TW201107547A - Carbon fiber strand exhibiting excellent mechanical property - Google Patents

Abstract

A carbon fiber strand for obtaining a fiber reinforced resin having high mechanical property is provided. The carbon fiber strand of this invention includes single fiber of carbon fiber, wherein the single fiber has no surface irregular structure extended along a length direction of the fiber in which the length of the structure is 0.6 μ m or more on a surface of the single fiber, and the single fiber has an irregular structure having a height difference (Rp-V) between a highest portion and a lowest portion of 5 to 25 nm on the surface of the single fiber and an average irregularity Ra of 2 to 6 nm, and a ratio of major to miner axes (major axis/miner axis) of a fiber section of the single fiber is 1.00 to 1.01. A weight per unit length of the single fiber of the corbon fiber is within a range of 0.030 to 0.042 mg/m, a strand strength is 5900 MPa or more, a strand elastic modulus measured by ASTM method is 250 to 380 GPa, and a knot strength is 900 N/mm2 or more.

Description

201107547 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a carbon fiber bundle for use in a fish reinforced resin having a highly dynamic and heat-generating tree, particularly for aircraft use. Fiber [Prior Art] A method for recombining a mechanical material and a resin of a resin-based molded article. In particular, the material is used as a structural material for aircraft, high-speed moving objects, and the like. = The higher the specificity, and the specific strength of the material, the ratio of the material is just too much. Therefore, the performance of the carbon fiber is required to achieve higher strength and high modulus. The following method is proposed in the literature: When the carbon fiber precursor propylene gn fiber bundle is obtained by the dry soil type, the square 4 method, the solidified yarn in the solvent-containing state is in the solvent-containing extension bath. Extend the structure and alignment uniformity. The coagulation yarn = stretching in a bath containing a solvent is a well-known method as a solvent stretching technique, and is a method of achieving stable elongation treatment by solvent plasticization. Because of the skill, the method is considered to be a method for obtaining a structure and a fiber having a uniform alignment of 13⁄4. However, 'H is extended by the fiber bundle containing the dissolved (four) in a swollen state, and the solvent existing inside the filament is extended and is rapidly extruded from the inside of the monofilament, so that the obtained monofilament = 4 201107547 is easily formed. A loose structure makes it impossible to obtain a fiber having a dense structure as a target. Further, Patent Document 2 proposes a technique of obtaining a precursor fiber excellent in strength discovery property by focusing on the pore distribution of the coagulated filament and drying and solidifying the coagulated filament having a high densification structure. The pore distribution obtained by mercury penetration meth〇d reflects the bulk property from the surface layer to the inside of the monofilament, and is excellent for evaluating the denseness of the fiber = the overall structure. A high-strength carbon fiber in which the formation of defective spots is suppressed can be obtained by using a precursor fiber bundle having an overall density of at least a predetermined level (levd). However, if the fracture state of the carbon fiber is observed, it can be found that the fiber having a very high value is referred to as _start·_ in the vicinity of Table 1. This phenomenon indicates that there is a defect point near the surface layer. That is, this technique is insufficient for producing a precursor fiber bundle excellent in compactness in the vicinity of the watch. Patent Document 3 proposes a method for producing an acrylonitrile-based precursor fiber bundle having a high density of the entire fiber and an extremely high denseness of the surface layer portion. In addition, the special offer of 4 towels 'to mention & (4) infiltration of the surface layer of the age will hinder the densification, so focus on the micro-voids in the surface layer, inhibit oil penetration, surgery. However, the technique of suppressing the infiltration of the oil agent and the technique of suppressing the formation of the defect point require very complicated steps, and thus it is difficult to obtain practical application. Therefore, the thief in the research technique is not sufficient to suppress the surface layer of the human fiber, and the effect of the high strength of the carbon fiber is not sufficient. . [Prior Art Document] 201107547 [Patent Document] Patent Document 1: Japanese Patent Laid-Open Publication No. Hei No. Hei-5-5224. Patent Publication No. Hei. [Problem of the Invention] It is an object of the present invention to provide a carbon fiber bundle for obtaining a fiber-reinforced resin having high mechanical properties. The above problems are solved by the following invention. The present invention is a carbon fiber bundle comprising a single fiber of a carbon fiber as described below, that is, a surface uneven structure having a length of 0.6 μm or more extending in a fiber length direction on a surface of the single fiber, and having a single fiber surface The height difference (Rp_v) between the highest part and the lowest part is 5 nm to 25 nm, the average unevenness Ha is a concave-convex structure of 2 nm to 6 nm, and the ratio of the long diameter to the short diameter of the fiber cross section of the single fiber (long diameter / The short diameter is 丨〇〇~丨〇1, and the weight of the single fiber _ per unit length of the carbon fiber is in the range of 0·_mg/m to 0.042 mg/m, and the strand strength is 59 〇〇Mpa or more. The elastic modulus of the strand measured by the American Society for Materials and Testing (American s〇ciety f〇r(10)丨叩Matenals, ASTM) method is 25〇Gpa 380 GPa 'the strength of the knot is 900 N/mm2 or more. Further, the knot strength is obtained by dividing the tensile fracture stress of the carbon fiber bundle of the nodule by the sectional area of the fiber bundle (weight and density per unit length. 夂) [Effect of the Invention] 6 201107547 A carbon fiber bundle provides a fiber-reinforced resin having high mechanical properties. Further, a carbon fiber bundle having more excellent properties is obtained by generating energy of the fracture surface of 3 〇 N/m or more. Further, by forming a carbon fiber bundle having a surface as described below, a carbon fiber composite material having very high mechanical properties can be obtained, that is, its surface is electrochemically measured (cyclic v 〇 tammetry) The obtained lpa value is 〇〇5 heart coffee 2~〇25 M/Cm 'The oxygen content of the carbon fiber surface determined by X-ray photoelectron spectroscopy (x-my Ph〇toelectron S_〇SC〇Py) The amount of functional groups (〇1S/C1S) is in the range of 〇.05~〇.1〇. The secrets of the Moon and other purposes, features and advantages can be more clearly as follows. , + & good example, and with the accompanying drawings, for details. [Embodiment] Carbon fiber table © exists along the fiber length is often important τ. Reason ===== Relationship between the fiber and the resin boundary (-heart =: coffin two basis difference, fiber-reinforced tree wax material that is - excellent by flawless method; one ^ ^ ^ performance compared to 201107547 Λ. structure) ( Surface unevenness extending along the longitudinal direction of the fiber on the surface of the single fiber. According to a general manufacturing method of the carbon fiber bundle, a normal carbon fiber has a surface uneven structure in which the two-dimensional axial direction is substantially parallel. The uneven structure is substantially parallel and along the fiber axis. The undulating structure extending in the direction: the concave Γ Γ is usually 5. The fine ~ hundreds of nm or so, the length is usually the same as the surface J Jμμη ° The surface concave and convex structure is usually called the surface of the single fiber along the length of the fiber The surface has a surface unevenness of 0.6 μm or more. Aspect 'The carbon fiber bundle of the present invention has a small uneven structure on the surface of the single fiber. The carbon fiber is monofilament, and the surface is uneven. The depth of the structure is determined by the circumferential length of 10 to the length of the fiber [of the range of the fiber surface = the lowest of the fiber (Rp_v) solution, the uniformity of the roughness (RP-V) and Ra can be used to sweep the atomic force Mirror (at〇mic f〇rce 嶋Pe, AFM) scan single fiber table = difference = 5n - average embossing degree 22 is better (RP_V) is 5 (10) called 8nm, Ra is 2nm~5 nm In the boundary phase of the composite material, the surface convex structure on t L μ 容易 is likely to become a large-sized surface concave portion of the stress concentration portion and the carbon fiber 8 201107547 is broken near the concave and convex structure. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The performance is greatly reduced. A more specific form of the uneven structure of the surface of each of the individual fibers constituting the carbon fiber of the present invention is as follows. The surface of the carbon fiber of the coke is composed of a plurality of fibrils in units of units. a concavo-convex structure in which the length of the fiber is extended in the longitudinal direction and a wrinkle-like structure of the length of the fiber, and the wrinkle-like knot is smaller than the size of the wrinkle-like structure, and the fine unevenness existing in each of the fibril bodies itself is not uniform. For constituting the carbon fiber of the present invention Each of the individual fibers has a small uneven structure in which the length of the fiber is extended in the longitudinal direction of the fiber and has a length of 〇6, and has a small size as compared with the uneven structure. The length of each of the original elements is 300 nm or less. The uneven structure is represented by the above-mentioned convex structure Ra. That is, the uneven structure is P - v ) and 1 · 〇 μηη on the surface of the single fiber, and the length in the fiber axis direction In the range surrounded by 1.0 μπι, the length (Rp-v) is 5 nm to 25 nm, and the average concavity Ra is a fluctuation of 2 low. Preferably, (Rp-v) is 5 nm to 18 nm, and Ra is -6 nm. The direction of the fine-sized uneven structure is not particularly ff5, and the fiber axis direction is parallel or perpendicular or has a certain angle. '"弋, can be combined with (single fiber fiber profile) & In addition, the single fiber of the present invention must be a single fiber fiber profile of 9 201107547 control and short diameter ratio (long diameter / short diameter) is 1.00~1.01 A single fiber having a cross section of a perfect circle or a nearly perfect circle. The reason is that the stress uniformity can be reduced by making the cross section of the single fiber a perfect circle. The comparison is preferably from 1.00 to 1.005. Further, for the same reason, the weight per unit length of the single fiber is 0.030 to 0.042 mg/m. The weight per unit length of the fiber (the basis weight per fiber) is small, indicating that the fiber diameter is small, and the unevenness of the structure existing in the cross-sectional direction is small, and the mechanical properties in the direction perpendicular to the fiber axis are high. Therefore, in the composite material, the resistance to stress in the direction perpendicular to the fiber axis is improved, whereby the mechanical properties as a composite material can be improved. (Carbon fiber bundle) In the present invention, in order to obtain a fiber-reinforced resin having excellent mechanical properties, the strand strength of the carbon fiber bundle must be 5,900 MPa or more. The strand strength of the carbon fiber bundle is preferably 6,000 MPa or more, more preferably 61 MPa or more. The higher the strand strength, the better, but as a composite material, considering the balance with the compressive strength (baiance), the strand strength is 1 〇〇〇〇Mpa. Further, in the present invention, in order to obtain a fiber-reinforced resin having excellent mechanical properties, the strand elastic modulus of the carbon fiber bundle must be 25 Å GPa to 38 Å GPa as measured by the ASTM method. If the modulus of elasticity is less than 250 GPa', sufficient mechanical properties cannot be found as a sufficient modulus of elasticity of the carbon fiber bundle. On the other hand, when the modulus of elasticity exceeds 38 〇Gpa, the graphite crystal size on the surface and inside of the carbon fiber increases, and as a result, the strength in the cross-sectional direction of the fiber and the compressive strength in the fiber axis direction are lowered, and the composite material cannot be satisfactorily obtained. The tensile and compression properties are balanced and the results are no 201107547 η: composite. Moreover, due to the fracture of the graphite crystal size on the surface, hiding (4) adhesion (4), the mechanical properties such as tensile strength in the complex direction, interlaminar shear strength, and in-plane frying X shrinkage strength are remarkably lowered.伸 卜 = 0 of the present type 'Important is the cross-sectional area of the drawn fiber bundle of the carbon fiber bundle of the nodule (the weight per unit length and more than the density. The above-mentioned nodule strength is more than ^, further preferably more than 1100 N/mm2 or more The monument can be used as a mechanical property to reflect the fiber bundles other than the direction of the fiber axis. In particular, it is easy to see that the material of the mouth perpendicular to the fiber axis is formed by quasi-isotropic lamination. In addition, in addition to the tensile and compressive stress in the direction of the fiber axis, the stress in the direction of the fiber axis is also added. In addition, in the case of the impact (such as the impact test), the material (4) The stress state is very different. The material (four degrees) becomes very important. Therefore, the i_NW' quasi-isotropic material cannot find sufficient = mechanical m-plane. When the nodule strength exceeds the ugly state 2, the dimension of the dimension Therefore, the knot strength should be 3000 I. In addition, the carbon fiber bundle of the present invention preferably generates energy for destroying the surface. For energy generation on the damaged surface, a laser (ι) can be used to form the surface. A hemispherical defect of a range of sizes, the elongation test causes the fiber to break at the hemispherical defect, and the size of the fiber and the size of the hemispherical defect are utilized by the following Griffith 11 201107547 (Griffkh) formula ( 1) Find σ = (2Ε/π〇1/2χ (breaking surface energy) 1/2 d) where σ is the breaking strength, E is the ultrasonic modulus of the carbon fiber bundle, and c is the hemispherical defect The size of the damaged surface is preferably more than 2 N/m, and more than 32 M/m. Among them, the energy generated by the damage is an indicator of the difficulty of carbon fiber damage, indicating the matrix strength. The material showing brittle failure is affected by the defect point. When the carbon fiber has the same defect point, the higher the matrix strength of the carbon fiber, the higher the breaking strength. In addition, the matrix resin for the two-performance composite material The adhesion to carbon fiber is high, and as a result, the critical fiber length as an indicator of stress transmission becomes shorter. Therefore, it can be recognized that the strength of the composite material reflects the strength at a shorter length, and the basis weight is On the other hand, when destroying the surface to generate energy ° m, it is necessary to reduce the orientation of the fiber axis direction. Therefore, the energy generated by the breakage should be 50 N / m or less. In the present invention, the electrochemical defeat method (cyclic voltammetry) The desired Ϊ ί is preferably 〇.05 —m2~〇.25 —m2. The added value is affected by the number of oxygen-containing functional groups, and the galvanic layer—(4). The convexity and the fine graphite structure on the surface of the carbon fiber. Dimension: or formation: yin::: 怀·大, the etching (etChing) of the carbon fiber interfering person #her (amon) enters the layer of the graphite crystal layer i of the composite i is more than the ipa value. It is known that an excellent machine is an interface having a site in which a suitable resin is present, a special 3 oxygen S group, and a smaller galvanic layer 12 201107547 6 is formed. …for. ·. 5 3 i=sexuality. On the other hand, if the -value is 〇~ the state of the inter-layer merging and the formation of μΑ/W~〇2〇 :2, the interface adhesion ♦ value is preferably 0. ' m, the step-by-step is better. 2 2~ $ φ in this & Ming towel, ideally X-ray photoelectron light = the amount of oxygen-containing functional group on the surface of the carbon fiber (喔(8) is suitable The carbon fiber in the blood circumference is produced. The reason is that it is very important to make the carbon fiber have a proper interfacial adhesion with the matrix resin. And the eight-seal towel is ideally the Xiangxin liver emission light 3 knives method (sensing power consumption) Polyatomic emission spectrometry, inductivdy C: Uf; nplasma at 〇mic emission spectrometry) measured under si 3 2, Oppm. In order to produce high-strength carbon fiber, usually containing pre-drive fiber bundle containing Wei oil (five) ie〇neQil) Oil agent. Weiyou's wealth is not good, and it can repel the release of the precursor fiber bundle. Therefore, it is considered that the diameter of the monofilament is very small, and it has a form of a multifilament tow formed by collecting the plurality of monofilaments, and is supplied to a high temperature treatment of tens of minutes to several hours under (4) of 200 C or more. Carbon fiber precursor fiber bundles are most suitable for use with oils. However, in the carbonized treated towel which is subjected to the flameproofing treatment, most of the Wei oil is decomposed and scattered, and the amount of the oxygen compound remaining on the surface of the carbon fiber is extremely small. In addition, 13

