JP2020029021A - Carbon fiber unwoven fabric composite - Google Patents
Carbon fiber unwoven fabric composite Download PDFInfo
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- JP2020029021A JP2020029021A JP2018155257A JP2018155257A JP2020029021A JP 2020029021 A JP2020029021 A JP 2020029021A JP 2018155257 A JP2018155257 A JP 2018155257A JP 2018155257 A JP2018155257 A JP 2018155257A JP 2020029021 A JP2020029021 A JP 2020029021A
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- 238000000034 method Methods 0.000 claims abstract description 41
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- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
- Nonwoven Fabrics (AREA)
- Paper (AREA)
Abstract
Description
本発明は、炭素繊維不織布と熱可塑性樹脂シートを積層してなる複合体に関する。 The present invention relates to a composite formed by laminating a carbon fiber nonwoven fabric and a thermoplastic resin sheet.
炭素繊維と樹脂を複合化してなる炭素繊維強化樹脂複合体は、金属材料に匹敵する強度・弾性率を有しながら、金属材料よりも比重が小さいため、部材の軽量化を図ることができ、また、発錆の問題もなく、酸やアルカリにも強いという性質を有していることから、電子機器材料、電気機器材料、土木材料、建築材料、自動車材料、航空機材料、各種製造業で使用されるロボット、ロール等の製造部品等で使用されている。 A carbon fiber reinforced resin composite formed by combining carbon fiber and a resin has a strength and an elastic modulus comparable to a metal material, but has a smaller specific gravity than a metal material. It has no rusting and is resistant to acids and alkalis, so it is used in electronic equipment materials, electrical equipment materials, civil engineering materials, building materials, automotive materials, aircraft materials, and various manufacturing industries. Used in manufacturing parts such as robots and rolls.
炭素繊維強化樹脂複合体は、長繊維織布、開繊織物、一方向性ウェブ、短繊維不織布等の炭素繊維布帛と、熱硬化性樹脂、熱可塑性樹脂等の樹脂とを複合させた複合体である。最も一般的な炭素繊維強化樹脂複合体は、長繊維布帛と熱硬化性樹脂とを複合させた複合体であるが、設計が難しい、均質材料ではない、成形加工時間が長い、高価等の課題があった。 The carbon fiber reinforced resin composite is a composite obtained by combining a carbon fiber cloth such as a long fiber woven fabric, an open fiber woven fabric, a unidirectional web, or a short fiber nonwoven fabric with a resin such as a thermosetting resin or a thermoplastic resin. It is. The most common carbon fiber reinforced resin composite is a composite of a long fiber fabric and a thermosetting resin, but is difficult to design, is not a homogeneous material, has a long processing time, is expensive, and other problems. was there.
これらの課題を解決する方法として、炭素繊維を含有する不織布（炭素繊維不織布）と熱可塑性樹脂とを複合した炭素繊維強化熱可塑性樹脂複合体が提案されている（例えば、特許文献１〜４参照）。炭素繊維不織布と熱可塑性樹脂が使用されることによって、易設計・加工性が得られ、成形加工時間の短縮が可能となっている。 As a method of solving these problems, a carbon fiber reinforced thermoplastic resin composite in which a nonwoven fabric containing carbon fibers (carbon fiber nonwoven fabric) is combined with a thermoplastic resin has been proposed (for example, see Patent Documents 1 to 4). ). By using the carbon fiber nonwoven fabric and the thermoplastic resin, easy design and workability can be obtained, and the molding process time can be shortened.
しかしながら、従来の炭素繊維不織布は、炭素繊維と熱可塑性樹脂粉末又は熱可塑性樹脂繊維とを含む炭素繊維不織布、炭素繊維のみを含む炭素繊維不織布等であるが、炭素繊維を乾式法又は湿式法で均一に分散することが難しく、得られる炭素繊維不織布の均一性は不十分であり、この炭素繊維不織布と熱可塑性樹脂とを複合した炭素繊維強化熱可塑性樹脂複合体は、表面状態が粗く、表面保護、装飾のために複合体表面に塗装した場合に塗膜の密着性が十分ではないという問題があった。 However, conventional carbon fiber nonwoven fabrics are carbon fiber nonwoven fabrics containing carbon fibers and thermoplastic resin powder or thermoplastic resin fibers, carbon fiber nonwoven fabrics containing only carbon fibers, and the like. It is difficult to disperse uniformly, the uniformity of the obtained carbon fiber nonwoven fabric is insufficient, and the carbon fiber reinforced thermoplastic resin composite of this carbon fiber nonwoven fabric and thermoplastic resin has a rough surface state, When applied to the composite surface for protection and decoration, there is a problem that the adhesion of the coating film is not sufficient.
本発明の課題は、表面性が良好で塗膜の密着性に優れた炭素繊維不織布複合体を提供することである。 An object of the present invention is to provide a carbon fiber nonwoven fabric composite having good surface properties and excellent adhesion of a coating film.
上記課題は、下記発明によって解決することができる。 The above problem can be solved by the following invention.
（１）炭素繊維と熱可塑性樹脂繊維を含有し、湿式抄紙法により形成された炭素繊維不織布と、熱可塑性樹脂シートとを積層した複合体であり、複合体表面の粗さ曲線から求められる算術平均高さ（Ｒａ）が１．０μｍ以下であり、かつ輪郭曲線要素の平均長さ（ＲＳｍ）が２００μｍ以下である炭素繊維不織布複合体。 (1) A composite comprising a carbon fiber nonwoven fabric formed by a wet papermaking method, containing a carbon fiber and a thermoplastic resin fiber, and a thermoplastic resin sheet laminated thereon, and an arithmetic operation obtained from a roughness curve of the composite surface A carbon fiber nonwoven fabric composite having an average height (Ra) of 1.0 μm or less and an average length (RSm) of a contour curve element of 200 μm or less.
（２）上記炭素繊維不織布のフラジール通気度の変動率が８％以下である（１）記載の炭素繊維不織布複合体。 (2) The carbon fiber nonwoven fabric composite according to (1), wherein the variation rate of the Frazier permeability of the carbon fiber nonwoven fabric is 8% or less.
（３）上記炭素繊維不織布がフィブリル化セルロース繊維を含有する（１）又は（２）記載の炭素繊維不織布複合体。 (3) The carbon fiber nonwoven fabric composite according to (1) or (2), wherein the carbon fiber nonwoven fabric contains fibrillated cellulose fibers.
本発明によれば、炭素繊維不織布と熱可塑性樹脂シートとを積層し、加熱加圧処理により複合体とした場合に、表面性が良好で、塗膜を形成した場合に、塗膜の密着性に優れた炭素繊維不織布複合体を得ることができる。 According to the present invention, carbon fiber nonwoven fabric and a thermoplastic resin sheet are laminated, and when a composite is formed by heating and pressing, the surface properties are good, and when a coating film is formed, the adhesion of the coating film The carbon fiber nonwoven fabric composite excellent in the above can be obtained.
本発明に係る炭素繊維不織布は、炭素繊維と熱可塑性樹脂繊維を含有し、湿式抄紙法により形成された炭素繊維不織布である。湿式抄紙法において、炭素繊維が水中で高速回転せん断型分散機を使って分散したスラリーを用い、形成された炭素繊維不織布のフラジール通気度の変動率が８％以下であることが好ましい。また、炭素繊維と熱可塑性樹脂繊維に加えて、フィブリル化セルロース繊維を含有させることが好ましい。 The carbon fiber nonwoven fabric according to the present invention is a carbon fiber nonwoven fabric containing carbon fibers and thermoplastic resin fibers and formed by a wet papermaking method. In the wet papermaking method, a slurry in which carbon fibers are dispersed in water using a high-speed rotary shearing type dispersing machine is used, and the fluctuation rate of the Frazier permeability of the formed carbon fiber nonwoven fabric is preferably 8% or less. Further, it is preferable that fibrillated cellulose fibers are contained in addition to the carbon fibers and the thermoplastic resin fibers.
炭素繊維としては、ポリアクリロニトリルを原料とするＰＡＮ系炭素繊維、ピッチ類を原料とするピッチ系炭素繊維、ポリアクリロニトリルを原料とするＰＡＮ系再生炭素繊維、ピッチ系炭素繊維を原料とするピッチ系再生炭素繊維が挙げられる。炭素繊維の繊維径は３〜２０μｍであることが好ましく、５〜１５μｍであることがより好ましい。また、炭素繊維の繊維長は１〜５０ｍｍであることが好ましく、３〜２０ｍｍであることがより好ましい。炭素繊維の含有量は、不織布中の全繊維に対して、５０〜９６質量％であることが好ましく、７０〜９３質量％であることがより好ましい。 Examples of the carbon fiber include PAN-based carbon fiber made from polyacrylonitrile, pitch-based carbon fiber made from pitch, PAN-based recycled carbon fiber made from polyacrylonitrile, and pitch-based regeneration made from pitch-based carbon fiber. Carbon fiber. The fiber diameter of the carbon fiber is preferably from 3 to 20 μm, more preferably from 5 to 15 μm. Further, the fiber length of the carbon fiber is preferably 1 to 50 mm, and more preferably 3 to 20 mm. The content of carbon fibers is preferably 50 to 96% by mass, and more preferably 70 to 93% by mass, based on all fibers in the nonwoven fabric.
