，且特徵在於：相對於二乙烯基芳香族化合物（a）與單乙烯基芳香族化合物（b）的合計100莫耳%，使用二乙烯基芳香族化合物（a）5莫耳%～95莫耳%、單乙烯基芳香族化合物（b）95莫耳%～5莫耳%，並且相對於所有單量體的合計100莫耳，使用路易斯鹼性化合物（c）0.005莫耳～500莫耳，使包含該些的聚合原料溶解於介電常數2.0～15.0的溶媒中製成均勻的溶液，於20℃～120℃的溫度下進行聚合而獲得。The present invention is a soluble polyfunctional vinyl aromatic copolymer which is selected from the group consisting of inorganic acids, organic sulfonic acids and perchloric acid compounds in the presence of a Lewis basic compound (c) as a promoter component. a method of producing a polyfunctional vinyl aromatic copolymer by polymerizing a divinyl aromatic compound (a) and a monovinyl aromatic compound (b) with one or more catalysts (d) in a group consisting of And characterized in that the divinyl aromatic compound (a) is used in an amount of from 5 mol% to 95 mol% based on 100 mol% of the total of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b). %, monovinyl aromatic compound (b) 95 mol% to 5 mol%, and using a Lewis basic compound (c) of 0.005 mol to 500 mol, relative to 100 mol of total of all single bodies. The polymerization raw material containing these is dissolved in a solvent having a dielectric constant of 2.0 to 15.0 to prepare a homogeneous solution, which is obtained by polymerization at a temperature of from 20 ° C to 120 ° C.

另外，本發明是所述可溶性多官能乙烯基芳香族共聚合物的製造方法，其是於作為促進劑成分的路易斯鹼性化合物（c）的存在下，使用選自由無機酸、有機磺酸及過氯酸系化合物所組成的群組中的一種以上的觸媒（d），使二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）聚合而製造可溶性多官能乙烯基芳香族共聚合物的方法，且特徵在於：相對於二乙烯基芳香族化合物（a）與單乙烯基芳香族化合物（b）的合計100莫耳%，使用二乙烯基芳香族化合物（a）5莫耳%～95莫耳%、單乙烯基芳香族化合物（b）95莫耳%～5莫耳%，並且相對於所有單量體的合計100莫耳，使用路易斯鹼性化合物（c）0.005莫耳～500莫耳，使包含該些的聚合原料溶解於介電常數2.0～15.0的溶媒中製成均勻的溶液，於20℃～120℃的溫度下進行聚合。Further, the present invention is a process for producing the soluble polyfunctional vinyl aromatic copolymer, which is selected from the group consisting of inorganic acids, organic sulfonic acids, and in the presence of a Lewis basic compound (c) as a promoter component. One or more catalysts (d) in the group consisting of perchloric acid-based compounds polymerize the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) to produce a soluble polyfunctional vinyl aromatic A method of a group co-polymer, characterized by using a divinyl aromatic compound (a) 5 with respect to 100 mol% of the total of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) Molar % to 95 mol %, monovinyl aromatic compound (b) 95 mol % to 5 mol %, and using a Lewis basic compound (c) 0.005 with respect to 100 mol of total of all the single bodies The molar amount is from 500 to 500 m, and the polymerization raw material containing the above is dissolved in a solvent having a dielectric constant of 2.0 to 15.0 to prepare a homogeneous solution, and polymerization is carried out at a temperature of from 20 ° C to 120 ° C.

於所述可溶性多官能乙烯基芳香族共聚合物的製造方法中，理想的是相對於路易斯鹼性化合物（c）1莫耳，於0.001莫耳～10莫耳的範圍內使用觸媒（d）。In the method for producing the soluble polyfunctional vinyl aromatic copolymer, it is preferred to use a catalyst in the range of 0.001 mol to 10 mol with respect to the Lewis basic compound (c) 1 mol. ).

另外，本發明是一種硬化性組成物，其特徵在於含有：所述可溶性多官能乙烯基芳香族共聚合物與自由基聚合起始劑。Further, the present invention is a curable composition comprising: the soluble polyfunctional vinyl aromatic copolymer and a radical polymerization initiator.

所述硬化性組成物可更含有熱硬化性樹脂或熱塑性樹脂。The curable composition may further contain a thermosetting resin or a thermoplastic resin.

該情況下，熱硬化性樹脂較佳為改質聚苯醚（XC）。另外，硬化性樹脂亦可為選自由1分子中具有2個以上的環氧基與芳香族結構的環氧樹脂、1分子中具有2個以上的環氧基與氰脲酸酯結構的環氧樹脂及/或1分子中具有2個以上的環氧基與脂環結構的環氧樹脂所組成的群組中的一種以上的環氧樹脂（XD）。另外，亦可為分子中具有1個以上的不飽和烴基的一種以上的乙烯基化合物（XF）。In this case, the thermosetting resin is preferably modified polyphenylene ether (XC). Further, the curable resin may be an epoxy resin having two or more epoxy groups and an aromatic structure in one molecule, and an epoxy having two or more epoxy groups and cyanurate structures in one molecule. One or more epoxy resins (XD) in a group consisting of a resin and/or an epoxy resin having two or more epoxy groups and an alicyclic structure in one molecule. Further, it may be one or more vinyl compounds (XF) having one or more unsaturated hydrocarbon groups in the molecule.

進而，本發明是一種使所述硬化性組成物硬化而成的硬化物、或使所述硬化性組成物成形為膜狀而成的膜。Further, the present invention is a cured product obtained by curing the curable composition or a film obtained by molding the curable composition into a film shape.

進而，本發明是一種硬化性複合材料，其包含所述硬化性組成物與基材，且特徵在於：以5重量%～90重量%的比例含有基材，另外，本發明是一種硬化複合材料，其特徵在於：使所述硬化性複合材料硬化而獲得，而且，本發明是一種積層體，其特徵在於：包括所述硬化複合材料的層與金屬箔層。Further, the present invention is a curable composite material comprising the curable composition and a substrate, and characterized in that the substrate is contained in a ratio of 5% by weight to 90% by weight, and the present invention is a hardened composite material. It is characterized in that the curable composite material is obtained by hardening, and the present invention is a laminate comprising a layer of the hardened composite material and a metal foil layer.

另外，本發明是一種帶有樹脂的金屬箔，其特徵在於：於金屬箔的一面上具有由所述硬化性組成物形成的膜，或者本發明是一種電路基板材料用清漆，其是使所述硬化性組成物溶解於有機溶劑中而成。Further, the present invention is a metal foil with a resin, characterized in that it has a film formed of the curable composition on one side of the metal foil, or the present invention is a varnish for a circuit board material, which is a The curable composition is dissolved in an organic solvent.

自本發明的可溶性多官能乙烯基芳香族共聚合物或包含其的材料所獲得的硬化物的耐熱性、相容性、透明性及韌性得到改善。另外，根據本發明的製造方法，可高效率地製造所述共聚合物。另外，藉由將本發明的可溶性多官能乙烯基芳香族共聚合物用作硬化性化合物，於分子內具有分子尺寸大的自由體積、且極性基少，故可獲得高度的低介電特性的硬化物，並可同時實現良好的黏著性、鍍敷性與濕熱歷程後的介電損耗正切特性。The heat resistance, compatibility, transparency, and toughness of the cured product obtained from the soluble polyfunctional vinyl aromatic copolymer of the present invention or a material containing the same are improved. Further, according to the production method of the present invention, the copolymer can be efficiently produced. Further, by using the soluble polyfunctional vinyl aromatic copolymer of the present invention as a curable compound, it has a large free molecular volume in a molecule and a small number of polar groups, so that a high degree of low dielectric properties can be obtained. Hardened material, and can achieve good adhesion, plating property and dielectric loss tangent after wet heat history.

本發明的可溶性多官能乙烯基芳香族共聚合物是於作為促進劑成分的路易斯鹼性化合物（c）的存在下，使用選自由無機酸、有機磺酸及過氯酸系化合物所組成的群組中的一種以上的觸媒（d），將包含二乙烯基芳香族化合物（a）及乙基乙烯基芳香族化合物（b）的單量體聚合而獲得的多官能乙烯基芳香族共聚合物，於所述共聚合物中具有由所述式（a1）～式（a3）所表示的源自二乙烯基芳香族化合物（a）的結構單元及由所述式（b1）所表示的源自乙基乙烯基芳香族化合物（b）的結構單元。另外，於所述共聚合物的末端具有由所述式（ta1）所表示的源自二乙烯基芳香族化合物（a）的含有伸乙烯基的末端基，或者由所述式（tb1）所表示的源自單乙烯基芳香族化合物（b）的含有伸乙烯基的末端基。而且，可溶於甲苯、二甲苯、四氫呋喃、二氯乙烷或氯仿。本發明的可溶性多官能乙烯基芳香族共聚合物於不產生誤解的情況下簡稱為可溶性多官能乙烯基芳香族共聚合物、或者僅簡稱為共聚合物。The soluble polyfunctional vinyl aromatic copolymer of the present invention is a group selected from the group consisting of inorganic acids, organic sulfonic acids, and perchloric acid compounds in the presence of a Lewis basic compound (c) as a promoter component. One or more catalysts (d) in the group, a polyfunctional vinyl aromatic copolymer obtained by polymerization of a monomeric body comprising a divinyl aromatic compound (a) and an ethyl vinyl aromatic compound (b) And a structural unit derived from the divinyl aromatic compound (a) represented by the formula (a1) to the formula (a3) and represented by the formula (b1) in the copolymer A structural unit derived from an ethyl vinyl aromatic compound (b). Further, at the end of the copolymer, there is a vinyl group-containing terminal group derived from the divinyl aromatic compound (a) represented by the formula (ta1), or by the formula (tb1) The vinyl group-containing terminal group derived from the monovinyl aromatic compound (b) is represented. Moreover, it is soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. The soluble polyfunctional vinyl aromatic copolymer of the present invention is simply referred to as a soluble polyfunctional vinyl aromatic copolymer, or simply a copolymer, without misunderstanding.

本發明的可溶性多官能乙烯基芳香族共聚合物於共聚合物中或末端具有源自二乙烯基芳香族化合物（a）的結構單元及源自乙基乙烯基芳香族化合物（b）的結構單元。由式（a1）、式（a2）、式（a3）、式（ta1）、式（b1）及式（tb1）所表示的結構單元的莫耳分率較佳為滿足下述式（1）。   0.2≦[（a1）+（a3）+（ta1）]/[（a1）+（a2）+（a3）+（b1）+（ta1）+（tb1）]≦0.9 ···（1）   所述式（1）的意義如下所述。若對反應性進行比較，則乙烯基比伸乙烯基高。（a1）與（ta1）的結構單元中包含側乙烯基。另外，（a3）的結構單元可視為於側乙烯基進行反應後。因此，規定（a1）+（a3）+（ta1）的合計莫耳分率。再者，（ta1）中亦包含伸乙烯基，但乙烯基處於優勢地位。 換言之，於製成硬化性樹脂組成物時，乙烯基（包含受到反應的側乙烯基）容易受到硬化反應。該結構單元為（a1）、（a3）及（ta1）。另一方面，於製成硬化性樹脂組成物時，伸乙烯基難以受到硬化反應。該結構單元為（a2）、（ta1）及（tb2 1）。另外，單(乙基)乙烯基芳香族化合物的單體的乙烯基以外的取代基於在聚合反應中受到1次反應後，不會受到除此以外的反應。該結構單元為（b1）及（tb1）。 若由所述式（1）所表示的合計莫耳分率超過0.9，則分子量增大，成形性下降。另一方面，若未滿0.2，則由（a1）所表示的側乙烯基的比例變少，內部烯烴結構成為主體，因此耐熱性及硬化性下降。更佳為0.5～0.7的範圍。The soluble polyfunctional vinyl aromatic copolymer of the present invention has a structural unit derived from the divinyl aromatic compound (a) and a structure derived from the ethyl vinyl aromatic compound (b) in or at the terminal of the copolymer. unit. The molar fraction of the structural unit represented by the formula (a1), the formula (a2), the formula (a3), the formula (ta1), the formula (b1), and the formula (tb1) preferably satisfies the following formula (1). . 0.2≦[(a1)+(a3)+(ta1)]/[(a1)+(a2)+(a3)+(b1)+(ta1)+(tb1)]≦0.9 ···(1) The meaning of the formula (1) is as follows. If the reactivity is compared, the vinyl group is higher than the vinyl group. The structural unit of (a1) and (ta1) contains a side vinyl group. Further, the structural unit of (a3) can be regarded as a reaction after the side vinyl group is reacted. Therefore, the total molar fraction of (a1) + (a3) + (ta1) is specified. Furthermore, (ta1) also contains vinyl, but vinyl is in an advantageous position. In other words, when the curable resin composition is formed, the vinyl group (including the side vinyl group subjected to the reaction) is easily subjected to the hardening reaction. The structural units are (a1), (a3), and (ta1). On the other hand, when a curable resin composition is produced, it is difficult for the vinyl group to undergo a hardening reaction. The structural units are (a2), (ta1), and (tb2) 1). Further, the substitution other than the vinyl group of the monomer of the mono(ethyl)vinyl aromatic compound is not subjected to the other reaction after being subjected to the primary reaction in the polymerization reaction. The structural units are (b1) and (tb1). When the total molar fraction represented by the above formula (1) exceeds 0.9, the molecular weight increases and the formability decreases. On the other hand, when it is less than 0.2, the ratio of the side vinyl group represented by (a1) becomes small, and the internal olefin structure becomes a main body, and heat resistance and hardenability fall. More preferably, it is in the range of 0.5 to 0.7.

另外，末端基的莫耳分率較佳為滿足下述。   （ta1）/[（ta1）+（tb1）]＞0.2 ···（2）   藉由由所述式（2）所表示的末端基的莫耳分率大於0.2，本發明的共聚合物具有良好的硬化性。另一方面，若由所述式（2）所表示的末端基的莫耳分率為0.2以下，則存在硬化性下降的傾向。更佳的下限為0.25，進而更佳的下限為0.40，進一步更佳的下限為0.50。另一方面，較佳的上限為0.95，更佳的上限為0.90，進而更佳的上限為0.85。若由所述式（1）所表示的合計莫耳分率超過0.95，則存在硬化物的成形加工性下降的傾向。Further, the molar fraction of the terminal group preferably satisfies the following. (ta1)/[(ta1)+(tb1)]>0.2 (2) The copolymer of the present invention has a molar fraction of the terminal group represented by the formula (2) of more than 0.2 Good hardenability. On the other hand, when the molar fraction of the terminal group represented by the above formula (2) is 0.2 or less, the curability tends to be lowered. A more preferred lower limit is 0.25, and a more preferred lower limit is 0.40, and a still more preferred lower limit is 0.50. On the other hand, the upper limit is preferably 0.95, the upper limit is more preferably 0.90, and the upper limit is more preferably 0.85. When the total molar fraction represented by the above formula (1) exceeds 0.95, the formability of the cured product tends to decrease.

含有乙烯基的單元的莫耳分率（a1）/[（a1）+（a2）+（a3）]較佳為0.2以上、未滿0.9。更佳為0.25～0.85，進而更佳為0.3～0.8。藉由以滿足所述關係的方式導入本發明的共聚合物的結構單元，可製成為低介電損耗正切、韌性高，且具有優異的耐熱性、與其他樹脂的相容性優異，透明性及成形加工性亦優異的樹脂組成物。若所述式（a1）的莫耳分率小於0.2，則耐熱性及成形加工性下降，若大於0.9，則存在無法維持與其他樹脂的相容性且對微細的配線圖案的樹脂填充性亦下降的傾向。 另一方面，含有伸乙烯基的單元（a2）及交聯結構單元（a3）的合計莫耳分率[（a2）+（a3）]/[（a1）+（a2）+（a3）]必須為0.1以上、未滿0.8。較佳為0.15～0.75，更佳為0.2～0.8。藉由以滿足所述關係的方式導入本發明的共聚合物的結構單元，可製成為低介電損耗正切、韌性高，且具有優異的耐熱性、與其他樹脂的相容性優異，透明性及成形加工性亦優異的樹脂組成物。若式（a2）及式（a3）的莫耳分率小於0.1，則存在成形加工性下降且對微細的配線圖案的樹脂填充性亦下降的傾向。另外，若大於0.8，則存在硬化反應性下降且耐熱性亦下降的傾向。The molar fraction (a1) / [(a1) + (a2) + (a3)] of the unit containing a vinyl group is preferably 0.2 or more and less than 0.9. More preferably, it is 0.25 to 0.85, and still more preferably 0.3 to 0.8. By introducing the structural unit of the copolymer of the present invention in such a manner as to satisfy the relationship, it is possible to obtain a low dielectric loss tangent, high toughness, excellent heat resistance, excellent compatibility with other resins, and transparency. And a resin composition excellent in moldability. When the molar fraction of the formula (a1) is less than 0.2, heat resistance and moldability are deteriorated, and if it is more than 0.9, compatibility with other resins cannot be maintained, and resin filling property to a fine wiring pattern is also The tendency to decline. On the other hand, the total molar fraction of the unit (a2) containing the vinyl group and the crosslinked structural unit (a3) [(a2) + (a3)] / [(a1) + (a2) + (a3)] Must be 0.1 or more and less than 0.8. It is preferably from 0.15 to 0.75, more preferably from 0.2 to 0.8. By introducing the structural unit of the copolymer of the present invention in such a manner as to satisfy the relationship, it is possible to obtain a low dielectric loss tangent, high toughness, excellent heat resistance, excellent compatibility with other resins, and transparency. And a resin composition excellent in moldability. When the molar fraction of the formula (a2) and the formula (a3) is less than 0.1, the moldability is lowered and the resin filling property to the fine wiring pattern is also lowered. On the other hand, when it is more than 0.8, the curing reactivity is lowered and the heat resistance is also lowered.

進而，本發明的可溶性多官能乙烯基芳香族共聚合物包含源自二乙烯基芳香族化合物（a）的結構單元（A）及源自單乙烯基芳香族化合物（b）的結構單元（B），結構單元（A）的莫耳分率（A）/{（A）+（B）}較佳為0.2～0.95，更佳為0.4～0.90，進而更佳為0.50莫耳～0.85莫耳的範圍。結構單元（B）的莫耳分率（B）/{（A）+（B）}是根據結構單元（A）的莫耳分率來計算。 就其他觀點而言，相對於所有結構單元的合計100莫耳%，較佳為包含結構單元（A）20莫耳%～950 莫耳%。源自二乙烯基芳香族化合物（a）的結構單元（A）包含作為用以表現耐熱性的交聯成分的乙烯基，另一方面，源自單乙烯基芳香族化合物（b）的結構單元（B）不具有參與硬化反應的乙烯基，因此賦予成形性等。因此，若結構單元（A）的莫耳分率不滿0.2，則硬化物的耐熱性不充分，若超過0.95，則成形加工性下降。即，若結構單元（A）的含量少，則伴隨交聯密度的下降，耐熱性下降，因此，於受到光導波管形成製程等中的熱歷程時，難以維持良好的形狀，若過多，則蝕刻特性惡化，難以形成微細結構優異的形狀的光導波管等。Further, the soluble polyfunctional vinyl aromatic copolymer of the present invention comprises a structural unit derived from the divinyl aromatic compound (a) (A) and a structural unit derived from the monovinyl aromatic compound (b) (B) The molar fraction (A) / {(A) + (B)} of the structural unit (A) is preferably from 0.2 to 0.95, more preferably from 0.4 to 0.90, still more preferably from 0.50 to 0.85 mol. The scope. The molar fraction (B) / {(A) + (B)} of the structural unit (B) is calculated based on the molar fraction of the structural unit (A). From other points of view, the total of 100 mol% relative to all structural units, preferably including structural unit (A) 20 mol% to 950 Moer%. The structural unit (A) derived from the divinyl aromatic compound (a) contains a vinyl group as a crosslinking component for expressing heat resistance, and on the other hand, a structural unit derived from the monovinyl aromatic compound (b) (B) Does not have a vinyl group which participates in a hardening reaction, and therefore imparts formability and the like. Therefore, when the molar fraction of the structural unit (A) is less than 0.2, the heat resistance of the cured product is insufficient, and when it exceeds 0.95, the moldability is lowered. In other words, when the content of the structural unit (A) is small, the heat resistance is lowered as the crosslinking density is lowered. Therefore, it is difficult to maintain a good shape when subjected to a heat history in the optical waveguide forming process or the like. The etching characteristics are deteriorated, and it is difficult to form an optical waveguide or the like having a shape excellent in fine structure.

具有1個乙烯基或伸乙烯基的結構單元，例如單元（a1）、單元（a2）對共聚合物賦予聚合性，使共聚合物變成多官能來作為硬化性樹脂。作為不具有乙烯基或伸乙烯基的結構單元的單元（a3）賦予交聯結構，增加分支度，但若交聯過度進行，則硬化而變成溶劑不溶性，因此必須存在不參與交聯的單元（a1）及單元（a2）。於本發明中，包含反應過程中生成的含有伸乙烯基的單元（a2）或含有伸乙烯基的末端基（ta1）、含有伸乙烯基的末端基（tb1）作為必需成分。A structural unit having one vinyl group or a vinyl group, for example, the unit (a1) and the unit (a2) impart polymerizability to the copolymer, and the copolymer becomes polyfunctional as a curable resin. The unit (a3) which is a structural unit having no vinyl group or vinyl group imparts a crosslinked structure and increases the degree of branching. However, if the crosslinking is excessively carried out, it hardens to become solvent-insoluble, and therefore it is necessary to have a unit which does not participate in crosslinking ( A1) and unit (a2). In the present invention, the vinyl group-containing unit (a2) or the vinyl group-containing terminal group (ta1) and the vinyl group-containing terminal group (tb1) which are formed during the reaction are contained as essential components.

相對於共聚合物中的所有結構單元的合計100莫耳%，具有源自乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的乙烯基或伸乙烯基的不飽和烴基的結構單元、即由式（a1）、式（a2）所表示的含有不飽和基的結構單元以及由式（ta1）、式（tb1）所表示的含有不飽和基的末端基的合計莫耳%較佳為40.0莫耳%～80.0莫耳%，更佳為50.0莫耳%～70.0莫耳%。100 parts by mole of all structural units in the copolymer, having a vinyl group or a vinyl group-derived unsaturated hydrocarbon group derived from the vinyl aromatic compound (a) and the monovinyl aromatic compound (b) The structural unit, that is, the structural unit containing an unsaturated group represented by the formula (a1) and the formula (a2), and the total molar % of the terminal group containing an unsaturated group represented by the formula (ta1) and the formula (tb1) It is preferably from 40.0% by mole to 80.0% by mole, more preferably from 50.0% by mole to 70.0% by mole.

於所述各式（a1）、式（a2）、式（a3）及式（ta1）中，R1 表示碳數6～30的芳香族烴基，但該些源自二乙烯基芳香族化合物（a），因此根據其說明來理解。具體而言，R1 較佳為碳數6～12的芳香族烴基，更佳為伸苯基、聯伸苯基或伸萘基。另外，於式（b1）及式（tb1）中，R2 表示碳數6～30的芳香族烴基，R3 表示氫或碳數1～12的烴基，但該些源自單乙烯基芳香族化合物（b），因此根據其說明來理解。具體而言，R2 較佳為碳數6～12的芳香族烴基，更佳為伸苯基、聯伸苯基或伸萘基。另外，R3 較佳為氫或碳數1～12的飽和烴基，更佳為氫或碳數1～6的飽和烴基，進而更佳為氫或碳數1～3的飽和烴基。In the above formulas (a1), (a2), (a3) and (ta1), R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, but these are derived from a divinyl aromatic compound ( a), so understand it according to its description. Specifically, R 1 is preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a stretching phenyl group, a stretching phenyl group or a stretching naphthyl group. Further, in the formulae (b1) and (tb1), R 2 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, and R 3 represents hydrogen or a hydrocarbon group having 1 to 12 carbon atoms, but these are derived from a monovinyl aromatic group. Compound (b) is therefore understood in accordance with the description thereof. Specifically, R 2 is preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a stretched phenyl group, a stretched phenyl group or an extended naphthyl group. Further, R 3 is preferably hydrogen or a saturated hydrocarbon group having 1 to 12 carbon atoms, more preferably hydrogen or a saturated hydrocarbon group having 1 to 6 carbon atoms, still more preferably hydrogen or a saturated hydrocarbon group having 1 to 3 carbon atoms.

本發明的可溶性多官能乙烯基芳香族共聚合物的Mn（此處，Mn是使用凝膠滲透層析法所測定的標準聚苯乙烯換算的數量平均分子量）為300～100,000，較佳為400～50,000，進而更佳為500～10,000。若Mn未滿300，則共聚合物中所包含的單官能的共聚合物的量增加，因此硬化物的耐熱性下降，另一方面，若Mn超過100,000，則容易生成凝膠、且黏度變高，因此導致成形加工性下降，故而欠佳。分子量分佈（Mw/Mn）的值為100.0以下，較佳為50.0以下，更佳為1.5～30.0。最佳為2.0～20.0。若Mw/Mn超過100.0，則產生共聚合物的加工特性惡化、產生凝膠等問題點。The Mn of the soluble polyfunctional vinyl aromatic copolymer of the present invention (here, Mn is a standard polystyrene-equivalent number average molecular weight measured by gel permeation chromatography) is 300 to 100,000, preferably 400. ～50,000, and more preferably 500 to 10,000. When Mn is less than 300, the amount of the monofunctional copolymer contained in the copolymer increases, so that the heat resistance of the cured product is lowered. On the other hand, when Mn exceeds 100,000, gelation is easily formed and viscosity is changed. It is high, and thus the formability is lowered, so that it is not preferable. The value of the molecular weight distribution (Mw/Mn) is 100.0 or less, preferably 50.0 or less, more preferably 1.5 to 30.0. The best is 2.0 to 20.0. When Mw/Mn exceeds 100.0, problems such as deterioration of processing characteristics of the copolymer and gelation occur.

