JPWO2010143681A1 - Carbon fiber bundle with excellent mechanical performance - Google Patents

Abstract

A carbon fiber bundle for obtaining a fiber reinforced resin having high mechanical properties is provided. There is no surface irregular structure with a length of 0.6 μm or more extending in the longitudinal direction of the fiber on the surface of the single fiber, and the average unevenness degree is 5-25 nm in height difference (Rp-v) between the highest and lowest parts of the surface of the single fiber. Ra has a concavo-convex structure of 2 to 6 nm, and comprises a single fiber of carbon fiber having a ratio of a long diameter to a short diameter (long diameter / short diameter) of a single fiber of 1.00 to 1.01. The mass per unit length of the single fiber is in the range of 0.030 to 0.042 mg / m, the strand strength is 5900 MPa or more, the strand elastic modulus measured by the ASTM method is 250 to 380 GPa, and the knot strength is A carbon fiber bundle that is a carbon fiber of 900 N / mm 2 or more.

Description

  The present invention relates to a carbon fiber bundle having excellent mechanical properties, particularly for obtaining a fiber reinforced resin having a high toughness and heat resistant resin for use in aircraft as a matrix.

  Conventionally, for the purpose of improving the mechanical properties of a resin-based molded product, it has been generally performed to combine a fiber with a resin as a reinforcing material. In particular, molding materials made by combining carbon fibers with excellent specific strength and specific elasticity with high-performance resins exhibit very excellent mechanical properties, so they should be used as structural materials for aircraft, high-speed moving bodies, etc. Is being actively promoted. In addition, there is a demand for higher strength and higher rigidity, and further there is a demand for a material excellent in specific strength and specific rigidity, and the realization of higher strength and higher elastic modulus is required for carbon fiber performance.

  For example, when a precursor acrylic fiber bundle for carbon fiber is obtained by a dry-wet spinning method, there is a method for improving the uniformity of structure and orientation by drawing a coagulated yarn containing a solvent in a solvent-containing drawing bath. This is proposed in Patent Document 1. Stretching the solidified yarn in a bath containing a solvent is a method generally known as a solvent stretching technique, and is a technique that enables a stable stretching process by solvent plasticization. Therefore, it is considered that the technique for obtaining fibers with high uniformity in structure and orientation is very excellent. However, by stretching a fiber bundle that contains a solvent and is in a swollen state, the solvent present inside the filament is rapidly squeezed out of the filament as it is stretched, so that the resulting filament can easily form a sparse structure. , It cannot have the intended dense structure.

  Further, Patent Document 2 proposes a technique for obtaining a precursor fiber excellent in strength development by paying attention to the pore distribution of the coagulated yarn and drying and densifying the coagulated yarn having a high densified structure. Yes. The pore distribution obtained by the mercury intrusion method reflects the bulk properties including the inside from the surface of the filament, and is a very excellent method for evaluating the denseness of the overall structure of the fiber. is there. High-strength carbon fibers with suppressed defect point formation can be obtained from precursor fiber bundles having an overall denseness level or higher. However, when the rupture state of the carbon fiber is observed, there is a very high ratio of the rupture start in the vicinity of the surface layer. This means that a defect point exists in the vicinity of the surface layer. That is, this technique is insufficient for producing a precursor fiber bundle having excellent denseness in the vicinity of the surface layer.

  Patent Document 3 proposes a method for producing an acrylonitrile-based precursor fiber bundle that has high density as a whole and extremely high density in the surface layer portion. Patent Document 4 proposes a technique that suppresses the penetration of the oil agent by focusing on the micro voids in the surface layer portion because the oil agent enters the fiber surface layer portion to inhibit densification. However, both the technology for suppressing the intrusion of oil and the technology for suppressing defect point formation are difficult to put into practical use because they require very complicated processes. For this reason, in the technique currently examined, the effect which suppresses the oil agent penetration | invasion to the surface layer part stably is inadequate, and it was the situation which cannot be said that the high-strength effect of carbon fiber is still a sufficient level.

JP-A-5-5224 JP-A-4-91230 Japanese Patent Publication No. 6-15722 Japanese Patent Laid-Open No. 11-124744

  An object of the present invention is to provide a carbon fiber bundle for obtaining a fiber reinforced resin having high mechanical properties.