再生炭素繊維とは、炭素繊維と樹脂を複合化してなる炭素繊維強化樹脂複合体等から得られる再生品である。炭素繊維強化樹脂複合体は、長繊維織布、開繊織物、一方向性ウェブ、長繊維不織布、短繊維不織布等の炭素繊維布帛と、熱硬化性樹脂、熱可塑性樹脂等の樹脂とを複合させた複合体である。最も一般的な炭素繊維強化樹脂複合体は、炭素長繊維布帛と熱硬化性樹脂とを複合させた複合体である。炭素繊維としては、アクリル繊維を用いたＰＡＮ系やピッチを用いたピッチ系炭素繊維が挙げられる。炭素繊維強化樹脂複合体から、熱処理法、焼結法、過熱法、過熱水蒸気法等の再生処理方法により、樹脂が除去されることによって得られる炭素繊維が再生炭素繊維である。 The recycled carbon fiber is a recycled product obtained from a carbon fiber reinforced resin composite obtained by compounding a carbon fiber and a resin. The carbon fiber reinforced resin composite is a composite of a carbon fiber cloth such as a long fiber woven fabric, an open fiber woven fabric, a unidirectional web, a long fiber nonwoven fabric, and a short fiber nonwoven fabric, and a resin such as a thermosetting resin or a thermoplastic resin. This is the composite. The most common carbon fiber reinforced resin composite is a composite of a carbon long fiber fabric and a thermosetting resin. Examples of the carbon fiber include a PAN-based carbon fiber using an acrylic fiber and a pitch-based carbon fiber using a pitch. The carbon fibers obtained by removing the resin from the carbon fiber reinforced resin composite by a regeneration treatment method such as a heat treatment method, a sintering method, a superheating method, and a superheated steam method are the regenerated carbon fibers.
本発明で用いられる再生炭素繊維は、炭素繊維自体の損傷を低減するため、窒素、アルゴン、水蒸気等の気体中で熱処理されたものが好ましい。熱処理温度としては、好ましくは４００℃から８００℃であり、更に好ましくは４５０℃から６００℃である。 The regenerated carbon fiber used in the present invention is preferably heat-treated in a gas such as nitrogen, argon, or water vapor in order to reduce damage to the carbon fiber itself. The heat treatment temperature is preferably from 400 ° C to 800 ° C, and more preferably from 450 ° C to 600 ° C.
熱可塑性樹脂繊維は、炭素繊維が不織布から脱離することを防止し、炭素繊維不織布に強度を付与するために添加される。熱可塑性樹脂繊維としては、ポリビニルアルコール（ビニロン）繊維、表面が低融点化されているポリエステル芯鞘繊維、未延伸ポリエステル繊維、ポリカーボネート（ＰＣ）繊維、ポリオレフィン繊維、表面が低融点化されているポリオレフィン芯鞘繊維、表面が酸変性ポリオレフィンよりなるポリオレフィン繊維、脂肪族ポリアミド繊維、未延伸ポリフェニレンスルフィド繊維、ポリエーテルケトンケトン繊維等が挙げられる。 The thermoplastic resin fiber is added to prevent the carbon fiber from detaching from the nonwoven fabric and to add strength to the carbon fiber nonwoven fabric. Examples of the thermoplastic resin fiber include polyvinyl alcohol (vinylon) fiber, polyester core-sheath fiber whose surface has a low melting point, undrawn polyester fiber, polycarbonate (PC) fiber, polyolefin fiber, and polyolefin whose surface has a low melting point. Core-sheath fibers, polyolefin fibers having a surface made of an acid-modified polyolefin, aliphatic polyamide fibers, undrawn polyphenylene sulfide fibers, polyether ketone ketone fibers, and the like.
熱可塑性樹脂繊維が融点を示す場合、融点は６０〜２６０℃であることが好ましく、６０〜２３０℃であることがより好ましく、６０〜１８０℃であることが更に好ましい。熱可塑性樹脂繊維の融点がこの温度範囲であることによって、不織布製造工程における加熱処理によって、結着性が付与され、炭素繊維不織布に強度が付与される。 When the thermoplastic resin fiber has a melting point, the melting point is preferably from 60 to 260 ° C, more preferably from 60 to 230 ° C, and still more preferably from 60 to 180 ° C. When the melting point of the thermoplastic resin fiber is within this temperature range, the heat treatment in the nonwoven fabric manufacturing process imparts binding properties and imparts strength to the carbon fiber nonwoven fabric.
熱可塑性樹脂繊維であるポリビニルアルコール（ビニロン）繊維は明確な融点を示さないが、水の存在下６０〜１００℃で溶融するため、湿式抄紙法においては、ドライヤーでの加熱処理によって、湿熱溶融して結着性が付与され、炭素繊維不織布に強度が付与される。 Polyvinyl alcohol (vinylon) fiber, which is a thermoplastic resin fiber, does not show a definite melting point, but melts at 60 to 100 ° C. in the presence of water. Thus, the binding property is given, and the strength is given to the carbon fiber nonwoven fabric.
熱可塑性樹脂繊維の繊維径は３〜４０μｍであることが好ましく、５〜２０μｍであることがより好ましい。また、熱可塑性樹脂繊維の繊維長は１〜２０ｍｍであることが好ましく、３〜１２ｍｍであることがより好ましい。 The fiber diameter of the thermoplastic resin fiber is preferably from 3 to 40 μm, more preferably from 5 to 20 μm. Further, the fiber length of the thermoplastic resin fiber is preferably 1 to 20 mm, more preferably 3 to 12 mm.
フィブリル化セルロース繊維とは、フィルム状ではなく、主に繊維軸と平行な方向に非常に細かく分割された部分を有する繊維状で、少なくとも一部が繊維径１μｍ以下であるセルロース繊維である。長さと幅のアスペクト比が２０〜１０００００であることが好ましい。また、変法濾水度が０〜７７０ｍｌであることが好ましく、０〜６００ｍｌであることがより好ましい。さらに、質量平均繊維長が０．１〜２ｍｍであることが好ましい。フィブリル化セルロース繊維の含有量は、不織布中の全繊維に対して、２〜２０質量％であることが好ましく、２〜１０質量％であることがより好ましい。フィブリル化セルロース繊維を含有させることにより、炭素繊維と熱可塑性樹脂繊維との結着性を向上させ、抄造性が良化すると共に、加熱加圧時の不織布層の崩れを抑制し均質性を高めることができる。本発明における変法濾水度は、ふるい板として線径０．１４ｍｍ、目開き０．１８ｍｍの金網（ＰＵＬＰ ＡＮＤ ＰＡＰＥＲ ＲＥＳＥＡＲＣＨ ＩＮＳＴＩＴＵＴＥ ＯＦ ＣＡＮＡＤＡ製）を用い、試料濃度を０．１％にした以外はＪＩＳ Ｐ８１２１−２：２０１２に準拠して測定した濾水度である。 The fibrillated cellulose fiber is not a film but a fiber having a very finely divided portion mainly in a direction parallel to the fiber axis, and at least a part of which has a fiber diameter of 1 μm or less. It is preferable that the aspect ratio of the length to the width is 20 to 100,000. The modified freeness is preferably from 0 to 770 ml, more preferably from 0 to 600 ml. Further, the mass average fiber length is preferably 0.1 to 2 mm. The content of the fibrillated cellulose fibers is preferably from 2 to 20% by mass, more preferably from 2 to 10% by mass, based on all the fibers in the nonwoven fabric. By containing fibrillated cellulose fibers, the binding properties between the carbon fibers and the thermoplastic resin fibers are improved, the papermaking properties are improved, and the collapse of the nonwoven fabric layer during heating and pressing is suppressed and the homogeneity is increased. be able to. The modified freeness in the present invention is as follows, except that a wire mesh (manufactured by PULP AND PAPER RESEARCH INSTITUTE OF CANADA) having a wire diameter of 0.14 mm and an opening of 0.18 mm is used as a sieve plate and the sample concentration is set to 0.1%. It is the freeness measured according to JIS P8121-2: 2012.
フィブリル化セルロース繊維用のセルロース材料としては、植物パルプ、溶剤紡糸セルロース、半合成セルロース等が挙げられる。植物パルプとしては、広葉樹材（Ｌ材）や針葉樹材（Ｎ材）を用いたクラフトパルプ（ＫＰ）、溶解パルプ（ＤＰ）、溶解クラフトパルプ（ＤＫＰ）等の木質系パルプが挙げられる。また、藁パルプ、麻パルプ、コットンパルプ、コットンリンターパルプ、ケナフパルプ等の非木質系パルプも挙げられる。市販品としては、セリッシュ（登録商標、ダイセルファインケム社製）が挙げられる。なお、セルロース材料の結晶形には、Ｉ型、II型、III型、IV型等があるが、耐熱性の観点から、Ｉ型、II型が好ましく、Ｉ型がより好ましい。Ｉ型のセルロース材料源としては、コットンパルプ、コットンリンターパルプ、麻パルプ、ケナフパルプ等の非木質系パルプで、リグニン及びヘミセルロースの含有量が低減されたパルプ、Ｌ材又はＮ材から得られる、リグニン及びヘミセルロースの含有量が低減されたＫＰ、ＤＰ、ＤＫＰ等の木質系パルプが挙げられる。特に、コットンパルプ、コットンリンターパルプ等のコットン系材料が好ましい。 Cellulose materials for fibrillated cellulose fibers include vegetable pulp, solvent-spun cellulose, semi-synthetic cellulose, and the like. Examples of the plant pulp include wood pulp such as kraft pulp (KP), dissolved pulp (DP), and dissolved kraft pulp (DKP) using hardwood (L) and softwood (N). Non-wood pulp such as straw pulp, hemp pulp, cotton pulp, cotton linter pulp, and kenaf pulp may also be used. Examples of commercially available products include Selish (registered trademark, manufactured by Daicel Finechem). The crystalline form of the cellulose material includes type I, type II, type III, type IV, and the like. From the viewpoint of heat resistance, type I and type II are preferred, and type I is more preferred. Examples of the type I cellulose material source include non-woody pulp such as cotton pulp, cotton linter pulp, hemp pulp, and kenaf pulp, which have a reduced content of lignin and hemicellulose; And wood-based pulp such as KP, DP, DKP, etc., in which the content of hemicellulose is reduced. In particular, cotton-based materials such as cotton pulp and cotton linter pulp are preferred.
