JP6331699B2 - Prepreg, laminated board and multilayer printed wiring board - Google Patents
Prepreg, laminated board and multilayer printed wiring board Download PDFInfo
- Publication number
- JP6331699B2 JP6331699B2 JP2014110635A JP2014110635A JP6331699B2 JP 6331699 B2 JP6331699 B2 JP 6331699B2 JP 2014110635 A JP2014110635 A JP 2014110635A JP 2014110635 A JP2014110635 A JP 2014110635A JP 6331699 B2 JP6331699 B2 JP 6331699B2
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- compound
- thermosetting resin
- resin composition
- prepreg
- Prior art date
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- 239000011342 resin composition Substances 0.000 claims description 42
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 17
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 16
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
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- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Description
本発明は、半導体パッケージやプリント配線板用に好適なプリプレグ、これを用いた積層板並びに多層プリント配線板に関する。 The present invention relates to a prepreg suitable for a semiconductor package or a printed wiring board, a laminated board using the prepreg, and a multilayer printed wiring board.
近年の電子機器の小型化及び高性能化の流れに伴い、プリント配線板では配線密度の高度化、高集積化が進展し、これにともなって、配線用積層板の耐熱性の向上による信頼性向上への要求が強まっている。特に、半導体用パッケージ基板では、部品実装時やパッケージ組み立て時において、チップと基板との熱膨張率の差に起因したそりが大きな課題となっており、低熱膨張率化が求められている。また、電気信号の高周波数化に対応する誘電特性も要求されてきている。 Along with the trend toward miniaturization and higher performance of electronic devices in recent years, printed wiring boards have become increasingly dense and highly integrated, and as a result, reliability has been improved by improving the heat resistance of laminated boards for wiring. There is an increasing demand for improvement. In particular, in a semiconductor package substrate, warpage caused by the difference in thermal expansion coefficient between the chip and the substrate is a major problem during component mounting and package assembly, and a low thermal expansion coefficient is required. In addition, dielectric characteristics corresponding to higher frequency of electric signals have been required.
プリント配線板用積層板は、エポキシ樹脂等を主剤とした樹脂組成物をガラス織布に塗工してプリプレグを得、これを一枚以上積層し、銅箔を配置し、プレスによって熱硬化したものが一般的である。エポキシ樹脂は、一般に絶縁性や耐熱性、コスト等のバランスに優れるが、熱膨張率が大きいため、芳香環を有するエポキシ樹脂の選択やシリカ等の無機充填材を高充填化することで低熱膨張化を図っている（特許文献１及び２参照）。無機充填材を高い割合で充填することにより、さらなる低熱膨張率化を図ることも可能であるが、無機充填材の充填量を増やすことは吸湿による絶縁信頼性の低下や樹脂組成物層−配線層間の密着力の不足、プレス成形不良を起こすことが知られている。他にも、シリコーン重合体を用いることにより、無機充填材を分散させ、高充填化する方法が知られている（特許文献３参照）。しかし、多層配線板における用途では、無機充填材の高充填化での低熱膨張率化には限界があった。 A laminated board for printed wiring boards is obtained by coating a glass woven fabric with a resin composition mainly composed of an epoxy resin or the like to obtain a prepreg, laminating one or more sheets, placing a copper foil, and thermosetting by pressing. Things are common. Epoxy resins generally have a good balance of insulation, heat resistance, cost, etc., but because of their large coefficient of thermal expansion, low thermal expansion can be achieved by selecting an epoxy resin with an aromatic ring and increasing the filling of inorganic fillers such as silica. (See Patent Documents 1 and 2). It is possible to further reduce the coefficient of thermal expansion by filling the inorganic filler at a high rate, but increasing the filling amount of the inorganic filler reduces the insulation reliability due to moisture absorption and the resin composition layer-wiring. It is known that the adhesion between layers is insufficient and press molding is poor. In addition, there is known a method in which an inorganic filler is dispersed and highly filled by using a silicone polymer (see Patent Document 3). However, for applications in multilayer wiring boards, there has been a limit to lowering the coefficient of thermal expansion by increasing the filling of the inorganic filler.
また、樹脂の選択或いは改良により、低熱膨張を達成することが試みられている。例えば、芳香環を有するエポキシ樹脂の公知例としては、ナフタレン骨格を有するエポキシ樹脂を用いた硬化性樹脂組成物（特許文献４）がある。また、従来、配線板用の樹脂組成物の低熱膨張率化は特許文献５及び６に示すように架橋密度を高め、ガラス転移温度（Ｔｇ）を高くして熱膨張率を低減する方法が一般的である。しかしながら、架橋密度を高めることは官能基間の分子鎖を短くすることであり、一定以上分子鎖を短くすることは反応性や樹脂強度等の点で困難である。このため、架橋密度を高める手法での低熱膨張率化には限界があった。
また、上記低熱膨張率化を行った場合でも、製造過程における内部応力によって、はんだ実装時にはそりを生じ、接続不良となる場合があった。
In addition, attempts have been made to achieve low thermal expansion by selecting or improving the resin. For example, as a known example of an epoxy resin having an aromatic ring, there is a curable resin composition using an epoxy resin having a naphthalene skeleton (Patent Document 4). Conventionally, the thermal expansion coefficient of a resin composition for a wiring board is generally reduced by increasing the crosslinking density and increasing the glass transition temperature (Tg) as shown in Patent Documents 5 and 6. Is. However, increasing the crosslink density is shortening the molecular chain between the functional groups, and shortening the molecular chain beyond a certain level is difficult in terms of reactivity and resin strength. For this reason, there was a limit to the reduction in the thermal expansion coefficient by the method of increasing the crosslinking density.
Even when the thermal expansion coefficient is reduced, the internal stress in the manufacturing process may cause warpage during solder mounting, resulting in poor connection.
本発明は、従来の無機充填材の高充填化や低熱膨張率及び良好な誘電特性を発現する樹脂の使用のみでは発現困難な、低熱膨張性、そり特性、誘電特性に優れるプリプレグ、これを用いた積層板及び多層プリント配線板を提供することを目的とする。 The present invention relates to a prepreg excellent in low thermal expansion, warpage, and dielectric characteristics, which is difficult to express only by using a conventional resin having high filling, low thermal expansion coefficient and good dielectric characteristics. An object of the present invention is to provide a laminated board and a multilayer printed wiring board.
本発明者らは、上記課題を解決するために鋭意研究した結果、Ｑガラスクロスを使用し、特定の熱硬化性樹脂組成物の層を含んでなるプリプレグが、上記課題を解決し得ることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a prepreg comprising a specific thermosetting resin composition layer using Q glass cloth can solve the above problems. The headline and the present invention were completed.
すなわち、本発明は、以下のプリプレグ、積層板及び多層プリント配線板を提供するものである。
１．Ｑガラスクロス（ａ）及び熱硬化性樹脂組成物の層を含んでなるプリプレグにおいて、前記熱硬化性樹脂組成物の層が、分子構造中に芳香族アゾメチン基を有するアミノ変性シロキサン化合物（Ｉ）及び分子構造中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物（ｂ）を配合してなる熱硬化性樹脂組成物を含有することを特徴とするプリプレグ。
２．分子構造中に芳香族アゾメチン基を有するアミノ変性シロキサン化合物（Ｉ）が、１分子中に少なくとも１個のアルデヒド基を有する芳香族アゾメチン化合物（ｃ）と、分子末端に少なくとも２個の一級アミノ基を有するシロキサン化合物（ｄ）とを反応させて得られる、上記１に記載のプリプレグ。
３．１分子中に少なくとも１個のアルデヒド基を有する芳香族アゾメチン化合物（ｃ）が、１分子中に少なくとも２個の一級アミノ基を有する芳香族アミン化合物（i）及び１分子中に少なくとも２個のアルデヒド基を有する芳香族アルデヒド化合物（ii）を反応させて得られる、上記２に記載のプリプレグ。
４．前記熱硬化性樹脂組成物が、さらに下記一般式（１）に示す酸性置換基を有するアミン化合物（ｅ）を配合してなる上記１〜３のいずれかに記載のプリプレグ。
５．前記熱硬化性樹脂組成物が、さらに熱可塑性エラストマー（ｆ）を配合してなる上記１〜４のいずれかに記載のプリプレグ。
６．前記熱硬化性樹脂組成物が、さらに他の熱硬化性樹脂（ｇ）を配合してなる上記１〜５のいずれかに記載のプリプレグ。
７．前記熱硬化性樹脂組成物が、さらに硬化促進剤（ｈ）を配合してなる上記１〜６のいずれかに記載のプリプレグ。
８．前記熱硬化性樹脂組成物が、さらに無機充填材を配合してなる上記１〜７のいずれかに記載のプリプレグ。
９．上記１〜８のいずれかに記載のプリプレグを用いて積層成形した得られた積層板。
１０．上記９に記載の積層板を用いて製造された多層プリント配線板。
That is, the present invention provides the following prepreg, laminate and multilayer printed wiring board.
1. A prepreg comprising a Q glass cloth (a) and a thermosetting resin composition layer, wherein the thermosetting resin composition layer has an amino-modified siloxane compound (I) having an aromatic azomethine group in the molecular structure And a thermosetting resin composition comprising a maleimide compound (b) having at least two N-substituted maleimide groups in the molecular structure.
2. The amino-modified siloxane compound (I) having an aromatic azomethine group in the molecular structure is composed of an aromatic azomethine compound (c) having at least one aldehyde group in one molecule and at least two primary amino groups at the molecular end. The prepreg according to 1 above, obtained by reacting a siloxane compound (d) having
3. An aromatic azomethine compound (c) having at least one aldehyde group in one molecule is an aromatic amine compound (i) having at least two primary amino groups in one molecule and at least 2 in one molecule. The prepreg according to 2 above, which is obtained by reacting an aromatic aldehyde compound (ii) having one aldehyde group.
4). The prepreg according to any one of the above 1 to 3, wherein the thermosetting resin composition further comprises an amine compound (e) having an acidic substituent represented by the following general formula (1).
5. The prepreg according to any one of the above 1 to 4, wherein the thermosetting resin composition is further blended with a thermoplastic elastomer (f).
6). The prepreg according to any one of 1 to 5 above, wherein the thermosetting resin composition further contains another thermosetting resin (g).
7). The prepreg according to any one of 1 to 6 above, wherein the thermosetting resin composition further contains a curing accelerator (h).
8). The prepreg according to any one of 1 to 7 above, wherein the thermosetting resin composition further contains an inorganic filler.
9. The obtained laminated board laminated | stacked using the prepreg in any one of said 1-8.
10. A multilayer printed wiring board produced using the laminate as described in 9 above.
本発明のプリプレグは、低熱膨張性、そり特性、誘電特性に優れ、これを用いた積層板及び多層プリント配線板は、高集積化された半導体パッケージや電子機器用プリント配線板として有用である。 The prepreg of the present invention is excellent in low thermal expansion properties, warpage characteristics, and dielectric characteristics, and a laminated board and multilayer printed wiring board using the prepreg are useful as highly integrated semiconductor packages and printed wiring boards for electronic devices.
