JP2018009280A - Sizing agent-stuck carbon fiber bundle and method for producing the same and method for producing pressure container using the sizing agent-bonded carbon fiber bundle - Google Patents
Sizing agent-stuck carbon fiber bundle and method for producing the same and method for producing pressure container using the sizing agent-bonded carbon fiber bundle Download PDFInfo
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- JP2018009280A JP2018009280A JP2017156269A JP2017156269A JP2018009280A JP 2018009280 A JP2018009280 A JP 2018009280A JP 2017156269 A JP2017156269 A JP 2017156269A JP 2017156269 A JP2017156269 A JP 2017156269A JP 2018009280 A JP2018009280 A JP 2018009280A
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 248
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 248
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 239
- 238000004513 sizing Methods 0.000 title claims abstract description 207
- 238000004519 manufacturing process Methods 0.000 title abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 116
- 238000000034 method Methods 0.000 claims abstract description 80
- 238000005136 cathodoluminescence Methods 0.000 claims description 9
- 229920005989 resin Polymers 0.000 abstract description 54
- 239000011347 resin Substances 0.000 abstract description 54
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- 238000005470 impregnation Methods 0.000 abstract description 14
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- 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 4
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- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 description 2
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
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- 239000001099 ammonium carbonate Substances 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
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- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 241000270666 Testudines Species 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 239000004760 aramid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- PRORZGWHZXZQMV-UHFFFAOYSA-N azane;nitric acid Chemical compound N.O[N+]([O-])=O PRORZGWHZXZQMV-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
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- 238000004364 calculation method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
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- MSJMDZAOKORVFC-UAIGNFCESA-L disodium maleate Chemical compound [Na+].[Na+].[O-]C(=O)\C=C/C([O-])=O MSJMDZAOKORVFC-UAIGNFCESA-L 0.000 description 1
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Abstract
Description
本発明は、サイジング剤が付着した炭素繊維束（以下、「サイジング剤付着炭素繊維束」ともいう）及びその製造方法並びにこのサイジング剤付着炭素繊維束を用いるＣＦＲＰ製圧力容器の製造方法に関する。 The present invention relates to a carbon fiber bundle to which a sizing agent is attached (hereinafter also referred to as “sizing agent-attached carbon fiber bundle”), a method for producing the same, and a method for producing a CFRP pressure vessel using the sizing agent-attached carbon fiber bundle.
炭素繊維や芳香族ポリアミド繊維等の強化繊維とマトリックス樹脂とからなる複合材料は、その高い比強度、比剛性を利用して、一般産業、自動車、スポーツ・レジャー、航空宇宙等の各分野において広く用いられており、これらの複合材料の工業的な用途は、近年、さらに拡大しつつある。複合材料の用途の拡大とともに、コンポジット物性を高く発現させる複合材料の製造方法に対する要求が高くなっている。 Composite materials consisting of reinforced fibers such as carbon fibers and aromatic polyamide fibers and matrix resins are widely used in general industries, automobiles, sports / leisure, aerospace, etc. by utilizing their high specific strength and specific rigidity. In recent years, the industrial applications of these composite materials have been further expanded. With the expansion of the use of composite materials, there is an increasing demand for methods for producing composite materials that exhibit high composite properties.
炭素繊維複合材料は、優れた機械的性質を有しているため、価格の低下とともに金属材料に代替されつつある。特に、軽くて強い特徴を生かし、コンクリート構造物の補修材、風力発電用の羽根、輸送用乗り物のボディやシャフトのような構造材、各種ＦＲＰ製圧力容器等への開発が盛んに行われており、それら用途の中でも炭素繊維を用いたＣＦＲＰ製圧力容器は小型軽量化が可能であるため、水素や天然ガスを燃料とする自動車の燃料貯蔵用の圧力容器等として広く開発が行われている。 Since the carbon fiber composite material has excellent mechanical properties, it is being replaced by a metal material as the price decreases. In particular, taking advantage of its light and strong features, it has been actively developed into repair materials for concrete structures, blades for wind power generation, structural materials such as body and shafts for transportation vehicles, and various FRP pressure vessels. Among these uses, CFRP pressure vessels using carbon fibers can be reduced in size and weight, and are widely developed as pressure vessels for fuel storage in automobiles using hydrogen or natural gas as fuel. .
このようなＦＲＰ製圧力容器は、芯材となるライナーの外表面に、マトリックス樹脂を含浸させた繊維を巻き付けるフィラメントワインド成形法（以下、「ＦＷ成形法」ともいう）によって主に製造されている。このＦＷ成形法は、ガラス繊維を用いて圧力容器を製造する場合に広く採用されてきた成形法であるが、炭素繊維を用いて圧力容器を製造する場合にも採用されている。しかし、炭素繊維を用いてＦＷ成形法により製造した圧力容器には、炭素繊維の持つ優れた繊維物性が十分に反映されていないという問題がある。 Such a pressure vessel made of FRP is mainly manufactured by a filament wind molding method (hereinafter also referred to as “FW molding method”) in which a fiber impregnated with a matrix resin is wound around the outer surface of a liner serving as a core material. . This FW molding method is a molding method that has been widely adopted when manufacturing pressure vessels using glass fibers, but is also used when manufacturing pressure vessels using carbon fibers. However, the pressure vessel manufactured by FW molding using carbon fibers has a problem that the excellent fiber properties of carbon fibers are not sufficiently reflected.
特許文献１には、炭素繊維の繊維径を細くし、繊維表面に襞を形成することにより、樹脂含浸性を向上させる方法が開示されている。しかし、炭素繊維の繊維径を細くしても、樹脂含浸性は十分に改善されない。 Patent Document 1 discloses a method for improving the resin impregnation property by reducing the fiber diameter of carbon fiber and forming wrinkles on the fiber surface. However, even if the fiber diameter of the carbon fiber is reduced, the resin impregnation property is not sufficiently improved.
特許文献２には、高い引張強度を有するＦＷ成形用炭素繊維束が開示されている。ＦＷ成形法においては、炭素繊維束に高い張力をかけて樹脂を含浸させている。そのため、工程中の固定ガイドやローラー等との擦過によって、炭素繊維束には毛羽立ちや糸切れが生じやすい。炭素繊維束の毛羽立ちや糸切れは、工程通過性や工程安定性を悪化させるだけでなく、最終成形物である圧力容器の性能にも悪影響を及ぼす。即ち、高い引張強度を有する炭素繊維束の物性を、複合材料の性能に十分に反映させることができない。そのため、ＦＷ成形法に用いられる炭素繊維には、耐擦過性、耐糸切れ性が求められる。 Patent Document 2 discloses a carbon fiber bundle for FW molding having high tensile strength. In the FW molding method, the carbon fiber bundle is impregnated with resin by applying high tension. For this reason, the carbon fiber bundle is likely to fluff or break due to rubbing with a fixed guide or a roller during the process. The fluff and thread breakage of the carbon fiber bundle not only deteriorate the process passability and process stability, but also adversely affect the performance of the pressure vessel as the final molded product. That is, the physical properties of the carbon fiber bundle having high tensile strength cannot be sufficiently reflected on the performance of the composite material. For this reason, the carbon fibers used in the FW molding method are required to have abrasion resistance and yarn breakage resistance.
耐擦過性、耐糸切れ性を向上させるために、炭素繊維束にサイジング剤を付与することは従来から広く行われている。例えば、特許文献３には、サイジング剤付与工程と乾燥工程とを交互に繰り返すサイジング剤の付与方法が開示されている。しかし、特許文献３で開示される方法では、炭素繊維束の外層部にサイジング剤が多く付着してしまい、炭素繊維束の内層部におけるサイジング剤の付着量が低下している。そのため、この炭素繊維束は、炭素繊維束の外層部に存在するサイジング剤によって、樹脂の含浸が妨げられやすい。その結果、得られる複合材料の性能は、炭素繊維束の物性を十分に反映したものとはならない。 In order to improve scratch resistance and thread breakage resistance, it has been widely practiced to apply a sizing agent to a carbon fiber bundle. For example, Patent Document 3 discloses a method for applying a sizing agent in which a sizing agent applying step and a drying step are alternately repeated. However, in the method disclosed in Patent Document 3, a large amount of the sizing agent adheres to the outer layer portion of the carbon fiber bundle, and the amount of the sizing agent attached to the inner layer portion of the carbon fiber bundle decreases. Therefore, the carbon fiber bundle is likely to be impeded by resin impregnation by a sizing agent present in the outer layer portion of the carbon fiber bundle. As a result, the performance of the obtained composite material does not sufficiently reflect the physical properties of the carbon fiber bundle.
本発明の目的は、耐擦過性及び耐糸切れ性を高く保持しつつも高い樹脂含浸性を有する、ＦＷ成形法に特に適したサイジング剤付着炭素繊維束及びその製造方法を提供することにある。また、本発明の他の目的は、前記サイジング剤付着炭素繊維束を用いて、ＦＷ成形法によりＣＦＲＰ製圧力容器を製造する方法を提供することにある。 An object of the present invention is to provide a sizing agent-attached carbon fiber bundle particularly suitable for the FW molding method and a method for producing the same, which has high resin impregnation property while maintaining high scratch resistance and yarn breakage resistance. . Another object of the present invention is to provide a method for producing a CFRP pressure vessel by the FW molding method using the sizing agent-attached carbon fiber bundle.
本発明者らは、上記課題について鋭意検討した結果、サイジング剤が付着したＦＷ成形用の炭素繊維束において、その内層部に十分な量のサイジング剤を付着させるとともに、外層部のサイジング剤付着量を抑制することにより、耐擦過性及び耐糸切れ性を高く保持したまま、樹脂含浸性を高くすることができることを見出した。そして、このようなサイジング剤付着炭素繊維束は、サイジング浴に炭素繊維束を浸漬した後、この炭素繊維束に気体を吹き付けて、炭素繊維束に付着するサイジング剤の一部を除去することにより製造することができることを見出し、本発明を完成するに至った。 As a result of intensive studies on the above problems, the present inventors have made it possible to attach a sufficient amount of sizing agent to the inner layer portion of the FW molding carbon fiber bundle to which the sizing agent has adhered, and the amount of sizing agent attached to the outer layer portion. It was found that the resin impregnation property can be increased while keeping the scratch resistance and the yarn breakage resistance high by suppressing. Such a sizing agent-attached carbon fiber bundle is obtained by immersing the carbon fiber bundle in a sizing bath and then blowing a gas on the carbon fiber bundle to remove a part of the sizing agent adhering to the carbon fiber bundle. The inventors have found that it can be manufactured and have completed the present invention.
上記課題を解決する本発明を以下に記載する。 The present invention for solving the above problems will be described below.