フィブリル化セルロースを得る方法としては、セルロース材料を水中で分散したスラリーを機械的に粉砕することにより、セルロース材料の繊維を解繊してミクロフィブリルを形成する方法が挙げられる。セルロース材料を解繊する装置としては、ディスクリファイナー、石臼型磨砕機、高圧ホモジナイザー、ボールミル、水中カウンターコリジョン法用装置、超音波破砕機等が挙げられる。これらの装置を適宜組み合わせて使用することもできる。 Examples of a method for obtaining fibrillated cellulose include a method in which a slurry in which a cellulose material is dispersed in water is mechanically pulverized, thereby fibrillating the fibers of the cellulose material to form microfibrils. Examples of the device for defibrating the cellulose material include a disc refiner, a stone mill type grinder, a high-pressure homogenizer, a ball mill, a device for an underwater counter collision method, and an ultrasonic crusher. These devices can be used in appropriate combination.
本発明における炭素繊維不織布は、湿式抄造法で製造された湿式不織布である。湿式抄造法では、炭素繊維と、熱可塑性樹脂繊維、フィブリル化セルロース繊維等を均一に水中に分散させ、その後、スクリーン（異物、塊等除去）等の工程を通り、最終の繊維濃度を０．０１〜０．５０質量％に調整されたスラリーが抄紙機で抄き上げられ、湿紙（湿潤状態の不織布）が得られる。繊維の分散性の均一化等のために、工程中で分散剤、消泡剤、親水化剤、帯電防止剤、高分子粘剤、離型剤、抗菌剤、殺菌剤等の薬品を添加する場合もある。 The carbon fiber nonwoven fabric in the present invention is a wet nonwoven fabric manufactured by a wet papermaking method. In the wet papermaking method, carbon fibers, thermoplastic resin fibers, fibrillated cellulose fibers, and the like are uniformly dispersed in water, and then subjected to a screen (removal of foreign matters, lumps, and the like), and the final fiber concentration is reduced to 0.1. The slurry adjusted to 01 to 0.50% by mass is made up by a paper machine, and a wet paper (wet nonwoven fabric) is obtained. Add chemicals such as dispersant, defoamer, hydrophilizing agent, antistatic agent, polymer thickener, mold release agent, antibacterial agent, bactericide, etc. in the process to make the fiber dispersibility uniform. In some cases.
炭素繊維不織布を製造する場合、一般的なパルパーでの分散処理の他に、繊維を水中で、高速回転せん断型分散機を使って分散したスラリーを用いると均一で地合の良好な炭素繊維不織布が得られ好ましい。「高速回転せん断型分散機」とは、分散刃を有して回転するローターと分散刃を有したステーターとの間に、繊維を含むスラリーを通過させ、スラリー中の繊維にせん断力を与えて分散させる分散機である。具体的な装置としては、シングルディスクリファイナー、ダブルディスクリファイナー、コニカルリファイナー等が挙げられる。 When manufacturing carbon fiber non-woven fabric, besides the dispersion treatment using a general pulper, using a slurry in which fibers are dispersed in water using a high-speed rotary shear type disperser, a uniform and well-formed carbon fiber non-woven fabric Is preferred. `` High-speed rotary shearing type dispersing machine '' means that a slurry containing fibers is passed between a rotor having a dispersing blade and a stator having a dispersing blade, and a shear force is applied to the fibers in the slurry. It is a dispersing machine for dispersing. Specific devices include a single disc refiner, a double disc refiner, a conical refiner, and the like.
さらに、均一に効率良く、炭素繊維を分散させたスラリーを得るためには、高速回転せん断型分散機が、高速回転する細かなスリットを持つリング状刃物を構造の一部に有する高速回転せん断分散機であることが有効である。高速回転する細かなスリットを持つリング状刃物を構造の一部に有する高速回転せん断分散機においては、スリット間で発生する流体力学的な衝撃波が、炭素繊維に有効に作用する。具体的な装置としては、トップファイナー（相川鉄工製）、完全離解機ＶＦ型（新浜ポンプ製作所製）、マイルダー（太平洋機工製）等が挙げられる。 Furthermore, in order to obtain a slurry in which carbon fibers are dispersed uniformly and efficiently, a high-speed rotary shearing disperser uses a high-speed rotary shearing disperser that has a ring-shaped blade with a fine slit that rotates at high speed as part of the structure. It is effective to be a machine. In a high-speed rotating shear disperser having a ring-shaped blade having a fine slit that rotates at a high speed as a part of its structure, a hydrodynamic shock wave generated between the slits effectively acts on carbon fibers. Specific devices include Topfiner (manufactured by Aikawa Iron Works), complete disintegrator VF (manufactured by Niihama Pump Works), and Milder (manufactured by Taiheiyo Kiko).
上記分散機を使って、炭素繊維を分散させたスラリーを得る際には、スラリー濃度、処理時間、分散機のローターの回転数、ステーターとローターとのクリアランス等を調整することによって、炭素繊維の分散性を適宜調整することができる。 When using the above disperser to obtain a slurry in which carbon fibers are dispersed, by adjusting the slurry concentration, processing time, the number of rotations of the rotor of the disperser, the clearance between the stator and the rotor, etc. Dispersibility can be adjusted appropriately.
抄紙機としては、例えば、長網、円網、傾斜ワイヤー等の抄紙網を単独で使用した抄紙機、同種又は異種の２以上の抄紙網がオンラインで設置されているコンビネーション抄紙機等を使用することができる。また、不織布が２層以上の多層構造の場合には、各々の抄紙機で抄き上げた湿紙を積層する抄き合わせ法や、一方の層を形成した後に、該層上に繊維を分散したスラリーを流延して積層とする流延法等で、不織布を製造することができる。繊維を分散したスラリーを流延する際に、先に形成した層は湿紙状態であっても、乾燥状態であってもいずれでも良い。また、２枚以上の乾燥状態の層を熱融着させて、多層構造の不織布とすることもできる。 As the paper machine, for example, a paper machine using a single net such as a long net, a circular net, or an inclined wire, or a combination paper machine in which two or more nets of the same type or different types are installed online is used. be able to. When the nonwoven fabric has a multilayer structure of two or more layers, a laminating method of laminating wet papers made by each paper machine, or forming one layer and then dispersing fibers on the layer. A nonwoven fabric can be manufactured by a casting method or the like in which the slurry thus obtained is cast and laminated. When the slurry in which the fibers are dispersed is cast, the previously formed layer may be in a wet paper state or a dry state. Alternatively, two or more layers in a dry state may be thermally fused to form a nonwoven fabric having a multilayer structure.
本発明において、不織布が多層構造である場合、各層の繊維配合が同一である多層構造であっても良く、各層の繊維配合が異なっている多層構造であっても良い。多層構造である場合、各層の目付が下がることにより、スラリーの繊維濃度を下げることができるため、不織布の地合が良くなり、その結果、不織布の地合の均一性が向上する。また、各層の地合が不均一であった場合でも、積層することで補填できる。さらに、抄紙速度を上げることができ、操業性が向上するという効果も得られる。 In the present invention, when the nonwoven fabric has a multi-layer structure, the non-woven fabric may have a multi-layer structure in which the fiber composition of each layer is the same, or a multi-layer structure in which the fiber composition of each layer is different. In the case of a multi-layer structure, since the fiber weight of the slurry can be reduced by reducing the basis weight of each layer, the formation of the nonwoven fabric is improved, and as a result, the uniformity of the formation of the nonwoven fabric is improved. Even if the formation of each layer is not uniform, it can be compensated by laminating. Further, the effect that the paper making speed can be increased and the operability is improved can be obtained.
湿式抄造法では、抄紙網で抄造された湿紙を必要に応じて、プレスロール等で加圧脱水し、含有水分量を制御した上で、ヤンキードライヤー、エアードライヤー、シリンダードライヤー、サクションドラム式ドライヤー、赤外方式ドライヤー等で乾燥することによって、シート状の湿式抄造不織布が得られる。 In the wet papermaking method, if necessary, the wet paper made by a papermaking net is dehydrated under pressure with a press roll, etc., and after controlling the water content, a Yankee dryer, air dryer, cylinder dryer, suction drum dryer is used. By drying with an infrared dryer or the like, a sheet-shaped wet-laid nonwoven fabric can be obtained.
本発明で用いられる炭素繊維不織布は、フラジール通気度の変動率が８％以下であると好ましく、より好ましくは６％以下、さらに好ましくは４％以下である。湿式抄造法による炭素繊維不織布の製造において、一般的なパルパーでの分散処理の他に、炭素繊維を水中で、高速回転せん断型分散機を使って分散したスラリーを用い、炭素繊維不織布のフラジール通気度の変動率を８％以下とすることにより、厚さのムラや繊維の分散の偏りがなく、均一性の高い炭素繊維不織布を得ることができる。 The carbon fiber nonwoven fabric used in the present invention preferably has a variation rate of the Frazier permeability of 8% or less, more preferably 6% or less, and still more preferably 4% or less. In the production of carbon fiber nonwoven fabric by wet papermaking, in addition to the dispersion treatment using a general pulper, a slurry in which carbon fibers are dispersed in water using a high-speed rotary shearing type disperser is used, and the Frazier aeration of the carbon fiber nonwoven fabric is performed. By setting the rate of change of the degree to 8% or less, it is possible to obtain a carbon fiber nonwoven fabric having high uniformity without unevenness in thickness and uneven distribution of fibers.
