JP2005336407A - Composite material excellent in surface smoothness - Google Patents
Composite material excellent in surface smoothness Download PDFInfo
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- JP2005336407A JP2005336407A JP2004160347A JP2004160347A JP2005336407A JP 2005336407 A JP2005336407 A JP 2005336407A JP 2004160347 A JP2004160347 A JP 2004160347A JP 2004160347 A JP2004160347 A JP 2004160347A JP 2005336407 A JP2005336407 A JP 2005336407A
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- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 229920005989 resin Polymers 0.000 claims abstract description 62
- 239000011347 resin Substances 0.000 claims abstract description 62
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000012779 reinforcing material Substances 0.000 claims abstract description 23
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- 238000013461 design Methods 0.000 claims abstract description 9
- 239000000835 fiber Substances 0.000 claims description 41
- 239000002759 woven fabric Substances 0.000 claims description 27
- 239000004744 fabric Substances 0.000 claims description 21
- 238000000465 moulding Methods 0.000 claims description 14
- 230000002787 reinforcement Effects 0.000 claims description 14
- 229920000647 polyepoxide Polymers 0.000 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 9
- 239000004643 cyanate ester Substances 0.000 claims description 4
- 238000001802 infusion Methods 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 238000001721 transfer moulding Methods 0.000 claims description 4
- 239000012784 inorganic fiber Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 claims description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920006287 phenoxy resin Polymers 0.000 claims description 2
- 239000013034 phenoxy resin Substances 0.000 claims description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 2
- 229920001567 vinyl ester resin Polymers 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 7
- 239000002990 reinforced plastic Substances 0.000 abstract 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 10
- 239000004917 carbon fiber Substances 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 9
- 239000011151 fibre-reinforced plastic Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003733 fiber-reinforced composite Substances 0.000 description 2
- 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 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000011074 autoclave method Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920006241 epoxy vinyl ester resin Polymers 0.000 description 1
- IPZIVCLZBFDXTA-UHFFFAOYSA-N ethyl n-prop-2-enoylcarbamate Chemical compound CCOC(=O)NC(=O)C=C IPZIVCLZBFDXTA-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Images
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- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
Description
本発明は、繊維強化プラスチック成形品として利用される、表面平滑性に優れた複合材料に関する。 The present invention relates to a composite material that is used as a fiber-reinforced plastic molded article and has excellent surface smoothness.
繊維強化プラスチック成形品は、従来、繊維強化材に予め樹脂を含浸したシートを用いたオートクレーブ成形が主流であった。
近年、繊維強化プラスチック成形品のコスト削減の要望が高く、従来のオートクレーブ成形方法から樹脂トランスファー成形法（ＲＴＭ法）またはレジンフィルムインフュージョン成形法(ＲＦＩ法）を用いた成形に移りつつある。 ＲＴＭ法またはＲＦＩ法は、熱硬化性樹脂を用いた成形法の一種であり、繊維強化プラスチック成形品は、繊維強化材を型に敷設した後、型のキャビティーに樹脂を注入し、または樹脂フィルムを型に敷設して、繊維強化材に樹脂を含浸させ硬化させることにより製造される。
Conventionally, a fiber reinforced plastic molded product has been mainly autoclave molding using a sheet in which a fiber reinforcing material is impregnated with a resin in advance.
In recent years, there is a high demand for cost reduction of fiber-reinforced plastic molded products, and the conventional autoclave molding method is being shifted to molding using a resin transfer molding method (RTM method) or a resin film infusion molding method (RFI method). The RTM method or the RFI method is a kind of molding method using a thermosetting resin, and a fiber reinforced plastic molded product is formed by injecting a resin into a mold cavity after laying a fiber reinforcing material on a mold, or a resin It is manufactured by laying a film in a mold, and impregnating and curing a resin in a fiber reinforcement.
オートクレーブ成形、ＲＴＭ法、ＲＦＩ法で使用する繊維強化材は、通常織物等のシート状に加工した繊維強化材を用いる。
シート状の繊維強化材としては様々な形態のものがあるが、織物、多軸織物が汎用されている。織物、多軸織物等のシート状繊維強化材を、繊維強化プラスチック成形品の表面に配置する場合、織目の凹凸、多軸織物のステッチ部の凹凸が成形品の表面に現れるため、成形品の平滑性が損なわれる欠点がある。
The fiber reinforcement used in the autoclave molding, the RTM method, and the RFI method is usually a fiber reinforcement processed into a sheet shape such as a fabric.