本發明的可溶性多官能乙烯基芳香族共聚合物可溶於選自甲苯、二甲苯、四氫呋喃、二氯乙烷或氯仿中的溶劑中，有利的是可溶於所述溶劑的任一者中。此處，所謂可溶於溶劑中，是指於25℃下，在溶劑100 g中溶解5 g以上，較佳為10 g以上。由於是可溶於溶劑中的多官能的共聚合物，因此必須為二乙烯基苯的乙烯基的一部分不進行交聯而殘存，且為適度的交聯度。聚合方法將後述。The soluble polyfunctional vinyl aromatic copolymer of the present invention is soluble in a solvent selected from the group consisting of toluene, xylene, tetrahydrofuran, dichloroethane or chloroform, and is advantageously soluble in any of the solvents . Here, the term "soluble in a solvent" means that 5 g or more, preferably 10 g or more, is dissolved in 100 g of a solvent at 25 ° C. Since it is a polyfunctional copolymer which is soluble in a solvent, it is necessary that a part of the vinyl group of divinylbenzene does not crosslink and remains, and it is moderate degree of crosslinking. The polymerization method will be described later.

本發明的可溶性多官能乙烯基芳香族共聚合物為具有由所述式（a1）、式（a2）、式（a3）及式（b1）所表示的結構單元以及由式（ta1）及式（tb1）所表示的末端基的共聚合物，因此對於主鏈具有剛性的醚系化合物及環氧系化合物的相容性高。因此，當使其與具有剛性結構的硬化型醚系化合物及環氧系化合物的硬化性樹脂組成物硬化時，成為均勻的硬化性或透明性優異者。The soluble polyfunctional vinyl aromatic copolymer of the present invention has a structural unit represented by the formula (a1), the formula (a2), the formula (a3) and the formula (b1), and a formula (ta1) and a formula Since the terminal group-based copolymer represented by (tb1) is compatible with the ether-based compound having an rigidity in the main chain and the epoxy-based compound. Therefore, when it is cured with a curable resin composition having a rigid structure of a hardening type ether compound and an epoxy compound, it is excellent in uniform hardenability or transparency.

繼而，對可有利地製造可溶性多官能乙烯基芳香族共聚合物的製造方法進行說明。Next, a method of producing a soluble polyfunctional vinyl aromatic copolymer which can be advantageously produced will be described.

較佳為可於作為促進劑成分的路易斯鹼性化合物（c）的存在下，使用選自由無機酸、有機磺酸及過氯酸系化合物所組成的群組中的一種以上的觸媒（d），使二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）反應而製造共聚合物。It is preferred to use one or more kinds of catalysts selected from the group consisting of inorganic acids, organic sulfonic acids, and perchloric acid compounds in the presence of the Lewis basic compound (c) as a promoter component. The divinyl aromatic compound (a) and the monovinyl aromatic compound (b) are reacted to produce a copolymer.

二乙烯基芳香族化合物（a）使共聚合物進行分支而變成多官能，並且於使共聚合物熱硬化時作為用以使耐熱性顯現的交聯成分發揮重要的作用。作為二乙烯基芳香族化合物（a）的例子，可較佳地使用二乙烯基苯（包含各異構體）、二乙烯基萘（包含各異構體）、二乙烯基聯苯（包含各異構體），但並不限定於該些化合物。另外，該些化合物可單獨使用、或將兩種以上組合使用。就成形加工性的觀點而言，更佳為二乙烯基苯（間體、對體或該些的異構體混合物）。The divinyl aromatic compound (a) branches into a polyfunctional group, and when the copolymer is thermally cured, it plays an important role as a crosslinking component for exhibiting heat resistance. As an example of the divinyl aromatic compound (a), divinylbenzene (including each isomer), divinylnaphthalene (including each isomer), and divinylbiphenyl (including each) can be preferably used. Isomers), but are not limited to these compounds. Further, these compounds may be used singly or in combination of two or more. From the viewpoint of mold processability, divinylbenzene (intermediate, parameric or a mixture of such isomers) is more preferable.

單乙烯基芳香族化合物（b）改善共聚合物的溶劑可溶性及加工性。作為單乙烯基芳香族化合物（b）的例子，有核烷基取代乙基乙烯基芳香族化合物、α-烷基取代乙基乙烯基芳香族化合物、β-烷基取代乙基乙烯基芳香族化合物、烷氧基取代乙基乙烯基芳香族化合物等，但並不受該些化合物限制。為了防止共聚合物的膠化，改善對於溶媒的溶解性、加工性，就成本及獲得的容易性的觀點而言，可特佳地使用乙基乙烯基苯（包含各異構體）、乙基乙烯基聯苯（包含各異構體）及乙基乙烯基萘（包含各異構體）。就介電特性與成本的觀點而言，更佳為乙基乙烯基苯（間體、對體或該些的異構體混合物）。The monovinyl aromatic compound (b) improves the solvent solubility and processability of the copolymer. Examples of the monovinyl aromatic compound (b) include a nucleus alkyl-substituted ethylvinyl aromatic compound, an α-alkyl-substituted ethylvinyl aromatic compound, and a β-alkyl-substituted ethylvinyl aromatic compound. A compound, an alkoxy-substituted ethylvinyl aromatic compound or the like is not limited by these compounds. In order to prevent gelation of the copolymer and improve solubility and processability to the solvent, ethylvinylbenzene (including each isomer) and B can be particularly preferably used from the viewpoint of cost and ease of availability. Vinylbiphenyl (containing each isomer) and ethylvinylnaphthalene (including each isomer). More preferably, it is ethylvinylbenzene (intermediate, parameric or a mixture of such isomers) from the viewpoint of dielectric properties and cost.

另外，於共聚合物的製造方法中，於無損本發明的效果的範圍內，除二乙烯基芳香族化合物（a）、單乙烯基芳香族化合物（b）以外，可使用三乙烯基芳香族化合物、三乙烯基脂肪族化合物或二乙烯基脂肪族化合物及單乙烯基脂肪族化合物等其他單量體（e），並將該些單元導入至共聚合物中。Further, in the method for producing a copolymer, trivinyl aromatic can be used in addition to the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) insofar as the effects of the present invention are not impaired. Other monoliths (e) such as a compound, a trivinyl aliphatic compound or a divinyl aliphatic compound, and a monovinyl aliphatic compound, and these units are introduced into the copolymer.

作為其他單量體（e）的具體例，可列舉1,3,5-三乙烯基苯、1,3,5-三乙烯基萘、1,2,4-三乙烯基環己烷、乙二醇二丙烯酸酯、丁二烯等，但並不受該些化合物限制。該些化合物可單獨使用、或將兩種以上組合使用。其他單量體（e）以於未滿所有單量體的30莫耳%的範圍內使用為宜。藉此，相對於共聚合物中的結構單元的總量，將源自其他單量體成分（e）的結構單元設為未滿30莫耳%的範圍內。Specific examples of the other monomer (e) include 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-trivinylcyclohexane, and B. Diol diacrylate, butadiene, etc., but not limited by these compounds. These compounds may be used singly or in combination of two or more. Other monoliths (e) are preferably used within a range of 30 mol% less than all of the monoliths. Thereby, the structural unit derived from the other monomer component (e) is set to be less than 30 mol% with respect to the total amount of the structural unit in the copolymer.

關於作為促進劑成分的路易斯鹼性化合物（c）的具體例，可列舉選自由以下化合物所組成的群組中的一種以上的路易斯鹼性化合物（c），所述化合物為1）乙酸乙酯、乙酸丁酯、乙酸苯酯、丙酸甲酯等酯系化合物、2）巰基丙酸甲酯、巰基丙酸乙酯等硫酯系化合物、3）甲基乙基酮、甲基異丁基酮、二苯甲酮等酮系化合物、4）甲基胺、乙基胺、丙基胺、丁基胺、環己基胺、甲基乙基胺、二甲基胺、二乙基胺、二丙基胺、二丁基胺等胺系化合物、5）二乙基醚、四氫呋喃等醚系化合物、6）二乙基硫醚、二苯基硫醚等硫醚系化合物、7）三丙基膦、三丁基膦、三己基膦、三環己基膦、三辛基膦、乙烯基膦、丙烯基膦、環己烯基膦、二烯基膦、三烯基膦等膦系化合物。該些之中，就與（d）成分的觸媒相乘地作用，並可容易地控制聚合速度及聚合物的分子量分佈的方面而言，可較佳地使用酯系化合物及酮系化合物。Specific examples of the Lewis basic compound (c) as a promoter component include one or more Lewis basic compounds (c) selected from the group consisting of 1) ethyl acetate. , an ester compound such as butyl acetate, phenyl acetate or methyl propionate; 2) a thioester compound such as methyl mercaptopropionate or ethyl mercaptopropionate; 3) methyl ethyl ketone or methyl isobutyl a ketone compound such as a ketone or a benzophenone; 4) a methylamine, an ethylamine, a propylamine, a butylamine, a cyclohexylamine, a methylethylamine, a dimethylamine, a diethylamine, and a An amine compound such as propylamine or dibutylamine; 5) an ether compound such as diethyl ether or tetrahydrofuran; 6) a thioether compound such as diethyl sulfide or diphenyl sulfide; and 7) tripropyl group. A phosphine-based compound such as a phosphine, a tributylphosphine, a trihexylphosphine, a tricyclohexylphosphine, a trioctylphosphine, a vinylphosphine, a propenylphosphine, a cyclohexenylphosphine, a dienylphosphine or a trialenylphosphine. Among these, an ester compound and a ketone compound can be preferably used in terms of multiplying the catalyst of the component (d) and easily controlling the polymerization rate and the molecular weight distribution of the polymer.

作為促進劑成分的路易斯鹼性化合物（c）為電子賦予性，於聚合反應時，藉由配位於作為聚合活性種的碳陽離子種的β位的氫，而控制觸媒（d）與β-氫之間的相互作用，調節β-氫脫離反應與乙烯基的1,2-加成反應間的相對反應頻率。因此，藉由添加路易斯鹼性化合物（c），本發明的可溶性多官能乙烯基芳香族共聚合物可廣泛地控制源自二乙烯基芳香族化合物及乙基乙烯基芳香族化合物的由式（a1）、式（a2）、式（a3）及式（b1）所表示的結構單元、以及由式（ta1）及式（tb1）所表示的末端基的存在比率。即，路易斯鹼性化合物（c）為如下化合物，所述化合物可控制由式（a1）、式（a2）、式（a3）及式（b1）所表示的結構單元、以及由式（ta1）及式（tb1）所表示的末端基的存在比率，可賦予共聚合物的耐熱性、韌性、低介電性等功能。The Lewis basic compound (c) as a promoter component is electron-donating, and at the time of polymerization, the catalyst (d) and β- are controlled by arranging hydrogen at the β-position of the carbocation species as a polymerization active species. The interaction between hydrogen regulates the relative reaction frequency between the β-hydrogen detachment reaction and the vinyl 1,2-addition reaction. Therefore, by adding the Lewis basic compound (c), the soluble polyfunctional vinyl aromatic copolymer of the present invention can broadly control the formula derived from the divinyl aromatic compound and the ethyl vinyl aromatic compound ( A1), the structural unit represented by the formula (a2), the formula (a3), and the formula (b1), and the existence ratio of the terminal group represented by the formula (ta1) and the formula (tb1). That is, the Lewis basic compound (c) is a compound which can control the structural unit represented by the formula (a1), the formula (a2), the formula (a3), and the formula (b1), and the formula (ta1) The ratio of the terminal groups represented by the formula (tb1) can impart functions such as heat resistance, toughness, and low dielectric properties of the copolymer.

以下示出此種反應的一例。 An example of such a reaction is shown below.

作為路易斯鹼性化合物（c），就反應性、獲得的容易性、硬化物的耐熱性的觀點而言，可較佳地使用乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸苯酯及甲基乙基酮以及甲基異丁基酮。就反應速度的觀點而言，可更佳地使用乙酸丙酯、乙酸丁酯、甲基乙基酮及甲基異丁基酮。As the Lewis basic compound (c), ethyl acetate, propyl acetate, butyl acetate, phenyl acetate, and A can be preferably used from the viewpoints of reactivity, ease of availability, and heat resistance of the cured product. Ketoethyl ketone and methyl isobutyl ketone. From the viewpoint of the reaction rate, propyl acetate, butyl acetate, methyl ethyl ketone, and methyl isobutyl ketone can be more preferably used.

相對於所有單量體100莫耳，路易斯鹼性化合物（c）為0.005莫耳～500莫耳，較佳為0.01莫耳～100莫耳，更佳為0.1莫耳～50莫耳。若未滿0.005莫耳，則不僅對由所述式（a1）所表示的重複結構單元的式（a2）及式（a3）的導入量減少，韌性等功能下降，而且耐熱性下降，硬化性亦惡化，因此成形加工性亦惡化。另一方面，若使用超過500莫耳，則除聚合速度顯著下降，生產性下降以外，介電特性惡化。The Lewis basic compound (c) is from 0.005 mol to 500 mol, preferably from 0.01 mol to 100 mol, more preferably from 0.1 mol to 50 mol, relative to 100 parts by mole of all the monoliths. When the amount of the formula (a2) and the formula (a3) of the repeating structural unit represented by the above formula (a1) is reduced, the function such as toughness is lowered, and the heat resistance is lowered, and the curability is lowered. It also deteriorates, so the formability also deteriorates. On the other hand, when the use exceeds 500 mol, the dielectric properties are deteriorated in addition to the decrease in the polymerization rate and the decrease in productivity.

聚合反應可使用二乙烯基芳香族化合物（a）、乙基乙烯基芳香族化合物（b）、路易斯鹼性化合物（c）及觸媒（d），在使包含該些的聚合原料類溶解於介電常數為2.0～15.0的溶媒中而成的均勻溶媒中，以20℃～120℃的溫度進行陽離子共聚合而獲得共聚合物。The polymerization reaction can use a divinyl aromatic compound (a), an ethyl vinyl aromatic compound (b), a Lewis basic compound (c), and a catalyst (d) to dissolve the polymerization raw material containing the above. In a homogeneous solvent obtained by using a solvent having a dielectric constant of 2.0 to 15.0, cationic copolymerization is carried out at a temperature of from 20 ° C to 120 ° C to obtain a copolymer.

作為觸媒（d），使用選自由無機酸、有機磺酸及過氯酸系化合物所組成的群組中的一種以上的觸媒（d）。As the catalyst (d), one or more kinds of catalysts (d) selected from the group consisting of inorganic acids, organic sulfonic acids, and perchloric acid-based compounds are used.

作為觸媒（d），只要是生成磺酸酯陰離子或過氯酸陰離子、且可接收電子對的化合物，則可無特別限制地使用。作為生成磺酸酯陰離子的無機酸，可列舉硫酸、氟硫酸、氯硫酸、雙氯硫酸等。作為有機磺酸的具體例，可列舉硫酸甲酯、三氟甲烷磺酸、全氟乙烷磺酸、苯磺酸、對甲苯磺酸、甲烷磺酸酐、苯磺酸酐等。作為生成過氯酸陰離子的過氯酸系化合物，可列舉過氯酸、過氯酸乙醯酯、過氯酸丁醯酯、苯甲醯基過氯酸酯、二氧鎓過氯酸酯、三苯基甲基過氯酸酯、卓鎓過氯酸酯等。該些觸媒可單獨使用、或將兩種以上組合使用。 就所獲得的共聚合物的分子量及分子量分佈的控制及聚合活性的觀點而言，可最佳地使用硫酸甲酯、三氟甲烷磺酸、對甲苯磺酸或甲烷磺酸酐。The catalyst (d) is not particularly limited as long as it is a compound which forms a sulfonate anion or a perchlorate anion and can receive an electron pair. Examples of the inorganic acid which forms the sulfonate anion include sulfuric acid, fluorosulfuric acid, chlorosulfuric acid, and dichlorosulfuric acid. Specific examples of the organic sulfonic acid include methyl sulfate, trifluoromethanesulfonic acid, perfluoroethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic anhydride, and benzenesulfonic anhydride. Examples of the perchloric acid-based compound which forms a perchloric acid anion include perchloric acid, acetamyl perchlorate, butyl phthalate, benzamidine perchlorate, and dioxins perchlorate. Triphenylmethyl perchlorate, Zhuojing perchlorate, and the like. These catalysts may be used singly or in combination of two or more. From the viewpoints of control of the molecular weight and molecular weight distribution of the obtained copolymer and polymerization activity, methyl sulfate, trifluoromethanesulfonic acid, p-toluenesulfonic acid or methanesulfonic anhydride can be preferably used.

關於觸媒（d），相對於作為促進劑的路易斯鹼性化合物（c）1莫耳，於0.001莫耳～10莫耳的範圍內使用觸媒（d），更佳為0.005莫耳～5莫耳。若超過10莫耳，則聚合速度變得過大，因此難以控制分子量分佈。With respect to the catalyst (d), the catalyst (d) is used in the range of 0.001 mol to 10 mol, more preferably 0.005 mol to 5, relative to the Lewis basic compound (c) 1 mol as a promoter. Moor. If it exceeds 10 mol, the polymerization rate becomes too large, so it is difficult to control the molecular weight distribution.

聚合反應較佳為於作為溶解所生成的可溶性多官能乙烯基芳香族共聚合物的溶媒的介電常數為2.0～15.0的一種以上的有機溶媒中進行。作為有機溶媒，只要是本質上不阻礙陽離子聚合，且溶解觸媒、聚合添加劑、促進劑、單量體及多官能乙烯基芳香族共聚合物，形成均勻溶液的化合物，且介電常數為2～15的範圍內，則並無特別限制，可單獨使用、或將兩種以上組合使用。若溶媒的介電常數未滿2，則分子量分佈變寬廣，因此欠佳，若超過15，則聚合速度顯著下降。The polymerization reaction is preferably carried out in one or more organic solvents having a dielectric constant of 2.0 to 15.0 as a solvent of the soluble polyfunctional vinyl aromatic copolymer produced by the dissolution. The organic solvent is a compound which forms a homogeneous solution as long as it does not inhibit cationic polymerization in nature and dissolves a catalyst, a polymerization additive, a promoter, a mono- and polyfunctional vinyl aromatic copolymer, and has a dielectric constant of 2 The range of ～15 is not particularly limited, and may be used singly or in combination of two or more. When the dielectric constant of the solvent is less than 2, the molecular weight distribution becomes broad, which is not preferable, and if it exceeds 15, the polymerization rate is remarkably lowered.

作為有機溶媒，就聚合活性、溶解性的平衡的觀點而言，特佳為甲苯、二甲苯、正己烷、環己烷、甲基環己烷或乙基環己烷。考慮到所獲得的聚合溶液的黏度或除熱的容易性，以於聚合結束時聚合溶液中的共聚合物的濃度變成1 wt%～90 wt%，較佳為變成10 wt%～80 wt%，特佳為變成20 wt%～70 wt%的方式決定溶媒的使用量為宜。當該濃度未滿1 wt%時，因聚合效率低而招致成本的增大，若超過90 wt%，則分子量及分子量分佈增大，招致成形加工性的下降。The organic solvent is particularly preferably toluene, xylene, n-hexane, cyclohexane, methylcyclohexane or ethylcyclohexane from the viewpoint of balance between polymerization activity and solubility. The concentration of the copolymer in the polymerization solution at the end of the polymerization becomes 1 wt% to 90 wt%, preferably 10 wt% to 80 wt%, in view of the viscosity of the obtained polymerization solution or the ease of heat removal. It is preferable to change the amount of the solvent to be 20 wt% to 70 wt%. When the concentration is less than 1% by weight, the polymerization efficiency is low and the cost is increased. When the concentration is more than 90% by weight, the molecular weight and the molecular weight distribution are increased to cause a decrease in moldability.

聚合反應溫度較佳為20℃～120℃，更佳為40℃～100℃。若聚合溫度過高，則反應的選擇性下降，因此產生分子量分佈的增大或凝膠的產生等問題點，若過低，則觸媒活性顯著下降，因此必須添加大量的觸媒。The polymerization temperature is preferably from 20 ° C to 120 ° C, more preferably from 40 ° C to 100 ° C. When the polymerization temperature is too high, the selectivity of the reaction is lowered. Therefore, problems such as an increase in molecular weight distribution or generation of a gel occur. If the polymerization activity is too low, the catalyst activity is remarkably lowered. Therefore, it is necessary to add a large amount of catalyst.

聚合反應停止後，回收共聚合物的方法並無特別限定，例如只要使用汽提法、利用不良溶媒的析出等通常所使用的方法即可。The method of recovering the copolymer after the polymerization reaction is stopped is not particularly limited, and for example, a method generally used such as a stripping method or precipitation by a poor solvent may be used.

繼而，對本發明的硬化性組成物進行說明。 本發明的硬化性組成物含有可溶性多官能乙烯基芳香族共聚合物（XA）與自由基聚合起始劑（亦稱為自由基聚合觸媒）（XB）。作為自由基聚合起始劑（XB），例如本發明的樹脂組成物如後述般藉由加熱等手段來產生交聯反應而硬化，但為了降低此時的反應溫度、或促進不飽和基的交聯反應，可含有自由基聚合起始劑（XB）來使用。以（XA）成分與（XB）成分的和為基準，用於該目的的自由基聚合起始劑的量為0.01 wt%～10 wt%，較佳為0.1 wt%～8 wt%。自由基聚合起始劑亦為自由基聚合觸媒，以下由自由基聚合起始劑來代表。Next, the curable composition of the present invention will be described. The curable composition of the present invention contains a soluble polyfunctional vinyl aromatic copolymer (XA) and a radical polymerization initiator (also referred to as a radical polymerization catalyst) (XB). As the radical polymerization initiator (XB), for example, the resin composition of the present invention is cured by a crosslinking reaction by heating or the like as described later, but in order to lower the reaction temperature at this time or to promote the crosslinking of the unsaturated group The reaction may be carried out by containing a radical polymerization initiator (XB). The amount of the radical polymerization initiator used for the purpose is from 0.01% by weight to 10% by weight, preferably from 0.1% by weight to 8% by weight based on the sum of the (XA) component and the (XB) component. The radical polymerization initiator is also a radical polymerization catalyst, and is represented by a radical polymerization initiator.

自由基聚合起始劑可使用公知的物質。若列舉具有代表性的例子，有苯甲醯基過氧化物、枯烯氫過氧化物、2,5-二甲基己烷-2,5-二氫過氧化物、2,5-二甲基-2,5-二(過氧化第三丁基)己炔-3、二-第三丁基過氧化物、第三丁基枯基過氧化物、α,α'-雙(過氧化第三丁基-間異丙基)苯、2,5-二甲基-2,5-二(過氧化第三丁基)己烷、二枯基過氧化物、過氧化間苯二甲酸二-第三丁酯、過氧化苯甲酸第三丁酯、2,2-雙(過氧化第三丁基)丁烷、2,2-雙(過氧化第三丁基)辛烷、2,5-二甲基-2,5-二(過氧化苯甲醯基)己烷、二(三甲基矽烷基)過氧化物、三甲基矽烷基三苯基矽烷基過氧化物等過氧化物，但並不限定於該些過氧化物。另外，雖然並非過氧化物，但亦可使用2,3-二甲基-2,3-二苯基丁烷。其中，用於本樹脂組成物的硬化的自由基聚合起始劑並不限定於該些例子。As the radical polymerization initiator, a known one can be used. Representative examples include benzammonium peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl Base-2,5-di(t-butylperoxy)hexyne-3, di-tert-butyl peroxide, tert-butyl cumyl peroxide, α,α'-double (peroxide Tributyl-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, peroxyisophthalic acid di- Third butyl ester, tert-butyl peroxybenzoate, 2,2-bis(tributylbutylbutoxide)butane, 2,2-bis(t-butylperoxy)octane, 2,5- a peroxide such as dimethyl-2,5-di(benzylidene peroxide)hexane, bis(trimethyldecyl)peroxide or trimethyldecyltriphenylsulfonylalkyl peroxide, However, it is not limited to these peroxides. Further, although it is not a peroxide, 2,3-dimethyl-2,3-diphenylbutane can also be used. Among them, the hardening radical polymerization initiator used for the present resin composition is not limited to these examples.

若相對於可溶性多官能乙烯基芳香族共聚合物（XA）100重量份，自由基聚合起始劑的調配量為0.01重量份～10重量份的範圍，則不會阻礙硬化反應而良好地進行反應。When the amount of the radical polymerization initiator is from 0.01 part by weight to 10 parts by weight based on 100 parts by weight of the soluble polyfunctional vinyl aromatic copolymer (XA), the curing reaction proceeds without hindering the curing reaction. reaction.

於含有可溶性多官能乙烯基芳香族共聚合物（XA）的硬化性組成物中，視需要可調配能夠與共聚合物（XA）進行共聚合的其他聚合性單體來進行硬化。In the curable composition containing the soluble polyfunctional vinyl aromatic copolymer (XA), other polymerizable monomers copolymerizable with the copolymer (XA) may be added and cured as needed.

此種可進行共聚合的聚合性單體可使用公知的物質。若列舉具有代表性的例子，則可列舉：苯乙烯、苯乙烯二聚體、α-甲基苯乙烯、α-甲基苯乙烯二聚體、二乙烯基苯、乙烯基甲苯、第三丁基苯乙烯、氯苯乙烯、二溴苯乙烯、乙烯基萘、乙烯基聯苯、苊、二乙烯基苄基醚、烯丙基苯基醚等。A well-known thing can be used for such a polymerizable monomer which can carry out copolymerization. As a representative example, styrene, styrene dimer, α-methyl styrene, α-methyl styrene dimer, divinyl benzene, vinyl toluene, and third butyl are exemplified. Styrene, chlorostyrene, dibromostyrene, vinylnaphthalene, vinylbiphenyl, anthracene, divinylbenzyl ether, allyl phenyl ether, and the like.