炭素繊維不織布において、フラジール通気度の変動率を８％以下にするために下記の方法が用いられる。炭素繊維と熱可塑性樹脂繊維を含有し、まず、炭素繊維を水中で、高速回転せん断型分散機を使って分散させ、次いで熱可塑性樹脂繊維等の繊維を加えてさらに分散させたスラリーを用いて湿式抄造法を用いて炭素繊維不織布を作製する。ここでフラジール通気度の変動率をより低減させるためには、（１）高速回転せん断型分散機での処理時間を長くする。（２）高速回転せん断型分散機の回転数を上げる。（３）ステーターとローターのクリアランスを狭くする、という方法で調整することができる。 In a carbon fiber nonwoven fabric, the following method is used to reduce the variation rate of the Frazier air permeability to 8% or less. Containing carbon fiber and thermoplastic resin fiber, first, using a slurry in which the carbon fiber is dispersed in water using a high-speed rotation shear type disperser, and then further dispersed by adding fibers such as thermoplastic resin fiber A carbon fiber nonwoven fabric is produced by a wet papermaking method. Here, in order to further reduce the fluctuation rate of the Frazier air permeability, (1) the processing time in the high-speed rotary shearing type dispersion machine is lengthened. (2) Increase the rotation speed of the high-speed rotary shearing type dispersion machine. (3) The clearance can be adjusted by narrowing the clearance between the stator and the rotor.
炭素繊維不織布のフラジール通気度の変動率は以下のようにして求めることができる。炭素繊維不織布から縦横５００ｍｍ角のシートを切り取り、ここから５０ｍｍ角の通気度測定用試料１００枚を作製し、ＪＩＳ Ｌ１０９６に規定される通気性Ａ法（フラジール形法）に準じて、通気性試験機（装置名：ＫＥＳ−Ｆ８−ＡＰ１、カトーテック（株）製）で通気度を測定し、試料１００枚の通気度の平均値（Ｐ１）と標準偏差（Ｐ２）を算出し、次の式（１）から求められる値を変動率（％）とした。
変動率（％）＝通気度の標準偏差（Ｐ２）／通気度の平均値（Ｐ１）×１００ （１）
The variation rate of the Frazier permeability of the carbon fiber nonwoven fabric can be determined as follows. A 500 mm square sheet is cut out from a carbon fiber nonwoven fabric, and 100 samples of a 50 mm square air permeability measurement sample are prepared from the sheet, and the air permeability test is performed according to the air permeability A method (Fragile method) specified in JIS L1096. The air permeability was measured using a machine (device name: KES-F8-AP1, manufactured by Kato Tech Co., Ltd.), and the average value (P1) and the standard deviation (P2) of the air permeability of 100 samples were calculated. The value obtained from (1) was defined as the rate of change (%).
Fluctuation rate (%) = Standard deviation of air permeability (P2) / Average value of air permeability (P1) × 100 (1)
本発明に係る熱可塑性樹脂シートに用いられる熱可塑性樹脂としては、ポリエチレン樹脂、ポリプロピレン樹脂、ポリブチレン樹脂等のポリオレフィン系樹脂；ポリメチルメタクリレート樹脂等のメタクリル系樹脂；ポリスチレン樹脂、ＡＢＳ樹脂、ＡＳ樹脂等のポリスチレン系樹脂；ポリエチレンテレフタレート（ＰＥＴ）樹脂、ポリブチレンテレフタレート（ＰＢＴ）樹脂、ポリトリメチレンテレフタレート樹脂、ポリエチレンナフタレート（ＰＥＮ）樹脂、ポリシクロヘキシレンジメチレンテレフタレート（ＰＣＴ）樹脂等のポリエステル系樹脂；６−ナイロン樹脂、６，６−ナイロン樹脂等のポリアミド（ＰＡ）樹脂；ポリ塩化ビニル樹脂；ポリオキシメチレン（ＰＯＭ）樹脂；ポリカーボネート（ＰＣ）樹脂；ポリフェニレンサルファイド（ＰＰＳ）樹脂；変性ポリフェニレンエーテル（ＰＰＥ）樹脂；ポリエーテルイミド（ＰＥＩ）樹脂；ポリスルホン（ＰＳＦ）樹脂；ポリエーテルスルホン（ＰＥＳ）樹脂；ポリケトン樹脂；ポリアリレート（ＰＡＲ）樹脂；ポリエーテルニトリル（ＰＥＮ）樹脂；ポリエーテルケトン（ＰＥＫ）樹脂；ポリエーテルエーテルケトン（ＰＥＥＫ）樹脂；ポリエーテルケトンケトン（ＰＥＫＫ）樹脂；ポリイミド（ＰＩ）樹脂；ポリアミドイミド（ＰＡＩ）樹脂；フッ素（Ｆ）樹脂；液晶ポリエステル樹脂等の液晶ポリマー樹脂；ポリスチレン系、ポリオレフィン系、ポリウレタン系、ポリエステル系、ポリアミド系、ポリブタジエン系、ポリイソプレン系又はフッ素系等の熱可塑性エラストマー；又はこれらの共重合体樹脂や変性樹脂；アイオノマー樹脂等が挙げられる。これらの樹脂の中から、１種又は２種以上を用いることができる。成形加工性の観点から、ポリプロピレン樹脂、ポリカーボネート樹脂、ポリアミド樹脂等が好ましく用いられる。 Examples of the thermoplastic resin used for the thermoplastic resin sheet according to the present invention include polyolefin resins such as polyethylene resin, polypropylene resin, and polybutylene resin; methacrylic resins such as polymethyl methacrylate resin; polystyrene resins, ABS resins, and AS resins. Polyester resins such as polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polytrimethylene terephthalate resin, polyethylene naphthalate (PEN) resin, polycyclohexylene dimethylene terephthalate (PCT) resin; Polyamide (PA) resin such as 6-nylon resin and 6,6-nylon resin; polyvinyl chloride resin; polyoxymethylene (POM) resin; polycarbonate (PC) resin; Poly (phenylene ether) (PPE) resin; polyetherimide (PEI) resin; polysulfone (PSF) resin; polyethersulfone (PES) resin; polyketone resin; polyarylate (PAR) resin; polyethernitrile ( PEN) resin; polyether ketone (PEK) resin; polyether ether ketone (PEEK) resin; polyether ketone ketone (PEKK) resin; polyimide (PI) resin; polyamide imide (PAI) resin; fluorine (F) resin; Liquid crystal polymer resin such as polyester resin; polystyrene-based, polyolefin-based, polyurethane-based, polyester-based, polyamide-based, polybutadiene-based, polyisoprene-based or fluorine-based thermoplastic elastomer; or copolymer resin or modified resin thereof ; Ionomer resins. One or more of these resins can be used. From the viewpoint of moldability, polypropylene resin, polycarbonate resin, polyamide resin and the like are preferably used.
アイオノマー樹脂としては、エチレン−不飽和カルボン酸共重合樹脂のカルボキシル基の一部を金属イオンで中和してなるエチレン系アイオノマー樹脂が挙げられる。カルボキシル基の１０モル％以上、好ましくは１０〜９０モル％を金属イオンで中和したものが使用される。金属イオンとしては、リチウム、ナトリウム等のアルカリ金属、カルシウム等のアルカリ土類金属、亜鉛、マグネシウム等の多価金属イオンを挙げることができる。 Examples of the ionomer resin include an ethylene ionomer resin obtained by neutralizing a part of a carboxyl group of an ethylene-unsaturated carboxylic acid copolymer resin with a metal ion. Those obtained by neutralizing 10 mol% or more, preferably 10 to 90 mol% of carboxyl groups with metal ions are used. Examples of the metal ion include alkali metals such as lithium and sodium, alkaline earth metals such as calcium, and polyvalent metal ions such as zinc and magnesium.
本発明の複合体は、上記の炭素繊維不織布と熱可塑性樹脂シートとを積層し、積層体の少なくとも最上部と最下部に熱可塑性樹脂シートを使用して、加熱加圧処理により形成した炭素繊維不織布複合体であって、複合体表面の粗さ曲線から求められる算術平均高さ（Ｒａ）が、１．０μｍ以下であり、輪郭曲線要素の平均長さ（ＲＳｍ）が、２００μｍ以下である。また、粗さ曲線から求められる算術平均高さ（Ｒａ）が、０．８μｍ以下であり、輪郭曲線要素の平均長さ（ＲＳｍ）が、１７０μｍ以下であることがより好ましく、粗さ曲線から求められる算術平均高さ（Ｒａ）が、０．７μｍ以下であり、輪郭曲線要素の平均長さ（ＲＳｍ）が、１６０μｍ以下であることが更に好ましい。炭素繊維不織布複合体の粗さ曲線から求められる算術平均高さ（Ｒａ）を小さくするためには、（１）使用する炭素繊維の繊維径を細くする。（２）フィブリル化セルロースを含有させ、さらに含有量を増やす。（３）表面に使用する熱可塑性樹脂シートの量を増やす、という方法で調整することができる。また、炭素繊維不織布複合体の輪郭曲線要素の平均長さ（ＲＳｍ）を小さくするためには、（１）炭素繊維を水中で、高速回転せん断型分散機を使用して分散し、炭素繊維不織布の地合を良化させる。（２）加熱加圧成形で使用する、平板を形成できる金型の表面の輪郭曲線要素の平均長さ（ＲＳｍ）を小さくする、という方法で調整することができる。 The composite of the present invention is obtained by laminating the above-mentioned carbon fiber nonwoven fabric and a thermoplastic resin sheet, and using a thermoplastic resin sheet at least at the uppermost portion and the lowermost portion of the laminate to form a carbon fiber formed by heating and pressing. In the nonwoven fabric composite, the arithmetic average height (Ra) obtained from the roughness curve of the composite surface is 1.0 μm or less, and the average length (RSm) of the contour curve element is 200 μm or less. The arithmetic average height (Ra) obtained from the roughness curve is preferably 0.8 μm or less, and the average length (RSm) of the contour curve element is more preferably 170 μm or less. More preferably, the arithmetic average height (Ra) obtained is 0.7 μm or less, and the average length (RSm) of the contour curve element is 160 μm or less. In order to reduce the arithmetic average height (Ra) obtained from the roughness curve of the carbon fiber nonwoven fabric composite, (1) the fiber diameter of the carbon fiber used is reduced. (2) Include fibrillated cellulose and further increase the content. (3) It can be adjusted by increasing the amount of the thermoplastic resin sheet used on the surface. Further, in order to reduce the average length (RSm) of the contour curve element of the carbon fiber nonwoven fabric composite, (1) carbon fibers are dispersed in water using a high-speed rotary shear disperser, To improve the formation. (2) It can be adjusted by a method of reducing the average length (RSm) of a contour curve element on the surface of a mold capable of forming a flat plate, which is used in hot press molding.
