JP2009191234A - Prepreg and thermosetting resin laminate - Google Patents
Prepreg and thermosetting resin laminate Download PDFInfo
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Description
本発明は、プリプレグおよび、当該プリプレグを用いた熱硬化性樹脂積層板に関する。 The present invention relates to a prepreg and a thermosetting resin laminate using the prepreg.
電気・電子機器等に使用される熱硬化性樹脂積層板は、フェノール樹脂配合ワニスなどの熱硬化性樹脂配合ワニスを基材に含浸乾燥させてプリプレグを調製し、該プリプレグを単独で使用又は複数枚積層し、用途に応じてこの片面または両面に接着剤付金属箔を重ね合わせた後、加熱加圧成形して製造されている（例えば、特許文献１参照）。
熱硬化性樹脂積層板の樹脂を含浸させる基材としては、従来、ガラス織布、ガラス不織布等のガラス繊維基材、ポリイミド繊維基材、ポリエステル繊維基材等の有機繊維基材、クラフト紙、リンター紙等の紙基材が用いられてきた。
しかしながら、ガラス繊維基材を用いた場合、積層板の外形又は穴をプレス加工する際に打抜いた箇所が毛羽立ったり、クラックが入るなど打抜き加工性が劣るという問題があった。紙基材を用いた場合、ガラス繊維基材と比べると打抜き加工性が改善されるものの、従来用いられてきたクラフト紙、リンター紙のような紙基材では、打抜いた箇所の毛羽立ちがなお問題となったり、特に低温加工時の場合など、打抜き加工性が不十分な場合があった。
Thermosetting resin laminates used in electrical and electronic equipment are prepared by impregnating and drying a thermosetting resin-containing varnish such as a phenolic resin-containing varnish on a base material, and the prepreg is used alone or in combination. It is manufactured by laminating and laminating a metal foil with an adhesive on one or both sides according to the application, and then heating and pressing (see, for example, Patent Document 1).
As a base material to impregnate the resin of the thermosetting resin laminate, conventionally, glass fiber base materials such as glass woven fabric and glass nonwoven fabric, polyimide fiber base materials, organic fiber base materials such as polyester fiber base materials, kraft paper, Paper substrates such as linter paper have been used.
However, when a glass fiber substrate is used, there has been a problem that the punching processability is inferior, such as the portion punched when the outer shape or the hole of the laminated plate is pressed or the crack is formed. When a paper base is used, the punching processability is improved compared to a glass fiber base, but with conventional paper bases such as kraft paper and linter paper, fuzz at the punched portion is still present. There are cases where punching workability is insufficient, such as in the case of problems or particularly during low-temperature processing.
本発明の目的は、熱硬化性樹脂積層板にした際に打抜き加工性に優れるプリプレグ、並びに、打抜き加工性に優れる熱硬化性樹脂積層板を提供することである。 An object of the present invention is to provide a prepreg excellent in punching processability when a thermosetting resin laminate is formed, and a thermosetting resin laminate excellent in punching processability.
このような目的は、下記（１）〜（５）記載の本発明により達成される。
（１）熱硬化性樹脂組成物を、基材に含浸してなるプリプレグであって、前記基材が、再生セルロース連続長繊維を７０重量％以上含む不織布又は織布であることを特徴とするプリプレグ。
（２）前記基材が、再生セルロース連続長繊維不織布又は織布であることを特徴とする、上記（１）に記載のプリプレグ。
（３）前記再生セルロース連続長繊維が、銅アンモニアレーヨン連続長繊維であることを特徴とする、上記（１）又は（２）に記載のプリプレグ。
（４）前記熱硬化性樹脂組成物が、エポキシ樹脂及び／又はフェノール樹脂を含むことを特徴とする、上記（１）乃至（３）のいずれかに記載のプリプレグ。
（５）上記（１）乃至（４）のいずれかに記載のプリプレグ１枚以上を成形してなる、熱硬化性樹脂積層板。
Such an object is achieved by the present invention described in the following (1) to (5).
(1) A prepreg obtained by impregnating a base material with a thermosetting resin composition, wherein the base material is a nonwoven fabric or a woven fabric containing 70% by weight or more of regenerated cellulose continuous long fibers. Prepreg.
(2) The prepreg according to (1) above, wherein the substrate is a regenerated cellulose continuous long fiber nonwoven fabric or woven fabric.
(3) The prepreg according to (1) or (2) above, wherein the regenerated cellulose continuous long fiber is a copper ammonia rayon continuous long fiber.
(4) The prepreg according to any one of (1) to (3) above, wherein the thermosetting resin composition contains an epoxy resin and / or a phenol resin.
(5) A thermosetting resin laminate obtained by molding one or more prepregs according to any one of (1) to (4).
本発明のプリプレグは、熱硬化性樹脂積層板にした際に打抜き加工性に優れるものであり、高精度の加工に適し、また打抜き加工時に粉塵が発生し難いという効果を奏する。また、本発明の熱硬化性樹脂積層板は、打抜き加工性に優れるものであり、高精度の加工に適し、また打抜き加工時に粉塵が発生し難いという効果を奏する。 The prepreg of the present invention is excellent in punching processability when formed into a thermosetting resin laminate, and is suitable for high-precision processing and has an effect that dust is hardly generated during the punching process. In addition, the thermosetting resin laminate of the present invention is excellent in punching processability, is suitable for high-precision processing, and produces an effect that dust is hardly generated during the punching process.
本発明に係るプリプレグは、熱硬化性樹脂組成物を基材に含浸してなるプリプレグであって、前記基材が、再生セルロース連続長繊維を７０重量％以上含む不織布又は織布であることを特徴とする。
本発明によれば、基材が再生セルロース連続長繊維を７０重量％以上含む不織布又は織布であることにより、熱硬化性樹脂積層板にした際に打抜き加工性に優れるプリプレグを得ることができる。なお、打抜き加工性とは、積層板の外形及び穴などをプレス加工する時の加工特性をいう。打抜き加工性を向上することで、従来困難であった高精度の加工が可能になったり、打抜き加工時に発生する粉塵が低減して電子部品の接続信頼性が向上したり、積層板を用いた物品の量産において低コスト化が可能になる等のメリットがある。
The prepreg according to the present invention is a prepreg formed by impregnating a base material with a thermosetting resin composition, and the base material is a nonwoven fabric or a woven fabric containing 70% by weight or more of regenerated cellulose continuous long fibers. Features.
