JP2002317382A - Carbon fiber bundle for woven fabric - Google Patents
Carbon fiber bundle for woven fabricInfo
- Publication number
- JP2002317382A JP2002317382A JP2001127036A JP2001127036A JP2002317382A JP 2002317382 A JP2002317382 A JP 2002317382A JP 2001127036 A JP2001127036 A JP 2001127036A JP 2001127036 A JP2001127036 A JP 2001127036A JP 2002317382 A JP2002317382 A JP 2002317382A
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- fiber bundle
- woven fabric
- manufactured
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 100
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 100
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000002759 woven fabric Substances 0.000 title claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000000835 fiber Substances 0.000 claims abstract description 18
- 238000004513 sizing Methods 0.000 claims abstract description 17
- 239000000284 extract Substances 0.000 claims abstract description 15
- 239000004753 textile Substances 0.000 claims description 16
- 239000003822 epoxy resin Substances 0.000 claims description 15
- 229920000647 polyepoxide Polymers 0.000 claims description 15
- -1 fatty acid esters Chemical class 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002184 metal Substances 0.000 abstract description 3
- 239000004744 fabric Substances 0.000 description 22
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000002131 composite material Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 238000000944 Soxhlet extraction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920003319 Araldite® Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- GWFGDXZQZYMSMJ-UHFFFAOYSA-N Octadecansaeure-heptadecylester Natural products CCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC GWFGDXZQZYMSMJ-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 2
- IIGMITQLXAGZTL-UHFFFAOYSA-N octyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCC IIGMITQLXAGZTL-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920003326 Araldite® GY 280 Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XUGNVMKQXJXZCD-UHFFFAOYSA-N isopropyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC(C)C XUGNVMKQXJXZCD-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 150000002888 oleic acid derivatives Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- BTAXGNQLYFDKEF-UHFFFAOYSA-N propyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCC BTAXGNQLYFDKEF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Woven Fabrics (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、広幅の織物用炭素
繊維束に関し、更に詳述すれば高強度かつ低製造コスト
の炭素繊維織物を製造することの出来る広幅の織物用炭
素繊維束に関する。前記炭素繊維織物は炭素繊維織物強
化樹脂等の複合材の製造に好適なものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wide-width carbon fiber bundle for textiles, and more particularly, to a wide-width carbon fiber bundle for textiles capable of producing a carbon fiber fabric having high strength and low production cost. The carbon fiber fabric is suitable for producing a composite material such as a carbon fiber fabric reinforced resin.
【０００２】[0002]
【従来の技術】従来、炭素繊維織物は高い強度を有する
ため、各種樹脂との複合材の形態で航空機等の高強度が
要求される分野の構造材等に利用されている。2. Description of the Related Art Conventionally, carbon fiber woven fabrics have high strength and are used in the form of composites with various resins for structural materials in fields requiring high strength such as aircraft.
【０００３】複合材等に用いられる炭素繊維織物は、通
常炭素繊維を複数本束ねた炭素繊維束を用いて製造され
る。炭素繊維織物の製造においては、太い炭素繊維束を
用いて炭素繊維織物を製造するほど製造コストの低減が
図れるので、従来もより太い炭素繊維束を用いて、より
低コストで低目付の炭素繊維織物を製造することが望ま
れている。[0003] A carbon fiber fabric used for a composite material or the like is usually manufactured using a carbon fiber bundle obtained by bundling a plurality of carbon fibers. In the production of carbon fiber fabrics, the production cost can be reduced as the carbon fiber fabric is produced using a thick carbon fiber bundle. It is desired to produce a woven fabric.
【０００４】しかし、太い炭素繊維束を用いて製造され
る炭素繊維織物は、その経糸と緯糸を構成する炭素繊維
束の交錯部において炭素繊維束が大きくクリンプされ
て、繊維密度が不均一になる。その結果、炭素繊維織物
の引張り強度が低くなる問題がある。[0004] However, in a carbon fiber woven fabric manufactured using a thick carbon fiber bundle, the carbon fiber bundle is greatly crimped at the intersection of the carbon fiber bundles constituting the warp and the weft, and the fiber density becomes uneven. . As a result, there is a problem that the tensile strength of the carbon fiber fabric is reduced.
【０００５】更に、太い炭素繊維束を用いて製造された
炭素繊維織物は、その目付や厚みが大きくなるため、プ
リプレグや織物強化樹脂複合材を製造する際の樹脂含浸
性が低下する。このため、これを用いて製造される炭素
繊維織物強化樹脂はその中に多数のボイドが包含されて
おり、高い強度特性が期待できなくなる。[0005] Further, the carbon fiber woven fabric produced using a thick carbon fiber bundle has a large basis weight and a large thickness, so that the resin impregnating property when producing a prepreg or a fabric reinforced resin composite material is reduced. For this reason, the carbon fiber woven fabric reinforced resin produced by using the same contains many voids therein, and high strength characteristics cannot be expected.
