JP2015174996A - polyphenylene ether powder - Google Patents

polyphenylene ether powder Download PDF

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JP2015174996A
JP2015174996A JP2014055229A JP2014055229A JP2015174996A JP 2015174996 A JP2015174996 A JP 2015174996A JP 2014055229 A JP2014055229 A JP 2014055229A JP 2014055229 A JP2014055229 A JP 2014055229A JP 2015174996 A JP2015174996 A JP 2015174996A
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ppe
powder
mass
varnish
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遠藤　正朗
Masao Endo
正朗 遠藤
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Asahi Kasei Corp
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Asahi Kasei E Materials Corp
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Abstract

PROBLEM TO BE SOLVED: To provide a PPE powder which is excellent in moldability and heat resistance, while generally retaining good original electric characteristics of PPE, and suitable for production of a prepreg or a resin sheet for high-frequency electronic circuit boards.SOLUTION: A PPE powder is aggregate of PPE particles and meets conditions (1) and (2). Condition (1): the PPE particles are secondary particles consisting of aggregate of primary particles. Condition (2): the powder has such a particle size distribution that 95 mass% or more and 100 mass% or less, relative to the total amount of the PPE powder, of the powder passes through a sieve of an opening of 250 μm and more than 10 mass% and equal to or less than 40 mass% of the powder passes through a sieve of an opening of 53 μm.

Description

本発明は、電子回路基板用材料等に好適に用いることが可能な、ポリフェニレンエーテル粉体に関する。   The present invention relates to a polyphenylene ether powder that can be suitably used as a material for an electronic circuit board.

近年、情報ネットワーク技術の著しい進歩、情報ネットワークを活用したサービスの拡大により、電子機器には情報量の大容量化、処理速度の高速化が求められている。デジタル信号を大容量かつ高速に伝達するためには信号の波長を短くするのが有効であり、信号の高周波化が進んでいる。ＰＰＥは誘電率、誘電正接等の高周波特性（すなわち誘電特性）が優れており、且つ、高い耐熱性を有するため、高周波数帯を利用する電子機器の電子回路基板用の絶縁材料として好適である。   In recent years, due to remarkable progress in information network technology and expansion of services utilizing information networks, electronic devices are required to have a large amount of information and a high processing speed. In order to transmit a large amount of digital signal at high speed, it is effective to shorten the wavelength of the signal, and the frequency of the signal is increasing. PPE has excellent high-frequency characteristics (that is, dielectric characteristics) such as dielectric constant and dielectric loss tangent, and has high heat resistance. Therefore, PPE is suitable as an insulating material for electronic circuit boards of electronic devices that use a high frequency band. .

ＰＰＥを電子回路基板用の絶縁材料として利用する方法としては、一旦、ＰＰＥを含む樹脂組成物からなる樹脂シート、或いはＰＰＥを含む樹脂組成物と基材とからなる樹脂シート（プリプレグ）を製造し、次いで、該樹脂シートと金属箔等他の構成材料とを積層し、プレス成型により基板に加工する方法が一般的である。ここで、樹脂シートやプリプレグの製造では、ＰＰＥに限らず樹脂組成物を有機溶剤に溶解させてワニスとするのが一般的であり、ＰＰＥにおいても同様の方法が特許文献１６等に多く記載されている。   As a method of using PPE as an insulating material for an electronic circuit board, a resin sheet made of a resin composition containing PPE or a resin sheet (prepreg) made of a resin composition containing PPE and a base material is once manufactured. Then, a method is generally used in which the resin sheet and other constituent materials such as metal foil are laminated and processed into a substrate by press molding. Here, in the production of resin sheets and prepregs, not only PPE but generally a resin composition is dissolved in an organic solvent to form a varnish, and many similar methods are also described in Patent Document 16 and the like for PPE. ing.

一方で、特許文献１３〜１５等には、ＰＰＥを有機溶剤に溶解させることなく、粉体のまま有機溶剤に分散させてワニスとする試みがなされている。ＰＰＥはトリクロロエチレンのようなハロゲン化炭化水素、又は６０℃以上に加熱したトルエン等の芳香族有機溶剤にしか溶解しないため、ＰＰＥを溶解した状態でワニスを作製するには、環境保護及び人的有害性の観点、或いは引火爆発に対する安全確保の観点から、取り扱いが限定されるためである。特許文献１３には、最大粒径が１５μｍ以下のＰＰＥとエポキシ樹脂と硬化剤を含有する樹脂組成物を基材に含浸、乾燥して得られるプリプレグが記載されている。特許文献１４には、粒子径が１０６μｍ以下のＰＰＥと熱硬化成分を含むワニスを用いるプリプレグの製造方法が記載されている。特許文献１５には、ＰＰＥと架橋性を有する樹脂と架橋助剤と溶剤を含む液を加熱して一旦ＰＰＥを溶解させた後、冷却し、粒子径が０．１〜１００μｍの粒子が分散した分散液を用いるプリプレグの製造方法が記載されている。   On the other hand, Patent Documents 13 to 15 and the like attempt to disperse PPE in an organic solvent as a varnish without dissolving PPE in the organic solvent. PPE is only soluble in halogenated hydrocarbons such as trichlorethylene or aromatic organic solvents such as toluene heated to 60 ° C or higher. This is because handling is limited from the viewpoint of safety or from the viewpoint of ensuring safety against a flammable explosion. Patent Document 13 describes a prepreg obtained by impregnating a substrate with a resin composition containing PPE having an maximum particle size of 15 μm or less, an epoxy resin, and a curing agent, and drying the substrate. Patent Document 14 describes a method for producing a prepreg using a varnish containing PPE having a particle size of 106 μm or less and a thermosetting component. In Patent Document 15, a liquid containing PPE, a resin having crosslinkability, a crosslinking aid, and a solvent is heated to dissolve PPE once, and then cooled to disperse particles having a particle diameter of 0.1 to 100 μm. A method for producing a prepreg using a dispersion is described.

ＰＰＥ粉体を工業的に製造する方法としては、芳香族炭化水素等を溶媒に用い、銅、マンガン、又はコバルトを含有する錯体触媒の存在下に１種或いは２種以上のフェノール化合物を酸化重合し、次いで反応液に貧溶媒若しくは貧溶媒と良溶媒混合液中を加えることでＰＰＥを析出させ分離する方法が知られている。或いは、芳香族炭化水素とアルコール等の混合溶媒を用いて、銅、マンガン、又はコバルトを含有する錯体触媒の存在下に１種或いは２種以上のフェノール化合物を酸化重合し、反応液中でＰＰＥを析出させ分離する方法が知られている。   As a method of industrially producing PPE powder, aromatic hydrocarbons or the like are used as a solvent, and one or more phenol compounds are oxidatively polymerized in the presence of a complex catalyst containing copper, manganese, or cobalt. Then, a method is known in which PPE is precipitated and separated by adding a poor solvent or a poor solvent and a good solvent mixture to the reaction solution. Alternatively, one or more phenolic compounds are oxidatively polymerized in the presence of a complex catalyst containing copper, manganese, or cobalt using a mixed solvent such as aromatic hydrocarbon and alcohol, and PPE is reacted in the reaction solution. There is known a method of precipitating and separating the.

しかしながら、反応溶液から析出させたＰＰＥ粒子は、通常、著しく微細な粒子（例えば３〜５０μｍの微細粒子）や著しく大きな粒子（例えば２ｍｍを超える粗大粒子）を多く含み、粒子径が不均一になってしまうのが一般的である。著しく微細な粒子や大きな粒子を含むことは、続くＰＰＥ製造工程において、析出したＰＰＥ粒子を分離する際の濾過工程における濾過時間の増大、乾燥工程、輸送工程における飛散や詰り等による輸送不良の問題を引き起こす。また、押出造粒で他成分と混練する際、押出し機の食い込み不良、溶融不良等の問題を引き起こす原因となっている。   However, PPE particles precipitated from the reaction solution usually contain a lot of extremely fine particles (for example, fine particles of 3 to 50 μm) and extremely large particles (for example, coarse particles exceeding 2 mm), and the particle diameter becomes nonuniform. It is common to end up. The inclusion of remarkably fine particles or large particles causes problems in transportation failure due to increased filtration time in the filtration process when separating the deposited PPE particles in the subsequent PPE production process, scattering and clogging in the drying process, and the transportation process. cause. Further, when kneading with other components by extrusion granulation, it causes a problem such as poor biting of the extruder and poor melting.

そのため、ＰＰＥを工業的に製造するにあたっては、ＰＰＥ粒子の不均一性を低減することが望まれており、解決方法について特許文献１〜１２等に様々な検討がなされてきた。   Therefore, when manufacturing PPE industrially, it is desired to reduce the non-uniformity of PPE particles, and various studies have been made on the solution methods in Patent Documents 1 to 12 and the like.

特許文献１〜３は、ＰＰＥの重合反応溶液からＰＰＥを析出分離する際の析出を制御することによって粒度を調整するＰＰＥの製造方法が記載されている。特許文献４、５には、湿潤固体状態のＰＰＥ粒子を加熱処理してＰＰＥを肥大化する方法が記載されている。特許文献６には、湿潤状態のＰＰＥと乾燥状態のＰＰＥ粉体と加熱しながら混合して造粒するＰＰＥの製造方法が記載されている。特許文献７、８には、重合反応後にＰＰＥを析出させた後のスラリーを湿式粉砕して粒度が調整されたＰＰＥ製造方法が記載されている。
特許文献９、１０には、ＰＰＥを一度圧縮成型した後に粉砕してＰＰＥの粒度を揃える方法が記載されている。特許文献１１には、粒径１０５μｍ以下の粒子の重量分率が３０％以下の、取り扱い性に優れるＰＰＥ粉粒体が記載されている。特許文献１２には、表面が平滑で、長径／短径比が１．０〜１．２の粒子含有率が８０質量％以上であり、平均粒径が１〜１００μｍである、取り扱い性に優れるＰＰＥを粉体が記載されている。 Patent Documents 1 to 3 describe a method for producing PPE in which the particle size is adjusted by controlling precipitation when PPE is precipitated and separated from a polymerization reaction solution of PPE. Patent Documents 4 and 5 describe a method of enlarging PPE by heat-treating PPE particles in a wet solid state. Patent Document 6 describes a method for producing PPE in which wet PPE and dry PPE powder are mixed and granulated while heating. Patent Documents 7 and 8 describe a method for producing PPE in which the particle size is adjusted by wet-grinding the slurry after precipitation of PPE after the polymerization reaction.
Patent Documents 9 and 10 describe a method in which PPE is once compression-molded and then pulverized to uniform the PPE particle size. Patent Document 11 describes a PPE granular material excellent in handleability in which the weight fraction of particles having a particle diameter of 105 μm or less is 30% or less. In Patent Document 12, the surface is smooth, the content ratio of particles having a major axis / minor axis ratio of 1.0 to 1.2 is 80% by mass or more, and the average particle size is 1 to 100 μm. PPE powder is described.

ＷＯ２００３／０６４４９９号パンフレットWO2003 / 064499 pamphlet 特開２００１−４００８７号公報Japanese Patent Laid-Open No. 2001-40087 特開２０１１−６６９１号公報JP 2011-6691 A 特開２００８−６９３８６号公報JP 2008-69386 A 特開平０６−１７２５４５号公報Japanese Patent Laid-Open No. 06-172545 特開２００６−２４１２５８号公報JP 2006-241258 A 特開２００１−１２２９６２号公報JP 2001-122962 A 特開２０００−２８１７９８号公報JP 2000-281798 A 特開２０００−３０２８７７号公報JP 2000-302877 A 特開２００１−７２７６３号公報JP 2001-72763 A 特開平６−１７２５４４号公報JP-A-6-172544 特開２０１０−４７６６２号公報JP 2010-47662 A 特開２００６−６３１１４号公報JP 2006-63114 A 特開２００３−３４７３１号公報JP 2003-34731 A 特開平７−２９２１２６号公報JP 7-292126 A 特開平０２−２３３７５８号公報Japanese Patent Laid-Open No. 02-233758

環境保護・人的有害性・引火爆発に対する安全確保の観点からハロゲン化炭化水素や６０℃以上に加熱した芳香族有機溶剤等の回避を試みた特許文献１３〜１６には、以下に示す課題があった。   Patent Documents 13 to 16 that try to avoid halogenated hydrocarbons and aromatic organic solvents heated to 60 ° C. or higher from the viewpoint of environmental protection, human harm, and safety against flammable explosions have the following problems. there were.

特許文献１３のＰＰＥを含む積層板は、最大粒径が１５μｍ以下、数平均分子量１，０００〜３，０００（数平均分子量１５，０００のＰＰＥを再分配反応して調製）のＰＰＥを用いることで、樹脂組成物を均一にさせることができ、その結果、小径ドリルの加工性に優れることが記載されている。しかしながら、数平均分子量１，０００〜３，０００のＰＰＥは、通常工業的に得られる数平均分子量が４，０００を超えるＰＰＥと比較して末端水酸基の数が多いため、誘電特性が低下してしまい、ＰＰＥ樹脂が本来有する誘電特性に優れる特性が損なわれる課題を有していた。一方で、通常工業的に得られる数平均分子量が４，０００を超えるＰＰＥを、該特許文献に記載されているように小さな粒径のＰＰＥに調製して用いると、粘度が著しく高くなりすぎるため塗工できない、或いは塗工できる範囲の粘度とすると固形分濃度を小さくする必要が生じ、塗工性に欠ける問題を有していた。更には、基材への含浸性に欠けるため、耐熱性に劣るものであった。   The laminated plate containing PPE of Patent Document 13 uses PPE having a maximum particle size of 15 μm or less and a number average molecular weight of 1,000 to 3,000 (prepared by redistributing PPE having a number average molecular weight of 15,000). It is described that the resin composition can be made uniform, and as a result, the workability of the small diameter drill is excellent. However, since PPE having a number average molecular weight of 1,000 to 3,000 usually has a larger number of terminal hydroxyl groups than PPE having a number average molecular weight of more than 4,000, which is industrially obtained, the dielectric properties are lowered. In other words, the PPE resin has a problem that the characteristic excellent in dielectric characteristics inherently deteriorated. On the other hand, when a PPE having a number average molecular weight of more than 4,000, which is usually industrially obtained, is prepared and used as a PPE having a small particle size as described in the patent document, the viscosity becomes extremely high. If the viscosity is in a range where coating is not possible or coating is possible, it is necessary to reduce the solid content concentration, resulting in a lack of coating properties. Furthermore, since the impregnation property to a base material is lacking, it was inferior to heat resistance.

特許文献１４のＰＰＥ含有プリプレグの製造方法は、ＰＰＥと熱硬化成分を含む樹脂組成物を水９０質量％以上の溶媒に展開したワニスを用いて製造するにあたり、粒径１０６μｍ以下のＰＰＥを用いることで、ガラスクロスに樹脂ワニスを含浸させた後の加熱工程で熱硬化性成分との相溶性が良好となり、ガラスクロスへの樹脂未含浸部が発生し難くなることが記載されている。しかしながら、特許文献１５に記載されている積層板は、該特許文献の実施例に示されているように、１ＭＨｚの誘電率で０．００２５〜０．０１０であり、近年の高周波特性に要求される電気特性としては不足するものであった。さらに、該特許文献１５のようにＰＰＥとの親和性がない水を用いれば、粒径１０６μｍ以下の小さなＰＰＥを用いても、塗工可能な粘度を得ることが可能であるが、乾燥工程で残存した水に起因して電気特性が著しく低下してしまうという問題があった。   The method for producing a PPE-containing prepreg of Patent Document 14 uses a PPE having a particle size of 106 μm or less when producing a resin composition containing PPE and a thermosetting component in a solvent of 90% by mass or more of water. In the heating process after impregnating the glass cloth with the resin varnish, the compatibility with the thermosetting component is improved, and the resin non-impregnated part in the glass cloth is hardly generated. However, the laminated plate described in Patent Document 15 has a dielectric constant of 1 MHz as 0.0025 to 0.010 as shown in the Examples of the Patent Document, and is required for recent high-frequency characteristics. The electrical characteristics are insufficient. Further, if water having no affinity for PPE is used as in Patent Document 15, it is possible to obtain a coatable viscosity even if a small PPE having a particle size of 106 μm or less is used. There has been a problem that the electrical characteristics are remarkably deteriorated due to the remaining water.