According to the present invention, when the base material is a non-woven fabric or a woven fabric containing 70% by weight or more of regenerated cellulose continuous long fibers, a prepreg excellent in punching processability when made into a thermosetting resin laminate can be obtained. . Note that the punching workability refers to processing characteristics when pressing the outer shape and holes of the laminated plate. By improving the punching processability, it has become possible to perform high-precision processing that was difficult in the past, reducing dust generated during punching process, improving the connection reliability of electronic components, and using laminates There are advantages such as cost reduction in mass production of articles.
本発明に係るプリプレグが、基材として再生セルロース連続長繊維を７０重量％以上含む不織布又は織布を用いることにより、打抜き加工性に優れるのは、従来のクラフト紙やリンター紙の紙基材に比べて、再生セルロース連続長繊維が比較的均一な形状を有していると共に、長繊維であるため、クラフト紙やリンター紙の短繊維と比べて、打抜き時に不織布または織布から脱落する繊維が少ないことなどに起因すると推定される。 The prepreg according to the present invention uses a nonwoven fabric or woven fabric containing 70% by weight or more of regenerated cellulose continuous long fiber as a base material, so that it is excellent in punching workability on a paper base material of conventional kraft paper or linter paper. Compared with the short fibers of kraft paper and linter paper, the regenerated cellulose continuous long fibers have a relatively uniform shape. It is presumed to be caused by a small amount.
まず、本発明で用いられる基材について説明する。
本発明で用いられるプリプレグの基材は、再生セルロース連続長繊維を７０重量％以上含む不織布又は織布である。３０重量％以下の範囲で含まれ得る、再生セルロース連続長繊維以外の繊維としても長繊維であることが好ましい。３０％重量以下の範囲で含まれ得る再生セルロース連続長繊維以外の繊維としては、例えばポリエステル、ポリアミド等の合成繊維が挙げられる。再生セルロース連続長繊維以外の繊維が含まれる場合の態様としては、例えばポリエステル繊維からなる不織布又は織布からなる層と再生セルロース連続長繊維を７０重量％以上含む不織布又は織布からなる層との多層複合体であっても良い。
First, the base material used by this invention is demonstrated.
The base material of the prepreg used in the present invention is a nonwoven fabric or a woven fabric containing 70% by weight or more of regenerated cellulose continuous long fibers. It is preferable that it is a long fiber also as fibers other than the regenerated cellulose continuous long fiber which can be contained in the range of 30% by weight or less. Examples of fibers other than regenerated cellulose continuous long fibers that can be contained in a range of 30% by weight or less include synthetic fibers such as polyester and polyamide. As an aspect in the case where fibers other than regenerated cellulose continuous long fibers are included, for example, a layer made of a nonwoven fabric or woven fabric made of polyester fiber and a layer made of a nonwoven fabric or woven fabric containing 70% by weight or more of regenerated cellulose continuous long fibers A multilayer composite may also be used.
中でも、本発明で用いられるプリプレグの基材は、再生セルロース連続長繊維１００％からなる不織布又は織布であることが、打抜き加工性の点から好ましい。また、再生セルロース連続長繊維としては、中でも銅アンモニアレーヨン連続長繊維が、打抜き加工性の点から好ましい。
本発明の好ましい基材としては、中でも銅アンモニアレーヨン連続長繊維不織布又は織布が好ましく、銅アンモニアレーヨン連続長繊維不織布としては例えば旭化成せんい株式会社製のベンリーゼ（登録商標）、銅アンモニアレーヨン連続長繊維織布としては例えば旭化成せんい株式会社製のベンベルグ（登録商標）がこれに相当する。
Among them, the base material of the prepreg used in the present invention is preferably a nonwoven fabric or a woven fabric made of 100% regenerated cellulose continuous long fibers from the viewpoint of punching workability. Moreover, as a regenerated cellulose continuous long fiber, a copper ammonia rayon continuous long fiber is especially preferable from the point of stamping workability.
As a preferable base material of the present invention, a copper ammonia rayon continuous long fiber non-woven fabric or a woven fabric is preferable, and as the copper ammonia rayon continuous long fiber non-woven fabric, for example, Benise (registered trademark) manufactured by Asahi Kasei Fibers Co., Ltd., copper ammonia rayon continuous length As the fiber woven fabric, for example, Bemberg (registered trademark) manufactured by Asahi Kasei Fibers Co., Ltd. corresponds to this.
銅アンモニアレーヨン連続長繊維不織布の製造方法は、異物を除去し、重合度を調整したコットンリンターを銅アンモニウム溶液に溶解させた原液を、細孔（原液吐出孔）を有する紡糸口金（紡口）から押し出し、水と共に漏斗内を落下させ、脱アンモニアさせることにより原液を凝固させつつ、延伸を行い、ネット上へ振り落としウエブを形成させる。この際、ネットを進行させながら、進行方向と垂直方向へ振動させることにより、ネットへ振り落とされる繊維はｓｉｎカーブを描くことになる。紡糸時の延伸は１００〜５００倍が可能であり、紡糸漏斗の形状と、その中を流下させる紡糸水量を変えることにより、延伸倍率の調整が任意に可能である。延伸倍率を変えることにより、単繊度や不織布の強度を変えることが可能である。また、紡糸水量や温度を変化させることにより、原液内に微量残留する低分子量セルロース、いわゆるヘミセルロースをコントロールすることも可能である。また、ネットの進行速度、振動幅を制御することにより、繊維配列方向を制御し、不織布としての強度や伸度等をコントロールすることが可能である。紡糸漏斗の形状としては、矩形型が好ましく、流下させる紡糸漏斗の長さは１００〜４００ｍｍ、流下出口のスリット幅は２〜５ｍｍが好ましい。紡糸に用いる紡口の原液吐出孔の直径は０．１〜０．５ｍｍが好ましく、形状は丸型が好ましい。 The copper ammonia rayon continuous long-fiber nonwoven fabric manufacturing method is a spinneret (spinner) having pores (stock solution discharge holes), a stock solution in which a cotton linter whose degree of polymerization has been removed and dissolved in a copper ammonium solution is removed. Then, it is dropped in the funnel together with water and deammoniated to solidify the stock solution, and then stretched to form a web on the net. At this time, the fiber that is shaken down to the net draws a sin curve by vibrating the net in a direction perpendicular to the traveling direction. Stretching at the time of spinning can be 100 to 500 times, and the stretching ratio can be arbitrarily adjusted by changing the shape of the spinning funnel and the amount of spinning water flowing down. By changing the draw ratio, the single fineness and the strength of the nonwoven fabric can be changed. It is also possible to control low-molecular weight cellulose, so-called hemicellulose, remaining in a small amount in the stock solution by changing the amount of spinning water and the temperature. Further, by controlling the traveling speed and vibration width of the net, it is possible to control the fiber arrangement direction and control the strength, elongation and the like of the nonwoven fabric. The shape of the spinning funnel is preferably a rectangular shape, and the length of the spinning funnel to be flowed down is preferably 100 to 400 mm, and the slit width of the flowing down outlet is preferably 2 to 5 mm. The diameter of the stock solution discharge hole of the spinning nozzle used for spinning is preferably 0.1 to 0.5 mm, and the shape is preferably round.
