JP7455466B2 - Base material for molding fiber-reinforced resin composites and fiber-reinforced resin composites - Google Patents
Base material for molding fiber-reinforced resin composites and fiber-reinforced resin composites Download PDFInfo
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本発明は、アラミド繊維からなる布帛と半硬化状態の熱硬化性樹脂とからなる繊維強化樹脂複合体成形用基材、およびそれを成形してなる繊維強化樹脂複合体に関する。 The present invention relates to a base material for molding a fiber-reinforced resin composite made of a fabric made of aramid fibers and a semi-cured thermosetting resin, and a fiber-reinforced resin composite formed by molding the same.
強化繊維からなる布帛と熱硬化性樹脂とからなる繊維強化樹脂複合体は、軽量で優れた機械特性を有することから、航空機材、車両部品、電子部品、家電製品の各種ハウジング等幅広い分野に使用され、軽量、かつ高剛性、高強度、耐摩耗性等の特性が要求される分野において有効に用いられている。 Fiber-reinforced resin composites made of reinforced fiber fabric and thermosetting resin are lightweight and have excellent mechanical properties, so they are used in a wide range of fields such as aircraft materials, vehicle parts, electronic parts, and various housings for home appliances. It is effectively used in fields that require properties such as light weight, high rigidity, high strength, and wear resistance.
繊維強化樹脂複合体は、例えば、炭素繊維、アラミド繊維、ガラス繊維等の強化繊維からなる布帛に熱硬化性樹脂を含浸させ、半硬化状態としたシート状等の基材（プリプレグ）を用いて製造されている。また、繊維強化樹脂複合体を得る方法の多くは、その取扱い性および賦形性から、半硬化状態としたシート状の基材（プリプレグ）を複数積層しオートクレーブ等で加熱加圧することにより硬化させる方法である。 Fiber-reinforced resin composites are made by using a sheet-like base material (prepreg) made by impregnating a fabric made of reinforcing fibers such as carbon fibers, aramid fibers, and glass fibers with a thermosetting resin and semi-curing the material. Manufactured. In addition, in many ways to obtain fiber-reinforced resin composites, from the viewpoint of ease of handling and shaping, multiple semi-cured sheet-like base materials (prepreg) are laminated and cured by heating and pressurizing them in an autoclave, etc. It's a method.
その一方で、使用する繊維強化樹脂複合体成形用基材では、該基材を構成する強化繊維からなる布帛に発生する布目曲がりが製品の品質に影響を及ぼす問題がある（特許文献１、特許文献２）。特に、有機繊維（例えばアラミド繊維）からなる布帛は、無機繊維からなる布帛と比べ、繊維の剛直性が低い（柔軟性が高い）ために、布目曲がりの影響をより受けやすく、複数積層する際に基材の向きを考慮して積層する必要があり、製造時の管理が煩雑になるという問題がある。 On the other hand, the fiber-reinforced resin composite molding base material used has a problem in that the bending of the fabric that occurs in the fabric made of reinforcing fibers that constitute the base material affects the quality of the product (Patent Document 1, Patent Document 1, Reference 2). In particular, fabrics made of organic fibers (e.g. aramid fibers) have lower fiber rigidity (higher flexibility) than fabrics made of inorganic fibers, so they are more susceptible to fabric bending, and when multiple layers are laminated. There is a problem in that it is necessary to take the orientation of the base materials into consideration when laminating the layers, making management during manufacturing complicated.
本発明は、上記事情に鑑みてなされたものであり、製造時の管理が簡便で、安定した品質を得ることが可能な繊維強化樹脂複合体成形用基材を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a base material for molding a fiber-reinforced resin composite, which is easy to manage during production and allows stable quality to be obtained.
本発明者等は上記目的を達成すべく誠意検討した結果、特定の繊維強化樹脂複合体成形用基材を用いることで、ランダムに積層・成形した製品の品質ばらつきを小さく抑えることができることを見出し、本発明に至った。 As a result of a sincere study to achieve the above objective, the present inventors discovered that by using a specific fiber-reinforced resin composite molding base material, it is possible to suppress the quality variation of randomly laminated and molded products to a small level. , led to the present invention.
