JP2011084611A - Fiber-reinforced wholly aromatic polyester resin molded product - Google Patents
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Description
本発明は、繊維補強樹脂成形体に関するものであり、特に強い衝撃を受けた場合であっても、衝撃吸収に優れ、材料の飛散を抑制する効果の高い成形体に関する。 The present invention relates to a fiber-reinforced resin molded body, and particularly to a molded body that is excellent in shock absorption and highly effective in suppressing material scattering even when subjected to a particularly strong impact.
自動車、鉄道、航空機などの高速移動物体は、その移動速度に由来した運動エネルギーによって、衝突の際には莫大な破壊力を発生し物体を破損させる。そして、物体の破損に伴って、破砕した破片が飛散し、その周囲に存在する物や人間などに甚大な被害を与える場合が少なくない。そのため、破壊に伴う物体の飛散を低減させることや、破損した破片などに飛来物の貫通を防ぐことは、安全上重要な課題である。 High-speed moving objects such as automobiles, railways, and airplanes generate enormous destructive force and break the objects at the time of collision by kinetic energy derived from the moving speed. In many cases, the broken pieces are scattered along with the breakage of the object, causing a great deal of damage to objects and humans existing around the broken pieces. For this reason, it is an important safety issue to reduce scattering of an object accompanying destruction and to prevent a flying object from penetrating a broken piece.
このような課題を解決するために、複数本の強化繊維束を一方向に引き揃えた強化繊維シートに熱可塑性樹脂繊維を不織状態で布帛とした熱可塑性樹脂不織布を重ね合わせて加熱しつつ加圧することにより、熱可塑性樹脂不織布を溶融させ強化繊維束中に熱可塑性樹脂を含浸させて、熱可塑性樹脂によるプリプレグ状態としてなる繊維強化熱可塑性樹脂シートが検討されている（例えば、特許文献１参照。）。しかしながら、特許文献１で記載の溶融させる熱可塑性樹脂不織布はその構造上、異方性が存在するため、溶融成形時に変形が生じ、均一な複合体が得られないため、安定した性能が得られないといった問題があった。 In order to solve such problems, a thermoplastic fiber nonwoven fabric in which a thermoplastic resin fiber is woven in a non-woven state is superposed and heated on a reinforcing fiber sheet in which a plurality of reinforcing fiber bundles are aligned in one direction. A fiber reinforced thermoplastic resin sheet in which a thermoplastic resin nonwoven fabric is melted by pressurization to impregnate a reinforced fiber bundle with a thermoplastic resin to form a prepreg state using the thermoplastic resin has been studied (for example, Patent Document 1). reference.). However, since the thermoplastic resin nonwoven fabric to be melted described in Patent Document 1 has anisotropy in its structure, deformation occurs during melt molding, and a uniform composite cannot be obtained, so that stable performance is obtained. There was no problem.
本発明の目的は、強度、弾性率、耐衝撃性、耐熱性、および振動減衰性を高い次元で兼ね備える繊維補強樹脂成形体を提供することにある。 An object of the present invention is to provide a fiber-reinforced resin molded body having strength, elastic modulus, impact resistance, heat resistance, and vibration damping properties at a high level.
本発明者等は、上記性能を有する繊維補強樹脂成形体を得るべく鋭意検討した結果、高強力で耐熱性を有する繊維で補強された全芳香族ポリエステル樹脂成形体が強度、弾性率、耐衝撃性、耐熱性、および振動減衰性を高い次元で兼ね備えることを見出し、本発明に到達した。 As a result of intensive studies to obtain a fiber-reinforced resin molded article having the above-mentioned performance, the present inventors have found that a wholly aromatic polyester resin molded article reinforced with high-strength and heat-resistant fibers has strength, elastic modulus, and impact resistance. The present invention has been found by combining high performance, heat resistance, and vibration damping properties at a high level.
すなわち本発明は、４００℃以上の温度で実質的に不融であり、かつ破断強度が１０ｃＮ／ｄｔｅｘ以上である高強力繊維により補強された全芳香族ポリエステル樹脂成形体であり、好ましくは高強力繊維が一方向性織物、二方向性織物、三軸織物、多軸織物のいずれかであり、その目付が１０〜５００ｇ／ｍ２、厚みが０．０３〜２ｍｍである上記の樹脂成形体であり、さらに好ましくは全芳香族ポリエステル樹脂の含有量が高強力繊維の重量に対して５〜２００％である上記の樹脂成形体である。 That is, the present invention is a wholly aromatic polyester resin molded body reinforced with high-strength fibers that are substantially infusible at a temperature of 400 ° C. or higher and have a breaking strength of 10 cN / dtex or higher, preferably high strength. In the above resin molded body, the fiber is any one of a unidirectional woven fabric, a bi-directional woven fabric, a triaxial woven fabric, and a multiaxial woven fabric, and has a basis weight of 10 to 500 g / m 2 and a thickness of 0.03 to 2 mm. More preferably, it is the above resin molded body in which the content of the wholly aromatic polyester resin is 5 to 200% with respect to the weight of the high strength fiber.