〔１〕 炭素繊維束にサイジング剤が０．８〜３．０質量％付着してなり、かつカソードルミネッセンス法により測定される炭素繊維束の外層部のサイジング剤発光カウント数（Ｓ）と、カソードルミネッセンス法により測定される炭素繊維束の内層部のサイジング剤発光カウント数（Ｉ）とが下式（１）
０．８＜ Ｉ／Ｓ ＜２．０ ・・・（１）
の関係を満たすことを特徴とするフィラメントワインド成形用のサイジング剤付着炭素繊維束。
[1] The sizing agent emission count (S) of the outer layer portion of the carbon fiber bundle, which is obtained by adhering 0.8 to 3.0% by mass of the sizing agent to the carbon fiber bundle and measured by the cathodoluminescence method, and the cathode The sizing agent emission count (I) of the inner layer portion of the carbon fiber bundle measured by the luminescence method is the following formula (1)
0.8 <I / S <2.0 (1)
A sizing agent-attached carbon fiber bundle for filament wind forming characterized by satisfying the following relationship:
〔２〕 サイジング剤を含むサイジング浴に炭素繊維束を浸漬して前記炭素繊維に前記サイジング剤を付着させた後、気体を吹き付けて前記炭素繊維束に付着する前記サイジング剤の一部を除去することを特徴とする〔１〕に記載のフィラメントワインド成形用のサイジング剤付着炭素繊維束の製造方法。 [2] After immersing the carbon fiber bundle in a sizing bath containing a sizing agent to adhere the sizing agent to the carbon fiber, a part of the sizing agent adhering to the carbon fiber bundle is removed by blowing a gas. The method for producing a carbon fiber bundle with attached sizing agent for filament wind forming as described in [1].
〔３〕 前記炭素繊維束の臨界張力が６５〜９５ｍＮ／ｍである〔２〕に記載のフィラメントワインド成形用のサイジング剤付着炭素繊維束の製造方法。 [3] The method for producing a sizing agent-attached carbon fiber bundle for filament wind forming according to [2], wherein a critical tension of the carbon fiber bundle is 65 to 95 mN / m.
〔４〕 前記サイジング浴に前記炭素繊維束を浸漬する回数が２〜１０回である〔２〕に記載のフィラメントワインド成形用のサイジング剤付着炭素繊維束の製造方法。 [4] The method for producing a sizing agent-attached carbon fiber bundle for filament winding molding according to [2], wherein the number of times the carbon fiber bundle is immersed in the sizing bath is 2 to 10 times.
〔５〕 サイジング剤を含むサイジング浴に炭素繊維束を浸漬して前記炭素繊維に前記サイジング剤を付着させた後、気体を吹き付けて前記炭素繊維束に付着する前記サイジング剤の一部を除去することにより、
前記炭素繊維束に前記サイジング剤が０．８〜３．０質量％付着してなり、かつカソードルミネッセンス法により測定される前記炭素繊維束の外層部のサイジング剤発光カウント数（Ｓ）と、カソードルミネッセンス法により測定される前記炭素繊維束の内層部のサイジング剤発光カウント数（Ｉ）とが下式（１）
０．８＜ Ｉ／Ｓ ＜２．０ ・・・（１）
の関係を満たすサイジング剤付着炭素繊維束を得る工程と、
前記サイジング剤付着炭素繊維束に樹脂を含浸させて樹脂含浸炭素繊維束を得る工程と、
前記樹脂含浸炭素繊維束を、中空部を有するライナーの外表面に巻回する工程と、
前記樹脂含浸炭素繊維束に含浸している前記樹脂を硬化する工程と、
を有することを特徴とする圧力容器の製造方法。
[5] After immersing the carbon fiber bundle in a sizing bath containing a sizing agent to adhere the sizing agent to the carbon fiber, a part of the sizing agent adhering to the carbon fiber bundle is removed by blowing a gas. By
A sizing agent emission count (S) of the outer layer portion of the carbon fiber bundle, wherein the sizing agent is attached to the carbon fiber bundle by 0.8 to 3.0% by mass and measured by a cathodoluminescence method, and a cathode The sizing agent emission count (I) of the inner layer part of the carbon fiber bundle measured by the luminescence method is the following formula (1)
0.8 <I / S <2.0 (1)
Obtaining a sizing agent-attached carbon fiber bundle satisfying the relationship of
Impregnating the sizing agent-attached carbon fiber bundle with a resin to obtain a resin-impregnated carbon fiber bundle;
Winding the resin-impregnated carbon fiber bundle around the outer surface of a liner having a hollow portion;
Curing the resin impregnated in the resin-impregnated carbon fiber bundle;
A method for producing a pressure vessel, comprising:
〔６〕 前記炭素繊維束の臨界張力が６５〜９５ｍＮ／ｍである〔５〕に記載の圧力容器の製造方法。 [6] The method for producing a pressure vessel according to [5], wherein the carbon fiber bundle has a critical tension of 65 to 95 mN / m.
〔７〕前記サイジング浴に前記炭素繊維束を浸漬する回数が２〜１０回である〔５〕又は〔６〕に記載の圧力容器の製造方法。 [7] The method for producing a pressure vessel according to [5] or [6], wherein the number of times the carbon fiber bundle is immersed in the sizing bath is 2 to 10 times.
本発明のサイジング剤付着炭素繊維束は、樹脂含浸性が高く、かつ耐擦過性及び耐糸切れ性が高い。そのため、このサイジング剤付着炭素繊維束は、ＦＷ成形に特に適する。そして、このサイジング剤付着炭素繊維束を用いてＦＷ成形法により製造するＣＦＲＰ製圧力容器の性能は、炭素繊維の繊維物性が十分に反映されたものとなる。 The sizing agent-attached carbon fiber bundle of the present invention has high resin impregnation properties, and high scratch resistance and yarn breakage resistance. Therefore, this sizing agent-attached carbon fiber bundle is particularly suitable for FW molding. The performance of the CFRP pressure vessel manufactured by the FW molding method using the sizing agent-attached carbon fiber bundle sufficiently reflects the fiber physical properties of the carbon fiber.
本発明のサイジング剤付着炭素繊維束の製造方法によれば、樹脂含浸性が高く、かつ耐擦過性及び耐糸切れ性が高いサイジング剤付着炭素繊維束を容易に得ることができる。 According to the method for producing a sizing agent-attached carbon fiber bundle of the present invention, it is possible to easily obtain a sizing agent-attached carbon fiber bundle having high resin impregnation properties and high scratch resistance and yarn breakage resistance.
以下、本発明のサイジング剤付着炭素繊維束及びその製造方法と、ＦＷ成形法による圧力容器の製造方法について説明する。 Hereinafter, the sizing agent-attached carbon fiber bundle of the present invention, a method for producing the same, and a method for producing a pressure vessel by the FW molding method will be described.
（１）サイジング剤付着炭素繊維束
本発明のサイジング剤付着炭素繊維束は、その外層部におけるカソードルミネッセンス法により測定されるサイジング剤発光カウント数（Ｓ）と、内層部におけるカソードルミネッセンス法（以下、「ＣＬ法」ともいう）により測定されるサイジング剤発光カウント数（Ｉ）とが下式（１）
０．８＜ Ｉ／Ｓ ＜２．０ ・・・（１）
の関係を満たすことを特徴としている。なお、以下、Ｉ／Ｓをサイジング剤発光強度比ともいう。
(1) Sizing agent-attached carbon fiber bundle The sizing agent-attached carbon fiber bundle of the present invention comprises a sizing agent emission count (S) measured by a cathodoluminescence method in the outer layer portion, and a cathodoluminescence method (hereinafter referred to as an inner layer portion). The sizing agent emission count (I) measured by “CL method”) is expressed by the following formula (1):
0.8 <I / S <2.0 (1)
It is characterized by satisfying the relationship. Hereinafter, I / S is also referred to as a sizing agent emission intensity ratio.
ここで、ＣＬ法により測定されるサイジング剤発光カウント数について説明する。ＣＬ法とは、電子線を試料に照射した際に放出される紫外・可視・近赤外領域の発光を検出する測定方法である。高分子化合物においては、共役二重結合を持つ分子が発光を示し、この発光量の積算値は、発光するサイジング剤分子の量に比例する。そのため、サイジング剤付着炭素繊維束の内層部と外層部とにおける発光量の積算値を比較することにより、サイジング剤付着炭素繊維束の内層部と外層部とにおけるサイジング剤の付着量比を測定することができる。なお、ＣＬ法により測定されるサイジング剤付着炭素繊維束の内層部のサイジング剤発光カウント数（Ｉ）とは、サイジング剤付着炭素繊維束をその軸に沿って２等分に切り割った際の断面中心部において測定される発光カウント数をいい、外層部のサイジング剤発光カウント数（Ｓ）とは、その切り割った炭素繊維束の非断面部において測定される発光カウント数をいう。 Here, the sizing agent emission count number measured by the CL method will be described. The CL method is a measurement method for detecting light emission in the ultraviolet / visible / near infrared region emitted when a sample is irradiated with an electron beam. In a polymer compound, a molecule having a conjugated double bond emits light, and the integrated value of the light emission amount is proportional to the amount of sizing agent molecules that emit light. Therefore, the ratio of the amount of sizing agent attached to the inner layer portion and the outer layer portion of the sizing agent-attached carbon fiber bundle is measured by comparing the integrated values of the light emission amounts in the inner layer portion and the outer layer portion of the sizing agent-attached carbon fiber bundle. be able to. The sizing agent emission count (I) of the inner layer portion of the sizing agent-attached carbon fiber bundle measured by the CL method is a value obtained by dividing the sizing agent-attached carbon fiber bundle into two equal parts along the axis. The luminescence count number measured at the central portion of the cross section is referred to, and the sizing agent luminescence count number (S) of the outer layer portion refers to the luminescence count number measured at the non-cross section portion of the cut carbon fiber bundle.
炭素繊維束の内層部に十分な量のサイジング剤が存在することで、樹脂を炭素繊維束内層部まで十分に含浸させるに足るエントロピーを得ることができる。Ｉ／Ｓが２．０以上になると、内層部のサイジング剤が過剰となりフィラメント同士を拘束するバインド効果が強くなる。その結果、樹脂を含浸させる際にサイジング剤付着炭素繊維束が十分に開繊されず、樹脂の含浸が不十分になる。 When a sufficient amount of the sizing agent is present in the inner layer portion of the carbon fiber bundle, entropy sufficient to sufficiently impregnate the resin up to the inner layer portion of the carbon fiber bundle can be obtained. When the I / S is 2.0 or more, the sizing agent in the inner layer portion becomes excessive, and the binding effect for restraining the filaments becomes strong. As a result, when impregnating the resin, the sizing agent-attached carbon fiber bundle is not sufficiently opened, and the impregnation of the resin becomes insufficient.
