JP2019060043A - Carbon fiber unwoven fabric - Google Patents
Carbon fiber unwoven fabric Download PDFInfo
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- JP2019060043A JP2019060043A JP2017185331A JP2017185331A JP2019060043A JP 2019060043 A JP2019060043 A JP 2019060043A JP 2017185331 A JP2017185331 A JP 2017185331A JP 2017185331 A JP2017185331 A JP 2017185331A JP 2019060043 A JP2019060043 A JP 2019060043A
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- 239000004744 fabric Substances 0.000 title abstract description 12
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- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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Abstract
Description
本発明は、炭素繊維強化樹脂複合体等に用いられる炭素繊維不織布に関する。 The present invention relates to a carbon fiber non-woven fabric used for a carbon fiber reinforced resin composite or the like.
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 resin has a strength and elastic modulus comparable to that of a metal material, but has a specific gravity smaller than that of a metal material, so that weight reduction of members can be achieved. In addition, it is used in electronic equipment materials, electrical equipment materials, civil engineering materials, construction materials, automobile materials, aircraft materials, and various manufacturing industries because it has no corrosion problems and is resistant to acids and alkalis. 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、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には、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 comprises a carbon fiber fabric such as a long fiber woven fabric, an open woven fabric, a unidirectional web, a long fiber nonwoven fabric, a short fiber nonwoven fabric and a resin such as a thermosetting resin or a thermoplastic resin. Complex. The most common carbon fiber reinforced resin composites are composites of a long carbon fiber fabric and a thermosetting resin, but are difficult to design, not homogeneous materials, long in molding and processing time, etc. There was an issue of
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１〜５参照）。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 for solving these problems, a carbon fiber reinforced thermoplastic resin composite in which a nonwoven fabric containing carbon fibers (carbon fiber nonwoven fabric) and a thermoplastic resin are combined has been proposed (see, for example, Patent Documents 1 to 5). ). By using the carbon fiber non-woven fabric and the thermoplastic resin, easy design and processability can be obtained, and the molding processing 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、また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の品質も満足できるものではなかった。 However, the conventional carbon fiber non-woven fabric is a carbon fiber non-woven fabric containing carbon fiber and thermoplastic resin powder or thermoplastic resin fiber, a carbon fiber non-woven fabric containing only carbon fiber, etc. It is difficult to disperse uniformly, the uniformity of the obtained carbon fiber non-woven fabric is insufficient, and the quality of the carbon fiber reinforced thermoplastic resin composite in which the carbon fiber non-woven fabric and the thermoplastic resin are composited can also be satisfied. It was not.
本発明の課題は、抄造性及び均一性に優れた炭素繊維不織布を提供することである。 An object of the present invention is to provide a carbon fiber non-woven fabric excellent in papermaking property and uniformity.
上記課題は、下記発明によって解決することができる。 The said subject is solvable by the following invention.
炭素繊維と熱可塑性樹脂繊維とフィブリル化セルロース繊維とを含有し、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されたスラリーを用いて湿式抄造法により形成された炭素繊維不織布であり、フラジール通気度の変動率が８％以下である炭素繊維不織布。 A carbon fiber non-woven fabric formed by a wet paper-making method using a slurry containing carbon fibers, thermoplastic resin fibers and fibrillated cellulose fibers, the carbon fibers being dispersed in water using a high-speed rotary shear type dispersing machine , Carbon fiber non-woven fabric having a variation rate of Frazier permeability of 8% or less.
本発明によれば、抄造性及び均一性に優れた炭素繊維不織布を提供することができる。 According to the present invention, it is possible to provide a carbon fiber non-woven fabric excellent in papermaking property and uniformity.
本発明の炭素繊維不織布は、炭素繊維と熱可塑性樹脂繊維とフィブリル化セルロース繊維とを含有し、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されたスラリーを用いて湿式抄造法により形成された炭素繊維不織布であり、フラジール通気度の変動率が８％以下である不織布である。 The carbon fiber non-woven fabric of the present invention contains carbon fiber, thermoplastic resin fiber and fibrillated cellulose fiber, and is produced by a wet paper-making method using a slurry in which the carbon fiber is dispersed in water using a high speed rotary shear type disperser. It is a formed carbon fiber non-woven fabric, and the variation rate of the Frazier air permeability is 8% or less.
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、ＰＡＮ系再生炭素繊維、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 carbon fibers include PAN-based carbon fibers made of polyacrylonitrile as a raw material, pitch-based carbon fibers made of pitches, PAN-based regenerated carbon fibers, and pitch-based regenerated carbon fibers. The fiber diameter of the carbon fiber is preferably 3 to 20 μm, and more preferably 5 to 15 μm. Moreover, it is preferable that it is 1-50 mm, and, as for the fiber length of carbon fiber, it is more preferable that it is 3-20 mm. The content of carbon fibers is preferably 50 to 96% by mass, and more preferably 70 to 93% by mass, with respect to all the 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、ポリアクリロニトリルを原料とするＰＡＮ系炭素繊維やピッチ類を原料とする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 formed by combining carbon fiber and resin. The carbon fiber reinforced resin composite comprises a carbon fiber fabric such as a long fiber woven fabric, an open woven fabric, a unidirectional web, a long fiber nonwoven fabric, a short fiber nonwoven fabric and a resin such as a thermosetting resin or a thermoplastic resin. Complex. The most common carbon fiber reinforced resin composite is a composite of a long carbon fiber fabric and a thermosetting resin. Examples of carbon fibers include PAN-based carbon fibers made of polyacrylonitrile as a raw material and pitch-based carbon fibers made of pitches as a raw material. The carbon fiber obtained by removing the resin from the carbon fiber reinforced resin composite by a heat treatment method, a sintering method, a superheat method, a superheated steam method or the like is a regenerated carbon fiber.