［プリプレグ］
本発明のプリプレグは、Ｑガラスクロス（ａ）及び熱硬化性樹脂組成物の層を含んでなり、例えば、Ｑガラスクロスに熱硬化性樹脂組成物を塗工して製造できる。
（Ｑガラスクロス（ａ））
本発明で用いたＱガラスクロス（ａ）とは、純度の高い石英ガラスを用いて作られたガラスクロスのことであり、製造方法については特に制限されないが、「特開２００４−９９３７６」の製造方法などを用いて製造される。さらに、厚み、目付け重量、ヤーン径なども様々な種類が製造できる。またＱガラスクロス（ａ）は優れた耐熱性、誘電特性、低熱膨張性を有している。
[Prepreg]
The prepreg of the present invention comprises a layer of Q glass cloth (a) and a thermosetting resin composition. For example, the prepreg can be produced by applying a thermosetting resin composition to Q glass cloth.
(Q glass cloth (a))
The Q glass cloth (a) used in the present invention is a glass cloth made using high-purity quartz glass, and the production method is not particularly limited, but the production of “JP 2004-99376” It is manufactured using a method or the like. Furthermore, various types of thickness, basis weight, yarn diameter, etc. can be manufactured. Q glass cloth (a) has excellent heat resistance, dielectric properties, and low thermal expansion.
（熱硬化性組成物の層）
本発明の熱硬化性樹脂組成物の層は、分子構造中に芳香族アゾメチン基を有するアミノ変性シロキサン化合物（Ｉ）及び分子構造中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物（ｂ）を配合してなる熱硬化性樹脂組成物を含有する。
また、分子構造中に芳香族アゾメチン基を有するアミノ変性シロキサン化合物（Ｉ）は、１分子中に少なくとも１個のアルデヒド基を有する芳香族アゾメチン化合物（ｃ）と、分子末端に少なくとも２個の一級アミノ基を有するシロキサン化合物（ｄ）とを反応させて得られる。
さらに、１分子中に少なくとも１個のアルデヒド基を有する芳香族アゾメチン化合物（ｃ）は、１分子中に少なくとも２個の一級アミノ基を有する芳香族アミン化合物（i）及び１分子中に少なくとも２個のアルデヒド基を有する芳香族アルデヒド化合物（ii）を反応させて得られる。
(Layer of thermosetting composition)
The layer of the thermosetting resin composition of the present invention comprises an amino-modified siloxane compound (I) having an aromatic azomethine group in the molecular structure and a maleimide compound (b) having at least two N-substituted maleimide groups in the molecular structure. ) Is included.
The amino-modified siloxane compound (I) having an aromatic azomethine group in the molecular structure includes an aromatic azomethine compound (c) having at least one aldehyde group in one molecule and at least two primary primaries at the molecular end. It is obtained by reacting with a siloxane compound (d) having an amino group.
Furthermore, the aromatic azomethine compound (c) having at least one aldehyde group in one molecule includes the aromatic amine compound (i) having at least two primary amino groups in one molecule and at least 2 in one molecule. It is obtained by reacting an aromatic aldehyde compound (ii) having one aldehyde group.
＜１分子中に少なくとも２個の一級アミノ基を有する芳香族アミン化合物（i）＞
本発明の１分子中に少なくとも２個の一級アミノ基を有する芳香族アミン化合物（i）としては、例えば、ｐ−フェニレンジアミン、ｍ−フェニレンジアミン、ｏ−フェニレンジアミン、３−メチル−１，４−ジアミノベンゼン、２，５−ジメチル−１，４−ジアミノベンゼン、４，４'−ジアミノジフェニルメタン、４，４'−ジアミノ−３，３'−ジメチル−ジフェニルメタン、４，４'−ジアミノ−３，３'−ジエチル−ジフェニルメタン、４，４'−ジアミノジフェニルエーテル、４，４'−ジアミノジフェニルスルホン、３，３'−ジアミノジフェニルスルホン、４，４'−ジアミノジフェニルケトン、ベンジジン、３，３'−ジメチル−４，４'−ジアミノビフェニル、２，２'−ジメチル−４，４'−ジアミノビフェニル、３，３'−ジヒドロキシベンジジン、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン、３，３−ジメチル−５，５−ジエチル−４，４−ジフェニルメタンジアミン、２，２−ビス（４−アミノフェニル）プロパン、２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパン、１，３−ビス（３−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，４−ビス（４−アミノフェノキシ）ベンゼン、４，４'−ビス（４−アミノフェノキシ）ビフェニル、ビス（４−（４−アミノフェノキシ）フェニル）スルホン、ビス（４−（３−アミノフェノキシ）フェニル）スルホン、９，９−ビス（４−アミノフェニル）フルオレン等が挙げられる。これらは単独で、又は２種類以上を混合して用いてもよい。
<Aromatic amine compound (i) having at least two primary amino groups in one molecule>
Examples of the aromatic amine compound (i) having at least two primary amino groups in one molecule of the present invention include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, and 3-methyl-1,4. -Diaminobenzene, 2,5-dimethyl-1,4-diaminobenzene, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3, 3'-diethyl-diphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, benzidine, 3,3'-dimethyl -4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxy Nidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis (4-aminophenyl) propane 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 9,9-bis (4-aminophenyl) fluorene and the like can be mentioned. You may use these individually or in mixture of 2 or more types.
これらの中で、例えば、反応時の反応性が高く、より高耐熱性化できる４，４'−ジアミノジフェニルメタン、３，３'−ジメチル−４，４'−ジアミノビフェニル、４，４'−ジアミノ−３，３'−ジメチル−ジフェニルメタン、４，４'−ジアミノ−３，３'−ジエチル−ジフェニルメタン、４，４'−ビス（４−アミノフェノキシ）ビフェニル、２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパン等がより好ましく、安価であることや溶剤への溶解性の点から４，４'−ジアミノジフェニルメタン、３，３'−ジメチル−４，４'−ジアミノビフェニル、４，４'−ジアミノ−３，３'−ジエチル−ジフェニルメタン、２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパンが好ましく、低熱膨張性や誘電特性の点から、４，４'−ジアミノ−３，３'−ジエチル−ジフェニルメタン、２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパンが特に好ましい。また、高弾性率化できるｐ−フェニレンジアミン、ｍ−フェニレンジアミン、３−メチル−１，４−ジアミノベンゼン、２，５−ジメチル−１，４−ジアミノベンゼンも好ましい。 Among these, for example, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino, which has high reactivity during the reaction and can be further improved in heat resistance. -3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis (4- (4 -Aminophenoxy) phenyl) propane and the like are more preferable and 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4, in view of low cost and solubility in a solvent, 4'-diamino-3,3'-diethyl-diphenylmethane and 2,2-bis (4- (4-aminophenoxy) phenyl) propane are preferred, and 4,4 is preferred from the viewpoint of low thermal expansion and dielectric properties. '-Diamino-3,3'-diethyl-diphenylmethane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane is particularly preferred. Further, p-phenylenediamine, m-phenylenediamine, 3-methyl-1,4-diaminobenzene, and 2,5-dimethyl-1,4-diaminobenzene capable of increasing the elastic modulus are also preferable.
＜１分子中に少なくとも２個のアルデヒド基を有する芳香族アルデヒド化合物（ii）＞
本発明の１分子中に少なくとも２個のアルデヒド基を有する芳香族アルデヒド化合物（ii）としては、例えば、テレフタルアルデヒド、イソフタルアルデヒド、ｏ−フタルアルデヒド、２，２’−ビピリジン−４，４’−ジカルボキシアルデヒド等が挙げられる。これらの中で、例えば、より低熱膨張化が可能であり、反応時の反応性が高く、溶剤溶解性にも優れ、商業的にも入手しやすいテレフタルアルデヒドが特に好ましい。
<Aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule>
Examples of the aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule of the present invention include terephthalaldehyde, isophthalaldehyde, o-phthalaldehyde, 2,2′-bipyridine-4,4′-. Dicarboxaldehyde etc. are mentioned. Among these, for example, terephthalaldehyde is particularly preferable because it can be further reduced in thermal expansion, has high reactivity during the reaction, is excellent in solvent solubility, and is easily available commercially.
（分子末端に少なくとも２個の一級アミノ基を有するシロキサン化合物（ｄ））
本発明の分子末端に少なくとも２個の一級アミノ基を有するシロキサン化合物（ｄ）としては、市販品を用いることができ、例えば、「ＫＦ−８０１０」（アミノ基当量４３０）、「Ｘ−２２−１６１Ａ」（アミノ基当量８００）、「Ｘ−２２−１６１Ｂ」（アミノ基当量１５００）、「ＫＦ−８０１２」（アミノ基当量２２００）、「ＫＦ−８００８」（アミノ基当量５７００）、「Ｘ−２２−９４０９」（アミノ基当量７００）、「Ｘ−２２−１６６０Ｂ−３」（アミノ基当量２２００）（以上、信越化学工業（株）製）、「ＢＹ−１６−８５３Ｕ」（アミノ基当量４６０）、「ＢＹ−１６−８５３」（アミノ基当量６５０）、「ＢＹ−１６−８５３Ｂ」（アミノ基当量２２００）（以上、東レ・ダウコーニング（株）製）等が挙げられ、 これらは単独で、又は２種類以上を混合して用いてもよい。
これらの中で、例えば、合成時の反応性が高く、低熱膨張性の点から「Ｘ−２２−１６１Ａ」、「Ｘ−２２−１６１Ｂ」、「ＫＦ−８０１２」、「Ｘ−２２−１６６０Ｂ−３」、「ＢＹ−１６−８５３Ｂ」が好ましく、相溶性に優れ、高弾性率化できる「Ｘ−２２−１６１Ａ」、「Ｘ−２２−１６１Ｂ」が特に好ましい。
(Siloxane compound (d) having at least two primary amino groups at the molecular terminals)
As the siloxane compound (d) having at least two primary amino groups at the molecular terminals of the present invention, commercially available products can be used. For example, “KF-8010” (amino group equivalent 430), “X-22— 161A "(amino group equivalent 800)," X-22-161B "(amino group equivalent 1500)," KF-8012 "(amino group equivalent 2200)," KF-8008 "(amino group equivalent 5700)," X- 22-9409 "(amino group equivalent 700)," X-22-1660B-3 "(amino group equivalent 2200) (above, manufactured by Shin-Etsu Chemical Co., Ltd.)," BY-16-853U "(amino group equivalent 460) ), “BY-16-853” (amino group equivalent 650), “BY-16-853B” (amino group equivalent 2200) (above, manufactured by Toray Dow Corning Co., Ltd.), and the like. They alone or may be used as a mixture of two or more.
Among these, for example, "X-22-161A", "X-22-161B", "KF-8012", "X-22-1660B-" are highly reactive at the time of synthesis and have low thermal expansion. 3 "and" BY-16-853B "are preferable, and" X-22-161A "and" X-22-161B "are particularly preferable because of excellent compatibility and high elastic modulus.
＜分子構造中に芳香族アゾメチン基を有するアミノ変性シロキサン化合物（Ｉ）＞
本発明において、芳香族アゾメチン基を有するアミノ変性シロキサン化合物（Ｉ）を得るための反応としては、始めに、１分子中に少なくとも２個の一級アミノ基を有する芳香族アミン化合物（i）と、１分子中に少なくとも２個のアルデヒド基を有する芳香族アルデヒド化合物（ii）とを有機溶媒中で脱水縮合反応させることにより、１分子中に少なくとも１個のアルデヒド基を有する芳香族アゾメチン化合物（ｃ）を得る。次いで、前記化合物（ｂ）と、分子末端に少なくとも２個の一級アミノ基を有するシロキサン化合物（ｄ）とを有機溶媒中で脱水縮合反応させることにより、芳香族アゾメチン基を有するアミノ変性シロキサン化合物（Ｉ）を得ることができる。
また、本反応は、本発明の芳香族アゾメチン基を有するアミノ変性シロキサン化合物（Ｉ）の分子中における、芳香族アゾメチン基の分子量制御が容易である特徴を有し、これを配合してなる樹脂組成物の高弾性率化に特に有効である。
<Amino-modified siloxane compound (I) having an aromatic azomethine group in the molecular structure>
In the present invention, as a reaction for obtaining an amino-modified siloxane compound (I) having an aromatic azomethine group, first, an aromatic amine compound (i) having at least two primary amino groups in one molecule; An aromatic azomethine compound (c) having at least one aldehyde group in one molecule is obtained by subjecting the aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule to a dehydration condensation reaction in an organic solvent. ) Next, the compound (b) and a siloxane compound (d) having at least two primary amino groups at the molecular terminals are subjected to a dehydration condensation reaction in an organic solvent, whereby an amino-modified siloxane compound having an aromatic azomethine group ( I) can be obtained.