201107547 L It is known that this residual Wei compound is the main cause of carbon fiber formation pores. Therefore, by controlling the cerium oxide compound to be less, it is possible to produce carbon fibers having less pores, and as a result, the strength of the carbon fiber bundle can be increased. More preferably, the amount of Si is 150 ppm or less, and further preferably, the amount of Si is 100 ppm or less. (Precursor fiber bundle and method for producing the same) The starting material for obtaining the carbon fiber bundle of the present invention is not particularly limited, and from the viewpoint of mechanical properties, it is preferably an acrylonitrile-based precursor fiber (hereinafter referred to as "Precursor fiber") to obtain the carbon fiber bundle of the present invention. The acrylonitrile-based copolymer constituting the precursor fiber is obtained from 96 wt% (by weight) or more of acrylonitrile and several copolymerizable monomers. More preferably, the composition ratio of acrylonitrile is 97 wt% or more. The copolymerization component other than acrylonitrile is suitably, for example, acrylic acid, methacrylic acid, itaconic acid, decyl acrylate, methyl methacrylate or the like. Acrylamide derivatives such as acrylamide, methacrylamide, N- mercapto acrylamide, N,N-dimercaptopropenylamine, vinyl acetate ( Vinylacetate) and so on. These may be used alone or in combination. A preferred copolymer is an acrylonitrile-based copolymer obtained by copolymerizing a monomer having one or more carboxyl groups as an essential component. A suitable method for copolymerizing a mixture of monomers may be, for example, redox polymerization in an aqueous solution, or suspension polymerization in a heterogeneous system 14 201107547, and emulsion polymerization using a dispersant, and any other polymerization method. The present invention is not limited by the difference in the polymerization method. For the precursor fiber, it is preferred to prepare the spinning by dissolving the above-mentioned nitrile compound in an organic solvent such as dimethyl acetamide or dimethylsulfoxide ^f C dimethylfornTamide. Silk stock solution. Since these organic solvents do not contain a metal component, the content of the metal component of the obtained carbon fiber bundle can be lowered. The concentration of the body component of the test is difficult to be 2 () (four) or more, and more than 21 wt%. The spinning method can be any of wet spinning, dry-wet spinning, and the spinning dope prepared by spinning the spinning nozzle prepared from the spout hole to the spun nozzle. After the air is filled with the condensed solution of the mixed solution of the temperature-controlled organic solvent and water, the money is washed and extended. As for cleaning green = can be used. In addition, the extension of the extracted coagulated filaments is carried out, and (4) the fibril formation is carried out to extend the material, and the temperature of the extension tank is preferably in the range of 4 〇 C 80C. If the temperature is not reached, the benefit method becomes forced extension and a uniform fibril structure cannot be formed. On the other hand, ==:,, the plasticization caused by heat becomes too large, and the desolvation of the surface of the wire is rapidly performed, etc., resulting in σ as a precursor fiber bundle, and 仟不句匀5 (TC~ bundle f is deteriorated. The better temperature is 75C. In addition, the concentration of the extension tank is preferably 3Qwt%~6〇15 201107547 2. If the concentration of the extension tank is less than 3G wt%, the extension cannot be confirmed. If the concentration of the stretching tank exceeds 6 〇wt%, the plasticizing effect becomes large, and the stable elongation is impaired. A more suitable concentration is 35% by weight. The stretching ratio in the stretching groove is preferably 2 times to 4 times. - 'Γίϊ 2 times, the extension is insufficient, and the desired original: fiber: structure cannot be formed. On the other hand, if the extension is more than 4 times, the fibril structure itself breaks and becomes very loose. The precursor fiber extension ratio of the structural form is 2.2 times to 3. 8 times, and the further step is more preferably 2 5 times to 3 times more. Further, after washing, the fiber bundle can be obtained by the expansion step in the solventless component. Extending in hot water, (4) - step to improve the alignment of the fiber to apply some relaxation to eliminate the previous step The extension of the strain. Compared with ==:: times ~ 2. ° times the extension, the high total extension times, using an oil containing a compound of Shihe oxygen, to reach 0 8 wt% i said New Zealand, recorded Wei. The drying densification is carried out by the method of silk (4), densification, and limitation. It is preferred to pass the fiber bundle through a plurality of heating methods. 'The dried densified acrylic fiber bundle is optionally steamed. Medium, 410 (rc~20 (in rc dry heat medium, or between 150 C~220 C heating rolls or on a hot plate extending 18 times to 6 (): after the stepping of the material and densification] The carbon fiber of the invention of the invention can be produced by the above-mentioned precursor fiber bundle by the following method. The precursor fiber is bundled in a hot air type flameproof furnace of 220 ° C to 2603⁄4. A flame-resistant filament having a flame-proof filament density of 1.335 g/cm 3 to 1.360 g/cm 3 is obtained through 30 minutes to 100 minutes. At this time, an elongation operation of 〇〇/〇 10% is carried out. In the flameproof reaction, there is The cyclization reaction caused by heat and the oxidation reaction caused by oxygen make it important to balance the two reactions. In order to balance the two reactions, the flame-proof treatment time is suitably 30 minutes to 100 minutes. When the flame-proof treatment time is less than 3 minutes, the portion of the single fiber that is not sufficiently oxidized is present, thereby Large structural unevenness occurs in the cross-sectional direction of the single fiber. As a result, the carbon fiber obtained has an uneven structure and high mechanical properties cannot be found. On the other hand, when the flame-proof treatment time exceeds 100 minutes, the single fiber is used. There is more oxygen in the portion close to the surface, and the heat treatment at a high temperature thereafter causes a reaction in which excess oxygen disappears to form a defect point. Therefore, high strength cannot be obtained. A better flame retardant treatment time is 40 minutes to 80 minutes. When the flame-proof filament density is less than 1.335 g/cm3, the flame-proofing is insufficient, and the decomposition reaction occurs by the heat treatment at the subsequent temperature, and a defect point is formed, so that high strength cannot be obtained. When the flameproof filament density exceeds 1 36 〇g/cm3, the oxygen content of the fiber increases. Therefore, by the heat treatment at a high temperature thereafter, excessive oxygen disappears and a defect is formed, so that high strength cannot be obtained. A more preferred range of flame resistance is L340 g/em 3 to 135 () g/cm 3 . In order to maintain and improve the alignment of the fibril structure forming the fibers, it is necessary to carry out moderate elongation in the flameproof furnace. If the elongation is less than 〇%, the alignment of the fibril structure cannot be maintained, and the structure of the carbon fiber is formed on the middle fiber shaft. 17 20110754: The alignment is insufficient. The thermal properties are excellent. On the other hand, if the elongation exceeds 1%, the fibril structure itself is broken, and the carbon after the damage is formed, and the point becomes a defect point, and a high-strength slave fiber cannot be obtained. A more preferable elongation is 3% to 8%. „In an inert environment such as nitrogen, with a temperature gradient of rc~8G (in the first carbonization furnace with a temperature gradient of rc, a 2% to 7% elongation is applied to the flame-proof fiber) to pass the flame-resistant fiber through the first - Carbonization I is suitable for a treatment temperature of 300 C to 800 ° C and is treated under a linear gradient. If the temperature of the flameproofing step is considered, the initial temperature is preferably above c. If the high temperature exceeds 80 Gt , the step filament becomes very brittle and it is difficult to proceed to the next step. A more suitable temperature range is the outline. c~75 (n: no particular limitation, preferably set to a linear gradient. % 'is unable to maintain the alignment of the fibril structure, the structural fiber of the carbon fiber _ the upper planting material is sufficient, and excellent mechanical properties cannot be found. On the other hand, if the elongation exceeds 7%, the fibril structure itself is broken and damaged. After the carbon fiber _ structure is formed, and the breaking point becomes a defect point, high-strength carbon fiber cannot be obtained. More preferably 5% elongation 〇 The appropriate heat treatment time in the first carbonization furnace is 1 〜 minutes to 3 〇 minutes. Not up to 1.G minutes' job temperature is urgent Increased decomposition reaction generated vigorously 'can not be obtained a high strength carbon fiber. If the processing for more than 3 billion minutes' pre-plasticizing step Charm influence exists, crystalline orientation degree drop