There are various forms of sheet-like fiber reinforcement, but woven fabrics and multiaxial fabrics are widely used. When sheet-like fiber reinforcements such as woven fabrics and multiaxial fabrics are placed on the surface of a fiber-reinforced plastic molded product, the unevenness of the texture and the unevenness of the stitches of the multiaxial fabric appear on the surface of the molded product. There is a drawback that the smoothness of the glass is impaired.
多軸織物を使用した場合、表面平滑性を向上させる方法として、多軸織物のステッチ糸に低融点ポリマーを使用し、繊維強化プラスチック成形品を成形する際、低融点ポリマーの融点以上で加熱成形し、ステッチ糸を溶融する方法が紹介されている（特許文献１）。しかし、低融点ポリマーをステッチ糸に使用した多軸織物を用いた場合でも、ステッチ糸が溶融される前の形状が保持され、ステッチ糸の周辺には、僅かな凹みが観察され、表面を完全に平滑にするのは困難である。また、表面平滑性を向上させる方法として、成形品の表面に、不織布等のサーフェースマットの使用やゲルコート剤を使用する方法が実施されている。しかし、サーフェースマットを使用しても、サーフェースマットの材質、厚み及びサーフェースマット材の下の層に使用する繊維強化材の種類によっては、製品表面が平滑にならない事がある。
本発明の目的は、平滑な表面（意匠性表面）を有する繊維強化プラスチック成形品を得るための、表面平滑性に優れた複合材料を提供することにある。 An object of the present invention is to provide a composite material excellent in surface smoothness for obtaining a fiber-reinforced plastic molded article having a smooth surface (designable surface).
本発明の目的・課題は、繊維強化材シート層と少なくともその一面に積層された不織布層からなる積層体と、該積層体に含浸せしめられたマトリックス樹脂とからなる表面平滑性に優れた複合材料によって達成される。 An object and problem of the present invention is a composite material excellent in surface smoothness comprising a laminate comprising a fiber reinforcement sheet layer, a nonwoven fabric layer laminated on at least one surface thereof, and a matrix resin impregnated in the laminate. Achieved by:
本発明の複合材料は、表面に不織布を使用し且つ内層の繊維強化材シートを適正化しているため、複合材料表面に凹凸が無く、表面平滑な成形面が得られる。そしてまた、平滑性に優れた意匠性表面を有する繊維強化複合材料（成形品を含む）が得られる。 Since the composite material of the present invention uses a non-woven fabric on the surface and optimizes the inner-layer fiber reinforcing material sheet, the composite material surface has no irregularities and a smooth surface can be obtained. Moreover, a fiber-reinforced composite material (including a molded product) having a design surface excellent in smoothness can be obtained.
本発明における複合材料は、繊維強化材シート層とそれに積層された不織布層からなる積層体と、この積層体に含浸せしめられたマトリックス樹脂とからなるものであるが、積層体は、繊維強化材シート層の片面に不織布層が積層されたものでも、繊維強化材シート層の両面に不織布層が積層されたものであっても良い。また、本発明における複合材料は、最終的に、種々の用途の繊維強化プラスチック成形品とされる場合に、複合材料を構成する不織布層の外表面に、意匠性樹脂層が、塗装その他の方法で形成される場合があるが、かかる態様のものも、本発明の範囲に含まれるものである。なお、本発明において、層とは、例えば、繊維強化材シート層と言う場合には、一枚の繊維強化材シートの場合もあるし、それを複数枚重ねたものであっても良い。 The composite material in the present invention comprises a laminate comprising a fiber reinforcing material sheet layer and a nonwoven fabric layer laminated thereon, and a matrix resin impregnated in the laminate. The nonwoven fabric layer may be laminated on one side of the sheet layer, or the nonwoven fabric layer may be laminated on both sides of the fiber reinforcing material sheet layer. Moreover, when the composite material in the present invention is finally formed into a fiber-reinforced plastic molded article for various uses, the design resin layer is applied to the outer surface of the nonwoven fabric layer constituting the composite material, and other methods are applied. However, such an embodiment is also included in the scope of the present invention. In the present invention, for example, when referring to a fiber reinforcing material sheet layer, the layer may be a single fiber reinforcing material sheet, or may be a stack of a plurality of sheets.
