JPH02276832A - Molding material - Google Patents
Molding materialInfo
- Publication number
- JPH02276832A JPH02276832A JP1097595A JP9759589A JPH02276832A JP H02276832 A JPH02276832 A JP H02276832A JP 1097595 A JP1097595 A JP 1097595A JP 9759589 A JP9759589 A JP 9759589A JP H02276832 A JPH02276832 A JP H02276832A
- Authority
- JP
- Japan
- Prior art keywords
- film
- fiber
- strength
- thermosetting resin
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012778 molding material Substances 0.000 title abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 14
- 229920000620 organic polymer Polymers 0.000 claims abstract description 9
- 238000010030 laminating Methods 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 19
- 238000005452 bending Methods 0.000 abstract description 12
- 239000004760 aramid Substances 0.000 abstract description 6
- 229920003235 aromatic polyamide Polymers 0.000 abstract description 6
- 230000000704 physical effect Effects 0.000 abstract description 5
- 238000007788 roughening Methods 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 238000002203 pretreatment Methods 0.000 abstract 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 11
- 239000004917 carbon fiber Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 239000012783 reinforcing fiber Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000009863 impact test Methods 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012669 compression test Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- XRASRVJYOMVDNP-UHFFFAOYSA-N 4-(7-azabicyclo[4.1.0]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=CC=C21 XRASRVJYOMVDNP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101100145155 Escherichia phage lambda cIII gene Proteins 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 208000037062 Polyps Diseases 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- -1 isocyanate compounds Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、高強度、高弾性率のフィルム層と繊維強化熱
硬化性樹脂層とを積層一体化したプリプレグ材料に関し
、更には、曲げ、引張、圧縮等の機械的強度に優れ、且
つ耐衝撃性が大きく改良された積層複合材料を製造する
ための熱硬化性樹脂成形用材料に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a prepreg material in which a film layer with high strength and a high modulus of elasticity and a fiber-reinforced thermosetting resin layer are laminated together, and furthermore, The present invention relates to a thermosetting resin molding material for producing a laminated composite material that has excellent mechanical strength such as tensile and compressive strength and greatly improved impact resistance.
（従来技術及びその問題点）
繊維強化熱硬化性樹脂複合材料は、優れた比強度、比弾
性率を有することから高強度、軽量、耐蝕性等が要求さ
れる分野、例えば、航空機構造部材あるいはラケットフ
レームやゴルフシャフト等のスポーツ用品などに広く使
用されている。しかしながら、該材料は、一般に靭性に
乏しく、耐衝撃性に問題があり、又さらには、−旦衝撃
的破壊を起こすと、強化繊維がささくれた鋭利な破壊面
を露出するという欠点を有する。そこで、マトリックス
樹脂である熱硬化性樹脂をゴム状重合体で変性する、あ
るいは熱可塑性樹脂を配合する等により改質することで
靭性の改良が図られているが未だ、満足するものは得ら
れていない。また、米国特許第３４７２７３０号あるい
は、特開昭６０−６３２２９号公報等において、インタ
ーリーフ層を有するプリプレグの概念が提案され、耐衝
撃性を改善する手法として注目に値するものの、繊維強
化層に比べてインターリーフ層の強度・弾性率が低い為
に生ずる、成形体の引張強度、曲げ強度等の機械的強度
の低下は切り捨てられ、破壊状態の改善には目も向けら
れていない。(Prior art and its problems) Fiber-reinforced thermosetting resin composite materials have excellent specific strength and specific modulus, so they are used in fields where high strength, light weight, and corrosion resistance are required, such as aircraft structural components and It is widely used in sports equipment such as racket frames and golf shafts. However, such materials generally have poor toughness, have problems with impact resistance, and furthermore, have the disadvantage that - once impact fracture occurs, a sharp fracture surface with broken reinforcing fibers is exposed. Therefore, attempts have been made to improve the toughness by modifying the thermosetting resin, which is the matrix resin, with a rubber-like polymer or by blending it with a thermoplastic resin, but so far, nothing satisfactory has been achieved. Not yet. In addition, the concept of prepreg having an interleaf layer was proposed in U.S. Pat. In this method, the decrease in mechanical strength such as tensile strength and bending strength of the molded body due to the low strength and elastic modulus of the interleaf layer is ignored, and no attention is paid to improving the fracture condition.