The tendency is low, and as a result, the mechanical properties of the obtained carbon fiber are impaired. A more suitable heat treatment time is from 1.2 minutes to 2.5 minutes. , Q 18 201107547 j-to / UL; il picker in the Tf environment, with a 1 〇〇 (rc ~ 16 〇〇 temperature gradient of the second carbonized towel, in the (four) state of the heat to obtain carbon fiber In addition, depending on the "additional temperature _ (four) temperature gradient ^ two stone reverse = towel, hide the environmental towel, under the tension (four) ride heat treatment. The temperature of the enslaving treatment is set according to the number of hybrid models of carbon fiber sensitivity. In order to obtain The carbon fiber having high strength characteristics preferably has a low temperature at the lowest temperature of the carbonization point 2, and 'because the treatment time is long to increase the elastic modulus', the maximum temperature can be lowered. By making the treatment time long, ^ Setting the degree gradient to be gentle' can effectively suppress the formation of defects'::: The temperature of the carbonization furnace is also affected by the temperature setting of the first carbonization furnace: 1曰〇5〇r^ 1〇〇〇C or more The temperature of the second carbonization furnace is preferably above. The temperature gradient is not controlled, and it is preferable to set the heat treatment time in the wire shoveling furnace to be suitable. U minutes to 5.0 minutes 2 = the rational time is better 2 .°~4.2 minutes. In this heat treatment, the fiber will be accompanied by a larger The degree of shrinkage, it is very important to heat the heat in the tension state. The appropriate is to tear ° ~ M%. If the elongation is not reached, the knot is short, the upward alignment is poor, and sufficient performance cannot be obtained. : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : That is, by electrolytic oxidation, chemical oxidation, and oxidation treatment of air oxidation, such as 19 201107547, it can be used in any kind; Bu:: Electricity: Oxidation treatment can achieve stable texture = i value (four) in 'for The easiest way to indicate the best surface treatment is to use the electrolytic oxidation (4) two-electrode oxidation treatment. At this time, compared with the same power, the electrolyte concentration of == is the same, ipa health will be greatly different. In the second day of the 1st 'preferably in the alkaline aqueous solution with a pH greater than 7', the bismuth, a: ', and the anode 'circulation 10 Coul (cob) / g ~ 200 Coul / g plant two enthalpy electrolytic oxidation By the oxidation treatment, the batch value 'MA/em ~ G · 25 M/cm 2 can be obtained. The electrolyte is preferably used: ammonium carbonate (a = in〇nium resistant), ammonium bicarbonate (fine surface - (10) buckle 6), hydroxide hydroxide, sodium hydroxide m hydroxide) P〇tassium hydroxide) and the like. =, the carbon fiber bundle of the present invention is supplied to the sizing treatment. The sizing agent is applied to a carbon fiber bundle by a roll dipping method, a contact method, or the like, using a solution obtained by dissolving in an organic solvent, an emulsifier, or the like, and dispersing the emulsion in water. _, touch the money and maintain the bundle, so that the upper polymerization can be performed >1=outer' can be adjusted by adjusting the concentration of the destructurizing liquid or adjusting the amount of extrusion, so that the money dimension table_上||剂_ the amount. Further, the money can be carried out by using heat, heat, a plate heating roller, various infrared heaters, or the like. The most suitable sizing agent composition I for the surface of the carbon fiber of the present invention is exemplified by (a) an epoxy resin having a radical (hereinafter suitably referred to as component (a)), and (b) a poly-based compound ( Hereinafter, it is suitably referred to as (b) component) and (c) 20 201107547 The diisocyanate g containing an aromatic ring (hereinafter referred to as the component (c) component product, that is, an amine phthalic acid vinegar modified epoxy resin. The reactive organisms obtained by directing the U) component on the quantity side required for the reaction to the reaction system are a mixture of an amino phthalate-modified epoxy resin and an unreacted material. n Further, a mixture of an amino phthalic acid-based epoxy resin enamel (4) component obtained by using an epoxy resin having no warp group (hereinafter, suitably referred to as a component (4)) may be mentioned. In addition, can you solve the wire? _Modified epoxy resin, a mixture of (a) component and (d) component. The epoxy group interacts very strongly with the oxygen-containing functional groups on the surface of the carbon fibers to allow the top breaker component to adhere firmly to the carbon fiber surface. Further, a plurality of "amino acid carboxylic acid S-bonding unit" which is a compound and an aromatic ring-containing diisocyanate can impart flexibility, and can impart enthalpy to the surface of the carbon fiber by utilizing the polarity of the aromatic acid aromatic ring. The strong epoxy group and the above-mentioned amine bismuth acetamate-modified epoxy resin are compounds which can be strongly adhered to: I-face enamel has flexibility. That is, such a sizing agent is composed of an interface layer firmly adhered to the surface of the carbon fiber, and the composite material obtained by impregnating the carbon fiber with the base (10) and hardening has excellent mechanical properties. The il/ or (a) component to be contained is not particularly limited, and the component (4) is not limited. The term (a) component can be, for example, a propylene-propylene ring (II), methyl epoxy. Propyl alcohol (methyl glydd〇1), double F, Weiweiri, (4) A type epoxy resin, iron glycidol g§ epoxy tree 201107547 tv/pif month I, etc. is especially good for double epoxy. These compounds have strong interaction with the surface of the carbon fiber due to the aromatic ring. Further, the reason is that the matrix resin used for the composite material is often used in the viewpoint of heat conductivity and rigidity, and the above compound has excellent phase-to-phase property with the secret resin. Two or more epoxy resins may be used as the component. Further, the component (b) is preferably an epoxy burnt adduct of the bispan A, a lipopeptide group, or a compound of the singular compound, or a shoulder of the compound. The reason is that the above-mentioned amine fluorene-modified epoxy resin becomes soft by the touch of the compound. The body of I can be listed as: Epoxy w 4 Moer ~ 14 Moer Additives of A. A, a oxy-propane-burning 2 Moules ~ 14 Moer Additives, Ethylene Ethylene of Double Age A, Ring-generation propylene block filaments plus galactic, polyethylene glycol (trimethylolpfopane), dico-propionic acid and the like. Further, the component (c) is not particularly limited. Particularly preferred is toluene diisocyanate or diterpene diacetoic acid vinegar (4) (10) diisocyanate) ° Further, the epoxy resin of the component (d) is not particularly limited. A resin having two or more epoxy groups in the knives is preferred. The reason is that the surface of the carbon fiber interacts strongly with the epoxy group, and the compounds can be firmly attached to the surface. There is no __ for the county-based miscellaneous class, and it is available for glycerin-based and alicyclic epoxy groups. Preferred epoxy resins can be used: double-preferred F-type epoxy resin, double-twisted A-type epoxy, brittle varnish-type Wei resin, dicyclopentadiene type epoxy resin (Epid〇n 22 201107547 HP-7200 series, Dainippon Ink Chemical Industry Co., Ltd.), trihydroxyphenyl oxime-type epoxy resin (Epikote 1032H60, Epikote 1032S50 'Japan Epoxy Resins Co., Ltd.), DPP A varnish type epoxy resin (Epikote 157S65, Epikote 157S70, Japan Epoxy Co., Ltd.), a bisphenol a alkylene oxide addition epoxy resin, and the like. When the above mixture containing the component (d) is produced, the component (a), the component (b), and the component (c) may be reacted with the component (d) at the same time as the component (d), or the urethane may be used. After the esterification reaction is completed, the component (d) is charged. Examples of the aqueous dispersion containing such a compound include Hydran N32® (manufactured by DIC Co., Ltd.) and the like. The carbon fiber of the present invention is obtained in order to make the carbon fiber of the present invention have a strand elastic modulus of 25 Å Gpa and calcined at a relatively high temperature. Therefore, there is