すなわち、本発明は、アラミド長繊維からなる、タテ糸密度（本／インチ）とヨコ糸密度（本／インチ）が同一、かつ、８～３０本／インチである二方向性織物と、半硬化状態の熱硬化性樹脂とからなり、次の（１）と（２）の両方を満たすことを特徴とする繊維強化樹脂複合体成形用基材を提供する。
（１）繊維強化樹脂複合体成形用基材の、ＪＩＳ Ｌ１０９６ ８．１２に準じて測定した布目曲がり率が５％以下
（２）繊維強化樹脂複合体成形用基材を用いて成形した繊維強化樹脂複合体の、ＪＩＳ
Ｋ７０１７に準じて３点曲げ装置で１０回測定した曲げ強度から算出される変動係数が、０．０５以下
That is, the present invention is directed to a bidirectional fabric made of aramid long fibers having the same warp thread density (threads/inch) and weft thread density (threads/inch) of 8 to 30 threads/inch , and a semi-cured fabric. Provided is a base material for molding a fiber-reinforced resin composite, characterized in that it is made of a thermosetting resin and satisfies both the following (1) and (2).
(1) The fiber-reinforced resin composite molding base material has a grain curvature of 5% or less as measured in accordance with JIS L1096 8.12. (2) Fiber reinforcement molded using the fiber-reinforced resin composite molding base material JIS for resin composites
The coefficient of variation calculated from the bending strength measured 10 times with a 3-point bending device according to K7017 is 0.05 or less
本発明の繊維強化樹脂複合体成形用基材においては、前記アラミド繊維からなる布帛が長繊維からなる一方向性織物または二方向性織物であることが好ましく、二方向性織物である場合は、該織物を構成するタテ糸密度とヨコ糸密度が同一であることがより好ましい。また前記アラミド繊維がポリパラフェニレンテレフタルアミド繊維であることがより好ましい。 In the base material for molding a fiber-reinforced resin composite of the present invention, it is preferable that the fabric made of aramid fibers is a unidirectional fabric or bidirectional fabric made of long fibers, and when it is a bidirectional fabric, It is more preferable that the warp yarn density and the weft yarn density constituting the woven fabric are the same. Moreover, it is more preferable that the aramid fiber is a polyparaphenylene terephthalamide fiber.
また、本発明は、前記の繊維強化樹脂複合体成形用基材を成形してなる繊維強化樹脂複合体を提供する。 The present invention also provides a fiber-reinforced resin composite formed by molding the above-described base material for molding a fiber-reinforced resin composite.
本発明によれば、製造時の管理が簡便であり、安定した品質を得ることが可能な繊維強化樹脂複合体成形用基材を提供することができる。 According to the present invention, it is possible to provide a base material for molding a fiber-reinforced resin composite, which is easy to manage during production and allows stable quality to be obtained.
本発明に係る繊維強化樹脂複合体成形用基材は、アラミド繊維からなる布帛と半硬化状態の熱硬化性樹脂とからなり、次の（１）と（２）の両方を満たすことを特徴とするものである。
（１）前記繊維強化樹脂複合体成形用基材の、ＪＩＳ Ｌ１０９６ ８．１２に準じて測定した布目曲がり率が５％以下
（２）前記繊維強化樹脂複合体成形用基材を用いて成形した繊維強化樹脂複合体の、ＪＩＳ Ｋ７０１７に準じて３点曲げ装置で１０回測定した曲げ強度から算出される変動係数が、０．０５以下
The fiber-reinforced resin composite molding base material according to the present invention is made of a fabric made of aramid fibers and a semi-cured thermosetting resin, and is characterized by satisfying both of the following (1) and (2). It is something to do.
(1) The fiber-reinforced resin composite molding base material has a grain curvature of 5% or less as measured in accordance with JIS L1096 8.12. (2) Molding using the fiber-reinforced resin composite molding base material The coefficient of variation calculated from the bending strength of the fiber-reinforced resin composite measured 10 times with a three-point bending device in accordance with JIS K7017 is 0.05 or less.
本発明に用いられるアラミド繊維とは、繊維を形成するポリマーの繰り返し単位中に、通常置換されていても良い二価の芳香族基を少なくとも一個有する繊維であって、アミド結合を少なくとも一個有する繊維であれば特に限定はなく、全芳香族ポリアミド繊維、又はアラミド繊維と称されるものであって良い。「置換されていても良い二価の芳香族基」とは、同一又は異なる１以上の置換基を有していても良い二価の芳香族基を意味する。 The aramid fiber used in the present invention is a fiber that has at least one divalent aromatic group that may be substituted in the repeating unit of the polymer forming the fiber, and has at least one amide bond. There is no particular limitation as long as it is, and it may be what is called a wholly aromatic polyamide fiber or an aramid fiber. "Optionally substituted divalent aromatic group" means a divalent aromatic group which may have one or more substituents that are the same or different.