また、繊維強化材料の別の問題点は、物性の大きな異方
性であり、一般には強化繊維の配向方向を変化させて積
層することによって擬似等労化を行っているものの、プ
リプレグの切り出しから正確な積ね合せまで多大の手間
と労力を必要とする。Another problem with fiber-reinforced materials is the large anisotropy of their physical properties, and although pseudo-equal labor is generally achieved by laminating the reinforcing fibers by changing their orientation, Accurate stacking requires a great deal of time and effort.
（発明が解決しようとする課題）
本発明は、引張強度、曲げ強度等の機械的強度が大きく
、しかも繊維配向方向以外にも優れた物性を有し、さら
には高い耐衝撃性を併せ持った複合材料を製造すること
ができる熱硬化性樹脂成形用材料を提供することを目的
とする。(Problems to be Solved by the Invention) The present invention provides a composite material that has high mechanical strength such as tensile strength and bending strength, and also has excellent physical properties other than the direction of fiber orientation, and also has high impact resistance. The object of the present invention is to provide a thermosetting resin molding material that can be used to produce a material.
（課題を解決するための手段）
即ち、本発明は、融点又は分解点が３００℃以上である
有機系重合体から実質的になり、３５ｋｇ／ｍ１以上の
引張強度および７００ ｋｇ／ｍｍ”以上の引張弾性率
を有するフィルム層と繊維強化熱硬化性樹脂層とを積層
してなる成形用の熱硬化性樹脂材料である。(Means for Solving the Problem) That is, the present invention consists essentially of an organic polymer having a melting point or decomposition point of 300° C. or higher, and has a tensile strength of 35 kg/m or higher and a tensile strength of 700 kg/mm” or higher. This is a thermosetting resin material for molding, which is formed by laminating a film layer having a tensile modulus and a fiber-reinforced thermosetting resin layer.
本発明において用いるフィルムは、下記の要件が必要で
ある。The film used in the present invention must meet the following requirements.
まず、第１に、フィルムは、３００℃未満には融点をも
たない有機系重合体から実質的に構成されている必要が
ある。融点が３００ ’Ｃ未満であると、樹脂の硬化等
のコンポジットの製造工程で、融解したり、熱変形した
りするので好ましくなく、また製品化されたあとも、使
用環境が少し厳しくなると性能が著しく低下することが
あるので好ましくない。このような高融点の有機系重合
体としては、アラミド、ポリイミド、ポリエーテルエー
テルケトン、全芳香族ポリエステル、ポリヘンライミダ
ゾール、ポリベンツビスチアゾール等が挙げられるが、
樹脂との接着の良さや以下に述べる高強度、高弾性率の
発現のし易さからアラミドとポリイミド、中でもアラミ
ドが好ましい。First, the film must be substantially composed of an organic polymer that does not have a melting point below 300°C. If the melting point is less than 300'C, it is undesirable because it will melt or be thermally deformed during the composite manufacturing process such as curing the resin, and even after it is commercialized, the performance may deteriorate if the usage environment is a little harsh. This is not preferable as it may cause a significant decrease. Examples of such high melting point organic polymers include aramid, polyimide, polyetheretherketone, wholly aromatic polyester, polyhenreimidazole, polybenzbisthiazole, etc.
Among aramid and polyimide, aramid is preferred because of its good adhesion with resin and ease of developing high strength and high elastic modulus as described below.
好ましく用いられるアラミドには下記の一般式（１）、
（ＩＩ）で表わされる構造のもの、またはこれらの共重
合体がある。Preferably used aramids have the following general formula (1),
There are those having the structure represented by (II) and copolymers thereof.
一＋−ＣＲ＋ ＣＮＨＲｚ Ｎ）ｌ←ト１−又
は −←Ｃ−Ｒ３−ＮＨ−ト１−
（＋）
（ｎ）
（式中において、Ｒ８、Ｒ２およびＲ８は、から選ばれ
、これらの水素原子がハロゲン、メチル、エチル、メト
キシ、ニトロ、ヌルホンなどの官能基で置換されていて
もよい。ｍ、ｎは平均重合度であり約５０〜１０００で
ある。）本発明に用いられるフィルムが特定の有機系重
合体から実質的になるという意味は、上記した特定の有
機系重合体以外の成分が、本発明の効果を損わない範囲
で少量含まれていてもよいことであり、例えば上記した
以外の有機系重合体、有機系低分子化合物、無機化合物
などを少量含有してもよい。1+-CR+ CNHRz N)l←1- or -←C-R3-NH-1- (+) (n) (In the formula, R8, R2 and R8 are selected from, and these hydrogen atoms may be substituted with a functional group such as halogen, methyl, ethyl, methoxy, nitro, or nurphone. m and n are the average degree of polymerization and are about 50 to 1000.) Consisting essentially of organic polymers means that components other than the above-mentioned specific organic polymers may be contained in small amounts within the range that does not impair the effects of the present invention. For example, the above-mentioned It may contain small amounts of other organic polymers, organic low molecular compounds, inorganic compounds, etc.