本発明のサイジング剤付着炭素繊維束は、サイジング剤によって付与される耐擦過性と耐糸切れ性とを高く保持しているため、ＦＷ成形工程における固定ガイドやローラー等との擦過による損傷を受け難い。また、このサイジング剤付着炭素繊維束は、外層部に付着したサイジング剤の一部を除去しているため、その外層部から内層部に向って樹脂を含浸させ易い。そのため、樹脂の含浸漏れを生じ難い。その結果、本発明のサイジング剤付着炭素繊維束を用いて製造される炭素繊維複合材料は、炭素繊維の本来有している繊維物性が十分に反映されて、性能の高いものとなる。 The sizing agent-attached carbon fiber bundle of the present invention retains high scratch resistance and yarn breakage resistance imparted by the sizing agent, and is therefore damaged by rubbing with a fixed guide or roller in the FW molding process. hard. Further, since this sizing agent-attached carbon fiber bundle removes a part of the sizing agent attached to the outer layer portion, it is easy to impregnate the resin from the outer layer portion toward the inner layer portion. Therefore, it is difficult to cause resin impregnation leakage. As a result, the carbon fiber composite material produced by using the sizing agent-attached carbon fiber bundle of the present invention sufficiently reflects the fiber physical properties originally possessed by the carbon fiber and has high performance.
このような炭素繊維束は、以下の方法によって製造することができる。 Such a carbon fiber bundle can be manufactured by the following method.
（２）サイジング剤付着炭素繊維束の製造方法
本発明のサイジング剤付着炭素繊維束の製造方法は、
複数の炭素繊維フィラメントからなる炭素繊維束をサイジング浴に浸漬する工程と、
該サイジング浴から引き揚げた炭素繊維束に気体を吹き付けることにより、炭素繊維束に付着しているサイジング剤の一部を除去する工程と、
を有して成る。上記工程を経て製造されるサイジング剤付着炭素繊維束は、その外層部におけるカソードルミネッセンス法により測定されるサイジング剤発光カウント数（Ｓ）と
、内層部におけるカソードルミネッセンス法により測定されるサイジング剤発光カウント数（Ｉ）とが下式（１）
０．８＜ Ｉ／Ｓ ＜２．０ ・・・（１）
の関係を満たすことを特徴としている。
(2) Method for producing sizing agent-attached carbon fiber bundle The method for producing a sizing agent-attached carbon fiber bundle of the present invention includes:
Immersing a carbon fiber bundle comprising a plurality of carbon fiber filaments in a sizing bath; and
Removing a part of the sizing agent adhering to the carbon fiber bundle by blowing gas onto the carbon fiber bundle drawn from the sizing bath;
It has. The sizing agent-attached carbon fiber bundle produced through the above-described steps is a sizing agent emission count (S) measured by the cathodoluminescence method in the outer layer portion and a sizing agent emission count measured by the cathodoluminescence method in the inner layer portion. The number (I) is the following formula (1)
0.8 <I / S <2.0 (1)
It is characterized by satisfying the relationship.
＜炭素繊維＞
本発明で用いられる炭素繊維は特に限定されないが、ピッチ系、レーヨン系、ポリアクリルニトリル（ＰＡＮ）系等の炭素繊維が使用できる。操作性及び工程通過性、機械強度を向上させるには、ＰＡＮ系の炭素繊維が好ましい。また、炭素繊維束のフィラメント数は、１０００〜５００００フィラメントが好ましく、３０００〜３００００フィラメントが特に好ましい。単繊維フィラメントの直径は、４〜１５μｍが好ましく、５〜１１μｍが特に好ましい。ストランド引張強度は、４００〜６００ｋｇｆ／ｍｍ２が好ましく、４５０〜５５０ｋｇｆ／ｍｍ２が特に好ましい。弾性率は、２０〜３５ｋｇｆ／ｍｍ２が好ましく、２４〜３０ｋｇｆ／ｍｍ２が特に好ましい。
<Carbon fiber>
The carbon fiber used in the present invention is not particularly limited, but carbon fibers such as pitch, rayon, and polyacrylonitrile (PAN) can be used. In order to improve operability, process passability, and mechanical strength, PAN-based carbon fibers are preferred. Further, the number of filaments of the carbon fiber bundle is preferably 1000 to 50000 filaments, particularly preferably 3000 to 30000 filaments. The diameter of the single fiber filament is preferably 4 to 15 μm, particularly preferably 5 to 11 μm. Strand tensile strength is preferably 400~600kgf / mm 2, 450~550kgf / mm 2 is particularly preferred. Modulus, preferably 20~35kgf / mm 2, 24~30kgf / mm 2 is particularly preferred.
このような炭素繊維は、市販品を用いてもよいが、以下の方法で前駆体繊維を紡糸し、これを耐炎化及び炭素化して製造することもできる。 A commercial product may be used as such a carbon fiber, but it can also be produced by spinning a precursor fiber by the following method and making it flameproof and carbonized.
（前駆体繊維）
炭素繊維の製造に用いる前駆体繊維としては、ＰＡＮ系繊維が好ましく用いられる。具体的には、アクリロニトリルを９０質量％以上、好ましくは９５質量％以上含有し、その他の単量体を１０質量％以下含有する単量体を単独又は共重合した紡糸原液を紡糸口金から紡出して製造する、ＰＡＮ系の粗原料繊維が好ましい。その他の単量体としては、イタコン酸、フマル酸、（メタ）アクリル酸エステルが例示される。
(Precursor fiber)
As the precursor fiber used for producing the carbon fiber, a PAN-based fiber is preferably used. Specifically, a spinning stock solution containing 90% by mass or more, preferably 95% by mass or more of acrylonitrile and 10% by mass or less of other monomers alone or copolymerized is spun from a spinneret. A PAN-based crude raw material fiber manufactured by Examples of other monomers include itaconic acid, fumaric acid, and (meth) acrylic acid esters.
紡糸方法としては、湿式、乾湿式、乾式紡糸方法のいずれの方法も用いることができるが、最終的に得られる炭素繊維が表面に襞を形成して樹脂との接着性が期待できるので、湿式紡糸方法が好ましい。なお、紡糸溶液としては、３０〜６０質量％の塩化亜鉛溶液に上記アクリル系重合体を溶解したものが好ましい。 As the spinning method, any of wet, dry wet, and dry spinning methods can be used. However, since the carbon fiber finally obtained can form wrinkles on the surface and can be expected to have adhesiveness with the resin, it is wet. A spinning method is preferred. In addition, as a spinning solution, what melt | dissolved the said acrylic polymer in 30-60 mass% zinc chloride solution is preferable.
なお、必要に応じて、紡糸ノズルに異型口金（例えば亀甲型）を用いて紡糸しても良い。また、紡糸原液の不純物を除去するために紡糸原液を濾過しても良い。紡糸原液の濾過は、工程安定化、強度・弾性率等の改善に大きく寄与する。そのため、得られる炭素繊維の繊維表面の多孔質化よりも、工程安定化、強度・弾性率等の改善が求められる場合には特に有効である。 If necessary, the spinning nozzle may be spun using a modified die (for example, a turtle shell type). Further, the spinning dope may be filtered in order to remove impurities from the spinning dope. Filtration of the spinning dope greatly contributes to process stabilization and improvement of strength and elastic modulus. Therefore, it is particularly effective when the stabilization of the process and the improvement of the strength and elastic modulus are required rather than making the carbon surface of the obtained carbon fiber porous.
上記粗原料繊維は、張力をかけながら洗浄処理及び湿熱延伸処理を施すが、洗浄工程及び湿熱延伸工程におけるトータル延伸倍率は１０〜１５倍とすることが好ましい。 The crude raw fiber is subjected to washing treatment and wet heat drawing treatment while applying tension, and the total draw ratio in the washing step and wet heat drawing step is preferably 10 to 15 times.
（耐炎化処理）
得られた前駆体繊維は、引き続き加熱空気中、２２０〜３００℃、好ましくは２３０〜２６０℃で熱処理して耐炎化繊維を得る。この時の処理は、一般的に、延伸倍率０．８５〜１．３０の範囲で処理されるが、高強度・高弾性率の炭素繊維を得るためには、延伸倍率０．９５〜１．３０がより好ましい。
(Flame resistance treatment)
The obtained precursor fiber is subsequently heat-treated in heated air at 220 to 300 ° C., preferably 230 to 260 ° C., to obtain flame resistant fibers. The treatment at this time is generally carried out in a range of a draw ratio of 0.85 to 1.30, but in order to obtain a carbon fiber having a high strength and a high elastic modulus, a draw ratio of 0.95 to 1. 30 is more preferable.
（炭素化処理）
上記耐炎化繊維は、従来の公知の方法によって炭素化される。例えば、窒素、アルゴン等の不活性ガス雰囲気下、好ましくは酸素濃度が０．０５体積ｐｐｍ未満の不活性ガス雰囲気下で昇温し、炭素化炉で徐々に温度を高めると共に、耐炎化繊維の張力を制御して焼成する。焼成温度は、６００〜２０００℃が好ましく、１０００〜１７００℃が特に好ましい。不活性ガスは、窒素が廉価であるため好ましい。
(Carbonization treatment)
The flame resistant fiber is carbonized by a conventionally known method. For example, the temperature is raised in an inert gas atmosphere such as nitrogen or argon, preferably in an inert gas atmosphere with an oxygen concentration of less than 0.05 ppm by volume, and the temperature is gradually increased in a carbonization furnace, and Firing with controlled tension. The firing temperature is preferably 600 to 2000 ° C, particularly preferably 1000 to 1700 ° C. As the inert gas, nitrogen is preferable because it is inexpensive.
本製造方法において用いる炭素繊維束は、その臨界張力が６５〜９５ｍＮ／ｍであることが好ましく、７０〜９０ｍＮ／ｍであることが特に好ましい。この範囲の臨界張力の炭素繊維束は、その内層部に十分な量のサイジング剤を含浸させることができる。炭素繊維束の臨界張力が６５ｍＮ／ｍ未満である場合、サイジング剤との濡れ性が低くなるため、炭素繊維束に十分な量のサイジング剤が付与されない。その結果、炭素繊維束とマトリックス樹脂との親和性が低下して、炭素繊維の本来有する繊維物性が炭素繊維複合材料の性能に十分に反映されない場合がある。また、臨界張力が９５ｍＮ／ｍを超える場合、サイジング剤との濡れ性は高くなるが、脆弱層と呼ばれる構造的に弱い酸化層が炭素繊維表面に形成される。その結果、得られる炭素繊維複合材料の性能が低下する場合がある。 The carbon fiber bundle used in this production method preferably has a critical tension of 65 to 95 mN / m, and particularly preferably 70 to 90 mN / m. A carbon fiber bundle having a critical tension in this range can be impregnated with a sufficient amount of a sizing agent in its inner layer portion. When the critical tension of the carbon fiber bundle is less than 65 mN / m, the wettability with the sizing agent is lowered, so that a sufficient amount of the sizing agent is not applied to the carbon fiber bundle. As a result, the affinity between the carbon fiber bundle and the matrix resin is lowered, and the fiber physical properties inherent to the carbon fiber may not be sufficiently reflected in the performance of the carbon fiber composite material. When the critical tension exceeds 95 mN / m, the wettability with the sizing agent increases, but a structurally weak oxide layer called a fragile layer is formed on the carbon fiber surface. As a result, the performance of the obtained carbon fiber composite material may deteriorate.