特許文献１５に記載の方法は、ＰＰＥ粉体を一旦有機溶剤に溶解させるため、ＰＰＥ粉体自体の粒度には影響を受けず、塗工時には、環境保護、人的有害性、引火爆発に対する安全確保の観点から取扱いが限定される有機溶剤を使わないで済む方法である。しかしながら、一旦加熱して溶解させたＰＰＥを冷却して粒子とする方法は再現性に欠け、工業的に安定性して粒子を製造するのが困難であるという問題を有している。また、塗工時には常温のトルエン等の有機溶剤を含有するワニスを取扱うことになるが、粒子を有機溶剤に溶解させる段階で依然加熱を必要とするため、引火爆発に対する安全性を確保するための追加の対処を必要とするという問題が解決されていない。   The method described in Patent Document 15 dissolves the PPE powder in an organic solvent, so it is not affected by the particle size of the PPE powder itself, and protects the environment, human harm, and safety against flammable explosions during coating. This is a method that does not require the use of an organic solvent whose handling is limited from the viewpoint of securing. However, the method of cooling the PPE once heated and dissolved to form particles is not reproducible, and has the problem that it is difficult to produce particles with industrial stability. In addition, varnish containing organic solvents such as toluene at room temperature will be handled at the time of coating, but heating is still required at the stage of dissolving the particles in the organic solvent, so as to ensure safety against flammable explosions. The issue of requiring additional action has not been resolved.

また、特許文献１〜１２に記載されている粒度範囲のＰＰＥ粉体を用いてワニスを形成する場合、以下に示す不具合を生じる問題があった。   Moreover, when forming a varnish using the PPE powder of the particle size range described in patent documents 1-12, there existed a problem which produces the malfunction shown below.

特許文献６、特許文献７、特許文献８、特許文献９、及び特許文献１０に記載される粉体は、微小粒子（０〜５３μｍ）含有量は少ないが、粗大粒子を多く含むＰＰＥ粉体である。特許文献１、特許文献２、特許文献４、特許文献５、及び特許文献１１に記載される粉体においては、微小粒子（０〜５３μｍ）の含有量が少ない。特許文献１２に記載される粉体においては、微小粒子（０〜５３μｍ）の含有量が多い。   The powders described in Patent Literature 6, Patent Literature 7, Patent Literature 8, Patent Literature 9, and Patent Literature 10 are PPE powders having a small amount of fine particles (0 to 53 μm) but containing a large amount of coarse particles. is there. In the powders described in Patent Document 1, Patent Document 2, Patent Document 4, Patent Document 5, and Patent Document 11, the content of fine particles (0 to 53 μm) is small. The powder described in Patent Document 12 has a high content of fine particles (0 to 53 μm).

特許文献６、特許文献７、特許文献８、特許文献９、及び特許文献１０に記載されているような大きな粒子を多く含むＰＰＥ粉体では、プレス成型過程におけるＰＰＥの溶融速度が遅く、成型性に欠けるため、配線の埋め込み性、接着性、及び耐熱性に優れない。一方、特許文献１、特許文献２、特許文献４、特許文献５、及び特許文献１１に記載されているような微小粒子を多く含むＰＰＥ粉体では、ワニスの粘度が高くなり基材への含浸性に欠けるため、耐熱性に優れない。また、特許文献３には３８μｍ未満の粒子が１０％未満であることのみ記載されており、他の粒子の粒径については一切記載がない。特許文献３は、ＰＰＥの微粒子を低減することのみを目的としており、３８μｍより大きい領域の粒度が制御されていない。   In PPE powder containing many large particles as described in Patent Literature 6, Patent Literature 7, Patent Literature 8, Patent Literature 9, and Patent Literature 10, the melting rate of PPE in the press molding process is slow, and the moldability Therefore, the wiring embedding property, adhesiveness, and heat resistance are not excellent. On the other hand, in the PPE powder containing a large amount of fine particles as described in Patent Document 1, Patent Document 2, Patent Document 4, Patent Document 5, and Patent Document 11, the viscosity of the varnish is increased and the base material is impregnated. Because of lack of properties, heat resistance is not excellent. Further, Patent Document 3 only describes that particles less than 38 μm are less than 10%, and there is no description about the particle size of other particles. Patent Document 3 is intended only to reduce the fine particles of PPE, and the particle size in a region larger than 38 μm is not controlled.

前記した状況の下、本発明が解決しようとする課題は、ＰＰＥが本来有する良好な電気特性を概ね維持しつつ、成型性、及び耐熱性に優れる高周波電子回路基板用途のプリプレグ又は樹脂シートを製造するために好適に用いることが可能な、ＰＰＥ粉体を提供することにある。   Under the circumstances described above, the problem to be solved by the present invention is to produce a prepreg or resin sheet for high-frequency electronic circuit boards that is excellent in moldability and heat resistance while generally maintaining the good electrical properties inherent in PPE. Therefore, it is intended to provide a PPE powder that can be suitably used for the purpose.

本発明者らは、上記課題を解決するために鋭意検討した結果、ＰＰＥ粒子の粒径を特定範囲とすること、具体的には粒径５３μｍ超２５０μｍ以下の粒子を主成分とし、且つ、粒径５３μｍ以下の微小粒子を特定量含有させ、更には粒径２５０μｍ超の粒子を極力含まないようにすることによって：（１）ＰＰＥ粉体を溶剤に分散させるときにままこの形成を抑制し、ＰＰＥ粗大塊を残存させないと共に、ＰＰＥ粉体内部に溶剤を十分に浸透させることができ；（２）ＰＰＥ粉体含有ワニスの基材への含浸性が良好であり；（３）プレス成型時に速い段階で微小ＰＰＥ粒子が溶融し樹脂全体の粘度を低減させるため成型性に優れ；且つ（４）成型時にＰＰＥ粉体を完全に溶融させることができるため樹脂成分が均一となり；これらによって、ＰＰＥ粉体を溶解させない状態でワニスを形成しても、成型性、耐熱性、接着性等の高周波基板として必要な特性を付与できることを見出し、かかる知見に基づき本発明を完成させるに至った。本発明は以下の構成を有する。   As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that the particle size of PPE particles is in a specific range, specifically, particles having a particle size of more than 53 μm and not more than 250 μm as main components, and By containing a specific amount of fine particles having a diameter of 53 μm or less and further containing particles having a particle size of more than 250 μm as much as possible: (1) Suppressing this formation while dispersing the PPE powder in a solvent, PPE coarse lumps do not remain, and the solvent can be sufficiently infiltrated into the PPE powder; (2) Good impregnation of the PPE powder-containing varnish into the substrate; (3) Fast during press molding The fine PPE particles melt at the stage to reduce the viscosity of the entire resin, and the moldability is excellent; and (4) the PPE powder can be completely melted at the time of molding, so that the resin component becomes uniform; It is formed varnish in a state that does not dissolve the E powder, moldability, heat resistance, found to be able to impart necessary characteristics as a high-frequency substrate such adhesion, and have completed the present invention based on this finding. The present invention has the following configuration.

［１］ ＰＰＥ粒子の集合体であるＰＰＥ粉体であって、以下の：
（１）ＰＰＥ粒子が一次粒子の集合体である二次粒子であること、
（２）ＰＰＥ粉体の全量基準で９５質量％以上１００質量％以下の粉体が目開き２５０μｍの篩を通過し、かつ１０質量％を超え４０質量％以下の粉体が目開き５３μｍの篩を通過する粒度分布を有すること、
を満たす、ＰＰＥ粉体。
［２］ 目開き１，０００μｍの篩を通過する粒度分布を有する、［１］に記載のＰＰＥ粉体。
［３］ 目開き５００μｍの篩を通過する粒度分布を有する、［１］に記載のＰＰＥ粉体。
［４］ 該ＰＰＥ粉体の全量基準で４５質量％以上８０質量％以下の粉体が目開き２５０μｍの篩を通過するが目開き１０６μｍの篩は通過しない粒度分布を有する、［１］〜［３］の何れか１項に記載のＰＰＥ粉体。
［５］ 該ＰＰＥ粉体の全量基準で１０質量％を超え３０質量％以下の粉体が目開き１０６μｍの篩を通過するが目開き５３μｍの篩は通過しない粒度分布を有する、［１］〜［４］の何れか１項に記載のＰＰＥ粉体。
［６］ 平均粒径が１００μｍを超え１８０μｍ以下である、［１］〜［５］の何れか１項に記載のＰＰＥ粉体。
［７］ 数平均分子量が４，０００以上４０，０００以下である、［１］〜［６］の何れか１項に記載のＰＰＥ粉体。 [1] A PPE powder that is an aggregate of PPE particles, which is:
(1) The PPE particles are secondary particles that are aggregates of primary particles.
(2) 95% by mass or more and 100% by mass or less of the powder on the basis of the total amount of the PPE powder passes through a sieve having an opening of 250 μm, and a powder of more than 10% by mass and 40% by mass or less is a sieve having an opening of 53 μm Having a particle size distribution passing through
PPE powder that satisfies
[2] The PPE powder according to [1], which has a particle size distribution passing through a sieve having an opening of 1,000 μm.
[3] The PPE powder according to [1], which has a particle size distribution passing through a sieve having an opening of 500 μm.
[4] A powder having a particle size distribution in which 45% by mass or more and 80% by mass or less of the powder on the basis of the total amount of the PPE powder passes through a sieve having an opening of 250 μm but does not pass through a sieve having an opening of 106 μm. 3] The PPE powder according to any one of the above.
[5] The PPE powder has a particle size distribution in which a powder of more than 10% by mass and less than 30% by mass passes through a sieve having an opening of 106 μm, but does not pass through a sieve having an opening of 53 μm. [4] The PPE powder according to any one of [4].
[6] The PPE powder according to any one of [1] to [5], wherein the average particle size is more than 100 μm and 180 μm or less.
[7] The PPE powder according to any one of [1] to [6], wherein the number average molecular weight is from 4,000 to 40,000.

本発明によれば、ＰＰＥが本来有する良好な電気特性を概ね維持しつつ、成型性、及び耐熱性に優れる高周波電子回路基板用途のプリプレグ又は樹脂シートを製造するために好適に用いることが可能な、ＰＰＥ粉体を提供することができる。   According to the present invention, it can be suitably used for producing a prepreg or a resin sheet for use in a high-frequency electronic circuit board that is excellent in moldability and heat resistance while generally maintaining good electrical properties inherent to PPE. , PPE powder can be provided.

実施例１におけるＰＰＥ粉体の走査型電子顕微鏡画像を示す図である。2 is a diagram showing a scanning electron microscope image of PPE powder in Example 1. FIG.

以下、本発明を実施するための例示の形態について詳細に説明する。なお、本発明は以下の説明に限定されるものではなく、その要旨の範囲内で適宜に変形して実施することができる。   Hereinafter, exemplary embodiments for carrying out the present invention will be described in detail. In addition, this invention is not limited to the following description, It can deform | transform and implement suitably in the range of the summary.

本発明の第一の実施形態（以下、単に「第一の実施形態」という。）は、ＰＰＥ粒子の集合体であるＰＰＥ粉体であって、ＰＰＥ粒子が一次粒子の集合体である二次粒子であり、ＰＰＥ粉体の全量基準で９５質量％以上１００質量％以下の粉体が目開き２５０μｍの篩を通過し、且つ１０質量％を超え３０質量％以下の粉体が目開き５３μｍの篩を通過する粒度分布を有するＰＰＥ粉体である。   A first embodiment of the present invention (hereinafter simply referred to as “first embodiment”) is a PPE powder that is an aggregate of PPE particles, and a secondary in which the PPE particles are aggregates of primary particles. A powder having a particle size of 95% by mass to 100% by mass on the basis of the total amount of PPE powder passes through a sieve having an opening of 250 μm, and a powder having a particle size of more than 10% and not more than 30% by mass has an opening of 53 μm. A PPE powder having a particle size distribution passing through a sieve.

第一の実施形態は、高周波用電子回路基板の材料であるプリプレグや樹脂シートの製造に用いる、ＰＰＥと有機溶剤とを含むワニスを作製するのに適したＰＰＥ粉体である。本実施の形態における前記ワニスは、環境保護・人的有害性・引火爆発に対する安全確保を簡便に行う観点から、トリクロロエチレンのようなハロゲン化炭化水素、又は６０℃以上に加熱したトルエン等の芳香族有機溶剤等の使用を回避し、上記以外の有機溶剤を用いたワニスである。また該ワニスには、ＰＰＥが有機溶剤に溶解していない状態で存在している。なお本開示で、ワニスにおいてＰＰＥが有機溶剤に溶解していないとは、ＰＰＥが実質的に溶解していないことを意図し、より典型的にはワニス中のＰＰＥ全量基準で有機溶剤中に溶解していないＰＰＥが５℃以上４０℃以下の温度条件に亘って７０質量％以上であることを意図する。本実施の形態のＰＰＥ粉体を用いることによって、ＰＰＥが溶解していない状態のワニスを用いても、粉落ちのない良好なプリプレグ又は樹脂シートが得られる。また更には、このようなプリプレグ又は樹脂シートを成型することで、耐熱性、成型性及び接着性に優れる基板を得ることができる。ＰＰＥが溶解していない状態で存在しているワニスによれば、ＰＰＥを溶解状態で存在させることに起因する、粘度変化、ＰＰＥ析出等の影響なく、安定してプリプレグ又は樹脂シートの製造を行うことができる。   The first embodiment is a PPE powder suitable for producing a varnish containing PPE and an organic solvent, which is used for manufacturing a prepreg or a resin sheet, which is a material for a high-frequency electronic circuit board. In the present embodiment, the varnish is a halogenated hydrocarbon such as trichloroethylene or an aromatic such as toluene heated to 60 ° C. or higher, from the viewpoint of simply ensuring environmental protection, human hazards, and safety against flammable explosions. A varnish that avoids the use of organic solvents and the like and uses organic solvents other than those described above. Moreover, in this varnish, PPE exists in the state which is not melt | dissolving in the organic solvent. In the present disclosure, PPE is not dissolved in an organic solvent in a varnish, which means that PPE is not substantially dissolved, and more typically dissolved in an organic solvent based on the total amount of PPE in the varnish. It is intended that the PPE that is not present is 70% by mass or more over a temperature condition of 5 ° C. or more and 40 ° C. or less. By using the PPE powder of the present embodiment, a good prepreg or resin sheet without powder falling can be obtained even if a varnish in which PPE is not dissolved is used. Furthermore, the board | substrate which is excellent in heat resistance, a moldability, and adhesiveness can be obtained by shape | molding such a prepreg or a resin sheet. According to the varnish existing in a state where the PPE is not dissolved, the prepreg or the resin sheet can be stably produced without the influence of viscosity change, PPE precipitation, etc. caused by the presence of the PPE in the dissolved state. be able to.

第一の実施形態のＰＰＥ粉体を構成するＰＰＥ粒子は、ＰＰＥの一次粒子の集合体である二次粒子である。本開示で、ＰＰＥ粒子は、実質的に二次粒子であることを意図し、より典型的には、ＰＰＥ粒子の全量基準で、二次粒子として存在する粒子が９０質量％以上であることを意図する。   The PPE particles constituting the PPE powder of the first embodiment are secondary particles that are aggregates of primary particles of PPE. In the present disclosure, PPE particles are intended to be substantially secondary particles, and more typically 90% by weight or more of particles present as secondary particles, based on the total amount of PPE particles. Intended.

いずれの理論にも拘束されるものではないが、ＰＰＥ一次粒子が集合した二次粒子を用い、該二次粒子の殆どの粒子を２５０μｍ以下の粒径とすることにより、ＰＰＥ粉体と有機溶剤とを混合してワニスを作製する際、ＰＰＥ粉体内部に有機溶剤を速やかに浸透させることができるため、安定して均一なワニスを得ることができる。また、前記ワニスを塗工し、有機溶剤を乾燥除去して得られるプリプレグ又は樹脂シートは、樹脂成分の粉落ちがなく取扱性に優れる。これはＰＰＥ粒子同士の接触点を必要量確保できるためと推測される。更には、前記プリプレグ又は樹脂シートをバッチ式或いは連続式の真空プレス（加熱加圧成形）にて成型する工程で、ＰＰＥ粒子を完全に溶融させることができるため、成型品中にＰＰＥ成分を均一に分布させることができ、優れた耐熱性、成型性、及び接着性を成型品に付与することができる。   Although not bound by any theory, PPE powder and organic solvent can be obtained by using secondary particles in which PPE primary particles are aggregated and making most of the secondary particles have a particle size of 250 μm or less. When the varnish is produced by mixing the organic solvent, the organic solvent can be rapidly infiltrated into the PPE powder, so that a stable and uniform varnish can be obtained. Moreover, the prepreg or resin sheet obtained by applying the varnish and drying and removing the organic solvent has no handleability of resin components and is excellent in handleability. This is presumably because a necessary amount of contact points between the PPE particles can be secured. Furthermore, since the PPE particles can be completely melted in the process of molding the prepreg or resin sheet in a batch or continuous vacuum press (heat press molding), the PPE component is uniformly distributed in the molded product. And can impart excellent heat resistance, moldability, and adhesiveness to the molded product.