アラミド繊維としては、パラ系アラミド繊維、メタ系アラミド繊維等を挙げることができるが、引張強さに優れているパラ系アラミド繊維が好ましい。このようなアラミド繊維は市販品として入手でき、その具体例としては、パラ系アラミド繊維として、例えば、ポリパラフェニレンテレフタルアミド繊維（米国デュポン社、東レ・デュポン（株）製、商品名「Ｋｅｖｌａｒ」（登録商標））、コポリパラフェニレン－３，４´－オキシジフェニレンテレフタルアミド繊維（帝人（株）製、商品名「テクノーラ」（登録商標））等を挙げることができる。これらのパラ系アラミド繊維の中でも、ポリパラフェニレンテレフタルアミド繊維が特に好ましい。 Examples of the aramid fibers include para-aramid fibers and meta-aramid fibers, but para-aramid fibers are preferred because of their excellent tensile strength. Such aramid fibers are available as commercial products, and specific examples include polyparaphenylene terephthalamide fibers (manufactured by DuPont, DuPont-Toray, Inc., trade name "Kevlar") as para-aramid fibers. (registered trademark)), copolyparaphenylene-3,4'-oxydiphenylene terephthalamide fiber (manufactured by Teijin Ltd., trade name "Technora" (registered trademark)), and the like. Among these para-aramid fibers, polyparaphenylene terephthalamide fibers are particularly preferred.
アラミド繊維の繊度（総繊度）は特に限定されないが、通常、５０～１０，０００ｄｔｅｘ、好ましくは２００～６，５００ｄｔｅｘ、より好ましくは７５０～３，５００ｄｔｅｘのものが用いられる。繊度の小さいパラ系アラミド繊維を用いると比較的薄い布帛が得られやすくなり、繊度の大きいパラ系アラミド繊維を用いると比較的厚い布帛が得られやすくなる。 The fineness (total fineness) of the aramid fibers is not particularly limited, but is usually 50 to 10,000 dtex, preferably 200 to 6,500 dtex, more preferably 750 to 3,500 dtex. When para-aramid fibers with a small fineness are used, relatively thin fabrics can be easily obtained, and when para-aramid fibers with a large fineness are used, relatively thick fabrics can be easily obtained.
繊維強化樹脂複合体成形用基材に用いられる布帛としては、織物、編物、フェルト、紙、不織布等を用いることができ、短繊維または長繊維を公知の方法で加工したものを用いることができる。布帛の厚さは特に限定されないが、積層成形体の軽量化、低コスト化および性能向上を図る観点からの好ましい厚さは０．０５ｍｍ～１ｍｍである。 As the fabric used for the base material for molding the fiber-reinforced resin composite, woven fabrics, knitted fabrics, felt, paper, non-woven fabrics, etc. can be used, and short fibers or long fibers processed by known methods can be used. . The thickness of the fabric is not particularly limited, but from the viewpoint of reducing the weight, cost, and performance of the laminated molded product, the preferred thickness is 0.05 mm to 1 mm.
織物としては、例えば、アラミド繊維束を一方向に配列させたトウシートや、アラミド繊維糸条を一方向または二方向に配列させた一方向性織物や二方向性織物、三方向に配列させた三軸織物等が挙げられる。編物としては、例えば、丸編機等のよこ編機、トリコット編機、ラッセル編機、ミラニーズ編機等のたて編機で製編したものが挙げられる。軽量性と耐衝撃性を両立させる観点からは、一方向性織物または二方向性織物が好ましい。織物密度（タテ糸およびヨコ糸密度）は、８～４０本／インチが好ましく、８～３０本／インチが好ましく、タテ糸密度とヨコ糸密度は同じであることが、品質ばらつきの点においてより好ましい。 Examples of woven fabrics include tow sheets in which aramid fiber bundles are arranged in one direction, unidirectional fabrics and bidirectional fabrics in which aramid fiber threads are arranged in one or two directions, and three-dimensional fabrics in which aramid fiber threads are arranged in three directions. Examples include shaft fabrics. Examples of knitted fabrics include those knitted using a weft knitting machine such as a circular knitting machine, a warp knitting machine such as a tricot knitting machine, a Russell knitting machine, a Milanese knitting machine, etc. From the viewpoint of achieving both lightness and impact resistance, unidirectional fabrics or bidirectional fabrics are preferred. The fabric density (warp yarn density and weft yarn density) is preferably 8 to 40 threads/inch, preferably 8 to 30 threads/inch, and it is better in terms of quality variation that the warp thread density and weft thread density are the same. preferable.