炭素繊維束の臨界張力を上記範囲にするためには、炭素繊維の製造工程において、炭素化処理後、表面処理を行うことが好ましい。表面処理の手法は特に限定されないが、薬液を用いる液相酸化、又は電解液溶液中で炭素繊維を陽極として電解処理する電解酸化、気相状態でプラズマ処理する気相酸化等を用いることができる。これらのうち、生産性、処理の均一性、安全性の観点から、電解酸化を用いることが好ましい。電解処理で用いる電解液の電解質は特に限定されないが、硫酸、硝酸、塩酸、リン酸、ホウ酸、炭酸等の無機酸； 酢酸、酪酸、シュウ酸、アクリル酸、マレイン酸等の有機酸； 硫酸アンモニウム、硫酸水素アンモニウム、硝酸アンモニウム、硝酸水素アンモニウム、リン酸２水素アンモニウム、リン酸水素２アンモニウム、炭酸アンモニウム、炭酸水素アンモニウム等のアンモニウム塩又はアンモニア； 水酸化ナトリウム、水酸化カリウム、水酸化バリウム等のアルカリ水酸化物； 炭酸ナトリウム、炭酸水素ナトリウム、リン酸ナトリウム、リン酸カリウム等の無機塩； マレイン酸ナトリウム、酢酸ナトリウム、酢酸カリウム、安息香酸ナトリウム等の有機塩； を単独又は２種類以上の混合物として用いることができる。 In order to bring the critical tension of the carbon fiber bundle into the above range, it is preferable to perform a surface treatment after the carbonization treatment in the carbon fiber production process. The method of surface treatment is not particularly limited, and liquid phase oxidation using a chemical solution, electrolytic oxidation in which electrolytic treatment is performed using carbon fiber as an anode in an electrolytic solution, and vapor phase oxidation in which plasma treatment is performed in a gas phase state can be used. . Of these, electrolytic oxidation is preferably used from the viewpoints of productivity, processing uniformity, and safety. The electrolyte of the electrolytic solution used in the electrolytic treatment is not particularly limited, but inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, boric acid and carbonic acid; organic acids such as acetic acid, butyric acid, oxalic acid, acrylic acid and maleic acid; ammonium sulfate Ammonium salt such as ammonium hydrogen sulfate, ammonium nitrate, ammonium hydrogen nitrate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium carbonate, ammonium hydrogen carbonate, etc .; alkali such as sodium hydroxide, potassium hydroxide, barium hydroxide Inorganic salts such as sodium carbonate, sodium hydrogen carbonate, sodium phosphate, and potassium phosphate; Organic salts such as sodium maleate, sodium acetate, potassium acetate, and sodium benzoate; alone or as a mixture of two or more Can be used.
電解液の温度は、０〜１００℃が好ましく、２５〜４５℃が特に好ましい。また、電解質の濃度は、５〜２５質量％が好ましく、８〜１２質量％が特に好ましい。電解処理は複数の電解槽を使用して行うことが好ましい。設備及びコスト、条件設定の煩雑さを考慮すれば、２〜１０槽を使用することが好ましい。電気量は、炭素繊維１ｇに対して、０．５クーロン以上であることが好ましく、２〜１００クーロンであることが特に好ましい。 The temperature of the electrolytic solution is preferably 0 to 100 ° C, particularly preferably 25 to 45 ° C. Moreover, 5-25 mass% is preferable and, as for the density | concentration of electrolyte, 8-12 mass% is especially preferable. The electrolytic treatment is preferably performed using a plurality of electrolytic cells. Considering the complexity of equipment, cost, and condition setting, it is preferable to use 2 to 10 tanks. The amount of electricity is preferably 0.5 coulombs or more, and particularly preferably 2 to 100 coulombs with respect to 1 g of carbon fiber.
上記電解処理を行うにあたっては、電解処理の前に電解処理で用いる電解液を炭素繊維束に予備含浸させておくことが好ましい。この予備含浸は、電解液を炭素繊維束の内層部に含浸させることができれば、どのような方法で行っても良い。しかし、炭素繊維は表面疎水性が高いため、電解液を単に満たした電解槽に炭素繊維束を通すだけでは、炭素繊維束の内層部に電解液が十分に含浸されない場合がある。そのため、炭素繊維束を電解槽に通すにあたっては、電解槽内の電解液に乱流を生じさせておくことが好ましい。乱流を生じさせる方法としては、シャワー、振動子の使用が挙げられる。 In performing the electrolytic treatment, it is preferable to pre-impregnate the carbon fiber bundle with an electrolytic solution used in the electrolytic treatment before the electrolytic treatment. This pre-impregnation may be performed by any method as long as the electrolytic solution can be impregnated into the inner layer portion of the carbon fiber bundle. However, since the carbon fiber has high surface hydrophobicity, the inner layer portion of the carbon fiber bundle may not be sufficiently impregnated with the electrolytic solution simply by passing the carbon fiber bundle through the electrolytic tank filled with the electrolytic solution. Therefore, when passing the carbon fiber bundle through the electrolytic cell, it is preferable to generate a turbulent flow in the electrolytic solution in the electrolytic cell. Examples of the method for generating turbulent flow include the use of a shower and a vibrator.
＜サイジング剤付与工程＞
本発明において用いられるサイジング剤としては、複合材料に用いるマトリックス樹脂に応じて選択することが好ましい。例えば、エポキシ樹脂、エポキシ変性ポリウレタン樹脂、ポリエステル樹脂、フェノール樹脂、ポリアミド樹脂、ポリウレタン樹脂、ポリイミド樹脂、ポリビニルアルコール樹脂、ポリビニルピロリドン樹脂、ポリエーテルスルホン樹脂等を単独で又は２種類以上を混合して用いることができる。
<Sizing agent application process>
The sizing agent used in the present invention is preferably selected according to the matrix resin used for the composite material. For example, an epoxy resin, an epoxy-modified polyurethane resin, a polyester resin, a phenol resin, a polyamide resin, a polyurethane resin, a polyimide resin, a polyvinyl alcohol resin, a polyvinyl pyrrolidone resin, a polyether sulfone resin, etc. are used alone or in combination of two or more. be able to.
上記樹脂は有機溶剤溶液として、又は水分散液として用いる。安全、環境等を考慮すると水分散液として用いることが好ましい。 The resin is used as an organic solvent solution or as an aqueous dispersion. In consideration of safety, environment, etc., it is preferably used as an aqueous dispersion.
炭素繊維束へのサイジング剤の付与方法としては、連続式とバッチ式とが挙げられるが、生産性が高い連続式で行うことが好ましい。 Examples of the method for applying the sizing agent to the carbon fiber bundle include a continuous method and a batch method, but it is preferable to carry out a continuous method with high productivity.
本発明の製造方法においては、炭素繊維束のサイジング浴への浸漬回数は、複数回であることが好ましく、２〜１０回であることがより好ましく、３〜５回であることが特に好ましい。１回の浸漬では、炭素繊維束の内層部に十分な量のサイジング剤が含浸されず、内層部の炭素繊維が十分にサイジング剤で被覆され難い。その結果、炭素繊維束の耐擦過性やマトリックス樹脂との親和性が不十分になる。また、１０回を超える浸漬は、工程数が増加して生産性が低下する。各サイジング浴に含まれるサイジング剤は、同一であっても異なっていても良いが、同一であることが好ましい。 In the production method of the present invention, the number of immersions of the carbon fiber bundle in the sizing bath is preferably a plurality of times, more preferably 2 to 10 times, and particularly preferably 3 to 5 times. In one dipping, the inner layer portion of the carbon fiber bundle is not impregnated with a sufficient amount of the sizing agent, and the carbon fibers in the inner layer portion are not sufficiently covered with the sizing agent. As a result, the abrasion resistance of the carbon fiber bundle and the affinity with the matrix resin become insufficient. Moreover, the immersion exceeding 10 times will increase the number of processes and reduce productivity. The sizing agents contained in each sizing bath may be the same or different, but are preferably the same.
サイジング浴への浸漬時間は、特に限定するものではないが、浸漬時間が長くなることは、工程が長くなることと同義であるので、５秒以下であることが好ましい。 The immersion time in the sizing bath is not particularly limited, but increasing the immersion time is synonymous with increasing the process, and therefore it is preferably 5 seconds or less.
本発明の製造方法においては、炭素繊維束のサイジング浴への複数回の各浸漬は連続的に行われ、各浸漬工程間に乾燥工程が存在しない。各浸漬工程間に乾燥工程が存在する場合、炭素繊維束の外層部に先ずサイジング剤が付着し、該乾燥工程でこれが乾燥することにより、内層部へのサイジング剤の含浸を妨げる。その結果、最終的に得られる炭素繊維複合材料において、炭素繊維束の内層部にマトリックス樹脂が十分に含浸せず、炭素繊維複合材料の性能が不十分になる。なお、後述する気体の吹き付けは、その吹き付け時間が１秒以下とごく短時間であるため、本発明においては上記の乾燥工程に該当しない。 In the production method of the present invention, the carbon fiber bundle is immersed in the sizing bath a plurality of times continuously, and there is no drying step between the immersion steps. When there is a drying step between the dipping steps, the sizing agent first adheres to the outer layer portion of the carbon fiber bundle, and this dries in the drying step, thereby preventing impregnation of the sizing agent into the inner layer portion. As a result, in the finally obtained carbon fiber composite material, the inner layer portion of the carbon fiber bundle is not sufficiently impregnated with the matrix resin, and the performance of the carbon fiber composite material becomes insufficient. In addition, since the spraying time of the gas mentioned later is as short as 1 second or less, it does not correspond to said drying process in this invention.
なお、サイジング剤の濃度及び温度や、浸漬時における炭素繊維束の張力等はサイジング剤の付着量が適性範囲内となるように適宜調整される。 In addition, the density | concentration and temperature of a sizing agent, the tension | tensile_strength of the carbon fiber bundle at the time of immersion, etc. are suitably adjusted so that the adhesion amount of a sizing agent may be in an appropriate range.
＜サイジング剤除去工程＞
サイジング剤が付着した炭素繊維束は、そのサイジング剤の一部が除去される。サイジング剤の除去は、サイジング剤が付着した炭素繊維束を連続的に走行させながら、炭素繊維束に向けて気体を吹き付けることによって行われる。より具体的には、炭素繊維束を平ローラーの円周面に接触させ、かつ、平ローラーの円周面に接触する炭素繊維束に向けて気体を吹き付けることによって行われる。これにより、炭素繊維束の外層側に付着しているサイジング剤の一部が除去される。その結果、炭素繊維束の内層部に十分な量のサイジング剤を含むとともに、外層部のサイジング剤付着量が減じられたサイジング剤付着炭素繊維束が得られる。
<Sizing agent removal process>
A part of the sizing agent is removed from the carbon fiber bundle to which the sizing agent is attached. The removal of the sizing agent is performed by blowing gas toward the carbon fiber bundle while continuously running the carbon fiber bundle to which the sizing agent is adhered. More specifically, the carbon fiber bundle is brought into contact with the circumferential surface of the flat roller, and gas is blown toward the carbon fiber bundle in contact with the circumferential surface of the flat roller. Thereby, a part of sizing agent adhering to the outer layer side of the carbon fiber bundle is removed. As a result, a sizing agent-attached carbon fiber bundle containing a sufficient amount of the sizing agent in the inner layer portion of the carbon fiber bundle and having a reduced amount of sizing agent attached to the outer layer portion is obtained.