本発明において、繊維強化材シートは、シート状の繊維強化材を意味する。そして、繊維強化材としては、特に制限はなく、複合材料に使用される繊維強化材であれば何でも使用できるが、炭素繊維、ガラス繊維、アラミド繊維が好ましい。繊維強化材シートとしては、連続したフィラメントをサイズ剤を用いて収束した束(ストランド）、織物、多軸織物等に加工したシート状物が適当である。織物の場合は、平織、２／２綾織、朱子織が好ましい。多軸織物の場合は、不織布に接している面の多軸織物の各ストランド間の隙間が、０．２ｍｍ以下であることが好ましい。 In the present invention, the fiber reinforcing material sheet means a sheet-like fiber reinforcing material. The fiber reinforcing material is not particularly limited, and any fiber reinforcing material used for composite materials can be used, but carbon fiber, glass fiber, and aramid fiber are preferable. As the fiber reinforcing material sheet, a sheet-like product obtained by processing continuous filaments into bundles (strands), woven fabrics, multiaxial woven fabrics and the like that are converged using a sizing agent is suitable. In the case of a woven fabric, plain weave, 2/2 twill weave, and satin weave are preferable. In the case of a multiaxial woven fabric, the gap between the strands of the multiaxial woven fabric in contact with the nonwoven fabric is preferably 0.2 mm or less.
繊維強化材シートとして織物を使用する場合、織物１層の厚みが０．２ｍｍ以下であり、且つ、（不織布層の厚み）÷（織物1層の厚み）の値が０．５以上であることが好ましい。織物の厚みが０.２ｍｍを超えていたり、または織物の厚みが０.２ｍｍ以下でも（不織布層の厚み）÷（織物1層の厚み）の値が０．５未満であると、複合材料の表面側に不織布を使用しても、内層の繊維強化材シート層の凹凸が表面に現れてしまうので、好ましくない。多軸織物の場合も、各ストランド間の隙間が０．２ｍｍを超えると、同様な現象が生じるので好ましくない。 When a woven fabric is used as the fiber reinforcement sheet, the thickness of one woven fabric is 0.2 mm or less, and the value of (thickness of non-woven fabric layer) ÷ (thickness of one woven fabric) is 0.5 or more. Is preferred. Even if the thickness of the woven fabric exceeds 0.2 mm, or the thickness of the woven fabric is 0.2 mm or less (thickness of the non-woven fabric layer) ÷ (thickness of one woven fabric layer) is less than 0.5, Even if a nonwoven fabric is used on the surface side, the irregularities of the inner fiber reinforcing material sheet layer appear on the surface, which is not preferable. Also in the case of a multiaxial woven fabric, if the gap between the strands exceeds 0.2 mm, the same phenomenon occurs, which is not preferable.
多軸織物とは、一方向に引き揃えた繊維強化材の束をシート状にして角度を変えて積層し、ナイロン糸、ポリエステル糸、ガラス繊維糸等のステッチ糸で、この積層体を厚さ方向に貫通して、積層体の表面と裏面の間を表面方向に沿って往復しステッチした織物をいう。
多軸織物は面対称となるように選択する事が好ましい。多軸織物の目付は、１００〜２０００ｇ／ｍ２が好ましく、２００〜８００ｇ／ｍ２がより好ましい。多軸織物の１層当たりの厚みは、０．１〜２ｍｍが好ましい。 好ましい多軸織物の例としては、〔４５／−４５／−４５／４５〕、〔０／−４５／−４５／０〕、〔０／＋４５／−４５／−４５／＋４５／０〕、〔０／＋４５／９０／−４５／−４５／９０／＋４５／０〕等を挙げることができる。
積重して面対称となる多軸織物の組合わせとしては、例えば〔４５／−４５〕及び〔−４５／４５〕、〔０／＋４５／−４５〕及び〔−４５／＋４５／０〕、〔０／＋４５／−４５／９０〕及び〔９０／−４５／＋４５／０〕等を挙げることができる。０、±４５、９０は、多軸織物を構成する各層の積層角度を表し、それぞれ一方向に引き揃えた繊維強化材の繊維軸方向が、織物の長さ方向に対して０°、±４５°、９０°であることを示している。積層角度はこれらの角度に限定されず、任意の角度とすることができる。
Multiaxial woven fabric is a bundle of fiber reinforcements aligned in one direction, laminated at different angles, and stitched yarns such as nylon yarn, polyester yarn, and glass fiber yarn. It refers to a woven fabric that penetrates in the direction and stitches by reciprocating along the surface direction between the front and back surfaces of the laminate.