次に本発明に用いられるフィルムは３５ｋｇ／ＩＩＩＩ
ｌｌｚ以上の引張強度および７００ ｋｇ／ｍｍ”以上
の引張弾性率を有している必要がある。Next, the film used in the present invention is 35 kg/III
It is necessary to have a tensile strength of 110 kg/mm" or more and a tensile modulus of 700 kg/mm" or more.
本発明で用いるフィルムは、従来汎用のものと比べれば
、これらの物性が抜きん出ていることは明らかであるが
、繊維強化樹脂層に対しては低いものであり最終成形品
の物性を極力低下させない為には、これらの要件が満足
されねばならず、好ましくは４５ ｋｇ／Ｉｒ１ｒａｚ
以上の引張強度を有していることであり、又は１０００
ｋｇ／ｍｍ”以上の引張弾性率を有していることである
。フィルムは、コンポジット製品としての抗張力の必要
な方向に引張強度や引張弾性率を増強した、謂ゆるテン
シライズドタイプが用いられてもよいが、もちろん、フ
ィルムとして、等方的な性能を有するものを用いた方が
、得られる成形体の機械的強度や寸法安定性に方向性が
少ないという点でよい。本発明において、引張強度と引
張弾性率は少くとも１つの方向が前記した値を満たして
いればよいが、好ましくは、任意に選んだ互いに直交す
る２つの方向の特性の平均値が前記した値を満している
ことである。It is clear that the film used in the present invention has outstanding physical properties when compared to conventional general-purpose ones, but it is low in properties relative to the fiber reinforced resin layer, so that the physical properties of the final molded product are not degraded as much as possible. In order for these requirements to be met, preferably 45 kg/Ir1raz
or more than 1000
The film must have a tensile modulus of at least 100 kg/mm".The film used is a so-called tensilized type, which has increased tensile strength and tensile modulus in the direction where tensile strength is required as a composite product. However, it is of course better to use a film with isotropic performance in that the resulting molded product has less directional properties in terms of mechanical strength and dimensional stability.In the present invention, It is sufficient that the tensile strength and tensile modulus satisfy the above values in at least one direction, but preferably, the average value of the properties in two arbitrarily selected directions orthogonal to each other satisfies the above values. It is that you are.
本発明において、補強効果を十分に発現させるために、
フィルムと熱硬化性樹脂とが十分な接着力をもつことが
好ましい。大きな接着力は、フィルム又はテープの表面
を粗にする（製膜上の工夫、製膜後の物理的又は化学的
なエツチング等）、表面に化学活性種を導入する（コロ
ナ放電処理、プラズマ処理、化学分解等）、接着用の含
浸前処理をする（エポキシ化合物、イソシアネート化合
物、レゾルシン・ホルマリン・ラテックス混合物等）、
又はこれらを組み合わせる等の方法が好ましく用いられ
、それにより達成される。In the present invention, in order to fully express the reinforcing effect,
It is preferable that the film and thermosetting resin have sufficient adhesive strength. A large adhesive force can be achieved by roughening the surface of the film or tape (devices in film formation, physical or chemical etching after film formation, etc.), or by introducing chemically active species to the surface (corona discharge treatment, plasma treatment, etc.). , chemical decomposition, etc.), impregnation pretreatment for adhesion (epoxy compounds, isocyanate compounds, resorcinol/formalin/latex mixtures, etc.),
Alternatively, methods such as a combination of these methods are preferably used and achieved.
本発明に用いられるフィルムの厚みは成形品における繊
維強化樹脂層との積層構成を考慮して適宜決定されるが
通常５〜１００μｍであり、好ましくは１０〜５０μｍ
である。また、望まれる成形品の特性によって、フィル
ム層を複数積層したものと一層以上の繊維強化樹脂層を
積層一体化して用いることも行なわれてよい。The thickness of the film used in the present invention is appropriately determined in consideration of the laminated structure with the fiber-reinforced resin layer in the molded product, but is usually 5 to 100 μm, preferably 10 to 50 μm.