カソードルミネッセンス法（以下、「ＣＬ法」ともいう）により測定されるこのサイジング剤付着炭素繊維束の外層部のサイジング剤発光カウント数（Ｓ）と、内層部のサイジング剤発光カウント数（Ｉ）とは、下式（１）
０．８＜ Ｉ／Ｓ ＜２．０ ・・・式（１）
の関係を満たしており、下式（２）
０．９＜ Ｉ／Ｓ ＜１．８ ・・・式（２）
の関係を満たすことが好ましく、下式（３）
１．０＜ Ｉ／Ｓ ＜１．６ ・・・式（３）
の関係を満たすことが特に好ましい。
The sizing agent emission count (S) of the outer layer portion of this sizing agent-attached carbon fiber bundle and the sizing agent emission count (I) of the inner layer portion measured by the cathodoluminescence method (hereinafter also referred to as “CL method”) Is the following formula (1)
0.8 <I / S <2.0 Formula (1)
The following equation (2)
0.9 <I / S <1.8 Formula (2)
It is preferable to satisfy the relationship of the following formula (3)
1.0 <I / S <1.6 Formula (3)
It is particularly preferable to satisfy this relationship.
吹き付ける気体の風速は、炭素繊維束表面において１５〜５０ｍ／秒であることが好ましい。風速が１５ｍ／秒以上である場合、炭素繊維束外層部の余剰なサイジング剤を十分に除去することができる。その結果、この炭素繊維束は、樹脂含浸工程において、内層部への樹脂の浸透性が向上する。風速が５０ｍ／秒を超える場合は、炭素繊維ストランドに乱れが生じ、毛羽立ちや、平ローラーへの巻き付きが起こり易い傾向がある。 The wind speed of the blowing gas is preferably 15 to 50 m / sec on the surface of the carbon fiber bundle. When the wind speed is 15 m / sec or more, the excess sizing agent in the carbon fiber bundle outer layer portion can be sufficiently removed. As a result, the carbon fiber bundle has improved resin permeability to the inner layer in the resin impregnation step. When the wind speed exceeds 50 m / sec, the carbon fiber strands are disturbed, and there is a tendency that fuzzing or winding around a flat roller easily occurs.
気体の吹き付け時間は、０．０１〜１秒であることが好ましく、０．０５〜０．５秒であることが特に好ましい。 The gas blowing time is preferably 0.01 to 1 second, and particularly preferably 0.05 to 0.5 second.
余剰のサイジング剤が除去された後のサイジング剤付着炭素繊維束における前記サイジング剤の付着量は、０．８〜３．０質量％であり、１．０〜２．０質量％であることが好ましい。サイジング剤の付着量が０．８質量％未満である場合、サイジング剤が炭素繊維を十分に覆うことが出来ない場合がある。その結果、炭素繊維束の耐擦過性が低下し、複合材料成形工程中において毛羽の発生が顕著になる傾向がある。また、サイジング剤の付着量が３．０質量％を超える場合、サイジング剤のバインダー効果が強過ぎて、炭素繊維束内への樹脂の浸透性が低下する場合がある。その結果、炭素繊維束の繊維物性が最終的に得られる炭素繊維複合材料の性能に反映され難い傾向がある。 The attached amount of the sizing agent in the sizing agent-attached carbon fiber bundle after the excess sizing agent is removed is 0.8 to 3.0% by mass, and 1.0 to 2.0% by mass. preferable. When the adhesion amount of the sizing agent is less than 0.8% by mass, the sizing agent may not be able to sufficiently cover the carbon fiber. As a result, the abrasion resistance of the carbon fiber bundle is lowered, and the generation of fluff tends to become remarkable during the composite material forming process. Moreover, when the adhesion amount of a sizing agent exceeds 3.0 mass%, the binder effect of a sizing agent is too strong and the permeability | transmittance of resin into a carbon fiber bundle may fall. As a result, the fiber physical properties of the carbon fiber bundle tend not to be reflected in the performance of the finally obtained carbon fiber composite material.
炭素繊維束の繊維物性を炭素繊維複合材料の性能に十分に反映させるには、マトリックス樹脂を炭素繊維束内層部に十分に含浸させ、複合材料の性能に寄与しない繊維を生じさせないことが必要である。そのためには、炭素繊維束内層部にマトリックス樹脂が含浸されるに足りるエントロピーが不可欠である。炭素繊維よりも、サイジング剤の方がマトリックス樹脂との親和性が高い。そのため、炭素繊維束内層部に十分な量のサイジング剤が付着するとともに、炭素繊維束外層部に付着したサイジング剤が減じられている状態を作り出すことにより、炭素繊維束内層部までマトリックス樹脂を十分に呼び込むことができる。その結果、炭素繊維束の繊維物性を最終的な炭素繊維複合材料の性能に十分に反映させることができる。 In order to fully reflect the fiber physical properties of the carbon fiber bundle in the performance of the carbon fiber composite material, it is necessary to sufficiently impregnate the matrix resin in the inner layer of the carbon fiber bundle so as not to generate fibers that do not contribute to the performance of the composite material. is there. For that purpose, entropy sufficient for the matrix resin to be impregnated into the inner layer of the carbon fiber bundle is indispensable. The sizing agent has a higher affinity with the matrix resin than the carbon fiber. Therefore, a sufficient amount of sizing agent adheres to the inner layer portion of the carbon fiber bundle, and by creating a state in which the sizing agent attached to the outer layer portion of the carbon fiber bundle is reduced, sufficient matrix resin is provided to the inner layer portion of the carbon fiber bundle. Can call into. As a result, the fiber physical properties of the carbon fiber bundle can be sufficiently reflected in the performance of the final carbon fiber composite material.
（３）ＦＷ成形法による圧力容器の製造方法
本発明においてＣＦＲＰ製圧力容器は、本発明のサイジング剤付着炭素繊維束を用いてＦＷ成形法により製造される。即ち、炭素繊維束に樹脂を含浸させながらライナー等に巻き付けた後、この樹脂を硬化させることによって製造される。このＦＷ成形法は、工程中のローラーやガイドとの擦過によって炭素繊維束の損傷を引起し易い。炭素繊維束が損傷すると工程通過性や工程安定性が低下するだけでなく、得られる炭素繊維複合材料の性能も低下する。
(3) Pressure vessel manufacturing method by FW molding method In the present invention, the CFRP pressure vessel is manufactured by the FW molding method using the sizing agent-attached carbon fiber bundle of the present invention. That is, it is manufactured by winding a carbon fiber bundle around a liner or the like while impregnating the resin with the resin, and then curing the resin. This FW molding method tends to cause damage to the carbon fiber bundle due to rubbing with rollers and guides in the process. When the carbon fiber bundle is damaged, not only the process passability and process stability are lowered, but also the performance of the obtained carbon fiber composite material is lowered.
前記サイジング剤付着炭素繊維束には、十分な量のサイジング剤が含浸されている。そのため、ローラーやガイドとの擦過が生じても、サイジング剤付着炭素繊維束に毛羽立ちや糸切れが生じ難い。また、サイジング剤付着炭素繊維束は、その外層部に付着しているサイジング剤量が少ない。そのため、このサイジング剤は、樹脂を含浸させる際の障害とならない。 The sizing agent-attached carbon fiber bundle is impregnated with a sufficient amount of sizing agent. Therefore, even if rubbing with a roller or a guide occurs, the sizing agent-attached carbon fiber bundle is less likely to fluff or break. Further, the sizing agent-attached carbon fiber bundle has a small amount of sizing agent attached to the outer layer portion thereof. Therefore, this sizing agent does not become an obstacle when impregnating the resin.
本発明においては、ＣＦＲＰ製圧力容器は前記サイジング剤付着炭素繊維束を用いてＦＷ成形法により製造される。本発明においては、予め製造されたサイジング剤付着炭素繊維束を用いても良いし、サイジング剤付着炭素繊維束の製造と、ＦＷ成形法によるＣＦＲＰ製圧力容器の製造とが連続的に行われても良い。 In the present invention, the CFRP pressure vessel is manufactured by the FW molding method using the sizing agent-attached carbon fiber bundle. In the present invention, a pre-manufactured sizing agent-attached carbon fiber bundle may be used, and the production of the sizing agent-attached carbon fiber bundle and the production of the CFRP pressure vessel by the FW molding method are performed continuously. Also good.
樹脂は、開繊ローラー等を用いてサイジング剤付着炭素繊維束を開繊しながら含浸させることが好ましい。 The resin is preferably impregnated while opening the sizing agent-attached carbon fiber bundle using an opening roller or the like.
樹脂（マトリックス樹脂）としては、熱硬化性樹脂が好ましい。例えば、エポキシ樹脂、不飽和ポリエステル樹脂、ビニルエステル樹脂、フェノール樹脂を用いることができる。また、樹脂には、硬化剤、脱泡剤等の添加剤を添加しても良い。硬化温度、効果時間などは従来公知であり、使用する樹脂に応じて適宜調整される。 As the resin (matrix resin), a thermosetting resin is preferable. For example, an epoxy resin, an unsaturated polyester resin, a vinyl ester resin, or a phenol resin can be used. Moreover, you may add additives, such as a hardening | curing agent and a defoaming agent, to resin. The curing temperature, effect time, and the like are conventionally known and are appropriately adjusted according to the resin used.
本発明におけるＣＦＲＰ製圧力容器の製造方法では、中空部を有するライナーの外表面に、樹脂が含浸されたサイジング剤付着炭素繊維束（以下、「樹脂含浸炭素繊維束」ともいう）がライナーの軸方向に配置される繊維強化樹脂層（Ａ）及び／又は、樹脂含浸炭素繊維束がライナーの軸方向に対してヘリカルに配置される繊維強化樹脂層（Ｂ）が積層される。なお、繊維強化樹脂層（Ａ）及び／又は繊維強化樹脂層（Ｂ）の積層構成は、所望の圧力容器の性能に応じて適宜決定される。 In the method for producing a CFRP pressure vessel in the present invention, a sizing agent-attached carbon fiber bundle impregnated with a resin (hereinafter also referred to as “resin-impregnated carbon fiber bundle”) is provided on the outer surface of a liner having a hollow portion. The fiber reinforced resin layer (A) arranged in the direction and / or the fiber reinforced resin layer (B) in which the resin-impregnated carbon fiber bundle is helically arranged with respect to the axial direction of the liner are laminated. In addition, the laminated structure of a fiber reinforced resin layer (A) and / or a fiber reinforced resin layer (B) is suitably determined according to the performance of a desired pressure vessel.
その後、樹脂含浸炭素繊維束に含浸されている樹脂は、その樹脂に応じた硬化方法によって硬化されて、ＣＦＲＰ製圧力容器が製造される。 Thereafter, the resin impregnated in the resin-impregnated carbon fiber bundle is cured by a curing method according to the resin to produce a CFRP pressure vessel.