The multiaxial fabric is preferably selected so as to be plane symmetric. Basis weight of the multiaxial fabric is preferably 100~2000g / m 2, 200~800g / m 2 is more preferable. The thickness per layer of the multiaxial fabric is preferably 0.1 to 2 mm. Examples of preferred multiaxial fabrics include [45 / −45 / −45 / 45], [0 / −45 / −45 / 0], [0 / + 45 / −45 / −45 / + 45/0], [ 0 / + 45/90 / −45 / −45 / 90 / + 45/0] and the like.
For example, [45 / −45] and [−45/45], [0 / + 45 / −45] and [−45 / + 45/0], [0 / + 45 / −45 / 90] and [90 / −45 / + 45/0] can be exemplified. 0, ± 45, 90 represents the stacking angle of each layer constituting the multiaxial fabric, and the fiber axis direction of the fiber reinforcement arranged in one direction is 0 °, ± 45 with respect to the length direction of the fabric. It indicates that the angle is 90 °. The stacking angle is not limited to these angles, and can be any angle.
本発明において用いられる不織布の材料は、複合材料に使用される繊維強化材であれば特に制限はなく、炭素繊維、ガラス繊維、アラミド繊維、ボロン繊維、金属繊維等を使用できるが、特に炭素繊維、ガラス繊維等の無機繊維が好ましい。本発明において、不織布層の外表面（繊維強化材シート層に接している面ではない方の面）に塗装等を施して意匠性樹脂層を形成する場合、成形に用いた離型剤を取り除くため、あるいは塗装の密着性を向上させるために、不織布層の外表面を目粗しすることが必要な場合がある。かかる場合、
不織布が有機繊維から構成されていると、目粗し操作によってフィブリル化した繊維のヒゲが表面に出てきて、その状態で塗装等を行うと、塗装面が平滑ではなくなる場合がある。従って、本発明においては、不織布層は無機繊維からなるものの方が好ましいのである。
なお、本発明において不織布とは、 マット、不織布、ペーパー
等、織物以外のもの（織ってないもの）を意味する。そして、不織布層とは、かかる不織布が一枚あるいは複数枚重ねられたものを意味する。かかる不織布層の厚みは ０．０５〜０．５ｍｍが適当で、０．１〜０．３ｍｍがより好ましい。
不織布の厚みが０.０５ｍｍ以下では、不織布の内層に使用する繊維強化材シートの凹凸が表面に現れ、表面平滑性が損なわれる。
また、０.５ｍｍ以上では、繊維強化複合材料の重量を増加させる問題があり、軽量化を目指す用途には適さない。
The material of the nonwoven fabric used in the present invention is not particularly limited as long as it is a fiber reinforcing material used for the composite material, and carbon fiber, glass fiber, aramid fiber, boron fiber, metal fiber, etc. can be used. Inorganic fibers such as glass fibers are preferred. In the present invention, when the outer surface of the nonwoven fabric layer (the surface that is not in contact with the fiber reinforcing material sheet layer) is coated to form the design resin layer, the release agent used for molding is removed. For this reason, or in order to improve the adhesion of the coating, it may be necessary to roughen the outer surface of the nonwoven fabric layer. In such a case,
If the nonwoven fabric is composed of organic fibers, the fibrillated fiber mustache will come out on the surface, and if coating or the like is performed in that state, the coated surface may not be smooth. Therefore, in the present invention, the nonwoven fabric layer is preferably made of inorganic fibers.
In addition, in this invention, a nonwoven fabric means things other than textiles (thing which is not woven), such as a mat, a nonwoven fabric, and paper. And a nonwoven fabric layer means what laminated | stacked one or more of this nonwoven fabric. The thickness of the nonwoven fabric layer is suitably 0.05 to 0.5 mm, more preferably 0.1 to 0.3 mm.
When the thickness of the nonwoven fabric is 0.05 mm or less, the unevenness of the fiber reinforcing material sheet used for the inner layer of the nonwoven fabric appears on the surface, and the surface smoothness is impaired.
On the other hand, when the thickness is 0.5 mm or more, there is a problem of increasing the weight of the fiber-reinforced composite material, which is not suitable for applications aiming at weight reduction.