The n-rh 笮 笮 七 反 , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,

invention. Further, in the present example, it was carried out by the following method. 23 201107547 Several single fibers of a carbon fiber bundle were placed on a sample stage, both ends were fixed, and then DGtite' was applied as a measurement sample. Atom atomic force microscope (manufactured by Seiko Instruments Co., Ltd., S "I3700/SPA-300 (trade name)), cantilever (Cantilever) made of nitrite (Xian (10)), in AFM mode The circumferential direction of the single fiber = the range of lOOOnm, one side is moved in a small amount of 1 〇〇〇 nm in the direction of the fiber axis, and the surface is repeatedly scanned, and the obtained low-frequency component of the fixed image is truncated by two-dimensional Fourier transform Conversion. From the plane image of the cross section of the single fiber obtained by the curvature removal, the height difference between the highest part and the lowest part in the range surrounded by the circumferential length 1 〇 μπι and the fiber axis direction length i 〇μηι is read. Ra calculated by the following formula (2).

Ra=={1/(LxxLy)> Ten,. (x, y) Nxdy (7) The central plane: parallel to the plane with the smallest deviation from the actual surface height, and the actual surface is divided into two halves in an equal volume, that is, surrounded by the plane and the actual surface and located a plane where the volume VI of both sides of the + face is equal to V2; f (x ' y): the difference between the actual surface and the center plane;

The size of the Lx, Ly _ X γ plane. Further, when measuring by an atomic force microscope, the presence or absence of a concave-convex structure having a length of 0.6 μm or more and a length of a concave-convex structure having a length of 3 〇〇 nm or less were measured. "2. Evaluation of cross-sectional shape of single fiber" The ratio of the long diameter to the short diameter (long diameter/short diameter) of the fiber cross section of the single fiber constituting the carbon fiber bundle was determined by the following method. 24 201107547 After the carbon fiber bundle for measurement was passed through a tube made of vinyl chloride resin having an inner diameter of 1 mm, the carbon fiber bundle was cut into a disk with a knife to prepare a sample. Then, the sample is placed on the sample stage of the scanning electron microscope (scanning e ectr〇n micr〇sc〇pe, $εμ) with the fiber profile facing upward, and then has a thickness of about 1 〇 nm. After splashing gold (Au), a scanning electron microscope (manufactured by Philips, product name: XL2 〇) was used, and the fiber profile was observed under an acceleration voltage of 7.00 kV and an actuation distance of 31 mm, and the fiber profile of the single fiber was measured. Long diameter and short diameter. 3. Evaluation of strand physical properties of fiber bundles A strand test body in which a carbon fiber bundle impregnated with a resin was prepared, and the strength was measured and evaluated based on 耵s R 7601. Among them, the elastic modulus is calculated using the strain range according to ASTM. "4. Measurement of Nodule Strength of Carbon Fiber Bundle" The measurement of the knot strength was carried out as follows. A 25 mm long grip is attached to both ends of a 150-length carbon fiber bundle as a test. Make a test, and apply a load of Q 1x1q_3 _ to align the carbon fiber bundles. Two knots were formed in the substantially central portion of the test body, and the clamps at the time of two stretching were "cut down. The speed was i 〇〇 mm / min ^ under the condition of real & 敎. The number of money was tested on 12 carbon fiber bundles. The minimum value and the maximum value are removed, and the average value of 1 G (four) is used as the measured value. "5. Measurement of energy generated on the surface of the carbon fiber bundle." The single fiber of the carbon fiber was cut into 2 cm, and the single fiber: In the thief of the single-fiber tensile test for the one-length coffee sample shown in the job 6, the excess portion exposed from the money is cut off and the sample is produced. Then, the samples fixed to the liner are irradiated with a laser, thereby forming a hemispherical defect. The laser interface system uses Micropoim (300 uJ pulse energy) manufactured by Photonic Instruments. The optical microscope necessary for laser concentrating uses ECLIPSE LV100 manufactured by Nikon Corporation. The aperture stop of the optical microscope is set to a minimum and the objective lens is set to 100 times. Under this condition, a laser beam having a wavelength of 435 nm after attenuating the laser intensity by attenuator is irradiated to the central portion of the sample in the central portion of the fiber axis direction and perpendicular to the fiber axis. Pulses form a hemispherical defect to obtain a sample. The sample attached to the backing paper was further sandwiched by a film so that the carbon fiber as a sample did not undergo shrinkage failure, and the film was filled with a viscous liquid to carry out a tensile test. Specifically, a film having a width of about 5 mm and a length of about 15 mm was prepared, and the film was attached to the upper portion of both sides of the liner of the sample using an adhesive material, and the liner was wrapped together with the film in such a manner as to cover the sample. The film was filled with an aqueous glycerin solution (ratio with respect to glycerin water of 2), and a tensile test was carried out at a tensile speed of α5 axis/axis to measure the breaking load.