このようにして製造されるＣＦＲＰ製圧力容器は、炭素繊維束の優れた繊維物性が十分に反映される。本製造方法で製造されるＣＦＲＰ製圧力容器の理論破壊圧に対する実破壊圧は、８５％以上であることが好ましく、９０％以上であることがより好ましく、９５％以上であることが特に好ましい。 The CFRP pressure vessel manufactured in this manner sufficiently reflects the excellent fiber properties of the carbon fiber bundle. The actual breaking pressure relative to the theoretical breaking pressure of the CFRP pressure vessel produced by this production method is preferably 85% or more, more preferably 90% or more, and particularly preferably 95% or more.
以下、実施例により本発明をより具体的に説明するが、本発明はこれに限定されるものではない。なお、実施例中の評価方法は、次の通りである。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to this. In addition, the evaluation method in an Example is as follows.
［ＣＬ法により測定されるサイジング剤の発光カウントの測定］
ＣＬ法によるサイジング剤の発光カウントの測定には、トプコン製 カラー蛍光電子顕微鏡を使用した。サイジング剤付着炭素繊維束をカーボンテープ上に固定して測定サンプルとした。測定条件は、加速電圧５ｋＶ、絞り径５０μｍ、電流モードＬＣＴ−Ｓ、ピクセルサイズ３、分光機スリットオープン、１０００倍とし、グレーティング分光法により２８０±１０ｎｍで３分間の積算発光量を測定した。
[Measurement of Luminescence Count of Sizing Agent Measured by CL Method]
A Topcon color fluorescent electron microscope was used to measure the luminescence count of the sizing agent by the CL method. A sizing agent-attached carbon fiber bundle was fixed on a carbon tape to obtain a measurement sample. The measurement conditions were an acceleration voltage of 5 kV, an aperture diameter of 50 μm, a current mode LCT-S, a pixel size of 3, a spectroscopic slit open, and a magnification of 1000 times, and an integrated emission amount for 3 minutes was measured at 280 ± 10 nm by grating spectroscopy.
［圧力容器破壊強度の評価方法］
長さ５０４ｍｍ、外径１６０ｍｍ、肉厚２ｍｍのボンベ形状アルミニウムライナーに、サイジング剤付着炭素繊維束を、以下の樹脂組成から成る樹脂に含浸させながら、バックテンション４ｋｇ／束、ワインディング速度０．５ｍ／ｓｅｃの速度でフープ層を１．６ｃｍピッチで１層巻き付けた後、ヘリカル層を１層積層した。その後、１２０℃の硬化炉で１１時間硬化させて、破壊強度評価用圧力容器を得た。
樹脂組成：
ビスフェノールＡ型エポキシ樹脂 ・・・１００質量部
４−メチルシクロヘキサン−１，２−ジカルボン酸無水物・・・８０質量部
ビスフェノールＡ型エポキシ樹脂としては、油化シェルエポキシ株式会社製のＥＰＯＮ８２８（商品名）を使用した。４−メチルシクロヘキサン−１，２−ジカルボン酸無水物としては、ＬＩＮＤＡＵ ＣＨＥＭＩＣＡＬ ＩＮＣ．製のＬｉｎｄｒｉｄｅ５２（商品名）を使用した。
[Method for evaluating pressure vessel breaking strength]
While a cylinder-shaped aluminum liner having a length of 504 mm, an outer diameter of 160 mm, and a wall thickness of 2 mm is impregnated with a sizing agent-attached carbon fiber bundle in a resin having the following resin composition, a back tension of 4 kg / bundle, a winding speed of 0.5 m / One hoop layer was wound at 1.6 cm pitch at a speed of sec, and then one helical layer was laminated. Thereafter, it was cured for 11 hours in a curing furnace at 120 ° C. to obtain a pressure vessel for fracture strength evaluation.
Resin composition:
Bisphenol A type epoxy resin: 100 parts by mass 4-methylcyclohexane-1,2-dicarboxylic acid anhydride: 80 parts by mass As the bisphenol A type epoxy resin, EPON828 manufactured by Yuka Shell Epoxy Co., Ltd. (trade name) )It was used. Examples of 4-methylcyclohexane-1,2-dicarboxylic anhydride include LINDU CHEMICAL INC. Made Lindride 52 (trade name) was used.
この破壊強度評価用圧力容器を、バースト試験装置を用いて４５ＭＰａ／ｓｅｃで水圧をかけて、実破壊圧（Ｐ１）を測定した。この測定は、各実施例及び比較例毎に３回実施し、それぞれ平均値を求めた。 This pressure vessel for fracture strength evaluation was subjected to water pressure at 45 MPa / sec using a burst test apparatus, and the actual fracture pressure (P 1 ) was measured. This measurement was performed three times for each example and comparative example, and an average value was obtained for each.
［タンク破壊強度発現率の計算］
Ａｌｇｏｒ ＦＥＡ ソフトウェアを使用し、有限要素解析で圧力容器の理論破壊圧（Ｐ０）を計算した。この理論破壊圧（Ｐ０）と上記実破壊圧（Ｐ１）の値から下式（３）
タンク破壊強度発現率（％） ＝ Ｐ１／Ｐ０ × １００ ・・・式（３）
によりタンク破壊強度発現率を計算した。
[Calculation of tank fracture strength rate]
The Algor FEA software was used to calculate the theoretical failure pressure (P 0 ) of the pressure vessel by finite element analysis. From the theoretical breaking pressure (P 0 ) and the actual breaking pressure (P 1 ), the following equation (3)
Tank breaking strength translation (%) = P 1 / P 0 × 100 ··· formula (3)
The tank breaking strength expression rate was calculated.
［臨界張力の測定方法］
炭素繊維束の臨界張力は、毛管浸透法により求めた。試験液としては、ＪＩＳ Ｋ６７６８に記載の液体、水（７３．０ｍＮ／ｍ）、メタノール（２２．６ｍＮ／ｍ）、ホルムアミド（５８．０ｍＮ／ｍ）、エチレングリコールモノエチルエーテル（３０．０ｍＮ／ｍ）を使用した。
[Measurement method of critical tension]
The critical tension of the carbon fiber bundle was determined by a capillary penetration method. As the test solution, the liquid described in JIS K6768, water (73.0 mN / m), methanol (22.6 mN / m), formamide (58.0 mN / m), ethylene glycol monoethyl ether (30.0 mN / m) )It was used.
［サイジング剤の付着量の測定］
サイジング剤付着炭素繊維束のチョップを約５ｇ採取し、質量（Ｗ１）を測定した。予め恒量にした坩堝の質量（Ｗ２）を量った後、前記チョップを坩堝に入れ、窒素雰囲気下で４５０±５℃の熱風循環式乾燥機内で３０分熱処理を行った。デシケーター内で室温まで冷却し、炭素繊維チョップが入った坩堝の質量（Ｗ３）を測定した。下式（４）
サイジング剤付着量(%)=(W1+W2-W3)/(W3-W2)×100 ・・・式（４）
によりサイジング剤付着量を計算した。
[Measurement of sizing agent adhesion]
About 5 g of chops of carbon fiber bundles attached to the sizing agent were collected, and the mass (W1) was measured. After measuring the mass (W2) of the crucible made constant in advance, the chop was placed in the crucible and heat-treated for 30 minutes in a hot air circulating dryer at 450 ± 5 ° C. in a nitrogen atmosphere. It cooled to room temperature within the desiccator, and measured the mass (W3) of the crucible containing the carbon fiber chop. The following formula (4)
Sizing agent adhesion amount (%) = (W1 + W2-W3) / (W3-W2) × 100 Formula (4)
The sizing agent adhesion amount was calculated by
［炭素繊維の樹脂含浸ストランド強度］
サイジング剤付着炭素繊維束の樹脂含浸ストランド強度は、ＪＩＳ・Ｒ・７６０８に規定された方法により測定した。
[Strength of carbon fiber resin-impregnated strand]
The resin-impregnated strand strength of the sizing agent-attached carbon fiber bundle was measured by a method defined in JIS R 7608.
［ファズの測定方法］
サイジング剤付着炭素繊維束を、１２５ｇの重りを乗せたウレタンシートの間を５０フィート／分の速度で２分間走行させ、ウレタンシートに溜まった炭素繊維量を測定した。
[Fuzz measurement method]
The sizing agent-attached carbon fiber bundle was run for 2 minutes at a speed of 50 feet / minute between urethane sheets on which a weight of 125 g was placed, and the amount of carbon fibers accumulated in the urethane sheet was measured.
［ＭＰＦの測定方法］
サイジング剤付着炭素繊維束を、２００ｇの張力をかけながら、５本のピンガイドの間を５０フィート／分の速度で２分間走行させた後、１２５ｇの重りを乗せたウレタンシートの間を通し、ウレタンフォームに溜まった炭素繊維量を測定した。
[Measurement method of MPF]
The sizing agent-attached carbon fiber bundle was run for two minutes at a speed of 50 feet / minute between five pin guides while applying a tension of 200 g, and then passed between urethane sheets loaded with a weight of 125 g. The amount of carbon fiber accumulated in the urethane foam was measured.
［実施例１］
アクリロニトリル９５質量％／アクリル酸メチル４質量％／イタコン酸１質量％よりなる共重合体紡糸原液を、常法により湿式紡糸し、水洗・オイリング・乾燥後、トータル延伸倍率が１４倍になるようにスチーム延伸を行い、０．６５デニールの繊度を有するフィラメント数２４，０００の前駆体繊維を得た。得られた前駆体繊維を加熱空気中で延伸しながら、２４０〜２５０℃の温度範囲内で耐炎化処理を行い、次いで窒素雰囲気中、３００〜１２００℃の温度範囲内で炭素化処理を行い、未電解処理炭素繊維束を得た。前記未電解処理炭素繊維束を、１０質量％の硫酸アンモニウム水溶液を電解質溶液とし、シャワーを用いて電解質溶液水面を乱流状態としたオーバーフロー浴に含浸した後、総電気量５０クーロン／ｇの電気条件で電解酸化処理を施した。電解酸化処理を施した炭素繊維束の臨界張力は７６ｍＮ／ｍであった。
[Example 1]
A copolymer spinning stock solution of 95% by mass of acrylonitrile / 4% by mass of methyl acrylate / 1% by mass of itaconic acid is wet-spun by a conventional method so that the total draw ratio is 14 times after washing with water, oiling and drying. Steam drawing was performed to obtain a precursor fiber with 24,000 filaments having a fineness of 0.65 denier. While stretching the obtained precursor fiber in heated air, flameproofing treatment is performed within a temperature range of 240 to 250 ° C, and then carbonization treatment is performed within a temperature range of 300 to 1200 ° C in a nitrogen atmosphere. An unelectrolyzed carbon fiber bundle was obtained. The unelectrolyzed carbon fiber bundle was impregnated in an overflow bath having a 10% by mass aqueous ammonium sulfate solution as an electrolyte solution and the electrolyte solution water surface in a turbulent state using a shower, and then the electrical condition of a total electricity of 50 coulombs / g. Then, an electrolytic oxidation treatment was performed. The critical tension of the carbon fiber bundle subjected to the electrolytic oxidation treatment was 76 mN / m.