本発明によれば、強度、弾性率、耐衝撃性、耐熱性および振動減衰性を高い次元で兼ね備え、特に強い衝撃を受けた場合であっても、衝撃吸収に優れ、材料の飛散を抑制する効果の高い繊維補強樹脂成形体を得ることができる。 According to the present invention, strength, elastic modulus, impact resistance, heat resistance, and vibration damping properties are combined at a high level, and even when subjected to particularly strong impact, it is excellent in shock absorption and suppresses scattering of materials. A highly effective fiber-reinforced resin molded product can be obtained.
以下、本発明について詳細に説明する。本発明の樹脂成形体は、４００℃以上温度で実質的に不融であり、かつ破断強度が１０ｃＮ／ｄｔｅｘ以上の高強力繊維により補強されていることが特徴である。
そのような本発明の高強力繊維としては、前記耐熱性及び破断強度を示す限り、金属繊維、無機繊維、有機繊維のいずれであってもよく、金属繊維としては、例えば、アルミニウム繊維、ステンレス繊維、チタン繊維などが例示でき、無機繊維としては、炭素繊維、セラミック繊維、石英繊維、ガラス繊維などが例示でき、有機繊維としては、アラミド繊維（例えば、メタ系アラミド繊維、パラ系アラミド繊維）、ポリパラフェニレンベンゾビスオキサゾール（ＰＢＯ）繊維、ポリベンズイミダゾール繊維、ポリアミドイミド繊維、ポリイミド繊維などが挙げられる。これらの繊維は、単独で、または二種以上を組み合わせて用いてもよい。
Hereinafter, the present invention will be described in detail. The resin molded body of the present invention is characterized by being substantially infusible at a temperature of 400 ° C. or higher and reinforced with high strength fibers having a breaking strength of 10 cN / dtex or higher.
Such a high strength fiber of the present invention may be any of a metal fiber, an inorganic fiber, and an organic fiber as long as it exhibits the heat resistance and breaking strength. Examples of the metal fiber include an aluminum fiber and a stainless fiber. In addition, titanium fibers and the like can be exemplified, examples of the inorganic fibers include carbon fibers, ceramic fibers, quartz fibers, and glass fibers. Examples of the organic fibers include aramid fibers (for example, meta aramid fibers and para aramid fibers), Examples include polyparaphenylene benzobisoxazole (PBO) fiber, polybenzimidazole fiber, polyamideimide fiber, and polyimide fiber. These fibers may be used alone or in combination of two or more.
また本発明の繊維補強樹脂成形体において、高強力繊維は織物の状態で補強されていることが好ましい。織物の形態としては経糸または緯糸のいずれか一方向に配列した一方向性織物、経糸および緯糸の双方に配列した二方向性織物、縦、横、斜めの三方向に配列した三軸織物、四方向以上の多方向に配列した多軸織物、一方向に揃えられた繊維束を別の糸で留める一方向性ノンクリンプドファブリック、複数の方向（例えば、二方向）に揃えられた繊維束をそれぞれ積層して別の糸で留める多方向性ノンクリンプドファブリック等が挙げられるが、これらのうち、軽量化と耐衝撃性とを両立させる観点から一方向性織物、二方向性織物、三軸織物、多軸織物のいずれかであることが好ましい。 In the fiber-reinforced resin molded article of the present invention, the high strength fiber is preferably reinforced in a woven state. As for the form of the woven fabric, the unidirectional woven fabric arranged in one direction of warp or weft, the bi-directional woven fabric arranged in both the warp and the weft, the triaxial woven fabric arranged in the longitudinal, transverse and diagonal directions, four Multi-axis fabric arranged in multiple directions more than one direction, Unidirectional non-crimped fabric that fastens fiber bundles aligned in one direction with different yarns, Fiber bundles aligned in multiple directions (for example, two directions) Multi-directional non-crimped fabrics that are laminated and fastened with separate yarns are included. Among these, unidirectional fabrics, bi-directional fabrics, triaxials from the viewpoint of achieving both weight reduction and impact resistance It is preferably either a woven fabric or a multiaxial woven fabric.