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 to reduce damage to the carbon fiber itself. The heat treatment temperature is preferably 400 ° C. to 800 ° C., more preferably 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、非結晶性の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。 Thermoplastic resin fibers are added to prevent carbon fibers from being detached from the non-woven fabric and to impart strength to the carbon fiber non-woven fabric. As a thermoplastic resin fiber, non-crystalline polyvinyl alcohol (vinylon) fiber, polyester core-sheath fiber whose surface has a low melting point, undrawn polyester fiber, polycarbonate (PC) fiber, polyolefin fiber, the surface has a low melting point Examples thereof include polyolefin core-sheath fibers, polyolefin fibers whose surface is made of acid-modified polyolefin, aliphatic polyamide fibers, undrawn polyphenylene sulfide fibers, and polyether ketone ketone fibers.
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く、８０〜１６０℃であることが特に好ましい。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 exhibits a melting point, the melting point is preferably 60 to 260 ° C., more preferably 60 to 230 ° C., still more preferably 60 to 180 ° C., and 80 to 160 ° C. Is particularly preferred. When the melting point of the thermoplastic resin fiber is in this temperature range, the binding property is imparted by the heat treatment in the nonwoven fabric production process, and the carbon fiber nonwoven fabric is imparted with strength.
熱可塑性樹脂繊維である非晶性の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℃で溶解するため、湿式抄造法においては、ドライヤーでの加熱処理によって、湿熱溶解して、結着性が付与され、炭素繊維不織布に強度が付与される。 Amorphous polyvinyl alcohol (vinylon) fiber which is a thermoplastic resin fiber does not show a clear melting point but dissolves at 60 to 100 ° C. in the presence of water. The wet heat is melted to give binding property, and the carbon fiber non-woven fabric is given strength.
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。熱可塑性樹脂繊維の含有量は、不織布中の全繊維に対して、２〜４０質量％であることが好ましい。 The fiber diameter of the thermoplastic resin fiber is preferably 3 to 40 μm, and more preferably 5 to 20 μm. The fiber length of the thermoplastic resin fiber is preferably 1 to 20 mm, and more preferably 3 to 12 mm. It is preferable that content of a thermoplastic resin fiber is 2-40 mass% with respect to all the fibers in a nonwoven fabric.
本発明に用いられる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、加熱及び加熱加圧時の不織布層の崩れを抑制し、炭素繊維強化熱可塑性樹脂複合体の均一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質量％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 used in the present invention is not a film but is a fiber having a portion finely divided mainly in a direction parallel to the fiber axis, and at least a portion of which is a fiber diameter of 1 μm or less It is a fiber. The aspect ratio of length to width is preferably 20 to 100,000. The modified freeness is preferably 0 to 770 ml, more preferably 0 to 600 ml. Furthermore, it is preferable that mass mean fiber length is 0.1-2 mm. The content of fibrillated cellulose fibers is preferably 2 to 20% by mass, and more preferably 2 to 10% by mass, with respect to all the fibers in the non-woven fabric. The incorporation of the fibrillated cellulose fiber improves the bondability between the carbon fiber and the thermoplastic resin fiber, improves the sheet-forming property, and suppresses the collapse of the non-woven fabric layer at the time of heating and heating and pressing. The uniformity of the fiber reinforced thermoplastic resin composite can be enhanced. In the modified method of the present invention, the sample concentration is 0.1 mass% using a wire mesh (PULP AND PAPER RESEARCH INSTITUTE OF CANADA) with a wire diameter of 0.14 mm and an opening of 0.18 mm as the sieve plate. 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、麻、コットン、コットンリンター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と、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等の木質系パルプとが挙げられる。特に、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 plant pulps include wood-based pulps such as kraft pulp (KP), dissolving pulp (DP), dissolving kraft pulp (DKP), etc. using hardwood (L) and softwood (N). In addition, non-wood-based pulps such as straw, hemp, cotton, cotton linters and the like can also be mentioned. As a commercial item, Celish (registered trademark, manufactured by Daicel Finechem Co., Ltd.) can be mentioned. In addition, although there exist I type, II type, III type, IV type etc. as a crystal form of a cellulose material, I-type and II type are preferable from a heat resistant viewpoint, and I type is more preferable. Non-wood-based pulps such as cotton pulp, cotton linter pulp, hemp pulp, kenaf pulp, etc., obtained from Type L cellulose material sources, pulps with reduced lignin and hemicellulose content, and L- or N-materials, Wood-based pulps such as KP, DP, DKP and the like in which the content of lignin and hemicellulose is reduced can be mentioned. In particular, cotton-based materials are preferred.
フィブリル化セルロース繊維を得るためには、セルロース材料が、まず、水中で分散され、機械的に粉砕される。そして、セルロース材料の繊維が解繊されてフィブリルが形成される。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、超音波破砕器等が挙げられる。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。 In order to obtain fibrillated cellulose fibers, the cellulose material is first dispersed in water and mechanically crushed. Then, the fibers of the cellulose material are disintegrated to form fibrils. As a device for disintegrating a cellulose material, a disc refiner, a millstone type grinder, a high pressure homogenizer, a ball mill, an apparatus for counter collision in water, an ultrasonic crusher and the like can be mentioned. These devices can be used in combination as appropriate.
本発明において、炭素繊維、熱可塑性樹脂繊維、フィブリル化セルロース繊維と共に用いることのできる繊維としては、フェノール樹脂繊維、メラミン樹脂繊維、尿素樹脂繊維、ポリウレタン繊維等の熱硬化性樹脂繊維、ガラス繊維等が挙げられる。 In the present invention, as fibers that can be used together with carbon fibers, thermoplastic resin fibers, and fibrillated cellulose fibers, thermosetting resin fibers such as phenol resin fibers, melamine resin fibers, urea resin fibers, polyurethane fibers, glass fibers, etc. Can be mentioned.
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 non-woven fabric in the present invention is a wet non-woven fabric produced by a wet sheet-forming method. In the wet sheet-forming method, carbon fibers, thermoplastic resin fibers, and fibrillated cellulose fibers are uniformly dispersed in water, and then passed through processes such as screen (removing foreign matter, lumps, etc.) to obtain a final fiber concentration of 0.01 The slurry adjusted to ̃0.50 mass% is made up by a paper machine to obtain a wet paper (nonwoven fabric in a wet state). Add chemicals such as dispersant, defoamer, hydrophilizing agent, antistatic agent, polymeric tackifier, mold release agent, antibacterial agent, bactericidal agent etc. in the process to equalize the dispersibility of fibers etc. In some cases.