It is. Furthermore, depending on the desired characteristics of the molded product, a plurality of film layers may be laminated and one or more fiber reinforced resin layers may be laminated and used in an integrated manner.
本発明で言う繊維強化熱硬化性樹脂層は、補強繊維に熱
硬化性樹脂を含浸して得られたプリプレグ材である。The fiber-reinforced thermosetting resin layer referred to in the present invention is a prepreg material obtained by impregnating reinforcing fibers with a thermosetting resin.
本発明に用いられる補強繊維としては、ガラス繊維、カ
ーボン繊維、アラミド繊維、ポリベンゾチアゾール繊維
、ポリベンゾチアゾール繊維、あるいはこれらを金属被
覆（例えばニッケルメッキを施したカーボン繊維等）し
たものや、また、アルミナ繊維、シリコンカーバイド繊
維等の無機繊維も含まれ、これらの繊維の２種以上を併
用することもできる。Examples of the reinforcing fibers used in the present invention include glass fibers, carbon fibers, aramid fibers, polybenzothiazole fibers, polybenzothiazole fibers, metal-coated fibers (for example, nickel-plated carbon fibers, etc.), and , alumina fiber, silicon carbide fiber, and the like, and two or more of these fibers can also be used in combination.
また繊維は一方向に引き揃えたシート状の形で、あるい
は織物の形で用いられ、特に等友釣な機械物性が要求さ
れる用途においては適当な長さにカットされた繊維がラ
ンダムに配向したマット状でも使用される。Fibers are also used in the form of sheets aligned in one direction or in the form of woven fabrics, and in applications where uniform mechanical properties are required, fibers are cut into appropriate lengths and randomly oriented. It is also used in matte form.
本発明に用いられる熱硬化性樹脂は特に限定されるもの
ではなく、例えば、エポキシ樹脂、フェノール樹脂、ポ
リイミド樹脂、ポリエステル樹脂などから選ばれる。ま
た、これらの樹脂に、紫外線吸収剤、難燃剤、酸化防止
剤、滑剤、着色剤、熱安定剤、老化防止剤、補強用短繊
維、補強用粉粒体、成形用薬剤、熱可塑性樹脂、エラス
トマーゴム状物、その他通常の樹脂添加剤が添加されて
いてもよい。The thermosetting resin used in the present invention is not particularly limited, and is selected from, for example, epoxy resins, phenol resins, polyimide resins, polyester resins, and the like. In addition, these resins include ultraviolet absorbers, flame retardants, antioxidants, lubricants, colorants, heat stabilizers, anti-aging agents, reinforcing short fibers, reinforcing powders, molding agents, thermoplastic resins, Elastomer rubbers and other usual resin additives may be added.
本発明の成形用材料は種々の方法で調製することができ
る。The molding material of the invention can be prepared in various ways.
例えば、Ｂ−ステージの繊維強化熱硬化性樹脂プリプレ
グとフィルムを圧着して製造する方法がある。あるいは
、熱硬化性樹脂を含浸した強化繊維シートとフィルムを
圧着後、加熱してＢ−ステージ化する方法がある。また
、フィルムにあらかじめ熱硬化性樹脂を溶融した状態で
塗布するか、または、適当な溶媒を用いた溶液あるいは
混合液の形で塗布した後、加熱脱溶媒しておき、これと
強化繊維を圧着後、加熱する方法も使用可能である。For example, there is a method of manufacturing by pressing a B-stage fiber-reinforced thermosetting resin prepreg and a film. Alternatively, there is a method in which a reinforcing fiber sheet impregnated with a thermosetting resin and a film are pressed together and then heated to B-stage the film. In addition, the thermosetting resin can be applied to the film in advance in a molten state, or it can be applied in the form of a solution or mixture using an appropriate solvent, and then the solvent is removed by heating, and this and the reinforcing fibers are crimped together. A method of heating after heating can also be used.