本発明のマトリックス樹脂としては、通常、成形品の製造に用いられる熱硬化性樹脂が使用できる。具体的には、エポキシ樹脂、不飽和ポリエステル樹脂、フェノール樹脂、ビニルエステル樹脂、シアン酸エステル樹脂、ウレタンアクリレート樹脂、フェノキシ樹脂、アルキド樹脂、ウレタン樹脂、マレイミド樹脂とシアン酸エステル樹脂の予備重合樹脂から選ばれる樹脂がある。これらは１種又は２種以上の混合物として用いることもできるし、また、用途によっては、一部熱可塑性樹脂と混合して用いることもできる。中でも、耐熱性、弾性率、耐薬品性に優れたエポキシ樹脂やビニルエステル樹脂が、特に好ましい。これらの熱硬化性樹脂には、硬化剤、硬化促進剤以外に、通常用いられる着色剤や各種添加剤等が含まれていてもよい。複合材料中の、マトリックス樹脂の含有率は、通常、１０〜７０重量％にあるのが適当である。 As the matrix resin of the present invention, a thermosetting resin usually used for producing a molded product can be used. Specifically, from epoxy resin, unsaturated polyester resin, phenol resin, vinyl ester resin, cyanate ester resin, urethane acrylate resin, phenoxy resin, alkyd resin, urethane resin, maleimide resin and prepolymerized resin of cyanate ester resin There are resins to be selected. These can also be used as a 1 type, or 2 or more types of mixture, and can also be mixed with a thermoplastic resin and used depending on a use. Of these, epoxy resins and vinyl ester resins excellent in heat resistance, elastic modulus, and chemical resistance are particularly preferable. These thermosetting resins may contain commonly used colorants and various additives in addition to the curing agent and the curing accelerator. The content of the matrix resin in the composite material is usually 10 to 70% by weight.
繊維強化材シート層と少なくともその一面に積層された不織布層からなる積層体と、この積層体に含浸せしめられたマトリックス樹脂とからなる本発明の複合材料において、不織布層の外表面（繊維強化材シート層に接している面ではない方の面）に、塗装等によって意匠性樹脂層が形成されている複合材料（成形品となっているものも含む）も、本発明の他の態様である。かかる樹脂層を形成するためには、例えば、アクリル系、アクリルウレタン系、フッ素系、シリコーン系、エポキシ系の樹脂を用いることができ、樹脂層には、染料や顔料などの着色剤を添加することもできる。かかる樹脂層は、繊維強化材シート層と不織布層からなる積層体とマトリックス樹脂から成形された複合材料に、意匠性樹脂層を塗布する方法、例えば、スプレー、バーコーター、ダイコーター、スピンナー方法によって形成することができる。 In the composite material of the present invention comprising a laminate comprising a fiber reinforcement sheet layer and a nonwoven fabric layer laminated on at least one surface thereof, and a matrix resin impregnated in the laminate, the outer surface of the nonwoven fabric layer (fiber reinforcement) A composite material (including a molded product) in which a designable resin layer is formed by painting or the like on the surface that is not in contact with the sheet layer is another aspect of the present invention. . In order to form such a resin layer, for example, acrylic, acrylurethane, fluorine, silicone, and epoxy resins can be used, and coloring agents such as dyes and pigments are added to the resin layer. You can also. Such a resin layer is formed by a method of applying a design resin layer to a composite material formed from a laminate formed of a fiber reinforcing material sheet layer and a nonwoven fabric layer and a matrix resin, for example, spray, bar coater, die coater, spinner method. Can be formed.
本発明において、繊維強化材シート層と不織布層からなる積層体とマトリックス樹脂から複合材料を成形する方法としては、従来公知の方法、例えば、オートクレーブ法、樹脂トランスファー成形法（ＲＴＭ法）、レジンフィルムインフュージョン成形法（ＲＦＩ成形法）を採用することができるが、特に、製造コストの削減の観点から、樹脂トランスファー成形法又はレジンフィルムインフュージョン成形法で低コスト、高品位の複合材料が得られるので適当である。 In the present invention, as a method of molding a composite material from a laminate comprising a fiber reinforcing material sheet layer and a nonwoven fabric layer and a matrix resin, a conventionally known method such as an autoclave method, a resin transfer molding method (RTM method), a resin film An infusion molding method (RFI molding method) can be adopted, but a low-cost, high-quality composite material can be obtained by a resin transfer molding method or a resin film infusion molding method, particularly from the viewpoint of reducing manufacturing costs. So it is appropriate.