一方で、粒径５３μｍ以下の微小なＰＰＥ粉体を特定量含有させることで、ワニスの分散安定性を向上させることができ、ＰＰＥ自体、及び加えて任意の無機フィラー等（用いる場合）の沈降又は分離等が発生しない安定なワニスを得ることができる。これはＰＰＥ粉体によるネットワーク構造が形成されるためと推測される。また、このようなＰＰＥ粉体は前記ワニスを用いて製造されるプリプレグ又は樹脂シートに良好な成膜性を与えることができるため、ＰＰＥを含む樹脂組成物中に有機及び／又は無機フィラーを多く配合させることを可能にし、樹脂組成の設計の自由度を大きくすることができ好ましい。更には、このようなＰＰＥ粉体は、前記プリプレグ又は樹脂シートをバッチ式或いは連続式の真空プレス（加熱加圧成形）にて成型する工程で、比較的速い段階で溶融するため、樹脂全体の粘度を低減させることが可能であり、その結果、優れた成型性を与えることができる。従って、本実施の形態のＰＰＥ粉体によれば、粉落ち等の少ないプリプレグが得られ、且つ、プレス成型工程での成型性にも優れ、更には得られる成型体に優れた耐熱性、成型性、及び接着性を付与することができる。   On the other hand, the dispersion stability of the varnish can be improved by containing a specific amount of fine PPE powder having a particle size of 53 μm or less, and the sedimentation of PPE itself and, in addition, any inorganic filler (if used) Alternatively, a stable varnish that does not cause separation or the like can be obtained. This is presumed to be due to the formation of a network structure of PPE powder. Moreover, since such PPE powder can give favorable film formability to the prepreg or resin sheet manufactured using the said varnish, many organic and / or inorganic fillers are contained in the resin composition containing PPE. It is possible to add them, and the degree of freedom in designing the resin composition can be increased, which is preferable. Furthermore, since such PPE powder is melted at a relatively fast stage in the process of molding the prepreg or the resin sheet by a batch-type or continuous-type vacuum press (heat press molding), The viscosity can be reduced, and as a result, excellent moldability can be provided. Therefore, according to the PPE powder of the present embodiment, a prepreg with less powder fall-off is obtained, the moldability in the press molding process is excellent, and the molded product obtained has excellent heat resistance and molding. And adhesiveness can be imparted.

＜ＰＰＥ＞
第一の実施形態のＰＰＥ粉体を構成するＰＰＥは、置換又は非置換のフェニレンエーテル単位構造から構成されるポリマーである。ＰＰＥは、本発明の作用効果を損なわない範囲でフェニレンエーテル単位構造以外の共重合成分単位を含んでもよいが、このような共重合成分単位の量は、全単位構造の数に対して、典型的には３０％以下、又は５％以下である。ＰＰＥは、好ましくは、下記一般式（１）： <PPE>
The PPE constituting the PPE powder of the first embodiment is a polymer composed of a substituted or unsubstituted phenylene ether unit structure. The PPE may contain copolymer component units other than the phenylene ether unit structure as long as the effects of the present invention are not impaired. The amount of such copolymer component units is typical with respect to the total number of unit structures. Specifically, it is 30% or less, or 5% or less. PPE is preferably the following general formula (1):

｛式中、Ｒ１、Ｒ２、Ｒ３及びＲ４は、各々独立して、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリール基、置換基を有してもよいアミノ基、ニトロ基又はカルボキシル基を表す。｝で表される繰返し構造単位を含む。上記一般式（１）で表される繰返し構造単位は、誘電特性及び耐熱性に優れている観点で有利である。 {Wherein R1, R2, R3 and R4 each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An aryl group that may be substituted, an amino group that may have a substituent, a nitro group, or a carboxyl group. } Is included. The repeating structural unit represented by the general formula (1) is advantageous from the viewpoint of excellent dielectric properties and heat resistance.

ＰＰＥの具体例としては、例えば、ポリ（２，６−ジメチル−１，４−フェニレンエーテル）、ポリ（２−メチル−６−エチル−１，４−フェニレンエーテル）、ポリ（２−メチル−６−フェニル−１，４−フェニレンエーテル）、ポリ（２，６−ジクロロ−１，４−フェニレンエーテル）等、更に、２，６−ジメチルフェノールと他のフェノール類（例えば、２，３，６−トリメチルフェノール、２−メチル−６−ブチルフェノール等）との共重合体、及び、２，６−ジメチルフェノールとビフェノール類又はビスフェノール類とをカップリングさせて得られるＰＰＥ共重合体、等が挙げられる。誘電特性及び耐熱性に優れており、且つ、商業的な生産技術が確立されており安定して利用できる観点で、特に好ましい例は、ポリ（２，６−ジメチル−１，４−フェニレンエーテル）である。   Specific examples of PPE include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl-6). -Phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (for example, 2,3,6-phenylene ether) And trimethylphenol, 2-methyl-6-butylphenol and the like, and PPE copolymers obtained by coupling 2,6-dimethylphenol and biphenols or bisphenols. A particularly preferred example is poly (2,6-dimethyl-1,4-phenylene ether) from the viewpoint of excellent dielectric properties and heat resistance, and a commercial production technique that has been established and can be used stably. It is.

ＰＰＥは分子末端のフェノール性水酸基が他の官能基で変性されている変性ＰＰＥであってもよい。上記の官能基は特に限定されるものではなく、ベンジル基、アリル基、プロパギル基、グリシジル基、ビニルベンジル基、メタクリル基等であることができる。また、不飽和カルボン酸や酸無水物との反応生成物であってもよい。その中でも、製造方法が簡易であるため産業的に入手しやすいこと、ＰＰＥ又はＰＰＥ含有樹脂組成物の硬化物の、基材又は銅箔等の金属箔との接着性が良好となる観点から好ましい変性ＰＰＥの例はマレイン化ＰＰＥである。   The PPE may be a modified PPE in which the phenolic hydroxyl group at the molecular end is modified with another functional group. The functional group is not particularly limited, and may be a benzyl group, an allyl group, a propargyl group, a glycidyl group, a vinylbenzyl group, a methacryl group or the like. Further, it may be a reaction product with an unsaturated carboxylic acid or an acid anhydride. Among them, it is preferable from the viewpoint that the production method is simple and easily available industrially, and that the cured product of PPE or PPE-containing resin composition has good adhesion to a metal foil such as a substrate or copper foil. An example of a modified PPE is maleated PPE.

ＰＰＥは、好ましくは、数平均分子量が４，０００以上４０，０００以下である。数平均分子量のより好ましい範囲は６，０００以上３０，０００以下であり、更に好ましい範囲は７，０００以上２７，０００以下、最も好ましい範囲は８，０００以上２５，０００以下である。   PPE preferably has a number average molecular weight of 4,000 to 40,000. A more preferable range of the number average molecular weight is 6,000 to 30,000, a further preferable range is 7,000 to 27,000, and a most preferable range is 8,000 to 25,000.

なお本開示を通じ、分子量（数平均分子量及び重量平均分子量）は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）を用い、標準ポリスチレン換算で測定される値である。典型的には、カラムにＳｈｏｄｅｘ ＬＦ−８０４×２（昭和電工株式会社製）、溶離液に５０℃のクロロホルム、検出器にＲＩ（屈折率計）を用いてＧＰＣ測定を行い、同条件で測定した標準ポリスチレン試料の分子量と溶出時間との関係式から、数平均分子量を算出する。   Throughout the present disclosure, the molecular weight (number average molecular weight and weight average molecular weight) is a value measured in terms of standard polystyrene using gel permeation chromatography (GPC). Typically, GPC measurement is performed under the same conditions by using Shodex LF-804 × 2 (manufactured by Showa Denko KK) as the column, chloroform at 50 ° C. as the eluent, and RI (refractometer) as the detector. The number average molecular weight is calculated from the relational expression between the molecular weight of the prepared standard polystyrene sample and the elution time.

ＰＰＥの数平均分子量が４，０００以上である場合、電子回路基板等において所望される、ＰＰＥ又はＰＥＥ含有樹脂組成物の硬化物のガラス転移温度、はんだ耐熱性を良好に与える点で好ましい。ＰＰＥの数平均分子量が４０，０００以下である場合、硬化物を得るための加熱加圧成形時等の樹脂組成物の溶融粘度が小さく、良好な成型性が得られる点で好ましい。   When the number average molecular weight of PPE is 4,000 or more, it is preferable in that the glass transition temperature and solder heat resistance of the cured product of the PPE- or PEE-containing resin composition, which is desired for an electronic circuit board or the like, is favorably provided. When the number average molecular weight of PPE is 40,000 or less, it is preferable in that the melt viscosity of the resin composition at the time of heat-pressure molding for obtaining a cured product is small and good moldability is obtained.

＜ＰＰＥ粉体＞
第一の実施形態のＰＰＥ粉体を構成するＰＰＥ粒子は、ＰＰＥ一次粒子の集合体である二次粒子である。本開示における一次粒子とは、外見上の幾何学的形態から判断して単位粒子と考えられるものを指す。具体的な例は、本開示の実施例１のＰＰＥ粒子の走査型電子顕微鏡での観察画像として図１に示すようなものである。ＰＰＥ粒子（二次粒子）表面の拡大写真から、互いの境界が明確な単位粒子（すなわち一次粒子）が集合しＰＰＥの二次粒子が形成されていることを確認することができる。ＰＰＥ粉体を構成するＰＰＥ粒子は全粒子が二次粒子であることが理想であるが、ＰＰＥ粉体の全量基準で９０質量％以上が二次粒子であれば本発明の効果が発現されうる。従って本開示において、ＰＰＥ粒子は、その全量基準での二次粒子の含有割合が９０質量％以上であることが意図される。二次粒子の含有割合の典型的な範囲は９０質量％以上１００質量％以下、好ましい範囲は９５質量％以上１００質量％以下、より好ましい範囲は９８質量％以上１００質量％以下、最も好ましい範囲は９９質量％以上１００質量％以下である。上記の二次粒子の含有割合は、光学顕微鏡、マイクロスコープなどでＰＰＥ粉体を観察しながら一次粒子と二次粒子とを分別し、それぞれの質量を測定する方法で確認される。このような二次粒子は、ＰＰＥをトルエン等の良溶媒に溶解させた後に、メタノール等の貧溶剤を加えてＰＰＥを析出させ単離する方法において、良溶媒の量、良溶媒と貧溶媒の比、温度、シア等を調製することによって得ることができる。また、ＰＰＥの一次粒子を、ＰＰＥをトルエン等の良溶媒に溶解した液等をバインダーとして用い、湿式造粒する方法によっても得ることができる。 <PPE powder>
The PPE particles constituting the PPE powder of the first embodiment are secondary particles that are aggregates of PPE primary particles. The primary particle in the present disclosure refers to what is considered to be a unit particle as judged from an apparent geometric form. A specific example is as shown in FIG. 1 as an observation image of the PPE particles of Example 1 of the present disclosure with a scanning electron microscope. From the enlarged photograph of the surface of the PPE particles (secondary particles), it can be confirmed that unit particles (that is, primary particles) whose boundaries are clear are aggregated to form secondary particles of PPE. It is ideal that all the PPE particles constituting the PPE powder are secondary particles. However, if 90% by mass or more of secondary particles are based on the total amount of the PPE powder, the effect of the present invention can be exhibited. . Therefore, in the present disclosure, the PPE particles are intended to have a secondary particle content of 90% by mass or more based on the total amount thereof. A typical range of the content ratio of the secondary particles is 90% by mass to 100% by mass, a preferable range is 95% by mass to 100% by mass, a more preferable range is 98% by mass to 100% by mass, and the most preferable range is It is 99 mass% or more and 100 mass% or less. The content ratio of the secondary particles is confirmed by a method of separating the primary particles and the secondary particles while observing the PPE powder with an optical microscope, a microscope, or the like, and measuring the respective masses. Such secondary particles are obtained by dissolving PPE in a good solvent such as toluene and then adding a poor solvent such as methanol to precipitate and isolate PPE. It can be obtained by adjusting the ratio, temperature, shear and the like. Moreover, the primary particle | grains of PPE can also be obtained by the method of carrying out wet granulation, using the liquid etc. which melt | dissolved PPE in good solvents, such as toluene, as a binder.

第一の実施形態のＰＰＥ粉体は、ＰＰＥ粉体の全量基準で９５質量％以上１００質量％以下が目開き２５０μｍの篩を通過する粒度分布を有する。ＰＰＥ粉体の全量基準で、目開き２５０μｍの篩を通過する粉体の好ましい範囲は、９８質量％以上１００質量％以下、さらに好ましい範囲は９９．５質量％以上１００質量％以下、最も好ましい範囲は９９．８質量％以上１００質量％以下である。   The PPE powder of the first embodiment has a particle size distribution in which 95% by mass or more and 100% by mass or less of the PPE powder pass through a sieve having an opening of 250 μm. A preferable range of the powder passing through the sieve having an opening of 250 μm based on the total amount of the PPE powder is 98% by mass to 100% by mass, and a more preferable range is 99.5% by mass to 100% by mass, and the most preferable range. Is 99.8 mass% or more and 100 mass% or less.

ここで、目開き２５０μｍの篩を通過する粉体の質量％は、ＪＩＳ規格に準拠する目開き２５０μｍ、直径２００ｍｍの篩を用い、ＰＰＥ粉体２０ｇをロータップ式篩振とう器を用いて１５分間で篩分け処理した際に上記篩を通過する粉体の割合である。   Here, the mass% of the powder passing through the sieve having a mesh size of 250 μm is a sieve having a mesh size of 250 μm and a diameter of 200 mm conforming to JIS standard, and 20 g of PPE powder is used for 15 minutes using a low-tap sieve shaker. It is the ratio of the powder which passes the said sieve when it sifts by.

９５質量％以上１００質量％以下が目開き２５０μｍの篩を通過する粉体であれば、ＰＰＥ粉体と有機溶剤とを混合してワニスを調製する際、ＰＰＥ粉体内部に有機溶剤を速やかに浸透させることができるため、安定して均一なワニスを得ることができる。また、前記ワニスを塗工し、有機溶剤を乾燥除去して得られるプリプレグ又は樹脂シートにおいても、ＰＰＥ粉体同士の接触点を必要量確保できるためと推測され、樹脂成分の粉落ちのない取扱性に優れたプリプレグ又は樹脂シートを得ることができる。更には、前記プリプレグ又は樹脂シートをバッチ式或いは連続式の真空プレス（加熱加圧成形）にて成型する工程で、ＰＰＥ粒子を完全に溶融させることができるため、成型品中にＰＰＥ成分を均一に分布させることができ、優れた耐熱性、成型性、及び接着性を付与することができる。   If 95% by mass or more and 100% by mass or less is a powder that passes through a sieve having an opening of 250 μm, when the varnish is prepared by mixing the PPE powder and the organic solvent, the organic solvent is quickly introduced into the PPE powder. Since it can be permeated, a stable and uniform varnish can be obtained. In addition, in the prepreg or resin sheet obtained by applying the varnish and drying and removing the organic solvent, it is presumed that a necessary amount of contact points between the PPE powders can be secured, and the resin component does not fall off. A prepreg or resin sheet having excellent properties can be obtained. Furthermore, since the PPE particles can be completely melted in the process of molding the prepreg or resin sheet in a batch or continuous vacuum press (heat press molding), the PPE component is uniformly distributed in the molded product. Can be distributed, and excellent heat resistance, moldability, and adhesiveness can be imparted.