本発明における粗さ曲線から求められる算術平均高さ（Ｒａ）及び輪郭曲線要素の平均長さ（ＲＳｍ）は、ＪＩＳ Ｂ０６０１−２００１に準拠した値であり、下記のようにして求めたものである。炭素繊維不織布複合体の塗料を塗布される面の塗料を塗布される前の面において、ＪＩＳ Ｂ０６５１−２００１に準拠した触針式表面粗さ測定機を使用し、カットオフ値０．８ｍｍ、送り速さ０．３ｍｍ／秒、評価長さ２５ｍｍの条件で、炭素繊維不織布複合体に使用した炭素繊維不織布の繊維の配向方向に５箇所、また繊維の配向方向と直交する方向に５箇所測定し、合計１０箇所の測定値の平均値を炭素繊維複合体の算術平均高さ（Ｒａ）、輪郭曲線要素の平均長さ（ＲＳｍ）とした。 The arithmetic average height (Ra) and the average length of contour curve elements (RSm) obtained from the roughness curve in the present invention are values based on JIS B0601-2001, and are obtained as follows. . On the surface of the carbon fiber nonwoven fabric composite to which the coating is applied before the coating is applied, a stylus-type surface roughness measuring device in accordance with JIS B0651-2001 is used, and a cutoff value of 0.8 mm is fed. Under the conditions of a speed of 0.3 mm / sec and an evaluation length of 25 mm, measurement was performed at five locations in the fiber orientation direction of the carbon fiber nonwoven fabric used in the carbon fiber nonwoven fabric composite, and at five locations in a direction perpendicular to the fiber orientation direction. The average value of the measured values at a total of 10 points was defined as the arithmetic average height (Ra) of the carbon fiber composite and the average length (RSm) of the contour curve element.
以下、実施例を挙げて本発明を具体的に説明するが、本発明は本実施例に限定されるものではない。 Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to the examples.
＜炭素繊維Ａ１＞
炭素繊維強化樹脂複合体（ＰＡＮ系炭素繊維、エポキシ系樹脂使用）を熱分解法により再生し、繊維長１０ｍｍに分級処理した平均繊維径７μｍの再生炭素繊維を炭素繊維Ａ１とした。
<Carbon fiber A1>
The carbon fiber reinforced resin composite (using PAN-based carbon fiber and epoxy-based resin) was regenerated by a pyrolysis method, and the regenerated carbon fiber having an average fiber diameter of 7 μm and classified into a fiber length of 10 mm was designated as carbon fiber A1.
＜炭素繊維Ａ２＞
炭素繊維強化樹脂複合体（ＰＡＮ系炭素繊維、エポキシ系樹脂使用）を過熱水蒸気法により再生し、繊維長１０ｍｍに分級処理した平均繊維径６μｍの再生炭素繊維を炭素繊維Ａ２とした。
<Carbon fiber A2>
A carbon fiber reinforced resin composite (using PAN-based carbon fiber and epoxy-based resin) was regenerated by a superheated steam method, and a regenerated carbon fiber having an average fiber diameter of 6 μm and classified into a fiber length of 10 mm was designated as carbon fiber A2.
＜熱可塑性樹脂繊維Ｂ１＞
平均繊維径１０μｍ、繊維長５ｍｍのポリプロピレン／ポリエチレン芯鞘型複合繊維を熱可塑性樹脂繊維Ｂ１とした。
<Thermoplastic resin fiber B1>
A polypropylene / polyethylene core-sheath composite fiber having an average fiber diameter of 10 μm and a fiber length of 5 mm was used as a thermoplastic resin fiber B1.
＜熱可塑性樹脂繊維Ｂ２＞
平均繊維径７μｍ、繊維長３ｍｍのポリビニルアルコール（ビニロン）繊維（水中溶解温度８０℃）を熱可塑性樹脂繊維Ｂ２とした。
<Thermoplastic resin fiber B2>
A polyvinyl alcohol (vinylon) fiber (dissolution temperature in water of 80 ° C.) having an average fiber diameter of 7 μm and a fiber length of 3 mm was used as a thermoplastic resin fiber B2.
＜フィブリル化セルロース繊維Ｃ１＞
コットンリンターパルプをパルパーで５分間分散した後、増幸産業社製マスコロイダー（登録商標、装置名：ＭＫＺＡ１２）を用いて、磨砕処理を行い、セルロース繊維を解繊し、変法濾水度２７０ｍｌのフィブリル化セルロース繊維Ｃ１を作製した。
<Fibrillated cellulose fiber C1>
After dispersing the cotton linter pulp with a pulper for 5 minutes, a grinding treatment is performed using a Mascolloider (registered trademark, device name: MKZA12) manufactured by Masuko Sangyo Co., Ltd. to disintegrate the cellulose fibers, and the modified freeness is 270 ml. The fibrillated cellulose fiber C1 was produced.
実施例１〜１２及び比較例１〜４
（炭素繊維の分散処理）
表１記載の装置、処理条件で炭素繊維の分散処理を行い、炭素繊維の水分散スラリーを得た。
Examples 1 to 12 and Comparative Examples 1 to 4
(Dispersion treatment of carbon fiber)
Dispersion treatment of the carbon fiber was performed under the apparatus and treatment conditions shown in Table 1 to obtain an aqueous dispersion of the carbon fiber.
（炭素繊維不織布の製造）
表２記載の繊維配合で抄造用スラリーを調製し、湿式抄造を実施した。
(Manufacture of carbon fiber nonwoven fabric)
A slurry for papermaking was prepared by mixing the fibers shown in Table 2, and wet papermaking was performed.
（複合体の製造）
厚さ１００μｍの熱可塑性樹脂（ポリプロピレン）シート１６枚と下記で製造した炭素繊維不織布１５枚を交互に積層し、１５ｃｍ角の平板を形成できる金型を使用し、熱プレス機で、温度２２０℃、１０ＭＰａ、５分間加熱加圧加工した後、室温に冷却して炭素繊維不織布複合体を製造した。なお、平板を形成できる金型は、複合体と接触する表面の粗さ曲線の算術平均高さ（Ｒａ）が０．１μｍ、輪郭曲線要素の平均長さ（ＲＳｍ）が２０μｍであるものを使用した。
(Production of composite)
Using a mold capable of forming a 15 cm square flat plate by alternately laminating 16 sheets of 100 μm thick thermoplastic resin (polypropylene) sheets and 15 sheets of carbon fiber nonwoven fabric produced below, using a hot press machine at a temperature of 220 ° C. After heating and pressing at 10 MPa for 5 minutes, the mixture was cooled to room temperature to produce a carbon fiber nonwoven fabric composite. A mold capable of forming a flat plate has an arithmetic mean height (Ra) of a surface roughness curve in contact with the composite of 0.1 μm and an average length (RSm) of a contour curve element of 20 μm. did.
（実施例１）
表１記載の装置、処理条件で分散処理を行い、得られた炭素繊維スラリーを使用し、表２記載の配合で炭素繊維、熱可塑性樹脂繊維を混合し、分散濃度０．２質量％とし、アジテーターで十分撹拌して抄造用スラリーを調製した。この抄造用スラリーを９０メッシュの金属ワイヤーを有した円網抄紙機で湿紙を形成し、プレスロールで加圧脱水した後、湿紙をタッチロールで加圧して１５０℃のヤンキードライヤーに密着させて乾燥し、坪量５０．４ｇ／ｍ２の炭素繊維不織布を得た。
次いで、この炭素繊維不織布１５枚と熱可塑性樹脂シートとを交互に積層し、実施例１の炭素繊維不織布複合体を製造した。
(Example 1)
Dispersion treatment was performed under the apparatus and processing conditions shown in Table 1, and the obtained carbon fiber slurry was used. Carbon fibers and thermoplastic resin fibers were mixed in the composition shown in Table 2 to give a dispersion concentration of 0.2% by mass. The slurry for papermaking was prepared by sufficiently stirring with an agitator. This papermaking slurry is formed into a wet paper by a mesh paper machine having a 90-mesh metal wire, and is dewatered under pressure by a press roll. Then, the wet paper is pressed by a touch roll and brought into close contact with a 150 ° C Yankee dryer. And dried to obtain a carbon fiber nonwoven fabric having a basis weight of 50.4 g / m 2 .