図面により、本発明の複合材料の態様について説明する。図１は、繊維強化材シート層１とその片面に積層された不織布層２とからなる積層体と、この積層体に含浸・硬化せしめられたマトリックス樹脂３からなる複合材料を示している。図２は、図１の複合材料の不織布層２の外表面に、意匠性樹脂層４が形成された複合材料を示している。以下、実施例により、本発明を詳述する。
The aspect of the composite material of the present invention will be described with reference to the drawings. FIG. 1 shows a composite material composed of a laminate composed of a fiber reinforcement sheet layer 1 and a nonwoven fabric layer 2 laminated on one side thereof, and a
炭素繊維ＨＴＡ−１２Ｋ（東邦テナックス社製）を使用した多軸織物（１）
（＋４５／−４５／−４５／＋４５の角度で４枚積層したもの、ストランド間の隙間が０.１ｍｍ、織物の目付８００ｇ／ｍ２）を、幅５００ｍｍ、長さ５００ｍｍにカットした。７００×７００ｍｍの離型処理したアルミ板の上に、不織布（炭素繊維で作られたペーパーであるＢＰ−１０３０Ａ−ＥＳ、目付け３０ｇ／ｍ２、東邦テナックス社製）、その上に多軸織物（１）
を２枚、その上に不織布（炭素繊維で作られたペーパーであるＢＰ−１０３０Ａ−ＥＳ、目付け３０ｇ／ｍ２、東邦テナックス社製）を重ねて積層体とした。
更に積層体の上に、離型性機能を付与した基材であるピールクロスのＲｅｌｅａｓｅ Ｐｌｙ Ｃ（ＡＩＲＴＥＣＨ社製）と樹脂拡散基材のＲｅｓｉｎ Ｆｌｏｗ ６０（ＡＩＲＴＥＣＨ社製）を積層した。
その後、樹脂注入口と樹脂排出口形成のためのホースを配置し、全体をナイロンバッグフィルムで覆い、シーラントテープで密閉し、内部を真空にした。続いてアルミ板を８０℃に加温し、バック内を５ｔｏｒｒ以下に減圧した後、樹脂注入口を通して、真空系内へエポキシ樹脂（ジャパンエポキシレジン社製ＥＰ８０７の１００質量部と、サンテクノケミカル社製ジェファーミンＴ-４０３の４５質量部の混合物）の注入を行った。 注入した混合樹脂がバック内に充満し、積層体に含浸した状態で８０℃で２時間保持し、本発明の複合材料を得た。 複合材料の断面厚みを測定したところ、表面の不織布部が０.２ｍｍ、多軸織物（１）が２枚で１．６ｍｍ、裏側の不織布部が０.２ｍｍであった。得られた複合材料の表面を目視評価したところ、凹凸が無くきれいな表面であった。
Multiaxial fabric using carbon fiber HTA-12K (Toho Tenax Co., Ltd.) (1)
(4 layers laminated at an angle of + 45 / −45 / −45 / + 45, a gap between strands of 0.1 mm, and a fabric basis weight of 800 g / m 2 ) was cut into a width of 500 mm and a length of 500 mm. A non-woven fabric (BP-1030A-ES which is a paper made of carbon fiber, basis weight 30 g / m 2 , manufactured by Toho Tenax Co., Ltd.) on a 700 × 700 mm release aluminum plate, and a multiaxial fabric ( 1)
And a non-woven fabric (BP-1030A-ES, which is a paper made of carbon fiber, 30 g / m 2 basis weight, manufactured by Toho Tenax Co., Ltd.).
Further, peel cross Release Ply C (manufactured by AIRTECH), which is a base material having a releasability function, and resin diffusion base material Resin Flow 60 (manufactured by AIRTECH) were laminated on the laminate.
Thereafter, a hose for forming a resin inlet and a resin outlet was disposed, the whole was covered with a nylon bag film, sealed with a sealant tape, and the inside was evacuated. Subsequently, the aluminum plate was heated to 80 ° C., and the pressure in the bag was reduced to 5 torr or less. Then, through the resin inlet, 100 parts by mass of epoxy resin (EP807 manufactured by Japan Epoxy Resin Co., Ltd. and Sun Techno Chemical Co., Ltd.) A mixture of 45 parts by weight of Jeffamine T-403). The injected mixed resin was filled in the bag, and maintained at 80 ° C. for 2 hours in a state of impregnating the laminate to obtain a composite material of the present invention. When the cross-sectional thickness of the composite material was measured, the nonwoven fabric portion on the surface was 0.2 mm, the multiaxial woven fabric (1) was 1.6 mm, and the nonwoven fabric portion on the back side was 0.2 mm. When the surface of the obtained composite material was visually evaluated, there was no unevenness and the surface was clean.