第一の実施形態のＰＰＥ粉体は、ＰＰＥ粉体の全量基準で１０質量％を超え４０質量％以下の粉体が目開き５３μｍの篩を通過する粒度分布を有するＰＰＥ粉体である。ＰＰＥ粉体の全量基準で、目開き５３μｍの篩を通過する粉体の好ましい範囲は、１１質量％以上３０質量％以下、さらに好ましい範囲は１２質量％以上２７質量％以下、最も好ましい範囲は１３質量％以上２５質量％以下である。ここで、目開き５３μｍの篩を通過する粉体の質量％は、ＪＩＳ規格に準拠する目開き５３μｍ、直径２００ｍｍの篩を用い、ＰＰＥ粉体２０ｇをロータップ式篩振とう器を用いて１５分間で篩分け処理した際に上記篩を通過する粉体の割合である。   The PPE powder of the first embodiment is a PPE powder having a particle size distribution in which a powder of more than 10% by weight and 40% by weight or less passes through a sieve having an opening of 53 μm based on the total amount of the PPE powder. The preferable range of the powder passing through the sieve having an aperture of 53 μm based on the total amount of the PPE powder is 11% by mass to 30% by mass, more preferably 12% by mass to 27% by mass, and the most preferable range is 13%. The mass is 25% by mass or more. Here, the mass% of the powder passing through the sieve having a mesh size of 53 μm is 15 minutes using a sieve having a mesh size of 53 μm and a diameter of 200 mm conforming to JIS standard and 20 g of PPE powder using a low-tap type sieve shaker. It is the ratio of the powder which passes the said sieve when it sifts by.

目開き５３μｍの篩を通過するＰＰＥ粒子を１０質量％を超える量含有するＰＰＥ粉体であれば、該ＰＰＥ粉体によるネットワーク構造が形成されると推測され、ワニスの分散安定性を向上させることができ、ＰＰＥ自身はもちろん、無機フィラー等を含有させた場合にも沈降又は分離等が発生しない安定なワニスを得ることができる。また、前記ワニスを用いて製造されるプリプレグ又は樹脂シートに成膜性を与えることができるため、ＰＰＥを含む樹脂組成物中に有機及び／又は無期フィラーを多く配合させることが可能であり、樹脂組成の設計の自由度が大きくなるため好ましい。更には、前記プリプレグ又は樹脂シートをバッチ式或いは連続式の真空プレス（加熱加圧成形）にて成型する工程で、比較的速い段階でＰＰＥを溶融させ、樹脂全体の粘度を低減させることが可能であり、その結果、優れた成型性を与えることができる。   If the PPE powder contains more than 10% by mass of PPE particles passing through a sieve having an opening of 53 μm, it is presumed that a network structure is formed by the PPE powder, and the dispersion stability of the varnish is improved. In addition to PPE itself, a stable varnish that does not cause sedimentation or separation when an inorganic filler or the like is contained can be obtained. Moreover, since the film forming property can be imparted to the prepreg or the resin sheet manufactured using the varnish, it is possible to add a lot of organic and / or indefinite filler in the resin composition containing PPE, and the resin This is preferable because the degree of freedom in designing the composition is increased. Furthermore, in the process of molding the prepreg or resin sheet with a batch or continuous vacuum press (heat press molding), it is possible to melt PPE at a relatively fast stage and reduce the viscosity of the entire resin. As a result, excellent moldability can be provided.

目開き５３μｍの篩を通過するＰＰＥ粒子が３０質量以下のＰＰＥ粉体であれば、ＰＰＥ粉体を溶剤に加える際にダマが形成され難く、或いはダマが形成されても速やかに解消されやすく、均一なワニスとできるため好ましい。また、ワニスの粘度が高くなりすぎるのを抑制できるため、ワニス中の固形分濃度を高くできるため好ましい。また、ワニスの含浸性も良好となり、耐熱性に優れる成形品が得られるため好ましい。   If PPE particles passing through a sieve having a mesh size of 53 μm are PPE powder of 30 mass or less, when adding PPE powder to a solvent, it is difficult to form lumps, or even if lumps are formed, they are easily resolved quickly. This is preferable because a uniform varnish can be obtained. Moreover, since it can suppress that the viscosity of a varnish becomes high too much, since the solid content density | concentration in a varnish can be made high, it is preferable. Moreover, since the impregnation property of a varnish also becomes favorable and the molded article excellent in heat resistance is obtained, it is preferable.

第一の実施形態においては、ＰＰＥ粉体の実質的に全てが、目開き１，０００μｍの篩を通過する粒度分布を有することが好ましく、目開き５００μｍの篩を通過する粒度分布を有することがより好ましい。ＰＰＥ粉体が上記の篩を通過する粒度分布を有することは、ＰＰＥ粉体を用いて作製したプリプレグ又は樹脂シートをバッチ式或いは連続式の真空プレス（加熱加圧成形）にて成型する工程で、ＰＰＥ粒子を完全に溶融させることができるため、成型品中にＰＰＥ成分を均一に分布させることができ、優れた耐熱性、成型性、及び接着性を付与することができる観点から有利である。なお、ＰＰＥ粉体の実質的に全てとは、ＰＰＥ粉体の全量基準で好ましくは９０質量％以上、より好ましくは９５質量％以上、更に好ましくは９８質量％以上、特に好ましくは９９質量％以上であることを意図する。   In the first embodiment, substantially all of the PPE powder preferably has a particle size distribution that passes through a sieve having an opening of 1,000 μm, and preferably has a particle size distribution that passes through a sieve having an opening of 500 μm. More preferred. The fact that the PPE powder has a particle size distribution that passes through the above-mentioned sieve means that the prepreg or resin sheet produced using the PPE powder is molded by a batch-type or continuous-type vacuum press (heat press molding). Since the PPE particles can be completely melted, the PPE component can be uniformly distributed in the molded product, which is advantageous from the viewpoint of imparting excellent heat resistance, moldability, and adhesiveness. . Note that substantially all of the PPE powder is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, and particularly preferably 99% by mass or more based on the total amount of the PPE powder. Intended to be.

また、第一の実施形態のＰＰＥ粉体は、ＰＰＥ粉体の全量基準で、４５質量％以上８０質量％以下の粉体が目開き２５０μｍの篩を通過するが目開き１０６μｍの篩は通過しないことが好ましい。また、１０質量％を超え３０質量％以下の粉体が目開き１０６μｍの篩を通過するが目開き５３μｍの篩は通過しない粒度分布を有することが好ましい。   Further, in the PPE powder of the first embodiment, 45 mass% or more and 80 mass% or less of the powder passes through a sieve having an opening of 250 μm, but does not pass through a sieve having an opening of 106 μm, based on the total amount of the PPE powder. It is preferable. Moreover, it is preferable that the powder having a particle size distribution exceeding 10% by mass and 30% by mass or less passes through a sieve having an opening of 106 μm but does not pass through a sieve having an opening of 53 μm.

目開き２５０μｍの篩を通過するが目開き１０６μｍの篩は通過しないＰＰＥ粉体、及び目開き１０６μｍの篩を通過するが目開き５３μｍの篩は通過しないＰＰＥ粉体のより好ましい範囲はそれぞれ５０質量％以上７７質量％以下、及び１１質量％以上２８質量％以下であり、さらに好ましい範囲はそれぞれ５５質量％以上７５質量％以下、及び１２質量％以上２６質量％以下である。   More preferable ranges of PPE powder that passes through a sieve having an opening of 250 μm but does not pass through a sieve having an opening of 106 μm and PPE powder that passes through a sieve having an opening of 106 μm but does not pass through a sieve having an opening of 53 μm are 50 masses. % To 77% by mass and 11% to 28% by mass, and more preferable ranges are 55% to 75% by mass and 12% to 26% by mass, respectively.

目開き２５０μｍの篩を通過するが目開き１０６μｍの篩は通過しないＰＰＥ粉体、及び目開き１０６μｍの篩を通過するが目開き５３μｍの篩は通過しないＰＰＥ粉体がそれぞれ４５質量％以上８０質量％以下、及び１０質量％を超え３０質量％以下であれば、ＰＰＥ粉体を溶剤へ添加してワニスを調製する工程で大きなままこの発生を抑制することができ、均一なワニスを得ることができるため好ましい。また、ＰＰＥ粉体の移送及び保管中にＰＰＥ粉体の粒度による偏析を抑制できるため、常に均一な粒度のＰＰＥ粉体による均一なワニスが得られるため好ましい。更には、ワニス等を製造する前に予め他の原料粉体と混合しておく工程を採る場合でも、他の原料粉体との混合均一性が良好となるため好ましい。   PPE powder that passes through a sieve having an opening of 250 μm but does not pass through a sieve having an opening of 106 μm and PPE powder that passes through a sieve having an opening of 106 μm but does not pass through a sieve having an opening of 53 μm are not less than 45% by mass and 80% by mass. % Or less, and more than 10% by mass and 30% by mass or less, the generation of varnish can be suppressed while the PPE powder is added to the solvent to prepare a varnish, and a uniform varnish can be obtained. This is preferable because it is possible. Further, since segregation due to the particle size of the PPE powder can be suppressed during the transfer and storage of the PPE powder, a uniform varnish of the PPE powder having a uniform particle size is always obtained, which is preferable. Furthermore, even when a step of mixing with other raw material powders in advance before manufacturing the varnish or the like is taken, it is preferable because the mixing uniformity with other raw material powders becomes good.

本開示の所望の粒度分布を有するＰＰＥ粉体は、ＰＰＥを篩分する方法、予め数種類の篩を用いて粒度の異なるＰＰＥ粉体を用意しておきこれらを適時混合する方法、ＰＰＥを粉砕する方法、ＰＰＥを造粒する方法、これら方法を組み合わせる方法等で得ることができる。   The PPE powder having the desired particle size distribution according to the present disclosure is a method of sieving PPE, a method of preparing PPE powders having different particle sizes using several types of sieves in advance, and mixing these in a timely manner, and pulverizing PPE. It can be obtained by a method, a method of granulating PPE, a method of combining these methods, or the like.

また、第一の実施形態のＰＰＥ粉体は、平均粒径が１００μｍを超え１８０μｍ以下であることが好ましい。ＰＰＥ粉体の平均粒径のより好ましい範囲は１００μｍを超え１６０μｍ以下、さらに好ましい範囲は１００μｍを超え１４０μｍ以下である。ＰＰＥ粉体の平均粒径が１００μｍを超え１８０μｍ以下であれば、ＰＰＥ粉末を溶剤へ添加してワニスを調製する工程で大きなままこの発生を抑制することができ、均一なワニスを得ることができるため好ましい。また、ＰＰＥ粉体の移送及び保管中にＰＰＥ粉体の粒度による偏析を抑制できるため、常に均一な粒度のＰＰＥ粉体による均一なワニスが得られるため好ましい。更には、ワニス等を製造する前に予め他の原料粉体と混合しておく工程を採る場合でも、他の原料粉体との混合均一性が良好となるため好ましい。平均粒径は以下に示す方法で測定される値である。先ず、ＰＰＥ粉体２０ｇをロータップ式篩振とう器で１５分間篩分処理する。篩分処理で用いる篩は、ＪＩＳ規格に準拠する目開き５００μｍ、２５０μｍ、２１２μｍ、１５０μｍ、１０６μｍ、７５μｍ、５３μｍ、３２μｍの篩（直径２００ｍｍ）である。各目開きを通過するＰＰＥ粉体の質量割合を測定し、積算質量百分率で表し、積算値５０％の粒度を平均粒径とする。   The PPE powder of the first embodiment preferably has an average particle size of more than 100 μm and 180 μm or less. A more preferable range of the average particle size of the PPE powder is more than 100 μm and 160 μm or less, and a more preferable range is more than 100 μm and 140 μm or less. If the average particle diameter of the PPE powder is more than 100 μm and 180 μm or less, the generation of the varnish can be suppressed while the PPE powder is added to the solvent to prepare a varnish, and a uniform varnish can be obtained. Therefore, it is preferable. Further, since segregation due to the particle size of the PPE powder can be suppressed during the transfer and storage of the PPE powder, a uniform varnish of the PPE powder having a uniform particle size is always obtained, which is preferable. Furthermore, even when a step of mixing with other raw material powders in advance before manufacturing the varnish or the like is taken, it is preferable because the mixing uniformity with other raw material powders becomes good. The average particle diameter is a value measured by the following method. First, 20 g of PPE powder is subjected to a sieving process for 15 minutes using a low-tap sieve shaker. The sieve used in the sieving treatment is a sieve (diameter 200 mm) having an opening of 500 μm, 250 μm, 212 μm, 150 μm, 106 μm, 75 μm, 53 μm, and 32 μm in accordance with JIS standards. The mass ratio of the PPE powder that passes through each mesh is measured, expressed as an integrated mass percentage, and the particle size with an integrated value of 50% is taken as the average particle size.

＜樹脂ワニス＞
本発明の第二の実施形態（以下、単に「第二の実施形態」という。）は、高周波用電子回路基板の材料であるプリプレグ又は樹脂シートの製造に用いる、第一の実施形態のＰＰＥ粉体が有機溶剤に分散している樹脂ワニスである。 <Resin varnish>
The second embodiment of the present invention (hereinafter simply referred to as “second embodiment”) is a PPE powder according to the first embodiment used for manufacturing a prepreg or a resin sheet that is a material for a high-frequency electronic circuit board. A resin varnish whose body is dispersed in an organic solvent.

該樹脂ワニスは、第一の実施形態に係るＰＰＥ粉体と有機溶剤との混合物であってもよく、第一の実施形態に係るＰＰＥ粉体とその他の樹脂（硬化性架橋樹脂等）、開始剤、及び各種添加剤等を組み合わせたＰＰＥ含有樹脂組成物と有機溶剤との混合物であってもよい。   The resin varnish may be a mixture of the PPE powder according to the first embodiment and an organic solvent, and the PPE powder according to the first embodiment and other resins (such as a curable crosslinking resin), start It may be a mixture of a PPE-containing resin composition and an organic solvent in which an additive, various additives, and the like are combined.

第二の実施形態の樹脂ワニスは、ワニス中にＰＰＥが溶解していない状態で存在しているにも関わらず、粉落ちのない良好なプリプレグ又は樹脂シートを得ることができるため好ましい。更には、プリプレグ又は樹脂シートの硬化物に優れた耐熱性、成型性、及び接着性を与えることができるため好ましい。   The resin varnish of the second embodiment is preferable because a good prepreg or resin sheet without powder falling can be obtained even though the resin varnish exists in a state where PPE is not dissolved in the varnish. Furthermore, it is preferable because excellent heat resistance, moldability, and adhesiveness can be imparted to the cured product of the prepreg or resin sheet.

［ＰＰＥ含有樹脂組成物］
第二の実施形態の樹脂ワニスは、ＰＰＥ含有樹脂組成物を含むことができる。ＰＰＥ含有樹脂組成物は、第一の実施形態のＰＰＥ粉体の他に、架橋型硬化性化合物を含んでもよい。ＰＰＥ含有樹脂組成物が架橋型硬化性化合物を含有する場合、該架橋型硬化性化合物とＰＰＥとを含む樹脂組成物に架橋を形成させることにより、ＰＰＥを含む成型品に機械的強度及び耐熱性を付与できるため好ましい。該架橋型硬化性化合物とＰＰＥとを含む樹脂組成物において架橋を形成する方法としては、架橋型硬化性化合物の架橋反応の開始剤として機能する化合物を更に配合して架橋反応を起こさせる方法を例示できるが、特に限定されるものではない。 [PPE-containing resin composition]
The resin varnish of the second embodiment can include a PPE-containing resin composition. The PPE-containing resin composition may contain a crosslinkable curable compound in addition to the PPE powder of the first embodiment. When the PPE-containing resin composition contains a crosslinkable curable compound, mechanical strength and heat resistance of the molded article containing PPE are formed by forming a crosslink in the resin composition containing the crosslinkable curable compound and PPE. Is preferable. As a method of forming a crosslink in a resin composition containing the crosslinkable curable compound and PPE, a method of causing a crosslink reaction by further adding a compound that functions as an initiator of a crosslink reaction of the crosslinkable curable compound. Although it can illustrate, it is not specifically limited.

架橋型硬化性化合物の典型的な例としては、分子内に２個以上の不飽和基をもつモノマーが好ましい。更に好ましくは、プレス成型過程でＰＰＥと相溶することができる、分子内に２個以上の不飽和基をもつモノマーが好ましい。   As a typical example of the crosslinkable curable compound, a monomer having two or more unsaturated groups in the molecule is preferable. More preferably, a monomer having two or more unsaturated groups in the molecule, which is compatible with PPE during the press molding process, is preferred.