上記した織物の目付は、軽量性と耐衝撃性とを両立する観点から、１０〜５００ｇ／ｍ２であることが好ましく、５０〜４００ｇ／ｍ２であることがより好ましい。目付が１０ｇ／ｍ２未満であるとハンドリング時に織物が破れる恐れがあり、一方５００ｇ／ｍ２より大きいと切断しにくい等加工性の問題がある。 The basis weight of the woven fabric described above is preferably 10 to 500 g / m 2 and more preferably 50 to 400 g / m 2 from the viewpoint of achieving both lightness and impact resistance. If the basis weight is less than 10 g / m 2 , the fabric may be broken at the time of handling. On the other hand, if the basis weight is more than 500 g / m 2 , there is a problem of workability such as difficulty in cutting.
さらに上記した織物の厚みは０．０３〜２ｍｍであることが好ましく、０．０７〜１．５ｍｍ程度が好ましい。厚みが０．０３ｍｍ未満であるとハンドリング時に織物が破れる恐れがあり、一方２ｍｍより大きいと切断しにくい等加工性の問題がある。 Furthermore, the thickness of the woven fabric described above is preferably 0.03 to 2 mm, and preferably about 0.07 to 1.5 mm. If the thickness is less than 0.03 mm, the fabric may be broken during handling, while if it is more than 2 mm, there is a problem of workability such as difficulty in cutting.
本発明で用いられる全芳香族ポリエステル樹脂は、芳香族ジオール、芳香族ジカルボン酸、芳香族ヒドロキシジカルボン酸等より重合して得られ、その中でも、溶融時に光学的異方性を示す溶融異方性ポリエステルが好ましい。本発明にいう溶融異方性ポリエステルとは、溶融相において光学的異方性（液晶性）を示す芳香族ポリエステルであり、例えば試料をホットステージに載せ窒素雰囲気下で加熱し、試料の透過光を観察することにより認定できる。 The wholly aromatic polyester resin used in the present invention is obtained by polymerization from aromatic diol, aromatic dicarboxylic acid, aromatic hydroxydicarboxylic acid, etc. Among them, melt anisotropy showing optical anisotropy at the time of melting Polyester is preferred. The melt-anisotropic polyester referred to in the present invention is an aromatic polyester that exhibits optical anisotropy (liquid crystallinity) in the melt phase. For example, a sample is placed on a hot stage and heated in a nitrogen atmosphere, and the transmitted light of the sample It can be recognized by observing
例えば、本発明で用いられる全芳香族ポリエステル樹脂は、例えば、下記化１及び化２に示す構成単位の組合せで構成される。 For example, the wholly aromatic polyester resin used in the present invention includes, for example, a combination of structural units represented by the following chemical formulas 1 and 2.
これらのうち、好ましくは化１および化２に示される反復構成単位の組合せのうち（５）、（６）、（７）および（９）からなるポリマーである。 Of these, a polymer comprising (5), (6), (7) and (9) among the combinations of repeating structural units represented by Chemical Formula 1 and Chemical Formula 2 is preferred.
より好ましくは、下記化３に示す（Ａ）および（Ｂ）の反復構成単位からなる部分が５０モル％以上である芳香族ポリエステルが好ましい。
さらに（Ａ）の反復構成単位に対する（Ｂ）の反復単位のモル比は（Ａ）：（Ｂ）＝１００：１〜５０、好ましくは（Ａ）：（Ｂ）＝１００：１〜４５、さらに好ましくは（Ａ）：（Ｂ）＝１００：１〜４０である。
More preferably, an aromatic polyester in which a portion composed of repeating structural units (A) and (B) shown in the following chemical formula 3 is 50 mol% or more is preferable.
Furthermore, the molar ratio of the repeating unit of (B) to the repeating structural unit of (A) is (A) :( B) = 100: 1-50, preferably (A) :( B) = 100: 1-45, Preferably (A) :( B) = 100: 1-40.
本発明で好適に用いられる全芳香族ポリエステルの融点は２５０〜３６０℃の範囲であることが好ましく、より好ましくは２６０〜３２０℃である。なお、ここでいう融点とは、ＪＩＳ Ｋ７１２１試験法に準拠し、示差走差熱量計（ＤＳＣ；メトラー社製「ＴＡ３０００」）で測定し、観察される主吸収ピーク温度である。 The melting point of the wholly aromatic polyester suitably used in the present invention is preferably in the range of 250 to 360 ° C, more preferably 260 to 320 ° C. The melting point referred to here is the main absorption peak temperature measured and observed with a differential scanning calorimeter (DSC; “TA3000” manufactured by METTLER) according to the JIS K7121 test method.