於包含可溶性多官能乙烯基芳香族共聚合物（XA）的硬化性組成物中，亦可調配已知的熱硬化性樹脂，例如乙烯酯樹脂、聚乙烯基苄基樹脂、不飽和聚酯樹脂、硬化型乙烯基樹脂、改質聚苯醚樹脂、順丁烯二醯亞胺樹脂、環氧樹脂、聚氰酸酯樹脂、酚樹脂等，或已知的熱塑性樹脂，例如聚苯乙烯、聚苯醚、聚醚醯亞胺、聚醚碸、聚苯硫醚（Polyphenylene sulfide，PPS）樹脂、聚環戊二烯樹脂、聚環烯烴樹脂等，或已知的熱塑性彈性體，例如苯乙烯-乙烯-丙烯共聚合物、苯乙烯-乙烯-丁烯共聚合物、苯乙烯-丁二烯共聚合物、苯乙烯-異戊二烯共聚合物、氫化苯乙烯-丁二烯共聚合物、氫化苯乙烯-異戊二烯共聚合物等，或橡膠類，例如聚丁二烯、聚異戊二烯。In the curable composition containing the soluble polyfunctional vinyl aromatic copolymer (XA), a known thermosetting resin such as a vinyl ester resin, a polyvinyl benzyl resin, or an unsaturated polyester resin may be blended. , hardened vinyl resin, modified polyphenylene ether resin, maleimide resin, epoxy resin, polycyanate resin, phenol resin, etc., or known thermoplastic resins such as polystyrene, poly Phenyl ether, polyether oximine, polyether oxime, polyphenylene sulfide (PPS) resin, polycyclopentadiene resin, polycycloolefin resin, etc., or known thermoplastic elastomers such as styrene - Ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, A hydrogenated styrene-isoprene copolymer or the like, or a rubber such as polybutadiene or polyisoprene.

硬化性組成物亦可含有可溶性多官能乙烯基芳香族共聚合物（XA）及自由基聚合起始劑（XB）且含有由下述式（7）所表示的改質聚苯醚（XC），特別是包含末端具有至少一個聚合性的不飽和雙鍵的基，例如酚性羥基、乙烯基、(甲基)丙烯酸基的改質聚苯醚（XC）。末端改質可溶性多官能乙烯基芳香族共聚合物（XA）與所述改質聚苯醚（XC）具有良好的相容性，克服伴隨相容性的下降的可靠性的下降這一問題，以任意的調配顯示出高度的低介電特性與韌性、進而成形性與層間剝離強度等特性經改良的特性。式（7）中，m表示1或2，L表示由下述式（8）所表示的聚苯醚鏈。M表示氫原子、由下述式（9）所表示的基，當m為1時，M不為氫原子，當m為2時，2個M的至少任一者不為氫原子。當m為1時，T表示氫原子，當m為2時，T表示伸烷基、由下述式（10）或下述式（11）所表示的基。式（8）中，n表示50以下的正的整數，R5 、R6 、R7 、及R8 分別獨立地表示氫原子、烷基、烯基、炔基、甲醯基、烷基羰基、烯基羰基、或炔基羰基。式（9）中，X為碳數1以上的有機基，有時亦包含氧原子。Y為乙烯基。j表示0或1的整數。式（10）中，R10 、R11 、R12 、及R13 分別獨立地表示氫原子、烷基、烯基、炔基、甲醯基、烷基羰基、烯基羰基、或炔基羰基。式（11）中，R14 、R15 、R16 、R17 、R18 、R19 、R20 、及R21 分別獨立地表示氫原子、烷基、烯基、炔基、甲醯基、烷基羰基、烯基羰基、或炔基羰基。F為包含碳數0的情況的碳數20以下的直鏈狀、分支狀或環狀的烴基。The curable composition may further contain a soluble polyfunctional vinyl aromatic copolymer (XA) and a radical polymerization initiator (XB) and contain a modified polyphenylene ether (XC) represented by the following formula (7). In particular, it includes a group having an unsaturated double bond having at least one polymerizable terminal at the terminal, such as a phenolic hydroxyl group, a vinyl group, or a (meth)acryl-based modified polyphenylene ether (XC). The terminally modified soluble polyfunctional vinyl aromatic copolymer (XA) has good compatibility with the modified polyphenylene ether (XC), and overcomes the problem of a decrease in reliability accompanying a decrease in compatibility. The characteristics such as high low dielectric properties and toughness, and further improved properties such as moldability and interlayer peel strength are exhibited by any combination. In the formula (7), m represents 1 or 2, and L represents a polyphenylene ether chain represented by the following formula (8). M represents a hydrogen atom and a group represented by the following formula (9). When m is 1, M is not a hydrogen atom, and when m is 2, at least one of the two M is not a hydrogen atom. When m is 1, T represents a hydrogen atom, and when m is 2, T represents an alkylene group, and a group represented by the following formula (10) or the following formula (11). In the formula (8), n represents a positive integer of 50 or less, and R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a decyl group or an alkylcarbonyl group. , alkenylcarbonyl, or alkynylcarbonyl. In the formula (9), X is an organic group having 1 or more carbon atoms, and may also contain an oxygen atom. Y is a vinyl group. j represents an integer of 0 or 1. In the formula (10), R 10 , R 11 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a decyl group, an alkylcarbonyl group, an alkenylcarbonyl group or an alkynylcarbonyl group. . In the formula (11), R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 and R 21 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or a formazan group. An alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. F is a linear, branched or cyclic hydrocarbon group having a carbon number of 20 or less in the case of having a carbon number of 0.

本實施形態中所使用的改質聚苯醚（XC）只要為由所述式（7）所表示的改質聚苯醚，則並無特別限定。The modified polyphenylene ether (XC) used in the present embodiment is not particularly limited as long as it is a modified polyphenylene ether represented by the above formula (7).

另外，由式（7）所表示的改質聚苯醚為式（7）中的m表示1或2者。即，具體而言，由式（7）所表示的改質聚苯醚為由T-L-M、或M-L-T-L-M所表示的改質聚苯醚。Further, the modified polyphenylene ether represented by the formula (7) is one in which the m in the formula (7) represents 1 or 2. Specifically, specifically, the modified polyphenylene ether represented by the formula (7) is a modified polyphenylene ether represented by T-L-M or M-L-T-L-M.

另外，L表示由式（8）所表示的聚苯醚鏈。於式（8）中，n表示50以下的正的整數。另外，R5 、R6 、R7 、及R8 分別獨立。即，R5 、R6 、R7 、及R8 分別可為相同的基，亦可為不同的基。另外，R5 、R6 、R7 、及R8 表示氫原子、烷基、烯基、炔基、甲醯基、烷基羰基、烯基羰基、或炔基羰基。其中，較佳為氫原子及烷基。Further, L represents a polyphenylene ether chain represented by the formula (8). In the formula (8), n represents a positive integer of 50 or less. Further, R 5 , R 6 , R 7 and R 8 are each independently. That is, R 5 , R 6 , R 7 and R 8 may each be the same group or may be different groups. Further, R 5 , R 6 , R 7 and R 8 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a decyl group, an alkylcarbonyl group, an alkenylcarbonyl group or an alkynylcarbonyl group. Among them, a hydrogen atom and an alkyl group are preferred.

另外，M表示氫原子、由式（9）所表示的基。另外，M於m為1的情況下，即於改質聚苯醚為T-L-M的情況下不為氫原子，表示由式（9）所表示的基。另外，M於m為2的情況下，即於改質聚苯醚為M-L-T-L-M的情況下，2個M的至少任一者不為氫原子，就硬化物的耐熱性與韌性這一理由而言，較佳為2個M均為由式（9）所表示的基。Further, M represents a hydrogen atom and a group represented by the formula (9). Further, when M is 1 in the case where m is 1 or less, that is, when the modified polyphenylene ether is T-L-M, it is not a hydrogen atom, and represents a group represented by the formula (9). Further, when M is 2, that is, when the modified polyphenylene ether is MLTLM, at least one of the two M is not a hydrogen atom, and the heat resistance and toughness of the cured product are considered. Preferably, two M's are the groups represented by the formula (9).

另外，T於m為1的情況下，即於改質聚苯醚為T-L-M的情況下表示氫原子。由T-L-M所表示的改質聚苯醚為由H-L-M所表示的改質聚苯醚。另外，T於m為2的情況下，即於改質聚苯醚為M-L-T-L-M的情況下，表示伸烷基、由式（10）所表示的基、或由式（11）所表示的基。其中，就硬化物的韌性與改質聚苯醚的可溶性這一理由而言，較佳為m為2，T為伸烷基，較佳為m為2，T為2,2-伸丙基。Further, when T is 1 in the case where m is 1, that is, when the modified polyphenylene ether is T-L-M, it represents a hydrogen atom. The modified polyphenylene ether represented by T-L-M is a modified polyphenylene ether represented by H-L-M. Further, when T is 2, that is, when the modified polyphenylene ether is M-L-T-L-M, it represents an alkylene group, a group represented by the formula (10), or a group represented by the formula (11). Among them, in terms of the toughness of the cured product and the solubility of the modified polyphenylene ether, m is preferably 2, T is an alkylene group, preferably m is 2, and T is 2,2-propanylpropyl. .

另外，式（10）中，R10 、R11 、R12 、及R13 分別獨立地表示氫原子、烷基、烯基、炔基、甲醯基、烷基羰基、烯基羰基、或炔基羰基。R10 、R11 、R12 、及R13 分別可為相同的基，亦可為不同的基。Further, in the formula (10), R 10 , R 11 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a decyl group, an alkylcarbonyl group, an alkenylcarbonyl group or an alkyne. Alkylcarbonyl. R 10 , R 11 , R 12 and R 13 may each be the same group or may be different groups.

作為於R5 ～R21 中所列舉的各官能基，具體而言，可列舉如下的基。Specific examples of the respective functional groups exemplified in R 5 to R 21 include the following groups.

烷基並無特別限定，例如較佳為碳數1～18的烷基，更佳為碳數1～10的烷基。具體而言，例如可列舉：甲基、乙基、丙基、己基、及癸基等。The alkyl group is not particularly limited, and is preferably, for example, an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, and an anthracenyl group.

另外，烯基並無特別限定，例如較佳為碳數2～18的烯基，更佳為碳數2～10的烯基。具體而言，例如可列舉：乙烯基、烯丙基、及3-丁烯基等。Further, the alkenyl group is not particularly limited, and is, for example, preferably an alkenyl group having 2 to 18 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms. Specific examples thereof include a vinyl group, an allyl group, and a 3-butenyl group.

另外，炔基並無特別限定，例如較佳為碳數2～18的炔基，更佳為碳數2～10的炔基。具體而言，例如可列舉：乙炔基、及丙-2-炔-1-基（炔丙基）等。Further, the alkynyl group is not particularly limited, and is preferably, for example, an alkynyl group having 2 to 18 carbon atoms, more preferably an alkynyl group having 2 to 10 carbon atoms. Specific examples thereof include an ethynyl group and a prop-2-yn-1-yl (propargyl group).

另外，烷基羰基只要是經烷基取代的羰基，則並無特別限定，例如較佳為碳數2～18的烷基羰基，更佳為碳數2～10的烷基羰基。具體而言，例如可列舉：乙醯基、丙醯基、丁醯基、異丁醯基、三甲基乙醯基、己醯基、辛醯基、及環己基羰基等。Further, the alkylcarbonyl group is not particularly limited as long as it is an alkyl group-substituted carbonyl group. For example, an alkylcarbonyl group having 2 to 18 carbon atoms is preferred, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferred. Specific examples thereof include an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, an isobutyl fluorenyl group, a trimethyl ethane group, a hexyl fluorenyl group, a octyl group, and a cyclohexyl carbonyl group.

另外，烯基羰基只要是經烯基取代的羰基，則並無特別限定，例如較佳為碳數3～18的烯基羰基，更佳為碳數3～10的烯基羰基。具體而言，例如可列舉：丙烯醯基、甲基丙烯醯基、及丁烯醯基等。Further, the alkenylcarbonyl group is not particularly limited as long as it is an alkenyl-substituted carbonyl group. For example, an alkenylcarbonyl group having 3 to 18 carbon atoms is preferred, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferred. Specific examples thereof include an acrylonitrile group, a methacryl fluorenyl group, and a butenyl group.

另外，炔基羰基只要是經炔基取代的羰基，則並無特別限定，例如較佳為碳數3～18的炔基羰基，更佳為碳數3～10的炔基羰基。具體而言，例如可列舉：炔丙醯基等。Further, the alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group, and is preferably, for example, an alkynylcarbonyl group having 3 to 18 carbon atoms, more preferably an alkynylcarbonyl group having 3 to 10 carbon atoms. Specifically, for example, a propargyl group or the like can be mentioned.

改質聚苯醚（XC）的數量平均分子量並無特別限定，但較佳為800～7000，更佳為1000～5000。最佳為1000～3000。另外，如上所述，n為50以下的正的整數，但較佳為如改質聚苯醚的數量平均分子量變成此種範圍內的數值。具體而言，較佳為1～50。再者，此處，數量平均分子量只要是藉由一般的分子量測定方法所測定者即可，具體而言，可列舉使用凝膠滲透層析法（Gel Permeation Chromatography，GPC）所測定的值等。The number average molecular weight of the modified polyphenylene ether (XC) is not particularly limited, but is preferably from 800 to 7,000, more preferably from 1,000 to 5,000. The best is 1000 to 3000. Further, as described above, n is a positive integer of 50 or less, but it is preferred that the number average molecular weight of the modified polyphenylene ether becomes a value within such a range. Specifically, it is preferably from 1 to 50. In addition, the number average molecular weight may be measured by a general molecular weight measurement method, and specific examples thereof include values measured by Gel Permeation Chromatography (GPC).

若改質聚苯醚（XC）的數量平均分子量為此種範圍內，則所獲得的硬化性組成物的硬化物的韌性與成形性變得更高。其原因在於：若改質聚苯醚的數量平均分子量為此種範圍內，則為分子量比較低者，因此一面維持韌性，一面改良流動性。通常的聚苯醚於使用此種低分子量者的情況下，存在硬化物的耐熱性與韌性下降的傾向。但是，本實施形態中所使用的改質聚苯醚（XC）因於末端具有聚合性的不飽和雙鍵，故藉由與乙烯基系的熱交聯型硬化性樹脂一同進行硬化，改質聚苯醚與熱交聯型硬化性樹脂的交聯適宜地進行，可獲得硬化物的耐熱性與韌性足夠高者。藉此，所獲得的硬化性組成物的硬化物可獲得耐熱性及韌性均優異者。When the number average molecular weight of the modified polyphenylene ether (XC) is within such a range, the toughness and formability of the cured product of the obtained curable composition become higher. The reason for this is that if the number average molecular weight of the modified polyphenylene ether is within such a range, the molecular weight is relatively low, and therefore the fluidity is improved while maintaining the toughness. When a normal polyphenylene ether is used in such a low molecular weight, the heat resistance and toughness of the cured product tend to decrease. However, since the modified polyphenylene ether (XC) used in the present embodiment has a polymerizable unsaturated double bond at the terminal, it is cured by being cured together with a vinyl-based heat-crosslinking type curable resin. The crosslinking of the polyphenylene ether and the heat-crosslinking type curable resin is suitably carried out, and the heat resistance and toughness of the cured product can be sufficiently high. Thereby, the cured product of the curable composition obtained can be excellent in heat resistance and toughness.

就提昇異種材料間的黏著可靠性這一理由而言，較佳的實施形態亦為：本發明的硬化性組成物含有可溶性多官能乙烯基芳香族共聚合物（XA）及自由基聚合起始劑（XB）且含有環氧樹脂（XD）及硬化劑（XE）。In order to improve the reliability of adhesion between dissimilar materials, a preferred embodiment is also that the curable composition of the present invention contains a soluble polyfunctional vinyl aromatic copolymer (XA) and a radical polymerization initiation. The agent (XB) also contains an epoxy resin (XD) and a hardener (XE).

作為（XD）成分的環氧樹脂，並無特別限制，較佳為使用選自由1分子中具有2個以上的環氧基與芳香族結構的環氧樹脂、1分子中具有2個以上的環氧基與氰脲酸酯結構的環氧樹脂、及/或1分子中具有2個以上的環氧基與脂環結構的環氧樹脂所組成的群組中的一種以上的環氧樹脂。作為（XD）成分，更佳為選自由雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、烷基苯酚酚醛清漆型環氧樹脂、伸二甲苯基改質苯酚酚醛清漆型環氧樹脂、伸二甲苯基改質烷基苯酚酚醛清漆型環氧樹脂、聯苯型環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、三縮水甘油基異氰脲酸酯、環己烷型環氧樹脂及金剛烷型環氧樹脂所組成的群組中的一種以上的環氧樹脂。The epoxy resin (XD) component is not particularly limited, and an epoxy resin having two or more epoxy groups and an aromatic structure in one molecule is preferably used, and two or more rings are contained in one molecule. One or more epoxy resins in the group consisting of an epoxy group having an oxy group and a cyanurate structure, and/or an epoxy resin having two or more epoxy groups and an alicyclic structure in one molecule. More preferably, it is selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alkyl phenol novolac type epoxy resin, and xylylene modification. Phenolic novolac type epoxy resin, xylylene modified alkyl phenol novolak type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, triglycidyl group One or more epoxy resins in the group consisting of isocyanurate, cyclohexane type epoxy resin and adamantane type epoxy resin.

作為用作（XD）成分的雙酚F型環氧樹脂，例如可列舉：將4,4'-亞甲基雙(2,6-二甲基苯酚)的二縮水甘油醚作為主成分的環氧樹脂、將4,4'-亞甲基雙(2,3,6-三甲基苯酚)的二縮水甘油醚作為主成分的環氧樹脂、將4,4'-亞甲基雙酚的二縮水甘油醚作為主成分的環氧樹脂。其中，較佳為將4,4'-亞甲基雙(2,6-二甲基苯酚)的二縮水甘油醚作為主成分的環氧樹脂。例如能夠以作為市售品的新日鐵住金化學股份有限公司製造的商品名YSLV-80XY的形態獲得。Examples of the bisphenol F-type epoxy resin used as the (XD) component include a ring containing a diglycidyl ether of 4,4′-methylenebis(2,6-dimethylphenol) as a main component. An oxy-resin, an epoxy resin containing 4,4'-methylenebis(2,3,6-trimethylphenol) diglycidyl ether as a main component, and 4,4'-methylene bisphenol Epoxy resin containing diglycidyl ether as a main component. Among them, an epoxy resin containing a diglycidyl ether of 4,4'-methylenebis(2,6-dimethylphenol) as a main component is preferred. For example, it can be obtained in the form of the trade name YSLV-80XY manufactured by Nippon Steel & Metal Chemical Co., Ltd., which is a commercial product.

作為聯苯型環氧樹脂，可列舉：4,4'-二縮水甘油基聯苯、及4,4'-二縮水甘油基-3,3',5,5'-四甲基聯苯等環氧樹脂。例如能夠以作為市售品的三菱化學股份有限公司製造的商品名YX-4000、YL-6121H的形態獲得。Examples of the biphenyl type epoxy resin include 4,4'-diglycidylbiphenyl and 4,4'-diglycidyl-3,3',5,5'-tetramethylbiphenyl, and the like. Epoxy resin. For example, it can be obtained in the form of the trade names YX-4000 and YL-6121H manufactured by Mitsubishi Chemical Corporation, which is a commercial item.

作為二環戊二烯型環氧樹脂，可列舉：二氧化二環戊二烯、及具有二環戊二烯骨架的苯酚酚醛清漆環氧單體等。Examples of the dicyclopentadiene type epoxy resin include dicyclopentadiene dioxide and a phenol novolac epoxy monomer having a dicyclopentadiene skeleton.

作為萘型環氧樹脂，可列舉：1,2-二縮水甘油基萘、1,5-二縮水甘油基萘、1,6-二縮水甘油基萘、1,7-二縮水甘油基萘、2,7-二縮水甘油基萘、三縮水甘油基萘、及1,2,5,6-四縮水甘油基萘、萘酚·芳烷基型環氧樹脂、萘骨架改質甲酚酚醛清漆型環氧樹脂、甲氧基萘改質甲酚酚醛清漆型環氧樹脂、伸萘基醚型環氧樹脂、甲氧基萘二亞甲基型環氧樹脂等改質萘型環氧樹脂等。Examples of the naphthalene type epoxy resin include 1,2-diglycidylnaphthalene, 1,5-diglycidylnaphthalene, 1,6-diglycidylnaphthalene, and 1,7-diglycidylnaphthalene. 2,7-diglycidylnaphthalene, triglycidylnaphthalene, and 1,2,5,6-tetraglycidylnaphthalene, naphthol aralkyl type epoxy resin, naphthalene skeleton modified cresol novolac Type epoxy resin, methoxy naphthalene modified cresol novolak type epoxy resin, naphthyl ether type epoxy resin, methoxy naphthalene type dimethyl epoxy resin, modified naphthalene type epoxy resin, etc. .

作為金剛烷型環氧樹脂，可列舉：1-(2,4-二縮水甘油氧基苯基)金剛烷、1-(2,3,4-三縮水甘油氧基苯基)金剛烷、1,3-雙(2,4-二縮水甘油氧基苯基)金剛烷、1,3-雙(2,3,4-三縮水甘油氧基苯基)金剛烷、2,2-雙(2,4-二縮水甘油氧基苯基)金剛烷、1-(2,3,4-三羥基苯基)金剛烷、1,3-雙(2,4-二羥基苯基)金剛烷、1,3-雙(2,3,4-三羥基苯基)金剛烷、及2,2-雙(2,4-二羥基苯基)金剛烷等。Examples of the adamantane type epoxy resin include 1-(2,4-diglycidoxyphenyl)adamantane, 1-(2,3,4-triglycidoxyphenyl)adamantane, and 1 , 3-bis(2,4-diglycidoxyphenyl)adamantane, 1,3-bis(2,3,4-triglycidoxyphenyl)adamantane, 2,2-dual (2 , 4-diglycidoxyphenyl)adamantane, 1-(2,3,4-trihydroxyphenyl)adamantane, 1,3-bis(2,4-dihydroxyphenyl)adamantane, 1 , 3-bis(2,3,4-trihydroxyphenyl)adamantane, and 2,2-bis(2,4-dihydroxyphenyl)adamantane, and the like.

環氧樹脂之中，就與（XA）成分的相容性、介電特性、及成形品的翹曲小的觀點而言，可適宜地使用：雙酚F型環氧樹脂、烷基苯酚酚醛清漆型環氧樹脂、伸二甲苯基改質苯酚酚醛清漆型環氧樹脂、伸二甲苯基改質烷基苯酚酚醛清漆型環氧樹脂、聯苯型環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、三縮水甘油基異氰脲酸酯、環己烷型環氧樹脂、金剛烷型環氧樹脂。Among the epoxy resins, a bisphenol F type epoxy resin or an alkyl phenol novolac can be suitably used from the viewpoints of compatibility with the (XA) component, dielectric properties, and warpage of the molded article. Varnish type epoxy resin, xylylene modified phenol novolac type epoxy resin, xylylene modified alkyl phenol novolac type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin , naphthalene type epoxy resin, triglycidyl isocyanurate, cyclohexane type epoxy resin, adamantane type epoxy resin.

用作（XD）成分的環氧樹脂的重量平均分子量（Mw）較佳為未滿1萬。更佳的Mw為600以下，進而更佳為200以上、550以下。當Mw未滿200時，存在該成分的揮發性變高，澆鑄膜·片的處理性變差的傾向。另一方面，若Mw超過1萬，則存在澆鑄膜·片容易變硬且變脆、澆鑄膜·片的硬化物的黏著性下降的傾向。The weight average molecular weight (Mw) of the epoxy resin used as the (XD) component is preferably less than 10,000. More preferably, the Mw is 600 or less, and more preferably 200 or more and 550 or less. When the Mw is less than 200, the volatility of the component is increased, and the handleability of the cast film/sheet tends to be deteriorated. On the other hand, when the Mw is more than 10,000, the cast film and the sheet tend to become hard and become brittle, and the adhesiveness of the cured product of the cast film and the sheet tends to decrease.

相對於（XA）成分100重量份，（XD）成分的含量較佳為下限為5重量份、且上限為100重量份。更佳為的下限為10重量份。另一方面，更佳的上限為80重量份，進而更佳的上限為60重量份。若（XD）成分的含量滿足所述較佳的下限，則可進一步提高澆鑄膜·片的硬化物的黏著性。若（XD）成分的含量滿足所述較佳的上限，則未硬化狀態下的澆鑄膜·片的操作性進一步變高，與玻璃布的密接性得到改良，可靠性變高。The content of the (XD) component is preferably a lower limit of 5 parts by weight and an upper limit of 100 parts by weight based on 100 parts by weight of the (XA) component. More preferably, the lower limit is 10 parts by weight. On the other hand, a more preferable upper limit is 80 parts by weight, and a still more preferred upper limit is 60 parts by weight. When the content of the (XD) component satisfies the above preferred lower limit, the adhesion of the cured product of the cast film and the sheet can be further improved. When the content of the (XD) component satisfies the above-described upper limit, the workability of the cast film and sheet in the uncured state is further increased, and the adhesion to the glass cloth is improved, and the reliability is improved.

（XE）成分的硬化劑較佳為自酚樹脂、或者具有芳香族骨架或脂環式骨架的酸酐、酸酐的氫化物、酸酐的改質物、羥基末端聚苯醚寡聚物、及活性酯化合物中適宜選擇。藉由使用該些較佳的硬化劑，可獲得成為耐熱性、耐濕性及介電特性的平衡優異的硬化物的硬化性組成物。The hardener of the (XE) component is preferably a phenol resin, an acid anhydride having an aromatic skeleton or an alicyclic skeleton, a hydride of an acid anhydride, an acid anhydride modified product, a hydroxyl terminated polyphenylene ether oligomer, and an active ester compound. Suitable for selection. By using these preferable hardeners, a curable composition which is a cured product excellent in heat resistance, moisture resistance, and dielectric properties can be obtained.