一方積層構成に関しては、上記の如きフィルム層と繊維
強化熱硬化性樹脂層とを各−層ずつ積層するか、または
これを更に複数層積層したものの他にあらかじめ熱硬化
性樹脂を塗布後、Ｂステージ化したフィルムを２層以上
積層したフィルム層と繊維強化熱硬化性樹脂層とをサイ
ドバイサイドで圧着積層したり、あるいは前者で後者を
サンドインチ状にはさむ形で積層して用いることもでき
る。また、円柱状の金型に繊維強化熱硬化性樹脂を捲回
積層したものに、片面に熱硬化性樹脂を塗布したフィル
ムを捲回し金型を除去することで円筒状の材料を製造す
ることも可能である。On the other hand, regarding the laminated structure, the film layer and the fiber-reinforced thermosetting resin layer as described above may be laminated one by one, or a plurality of layers may be laminated together. A film layer obtained by laminating two or more staged films and a fiber-reinforced thermosetting resin layer may be laminated side-by-side by pressure bonding, or the former may be laminated with the latter sandwiched between the latter in a sandwich-like manner. Alternatively, a cylindrical material can be manufactured by winding a film coated with thermosetting resin on one side of a cylindrical mold by winding and laminating fiber-reinforced thermosetting resin and removing the mold. is also possible.
本発明の成形用材料から複合材料を成形する方法は、何
ら制限されず、種々の方法で、いろいろな形状の成形体
に加工することができる。The method of molding a composite material from the molding material of the present invention is not limited at all, and it can be processed into molded bodies of various shapes by various methods.
（実施例） 次に、本発明を実施例を用いて詳細に説明する。(Example) Next, the present invention will be explained in detail using examples.
参考例Ｉ アラミドフィルムの製造
対数粘度（９８％濃硫酸中に溶解して、Ｃ−０，５ｇ／
１００＋ｊ！にて、３０℃で測定）が５．５のポリｐ
フェニレンテレフタルアミド（ＰＰＴＡと略す）を９９
．５％の硫酸にポリマー濃度１２％で溶解し、光学異方
性のあるドープを得た。このドープを真空下に脱気し、
濾過したのち、ギアポンプを通して、スリットダイから
押出し、鏡面に慶いたタンタル類のベルトにキャストし
、相対湿度約４０％の約９０℃の空気の雰囲気のゾーン
を通して、流延ドープを光学等方化し、ベルトとともに
２０′Ｃの３０％硫酸水溶液中に導いて凝固させた。次
いで、凝固フィルムをベルトからひきはがし、カセイソ
ーダ水溶液で中和し、水洗した。洗浄の終了したフィル
ムを乾燥させずに、ローラで長さ方向に約１．１５倍延
伸し、次いでテンターで幅方向に１．３倍延伸したのち
、定長に保持しつつ、２００℃で乾燥し更に３００℃で
定長熱処理した。Reference Example I Manufacture of aramid film Logarithmic viscosity (dissolved in 98% concentrated sulfuric acid, C-0.5g/
100+j! Polyp with a temperature of 5.5 (measured at 30°C)
Phenylene terephthalamide (abbreviated as PPTA) 99
．． A dope with optical anisotropy was obtained by dissolving the polymer in 5% sulfuric acid at a polymer concentration of 12%. This dope is degassed under vacuum,
After filtration, the cast dope is extruded through a gear pump, extruded through a slit die, cast onto a tantalum belt with a mirror finish, and passed through an air atmosphere zone at about 90°C with a relative humidity of about 40% to optically isotropicize the cast dope. The belt was introduced into a 30% aqueous sulfuric acid solution at 20'C and coagulated. The coagulated film was then peeled off from the belt, neutralized with an aqueous solution of caustic soda, and washed with water. Without drying the washed film, it was stretched approximately 1.15 times in the length direction using rollers, then 1.3 times in the width direction using a tenter, and then dried at 200°C while maintaining the film at a constant length. Then, it was further heat-treated at 300°C for a fixed length.
上記、条件下で１０ａｍ及び２５ａｍのＰＰＴＡ フィ
ルムを製造した。10 am and 25 am PPTA films were manufactured under the above conditions.
得られたフィルムは淡黄色透明で、熱分析において５０
０℃以下には転移温度は見られなかった。The resulting film was pale yellow and transparent, with a thermal analysis of 50
No transition temperature was observed below 0°C.
これらのフィルムの機械物性を第１表に示す。The mechanical properties of these films are shown in Table 1.