In addition, this reaction has a feature that the molecular weight of the aromatic azomethine group in the molecule of the amino-modified siloxane compound (I) having an aromatic azomethine group of the present invention can be easily controlled, and a resin obtained by blending this This is particularly effective for increasing the elastic modulus of the composition.
脱水縮合反応に使用される有機溶媒は、例えばエタノール、プロパノール、ブタノール、メチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のアルコール系溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤、テトラヒドロフラン等のエーテル系溶剤、トルエン、キシレン、メシチレン等の芳香族系溶剤、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等の窒素原子含有溶剤、ジメチルスルホキシド等の硫黄原子含有溶剤、γ−ブチロラクトン等のエステル系溶剤などが挙げられ、１種又は２種以上を混合して使用できる。これらの中で、例えば、溶解性の点からプロピレングリコールモノメチルエーテル、シクロヘキサノン、トルエン、ジメチルホルムアミド、ジメチルアセトアミド、γ−ブチロラクトン等が好ましく、揮発性が高くプリプレグの製造時に残溶剤として残りにくいプロピレングリコールモノメチルエーテル、トルエンがより好ましい。また、この反応は脱水縮合反応であるため副生成物として水が生成される。この副生成物である水を除去する目的で、例えば、芳香族系溶剤との共沸により副生成物である水を除去しながら反応することが望ましい。 Examples of the organic solvent used in the dehydration condensation reaction include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, tetrahydrofuran, and the like. Ether solvents, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, sulfur atom-containing solvents such as dimethylsulfoxide, and ester systems such as γ-butyrolactone A solvent etc. are mentioned, 1 type (s) or 2 or more types can be mixed and used. Among these, for example, propylene glycol monomethyl ether, cyclohexanone, toluene, dimethylformamide, dimethylacetamide, γ-butyrolactone and the like are preferable from the viewpoint of solubility, and propylene glycol monomethyl which is highly volatile and hardly remains as a residual solvent at the time of manufacturing a prepreg. Ether and toluene are more preferable. Moreover, since this reaction is a dehydration condensation reaction, water is produced as a by-product. For the purpose of removing water as a by-product, it is desirable to react while removing water as a by-product by azeotropy with an aromatic solvent, for example.
脱水縮合反応には、必要により任意に反応触媒を使用することができ、反応触媒の例としては、ｐ−トルエンスルホン酸等の酸性触媒、トリエチルアミン、ピリジン、トリブチルアミン等のアミン類、メチルイミダゾール、フェニルイミダゾール等のイミダゾール類、トリフェニルホスフィン等のリン系触媒などが挙げられ、１種又は２種以上を混合して使用できる。脱水縮合反応を効率よく進行させるため、例えば、ｐ−トルエンスルホン酸等の酸性触媒が好ましい。 In the dehydration condensation reaction, a reaction catalyst can be optionally used as necessary. Examples of the reaction catalyst include acidic catalysts such as p-toluenesulfonic acid, amines such as triethylamine, pyridine and tributylamine, methylimidazole, Examples thereof include imidazoles such as phenylimidazole, phosphorus-based catalysts such as triphenylphosphine, and the like, which can be used alone or in combination. In order to advance the dehydration condensation reaction efficiently, for example, an acidic catalyst such as p-toluenesulfonic acid is preferable.
始めに、１分子中に少なくとも２個のアミノ基を有する芳香族アミン化合物（i）と、１分子中に少なくとも２個のアルデヒド基を有する芳香族アルデヒド化合物（ii）とを有機溶媒中で脱水縮合反応させることにより、１分子中に少なくとも１個のアルデヒド基を有する芳香族アゾメチン化合物（ｃ）を得る。
ここで、１分子中に少なくとも２個のアミノ基を有する芳香族アミン化合物（i）と１分子中に少なくとも２個のアルデヒド基を有する芳香族アルデヒド化合物（ii）との配合量は、例えば、芳香族アミン化合物（i）の一級アミノ基数〔芳香族アミン化合物（i）の配合量／芳香族アミン化合物（i）の一級アミノ基当量〕が、芳香族アルデヒド化合物（ii）のアルデヒド基数〔芳香族アルデヒド化合物（ii）の配合量／芳香族アルデヒド化合物（ii）のアルデヒド基当量〕の０．１倍〜５．０倍の範囲になるように使用することが望ましい。０．１倍以上とすることにより、本反応により得られる芳香族アゾメチン化合物の分子量が低下することなく、また、５．０倍以下とすることにより、溶媒への溶解性が低下することがない。
First, an aromatic amine compound (i) having at least two amino groups in one molecule and an aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule are dehydrated in an organic solvent. By carrying out the condensation reaction, an aromatic azomethine compound (c) having at least one aldehyde group in one molecule is obtained.
Here, the blending amount of the aromatic amine compound (i) having at least two amino groups in one molecule and the aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule is, for example, The number of primary amino groups in the aromatic amine compound (i) [the amount of the aromatic amine compound (i) / the primary amino group equivalent of the aromatic amine compound (i)] is the number of aldehyde groups in the aromatic aldehyde compound (ii) [aromatic The blending amount of the aromatic aldehyde compound (ii) / the aldehyde group equivalent of the aromatic aldehyde compound (ii)] is desirably used in a range of 0.1 to 5.0 times. By setting it to 0.1 times or more, the molecular weight of the aromatic azomethine compound obtained by this reaction does not decrease, and by setting it to 5.0 times or less, the solubility in a solvent does not decrease. .
また、有機溶媒の配合量は、例えば、芳香族アミン化合物（i）及び芳香族アルデヒド化合物（ii）の樹脂成分の総和１００質量部に対して、２５〜２０００質量部とすることが好ましく、４０〜１０００質量部とすることがより好ましく、４０〜５００質量部とすることが特に好ましい。有機溶媒の配合量を２５質量部以上とすることにより、溶解性が不足することなく、また２０００質量部以下とすることにより、反応に長時間を要することがない。 Moreover, it is preferable that the compounding quantity of an organic solvent shall be 25-2000 mass parts with respect to 100 mass parts of total of the resin component of an aromatic amine compound (i) and aromatic aldehyde compound (ii), for example, It is more preferable to set it as -1000 mass parts, and it is especially preferable to set it as 40-500 mass parts. By setting the blending amount of the organic solvent to 25 parts by mass or more, the solubility does not become insufficient, and by setting it to 2000 parts by mass or less, the reaction does not take a long time.
上記の原料、有機溶媒、必要により反応触媒を反応釜に仕込み、必要により加熱・保温しながら０．１時間から１０時間攪拌し脱水縮合反応させることにより、芳香族アゾメチン化合物（ｃ）が得られる。
反応温度は、例えば、７０〜１５０℃が好ましく、副生成物である水を除去しながら反応することが望ましく、反応温度は１００〜１３０がより好ましい。温度を７０℃以上とすることにより、反応速度が遅くなることがなく、温度を１５０℃以下とすることにより、反応溶媒に高沸点の溶媒を必要とせず、プリプレグを製造する際、残溶剤が残りにくく、耐熱性が低下することがない。
An aromatic azomethine compound (c) is obtained by charging the above raw materials, organic solvent, and if necessary, a reaction catalyst in a reaction kettle, and stirring and dehydrating and condensing for 0.1 to 10 hours while heating and holding as necessary. .
The reaction temperature is preferably 70 to 150 ° C., for example, and it is desirable to react while removing water as a by-product, and the reaction temperature is more preferably 100 to 130. When the temperature is set to 70 ° C. or higher, the reaction rate is not slowed down, and when the temperature is set to 150 ° C. or lower, the reaction solvent does not require a high boiling point solvent, and the residual solvent is produced when the prepreg is produced. It is hard to remain and heat resistance does not decrease.
次いで、前記反応により得られた芳香族アゾメチン化合物（ｃ）と、分子末端に少なくとも２個のアミノ基を有するシロキサン化合物（ｄ）とを有機溶媒中で脱水縮合反応させることにより、芳香族アゾメチン基を有するアミノ変性シロキサン化合物（Ｉ）を得ることができる。
ここで、芳香族アゾメチン化合物（ｃ）とシロキサン化合物（ｄ）との配合量は、例えば、シロキサン化合物（ｄ）の一級アミノ基数〔シロキサン化合物（ｄ）の配合量／シロキサン化合物（ｄ）の一級アミノ基当量〕が、芳香族アゾメチン化合物（ｃ）のアルデヒド基数〔芳香族アゾメチン化合物（ｃ）の配合量／芳香族アゾメチン化合物（ｃ）のアルデヒド基当量〕の１．０〜１０．０倍の範囲になるように使用されることが望ましい。１．０倍以上とすることにより、溶媒への溶解性が低下することなく、また、１０．０倍以下とすることにより、芳香族アゾメチン基を有するアミノ変性シロキサン化合物（Ｉ）を配合してなる熱硬化性樹脂の弾性率が低下することがない。
Next, the aromatic azomethine compound (c) obtained by the above reaction and the siloxane compound (d) having at least two amino groups at the molecular ends are subjected to a dehydration condensation reaction in an organic solvent, thereby producing an aromatic azomethine group. An amino-modified siloxane compound (I) having the following can be obtained.
Here, the compounding amount of the aromatic azomethine compound (c) and the siloxane compound (d) is, for example, the number of primary amino groups of the siloxane compound (d) [the compounding amount of the siloxane compound (d) / the primary compound of the siloxane compound (d). The amino group equivalent] is 1.0 to 10.0 times the number of aldehyde groups of the aromatic azomethine compound (c) [the amount of the aromatic azomethine compound (c) / the aldehyde group equivalent of the aromatic azomethine compound (c)]. It is desirable to be used to be in range. By making it 1.0 times or more, the solubility in the solvent is not lowered, and by making it 10.0 times or less, the amino-modified siloxane compound (I) having an aromatic azomethine group is blended. The elastic modulus of the resulting thermosetting resin does not decrease.
また、有機溶媒の配合量は、例えば、芳香族アゾメチン化合物（ｃ）及びシロキサン化合物（ｄ）の樹脂成分の総和１００質量部に対して、２５〜２０００質量部とすることが好ましく、４０〜１０００質量部とすることがより好ましく、４０〜５００質量部とすることが特に好ましい。有機溶媒の配合量を２５質量部以上とすることにより、溶解性が不足することなく、また２０００質量部以下とすることにより、反応に長時間を要することがない。 Moreover, it is preferable that the compounding quantity of an organic solvent shall be 25-2000 mass parts with respect to 100 mass parts of sum total of the resin component of an aromatic azomethine compound (c) and a siloxane compound (d), for example, 40-1000. It is more preferable to set it as a mass part, and it is especially preferable to set it as 40-500 mass parts. By setting the blending amount of the organic solvent to 25 parts by mass or more, the solubility does not become insufficient, and by setting it to 2000 parts by mass or less, the reaction does not take a long time.