【０００６】また、太い炭素繊維束を用いて製造された
低目付の炭素繊維織物を用いて製造された炭素繊維織物
強化樹脂は、炭素繊維束間の空隙が多くなる。このた
め、高強度の炭素繊維織物強化樹脂は得られない。[0006] Further, in a carbon fiber woven fabric reinforced resin manufactured using a low-weight carbon fiber woven fabric manufactured using a thick carbon fiber bundle, voids between the carbon fiber bundles increase. Therefore, a high-strength carbon fiber fabric reinforced resin cannot be obtained.
【０００７】上記問題を解決するため、糸幅／糸厚みが
３０以上、繊度が３０００〜２００００デニールの撚り
のない扁平炭素繊維糸条を用いて製造された、目付が１
００〜３００ｇ／ｍ2の扁平糸織物を樹脂複合材に用い
る技術が提案されている（特開平６−１３６６３２号公
報、日本複合材料学会誌 ２６，２（２０００），６９
−７９）。[0007] In order to solve the above-mentioned problem, the basis weight is 1 using a non-twisted flat carbon fiber yarn having a yarn width / thickness of 30 or more and a fineness of 3000 to 20000 denier.
A technique of using a flat yarn woven fabric having a thickness of 100 to 300 g / m 2 as a resin composite material has been proposed (Japanese Patent Application Laid-Open No. Hei 6-136632, Journal of the Japan Society for Composite Materials 26, 2 (2000), 69).
-79).
【０００８】しかし、上記提案は扁平糸織物の製造方法
に発明の主力がおかれており、強度特性等のより優れた
低目付織物の製造用広幅炭素繊維糸条に関する十分な検
討は従来なされていないのが現状である。However, in the above-mentioned proposal, the main feature of the present invention is a method of manufacturing a flat yarn woven fabric, and a sufficient study on a wide carbon fiber yarn for manufacturing a low-weight woven fabric having more excellent strength characteristics has been made. There is no present.
【０００９】[0009]
【発明が解決しようとする課題】本発明者らは、複合材
用の高特性低目付炭素繊維織物を製造する目的でその原
料である幅広の炭素繊維束を種々検討した結果、低目付
の炭素繊維織物の製造用炭素繊維束としては、繊維束の
形状と、サイズ剤の粘度及び摩擦係数とが重要な要素に
なっていることを知得した。本発明は、上記発見に基づ
き完成するに至ったものである。従って、本発明の目的
とするところは、低目付、高強度且つ安価なの炭素繊維
織物の製造用炭素繊維束を提供することにある。SUMMARY OF THE INVENTION The present inventors have conducted various studies on a wide carbon fiber bundle as a raw material for the purpose of producing a high-performance, low-weight carbon fiber woven fabric for a composite material. It has been found that the shape of the fiber bundle, the viscosity of the sizing agent and the coefficient of friction are important factors for the carbon fiber bundle for producing a fiber fabric. The present invention has been completed based on the above findings. Accordingly, an object of the present invention is to provide a carbon fiber bundle for producing a carbon fiber fabric having a low basis weight, a high strength and a low cost.
【００１０】[0010]
【課題を解決するための手段】上記目的を達成する本発
明は、以下に記載するものである。The present invention to achieve the above object is as described below.
【００１１】〔１〕 サイズ剤を含有する織物用炭素繊
維束であって、扁平率（Ｌ／Ｄ）が３０〜１００、Ｆ／
Ｍ摩擦係数が２．５以下で、前記織物用炭素繊維束から
抽出した抽出物の５０℃における粘度が１００〜１００
０ポイズであることを特徴とする織物用炭素繊維束。[1] A carbon fiber bundle for textiles containing a sizing agent, having an oblateness (L / D) of 30 to 100, F /
M The coefficient of friction is 2.5 or less, and the viscosity at 50 ° C. of the extract extracted from the carbon fiber bundle for woven fabric is 100 to 100.
A carbon fiber bundle for woven fabric, which has zero poise.
【００１２】〔２〕 抽出物が固形エポキシ樹脂を５０
〜８０質量％含有する〔１〕に記載の織物用繊維束。[2] The extract contains 50 solid epoxy resins.
The fiber bundle for textiles according to [1], which contains about 80% by mass.
【００１３】〔３〕 抽出物が高級脂肪酸エステルを３
〜１５質量％含有する〔１〕又は〔２〕に記載の織物用
繊維束。[3] The extract contains 3 higher fatty acid esters.
The fiber bundle for a woven fabric according to [1] or [2], which contains about 15% by mass.