参考例２ 繊維強化熱硬化性樹脂の製造エポキシ樹脂
（化成ファイバーライト社製、”７７１４） （メチル
エチルケトン混合液、固形分５０重世％）を一方向に引
きそろえたＰＡＮ系炭素繊維（旭日本カーボンファイバ
ー社製ハイカーボロン＠１２ｋ）に含浸しつつ、これを
シリコン離型紙を巻き付けた５００ｍｍφのドラム上に
巻き取った。Reference Example 2 Production of fiber-reinforced thermosetting resin PAN-based carbon fiber (Asahi Nippon Carbon) made of epoxy resin (manufactured by Kasei Fiberlite Co., Ltd., "7714") (methyl ethyl ketone mixed liquid, solid content 50%) aligned in one direction While impregnated with Hicarboron@12k (manufactured by Fiber Co., Ltd.), this was wound onto a 500 mm diameter drum wrapped with silicone release paper.
これを繊維方向と直角な方向に切り開き、１００℃で３
０分加熱して一方向プリブレグを調製した。Cut this in the direction perpendicular to the fiber direction and heat it at 100℃ for 3 minutes.
A unidirectional pre-reg was prepared by heating for 0 minutes.
繊維の体積含有率が６３％、厚さは約０．２ｍｍであっ
た。The fiber volume content was 63% and the thickness was about 0.2 mm.
実施例１
厚さ１０μｍのＰＰＴＡフィルムを炭素繊維一方向プリ
プレグと各−層ずつホントラミネークロールで圧着して
成形用材料とした。Example 1 A PPTA film having a thickness of 10 μm was bonded to a carbon fiber unidirectional prepreg layer by layer using a real laminate roll to obtain a molding material.
これを１５０ｍｍＸ１５０ｍｍの大きさに切り出し１８
Ｎ積層し、オートクレーブ中で、１４０℃で３時間、４
ｋｇ／ｃＩＩＩの窒素圧下におき硬化成形し、厚さ約３
１１ＩＩ１１の平板を得た。Cut this into a size of 150mm x 150mm 18
N layered and in an autoclave at 140°C for 3 hours, 4
Cured and molded under nitrogen pressure of kg/cIII, with a thickness of approximately 3
11II11 plates were obtained.
この平板から幅１０００皿、長さ１５０圓の０゜曲げ試
験片を切り出し、島津製作所製万能試験機ＡＣ−１０Ｔ
Ａで曲げ破壊強度を測定した。A 0° bending test piece with a width of 1,000 plates and a length of 150 mm was cut out from this flat plate, and was tested using a universal testing machine AC-10 manufactured by Shimadzu Corporation.
Bending fracture strength was measured in A.
破壊した試験片は２つに折れたが飛散はしなかった。曲
げ破壊強度を第２表に示す。The destroyed test piece broke in two, but did not scatter. The bending fracture strength is shown in Table 2.
実施例２
炭素繊維プリプレグを１５０ｍｍＸ１５０■の大きさに
切り出し１０層積層し、その両側に予め、”７７１４エ
ポキシを１０μｍの厚さで塗布しＢステージ化した２５
μｍのＰＰＴＡフィルムを各４層ずつ、ラミネークロー
ルで圧着し、サンドインチ型の成形用材料とした。Example 2 Carbon fiber prepreg was cut out to a size of 150 mm x 150 cm and 10 layers were laminated, and both sides of the prepreg were pre-coated with ``7714 epoxy to a thickness of 10 μm to form a B stage.
Four layers of PPTA films each having a thickness of 1.5 μm were pressed together using a lamination roll to obtain a sandwich-type molding material.
これを実施例１と同じ条件下に硬化成形し、約２鴫厚の
平板を得、幅１２．７ ｍｍ、長さ１００ｍｍの０°曲
げ試験片を切り出した。This was cured and molded under the same conditions as in Example 1 to obtain a flat plate with a thickness of about 2 mm, and a 0° bending test piece with a width of 12.7 mm and a length of 100 mm was cut out.
曲げ破壊後の試験片は、くの字に曲がったものの破断は
しなかった。曲げ破壊強度を第２表に示す。The test piece after the bending fracture was bent in a dogleg shape but did not break. The bending fracture strength is shown in Table 2.
比較例１
炭素繊維プリプレグを１５０ｍｍＸ１５０ｍｍにカット
し１９層積層し、実施例１と同じ条件下にオートクレー
ブ成形し、平板を得、０°曲げ試験に供した。Comparative Example 1 Carbon fiber prepreg was cut into 150 mm x 150 mm, 19 layers were laminated, and autoclaved under the same conditions as in Example 1 to obtain a flat plate, which was subjected to a 0° bending test.