また、不織布の均一性を確保する意味から、ウエブを積層して不織布化することが好ましく、その積層枚数は３〜１０枚が好ましい。積層後のウエブを、例えば、特許第７８７９１４号公報、特許第８７７５７９号公報に記載の方法により、ウエブ状態でセルロースを再生させたり、精練したりした後、高圧水流により繊維交絡させた不織布を製造することもできる。この際に、不織布に穴や凹凸をつけたりすることが、高圧水流の条件や不織布の下及び／又は上に配置されるネットの柄によって可能となる。得られた不織布は、乾燥、巻き取り品として得ることができる。紡糸から巻き取りまでが一連の工程で成されるため、繊維が切断されずに連続的に繋がっている。 Moreover, it is preferable to laminate | stack a web from the meaning which ensures the uniformity of a nonwoven fabric, and the number of lamination | stacking is preferable 3-10 sheets. Produces a nonwoven fabric in which the laminated web is entangled with high-pressure water flow after regenerating or scouring cellulose in the web state, for example, by the method described in Japanese Patent Nos. 787914 and 877579. You can also At this time, it is possible to make holes or irregularities in the nonwoven fabric depending on the conditions of the high-pressure water flow and the net handle disposed under and / or above the nonwoven fabric. The obtained nonwoven fabric can be obtained as a dried or wound product. Since spinning to winding are performed in a series of steps, the fibers are connected continuously without being cut.
本発明の基材に用いられる不織布又は織布は、目付及び厚みは、用途により適宜選択が可能である。樹脂を含浸させる点、及び強度や硬さ等の性能の点から、通常、目付が８〜１５０ｇ／ｍ２が好ましく、より好ましくは１０〜１２０ｇ／ｍ２、更に好ましくは２０〜１００ｇ／ｍ２である。また、厚みは通常、０．０３〜１ｍｍが好ましく、より好ましくは０．０５〜０．８ｍｍである。 The basis weight and thickness of the nonwoven fabric or woven fabric used for the substrate of the present invention can be appropriately selected depending on the application. That is impregnated with a resin, and the strength and performance such as hardness points, usually, preferably 8~150g / m 2 is the mass per unit area, more preferably 10~120g / m 2, more preferably 20 to 100 g / m 2 It is. Moreover, 0.03-1 mm is preferable normally as thickness, More preferably, it is 0.05-0.8 mm.
次に、本発明で用いられる熱硬化性樹脂組成物について説明する。
熱硬化性樹脂組成物に含まれる熱硬化性樹脂は、適当な粘性をもつ液体を原料とし，加熱すると網状構造となって不溶不融の状態に硬化する合成樹脂をいう。熱硬化性樹脂としては、尿素樹脂，メラミン樹脂，フェノール樹脂，エポキシ樹脂，不飽和ポリエステル樹脂，アルキド樹脂，ウレタン樹脂などが挙げられる。
Next, the thermosetting resin composition used in the present invention will be described.
The thermosetting resin contained in the thermosetting resin composition refers to a synthetic resin that uses a liquid having an appropriate viscosity as a raw material and forms a network structure and cures in an insoluble and infusible state when heated. Examples of the thermosetting resin include urea resin, melamine resin, phenol resin, epoxy resin, unsaturated polyester resin, alkyd resin, and urethane resin.
本発明のプリプレグに用いられる熱硬化性樹脂としては、エポキシ樹脂及び／又はフェノール樹脂が好ましい。
エポキシ樹脂としては、分子内に２個以上のエポキシ基を有するものであればよく、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノール型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、脂環式エポキシ樹脂、グリシジルアミン型エポキシ樹脂等が挙げられ、またこれらを臭素化したものであってもよい。また、これらのエポキシ樹脂の分子量は特に制限はなく、何種類かを併用しても良い。
The thermosetting resin used in the prepreg of the present invention is preferably an epoxy resin and / or a phenol resin.
Any epoxy resin may be used as long as it has two or more epoxy groups in the molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol type epoxy resin, phenol novolac type An epoxy resin, a cresol novolac type epoxy resin, an alicyclic epoxy resin, a glycidylamine type epoxy resin, and the like may be mentioned, and these may be brominated. In addition, the molecular weight of these epoxy resins is not particularly limited, and several types may be used in combination.
エポキシ樹脂組成物にて用いられる硬化剤としては、公知のものが使用可能であり、例えば、後述するようなノボラック型フェノール樹脂や１，１，１−トリスヒドロキシフェニルエタン等の多価フェノール類、芳香族アミン、脂肪族アミン等のアミン系硬化剤、酸無水物、ジシアンジアミド、ヒドラジド化合物等が挙げられる。好ましくは、ジシアンジアミドあるいは多価フェノール類である。 As the curing agent used in the epoxy resin composition, known ones can be used. For example, polyphenols such as novolak type phenol resin and 1,1,1-trishydroxyphenylethane as described later, Examples include amine-based curing agents such as aromatic amines and aliphatic amines, acid anhydrides, dicyandiamide, hydrazide compounds, and the like. Preferably, they are dicyandiamide or polyhydric phenols.