本発明では、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、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る。本発明において、「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。 In the present invention, in the case of producing a carbon fiber non-woven fabric, a slurry in which carbon fibers are dispersed in water using a high-speed rotary shear type disperser is used in addition to dispersion processing with a common pulper. In the present invention, the "high-speed rotational shear type disperser" refers to a fiber-containing slurry passing between a rotating rotor having a dispersing blade and a stator having a dispersing blade, and shearing of the fibers in the slurry. It is a disperser that gives power and disperses. As a specific apparatus, a single disc refiner, a double disc refiner, a conical refiner and the like can be mentioned.
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 rotational shear dispersion machine has a high-speed rotational shear dispersion having a ring-shaped blade with fine slits rotating at high speed in a part of its structure. It is effective to be a machine. In a high-speed rotary shear disperser having a ring-shaped blade having a fine slit rotating at a high speed in a part of the structure, a hydrodynamic shock wave generated between the slits effectively acts on the carbon fiber. As a specific apparatus, Topfiner (made by Aikawa Iron Works), complete-disintegrating machine VF type (made by Shinhama Pump Mfg. Co., Ltd.), milder (made by Pacific Kiko) etc. are mentioned.
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 a slurry in which carbon fibers are dispersed is obtained using the above-mentioned disperser, the concentration of carbon fibers, the processing time, the number of revolutions of the rotor of the disperser, the clearance between the stator and the rotor, etc. The dispersibility can be adjusted appropriately.
本発明で用いられる熱可塑性樹脂繊維やフィブリル化セルロース繊維等は、炭素繊維とは別にパルパー等で分散した後、水中で高速せん断型分散機を使って分散した炭素繊維スラリーと混合しても構わないし、炭素繊維と共に水中で高速せん断型分散機を使って分散しても構わない。 The thermoplastic resin fibers, fibrillated cellulose fibers and the like used in the present invention may be dispersed with a pulper or the like separately from the carbon fibers and then mixed with the carbon fiber slurry dispersed in water using a high speed shear type dispersing machine. Alternatively, it may be dispersed in water with a carbon fiber using a high-speed shear disperser.
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 making machine, for example, a paper making machine using a single paper making machine such as a long wire, circular wire, inclined wire, etc., a combination paper making machine etc. in which two or more paper making networks of the same or different kinds are installed online be able to. When the nonwoven fabric has a multilayer structure of two or more layers, a method of laminating wet paper webs produced by each paper machine, or one of the layers is formed, and then fibers are dispersed on the layer. A non-woven fabric can be manufactured by a casting method in which the obtained slurry is cast to make a laminate. When the slurry in which the fibers are dispersed is cast, the layer previously formed may be in a wet paper state or in a dry state. In addition, two or more dried layers can be heat-sealed 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、各層の地合が良くなり、その結果、不織布全体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 non-woven fabric has a multilayer structure, the fiber composition of each layer may be the same, or the fiber composition of each layer may be different. In the case of a multilayer structure, the fiber density of the slurry can be lowered by lowering the basis weight of each layer, so that the formation of each layer is improved, and as a result, the uniformity of the formation of the entire nonwoven fabric is improved. Moreover, even if the formation of each layer is uneven, it can be compensated by laminating. Furthermore, the papermaking speed can be increased, and the effect of improving the operability can also 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、シート状の湿式不織布が得られる。湿紙をプレスロール等で加圧する場合、圧力は、好ましくは５０〜１０００Ｎ／ｃｍであり、より好ましくは２００〜８００Ｎ／ｃｍである。湿紙の乾燥の際に、ヤンキードライヤー等の熱ロールに密着させて熱圧乾燥させることによって、密着させた面の平滑性が向上する。熱圧乾燥とは、タッチロール等で熱ロールに湿紙を押しつけて乾燥させることを言う。熱ロールの表面温度は、１００〜１８０℃が好ましく、１００〜１６０℃がより好ましく、１１０〜１６０℃が更に好ましい。圧力は、好ましくは３０〜８００Ｎ／ｃｍであり、より好ましくは５０〜５００Ｎ／ｃｍである。 In the wet papermaking method, the wet paper web made by papermaking net is pressurized and dewatered with a press roll etc. if necessary, and the moisture content is controlled, then Yankee dryer, air dryer, cylinder dryer, suction drum type dryer By drying with an infrared dryer or the like, a sheet-like wet nonwoven fabric can be obtained. When the wet paper is pressed by a press roll or the like, the pressure is preferably 50 to 1000 N / cm, more preferably 200 to 800 N / cm. When the wet paper is dried, by bringing it into close contact with a heat roll such as a Yankee drier and performing heat and pressure drying, the smoothness of the adhered surface is improved. The heat and pressure drying refers to pressing the wet paper against the heat roll with a touch roll or the like to dry it. 100-180 degreeC is preferable, as for the surface temperature of a heat roll, 100-160 degreeC is more preferable, and 110-160 degreeC is still more preferable. The pressure is preferably 30 to 800 N / cm, more preferably 50 to 500 N / cm.
本発明の炭素繊維不織布はフラジール通気度の変動率が８％以下であり、好ましくは６％以下、より好ましくは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、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、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 non-woven fabric of the present invention has a variation rate of the flanged air permeability of 8% or less, preferably 6% or less, more preferably 4% or less. In the production of carbon fiber non-woven fabric by the wet sheet-forming method, in addition to dispersion processing with a common pulper, a slurry in which carbon fibers are dispersed in water using a high-speed rotary shear type disperser is used. By setting the variation rate to 8% or less, it is possible to obtain a carbon fiber non-woven fabric having high uniformity without causing uneven distribution of fibers.