実施例１の多軸織物（１）の代わりに、炭素繊維ＨＴＡ−３Ｋ（東邦テナックス社製）を使用した平織物Ｗ-3101（目付２００ｇ／ｍ２）を８枚使用した以外は、実施例１と同様な方法で、本発明の複合材料を得た。複合材料の断面厚みを測定したところ、表面の不織布部が０.２ｍｍ、平織物部が８枚で１．６ｍｍ、裏側の不織布部が０.２ｍｍであった。得られた複合材料の表面を目視評価したところ、凹凸が無くきれいな表面であった。 Example except that eight plain fabrics W-3101 (weight per unit area: 200 g / m 2 ) using carbon fiber HTA-3K (manufactured by Toho Tenax Co., Ltd.) were used instead of the multiaxial fabric (1) of Example 1. 1 was used to obtain the composite material of the present invention. When the cross-sectional thickness of the composite material was measured, the nonwoven fabric portion on the surface was 0.2 mm, the plain woven fabric portion was 1.6 mm, and the nonwoven fabric portion on the back side was 0.2 mm. When the surface of the obtained composite material was visually evaluated, there was no unevenness and the surface was clean.
実施例２で作製した複合材料の表面を、＃600番のサンドペーパーで研磨し離型剤を除去後、スプレーガンでウレタン塗装（関西ペイント製 レタンＰＧ２Ｋホワイト）を行った。塗装の厚みは０．１ｍｍであった。得られた複合材料の表面を目視評価したところ、凹凸が無くきれいな表面であった。 The surface of the composite material produced in Example 2 was polished with # 600 sandpaper to remove the mold release agent, and then urethane coating (Kansai Paint Retan PG2K White) was performed with a spray gun. The coating thickness was 0.1 mm. When the surface of the obtained composite material was visually evaluated, there was no unevenness and the surface was clean.
ビスフェノールＡ型エポキシ樹脂、エピコート８３４（ジャパンエポキシレジン社製）を７７部、エピコート１００１（ジャパンエポキシレジン社製）を２３部、ジシアンジアミド（ジャパンエポキシレジン社製）を５部、３−（３，４−ジクロロフェニル）−１，１−ジメチルユリア（保士谷化学工業社製）を５部計量し、７０℃でロールミルで混錬し、樹脂組成物を得た。
その後、７０℃でドクターブレード法により樹脂目付１３００ｇ／ｍ２の樹脂フィルムを得た。
77 parts of bisphenol A type epoxy resin, Epicoat 834 (manufactured by Japan Epoxy Resin), 23 parts of Epicoat 1001 (manufactured by Japan Epoxy Resin), 5 parts of dicyandiamide (manufactured by Japan Epoxy Resin), 3- (3,4 -Dichlorophenyl) -1,1-dimethylurea (manufactured by Hoshigaya Chemical Industry Co., Ltd.) was weighed in 5 parts and kneaded with a roll mill at 70 ° C. to obtain a resin composition.
Thereafter, a resin film having a resin basis weight of 1300 g / m 2 was obtained at 70 ° C. by a doctor blade method.
炭素繊維ＨＴＡ−１２Ｋ（東邦テナックス社製）を使用した多軸織物（１）（＋４５／−４５／−４５／＋４５の角度で４枚積層したもの、ストランド間の隙間が０.１ｍｍ、織物の目付８００ｇ／ｍ２）を幅５００ｍｍ、長さ５００ｍｍにカットした。７００×７００ｍｍの離型処理したアルミ板の上に、不織布（炭素繊維で作られたペーパーであるＢＰ−１０３０Ａ−ＥＳ、目付け３０ｇ／ｍ２、東邦テナックス社製）、その上に多軸織物（１）
を２枚、その上に不織布（炭素繊維で作られたペーパーであるＢＰ−１０３０Ａ−ＥＳ、目付け３０ｇ／ｍ２、東邦テナックス社製）を重ねて積層体とした。
積層体の上に上記樹脂フィルムを重ね、全体をナイロンバッグフィルムで覆い、シーラントテープで密閉し、内部を真空にした。その後、硬化炉内で１３０℃で２時間、真空ポンプで減圧しながら加熱硬化し、本発明の複合材料を得た。複合材料の断面厚みを測定したところ、表面の不織布部が０.２ｍｍ、多軸織物（１）が２枚で１．６ｍｍ、裏側の不織布部が０.２ｍｍであった。得られた複合材料の表面を目視評価したところ、凹凸が無くきれいな表面であった。
Multiaxial woven fabric (1) using carbon fiber HTA-12K (manufactured by Toho Tenax Co., Ltd.) (4 layers laminated at an angle of + 45 / −45 / −45 / + 45, the gap between strands is 0.1 mm, A basis weight of 800 g / m 2 ) was cut into a width of 500 mm and a length of 500 mm. A non-woven fabric (BP-1030A-ES which is a paper made of carbon fiber, 30 g / m 2 basis weight, manufactured by Toho Tenax Co., Ltd.) on a 700 × 700 mm release aluminum plate, and a multiaxial fabric ( 1)
And a non-woven fabric (BP-1030A-ES, which is a paper made of carbon fiber, 30 g / m 2 basis weight, manufactured by Toho Tenax Co., Ltd.).