なお、前記全芳香族ポリエステルには、本発明の効果を損なわない範囲で、ポリエチレンテレフタレート、変性ポリエチレンテレフタレート、ポリオレフィン、ポリカーボネート、ポリアミド、ポリフェニレンサルファイド、ポリエーテルエーテルケトン、フッ素樹脂等の熱可塑性ポリマーを添加してもよい。 The total aromatic polyester is added with a thermoplastic polymer such as polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyamide, polyphenylene sulfide, polyetheretherketone, and fluororesin as long as the effects of the present invention are not impaired. May be.
本発明の全芳香族ポリエステル樹脂を前記高強力繊維で補強する方法としては、溶融または溶解した全芳香族ポリエステル樹脂に高強力繊維からなる布帛を含浸することにより複合化してもよいし、該布帛と、布帛状またはシート状の全芳香族ポリエステル樹脂とを積層し、加熱して複合化してもよいし、または全芳香族ポリエステル樹脂を含むエマルジョンを該布帛に含浸、乾燥後、積層して加熱により複合化してもよい。この中で、簡便に積層体を製造するためには、布帛状またはシート状の全芳香族ポリエステル樹脂を用いるのが好ましい。更には、その布帛状またはシート状の全芳香族ポリエステル樹脂は、織物であることが好ましい。織物の場合、異方性が少ないため溶融成形時も変形が生じにくく、均一な複合体が得られやすいためである。 As a method of reinforcing the wholly aromatic polyester resin of the present invention with the high-strength fibers, the wholly aromatic polyester resin melted or dissolved may be impregnated with a cloth made of high-strength fibers, or the cloth may be combined. And a fabric-like or sheet-like wholly aromatic polyester resin may be laminated and heated to be combined, or an emulsion containing a wholly aromatic polyester resin is impregnated into the fabric, dried, then laminated and heated. May be combined. Among these, it is preferable to use a cloth-like or sheet-like wholly aromatic polyester resin in order to easily produce a laminate. Furthermore, the cloth-like or sheet-like wholly aromatic polyester resin is preferably a woven fabric. This is because in the case of a woven fabric, since there is little anisotropy, deformation hardly occurs even during melt molding, and a uniform composite is easily obtained.
布帛状またはシート状の全芳香族ポリエステル樹脂が織物である場合、織物の形態としては経糸または緯糸のいずれか一方向に配列した一方向性織物、経糸および緯糸の双方に配列した二方向性織物、縦、横、斜めの三方向に配列した三軸織物、四方向以上の多方向に配列した多軸織物、一方向に揃えられた繊維束を別の糸で留める一方向性ノンクリンプドファブリック、複数の方向（例えば、二方向）に揃えられた繊維束をそれぞれ積層して別の糸で留める多方向性ノンクリンプドファブリック等が挙げられるが、これらのうち、軽量化と耐衝撃性とを両立させ、かつ溶融成形時の変形を抑える観点から、二方向性織物、三軸織物、多軸織物、多方向性ノンクリンプドファブリックのいずれかであることが好ましい。 When the fabric-like or sheet-like wholly aromatic polyester resin is a woven fabric, the woven fabric may be a unidirectional fabric arranged in one direction of warp or weft, or a bi-directional fabric arranged in both warp and weft. , Triaxial fabric arranged in three directions, vertical, horizontal and diagonal, multiaxial fabric arranged in more than four directions, unidirectional non-crimped fabric that fastens fiber bundles aligned in one direction with different yarns And multi-directional non-crimped fabrics in which fiber bundles aligned in a plurality of directions (for example, two directions) are stacked and fastened with different yarns. Among these, weight reduction and impact resistance From the viewpoints of satisfying the above and suppressing deformation at the time of melt molding, it is preferably any one of bi-directional woven fabric, triaxial woven fabric, multi-axial woven fabric, and multi-directional non-crimped fabric.
本発明において、全芳香族ポリエステルの含有量は高強力繊維の重量に対して５〜２００％の範囲であることが好ましく、１０〜１８０％の範囲であることがより好ましく、１５〜１６０％の範囲であることがより好ましい。全芳香族ポリエステルの含有量が高強力繊維の重量に対して５％未満であると、高強力繊維同士を接着するだけの絶対量が不足するため均一な積層体を形成できないなどの問題があり、一方２００％を越えると高強力繊維の存在比率が少なく、該繊維の性能が十分に顕在化できない等の問題がある。 In the present invention, the content of the wholly aromatic polyester is preferably in the range of 5 to 200%, more preferably in the range of 10 to 180%, and more preferably in the range of 15 to 160% with respect to the weight of the high strength fiber. A range is more preferable. If the total aromatic polyester content is less than 5% based on the weight of the high-strength fibers, there is a problem that a uniform laminate cannot be formed because the absolute amount for bonding the high-strength fibers is insufficient. On the other hand, if it exceeds 200%, there is a problem that the ratio of the high-strength fibers is small and the performance of the fibers cannot be sufficiently manifested.