本発明の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とフィブリル化セルロースを含有し、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）高速せん断型分散機での処理時間を長くする。（２）高速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。また（４）抄造時のプレスロール圧を２００〜８００Ｎ／ｃｍのより好ましい範囲に調整する。（５）抄造時のタッチロール圧を５０〜５００Ｎ／ｃｍのより好ましい範囲に調整する、という方法でフラジール通気度の変動率を低減することができる。 In the carbon fiber non-woven fabric of the present invention, the following method is used to make the variation rate of the Frazier permeability not more than 8%. A carbon fiber non-woven fabric is produced using a wet sheet-forming method using a slurry containing carbon fibers, thermoplastic resin fibers and fibrillated cellulose and dispersing the carbon fibers in water using a high-speed rotary shear type disperser. Here, in order to further reduce the variation rate of the Frazier's permeability, (1) the processing time in the high-speed shear disperser is lengthened. (2) Increase the rotational speed of the high speed shear type dispersing machine. (3) Adjustment can be made by narrowing the clearance between the stator and the rotor. (4) The press roll pressure at the time of paper making is adjusted to a more preferable range of 200 to 800 N / cm. (5) It is possible to reduce the variation rate of the Frazier's permeability by adjusting the touch roll pressure at the time of paper making to a more preferable range of 50 to 500 N / cm.
本発明における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 Ｌ １０９６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 in the present invention can be determined as follows. A sheet of 500 mm square is cut from a carbon fiber non-woven fabric, and 100 samples of 50 mm square air permeability measurement are prepared therefrom, and air permeable according to the air permeable A method (Frazil type method) defined in JIS L 1096 The air permeability is measured with a tester (apparatus name: KES-F8-AP1, manufactured by Kato Tech Co., Ltd.), and the average value (P1) and standard deviation (P2) of the air permeability of 100 samples are calculated. The value obtained from the equation (1) was taken as the fluctuation rate (%).
Change rate (%) = standard deviation of air permeability (P2) / average value of air permeability (P1) x 100 (1)
本発明の炭素繊維不織布は、例えば熱可塑性樹脂フィルムと積層して、加熱処理又は加熱加圧処理することによって、炭素繊維強化熱可塑性樹脂複合体として用いることもできる。 The carbon fiber non-woven fabric of the present invention can also be used as a carbon fiber-reinforced thermoplastic resin composite, for example, by laminating it with a thermoplastic resin film and subjecting it to heat treatment or heat and pressure treatment.
熱可塑性樹脂フィルムの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。 As thermoplastic resin of thermoplastic resin film, Polyolefin resin such as polyethylene resin, polypropylene resin, polybutylene resin; Methacrylic resin such as polymethyl methacrylate resin; Polystyrene resin such as polystyrene resin, ABS resin, AS resin; Polyethylene Polyester resins such as terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polytrimethylene terephthalate resin, polyethylene naphthalate (PEN) resin, polycyclohexylene dimethylene terephthalate (PCT) resin; 6-nylon resin, 6 , 6-nylon resin etc .; polyamide (PA) resin; polyvinyl chloride resin; polyoxymethylene (POM) resin; polycarbonate (PC) resin; polyphenylene sulfide (PPS) resin Modified polyphenylene ether (PPE) resin, polyether imide (PEI) resin, polysulfone (PSF) resin, polyether sulfone (PES) resin, polyketone resin, polyarylate (PAR) resin, polyether nitrile (PEN) resin, poly Ether 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 such as liquid crystal polyester resin Polymer resins; Thermoplastic elastomers such as polystyrenes, polyolefins, polyurethanes, polyesters, polyamides, polybutadienes, polyisoprenes or fluorines; or copolymer resins or modified resins thereof; ionomer resins And the like. Among these resins, one or more can be used. From the viewpoint of molding processability, 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 ethylene ionomer resins obtained by neutralizing a part of carboxyl groups of an ethylene-unsaturated carboxylic acid copolymer resin with metal ions. What neutralized 10 mol% or more of a carboxyl group, preferably 10-90 mol% with a metal ion is 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.
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。 EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples.
＜炭素繊維Ａ１＞
平均繊維径９μｍ、繊維長８ｍｍのＰＡＮ系炭素繊維（再生していない炭素繊維）を炭素繊維Ａ１とした。
<Carbon fiber A1>
A PAN-based carbon fiber (unregenerated carbon fiber) having an average fiber diameter of 9 μm and a fiber length of 8 mm was used as a 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６ｍｍ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Ａ２とした。
<Carbon fiber A2>
A carbon fiber reinforced resin composite (PAN-based carbon fiber, epoxy resin used) was regenerated by the superheated steam method, and a recycled carbon fiber having an average fiber diameter of 7 μm obtained by classification processing to a fiber length of 6 mm was used as a carbon fiber A2.
＜熱可塑性樹脂繊維Ｂ１＞
平均繊維径１０μｍ、繊維長５ｍｍの熱融着性ポリエチレンテレフタレート芯鞘繊維を熱可塑性樹脂繊維Ｂ１とした。
<Thermoplastic resin fiber B1>
A heat-fusible polyethylene terephthalate core-sheath 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１１μｍ、繊維長３ｍｍのビニロン繊維（水中溶解温度７０℃）を熱可塑性樹脂繊維Ｂ２とした。
<Thermoplastic resin fiber B2>
A vinylon fiber having an average fiber diameter of 11 μm and a fiber length of 3 mm (a water melting temperature of 70 ° C.) was used as a thermoplastic resin fiber B2.
＜フィブリル化セルロース繊維Ｃ１＞
リンターパルプをパルパーで５分間解繊した後、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、変法濾水度２５０ｍｌのフィブリル化セルロース繊維Ｃ１を作製した。
<Fibrilized cellulose fiber C1>
After pulsing the linter pulp for 5 minutes with a pulper, it is ground using Masko Royder (registered trademark, device name: MKZA12) manufactured by Masuko Sangyo Co., Ltd., and fibrillated cellulose fiber C1 having a modified freeness of 250 ml Made.
＜セルロース繊維Ｃ２＞
リンターパルプをパルパーで５分間解繊したものをフィブリル化していないセルロース繊維Ｃ２とした。
<Cellulose fiber C2>
The linter pulp that has been fibrillated for 5 minutes with a pulper is used as unfibrillated cellulose fiber C2.