The said subject is solved by the following this invention.
In the present invention, the surface of the single fiber does not have a surface uneven structure having a length of 0.6 μm or more extending in the longitudinal direction of the fiber, and the height difference (Rp-v) between the highest part and the lowest part of the surface of the single fiber is 5 to 25 nm. The carbon fiber has a concavo-convex structure with an average roughness Ra of 2 to 6 nm, and the ratio of the major axis to the minor axis (major axis / minor axis) of the fiber section of the single fiber is 1.00 to 1.01. It consists of fibers, the mass per unit length of a single fiber is in the range of 0.030 to 0.042 mg / m, the strand strength is 5900 MPa or more, the strand elastic modulus measured by the ASTM method is 250 to 380 GPa, The carbon fiber bundle is a carbon fiber having a knot strength of 900 N / mm ² or more.
The knot strength is obtained by dividing the tensile breaking stress of a carbon fiber bundle knotted by the cross-sectional area (mass and density per unit length) of the fiber bundle.

  According to the carbon fiber bundle of the present invention, it is possible to provide a fiber reinforced resin having high mechanical properties.

  Further, when the fracture surface generation energy is 30 N / m or more, a carbon fiber bundle having more excellent performance is obtained.

Furthermore, the ipa value calculated | required by the electrochemical measuring method (cyclic voltammetry) is 0.05-0.25 microampere / cm < ² >, and the oxygen containing functional property of the carbon fiber surface calculated | required by X ray photoelectron spectroscopy By using a carbon fiber bundle having a surface such that the base amount (O1S / C1S) is in the range of 0.05 to 0.10, a carbon fiber composite material having very high mechanical performance can be obtained.

  The surface uneven structure extending in the longitudinal direction of the fiber existing on the surface of the carbon fiber and the sizing agent attached to the surface play a very important role in expressing the mechanical properties of the fiber reinforced resin material using the carbon fiber as a reinforcing material. This is because the surface concavo-convex structure and the sizing agent attached to the surface are directly related to the formation of the interfacial phase between the carbon fiber and the resin and the characteristics thereof. The mechanical performance of the fiber reinforced resin material is affected by the performance of each of the three elements constituting the fiber, matrix resin, and interfacial phase. If even one of these three elements has poor performance, the fiber-reinforced resin material cannot exhibit excellent mechanical performance.

(Uneven surface structure extending in the longitudinal direction of the fiber on the surface of the single fiber)
Due to the general manufacturing method of carbon fiber bundles, ordinary carbon fibers have a surface uneven structure substantially parallel to the fiber axis direction. This concavo-convex structure has a wavy structure that is substantially parallel to the fiber axis and extends in the fiber axis direction. The depth of the unevenness is usually about 50 nm to several hundred nm, and the length is usually about 0.6 μm to several μm, and in some cases, several tens of μm. This surface concavo-convex structure is usually referred to as a surface defect.
The carbon fiber bundle of the present invention does not have an uneven surface structure having a length of 0.6 μm or more extending in the longitudinal direction of the fiber on the surface of the single fiber.

  On the other hand, the carbon fiber bundle of the present invention has a concavo-convex structure having a smaller size than the concavo-convex structure on the surface of the single fiber. The depth of the surface uneven structure existing in the single fiber of the carbon fiber is the difference in height between the highest part and the lowest part of the fiber surface in a range surrounded by a circumferential length of 1.0 μm and a length in the fiber axis direction of 1.0 μm. It is defined by (Rp-v) and average unevenness Ra. The (Rp-v) and Ra are obtained by scanning the surface of a single fiber using a scanning atomic force microscope (AFM). It is desirable that the height difference (Rp-v) is 5 to 25 nm and the average roughness Ra is 2 to 6 nm. More preferably, (Rp-v) is 5 to 18 nm, and Ra is 2 to 5 nm.

  In the present invention, each single fiber constituting the carbon fiber does not have a surface uneven structure having a length of 0.6 μm or more extending in the longitudinal direction of the fiber on the surface of the single fiber. In the interfacial phase of the composite material, such a large-sized surface uneven structure tends to be a stress concentration portion. Furthermore, the carbon fiber structure near the concavo-convex structure has low fracture toughness. Therefore, in the surface uneven structure of this size, even in the state where the stress level applied to the composite material is not so high, the vicinity of the uneven structure is likely to be the starting point of interface fracture. As a result, the mechanical performance of the composite material is greatly reduced.