The resin film was stacked on the laminate, and the whole was covered with a nylon bag film, sealed with a sealant tape, and the inside was evacuated. Thereafter, it was cured by heating in a curing furnace at 130 ° C. for 2 hours while reducing the pressure with a vacuum pump to obtain a composite material of the present invention. When the cross-sectional thickness of the composite material was measured, the nonwoven fabric portion on the surface was 0.2 mm, the multiaxial woven fabric (1) was 1.6 mm, and the nonwoven fabric portion on the back side was 0.2 mm. When the surface of the obtained composite material was visually evaluated, there was no unevenness and the surface was clean.
［比較例１］（不織布層を用いない例）
炭素繊維ＨＴＡ−３Ｋ（東邦テナックス社製）を使用した平織物Ｗ-3101（目付２００ｇ／ｍ２）を幅５００ｍｍ、長さ５００ｍｍにカットした。７００×７００ｍｍの離型処理したアルミ板上に、平織物を８枚重ねて積層体とした。
更に積層体の上に、離型性機能を付与した基材であるピールクロスのＲｅｌｅａｓｅ Ｐｌｙ Ｃ（ＡＩＲＴＥＣＨ社製）と樹脂拡散基材のＲｅｓｉｎ Ｆｌｏｗ ６０（ＡＩＲＴＥＣＨ社製）を積層した。その後は、実施例１と同様な方法で本発明の複合材料を得た。得られた複合材料の表面を目視評価したところ、ＨＴＡ−３Ｋのストランド幅の２ｍｍ間隔で凹凸があり、平滑な面は得られなかった。
[Comparative Example 1] (Example using no nonwoven fabric layer)
A plain fabric W-3101 (weight per unit area: 200 g / m 2 ) using carbon fiber HTA-3K (manufactured by Toho Tenax Co., Ltd.) was cut into a width of 500 mm and a length of 500 mm. Eight plain fabrics were stacked on a 700 × 700 mm release aluminum plate to form a laminate.
Further, peel cross Release Ply C (manufactured by AIRTECH), which is a base material having a releasability function, and resin diffusion base material Resin Flow 60 (manufactured by AIRTECH) were laminated on the laminate. Thereafter, the composite material of the present invention was obtained in the same manner as in Example 1. When the surface of the obtained composite material was visually evaluated, there were irregularities at intervals of 2 mm of the strand width of HTA-3K, and a smooth surface was not obtained.
［比較例２］
比較例１で作製した複合材料の表面を＃600番のサンドペーパーで研磨し離型剤を除去後、スプレーガンでウレタン塗装（関西ペイント製 レタンＰＧ２Ｋホワイト）を行った。塗装の厚みは０．１ｍｍであった。得られた複合材料の表面を目視評価したところ、表面は２ｍｍ間隔で凹凸があり、平滑な面は得られなかった。
[Comparative Example 2]
The surface of the composite material produced in Comparative Example 1 was polished with # 600 sandpaper to remove the mold release agent, and then urethane coating (retane PG2K white manufactured by Kansai Paint) was performed with a spray gun. The coating thickness was 0.1 mm. When the surface of the obtained composite material was visually evaluated, the surface was uneven at intervals of 2 mm, and a smooth surface was not obtained.
本発明によって得られた表面平滑性に優れた複合材料は、優れた意匠性表面を有する種々の繊維強化プラスチック成形品として利用される。 The composite material excellent in surface smoothness obtained by the present invention is used as various fiber-reinforced plastic molded articles having an excellent design surface.
１ 繊維強化材シート層
２ 不織布層
３ マトリックス樹脂
４ 意匠性樹脂層
DESCRIPTION OF SYMBOLS 1 Fiber reinforcing material sheet layer 2
Claims (11)
０．０５〜０．５ｍｍである、請求項１〜４記載の表面平滑性に優れた複合材料。 The composite material excellent in surface smoothness according to claim 1, wherein the nonwoven fabric layer has a thickness of 0.05 to 0.5 mm.
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