プレス成型過程で架橋型硬化性化合物とＰＰＥとが相溶することにより、ＰＰＥ粒子が溶融し、ＰＰＥ以外の硬化性成分を含む樹脂組成物と均一となるため好ましい。また、樹脂組成物の溶融粘度を低減し成型性を向上できるため好ましい。ここで、プレス成型過程でＰＰＥと相溶できる成分として、架橋型硬化性化合物以外の成分を用いることも可能であるが、架橋型硬化性化合物にこのようなＰＰＥとの相溶機能を持たせることにより、樹脂組成物を構成する成分の種類を少なくできるため好ましい。   It is preferable that the crosslinkable curable compound and PPE are compatible in the press molding process, so that the PPE particles are melted and become uniform with the resin composition containing a curable component other than PPE. Moreover, since the melt viscosity of a resin composition can be reduced and a moldability can be improved, it is preferable. Here, as a component compatible with PPE in the press molding process, it is possible to use a component other than the crosslinkable curable compound, but the crosslinkable curable compound has a compatible function with such PPE. This is preferable because the types of components constituting the resin composition can be reduced.

分子内に２個以上の不飽和基をもつモノマーとしては、トリアリルイソシアヌレート（ＴＡＩＣ）、トリアリルシアヌレート（ＴＡＣ）、トリメタリルシアヌレート、トリメチロールプロパントリメタクリレート、ジビニルベンゼン、ジビニルナフタレン、ジアリルフタレート、ジアリルシアヌレート等が挙げられ、中でもＰＰＥとの相溶性の良好なＴＡＩＣが好ましい。   Monomers having two or more unsaturated groups in the molecule include triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), trimethallyl cyanurate, trimethylolpropane trimethacrylate, divinylbenzene, divinylnaphthalene, diallyl. Examples thereof include phthalate and diallyl cyanurate, and among them, TAIC having good compatibility with PPE is preferable.

樹脂組成物中の架橋型硬化性化合物の好ましい含有量は、ＰＰＥ含有樹脂組成物１００質量％を基準として、５質量％以上４０質量％以下である。架橋型硬化性化合物の含有量のより好ましい範囲は１０質量％以上３０質量％以下、更に好ましい範囲は１４質量％以上２４質量％以下である。該架橋型硬化性化合物の含有量が５質量％以上である場合、ＰＰＥ含有樹脂組成物の溶融粘度を良好に低減させることができ、加熱加圧成型等による成型性が良好となる。また、ＰＰＥ含有樹脂組成物の耐熱性を向上させることができる。一方、該架橋型硬化性化合物の量が４０質量％以下である場合、ＰＰＥの有する優れた誘電率及び誘電正接を発現することができる。   The preferable content of the crosslinkable curable compound in the resin composition is 5% by mass or more and 40% by mass or less based on 100% by mass of the PPE-containing resin composition. A more preferable range of the content of the crosslinkable curable compound is 10% by mass to 30% by mass, and a further preferable range is 14% by mass to 24% by mass. When the content of the crosslinkable curable compound is 5% by mass or more, the melt viscosity of the PPE-containing resin composition can be satisfactorily reduced, and the moldability by heat and pressure molding or the like becomes good. Moreover, the heat resistance of the PPE-containing resin composition can be improved. On the other hand, when the amount of the crosslinkable curable compound is 40% by mass or less, the excellent dielectric constant and dielectric loss tangent of PPE can be expressed.

また、ＰＰＥ含有樹脂組成物は、第一の実施形態のＰＰＥ粉体に加え、例えば以下に説明するような成分を任意に含有できる。   In addition to the PPE powder of the first embodiment, the PPE-containing resin composition can optionally contain, for example, components as described below.

例えば、ＰＰＥ含有樹脂組成物は、ＰＰＥに加えて、追加の樹脂（例えば、熱可塑性樹脂、熱硬化性樹脂等）を含有できる。熱可塑性樹脂としては、エチレン、プロピレン、ブタジエン、イソプレン、スチレン、ジビニルベンゼン、メタクリル酸、アクリル酸、メタクリル酸エステル、アクリル酸エステル、塩化ビニル、アクリロニトリル、無水マレイン酸、酢酸ビニル、四フッ化エチレン等のビニル化合物の単独重合体及び２種以上のビニル化合物の共重合体、並びに、ポリアミド、ポリイミド、ポリカーボネート、ポリエステル、ポリアセタール、ポリフェニレンスルフィド、ポリエチレングリコール等を例として挙げることができる。これらの中でもスチレンの単独重合体、スチレン−ブタジエン共重合体、及びスチレン−エチレン−ブタジエン共重合体が、ＰＰＥ含有樹脂組成物の溶剤への溶解性及び成型性の観点から好ましい。熱硬化性樹脂としては、フェノール樹脂、エポキシ樹脂、及びシアネートエステル類を例として挙げることができる。上記熱可塑性樹脂及び熱硬化性樹脂は、酸無水物、エポキシ化合物、アミン等の官能化化合物で変成されたものでもよい。   For example, the PPE-containing resin composition can contain an additional resin (for example, a thermoplastic resin, a thermosetting resin, etc.) in addition to PPE. Thermoplastic resins include ethylene, propylene, butadiene, isoprene, styrene, divinylbenzene, methacrylic acid, acrylic acid, methacrylic ester, acrylic ester, vinyl chloride, acrylonitrile, maleic anhydride, vinyl acetate, ethylene tetrafluoride, etc. Examples thereof include homopolymers of vinyl compounds and copolymers of two or more vinyl compounds, and polyamides, polyimides, polycarbonates, polyesters, polyacetals, polyphenylene sulfides, polyethylene glycols, and the like. Among these, a homopolymer of styrene, a styrene-butadiene copolymer, and a styrene-ethylene-butadiene copolymer are preferable from the viewpoints of solubility of the PPE-containing resin composition in a solvent and moldability. As a thermosetting resin, a phenol resin, an epoxy resin, and cyanate ester can be mentioned as an example. The thermoplastic resin and the thermosetting resin may be modified with a functional compound such as an acid anhydride, an epoxy compound, or an amine.

追加の樹脂の使用量は、ＰＰＥ１００質量部に対して、好ましくは１０質量部以上、より好ましくは１５質量部以上、更に好ましくは２０質量部以上であり、ＰＰＥによって優れた誘電特性及び耐熱性を発現させる点から、好ましくは５０質量部以下、より好ましくは４０質量部以下、更に好ましくは３０質量部以下である。   The amount of the additional resin used is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and still more preferably 20 parts by mass or more, with respect to 100 parts by mass of PPE. From the point of expression, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably 30 parts by mass or less.

ＰＰＥ含有樹脂組成物は、目的に応じ、適当な添加剤を更に含有してもよい。特に、樹脂組成物が更に難燃剤を含む場合、本実施の形態のＰＰＥ含有樹脂組成物が有する良好な成形性、耐吸水性、はんだ耐熱性、及び接着性（例えば、多層板における層間の剥離強度、又は硬化物と銅箔等との剥離強度）に優れるプリント配線板等が得られる利点に加え、難燃性を付与できる点で好適である。   The PPE-containing resin composition may further contain an appropriate additive depending on the purpose. In particular, when the resin composition further contains a flame retardant, the PPE-containing resin composition of the present embodiment has good moldability, water absorption resistance, solder heat resistance, and adhesiveness (for example, delamination between layers in a multilayer board) In addition to the advantage that a printed wiring board having excellent strength or peel strength between a cured product and copper foil or the like can be obtained, it is preferable in that it can impart flame retardancy.

難燃剤としては、燃焼のメカニズムを阻害する機能を有するものであれば特に制限されず、三酸化アンチモン、水酸化アルミニウム、水酸化マグネシウム、ほう酸亜鉛等の無機難燃剤、ヘキサブロモベンゼン、デカブロモジフェニルエタン、４，４−ジブロモビフェニル、エチレンビステトラブロモフタルイミド等の芳香族臭素化合物、レゾルシノールビス−ジフェニルホスフェート、レゾルシノールビス−ジキシレニルホスフェート等のリン系難燃剤等が挙げられる。中でも、得られる硬化物の誘電率及び誘電正接を低く抑えられる観点からデカブロモジフェニルエタン等が好ましい。   The flame retardant is not particularly limited as long as it has a function of inhibiting the combustion mechanism. Inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, hexabromobenzene, decabromodiphenyl Examples include ethane, aromatic bromine compounds such as 4,4-dibromobiphenyl and ethylenebistetrabromophthalimide, and phosphorus-based flame retardants such as resorcinol bis-diphenyl phosphate and resorcinol bis-dixylenyl phosphate. Of these, decabromodiphenylethane and the like are preferable from the viewpoint of keeping the dielectric constant and dielectric loss tangent of the obtained cured product low.

難燃剤の使用量は、使用する難燃剤によって異なり、特に限定するものでないが、ＵＬ規格９４Ｖ−０レベルの難燃性を維持する観点から、ＰＰＥと架橋型硬化性化合物（用いる場合）との合計１００質量部に対して好ましくは５質量部以上、より好ましくは１０質量部以上、更に好ましくは１５質量部以上である。また、得られる硬化物の誘電率及び誘電正接を小さく維持できる観点から、上記使用量は、好ましくは５０質量部以下、より好ましくは４５質量部以下、更に好ましくは４０質量部以下である。   The amount of flame retardant used varies depending on the flame retardant used and is not particularly limited. From the viewpoint of maintaining flame retardancy at the UL standard 94V-0 level, the amount of PPE and the crosslinkable curable compound (if used) Preferably it is 5 mass parts or more with respect to a total of 100 mass parts, More preferably, it is 10 mass parts or more, More preferably, it is 15 mass parts or more. Moreover, from the viewpoint that the dielectric constant and dielectric loss tangent of the obtained cured product can be kept small, the amount used is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and still more preferably 40 parts by mass or less.

その他、添加剤としては、熱安定剤、酸化防止剤、ＵＶ吸収剤、界面活性剤、滑剤、充填剤、ポリマー添加剤等が挙げられる。これらの添加剤の使用量は所望に応じて当業者によって適宜設定される。   In addition, examples of the additive include a heat stabilizer, an antioxidant, a UV absorber, a surfactant, a lubricant, a filler, and a polymer additive. The amount of these additives used is appropriately set by those skilled in the art as desired.

第二の実施形態において、ＰＰＥの好ましい含有量は、ＰＰＥ含有樹脂組成物の質量１００質量％を基準として、２０質量％以上６０質量％以下であることが好ましい。ＰＰＥの樹脂組成物に占める割合のより好ましい範囲は２５質量％以上５５質量％以下、更に好ましい範囲は２８質量％以上５０質量％以下である。ＰＰＥのＰＰＥ含有樹脂組成物に占める割合が２０質量％以上の場合、ＰＰＥが本来有する良好な電気特性の寄与により、該ＰＰＥ含有樹脂組成物の硬化物の電気特性が優れたものとなるため好ましい。ＰＰＥの樹脂組成物に占める割合が６０質量％以下の場合、硬化物を得るための加熱加圧成形時等の溶融粘度が高くなりすぎるのを防ぎ、均一で良好な成形性が得られる点で好ましい。   In 2nd embodiment, it is preferable that preferable content of PPE is 20 to 60 mass% on the basis of 100 mass% of PPE containing resin compositions. A more preferable range of the proportion of PPE in the resin composition is 25% by mass to 55% by mass, and a further preferable range is 28% by mass to 50% by mass. When the proportion of PPE in the PPE-containing resin composition is 20% by mass or more, it is preferable because the electric properties of the cured product of the PPE-containing resin composition are excellent due to the contribution of the good electric properties inherent in PPE. . When the proportion of PPE in the resin composition is 60% by mass or less, the melt viscosity at the time of heat-pressure molding for obtaining a cured product is prevented from becoming too high, and uniform and good moldability is obtained. preferable.

［有機溶剤］
第二の実施形態において樹脂ワニスが含有する有機溶剤は、ワニス中においてＰＰＥを実質的に溶解させない溶剤であれば特に限定されない。ここで、実質的に溶解させないとは、５℃以上４０℃以下の温度条件に亘ってＰＰＥの７０質量％以上が溶解しないことを示す。溶解していないＰＰＥのより好ましい範囲は８０質量％以上、さらに好ましい範囲は９０質量％以上であり、最も好ましいのは９５質量％以上である。ＰＰＥを溶解させない有機溶剤は、ワニスの良好な安定性を与えるため好ましい。 [Organic solvent]
The organic solvent contained in the resin varnish in the second embodiment is not particularly limited as long as it does not substantially dissolve PPE in the varnish. Here, substantially not dissolving means that 70% by mass or more of PPE is not dissolved over a temperature condition of 5 ° C. or more and 40 ° C. or less. A more preferable range of undissolved PPE is 80% by mass or more, a further preferable range is 90% by mass or more, and most preferable is 95% by mass or more. Organic solvents that do not dissolve PPE are preferred because they give good varnish stability.

ＰＰＥを溶解させない有機溶剤としては、トルエン、キシレン、スチレン等の芳香族炭化水素類、メタノール、エタノール、プロパノール、イソプロピルアルコール、１−ブタノール、２−ブタノール、イソブチルアルコール、イソペンチルアルコール等のアルコール類、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸イソブチル、酢酸ペンチル、酢酸イソペンチル等のエステル類、エチルエーテル、１，４−ジオキサン、テトラヒドロフラン等のエーテル類、アセトン、メチルエチルケトン、メチルブチルケトン、メチルイソブチルケトン等のケトン類、エチレングリコールモノメチルエーテル、エチレングリコールものエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノエチルエーテルアセテート等のグリコールエーテル類、シクロヘキセン、シクロペンタノン、シクロヘキサノン、メチルシクロヘキサノン、シクロヘキサノール、メチルシクロヘキサノール等の脂環式炭化水素類、ノルマルヘキサ等の脂肪族炭化水素に例示される有機溶剤から１種類以上を選択して用いることができる。なかでも、ＰＰＥ粉体に有機溶剤が浸透したときにＰＰＥ粉体を柔らかくすることができ、塗工表面を平滑にしたり、ワニスの基材への含浸性が良好となるという観点から、ＰＰＥとＳＰ値が近い溶剤が好ましく、より具体的にはＳＰ値が７．５〜１１．５の範囲にある溶剤としてトルエン、キシレン、スチレン、シクロヘキセン、シクロペンタノン、及びシクロヘキサノンからなる群から選択される１種以上を含む溶剤が好ましい。   Examples of organic solvents that do not dissolve PPE include aromatic hydrocarbons such as toluene, xylene, and styrene, alcohols such as methanol, ethanol, propanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, and isopentyl alcohol. Esters such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, ethers such as ethyl ether, 1,4-dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, methyl butyl ketone , Ketones such as methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono From organic solvents exemplified by glycol ethers such as tilether acetate, alicyclic hydrocarbons such as cyclohexene, cyclopentanone, cyclohexanone, methylcyclohexanone, cyclohexanol and methylcyclohexanol, and aliphatic hydrocarbons such as normal hexa One or more types can be selected and used. Among these, from the viewpoint that the PPE powder can be softened when the organic solvent penetrates into the PPE powder, and the coated surface is smoothed or the impregnation property of the varnish to the base material is improved. A solvent having a close SP value is preferred, and more specifically, the solvent having an SP value in the range of 7.5 to 11.5 is selected from the group consisting of toluene, xylene, styrene, cyclohexene, cyclopentanone, and cyclohexanone. Solvents containing one or more are preferred.

また、第二の実施形態のワニスは、不純物として微量の水を含んでいても構わない。不純物としての水の混入の好ましい範囲は１質量％以下であり、より好ましい範囲は０．５質量％以下、さらに好ましい範囲は０．１質量％以下、最も好ましい範囲は０．０１質量％以下であり、混入がないのが理想である。   Moreover, the varnish of 2nd embodiment may contain a trace amount water as an impurity. A preferable range of mixing water as an impurity is 1% by mass or less, a more preferable range is 0.5% by mass or less, a further preferable range is 0.1% by mass or less, and a most preferable range is 0.01% by mass or less. Ideally, there should be no contamination.