Then, the sample which was divided into two halves in the tensile test was taken out from the master paper, and was carefully washed with water, and then naturally dried. Weaving, in the form of the fracture surface of the sample 'with carbon paste (Μ - the sample is fixed in SEM to make SEM observation sample. Fine Japanese electronics company manufacturing voltage is 10kv~15kv' magnification is drawn ~ 15000) on the obtained observation sample The fracture surface is made to look at 26 201107547^. / ν/ριί

The obtained SEM image analysis software was subjected to image analysis and area. For example, by wheeling into a personal computer, the image is used to measure the size of the hemispherical defect and the fiber section is used to plot the fracture load/fiber cross-sectional area = breaking strength (σ) and the size of the hemispherical defect (8). Slope. (2Ε/π〇1/2x (breaking surface generates energy) 2 (1) ... According to the formula (1), the energy generated by the fracture surface is obtained by the calculated slope and the ultrasonic elastic modulus (Ε) of the carbon fiber bundle. 6. Measurement of ipa value of carbon fiber bundle" The ipa value was measured by the following method: The electrolyte was adjusted to a pH of 3 using a 5% phosphoric acid aqueous solution, and nitrogen gas was bubbled to eliminate the influence of dissolved oxygen. One electrode and 'being in the electrolyte' counter electrode uses a platinum electrode having a charged surface area. Here, the reference electrode is an Ag/AgCl electrode. The sample is in the form of a 12,000 tow having a length of 50 mm. (filament tow) The scanning range of the potential applied between the carbon fiber electrode and the platinum electrode was set to -0.2 V to +〇·8 V 'the scanning speed was set to 2.0 mV/sec. Using the Χ-.γ recorder (XY recorder) The current-voltage curve is plotted and scanned three times or more. At the stage where the curve is stable, the current value i is read with respect to the potential of +0.4 V of the Ag/AgCl reference electrode as a reference potential, and ipa is calculated according to the following formula (3). Value. ipa=l (μΑ) / sample length ( Cm) χ{4πχ unit area weight (g/cm) X filament number/density (g/cm3) }1/2 (3) 27 201107547 From the length of the sample, as described in JIS R7601; 5* method The apparent surface area was calculated from the obtained sample density and unit area weight, and the ipa value was obtained by dividing the current value i. This measurement was carried out using a cyclic voltammetric analyzer P-ι 1 type manufactured by Ryumoto Seisakusho Co., Ltd. 7. Measurement of the amount of Si in the carbon fiber bundle" A sample of the carbon fiber bundle was placed in a platinum crucible having a known empty weight, and was ashed in a muffle furnace of 600 C to 700 C to measure the twisting. The ash is determined by weight, and then a predetermined amount of sodium carbonate is added, melted in a burner, and dissolved in deionized water while being fixed in a polyethylene measuring flask of (5) by ICP atomic emission spectrometry. The Si content of the sample was quantified. (Preparation Example 1 to Production Example 7 of the precursor fiber bundle) Precursor fiber (1) An acrylonitrile-based polymer having a composition of 98 wt% of acrylonitrile and 2 wt% of mercaptoacrylic acid Dissolved in dimethyl decylamine to prepare 23 5 wt% of the spinning dope. The spinning dope was self-configured with a diameter. .15mm, a number of 2000 injection nozzles are spun in a spinning nozzle for dry-wet spinning, that is, after being spun out into the air and passing through a space of about 5 mm, the temperature is 1 充满. The coagulation solution of the aqueous solution containing 79.0 wt〇/〇 dimercaptocarboxamide in °C was solidified 'extracted coagulated silk. Then it was extended 1.1 times in air, and then filled with tempering temperature of 6 (TC containing 35 wt% The extended solution of the aqueous solution of decylamine was extended 2.5 times. After stretching, the step fiber bundle containing the solvent is washed with clean water, and then '95. The hot water of the crucible extends 1.4 times. Then, on the 28 201107547 *; TO ! \J\Jli fiber bundles, the amines were changed to (4) oxygen as the main component (4) in a manner of 1.1 wt%, and the ship was densified. The densely woven fiber bundles of the dry ship are extended 2.6 times in the heating zone, and after further stepwise adjustment and densification, the 4 (tetra) nitrile edge __ dimensional bundle is taken up. Lai Wei's fineness is 0.77 dtex. The precursor fiber (2) was changed to 29 times in addition to the stretching ratio before the water washing treatment, and the hot water towel stretching ratio after washing was changed to 1 > twice, under the same conditions as the precursor fiber bundle (1). A precursor fiber bundle (7) is obtained. Precursor fiber (3) A pre-Lengling bundle (1) was obtained under the same conditions as the precursor filament (2) except that the fineness of the ruthenium fiber was changed to 〇 67 dtex. Precursor fiber (4) A precursor fiber bundle (4) was obtained under the same conditions as the precursor fiber bundle (7) except that the fineness of the ruthenium fiber was changed to 〇 9 〇 dtex. Precursor fiber (5) In addition to changing the stretching ratio before the water washing treatment to 41 times, the stretching ratio in the hot water after washing was changed to 〇.99 times, and the heating ratio was 2.4 times. The precursor fiber bundle (5) is obtained under the same conditions as the bulk fiber bundle (1). In the precursor fiber (6), the stretching ratio before the water washing treatment was changed to 丨9 times, and the stretching ratio in the hot water after washing was changed to 2.0 times, and the same conditions as in the precursor fiber bundle (1). The precursor fiber bundle (6) is obtained. 29 201107547 Precursor fiber (7) A precursor fiber bundle (7) was obtained under the same conditions as the precursor fiber bundle (2) except that the fineness of the precursor fiber was changed to 1.0 dtex. The manufacturing conditions of the precursor fiber bundles (1) to (7) are shown in Table 1. 30 201107547 Table 1 Precursor fiber spinning conditions Precursor fiber condensation H] Bath air in the extension tank hot water dry heat extension fineness temperature (°C) Concentration (%) Extension ratio temperature (°c) Concentration (%) Extension ratio Extension ratio magnification dtex precursor (1) 10 79.0 1.1 60 35 2.5 1.4 2.6 0.77 precursor (2) 10 79.0 1.1 60 35 2.9 1.2 2.6 0.77 precursor (3) 10 79.0 1.1 60 35 2.9 1.2 2.6 0 67 precursor C 4) 10 79.0 1.1 60 35 2.9 1.2 2.6 0 90 such as horse 5 body Q 5 ) 10 79.0 1.1 60 35 4.1 0.99 2.4 0 77 刖 drive cat 10 79.0 1.1 60 35 1.9 2.0 2.4 0.77 precursor (7 ) -it- VIST ΟΑ/1 η \ 10 79.0 1.1 60 35 2.9 1.2 2.6 1 00 No 5 body (8 eve 5 77.0 1.3 60 0 2.0 2.0 1.9 0.77 (Case 1 to Example 7, Comparative Example 1 to Comparative Example 4) (Carbon fiber bundle) Preparation) Introducing a plurality of precursor fiber bundles (1), (2), (3), (4), (5), (6), or (7) into a flameproof furnace in a state of being aligned in parallel The additional heat of the precursor fiber bundle is 22 (rc~28 (rc air), thereby preventing the precursor fiber bundle from being flame-proofed to obtain a density of防 345 g/em3 of flame-proof fiber bundle. The elongation is set to 6%, and the flame-proof treatment time is set to 7 〇 minutes. One mountain, then, in nitrogen, has a temperature gradient of 300 〇 〇〇 7 〇〇. In the first stone reversal, one of the flame-retardant fiber bundles is applied with a 4.5% elongation to pass through the furnace, and the temperature gradient is set to a linear gradient. The processing time is set to 2.0 minutes. In a nitrogen atmosphere, it can be set to 100 (TC~1_. (: 31 201107547, the first sin furnace, the specified temperature shown in Table 2 or Table 3) is programmed and processed. Then in a nitrogen atmosphere. The carbon fiber bundle was obtained by heat treatment using a third carbon tilt which can be set to a gradient of 1200 deg / cc, and the total elongation of the second carbonization furnace and the second rabbit furnace. _4 G%, the treatment time is 35 minutes. In the mountains, the carbon fiber bundle is passed through an aqueous solution of ammonium hydrogencarbonate, and the slave fiber is used as the anode, and the carbon fiber is treated as 4 〇Coul per 丨 (four). The electric raft is energized between the carbon fiber bundle and the opposite electrode, and is heated with 902⁄4 of warm water. Washed and dried. Then, 5 wt% of Hydran N320 (hereinafter referred to as "sizing agent 1") was attached to the carbon fiber bundle, and wound up on a bobbin (b〇bbin) to obtain a carbon fiber bundle. (Preparation of a unidirectional prepreg) The release of a B-staged epoxy resin #4i〇 (180〇C hardened type) (manufactured by Mitsubishi Rayon Co., Ltd.) was released. On the paper, 156 carbon fiber bundles drawn from the bobbin are aligned, and the carbon fiber bundle is impregnated with the epoxy resin by heating the crimping rolls. A unidirectionally aligned prepreg (hereinafter referred to as "UD prepreg" having a resin content of about 33 wt%" having a carbon fiber basis weight of 125 g/m2 and a width of 500 mm is formed thereon. ). (Formation of Laminates and Evaluation of Mechanical Properties) The laminate was formed by using the above UD prepreg, and the 0° tensile strength of the laminate was measured by an evaluation method according to ASTM D3039. The production conditions and evaluation results of the carbon fiber bundle are shown in Tables 2 and 3. Further, in any of the examples, the surface of the single fiber has no surface uneven structure extending in the longitudinal direction of the fiber and having a length of 0.6 μm or more, and a minute-sized uneven structure having a length of 300 nm or less is confirmed. 33 201107547 <Ν<