用作（XE）成分的硬化劑的酚樹脂並無特別限定。作為酚樹脂的具體例，可列舉：苯酚酚醛清漆、鄰甲酚酚醛清漆、對甲酚酚醛清漆、第三丁基苯酚酚醛清漆、二環戊二烯甲酚、聚對乙烯基苯酚、雙酚A型酚醛清漆、苯酚芳烷基樹脂、萘酚芳烷基樹脂、聯苯型苯酚酚醛清漆樹脂、聯苯型萘酚酚醛清漆樹脂、十氫萘改質酚醛清漆、聚(二-鄰羥基苯基)甲烷、聚(二-間羥基苯基)甲烷、或聚(二-對羥基苯基)甲烷等。其中，為了進一步提高絕緣片的柔軟性及阻燃性，較佳為具有三聚氰胺骨架的酚樹脂、具有三嗪骨架的酚樹脂、或具有烯丙基的酚樹脂。The phenol resin used as the hardener of the (XE) component is not particularly limited. Specific examples of the phenol resin include phenol novolac, o-cresol novolac, p-cresol novolac, t-butylphenol novolac, dicyclopentadienyl cresol, poly-p-vinylphenol, and bisphenol. Type A novolak, phenol aralkyl resin, naphthol aralkyl resin, biphenyl type phenol novolak resin, biphenyl type naphthol novolac resin, decahydronaphthalene modified novolac, poly(di-o-hydroxybenzene) Methane, poly(di-m-hydroxyphenyl)methane, or poly(di-p-hydroxyphenyl)methane, and the like. Among them, in order to further improve the flexibility and flame retardancy of the insulating sheet, a phenol resin having a melamine skeleton, a phenol resin having a triazine skeleton, or a phenol resin having an allyl group is preferable.

作為酚樹脂的市售品，例如可列舉：MEH-8005、MEH-8010及NEH-8015（以上均為明和化成公司製造），YLH903（日本環氧樹脂（Japan Epoxy Resins）公司製造），LA-7052、LA-7054、LA-7751、LA1356及LA3018-50P（以上均為迪愛生（DIC）公司製造），以及PS6313及PS6492（群榮化學公司製造）等。As a commercial item of the phenol resin, for example, MEH-8005, MEH-8010, and NEH-8015 (all of which are manufactured by Mingwa Chemical Co., Ltd.), YLH903 (made by Japan Epoxy Resins Co., Ltd.), LA- 7052, LA-7054, LA-7751, LA1356, and LA3018-50P (all of which are manufactured by Diane Health (DIC) Co., Ltd.), and PS6313 and PS6492 (manufactured by Qunrong Chemical Co., Ltd.).

關於用作（XE）成分的硬化劑的具有芳香族骨架的酸酐、其氫化物或改質物，結構亦無特別限定。作為具有芳香族骨架的酸酐、其氫化物或改質物，例如可列舉：苯乙烯/順丁烯二酸酐共聚合物、二苯甲酮四羧酸酐、均苯四甲酸酐、偏苯三甲酸酐、4,4'-氧基二鄰苯二甲酸酐、苯基乙炔基鄰苯二甲酸酐、甘油雙(脫水偏苯三酸酯)單乙酸酯、乙二醇雙(脫水偏苯三酸酯)、甲基四氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、及三烷基四氫鄰苯二甲酸酐、甲基納迪克酸酐、三烷基四氫鄰苯二甲酸酐、或者具有二環戊二烯骨架的酸酐或該酸酐的改質物等。The acid anhydride having an aromatic skeleton, a hydrogenated product or a modified product thereof, which is used as a curing agent for the (XE) component, is not particularly limited in its structure. Examples of the acid anhydride having an aromatic skeleton, a hydrogenated product or a modified product thereof include a styrene/maleic anhydride copolymer, benzophenone tetracarboxylic anhydride, pyromellitic anhydride, and trimellitic anhydride. 4,4'-oxydiphthalic anhydride, phenylethynylphthalic anhydride, glycerol bis(hydrogen trimellitate) monoacetate, ethylene glycol bis(hydrogen trimellitate) ), methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride Or an acid anhydride having a dicyclopentadiene skeleton or a modified product of the acid anhydride.

作為具有芳香族骨架的酸酐、其氫化物或改質物的市售品，可列舉：SMA RESIN EF30、SMA RESIN EF40、SMA RESIN EF60及SMA RESIN EF80（以上均為日本沙多瑪（Sartomer·Japan）公司製造），ODPA-M及PEPA（以上均為瑪耐科（Manac）公司製造），RIKACID MTA10、RIKACID MTA15、RIKACID TMTA、RIKACID TMEG-100、RIKACID TMEG-200、RIKACID TMEG-300、RIKACID TMEG-500、RIKACID TMEG-S、RIKACID TH、RIKACID HT-1A、RIKACID HH、RIKACID MH-700、RIKACID MT-500、RIKACID DSDA及RIKACID TDA100（以上均為新日本理化公司製造），以及EPICLON B4400、EPICLON B650、及EPICLON B570（以上均為迪愛生公司製造）等。Commercial products including an aromatic skeleton, an hydride or a modified product thereof include SMA RESIN EF30, SMA RESIN EF40, SMA RESIN EF60, and SMA RESIN EF80 (all of which are Sartomer Japan). Made by the company), ODPA-M and PEPA (all manufactured by Manac), RIKACID MTA10, RIKACID MTA15, RIKACID TMTA, RIKACID TMEG-100, RIKACID TMEG-200, RIKACID TMEG-300, RIKACID TMEG- 500, RIKACID TMEG-S, RIKACID TH, RIKACID HT-1A, RIKACID HH, RIKACID MH-700, RIKACID MT-500, RIKACID DSDA and RIKACID TDA100 (all manufactured by Nippon Chemical and Chemical Co., Ltd.), and EPICLON B4400, EPICLON B650 And EPICLON B570 (all of which are manufactured by Di Aisheng Co., Ltd.).

具有脂環式骨架的酸酐、其氫化物或改質物較佳為具有多脂環式骨架的酸酐、其氫化物或改質物，或者藉由萜烯系化合物與順丁烯二酸酐的加成反應所獲得的具有脂環式骨架的酸酐、其氫化物或改質物。於此情況下，可進一步提高絕緣片的柔軟性、耐濕性或黏著性。另外，作為具有脂環式骨架的酸酐、其氫化物或改質物，亦可列舉：甲基納迪克酸酐、具有二環戊二烯骨架的酸酐或其改質物等。The acid anhydride having an alicyclic skeleton, a hydride or a modified product thereof is preferably an acid anhydride having a polycyclic ring skeleton, a hydride or a modified product thereof, or an addition reaction of a terpene compound with maleic anhydride. The obtained anhydride having an alicyclic skeleton, a hydride thereof or a modified product thereof. In this case, the flexibility, moisture resistance, or adhesion of the insulating sheet can be further improved. Further, examples of the acid anhydride having an alicyclic skeleton, a hydrogenated product or a modified product thereof include methyl nadic anhydride, an acid anhydride having a dicyclopentadiene skeleton, or a modified product thereof.

作為具有脂環式骨架的酸酐、其氫化物或改質物的市售品，可列舉：RIKACID HNA及RIKACID HNA100（以上均為新日本理化公司製造），以及EPICURE YH306、EPICURE YH307、EPICURE YH308H及EPICURE YH309（以上均為日本環氧樹脂公司製造）等。As a commercial product of an alicyclic skeleton anhydride, a hydride or a modified product thereof, RIKACID HNA and RIKACID HNA100 (all of which are manufactured by Shin-Nippon Chemical Co., Ltd.), and EPICURE YH306, EPICURE YH307, EPICURE YH308H, and EPICURE are exemplified. YH309 (all of which are manufactured by Nippon Epoxy Co., Ltd.) and the like.

作為（XE）成分，亦可使用羥基末端聚苯醚寡聚物。可列舉由下述式（12）所表示的羥基末端聚苯醚寡聚物。式（12）中，p表示1或2，E表示由下述式（13）所表示的聚苯醚鏈，G表示氫原子，p表示1或2的整數。當p為1時，V表示氫原子，當p為2時，V表示伸烷基、由下述式（14）或式（15）所表示的基。式（13）中，q表示50以下的正的整數，R22 、R23 、R24 、及R25 分別獨立地表示氫原子、烷基、烯基、炔基、甲醯基、烷基羰基、烯基羰基、或炔基羰基。式（14）中，R26 、R27 、R28 、及R29 分別獨立地表示氫原子、烷基、烯基、炔基、甲醯基、烷基羰基、烯基羰基、或炔基羰基。式（15）中，R30 、R31 、R32 、R33 、R34 、R35 、R36 、及R37 分別獨立地表示氫原子、烷基、烯基、炔基、甲醯基、烷基羰基、烯基羰基、或炔基羰基。W為包含碳數0的情況的碳數20以下的直鏈狀、分支狀或環狀的烴基。As the (XE) component, a hydroxyl-terminated polyphenylene ether oligomer can also be used. The hydroxyl-terminated polyphenylene ether oligomer represented by the following formula (12) is mentioned. In the formula (12), p represents 1 or 2, E represents a polyphenylene ether chain represented by the following formula (13), G represents a hydrogen atom, and p represents an integer of 1 or 2. When p is 1, V represents a hydrogen atom, and when p is 2, V represents an alkylene group, and a group represented by the following formula (14) or formula (15). In the formula (13), q represents a positive integer of 50 or less, and R 22 , R 23 , R 24 and R 25 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a decyl group or an alkylcarbonyl group. , alkenylcarbonyl, or alkynylcarbonyl. In the formula (14), R 26 , R 27 , R 28 and R 29 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a decyl group, an alkylcarbonyl group, an alkenylcarbonyl group or an alkynylcarbonyl group. . In the formula (15), R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 and R 37 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or a decyl group. An alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. W is a linear, branched or cyclic hydrocarbon group having a carbon number of 20 or less in the case of having a carbon number of 0.

作為（XE）成分，亦可使用活性酯化合物。只要是具有活性酯基者即可，但於本發明中，較佳為分子內具有至少兩個活性酯基的化合物。As the (XE) component, an active ester compound can also be used. As long as it has an active ester group, in the present invention, a compound having at least two active ester groups in the molecule is preferred.

作為用作（XE）成分的活性酯化合物，就耐熱性等的觀點而言，較佳為自使羧酸化合物及/或硫代羧酸化合物與羥基化合物及/或硫醇化合物進行反應而成者所獲得的活性酯化合物，更佳為自使羧酸化合物與選自由酚化合物、萘酚化合物及硫醇化合物所組成的群組中的一種或兩種以上進行反應而成者所獲得的活性酯化合物，特佳為自使羧酸化合物與具有酚性羥基的芳香族化合物進行反應而成者獲得、且分子內具有至少兩個活性酯基的芳香族化合物。活性酯化合物可為直鏈狀或多分支狀，若例示活性酯化合物源自分子內具有至少兩種羧酸的化合物的情況，則當此種分子內具有至少兩種羧酸的化合物含有脂肪族鏈時，可提高與環氧樹脂的相容性，另外，當具有芳香族環時，可提高耐熱性。The active ester compound used as the (XE) component is preferably a reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound from the viewpoint of heat resistance and the like. The active ester compound obtained is more preferably an activity obtained by reacting a carboxylic acid compound with one or more selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound. The ester compound is particularly preferably an aromatic compound obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group and having at least two active ester groups in the molecule. The active ester compound may be linear or multi-branched. If the active ester compound is exemplified by a compound having at least two carboxylic acids in the molecule, the compound having at least two carboxylic acids in the molecule contains an aliphatic group. In the case of a chain, compatibility with an epoxy resin can be improved, and when it has an aromatic ring, heat resistance can be improved.

作為用以形成活性酯化合物的羧酸化合物的具體例，可列舉：苯甲酸、乙酸、丁二酸、順丁烯二酸、衣康酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、均苯四甲酸等。該些之中，就耐熱性的觀點而言，較佳為丁二酸、順丁烯二酸、衣康酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸，更佳為鄰苯二甲酸、間苯二甲酸、對苯二甲酸，進而更佳為間苯二甲酸、對苯二甲酸。 作為用以形成活性酯化合物的硫代羧酸化合物的具體例，可列舉：硫代乙酸、硫代苯甲酸等。Specific examples of the carboxylic acid compound for forming the active ester compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and p-benzoic acid. Formic acid, pyromellitic acid, and the like. Among these, from the viewpoint of heat resistance, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and more preferably phthalic acid are preferred. Dicarboxylic acid, isophthalic acid, terephthalic acid, and more preferably isophthalic acid or terephthalic acid. Specific examples of the thiocarboxylic acid compound for forming the active ester compound include thioacetic acid and thiobenzoic acid.

作為用以形成活性酯化合物的羥基化合物的具體例，可列舉：對苯二酚、間苯二酚、雙酚A、雙酚F、雙酚S、酚酞啉、甲基化雙酚A、甲基化雙酚F、甲基化雙酚S、苯酚、鄰甲酚、間甲酚、對甲酚、兒茶酚、α-萘酚、β-萘酚、1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯甲酮、三羥基二苯甲酮、四羥基二苯甲酮、均苯三酚、苯三醇、二環戊二烯基二苯酚、苯酚酚醛清漆等。該些之中，就耐熱性、溶解性的觀點而言，較佳為1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯甲酮、三羥基二苯甲酮、四羥基二苯甲酮、二環戊二烯基二苯酚、苯酚酚醛清漆，更佳為二羥基二苯甲酮、三羥基二苯甲酮、四羥基二苯甲酮、二環戊二烯基二苯酚、苯酚酚醛清漆，進而更佳為二環戊二烯基二苯酚、苯酚酚醛清漆。 作為用以形成活性酯化合物的硫醇化合物的具體例，可列舉：苯二硫醇、三嗪二硫醇等。Specific examples of the hydroxy compound used to form the active ester compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenol porphyrin, methylated bisphenol A, and A. Bisphenol B, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1 ,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, pyrogallol, benzenetriol, dicyclopentadiene Diphenol, phenol novolac, etc. Among these, from the viewpoint of heat resistance and solubility, preferred are 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, phenol novolac, more preferably dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone Further, dicyclopentadienyl diphenol, phenol novolak, and more preferably dicyclopentadienyl diphenol or phenol novolak. Specific examples of the thiol compound for forming the active ester compound include benzenedithiol and triazinedithiol.

作為活性酯化合物，例如可使用：日本專利特開2002-12650號公報及日本專利特開2004-277460號公報中揭示的活性酯化合物、或市售的活性酯化合物。作為市售的活性酯化合物，例如可列舉：商品名「EXB9451、EXB9460、EXB9460S、HPC-8000-65T」（以上，迪愛生公司製造）、商品名「DC808」（日本環氧樹脂公司製造）、商品名「YLH1026」（日本環氧樹脂公司製造）等。 活性酯化合物的製造方法並無特別限定，可藉由公知的方法來製造，例如可藉由羧酸化合物及/或硫代羧酸化合物與羥基化合物及/或硫醇化合物的縮合反應而獲得。 相對於環氧樹脂（XD）100重量份，活性酯化合物（XE）的調配量較佳為20重量份～120重量份，更佳為40重量份～100重量份，進而更佳為50重量份～90重量份的範圍。藉由將活性酯化合物（XE）的調配量設為所述範圍，可提昇作為硬化物的介電特性、耐熱性及線膨脹係數。As the active ester compound, for example, an active ester compound disclosed in Japanese Laid-Open Patent Publication No. 2002-12650 and Japanese Patent Laid-Open No. 2004-277460, or a commercially available active ester compound can be used. Examples of the commercially available active ester compound include "EXB9451, EXB9460, EXB9460S, and HPC-8000-65T" (above, manufactured by Di Ai Sang Co., Ltd.) and trade name "DC808" (manufactured by Nippon Epoxy Co., Ltd.). Trade name "YLH1026" (made by Nippon Epoxy Co., Ltd.). The method for producing the active ester compound is not particularly limited, and it can be produced by a known method, and can be obtained, for example, by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. The compounding amount of the active ester compound (XE) is preferably from 20 parts by weight to 120 parts by weight, more preferably from 40 parts by weight to 100 parts by weight, still more preferably 50 parts by weight, based on 100 parts by weight of the epoxy resin (XD). ～90 parts by weight of the range. By setting the amount of the active ester compound (XE) to the above range, the dielectric properties, heat resistance, and linear expansion coefficient of the cured product can be improved.

作為用作（XE）成分的硬化劑，就與（XA）成分的相容性及耐濕性、黏著性的觀點而言，更佳為鄰甲酚酚醛清漆、對甲酚酚醛清漆、第三丁基苯酚酚醛清漆、二環戊二烯甲酚、聚對乙烯基苯酚、伸二甲苯基改質酚醛清漆、聚(二-鄰羥基苯基)甲烷、聚(二-間羥基苯基)甲烷、聚(二-對羥基苯基)甲烷、甲基納迪克酸酐、三烷基四氫鄰苯二甲酸酐、具有二環戊二烯骨架的酸酐或其改質物、羥基末端聚苯醚寡聚物、或活性酯化合物。The curing agent used as the (XE) component is more preferably o-cresol novolac, p-cresol novolac, and third, from the viewpoint of compatibility with the (XA) component, moisture resistance, and adhesion. Butyl phenol novolac, dicyclopentadiene cresol, poly-p-vinyl phenol, xylylene modified novolac, poly(di-o-hydroxyphenyl)methane, poly(di-m-hydroxyphenyl)methane, Poly(di-p-hydroxyphenyl)methane, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, anhydride having a dicyclopentadiene skeleton or modified product thereof, hydroxyl terminated polyphenylene ether oligomer Or an active ester compound.

藉由在本發明的包含可溶性多官能乙烯基芳香族共聚合物（XA）的硬化性組成物中併用熔融二氧化矽、結晶二氧化矽、氧化鋁、氮化矽、氮化鋁等無機質填充材，十溴二苯基乙烷、溴化聚苯乙烯等阻燃性賦予劑，作為要求介電特性或阻燃性或者耐熱性的電氣零件材料或電子零件材料，特別是半導體密封材料或電路基板用清漆而特別有用。By using an inorganic material such as molten cerium oxide, crystalline cerium oxide, aluminum oxide, cerium nitride or aluminum nitride in the curable composition containing the soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention. A flame retardant imparting agent such as decabromodiphenylethane or brominated polystyrene, which is an electrical component material or an electronic component material, particularly a semiconductor sealing material or circuit, which requires dielectric properties or flame retardancy or heat resistance. The substrate is particularly useful for varnishes.

當用於電路基板材料用清漆中時，可藉由使本發明的硬化性組成物溶解於甲苯、二甲苯、四氫呋喃、二氧雜環戊烷等有機溶劑來製造。再者，作為電路基板材料，具體而言，可列舉：印刷配線基板、印刷電路板、柔性印刷配線板、增層配線板等。When it is used in a varnish for a circuit board material, it can be produced by dissolving the curable composition of the present invention in an organic solvent such as toluene, xylene, tetrahydrofuran or dioxolane. In addition, specific examples of the circuit board material include a printed wiring board, a printed circuit board, a flexible printed wiring board, and a build-up wiring board.

使本發明的包含可溶性多官能乙烯基芳香族共聚合物（XA）的硬化性組成物硬化所獲得的硬化物可用作成型物、積層物、澆鑄物、黏著劑、塗膜、膜。例如，半導體密封材料的硬化物為澆鑄物或成型物，作為獲得該用途的硬化物的方法，可藉由利用澆鑄、或轉注成形機、射出成形機等來使硬化性組成物成形，進而於80℃～230℃下加熱0.5小時～10小時來獲得硬化物。另外，電路基板用清漆的硬化物為積層物，作為獲得該硬化物的方法，可使電路基板用清漆含浸於玻璃纖維、碳纖維、聚酯纖維、聚醯胺纖維、氧化鋁纖維、紙等基材中並進行加熱乾燥而獲得預浸體，然後單獨將該預浸體彼此積層、或與銅箔等金屬箔積層並進行熱壓成形而獲得該硬化物。The cured product obtained by curing the curable composition containing the soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention can be used as a molded product, a laminate, a cast material, an adhesive, a coating film, and a film. For example, the cured product of the semiconductor sealing material is a cast material or a molded product, and as a method of obtaining a cured product for the use, the curable composition can be formed by casting, a transfer molding machine, an injection molding machine, or the like, and further The cured product is obtained by heating at 80 ° C to 230 ° C for 0.5 hour to 10 hours. Further, the cured product of the varnish for a circuit board is a laminate, and as a method for obtaining the cured product, the circuit board varnish may be impregnated with a glass fiber, a carbon fiber, a polyester fiber, a polyamide fiber, an alumina fiber, or a paper. The prepreg is obtained by heating and drying the material, and then the prepreg is laminated on each other or laminated with a metal foil such as copper foil and hot press-molded to obtain the cured product.

藉由調配鈦酸鋇等無機的高介電體粉末、或肥粒鐵等無機磁性體，作為電子零件用材料、特別是高頻電子零件材料有用。An inorganic high dielectric powder such as barium titanate or an inorganic magnetic material such as ferrite iron is used as a material for an electronic component, particularly a high-frequency electronic component material.

與後述的硬化複合材料相同，本發明的硬化性組成物可與金屬箔（包含金屬板的含義。以下相同）貼合來使用。Similarly to the hardened composite material to be described later, the curable composition of the present invention can be used in combination with a metal foil (in the meaning of a metal plate, the same applies hereinafter).

繼而，對本發明的硬化性組成物的硬化性複合材料與其硬化體進行說明。為了提高機械強度、增大尺寸穩定性，而向由本發明的硬化性組成物形成的硬化性複合材料中添加基材。Next, the curable composite material of the curable composition of the present invention and the cured body thereof will be described. In order to improve mechanical strength and increase dimensional stability, a substrate is added to the curable composite material formed of the curable composition of the present invention.

作為此種基材，可使用公知的基材，例如可列舉紗束布、布、切股氈、表面氈等各種玻璃布，石棉布、金屬纖維布、其他合成或天然的無機纖維布，自全芳香族聚醯胺纖維、全芳香族聚酯纖維、聚苯并噁唑纖維等液晶纖維所獲得的織布或不織布，自聚乙烯醇纖維、聚酯纖維、丙烯酸纖維等合成纖維所獲得的織布或不織布，棉布、麻布、毛氈等天然纖維布，碳纖維布、牛皮紙、棉紙、紙-玻璃混纖紙等天然纖維素系布等布類、紙類等，可分別單獨使用或者併用兩種以上。As such a substrate, a known substrate can be used, and examples thereof include various glass cloths such as a yarn bundle cloth, a cloth, a stranded felt, and a surface felt, asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloth. A woven or non-woven fabric obtained from liquid crystal fibers such as wholly aromatic polyamide fibers, wholly aromatic polyester fibers, and polybenzoxazole fibers, obtained from synthetic fibers such as polyvinyl alcohol fibers, polyester fibers, and acrylic fibers. Weaving or non-woven fabrics, cotton, linen, felt and other natural fiber fabrics, carbon fiber cloth, kraft paper, cotton paper, paper-glass mixed fiber paper and other natural cellulose fabrics, such as cloth, paper, etc., can be used alone or in combination More than one species.

於硬化性複合材料中，基材的使用量以5 wt%～90 wt%，較佳為10 wt%～80 wt%，更佳為20 wt%～70 wt%為宜。若基材少於5 wt%，則複合材料的硬化後的尺寸穩定性或強度並不充分，另外，若基材多於90 wt%，則複合材料的介電特性差而欠佳。 於硬化性複合材料中，為了改善樹脂與基材的界面的黏著性，視需要可使用偶合劑。作為偶合劑，可使用矽烷偶合劑、鈦酸酯偶合劑、鋁系偶合劑、鋁鋯偶合劑等一般的偶合劑。In the curable composite material, the substrate is used in an amount of 5 wt% to 90 wt%, preferably 10 wt% to 80 wt%, more preferably 20 wt% to 70 wt%. If the substrate is less than 5% by weight, the dimensional stability or strength of the composite after curing is insufficient, and if the substrate is more than 90% by weight, the dielectric properties of the composite are poor and poor. In the curable composite material, in order to improve the adhesion of the interface between the resin and the substrate, a coupling agent may be used as needed. As the coupling agent, a general coupling agent such as a decane coupling agent, a titanate coupling agent, an aluminum coupling agent, or an aluminum zirconium coupling agent can be used.

作為製造硬化性複合材料的方法，例如可列舉如下的方法：使硬化性組成物與視需要的其他成分均勻地溶解或分散於所述芳香族系、酮系等的溶媒或其混合溶媒中，含浸於基材中後，進行乾燥。含浸藉由浸漬（dipping）、塗佈等來進行。含浸視需要亦可重複多次，此時亦可使用組成或濃度不同的多種溶液來重複含浸，並最終調整成所希望的樹脂組成及樹脂量。The method of producing a curable composite material is, for example, a method in which a curable composition and other components as necessary are uniformly dissolved or dispersed in a solvent such as an aromatic or ketone system or a mixed solvent thereof. After being impregnated into the substrate, it is dried. The impregnation is carried out by dipping, coating, or the like. The impregnation may be repeated as many times as necessary. In this case, the impregnation may be repeated using a plurality of solutions having different compositions or concentrations, and finally adjusted to a desired resin composition and resin amount.

藉由利用加熱等方法使硬化性複合材料硬化而獲得硬化複合材料。其製造方法並無特別限定，例如可使多片硬化性複合材料疊加，與在加熱加壓下使各層間黏著的同時進行熱硬化，而獲得所期望的厚度的硬化複合材料。另外，亦可將黏著硬化過一次的硬化複合材料與硬化性複合材料組合來獲得新的層構成的硬化複合材料。積層成形與硬化通常利用熱壓等來同時進行，但亦可分別單獨進行兩者。即，可利用熱處理或其他方法對事先進行積層成形所獲得的未硬化或半硬化的複合材料進行處理，藉此使其硬化。The hardened composite material is obtained by curing the curable composite material by a method such as heating. The production method is not particularly limited. For example, a plurality of sheets of the curable composite material may be superposed and thermally cured while being adhered to each layer under heat and pressure to obtain a hardened composite material having a desired thickness. Alternatively, a hardened composite material having a new layer composition may be obtained by combining a hardened composite material which has been adhesively cured once and a curable composite material. Laminating and hardening are usually carried out simultaneously by hot pressing or the like, but they may be carried out separately. That is, the uncured or semi-hardened composite material obtained by laminating in advance may be treated by heat treatment or other methods to thereby harden it.