＜ワニスの製造方法＞
第二の実施形態の樹脂ワニスの製造方法は、第一の実施形態のＰＰＥ粉体又はこれを含む樹脂組成物を有機溶剤と混合し、ＰＰＥ粉体が溶解していない状態のワニスを調製できる方法であれば、特に限定されるものではない。ＰＰＥ粉体と有機溶剤とを混合し、撹拌翼、ホモジナイザー等を用いて撹拌、混合することにより、ＰＰＥ粉体が実質的に溶解することなく分散した樹脂ワニスを得ることができる。 <Method for producing varnish>
The method for producing the resin varnish of the second embodiment can prepare the varnish in which the PPE powder is not dissolved by mixing the PPE powder of the first embodiment or the resin composition containing the same with an organic solvent. If it is a method, it will not specifically limit. By mixing PPE powder and an organic solvent, stirring and mixing using a stirring blade, a homogenizer, etc., a resin varnish in which the PPE powder is dispersed without substantially dissolving can be obtained.

なかでも、樹脂ワニスの状態で、第一の実施形態のＰＰＥ粉体の粒度を保持するため、撹拌翼等を用いて緩やかに撹拌するのが好ましい。   Especially, in order to maintain the particle size of the PPE powder of the first embodiment in the state of the resin varnish, it is preferable to gently stir using a stirring blade or the like.

＜電子回路基板材料＞
本発明における第三の実施形態は、第二の実施形態に係る樹脂ワニスを用いて形成される電子回路基板材料である。電子回路基板材料の具体的な例は、樹脂フィルム、基材と樹脂との含浸複合体（本開示で、「プリプレグ」ともいう。）、若しくは樹脂付金属箔、又はこれらの少なくとも１種を含む積層体である。 <Electronic circuit board materials>
3rd embodiment in this invention is electronic circuit board material formed using the resin varnish which concerns on 2nd embodiment. Specific examples of the electronic circuit board material include a resin film, an impregnated composite of a base material and a resin (also referred to as “prepreg” in the present disclosure), a metal foil with resin, or at least one of these. It is a laminate.

［樹脂フィルム］
第三の実施形態の１つである樹脂フィルムは、第二の実施形態に係る樹脂ワニスを単独で、或いは支持フィルム等の支持体の上に塗布した後樹脂ワニス中の有機溶剤を乾燥除去して、製膜することで得ることができる。 [Resin film]
The resin film that is one of the third embodiments is a resin film according to the second embodiment, which is applied alone or on a support such as a support film, and then the organic solvent in the resin varnish is removed by drying. And can be obtained by film formation.

支持体としては、ポリエチレン、ポリプロピレン、ポリ塩化ビニル等のポリオレフィン；ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル；ポリカーボネート；ポリイミド；銅箔、アルミ箔等の金属箔；離形紙等を挙げることができる。なお、支持体はマッド処理、コロナ処理、離形処理等の化学的、又は物理的な処理を施してあってもよい。   Examples of the support include polyolefin such as polyethylene, polypropylene and polyvinyl chloride; polyester such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate; polyimide; metal foil such as copper foil and aluminum foil; The support may be subjected to chemical or physical treatment such as mud treatment, corona treatment, and mold release treatment.

本実施形態の樹脂フィルムは、多層プリント配線板等の積層体の層間絶縁シート、接着フィルム等として好適に用いることができる。   The resin film of the present embodiment can be suitably used as an interlayer insulating sheet, an adhesive film or the like of a laminate such as a multilayer printed wiring board.

［基材と樹脂との含浸複合体（プリプレグ）］
第三の実施形態の１つであるプリプレグは、第二の実施形態に係る樹脂ワニスを基材に含浸させた後、熱風乾燥機等で樹脂ワニス中の有機溶剤を乾燥除去して得ることができる。 [Impregnated composite of substrate and resin (prepreg)]
The prepreg which is one of the third embodiments can be obtained by impregnating the base material with the resin varnish according to the second embodiment and then drying and removing the organic solvent in the resin varnish with a hot air dryer or the like. it can.

本実施形態のプリプレグは、樹脂ワニスに含まれていた固形分が基材中に含浸された構造をとるのが特徴である。但し、該固形分がプリプレグ表面に層を形成した構造をとっても、該プリプレグの硬化物を得るためのプレス成型によって基材中に固形分の硬化物が含浸された構造となれば、何ら問題はない。   The prepreg of this embodiment is characterized in that it has a structure in which the solid content contained in the resin varnish is impregnated in the base material. However, even if the solid content has a structure in which a layer is formed on the surface of the prepreg, there is no problem if the solid content is impregnated in the base material by press molding to obtain a cured product of the prepreg. Absent.

本実施の形態に係るプリプレグに用いる基材としては、ロービングクロス、クロス、チョップドマット、サーフェシングマット等の各種ガラス布；アスベスト布、金属繊維布、及びその他合成若しくは天然の無機繊維布；全芳香族ポリアミド繊維、全芳香族ポリエステル繊維、ポリベンゾオキサゾール繊維等の液晶繊維から得られる織布又は不織布；綿布、麻布、フェルト等の天然繊維布；カーボン繊維布、クラフト紙、コットン紙、紙−ガラス混繊糸から得られる布等の天然セルロース系基材；ポリテトラフルオロエチレン多孔質フィルム；等を単独で、又は２種以上組合せて用いることができる。   As a base material used for the prepreg according to the present embodiment, various glass cloths such as roving cloth, cloth, chopped mat, and surfacing mat; asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloth; Woven or non-woven fabrics obtained from liquid crystal fibers such as aromatic polyamide fibers, wholly aromatic polyester fibers, polybenzoxazole fibers; natural fiber fabrics such as cotton cloth, linen cloth, felt; carbon fiber cloth, kraft paper, cotton paper, paper-glass A natural cellulose-based substrate such as a cloth obtained from a mixed yarn; a polytetrafluoroethylene porous film; and the like can be used alone or in combination of two or more.

プリプレグにおける樹脂組成物固形分含有率（すなわち具体的にはＰＰＥ、架橋型硬化性化合物、及びその他の任意成分（用いる場合）の合計の含有率）は、基材の厚さ及びプリプレグの使用目的に応じて適宜設定すればよく、例えば基材としてガラスクロスを使用した場合、ガラスクロスの誘電率は樹脂組成物固形分（特に樹脂）の誘電率に比べて高いため、樹脂組成物固形分の含有率を増やした方が誘電特性的に有利となる。一般的には、プリプレグの樹脂組成物固形分含有率は、プリプレグを例えば電子回路基板用の絶縁材料として使用した際に、優れた絶縁信頼性と電気特性（特に誘電特性）を向上させる観点、及び成型性を良好にする観点から、好ましくは３０質量％以上、より好ましくは４０質量％以上、更に好ましくは５０質量％以上である。また、プリプレグを硬化させて得られる硬化物の剛性を向上する観点から、好ましくは９０質量％以下、より好ましくは８０質量％以下、更に好ましくは７０質量％以下である。   The resin composition solid content in the prepreg (specifically, the total content of PPE, the crosslinkable curable compound, and other optional components (if used)) is the thickness of the substrate and the intended use of the prepreg For example, when glass cloth is used as the base material, the dielectric constant of the glass cloth is higher than the dielectric constant of the resin composition solid content (particularly the resin). Increasing the content is advantageous in terms of dielectric characteristics. In general, the resin composition solid content of the prepreg is such that when the prepreg is used, for example, as an insulating material for an electronic circuit board, excellent insulation reliability and electrical characteristics (particularly dielectric characteristics) are improved. And from a viewpoint of making moldability favorable, Preferably it is 30 mass% or more, More preferably, it is 40 mass% or more, More preferably, it is 50 mass% or more. Moreover, from a viewpoint of improving the rigidity of the hardened | cured material obtained by hardening a prepreg, Preferably it is 90 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 70 mass% or less.

［樹脂付金属箔］
第三の実施形態の１つである樹脂付金属箔は、第二の実施形態に係る樹脂ワニスを金属箔に塗布した後、熱風乾燥機等で樹脂ワニス中の有機溶剤を乾燥除去して得ることができる。 [Metal foil with resin]
The metal foil with resin which is one of the third embodiments is obtained by applying the resin varnish according to the second embodiment to the metal foil, and then drying and removing the organic solvent in the resin varnish with a hot air dryer or the like. be able to.

上述の通り、本実施形態によれば、電子回路基板の製造に必要なプリプレグ又は樹脂シートの製造において、環境保護・人的有害性・引火爆発に対する安全確保を簡便に行う観点から、ハロゲン化炭化水素や６０℃以上に加熱した芳香族有機溶剤等の使用を実質的に回避して（すなわちこれら以外の、ＰＰＥの溶解性に欠ける溶剤を用いて）、成型性及び耐熱性に優れる樹脂付金属箔を形成するのに適したワニスを、ＰＰＥ粉体が残存する（完全に溶解はしていない）状態で、形成することを可能にするＰＰＥ粉体を提供することができる。   As described above, according to the present embodiment, in the production of a prepreg or a resin sheet necessary for the production of an electronic circuit board, halogenated carbonization is performed from the viewpoint of simply ensuring environmental protection, human harm, and safety against a flammable explosion. Resin metal with excellent moldability and heat resistance by substantially avoiding the use of hydrogen or aromatic organic solvents heated to 60 ° C. or higher (ie, using a solvent other than these that lacks PPE solubility) A varnish suitable for forming a foil can be provided in a PPE powder that allows the PPE powder to be formed with the PPE powder remaining (not completely dissolved).

本実施形態に用いる金属箔は特に限定はないが、例えば、アルミ箔、銅箔等を用いることができ、中でも銅箔は電気抵抗が低いため好ましい。   The metal foil used in the present embodiment is not particularly limited. For example, an aluminum foil, a copper foil, or the like can be used. Among these, a copper foil is preferable because of its low electric resistance.

［積層体］
本実施形態に係る積層体は、典型的には、１枚又は複数枚の上記の樹脂フィルム及びプリプレグを銅箔等の基板と重ねた後、プレス成型によりＰＰＥ含有樹脂組成物を硬化させて絶縁層を形成することにより製造することができる。銅箔の代わりに前述の樹脂付金属箔を用いることも可能である。 [Laminate]
The laminate according to this embodiment is typically insulated by laminating one or more of the above resin films and prepreg with a substrate such as a copper foil, and then curing the PPE-containing resin composition by press molding. It can be manufactured by forming a layer. It is also possible to use the aforementioned resin-coated metal foil instead of the copper foil.

金属箔としては、例えば、アルミ箔、銅箔等を用いることができ、中でも銅箔は電気抵抗が低いため好ましい。金属箔と組合せる樹脂フィルム及びプリプレグは１枚でも複数枚でもよく、用途に応じて片面又は両面に金属箔を重ねて積層板に加工する。   As the metal foil, for example, an aluminum foil, a copper foil or the like can be used, and among them, the copper foil is preferable because of its low electric resistance. The resin film and prepreg to be combined with the metal foil may be one sheet or a plurality of sheets, and the metal foil is overlapped on one side or both sides depending on the use, and processed into a laminate.

該積層体は、好ましくは、樹脂ワニスの固形分の硬化物と金属箔とが重なって密着している。このような積層体は、優れた絶縁信頼性及び機械特性を有するため、電子回路基板の材料として好適に用いることができる。   Preferably, the laminate is in close contact with the cured product of the solid content of the resin varnish and the metal foil. Such a laminate can be suitably used as a material for an electronic circuit board because it has excellent insulation reliability and mechanical properties.

以下、実施例により、本発明の幾つかの実施の形態を更に詳しく説明するが、本発明は以下の実施例により何ら限定されるものではない。   Hereinafter, some embodiments of the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples.

実施例、比較例及び製造例中の各物性は、以下の方法によって測定した。   Each physical property in Examples, Comparative Examples and Production Examples was measured by the following method.

（１）ワニス安定性の評価
調合したワニスを５００ｇを１Ｌビーカーに分取し、２３℃±２℃の恒温室で５時間静置後、（ｉ）原材料の分散状態、（ｉｉ）分離の有無、（ｉｉｉ）沈殿の有無、（ｉｖ）粘度安定性、の４項目について観察評価した。（ｉｖ）粘度安定性に関しては、調合直後と５時間後との粘度の差が５％以内のものを、粘度安定性を有するとした。（ｉ）原材料の凝集等がなく確実に分散されていること、（ｉｉ）分離がないこと、（ｉｉｉ）沈殿がないこと、及び（ｉｖ）粘度安定性を有すること、の全てを満たすワニスを、本ワニス安定性試験において「合格」とし、そうでないワニスを「不合格」とした。 (1) Evaluation of varnish stability 500 g of the prepared varnish was dispensed into a 1 L beaker and left in a thermostatic chamber at 23 ° C. ± 2 ° C. for 5 hours, (i) dispersed state of raw materials, (ii) presence or absence of separation. The following four items were observed and evaluated: (iii) Presence / absence of precipitation, and (iv) Viscosity stability. (Iv) Concerning the viscosity stability, those having a viscosity difference within 5% immediately after the preparation and after 5 hours are regarded as having the viscosity stability. A varnish satisfying all of (i) that there is no aggregation of raw materials and the like is reliably dispersed, (ii) that there is no separation, (iii) that there is no precipitation, and (iv) that it has viscosity stability. In this varnish stability test, it was determined as “pass”, and other varnishes were determined as “fail”.

（２）積層板の誘電率、誘電正接の測定（１０ＧＨｚ）
積層板の１０ＧＨｚにおける誘電率及び誘電正接を、ネットワークアナライザーを用いた空洞共振法で、２３℃、相対湿度６５±５％の環境下で測定した。
積層板の作製
プリプレグを８枚重ね、室温から昇温速度３℃／分で加熱しながら圧力５ｋｇ／ｃｍ2の条件で真空プレスを行い、１３０℃まで達したら昇温速度３℃／分で加熱しながら圧力３０ｋｇ／ｃｍ2の条件で真空プレスを行い、２００℃まで達したら温度を２００℃に保ったまま圧力３０ｋｇ／ｃｍ2、時間６０分間の条件で真空プレスを行うことによって積層板を作製した。 (2) Measurement of dielectric constant and dielectric loss tangent of laminate (10 GHz)
The dielectric constant and dielectric loss tangent of the laminate at 10 GHz were measured by a cavity resonance method using a network analyzer in an environment of 23 ° C. and relative humidity of 65 ± 5%.
Laminate preparation Eight prepregs are stacked, vacuum pressed under conditions of a pressure of 5 kg / cm 2 while heating from room temperature at a heating rate of 3 ° C./min. When reaching 130 ° C., heating is performed at a heating rate of 3 ° C./min. Then, vacuum pressing is performed under the condition of pressure 30 kg / cm 2 , and when the temperature reaches 200 ° C., the laminate is manufactured by performing vacuum pressing under the conditions of pressure 30 kg / cm 2 and time 60 minutes while maintaining the temperature at 200 ° C. did.

誘電率、誘電正接の測定
上記積層板を、５０ｍｍ×１．８ｍｍの大きさに切り出し、誘電率及び誘電正接の測定用試料とした。測定用試料を１０５℃±２℃のオーブンに入れ２時間乾燥させた後、２３℃、相対湿度６５±５％の環境下に９６±５時間置いて、測定試料の調整を行った。 Measurement of dielectric constant and dielectric loss tangent The laminate was cut into a size of 50 mm × 1.8 mm, and used as a sample for measuring the dielectric constant and dielectric loss tangent. The measurement sample was placed in an oven at 105 ° C. ± 2 ° C. and dried for 2 hours, and then placed in an environment of 23 ° C. and relative humidity 65 ± 5% for 96 ± 5 hours to prepare the measurement sample.

測定装置には、ネットワークアナライザー（Ｎ５２３０Ａ、ＡｇｉｌｅｎｔＴｅｃｈｎｏｌｏｇｉｅｓ社製）、関東電子応用開発社製の空洞共振器（Ｃａｖｉｔｙ Ｒｅｓｏｒｎａｔｏｒ Ｓシリーズ）を用いた。   A network analyzer (N5230A, manufactured by Agilent Technologies) and a cavity resonator (Cavity Resonator S series) manufactured by Kanto Electronics Application Development Co., Ltd. were used for the measurement device.