この炭素繊維束をエポキシ変性ウレタンを主剤とするサイジング浴（濃度３３ｇ／ｌ）にディップ方式により３回浸漬した。２回目及び３回目の浸漬後においてローラー表面上を走行している炭素繊維束にブロワーを用いて圧縮空気を吹き付けた（風速２．８ｍ／０．１秒）。乾燥工程を経た後、ワインダーを用いてボビンに巻き取り、密度１．７９ｇ／ｃｍ３、ストランド強度４７００ＭＰａ、サイジング剤発光強度比（Ｉ／Ｓ）が１．５のサイジング剤付着炭素繊維束を得た。得られたサイジング剤付着炭素繊維束のサイジング剤付着量及びサイジング剤発光強度比（Ｉ／Ｓ）、ファズ、ＭＰＦを表１に示した。 This carbon fiber bundle was immersed in a sizing bath (concentration: 33 g / l) containing epoxy-modified urethane as a main component by a dip method three times. After the second and third immersions, compressed air was blown onto the carbon fiber bundles running on the roller surface using a blower (wind speed 2.8 m / 0.1 second). After passing through the drying process, it is wound around a bobbin using a winder to obtain a sizing agent-attached carbon fiber bundle having a density of 1.79 g / cm 3 , a strand strength of 4700 MPa, and a sizing agent emission intensity ratio (I / S) of 1.5. It was. Table 1 shows the sizing agent adhesion amount, sizing agent emission intensity ratio (I / S), fuzz, and MPF of the obtained sizing agent-attached carbon fiber bundle.
このサイジング剤付着炭素繊維束を用いて、前述の圧力容器破壊強度の評価方法に従って、破壊強度評価用圧力容器を製造した。得られた破壊強度評価用圧力容器について内圧試験を行ったところ、破壊強度は５２ＭＰａであり、タンク破壊強度発現率は１０１．７％と非常に高い値であった。 Using this sizing agent-attached carbon fiber bundle, a pressure vessel for fracture strength evaluation was produced according to the above-described method for evaluating the pressure vessel fracture strength. When an internal pressure test was performed on the obtained pressure vessel for fracture strength evaluation, the fracture strength was 52 MPa and the tank fracture strength expression rate was a very high value of 101.7%.
［実施例２］
実施例１で得た電解酸化処理後の炭素繊維束を、不飽和ポリエステルを主剤とするサイジング浴（濃度３３ｇ／ｌ）にディップ方式により３回浸漬した。３回目の浸漬後においてローラー表面上を走行している炭素繊維束にブロワーを用いて圧縮空気を吹き付けた（風速２．１ｍ／０．１秒）。乾燥工程を経た後、ワインダーを用いてボビンに巻き取り、密度１．７９ｇ／ｃｍ３、ストランド強度４６００ＭＰａ、サイジング剤発光強度比（Ｉ／Ｓ）が１．０のサイジング剤付着炭素繊維束を得た。得られたサイジング剤付着炭素繊維束のサイジング剤付着量及びサイジング剤発光強度比（Ｉ／Ｓ）、ファズ、ＭＰＦを表１に示した。
[Example 2]
The carbon fiber bundle after the electrolytic oxidation treatment obtained in Example 1 was immersed three times in a sizing bath (concentration 33 g / l) containing an unsaturated polyester as a main component by a dip method. After the third immersion, compressed air was blown onto the carbon fiber bundle running on the roller surface using a blower (wind speed 2.1 m / 0.1 second). After passing through the drying step, the winder is wound around a bobbin to obtain a sizing agent-attached carbon fiber bundle having a density of 1.79 g / cm 3 , a strand strength of 4600 MPa, and a sizing agent emission intensity ratio (I / S) of 1.0. It was. Table 1 shows the sizing agent adhesion amount, sizing agent emission intensity ratio (I / S), fuzz, and MPF of the obtained sizing agent-attached carbon fiber bundle.
このサイジング剤付着炭素繊維束を用いて、前述の圧力容器破壊強度の評価方法に従って、破壊強度評価用圧力容器を製造した。得られた破壊強度評価用圧力容器について内圧試験を行ったところ、破壊強度は４８ＭＰａであり、タンク破壊強度発現率は９５．７％と非常に高い値であった。 Using this sizing agent-attached carbon fiber bundle, a pressure vessel for fracture strength evaluation was produced according to the above-described method for evaluating the pressure vessel fracture strength. When an internal pressure test was performed on the obtained pressure vessel for fracture strength evaluation, the fracture strength was 48 MPa, and the tank fracture strength expression rate was a very high value of 95.7%.
［実施例３］
実施例１で得た炭素繊維前駆体繊維を用い、得られた前駆体繊維を加熱空気中で延伸しながら、２４０〜２５０℃の温度範囲内で耐炎化処理を行い、次いで窒素雰囲気中、３００〜１３００℃の温度範囲内で炭素化処理を行い、未電解処理炭素繊維を得た。
[Example 3]
Using the carbon fiber precursor fiber obtained in Example 1, the obtained precursor fiber was subjected to flameproofing treatment within a temperature range of 240 to 250 ° C. while being stretched in heated air, and then in a nitrogen atmosphere, 300 Carbonization treatment was performed within a temperature range of ˜1300 ° C. to obtain unelectrolyzed carbon fibers.
前記未電解処理炭素繊維束を、１０質量％の硫酸アンモニウム水溶液を電解質溶液とし、シャワーを用いて電解質溶液水面を乱流状態としたオーバーフロー浴に含浸した後、総電気量６０クーロン／ｇの電気条件で電解酸化処理を施した。電解酸化処理を施した炭素繊維束の臨界張力は７８ｍＮ／ｍであった。 The unelectrolyzed carbon fiber bundle was impregnated in an overflow bath in which the electrolyte solution water surface was turbulent using a 10% by mass ammonium sulfate aqueous solution and a shower was used. Then, an electrolytic oxidation treatment was performed. The critical tension of the carbon fiber bundle subjected to the electrolytic oxidation treatment was 78 mN / m.
電解酸化処理後の炭素繊維束を、エポキシ変性ウレタンを主剤とするサイジング浴（濃度３３ｇ／ｌ）にディップ方式により３回浸漬した。３回目の浸漬後においてローラー表面上を走行している炭素繊維束にブロワーを用いて圧縮空気を吹き付けた（風速２．５ｍ／０．１秒）。乾燥工程を経た後、ワインダーを用いてボビンに巻き取り、密度１．８１ｇ／ｃｍ３、ストランド強度４６００ＭＰａ、サイジング剤発光強度比（Ｉ／Ｓ）が０．９のサイジング剤付着炭素繊維束を得た。得られたサイジング剤付着炭素繊維束のサイジング剤付着量及びサイジング剤発光強度比（Ｉ／Ｓ）、ファズ、ＭＰＦを表１に示した。 The carbon fiber bundle after the electrolytic oxidation treatment was immersed three times in a sizing bath (concentration 33 g / l) containing epoxy-modified urethane as a main component by a dip method. After the third immersion, compressed air was blown onto the carbon fiber bundle running on the roller surface using a blower (wind speed 2.5 m / 0.1 second). After passing through the drying process, it is wound around a bobbin using a winder to obtain a sizing agent-attached carbon fiber bundle having a density of 1.81 g / cm 3 , a strand strength of 4600 MPa, and a sizing agent emission intensity ratio (I / S) of 0.9. It was. Table 1 shows the sizing agent adhesion amount, sizing agent emission intensity ratio (I / S), fuzz, and MPF of the obtained sizing agent-attached carbon fiber bundle.
このサイジング剤付着炭素繊維束を用いて、前述の圧力容器破壊強度の評価方法に従って、破壊強度評価用圧力容器を製造した。得られた破壊強度評価用圧力容器について内圧試験を行ったところ、破壊強度は４３ＭＰａであり、タンク破壊強度発現率は９２．３％と非常に高い値であった。 Using this sizing agent-attached carbon fiber bundle, a pressure vessel for fracture strength evaluation was produced according to the above-described method for evaluating the pressure vessel fracture strength. When an internal pressure test was performed on the obtained pressure vessel for fracture strength evaluation, the fracture strength was 43 MPa, and the tank fracture strength expression rate was a very high value of 92.3%.
［実施例４］
実施例３で得た電解酸化処理後の炭素繊維束を、不飽和ポリエステルを主剤とするサイジング浴（濃度３２ｇ／ｌ）にディップ方式により３回浸漬した。２回目及び３回目の浸漬後においてローラー表面上を走行している炭素繊維束にブロワーを用いて圧縮空気を吹き付けた（風速２．８ｍ／０．１秒）。乾燥工程を経た後、ワインダーを用いてボビンに巻き取り、密度１．８１ｇ／ｃｍ３、ストランド強度４６００ＭＰａ、サイジング剤発光強度比（Ｉ／Ｓ）が１．２のサイジング剤付着炭素繊維を得た。得られたサイジング剤付着炭素繊維束のサイジング剤付着量及びサイジング剤発光強度比（Ｉ／Ｓ）、ファズ、ＭＰＦを表１に示した。
[Example 4]
The carbon fiber bundle after the electrolytic oxidation treatment obtained in Example 3 was immersed three times in a sizing bath (concentration 32 g / l) containing unsaturated polyester as a main component by a dip method. After the second and third immersions, compressed air was blown onto the carbon fiber bundles running on the roller surface using a blower (wind speed 2.8 m / 0.1 second). After passing through the drying step, the sizing agent-attached carbon fiber having a density of 1.81 g / cm 3 , a strand strength of 4600 MPa, and a sizing agent emission intensity ratio (I / S) of 1.2 was obtained using a winder. . Table 1 shows the sizing agent adhesion amount, sizing agent emission intensity ratio (I / S), fuzz, and MPF of the obtained sizing agent-attached carbon fiber bundle.
このサイジング剤付着炭素繊維束を用いて、前述の圧力容器破壊強度の評価方法に従って、破壊強度評価用圧力容器を製造した。得られた破壊強度評価用圧力容器について内圧試験を行ったところ、破壊強度は４５ＭＰａであり、タンク破壊強度発現率は９９．４％と非常に高い値であった。 Using this sizing agent-attached carbon fiber bundle, a pressure vessel for fracture strength evaluation was produced according to the above-described method for evaluating the pressure vessel fracture strength. When an internal pressure test was performed on the obtained pressure vessel for fracture strength evaluation, the fracture strength was 45 MPa, and the tank fracture strength expression rate was a very high value of 99.4%.
［実施例５］
実施例１で得た電解酸化処理前の炭素繊維束に、電解液を炭素繊維束に含浸させることなく、電解質溶液として８質量％の硫酸アンモニウム水溶液を電解質水溶液として用い、総電気量３０クーロン／ｇの電気条件で電解酸化処理を行った。電解酸化処理を施した炭素繊維束の臨界張力は７５ｍＮ／ｍであった。
[Example 5]
The carbon fiber bundle obtained in Example 1 was not impregnated with the carbon fiber bundle, and an 8 mass% ammonium sulfate aqueous solution was used as the electrolyte solution, and the total amount of electricity was 30 coulombs / g. The electrolytic oxidation treatment was performed under the electrical conditions of The critical tension of the carbon fiber bundle subjected to the electrolytic oxidation treatment was 75 mN / m.