引張強度の高い布帛を得るという点では、短繊維よりも長繊維（フィラメント糸）を用いた布帛が望ましく、かかる長繊維フィラメント糸にタスラン加工やインターレース加工等を施したエアー交絡糸；加撚－熱固定－解撚糸（捲縮糸）；仮撚加工糸；押込加工糸等も用いることができる。 In terms of obtaining fabrics with high tensile strength, fabrics using long fibers (filament yarns) are more desirable than short fibers, and air-entangled yarns in which such long fiber filament yarns are subjected to taslan processing, interlace processing, etc.; Heat-set-untwisted yarn (crimped yarn); false twisted yarn; pressed yarn, etc. can also be used.
布帛の目付（単位面積当りの質量）は、２０～１，０００ｇ／ｍ２が好ましく、より好ましくは５０～６００ｇ／ｍ２の範囲内である。布帛の目付が小さすぎると任意の製品厚みを得るための積層数が多くなり作業性が悪化し、目付が大きすぎると樹脂の種類によっては樹脂との接着性に劣ることがあり、アラミド繊維がフィブリル化して成形後の外観を損ない、成形体の重量化に繋がったりする。 The basis weight (mass per unit area) of the fabric is preferably from 20 to 1,000 g/m 2 , more preferably from 50 to 600 g/m 2 . If the fabric weight is too small, the number of layers required to obtain the desired product thickness will increase, resulting in poor workability.If the fabric weight is too large, depending on the type of resin, the adhesion to the resin may be poor, and aramid fibers may It becomes fibrillated, impairs the appearance after molding, and leads to an increase in the weight of the molded product.
布帛の布目曲がり率（％）は、ＪＩＳ Ｌ１０９６ ８．１２に従って測定した値が３％以下であることが、繊維強化樹脂複合体成形用基材の布目曲がり率を小さくする点において好ましく、２％以下であることがより好ましい。 The grain curvature ratio (%) of the fabric is preferably 3% or less as measured in accordance with JIS L1096 8.12 in order to reduce the grain curvature ratio of the base material for molding a fiber-reinforced resin composite, and 2% or less. It is more preferable that it is below.
本発明で用いられる、半硬化状態の熱硬化性樹脂としては、特に限定されず、例えば、エポキシ系樹脂、シアネート系樹脂、ビスマレイミド系樹脂、ベンゾオキサジン系樹脂等が挙げられるが、耐熱性、力学特性およびアラミド繊維との接着性のバランスに優れていることから、エポキシ系樹脂を用いることが好ましい。 The semi-cured thermosetting resin used in the present invention is not particularly limited and includes, for example, epoxy resins, cyanate resins, bismaleimide resins, benzoxazine resins, etc. It is preferable to use an epoxy resin because it has an excellent balance of mechanical properties and adhesiveness with aramid fibers.