上記の原料、有機溶媒、必要により反応触媒を反応釜に仕込み、必要により加熱及び保温しながら０．１時間から１０時間攪拌し脱水縮合反応させることにより、芳香族アゾメチン基を有するアミノ変性シロキサン化合物（Ｉ）が得られる。
反応温度は、例えば、７０〜１５０℃が好ましく、副生成物である水を除去しながら反応することが望ましく、反応温度は１００〜１３０がより好ましい。温度を７０℃以上とすることにより、反応速度が遅くなることがなく、温度を１５０℃以下とすることにより、反応溶媒に高沸点の溶媒を必要とせず、プリプレグを製造する際、残溶剤が残りにくく、耐熱性が低下することがない。
An amino-modified siloxane compound having an aromatic azomethine group by charging the above raw materials, an organic solvent, and if necessary, a reaction catalyst in a reaction kettle and stirring and dehydrating for 0.1 to 10 hours while heating and holding as necessary. (I) is obtained.
The reaction temperature is preferably 70 to 150 ° C., for example, and it is desirable to react while removing water as a by-product, and the reaction temperature is more preferably 100 to 130. When the temperature is set to 70 ° C. or higher, the reaction rate is not slowed down, and when the temperature is set to 150 ° C. or lower, the reaction solvent does not require a high boiling point solvent, and the residual solvent is produced when the prepreg is produced. It is hard to remain and heat resistance does not decrease.
上記の反応により得られた芳香族アゾメチン基を有するアミノ変性シロキサン化合物（Ｉ）は、ＩＲ測定を行うことにより確認することができる。ＩＲ測定により、アゾメチン基（−Ｎ＝ＣＨ−）に起因する１６２０ｃｍ-1のピークが出現することを確認し、また、一級アミノ基に起因する３４４０ｃｍ-1、及び３３７０ｃｍ-1付近のピークが存在することを確認することにより、良好に反応が進行し、所望の化合物が得られていることを確認することができる。また、重量平均分子量（Ｍｗ）は、特に限定されないが、例えば、１，０００〜３００，０００が好ましく、特に６，０００〜１５０，０００が好ましい。重量平均分子量（Ｍｗ）が前記下限値未満であると低収縮性、低熱膨張性が低下する場合が有り、前記上限値を超えると相溶性、弾性率が低下する場合が有る。なお、重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）により測定を行い、標準ポリスチレンを用いて作製した検量線により換算したものである。
測定装置としては、例えばオートサンプラー（東ソー（株）製ＡＳ−８０２０）、カラムオーブン（日本分光（株）製８６０−Ｃ０）、ＲＩ検出器（日本分光（株）製８３０−ＲＩ）、ＵＶ／ＶＩＳ検出器（日本分光（株）製８７０−ＵＶ）、ＨＰＬＣポンプ（日本分光（株）製８８０−ＰＵ）を使用することが可能である。
また、使用カラムとしては、例えば、東ソー（株）製 ＴＳＫｇｅｌ ＳｕｐｅｒＨＺ２０００，２３００を使用でき、測定条件としては、例えば、測定温度 ４０℃、流量 ０．５ｍｌ/ｍｉｎ、溶媒をテトラヒドロフランとすることで、測定可能である。
The amino-modified siloxane compound (I) having an aromatic azomethine group obtained by the above reaction can be confirmed by performing IR measurement. The IR measurement, to confirm that the peak of 1620 cm -1 attributable to the azomethine group (-N = CH-) appears, also, at 3,440 cm -1 due to the primary amino group, and there is a peak of 3370cm around -1 By confirming that the reaction is carried out, it can be confirmed that the reaction proceeds well and the desired compound is obtained. Moreover, although a weight average molecular weight (Mw) is not specifically limited, For example, 1,000-300,000 are preferable and 6,000-150,000 are especially preferable. If the weight average molecular weight (Mw) is less than the lower limit, low shrinkage and low thermal expansion may be reduced, and if the upper limit is exceeded, compatibility and elastic modulus may be reduced. The weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) and converted by a calibration curve produced using standard polystyrene.
Examples of the measuring apparatus include an auto sampler (AS-8020 manufactured by Tosoh Corporation), a column oven (860-C0 manufactured by JASCO Corporation), an RI detector (830-RI manufactured by JASCO Corporation), UV / It is possible to use a VIS detector (870-UV manufactured by JASCO Corporation) or an HPLC pump (880-PU manufactured by JASCO Corporation).
In addition, as the column used, for example, TSKgel SuperHZ2000, 2300 manufactured by Tosoh Corporation can be used, and the measurement conditions are, for example, a measurement temperature of 40 ° C., a flow rate of 0.5 ml / min, and a solvent as tetrahydrofuran. Is possible.
＜分子構造中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物（ｂ）＞
１分子構造中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物（ｂ）としては、例えば、ビス（４−マレイミドフェニル）メタン、ポリフェニルメタンマレイミド、ビス（４−マレイミドフェニル）エーテル、ビス（４−マレイミドフェニル）スルホン、３，３−ジメチル−５，５−ジエチル−４，４−ジフェニルメタンビスマレイミド、４−メチル−１，３−フェニレンビスマレイミド、ｍ−フェニレンビスマレイミド、２，２−ビス（４−（４−マレイミドフェノキシ）フェニル）プロパン等が挙げられ、１種又は２種以上を混合して使用できる。
<Maleimide compound (b) having at least two N-substituted maleimide groups in the molecular structure>
Examples of the maleimide compound (b) having at least two N-substituted maleimide groups in one molecular structure include bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2- Bis (4- (4-maleimidophenoxy) phenyl) propane and the like can be mentioned, and one kind or a mixture of two or more kinds can be used.
これらの中で、反応率が高く、より高耐熱性化できるビス（４−マレイミドフェニル）メタン、ビス（４−マレイミドフェニル）スルホン、３，３−ジメチル−５，５−ジエチル−４，４−ジフェニルメタンビスマレイミド、２，２−ビス（４−（４−マレイミドフェノキシ）フェニル）プロパンが好ましく、溶剤への溶解性の点から、３，３−ジメチル−５，５−ジエチル−４，４−ジフェニルメタンビスマレイミド、ビス（４−マレイミドフェニル）メタンがより好ましく、安価である点からビス（４−マレイミドフェニル）メタンが特に好ましい。
なお、配合量としては、熱硬化性樹脂組成物中の固形分換算樹脂成分合計量１００質量部に対して、３０〜８０質量部程度が好ましく、より好ましくは３５〜６５質量部程度である。この範囲の配合量とすることで、弾性率及び低熱膨張性が向上するため好ましい。
Among these, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-, which has a high reaction rate and can have higher heat resistance. Diphenylmethane bismaleimide and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane are preferable, and 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane is preferable from the viewpoint of solubility in a solvent. Bismaleimide and bis (4-maleimidophenyl) methane are more preferred, and bis (4-maleimidophenyl) methane is particularly preferred because it is inexpensive.
In addition, as a compounding quantity, about 30-80 mass parts is preferable with respect to 100 mass parts of solid content conversion resin components in a thermosetting resin composition, More preferably, it is about 35-65 mass parts. The blending amount within this range is preferable because the elastic modulus and low thermal expansion are improved.
＜酸性置換基を有するアミン化合物（ｅ）＞
本発明の熱硬化性樹脂組成物は、下記一般式（１）に示す酸性置換基を有するアミン化合物（ｅ）をさらに配合させることができる。
The thermosetting resin composition of the present invention can further contain an amine compound (e) having an acidic substituent represented by the following general formula (1).
酸性置換基を有するアミン化合物（ｅ）は、例えば、ｍ−アミノフェノール、ｐ−アミノフェノール、ｏ−アミノフェノール、ｐ−アミノ安息香酸、ｍ−アミノ安息香酸、ｏ−アミノ安息香酸、ｏ−アミノベンゼンスルホン酸、ｍ−アミノベンゼンスルホン酸、ｐ−アミノベンゼンスルホン酸、３，５−ジヒドロキシアニリン、３，５−ジカルボキシアニリン等が挙げられ、これらの中で、溶解性や合成の収率の点からｍ−アミノフェノール、ｐ−アミノフェノール、ｏ−アミノフェノール、ｐ−アミノ安息香酸、ｍ−アミノ安息香酸、及び３，５−ジヒドロキシアニリンが好ましく、耐熱性の点からｍ−アミノフェノール及びｐ−アミノフェノールがより好ましく、低熱膨張性の点からｐ−アミノフェノールが特に好ましい。
配合量としては、熱硬化性樹脂組成物中の固形分換算樹脂成分合計量１００質量部に対して、０．５〜１０質量部程度が好ましく、より好ましくは０．７〜３％質量部程度である。この範囲の配合量とすることで、耐熱性及び低熱膨張性が向上するため好ましい。
The amine compound (e) having an acidic substituent is, for example, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o-amino. Benzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, etc., and among these, solubility and synthesis yield From the viewpoint, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline are preferable, and m-aminophenol and p are preferable from the viewpoint of heat resistance. -Aminophenol is more preferable, and p-aminophenol is particularly preferable from the viewpoint of low thermal expansion.
As a compounding quantity, about 0.5-10 mass parts is preferable with respect to 100 mass parts of solid component conversion resin component total amount in a thermosetting resin composition, More preferably, about 0.7-3% mass part is preferable. It is. Since the heat resistance and the low thermal expansion are improved, the blending amount in this range is preferable.
以上のような、芳香族アゾメチン基を有するアミノ変性シロキサン化合物（Ｉ）、１分子構造中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物（ｂ）及び酸性置換基を有するアミン化合物（ｅ）は、それぞれ熱硬化性樹脂組成物に配合されていてもよいが、これらの化合物（Ｉ）、（ｄ）及び（ｅ）を、必要により加熱及び保温し、あらかじめ反応させておくこともできる。
この際のマレイミド化合物（ｂ）の配合量は、ゲル化の防止と耐熱性の観点から、マレイミド化合物（ｂ）のマレイミド基の当量が、アミン化合物（Ｉ）及び（ｅ）の一級アミノ基の当量を超える範囲であることが望ましい。なお、アミン化合物（Ｉ）の量はアミン化合物（ｅ）の量の７〜３５倍程度であることが、耐熱性の点から好ましい。
マレイミド化合物（ｂ）の反応の温度は７０〜２００℃とすることが好ましく、反応時間は０．５〜１０時間とすることが好ましい。
As described above, the amino-modified siloxane compound (I) having an aromatic azomethine group, the maleimide compound (b) having at least two N-substituted maleimide groups in the molecular structure, and the amine compound having an acidic substituent (e ) May be blended in the thermosetting resin composition, respectively, but these compounds (I), (d) and (e) may be heated and kept warm if necessary, and reacted in advance. .
The compounding amount of the maleimide compound (b) at this time is such that the equivalent of the maleimide group of the maleimide compound (b) is that of the primary amino group of the amine compounds (I) and (e) from the viewpoint of prevention of gelation and heat resistance. A range exceeding the equivalent is desirable. In addition, it is preferable from a heat resistant point that the quantity of amine compound (I) is about 7 to 35 times the quantity of amine compound (e).
The reaction temperature of the maleimide compound (b) is preferably 70 to 200 ° C., and the reaction time is preferably 0.5 to 10 hours.