実施例１〜１３及び比較例１〜４
（炭素繊維の分散処理）
分散機１を用いて表１記載の処理時間で分散後、比較例１及び２以外は分散機２を用いて表１記載の処理時間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 13 and Comparative Examples 1 to 4
(Dispersion treatment of carbon fiber)
After dispersion using the dispersing machine 1 for the treatment time shown in Table 1, carbon fiber dispersion treatment is carried out using the dispersing machine 2 for the treatment time shown in Table 1 except for Comparative Examples 1 and 2. I got
（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、表２記載のプレスロール圧、タッチロール圧、ドライヤー温度の条件で抄造を実施した。
(Manufacture of carbon fiber non-woven fabric)
A slurry for papermaking was prepared with the fiber blending described in Table 2, and papermaking was carried out under the conditions of press roll pressure, touch roll pressure, and dryer temperature described in Table 2.
（実施例１）
表１記載の装置、条件で分散処理を行い、得られた炭素繊維スラリーと、パルパーで５分間分散処理した熱可塑性樹脂繊維、フィブリル化セルロース繊維を表２記載の配合で混合し、分散濃度０．２質量％に水で希釈し、アジテーターで３０分間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、プレスロール圧５００Ｎ／ｃｍで加圧脱水した後、１４０℃のヤンキードライヤーに接触させ、タッチロール圧３００Ｎ／ｃｍで圧着乾燥させて、目付５０．２ｇ／ｍ２の炭素繊維不織布を得た。
Example 1
Dispersion treatment is carried out under the conditions described in Table 1, and the resulting carbon fiber slurry is mixed with thermoplastic resin fibers and fibrillated cellulose fibers dispersed for 5 minutes with a pulper according to the composition described in Table 2 and the dispersion concentration is 0. The mixture was diluted with water to 2% by mass and stirred for 30 minutes with an agitator to prepare a sheet-forming slurry. A wet paper is formed on the circular form paper machine having a 90 mesh metal wire, and this papermaking slurry is subjected to pressure dewatering at a press roll pressure of 500 N / cm, and then brought into contact with a Yankee drier at 140 ° C. The pressure-sensitive adhesive was dried at a pressure of 1 / cm to obtain a carbon fiber non-woven fabric having a fabric weight of 50.2 g / m 2 .
（実施例２）
表１記載の装置、条件で分散処理を行い、得られた炭素繊維スラリーと、パルパーで５分間分散処理した熱可塑性樹脂繊維、フィブリル化セルロース繊維を表２記載の配合で混合した以外は、実施例１と同様にして、目付５０．５ｇ／ｍ２の炭素繊維不織布を得た。
(Example 2)
It is carried out except that the dispersion processing is carried out under the conditions of Table 1 and conditions and the obtained carbon fiber slurry, the thermoplastic resin fibers dispersed for 5 minutes with a pulper, and the fibrillated cellulose fibers are mixed according to the composition described in Table 2. In the same manner as Example 1, a carbon fiber non-woven fabric having a basis weight of 50.5 g / m 2 was obtained.
（実施例３）
表１記載の装置、条件で分散処理を行い、得られた炭素繊維スラリーと、パルパーで５分間分散処理した熱可塑性樹脂繊維、フィブリル化セルロース繊維を表２記載の配合で混合した以外は、実施例１と同様にして、目付５０．４ｇ／ｍ２の炭素繊維不織布を得た。
(Example 3)
It is carried out except that the dispersion processing is carried out under the conditions of Table 1 and conditions and the obtained carbon fiber slurry, the thermoplastic resin fibers dispersed for 5 minutes with a pulper, and the fibrillated cellulose fibers are mixed according to the composition described in Table 2. In the same manner as Example 1, a carbon fiber non-woven fabric having a basis weight of 50.4 g / m 2 was obtained.
（実施例４）
表１記載の装置、条件で分散処理を行い、得られた炭素繊維スラリーと、パルパーで５分間分散処理した熱可塑性樹脂繊維、フィブリル化セルロース繊維を表２記載の配合で混合した以外は、実施例１と同様にして、目付５０．６ｇ／ｍ２の炭素繊維不織布を得た。
(Example 4)
It is carried out except that the dispersion processing is carried out under the conditions of Table 1 and conditions and the obtained carbon fiber slurry, the thermoplastic resin fibers dispersed for 5 minutes with a pulper, and the fibrillated cellulose fibers are mixed according to the composition described in Table 2. In the same manner as Example 1, a carbon fiber non-woven fabric having a basis weight of 50.6 g / m 2 was obtained.
（実施例５）
表１記載の装置、条件で分散処理を行い、得られた炭素繊維スラリーと、パルパーで５分間分散処理した熱可塑性樹脂繊維、フィブリル化セルロース繊維を表２記載の配合で混合し、プレスロール圧を６００Ｎ／ｃｍとし、ヤンキードライヤー温度を１５０℃とし、タッチロール圧を４００Ｎ／ｃｍとした以外は、実施例１と同様にして、目付５０．３ｇ／ｍ２の炭素繊維不織布を得た。
(Example 5)
Dispersion treatment is performed under the conditions described in Table 1 under the conditions described in Table 1 and the obtained carbon fiber slurry is mixed with thermoplastic resin fibers and fibrillated cellulose fibers dispersed for 5 minutes with a pulper according to the composition described in Table 2 and press roll pressure was a 600N / cm, a Yankee dryer temperature was 0.99 ° C., except that the touch roll pressure and 400 N / cm, the same procedure as in example 1 to obtain a carbon fiber nonwoven fabric having a basis weight of 50.3 g / m 2.
（実施例６）
表１記載の装置、条件で分散処理を行い、得られた炭素繊維スラリーと、パルパーで５分間分散処理した熱可塑性樹脂繊維、フィブリル化セルロース繊維を表２記載の配合で混合した以外は、実施例５と同様にして、目付５０．５ｇ／ｍ２の炭素繊維不織布を得た。
(Example 6)
It is carried out except that the dispersion processing is carried out under the conditions of Table 1 and conditions and the obtained carbon fiber slurry, the thermoplastic resin fibers dispersed for 5 minutes with a pulper, and the fibrillated cellulose fibers are mixed according to the composition described in Table 2. In the same manner as in Example 5, a carbon fiber non-woven fabric having a basis weight of 50.5 g / m 2 was obtained.