エポキシ系樹脂としては、特に限定されるものではなく、ビスフェノール型エポキシ樹脂、アミン型エポキシ樹脂、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、レゾルシノール型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ビフェニル骨格を有するエポキシ樹脂、イソシアネート変性エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、ジグリシジルアニリン誘導体等の中から１種以上を選択して用いることができる。 Epoxy resins are not particularly limited, and include bisphenol type epoxy resins, amine type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, resorcinol type epoxy resins, phenol aralkyl type epoxy resins, and naphthol aralkyl type epoxy resins. Select one or more from epoxy resins, dicyclopentadiene type epoxy resins, epoxy resins having a biphenyl skeleton, isocyanate-modified epoxy resins, tetraphenylethane type epoxy resins, triphenylmethane type epoxy resins, diglycidylaniline derivatives, etc. It can be used as
エポキシ系樹脂を繊維強化樹脂複合体成形用基材のマトリックス樹脂として用いる場合、エポキシ系樹脂の２５℃における粘度は５００Ｐａ・ｓ以上であることが好ましく、より好ましくは１０００Ｐａ・ｓ以上である。ここで、粘度とは、動的粘弾性測定装置（レオメーターＲＤＡ２：レオメトリックス社製、または、レオメーターＡＲＥＳ：ＴＡインスツルメント社製）を用い、直径４０ｍｍのパラレルプレートを用い、周波数０．５Ｈｚ、Ｇａｐ１ｍｍで測定を行った複素粘性率η＊のことを指す。２５℃における粘度をかかる範囲にすることで繊維強化樹脂複合体成形用基材とした際に室温で樹脂が流動しにくくなり、強化繊維含有量のばらつきが抑制できることに加え、成形時の取り扱いに適切なタック性を有する繊維強化樹脂複合体成形用基材が得られる。 When an epoxy resin is used as a matrix resin for a substrate for molding a fiber-reinforced resin composite, the viscosity of the epoxy resin at 25° C. is preferably 500 Pa·s or more, more preferably 1000 Pa·s or more. Here, viscosity is measured using a dynamic viscoelasticity measuring device (rheometer RDA2: manufactured by Rheometrics, or rheometer ARES: manufactured by TA Instruments) using a parallel plate with a diameter of 40 mm, and using a frequency of 0. It refers to the complex viscosity η* measured at 5 Hz and a gap of 1 mm. By setting the viscosity at 25°C within this range, the resin becomes difficult to flow at room temperature when used as a base material for molding a fiber-reinforced resin composite, and in addition to suppressing variations in reinforcing fiber content, it also becomes easier to handle during molding. A fiber-reinforced resin composite molding base material having appropriate tackiness is obtained.
本発明のエポキシ系樹脂を繊維強化樹脂複合体成形用基材のマトリックス樹脂として用いる場合、繊維強化樹脂複合体成形用基材のタックやドレープの観点から、エポキシ系樹脂の８０℃における初期粘度は０．５～２００Ｐａ・ｓの範囲にあることが好ましい。８０℃における初期粘度が０．５Ｐａ・ｓ以上であると繊維強化樹脂複合体の成形時に過剰な樹脂フローが生じにくくなり、強化繊維含有量のばらつきを抑制できる。一方、８０℃における初期粘度が２００Ｐａ・ｓ以下であると、繊維強化樹脂複合体成形用基材を製造する際に強化繊維にエポキシ系樹脂を充分に含浸でき、得られた繊維強化樹脂複合体にボイドが生じにくくなるため、繊維強化樹脂複合体の強度低下を抑制できる。エポキシ系樹脂の８０℃における初期粘度は、繊維強化樹脂複合体成形用基材製造工程において、強化繊維にエポキシ系樹脂が含浸しやすく、高い繊維質量含有率の繊維強化樹脂複合体を製造するために１～１５０Ｐａ・ｓの範囲にあることがより好ましく、５～１００Ｐａ・ｓの範囲にあることがさらに好ましい。 When the epoxy resin of the present invention is used as a matrix resin for a base material for molding a fiber-reinforced resin composite, the initial viscosity of the epoxy resin at 80°C is It is preferably in the range of 0.5 to 200 Pa·s. When the initial viscosity at 80° C. is 0.5 Pa·s or more, excessive resin flow is less likely to occur during molding of the fiber-reinforced resin composite, and variations in the reinforcing fiber content can be suppressed. On the other hand, when the initial viscosity at 80° C. is 200 Pa·s or less, the reinforcing fibers can be sufficiently impregnated with the epoxy resin when producing the base material for molding the fiber-reinforced resin composite, and the obtained fiber-reinforced resin composite Since voids are less likely to occur in the fiber-reinforced resin composite, deterioration in strength of the fiber-reinforced resin composite can be suppressed. The initial viscosity of the epoxy resin at 80°C is determined by the fact that the reinforcing fibers are easily impregnated with the epoxy resin during the manufacturing process of the base material for forming the fiber-reinforced resin composite, and the fiber-reinforced resin composite with a high fiber mass content can be manufactured. It is more preferably in the range of 1 to 150 Pa·s, and even more preferably in the range of 5 to 100 Pa·s.