【００１４】以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
【００１５】[0015]
【発明の実施の形態】本発明織物用炭素繊維束を構成す
る炭素繊維は、特に制限が無く、ピッチ系、液晶系、レ
ーヨン系、アクリロニトリル系等の何れの炭素繊維も使
用できるが、アクリロニトリル系炭素繊維が生産性やコ
ストや性能の点で好ましい。炭素繊維の繊度、強度等の
特性も特に制限が無く、従来のものが何れも使用でき
る。BEST MODE FOR CARRYING OUT THE INVENTION The carbon fibers constituting the carbon fiber bundle for textiles of the present invention are not particularly limited, and any carbon fibers such as pitch-based, liquid-crystal-based, rayon-based and acrylonitrile-based carbon fibers can be used. Carbon fibers are preferred in terms of productivity, cost and performance. The characteristics of the carbon fiber such as fineness and strength are not particularly limited, and any of conventional carbon fibers can be used.
【００１６】本発明織物用炭素繊維束は、サイズ剤を用
いて上記炭素繊維を所定の扁平率の形状に束ねたもので
ある。この炭素繊維束を構成する炭素繊維の数は１００
０（１ｋ）〜５００００（５０ｋ）本が好ましく、１２
０００（１２ｋ）〜４８０００（４８ｋ）本が更に好ま
しい。The carbon fiber bundle for textiles of the present invention is obtained by bundling the above carbon fibers into a shape having a predetermined flatness using a sizing agent. The number of carbon fibers constituting this carbon fiber bundle is 100
0 (1 k) to 50,000 (50 k) are preferable, and 12
000 (12k) to 48000 (48k) are more preferable.
【００１７】本発明織物用炭素繊維束の扁平率は３０〜
１００で、４０〜７０がより好ましい。炭素繊維束の扁
平率が３０未満の場合は、これを用いて製造した炭素繊
維織物の厚さ方向におけるクリンプが大きくなり、引張
り強度が低下するので好ましくない。また、扁平率が１
００を超える場合は、これを用いて製造した炭素繊維織
物は炭素繊維束間の空隙（目開き）が大きくなる。この
ため、これを用いて複合材を製造すると、樹脂中にボイ
ドが多くなり、複合材の物性値のばらつきが大きくな
り、物性値が低下する原因になる。The flatness of the carbon fiber bundle for textiles of the present invention is 30 to
With 100, 40-70 is more preferable. If the flatness of the carbon fiber bundle is less than 30, the crimp in the thickness direction of the carbon fiber fabric produced using the same becomes large, and the tensile strength is undesirably reduced. In addition, the flatness is 1
If it exceeds 00, the carbon fiber woven fabric produced therefrom has large voids (openings) between carbon fiber bundles. For this reason, when a composite material is manufactured by using this, the voids increase in the resin, the physical property values of the composite material vary widely, and the physical property values are reduced.
【００１８】ここで、扁平率は下記式（１）で定義され
る。Here, the oblateness is defined by the following equation (1).
【００１９】[0019]
【数１】扁平率＝Ｌ／Ｄ （１） （Ｌ：繊維束の幅、Ｄ：繊維束の厚み） 本発明織物用炭素繊維束に付着しているサイズ剤等であ
って、ソックスレー抽出したサイズ剤を主成分とする抽
出物の粘度は、５０℃において１００〜１０００ポイズ
であり、好ましくは４００〜８００ポイズである。ソッ
クスレー抽出した抽出物の粘度が１０００ポイズを超え
る場合は、炭素繊維織物製造の際に織機における毛羽量
が増大する。また、ソックスレー抽出した抽出物の粘度
が１００ポイズ未満の場合は、繊維束中の繊維の集束性
が悪い。このため、この炭素繊維束を用いて炭素繊維織
物を製造する際の作業性が悪くなる。## EQU1 ## Flatness = L / D (1) (L: width of fiber bundle, D: thickness of fiber bundle) A sizing agent or the like adhered to the carbon fiber bundle for woven fabric of the present invention, which was subjected to Soxhlet extraction. The viscosity of the extract containing a sizing agent as a main component is 100 to 1000 poise at 50 ° C., preferably 400 to 800 poise. If the viscosity of the Soxhlet-extracted extract exceeds 1000 poise, the amount of fluff in the loom increases during the production of the carbon fiber fabric. If the viscosity of the extract obtained by Soxhlet extraction is less than 100 poise, the convergence of the fibers in the fiber bundle is poor. For this reason, workability at the time of manufacturing a carbon fiber fabric using this carbon fiber bundle is deteriorated.
【００２０】炭素繊維束からサイズ剤等をソックスレー
抽出する方法としては特に制限が無く、通常の操作条件
に従って行えばよい。具体的には、抽出用剤としてアセ
トン等の極性溶媒を用いて６０〜２４０分間抽出する方
法が例示できる。The method for soxhlet extraction of a sizing agent and the like from the carbon fiber bundle is not particularly limited, and may be performed under ordinary operating conditions. Specifically, a method of extracting for 60 to 240 minutes using a polar solvent such as acetone as an extraction agent can be exemplified.