成形及硬化可於溫度：80℃～300℃、壓力：0.1 kg/cm2 ～1000 kg/cm2 、時間：1分鐘～10小時的範圍，更佳為溫度：150℃～250℃、壓力1 kg/cm2 ～500 kg/cm2 、時間：1分鐘～5小時的範圍內進行。Forming and hardening can be carried out at a temperature of 80 ° C to 300 ° C, a pressure of 0.1 kg / cm 2 to 1000 kg / cm 2 , a time of 1 minute to 10 hours, more preferably a temperature of 150 ° C to 250 ° C, a pressure of 1 Kg/cm 2 to 500 kg/cm 2 and time: 1 minute to 5 hours.

於本發明中，所謂積層體，是指包含所述硬化複合材料的層與金屬箔的層者。作為此處所使用的金屬箔，例如可列舉銅箔、鋁箔等。其厚度並無特別限定，但為3 μm～200 μm，更佳為3 μm～105 μm的範圍。In the present invention, the term "laminate" means a layer including a layer of the hardened composite material and a metal foil. Examples of the metal foil used herein include a copper foil, an aluminum foil, and the like. The thickness thereof is not particularly limited, but is in the range of 3 μm to 200 μm, more preferably 3 μm to 105 μm.

作為製造積層體的方法，例如可列舉如下的方法：以對應於目的的層構成將自硬化性組成物與基材所獲得的硬化性複合材料與金屬箔積層，並與在加熱加壓下使各層間黏著的同時進行熱硬化。於硬化性組成物的積層體中，以任意的層構成將硬化複合材料與金屬箔積層。金屬箔可用作表層或中間層。此外，亦可將積層與硬化重複多次來進行多層化。As a method of producing a laminated body, for example, a method of laminating a curable composite material obtained from a curable composition and a substrate with a metal foil in a layer composition corresponding to the purpose, and making it under heat and pressure The layers are adhered while being thermally hardened. In the laminate of the curable composition, the hardened composite material and the metal foil are laminated in an arbitrary layer configuration. The metal foil can be used as a surface layer or an intermediate layer. Further, the laminate and the hardening may be repeated a plurality of times to perform multilayering.

與金屬箔的黏著亦可使用黏著劑。作為黏著劑，可列舉環氧系、丙烯酸系、酚系、氰基丙烯酸酯系等，但並不特別限定於該些黏著劑。積層成形與硬化可在與硬化複合材料的製造相同的條件下進行。Adhesives can also be used for adhesion to metal foil. Examples of the adhesive include an epoxy resin, an acrylic resin, a phenol resin, and a cyanoacrylate resin. However, the adhesive is not particularly limited. The buildup and hardening can be carried out under the same conditions as the manufacture of the hardened composite.

於本發明中，所謂膜，是指將所述硬化性組成物成形為膜狀而成者。其厚度並無特別限定，但為3 μm～200 μm，更佳為5 μm～105 μm的範圍。 作為製造膜的方法，並無特別限定，例如可列舉如下的方法等：使硬化性組成物與視需要的其他成分均勻地溶解或分散於芳香族系、酮系等的溶媒或其混合溶媒中，塗佈於聚對苯二甲酸乙二酯（Polyethylene terephthalate，PET）膜等樹脂膜上後進行乾燥。塗佈視需要亦可重複多次，此時亦可使用組成或濃度不同的多種溶液來重複塗佈，並最終調整成所希望的樹脂組成及樹脂量。In the present invention, the film means that the curable composition is formed into a film shape. The thickness thereof is not particularly limited, but is in the range of 3 μm to 200 μm, more preferably 5 μm to 105 μm. The method of producing the film is not particularly limited, and examples thereof include a method in which a curable composition and other components as needed are uniformly dissolved or dispersed in a solvent such as an aromatic or ketone system or a mixed solvent thereof. It is applied to a resin film such as a polyethylene terephthalate (PET) film and then dried. The coating may be repeated as many times as necessary. In this case, the coating may be repeated using a plurality of solutions having different compositions or concentrations, and finally adjusted to a desired resin composition and resin amount.

於本發明中，所謂帶有樹脂的金屬箔，是指包含所述硬化性組成物與金屬箔者。作為此處所使用的金屬箔，例如可列舉銅箔、鋁箔等。其厚度並無特別限定，但為3 μm～200 μm，更佳為5 μm～105 μm的範圍。In the present invention, the metal foil with a resin refers to a material containing the curable composition and the metal foil. Examples of the metal foil used herein include a copper foil, an aluminum foil, and the like. The thickness thereof is not particularly limited, but is in the range of 3 μm to 200 μm, more preferably 5 μm to 105 μm.

作為製造帶有樹脂的金屬箔的方法，並無特別限定，例如可列舉如下的方法：使硬化性組成物與視需要的其他成分均勻地溶解或分散於芳香族系、酮系等的溶媒或其混合溶媒中，塗佈於金屬箔上後進行乾燥。塗佈視需要亦可重複多次，另外，此時亦可使用組成或濃度不同的多種溶液來重複塗佈，並最終調整成所希望的樹脂組成及樹脂量。The method for producing the metal foil with a resin is not particularly limited, and examples thereof include a method in which a curable composition and other components as necessary are uniformly dissolved or dispersed in a solvent such as an aromatic or ketone system or The mixed solvent is applied to a metal foil and then dried. The coating may be repeated as many times as necessary, and in this case, the coating may be repeated using a plurality of solutions having different compositions or concentrations, and finally adjusted to a desired resin composition and resin amount.

本發明的可溶性多官能乙烯基芳香族共聚合物可加工為成形材、片或膜，於電氣產業、太空·飛機產業等領域中，可用於能夠滿足低介電常數、低吸水率、高耐熱性等特性的低介電材料、絕緣材料、耐熱材料、結構材料等。尤其，可用作單面、雙面、多層印刷基板，柔性印刷基板，增層基板等。進而，可應用於半導體關連材料或光學用材料，進而可應用於塗料、感光性材料、黏著劑、污水處理劑、重金屬捕獲劑、離子交換樹脂、抗靜電劑、抗氧化劑、防霧劑、防鏽劑、防染劑、殺菌劑、防蟲劑、醫用材料、凝聚劑、界面活性劑、潤滑劑、固體燃料用黏合劑、導電處理劑等。The soluble polyfunctional vinyl aromatic copolymer of the present invention can be processed into a shaped material, a sheet or a film, and can be used in the fields of the electrical industry, the space and the aircraft industry, and can be used to satisfy a low dielectric constant, a low water absorption rate, and a high heat resistance. Low dielectric materials such as properties, insulating materials, heat resistant materials, structural materials, and the like. In particular, it can be used as a single-sided, double-sided, multi-layer printed substrate, a flexible printed substrate, a build-up substrate, or the like. Further, it can be applied to a semiconductor related material or an optical material, and can be applied to a coating material, a photosensitive material, an adhesive, a sewage treatment agent, a heavy metal capturing agent, an ion exchange resin, an antistatic agent, an antioxidant, an antifogging agent, and an anti-fogging agent. Rust, anti-dyeing agent, bactericide, insect repellent, medical material, coagulant, surfactant, lubricant, binder for solid fuel, conductive treatment agent, etc.

本發明的硬化性組成物提供於嚴酷的熱歷程後亦具有高度的介電特性（低介電常數·低介電損耗正切）、且即便於嚴酷的環境下亦具有高密接可靠性的硬化物，並且樹脂流動性優異、低線膨脹、配線埋入平坦性優異。因此，於電氣·電子產業、太空·飛機產業等領域中，可提供對應於近年來強烈要求的小型·薄型化且無翹曲等成形不良現象的硬化成形品作為介電材料、絕緣材料、耐熱材料、結構材料等。進而，因配線埋入平坦性及與異種材料的密接性優異，故可實現可靠性優異的樹脂組成物、硬化物或含有其的材料。 [實施例]The curable composition of the present invention is provided with a high dielectric property (low dielectric constant, low dielectric loss tangent) after a severe thermal history, and a cured product having high adhesion reliability even in a severe environment. Further, the resin is excellent in fluidity, low in linear expansion, and excellent in wiring embedding. For this reason, in the fields of the electrical and electronic industries, the space and the aircraft industry, it is possible to provide a hardened molded article that is small, thin, and has no formation defects such as warpage, which has been strongly demanded in recent years, as a dielectric material, an insulating material, and heat resistance. Materials, structural materials, etc. Further, since the wiring is buried in flatness and excellent in adhesion to a dissimilar material, a resin composition, a cured product, or a material containing the same can be realized. [Examples]

以下，藉由實施例來對本發明進行具體說明，但本發明並不限定於該些實施例。再者，各例中的份均為重量份，物性的測定藉由以下所示的方法來進行。Hereinafter, the invention will be specifically described by way of examples, but the invention is not limited to the examples. In addition, the parts in each case are all a weight part, and the physical property is measured by the method shown below.

1）共聚合物（可溶性多官能芳香族共聚合物）的分子量及分子量分佈 分子量及分子量分佈測定是使用GPC（東曹製造，HLC-8120GPC），將四氫呋喃用於溶媒，以流量1.0 ml/min、管柱溫度38℃，使用利用單分散聚苯乙烯的校準曲線來進行。1) Molecular weight and molecular weight distribution of the copolymer (soluble polyfunctional aromatic copolymer) The molecular weight and molecular weight distribution were measured by using GPC (manufactured by Tosoh Corporation, HLC-8120GPC), and tetrahydrofuran was used for the solvent at a flow rate of 1.0 ml/min. The column temperature was 38 ° C and was carried out using a calibration curve using monodisperse polystyrene.

2）共聚合物的結構 使用日本電子製造的JNM-LA600型核磁共振分光裝置，藉由13 C-核磁共振（Nuclear Magnetic Resonance，NMR）及1 H-NMR分析來決定。使用氯仿-d1 作為溶媒，並使用四甲基矽烷的共振線作為內部標準。2) The structure of the copolymer was determined by 13 C-nuclear magnetic resonance (NMR) and 1 H-NMR analysis using a JNM-LA600 type nuclear magnetic resonance spectroscopic device manufactured by JEOL. Chloroform-d 1 was used as a solvent, and a resonance line of tetramethylnonane was used as an internal standard.

3）末端基的分析 關於共聚合物的末端基，使用島津製作所製造的GC-2010型氣相層析儀測定裝置，以4-乙醯基聯苯作為內部標準物質，測定聚合時的各單體的消耗量。進而，數量平均分子量的測定是使用GPC（東曹製造，HLC-8120GPC），將四氫呋喃用於溶媒，以流量1.0 ml/min、管柱溫度38℃，使用利用單分散聚苯乙烯的校準曲線來進行。然後，使用日本電子製造的JNM-LA600型核磁共振分光裝置，藉由13 C-NMR及1 H-NMR分析來決定乙烯基、伸乙烯基等共聚合物的結構單元的含量。使用氯仿-d1 作為溶媒，並使用四甲基矽烷的共振線作為內部標準。而且，根據該些的測定結果，算出ta1及tb1的含量。3) Analysis of the terminal group The terminal group of the copolymer was measured using a GC-2010 gas chromatograph measuring apparatus manufactured by Shimadzu Corporation, and 4-ethyl fluorenylbiphenyl was used as an internal standard substance to measure each single sheet during polymerization. Body consumption. Further, the number average molecular weight was measured by using GPC (manufactured by Tosoh Corporation, HLC-8120GPC), and tetrahydrofuran was used as a solvent at a flow rate of 1.0 ml/min and a column temperature of 38 ° C, using a calibration curve using monodisperse polystyrene. get on. Then, the content of the structural unit of the copolymer such as a vinyl group or a vinyl group was determined by 13 C-NMR and 1 H-NMR analysis using a JNM-LA600 type nuclear magnetic resonance spectroscopic device manufactured by JEOL. Chloroform-d 1 was used as a solvent, and a resonance line of tetramethylnonane was used as an internal standard. Then, based on the measurement results, the contents of ta1 and tb1 were calculated.

4）硬化物的玻璃轉移溫度（Tg）及軟化溫度測定 以乾燥後的厚度變成20 μm的方式，將共聚合物溶液均勻地塗佈於玻璃基板上，使用加熱板於90分下加熱30分鐘來進行乾燥。將玻璃基板與所獲得的樹脂膜一同設置於熱機械分析儀（Thermomechanical Analyzer，TMA）（熱機械分析裝置）上，於氮氣氣流下，以昇溫速度10℃/min昇溫至220℃為止，進而於220℃下進行20分鐘加熱處理，藉此去除殘存的溶媒，並且使共聚合物硬化。將玻璃基板放置冷卻至室溫為止後，使分析用探針接觸TMA測定裝置中的試樣，於氮氣氣流下，以昇溫速度10℃/min自30℃至360℃為止進行掃描測定，並藉由切線法來求出軟化溫度。 關於玻璃轉移溫度，將所述試驗片設置於動態機械分析儀（Dynamic Mechanical Analyzer，DMA）（動態黏彈性裝置）測定裝置上，於氮氣氣流下，以昇溫速度3℃/min自30℃至320℃為止進行掃描，藉此進行測定，並藉由tanδ曲線的峰頂來求出Tg。4) Glass transition temperature (Tg) and softening temperature of the cured product. The copolymer solution was uniformly applied to the glass substrate so that the thickness after drying became 20 μm, and heated at 90 minutes for 30 minutes using a hot plate. To dry. The glass substrate was placed on a thermomechanical analyzer (TMA) (thermomechanical analyzer) together with the obtained resin film, and the temperature was raised to 220 ° C at a temperature increase rate of 10 ° C / min under a nitrogen gas flow, and further The heat treatment was carried out at 220 ° C for 20 minutes, thereby removing the remaining solvent and hardening the copolymer. After the glass substrate was left to cool to room temperature, the probe for analysis was brought into contact with the sample in the TMA measuring apparatus, and the scanning was carried out at a temperature increase rate of 10 ° C/min from 30 ° C to 360 ° C under a nitrogen gas stream. The softening temperature was determined by a tangent method. Regarding the glass transition temperature, the test piece was placed on a Dynamic Mechanical Analyzer (DMA) (Dynamic Viscoelastic Device) measuring device under a nitrogen gas flow rate at a temperature increase rate of 3 ° C/min from 30 ° C to 320 The measurement was performed by scanning at ° C, and Tg was obtained from the peak top of the tan δ curve.

5）耐熱性評價及耐熱變色性的測定 共聚合物的耐熱性評價是將試樣設置於熱重分析儀（Thermal Gravimetric Analyzer，TGA）（熱天平）測定裝置上，於氮氣氣流下，以昇溫速度10℃/min自30℃至400℃為止進行掃描，藉此進行測定，並求出350℃下的重量減少作為耐熱性。另一方面，耐熱變色性的測定是將共聚合物6.0 g、甲基丙烯酸苄酯4.0 g、及過氧化-2-乙基己酸第三丁酯（日本油脂（股）製造，Perbutyl O）0.02 g混合，於氮氣氣流下以200℃加熱1小時，而獲得硬化物。然後，以目視確認所獲得的硬化物的變色量，並分類成○：無熱變色，△：淡黃色，×：黃色，藉此進行耐熱變色性的評價。5) Evaluation of heat resistance and measurement of heat-resistant discoloration The heat resistance of the copolymer was evaluated by placing the sample on a Thermogravimetric Analyzer (TGA) (thermal balance) measuring device and heating it under a nitrogen gas stream. The measurement was performed by scanning at a rate of 10 ° C/min from 30 ° C to 400 ° C, and the weight reduction at 350 ° C was determined as heat resistance. On the other hand, the heat discoloration resistance was measured by adding 6.0 g of a copolymer, 4.0 g of benzyl methacrylate, and tert-butyl peroxy-2-ethylhexanoate (manufactured by Nippon Oil & Fat Co., Ltd., Perbutyl O). The mixture was mixed at 0.02 g, and heated at 200 ° C for 1 hour under a nitrogen gas stream to obtain a cured product. Then, the amount of discoloration of the obtained cured product was visually confirmed, and classified into ○: no thermal discoloration, Δ: pale yellow, and ×: yellow, whereby the heat discoloration resistance was evaluated.

6）相容性的測定 共聚合物與環氧樹脂的相容性的測定是使試樣5.0 g、環氧樹脂（液狀雙酚A型環氧樹脂：日本環氧樹脂公司製造，Epikote828）3.0 g、及酚樹脂（三聚氰胺骨架系酚樹脂：群榮化學工業公司製造，PS-6492）2.0 g溶解於甲基乙基酮（Methyl Ethyl Ketone，MEK）10 g中，以目視確認溶解後的試樣的透明性，並分類成○：透明，△：半透明，×：不透明或未溶解，藉此進行相容性的評價。6) Determination of compatibility The compatibility of the copolymer and the epoxy resin was measured by making 5.0 g of a sample, epoxy resin (liquid bisphenol A type epoxy resin: manufactured by Nippon Epoxy Co., Ltd., Epikote 828) 3.0 g, and phenol resin (melamine skeleton phenol resin: manufactured by Qunrong Chemical Industry Co., Ltd., PS-6492) 2.0 g dissolved in 10 g of methyl ethyl ketone (Methyl Ethyl Ketone, MEK), visually confirmed after dissolution The transparency of the sample was classified into ○: transparent, Δ: translucent, and ×: opaque or undissolved, whereby the compatibility was evaluated.

實施例1 將二乙烯基苯（1,4-二乙烯基苯及1,3-二乙烯基苯的混合物，以下的例亦相同）1.82莫耳（259.6 mL）、乙基乙烯基苯（1-乙基-4-乙烯基苯及1-乙基-3-乙烯基苯的混合物，以下的例亦相同）0.43莫耳（60.9 mL）、乙酸正丁酯0.28莫耳（36.9 mL）及甲苯140 mL投入至1.0 L的反應器內，於70℃下添加使40毫莫耳的甲烷磺酸溶解於乙酸正丁酯0.12莫耳（15.7 mL）中而成的溶液，並進行6小時反應。藉由氫氧化鈣來使聚合溶液停止後，將活性氧化鋁作為助濾劑而進行過濾。然後，於60℃下減壓脫揮，並回收聚合物。秤量所獲得的聚合物，確認獲得222.6 g的共聚合物A。Example 1 Divinylbenzene (a mixture of 1,4-divinylbenzene and 1,3-divinylbenzene, the same applies to the following examples) 1.82 mol (259.6 mL), ethylvinylbenzene (1) - a mixture of ethyl-4-vinylbenzene and 1-ethyl-3-vinylbenzene, the same is true for the following examples) 0.43 mol (60.9 mL), n-butyl acetate 0.28 mol (36.9 mL) and toluene 140 mL was placed in a 1.0 L reactor, and a solution obtained by dissolving 40 mmol of methanesulfonic acid in 0.12 mol of n-butyl acetate (15.7 mL) was added at 70 ° C, and the reaction was carried out for 6 hours. After the polymerization solution was stopped by calcium hydroxide, activated alumina was filtered as a filter aid. Then, the mixture was degassed under reduced pressure at 60 ° C, and the polymer was recovered. The obtained polymer was weighed to confirm that 222.6 g of the copolymer A was obtained.

所獲得的共聚合物A的Mn為1085，Mw為12400，Mw/Mn為11.4。藉由進行GC分析、GPC測定、傅立葉轉換紅外光譜術（Fourier transform infrared spectroscopy，FT-IR）、13 C-NMR及1 H-NMR分析，共聚合物A進行由所述式（a1）、式（a2）、式（a3）、式（ta1）、式（b1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的結構單元的定量。根據其結果，根據式[（a1）+（a3）+（ta1）]/[（a1）+（a2）+（a3）+（b1）+（ta1）+（tb1）]而算出的含有源自二乙烯基芳香族化合物（a）的特定的不飽和烴基的結構單元的莫耳分率為0.51。另外，根據由式（ta1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的共聚合物A的末端結構單元的含量，根據式（ta1）/[（ta1）+（tb1）]而算出的含有乙烯基的末端結構單元的莫耳分率為0.67。而且，共聚合物A含有84.0莫耳%的源自二乙烯基芳香族化合物（a）的結構單元及合計16.0莫耳%的源自單乙烯基芳香族化合物（b）的結構單元。共聚合物A中所含的由所述式（a1）、式（a2）、式（ta1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的不飽和烴基含量為64.2莫耳%。 另外，硬化物的DMA測定的結果，Tg為256℃。另一方面，硬化物的TMA測定的結果，軟化溫度為300℃以上。TGA測定的結果，350℃下的重量減少為1.21 wt%，耐熱變色性為○。另一方面，與環氧樹脂的相容性為○。 共聚合物A可溶於甲苯、二甲苯、四氫呋喃（Tetrahydrofuran，THF）、二氯乙烷、二氯甲烷、氯仿中，未看見凝膠的生成。The obtained copolymer A had an Mn of 1085, a Mw of 12,400, and a Mw/Mn of 11.4. By performing GC analysis, GPC measurement, Fourier transform infrared spectroscopy (FT-IR), 13 C-NMR and 1 H-NMR analysis, the copolymer A is subjected to the formula (a1) Structural unit derived from divinyl aromatic compound (a) and monovinyl aromatic compound (b) represented by formula (a2), formula (a3), formula (ta1), formula (b1) and formula (tb1) Quantification. According to the result, the source containing the equation [(a1)+(a3)+(ta1)]/[(a1)+(a2)+(a3)+(b1)+(ta1)+(tb1)] The structural unit of the specific unsaturated hydrocarbon group derived from the divinyl aromatic compound (a) has a molar fraction of 0.51. Further, the content of the terminal structural unit derived from the copolymer of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (ta1) and the formula (tb1) is The molar fraction of the terminal structural unit containing a vinyl group calculated by the formula (ta1) / [(ta1) + (tb1)] was 0.67. Further, the copolymer A contained 84.0 mol% of a structural unit derived from the divinyl aromatic compound (a) and a total of 16.0 mol% of a structural unit derived from the monovinyl aromatic compound (b). The divinyl aromatic compound (a) and the monovinyl aromatic group represented by the formula (a1), the formula (a2), the formula (ta1) and the formula (tb1) contained in the copolymer A are derived. The unsaturated hydrocarbon group content of the compound (b) was 64.2 mol%. Further, as a result of DMA measurement of the cured product, Tg was 256 °C. On the other hand, as a result of TMA measurement of the cured product, the softening temperature was 300 ° C or higher. As a result of TGA measurement, the weight loss at 350 ° C was 1.21 wt%, and the heat discoloration resistance was ○. On the other hand, the compatibility with the epoxy resin was ○. The copolymer A was soluble in toluene, xylene, tetrahydrofuran (THF), dichloroethane, dichloromethane, chloroform, and no gel formation was observed.

實施例2 將二乙烯基苯1.82莫耳（259.6 mL）、乙基乙烯基苯0.43莫耳（60.9 mL）、乙酸正丁酯0.28莫耳（36.9 mL）及甲苯140 mL投入至1.0 L的反應器內，於70℃下添加使40毫莫耳的對甲苯磺酸·一水合物溶解於乙酸正丁酯0.12莫耳（15.7 mL）中而成的溶液，並進行6小時反應。藉由氫氧化鈣來使聚合溶液停止後，將活性氧化鋁作為助濾劑而進行過濾。然後，於60℃下減壓脫揮，並回收聚合物。秤量所獲得的聚合物，確認獲得124.3 g的共聚合物B。Example 2 Divinylbenzene 1.82 mol (259.6 mL), ethylvinylbenzene 0.43 mol (60.9 mL), n-butyl acetate 0.28 mol (36.9 mL) and toluene 140 mL were put into a reaction of 1.0 L. A solution obtained by dissolving 40 mmol of p-toluenesulfonic acid monohydrate in 0.12 mol of n-butyl acetate (15.7 mL) was added at 70 ° C, and the reaction was carried out for 6 hours. After the polymerization solution was stopped by calcium hydroxide, activated alumina was filtered as a filter aid. Then, the mixture was degassed under reduced pressure at 60 ° C, and the polymer was recovered. The obtained polymer was weighed to confirm that 124.3 g of the copolymer B was obtained.