本発明の繊維強化樹脂複合体成形用基材は、アラミド繊維からなる布帛に半硬化状態の熱硬化性樹脂を含浸してなるものであり、その含浸させる手段は特に限定されるものではなく、公知の製造方法を用いて製造することができる。例えば、半硬化状態の熱硬化性樹脂組成物をメチルエチルケトン、メタノール等の溶媒に溶解して低粘度化し、繊維強化樹脂複合体成形用基材に含浸させるウェット法、および、半硬化状態の熱硬化性樹脂組成物を加熱により低粘度化し、含浸させるホットメルト法（ドライ法）等を挙げることができる。ウェット法は、強化繊維からなる布帛を熱硬化性樹脂組成物の溶液に浸漬した後、引き上げ、オーブン等を用いて溶媒を蒸発させる方法である。ホットメルト法は、加熱により低粘度化した熱硬化性樹脂組成物を直接、強化繊維からなる布帛に含浸させる方法であり、半硬化状態の熱硬化性樹脂組成物を加熱加圧することにより、強化繊維からなる布帛に樹脂を含浸させる方法である。ホットメルト法によれば、プリプレグ中に残留する溶媒が実質上皆無となるため好ましい。
なお、半硬化状態の熱硬化性樹脂組成物には、必要に応じて、例えば、カップリング剤、硬化促進剤、硬化剤、充填材等の公知の添加剤を配合したものを用いることができる。
The fiber-reinforced resin composite molding base material of the present invention is made by impregnating a fabric made of aramid fibers with a semi-cured thermosetting resin, and the means for impregnating the fabric is not particularly limited. It can be manufactured using a known manufacturing method. For example, a wet method in which a thermosetting resin composition in a semi-cured state is dissolved in a solvent such as methyl ethyl ketone or methanol to lower the viscosity and impregnated into a base material for molding a fiber-reinforced resin composite, and a thermosetting method in a semi-cured state. Examples include a hot-melt method (dry method) in which the viscosity of a viscous resin composition is reduced by heating and impregnation is carried out. The wet method is a method in which a fabric made of reinforcing fibers is immersed in a solution of a thermosetting resin composition, then pulled up, and the solvent is evaporated using an oven or the like. The hot melt method is a method in which a fabric made of reinforcing fibers is directly impregnated with a thermosetting resin composition whose viscosity has been reduced by heating. This method involves impregnating a fabric made of fibers with resin. The hot melt method is preferable because substantially no solvent remains in the prepreg.
In addition, the thermosetting resin composition in a semi-cured state may contain known additives such as a coupling agent, a curing accelerator, a curing agent, a filler, etc., if necessary. .
本発明の繊維強化樹脂複合体成形用基材におけるアラミド繊維の占める割合（Ｖｆ）は、前記基材全体を１００とした場合で１０～９０体積％、好ましくは２０～８０体積％、より好ましくは３０～７０体積％である。前記基材全体に占める割合が、１０体積％未満であると製品中にボイド（空隙）が生じ製品特性が悪化する恐れがあり、９０体積％を超えると繊維による補強効果が十分に得られない恐れがある。 The ratio (Vf) of aramid fibers in the substrate for molding the fiber-reinforced resin composite of the present invention is 10 to 90% by volume, preferably 20 to 80% by volume, more preferably It is 30 to 70% by volume. If the proportion of the fiber in the entire base material is less than 10% by volume, voids may occur in the product and the product properties may deteriorate; if it exceeds 90% by volume, the reinforcing effect of the fibers may not be sufficient. There is a fear.
本発明の繊維強化樹脂複合体成形用基材の布目曲がり率は、ＪＩＳ Ｌ１０９６に記載の方法で測定した布目曲がり率が５％以下であることが重要であり、より好ましくは３％以下、さらに好ましくは２％以下である。布目曲がり率がこの範囲にあると、ランダムに積層した場合であっても成形後の品質ばらつきを抑えることができるため、工程・品質管理上有用である。 It is important that the fiber-reinforced resin composite molding base material of the present invention has a grain curvature of 5% or less, more preferably 3% or less, as measured by the method described in JIS L1096. Preferably it is 2% or less. When the grain curvature is within this range, it is possible to suppress variations in quality after molding even when laminated at random, which is useful in terms of process and quality control.