曲げ破壊した試験は完全に破断し周囲に飛散した。曲げ
破壊強度を第２表に示す。In the test that caused bending failure, it completely broke and was scattered around. The bending fracture strength is shown in Table 2.
実施例３
テフロンフィルムを巻いて径９１Ｔｌ１１１としたステ
ンレスの円柱状金型に、炭素繊維プリプレグを繊維軸が
長さ方向と一致する様に４層捲回した後、更に実施例２
と同様のエポキシ塗工ＰＰＴＡフィルムを４層または１
．０層捲回し、金型を除去して円筒状の成形用材料２種
を得た。Example 3 After winding four layers of carbon fiber prepreg in a stainless steel cylindrical mold with a diameter of 91Tl111 by wrapping a Teflon film so that the fiber axis coincides with the length direction, Example 2
4 layers or 1 layer of epoxy-coated PPTA film similar to
．． After 0-layer winding, the mold was removed to obtain two kinds of cylindrical molding materials.
これにテフロンフィルムを巻き付は内径１２ｍｍのステ
ンレス管に押し込み、エアバッグで内側から加圧（４ｋ
ｇ／Ｃ１ａ）しつつ１４０゛Ｃ×２時間加熱硬化して、
内径約１０ｍｍ、肉厚約１ｍｍの管を得た。Wrapping a Teflon film around this, we pushed it into a stainless steel tube with an inner diameter of 12 mm, and then pressurized it from the inside with an air bag (4k
g/C1a) and heat curing at 140°C for 2 hours.
A tube with an inner diameter of about 10 mm and a wall thickness of about 1 mm was obtained.
これを長さ６５ｍｍに切り出し、秤量１５０ｋｇ −ｃ
ｍ（ハンマー重量３．８７４ｋｇ、振上げ角１３５度）
でアイゾツト衝撃試験を行った結果、消費エネルギーは
、第３表に示す通りとなった。Cut this into a length of 65 mm, weighing 150 kg -c
m (hammer weight 3.874 kg, swinging angle 135 degrees)
As a result of conducting an Izot impact test, the energy consumption was as shown in Table 3.
アイゾツト衝撃試験後の試験片は、くの字に座屈し内部
の炭素繊維強化層は繊維軸に沿って破壊するものの、外
層は破壊することなく、従って鋭利な破壊面が露出する
ことはなかった。After the Izotsu impact test, the test piece buckled in a dogleg shape and the internal carbon fiber reinforced layer broke along the fiber axis, but the outer layer did not break, so no sharp fracture surface was exposed. .
また、成形体の一部を長さ１５ＩＩＩＩ１１に切り出し
、管の長さ方向と、径方向の圧縮試験を１ｍｍ１分の圧
縮速さで実施し圧縮破壊強度（軸圧縮強度及び面圧縮強
度）を測定した。In addition, a part of the molded body was cut out to a length of 15III11, and a compression test was performed in the length direction and radial direction of the tube at a compression speed of 1 mm/min to measure the compressive fracture strength (axial compressive strength and surface compressive strength). did.
その結果を第３表に示す。The results are shown in Table 3.
比較例２
炭素繊維プリプレグのみを実施例３と同様の金型に６層
、繊維軸が長さ方向と一致する様に捲回して、成形用材
料とし実施例３と同様の条件で成形し２種の管を得た。Comparative Example 2 Only carbon fiber prepreg was wound in 6 layers in the same mold as in Example 3 so that the fiber axis coincided with the length direction, and used as a molding material and molded under the same conditions as in Example 3. I got a tube of seeds.
アイゾツト衝撃及び圧縮試験の結果を第３表に示す。The results of the Izot impact and compression tests are shown in Table 3.
試験の際、これらの管は繊維配向方向に沿ってバラバラ
に破壊し飛散した。During the test, these tubes broke apart and scattered along the fiber orientation direction.
比較例３
炭素繊維プリプレグのみを６層、長さ方向に対して４５
度の積層角で積層して円筒状の材料を得、実施例３と同
様の条件下に成形して管を調製した。Comparative Example 3 6 layers of carbon fiber prepreg only, 45 layers in the length direction
A cylindrical material was obtained by laminating the material at a lamination angle of 1.5 degrees, and the material was molded under the same conditions as in Example 3 to prepare a tube.
アイゾツト衝撃及び圧縮試験の結果を第３表に示す。The results of the Izot impact and compression tests are shown in Table 3.