【００２１】本発明織物用炭素繊維束は、繊維／金属
（Ｆ／Ｍ）摩擦係数が２．５以下であり、１．３〜２．
１がより好ましい。繊維／金属摩擦係数が２．５を超え
る場合は、炭素繊維織物製造の際に、毛羽量が増大する
ため好ましくない。The carbon fiber bundle for woven fabric of the present invention has a fiber / metal (F / M) friction coefficient of 2.5 or less, and 1.3 to 2.
1 is more preferred. If the fiber / metal friction coefficient is more than 2.5, the amount of fluff is undesirably increased during the production of carbon fiber fabric.
【００２２】本発明織物用炭素繊維束に用いるサイズ剤
は、上述のように、ソックスレー抽出した抽出物の粘度
が上記範囲内になるものであって、且つ抽出物中の固形
エポキシ樹脂成分が５０〜８５質量％含有されたエマル
ジョンタイプのものが好ましい。エポキシ樹脂成分とし
ては、液状及び固形状の、ビスフェノールＡ型エポキシ
樹脂がある。As described above, the sizing agent used for the carbon fiber bundle for textiles of the present invention has a viscosity of the Soxhlet-extracted extract within the above range, and the solid epoxy resin component in the extract has a viscosity of 50%. Emulsion type emulsions containing up to 85% by mass are preferred. Epoxy resin components include liquid and solid bisphenol A type epoxy resins.
【００２３】固形エポキシ樹脂成分比が５０質量％未満
の場合、炭素繊維束の集束性が悪くなり、炭素繊維織物
を製造する際の作業性が悪くなる。また、８５質量％を
超える場合は、炭素繊維束の収束性が高くなりすぎるた
め、炭素繊維織物の厚さ方向のクリンプが大きくなり、
引っ張り強度が低下する。When the ratio of the solid epoxy resin component is less than 50% by mass, the convergence of the carbon fiber bundle is deteriorated, and the workability in producing the carbon fiber fabric is deteriorated. On the other hand, if it exceeds 85% by mass, the convergence of the carbon fiber bundle becomes too high, so that the crimp in the thickness direction of the carbon fiber woven fabric increases,
The tensile strength decreases.
【００２４】液状のビスフェノールＡ型エポキシ樹脂に
は、分子量３００〜５００のビスフェノールＡ型エポキ
シ樹脂が挙げられ、具体的にはエピコート８１５、エピ
コート８２８、エピコート８３４（商品名 油化シェル
エポキシ社製）、アラルダイト２５０、アラルダイトＧ
Ｙ２６０、アラルダイトＧＹ２８０（商品名 チバガイ
ギー社製）等が例示できる。Examples of the liquid bisphenol A type epoxy resin include bisphenol A type epoxy resins having a molecular weight of 300 to 500. Specifically, Epicoat 815, Epicoat 828, Epicoat 834 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), Araldite 250, Araldite G
Y260, Araldite GY280 (trade name, manufactured by Ciba-Geigy) and the like.
【００２５】固形状のビスフェノールＡ型エポキシ樹脂
には、分子量７００〜４０００以上のビスフェノールＡ
型エポキシ樹脂が挙げられ、具体的にはエピコート１０
０１、エピコート１００２、エピコート１００４、エピ
コート１００７（商品名 油化シェルエポキシ社製）、
アラルダイト６０７１、アラルダイト６０８４、アラル
ダイト６０９７（商品名 チバガイギー社製）等が例示
できる。Solid bisphenol A type epoxy resins include bisphenol A having a molecular weight of 700 to 4000 or more.
Type epoxy resin, specifically, Epicoat 10
01, Epicoat 1002, Epicoat 1004, Epicoat 1007 (trade name, manufactured by Yuka Shell Epoxy),
Araldite 6071, Araldite 6084, Araldite 6097 (trade name, manufactured by Ciba Geigy) can be exemplified.
【００２６】固形エポキシ樹脂成分以外の成分として
は、高級脂肪酸エステルを３〜１５質量％含有すること
が好ましい。高級脂肪酸エステル含有率が３質量％未満
の場合、十分な摩擦低減効果が得られない。１５質量％
を超える場合、集束性が悪くなり、炭素繊維織物を製造
する際の作業性が悪くなる。As a component other than the solid epoxy resin component, a higher fatty acid ester is preferably contained in an amount of 3 to 15% by mass. When the higher fatty acid ester content is less than 3% by mass, a sufficient friction reducing effect cannot be obtained. 15% by mass
When it exceeds, the convergence deteriorates, and the workability when producing the carbon fiber fabric deteriorates.