（実施例７）
表１記載の装置、条件で分散処理を行い、得られた炭素繊維スラリーと、パルパーで５分間分散処理した熱可塑性樹脂繊維、フィブリル化セルロース繊維を表２記載の配合で混合した以外は、実施例５と同様にして、目付５０．４ｇ／ｍ２の炭素繊維不織布を得た。
(Example 7)
It is carried out except that the dispersion processing is carried out under the conditions of Table 1 and conditions and the obtained carbon fiber slurry, the thermoplastic resin fibers dispersed for 5 minutes with a pulper, and the fibrillated cellulose fibers are mixed according to the composition described in Table 2. In the same manner as in Example 5, a carbon fiber non-woven fabric having a basis weight of 50.4 g / m 2 was obtained.
（実施例８）
表１記載の装置、条件で分散処理を行い、得られた炭素繊維スラリーと、パルパーで５分間分散処理した熱可塑性樹脂繊維、フィブリル化セルロース繊維を表２記載の配合で混合した以外は、実施例５と同様にして、目付５０．７ｇ／ｍ２の炭素繊維不織布を得た。
(Example 8)
It is carried out except that the dispersion processing is carried out under the conditions of Table 1 and conditions and the obtained carbon fiber slurry, the thermoplastic resin fibers dispersed for 5 minutes with a pulper, and the fibrillated cellulose fibers are mixed according to the composition described in Table 2. In the same manner as in Example 5, a carbon fiber non-woven fabric having a basis weight of 50.7 g / m 2 was obtained.
（実施例９）
表１記載の装置、条件で分散処理を行い、得られた炭素繊維スラリーと、パルパーで５分間分散処理した熱可塑性樹脂繊維、フィブリル化セルロース繊維を表２記載の配合で混合した以外は、実施例５と同様にして、目付５０．２ｇ／ｍ２の炭素繊維不織布を得た。
(Example 9)
It is carried out except that the dispersion processing is carried out under the conditions of Table 1 and conditions and the obtained carbon fiber slurry, the thermoplastic resin fibers dispersed for 5 minutes with a pulper, and the fibrillated cellulose fibers are mixed according to the composition described in Table 2. In the same manner as in Example 5, a carbon fiber non-woven fabric having a basis weight of 50.2 g / m 2 was obtained.
（実施例１０）
表１記載の装置、条件で分散処理を行い、得られた炭素繊維スラリーと、パルパーで５分間分散処理した熱可塑性樹脂繊維、フィブリル化セルロース繊維を表２記載の配合で混合し、実施例５と同様に抄造用スラリーを調製し、抄造時のプレスロール圧を１００Ｎ／ｃｍとした以外は、実施例５と同様にして、目付５０．６ｇ／ｍ２の炭素繊維不織布を得た。
(Example 10)
Dispersion treatment is carried out under the conditions described in Table 1 under the conditions described in Table 1, and the resulting carbon fiber slurry is mixed with thermoplastic resin fibers and fibrillated cellulose fibers dispersed for 5 minutes with a pulper according to the composition described in Table 2 and Example 5 A sheet-forming slurry was prepared in the same manner as in the above, and a carbon fiber non-woven fabric with a fabric weight of 50.6 g / m 2 was obtained in the same manner as Example 5, except that the press roll pressure during sheet forming was 100 N / cm.
（実施例１１）
表１記載の装置、条件で分散処理を行い、得られた炭素繊維スラリーと、パルパーで５分間分散処理した熱可塑性樹脂繊維、フィブリル化セルロース繊維を表２記載の配合で混合し、実施例５と同様に抄造用スラリーを調製し、抄造時のプレスロール圧を９００Ｎ／ｃｍとした以外は、実施例５と同様にして、目付５０．４ｇ／ｍ２の炭素繊維不織布を得た。
(Example 11)
Dispersion treatment is carried out under the conditions described in Table 1 under the conditions described in Table 1, and the resulting carbon fiber slurry is mixed with thermoplastic resin fibers and fibrillated cellulose fibers dispersed for 5 minutes with a pulper according to the composition described in Table 2 and Example 5 A sheet-forming slurry was prepared in the same manner as in the above, and a carbon fiber non-woven fabric with a fabric weight of 50.4 g / m 2 was obtained in the same manner as Example 5, except that the press roll pressure during sheet forming was 900 N / cm.
（実施例１２）
表１記載の装置、条件で分散処理を行い、得られた炭素繊維スラリーと、パルパーで５分間分散処理した熱可塑性樹脂繊維、フィブリル化セルロース繊維を表２記載の配合で混合し、実施例５と同様に抄造用スラリーを調製し、抄造時のタッチロール圧を６００Ｎ／ｃｍとした以外は、実施例５と同様にして、目付５０．１ｇ／ｍ２の炭素繊維不織布を得た。
(Example 12)
Dispersion treatment is carried out under the conditions described in Table 1 under the conditions described in Table 1, and the resulting carbon fiber slurry is mixed with thermoplastic resin fibers and fibrillated cellulose fibers dispersed for 5 minutes with a pulper according to the composition described in Table 2 and Example 5 A slurry for sheet-making was prepared in the same manner as in Example 5. A carbon fiber non-woven fabric with a fabric weight of 50.1 g / m 2 was obtained in the same manner as in Example 5 except that the touch roll pressure during sheet-making was 600 N / cm.
（実施例１３）
表１記載の装置、条件で分散処理を行い、得られた炭素繊維スラリーと、パルパーで５分間分散処理した熱可塑性樹脂繊維、フィブリル化セルロース繊維を表２記載の配合で混合し、実施例５と同様に抄造用スラリーを調製し、抄造時のタッチロール圧を４０Ｎ／ｃｍとした以外は、実施例５と同様にして、目付５０．５ｇ／ｍ２の炭素繊維不織布を得た。
(Example 13)
Dispersion treatment is carried out under the conditions described in Table 1 under the conditions described in Table 1, and the resulting carbon fiber slurry is mixed with thermoplastic resin fibers and fibrillated cellulose fibers dispersed for 5 minutes with a pulper according to the composition described in Table 2 and Example 5 A slurry for papermaking was prepared in the same manner as in the above, and a carbon fiber nonwoven fabric with a fabric weight of 50.5 g / m 2 was obtained in the same manner as in Example 5 except that the touch roll pressure at the time of papermaking was 40 N / cm.