所獲得的共聚合物B的Mn為748，Mw為3420，Mw/Mn為4.57。藉由進行GC分析、GPC測定、FT-IR、13 C-NMR及1 H-NMR分析，共聚合物B進行由式（a1）、式（a2）、式（a3）、式（ta1）、式（b1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的結構單元的定量。根據其結果，根據式[（a1）+（a3）+（ta1）]/[（a1）+（a2）+（a3）+（b1）+（ta1）+（tb1）]而算出的含有源自二乙烯基芳香族化合物（a）的特定的不飽和烴基的結構單元的莫耳分率為0.60。另外，根據由式（ta1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的共聚合物B的末端結構單元的含量，根據式（ta1）/[（ta1）+（tb1）]而算出的含有乙烯基的末端結構單元的莫耳分率為0.71。而且，共聚合物B含有82.3莫耳%的源自二乙烯基芳香族化合物（a）的結構單元及合計17.7莫耳%的源自單乙烯基芳香族化合物（b）的結構單元。共聚合物B中所含的由所述式（a1）、式（a2）、式（ta1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的不飽和烴基含量為67.8莫耳%。 另外，硬化物的DMA測定的結果，Tg為247℃。另一方面，硬化物的TMA測定的結果，軟化溫度為300℃以上。TGA測定的結果，350℃下的重量減少為1.41 wt%，耐熱變色性為○。另一方面，與環氧樹脂的相容性為○。 共聚合物B可溶於甲苯、二甲苯、THF、二氯乙烷、二氯甲烷、氯仿中，未看見凝膠的生成。The obtained copolymer B had Mn of 748, Mw of 3,420, and Mw/Mn of 4.57. By performing GC analysis, GPC measurement, FT-IR, 13 C-NMR, and 1 H-NMR analysis, the copolymer B is subjected to the formula (a1), the formula (a2), the formula (a3), the formula (ta1), The quantification of the structural unit derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (b1) and the formula (tb1). According to the result, the source containing the equation [(a1)+(a3)+(ta1)]/[(a1)+(a2)+(a3)+(b1)+(ta1)+(tb1)] The structural unit of the specific unsaturated hydrocarbon group derived from the divinyl aromatic compound (a) has a molar fraction of 0.60. Further, the content of the terminal structural unit derived from the copolymer of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (ta1) and the formula (tb1) is The molar fraction of the terminal structural unit containing a vinyl group calculated by the formula (ta1) / [(ta1) + (tb1)] was 0.71. Further, the copolymer B contains 82.3 mol% of a structural unit derived from the divinyl aromatic compound (a) and a total of 17.7 mol% of a structural unit derived from the monovinyl aromatic compound (b). The divinyl aromatic compound (a) and the monovinyl aromatic group represented by the formula (a1), the formula (a2), the formula (ta1) and the formula (tb1) contained in the copolymer B. The unsaturated hydrocarbon group content of the compound (b) was 67.8 mol%. Further, as a result of DMA measurement of the cured product, Tg was 247 °C. On the other hand, as a result of TMA measurement of the cured product, the softening temperature was 300 ° C or higher. As a result of TGA measurement, the weight loss at 350 ° C was 1.41 wt%, and the heat discoloration resistance was ○. On the other hand, the compatibility with the epoxy resin was ○. The copolymer B was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, chloroform, and no gel formation was observed.

比較例1 將二乙烯基苯2.03莫耳（288.5 mL）、乙基乙烯基苯0.084莫耳（12.0 mL）、苯乙烯2.11莫耳（241.7 mL）、甲基丙烯酸2-苯氧基乙酯2.25莫耳（427.3 mL）、乙酸丁酯100.0 mL、及甲苯1150 mL投入至3.0 L的反應器內，於50℃下添加300毫莫耳的三氟化硼的二乙基醚錯合物，並進行4小時反應。藉由碳酸氫鈉水溶液來使聚合溶液停止後，利用純水將油層清洗3次，於室溫下將反應混合液投入至大量的甲醇中，使聚合物析出。利用甲醇對所獲得的聚合物進行清洗，並進行濾除、乾燥、秤量，而獲得282.4 g的共聚合物C。Comparative Example 1 Divinylbenzene 2.03 mol (288.5 mL), ethyl vinylbenzene 0.084 mol (12.0 mL), styrene 2.11 mol (241.7 mL), 2-phenoxyethyl methacrylate 2.25 Moore (427.3 mL), butyl acetate 100.0 mL, and 1150 mL of toluene were charged into a 3.0 L reactor, and 300 mmoles of boron trifluoride diethyl ether complex was added at 50 ° C, and The reaction was carried out for 4 hours. After the polymerization solution was stopped by an aqueous solution of sodium hydrogencarbonate, the oil layer was washed three times with pure water, and the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a polymer. The obtained polymer was washed with methanol, filtered, dried, and weighed to obtain 282.4 g of a copolymer C.

所獲得的共聚合物C的Mn為2030，Mw為5180，Mw/Mn為2.55。藉由進行13 C-NMR及1 H-NMR分析，共聚合物C觀察到源自甲基丙烯酸2-苯氧基乙酯末端的共振線。進行共聚合物C的元素分析結果的結果，C：87.3 wt%，H：7.4 wt%，O：5.2 wt%。 根據元素分析結果與標準聚苯乙烯換算的數量平均分子量所算出的可溶性多官能乙烯基芳香族聚合物的源自甲基丙烯酸2-苯氧基乙酯的結構單元的導入量（c1）為2.3（個/分子）。藉由進行GC分析、GPC測定、FT-IR、13 C-NMR及1 H-NMR分析，共聚合物C進行由所述式（a1）、式（a2）、式（a3）、式（ta1）、式（b1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及乙基乙烯基芳香族化合物（b）的結構單元的定量。根據其結果，於所述結構單元內，未觀察到由式（a2）、式（ta1）及式（tb1）所表示的結構單元。因此，根據式[（a1）+（a3）+（ta1）]/[（a1）+（a2）+（a3）+（b1）+（ta1）+（tb1）]而算出的含有源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的特定的不飽和烴基的結構單元的莫耳分率為0.59。 另一方面，關於由式（ta1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的共聚合物C的末端結構單元的含量，由式（ta1）及式（tb1）所表示的結構單元的任一者於分析中，均未被檢測出，因此可認為藉由式（ta1）/[（ta1）+（tb1）]而算出的含有乙烯基的末端結構單元的莫耳分率為0。另外，含有59.2莫耳%的源自二乙烯基苯的結構單元及合計40.8莫耳%的源自苯乙烯與乙基苯的結構單元（末端結構單元除外）。共聚合物C中所含有的乙烯基含量為35.3莫耳%（末端結構單元除外）。 另外，硬化物的DMA測定的結果，Tg為197℃。硬化物的TMA測定的結果，軟化溫度為300℃以上。TGA測定的結果，350℃下的重量減少為4.86 wt%，耐熱變色性為○。另一方面，與環氧樹脂的相容性為△。 共聚合物C可溶於甲苯、二甲苯、THF、二氯乙烷、二氯甲烷、氯仿中，未看見凝膠的生成。The obtained copolymer C had an Mn of 2030, a Mw of 5,180 and a Mw/Mn of 2.55. The resonance line derived from the terminal of 2-phenoxyethyl methacrylate was observed by the copolymer C by 13 C-NMR and 1 H-NMR analysis. As a result of performing elemental analysis of the copolymer C, C: 87.3 wt%, H: 7.4 wt%, and O: 5.2 wt%. The amount of introduction (c1) of the structural unit derived from 2-phenoxyethyl methacrylate of the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis result and the number average molecular weight in terms of standard polystyrene was 2.3. (one / molecule). By performing GC analysis, GPC measurement, FT-IR, 13 C-NMR, and 1 H-NMR analysis, the copolymer C is subjected to the formula (a1), the formula (a2), the formula (a3), and the formula (ta1). The quantification of the structural unit derived from the divinyl aromatic compound (a) and the ethyl vinyl aromatic compound (b) represented by the formula (b1) and the formula (tb1). According to the results, structural units represented by the formula (a2), the formula (ta1), and the formula (tb1) were not observed in the structural unit. Therefore, the content calculated according to the formula [(a1)+(a3)+(ta1)]/[(a1)+(a2)+(a3)+(b1)+(ta1)+(tb1)] is derived from two The structural unit of the specific unsaturated hydrocarbon group of the vinyl aromatic compound (a) and the monovinyl aromatic compound (b) has a molar fraction of 0.59. On the other hand, the content of the terminal structural unit derived from the copolymer of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (ta1) and the formula (tb1) Any one of the structural units represented by the formula (ta1) and the formula (tb1) is not detected in the analysis, and therefore it can be considered that by the formula (ta1) / [(ta1) + (tb1)] The calculated vinyl group-containing terminal structural unit had a molar fraction of 0. Further, it contained 59.2 mol% of structural units derived from divinylbenzene and a total of 40.8 mol% of structural units derived from styrene and ethylbenzene (excluding terminal structural units). The vinyl content contained in the copolymer C was 35.3 mol% (except for the terminal structural unit). Further, as a result of DMA measurement of the cured product, Tg was 197 °C. As a result of TMA measurement of the cured product, the softening temperature was 300 ° C or higher. As a result of TGA measurement, the weight loss at 350 ° C was 4.86 wt%, and the heat discoloration resistance was ○. On the other hand, the compatibility with the epoxy resin is Δ. The copolymer C was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, chloroform, and no gel formation was observed.

比較例2 將二乙烯基苯1.82莫耳（259.6 mL）、乙基乙烯基苯0.43莫耳（60.9 mL）及甲苯140 mL投入至1.0 L的反應器內，於70℃下添加40毫莫耳的對甲苯磺酸·一水合物，並進行6小時反應。藉由氫氧化鈣來使聚合溶液停止後，將活性氧化鋁作為助濾劑而進行過濾。然後，於60℃下減壓脫揮，並回收聚合物。秤量所獲得的聚合物，確認獲得187.3 g的共聚合物D。Comparative Example 2 Divinylbenzene 1.82 mol (259.6 mL), ethylvinylbenzene 0.43 mol (60.9 mL) and toluene 140 mL were placed in a 1.0 L reactor, and 40 mmol was added at 70 ° C. p-Toluenesulfonic acid·monohydrate and reacted for 6 hours. After the polymerization solution was stopped by calcium hydroxide, activated alumina was filtered as a filter aid. Then, the mixture was degassed under reduced pressure at 60 ° C, and the polymer was recovered. The obtained polymer was weighed to confirm that 187.3 g of the copolymer D was obtained.

所獲得的共聚合物D的Mn為1024，Mw為7820，Mw/Mn為7.64。進行GC分析、GPC測定、FT-IR、13 C-NMR及1 H-NMR分析的結果，進行由所述式（a1）、式（a2）、式（a3）、式（ta1）、式（b1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及乙基乙烯基芳香族化合物（b）的結構單元的定量。根據其結果，關於共聚合物D，根據式[（a1）+（a3）+（ta1）]/[（a1）+（a2）+（a3）+（b1）+（ta1）+（tb1）]而算出的含有源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的特定的不飽和烴基的結構單元的莫耳分率為0.04。另外，根據由式（ta1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的共聚合物B的末端結構單元的含量，根據式（ta1）/[（ta1）+（tb1）]而算出的含有乙烯基的末端結構單元的莫耳分率為0.05。而且，共聚合物D含有83.1莫耳%的源自二乙烯基苯的結構單元及合計16.9莫耳%的源自單乙烯基苯的結構單元。共聚合物D中所含的由所述式（a1）～式（a3）所表示的源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的不飽和烴基含量為81.3莫耳%。 另外，硬化物的DMA測定的結果，Tg為136℃。另一方面，硬化物的TMA測定的結果，軟化溫度為125℃。TGA測定的結果，350℃下的重量減少為7.31 wt%，耐熱變色性為△。另一方面，與環氧樹脂的相容性為○。 共聚合物D可溶於甲苯、二甲苯、THF、二氯乙烷、二氯甲烷、氯仿中，未看見凝膠的生成。The obtained copolymer D had an Mn of 1024, a Mw of 7820, and a Mw/Mn of 7.64. The results of GC analysis, GPC measurement, FT-IR, 13 C-NMR, and 1 H-NMR analysis were carried out, and the formula (a1), the formula (a2), the formula (a3), the formula (ta1), and the formula (a) were carried out. B1) and the quantitative amount of the structural unit derived from the divinyl aromatic compound (a) and the ethyl vinyl aromatic compound (b) represented by the formula (tb1). According to the results, regarding the copolymer D, according to the formula [(a1) + (a3) + (ta1)] / [(a1) + (a2) + (a3) + (b1) + (ta1) + (tb1) The molar fraction of the structural unit containing the specific unsaturated hydrocarbon group derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) was 0.04. Further, the content of the terminal structural unit derived from the copolymer of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (ta1) and the formula (tb1) is The molar fraction of the terminal structural unit containing a vinyl group calculated by the formula (ta1) / [(ta1) + (tb1)] was 0.05. Further, the copolymer D contained 83.1 mol% of structural units derived from divinylbenzene and a total of 16.9 mol% of structural units derived from monovinylbenzene. The content of the unsaturated hydrocarbon group derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the above formula (a1) to formula (a3) contained in the copolymer D is 81.3% of the mole. Further, as a result of DMA measurement of the cured product, Tg was 136 °C. On the other hand, as a result of TMA measurement of the cured product, the softening temperature was 125 °C. As a result of TGA measurement, the weight loss at 350 ° C was 7.31 wt%, and the heat discoloration resistance was Δ. On the other hand, the compatibility with the epoxy resin was ○. The copolymer D was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, chloroform, and no gel formation was observed.

實施例3 將二乙烯基聯苯1.80莫耳（324.4 g）、乙基乙烯基聯苯0.45莫耳（81.1 g）、乙酸正丁酯0.28莫耳（36.9 mL）及甲苯140 mL投入至1.0 L的反應器內，於70℃下添加使40毫莫耳的甲烷磺酸溶解於乙酸正丁酯0.12莫耳（15.7 mL）中而成的溶液，並進行6小時反應。藉由氫氧化鈣來使聚合溶液停止後，將活性氧化鋁作為助濾劑而進行過濾。然後，於60℃下減壓脫揮，並回收聚合物。秤量所獲得的聚合物，確認獲得259.5 g的共聚合物E。Example 3 Divinylbiphenyl 1.80 mole (324.4 g), ethyl vinylbiphenyl 0.45 mol (81.1 g), n-butyl acetate 0.28 mol (36.9 mL) and toluene 140 mL were put into 1.0 L In the reactor, a solution obtained by dissolving 40 mmol of methanesulfonic acid in 0.12 mol of n-butyl acetate (15.7 mL) was added at 70 ° C, and the reaction was carried out for 6 hours. After the polymerization solution was stopped by calcium hydroxide, activated alumina was filtered as a filter aid. Then, the mixture was degassed under reduced pressure at 60 ° C, and the polymer was recovered. The obtained polymer was weighed to confirm that 259.5 g of the copolymer E was obtained.

所獲得的共聚合物E的Mn為1342，Mw為13960，Mw/Mn為10.4。藉由進行GC分析、GPC測定、FT-IR、13 C-NMR及1 H-NMR分析，共聚合物E進行由所述式（a1）、式（a2）、式（a3）、式（ta1）、式（b1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的結構單元的定量。根據其結果，根據式[（a1）+（a3）+（ta1）]/[（a1）+（a2）+（a3）+（b1）+（ta1）+（tb1）]而算出的含有源自二乙烯基芳香族化合物（a）的特定的不飽和烴基的結構單元的莫耳分率為0.60。另外，根據由式（ta1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的共聚合物E的末端結構單元的含量，根據式（ta1）/[（ta1）+（tb1）]而算出的含有乙烯基的末端結構單元的莫耳分率為0.57。而且，共聚合物E含有82.6莫耳%的源自二乙烯基芳香族化合物（a）的結構單元及合計17.4莫耳%的源自單乙烯基芳香族化合物（b）的結構單元。共聚合物E中所含的由所述式（a1）、式（a2）、式（ta1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的不飽和烴基含量為68.2莫耳%。 另外，硬化物的DMA測定的結果，Tg為271℃。另一方面，硬化物的TMA測定的結果，軟化溫度為300℃以上。TGA測定的結果，350℃下的重量減少為1.36 wt%，耐熱變色性為○。另一方面，與環氧樹脂的相容性為○。 共聚合物E可溶於甲苯、二甲苯、THF、二氯乙烷、二氯甲烷、氯仿中，未看見凝膠的生成。The obtained copolymer E had an Mn of 1,342, a Mw of 13,960, and a Mw/Mn of 10.4. By performing GC analysis, GPC measurement, FT-IR, 13 C-NMR, and 1 H-NMR analysis, the copolymer E is subjected to the formula (a1), the formula (a2), the formula (a3), and the formula (ta1). The quantification of the structural unit derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (b1) and the formula (tb1). According to the result, the source containing the equation [(a1)+(a3)+(ta1)]/[(a1)+(a2)+(a3)+(b1)+(ta1)+(tb1)] The structural unit of the specific unsaturated hydrocarbon group derived from the divinyl aromatic compound (a) has a molar fraction of 0.60. Further, the content of the terminal structural unit derived from the copolymer of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (ta1) and the formula (tb1) is The molar fraction of the terminal structural unit containing a vinyl group calculated by the formula (ta1) / [(ta1) + (tb1)] was 0.57. Further, the copolymer E contains 82.6 mol% of a structural unit derived from the divinyl aromatic compound (a) and a total of 17.4 mol% of a structural unit derived from the monovinyl aromatic compound (b). The divinyl aromatic compound (a) and the monovinyl aromatic group represented by the formula (a1), the formula (a2), the formula (ta1) and the formula (tb1) contained in the copolymer E are contained. The unsaturated hydrocarbon group content of the compound (b) was 68.2 mol%. Further, as a result of DMA measurement of the cured product, Tg was 271 °C. On the other hand, as a result of TMA measurement of the cured product, the softening temperature was 300 ° C or higher. As a result of TGA measurement, the weight loss at 350 ° C was 1.36 wt%, and the heat discoloration resistance was ○. On the other hand, the compatibility with the epoxy resin was ○. The copolymer E was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, chloroform, and no gel formation was observed.

實施例4 將二乙烯基苯1.82莫耳（259.6 mL）、乙基乙烯基苯0.43莫耳（60.9 mL）、乙酸正丁酯0.28莫耳（36.9 mL）及甲苯140 mL投入至1.0 L的反應器內，於60℃下添加使60毫莫耳的甲烷磺酸溶解於乙酸正丁酯0.12莫耳（15.7 mL）中而成的溶液，並進行12小時反應。藉由氫氧化鈣來使聚合溶液停止後，將活性氧化鋁作為助濾劑而進行過濾。然後，於60℃下減壓脫揮，並回收聚合物。秤量所獲得的聚合物，確認獲得167.8 g的共聚合物F。Example 4 Divinylbenzene 1.82 mol (259.6 mL), ethyl vinylbenzene 0.43 mol (60.9 mL), n-butyl acetate 0.28 mol (36.9 mL) and toluene 140 mL were put into a reaction of 1.0 L. A solution obtained by dissolving 60 mmol of methanesulfonic acid in 0.12 mol of n-butyl acetate (15.7 mL) was added at 60 ° C, and the reaction was carried out for 12 hours. After the polymerization solution was stopped by calcium hydroxide, activated alumina was filtered as a filter aid. Then, the mixture was degassed under reduced pressure at 60 ° C, and the polymer was recovered. The obtained polymer was weighed to confirm that 167.8 g of the copolymer F was obtained.

所獲得的共聚合物F的Mn為1450，Mw為19700，Mw/Mn為13.6。藉由進行GC分析、GPC測定、FT-IR、13 C-NMR及1 H-NMR分析，共聚合物A進行由所述式（a1）、式（a2）、式（a3）、式（ta1）、式（b1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及乙基乙烯基芳香族化合物（b）的結構單元的定量。根據其結果，根據式[（a1）+（a3）+（ta1）]/[（a1）+（a2）+（a3）+（b1）+（ta1）+（tb1）]而算出的含有源自二乙烯基芳香族化合物（a）及乙基乙烯基芳香族化合物（b）的特定的不飽和烴基的結構單元的莫耳分率為0.74。另外，根據由式（ta1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的共聚合物F的末端結構單元的含量，根據式（ta1）/[（ta1）+（tb1）]而算出的含有乙烯基的末端結構單元的莫耳分率為0.61。而且，共聚合物F含有83.6莫耳%的源自二乙烯基芳香族化合物（a）的結構單元及合計16.4莫耳%的源自單乙烯基芳香族化合物（a）的結構單元。共聚合物F中所含的由所述式（a1）、式（a2）、式（ta1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及乙基乙烯基芳香族化合物（b）的不飽和烴基含量為58.6莫耳%。 另外，硬化物的DMA測定的結果，Tg為271℃。另一方面，硬化物的TMA測定的結果，軟化溫度為300℃以上。TGA測定的結果，350℃下的重量減少為1.12 wt%，耐熱變色性為○。另一方面，與環氧樹脂的相容性為○。 共聚合物F可溶於甲苯、二甲苯、THF、二氯乙烷、二氯甲烷、氯仿中，未看見凝膠的生成。The obtained copolymer F had an Mn of 1,450, a Mw of 19,700 and a Mw/Mn of 13.6. By performing GC analysis, GPC measurement, FT-IR, 13 C-NMR and 1 H-NMR analysis, the copolymer A is subjected to the formula (a1), the formula (a2), the formula (a3), and the formula (ta1). The quantification of the structural unit derived from the divinyl aromatic compound (a) and the ethyl vinyl aromatic compound (b) represented by the formula (b1) and the formula (tb1). According to the result, the source containing the equation [(a1)+(a3)+(ta1)]/[(a1)+(a2)+(a3)+(b1)+(ta1)+(tb1)] The structural unit of the specific unsaturated hydrocarbon group derived from the divinyl aromatic compound (a) and the ethyl vinyl aromatic compound (b) has a molar fraction of 0.74. Further, the content of the terminal structural unit derived from the copolymer of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (ta1) and the formula (tb1) is The molar fraction of the terminal structural unit containing a vinyl group calculated by the formula (ta1) / [(ta1) + (tb1)] was 0.61. Further, the copolymer F contains 83.6 mol% of a structural unit derived from the divinyl aromatic compound (a) and a total of 16.4 mol% of a structural unit derived from the monovinyl aromatic compound (a). The divinyl aromatic compound (a) and the ethyl vinyl aromatic group represented by the formula (a1), the formula (a2), the formula (ta1) and the formula (tb1) contained in the copolymer F are contained. The content of the unsaturated hydrocarbon group of the group compound (b) was 58.6 mol%. Further, as a result of DMA measurement of the cured product, Tg was 271 °C. On the other hand, as a result of TMA measurement of the cured product, the softening temperature was 300 ° C or higher. As a result of TGA measurement, the weight loss at 350 ° C was 1.12 wt%, and the heat discoloration resistance was ○. On the other hand, the compatibility with the epoxy resin was ○. The copolymer F was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, chloroform, and no gel formation was observed.

使用實施例1～實施例4及比較例1～比較例2中所獲得的共聚合物A～共聚合物F，根據下述方法進行使用該些樹脂的硬化性樹脂組成物的清漆及硬化物的特性的評價。Using the copolymer A to the copolymer F obtained in each of Examples 1 to 4 and Comparative Examples 1 to 2, varnishes and cured products of the curable resin composition using the resins were subjected to the following methods. Evaluation of the characteristics.

7）溶液黏度 硬化性樹脂組成物的溶液黏度是使用E型黏度計，於測定溫度：25℃下進行測定。7) Solution viscosity The solution viscosity of the curable resin composition was measured using an E-type viscometer at a measurement temperature of 25 °C.

8）彎曲強度及彎曲斷裂伸長率 用於彎曲試驗的試驗片是將將硬化性樹脂組成物硬化性樹脂組成物的清漆裝載於真空壓製成形機的下方的模具上，並於加熱真空下使溶劑脫揮。其後，裝載上模，於真空下進行加熱壓製，並於200℃下保持1小時，藉此使厚度：1.0 mm的平板成形。自進行成形所獲得的平板製作寬度：5.0 mm、厚度：1.0 mm、長度：120 mm的試驗片，並進行彎曲試驗。所製作的彎曲試驗片的彎曲強度及彎曲斷裂伸長率是使用萬能試驗裝置進行測定。而且，彎曲強度及彎曲斷裂伸長率是將相對於成為基準的調配的測定值變成未滿±10%的值者評價為○，將相對於成為基準的調配的測定值變成10%以上的值者評價為◎，將相對於成為基準的調配的測定值變成-10%～-20%的範圍的值者評價為△，將相對於成為基準的調配的測定值變成-20%以下的值者評價為×。8) Bending strength and bending elongation at break The test piece for the bending test was obtained by loading a varnish having a curable resin composition curable resin composition on a mold below the vacuum press molding machine, and heating the solvent under vacuum. Take off. Thereafter, the upper mold was placed, heated and pressed under vacuum, and kept at 200 ° C for 1 hour, whereby a flat plate having a thickness of 1.0 mm was formed. A test piece having a width of 5.0 mm, a thickness of 1.0 mm, and a length of 120 mm obtained by forming was subjected to a bending test. The bending strength and the bending elongation at break of the produced bending test piece were measured using a universal test apparatus. In addition, the bending strength and the bending elongation at break are evaluated as ○ with a value of less than ±10% of the measured value of the standard preparation, and a value of 10% or more with respect to the measured value of the standard. In the case of the value of the range of the range of -10% to -20%, the value of the measurement value of the standard is Δ%, and the value of the measurement value based on the standard is -20% or less. For ×.

9）線膨脹係數及玻璃轉移溫度 用於硬化性樹脂組成物的線膨脹係數及玻璃轉移溫度的試驗的試驗片是將將硬化性樹脂組成物硬化性樹脂組成物的清漆裝載於真空壓製成形機的下方的平板形狀的模具上，並於加熱真空下使溶劑脫揮。其後，隔著0.2 mm的間隔物裝載上模，於真空下進行加熱壓製，並於200℃下保持1小時，藉此使厚度：0.2 mm的平板成形。自進行成形所獲得的平板製作寬度：3.0 mm、厚度：0.2 mm、長度：40 mm的試驗片，並僅設置於TMA（熱機械分析裝置）的上方的夾頭上，於氮氣氣流下，以昇溫速度10℃/min昇溫至220℃為止，進而於220℃下進行20分鐘加熱處理，藉此去除殘存的溶媒，並且進行試驗片中的成形應變的去除。將TMA放置冷卻至室溫為止後，將TMA測定裝置中的試驗片的下側亦設置於分析用探針上，於氮氣氣流下，以昇溫速度10℃/min自30℃至360℃為止進行掃描測定，並根據0℃～40℃中的尺寸變化來算出線膨脹係數。 另外，關於玻璃轉移溫度，將所述試驗片設置於DMA（動態黏彈性裝置）測定裝置上，於氮氣氣流下，以昇溫速度3℃/min自30℃至320℃為止進行掃描，藉此進行測定，並藉由tanδ曲線的峰頂來求出Tg。9) Linear expansion coefficient and glass transition temperature The test piece for the test of the linear expansion coefficient and the glass transition temperature of the curable resin composition is a varnish in which the curable resin composition curable resin composition is loaded on a vacuum press molding machine. The bottom of the plate is shaped on the mold and the solvent is devolatilized under a heated vacuum. Thereafter, the upper mold was placed through a spacer of 0.2 mm, heated and pressed under vacuum, and held at 200 ° C for 1 hour, whereby a flat plate having a thickness of 0.2 mm was formed. A test piece having a width of 3.0 mm, a thickness of 0.2 mm, and a length of 40 mm obtained by forming was set only on a chuck above the TMA (thermomechanical analysis device), and was heated under a nitrogen gas stream. The temperature was raised to 220 ° C at a rate of 10 ° C / min, and further heat treatment was performed at 220 ° C for 20 minutes, thereby removing the remaining solvent and removing the forming strain in the test piece. After the TMA was left to cool to room temperature, the lower side of the test piece in the TMA measuring apparatus was also placed on the analysis probe, and the temperature was increased from 10 ° C to 360 ° C at a temperature increase rate of 10 ° C/min under a nitrogen gas stream. The measurement was performed by scanning, and the coefficient of linear expansion was calculated from the dimensional change in the range of 0 ° C to 40 ° C. Further, regarding the glass transition temperature, the test piece was placed on a DMA (Dynamic Viscoelastic Device) measuring device, and scanned at a temperature increase rate of 3 ° C/min from 30 ° C to 320 ° C under a nitrogen gas flow. The Tg was determined by the peak top of the tan δ curve.