本発明の繊維強化樹脂複合体成形用基材を用いて繊維強化樹脂複合体を成形する場合、繊維強化樹脂複合体成形用基材は１枚、または複数枚が積層される。例えば、繊維強化樹脂複合体成形用基材が一定規則に従って積層されてもよいし、ランダムに配置されるように積層されてもよい。成形する方法に特に規定はなく、任意の成形方法（フィラメントワインディング、オートクレーブ、シートワインディング、プレス成形等）を採ることができる。 When molding a fiber-reinforced resin composite using the fiber-reinforced resin composite molding base material of the present invention, one or more fiber-reinforced resin composite molding base materials are laminated. For example, the fiber-reinforced resin composite molding substrates may be laminated according to a certain rule, or may be laminated so as to be randomly arranged. There are no particular restrictions on the molding method, and any molding method (filament winding, autoclave, sheet winding, press molding, etc.) can be used.
以下に実施例を挙げて本発明をさらに具体的に説明するが、本発明はそれらに限定されるものではない。また、以下の実施例等において、特に言及する場合を除き、「質量部」は「部」と略記する。なお、実施例中に記載の評価方法は以下の通りである。 The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto. In addition, in the following Examples and the like, "parts by mass" is abbreviated as "parts" unless otherwise specified. Note that the evaluation method described in the examples is as follows.
［基材の布目曲がり率］
得られた繊維強化樹脂複合体成形用基材について、ＪＩＳ Ｌ１０９６：２０１０ ８．１２に準じて測定を行った。測定は３ヵ所実施し、平均値を算出した。
[Grain curvature rate of base material]
The obtained fiber-reinforced resin composite molding substrate was measured in accordance with JIS L1096:2010 8.12. Measurements were performed at three locations, and the average value was calculated.
［繊維体積率（Ｖｆ）］
得られた繊維強化樹脂複合体成形用基材について、使用したアラミド繊維布帛の目付（ｇ／ｍ２）、単位面積当たりの重量、使用したアラミド繊維および熱硬化性樹脂の密度（ｇ／ｃｍ３）から、全体を１００とした場合の繊維の占める体積比率を求めた。
[Fiber volume fraction (Vf)]
Regarding the obtained fiber-reinforced resin composite molding base material, the basis weight (g/m 2 ) of the aramid fiber fabric used, the weight per unit area, and the density (g/cm 3 ) of the aramid fiber and thermosetting resin used. ), the volume ratio occupied by the fibers was determined when the whole was set as 100.
［曲げ強度・曲げ弾性率 変動係数］
得られた繊維強化樹脂複合体成形体について、２３℃、相対湿度５０％環境下で１週間静置した後、ＪＩＳ Ｋ７０１７に準じて、３点曲げ装置で曲げ強度および曲げ弾性率を１０サンプル分測定し、１０サンプルの物性値の変動係数（標準偏差／平均値）を算出した。
[Bending strength/flexural modulus variation coefficient]
The obtained fiber-reinforced resin composite molded product was allowed to stand for one week at 23°C and 50% relative humidity, and then the bending strength and bending modulus of 10 samples were measured using a three-point bending device in accordance with JIS K7017. The coefficient of variation (standard deviation/average value) of the physical property values of the 10 samples was calculated.
実験で使用したアラミド繊維布帛の詳細を表１に示す。 Details of the aramid fiber fabric used in the experiment are shown in Table 1.
（熱硬化性樹脂の調製）
三菱ケミカル社製ｊＥＲ８２８（ビスフェノールＡグリシジルエーテル；エポキシ当量１８９ｇ／ｅｑ）５０質量％および三菱ケミカル社製ｊＥＲ１００１（ビスフェノールＡグリシジルエーテル；エポキシ当量４７５ｇ／ｅｑ）５０質量％とからなる主剤１００部に対し、ジシアンジアミド５部、および３－（３、４－ジクロロフェニル）－１、１－ジメチル尿素５部を硬化剤として加えた後に均一に混合し、一液硬化エポキシ樹脂組成物を得た。得られた一液硬化エポキシ樹脂組成物の２５℃における粘度は６５，０００Ｐａ・ｓであり、８０℃における粘度は１８Ｐａ・ｓであった。
(Preparation of thermosetting resin)
For 100 parts of a main agent consisting of 50% by mass of jER828 (bisphenol A glycidyl ether; epoxy equivalent 189 g/eq) manufactured by Mitsubishi Chemical and 50% by mass of jER1001 (bisphenol A glycidyl ether; epoxy equivalent 475 g/eq) manufactured by Mitsubishi Chemical, 5 parts of dicyandiamide and 5 parts of 3-(3,4-dichlorophenyl)-1,1-dimethylurea were added as curing agents and mixed uniformly to obtain a one-component cured epoxy resin composition. The obtained one-component cured epoxy resin composition had a viscosity of 65,000 Pa·s at 25°C and a viscosity of 18 Pa·s at 80°C.