Jao/, οο inch ε Example 8 Precursor (2) 1050-1250 1 inch 1.005 1 0.035 1 6350 260 1250 v〇0.18 | 0.13 o 3240 Example 7 Precursor (2) 1200-1500 1550-1800 inch 1 1.005 1_ 0.035 1 6050 910 0.09 1 0.07 | CN o 3020 Example 6 Precursor (2) 1100-1301 1300-1501 wj Inch 1.005 1_ 0.035 6500 (N 1100 0.16 d S o 3300 Example 5 Precursor (2) 1050-1250 1250-1450 In inch 1.005 0.035 6700 S 1200 cn 0.17 ! 0.11 S o 3400 Example 4 Precursor (4) 1250-1300 1350-1550 Inch 1.005 0.041 6100 325 1000 en 0.15 ! 0.09 o 3100 Example 3 Precursor (3) 1250-1300 1350 -1550 inch 1.005 0.030 6400 m 1100 苤0.15 I 0.09 ! oo 3180 i Example 2 Precursor (2) 1250-1300 1350-1550 Inch 1.005 0.035 6300 335 1040 ro m 0.15 i 0.09 ! 120 o 3150 Example 1 Precursor (1 1250-1300 1350-1550 CO 1.005 0.035 6050 330 950 (N 0.15 i 0.09 o 3000 Carbon fiber bundle precursor fiber bundle type 2nd carbonization furnace temperature condition (°C) 3rd carbonization furnace temperature condition (°C) Height difference ( Rp-V) (nm) /-NI CO eti profile long diameter / short diameter single fiber unit area weight (mg/m) Strand strength (MPa) Strand elastic modulus (GPa) Nodule strength (N/mm2) Destruction energy (N/m) iPa (μΑ/cm2) | OIS/CIS i Si amount (ppm) Metal content (ppm) 〇° tensile strength of laminated sheets (60 vol% conversion) MPa inch e 201107547 jno / upii Table 3 Carbon fiber bundles Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Precursor fiber bundle type Precursor (5) Precursor (6) Precursor (7) Precursor (6) Precursor (8) 2nd carbonization furnace temperature condition (°C) 1250-1300 1250-1300 1250-1300 1200-1500 1250-1300 3 Carbonization furnace temperature conditions α) 1350-1550 1350-1550 1350-1550 1550-1800 1350-1550 Height difference (Rp-v ) (nm) 29 13 23 13 8 Ra (nm) 8 3 6 3 2 Long diameter of the profile / Short diameter 1.005 1.005 1.005 1.005 1.005 Single fiber basis weight (mg/m) 0.035 0.035 0.045 0.045 0.045 Strand strength (MPa) 5400 5700 5750 5200 5950 Strand elastic modulus (GPa) 330 330 315 355 325 Nodule strength (N /mm2) 650 750 850 630 790 Destruction energy (N/m) 29 30 30 28 29 iPa (μΑ/cm2) 0.18 0.15 0.15 0.09 0.15 OIS/CIS 0.12 0.10 0.09 0. 07 0.11 Si amount (ppm) 300 220 160 210 230 Metal content (ppm) 40 40 40 40 40 0° tensile strength of laminate (60 vol% conversion) MPa 2650 2700 2700 2400 2850 (Production example of precursor fiber bundle) 8) A spinning dope prepared in the same manner as in Production Example 1 was spun from a spinning nozzle equipped with a discharge hole having a diameter of 0.13 mm and a number of 2000, and dry-wet spinning was carried out. That is, it is spun out into the air and passed through a space of about 5 mm 35 201107547, and then solidified in a coagulating liquid containing an aqueous solution containing 77.0 wt% of dimethylguanamine at a temperature of 5 ° C to extract a coagulated wire. . Then, after extending 1.3 times in the air, it was extended 2.0 times in an extension tank filled with an aqueous solution adjusted to a temperature of 60 °C. After extension, the step fiber bundle was washed with clean water and then extended 2.0 times in hot water at 95 °C. Next, an oil agent containing an amine-based modified oxime as a main component was applied to the fiber bundle at a rate of 1.0 w t %, and dried and densified. The dried densified fiber bundle was extended 1.9 times between the heating rolls to further increase the alignment and densification, and then taken up to obtain a precursor fiber bundle. The fiber has a fineness of 0.77 dtex. (Example 8) A carbon fiber bundle was produced under the same calcination conditions as in Example 5 except that the third carbonization furnace was not used. Further, a laminate was produced in the same manner, and mechanical performance evaluation was performed to obtain the results of Table 2. Further, the surface of the single fiber did not have a surface uneven structure extending in the longitudinal direction of the fiber and having a length of 0.6 μm or more, and a small-sized uneven structure having a length of 300 nm or less was confirmed. (Example 9 to Example 11, Comparative Example 6 to Comparative Example 8) A carbon fiber bundle was obtained in the same manner as in Example 2 except that the calcination conditions were changed. The evaluation results are shown in Table 4. Further, in any of the examples, the surface of the single fiber has no surface uneven structure extending in the longitudinal direction of the fiber and having a length of 0.6 μm or more, and a small-sized uneven structure having a length of 300 nm or less is grafted. Table 4 36 201107547 JU0 Bu 8 inch ε Comparative Example 8 jj i , 丨 1 , 1 诛 city: 硪 -6.5% inch 1.005 0.035 5500 〇 1 - Η CO o OO 0.15 0.09 o 2600 Example 11 Δ Δ3 5 'Ί Μ Μ Zhu City: < -5.2% Inch 1.005 0.035 6050 mg 0.15 0.09 o 2980 Comparative Example 7 ♦ 5 1 7.2% Inch 1.005 0.033 5400 CO mo 00 cs 0.15 0.09 o 2500 Example 10 Ιΐφί Capture 3 5 1 City: Zhu 6.5% Inch 1.005 0.034 5900 Ό m cn o OS 0.15 0.09 o 2950 Comparative Example 6 Flame Resistance Elongation | _i 10.5% CN Inch 1.005 0.033 5300 O moo 0.15 0.09 o 2550 Example 9 Flame Resistance Elongation 8.0% Inch 1.05 0.034 6000 00 CO 〇 \ 0.15 0.09 o 3000 Carbon fiber bundle is different from the change condition of example 2 Project height difference (Rp-v) (nm) 1 «3 Pi section long diameter / short diameter single fiber unit area weight (mg / m) strand strength ( MPa) Strand elastic modulus (GPa) Destruction energy (N/m) Nodule strength (N/mm2) iPa (μΑ/cm2) 01S/C1S Si amount (ppm) Metal content (ppm) > δ 4 〇, 2 Forget: § _ sister ε ε 201107547 JT〇 / vpif (Example 12 and Example 13) In addition to changing the surface treatment conditions, The same manner as Example 5 to obtain a carbon fiber bundle. The evaluation results are shown in Table 5. Further, in any of the examples, the surface of the single fiber has no surface uneven structure extending in the longitudinal direction of the fiber and having a length of 0.6 μm or more, and a fine-sized uneven structure having a length of 300 nm or less has been confirmed. (Examples 14 to 16) A carbon fiber bundle was obtained in the same manner as in Example 5 except that the kind and the amount of the sizing agent were changed. The evaluation results are shown in Table 5. In any of the examples, the surface of the single fiber did not have a surface uneven structure extending in the longitudinal direction of the fiber and having a length of 〇.6 μηι or more, and a small-sized uneven structure having a length of 3 〇〇 nm or less was confirmed. Further, the sizing agent 2, the sizing agent 3, and the sizing agent 4 were prepared in the following manner. (Sizing agent 2) 80 parts by weight of "EPik〇te 828" manufactured by Japan Epoxy Resin Co., Ltd. as a main component, and 20 parts by weight of "JMunrniem" manufactured by Asahi Kasei Co., Ltd. as an emulsifier, The aqueous dispersion was prepared by phase inversion (10). (Sizing agent 3) Into the flask, a mixture of bisphenol A, propylene glycol, trimethyl methacrylate 8 8 mol, and an ear adduct 1. Polyol 3.2 mol, and then added ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ 0.2 g of sodium dilaurate was stirred until the mixtures reached homogeneity. Here, methyl ethyl ketone as a viscosity adjuster is added as needed. The addition zone was added dropwise to the homogeneously dissolved mixture. The xylene diisocyanate was 3.4 mol, and the polymerization of the urethane prepolymer was carried out while stirring at a reaction temperature of 50 C and a reaction time of 2 hours. Then, 0.25 mol of Epikote 834 (manufactured by JER Co., Ltd.) was added to react with an isocyanate group at the terminal of the urethane prepolymer, whereby an epoxy-modified amine phthalate resin was obtained. 90 parts by weight of the epoxy-modified amine phthalate resin was mixed with 1 part by weight of rPlur〇nic F88" manufactured by Asahi Kasei Co., Ltd. as an emulsifier, to prepare an aqueous dispersion. (Sizing agent 4) Into the flask, polyethylene glycol 400 2.5 m, Epikote 834 (manufactured by JER Yuehe Co., Ltd.) 0.7 mol was charged, and then 2,6-di (third butyl) as a reaction inhibitor was added. 4) Nonylphenol (BHT) 〇 25 g, 0.1 g of dibutyltin dilaurate as a reaction catalyst, and stirred until the mixture reached a uniform sentence. Here, the mercaptoethyl ketone as a viscosity adjuster is added as needed. An epoxy modified amino phthalate was obtained by dropwise addition of m-xylylene diisocyanate 2 7 mol to the uniformly dissolved mixture, and reacting at a reaction temperature of 4 〇〇c and a reaction time of 2 hours while stirring. Resin. The weight of the epoxy modified urethane resin was adjusted to 8 parts by weight of r plur〇nic F88" manufactured by Asahi Kasei Co., Ltd. as an emulsifier. 39 201107547 JU0Z-8 inch e Example 16 Sizing agent sizing agent 4 (with an adhesion of 0.4 wt%) 〇0.17 r—Η rH o 3350 Example 15 Sizing agent 1 | Sizing agent 3 (with an adhesion of 0.4 wt%) ο 0.17 0.11 1 3410 Example 14 Sizing agent sizing agent 2 (adhesion amount 0.4 wt%) ο ι> vcT 0.17 0.11 3050 Example 13 Surface treatment hydrogencarbonate 200 Coul/g ο ο ν 〇 0.24 0.16 3280 Example 12 Surface treatment of ammonium nitrate 8% 20 Coul/g ο inch Λ νο" 0.40 0.19 3000 carbon fiber bundle 冢απ CE 奉κ-strand strength (MPa) iPa (μΑ/cm2) OIS/CIS test r H 4郏O Np 〇0s * 201107547 JHO /νριι [Industrial Applicability] Material The carbon fiber bundle of the present invention can be used as a structure of "high-speed moving body, etc. Although the present invention has been disclosed as a preferred embodiment as above, the present invention is limited to any familiarity. The skilled person, in the residual target range of the present invention, can make some modifications and 7 arsenic range. The protection of the invention is attached to the patent application scope [Simple description of the drawing] No [Main component symbol description 】