以上の反応の際に使用される有機溶媒は、特に制限されないが、例えばエタノール、プロパノール、ブタノール、メチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のアルコール系溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤、酢酸エチルエステルやγ−ブチロラクトン等のエステル系溶剤、テトラヒドロフラン等のエーテル系溶剤、トルエン、キシレン、メシチレン等の芳香族系溶剤、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等の窒素原子含有溶剤、ジメチルスルホキシド等の硫黄原子含有溶剤などが挙げられ、１種又は２種以上を混合して使用できる。
これらの中で、溶解性の点からシクロヘキサノン、プロピレングリコールモノメチルエーテル、メチルセロソルブ、γ−ブチロラクトン、ジメチルアセトアミドが好ましく、低毒性であることや揮発性が高くプリプレグの製造時に残溶剤として残りにくい点から、シクロヘキサノン、プロピレングリコールモノメチルエーテル、ジメチルアセトアミドが特に好ましい。
The organic solvent used in the above reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents, ester solvents such as ethyl acetate and γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone Examples thereof include an atom-containing solvent, a sulfur atom-containing solvent such as dimethyl sulfoxide, and the like, which can be used alone or in combination.
Among these, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, γ-butyrolactone, and dimethylacetamide are preferable from the viewpoint of solubility, and low toxicity and high volatility make it difficult to remain as a residual solvent during prepreg production. , Cyclohexanone, propylene glycol monomethyl ether, and dimethylacetamide are particularly preferable.
有機溶媒の配合量は、溶解性と反応時間の観点から、芳香族アゾメチン基を有するアミノ変性シロキサン化合物（Ｉ）、１分子構造中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物（ｂ）及び酸性置換基を有するアミン化合物（ｅ）の合計量１００質量部当たり、２５〜１０００質量部とすることが好ましく、４０〜７００質量部とすることがより好ましい。 From the viewpoint of solubility and reaction time, the organic solvent is blended in an amino-modified siloxane compound (I) having an aromatic azomethine group and a maleimide compound (b) having at least two N-substituted maleimide groups in one molecular structure. ) And an amine compound (e) having an acidic substituent, the total amount is preferably 25 to 1000 parts by mass, more preferably 40 to 700 parts by mass, per 100 parts by mass.
＜熱可塑性エラストマー（ｆ）＞
本発明の熱硬化性樹脂組成物は、さらに熱可塑性エラストマー（ｆ）を配合させることができる。
熱可塑性エラストマー（ｆ）としては、例えば、スチレン系エラストマー、オレフィン系エラストマー、ウレタン系エラストマー、ポリエステル系エラストマー、ポリアミド系エラストマー、アクリル系エラストマー、シリコーン系エラストマーやその誘導体などが挙げられる。これらは、ハードセグメント成分とソフトセグメント成分かを有しており、一般に前者が耐熱性及び強度に、後者が柔軟性及び強靭性に寄与している。これらは、１種を単独で又は２種以上を混合して使用できる。
<Thermoplastic elastomer (f)>
The thermosetting resin composition of the present invention can further contain a thermoplastic elastomer (f).
Examples of the thermoplastic elastomer (f) include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, silicone elastomers and derivatives thereof. These have a hard segment component and a soft segment component. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. These can be used individually by 1 type or in mixture of 2 or more types.
また、これらエラストマーとしては、分子末端又は分子鎖中に反応性官能基を有するものを用いることができる。反応性官能基としては、例えば、エポキシ基、水酸基、カルボキシル基、アミノ基、アミド基、イソシアナト基、アクリル基、メタクリル基、ビニル基等が挙げられる。これら反応性官能基を分子末端又は分子鎖中に有することにより、樹脂への相溶性が向上し、本発明の熱硬化性樹脂組成物の硬化時に発生する内部応力をより効果的に低減することができ、結果として、基板の反りを顕著に低減することが可能となる。 Moreover, as these elastomers, those having a reactive functional group at the molecular terminal or molecular chain can be used. Examples of the reactive functional group include an epoxy group, a hydroxyl group, a carboxyl group, an amino group, an amide group, an isocyanato group, an acryl group, a methacryl group, and a vinyl group. By having these reactive functional groups in the molecular terminal or molecular chain, compatibility with the resin is improved, and internal stress generated during curing of the thermosetting resin composition of the present invention is more effectively reduced. As a result, it is possible to significantly reduce the warpage of the substrate.
これらのエラストマーの中で、例えば、耐熱性、絶縁信頼性の点で、スチレン系エラストマー、オレフィン系エラストマー、ポリアミド系エラストマー、及びシリコーン系エラストマーが好ましい。 Among these elastomers, for example, styrene elastomers, olefin elastomers, polyamide elastomers, and silicone elastomers are preferable from the viewpoint of heat resistance and insulation reliability.
また、これらエラストマーの分子末端又は分子鎖中に有する反応性官能基は、例えば、金属箔との密着性の点で、エポキシ基、水酸基、カルボキシル基、アミノ基、及びアミド基が好ましく、耐熱性、絶縁信頼性の点から、エポキシ基、水酸基、及びアミノ基が特に好ましい。 Further, the reactive functional group possessed in the molecular terminal or molecular chain of these elastomers is preferably, for example, an epoxy group, a hydroxyl group, a carboxyl group, an amino group, and an amide group in terms of adhesion to the metal foil. From the viewpoint of insulation reliability, an epoxy group, a hydroxyl group, and an amino group are particularly preferable.
熱可塑性エラストマー（ｆ）成分の配合量は、例えば、樹脂成分の総和１００質量部に対して、０．１〜５０質量部であることが好ましく、２〜３０質量部であることが、樹脂の相溶性が良く、硬化物の低収縮性、低熱膨張性を効果的に発現できる点からより好ましい The blending amount of the thermoplastic elastomer (f) component is, for example, preferably 0.1 to 50 parts by mass, and 2 to 30 parts by mass with respect to 100 parts by mass of the total resin components. It is more preferable because it has good compatibility and can effectively exhibit low shrinkage and low thermal expansion of the cured product.
＜他の熱硬化性樹脂（ｇ）＞
さらに，本発明の熱硬化性樹脂組成物には、分子構造中に芳香族アゾメチン基を有するアミノ変性シロキサン化合物（Ｉ）、分子構造中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物（ｂ）及び所望により酸性置換基を有するアミン化合物（ｅ）を配合してなる熱硬化性樹脂組成物以外の他の熱硬化性樹脂（ｇ）を配合してもよく、このような熱硬化性樹脂（ｇ）としては、例えば、エポキシ樹脂、フェノール樹脂、不飽和イミド樹脂、シアネート樹脂、イソシアネート樹脂、ベンゾオキサジン樹脂、オキセタン樹脂、アミノ樹脂、不飽和ポリエステル樹脂、アリル樹脂、ジシクロペンタジエン樹脂、シリコーン樹脂、トリアジン樹脂、メラミン樹脂等が挙げられ、これらの１種又は２種以上を混合して使用できる。これらの中で、成形性や電気絶縁性の点からエポキシ樹脂、シアネート樹脂が好ましい。
<Other thermosetting resin (g)>
Furthermore, the thermosetting resin composition of the present invention includes an amino-modified siloxane compound (I) having an aromatic azomethine group in the molecular structure, and a maleimide compound having at least two N-substituted maleimide groups in the molecular structure ( Other thermosetting resins (g) other than the thermosetting resin composition obtained by mixing b) and, if desired, the amine compound (e) having an acidic substituent may be blended. Examples of the resin (g) include epoxy resins, phenol resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, and silicones. Resins, triazine resins, melamine resins and the like can be mentioned, and one or more of these can be mixed and used. Among these, epoxy resins and cyanate resins are preferable from the viewpoint of moldability and electrical insulation.
エポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ樹脂、スチルベン型エポキシ樹脂、トリアジン骨格含有エポキシ樹脂、フルオレン骨格含有エポキシ樹脂、トリフェノールフェノールメタン型エポキシ樹脂、ビフェニル型エポキシ樹脂、キシリレン型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、脂環式エポキシ樹脂、多官能フェノール類及びアントラセン等の多環芳香族類のジグリシジルエーテル化合物及びこれらにリン化合物を導入したリン含有エポキシ樹脂などが挙げられ、これらの中で、耐熱性、難燃性の点からビフェニルアラルキル型エポキシ樹脂、ナフタレン型エポキシ樹脂が好ましい。これらは１種又は２種以上を混合して使用できる。 Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin. , Stilbene type epoxy resin, Triazine skeleton containing epoxy resin, Fluorene skeleton containing epoxy resin, Triphenolphenol methane type epoxy resin, Biphenyl type epoxy resin, Xylylene type epoxy resin, Biphenyl aralkyl type epoxy resin, Naphthalene type epoxy resin, Dicyclopentadiene -Type epoxy resin, alicyclic epoxy resin, polyfunctional phenols and diglycidyl ether compounds of polycyclic aromatics such as anthracene Beauty These and phosphorus-containing epoxy resin obtained by introducing a phosphorus compound listed, among these, heat resistance, biphenyl aralkyl type epoxy resin from the viewpoint of flame retardancy, naphthalene type epoxy resins are preferred. These can be used alone or in combination of two or more.
また、シアネート樹脂としては、例えば、ノボラック型シアネート樹脂、ビスフェノールＡ型シアネート樹脂、ビスフェノールＥ型シアネート樹脂、テトラメチルビスフェノールＦ型シアネート樹脂などのビスフェノール型シアネート樹脂及びこれらが一部トリアジン化したプレポリマー等を挙げることができる。これらの中で耐熱性、難燃性の点からノボラック型シアネート樹脂が好ましい。これらは１種又は２種以上を混合して使用できる。 Examples of the cyanate resin include novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, and bisphenol type cyanate resin such as tetramethylbisphenol F type cyanate resin, and prepolymers in which these are partially triazine. Can be mentioned. Among these, a novolak type cyanate resin is preferable from the viewpoint of heat resistance and flame retardancy. These can be used alone or in combination of two or more.
なお、これらの熱硬化性樹脂（ｇ）の配合量としては、熱硬化性樹脂組成物中の固形分換算樹脂成分合計量１００質量部に対して、５〜５０質量部程度が好ましく、１０〜４０質量部程度であることがより好ましい。 In addition, as a compounding quantity of these thermosetting resins (g), about 5-50 mass parts is preferable with respect to 100 mass parts of solid content conversion resin components in a thermosetting resin composition, More preferred is about 40 parts by mass.
＜硬化促進剤（ｈ）＞
本発明の熱硬化性樹脂組成物は、さらに硬化促進剤（ｈ）を配合させることができる。硬化促進剤（ｈ）としては、例えば、ナフテン酸亜鉛、ナフテン酸コバルト、オクチル酸スズ、オクチル酸コバルト、ビスアセチルアセトナートコバルト（ＩＩ）、トリスアセチルアセトナートコバルト（ＩＩＩ）等の有機金属塩、イミダゾール類及びその誘導体、ホスフィン類及びホスホニウム塩等の有機リン系化合物、第二級アミン類、第三級アミン類、及び第四級アンモニウム塩等が挙げられ、これらの１種を単独で又は２種以上を混合して使用できる。これらの中で、例えば、促進効果と保存安定性の点から、ナフテン酸亜鉛、イミダゾール誘導体、ホスホニウム塩が好ましい。
<Curing accelerator (h)>
The thermosetting resin composition of the present invention can further contain a curing accelerator (h). Examples of the curing accelerator (h) include organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonatocobalt (II), and trisacetylacetonatecobalt (III). Examples thereof include imidazoles and derivatives thereof, organic phosphorus compounds such as phosphines and phosphonium salts, secondary amines, tertiary amines, and quaternary ammonium salts. A mixture of seeds or more can be used. Among these, for example, zinc naphthenate, imidazole derivatives, and phosphonium salts are preferable from the viewpoint of the promoting effect and the storage stability.