【００２７】高級脂肪酸エステルの具体例としては、メ
チルステアレート、エチルステアレート、プロピルステ
アレート、ブチルステアレート、オクチルステアレー
ト、ステアリルステアレート等のステアリン酸エステ
ル、イソプロピルパルミテート等のオレイン酸エステル
等が挙げられる。Specific examples of higher fatty acid esters include stearic acid esters such as methyl stearate, ethyl stearate, propyl stearate, butyl stearate, octyl stearate and stearyl stearate, and oleic acid esters such as isopropyl palmitate. Is mentioned.
【００２８】本発明織物用炭素繊維束に用いるサイズ剤
を炭素繊維束に付与するに際して、前記樹脂組成物の水
エマルジョン、アセトン等の有機溶剤溶液にて付与し、
次いで乾燥することによってサイズ剤を付与することが
できる。安全性を考慮すると水エマルジョンを使用する
ことが好ましい。When the sizing agent to be used for the carbon fiber bundle for textiles of the present invention is applied to the carbon fiber bundle, the sizing agent is applied with an organic solvent solution such as water emulsion or acetone of the resin composition,
Subsequently, the sizing agent can be provided by drying. Considering safety, it is preferable to use a water emulsion.
【００２９】前記樹脂組成物を水エマルジョンにするに
は、界面活性剤を使用することができる。このような界
面活性剤としては、ノニオン系、カチオン系、アニオン
系界面活性剤が挙げられるが、水エマルジョン溶液とし
た際の溶液安定性の面から、ノニオン系界面活性剤を使
用することが好ましい。この界面活性剤の配合比は、質
量比で樹脂組成物／界面活性剤＝９０／１０〜７０／３
０が好ましい。In order to make the resin composition into a water emulsion, a surfactant can be used. Examples of such a surfactant include nonionic, cationic, and anionic surfactants. From the viewpoint of solution stability when a water emulsion solution is used, it is preferable to use a nonionic surfactant. . The mixing ratio of this surfactant is as follows: resin composition / surfactant = 90/10 to 70/3 in mass ratio.
0 is preferred.
【００３０】この界面活性剤の配合比がこの量比未満の
場合は、樹脂組成物の乳化が難しくなる。この界面活性
剤の配合比がこの量比を超える場合は、成型物とした際
のコンポジット物性が低下する。If the amount of the surfactant is less than the above ratio, it becomes difficult to emulsify the resin composition. When the compounding ratio of this surfactant exceeds this amount ratio, the composite physical properties when molded are reduced.
【００３１】以下、実施例により本発明を更に具体的に
説明する。Hereinafter, the present invention will be described more specifically with reference to examples.
【００３２】[0032]
【実施例】実施例１〜５、比較例１〜３ （織物用炭素繊維束の製造）未サイジングの炭素繊維束
（東邦レーヨン製ベスファイト（登録商標）、１２００
０フィラメント、引張強度４７００ＭＰａ、引張弾性率
２４５ＧＰａ）を連続的に、サイジング浴（３質量％水
エマルジョン）に浸漬した後、ローラーで余分の水分を
除去し、表面温度１３０℃のヒートローラー（直径３０
０ｍｍ、梨地仕上げ）に２０秒間接触乾燥させ、サイズ
処理した織物用炭素繊維束を製造した。EXAMPLES Examples 1 to 5 and Comparative Examples 1 to 3 (Production of carbon fiber bundle for woven fabric) Unsized carbon fiber bundle (Vesfite (registered trademark), 1200, manufactured by Toho Rayon)
0 filaments, a tensile strength of 4700 MPa, and a tensile modulus of 245 GPa) were continuously immersed in a sizing bath (3% by mass water emulsion), and excess water was removed with a roller.
(0 mm, satin finish) for 20 seconds to produce sized carbon fiber bundles for textiles.
【００３３】用いたサイズ剤は油化シェルエポキシ
（株）社製ビスフェノールＡ系エポキシ樹脂（エピコー
トＥＰ８２８、ＥＰ１００１、ＥＰ１００２）、旭電化
社製ウレタン変性エポキシＥＰＵ６、及びＤＩＣ社製ウ
レタン変性エポキシＮ３２０であった。The sizing agents used were bisphenol A-based epoxy resins (Epicoat EP828, EP1001, EP1002) manufactured by Yuka Shell Epoxy Co., Ltd., urethane-modified epoxy EPU6 manufactured by Asahi Denka, and urethane-modified epoxy N320 manufactured by DIC. Was.
【００３４】サイズ剤と併用した乳化剤はＰＯＥひまし
油エーテル（松本油脂製薬社製）、ＰＯ／ＰＥポリエー
テル（松本油脂製薬社製 数平均分子量Ｍｗ＝１６００
０）、ポリオキシエチレンジスチリルフェニルエーテル
（商品名 サミット７２３）であった。更に、高級脂肪
酸エステルとして、オクチルステアレート（新日本理化
社製 エヌジュルブ ＯＳ（商品名））、ステアリルス
テアレート（新日本理化製 エヌジェルブＳＳ（商品
名））を用いた。The emulsifier used in combination with the sizing agent is POE castor oil ether (manufactured by Matsumoto Yushi Seiyaku) and PO / PE polyether (manufactured by Matsumoto Yushi Seiyaku) having a number average molecular weight Mw = 1600.