以下、実施例により本発明をより詳細に説明するが、本発明は本実施例により何等限定されるものではない。なお、以下の実施例において、繊維繊度、成形板の弾性率、耐衝撃性、耐熱性は下記の方法により測定したものを示す。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by this Example. In the following examples, fiber fineness, elastic modulus of molded plate, impact resistance, and heat resistance are those measured by the following methods.
［繊維強度 ｃＮ／ｄｔｅｘ］
ＪＩＳ Ｌ１０１３に準拠して測定した。
[Fiber strength cN / dtex]
Measurement was performed in accordance with JIS L1013.
［成形板の曲げ弾性率］
JIS K７０１７に準拠して測定を実施した。評価としては、曲げ弾性率が５ＧＰａ以上を○、１〜５ＧＰａを△、１ＧＰａ未満を×として判定した。
[Bending elastic modulus of molded plate]
Measurement was performed in accordance with JIS K7017. As the evaluation, the flexural modulus was determined to be 5 GPa or more as ◯, 1 to 5 GPa as Δ, and less than 1 GPa as x.
［成形板の耐衝撃性］
１００ｍｍ×１００ｍｍ×２〜３ｍｍの試験片に対して、落錘グラフィックインパクトテスター（（株）東洋精機製作所製）を用い、ＪＩＳ Ｋ−７２１１ プラスチック−硬質プラスチック パンクチャー衝撃試験方法に基づき、測定を実施した。測定条件としては、ストライカー径１２．７ｍｍ、ホルダー径７６ｍｍ、落下高さ１００ｃｍ、ウェイト１４．５ｋｇ、衝撃速度４．４ｍ／秒にて実施した。評価としては、パンクチャーエネルギーが２０Ｊ以上を○、５〜２０Ｊを△、５Ｊ未満を×として判定した。
[Shock resistance of molded plate]
Using a falling weight graphic impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) for a test piece of 100 mm x 100 mm x 2 to 3 mm, measurement was performed based on the JIS K-7111 plastic-hard plastic puncture impact test method. did. The measurement conditions were a striker diameter of 12.7 mm, a holder diameter of 76 mm, a drop height of 100 cm, a weight of 14.5 kg, and an impact speed of 4.4 m / sec. As an evaluation, the puncture energy was determined as ◯ when the puncture energy was 20 J or more, Δ as 5-20 J, and X as less than 5 J.
［成形板の耐熱性］
示差熱熱重量同時測定装置（島津製作所株式会社製「ＤＴＧ−５０」）を使用して、試験片を、窒素雰囲気下、３０℃から４５０℃まで１０℃／分で加熱した。４５０℃に昇温した時点での試験片の重量保持率が９０％以上である場合に耐熱性を○と評価し、９０〜７０％を△、７０％未満を×と評価した。
[Heat resistance of molded plate]
The test piece was heated from 30 ° C. to 450 ° C. at 10 ° C./min under a nitrogen atmosphere using a differential thermothermal gravimetric simultaneous measurement device (“DTG-50” manufactured by Shimadzu Corporation). When the weight retention rate of the test piece when the temperature was raised to 450 ° C. was 90% or more, the heat resistance was evaluated as “good”, 90-70% was evaluated as “Δ”, and less than 70% was evaluated as “x”.
［振動減衰性］
動的粘弾性測定装置（オリエンテック社製バイブロンＤＤＶ−ＩＩＩ）を用い、１００Ｈｚ、２３℃下において内部損失を測定した。内部損失が０．０３以上である場合を○、０．０１〜０．０３である場合を△、０．０１以下である場合を×として、振動減衰性を判定した。
[Vibration damping]
Using a dynamic viscoelasticity measuring apparatus (Orientec Vibron DDV-III), internal loss was measured at 100 Hz under 23 ° C. The vibration damping property was determined with ◯ when the internal loss was 0.03 or more, Δ when 0.01 to 0.03, and x when 0.01 or less.