試験により管は２つに破壊し、炭素繊維の鋭利な破壊面
が露出した。During the test, the tube broke in two, exposing the sharp broken surface of the carbon fiber.
（発明の効果）
本発明の成形用材料は、強化用繊維と共に引張強度・弾
性率が極めて大きく、耐熱性の優れたフィルム層を一体
化させて使用し、これによって成形した複合材料は、優
秀な機械的強度を有し、且つこれまでにない高い耐衝撃
性を有するという極めて優れた効果を示すものである。(Effects of the Invention) The molding material of the present invention uses reinforcing fibers in combination with a film layer that has extremely high tensile strength and elastic modulus and excellent heat resistance, and the composite material molded using this is excellent. This material has excellent mechanical strength and unprecedented impact resistance.
また、極めて手間と技術を要するアングルプライ積層に
よる機械物性の等力比効果も容易に達成され、工業的製
造において大きな意義を有するものである。In addition, the isoforce ratio effect on mechanical properties can be easily achieved through angle ply lamination, which requires a great deal of effort and skill, and is of great significance in industrial manufacturing.
従って本発明の成形用材料は、これらの特徴を活かして
様々の形状に賦形することにより、例えばゴルフクラブ
シャフトやテニスラケットフレーム等スポーツやレジャ
ーの分野から航空機の構造部材等航空宇宙分野において
も極めて好ましく利用される。Therefore, the molding material of the present invention can be formed into various shapes by taking advantage of these characteristics, and can be used in the field of sports and leisure, such as golf club shafts and tennis racket frames, as well as in the aerospace field, such as structural members of aircraft. Very preferably used.
特許出願人 旭化成工業株式会社Patent applicant: Asahi Kasei Industries, Ltd.
Claims (1)
実質的になり、３５ｋｇ／ｍｍ＾２以上の引張強度およ
び７００ｋｇ／ｍｍ＾２以上の引張弾性率を有するフィ
ルム層と繊維強化熱硬化性樹脂層とを積層してなる成形
用の熱硬化性樹脂材料。A fiber-reinforced thermosetting film layer consisting essentially of an organic polymer having a melting point or decomposition point of 300°C or higher and having a tensile strength of 35 kg/mm^2 or higher and a tensile modulus of 700 kg/mm^2 or higher. A thermosetting resin material for molding made by laminating resin layers.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1097595A JP2882638B2 (en) | 1989-04-19 | 1989-04-19 | Molding material |
| CA 2026113 CA2026113C (en) | 1989-01-25 | 1990-01-25 | Prepreg, composite molded body, and method of manufacture of the composite molded body |
| KR1019900702133A KR930003894B1 (en) | 1989-01-25 | 1990-01-25 | New prepreg and composite molding and production of composite molding |
| PCT/JP1990/000085 WO1990008802A1 (en) | 1989-01-25 | 1990-01-25 | New prepreg and composite molding, and production of composite molding |
| DE69032210T DE69032210D1 (en) | 1989-01-25 | 1990-01-25 | PRE-IMPREGNATED COMPOSITE MOLDS AND PRODUCTION OF A COMPOSITE MOLD |
| EP90902370A EP0541795B1 (en) | 1989-01-25 | 1990-01-25 | New prepreg and composite molding, and production of composite molding |
| TW079100742A TW205053B (en) | 1989-01-25 | 1990-02-02 | |
| US08/034,171 US5597631A (en) | 1989-01-25 | 1993-02-12 | Prepreg, composite molding body, and method of manufacture of the composite molded body |
| US08/709,188 US5770313A (en) | 1989-01-25 | 1996-09-06 | Prepreg, composite molded body and method of manufacture of the composite molded body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1097595A JP2882638B2 (en) | 1989-04-19 | 1989-04-19 | Molding material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02276832A true JPH02276832A (en) | 1990-11-13 |
| JP2882638B2 JP2882638B2 (en) | 1999-04-12 |
Family
ID=14196590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1097595A Expired - Fee Related JP2882638B2 (en) | 1989-01-25 | 1989-04-19 | Molding material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2882638B2 (en) |
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| JP2013071846A (en) * | 2011-09-28 | 2013-04-22 | Boeing Co:The | Material placement system |
| US10137648B2 (en) | 2011-09-28 | 2018-11-27 | The Boeing Company | Material placement system |
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| JP2882638B2 (en) | 1999-04-12 |
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