0), polyoxyethylene distyryl phenyl ether (trade name: Summit 723). Further, as higher fatty acid esters, octyl stearate (Edjurub OS (trade name) manufactured by Nippon Rika Co., Ltd.) and stearyl stearate (Engelbu SS (trade name) manufactured by Nippon Rika Co., Ltd.) were used.
【００３５】得られた織物用炭素繊維束を用いて以下の
各評価試験を行った。その結果を表１にまとめて示し
た。The following evaluation tests were performed using the obtained carbon fiber bundle for textiles. The results are summarized in Table 1.
【００３６】（１）抽出物の粘度 サイズ処理された炭素繊維束一回５ｇを繰返し合計約２
００ｇをソックスレー抽出器を用いてアセトン合計２５
０ｍｌで抽出した。アセトンを留去して得られた残渣
（サイズ剤を主成分とする抽出物）の粘度を（株）レオ
ロジ製、粘度計ＭＲ−５００を用いて測定した。(1) Viscosity of the extract 5 g of the sized carbon fiber bundle is repeated at a time to obtain a total of about 2 g.
00g using a Soxhlet extractor for a total of 25
Extracted with 0 ml. The viscosity of the residue obtained by distilling off acetone (extract containing a sizing agent as a main component) was measured using a viscometer MR-500 manufactured by Rheology Co., Ltd.
【００３７】（２）扁平率 炭素繊維束の幅（Ｌ）、厚み（Ｄ）を以下の方法で５回
測定し（Ｎ＝５）、その平均値を求めた。 幅：株式会社キーエンス製イメージセンサー（センサー
ヘッドＶＧ−０３５、コントローラーＶＧ−３００）を
用いて測定した。 厚み：厚みゲージ（株式会社ミツトヨ製厚みゲージ Ｎ
ｏ．２０５０Ｆ）を用いて測定した。(2) Flatness The width (L) and thickness (D) of the carbon fiber bundle were measured five times by the following method (N = 5), and the average value was obtained. Width: Measured using an image sensor (sensor head VG-035, controller VG-300) manufactured by Keyence Corporation. Thickness: Thickness gauge (Thickness gauge made by Mitutoyo Corporation N
o. 2050F).
【００３８】（３）摩擦係数 図１に示すように、サイズ処理された炭素繊維束２がス
テンレス棒４表面と１２０°の接触角で接触しながら通
過するように、５本の直径２ｍｍのクロムメッキしたス
テンレス棒４を１５ｍｍ間隔でジグザグに配置した。こ
の５本のステンレス棒４間にサイズ処理された炭素繊維
束２をジグザグに掛け、２３ｇ（Ｔ１）の荷重６下で３
ｍ／分の速度で８分間走行させた。この際の張力（Ｔ
２）をロードセル８で連続的に測定し、摩擦係数を下記
式（２）により算出した。(3) Coefficient of friction As shown in FIG. 1, five pieces of chrome having a diameter of 2 mm were passed so that the sized carbon fiber bundle 2 passed therethrough at a contact angle of 120 ° with the surface of the stainless steel rod 4. The plated stainless steel rods 4 were zigzag at intervals of 15 mm. The sized carbon fiber bundle 2 is zigzagged between the five stainless steel rods 4, and is subjected to 3 g under a load 6 of 23 g (T1).
It was run for 8 minutes at a speed of m / min. At this time, the tension (T
2) was continuously measured with the load cell 8, and the friction coefficient was calculated by the following equation (2).