（３）積層板のはんだ耐熱性の評価
積層板の作製
プリプレグを２枚重ね、その上下に銅箔（厚み１２μｍ、ＧＴＳ−ＭＰ箔、古川電気工業株式会社製）を重ね合わせたものを、室温から昇温速度３℃／分で加熱しながら圧力５ｋｇ／ｃｍ2の条件で真空プレスを行い、１３０℃まで達したら昇温速度３℃／分で加熱しながら圧力３０ｋｇ／ｃｍ2の条件で真空プレスを行い、２００℃まで達したら温度を２００℃に保ったまま圧力３０ｋｇ／ｃｍ2、時間６０分間の条件で真空プレスを行うことによって両面銅張積層板を得た。次いで、銅箔をエッチングにて除去し、積層板を得た。 (3) Evaluation of solder heat resistance of laminated board
Two prepregs for producing a laminate were stacked, and a copper foil (thickness 12 μm, GTS-MP foil, manufactured by Furukawa Electric Co., Ltd.) superimposed on the top and bottom was heated from room temperature at a heating rate of 3 ° C./min. While pressing at a pressure of 5 kg / cm 2, when the pressure reaches 130 ° C., the vacuum press is performed at a pressure of 30 kg / cm 2 while heating at a heating rate of 3 ° C./min. A double-sided copper-clad laminate was obtained by performing vacuum pressing under the conditions of a pressure of 30 kg / cm 2 and a time of 60 minutes while maintaining the temperature at 200 ° C. Next, the copper foil was removed by etching to obtain a laminate.

積層板の前処理（吸水加速処理）
積層板を５０ｍｍ角に切り出し試験片を作製した。該試験片を１３０℃で３０分乾燥した後、次いで、温度：１２１℃、圧力：２ａｔｍ、時間：４時間、の条件で加速試験を行った。 Pretreatment of laminates (accelerated water absorption treatment)
The laminate was cut into 50 mm squares to produce test pieces. The test piece was dried at 130 ° C. for 30 minutes, and then an accelerated test was performed under the conditions of temperature: 121 ° C., pressure: 2 atm, and time: 4 hours.

積層板のはんだ耐熱性試験（２８８℃）
吸水加速処理後の積層板を、２８８℃のはんだ浴に２０秒間浸漬し、目視による観察を行った。２８８℃のはんだ浴へ浸漬しても、膨れ、剥離及び白化の何れも確認されなかった積層板については「合格」と評価した。２８８℃のはんだ浴への浸漬により、膨れ又は白化が発生した積層板は「不合格」と評価した。 Solder heat resistance test of laminated board (288 ° C)
The laminated board after the water absorption acceleration treatment was immersed in a solder bath at 288 ° C. for 20 seconds and visually observed. Even if it was immersed in a solder bath at 288 ° C., a laminate that was not confirmed to be swollen, peeled off or whitened was evaluated as “pass”. A laminated board in which swelling or whitening occurred due to immersion in a solder bath at 288 ° C. was evaluated as “failed”.

（４）成型性の評価
プレス成型によって得られる積層板を観察し、評価した。 (4) Evaluation of moldability The laminate obtained by press molding was observed and evaluated.

積層板の作製
プリプレグを２枚重ね、その上下に銅箔（厚み１２μｍ、ＧＴＳ−ＭＰ箔、古川電気工業株式会社製）を重ね合わせたものを、室温から昇温速度３℃／分で加熱しながら圧力５ｋｇ／ｃｍ2の条件で真空プレスを行い、１３０℃まで達したら昇温速度３℃／分で加熱しながら圧力３０ｋｇ／ｃｍ2の条件で真空プレスを行い、２００℃まで達したら温度を２００℃に保ったまま圧力３０ｋｇ／ｃｍ2、時間６０分間の条件で真空プレスを行うことによって両面銅張積層板を得た。次いで、銅箔をエッチングにて除去し、成型性評価用の積層板を得た。 Two prepregs for producing a laminate were stacked, and a copper foil (thickness 12 μm, GTS-MP foil, manufactured by Furukawa Electric Co., Ltd.) superimposed on the top and bottom was heated from room temperature at a heating rate of 3 ° C./min. While pressing at a pressure of 5 kg / cm 2, when the pressure reaches 130 ° C., the vacuum press is performed at a pressure of 30 kg / cm 2 while heating at a heating rate of 3 ° C./min. A double-sided copper-clad laminate was obtained by performing vacuum pressing under the conditions of a pressure of 30 kg / cm 2 and a time of 60 minutes while maintaining the temperature at 200 ° C. Next, the copper foil was removed by etching to obtain a laminate for moldability evaluation.

成型性の評価
積層板を目視で観察し、基板表面（圧縮面と水平方向）の樹脂層が均一なものを「合格」とした。基板表面の樹脂層が均一でない場合（例えば斑点模様が観察された場合、或いは、ガラスクロスの糸目に沿って白く見える白化が観察された場合）は「不合格」とした。 Evaluation of moldability The laminated board was visually observed, and the one having a uniform resin layer on the substrate surface (the compression surface and the horizontal direction) was regarded as “pass”. When the resin layer on the substrate surface was not uniform (for example, when a spotted pattern was observed, or when whitening that appeared white along the thread of the glass cloth was observed), it was determined as “failed”.

（５）接着性の評価（積層板の銅箔ピール強度の測定）
銅張積層板の銅箔を一定速度で引き剥がす際の応力を測定した。 (5) Evaluation of adhesion (measurement of copper foil peel strength of laminated sheet)
The stress when peeling the copper foil of the copper clad laminate at a constant speed was measured.

積層板の作製
プリプレグを２枚重ね、その上下に銅箔（厚み３５μｍ、ＧＴＳ−ＭＰ箔、古川電気工業株式会社製）を重ね合わせたものを、室温から昇温速度３℃／分で加熱しながら圧力５ｋｇ／ｃｍ2の条件で真空プレスを行い、１３０℃まで達したら昇温速度３℃／分で加熱しながら圧力３０ｋｇ／ｃｍ2の条件で真空プレスを行い、２００℃まで達したら温度を２００℃に保ったまま圧力３０ｋｇ／ｃｍ2、時間６０分間の条件で真空プレスを行うことによって両面銅張積層板を作製した。 Two prepregs for producing a laminated plate were stacked, and a copper foil (thickness 35 μm, GTS-MP foil, manufactured by Furukawa Electric Co., Ltd.) was stacked on the top and bottom and heated from room temperature at a heating rate of 3 ° C./min. While pressing at a pressure of 5 kg / cm 2, when the pressure reaches 130 ° C., the vacuum press is performed at a pressure of 30 kg / cm 2 while heating at a heating rate of 3 ° C./min. A double-sided copper-clad laminate was produced by performing vacuum pressing under the conditions of a pressure of 30 kg / cm 2 and a time of 60 minutes while maintaining the temperature at 200 ° C.

銅箔ピール強度の測定
プリント配線板用銅張積層板試験方法の規格ＪＩＳ Ｃ ６４８１に準拠した。測定試料を、幅１５ｍｍ×長さ１５０ｍｍのサイズに切り出し、オートグラフ（ＡＧ−５０００Ｄ、株式会社島津製作所製）を用い、銅箔を除去面に対し９０℃の角度で５０ｍｍ／分の速度で引き剥がした際の荷重の平均値を測定し、５回の測定の平均値を求めた。 Measurement of copper foil peel strength The test was conducted in accordance with the standard JIS C 6481 of the test method for copper-clad laminates for printed wiring boards. A measurement sample was cut into a size of 15 mm wide × 150 mm long, and an autograph (AG-5000D, manufactured by Shimadzu Corporation) was used to pull the copper foil at an angle of 90 ° C. at a speed of 50 mm / min with respect to the removal surface. The average value of the load at the time of peeling was measured, and the average value of five measurements was obtained.

（６）積層板のガラス転移温度（Ｔｇ）の測定
動的粘弾性を測定し、ｔａｎδが最大となる温度を求めた。 (6) Measurement of glass transition temperature (Tg) of laminated plate The dynamic viscoelasticity was measured and the temperature at which tan δ was maximized was determined.

積層板の作製
プリプレグを２枚重ね、その上下に厚み１２μｍの銅箔（ＧＴＳ−ＭＰ箔、古川電気工業株式会社製）を重ね合わせたものを最終到達温度２００℃、最終到達圧力３０ｋｇ／ｃｍ2の条件で真空プレスを行い、両面銅張積層板を得た後、銅箔をエッチングにて除去して積層板を得た。 Two prepregs for producing a laminate were stacked, and a copper foil (GTS-MP foil, manufactured by Furukawa Electric Co., Ltd.) having a thickness of 12 μm was stacked on the top and bottom, with a final ultimate temperature of 200 ° C. and a final ultimate pressure of 30 kg / cm 2. A vacuum press was performed under the above conditions to obtain a double-sided copper-clad laminate, and then the copper foil was removed by etching to obtain a laminate.

Ｔｇの測定
測定装置に動的粘弾性装置（ＲＨＥＯＶＩＢＲＯＮ モデルＤＤＶ−０１ＦＰ、ＯＲＩＥＮＴＥＣ社製）を用い、試験片：長さ約３５ｍｍ、幅約１２．５ｍｍｍ及び厚さ約０．３ｍｍ、ひっぱりモード、周波数：１０ｒａｄ／ｓの条件で測定を行った。 Using a dynamic viscoelastic device (RHEOVIBRON model DDV-01FP, manufactured by ORIENTEC) as a measurement device for Tg , test piece: length of about 35 mm, width of about 12.5 mm, thickness of about 0.3 mm, pulling mode, frequency : Measurement was performed under the condition of 10 rad / s.

実施例、比較例において使用した原材料を以下に示す。   The raw materials used in the examples and comparative examples are shown below.

＜ＰＰＥ＞
ポリフェニレンエーテル−１：Ｓ２０２Ａ（旭化成ケミカルズ製、数平均分子量１９，０００）
ポリフェニレンエーテル−２：Ｓ２０３Ａ（旭化成ケミカルズ製、数平均分子量１０，０００）
ポリフェニレンエーテル−３：製造例１で得られるマレイン化ＰＰＥ
ポリフェニレンエーテル−４：製造例２で得られる低分子量ＰＰＥ
ポリフェニレンエーテル−５：製造例３で得られる低分子量・ビニルベンジル化ＰＰＥ
＜架橋型硬化性化合物＞
トリアリルイソシアヌレート：ＴＡＩＣ（日本化成製）
＜その他成分＞
ＳＥＢＳ：タフテックＨ１０４１（旭化成ケミカルズ製）
シリカ：球状シリカ（龍森製）
デカブロモジフェニルエタン：ＳＡＹＴＥＸ８０１０（アルベマールジャパン製）
α，α’−ビス（ｔ−ブチルパーオキシ−ｍ−イソプロピル）ベンゼン：パーブチルＰ（日油製） <PPE>
Polyphenylene ether-1: S202A (manufactured by Asahi Kasei Chemicals, number average molecular weight 19,000)
Polyphenylene ether-2: S203A (manufactured by Asahi Kasei Chemicals, number average molecular weight 10,000)
Polyphenylene ether-3: maleated PPE obtained in Production Example 1
Polyphenylene ether-4: low molecular weight PPE obtained in Production Example 2
Polyphenylene ether-5: Low molecular weight vinylbenzylated PPE obtained in Production Example 3
<Crosslinked curable compound>
Triallyl isocyanurate: TAIC (Nippon Kasei)
<Other ingredients>
SEBS: Tuftec H1041 (Asahi Kasei Chemicals)
Silica: Spherical silica (manufactured by Tatsumori)
Decabromodiphenylethane: SAYTEX8010 (manufactured by Albemarle Japan)
α, α'-bis (t-butylperoxy-m-isopropyl) benzene: perbutyl P (manufactured by NOF Corporation)

＜製造例１ マレイン化ＰＰＥ＞
ポリフェニレンエーテル−１（Ｓ２０２Ａ、旭化成ケミカルズ社製）１００質量部と無水マレイン酸１．５質量部（和光純薬社製）、及び２，５−ジメチル２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン（パーヘキサ２５Ｂ、日本油脂製）１．０質量部を室温でドライブレンドした後、シリンダー温度３００℃、スクリュー回転数２３０ｒｐｍの条件で２軸押出し機により押出し、ＰＰＥと無水マレイン酸との反応生成物を得た。得られたＰＰＥと無水マレイン酸との反応生成物の数平均分子量は１７，０００であった。 <Production Example 1 Maleated PPE>
100 parts by mass of polyphenylene ether-1 (S202A, manufactured by Asahi Kasei Chemicals), 1.5 parts by mass of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.), and 2,5-dimethyl-2,5-di (t-butylperoxy) After 1.0 parts by mass of hexane (Perhexa 25B, manufactured by NOF Corporation) is dry blended at room temperature, it is extruded with a twin screw extruder under conditions of a cylinder temperature of 300 ° C. and a screw rotation speed of 230 rpm, and a reaction product of PPE and maleic anhydride. I got a thing. The number average molecular weight of the reaction product of the obtained PPE and maleic anhydride was 17,000.

＜製造例２：低分子量・ポリフェニレンエーテル＞
９０℃に加温されたオイルバスに１０Ｌのフラスコを設置し、フラスコ内部に毎分３０ｍｌで窒素ガスを導入した。以降、操作は常に窒素ガス気流下で行った。ここに、ポリフェニレンエーテル−１（Ｓ２０２Ａ、旭化成ケミカルズ社製）１ｋｇ、及びトルエン３ｋｇを入れ、攪拌溶解させた。更に８０ｇのビスフェノールＡ（東京化成工業製）をメタノール３５０ｇに溶かした溶液を上記フラスコに攪拌しながら加えた。５分間攪拌を続けた後、６質量％ナフテン酸コバルトミネラルスピリット溶液（和光純薬工業製）３ｍｌを注射器で加え、５分間攪拌を続けた。続いてベンゾイルパーオキサイド（ナイパーＢＭＴ Ｋ−４０／日油製、ベンゾイルパーオキサイドの４０質量％キシレン溶液）溶液３７５ｇにトルエン１１２５ｇを加えて、ベンゾイルパーオキサイド濃度が１０質量％になるように希釈した溶液を滴下ロートに入れ、上記フラスコに２時間かけて滴下していった。滴下終了後、更に２時間加熱及び攪拌を続け、低分子量化ポリフェニレンエーテルを得た。得られた低分子量化ポリフェニレンエーテルの数平均分子量は３，０００であった。 <Production Example 2: Low molecular weight polyphenylene ether>
A 10 L flask was placed in an oil bath heated to 90 ° C., and nitrogen gas was introduced into the flask at a rate of 30 ml per minute. Thereafter, the operation was always performed under a nitrogen gas stream. Here, 1 kg of polyphenylene ether-1 (S202A, manufactured by Asahi Kasei Chemicals) and 3 kg of toluene were added and dissolved by stirring. Further, a solution obtained by dissolving 80 g of bisphenol A (manufactured by Tokyo Chemical Industry Co., Ltd.) in 350 g of methanol was added to the flask with stirring. After stirring for 5 minutes, 3 ml of 6 mass% cobalt naphthenate mineral spirit solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added with a syringe, and stirring was continued for 5 minutes. Subsequently, 1125 g of toluene was added to 375 g of a solution of benzoyl peroxide (manufactured by Niper BMT K-40 / Nichiyo, 40 mass% xylene solution of benzoyl peroxide), and the solution was diluted so that the benzoyl peroxide concentration was 10 mass%. Was placed in a dropping funnel and dropped into the flask over 2 hours. After completion of the dropwise addition, the mixture was further heated and stirred for 2 hours to obtain a low molecular weight polyphenylene ether. The number average molecular weight of the obtained low molecular weight polyphenylene ether was 3,000.