硬化促進剤の配合量は、例えば、樹脂成分の総和１００質量部に対して０．０１〜３．０質量部であることが好ましく、０．０５〜１．５質量部であることがより好ましい。硬化促進剤の配合量を樹脂成分の総和１００質量部に対して０．０１〜３．０質量部にすることで、促進効果と保存安定性を良好に保つことができる。 The blending amount of the curing accelerator is, for example, preferably 0.01 to 3.0 parts by mass, and more preferably 0.05 to 1.5 parts by mass with respect to 100 parts by mass of the total resin components. . By making the compounding quantity of a hardening accelerator 0.01-3.0 mass parts with respect to 100 mass parts of sum total of a resin component, a promotion effect and storage stability can be kept favorable.
＜無機充填剤＞
本発明の熱硬化性樹脂組成物には、任意に無機充填材を配合することができる。無機充填材としては、シリカ、アルミナ、タルク、マイカ、カオリン、水酸化アルミニウム、ベーマイト、水酸化マグネシウム、ホウ酸亜鉛、スズ酸亜鉛、酸化亜鉛、酸化チタン、窒化ホウ素、炭酸カルシウム、硫酸バリウム、ホウ酸アルミニウム、チタン酸カリウム、ＥガラスやＴガラス、Ｄガラス等のガラス粉や中空ガラスビーズ等が挙げられ、これらの１種又は２種以上を混合して使用できる。
<Inorganic filler>
An inorganic filler can be arbitrarily blended in the thermosetting resin composition of the present invention. Inorganic fillers include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, and boron. Examples thereof include aluminum oxide, potassium titanate, glass powder such as E glass, T glass, and D glass, and hollow glass beads. These can be used alone or in combination.
無機充填材としては、誘電特性、耐熱性、低熱膨張性の点からシリカが特に好ましい。シリカとしては、例えば、湿式法で製造され含水率の高い沈降シリカと、乾式法で製造され結合水等をほとんど含まない乾式法シリカが挙げられ、乾式法シリカとしてはさらに、製造法の違いにより破砕シリカ、フュームドシリカ、溶融球状シリカが挙げられる。これらの中で、低熱膨張性及び樹脂に充填した際の高流動性から溶融球状シリカが好ましい。 As the inorganic filler, silica is particularly preferable from the viewpoints of dielectric properties, heat resistance, and low thermal expansion. Examples of the silica include a precipitated silica produced by a wet method and having a high water content, and a dry method silica produced by a dry method and containing almost no bound water. The dry method silica further includes differences in production methods. Examples include crushed silica, fumed silica, and fused spherical silica. Among these, fused spherical silica is preferable because of its low thermal expansion and high fluidity when filled in a resin.
無機充填材として溶融球状シリカを用いる場合、その平均粒子径は０．１〜１０μｍであることが好ましく、０．３〜８μｍであることがより好ましい。該溶融球状シリカの平均粒子径を０．１μｍ以上にすることで、樹脂に高充填した際の流動性を良好に保つことができ、さらに１０μｍ以下にすることで、粗大粒子の混入確率を減らし粗大粒子起因の不良の発生を抑えることができる。ここで、平均粒子径とは、粒子の全体積を１００％として粒子径による累積度数分布曲線を求めた時、体積５０％に相当する点の粒子径のことであり、レーザ回折散乱法を用いた粒度分布測定装置等で測定することができる。 When fused spherical silica is used as the inorganic filler, the average particle size is preferably 0.1 to 10 μm, and more preferably 0.3 to 8 μm. By setting the average particle diameter of the fused spherical silica to 0.1 μm or more, the fluidity when the resin is highly filled can be kept good, and by setting it to 10 μm or less, the mixing probability of coarse particles is reduced. Generation of defects due to coarse particles can be suppressed. Here, the average particle diameter is a particle diameter at a point corresponding to a volume of 50% when a cumulative frequency distribution curve based on the particle diameter is obtained with the total volume of the particles as 100%, and a laser diffraction scattering method is used. It can be measured with a particle size distribution measuring device.
無機充填材の配合量は、熱硬化性樹脂組成物中の固形分換算樹脂成分合計量１００質量部当たり２０〜３００質量部であることが好ましく、５０〜２００質量部であることがより好ましい。無機充填材の配合量を２０〜３００質量部にすることで、プリプレグの成形性と低熱膨張性を良好に保つことができる。 It is preferable that the compounding quantity of an inorganic filler is 20-300 mass parts per 100 mass parts of solid content conversion resin component total amount in a thermosetting resin composition, and it is more preferable that it is 50-200 mass parts. By making the compounding quantity of an inorganic filler into 20-300 mass parts, the moldability and low thermal expansibility of a prepreg can be kept favorable.
＜その他の成分＞
本発明の熱硬化性樹脂組成物には、樹脂組成物として熱硬化性の性質を損なわない程度に、熱可塑性樹脂、有機充填材、難燃剤、紫外線吸収剤、酸化防止剤、光重合開始剤、蛍光増白剤及び接着性向上剤等を使用できる。
<Other ingredients>
The thermosetting resin composition of the present invention includes a thermoplastic resin, an organic filler, a flame retardant, an ultraviolet absorber, an antioxidant, and a photopolymerization initiator as long as the thermosetting properties of the resin composition are not impaired. In addition, fluorescent brighteners and adhesion improvers can be used.
熱可塑性樹脂の例としては、ポリエチレン、ポリプロピレン、ポリスチレン、ポリフェニレンエーテル樹脂、フェノキシ樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、ポリイミド樹脂、キシレン樹脂、ポリフェニレンスルフィド樹脂、ポリエーテルイミド樹脂、ポリエーテルエーテルケトン樹脂、ポリエーテルイミド樹脂、シリコーン樹脂、テトラフルオロエチレン樹脂等が挙げられる。 Examples of thermoplastic resins include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, poly Examples include ether ether ketone resins, polyether imide resins, silicone resins, and tetrafluoroethylene resins.
有機充填材の例としては、ポリエチレン、ポリプロピレン、ポリスチレン、ポリフェニレンエーテル樹脂、シリコーン樹脂、テトラフルオロエチレン樹脂等よりなる構造の樹脂フィラー、アクリル酸エステル系樹脂、メタクリル酸エステル系樹脂、共役ジエン系樹脂等よりなるゴム状態のコア層と、アクリル酸エステル系樹脂、メタクリル酸エステル系樹脂、芳香族ビニル系樹脂、シアン化ビニル系樹脂等よりなるガラス状態のシェル層を持つコアシェル構造の樹脂フィラーが挙げられる。なお、ポリエチレン、ポリプロピレン、ポリスチレン及びポリフェニレンエーテル樹脂は、熱可塑性樹脂としても使用可能である。 Examples of organic fillers include resin fillers made of polyethylene, polypropylene, polystyrene, polyphenylene ether resins, silicone resins, tetrafluoroethylene resins, acrylic ester resins, methacrylic ester resins, conjugated diene resins, etc. And a core-shell structure resin filler having a rubbery core layer and a glassy shell layer made of an acrylic ester resin, a methacrylic ester resin, an aromatic vinyl resin, a vinyl cyanide resin, or the like. . Polyethylene, polypropylene, polystyrene, and polyphenylene ether resins can also be used as thermoplastic resins.
難燃剤の例としては、臭素や塩素を含有する含ハロゲン系難燃剤、トリフェニルホスフェート、トリクレジルホスフェート、トリスジクロロプロピルホスフェート、リン酸エステル系化合物、赤リン等のリン系難燃剤、スルファミン酸グアニジン、硫酸メラミン、ポリリン酸メラミン、メラミンシアヌレート等の窒素系難燃剤、シクロホスファゼン、ポリホスファゼン等のホスファゼン系難燃剤、三酸化アンチモン等の無機系難燃剤が挙げられる。 Examples of flame retardants include halogen-containing flame retardants containing bromine and chlorine, triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric ester compounds, phosphorous flame retardants such as red phosphorus, sulfamic acid Nitrogen flame retardants such as guanidine, melamine sulfate, melamine polyphosphate and melamine cyanurate, phosphazene flame retardants such as cyclophosphazene and polyphosphazene, and inorganic flame retardants such as antimony trioxide.
その他、紫外線吸収剤の例としてはベンゾトリアゾール系紫外線吸収剤、酸化防止剤の例としてはヒンダードフェノール系やヒンダードアミン系酸化防止剤、光重合開始剤の例としてはベンゾフェノン類、ベンジルケタール類、チオキサントン系の光重合開始剤、蛍光増白剤の例としてはスチルベン誘導体の蛍光増白剤、接着性向上剤の例としては尿素シラン等の尿素化合物やシラン系、チタネート系、アルミネート系等のカップリング剤が挙げられる。
また、配合時、無機充填材をシラン系、チタネート系等のカップリング剤、シリコーンオリゴマー等の表面処理剤で前処理、又はインテグラルブレンド処理することも好ましい。
Other examples of UV absorbers include benzotriazole UV absorbers, examples of antioxidants include hindered phenols and hindered amines, and examples of photopolymerization initiators include benzophenones, benzyl ketals, and thioxanthone. Examples of photopolymerization initiators and fluorescent brighteners include stilbene derivative fluorescent brighteners, and adhesion improvers such as urea compounds such as urea silane and silane, titanate and aluminate cups. A ring agent is mentioned.
Further, at the time of blending, it is also preferable that the inorganic filler is pretreated with an silane-based or titanate-based coupling agent or a surface-treating agent such as a silicone oligomer, or an integral blend treatment.
［ワニス］
本発明の熱硬化性樹脂組成物は、通常、希釈溶媒として有機溶媒を使用し、ワニスとして使用される。該有機溶媒は特に制限されないが、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒、メチルセロソルブ等のアルコール系溶媒、テトラヒドロフランなどのエーテル系溶媒、トルエン、キシレン、メシチレン等の芳香族系溶媒などが挙げられる。これらは１種又は２種以上を混合して使用できる。
最終的に得られるワニス中の樹脂組成物は、ワニス全体の４０〜９０質量％であることが好ましく、５０〜８０質量％であることがより好ましい。ワニス中の樹脂組成物の含有量を４０〜９０質量％にすることで、塗工性を良好に保ち、適切な樹脂組成物付着量のプリプレグを得ることができる。
[varnish]
The thermosetting resin composition of the present invention is usually used as a varnish using an organic solvent as a diluting solvent. The organic solvent is not particularly limited. For example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohol solvents such as methyl cellosolve, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, and mesitylene. System solvents and the like. These can be used alone or in combination of two or more.
It is preferable that the resin composition in the varnish finally obtained is 40 to 90 mass% of the whole varnish, and it is more preferable that it is 50 to 80 mass%. By setting the content of the resin composition in the varnish to 40 to 90% by mass, it is possible to maintain good coatability and obtain a prepreg having an appropriate resin composition adhesion amount.