（比較例１）
表１記載の装置、条件で分散処理を行い、得られた炭素繊維スラリーと、パルパーで５分間分散処理した熱可塑性樹脂繊維、フィブリル化セルロース繊維を表２記載の配合で混合した以外は、実施例１と同様にして、目付５０．３ｇ／ｍ２の炭素繊維不織布を得た。
(Comparative example 1)
It is carried out except that the dispersion processing is carried out under the conditions of Table 1 and conditions and the obtained carbon fiber slurry, the thermoplastic resin fibers dispersed for 5 minutes with a pulper, and the fibrillated cellulose fibers are mixed according to the composition described in Table 2. In the same manner as Example 1, a carbon fiber non-woven fabric having a basis weight of 50.3 g / m 2 was obtained.
（比較例２）
表１記載の装置、条件で分散処理を行い、得られた炭素繊維スラリーと、パルパーで５分間分散処理した熱可塑性樹脂繊維、フィブリル化セルロース繊維を表２記載の配合で混合した以外は、実施例５と同様にして、目付５０．２ｇ／ｍ２の炭素繊維不織布を得た。
(Comparative example 2)
It is carried out except that the dispersion processing is carried out under the conditions of Table 1 and conditions and the obtained carbon fiber slurry, the thermoplastic resin fibers dispersed for 5 minutes with a pulper, and the fibrillated cellulose fibers are mixed according to the composition described in Table 2. In the same manner as in Example 5, a carbon fiber non-woven fabric having a basis weight of 50.2 g / m 2 was obtained.
（比較例３）
表１記載の装置、条件で分散処理を行い、得られた炭素繊維スラリーと、パルパーで５分間分散処理した熱可塑性樹脂繊維、フィブリル化セルロース繊維を表２記載の配合で混合した以外は、実施例１と同様にして、目付５０．６ｇ／ｍ２の炭素繊維不織布を得た。
(Comparative example 3)
It is carried out except that the dispersion processing is carried out under the conditions of Table 1 and conditions and the obtained carbon fiber slurry, the thermoplastic resin fibers dispersed for 5 minutes with a pulper, and the fibrillated cellulose fibers are mixed according to the composition described in Table 2. In the same manner as Example 1, a carbon fiber non-woven fabric having a basis weight of 50.6 g / m 2 was obtained.
（比較例４）
表１記載の装置、条件で分散処理を行い、得られた炭素繊維スラリーと、パルパーで５分間分散処理した熱可塑性樹脂繊維、フィブリル化セルロース繊維を表２記載の配合で混合した以外は、実施例１と同様にして、目付５０．５ｇ／ｍ２の炭素繊維不織布を得た。
(Comparative example 4)
It is carried out except that the dispersion processing is carried out under the conditions of Table 1 and conditions and the obtained carbon fiber slurry, the thermoplastic resin fibers dispersed for 5 minutes with a pulper, and the fibrillated cellulose fibers are mixed according to the composition described in Table 2. In the same manner as Example 1, a carbon fiber non-woven fabric having a basis weight of 50.5 g / m 2 was obtained.
（抄造性の評価）
実施例及び比較例において、炭素繊維不織布の抄造性を次の項目（ａ）及び（ｂ）で評価した。（ａ）金属ワイヤーからウエットフェルトへの湿紙（湿潤状態の不織布）の転写性、（ｂ）乾燥後のドライヤーからの剥離不良による炭素繊維の脱落状態。（ａ）については、湿紙中の繊維が金属ワイヤーに全く残留せず非常に良い場合を「◎」、僅かに繊維は残留するが良いと判断する場合を「○」、繊維の残留が見られやや悪いと判断する場合を「△」、繊維の残留が多く悪いと判断する場合を「×」とした。（ｂ）については、ドライヤーからの剥離が非常に良く繊維の脱落が全く無い場合を「◎」、剥離は良いが繊維の脱落が僅かにある場合を「○」、剥離がやや悪く繊維の脱落が少しある場合を「△」、剥離が悪く繊維の脱落が多い場合を「×」とした。尚、本発明の炭素繊維不織布の条件を満たす抄造性は、「△」以上の評価を有するものである。結果を表３に示す。
(Evaluation of formability)
In Examples and Comparative Examples, the paper forming property of the carbon fiber non-woven fabric was evaluated by the following items (a) and (b). (A) Transferability of wet paper (nonwoven fabric in a wet state) from metal wire to wet felt, (b) Falling state of carbon fiber due to poor peeling from the dryer after drying. As for (a), when the fibers in the wet paper do not remain at all in the metal wire at all, it is very good "、", and when it is judged that the fibers remain slightly but good, "○" In the case where it was judged that the fiber was a little bad was taken as “Δ”, and in the case where it was judged that the remaining amount of the fiber was bad, it was taken as “×”. As for (b), when the peeling from the drier is very good and there is no detachment of the fiber at all “◎”, the detachment is good but when the detachment of the fiber is slightly “O”, the detachment is somewhat bad and the fiber falls off In the case where there was a slight amount of “A”, the case in which the peeling was poor and the number of fibers dropped was “C”. In addition, the paper-forming property which satisfy | fills the conditions of the carbon fiber nonwoven fabric of this invention has evaluation of "(triangle | delta)" or more. The results are shown in Table 3.
（均一性の評価）
実施例及び比較例で得られた炭素繊維不織布から縦横２５０ｍｍ角のシートを切り取り、この炭素繊維不織布を透過光で観察し、シート中に存在する欠点（離解せず束になった状態の繊維及び繊維が撚れて凝集した塊）の数を数えた。欠点の数が少ない方が均一性に優れ好ましい。結果を表３に示す。
(Evaluation of uniformity)
A sheet of 250 mm square is cut out from the carbon fiber non-woven fabric obtained in Examples and Comparative Examples, and this carbon fiber non-woven fabric is observed by transmitted light, and the defects present in the sheet (fibers in a bundle without breaking up and The number of fibers (twisted and aggregated) was counted. The smaller the number of defects, the better the uniformity and the better. The results are shown in Table 3.