10）介電常數及介電損耗正切 依據JIS C2565規格，藉由AET股份有限公司製造的空腔諧振器法介電常數測定裝置，並使用絕對乾燥後在23℃、濕度50%的室內保管24小時後的硬化物平板試驗片，測定18 GHz中的介電常數及介電損耗正切。 另外，將硬化物平板試驗片於85℃、相對濕度85%中放置2週後，進行介電常數及介電損耗正切的測定，並測定耐濕熱試驗後的介電常數及介電損耗正切。10) The dielectric constant and the dielectric loss tangent are stored in a chamber of 23 ° C and a humidity of 50% by using a cavity resonator dielectric constant measuring device manufactured by AET Co., Ltd. according to JIS C2565 specifications. The hardened flat test piece after an hour was measured for dielectric constant and dielectric loss tangent at 18 GHz. Further, the cured flat plate test piece was allowed to stand at 85 ° C and a relative humidity of 85% for 2 weeks, and then the dielectric constant and dielectric loss tangent were measured, and the dielectric constant and dielectric loss tangent after the moisture heat resistance test were measured.

11）銅箔剝離強度 將玻璃布（E玻璃，單位面積重量為71 g/m2 ）浸漬於熱硬化性樹脂組成物的清漆中來進行含浸，並於80℃的空氣烘箱中進行10分鐘乾燥。此時，以所獲得的預浸體的樹脂含量（R.C）變成50 wt%的方式進行調整。 使用該預浸體，以成形後的厚度變成約0.6 mm～1.0 mm的方式，視需要將多片所述硬化性複合材料疊加，於其兩面放置厚度為18 μm的銅箔（商品名為F2-WS銅箔，Rz：2.0 μm，Ra：0.3 μm）並藉由真空壓製成形機來進行成形硬化而獲得評價用積層體。硬化條件為以3℃/min昇溫，並於壓力3 MPa下以200℃保持60分鐘，而獲得評價用覆銅積層板。11) Copper foil peeling strength Glass cloth (E glass, unit weight: 71 g/m 2 ) was immersed in a varnish of a thermosetting resin composition, impregnated, and dried in an air oven at 80 ° C for 10 minutes. . At this time, the adjustment was carried out so that the resin content (RC) of the obtained prepreg became 50 wt%. Using the prepreg, a plurality of sheets of the curable composite material are superposed as needed, and a copper foil having a thickness of 18 μm is placed on both sides thereof (trade name is F2) so that the thickness after molding becomes about 0.6 mm to 1.0 mm. -WS copper foil, Rz: 2.0 μm, Ra: 0.3 μm) and form-hardened by a vacuum press molding machine to obtain a laminate for evaluation. The hardening conditions were such that the temperature was raised at 3 ° C/min and held at 200 ° C for 60 minutes under a pressure of 3 MPa to obtain a copper-clad laminate for evaluation.

自以所述方式獲得的積層體硬化物切出寬度為20 mm、長度為100 mm的試驗片，於銅箔面切入寬度為10 mm的平行的切口後，在相對於面為90°的方向上以50 mm/min的速度連續地剝離銅箔，利用拉伸試驗機測定此時的應力，將其應力的最低值記錄為銅箔剝離強度。（依據JIS C 6481）。耐濕熱性試驗後的銅箔剝離強度的試驗是將所述試驗片於85℃、相對濕度85%中放置2週後，以與所述相同的方式進行測定。A test piece having a width of 20 mm and a length of 100 mm was cut out from the cured product obtained in the manner described above, and a parallel slit having a width of 10 mm was cut into the copper foil surface in a direction of 90° with respect to the surface. The copper foil was continuously peeled off at a speed of 50 mm/min, and the stress at this time was measured by a tensile tester, and the lowest value of the stress was recorded as the peeling strength of the copper foil. (According to JIS C 6481). The copper foil peeling strength test after the moisture heat resistance test was carried out by placing the test piece at 85 ° C and a relative humidity of 85% for 2 weeks, and then measuring in the same manner as described above.

12）鍍銅剝離強度 ·帶有鍍銅的積層板的製作 於40℃下，使前項所製作的覆銅積層板於過硫酸銨150 g/L的水溶液中浸漬20分鐘來對銅箔進行蝕刻去除。12) Copper peeling strength. Preparation of laminated plate with copper plating. The copper-clad laminate produced in the preceding paragraph was immersed in an aqueous solution of ammonium persulfate 150 g/L for 20 minutes at 40 ° C to etch the copper foil. Remove.

繼而，利用浸漬法，於80℃下，在膨潤水溶液的Circuposit MLB Conditioner211（日本羅門哈斯（Rohm and Haas Japan）股份有限公司製造，商品名）中對未抽出試樣的積層板進行5分鐘浸漬處理。進而，於流水洗的室溫下進行3分鐘處理後，使用Circuposit MLB Promoter213（日本羅門哈斯股份有限公司製造，商品名）作為過錳酸強鹼水溶液，同樣地利用浸漬法於80℃下進行10分鐘浸漬處理。Then, the laminate of the unextracted sample was immersed in a swellable aqueous solution of Circuposit MLB Conditioner 211 (manufactured by Rohm and Haas Japan Co., Ltd., trade name) at 80 ° C for 5 minutes. deal with. Furthermore, after performing the treatment for 3 minutes at room temperature of the water-washing, Circuposit MLB Promoter 213 (trade name, manufactured by Rohm and Haas Co., Ltd., Japan) was used as a strong aqueous solution of permanganic acid, and the same method was carried out at 80 ° C by a dipping method. Immersion treatment for 10 minutes.

繼而，使用MLB Neutralizer216（日本羅門哈斯股份有限公司製造，商品名）作為中和液，利用浸漬法於40℃下進行5分鐘浸漬處理。於流水洗的室溫下進行3分鐘處理後，使用調節液的CLC-501（商品名，日立化成工業股份有限公司製造）於60℃下進行5分鐘處理，並進行流水洗，於預浸液PD-201（商品名，日立化成工業股份有限公司製造）水溶液中，在室溫下進行3分鐘處理，然後於含有金屬鈀液HS-202B（商品名，日立化成工業股份有限公司製造）的水溶液中，在室溫下進行10分鐘處理，並進行水洗，然後於活化處理液ADP-501（商品名，日立化成工業股份有限公司製造）水溶液中，在室溫下進行5分鐘處理。而且，使用Cust-201作為無電解鍍銅液，利用浸漬法於室溫下進行15分鐘浸漬處理，藉此於積層板的兩面形成無電解銅厚為0.5 μm的基底銅，進而利用電解銅鍍敷加厚至銅厚為20 μm為止。Then, MLB Neutralizer 216 (trade name, manufactured by Rohm and Haas Co., Ltd., Japan) was used as a neutralizing liquid, and immersion treatment was performed at 40 ° C for 5 minutes by a dipping method. After being treated for 3 minutes at room temperature under running water, CLC-501 (trade name, manufactured by Hitachi Chemical Co., Ltd.) using a conditioning solution was treated at 60 ° C for 5 minutes, and washed with water for prepreg. PD-201 (trade name, manufactured by Hitachi Chemical Co., Ltd.) was treated in an aqueous solution containing a metal palladium liquid HS-202B (trade name, manufactured by Hitachi Chemical Co., Ltd.) for 3 minutes at room temperature. In the above, the mixture was treated at room temperature for 10 minutes, and washed with water, and then treated in an aqueous solution of the activation treatment liquid ADP-501 (trade name, manufactured by Hitachi Chemical Co., Ltd.) for 5 minutes at room temperature. Further, Cust-201 was used as an electroless copper plating solution, and immersion treatment was performed for 15 minutes at room temperature by a dipping method to form a base copper having an electroless copper thickness of 0.5 μm on both sides of the laminated plate, and further electroplated with electrolytic copper. Apply thicker to a copper thickness of 20 μm.

而且，自所述帶有鍍層的試驗用積層板硬化物，藉由蝕刻來加工成銅寬為10 mm、長度為100 mm的線，將其一端剝下並利用夾具夾持，依據JIS-C-6421，將於室溫中在垂直方向上剝離約50 mm時的負荷的最低值記錄為鍍銅剝離強度。Further, the hardened layer for the test laminate with the plating was processed by etching into a wire having a copper width of 10 mm and a length of 100 mm, and one end thereof was peeled off and clamped by a jig, according to JIS-C. -6421, the lowest value of the load when peeling off about 50 mm in the vertical direction at room temperature was recorded as the copper peeling strength.

13）成形性 使用前項中進行了成形的評價用覆銅積層板，呈格子狀地製作圖案化成線寬（L）為0.5 mm、線間隔（S）為1.0 mm（L/S=0.5/1.0 mm）的芯材。對該芯材進行黑化處理，繼而，於其上進而積層預浸體，進行2次成形，藉此製作內層為格子狀圖案的評價用積層基板。針對所製作的評價用積層基板，例如確認是否產生由樹脂清漆的流動性不足所形成的空隙等缺陷。其後，將該評價用積層基板於沸水中浸漬4小時後，浸漬於280℃的焊料槽中。此時，將無法確認空隙的存在，浸漬於焊料槽中後亦未看到膨脹、層間剝離、白點（白斑）等不良現象的產生者評價為「○」，將未看到所述不良現象的產生，但產生了翹曲或滲出（bleed out）（調配物的分離）者評價為「△」，將產生了所述不良現象者評價為「×」。13) Formability The copper-clad laminate for evaluation which was formed in the previous paragraph was patterned in a lattice form to have a line width (L) of 0.5 mm and a line spacing (S) of 1.0 mm (L/S = 0.5/1.0). Mm) core material. The core material was subjected to a blackening treatment, and then a prepreg was laminated thereon, and molding was performed twice to prepare a laminated substrate for evaluation in which the inner layer was a lattice pattern. For the laminated substrate for evaluation to be produced, for example, it is confirmed whether or not a defect such as a void formed by insufficient fluidity of the resin varnish occurs. Thereafter, the laminated substrate for evaluation was immersed in boiling water for 4 hours, and then immersed in a solder bath at 280 °C. In this case, the presence of voids could not be confirmed, and the occurrence of defects such as swelling, interlayer peeling, and white spots (white spots) was not observed in the solder bath, and was evaluated as "○", and the defect was not observed. The occurrence of warpage or bleed out (separation of the formulation) was evaluated as "△", and the person who caused the defect was evaluated as "x".

實施例5 使實施例1中所獲得的共聚合物-A 20 g與作為聚合起始劑的Percumyl P 0.2 g、作為硬化促進劑、作為抗氧化劑的AO-60 0.2 g溶解於甲苯8.6 g中而獲得硬化性樹脂組成物（清漆A）。Example 5 20 g of the copolymer-A obtained in Example 1 was dissolved in 0.2 g of Percumyl P as a polymerization initiator, and 0.2 g of AO-60 as an antioxidant as an antioxidant in 8.6 g of toluene. A curable resin composition (varnish A) was obtained.

將所製備的清漆A滴加於下模上，於減壓下以130℃使溶媒脫揮後，組合堆起模具，於200℃、3 MPa的條件下進行1小時真空加壓壓製，而進行熱硬化。針對所獲得的厚度：0.2 mm的硬化物平板試驗片，測定以18 GHz的介電常數與介電損耗正切為首的各種特性。另外，將硬化物平板試驗片於85℃、相對濕度85%下放置2週後，進行介電常數及介電損耗正切的測定，並測定耐濕熱試驗後的介電常數及介電損耗正切。將藉由該些測定所獲得的結果示於表1中。The prepared varnish A was added dropwise to the lower mold, and the solvent was devolatilized at 130 ° C under reduced pressure, and then the mold was stacked and stacked under vacuum at 200 ° C and 3 MPa for 1 hour. Heat hardened. For each of the obtained cured flat plate test pieces having a thickness of 0.2 mm, various characteristics including a dielectric constant of 18 GHz and a dielectric loss tangent were measured. Further, the cured flat plate test piece was allowed to stand at 85 ° C and a relative humidity of 85% for 2 weeks, and then the dielectric constant and dielectric loss tangent were measured, and the dielectric constant and dielectric loss tangent after the moisture heat resistance test were measured. The results obtained by these measurements are shown in Table 1.

實施例6～實施例8、比較例3～比較例4 除設為表1中所示的調配配方以外，以與實施例5相同的方法獲得硬化性樹脂組成物（清漆）。而且，以與實施例5相同的方式製作硬化物平板試驗片，並對與實施例5相同的項目進行試驗·評價。將藉由該些試驗所獲得的結果示於表1中。Example 6 to Example 8 and Comparative Example 3 to Comparative Example 4 A curable resin composition (varnish) was obtained in the same manner as in Example 5 except that the formulation was as shown in Table 1. Further, a cured flat plate test piece was produced in the same manner as in Example 5, and the same items as in Example 5 were tested and evaluated. The results obtained by these tests are shown in Table 1.

[表1] [Table 1]

實施例9～實施例23、比較例5～比較例7 除設為表2及表3中所示的調配配方以外，以與實施例5類似的方法獲得硬化性樹脂組成物（清漆）。而且，以與實施例5相同的方式製作硬化物平板試驗片，並對與實施例5相同的項目進行試驗·評價。將藉由該些試驗所獲得的結果示於表1中。進而，使用該些實施例及比較例中所示的清漆，根據所述11）～13）中所記載的方法，製作預浸體、試驗用覆銅積層板、及試驗用帶有鍍層的積層板，並進行銅箔剝離強度、鍍銅剝離強度、及成形性的評價。將試驗結果示於表2及表3中。Example 9 to Example 23 and Comparative Example 5 to Comparative Example 7 A curable resin composition (varnish) was obtained in the same manner as in Example 5 except that the formulation shown in Tables 2 and 3 was used. Further, a cured flat plate test piece was produced in the same manner as in Example 5, and the same items as in Example 5 were tested and evaluated. The results obtained by these tests are shown in Table 1. Further, using the varnishes shown in the examples and the comparative examples, a prepreg, a copper-clad laminate for test, and a laminate with a test layer were prepared according to the methods described in the above 11) to 13). The plate was evaluated for copper foil peel strength, copper plating peel strength, and formability. The test results are shown in Tables 2 and 3.

實施例24 將二乙烯基苯8.91莫耳（1269.1 mL）、乙基乙烯基苯2.09莫耳（297.7 mL）、甲基乙基酮0.40莫耳（36.3 mL）、甲苯1100 mL投入至3.0 L的反應器內，於70℃下添加使0.50毫莫耳的三氟甲烷磺酸溶解於甲基乙基酮0.10莫耳（9.0 mL）中而成的溶液，並進行6小時反應。藉由碳酸氫鈉水溶液來使聚合溶液停止後，進行水洗，將活性氧化鋁作為助濾劑而進行過濾。然後，於60℃下減壓脫揮，並回收聚合物。秤量所獲得的聚合物，確認獲得1698.7 g的共聚合物G。Example 24 Divinylbenzene 8.91 mol (1269.1 mL), ethyl vinylbenzene 2.09 mol (297.7 mL), methyl ethyl ketone 0.40 mol (36.3 mL), toluene 1100 mL was charged to 3.0 L. In the reactor, a solution obtained by dissolving 0.50 mmol of trifluoromethanesulfonic acid in methyl ethyl ketone 0.10 mol (9.0 mL) was added at 70 ° C, and the reaction was carried out for 6 hours. After the polymerization solution was stopped by an aqueous solution of sodium hydrogencarbonate, it was washed with water, and the activated alumina was filtered as a filter aid. Then, the mixture was degassed under reduced pressure at 60 ° C, and the polymer was recovered. The obtained polymer was weighed to confirm that 1698.7 g of the copolymer G was obtained.

所獲得的共聚合物G的Mn為884，Mw為11800，Mw/Mn為13.4。藉由進行GC分析、GPC測定、FT-IR、13 C-NMR及1 H-NMR分析，共聚合物G進行由所述式（a1）、式（a2）、式（a3）、式（ta1）、式（b1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的重複結構單元的定量。根據其結果，根據式[（a1）+（a3）+（ta1）]/[（a1）+（a2）+（a3）+（b1）+（ta1）+（tb1）]而算出的含有源自二乙烯基芳香族化合物（a）的特定的不飽和烴基的結構單元的莫耳分率為0.54。另外，根據由式（ta1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的共聚合物A的末端結構單元的含量，根據式（ta1）/[（ta1）+（tb1）]而算出的含有乙烯基的末端結構單元的莫耳分率為0.71。而且，共聚合物G含有82.4莫耳%的源自二乙烯基芳香族化合物（a）的結構單元及合計17.6莫耳%的源自單乙烯基芳香族化合物（b）的結構單元。共聚合物G中所含的由所述式（a1）、式（a2）、式（ta1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的不飽和烴基含量為64.7莫耳%。 另外，硬化物的DMA測定的結果，Tg為264℃。另一方面，硬化物的TMA測定的結果，軟化溫度為300℃以上。TGA測定的結果，350℃下的重量減少為1.35 wt%，耐熱變色性為○。另一方面，與環氧樹脂的相容性為○。 共聚合物G可溶於甲苯、二甲苯、THF、二氯乙烷、二氯甲烷、氯仿中，未看見凝膠的生成。The obtained copolymer G had an Mn of 884, a Mw of 11,800 and a Mw/Mn of 13.4. By performing GC analysis, GPC measurement, FT-IR, 13 C-NMR, and 1 H-NMR analysis, the copolymer G is subjected to the formula (a1), the formula (a2), the formula (a3), and the formula (ta1). The quantification of the repeating structural unit derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (b1) and the formula (tb1). According to the result, the source containing the equation [(a1)+(a3)+(ta1)]/[(a1)+(a2)+(a3)+(b1)+(ta1)+(tb1)] The structural unit of the specific unsaturated hydrocarbon group derived from the divinyl aromatic compound (a) has a molar fraction of 0.54. Further, the content of the terminal structural unit derived from the copolymer of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (ta1) and the formula (tb1) is The molar fraction of the terminal structural unit containing a vinyl group calculated by the formula (ta1) / [(ta1) + (tb1)] was 0.71. Further, the copolymer G contains 82.4 mol% of a structural unit derived from the divinyl aromatic compound (a) and a total of 17.6 mol% of a structural unit derived from the monovinyl aromatic compound (b). The divinyl aromatic compound (a) and the monovinyl aromatic group represented by the formula (a1), the formula (a2), the formula (ta1) and the formula (tb1) contained in the copolymer G are derived from The unsaturated hydrocarbon group content of the compound (b) was 64.7 mol%. Further, as a result of DMA measurement of the cured product, Tg was 264 °C. On the other hand, as a result of TMA measurement of the cured product, the softening temperature was 300 ° C or higher. As a result of TGA measurement, the weight loss at 350 ° C was 1.35 wt%, and the heat discoloration resistance was ○. On the other hand, the compatibility with the epoxy resin was ○. The copolymer G was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, chloroform, and no gel formation was observed.

實施例25 將二乙烯基苯8.91莫耳（1269.1 mL）、乙基乙烯基苯2.09莫耳（297.7 mL）、苯乙烯1.00莫耳（115.0 mL）、乙酸丙酯0.40莫耳（46.0 mL）、甲苯1000mL投入至3.0 L的反應器內，於50℃下添加使0.70毫莫耳的三氟甲烷磺酸溶解於乙酸丙酯0.10莫耳（11.5 mL）中而成的溶液，並進行7小時反應。藉由碳酸氫鈉水溶液來使聚合溶液停止後，進行水洗。然後，於60℃下減壓脫揮，並回收聚合物。秤量所獲得的聚合物，確認獲得1643.5 g的共聚合物H。Example 25 Divinylbenzene 8.91 moles (1269.1 mL), ethylvinylbenzene 2.09 moles (297.7 mL), styrene 1.00 moles (115.0 mL), propyl acetate 0.40 moles (46.0 mL), 1000 mL of toluene was placed in a 3.0 L reactor, and a solution obtained by dissolving 0.70 mmol of trifluoromethanesulfonic acid in 0.10 mol (11.5 mL) of propyl acetate was added at 50 ° C, and a reaction was carried out for 7 hours. . After the polymerization solution was stopped by an aqueous solution of sodium hydrogencarbonate, it was washed with water. Then, the mixture was degassed under reduced pressure at 60 ° C, and the polymer was recovered. The obtained polymer was weighed to confirm that 1643.5 g of the copolymer H was obtained.

所獲得的共聚合物H的Mn為947，Mw為13800，Mw/Mn為14.6。藉由進行GC分析、GPC測定、FT-IR、13 C-NMR及1 H-NMR分析，共聚合物H進行由所述式（a1）、式（a2）、式（a3）、式（ta1）、式（b1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的重複結構單元的定量。根據其結果，根據式[（a1）+（a3）+（ta1）]/[（a1）+（a2）+（a3）+（b1）+（ta1）+（tb1）]而算出的含有源自二乙烯基芳香族化合物（a）的特定的不飽和烴基的結構單元的莫耳分率為0.51。另外，根據由式（ta1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的共聚合物H的末端結構單元的含量，根據式（ta1）/[（ta1）+（tb1）]而算出的含有乙烯基的末端結構單元的莫耳分率為0.65。而且，共聚合物H含有83.1莫耳%的源自二乙烯基芳香族化合物（a）的結構單元及合計16.9莫耳%的源自單乙烯基芳香族化合物（b）的結構單元。共聚合物H中所含的由所述式（a1）、式（a2）、式（ta1）及式（tb1）所表示的源自二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）的不飽和烴基含量為61.3莫耳%。 另外，硬化物的DMA測定的結果，Tg為217℃。另一方面，硬化物的TMA測定的結果，軟化溫度為300℃以上。TGA測定的結果，350℃下的重量減少為1.42 wt%，耐熱變色性為○。另一方面，與環氧樹脂的相容性為○。 共聚合物H可溶於甲苯、二甲苯、THF、二氯乙烷、二氯甲烷、氯仿中，未看見凝膠的生成。The obtained copolymer H had an Mn of 947, a Mw of 13,800 and a Mw/Mn of 14.6. By performing GC analysis, GPC measurement, FT-IR, 13 C-NMR, and 1 H-NMR analysis, the copolymer H is subjected to the formula (a1), the formula (a2), the formula (a3), and the formula (ta1). The quantification of the repeating structural unit derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (b1) and the formula (tb1). According to the result, the source containing the equation [(a1)+(a3)+(ta1)]/[(a1)+(a2)+(a3)+(b1)+(ta1)+(tb1)] The structural unit of the specific unsaturated hydrocarbon group derived from the divinyl aromatic compound (a) has a molar fraction of 0.51. Further, the content of the terminal structural unit derived from the copolymer of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (ta1) and the formula (tb1) is The molar fraction of the terminal structural unit containing a vinyl group calculated by the formula (ta1) / [(ta1) + (tb1)] was 0.65. Further, the copolymer H contains 83.1 mol% of a structural unit derived from the divinyl aromatic compound (a) and a total of 16.9 mol% of a structural unit derived from the monovinyl aromatic compound (b). The divinyl aromatic compound (a) and the monovinyl aromatic group represented by the formula (a1), the formula (a2), the formula (ta1) and the formula (tb1) contained in the copolymer H are contained. The unsaturated hydrocarbon group content of the compound (b) was 61.3 mol%. Further, as a result of DMA measurement of the cured product, Tg was 217 °C. On the other hand, as a result of TMA measurement of the cured product, the softening temperature was 300 ° C or higher. As a result of TGA measurement, the weight loss at 350 ° C was 1.42 wt%, and the heat discoloration resistance was ○. On the other hand, the compatibility with the epoxy resin was ○. The copolymer H was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, chloroform, and no gel formation was observed.

實施例26、實施例27 使用實施例24、實施例25中所獲得的共聚合物G、共聚合物H，設為表4中所示的調配配方，除此以外，以與實施例5相同的方法獲得硬化性樹脂組成物（清漆）。而且，以與實施例5相同的方式製作硬化物平板試驗片，並對與實施例5相同的項目進行試驗·評價。將藉由該些試驗所獲得的結果示於表4中。Example 26 and Example 27 The copolymers G and the copolymer H obtained in Example 24 and Example 25 were used in the formulation shown in Table 4, except that the same procedure as in Example 5 was carried out. The method obtains a curable resin composition (varnish). Further, a cured flat plate test piece was produced in the same manner as in Example 5, and the same items as in Example 5 were tested and evaluated. The results obtained by these tests are shown in Table 4.