［積層板］
本発明における積層板は、前述の本発明のプリプレグを用いて、積層成形して、形成することができる。本発明のプリプレグを例えば１〜２０枚重ね、その片面又は両面に銅及びアルミニウム等の金属箔を配置した構成で積層成形することにより製造することができる。金属箔は、電気絶縁材料用途で用いるものであれば特に制限されない。また、成形条件は、例えば、電気絶縁材料用積層板及び多層板の手法が適用でき、より具体的には、多段プレス、多段真空プレス、連続成形機、オートクレーブ成形機を使用し、温度１００〜２５０℃、圧力２〜１００ｋｇｆ／ｃｍ2、加熱時間０．１〜５時間の範囲で成形することができる。
[Laminated board]
The laminate in the present invention can be formed by laminate molding using the prepreg of the present invention described above. The prepreg of the present invention can be produced, for example, by laminating and molding 1 to 20 sheets, and laminating and forming a metal foil such as copper and aluminum on one or both sides thereof. The metal foil is not particularly limited as long as it is used for electrical insulating material applications. In addition, as the molding conditions, for example, a method of a laminated plate for an electrical insulating material and a multilayer plate can be applied. More specifically, a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine is used, and a temperature of 100 to It can be molded at 250 ° C., a pressure of 2 to 100 kgf / cm 2 , and a heating time of 0.1 to 5 hours.
［多層プリント配線板］
本発明の多層プリント配線板は、本発明の積層板を用いて製造されたものである。本発明における多層プリント配線板は、前記積層板の表面に回路を形成して製造される。すなわち、本発明に係る積層板の導体層を通常のエッチング法によって配線加工し、前述のプリプレグを介して配線加工した積層板を複数積層し、加熱プレス加工することによって一括して多層化する。その後、ドリル加工又はレーザ加工によるスルーホール又はブラインドビアホールの形成と、メッキ又は導電性ペーストによる層間配線の形成を経て多層プリント配線板を製造することができる。
[Multilayer printed wiring board]
The multilayer printed wiring board of this invention is manufactured using the laminated board of this invention. The multilayer printed wiring board in the present invention is manufactured by forming a circuit on the surface of the laminated board. That is, the conductor layer of the laminated board according to the present invention is subjected to wiring processing by a normal etching method, and a plurality of laminated boards subjected to wiring processing through the above-described prepreg are laminated and subjected to hot press processing to be multilayered at once. Then, a multilayer printed wiring board can be manufactured through formation of a through hole or blind via hole by drilling or laser processing and formation of an interlayer wiring by plating or conductive paste.
次に、下記の実施例により本発明について更に詳しく説明するが、これらの実施例は本発明をいかなる意味においても制限するものではない。
なお、各実施例及び比較例で得られた積層板を用いて、ガラス転移温度、熱膨張率、銅付きはんだ耐熱性、そり特性、誘電特性について以下の方法で測定し、評価した。
Next, the present invention will be described in more detail with reference to the following examples, but these examples are not intended to limit the present invention in any way.
In addition, it measured and evaluated by the following methods about the glass transition temperature, the thermal expansion coefficient, the solder heat resistance with copper, a curvature characteristic, and a dielectric characteristic using the laminated board obtained by each Example and the comparative example.
（１）ガラス転移温度（Ｔｇ）の測定
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた５ｍｍ角の評価基板を作製し、ＴＭＡ試験装置（ＴＡインスツルメント社製、Ｑ４００）を用いて圧縮法で熱機械分析をおこなった。評価基板を前記装置にＺ方向に装着後、荷重５ｇ、昇温速度１０℃／分の測定条件にて連続して２回測定した。２回目の測定における熱膨張曲線の異なる接線の交点で示されるＴｇを求め、耐熱性を評価した。
(1) Measurement of glass transition temperature (Tg) A 5 mm square evaluation board from which a copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and a TMA test apparatus (TA Instruments, Q400) was prepared. ) Was used for thermomechanical analysis by the compression method. After mounting the evaluation substrate on the apparatus in the Z direction, the measurement substrate was measured twice continuously under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The Tg indicated by the intersection of tangents with different thermal expansion curves in the second measurement was determined, and the heat resistance was evaluated.
（２）熱膨張率の測定
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた長さ４ｃｍ×幅４ｍｍの評価基板を作製し、ＴＭＡ試験装置（ＴＡインスツルメント社製、Ｑ４００）を用いて引張法で熱機械分析をおこなった。評価基板を前記装置に装着後、荷重４０ｇ、昇温速度１０℃／分の測定条件にて連続して２回測定した。２回目の測定における３０℃から１００℃までの平均熱膨張率を算出し、これを熱膨張率の値とした。これは、精度を向上させるため、２回目の測定結果を用いたものである。
(2) Measurement of thermal expansion coefficient An evaluation board having a length of 4 cm and a width of 4 mm from which the copper foil was removed by immersing the copper-clad laminate in a copper etching solution was prepared, and a TMA test apparatus (manufactured by TA Instruments Inc., Q400) was used to perform thermomechanical analysis by the tensile method. After mounting the evaluation substrate on the apparatus, the measurement was continuously performed twice under the measurement conditions of a load of 40 g and a heating rate of 10 ° C./min. The average coefficient of thermal expansion from 30 ° C. to 100 ° C. in the second measurement was calculated and used as the value of the coefficient of thermal expansion. This is to use the second measurement result in order to improve accuracy.
（３）銅付きはんだ耐熱性の評価
銅張積層板から２５ｍｍ角の評価基板を作製し、温度２８８℃のはんだ浴に、１２０分間評価基板をフロートし、外観を観察することにより銅付きはんだ耐熱性を評価した。
(3) Evaluation of solder heat resistance with copper Solder heat resistance with copper by preparing a 25 mm square evaluation substrate from a copper clad laminate, floating the evaluation substrate in a solder bath at a temperature of 288 ° C. for 120 minutes, and observing the appearance Sex was evaluated.
（４）そり量の評価
ＡＫＲＯＭＥＴＲＩＸ社製、サーモレイＰＳ２００シャドーモアレ分析を用いて、基板のそり量を評価した。基板のサンプルサイズは４０ｍｍ×４０ｍｍとし、測定エリアは３６ｍｍ×３６ｍｍとした。室温から２６０℃まで加熱し、その後５０℃まで冷却した時のそり量を測定した。
(4) Evaluation of warpage amount The warpage amount of the board | substrate was evaluated using the AKROMETRIX company make and thermoray PS200 shadow moire analysis. The sample size of the substrate was 40 mm × 40 mm, and the measurement area was 36 mm × 36 mm. The amount of warpage when heated from room temperature to 260 ° C. and then cooled to 50 ° C. was measured.
（５）誘電特性（比誘電率及び誘電正接）
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた１００ｍｍ×２ｍｍの評価基板を作製し、空洞共振機装置（関東電子応用開発社製）を用いて、周波数１ＧＨｚでの比誘電率及び誘電正接を測定した。
(5) Dielectric properties (dielectric constant and dielectric loss tangent)
A 100 mm × 2 mm evaluation board from which the copper foil was removed by immersing the copper clad laminate in a copper etching solution was prepared, and a dielectric constant at a frequency of 1 GHz was obtained using a cavity resonator device (manufactured by Kanto Electronics Development Co., Ltd.). The rate and dielectric loss tangent were measured.
（実施例１〜１７及び比較例１〜６）
以下に示す各成分を表１〜４に示した配合割合（質量部）で混合し、溶媒にメチルエチルケトンを用いて樹脂分６５質量％のワニスを作製した。次に、このワニスを用いて、厚さ０．０４５ｍｍのガラスクロスに含浸塗工し、１６０℃で１０分加熱乾燥して、プレス成形後厚みが０．０６ｍｍとなる樹脂分のプリプレグを得た。
このプリプレグを２枚重ね、１２μｍの電解銅箔を上下に配置し、圧力２．５ＭＰａ、温度２４０℃で６０分間プレスを行って、銅張積層板を得た。得られた銅張積層板の試験・評価した結果を表１〜４に示す。
(Examples 1-17 and Comparative Examples 1-6)
Each component shown below was mixed by the mixture ratio (mass part) shown to Tables 1-4, and the varnish of resin content 65 mass% was produced using the methyl ethyl ketone for the solvent. Next, using this varnish, a glass cloth having a thickness of 0.045 mm was impregnated and dried at 160 ° C. for 10 minutes to obtain a resin prepreg having a thickness of 0.06 mm after press molding. .
Two pieces of this prepreg were stacked, 12 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 2.5 MPa and a temperature of 240 ° C. for 60 minutes to obtain a copper-clad laminate. The test and evaluation results of the obtained copper-clad laminate are shown in Tables 1 to 4.
Ｑガラスクロス（ａ）
〔規格：１０７８（ＩＰＣ名称）、ヤーン：Ｄ４５０（ＩＰＣ名称）、ヤーンの本数（たて/よこ：５４×５４）〕
Q glass cloth (a)
[Standard: 1078 (IPC name), yarn: D450 (IPC name), number of yarns (vertical / width: 54 × 54)]
芳香族アミン化合物（i）
(i−１) ４，４’−ジアミノ−３，３’−ジエチル−ジフェニルメタン
〔日本化薬（株）製；商品名：ＫＡＹＡＨＡＲＤ Ａ−Ａ〕
(i−２)２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパン
〔和歌山精化工業（株）製；商品名：ＢＡＰＰ〕
Aromatic amine compounds (i)
(i-1) 4,4′-diamino-3,3′-diethyl-diphenylmethane [manufactured by Nippon Kayaku Co., Ltd .; trade name: KAYAHARD AA]
(i-2) 2,2-bis (4- (4-aminophenoxy) phenyl) propane [Wakayama Seika Kogyo Co., Ltd .; trade name: BAPP]
芳香族アルデヒド化合物（ii）
・ＴＰＡＬ：テレフタルアルデヒド〔東レ・ファインケミカル（株）製〕
Aromatic aldehyde compounds (ii)
・ TPAL: terephthalaldehyde (manufactured by Toray Fine Chemical Co., Ltd.)
分子末端に少なくとも２個の一級アミノ基を有するシロキサン化合物（ｄ）
両末端ジアミン変性シロキサン
〔信越化学工業（株）製；商品名：Ｘ−２２−１６１Ｂ〕
Siloxane compound (d) having at least two primary amino groups at the molecular ends
Both-end diamine-modified siloxane [Shin-Etsu Chemical Co., Ltd .; trade name: X-22-161B]
少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物（ｂ）
（ｄ−１）ビス（４−マレイミドフェニル）メタン
〔ケイ・アイ化成（株）製；商品名：ＢＭＩ〕
（ｄ−２）２，２−ビス（４−（４−マレイミドフェノキシ）フェニル）プロパン
〔大和化成工業（株）製；商品名：ＢＭＩ−４０００〕
Maleimide compound (b) having at least two N-substituted maleimide groups
(D-1) Bis (4-maleimidophenyl) methane [manufactured by Kei-I Kasei Co., Ltd .; trade name: BMI]
(D-2) 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane [manufactured by Daiwa Kasei Kogyo Co., Ltd .; trade name: BMI-4000]
酸性置換基を有するアミン化合物（ｅ）
ｐ−アミノフェノール〔関東化学（株）製〕
Amine compound having acidic substituent (e)
p-aminophenol [manufactured by Kanto Chemical Co., Inc.]