Next, 15 carbon fiber nonwoven fabrics and a thermoplastic resin sheet were alternately laminated to produce a carbon fiber nonwoven fabric composite of Example 1.
（実施例２）
表１記載の装置、処理条件で分散処理を行い、得られた炭素繊維スラリーを使用し、表２記載の配合で炭素繊維、熱可塑性樹脂繊維を混合した以外は、実施例１と同様にして、坪量５０．３ｇ／ｍ２の炭素繊維不織布を得た。
次いで、実施例１と同様にこの炭素繊維不織布と熱可塑性樹脂シートと交互に積層し、実施例２の炭素繊維不織布複合体を製造した。
(Example 2)
Dispersion treatment was performed under the apparatus and processing conditions shown in Table 1, and the obtained carbon fiber slurry was used. In the same manner as in Example 1 except that carbon fibers and thermoplastic resin fibers were mixed in the composition shown in Table 2, Thus, a carbon fiber nonwoven fabric having a basis weight of 50.3 g / m 2 was obtained.
Next, the carbon fiber nonwoven fabric and the thermoplastic resin sheet were alternately laminated in the same manner as in Example 1 to produce a carbon fiber nonwoven fabric composite of Example 2.
（実施例３）
表１記載の装置、処理条件で分散処理を行い、得られた炭素繊維スラリーを使用し、表２記載の配合で炭素繊維、熱可塑性樹脂繊維、及びフィブリル化セルロース繊維を混合した以外は、実施例１と同様にして、坪量５０．５ｇ／ｍ２の炭素繊維不織布を得た。
次いで、実施例１と同様にこの炭素繊維不織布と熱可塑性樹脂シートと交互に積層し、実施例３の炭素繊維不織布複合体を製造した。
(Example 3)
Dispersion treatment was carried out using the apparatus and processing conditions shown in Table 1, and the obtained carbon fiber slurry was used. Carbon fiber, thermoplastic resin fiber, and fibrillated cellulose fiber were mixed in the composition shown in Table 2, and the procedure was carried out. In the same manner as in Example 1, a carbon fiber nonwoven fabric having a basis weight of 50.5 g / m 2 was obtained.
Next, the carbon fiber nonwoven fabric and the thermoplastic resin sheet were alternately laminated in the same manner as in Example 1 to produce a carbon fiber nonwoven fabric composite of Example 3.
（実施例４）
表１記載の装置、処理条件で分散処理を行い、得られた炭素繊維スラリーを使用し、表２記載の配合で炭素繊維、熱可塑性樹脂繊維、及びフィブリル化セルロース繊維を混合した以外は、実施例１と同様にして、坪量５０．２ｇ／ｍ２の炭素繊維不織布を得た。
次いで、実施例１と同様にこの炭素繊維不織布と熱可塑性樹脂シートと交互に積層し、実施例４の炭素繊維不織布複合体を製造した。
(Example 4)
Dispersion treatment was carried out using the apparatus and processing conditions shown in Table 1, and the obtained carbon fiber slurry was used. Carbon fiber, thermoplastic resin fiber, and fibrillated cellulose fiber were mixed in the composition shown in Table 2, and the procedure was carried out. In the same manner as in Example 1, a carbon fiber nonwoven fabric having a basis weight of 50.2 g / m 2 was obtained.
Next, the carbon fiber nonwoven fabric and the thermoplastic resin sheet were alternately laminated in the same manner as in Example 1 to produce a carbon fiber nonwoven fabric composite of Example 4.
（実施例５）
表１記載の装置、処理条件で分散処理を行い、得られた炭素繊維スラリーを使用し、表２記載の配合で炭素繊維、熱可塑性樹脂繊維、及びフィブリル化セルロース繊維を混合した以外は、実施例１と同様にして、坪量５０．３ｇ／ｍ２の炭素繊維不織布を得た。
次いで、実施例１と同様にこの炭素繊維不織布と熱可塑性樹脂シートと交互に積層し、実施例５の炭素繊維不織布複合体を製造した。
(Example 5)
Dispersion treatment was carried out using the apparatus and processing conditions shown in Table 1, and the obtained carbon fiber slurry was used. Carbon fiber, thermoplastic resin fiber, and fibrillated cellulose fiber were mixed in the composition shown in Table 2, and the procedure was carried out. In the same manner as in Example 1, a carbon fiber nonwoven fabric having a basis weight of 50.3 g / m 2 was obtained.
Next, the carbon fiber nonwoven fabric and the thermoplastic resin sheet were alternately laminated in the same manner as in Example 1 to produce a carbon fiber nonwoven fabric composite of Example 5.
（実施例６）
表１記載の装置、処理条件で分散処理を行い、得られた炭素繊維スラリーを使用し、表２記載の配合で炭素繊維、熱可塑性樹脂繊維、及びフィブリル化セルロース繊維を混合した以外は、実施例１と同様にして、坪量５０．１ｇ／ｍ２の炭素繊維不織布を得た。
次いで、実施例１と同様にこの炭素繊維不織布と熱可塑性樹脂シートと交互に積層し、実施例６の炭素繊維不織布複合体を製造した。
(Example 6)
Dispersion treatment was carried out using the apparatus and processing conditions shown in Table 1, and the obtained carbon fiber slurry was used. Carbon fiber, thermoplastic resin fiber, and fibrillated cellulose fiber were mixed in the composition shown in Table 2, and the procedure was carried out. In the same manner as in Example 1, a carbon fiber nonwoven fabric having a basis weight of 50.1 g / m 2 was obtained.
Next, the carbon fiber nonwoven fabric and the thermoplastic resin sheet were alternately laminated in the same manner as in Example 1 to produce a carbon fiber nonwoven fabric composite of Example 6.
（実施例７）
表１記載の装置、処理条件で分散処理を行い、得られた炭素繊維スラリーを使用し、表２記載の配合で炭素繊維、熱可塑性樹脂繊維、及びフィブリル化セルロース繊維を混合した以外は、実施例１と同様にして、坪量５０．５ｇ／ｍ２の炭素繊維不織布を得た。
次いで、実施例１と同様にこの炭素繊維不織布と熱可塑性樹脂シートと交互に積層し、実施例７の炭素繊維不織布複合体を製造した。
(Example 7)
Dispersion treatment was carried out using the apparatus and processing conditions shown in Table 1, and the obtained carbon fiber slurry was used. Carbon fiber, thermoplastic resin fiber, and fibrillated cellulose fiber were mixed in the composition shown in Table 2, and the procedure was carried out. In the same manner as in Example 1, a carbon fiber nonwoven fabric having a basis weight of 50.5 g / m 2 was obtained.
Next, the carbon fiber nonwoven fabric and the thermoplastic resin sheet were alternately laminated in the same manner as in Example 1 to produce a carbon fiber nonwoven fabric composite of Example 7.
（実施例８）
表１記載の装置、処理条件で分散処理を行い、得られた炭素繊維スラリーを使用し、表２記載の配合で炭素繊維、熱可塑性樹脂繊維、及びフィブリル化セルロース繊維を混合した以外は、実施例１と同様にして、坪量５０．６ｇ／ｍ２の炭素繊維不織布を得た。
次いで、実施例１と同様にこの炭素繊維不織布と熱可塑性樹脂シートと交互に積層し、実施例８の炭素繊維不織布複合体を製造した。
(Example 8)
Dispersion treatment was carried out using the apparatus and processing conditions shown in Table 1, and the obtained carbon fiber slurry was used. Carbon fiber, thermoplastic resin fiber, and fibrillated cellulose fiber were mixed in the composition shown in Table 2, and the procedure was carried out. In the same manner as in Example 1, a carbon fiber nonwoven fabric having a basis weight of 50.6 g / m 2 was obtained.
Next, the carbon fiber nonwoven fabric and the thermoplastic resin sheet were alternately laminated in the same manner as in Example 1 to produce a carbon fiber nonwoven fabric composite of Example 8.
（実施例９）
表１記載の装置、処理条件で分散処理を行い、得られた炭素繊維スラリーを使用し、表２記載の配合で炭素繊維、熱可塑性樹脂繊維、及びフィブリル化セルロース繊維を混合した以外は、実施例１と同様にして、坪量５０．２ｇ／ｍ２の炭素繊維不織布を得た。
次いで、実施例１と同様にこの炭素繊維不織布と熱可塑性樹脂シートと交互に積層し、実施例９の炭素繊維不織布複合体を製造した。
(Example 9)
Dispersion treatment was carried out using the apparatus and processing conditions shown in Table 1, and the obtained carbon fiber slurry was used. Carbon fiber, thermoplastic resin fiber, and fibrillated cellulose fiber were mixed in the composition shown in Table 2, and the procedure was carried out. In the same manner as in Example 1, a carbon fiber nonwoven fabric having a basis weight of 50.2 g / m 2 was obtained.
Next, the carbon fiber nonwoven fabric and the thermoplastic resin sheet were alternately laminated in the same manner as in Example 1 to produce a carbon fiber nonwoven fabric composite of Example 9.
（実施例１０）
表１記載の装置、処理条件で分散処理を行い、得られた炭素繊維スラリーを使用し、表２記載の配合で炭素繊維、熱可塑性樹脂繊維、及びフィブリル化セルロース繊維を混合した以外は、実施例１と同様にして、坪量５０．４ｇ／ｍ２の炭素繊維不織布を得た。
次いで、実施例１と同様にこの炭素繊維不織布と熱可塑性樹脂シートと交互に積層し、実施例１０の炭素繊維不織布複合体を製造した。
(Example 10)
Dispersion treatment was carried out using the apparatus and processing conditions shown in Table 1, and the obtained carbon fiber slurry was used. Carbon fiber, thermoplastic resin fiber, and fibrillated cellulose fiber were mixed in the composition shown in Table 2, and the procedure was carried out. In the same manner as in Example 1, a carbon fiber nonwoven fabric having a basis weight of 50.4 g / m 2 was obtained.