一方、フェノール樹脂としては、例えば未変性のノボラック型フェノール樹脂、ビスフェノールＡ型ノボラック型フェノール樹脂、ビスフェノールＦ型ノボラック型フェノール樹脂、クレゾールノボラック型フェノール樹脂、アルキルフェノールノボラック型フェノール樹脂等のノボラック型フェノール樹脂、未変性のレゾール型フェノール樹脂、桐油、アマニ油、クルミ油等の乾性油変性レゾール型フェノール樹脂、大豆油、綿実油、サフラワー油等の半乾性油変性レゾール型フェノール樹脂等の油変性レゾール型フェノール樹脂等のレゾール型フェノール樹脂が挙げられる。 On the other hand, as the phenol resin, for example, a novolak type phenol resin such as unmodified novolak type phenol resin, bisphenol A type novolak type phenol resin, bisphenol F type novolak type phenol resin, cresol novolac type phenol resin, alkylphenol novolak type phenol resin, Oil-modified resole phenol such as unmodified resole phenol resin, dry oil modified resole phenol resin such as tung oil, linseed oil, walnut oil, semi-dry oil modified resole phenol resin such as soybean oil, cottonseed oil, safflower oil Examples thereof include resol type phenol resins such as resins.
これらの中でも前記フェノール樹脂は、油変性フェノール樹脂（特に油変性レゾール型フェノール樹脂）を含むものであることが好ましい。これにより、打抜き加工性を向上することができる。これらの中でも桐油変性レゾール型フェノール樹脂が好ましい。前記油変性フェノール樹脂の油変性量は、特に限定されないが、油変性フェノール樹脂全体の５〜５０重量％が好ましく、特に１０〜３０重量％が好ましい。変性量が前記下限値未満であると打抜き加工性を向上する効果が低下する場合があり、前記上限値を超えると耐熱性を向上する効果が低下する場合がある。 Among these, the phenol resin preferably contains an oil-modified phenol resin (particularly an oil-modified resol type phenol resin). Thereby, punching workability can be improved. Among these, tung oil-modified resol type phenol resin is preferable. The amount of oil modification of the oil-modified phenol resin is not particularly limited, but is preferably 5 to 50% by weight, particularly preferably 10 to 30% by weight, based on the whole oil-modified phenol resin. If the amount of modification is less than the lower limit, the effect of improving punching workability may be reduced, and if it exceeds the upper limit, the effect of improving heat resistance may be reduced.
また、前記フェノール樹脂は、レゾール型フェノール樹脂と、ノボラック型フェノール樹脂との混合物を含むことが好ましい。これにより、寸法特性を向上することができる。
前記レゾール型フェノール樹脂と、前記ノボラック型フェノール樹脂との混合比率は、特に限定されないが、重量比で９：１〜４：６が好ましく、特に：８：２〜６：４が好ましい。重量比が前記範囲内であると、特に寸法安定性を向上することができる。
前記ノボラック型フェノール樹脂の２核体の含有量は、特に限定されないが、フェノール樹脂全体の１５重量％以上であることが好ましく、特に２０〜８０重量％以上であることが好ましい。含有量が前記下限値未満であると、耐熱性と打抜き加工性を向上する効果が低下する場合があり、前記上限値を超えると硬化性が低下し、電気特性が低下する場合がある。
Moreover, it is preferable that the said phenol resin contains the mixture of a resol type phenol resin and a novolak type phenol resin. Thereby, a dimensional characteristic can be improved.
The mixing ratio of the resol type phenol resin and the novolac type phenol resin is not particularly limited, but is preferably 9: 1 to 4: 6, and particularly preferably 8: 2 to 6: 4, by weight. When the weight ratio is within the above range, dimensional stability can be particularly improved.
The content of the binuclear body of the novolac type phenol resin is not particularly limited, but is preferably 15% by weight or more, particularly preferably 20 to 80% by weight or more of the entire phenol resin. When the content is less than the lower limit, the effect of improving heat resistance and punching workability may be reduced, and when the content exceeds the upper limit, curability may be reduced and electrical characteristics may be reduced.
上述のような２核体含有量を有するノボラック型フェノール樹脂を製造する方法としては、フェノール類とアルデヒド類とを、通常用いられるシュウ酸等の酸触媒で反応させた後、蒸留等する方法、およびフェノール類とアルデヒド類とを有機ホスホン酸を触媒として反応させる方法等が挙げられる。これらの中でも触媒と有機ホスホン酸を用いる方法が好ましい。これにより、蒸留等の後工程を省略でき、作業性を向上することができる。また、有機ホスホン酸を触媒として用いて得られるノボラック型フェノール樹脂は、未反応のフリーフェノール量が少ないため、有害な物質が少なく作業環境をも向上することができる。 As a method for producing a novolak type phenolic resin having a binuclear content as described above, phenol and aldehyde are reacted with a commonly used acid catalyst such as oxalic acid, followed by distillation or the like. And a method of reacting phenols with aldehydes using an organic phosphonic acid as a catalyst. Among these, a method using a catalyst and an organic phosphonic acid is preferable. Thereby, post processes, such as distillation, can be omitted and workability can be improved. Moreover, since the novolak-type phenol resin obtained using an organic phosphonic acid as a catalyst has few unreacted free phenol amounts, there are few harmful substances and it can improve a working environment.
更に、フェノール樹脂を主体としたフェノール樹脂組成物とする場合であっても、更に前述のようなエポキシ樹脂を含むことが好ましい。これにより、寸法特性を特に向上することができる。
この場合のエポキシ樹脂の含有量は、特に限定されないが、フェノール樹脂組成物全体の５〜３０重量％が好ましく、特に１０〜２０重量％が好ましい。含有量が前記範囲内であると、特に寸法安定性を向上することができる。
Further, even when a phenol resin composition mainly composed of a phenol resin is used, it is preferable to further include the epoxy resin as described above. Thereby, a dimensional characteristic can be improved especially.
The content of the epoxy resin in this case is not particularly limited, but is preferably 5 to 30% by weight, particularly preferably 10 to 20% by weight, based on the entire phenol resin composition. When the content is within the above range, dimensional stability can be particularly improved.
本発明に用いられる熱硬化性樹脂組成物は、特に限定されないが、リン化合物を含んでも良い。これにより、ノンハロゲンで難燃性を付与することができる。更に、打抜き加工性を向上することができる。リン化合物としては、例えばリン酸エステル、縮合リン酸エステル、ホスフィンオキサイド等を挙げることができる。たとえばリン酸エステルとしては、例えばトリエチルホスフェイト、トリブチルホスフェイト、トリフェニルホスフェイト、トリクレジルホスフェイト、クレジルジフェニルホスフェイト、レゾルシルジフェニルホスフェイト、トリイソプロピルフェニルホスフェイト等が挙げられ、これらは１種または２種以上の混合系として使用される。この中で、トリフェニルホスフェイト、トリクレジルホスフェイト、クレジルジフェニルホスフェイトの中から選ばれる一種以上のリン化合物が入手の容易性の点で好ましい。 The thermosetting resin composition used in the present invention is not particularly limited, but may contain a phosphorus compound. Thereby, flame retardance can be imparted with non-halogen. Furthermore, punching workability can be improved. Examples of phosphorus compounds include phosphate esters, condensed phosphate esters, and phosphine oxides. Examples of phosphoric acid esters include triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, resorcyl diphenyl phosphate, triisopropyl phenyl phosphate, and the like. Is used as one or a mixture of two or more. Among these, at least one phosphorus compound selected from triphenyl phosphate, tricresyl phosphate, and cresyl diphenyl phosphate is preferable in terms of availability.