【００３９】[0039]
【数２】 摩擦係数＝ｌｎ（Ｔ２／Ｔ１） （２） （４）擦過毛羽量 サイズ処理された炭素繊維束がステンレス棒表面と１２
０°の接触角で接触しながら通過するように、５本の直
径２ｍｍのクロムメッキしたステンレス棒を１５ｍｍ間
隔でジグザグに配置した。この５本のステンレス棒間に
サイズ処理された炭素繊維束をジグザグに掛け、ボビン
からの炭素繊維束解舒テンションを２００ｇ／繊維束に
設定して、炭素繊維束を擦過させた。擦過後の炭素繊維
束をウレタンスポンジ（寸法３２ｍｍｘ６４ｍｍｘ１０
ｍｍ、質量０．２５ｇ）２枚の間に挟み込み、１２５ｇ
の錘をウレタンスポンジ全面に均等にかけた。炭素繊維
束を１５ｍ／分の速度で２分間通過させてスポンジに付
着した毛羽の質量を擦過毛羽量とした。## EQU2 ## Friction coefficient = ln (T2 / T1) (2) (4) Abrasive fluff amount The sized carbon fiber bundles are
Five chrome-plated stainless steel rods having a diameter of 2 mm were arranged in a zigzag manner at intervals of 15 mm so as to pass while contacting at a contact angle of 0 °. The sized carbon fiber bundle was zigzagged between the five stainless steel bars, and the carbon fiber bundle unwinding tension from the bobbin was set at 200 g / fiber bundle, and the carbon fiber bundle was rubbed. The rubbed carbon fiber bundle is urethane sponge (size 32 mm x 64 mm x 10
mm, mass 0.25g) sandwiched between two sheets, 125g
Weight was evenly applied over the entire urethane sponge. The mass of fluff adhering to the sponge after passing the carbon fiber bundle at a speed of 15 m / min for 2 minutes was defined as the amount of fluff.
【００４０】（炭素繊維織物の製造）上記サイズ処理さ
れた炭素繊維束を用いて、綾織、目付３８０ｇ／ｍ2の
織物を製造した。この製造した織物の表面を目視観察
し、毛羽立ち状態、目すき状態を評価し、炭素繊維織物
の品位として表１に示した。(Production of carbon fiber woven fabric) Twill woven fabric having a basis weight of 380 g / m 2 was produced using the carbon fiber bundle sized as described above. The surface of the manufactured woven fabric was visually observed, and the fluffed state and the glazed state were evaluated. The quality of the carbon fiber woven fabric is shown in Table 1.
【００４１】（炭素繊維織物プリプレグの製造）チバガ
イギー社製フェーノールノボラック型エポキシ樹脂ＥＰ
Ｎ１１３８（商品名）７０質量部、油化シェルエポキシ
社製ビスフェノールＡ型エポキシ樹脂エピコート８３４
（商品名）１２質量部、同社製ビスフェノールＡ型エポ
キシ樹脂エピコート１００２（商品名）１８質量部を混
合した。これに更に硬化剤ジシアンジアミドを５質量
部、硬化促進剤３−（３，４ジクロロフェニル）−１，
１ジメチルウレアを３質量部を加え、プリプレグ製造用
樹脂組成物を得た。(Manufacture of carbon fiber woven prepreg) Phenol novolak type epoxy resin EP manufactured by Ciba Geigy
N1138 (trade name) 70 parts by mass, Bisphenol A type epoxy resin Epicoat 834 manufactured by Yuka Shell Epoxy Co., Ltd.
12 parts by mass (trade name) and 18 parts by mass of Bisphenol A type epoxy resin Epicoat 1002 (trade name) manufactured by the company were mixed. Further, 5 parts by mass of a curing agent dicyandiamide and a curing accelerator 3- (3,4 dichlorophenyl) -1,
3 parts by mass of 1-dimethylurea was added to obtain a resin composition for producing a prepreg.
【００４２】この樹脂組成物をフィルムコータを用いて
剥離紙上に塗布し、更に前記炭素繊維織物を加熱下押圧
して樹脂組成物を織物に含浸させた。これにより炭素繊
維目付３８０ｇ／ｍ2、樹脂含有率３７質量％の炭素繊
維織物プリプレグを得た。This resin composition was applied on release paper using a film coater, and the carbon fiber fabric was pressed under heating to impregnate the resin composition into the fabric. As a result, a carbon fiber fabric prepreg having a carbon fiber weight of 380 g / m 2 and a resin content of 37% by mass was obtained.
【００４３】上記のようにして製造した炭素繊維織物プ
リプレグを成型後の厚みが３ｍｍとなるように複数枚積
層して金型に入れ、１２０℃で２時間、６８６０ＭＰａ
の圧力で成型し、一方向性炭素繊維織物強化成型板（Ｃ
ＦＲＰ板）を得た。このＣＦＲＰ板の層間剪断強度（Ｉ
ＬＳＳ）をＡＳＴＭ−Ｄ−２３４４に準拠して室温で測
定した。結果を表１に示した。A plurality of the carbon fiber woven prepregs produced as described above were laminated so that the thickness after molding became 3 mm, placed in a mold, and placed at 120 ° C. for 2 hours at 6860 MPa.
Molded under the pressure of unidirectional carbon fiber fabric reinforced molded plate (C
FRP plate). The interlaminar shear strength (I
LSS) was measured at room temperature according to ASTM-D-2344. The results are shown in Table 1.