Claims (1)

1 1201107547 VII. Patent application: 1. A carbon fiber bundle comprising a single fiber of carbon fiber as described below, that is, a surface uneven structure having a length of 0.6 μηι or more extending on the surface of the single fiber without extending along the longitudinal direction of the fiber The height difference (Rp_v) between the highest part and the lowest part of the surface of the single fiber is 5 nrn~25 nm, the average unevenness Ra is 2 nm~6 nm, and the long diameter and shortness of the fiber cross section of the single fiber The ratio of the diameter (long diameter/short diameter) is 1 (8) to 1 〇 1 ', and the weight per unit length of the single fiber of the carbon fiber is in the range of 〇3〇mg/m~〇〇42 mg/m, The wire strength is 5900 MPa or more, and the strand elastic modulus measured by the ASTM method is 25 〇 GPa to 38 〇 GPa, and the knot strength is 900 N/mm 2 or more. 2. A carbon fiber bundle comprising a single fiber of carbon fiber as described below, that is, a surface of the single fiber having no uneven structure extending in the longitudinal direction of the fiber and having a length of 0.6 μm or more, and having a length of 3〇〇 Below nm, the height difference (Rp_v) between the highest part and the lowest part of the surface of the single fiber is 5 nm to 25 nm, the average unevenness Ra is 2 nm to 6 nm, and the long diameter and shortness of the fiber cross section of the single fiber The ratio of the diameter (long diameter/short diameter) is 1 (8) to 1.01, and the weight per unit length of the single fiber of the carbon fiber is in the range of 0.030 mg/m to 0.042 mg/m, and the strand strength is 59 〇〇Mpa. The above-mentioned strand elastic modulus measured by the ASTM method is 25 〇Gpa~38〇GPa, and the knot strength is 9〇〇N/mm2 or more. 3. If you apply for a patent scope! The carbon fiber bundle according to Item 2, wherein a hemispherical defect having a predetermined range is formed on the surface of the single fiber by a laser, and the fiber is subjected to the hemispherical defect by a tensile test 42 201107547 jio / υμιϋ Π :: ' ί The fiber's breaking strength and hemispherical defects have a large energy of 3 GN/m or more: (4) Destructive surface = (2Ε/π〇1/2X (breaking surface energy) 1/2(1) number, Γ half The ultrasonic value of the carbon fiber bundle is 4 inflammatory. For example, the ipa value obtained by electrochemical measurement (cyclic voltammetry) of carbon H as described in any of items 1 to 3 of the patent range is hereinafter. 〇〇5 |^A/Cm2 η i 2 μ /em 'Using X-ray photoelectron light, the amount of oxygen-containing functional groups (01S/C1S) on the surface of the above carbon fiber is in the range of 0.05 to 0.15. The carbon fiber bundle according to any one of the items 1 to 4, wherein the amount of Si measured by 1CP atomic emission spectrometry is 200 ppm or less. 6. In the scope of the patent application, items 5 to 5 Any of the carbons as described in the present invention, which are tightened by the following sizing agent composition, The polymerization agent composition comprises: (a) an amino phthalate modified epoxy resin having a transbasic epoxy resin, (b) a polyhydroxy compound, and (c) a diisocyanate containing an aromatic ring; Or comprising: a mixture of the urethane-modified epoxy resin and (a) an epoxy resin having a trans-base group and/or (d) an epoxy resin having no hydroxyl group. The carbon fiber bundle, wherein the (a) epoxy group having a warp group is a bisphenol type epoxy resin. 8. The carbon fiber bundle according to claim 6 or claim 7, 43 201107547 wherein b) the polyhydroxy compound is any one of an alkylene oxide adduct of bisphenol A, an aliphatic poly-based compound, and a poly-based mono-reactive compound or a mixture of such compounds. The carbon fiber bundle according to any one of the items 6 to 8, wherein the (c) aromatic ring-containing diisocyanate is toluene diisocyanate or xylene diisocyanate. 10. The scope of claims 1 to 9 A carbon fiber bundle according to any one of the preceding claims, wherein The metal containing the test metal, soil test metal, zinc, iron and metal shall be less than 50 ppm in total. 44 201107547 IV. Designation of representative drawings: (1) The representative representative of the case is: None (2) A brief description of the symbol of the representative figure: No. 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: No 201107547 For the younger brother is Chinese_书___ .........*-3⁄43⁄4 Modified bowing period of 10 years to use 4$ j -7- '.t method to obtain excellent composite materials and ',---------------一一一^ Enlarge, fiber age ^ A \ , due to the graphite crystal size of the surface < 90 of the composite material. ^ ^, the adhesion of the matrix tree wax is reduced, resulting in complex ii =. N;. (4) Material 9°. Nw or more. The intensity of the upper ship section is more 〇, and the better the step is to make 2 or more. The fiber outside the direction of the axis of the axis; ^ can easily see the direction perpendicular to the fiber axis by quasi-isotropic lamination to form a material, forming a complex I, ', in addition to the fiber axis direction of the stretching, compression In addition to stress, also the stress in the direction of the dimension axis. In addition, in the case where phase, interstitial, and/or k are applied as in the impact test, the state of stress generated inside the material is very complex and heterogeneous, and the strength (4) which is not in the direction of the fiber axis is important. Therefore, if the knot strength is less than 900 NW, the quasi-isotropic material cannot find sufficient mechanical properties. On the other hand, when the knot strength exceeds 3 〇〇〇 running melon 2, it is necessary to reduce the orientation of the fiber axis direction. Therefore, the knot strength should be 3_N/mm2 or less. Further, the carbon fiber bundle of the present invention preferably has a breaking surface generating energy of 30 N/m or more. For the energy generated by the damage surface, a hemispherical defect having a predetermined range can be formed on the surface of the single fiber by using a laser, and the fiber is broken at the hemispherical defect portion by a tensile test, and the fiber is broken. The strength and the size of the hemispherical defect are obtained by using the following Griffith 11 201107547 IE date: 99 years, 1 month, 4th, and the 99118900 Chinese manual without the slash correction stomach (Griffith) formula (1). σ= (2Ε/π〇1/2χ (breaking surface energy) 1/2 (1), medium σ is the breaking strength, £ is the ultrasonic _ number of the fiber and the beam, and C is a hemispherical defect. The size of the damaged surface generates energy = N / m or more 'further better than 32] S [ / m or more ... ... one of which, the energy generated by the damage is an indicator of the difficulty of carbon fiber damage, indicating the matrix strength (matrix stmigth). Carbon _ ^ _跪: Bad ^ Material's tensile strength is affected by the defect point. When the rhyme dimension has the same defect, the higher the matrix strength of the carbon fiber, the higher the damage strength. Then, the critical fiber length of the fruit, which is the index of stress transmission, becomes shorter. Thus, the intensity of =卞! reflects the strength at a shorter length, and the strength of the matrix is two important indicators. On the other hand, when the surface is destroyed, the energy generated by the bad surface should be 利用 中 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用a large degree of engraving (ethehing) of carbon fiber door 1 aniGn) The rabbit fiber that enters the interlayer of the graphite crystal layer has a large presence of oxygen-containing green, and the occupational fishing, the galvanic layer 201107547 Revision date: October 4, 1999 Japanese Patent No. 99118900 No-line correction page Amino phthalate-modified epoxy resin which is a reaction product of an aromatic ring-containing diisocyanate (hereinafter referred to as component (c)). The reaction filament obtained by introducing the excess amount of the component (a) required for the reaction into the reaction system, that is, the amino acid formic acid, is a mixture of the epoxy resin and the unreacted material of the component (4). A mixture of an amine phthalic acid-modified epoxy resin disc (4) 〇❹ it obtained by using an epoxy resin having no warp group (hereinafter referred to as a component (4) as appropriate) is exemplified. Epoxy resin, U) as a mixture of (d) components. The interaction of the epoxy group with the oxygen-containing functional group of the cotton surface makes it possible to firmly adhere the sizing agent component to the surface of the carbon fiber. And containing aromatic rings The isocyanic acid produced by the diisocyanate vinegar can be made to interact with each other by using the amino carboxylic acid phase :: the amine group having the polarity of the carbon fiber surface and the epoxy group having the polar group and the above Amino carboxylic acid ketone bond 砉 :: 目 酉曰 酉曰 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 : Because of: two: ̄ 酬 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂Epoxy resin, acid glycidyl vinegar epoxy tree 201107547 Revision date: October 4, 1999 is the 99118900 Chinese manual without a slash correction page. It is especially suitable for double age epoxy resin. These compounds have strong interaction with the surface of the fiber due to the aromatic ring. Further, in view of heat resistance and straightness, an epoxy resin having an aromatic ring is often used as a matrix resin for a composite material, and the above compound is excellent in compatibility with the substrates. Two or more epoxy resins may be used as the component (a). Further, (b) "different is an epoxidized calcined adduct, a fatty sulphate compound, a multi-secret single compound, and θ is composed of a mixture of these compounds. It is the fact that these compounds make the above-mentioned aminocarboxylic acid soft from the epoxy resin which is intended to be modified. And body two: two: Yuan Oxygen Boiler 4 Moule ~ 14 Moer Additives, Double Fracture A Ring = Mo: Additives, A's Epoxy Institute, Ethylene Acetate & Lose & Silk Addition, red diol (saki her kiss (10), two methyl (5) methyl. 