前記リン化合物の含有量は、特に限定されないが、熱硬化性樹脂組成物全体、５〜３０重量％が好ましく、特に７〜２０重量％が好ましい。含有量が前記下限値未満であると難燃性が低下する場合があり、前記上限値を超えると電気絶縁性、耐熱性が低下する場合がある。 Although content of the said phosphorus compound is not specifically limited, The whole thermosetting resin composition, 5 to 30 weight% is preferable, and 7 to 20 weight% is especially preferable. If the content is less than the lower limit, flame retardancy may be reduced, and if the content exceeds the upper limit, electrical insulation and heat resistance may be reduced.
また、ノンハロゲンでの難燃性が要求されない場合、ハロゲン化合物を添加することもできる。前記ハロゲン化合物としては、例えばテトラブロモビスフェノールＡ（ＴＢＢＡ）、ＴＢＢＡ−エポキシオリゴマー等が挙げられる。
前記ハロゲン化合物の含有量は、特に限定されないが、熱硬化性樹脂組成物全体の５〜５０重量％が好ましく、特に１０〜３０重量％が好ましい。含有量が前記範囲内であると特に難燃性を向上することができることに加え、耐熱性と打抜き加工性を向上することができる。
In addition, a halogen compound can be added when flame resistance without a halogen is not required. Examples of the halogen compound include tetrabromobisphenol A (TBBA) and TBBA-epoxy oligomer.
Although content of the said halogen compound is not specifically limited, 5 to 50 weight% of the whole thermosetting resin composition is preferable, and 10 to 30 weight% is especially preferable. When the content is within the above range, in addition to improving flame retardancy, heat resistance and punching workability can be improved.
また、本発明の熱硬化性樹脂組成物では、本発明の目的に反しない範囲において、アミノ樹脂等の難燃性化合物や、アミン類、イミダゾール化合物等の硬化促進剤を配合することができる。前記アミノ樹脂としては、例えばメラミン樹脂、グアナミン樹脂などであるが、難燃化の効果を高めるためにはメラミン樹脂が好ましい。アミノ樹脂は、メラミンやグアナミンなどのアミノ化合物とホルムアルデヒド等のアルデヒド類との初期反応物であり、それらのメチロール基の一部または全部をメタノール、ブタノール等の低級アルコールでエーテル化したものも含まれる。 In the thermosetting resin composition of the present invention, a flame retardant compound such as an amino resin, or a curing accelerator such as an amine or an imidazole compound can be blended within a range not departing from the object of the present invention. Examples of the amino resin include a melamine resin and a guanamine resin, and a melamine resin is preferable in order to enhance the effect of flame retardancy. The amino resin is an initial reaction product of an amino compound such as melamine or guanamine and an aldehyde such as formaldehyde, and some of these methylol groups are etherified with a lower alcohol such as methanol or butanol. .
本発明の熱硬化性樹脂組成物には、使途により更に、離型剤、表面処理剤、充填剤等の公知の添加剤を加えても良い。離型剤としてはワックス類、ステアリン酸亜鉛等を、さらに表面処理剤としてはシランカップリング剤等を挙げることができる。充填剤としてはシリカ、水酸化アルミニウム、アルミナ、タルク、クレー、炭酸カルシウム等を挙げることができる。 You may add well-known additives, such as a mold release agent, a surface treating agent, and a filler, to the thermosetting resin composition of this invention further by the use. Examples of the mold release agent include waxes and zinc stearate, and examples of the surface treatment agent include a silane coupling agent. Examples of the filler include silica, aluminum hydroxide, alumina, talc, clay, calcium carbonate and the like.
本発明に係るプリプレグは、熱硬化性樹脂組成物を基材に含浸してなるものである。ここで本発明のプリプレグにおける含浸とは、基材の全体のみならず、一部に含浸しているものも含まれる。ここで、一部とは基材の厚み方向の一部であっても良いし、基材の全表面に対する一部の表面にのみ含浸しているものであっても良い。 The prepreg according to the present invention is obtained by impregnating a base material with a thermosetting resin composition. Here, the impregnation in the prepreg of the present invention includes not only the whole substrate but also a part impregnated. Here, the part may be a part in the thickness direction of the base material, or may be impregnated only on a part of the surface relative to the entire surface of the base material.
熱硬化性樹脂組成物を前記基材に含浸させるためには、通常、熱硬化性樹脂組成物を希釈剤で希釈し、熱硬化性樹脂ワニスとする。それから、当該熱硬化性樹脂ワニスを基材に含浸する。
前記希釈剤としては、例えば水、トルエン、アセトン、メチルエチルケトン等のケトン類、ジエチルエーテル、エチレングリコールモノメチルエーテル等のエーテル類、メタノール、エタノールおよびプロパノール等のアルコール類、ジメチルホルムアミド等のアミド類等が挙げられる。入手が容易であり、かつ揮発させるのが容易であるからである。
前記熱硬化性樹脂ワニスの固形分は、特に限定されないが、２０〜８０重量％が好ましく、特に４０〜６０重量％が好ましい。固形分が前記範囲内であると、基材への含浸性に特に優れる。
In order to impregnate the base material with the thermosetting resin composition, the thermosetting resin composition is usually diluted with a diluent to obtain a thermosetting resin varnish. Then, the base material is impregnated with the thermosetting resin varnish.
Examples of the diluent include water, toluene, acetone, ketones such as methyl ethyl ketone, ethers such as diethyl ether and ethylene glycol monomethyl ether, alcohols such as methanol, ethanol and propanol, amides such as dimethylformamide, and the like. It is done. It is because it is easy to obtain and is easy to volatilize.
The solid content of the thermosetting resin varnish is not particularly limited, but is preferably 20 to 80% by weight, and particularly preferably 40 to 60% by weight. When the solid content is within the above range, the substrate is particularly excellent in impregnation properties.