電解酸化処理後の炭素繊維束を、エポキシ変性ウレタンを主剤とするサイジング浴（濃度３４ｇ／ｌ）にディップ方式により１回浸漬した。ローラー表面上を走行している炭素繊維束にブロワーを用いて圧縮空気を吹き付けた（風速２．８ｍ／０．１秒）。乾燥工程を経た後、ワインダーを用いてボビンに巻き取り、密度１．７９ｇ／ｃｍ３、ストランド強度４４００ＭＰａ、サイジング剤発光強度比（Ｉ／Ｓ）が０．８のサイジング剤付着炭素繊維を得た。得られたサイジング剤付着炭素繊維束のサイジング剤付着量及びサイジング剤発光強度比（Ｉ／Ｓ）、ファズ、ＭＰＦを表１に示した。 The carbon fiber bundle after the electrolytic oxidation treatment was immersed once in a sizing bath (concentration: 34 g / l) mainly composed of epoxy-modified urethane by a dip method. Compressed air was blown onto the carbon fiber bundle running on the roller surface using a blower (wind speed 2.8 m / 0.1 sec). After passing through the drying step, the sizing agent-attached carbon fiber having a density of 1.79 g / cm 3 , a strand strength of 4400 MPa, and a sizing agent emission intensity ratio (I / S) of 0.8 was obtained using a winder. . Table 1 shows the sizing agent adhesion amount, sizing agent emission intensity ratio (I / S), fuzz, and MPF of the obtained sizing agent-attached carbon fiber bundle.
このサイジング剤付着炭素繊維束を用いて、前述の圧力容器破壊強度の評価方法に従って、破壊強度評価用圧力容器を製造した。得られた破壊強度評価用圧力容器について内圧試験を行ったところ、破壊強度は４７ＭＰａであり、タンク破壊強度発現率は８８．２％であった。 Using this sizing agent-attached carbon fiber bundle, a pressure vessel for fracture strength evaluation was produced according to the above-described method for evaluating the pressure vessel fracture strength. When the internal pressure test was done about the obtained pressure vessel for fracture strength evaluation, the fracture strength was 47 MPa and the tank fracture strength expression rate was 88.2%.
［比較例１］
実施例１で得た電解酸化処理前の炭素繊維束に、８質量％の硫酸アンモニウム水溶液を電解質溶液として用い、実施例１と同様に電解液を炭素繊維束に含浸させた。その後、総電気量１５クーロン／ｇの電気条件で電解酸化処理を施した。電解酸化処理を施した炭素繊維束の臨界張力は６６ｍＮ／ｍであった。
[Comparative Example 1]
The carbon fiber bundle obtained in Example 1 was impregnated with the electrolytic solution in the same manner as in Example 1 using an 8% by mass ammonium sulfate aqueous solution as the electrolyte solution. Thereafter, electrolytic oxidation treatment was performed under electrical conditions of a total electricity of 15 coulomb / g. The critical tension of the carbon fiber bundle subjected to the electrolytic oxidation treatment was 66 mN / m.
電解酸化処理後の炭素繊維束を、エポキシ変性ウレタンを主剤とするサイジング浴（濃度３７ｇ／ｌ）にディップ方式により１回浸漬した。その後、ローラー表面上を走行している炭素繊維束にブロワーを用いて圧縮空気を吹き付けた（風速２．８ｍ／０．１秒）。乾燥工程を経た後、ワインダーを用いてボビンに巻き取り、密度１．７９ｇ／ｃｍ３、ストランド強度５３００ＭＰａ、サイジング剤発光強度比（Ｉ／Ｓ）が０．７のサイジング剤付着炭素繊維を得た。得られたサイジング剤付着炭素繊維束のサイジング剤付着量及びサイジング剤発光強度比（Ｉ／Ｓ）、ファズ、ＭＰＦを表１に示した。 The carbon fiber bundle after the electrolytic oxidation treatment was immersed once in a sizing bath (concentration: 37 g / l) mainly composed of epoxy-modified urethane by a dip method. Thereafter, compressed air was blown onto the carbon fiber bundle running on the roller surface using a blower (wind speed 2.8 m / 0.1 second). After passing through the drying step, the winder was wound around a bobbin to obtain a sizing agent-attached carbon fiber having a density of 1.79 g / cm 3 , a strand strength of 5300 MPa, and a sizing agent emission intensity ratio (I / S) of 0.7. . Table 1 shows the sizing agent adhesion amount, sizing agent emission intensity ratio (I / S), fuzz, and MPF of the obtained sizing agent-attached carbon fiber bundle.
このサイジング剤付着炭素繊維束を用いて前述の圧力容器破壊強度の評価方法に従って、破壊強度評価用圧力容器を製造した。得られた破壊強度評価用圧力容器について内圧試験を行ったところ、破壊強度は４７ＭＰａであり、タンク破壊強度発現率は８１．０％であった。 Using this sizing agent-attached carbon fiber bundle, a pressure vessel for fracture strength evaluation was produced in accordance with the aforementioned method for evaluating the pressure vessel fracture strength. When the internal pressure test was done about the obtained pressure vessel for fracture strength evaluation, the fracture strength was 47 MPa and the tank fracture strength expression rate was 81.0%.
比較例１では、サイジング剤発光強度比（Ｉ／Ｓ）が０．７と低く、サイジング剤が炭素繊維束内層部に十分に含浸していなかったため、得られた圧力容器のタンク破壊強度発現率は低い値となった。 In Comparative Example 1, the sizing agent emission intensity ratio (I / S) was as low as 0.7, and the sizing agent was not sufficiently impregnated in the inner layer of the carbon fiber bundle. Became low.
［比較例２］
実施例１で得た電解酸化処理前の炭素繊維束に、電解液を炭素繊維束に含浸させることなく、電解質溶液として８質量％の硫酸アンモニウム水溶液を電解質溶液として用い、総電気量１０クーロン／ｇの電気条件で電解酸化処理を施した。電解酸化処理を施した炭素繊維束の臨界張力は４０ｍＮ／ｍであった。
[Comparative Example 2]
The carbon fiber bundle obtained in Example 1 before the electrolytic oxidation treatment was not impregnated with the electrolytic solution, and an 8 mass% ammonium sulfate aqueous solution was used as the electrolyte solution, and the total amount of electricity was 10 coulomb / g. The electrolytic oxidation treatment was performed under the electrical conditions. The critical tension of the carbon fiber bundle subjected to the electrolytic oxidation treatment was 40 mN / m.
電解酸化処理後の炭素繊維束を、エポキシ変性ウレタンを主剤とするサイジング浴（濃度３８ｇ／ｌ）にディップ方式により１回浸漬した。その後、ローラー表面上を走行している炭素繊維束にブロワーを用いて圧縮空気を吹き付けた（風速３．５ｍ／０．１秒）。乾燥工程を経た後、ワインダーを用いてボビンに巻き取り、密度１．７９ｇ／ｃｍ３、ストランド強度５０００ＭＰａ、サイジング剤発光強度比（Ｉ／Ｓ）が０．６のサイジング剤付着炭素繊維を得た。得られたサイジング剤付着炭素繊維束のサイジング剤付着量及びサイジング剤発光強度比（Ｉ／Ｓ）、ファズ、ＭＰＦを表１に示した。 The carbon fiber bundle after the electrolytic oxidation treatment was immersed once in a sizing bath (concentration: 38 g / l) mainly composed of epoxy-modified urethane by a dip method. Thereafter, compressed air was blown onto the carbon fiber bundle running on the roller surface using a blower (wind speed 3.5 m / 0.1 second). After passing through the drying step, the winder was wound around a bobbin to obtain a sizing agent-attached carbon fiber having a density of 1.79 g / cm 3 , a strand strength of 5000 MPa, and a sizing agent emission intensity ratio (I / S) of 0.6. . Table 1 shows the sizing agent adhesion amount, sizing agent emission intensity ratio (I / S), fuzz, and MPF of the obtained sizing agent-attached carbon fiber bundle.
このサイジング剤付着炭素繊維束を用いて、前述の圧力容器破壊強度の評価方法に従って、破壊強度評価用圧力容器を製造した。得られた破壊強度評価用圧力容器について内圧試験を行ったところ、破壊強度は４７ＭＰａであり、タンク破壊強度発現率は８０．０％であった。 Using this sizing agent-attached carbon fiber bundle, a pressure vessel for fracture strength evaluation was produced according to the above-described method for evaluating the pressure vessel fracture strength. When the internal pressure test was done about the obtained pressure vessel for breaking strength evaluation, the breaking strength was 47 MPa and the tank breaking strength expression rate was 80.0%.
比較例２では、サイジング剤発光強度比（Ｉ／Ｓ）が０．６と低く、サイジング剤が炭素繊維束内層部に十分に含浸していなかったため、得られた圧力容器のタンク破壊強度発現率は低い値となった。 In Comparative Example 2, the sizing agent emission intensity ratio (I / S) was as low as 0.6, and the sizing agent was not sufficiently impregnated in the carbon fiber bundle inner layer portion. Became low.
Claims (1)
１．２＜ Ｉ／Ｓ ＜２．０ ・・・（１）
の関係を満たすことを特徴とするフィラメントワインド成形用のサイジング剤付着炭素繊維束。
Sizing agent emission count of carbon fiber bundle outer layer measured by cathodoluminescence method with sizing agent adhering to carbon fiber bundle with critical tension of 70-90 mN / m attached by 0.8-3.0 mass% The number (S) and the sizing agent emission count (I) of the inner layer part of the carbon fiber bundle measured by the cathodoluminescence method are expressed by the following formula (1)
1.2 <I / S <2.0 (1)
A sizing agent-attached carbon fiber bundle for filament wind forming characterized by satisfying the following relationship:
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| JP2002069754A (en) * | 2000-08-31 | 2002-03-08 | Toho Tenax Co Ltd | Carbon fiber having high strength and high elongation, and forming material of the same |
| JP2002339222A (en) * | 2001-05-10 | 2002-11-27 | Toho Tenax Co Ltd | Method for applying sizing agent to carbon fiber strand and apparatus therefor |
| JP2003278032A (en) * | 2002-03-18 | 2003-10-02 | Toray Ind Inc | Method for sizing carbon fiber |
| JP2004106552A (en) * | 2002-09-17 | 2004-04-08 | Mitsubishi Rayon Co Ltd | Composite pressure vessel or composite tube, and composite intermediate |
| JP2008274520A (en) * | 2007-04-04 | 2008-11-13 | Toray Ind Inc | Sizing agent for carbon fiber and carbon fiber bundle |
| WO2011013691A1 (en) * | 2009-07-31 | 2011-02-03 | 新日本製鐵株式会社 | Laminated steel plate |
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