【００４４】[0044]
【表１】 [Table 1]
【００４５】[0045]
【発明の効果】本発明の織物用炭素繊維束は、その抽出
物の５０℃における粘度が１００〜１０００ポイズで、
且つ扁平率が３０〜１００であるので、低目付で、引張
強度が高い炭素繊維織物を低コストで製造できる。この
製造した炭素繊維織物は樹脂と共に高性能なプリプレグ
や複合材を製造する用途に好適なものである。According to the carbon fiber bundle for textiles of the present invention, the viscosity of the extract at 50 ° C. is 100 to 1000 poise,
In addition, since the oblateness is 30 to 100, a carbon fiber woven fabric having a low basis weight and a high tensile strength can be manufactured at low cost. The produced carbon fiber fabric is suitable for use in producing a high-performance prepreg or composite material together with a resin.
【図面の簡単な説明】[Brief description of the drawings]
【図１】本発明の織物用炭素繊維束の摩擦抵抗を測定す
る方法を示す説明図である。FIG. 1 is an explanatory view showing a method for measuring the frictional resistance of a carbon fiber bundle for textiles according to the present invention.
２ 繊維束 ４ ステンレス棒 ６ 荷重 ８ ロードセル 2 Fiber bundle 4 Stainless steel rod 6 Load 8 Load cell
───────────────────────────────────────────────────── フロントページの続き (72)発明者 坂元 肇 静岡県駿東郡長泉町上土狩234 東邦レー ヨン株式会社内 (72)発明者 梅元 禎孝 静岡県駿東郡長泉町上土狩234 東邦レー ヨン株式会社内 Ｆターム(参考） 4L033 AA09 AB01 AC12 AC15 BA14 BA21 CA49 4L048 AA05 AB07 AB11 AB13 AC09 AC10 AC14 AC17 CA01 CA02 CA15 DA24 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hajime Sakamoto 234 Toho Rayon Co., Ltd., Nagaizumi-cho, Sunto-gun, Shizuoka Prefecture F term (reference) 4L033 AA09 AB01 AC12 AC15 BA14 BA21 CA49 4L048 AA05 AB07 AB11 AB13 AC09 AC10 AC14 AC17 CA01 CA02 CA15 DA24
Claims (3)
あって、扁平率（Ｌ／Ｄ）が３０〜１００、Ｆ／Ｍ摩擦
係数が２．５以下で、前記織物用炭素繊維束から抽出し
た抽出物の５０℃における粘度が１００〜１０００ポイ
ズであることを特徴とする織物用炭素繊維束。1. A woven fabric carbon fiber bundle containing a sizing agent, wherein the aspect ratio (L / D) is 30 to 100, the F / M coefficient of friction is 2.5 or less, and A carbon fiber bundle for textiles, wherein the extracted extract has a viscosity at 50 ° C of 100 to 1000 poise.
質量％含有する請求項１に記載の織物用繊維束。2. The extract comprises 50 to 80 solid epoxy resins.
The textile fiber bundle according to claim 1, which is contained by mass%.
質量％含有する請求項１又は２に記載の織物用繊維束。3. The extract contains 3 to 15 higher fatty acid esters.
The fiber bundle for textiles according to claim 1, wherein the fiber bundle is contained by mass%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001127036A JP2002317382A (en) | 2001-04-25 | 2001-04-25 | Carbon fiber bundle for woven fabric |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001127036A JP2002317382A (en) | 2001-04-25 | 2001-04-25 | Carbon fiber bundle for woven fabric |
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| Publication Number | Publication Date |
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| JP2002317382A true JP2002317382A (en) | 2002-10-31 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2001127036A Pending JP2002317382A (en) | 2001-04-25 | 2001-04-25 | Carbon fiber bundle for woven fabric |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10544275B2 (en) | 2015-01-21 | 2020-01-28 | Toray Industries, Inc. | Sizing agent coated carbon fiber bundle, method for manufacturing same, prepreg, and carbon fiber reinforced composite material |
| CN110983778A (en) * | 2019-12-13 | 2020-04-10 | 西安鑫垚陶瓷复合材料有限公司 | Sizing method for improving wear resistance of carbon fiber |
-
2001
- 2001-04-25 JP JP2001127036A patent/JP2002317382A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10544275B2 (en) | 2015-01-21 | 2020-01-28 | Toray Industries, Inc. | Sizing agent coated carbon fiber bundle, method for manufacturing same, prepreg, and carbon fiber reinforced composite material |
| US11390720B2 (en) | 2015-01-21 | 2022-07-19 | Toray Industries, Inc. | Sizing agent coated carbon fiber bundle, method for manufacturing same, prepreg, and carbon fiber reinforced composite material |
| EP3208376B1 (en) * | 2015-01-21 | 2022-08-03 | Toray Industries, Inc. | Sizing agent-coated carbon fiber bundle, method for manufacturing same, prepreg, and carbon fiber-reinforced composite material |
| CN110983778A (en) * | 2019-12-13 | 2020-04-10 | 西安鑫垚陶瓷复合材料有限公司 | Sizing method for improving wear resistance of carbon fiber |
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