Next, the carbon fiber nonwoven fabric and the thermoplastic resin sheet were alternately laminated in the same manner as in Example 1 to produce a carbon fiber nonwoven fabric composite of Example 10.
（実施例１１）
表１記載の装置、処理条件で分散処理を行い、得られた炭素繊維スラリーを使用し、表２記載の配合で炭素繊維、熱可塑性樹脂繊維、及びフィブリル化セルロース繊維を混合した以外は、実施例１と同様にして、坪量５０．２ｇ／ｍ２の炭素繊維不織布を得た。
次いで、実施例１と同様にこの炭素繊維不織布と熱可塑性樹脂シートと交互に積層し、実施例１１の炭素繊維不織布複合体を製造した。
(Example 11)
Dispersion treatment was carried out using the apparatus and processing conditions shown in Table 1, and the obtained carbon fiber slurry was used. Carbon fiber, thermoplastic resin fiber, and fibrillated cellulose fiber were mixed in the composition shown in Table 2, and the procedure was carried out. In the same manner as in Example 1, a carbon fiber nonwoven fabric having a basis weight of 50.2 g / m 2 was obtained.
Next, the carbon fiber nonwoven fabric and the thermoplastic resin sheet were alternately laminated in the same manner as in Example 1 to produce a carbon fiber nonwoven fabric composite of Example 11.
（実施例１２）
表１記載の装置、処理条件で分散処理を行い、得られた炭素繊維スラリーを使用し、表２記載の配合で炭素繊維、熱可塑性樹脂繊維、及びフィブリル化セルロース繊維を混合した以外は、実施例１と同様にして、坪量５０．０ｇ／ｍ２の炭素繊維不織布を得た。
次いで、実施例１と同様にこの炭素繊維不織布と熱可塑性樹脂シートと交互に積層し、実施例１２の炭素繊維不織布複合体を製造した。
(Example 12)
Dispersion treatment was carried out using the apparatus and processing conditions shown in Table 1, and the obtained carbon fiber slurry was used. Carbon fiber, thermoplastic resin fiber, and fibrillated cellulose fiber were mixed in the composition shown in Table 2, and the procedure was carried out. In the same manner as in Example 1, a carbon fiber nonwoven fabric having a basis weight of 50.0 g / m 2 was obtained.
Next, the carbon fiber nonwoven fabric and the thermoplastic resin sheet were alternately laminated in the same manner as in Example 1 to produce a carbon fiber nonwoven fabric composite of Example 12.
（比較例１）
表１記載の装置、処理条件で分散処理を行い、得られた炭素繊維スラリーを使用し、表２記載の配合で炭素繊維、熱可塑性樹脂繊維を混合した以外は、実施例１と同様にして、坪量５０．３ｇ／ｍ２の炭素繊維不織布を得た。
次いで、実施例１と同様にこの炭素繊維不織布と熱可塑性樹脂シートと交互に積層し、比較例１の炭素繊維不織布複合体を製造した。
(Comparative Example 1)
Dispersion treatment was performed under the apparatus and processing conditions shown in Table 1, and the obtained carbon fiber slurry was used. In the same manner as in Example 1 except that carbon fibers and thermoplastic resin fibers were mixed in the composition shown in Table 2, Thus, a carbon fiber nonwoven fabric having a basis weight of 50.3 g / m 2 was obtained.
Next, the carbon fiber nonwoven fabric and the thermoplastic resin sheet were alternately laminated in the same manner as in Example 1 to produce a carbon fiber nonwoven fabric composite of Comparative Example 1.
（比較例２）
表１記載の装置、処理条件で分散処理を行い、得られた炭素繊維スラリーを使用し、表２記載の配合で炭素繊維、熱可塑性樹脂繊維を混合した以外は、実施例１と同様にして、坪量５０．４ｇ／ｍ２の炭素繊維不織布を得た。
次いで、実施例１と同様にこの炭素繊維不織布と熱可塑性樹脂シートと交互に積層し、比較例２の炭素繊維不織布複合体を製造した。
(Comparative Example 2)
Dispersion treatment was performed under the apparatus and processing conditions shown in Table 1, and the obtained carbon fiber slurry was used. In the same manner as in Example 1 except that carbon fibers and thermoplastic resin fibers were mixed in the composition shown in Table 2, Thus, a carbon fiber nonwoven fabric having a basis weight of 50.4 g / m 2 was obtained.
Next, the carbon fiber nonwoven fabric and the thermoplastic resin sheet were alternately laminated in the same manner as in Example 1 to produce a carbon fiber nonwoven fabric composite of Comparative Example 2.
（比較例３）
表１記載の装置、処理条件で分散処理を行い、得られた炭素繊維スラリーを使用し、表２記載の配合で炭素繊維、熱可塑性樹脂繊維を混合した以外は、実施例１と同様にして、坪量５０．２ｇ／ｍ２の炭素繊維不織布を得た。
次いで、実施例１と同様にこの炭素繊維不織布と熱可塑性樹脂シートと交互に積層し、比較例３の炭素繊維不織布複合体を製造した。
(Comparative Example 3)
Dispersion treatment was performed under the apparatus and processing conditions shown in Table 1, and the obtained carbon fiber slurry was used. In the same manner as in Example 1 except that carbon fibers and thermoplastic resin fibers were mixed in the composition shown in Table 2, Thus, a carbon fiber nonwoven fabric having a basis weight of 50.2 g / m 2 was obtained.
Next, the carbon fiber nonwoven fabric and the thermoplastic resin sheet were alternately laminated in the same manner as in Example 1 to produce a carbon fiber nonwoven fabric composite of Comparative Example 3.
（比較例４）
表１記載の装置、処理条件で分散処理を行い、得られた炭素繊維スラリーを使用し、表２記載の配合で炭素繊維、熱可塑性樹脂繊維、及びフィブリル化セルロース繊維を混合した以外は、実施例１と同様にして、坪量５０．３ｇ／ｍ２の炭素繊維不織布を得た。
次いで、実施例１と同様にこの炭素繊維不織布と熱可塑性樹脂シートと交互に積層し、比較例４の炭素繊維不織布複合体を製造した。
(Comparative Example 4)
Dispersion treatment was carried out using the apparatus and processing conditions shown in Table 1, and the obtained carbon fiber slurry was used. Carbon fiber, thermoplastic resin fiber, and fibrillated cellulose fiber were mixed in the composition shown in Table 2, and the procedure was carried out. In the same manner as in Example 1, a carbon fiber nonwoven fabric having a basis weight of 50.3 g / m 2 was obtained.
Next, the carbon fiber nonwoven fabric and the thermoplastic resin sheet were alternately laminated in the same manner as in Example 1 to produce a carbon fiber nonwoven fabric composite of Comparative Example 4.
（フラジール通気度の変動率の評価）
実施例及び比較例で得られた炭素繊維不織布から縦横５００ｍｍ角のシートを切り取り、ここから５０ｍｍ角の通気度測定用試料１００枚を作製し、ＪＩＳ Ｌ１０９６に規定される通気性Ａ法（フラジール形法）に準じて、通気性試験機（装置名：ＫＥＳ−Ｆ８−ＡＰ１、カトーテック（株）製）で通気度を測定し、試料１００枚の通気度の平均値（Ｐ１）と標準偏差（Ｐ２）を算出し、次の式（１）から変動率を求めた。結果を表３に示す。
変動率（％）＝通気度の標準偏差（Ｐ２）／通気度の平均値（Ｐ１）×１００ （１）
(Evaluation of fluctuation rate of Frazier air permeability)
A 500 mm square sheet is cut out from the carbon fiber nonwoven fabric obtained in each of the examples and comparative examples, and 100 pieces of 50 mm square samples for measuring the air permeability are prepared therefrom. The air permeability A method (Fragile type) specified in JIS L1096 Method), the air permeability was measured with a gas permeability tester (device name: KES-F8-AP1, manufactured by Kato Tech Co., Ltd.), and the average value (P1) and the standard deviation (P1) of the gas permeability of 100 samples were measured. P2) was calculated, and the rate of change was determined from the following equation (1). Table 3 shows the results.
Fluctuation rate (%) = Standard deviation of air permeability (P2) / Average value of air permeability (P1) × 100 (1)
（炭素繊維不織布複合体の表面性の評価）
複合体の表面性の評価として、複合体の塗料を塗布される面の塗料を塗布される前の面において、（株）東京精密製の表面粗さ測定機サーフコム１４００Ｄ−１３を使用し、カットオフ値０．８ｍｍ、送り速さ０．３ｍｍ／ｓ、評価長さ２５ｍｍの条件で、粗さ曲線の算術平均高さ（Ｒａ）及び輪郭曲線要素の平均長さ（ＲＳｍ）を測定し、１つの複合体あたり、最表層に使用した炭素繊維不織布の繊維の配向方向に５箇所、また繊維の配向方向と直交する方向に５箇所測定し、合計１０箇所の測定を行い、その平均値を求めた。結果を表３に示す。
(Evaluation of surface properties of carbon fiber nonwoven fabric composite)
As an evaluation of the surface properties of the composite, the surface of the surface to which the coating of the composite was applied before the coating was applied was cut using a surface roughness measuring machine Surfcom 1400D-13 manufactured by Tokyo Seimitsu Co., Ltd. The arithmetic average height (Ra) of the roughness curve and the average length (RSm) of the contour curve element were measured under the conditions of an off value of 0.8 mm, a feed speed of 0.3 mm / s, and an evaluation length of 25 mm. For each composite, five points were measured in the direction of fiber orientation of the carbon fiber nonwoven fabric used for the outermost layer, and five points in a direction perpendicular to the direction of fiber orientation, and a total of ten points were measured, and the average value was obtained. Was. Table 3 shows the results.