（変性シロキサン化合物含有溶液の製造実施例１，２）
製造実施例１：芳香族アゾメチン基を有するアミノ変性シロキサン化合物（Ｉ−１）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、４，４’−ジアミノ−３，３’−ジエチル−ジフェニルメタン(i−１)：１２．９ｇ、テレフタルアルデヒド(ii）：１７．１ｇ、プロピレングリコールモノメチルエーテル：４５．０ｇを入れ、１１５℃で４時間反応した後、１３０℃まで昇温して常圧濃縮により脱水し、芳香族アゾメチン化合物含有溶液（樹脂成分：６０質量％）を得た。
次に、上記反応溶液に、Ｘ−２２−１６１Ｂ（c）：３２５．５ｇ、プロピレングリコールモノメチルエーテル：５１３．３ｇを入れ、１１５℃で４時間反応した後、１３０℃まで昇温して常圧濃縮により脱水し、芳香族アゾメチン基を有する変性シロキサン化合物（Ｉ−１）含有溶液（樹脂成分：９０質量％）を得た。
(Production Examples 1 and 2 of Modified Siloxane Compound-Containing Solution)
Production Example 1: Production of amino-modified siloxane compound (I-1) having an aromatic azomethine group In a reaction vessel with a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. 4,4′-diamino-3,3′-diethyl-diphenylmethane (i-1): 12.9 g, terephthalaldehyde (ii): 17.1 g, propylene glycol monomethyl ether: 45.0 g, and at 115 ° C. After reacting for 4 hours, the temperature was raised to 130 ° C. and dehydration was performed by normal pressure concentration to obtain an aromatic azomethine compound-containing solution (resin component: 60% by mass).
Next, X-22-161B (c): 325.5 g and propylene glycol monomethyl ether: 513.3 g were added to the reaction solution, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and normal pressure. It dehydrated by concentration and the modified siloxane compound (I-1) containing solution (resin component: 90 mass%) which has an aromatic azomethine group was obtained.
製造実施例２：芳香族アゾメチン基を有するアミノ変性シロキサン化合物（Ｉ−２）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、２，５−ジメチル−１，４−ジアミノベンゼン：８．７ｇ、テレフタルアルデヒド(ii）：２１．３ｇ、プロピレングリコールモノメチルエーテル：４５．０ｇを入れ、１１５℃で４時間反応した後、１３０℃まで昇温して常圧濃縮により脱水し、芳香族アゾメチン化合物含有溶液（樹脂成分：６０質量％）を得た。
次に、上記反応溶液に、Ｘ−２２−１６１Ｂ（c）：４１３．８ｇ、プロピレングリコールモノメチルエーテル：６４５．７ｇを入れ、１１５℃で４時間反応した後、１３０℃まで昇温して常圧濃縮により脱水し、芳香族アゾメチン基を有する変性シロキサン化合物（Ｉ−２）含有溶液（樹脂成分：９０質量％）を得た。
Production Example 2: Production of amino-modified siloxane compound (I-2) having an aromatic azomethine group In a reaction vessel with a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. 2,5-dimethyl-1,4-diaminobenzene: 8.7 g, terephthalaldehyde (ii): 21.3 g, propylene glycol monomethyl ether: 45.0 g, reacted at 115 ° C. for 4 hours, then 130 ° C. The mixture was heated to room temperature and dehydrated by normal pressure concentration to obtain an aromatic azomethine compound-containing solution (resin component: 60% by mass).
Next, X-22-161B (c): 413.8 g and propylene glycol monomethyl ether: 645.7 g were added to the reaction solution, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and normal pressure. It dehydrated by concentration and the modified siloxane compound (I-2) containing solution (resin component: 90 mass%) which has an aromatic azomethine group was obtained.
（変性イミド樹脂含有溶液の製造実施例３，４）
製造実施例３：芳香族アゾメチン基を有する変性イミド樹脂（Ｊ−１）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、芳香族アゾメチン基を有する変性シロキサン化合物（Ｉ−１）含有溶液（樹脂成分：９０質量％）：７７．８g、２，２−ビス（４−（４−マレイミドフェノキシ）フェニル）プロパン（ｄ−２）：２４６．９ｇ、プロピレングリコールモノメチルエーテル：４２５．３gを入れ、１１５℃で４時間反応した後、１３０℃まで昇温して常圧濃縮し、芳香族アゾメチン基を有する変性イミド樹脂（Ｊ−１）含有溶液（樹脂成分：６０質量％）を得た。
(Production Examples 3 and 4 of modified imide resin-containing solution)
Production Example 3 Production of Modified Imide Resin (J-1) Having Aromatic Azomethine Group In a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. Modified siloxane compound (I-1) -containing solution having an aromatic azomethine group (resin component: 90% by mass): 77.8 g, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane (d-2) ): 246.9 g, propylene glycol monomethyl ether: 425.3 g, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and concentrated at normal pressure to give a modified imide resin having an aromatic azomethine group (J- 1) A containing solution (resin component: 60% by mass) was obtained.
製造実施例４：酸性置換基と芳香族アゾメチン基を有する変性イミド樹脂（Ｋ−１）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、芳香族アゾメチン基を有する変性シロキサン化合物（Ｉ−１）含有溶液（樹脂成分：９０質量％）：９４．７g、２，２−ビス（４−（４−マレイミドフェノキシ）フェニル）プロパン（ｄ−２）：２２５．６ｇ、ｐ−アミノフェノール（ｅ）：２．３ｇ、プロピレングリコールモノメチルエーテル：４２７．４gを入れ、１１５℃で４時間反応した後、１３０℃まで昇温して常圧濃縮し、酸性置換基と芳香族アゾメチン基を有する変性イミド樹脂（Ｋ−１）含有溶液（樹脂成分：６０質量％）を得た。
Production Example 4 Production of Modified Imide Resin (K-1) Having Acid Substituent and Aromatic Azomethine Group Heating and cooling capacity of 2 liters equipped with thermometer, stirrer and moisture meter with reflux condenser Modified siloxane compound (I-1) -containing solution having an aromatic azomethine group (resin component: 90% by mass): 94.7 g, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane in a reaction vessel (D-2): 225.6 g, p-aminophenol (e): 2.3 g, propylene glycol monomethyl ether: 427.4 g were added, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. The solution was concentrated under pressure to obtain a modified imide resin (K-1) -containing solution (resin component: 60% by mass) having an acidic substituent and an aromatic azomethine group.
熱可塑性エラストマー（ｆ）
（ｆ−１）タフテックＨ１０４３：水添スチレン−ブタジエン共重合樹脂〔旭化成ケミカルズ（株）製、商品名〕
（ｆ−２）Ｍ１９１３：カルボン酸変性水添スチレン−ブタジエン共重合樹脂〔旭化成ケミカルズ（株）製〕
Thermoplastic elastomer (f)
(F-1) Tuftec H1043: Hydrogenated styrene-butadiene copolymer resin (trade name, manufactured by Asahi Kasei Chemicals Corporation)
(F-2) M1913: Carboxylic acid-modified hydrogenated styrene-butadiene copolymer resin (manufactured by Asahi Kasei Chemicals Corporation)
熱硬化性樹脂（ｇ）
（ｇ−１）α−ナフトール／クレゾールノボラック型エポキシ樹脂
〔日本化薬（株）製；商品名：ＮＣ−７０００Ｌ〕
（ｇ−２）ノボラック型シアネート樹脂
〔ロンザジャパン（株）製、商品名：ＰＴ−３０〕
Thermosetting resin (g)
(G-1) α-naphthol / cresol novolac type epoxy resin [manufactured by Nippon Kayaku Co., Ltd .; trade name: NC-7000L]
(G-2) Novolac-type cyanate resin [Lonza Japan Co., Ltd., trade name: PT-30]
硬化促進剤（ｈ）
（ｈ−１）ナフテン酸亜鉛（ＩＩ）
〔ナフテン酸亜鉛８％ミネラルスピリット溶液〔東京化成（株）製〕〕
（ｈ−２）イソシアネートマスクイミダゾール
〔第一工業製薬（株）製、商品名：Ｇ−８００９Ｌ〕
（ｈ−３）テトラフェニルホスホニウムテトラ-ｐ-トリルボレート
〔北興化学工業（株）製、商品名：ＴＰＰ−ＭＫ〕
Curing accelerator (h)
(H-1) Zinc naphthenate (II)
[Zinc naphthenate 8% mineral spirit solution [manufactured by Tokyo Chemical Industry Co., Ltd.]]
(H-2) Isocyanate mask imidazole [Daiichi Kogyo Seiyaku Co., Ltd., trade name: G-8809L]
(H-3) Tetraphenylphosphonium tetra-p-tolylborate [Hokuko Chemical Co., Ltd., trade name: TPP-MK]
無機充填材：溶融球状シリカ（（株）アドマテックス製：商品名：ＳＣ２０５０−ＫＮＫ） Inorganic filler: fused spherical silica (manufactured by Admatechs Co., Ltd .: trade name: SC2050-KNK)
Ｅガラスクロス：〔日東紡績（株）製〕
Ｔガラスクロス：〔日東紡績（株）製〕
E glass cloth: [Nittobo Co., Ltd.]
T glass cloth: [Nitto Boseki Co., Ltd.]
表１〜４から明らかなように、本発明の実施例では、比較例と比較し、熱膨張率、そり特性、誘電特性に優れている。 As is apparent from Tables 1 to 4, the examples of the present invention are superior in thermal expansion coefficient, warpage characteristics, and dielectric characteristics as compared with the comparative examples.
本発明のプリプレグを積層成形することにより製造した積層板、及び該積層板を用いて製造されてなる多層プリント配線板は、熱膨張率、そり特性、誘電特性に優れ、電子機器用プリント配線板として有用である。 A laminated board produced by laminating the prepreg of the present invention, and a multilayer printed wiring board produced using the laminated board are excellent in thermal expansion coefficient, warpage characteristic, dielectric characteristic, and printed wiring board for electronic equipment Useful as.
Claims (10)
前記熱硬化性樹脂組成物が、分子構造中に芳香族アゾメチン基を有するアミノ変性シロキサン化合物（Ｉ）及び分子構造中に少なくとも２個のＮ−置換マレイミド基を有するマレイミド化合物（ｂ）を配合してなる熱硬化性樹脂組成物であることを特徴とするプリプレグ。 In Q glass cloth (a) and prepreg comprising a thermosetting resin composition,
The thermosetting resin composition by blending an amino-modified siloxane compound having an aromatic azomethine group in the molecular structure (I) and a maleimide compound having at least two N- substituted maleimide group in a molecular structure (b) A prepreg characterized by being a thermosetting resin composition.
（式（１）中、Ｒ1は各々独立に、酸性置換基である水酸基、カルボキシル基又はスルホン酸基を、Ｒ2は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、かつｘとｙの和は５である。） The prepreg according to any one of claims 1 to 3, wherein the thermosetting resin composition further comprises an amine compound (e) having an acidic substituent represented by the following general formula (1).
(In formula (1), each R 1 independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and each R 2 independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.)
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| JPS63264635A (en) * | 1987-04-21 | 1988-11-01 | Teijin Ltd | Azomethine-containing polyorganosiloxane |
| US5068292A (en) * | 1989-07-11 | 1991-11-26 | Gencorp Inc. | In-situ composites |
| JP2001207055A (en) * | 2000-01-25 | 2001-07-31 | Nitto Denko Corp | Carbodiimide resin composition |
| JP5589470B2 (en) * | 2010-03-18 | 2014-09-17 | 日立化成株式会社 | Bismaleimide derivative and method for producing the same, thermosetting resin composition, prepreg and laminate |
| JP6019883B2 (en) * | 2012-07-25 | 2016-11-02 | 日立化成株式会社 | Thermosetting resin composition, prepreg, laminate and multilayer printed wiring board using the same |
| CN104736589B (en) * | 2012-10-19 | 2017-05-24 | 三菱瓦斯化学株式会社 | Resin composition, pre-preg, laminate, metal foil-clad laminate, and printed wiring board |
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