［実施例１］
（１）高強力繊維として、ヤーン強度２３．９ｃＮ／ｄｔｅｘのカーボン繊維で構成される二方向性織物（東邦テナックス（株）製、「ベスファイト Ｗ−３１０１」平織、目付２００ｇ／ｍ２、厚み０．２５ｍｍ）を用いた。
（２）次に全芳香族ポリエステル繊維（株式会社クラレ製「ベクトランＨＴ」）フィラメント（１６７０ｄｔｅｘ／６００フィラメント）の二方向性織物を作製した。この織物の目付は１７０ｇ／ｍ２であった。
（３）上記（１）、（２）の織物を交互に重ねて各８枚ずつ積層した後、温度３４０℃、圧力２０ｋｇ／ｃｍ２にて３０秒間熱プレスを実施し、厚さ２．５ｍｍ、目付２８７０ｇ／ｍ２の成形板を製造した。このとき、上記（２）の織物を溶融させ、樹脂化した後の樹脂含有量は４４．３重量％であった。得られた成形板の弾性率は実用性に十分耐えるものであり、耐衝撃性、耐熱性、振動減衰性とも優れていた。結果を表１に示す。
[Example 1]
(1) Bidirectional woven fabric composed of carbon fiber having a yarn strength of 23.9 cN / dtex as a high-strength fiber (manufactured by Toho Tenax Co., Ltd., “Besfite W-3101” plain weave, basis weight 200 g / m 2 , thickness 0.25 mm) was used.
(2) Next, a bi-directional woven fabric of wholly aromatic polyester fibers (“Vectran HT” manufactured by Kuraray Co., Ltd.) filaments (1670 dtex / 600 filaments) was produced. The fabric weight of this woven fabric was 170 g / m 2 .
(3) The fabrics of the above (1) and (2) were alternately stacked and each 8 layers were stacked, and then hot pressing was performed at a temperature of 340 ° C. and a pressure of 20 kg / cm 2 for 30 seconds, and the thickness was 2.5 mm. A molded plate having a basis weight of 2870 g / m 2 was produced. At this time, the resin content after the woven fabric of (2) was melted and converted into a resin was 44.3% by weight. The elastic modulus of the obtained molded plate sufficiently withstands practicality, and was excellent in impact resistance, heat resistance, and vibration damping properties. The results are shown in Table 1.
［実施例２］
全芳香族ポリエステル繊維として株式会社クラレ製「ベクトランＵＭ」フィラメント（１５８０ｄｔｅｘ／２００フィラメント）を用いて二方向性織物を作製し、該織物と、実施例１と同じカーボン繊維織物とを、実施例１と同様に交互に重ねて各８枚ずつ積層した後、温度３７０℃、圧力２０ｋｇ／ｃｍ２にて３０秒間熱プレスを実施し、厚さ２．４ｍｍ、目付２９３０ｇ／ｍ２の成形板を製造した。このとき、前記全芳香族ポリエステルの織物を溶融させ、樹脂化した後の樹脂含有量は４５．４重量％であった。得られた成形板の弾性率は実用性に十分耐えるものであり、耐衝撃性、耐熱性、振動減衰性とも優れていた。結果を表１に示す。
[Example 2]
A bi-directional woven fabric was prepared using “Vectran UM” filament (1580 dtex / 200 filament) manufactured by Kuraray Co., Ltd. as a wholly aromatic polyester fiber, and the woven fabric and the same carbon fiber woven fabric as in Example 1 were prepared in Example 1. As shown in Fig. 8, after alternately stacking 8 sheets each, hot pressing is performed at a temperature of 370 ° C and a pressure of 20 kg / cm 2 for 30 seconds to produce a molded plate having a thickness of 2.4 mm and a basis weight of 2930 g / m 2. did. At this time, the resin content after melting and resinating the wholly aromatic polyester woven fabric was 45.4% by weight. The elastic modulus of the obtained molded plate sufficiently withstands practicality, and was excellent in impact resistance, heat resistance, and vibration damping properties. The results are shown in Table 1.
［実施例３］
全芳香族ポリエステル繊維として株式会社クラレ製「ベクトランＮＴ」フィラメント（１６７０ｄｔｅｘ／６００フィラメント）を用いて二方向性織物を作製し、該織物と、実施例１と同じカーボン繊維織物とを、実施例１と同様に交互に重ねて各８枚ずつ積層した後、温度３００℃、圧力２０ｋｇ／ｃｍ２にて３０秒間熱プレスを実施し、厚さ２．４ｍｍ、目付２８４０ｇ／ｍ２の成形板を製造した。このとき、前記全芳香族ポリエステルの織物を溶融させ、樹脂化した後の樹脂含有量は４３．７重量％であった。得られた成形板の弾性率は実用性に十分耐えるものであり、耐衝撃性、耐熱性、振動減衰性とも優れていた。結果を表１に示す。
[Example 3]
A bi-directional woven fabric was prepared using “Vectran NT” filament (1670 dtex / 600 filament) manufactured by Kuraray Co., Ltd. as a wholly aromatic polyester fiber, and the woven fabric and the same carbon fiber woven fabric as in Example 1 were prepared in Example 1. As shown in Fig. 8, after alternately stacking 8 sheets each, heat press for 30 seconds at a temperature of 300 ° C and a pressure of 20 kg / cm 2 to produce a molded plate having a thickness of 2.4 mm and a basis weight of 2840 g / m 2. did. At this time, the resin content after the woven fabric of the wholly aromatic polyester was melted and converted into a resin was 43.7% by weight. The elastic modulus of the obtained molded plate sufficiently withstands practicality, and was excellent in impact resistance, heat resistance, and vibration damping properties. The results are shown in Table 1.