前記熱硬化性樹脂ワニスを前記基材に含浸する方法としては、例えば基材をフェノール樹脂ワニスに浸漬する方法、各種コーターによる塗布する方法、スプレーによる吹き付ける方法等が挙げられる。これらの中でも、基材を熱硬化性樹脂ワニスに浸漬する方法が好ましい。これにより、基材に対する熱硬化性樹脂組成物の含浸性を向上することができる。なお、基材を熱硬化性樹脂ワニスに浸漬する場合、通常の含浸塗布設備を使用することができる。
そして、含浸後、適宜加熱して前記希釈剤を揮発させて乾燥し、プリプレグを得る。
Examples of the method of impregnating the base material with the thermosetting resin varnish include a method of immersing the base material in a phenolic resin varnish, a method of applying with various coaters, and a method of spraying with a spray. Among these, the method of immersing a base material in a thermosetting resin varnish is preferable. Thereby, the impregnation property of the thermosetting resin composition with respect to a base material can be improved. In addition, when a base material is immersed in a thermosetting resin varnish, a normal impregnation coating equipment can be used.
And after impregnation, it heats suitably and volatilizes the said diluent, and it dries, and obtains a prepreg.
次に、熱硬化性樹脂積層板について説明する。
本発明の熱硬化性樹脂積層板は、前記プリプレグの少なくとも１枚以上を成形してなるものである。本発明の熱硬化性樹脂積層板は、最も外側の片面または両面に導体層を有していても良い。本発明の熱硬化性樹脂積層板は、前記プリプレグ２枚以上を成形してなるときは、前記プリプレグ２枚以上を加熱加圧成形して樹脂積層板を製造することができる。本発明の熱硬化性樹脂積層板は更に、プリプレグの最も外側の片面または両面に導体層を積層して加熱加圧成形しても良い。前記本発明に係るプリプレグが１枚のときは、必要に応じて他のプリプレグ及び／又はプリプレグの片面または両面に導体層を積層して得ることができる。前記導体層は、例えば、金属箔や、銀ペーストのような導電性ペーストを用いて形成される。前記金属箔を構成する金属としては、例えば銅または銅系合金、アルミまたはアルミ系合金等が挙げられる。
Next, the thermosetting resin laminate will be described.
The thermosetting resin laminate of the present invention is formed by molding at least one of the prepregs. The thermosetting resin laminate of the present invention may have a conductor layer on the outermost side or both sides. When the thermosetting resin laminate of the present invention is formed by molding two or more of the prepregs, a resin laminate can be produced by heating and pressing the two or more of the prepregs. The thermosetting resin laminate of the present invention may further be heat-pressed by laminating a conductor layer on the outermost one or both sides of the prepreg. When the number of the prepregs according to the present invention is one, it can be obtained by laminating a conductor layer on one side or both sides of another prepreg and / or prepreg as necessary. The conductor layer is formed using, for example, a metal foil or a conductive paste such as a silver paste. Examples of the metal constituting the metal foil include copper, a copper-based alloy, aluminum, an aluminum-based alloy, and the like.
本発明に係るプリプレグ、及び熱硬化性樹脂積層板は、打抜き加工が必要な積層板用途であれば特に限定されることなく用いることができる。例えば、フレキ補強板、ボリウム、スイッチ、各種一般電子部品などが挙げられる。 The prepreg and thermosetting resin laminate according to the present invention can be used without any particular limitation as long as they are used for laminates that require punching. For example, a flexible reinforcing plate, a volume, a switch, various general electronic components, and the like can be given.
以下、本発明を実施例に基づいて詳細に説明するが、本発明はこれに限定されるものではない。
［低分子量メチロールフェノール樹脂（ワニスａ）の合成］
フェノール１０００ｇ、３７％ホルムアルデヒド水溶液９８０ｇ、トリエチルアミン２０ｇからなる混合物を６０℃で２時間反応させ、次に減圧下で濃縮し、これをメタノールで希釈して樹脂分５０％のフェノール樹脂ワニスａを得た。
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to this.
[Synthesis of low molecular weight methylolphenol resin (varnish a)]
A mixture consisting of 1000 g of phenol, 980 g of 37% formaldehyde aqueous solution and 20 g of triethylamine was reacted at 60 ° C. for 2 hours, then concentrated under reduced pressure, and diluted with methanol to obtain a phenol resin varnish a having a resin content of 50%. .
［油変性フェノール樹脂（ワニスｂ）の合成］
フェノール１６００ｇと桐油１３００ｇをパラトルエンスルホン酸の存在下、９５℃で２時間反応させて、次いでパラホルムアルデヒド６５０ｇ、ヘキサメチレンテトラミン３０ｇ、トルエン２０００ｇを加えて９０℃で２時間反応後、減圧下で濃縮し、これをトルエンとメタノールの混合溶媒で希釈して樹脂分５０％の油変性フェノール樹脂ワニスｂを得た。
[Synthesis of oil-modified phenolic resin (varnish b)]
1600 g of phenol and 1300 g of tung oil were reacted in the presence of paratoluenesulfonic acid at 95 ° C. for 2 hours, then 650 g of paraformaldehyde, 30 g of hexamethylenetetramine and 2000 g of toluene were added, reacted at 90 ° C. for 2 hours, and concentrated under reduced pressure. This was diluted with a mixed solvent of toluene and methanol to obtain an oil-modified phenol resin varnish b having a resin content of 50%.
《実施例１》
ワニスａ２０重量部とワニスｂ８０重量部を配合したワニスを、再生セルロース連続長繊維不織布であるベンリーゼ（登録商標）（ＳＤ３０Ｇ：目付３０．０ｇ／ｍ２、厚み０．２８ｍｍ：旭化成せんい株式会社製）に塗布、含浸し、１５０℃の温度で乾燥して樹脂付着量５０重量％のプリプレグを得た。このプリプレグ１０枚を重ね合わせ、１６０℃、８０ｋｇ／ｃｍ２で６０分間加熱加圧成形して板厚０．８ｍｍの積層板Ａを得た。
Example 1
A varnish blended with 20 parts by weight of varnish a and 80 parts by weight of varnish b, Benlyse (registered trademark) which is a regenerated cellulose continuous long-fiber nonwoven fabric (SD30G: basis weight 30.0 g / m 2 , thickness 0.28 mm: manufactured by Asahi Kasei Fibers) And impregnated and dried at a temperature of 150 ° C. to obtain a prepreg having a resin adhesion amount of 50% by weight. Ten prepregs were stacked and heat-press molded at 160 ° C. and 80 kg / cm 2 for 60 minutes to obtain a laminate A having a plate thickness of 0.8 mm.