＜製造例３：低分子量・ビニルベンジル化ポリフェニレンエーテル＞
製造例２と同様の方法で、メタノールを添加してポリフェニレンエーテルを沈殿させる前の工程まで行い、低分子量・ポリフェニレンエーテルを含む反応液を得た。該反応液の温度を５０℃に下げ、水酸化ナトリウム３４０ｇをイオン交換水３０５０ｇに溶解させた水溶液とテトラブチルアンモニウムヨード（和光純薬工業製）３１ｇとを加えて、５分間撹拌した。続いて、クロロメチルスチレン（和光純薬工業製）１２９０ｇを加えてから温度５０℃で４時間撹拌を続け、低分子量・ビニルベンジル化ポリフェニレンエーテルを含む反応液を得た。これに多量のメタノールを加え、低分子量・ビニルベンジル化ポリフェニレンエーテルを沈殿させ、ろ別後、乾燥させて低分子量・ビニルベンジル化ポリフェニレンエーテルを得た。得られた低分子量・ビニルベンジル化ポリフェニレンエーテルの数平均分子量は３，１００であった。 <Production Example 3: Low molecular weight vinylbenzylated polyphenylene ether>
The same process as in Production Example 2 was repeated until methanol was added to precipitate polyphenylene ether to obtain a reaction solution containing low molecular weight polyphenylene ether. The temperature of the reaction solution was lowered to 50 ° C., an aqueous solution in which 340 g of sodium hydroxide was dissolved in 3050 g of ion-exchanged water and 31 g of tetrabutylammonium iodide (manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred for 5 minutes. Subsequently, after adding 1290 g of chloromethylstyrene (manufactured by Wako Pure Chemical Industries, Ltd.), stirring was continued at a temperature of 50 ° C. for 4 hours to obtain a reaction solution containing a low molecular weight / vinylbenzylated polyphenylene ether. A large amount of methanol was added thereto to precipitate low molecular weight / vinylbenzylated polyphenylene ether, which was filtered off and dried to obtain low molecular weight / vinylbenzylated polyphenylene ether. The number average molecular weight of the obtained low molecular weight vinylbenzylated polyphenylene ether was 3,100.

＜実施例１〜９、比較例１〜４＞
先ず、ポリフェニレンエーテル−１〜５を万能粉砕機（ＩＫＡ社製、星形カッター）を用いて粉砕し、次いで乳鉢ですり潰して、表１に示す粒度分布を有するＰＰＥ粉体を得た。実施例１で得たＰＰＥ粉体について、走査型電子顕微鏡（日立ハイテク社製 Ｕ８０１０）を用いた形態観察を行った。図１は、実施例１におけるＰＰＥ粉体の走査型電子顕微鏡画像を示す図である。
次いで、表１に示すＰＰＥ粉体を用い、表２に示す樹脂組成のワニスを、トルエンとメタノールとの混合溶剤（混合質量比９９：１）を用いて調合した。１０ＬのＳＵＳ製容器を用い、７ｋｇのワニスを調合した。ＰＰＥ粉体、及びその他の原料と混合溶剤の混合は、予め十字パドル撹拌翼を用いて混合溶剤を撹拌させておき、その上からＰＰＥ粉体及びその他の原料を添加して行った。このときＰＰＥ粉体は、約１ｋｇ／１分の速さで添加した。 <Examples 1-9, Comparative Examples 1-4>
First, polyphenylene ethers 1 to 5 were pulverized using an all-purpose pulverizer (IKA, star cutter), and then ground in a mortar to obtain PPE powder having the particle size distribution shown in Table 1. The PPE powder obtained in Example 1 was subjected to form observation using a scanning electron microscope (U8010 manufactured by Hitachi High-Tech). 1 is a view showing a scanning electron microscope image of PPE powder in Example 1. FIG.
Next, using the PPE powder shown in Table 1, a varnish having a resin composition shown in Table 2 was prepared using a mixed solvent of toluene and methanol (mixing mass ratio 99: 1). Using a 10 L SUS container, 7 kg of varnish was prepared. The mixing of the PPE powder and other raw materials with the mixed solvent was carried out by previously stirring the mixed solvent using a cross paddle stirring blade and adding the PPE powder and other raw materials from above. At this time, the PPE powder was added at a rate of about 1 kg / 1 min.

次いで、上記ワニスをガラスクロス（旭シュエーベル株式会社製、商品名「２１１６」）に含浸させ、乾燥することにより樹脂組成物固形分含有量５４質量％のプリプレグを得た。   Next, the varnish was impregnated into a glass cloth (trade name “2116”, manufactured by Asahi Schavel Co., Ltd.) and dried to obtain a prepreg having a resin composition solid content of 54 mass%.

［試験例１］ワニス安定性評価
実施例１〜９、及び比較例１〜４で得られたワニスの安定性を、前述の方法で評価した。 [Test Example 1] Varnish stability evaluation The stability of the varnishes obtained in Examples 1 to 9 and Comparative Examples 1 to 4 was evaluated by the method described above.

実施例１〜９、及び比較例１、４のワニスは、分離及び沈殿がなく、粘度変化もなく、安定したワニスであった。   The varnishes of Examples 1 to 9 and Comparative Examples 1 and 4 were stable varnishes without separation and precipitation, no viscosity change.

比較例２のワニスは、ワニス底面にシリカフィラー及び難燃剤が沈降してしまった。ＰＰＥ粉体中の粒径５３μｍ以下のＰＰＥ粒子の存在量が少ないため、分散安定性に欠けたと推測される。   In the varnish of Comparative Example 2, the silica filler and the flame retardant settled on the bottom surface of the varnish. It is presumed that the dispersion stability was lacking because the abundance of PPE particles having a particle size of 53 μm or less in the PPE powder was small.

比較例３のワニスは、ＰＰＥの凝集体が存在した。ＰＰＥを混合溶剤に添加した際にできたままこが崩れず、残存してしまったためと推測される。   The varnish of Comparative Example 3 had PPE aggregates. It is presumed that when PPE was added to the mixed solvent, it did not collapse and remained.

［試験例２］積層板評価
実施例１〜９、及び比較例１〜４で得られたプリプレグを用い、前述の方法にて、誘電率、誘電正接、はんだ耐熱性、成型性、及び接着性（銅箔ピール強度）の評価を行った。結果を表３に示した。 [Test Example 2] Laminate Evaluation Using the prepregs obtained in Examples 1 to 9 and Comparative Examples 1 to 4, the dielectric constant, dielectric loss tangent, solder heat resistance, moldability, and adhesiveness were as described above. (Copper foil peel strength) was evaluated. The results are shown in Table 3.

実施例１〜９の積層板は、十分低い誘電率及び誘電正接を有しつつ、はんだ耐熱性、及び成型性に優れ、更に銅箔ピール強度も高く、優れた性能を示した。特に、実施例１〜７及び９では、実施例８と比べて誘電率及び誘電正接がより低く良好であった。これはポリフェニレンエーテル−１〜３及び５では、ポリフェニレンエーテル−４と比べて、ＰＰＥに由来する水酸基量がより少ないことに起因すると推測される。また、実施例１〜８では、実施例９と比べて銅箔ピール強度がより良好であった。これはＰＰＥの末端水酸基がビニルベンジル基で置換されているポリフェニレンエーテル−５と比べて、ポリフェニレンエーテル−１〜４では末端水酸基量が残存していることに起因すると推測される。   The laminates of Examples 1 to 9 had a sufficiently low dielectric constant and dielectric loss tangent, were excellent in solder heat resistance and moldability, and also had high copper foil peel strength, and exhibited excellent performance. In particular, in Examples 1 to 7 and 9, the dielectric constant and dielectric loss tangent were lower and better than in Example 8. This is presumed to be due to the fact that the amount of hydroxyl groups derived from PPE is less in polyphenylene ethers 1 to 3 and 5 than in polyphenylene ether-4. Moreover, in Examples 1-8, compared with Example 9, copper foil peel strength was more favorable. This is presumed to be due to the remaining amount of terminal hydroxyl groups in polyphenylene ethers 1 to 4 compared to polyphenylene ether-5 in which the terminal hydroxyl groups of PPE are substituted with vinylbenzyl groups.

比較例１の積層板では、基板上に斑点模様があり樹脂成分が均一でなく、はんだ耐熱試験では膨れが発生してしまい、また、銅箔ピール強度も低いものであった。ＰＰＥが圧密充填されたペレットをＰＰＥ粉体の出発原料としており一次粒子であるため、ワニス中でのＰＰＥ粉体への溶剤浸透が不十分であり、プリプレグ中にＰＰＥが密に存在する部位が存在し、プレス成型過程でＰＰＥが完全に溶融することができず、他樹脂成分と均一になれなかったためと推測される。   In the laminated board of Comparative Example 1, there was a spotted pattern on the substrate, the resin component was not uniform, swelling occurred in the solder heat resistance test, and the copper foil peel strength was low. PPE compaction-filled pellets are used as starting materials for PPE powder, and are primary particles. Therefore, solvent penetration into the PPE powder in the varnish is insufficient, and there is a site where PPE is densely present in the prepreg. It is presumed that PPE could not be completely melted during the press molding process and could not be made uniform with other resin components.

比較例２の積層板では、かすれが存在した。又はんだ耐熱試験では、ガラス糸に沿った白化が生じてしまった。これは、プレス成型時の樹脂成分の流動性が不十分だったためである。ＰＰＥ粉体中に粒径５３μｍ以下の微粒子が少なかったため、成型過程での粘度が低減されなかったと推測される。   In the laminate of Comparative Example 2, faintness was present. In the heat resistance test, whitening along the glass yarn occurred. This is because the fluidity of the resin component during press molding was insufficient. It is estimated that the viscosity in the molding process was not reduced because there were few fine particles having a particle size of 53 μm or less in the PPE powder.

比較例３の積層板では、はんだ耐熱試験で膨れが発生してしまった。これは、ワニス中に存在したＰＰＥ凝集物が、プレス成型過程中で完全に溶融されず、樹脂組成が均一にならず、プリプレグ間の接着力の弱い部分が起点となって膨れが発生したと推測される。   In the laminated board of Comparative Example 3, blistering occurred in the solder heat resistance test. This is because the PPE agglomerates present in the varnish were not completely melted during the press molding process, the resin composition was not uniform, and the swelling occurred due to the weak adhesive force between the prepregs. Guessed.

比較例４の積層板は、基板上に斑点模様があり樹脂成分が均一でなく、はんだ耐熱試験では膨れが発生してしまい、また、銅箔ピール強度も低いものであった。粒径２５０μｍを超える粗大ＰＰＥの含有量が多いため、プレス成型過程での溶融・均一化が不十分であったためと推測される。   The laminate of Comparative Example 4 had a speckled pattern on the substrate, the resin component was not uniform, swollen in the solder heat resistance test, and the copper foil peel strength was low. It is presumed that because the content of coarse PPE having a particle size exceeding 250 μm is large, melting and homogenization during the press molding process was insufficient.

＜実施例１０〜１６＞
原材料の添加方法を変えた以外、それぞれ実施例１〜７と同様の方法でワニスを調合した。 <Examples 10 to 16>
Varnishes were prepared in the same manner as in Examples 1 to 7, respectively, except that the raw material addition method was changed.

原材料の添加方法
（１）先ず、ワニス７ｋｇの調合に必要な量の５倍量（質量基準）のＰＰＥ粉体、シリカ、難燃剤、及び開始剤を計り取り、全てをポリ袋に入れ、激しく１分間混合した後、緩やかに３分間混合して、ＰＰＥ粉体、シリカ、難燃剤、及び開始剤の混合粉体を調製した。 Raw material addition method (1) First, weigh 5 times (mass basis) PPE powder, silica, flame retardant, and initiator required to prepare 7kg of varnish, put everything in a plastic bag, After mixing for 1 minute, the mixture was gently mixed for 3 minutes to prepare a mixed powder of PPE powder, silica, flame retardant, and initiator.

（２）トルエンとメタノールとの混合溶剤にＳＥＢＳとＴＡＩＣとを溶解させた後に、上記（１）で調製した混合粉体からワニス７ｋｇに必要な量を計り取り、添加した。混合粉体は、約１ｋｇ／１分の速さで添加した。 (2) After SEBS and TAIC were dissolved in a mixed solvent of toluene and methanol, an amount necessary for 7 kg of varnish was measured from the mixed powder prepared in the above (1) and added. The mixed powder was added at a rate of about 1 kg / min.

次いで、上記ワニスをガラスクロス（旭シュエーベル株式会社製、商品名「２１１６」）に含浸させ、乾燥することにより樹脂組成物固形分含有量５４質量％のプリプレグを得た。   Next, the varnish was impregnated into a glass cloth (trade name “2116”, manufactured by Asahi Schavel Co., Ltd.) and dried to obtain a prepreg having a resin composition solid content of 54 mass%.

同様に、ＰＰＥ粉体、シリカ、難燃剤、及び開始剤の混合粉体原料を用いてワニス調製、及びプリプレグ作製を３回繰り返し実施した。   Similarly, varnish preparation and prepreg preparation were repeated three times using a mixed powder raw material of PPE powder, silica, flame retardant, and initiator.

［試験例３］基板特性のバラツキ
実施例１０〜１６で得られたプリプレグを用い、前述の方法にて、誘電正接、及びガラス転移温度の評価を行い、結果を表４に示した。 [Test Example 3] Variation in substrate characteristics Using the prepregs obtained in Examples 10 to 16, the dielectric loss tangent and the glass transition temperature were evaluated by the methods described above, and the results are shown in Table 4.

実施例１０〜１３及び１６は、４回の繰り返し製造において、誘電正接、及びガラス転移温度のバラツキが極めて小さいものが得られた。一方、実施例１４、１５では、４回の繰り返し製造毎の誘電正接、及びガラス転移温度のバラツキが実施例１０〜１３及び１６と比べると大きかった。   In Examples 10 to 13 and 16, in the repeated production four times, those having extremely small variations in dielectric loss tangent and glass transition temperature were obtained. On the other hand, in Examples 14 and 15, the variation in the dielectric loss tangent and the glass transition temperature for each of the four repeated productions were larger than those in Examples 10 to 13 and 16.

本開示のＰＰＥ粉体は、成型性、及び耐熱性に優れる高周波電子回路基板用途のプリプレグ又は樹脂シート等を製造するために好適に適用され得る。   The PPE powder of the present disclosure can be suitably applied to produce a prepreg or a resin sheet for use in a high-frequency electronic circuit board that is excellent in moldability and heat resistance.

Claims (7)

ＰＰＥ粒子の集合体であるＰＰＥ粉体であって、以下の：
（１）ＰＰＥ粒子が一次粒子の集合体である二次粒子であること、
（２）ＰＰＥ粉体の全量基準で９５質量％以上１００質量％以下の粉体が目開き２５０μｍの篩を通過し、かつ１０質量％を超え４０質量％以下の粉体が目開き５３μｍの篩を通過する粒度分布を有すること、
を満たす、ＰＰＥ粉体。 A PPE powder that is an aggregate of PPE particles, the following:
(1) The PPE particles are secondary particles that are aggregates of primary particles.
(2) 95% by mass or more and 100% by mass or less of the powder on the basis of the total amount of the PPE powder passes through a sieve having an opening of 250 μm, and a powder of more than 10% by mass and 40% by mass or less is a sieve having an opening of 53 μm Having a particle size distribution passing through
PPE powder that satisfies 目開き１，０００μｍの篩を通過する粒度分布を有する、請求項１に記載のＰＰＥ粉体。   The PPE powder according to claim 1, which has a particle size distribution passing through a sieve having an opening of 1,000 µm. 目開き５００μｍの篩を通過する粒度分布を有する、請求項１に記載のＰＰＥ粉体。    The PPE powder according to claim 1, which has a particle size distribution passing through a sieve having an opening of 500 µm. 前記ＰＰＥ粉体の全量基準で４５質量％以上８０質量％以下の粉体が目開き２５０μｍの篩を通過するが目開き１０６μｍの篩は通過しない粒度分布を有する、請求項１〜３の何れか１項に記載のＰＰＥ粉体。   The powder according to any one of claims 1 to 3, wherein a powder having a particle size distribution of 45 mass% or more and 80 mass% or less based on the total amount of the PPE powder passes through a sieve having an opening of 250 µm but does not pass through a sieve having an opening of 106 µm. The PPE powder according to item 1. 前記ＰＰＥ粉体の全量基準で１０質量％を超え３０質量％以下の粉体が目開き１０６μｍの篩を通過するが目開き５３μｍの篩は通過しない粒度分布を有する、請求項１〜４の何れか１項に記載のＰＰＥ粉体。   The powder according to any one of claims 1 to 4, wherein the PPE powder has a particle size distribution in which a powder of more than 10% by mass and less than 30% by mass passes through a sieve having an opening of 106 µm but does not pass through a sieve having an opening of 53 µm. The PPE powder according to claim 1. 平均粒径が１００μｍを超え１８０μｍ以下である、請求項１〜５の何れか１項に記載のＰＰＥ粉体。   The PPE powder according to any one of claims 1 to 5, which has an average particle size of more than 100 µm and 180 µm or less. 数平均分子量が４，０００以上４０，０００以下である、請求項１〜６の何れか１項に記載のＰＰＥ粉体。   The PPE powder according to any one of claims 1 to 6, wherein the number average molecular weight is from 4,000 to 40,000.
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