[表2] [Table 2]

[表3] [table 3]

[表4] [Table 4]

再者，表1～表4中使用的成分如下所述。 改質PPE-A：兩末端具有乙烯基的聚伸苯基寡聚物（Mn=1160，三菱瓦斯化學（股份）製造，2,2',3,3',5,5'-六甲基聯苯-4,4'-二醇·2,6-二甲基苯酚縮聚物與氯甲基苯乙烯的反應產物） 改質PPE-B：兩末端具有乙烯基的聚伸苯基寡聚物（Mn=2270，三菱瓦斯化學（股份）製造，2,2',3,3',5,5'-六甲基聯苯-4,4'-二醇·2,6-二甲基苯酚縮聚物與氯甲基苯乙烯的反應產物） 改質PPE-C：一末端具有乙烯基的聚伸苯基寡聚物（Mn=2340，聚苯醚（沙伯基礎創新塑膠（SABIC Innovative Plastics）公司製造的SA120）與氯甲基苯乙烯的反應產物） TAIC：三烯丙基異氰脲酸酯（日本化成股份有限公司製造） DCP：三環癸烷二甲醇二甲基丙烯酸酯（新中村化學工業股份有限公司製造） A-DCP：三環癸烷二甲醇二丙烯酸酯（新中村化學工業股份有限公司製造） 鄰甲酚酚醛清漆型環氧樹脂：Epotohto YDCN-700-3（低黏度型，新日鐵住金化學股份有限公司製造） 雙酚F型液狀環氧樹脂：Epikote806L，Mw=370（日本環氧樹脂公司製造） 萘骨架液狀環氧樹脂：EPICLON HP-4032D，Mw=304（迪愛生公司製造） 萘酚型環氧樹脂：ESN-475V，環氧當量：340（新日鐵住金化學公司製造） 雙酚A型液狀環氧樹脂：Epikote828US，Mw=370（日本環氧樹脂公司製造） 茀骨架環氧樹脂：大阪燃氣化學公司製造，商品名：ONCOAT EX1011，Mw=486 改質PPE-D：兩末端具有環氧基的聚伸苯基寡聚物（Mn=1180，三菱瓦斯化學（股份）製造，2,2',3,3',5,5'-六甲基聯苯-4,4'-二醇·2,6-二甲基苯酚縮聚物與表氯醇的反應產物） 聯苯骨架酚樹脂：明和化成公司製造，MEH-7851-S 三聚氰胺骨架系酚樹脂：群榮化學工業公司製造，PS-6492 含有烯丙基的骨架酚樹脂：日本環氧樹脂公司製造，YLH-903 脂環式骨架酸酐：新日本理化公司製造，MH-700 芳香族骨架酸酐：日本沙多瑪（Sartomer·Japan）公司製造，SMA RESIN EF60 苯乙烯系共聚合物：KRATON A1535（科騰聚合物有限公司（Kraton Polymers LLC）製造） 苯氧基樹脂：重量平均分子量為37000，三菱化學（股份）製造的「YL7553BH30」（不揮發成分為30質量%的MEK與環己酮的1：1溶液） 非晶球狀二氧化矽：雅都瑪（Admatechs）公司製造，SE2050 SPE，平均粒徑為0.5 μm（利用苯基矽烷偶合劑進行處理） 自由基聚合起始劑：Percumyl D、Percumyl P、日油製造，Nofmer BC-90（2,3-二甲基-2,3-二苯基丁烷） 硬化促進劑：三苯基膦 穩定劑：Adekastab AO-60 [產業上之可利用性]In addition, the components used in Tables 1 to 4 are as follows. Modified PPE-A: Polyphenylene oligomer with vinyl group at both ends (Mn=1160, manufactured by Mitsubishi Gas Chemical Co., Ltd., 2,2',3,3',5,5'-hexamethyl The reaction product of biphenyl-4,4'-diol-2,6-dimethylphenol polycondensate and chloromethylstyrene) modified PPE-B: polyphenylene oligomer having vinyl groups at both ends (Mn=2270, manufactured by Mitsubishi Gas Chemical Co., Ltd., 2,2',3,3',5,5'-hexamethylbiphenyl-4,4'-diol·2,6-dimethylphenol The reaction product of a polycondensate with chloromethylstyrene) Modified PPE-C: a polyphenylene oligomer having a vinyl group at one end (Mn=2340, polyphenylene ether (SABIC Innovative Plastics) The reaction product of SA120) and chloromethylstyrene manufactured by the company) TAIC: triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.) DCP: tricyclodecane dimethanol dimethacrylate (Xinzhongcun) Chemical Industry Co., Ltd.) A-DCP: Tricyclodecane Dimethanol Diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) O-cresol novolak-type epoxy resin: Epotohto YDCN-700-3 (low viscosity) Type, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) Bisphenol F type liquid epoxy resin: Epikote 806L, Mw = 370 (manufactured by Nippon Epoxy Co., Ltd.) Naphthalene skeleton liquid epoxy resin: EPICLON HP-4032D, Mw= 304 (manufactured by Di Aisheng Co., Ltd.) Naphthol type epoxy resin: ESN-475V, epoxy equivalent: 340 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) Bisphenol A type liquid epoxy resin: Epikote 828 US, Mw = 370 (Japanese ring) Oxygen resin company) Epoxy resin: manufactured by Osaka Gas Chemical Co., Ltd., trade name: ONCOAT EX1011, Mw=486 Modified PPE-D: Polyphenylene oligomer with epoxy group at both ends (Mn= 1180, manufactured by Mitsubishi Gas Chemical Co., Ltd., 2,2',3,3',5,5'-hexamethylbiphenyl-4,4'-diol·2,6-dimethylphenol polycondensate Reaction product of epichlorohydrin) Biphenyl skeleton phenol resin: manufactured by Minghe Chemical Co., Ltd., MEH-7851-S Melamine skeleton phenol resin: manufactured by Qunrong Chemical Industry Co., Ltd., PS-6492 Structural phenol resin containing allyl group: Japanese ring Manufactured by Oxygen Resin, YLH-903 alicyclic skeleton anhydride: manufactured by Nippon Chemical and Chemical Co., Ltd., MH-700 aromatic Skeletal Anhydride: Manufactured by Sartomer Japan, SMA RESIN EF60 Styrene-based copolymer: KRATON A1535 (Kraton Polymers LLC) Phenoxy resin: Weight average molecular weight 37000, "YL7553BH30" manufactured by Mitsubishi Chemical Corporation (a non-volatile content of 30% by mass of a 1:1 solution of MEK and cyclohexanone) Amorphous spherical cerium oxide: manufactured by Admatechs, SE2050 SPE, average particle size 0.5 μm (treated with phenyl decane coupling agent) Free radical polymerization initiator: Percumyl D, Percumyl P, manufactured by Nippon Oil, Nofmer BC-90 (2,3-dimethyl-2, 3-diphenylbutane) hardening accelerator: triphenylphosphine stabilizer: Adekastab AO-60 [industrial availability]

本發明的可溶性多官能乙烯基芳香族共聚合物可加工為成形材、片或膜，於電氣電子產業、宇宙·飛機產業等領域中可用於低介電材料、絕緣材料、耐熱材料、結構材料等。另外，可應用於半導體關聯材料、光學用材料、塗料、感光性材料、黏著劑、污水處理劑、重金屬捕獲劑、離子交換樹脂、防靜電劑、抗氧化劑、防霧劑、防鏽劑、防染劑、殺菌劑、防蟲劑、醫用材料、凝聚劑、界面活性劑、潤滑劑、固體燃料用黏合劑、導電處理劑等。The soluble polyfunctional vinyl aromatic copolymer of the present invention can be processed into a shaped material, a sheet or a film, and can be used for a low dielectric material, an insulating material, a heat resistant material, a structural material in the fields of the electric and electronic industry, the space industry, and the like. Wait. In addition, it can be applied to semiconductor related materials, optical materials, paints, photosensitive materials, adhesives, sewage treatment agents, heavy metal capture agents, ion exchange resins, antistatic agents, antioxidants, antifogging agents, rust inhibitors, and anti Dyeing agents, bactericides, insect repellents, medical materials, coagulants, surfactants, lubricants, binders for solid fuels, conductive treatment agents, and the like.

無no

無no

無no

Claims (17)

一種可溶性多官能乙烯基芳香族共聚合物，其是含有源自二乙烯基芳香族化合物（a）的結構單元及源自單乙烯基芳香族化合物（b）的結構單元的多官能乙烯基芳香族共聚合物，且特徵在於：源自二乙烯基芳香族化合物（a）的結構單元具有由下述式（a1）所表示的含有乙烯基的單元、由下述式（a2）所表示的含有伸乙烯基的單元及由下述式（a3）所表示的交聯結構單元以及由下述式（ta1）所表示的含有伸乙烯基的末端單元，且源自單乙烯基芳香族化合物（b）的結構單元具有由下述式（b1）所表示的結構單元及由下述式（tb1）所表示的含有伸乙烯基的末端單元，並且為溶劑可溶性、且具有聚合性；（式中，R1 表示碳數6～30的芳香族烴基）（式中，R1 的含義與式（a1）相同）（式中，R1 的含義與式（a1）相同）（式中，R1 的含義與式（a1）相同）（式中，R2 表示碳數6～30的芳香族烴基，R3 表示氫或碳數6～30的烴基）（式中，R2 、R3 的含義與式（b1）相同）。A soluble polyfunctional vinyl aromatic copolymer which is a polyfunctional vinyl aromatic group containing a structural unit derived from a divinyl aromatic compound (a) and a structural unit derived from a monovinyl aromatic compound (b) And a structural unit derived from the divinyl aromatic compound (a) having a vinyl group-containing unit represented by the following formula (a1) and represented by the following formula (a2) a unit containing a vinyl group and a crosslinked structural unit represented by the following formula (a3) and a terminal group containing a vinyl group represented by the following formula (ta1), and derived from a monovinyl aromatic compound ( The structural unit of b) has a structural unit represented by the following formula (b1) and a terminal group containing a vinyl group represented by the following formula (tb1), and is solvent-soluble and polymerizable; (wherein R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms) (wherein, R 1 has the same meaning as in formula (a1)) (wherein, R 1 has the same meaning as in formula (a1)) (wherein, R 1 has the same meaning as in formula (a1)) (wherein R 2 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms; and R 3 represents hydrogen or a hydrocarbon group having 6 to 30 carbon atoms) (wherein, R 2 and R 3 have the same meanings as in the formula (b1)). 如申請專利範圍第1項所述的可溶性多官能乙烯基芳香族共聚合物，其含有源自二乙烯基芳香族化合物（a）的結構單元20莫耳%～95莫耳%，且由所述式（a1）、式（a2）、式（a3）、式（ta1）、式（b1）及式（tb1）所表示的結構單元的莫耳分率滿足下述式（1）及下述式（2），   0.2≦[（a1）+（a3）+（ta1）]/[（a1）+（a2）+（a3）+（b1）+（ta1）+（tb1）]≦0.9 ···（1） （ta1）/[（ta1）+（tb1）]＞0.2 ···（2）   數量平均分子量Mn為300～100,000，分子量分佈（Mw/Mn）為100.0以下，且可溶於甲苯、二甲苯、四氫呋喃、二氯乙烷或氯仿。The soluble polyfunctional vinyl aromatic copolymer according to claim 1, which contains 20% by mole of the structural unit derived from the divinyl aromatic compound (a), and is The molar fraction of the structural unit represented by the formula (a1), the formula (a2), the formula (a3), the formula (ta1), the formula (b1), and the formula (tb1) satisfies the following formula (1) and the following Equation (2), 0.2≦[(a1)+(a3)+(ta1)]/[(a1)+(a2)+(a3)+(b1)+(ta1)+(tb1)]≦0.9 ·· (1) (ta1) / [(ta1) + (tb1)] > 0.2 · (2) The number average molecular weight Mn is 300 to 100,000, the molecular weight distribution (Mw/Mn) is 100.0 or less, and is soluble in toluene. , xylene, tetrahydrofuran, dichloroethane or chloroform. 一種可溶性多官能乙烯基芳香族共聚合物，其是於作為促進劑成分的路易斯鹼性化合物（c）的存在下，使用選自由無機酸、有機磺酸及過氯酸系化合物所組成的群組中的一種以上的觸媒（d），使二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）聚合而製造多官能乙烯基芳香族共聚合物的方法，且特徵在於：相對於二乙烯基芳香族化合物（a）與單乙烯基芳香族化合物（b）的合計100莫耳%，使用二乙烯基芳香族化合物（a）5莫耳%～95莫耳%、單乙烯基芳香族化合物（b）95莫耳%～5莫耳%，並且相對於所有單量體的合計100莫耳，使用路易斯鹼性化合物（c）0.005莫耳～500莫耳，使包含該些的聚合原料溶解於介電常數2.0～15.0的溶媒中製成均勻的溶液，於20℃～120℃的溫度下進行聚合而獲得。A soluble polyfunctional vinyl aromatic copolymer which is selected from the group consisting of inorganic acids, organic sulfonic acids and perchloric acid compounds in the presence of a Lewis basic compound (c) as a promoter component a method of producing a polyfunctional vinyl aromatic copolymer by polymerizing a divinyl aromatic compound (a) and a monovinyl aromatic compound (b) by using one or more catalysts (d) in the group, and is characterized in that : a total of 100 mol% based on the total of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b), using a divinyl aromatic compound (a) 5 mol% to 95 mol%, single The vinyl aromatic compound (b) is 95% by mole to 5 mol%, and the Lewis basic compound (c) is used in an amount of from 0.005 mol to 500 mol with respect to 100 mol of total of all the monomeric bodies. Some of the polymerization raw materials are dissolved in a solvent having a dielectric constant of 2.0 to 15.0 to prepare a homogeneous solution, which is obtained by polymerization at a temperature of from 20 ° C to 120 ° C. 一種多官能乙烯基芳香族共聚合物的製造方法，製造如申請專利範圍第1項所述的多官能乙烯基芳香族共聚合物，所述製造方法是於作為促進劑成分的路易斯鹼性化合物（c）的存在下，使用選自由無機酸、有機磺酸及過氯酸系化合物所組成的群組中的一種以上的觸媒（d），使二乙烯基芳香族化合物（a）及單乙烯基芳香族化合物（b）聚合而製造多官能乙烯基芳香族共聚合物的方法，且特徵在於：相對於二乙烯基芳香族化合物（a）與單乙烯基芳香族化合物（b）的合計100莫耳%，使用二乙烯基芳香族化合物（a）5莫耳%～95莫耳%、單乙烯基芳香族化合物（b）95莫耳%～5莫耳%，並且相對於所有單量體的合計100莫耳，使用路易斯鹼性化合物（c）0.005莫耳～500莫耳，使包含該些的聚合原料溶解於介電常數2.0～15.0的溶媒中製成均勻的溶液，於20℃～120℃的溫度下進行聚合。A method for producing a polyfunctional vinyl aromatic copolymer, which comprises the polyfunctional vinyl aromatic copolymer according to claim 1, wherein the method is a Lewis basic compound as a promoter component In the presence of (c), one or more catalysts (d) selected from the group consisting of inorganic acids, organic sulfonic acids, and perchloric acid-based compounds are used to make the divinyl aromatic compound (a) and the single A method for producing a polyfunctional vinyl aromatic copolymer by polymerization of a vinyl aromatic compound (b), and characterized by a total of a divinyl aromatic compound (a) and a monovinyl aromatic compound (b) 100 mol%, using divinyl aromatic compound (a) 5 mol% to 95 mol%, monovinyl aromatic compound (b) 95 mol% to 5 mol%, and relative to all single amounts The total amount of the body is 100 moles, and the Lewis basic compound (c) is used in an amount of 0.005 to 500 moles, and the polymerization raw material containing the above is dissolved in a solvent having a dielectric constant of 2.0 to 15.0 to prepare a uniform solution at 20 ° C. ~120 ° C temperature Polymerized. 如申請專利範圍第4項所述的可溶性多官能乙烯基芳香族共聚合物的製造方法，其中相對於路易斯鹼性化合物（c）1莫耳，於0.001莫耳～10莫耳的範圍內使用觸媒（d）。The method for producing a soluble polyfunctional vinyl aromatic copolymer according to claim 4, wherein the Lewis basic compound (c) is used in a range of from 0.001 mol to 10 mol. Catalyst (d). 一種硬化性組成物，其特徵在於含有：如申請專利範圍第1項所述的可溶性多官能乙烯基芳香族共聚合物與自由基聚合起始劑。A curable composition comprising: a soluble polyfunctional vinyl aromatic copolymer as described in claim 1 of the patent application, and a radical polymerization initiator. 如申請專利範圍第6項所述的硬化性組成物，其更含有熱硬化性樹脂或熱塑性樹脂。The curable composition according to claim 6, further comprising a thermosetting resin or a thermoplastic resin. 如申請專利範圍第7項所述的硬化性組成物，其中所述熱硬化性樹脂為改質聚苯醚（XC）。The curable composition according to claim 7, wherein the thermosetting resin is a modified polyphenylene ether (XC). 如申請專利範圍第7項所述的硬化性組成物，其中所述熱硬化性樹脂為選自由1分子中具有2個以上的環氧基與芳香族結構的環氧樹脂、1分子中具有2個以上的環氧基與氰脲酸酯結構的環氧樹脂及/或1分子中具有2個以上的環氧基與脂環結構的環氧樹脂所組成的群組中的一種以上的環氧樹脂（XD）。The curable composition according to claim 7, wherein the thermosetting resin is an epoxy resin having two or more epoxy groups and an aromatic structure in one molecule, and has 2 in one molecule. One or more epoxy groups of one or more epoxy groups having an epoxy group and a cyanurate structure and/or an epoxy resin having two or more epoxy groups and an alicyclic structure in one molecule Resin (XD). 如申請專利範圍第7項所述的硬化性組成物，其中所述熱硬化性樹脂為分子中具有1個以上的不飽和烴基的一種以上的乙烯基化合物（XF）。The curable composition according to claim 7, wherein the thermosetting resin is one or more vinyl compounds (XF) having one or more unsaturated hydrocarbon groups in the molecule. 一種硬化物，其是使如申請專利範圍第6項至第10項中任一項所述的硬化性組成物硬化而成。A cured product obtained by curing the curable composition according to any one of claims 6 to 10. 一種膜，其是使如申請專利範圍第6項至第10項中任一項所述的硬化性組成物成形為膜狀而成。A film obtained by molding the curable composition according to any one of claims 6 to 10 into a film shape. 一種硬化性複合材料，其包含如申請專利範圍第6項至第10項中任一項所述的硬化性組成物與基材，且特徵在於：以5重量%～90重量%的比例含有基材。A curable composite material comprising the curable composition and the substrate according to any one of claims 6 to 10, characterized in that the base is contained in a ratio of from 5% by weight to 90% by weight. material. 一種硬化複合材料，其特徵在於：使如申請專利範圍第13項所述的硬化性複合材料硬化而獲得。A hardened composite material obtained by hardening a curable composite material according to claim 13 of the patent application. 一種積層體，其特徵在於：具有如申請專利範圍第14項所述的硬化複合材料的層與金屬箔層。A laminate comprising a layer of a hardened composite material as described in claim 14 of the patent application and a metal foil layer. 一種帶有樹脂的金屬箔，其特徵在於：於金屬箔的一面上具有由如申請專利範圍第6項至第10項中任一項所述的硬化性組成物形成的膜。A metal foil with a resin, comprising a film formed of a curable composition according to any one of claims 6 to 10, on one side of the metal foil. 一種電路基板材料用清漆，其是使如申請專利範圍第6項至第10項中任一項所述的硬化性組成物溶解於有機溶劑中而成。A varnish for a circuit board material obtained by dissolving a curable composition according to any one of claims 6 to 10 in an organic solvent.
TW105143267A 2015-12-28 2016-12-27 Soluble polyfunctional vinyl aromatic copolymer, its production method, hardenable composition and its application TWI706963B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015256924 2015-12-28
JP2015-256924 2015-12-28

Publications (2)

Publication Number Publication Date
TW201736413A true TW201736413A (en) 2017-10-16
TWI706963B TWI706963B (en) 2020-10-11

Family

ID=59225270

Family Applications (1)

Application Number Title Priority Date Filing Date
TW105143267A TWI706963B (en) 2015-12-28 2016-12-27 Soluble polyfunctional vinyl aromatic copolymer, its production method, hardenable composition and its application

Country Status (3)

Country Link
JP (1) JP6833723B2 (en)
TW (1) TWI706963B (en)
WO (1) WO2017115813A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111285980A (en) * 2018-12-06 2020-06-16 台燿科技股份有限公司 Halogen-free low dielectric resin composition, prepreg, metal foil laminate and printed wiring board using the same

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG11201909128TA (en) 2017-03-30 2019-10-30 Nippon Steel Chemical & Material Co Ltd Soluble polyfunctional vinyl aromatic copolymer, method for producing same, curable resin composition and cured product thereof
CN109385021A (en) * 2017-08-04 2019-02-26 广东生益科技股份有限公司 A kind of compositions of thermosetting resin and prepreg and metal-clad laminate using its production
CN109385018A (en) * 2017-08-04 2019-02-26 广东生益科技股份有限公司 A kind of compositions of thermosetting resin and prepreg and metal-clad laminate using its production
WO2020175537A1 (en) * 2019-02-28 2020-09-03 三菱瓦斯化学株式会社 Resin composition, prepreg, metal foil-clad laminate board, resin composite sheet, and, printed circuit board
WO2023026829A1 (en) 2021-08-25 2023-03-02 三菱瓦斯化学株式会社 Resin composition, cured object, prepreg, metal-foil-clad laminate, resin sheet, and printed wiring board

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4338951B2 (en) * 2002-10-01 2009-10-07 新日鐵化学株式会社 Soluble polyfunctional vinyl aromatic copolymer and polymerization method thereof
JP4842024B2 (en) * 2006-06-15 2011-12-21 新日鐵化学株式会社 Soluble polyfunctional vinyl aromatic copolymer and method for producing the same
JP5162149B2 (en) * 2007-03-27 2013-03-13 新日鉄住金化学株式会社 Method for producing soluble polyfunctional vinyl aromatic copolymer and copolymer thereof
KR101640855B1 (en) * 2008-03-04 2016-07-19 신닛테츠 수미킨 가가쿠 가부시키가이샤 Polyfunctional vinyl aromatic copolymer, process for producing the same, and resin composition
JP5249095B2 (en) * 2009-03-12 2013-07-31 新日鉄住金化学株式会社 Terminal-modified soluble polyfunctional vinyl aromatic copolymer, process for producing the same, curable resin composition, and cured product
WO2014157131A1 (en) * 2013-03-25 2014-10-02 新日鉄住金化学株式会社 Curable resin composition, cured product, and optical article

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111285980A (en) * 2018-12-06 2020-06-16 台燿科技股份有限公司 Halogen-free low dielectric resin composition, prepreg, metal foil laminate and printed wiring board using the same
TWI700332B (en) * 2018-12-06 2020-08-01 台燿科技股份有限公司 Halogen-free low dielectric resin composition, and pre-preg, metal-clad laminate, and printed circuit board prepared using the same
US11015052B2 (en) 2018-12-06 2021-05-25 Taiwan Union Technology Corporation Halogen-free low dielectric resin composition, and prepreg, metal-clad laminate, and printed circuit board prepared using the same
CN111285980B (en) * 2018-12-06 2023-02-28 台燿科技股份有限公司 Halogen-free low dielectric resin composition, prepreg, metal foil laminate and printed wiring board using the same

Also Published As

Publication number Publication date
WO2017115813A1 (en) 2017-07-06
JPWO2017115813A1 (en) 2018-10-18
TWI706963B (en) 2020-10-11
JP6833723B2 (en) 2021-02-24

Similar Documents

Publication Publication Date Title
TWI750360B (en) Soluble polyfunctional vinyl aromatic copolymer, its production method, curable resin composition and its cured product, curable composite material, cured composite material, laminate, metal foil with resin, and varnish for circuit board material
JP6995534B2 (en) Soluble polyfunctional vinyl aromatic copolymer, its production method, curable resin composition and its cured product
TWI706963B (en) Soluble polyfunctional vinyl aromatic copolymer, its production method, hardenable composition and its application
JP7051333B2 (en) Curable resin composition, its cured product, curable composite material, metal leaf with resin, and varnish for circuit board material
JP6580849B2 (en) Terminal-modified soluble polyfunctional vinyl aromatic copolymer and process for producing the same
TW201625703A (en) Terminal-modified soluble polyfunctional vinyl aromatic copolymer, and curable resin composition and optical waveguide produced using same
JP7409369B2 (en) Resin compositions, prepregs, metal foil laminates, resin composite sheets, and printed wiring boards
CN113490596A (en) Resin composition, prepreg, metal foil-clad laminate, resin composite sheet, and printed wiring board
CN112313265A (en) Resin composition and use thereof
WO2019130735A1 (en) Polyphenylene ether resin composition, prepreg using same, film with resin, metal foil with resin, metal-clad laminate and wiring board
JP2019178310A (en) Curable resin composition, cured article thereof, curable composite material, metal foil with resin, and resin material for circuit board material
WO2022244728A1 (en) Resin composition, prepreg using same, film with resin, metal foil with resin, metal-clad laminate, and wiring board
TW202210584A (en) Resin composition, prepreg, film provided with resin, metal foil provided with resin, metal-clad laminate, and wiring board
JP7123731B2 (en) Resin materials and multilayer printed wiring boards
JP5797147B2 (en) Aromatic dihydroxy compound, vinyl benzyl ether compound, and curable composition containing the same
TWI830741B (en) Resin compositions and their applications
TW202323427A (en) Resin composition, prepreg, metal foil-clad laminated sheet, composite resin sheet, printed wiring board, and semiconductor device
WO2023171553A1 (en) Resin composition, cured product, prepreg, metal-foil-clad laminate, resin composite sheet, printed circuit board, and semiconductor device
TW202330789A (en) Resin composition, prepreg, metal-foil-clad laminate, resin composite sheet, printed circuit board, and semiconductor device
TW202330788A (en) Resin composition, prepreg, metal foil-clad laminate board, resin composite sheet, printed wiring board, and semiconductor device
WO2023171554A1 (en) Resin composition, cured product, prepreg, metal-foil-clad laminate, resin composite sheet, printed circuit board, and semiconductor device
JP2023007603A (en) Thermosetting resin composition and applications therefor
JP2016010938A (en) Method for producing laminate