［実施例４］
（１）ガラス繊維（「日東紡株式会社製、「WF 230 100 BS6」、ヤーン強度１３．１ｃＮ／ｄｔｅｘ」を用いて、目付２００ｇ／ｍ２、厚み０．２５ｍｍの二方向性織物を作製した。
（２）上記（１）と、実施例１の（２）で作製した織物とを交互に重ねて各８枚ずつ積層した後、温度３４０℃、圧力２０ｋｇ／ｃｍ２にて３０秒間熱プレスを実施し、厚さ２．４ｍｍ、目付２８９０ｇ／ｍ２の成形板を製造した。このとき、上記（２）の織物を溶融させ、樹脂化した後の樹脂含有量は４４．６重量％であった。得られた成形板の弾性率は実用性に十分耐えるものであり、耐衝撃性、耐熱性、振動減衰性とも優れていた。結果を表１に示す。
[Example 4]
(1) Using a glass fiber (“Nittobo Co., Ltd.,“ WF 230 100 BS6 ”, yarn strength 13.1 cN / dtex”), a bi-directional woven fabric having a basis weight of 200 g / m 2 and a thickness of 0.25 mm was produced. .
(2) The above fabric (1) and the fabric produced in (2) of Example 1 were alternately stacked and each 8 layers were stacked, and then hot pressed at a temperature of 340 ° C. and a pressure of 20 kg / cm 2 for 30 seconds. This was carried out to produce a molded plate having a thickness of 2.4 mm and a basis weight of 2890 g / m 2 . At this time, the resin content after the woven fabric (2) was melted and converted into a resin was 44.6% by weight. The elastic modulus of the obtained molded plate sufficiently withstands practicality, and was excellent in impact resistance, heat resistance, and vibration damping properties. The results are shown in Table 1.
［実施例５］
（１）アラミド繊維（「東レ・デュポン（株）製、「ケブラー４９」、ヤーン強度２０．８ｃＮ／ｄｔｅｘ」を用いて、目付１７０ｇ／ｍ２、厚み０．２６ｍｍの二方向性織物を作製した。
（２）上記（１）と、実施例１の（２）で作成した織物とを交互に重ねて各８枚ずつ積層した後、温度３４０℃、圧力２０ｋｇ／ｃｍ２にて３０秒間熱プレスを実施し、厚さ２．３ｍｍ、目付２６８０ｇ／ｍ２の成形板を製造した。このとき、上記（２）の織物を溶融させ、樹脂化した後の樹脂含有量は４９．３重量％であった。得られた成形板の弾性率は実用性に十分耐えるものであり、耐衝撃性、耐熱性、振動減衰性とも優れていた。結果を表１に示す。
[Example 5]
(1) A bi-directional woven fabric having a basis weight of 170 g / m 2 and a thickness of 0.26 mm was prepared using an aramid fiber (“Kevlar 49” manufactured by Toray DuPont Co., Ltd., yarn strength 20.8 cN / dtex). .
(2) After the above (1) and the fabric prepared in (2) of Example 1 are alternately stacked, 8 sheets each are stacked, and then hot-pressed at a temperature of 340 ° C. and a pressure of 20 kg / cm 2 for 30 seconds. This was carried out to produce a molded plate having a thickness of 2.3 mm and a basis weight of 2680 g / m 2 . At this time, the resin content after the woven fabric of (2) was melted and converted into a resin was 49.3% by weight. The elastic modulus of the obtained molded plate sufficiently withstands practicality, and was excellent in impact resistance, heat resistance, and vibration damping properties. The results are shown in Table 1.