（複合体の塗装密着性の評価）
複合体の表面にアクリル樹脂系塗料を乾燥膜厚が１５μｍになるようにスプレー塗布したのち、８０℃で２０分間乾燥、２３℃、５０％の環境中で１２時間静置して試験片を作成した。この試験片の表面に、ＪＩＳ Ｋ５６００−５−６に準拠し、複合体まで達する６本の格子状の切り込みを入れた試験片を作成し、ニチバン製セロテープ（登録商標）を試験片に貼り付けた後、これを約０．８秒で引き剥がして、塗膜が剥離した格子の個数を数えた。この試験を各試験片で２回実施し、その平均値を求めた。結果を表３に示す。
(Evaluation of coating adhesion of composite)
An acrylic resin-based paint is spray-coated on the surface of the composite to a dry film thickness of 15 μm, dried at 80 ° C. for 20 minutes, and left at 23 ° C. and 50% environment for 12 hours to prepare a test piece. did. In accordance with JIS K5600-5-6, on the surface of this test piece, a test piece having six lattice-shaped cuts reaching the composite was prepared, and Nichiban Cellotape (registered trademark) was attached to the test piece. After that, this was peeled off in about 0.8 seconds, and the number of grids from which the coating film was peeled was counted. This test was performed twice on each test piece, and the average value was determined. Table 3 shows the results.
実施例で得られた炭素繊維不織布複合体は、みな表面性が良好で、塗膜を形成した場合に、塗膜の密着性に優れた炭素繊維不織布複合体であった。 All of the carbon fiber nonwoven fabric composites obtained in the examples were carbon fiber nonwoven fabric composites having good surface properties and excellent adhesion of the coating film when formed.
実施例１〜３を比較すると、粗さ曲線から求められる算術平均高さ（Ｒａ）が、０．８μｍ以下で、かつ輪郭曲線要素の平均長さ（ＲＳｍ）が、１７０μｍ以下であり、フィブリル化セルロース繊維を含有する実施例３で得られた炭素繊維不織布複合体は、実施例１及び実施例２に比べ、塗膜の密着性に優れている。 Comparing Examples 1 to 3, the arithmetic average height (Ra) obtained from the roughness curve is 0.8 μm or less, and the average length (RSm) of the contour curve element is 170 μm or less. The carbon fiber nonwoven fabric composite obtained in Example 3 containing cellulose fibers is superior in the adhesion of the coating film as compared with Examples 1 and 2.
実施例３と実施例４を比較すると、粗さ曲線から求められる算術平均高さ（Ｒａ）が、０．７μｍ以下で、かつ輪郭曲線要素の平均長さ（ＲＳｍ）が、１６０μｍ以下であり、トップファイナーを使用して炭素繊維不織布の通気度の変動率を４％以下とした実施例４の方が実施例３より、塗膜の密着性に優れている。 Comparing Example 3 with Example 4, the arithmetic average height (Ra) obtained from the roughness curve is 0.7 μm or less, and the average length (RSm) of the contour curve element is 160 μm or less, Example 4 in which the rate of change of the air permeability of the carbon fiber nonwoven fabric was set to 4% or less by using a top finisher was superior to Example 3 in the adhesion of the coating film.
実施例１と実施例２を比較すると、炭素繊維含有量が７０質量％以上である実施例２の方が、粗さ曲線から求められる算術平均高さ（Ｒａ）及び輪郭曲線要素の平均長さ（ＲＳｍ）が小さく、実施例１に比べ好ましい。 Comparing Example 1 with Example 2, Example 2 in which the carbon fiber content is 70% by mass or more has the arithmetic average height (Ra) obtained from the roughness curve and the average length of the contour curve element. (RSm) is small, which is preferable as compared with the first embodiment.
実施例４〜６を比較すると、粗さ曲線から求められる算術平均高さ（Ｒａ）及び輪郭曲線要素の平均長さ（ＲＳｍ）が小さい方が、剥離個数が少なく、塗膜の密着性に優れていてより好ましい。 Comparing Examples 4 to 6, the smaller the arithmetic average height (Ra) and the average length of the contour curve element (RSm) obtained from the roughness curve are, the smaller the number of peeling is, and the better the adhesion of the coating film is. Is more preferable.
実施例７〜１２を比較すると、実施例７〜１１は、粗さ曲線から求められる算術平均高さ（Ｒａ）が０．７μｍ以下で、かつ輪郭曲線要素の平均長さ（ＲＳｍ）が、１６０μｍ以下であり、得られた炭素繊維不織布複合体は、粗さ曲線から求められる算術平均高さ（Ｒａ）が０．７μｍを超え、かつ輪郭曲線要素の平均長さ（ＲＳｍ）が、１６０μｍを超えている実施例１２に比べて、塗膜の密着性に優れていてより好ましい。また、実施例７〜１１の中では、粗さ曲線から求められる算術平均高さ（Ｒａ）及び輪郭曲線要素の平均長さ（ＲＳｍ）が小さい方が、剥離個数が少なく、塗膜の密着性に優れていてより好ましい。 Comparing Examples 7 to 12, in Examples 7 to 11, the arithmetic average height (Ra) obtained from the roughness curve is 0.7 μm or less, and the average length (RSm) of the contour curve element is 160 μm. The resulting carbon fiber nonwoven fabric composite has an arithmetic average height (Ra) determined from a roughness curve of more than 0.7 μm and an average length (RSm) of a contour curve element of more than 160 μm. As compared with Example 12, which is excellent, the adhesion of the coating film is excellent and more preferable. In Examples 7 to 11, the smaller the arithmetic average height (Ra) and the average length (RSm) of the contour curve elements obtained from the roughness curves, the smaller the number of peeled pieces and the better the adhesion of the coating film. And more preferred.
比較例１及び比較例２は、炭素繊維を水中で高速回転せん断型分散機を使用してスラリー化しておらず、複合体形成に使用した炭素繊維不織布の通気度の変動率は８％を超えて大きく、炭素繊維不織布複合体の粗さ曲線から求められる算術平均高さ（Ｒａ）が１．０μｍを超え、かつ輪郭曲線要素の平均長さ（ＲＳｍ）も２００μｍを超えており、得られた炭素繊維不織布複合体の表面は非常に粗く、塗膜の密着性が劣っている。 In Comparative Examples 1 and 2, carbon fibers were not slurried in water using a high-speed rotary shearing disperser, and the rate of change of the air permeability of the carbon fiber nonwoven fabric used for forming the composite exceeded 8%. The arithmetic average height (Ra) obtained from the roughness curve of the carbon fiber nonwoven fabric composite exceeds 1.0 μm, and the average length (RSm) of the contour curve element also exceeds 200 μm. The surface of the carbon fiber nonwoven fabric composite is very rough, and the adhesion of the coating film is poor.
比較例３は炭素繊維をリファイナーを使用してスラリー化しているが、処理時間が短く、炭素繊維不織布複合体形成に使用した炭素繊維不織布の通気度の変動率は８％を超えており、複合体の粗さ曲線から求められる算術平均高さ（Ｒａ）は１．０μｍ以下であるものの、輪郭曲線要素の平均長さ（ＲＳｍ）が、２００μｍを超えており、得られた炭素繊維不織布複合体の表面は粗く、実施例１に比べ、塗膜の密着性が劣っている。 In Comparative Example 3, carbon fibers were slurried using a refiner, but the treatment time was short, and the rate of change in air permeability of the carbon fiber nonwoven fabric used for forming the carbon fiber nonwoven fabric composite exceeded 8%. Although the arithmetic average height (Ra) obtained from the body roughness curve is 1.0 μm or less, the average length (RSm) of the contour curve element exceeds 200 μm, and the obtained carbon fiber nonwoven fabric composite Is rough and the adhesion of the coating film is inferior to that of Example 1.
比較例４は炭素繊維をパルパーで長時間分散してスラリー化しているが、炭素繊維不織布複合体形成に使用した炭素繊維不織布の通気度の変動率は８％を超えており、複合体の粗さ曲線から求められる算術平均高さ（Ｒａ）は１．０μｍを超えており、輪郭曲線要素の平均長さ（ＲＳｍ）は２００μｍ以下であるものの、得られた炭素繊維不織布複合体の表面は粗く、実施例１２に比べ、塗膜の密着性が劣っている。 In Comparative Example 4, the carbon fibers were dispersed in a pulper for a long time to form a slurry. However, the rate of change in the air permeability of the carbon fiber nonwoven fabric used to form the carbon fiber nonwoven fabric composite exceeded 8%, and the composite was rough. Although the arithmetic average height (Ra) obtained from the height curve exceeds 1.0 μm and the average length (RSm) of the contour curve element is 200 μm or less, the surface of the obtained carbon fiber nonwoven fabric composite has a rough surface. The adhesion of the coating film was inferior to that of Example 12.
本発明の炭素繊維不織布複合体は、電子機器材料、電気機器材料、土木材料、建築材料、自動車材料、航空機材料、各種製造業で使用されるロボット、ロール等の製造部品等に利用可能である。 The carbon fiber nonwoven fabric composite of the present invention can be used for electronic device materials, electric device materials, civil engineering materials, building materials, automobile materials, aircraft materials, and manufacturing parts such as robots and rolls used in various manufacturing industries. .
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