（実施例１～２、比較例１～２）
表１のアラミド繊維布帛に、事前に調製したエポキシ樹脂を、ホットメルト法（ドライ法）にて含浸させ、繊維強化樹脂複合体成形用基材を得た。各水準の繊維体積率はすべて５０体積％であった。得られた繊維強化樹脂複合体成形用基材を５枚、ランダムに積層しオートクレーブにて加圧・加熱（１３５℃×０．５ＭＰａ×２時間）を行い、繊維強化樹脂複合体を得た。各水準について、前記した測定方法で各種評価を行った結果を表２に示す。
(Examples 1-2, Comparative Examples 1-2)
The aramid fiber fabric shown in Table 1 was impregnated with an epoxy resin prepared in advance by a hot melt method (dry method) to obtain a base material for molding a fiber-reinforced resin composite. The fiber volume percentage at each level was all 50% by volume. Five sheets of the obtained fiber-reinforced resin composite molding substrates were randomly laminated and pressurized and heated in an autoclave (135°C x 0.5 MPa x 2 hours) to obtain a fiber-reinforced resin composite. Table 2 shows the results of various evaluations for each level using the measurement methods described above.
表２の結果から、比較例１および比較例２の繊維強化樹脂複合体成形用基材は、曲げ強度および曲げ弾性率の変動係数が大きく、繊維強化樹脂複合体の品質にばらつきが大きいことがわかる。一方、本発明の繊維強化樹脂複合体成形用基材（実施例１～２）は、曲げ強度および曲げ弾性率の変動係数が小さく、成形時にランダムに積層した場合にもばらつきの少ない、高品質な繊維強化樹脂複合体を得られることがわかる。 From the results in Table 2, it can be seen that the fiber-reinforced resin composite molding base materials of Comparative Examples 1 and 2 had large coefficients of variation in bending strength and flexural modulus, and there were large variations in the quality of the fiber-reinforced resin composites. Recognize. On the other hand, the fiber-reinforced resin composite molding base materials of the present invention (Examples 1 and 2) have a small coefficient of variation in bending strength and flexural modulus, and are of high quality with little variation even when laminated randomly during molding. It can be seen that a fiber-reinforced resin composite can be obtained.
本発明の繊維強化樹脂複合体成形用基材並びに繊維強化樹脂複合体は、管理が簡便でありながらその品質ばらつきが小さいことから、自動車、列車、航空機等の部品、カバン製品の部品やハウジング材、アタッシュケース、スーツケース等のカバンのボディ、インテリア剤、防護材、家具、楽器、家庭用品等、各種成形品に好適に利用することができる。
The fiber-reinforced resin composite molding base material and fiber-reinforced resin composite of the present invention are easy to manage and have small quality variations, so they can be used as parts for automobiles, trains, aircraft, etc., parts for bag products, and housing materials. It can be suitably used for various molded products such as the bodies of bags such as attache cases and suitcases, interior decoration materials, protective materials, furniture, musical instruments, and household goods.
Claims (3)
（１）繊維強化樹脂複合体成形用基材の、ＪＩＳ Ｌ１０９６ ８．１２に準じて測定した布目曲がり率が５％以下
（２）繊維強化樹脂複合体成形用基材を用いて成形した繊維強化樹脂複合体の、ＪＩＳ Ｋ７０１７に準じて３点曲げ装置で１０回測定した曲げ強度から算出される変動係数が、０．０５以下 A bidirectional fabric made of aramid long fibers and having the same warp thread density (threads/inch) and weft thread density (threads/inch) of 8 to 30 threads/inch, and a thermosetting resin in a semi-cured state. A base material for molding a fiber-reinforced resin composite, characterized in that it satisfies both the following (1) and (2).
(1) The fiber-reinforced resin composite molding base material has a grain curvature of 5% or less as measured in accordance with JIS L1096 8.12. (2) Fiber reinforcement molded using the fiber-reinforced resin composite molding base material The coefficient of variation calculated from the bending strength of the resin composite measured 10 times with a three-point bending device in accordance with JIS K7017 is 0.05 or less.
A fiber-reinforced resin composite formed by molding the base material for molding a fiber-reinforced resin composite according to claim 1 or 2 .
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