［比較例１］
実施例１において、全芳香族ポリエステル繊維の代わりに熱可塑性エラストマー（株式会社クラレ製「セプトン２００２」）からなる不織布を用い、カーボン繊維からなる二方向性織物と、熱可塑性エラストマー不織布とを、平織物／不織布＝１枚／６枚の割合で交互に積層し、総積層量を平織物／不織布＝８枚／４８枚とした後、温度２００℃、圧力４０ｋｇ／ｃｍ２にて３０秒間熱プレスを実施し、厚さ２．５ｍｍ、目付２３５０ｇ／ｍ２の成形板を製造した。このとき、前記不織布を溶融させ、樹脂化した後の樹脂含有量は３１．９重量％であった。得られた成形板は弾性率がやや低く、耐衝撃性、振動減衰性は優れていたが、耐熱性がやや劣るものであった。結果を表１に示す。
[Comparative Example 1]
In Example 1, a non-woven fabric made of a thermoplastic elastomer (“Septon 2002” manufactured by Kuraray Co., Ltd.) is used in place of the wholly aromatic polyester fiber, and a bidirectional fabric made of carbon fiber and a thermoplastic elastomer non-woven fabric are flattened. Fabric / nonwoven fabric = alternately laminated at a ratio of 1 sheet / 6 sheets, and the total amount of laminated sheets is plain woven fabric / nonwoven fabric = 8 sheets / 48 sheets, and then hot pressed at a temperature of 200 ° C. and a pressure of 40 kg / cm 2 for 30 seconds. Then, a molded plate having a thickness of 2.5 mm and a basis weight of 2350 g / m 2 was produced. At this time, the resin content after melting and converting the nonwoven fabric to resin was 31.9% by weight. The resulting molded plate had a slightly lower elastic modulus and was excellent in impact resistance and vibration damping properties, but was slightly inferior in heat resistance. The results are shown in Table 1.
［比較例２］
実施例１において、全芳香族ポリエステル繊維の代わりにアラミド繊維（「東レ・デュポン（株）製、「ケブラー４９」」からなる二方向性織物を用い、各織物をそれぞれ８枚ずつ積層し、実施例１と同じ成形条件にて積層体の成形を試みたが、アラミド繊維が融解しないため、成形不能であった。結果を表１に示す。
[Comparative Example 2]
In Example 1, instead of a wholly aromatic polyester fiber, a bi-directional woven fabric made of aramid fibers (“Kevlar 49” manufactured by Toray DuPont Co., Ltd.) was used, and each of the woven fabrics was laminated by 8 pieces each. An attempt was made to mold the laminate under the same molding conditions as in Example 1. However, since the aramid fibers did not melt, molding was impossible, and the results are shown in Table 1.
［比較例３］
（１）多官能エポキシ樹脂（ジャパンエポキシレジン社製「ＹＬ６０４６Ｂ８０」）１３０質量部と、ノボラック型硬化剤（ジャパンエポキシレジン社製「ＹＬＨ１２９Ｂ６５」）７０質量部と、イミダゾール型硬化促進剤「ジャパンエポキシレジン社製「ＥＭＩ２４」」０．３質量部、およびメチルエチルケトン１３０質量部を混合し、マトリックス樹脂（ワニス）を調製した。
（２）実施例１の（１）で用意したカーボン繊維製二方向性織物に対して、上記（１）のワニスを含浸させ、１５０℃で乾燥しプリプレグを作製した。このプリプレグを８枚重ね、４０ｋｇｆ／ｃｍ２下の圧力で、１７０℃×６０分間保持して、熱プレスし積層一体化させた。得られた成形板は弾性率は高いが、耐衝撃性及び耐熱性、振動減衰性がやや劣るものであった。結果を表１に示す。
[Comparative Example 3]
(1) 130 parts by mass of a polyfunctional epoxy resin (“YL6046B80” manufactured by Japan Epoxy Resin), 70 parts by mass of a novolak type curing agent (“YLH129B65” manufactured by Japan Epoxy Resin), and an imidazole type curing accelerator “Japan Epoxy Resin” A matrix resin (varnish) was prepared by mixing 0.3 part by mass of “EMI24” manufactured by the company and 130 parts by mass of methyl ethyl ketone.
(2) The carbon fiber bidirectional fabric prepared in (1) of Example 1 was impregnated with the varnish of (1) above and dried at 150 ° C. to prepare a prepreg. Eight prepregs were stacked, held at 170 ° C. for 60 minutes under a pressure of 40 kgf / cm 2 , hot pressed, and laminated and integrated. The obtained molded plate had a high elastic modulus, but was slightly inferior in impact resistance, heat resistance and vibration damping. The results are shown in Table 1.
本発明の繊維補強樹脂複合体は、強度、弾性率、耐衝撃性、耐熱性、および振動減衰性を高い次元で兼ね備え、特に強い衝撃を受けた場合であっても、衝撃吸収に優れ、材料の飛散を抑制する効果が高いので、衝撃板、自動車、鉄道、航空機などの高速移動物体や各種建造物などに付加される耐衝撃材料として好適に適用可能である。 The fiber reinforced resin composite of the present invention has high strength, elastic modulus, impact resistance, heat resistance, and vibration damping properties, and is excellent in shock absorption even when subjected to particularly strong impacts. Therefore, it can be suitably applied as an impact resistant material added to high-speed moving objects such as impact plates, automobiles, railways, and aircraft, and various buildings.
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