《実施例２》
ワニスａ２０重量部とワニスｂ８０重量部を配合したワニスを、再生セルロース連続長繊維不織布であるベンリーゼ（登録商標）（ＳＥ３８４：目付３８．０ｇ／ｍ２、厚み０．３０ｍｍ：旭化成せんい株式会社製）に塗布、含浸し、１５０℃の温度で乾燥して樹脂付着量５０重量％のプリプレグを得た。このプリプレグ８枚を重ね合わせ、１６０℃、８０ｋｇ／ｃｍ２で６０分間加熱加圧成形して板厚０．８ｍｍの積層板Ｂを得た。
Example 2
A varnish blended with 20 parts by weight of varnish a and 80 parts by weight of varnish b is Benlyse (registered trademark) (SE384: basis weight 38.0 g / m 2 , thickness 0.30 mm: manufactured by Asahi Kasei Corporation). And impregnated and dried at a temperature of 150 ° C. to obtain a prepreg having a resin adhesion amount of 50% by weight. Eight of these prepregs were stacked and heat-press molded at 160 ° C. and 80 kg / cm 2 for 60 minutes to obtain a laminate B having a plate thickness of 0.8 mm.
《実施例３》
ワニスａ２０重量部とワニスｂ８０重量部を配合したワニスを、再生セルロース連続長繊維織布であるベンベルグ（登録商標）（ＡＫ４９３０：８１．０ｇ／ｍ２：旭化成せんい株式会社製）に塗布、含浸し、１５０℃の温度で乾燥して樹脂付着量５０重量％のプリプレグを得た。このプリプレグ４枚を重ね合わせ、１６０℃、８０ｋｇ／ｃｍ２で６０分間加熱加圧成形して板厚０．８ｍｍの積層板Ｃを得た。
Example 3
A varnish blended with 20 parts by weight of varnish a and 80 parts by weight of varnish b was applied to and impregnated onto a bermberg (registered trademark) (AK4930: 81.0 g / m 2 : Asahi Kasei Fibers Co., Ltd.), a continuous cellulose continuous fiber woven fabric. And dried at a temperature of 150 ° C. to obtain a prepreg having a resin adhesion amount of 50% by weight. The four prepregs were superposed and heated and pressed at 160 ° C. and 80 kg / cm 2 for 60 minutes to obtain a laminate C having a plate thickness of 0.8 mm.
《比較例１》
ワニスａ２０重量部とワニスｂ８０重量部を配合したワニスを、クラフト紙（３８．０ｇ／ｍ２）に塗布、含浸し、１５０℃の温度で乾燥して樹脂付着量５０重量％のプリプレグを得た。このプリプレグ８枚を重ね合わせ、１６０℃、８０ｋｇ／ｃｍ２で６０分間加熱加圧成形して板厚０．８ｍｍの積層板Ｄを得た。
<< Comparative Example 1 >>
Varnish containing 20 parts by weight of varnish a and 80 parts by weight of varnish b was applied and impregnated on kraft paper (38.0 g / m 2 ) and dried at a temperature of 150 ° C. to obtain a prepreg having a resin adhesion amount of 50% by weight. . Eight of these prepregs were superposed and heated and pressed at 160 ° C. and 80 kg / cm 2 for 60 minutes to obtain a laminate D having a thickness of 0.8 mm.
《比較例２》
ワニスａ２０重量部とワニスｂ８０重量部を配合したワニスを、ガラス織布（３８．０ｇ／ｍ２）に塗布、含浸し、１５０℃の温度で乾燥して樹脂付着量５０重量％のプリプレグを得た。このプリプレグ８枚を重ね合わせ、１６０℃、８０ｋｇ／ｃｍ２で６０分間加熱加圧成形して板厚０．８ｍｍの積層板Ｅを得た。
<< Comparative Example 2 >>
Varnish blended with 20 parts by weight of varnish a and 80 parts by weight of varnish b was applied to a glass woven fabric (38.0 g / m 2 ), impregnated, and dried at a temperature of 150 ° C. to obtain a prepreg having a resin adhesion amount of 50% by weight. It was. Eight of these prepregs were superposed and heat-press molded at 160 ° C. and 80 kg / cm 2 for 60 minutes to obtain a laminate E having a plate thickness of 0.8 mm.
《実施例４》
ビスフェノールＡ型エポキシ樹脂（エポキシ当量４８０ｇ／ｅｑ）１００重量部に、ジシアンジアミド重量２部、２−エチル−４−メチルイミダゾール０．２重量部、ジメチルホルムアミド２０重量部およびアセトン４０重量部を加えて攪拌し、エポキシ樹脂ワニスを調製した。次に、再生セルロース連続長繊維不織布であるベンリーゼ（登録商標）（ＳＤ３０Ｇ：目付３０．０ｇ／ｍ２、厚み０．２８ｍｍ：旭化成せんい株式会社製）に、調製したエポキシ樹脂ワニスを塗布、含浸し、１６０℃の温度で乾燥して樹脂付着量５０重量％のプリプレグを得た。このプリプレグ１０枚を重ね合わせ、１７０℃、４０ｋｇ／ｃｍ２で９０分間加熱加圧成形して板厚０．８ｍｍの積層板Ｆを得た。
Example 4
To 100 parts by weight of a bisphenol A type epoxy resin (epoxy equivalent 480 g / eq), add 2 parts by weight of dicyandiamide, 0.2 part by weight of 2-ethyl-4-methylimidazole, 20 parts by weight of dimethylformamide and 40 parts by weight of acetone and stir. An epoxy resin varnish was prepared. Next, the prepared epoxy resin varnish is applied and impregnated onto Benlyse (registered trademark) (SD30G: basis weight 30.0 g / m 2 , thickness 0.28 mm: manufactured by Asahi Kasei Fibers Co., Ltd.), which is a regenerated cellulose continuous long-fiber nonwoven fabric. And dried at a temperature of 160 ° C. to obtain a prepreg having a resin adhesion amount of 50% by weight. Ten prepregs were stacked and heat-press molded at 170 ° C. and 40 kg / cm 2 for 90 minutes to obtain a laminate F having a plate thickness of 0.8 mm.