丨 罐 )), dimethopropionate and so on. Further, the component (4) is not particularly limited. Particularly preferred is toluene diisocyanate or - diisocy minus). m - a resin with more than two lobe based on Uylene 异. The reason is that the interaction between the surface and the epoxy group is strong, and the compounds are strong on the surface. There is no _ φ) for the surface of the county base, and ® A ^ j is used for the chlorohydrin group. _ Epoxy Reversible: Resin, Bisphenol A Type Epoxy Resin, Novolac:: ( dicydopenta^ene type ) ^ 22 201107547 ΕΠ 叹 2 2 玢66^1113: 矾Μ3Ι_ Dust 戡_1«佧黯006ΟΟΙ 166 派赖〇' >ο, ΙΡΚ than car example 8 take Λ 3 5 '丨1 Ί ^ -6.5% inch 1.005 Τ S S 500 500 500 500 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 City: --5.2% m inch 1 1.005 ί_ 0.035 6050 m 窆ON o 0.09 ο 2980 Comparative Example 7 Ulj>i 5 1 City: 跻7.2% cn inch 1.005 0.033 5400 m ro o in 00 CN vn o 0.09 ο 2500 Example 10 Take JJ 5 1 City: Fast 6.5% Inch 1.005 0.034 5900 vo m cn 〇 ON 0.15 L^O—9 ο 2950 Comparative Example 6 Flameproofing elongation 10.5% CN Inch 1.005 0.033 5300 omo Bu 0.15 0.09 < ο 2550 Example 9 8.0% CO Inch 1.005 0.034 6000 00 m ON 0.15 0.09 ^"4 ο 3000 Carbon fiber bundle is different from the change condition of Example 2 Item height difference (Rp-V) (nm) Ra (nm) Profile length/short Single fiber per unit area Weight (mg/m) Strand strength (MPa) Strand elastic modulus (GPa) Nodule strength (N/mm2) Destruction energy Quantity (N/m) iPa (μΑ/cm2) 01S/C1S Si amount (ppm) Metal content (ppm) 1. Want to take 4 〇 ^ ° 201107547 Revision date: October 4, 1999 is the 99118900 Chinese manual Scribing correction page (Example 12 and Example 13) A carbon fiber bundle was obtained in the same manner as in Example 5 except that the surface treatment conditions were changed. The evaluation results are shown in Table 5. Further, in any of the examples, the surface of the single fiber has no surface uneven structure extending in the longitudinal direction of the fiber and having a length of 〇 6 μΠ1 or more, and a fine-sized uneven structure having a length of 300 nm or less has been confirmed. (Example 14 to Example 16) A carbon fiber bundle was obtained in the same manner as in Example 5 except that the type and the amount of the sizing agent were changed. The evaluation results are shown in Table 5. In any of the examples, the surface of the single fiber has no surface uneven structure extending in the longitudinal direction of the fiber and having a length of 〇·6 μm or more, and a small-sized uneven structure having a length of less than . The Φ external watering agent 2, the uppering agent 3, and the sputum agent 4 are prepared as follows. (Sizing agent 2) ^ 乍 manufactured by Japan Epoxy Resin Co., Ltd. as the main agent. Γ! 2 "8" 8G rereading, Asahi Chemical Co., Ltd. as an emulsifier is limited to prepare an aqueous dispersion.重 U , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , .6 Mo's shape (first day H Mo' and then added 2,6-di (second butyl) 4_mercaptobenzene (酣) Q 5g as a reaction catalyst 38 201107547 [Industrial Applicability] The money beam of the present invention can be used as an aircraft material. Structure of a moving body or the like Although the present invention has been disclosed in a preferred embodiment, the cup button outer feather LL bucket - soil However, it is not intended to be used in the context of the invention, and may be modified and retouched without departing from the spirit of the invention, and thus the scope of the invention is defined by the scope of the appended claims. Quasi. ', sigh [Simplified description of the schema] Benefit [main component symbol description] Yi t Ο 41 201107547 Revision period: 99 years l 〇 4 For the Chinese patent model No. ___ VII, the scope of application for patent: a carbon fiber bundle 'containing a single fiber of the carbon fiber as described below; the surface of the single age does not extend along the length of the fiber and the length (four). / Γ The surface uneven structure, and the height difference (Κρ·ν) of the highest part and the lowest part of the surface of the single fiber is 5 _~25 nm, the average unevenness 2 is a concave-convex structure of 2 nm 〜6 _, and the fiber cross-section of the single fiber The ratio of the diameter (long diameter/short diameter) (four) to 1.01, and the weight per unit length of the carbon fiber in the early age is in the fine G/m~0042 In the range of mg/m, the strand strength is 5900 MPa or more, and the ASTM method = then the (10) line elastic modulus is used, and the nodule strength is 900 N/mm or more. A type of shunting bundle comprising a heterogeneous single fiber as described below on the surface of the monofilament, without extending along the length of the fiber and long Ϊ is a concavo-convex structure of 6 μΠ1 or more and has a length of 300 rnn or less, and the height difference (Rp_v) of the highest and the lowest part of the early fiber table is 5 nm to 25 nm. The average unevenness is 2 nm to 6 _. And the ratio of the long diameter to the short diameter (long diameter/minor diameter) of the single-dimensional fiber section is 1.00 1.01 and the weight per unit length of the single fiber of the edge carbon fiber is 0.030 mg/m~〇.042 mg/ In the range of m, the strand strength is 5900 MPa or more, the strand elastic modulus measured by the ASTM method is 250 GPa to 380 GPa, and the knot strength is 900 N/mm 2 or more. Gans 3. For example, the carbon fiber bundle described in the first or second item of the May patent (4) uses a laser to form a hemispherical defect of a size in the range of a single surface, by a tensile test. The above-mentioned fibers are in the above-mentioned hemispherical shape. 42 201107547 is the 119th brain No. 0 Chinese patent range without a slash correction. The correction date is on October 4, 1999, and the rupture strength and hemispherical defects of the above fibers are broken. The large J uses the fracture surface obtained by Griffith's formula (1) to generate energy of 30 N/m or more: σ = (2E/?tC) 1/2Χ (breaking surface generates energy) 1/2 (1) , σ is the breaking strength, Ε is the ultrasonic elastic modulus of the carbon fiber bundle, and C is the size of the hemispherical defect. 4. If the carbon fiber bundle is referred to in item i or item 2 of the patent scope, ❹=use electrification The ipa value obtained by the method of measurement (cyclic voltammetry) is + μΑ/=~〇·25 _/cm2 'The amount of oxygen-containing functional group on the surface of the carbon fiber is determined by the ray-ray photoelectron spectroscopy method (〇ls /cls) is in the range of 〇〇5 to 〇·15. 1 Apply for the carbon described in item 1 or 2 of the patent scope. Dimensional beam, ' ^pm below. 1〇> Atomic emission spectrometry determined the amount of Si is 200. After 6 times miin1 2 items of fiber bundle 'ring; multi-homed compound and (4) contains aromatic or inclusion reaction product That is, the amine group (4) is intended to modify the epoxy resin; 7 , a mixture of the oxy group-containing oxy-resin. (a) The carbon fiber bundle of the ninth item, wherein the above-mentioned 8:, f 2 The Huang 3 resin is a bisphenol type epoxy resin. ' (b) The carbon fiber bundle described in Item 6 of the above, wherein the above-mentioned compound is a double-test A epoxy burnt adduct, Aliphatic poly 43 201107547 is the Chinese patent scope of No. 99118900. There is no slash correction. This revision date: any one of the base compound and the polycarboxy mono-rebel compound on October 4, 1999 or a mixture of these compounds. The carbon fiber bundle according to claim 6, wherein the (c) aromatic ring-containing diisocyanate is toluene diisocyanate or diterpene diisocyanate. 10. According to claim 1 or 2 Carbon fiber bundle, which comprises alkali metal, soil test metal, zinc, iron Ming the total amount of metal contained in the gauge is less than 50 ppm. 44