更にこのシートの地合ムラを目視で評価した。ここで地合ムラとは、不織布を透過光で観察した場合に濃淡差が生じる部分があることを示す。シートに地合ムラが無い場合を「◎」、地合ムラが僅かにある場合を「○」、地合ムラがやや多い場合を「△」、地合ムラが多い場合を「×」とした。地合ムラが少ない方が均一性に優れ好ましい。尚、本発明の炭素繊維不織布の条件を満たす均一性は、欠点が１５個以下で地合ムラが「△」以上の評価を有するものである。結果を表３に示す。 Further, unevenness in formation of this sheet was visually evaluated. Here, the formation unevenness indicates that there is a portion where a difference in density occurs when the nonwoven fabric is observed by transmitted light. The case where there is no texture unevenness on the sheet is "◎", the case where there is slight texture unevenness is "○", the case where texture unevenness is slightly larger is "△", and the case where texture unevenness is large is "x" . Less unevenness of formation is preferable because of excellent uniformity. In addition, the uniformity which satisfy | fills the conditions which satisfy | fill the conditions of the carbon fiber nonwoven fabric of this invention has a defect, and has 15 evaluations or more of formation unevenness | corrugation "(triangle | delta)" or more. The results are shown in Table 3.
（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 Ｌ １０９６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）
(Assessing the rate of change of the air permeability of the flange)
A sheet of 500 mm square is cut out from the carbon fiber non-woven fabric obtained in Examples and Comparative Examples, and 100 samples of air permeability measurement of 50 mm square are prepared therefrom, and air permeability A method (Frazil specified in JIS L 1096) Permeability is measured with a breathability tester (apparatus name: KES-F8-AP1, manufactured by Kato Tech Co., Ltd.) according to the method), and the average value (P1) and standard deviation of the permeability of 100 samples (P2) was calculated, and the fluctuation rate was determined from the following equation (1). The results are shown in Table 3.
Change rate (%) = standard deviation of air permeability (P2) / average value of air permeability (P1) x 100 (1)
実施例で得られた炭素繊維不織布は、抄造性が良好で、均一性に優れている。 The carbon fiber non-woven fabric obtained in the examples has a good sheet-forming property and is excellent in uniformity.
実施例１〜４を比較すると、通気度変動率が４％以下である実施例２及び実施例３で得られた炭素繊維不織布は、実施例１及び実施例４に比べ、抄造性に優れ、欠点や地合ムラが少なく、より優れている。 Comparing Examples 1 to 4, the carbon fiber non-woven fabrics obtained in Example 2 and Example 3 having the air permeability fluctuation rate of 4% or less are excellent in sheet-forming property as compared with Example 1 and Example 4, Less defects and uneven texture, better.
実施例５〜１３を比較すると、通気度変動率が４％以下である実施例７及び実施例８で得られた炭素繊維不織布は、抄造性に優れ、欠点や地合ムラが非常に少なく、特に優れている。 Comparing Examples 5 to 13, the carbon fiber non-woven fabrics obtained in Example 7 and Example 8 having the air permeability fluctuation rate of 4% or less are excellent in the paper-forming property, and have very few defects and unevenness in formation, Especially good.
実施例２と実施例４を比較すると、炭素繊維含有量が７０質量部以上である実施例２の方が、通気度変動率が低く、抄造性に優れ、欠点や地合ムラが少なく優れている。 Comparing Example 2 and Example 4, Example 2 having a carbon fiber content of 70 parts by mass or more has a lower air permeability fluctuation rate, is excellent in sheet forming property, is less in defects and formation unevenness, and is excellent. There is.
実施例６、実施例１０、及び実施例１１を比較すると、プレスロール圧がより好ましい範囲である実施例６は、通気度変動率が低く、抄造性に優れ、欠点や地合ムラが少なく優れている。 When Example 6, Example 10, and Example 11 are compared, Example 6 whose press roll pressure is in a more preferable range has a low permeability fluctuation rate, is excellent in paper formability, is less excellent in defects and formation unevenness, and is excellent ing.
実施例６、実施例１２、及び実施例１３を比較すると、タッチロール圧がより好ましい範囲である実施例６は、通気度変動率が低く、抄造性に優れ、欠点や地合ムラが少なく優れている。 When Example 6, Example 12, and Example 13 are compared, Example 6 whose touch roll pressure is in a more preferable range has a low permeability fluctuation rate, is excellent in paper formability, is less excellent in defects and formation unevenness, and is excellent ing.
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、通気度変動率が８％を大きく超えて高く、抄造性が非常に悪く、欠点や地合ムラが多く均一性に劣っている。 In Comparative Example 1 and Comparative Example 2, carbon fibers are not slurried in water using a high-speed rotary-shearing disperser, the air permeability fluctuation rate is much higher than 8%, and the sheet-forming property is very bad. There are many defects and unevenness of formation and the uniformity is inferior.
比較例３はセルロース繊維がフィブリル化されておらず、通気度変動率は８％を超えていないものの、本発明の条件を満たしておらず、実施例１に比べ劣っている。 Although the cellulose fiber is not fibrillated and the air permeability fluctuation rate does not exceed 8% in Comparative Example 3, the conditions of the present invention are not satisfied and it is inferior to Example 1.
比較例４は熱可塑性樹脂繊維を含有しておらず、通気度変動率は８％を超えていないものの、本発明の条件を満たしておらず、実施例１に比べ劣っている。 Comparative Example 4 contains no thermoplastic resin fiber, and although the air permeability fluctuation rate does not exceed 8%, it does not satisfy the conditions of the present invention and is inferior to Example 1.
本発明の炭素繊維不織布は、熱可塑性樹脂や熱硬化性樹脂と複合して、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 non-woven fabric of the present invention is combined with a thermoplastic resin or a thermosetting resin, and used in electronic equipment materials, electrical equipment materials, civil engineering materials, building materials, automobile materials, aircraft materials, and various manufacturing industries. It can be used for manufacturing parts such as rolls.
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| JP2017106130A (en) * | 2015-12-08 | 2017-06-15 | 三菱製紙株式会社 | Carbon short fiber unwoven fabric and composite body |
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| JP2021080615A (en) * | 2019-11-22 | 2021-05-27 | 三菱製紙株式会社 | Carbon short fiber nonwoven fabric |
| JP7077292B2 (en) | 2019-11-22 | 2022-05-30 | 三菱製紙株式会社 | Carbon staple fiber non-woven fabric |
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