《実施例５》
実施例１で調製したエポキシ樹脂ワニスを、再生セルロース連続長繊維不織布であるベンリーゼ（登録商標）（ＳＥ３８４：目付３８．０ｇ／ｍ２、厚み０．３０ｍｍ：旭化成せんい株式会社製）に塗布、含浸し、１６０℃の温度で乾燥して樹脂付着量５０重量％のプリプレグを得た。このプリプレグ８枚を重ね合わせ、１７０℃、４０ｋｇ／ｃｍ２で９０分間加熱加圧成形して板厚０．８ｍｍの積層板Ｇを得た。
Example 5
The epoxy resin varnish prepared in Example 1 was applied and impregnated onto Benlyse (registered trademark) (SE384: basis weight 38.0 g / m 2 , thickness 0.30 mm: manufactured by Asahi Kasei Fibers Co., Ltd.), which is a regenerated cellulose continuous long-fiber nonwoven fabric. And dried at a temperature of 160 ° C. to obtain a prepreg having a resin adhesion amount of 50% by weight. Eight of these prepregs were superposed and heated and pressed at 170 ° C. and 40 kg / cm 2 for 90 minutes to obtain a laminate G having a thickness of 0.8 mm.
《実施例６》
実施例１で調製したエポキシ樹脂ワニスを、再生セルロース連続長繊維織布であるベンベルグ（登録商標）（ＡＫ４９３０：８１．０ｇ／ｍ２：旭化成せんい株式会社製）に塗布、含浸し、１６０℃の温度で乾燥して樹脂付着量５０重量％のプリプレグを得た。このプリプレグ４枚を重ね合わせ、１７０℃、４０ｋｇ／ｃｍ２で９０分間加熱加圧成形して板厚０．８ｍｍの積層板Ｈを得た。
Example 6
The epoxy resin varnish prepared in Example 1 was applied and impregnated onto a regenerated cellulose continuous long fiber woven fabric, Bemberg (registered trademark) (AK4930: 81.0 g / m 2 : manufactured by Asahi Kasei Fibers Co., Ltd.). Drying at a temperature yielded a prepreg with a resin adhesion of 50% by weight. The four prepregs were superposed and heated and pressed at 170 ° C. and 40 kg / cm 2 for 90 minutes to obtain a laminate H having a plate thickness of 0.8 mm.
《比較例３》
実施例１で調製したエポキシ樹脂ワニスを、リンター紙（８１．０ｇ／ｍ２）に塗布、含浸し、１６０℃の温度で乾燥して樹脂付着量５０重量％のプリプレグを得た。このプリプレグ４枚を重ね合わせ、１７０℃、４０ｋｇ／ｃｍ２で９０分間加熱加圧成形して板厚０．８ｍｍの積層板Ｉを得た。
<< Comparative Example 3 >>
The epoxy resin varnish prepared in Example 1 was applied and impregnated on linter paper (81.0 g / m 2 ), and dried at a temperature of 160 ° C. to obtain a prepreg having a resin adhesion amount of 50% by weight. The four prepregs were stacked and heat-press molded at 170 ° C. and 40 kg / cm 2 for 90 minutes to obtain a laminate I having a thickness of 0.8 mm.
《比較例４》
実施例１で調製したエポキシ樹脂ワニスを、ガラス織布（８１．０ｇ／ｍ２）に塗布、含浸し、１６０℃の温度で乾燥して樹脂付着量５０重量％のプリプレグを得た。このプリプレグ４枚を重ね合わせ、１６０℃、８０ｋｇ／ｃｍ２で６０分間加熱加圧成形して板厚０．８ｍｍの積層板Ｊを得た。
<< Comparative Example 4 >>
The epoxy resin varnish prepared in Example 1 was coated and impregnated on a glass woven fabric (81.0 g / m 2 ), and dried at a temperature of 160 ° C. to obtain a prepreg having a resin adhesion amount of 50% by weight. The four prepregs were superposed and heated and pressed at 160 ° C. and 80 kg / cm 2 for 60 minutes to obtain a laminate J having a plate thickness of 0.8 mm.
積層板の評価：
打抜き加工性を、 ＡＳＴＭ Ｄ６１７−４４により評価した。その結果を表１に示す。
Laminate evaluation:
Punching workability was evaluated according to ASTM D617-44. The results are shown in Table 1.
Claims (5)
前記基材が、再生セルロース連続長繊維を７０重量％以上含む不織布又は織布であることを特徴とするプリプレグ。 A prepreg obtained by impregnating a base material with a thermosetting resin composition,
The prepreg is characterized in that the substrate is a nonwoven fabric or a woven fabric containing 70% by weight or more of regenerated cellulose continuous long fibers.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015053226A1 (en) * | 2013-10-07 | 2015-04-16 | 日東紡績株式会社 | Long cellulose fibers having high strength and high elasticity |
| WO2015194271A1 (en) * | 2014-06-18 | 2015-12-23 | ダイセルポリマー株式会社 | Fiber-reinforced resin composition |
| CN112157927A (en) * | 2020-09-08 | 2021-01-01 | 江苏澳盛复合材料科技有限公司 | Forming process of thermosetting material in LDS process and product thereof |
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| JPH0452967A (en) * | 1990-06-20 | 1992-02-20 | Nec Corp | And operation processing system for set file |
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| JPH0452967A (en) * | 1990-06-20 | 1992-02-20 | Nec Corp | And operation processing system for set file |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015053226A1 (en) * | 2013-10-07 | 2015-04-16 | 日東紡績株式会社 | Long cellulose fibers having high strength and high elasticity |
| JPWO2015053226A1 (en) * | 2013-10-07 | 2017-03-09 | 日東紡績株式会社 | High strength and high elastic cellulose filament |
| WO2015194271A1 (en) * | 2014-06-18 | 2015-12-23 | ダイセルポリマー株式会社 | Fiber-reinforced resin composition |
| JP2016020465A (en) * | 2014-06-18 | 2016-02-04 | ダイセルポリマー株式会社 | Fiber reinforced resin composition |
| CN106459439A (en) * | 2014-06-18 | 2017-02-22 | 大赛璐塑料株式会社 | Fiber-reinforced resin composition |
| US11338475B2 (en) | 2014-06-18 | 2022-05-24 | Daicel Polymer Ltd. | Fiber-reinforced resin composition |
| CN112157927A (en) * | 2020-09-08 | 2021-01-01 | 江苏澳盛复合材料科技有限公司 | Forming process of thermosetting material in LDS process and product thereof |
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