A more specific aspect of the uneven structure on the surface of each single fiber constituting the carbon fiber of the present invention is as follows.
Usually, the surface of the carbon fiber has a concavo-convex structure that is a ridge-like structure with a length of 0.6 μm or more extending in the longitudinal direction of the fiber, and a size larger than the concavo-convex structure that is this cocoon-like structure. Is small, and has a fine concavo-convex structure existing in each fibril body itself.
That is, the surface of each single fiber constituting the carbon fiber of the present invention does not have an uneven structure with a length of 0.6 μm or more extending in the longitudinal direction of the fiber, and the size is smaller than such an uneven structure. Only the minute uneven structure existing in each fibril body is present. Further, the minute uneven structure has a length of 300 nm or less. This uneven structure is indicated by the above (Rp-v) and Ra. In other words, the height difference (Rp-v) is 5 to 25 nm and the average roughness Ra is 2 to 6 nm within the range surrounded by the circumferential length of 1.0 μm and the fiber axis direction length of 1.0 μm. It is undulating. Preferably, (Rp-v) is 5 to 18 nm and Ra is 2 to 5 nm. There is no particular limitation on the direction of the minute concavo-convex structure, and it is parallel to, perpendicular to, or at a certain angle to the fiber axis direction.

(Fiber cross section of single fiber)
Further, the ratio of the major axis to the minor axis (major axis / minor axis) of the fiber cross section of the single fiber is required to be a single fiber having a perfect circle or a cross section close to a perfect circle. is there. This is because, due to the perfect circle, the structural uniformity in the vicinity of the fiber surface is excellent, so that stress concentration can be reduced. This ratio is preferably 1.00 to 1.005. Furthermore, for the same reason, the mass per unit length of the single fiber is 0.030 to 0.042 mg / m. The small mass per unit length of the fiber (single fiber basis weight) means that the fiber diameter is small, the non-uniformity of the structure existing in the cross-sectional direction is small, and the mechanical performance in the direction perpendicular to the fiber axis is high. means. Therefore, in the composite material, resistance to stress in a direction perpendicular to the fiber axis is improved, and the mechanical performance as the composite material can be increased.

(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 needs to be 5900 MPa or more. The strand strength of the carbon fiber bundle is preferably 6000 MPa or more, more preferably 6100 MPa or more. Higher strand strength is preferable, but 10,000 MPa is sufficient as a composite material in consideration of the balance with compressive strength. 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 needs to be 250 to 380 GPa as measured by the ASTM method. If the elastic modulus is less than 250 GPa, the elastic modulus as a carbon fiber bundle is insufficient, and sufficient mechanical properties cannot be expressed. On the other hand, when the elastic modulus exceeds 380 GPa, the surface and internal graphite crystal sizes of the carbon fibers increase, and the fiber cross-sectional direction strength and fiber axis direction compressive strength decrease accordingly, and the tensile and compression performance as a composite material The balance is not good and as a result, an excellent composite material cannot be obtained. Furthermore, the inactivation progresses due to the enlargement of the surface graphite crystal size, and the adhesiveness with the matrix resin decreases, and the tensile strength, interlaminar shear strength, in-plane shear strength and 0 ° of the composite material are reduced. A significant decrease in mechanical performance such as compressive strength appears.

Furthermore, in the present invention, it is important that the knot strength obtained by dividing the tensile breaking stress of the carbon fiber bundles knotted by the cross-sectional area (mass and density per unit length) of the fiber bundle is 900 N / mm ² or more. . More preferably, it is 1000 N / mm ² or more, and still more preferably 1100 N / mm ² or more. The knot strength can be an index reflecting the mechanical performance of the fiber bundle other than in the fiber axis direction, and particularly the performance in the direction perpendicular to the fiber axis can be easily seen. In a composite material, a material is often formed by quasi-isotropic lamination, and a complex stress field is formed. At that time, in addition to tensile and compressive stresses in the fiber axis direction, stresses in the fiber axis direction are also generated. Furthermore, when a relatively high-speed strain is applied as in an impact test, the stress state generated in the material is quite complicated, and the strength in a direction different from the fiber axis direction is important. Therefore, when the knot strength is less than 900 N / mm ² , sufficient mechanical performance is not exhibited in the pseudo-isotropic material. On the other hand, when it exceeds 3000 N / mm ² , it is necessary to lower the orientation in the fiber axis direction. Therefore, the nodule strength should be 3000 N / mm ² or less.

  The carbon fiber bundle of the present invention preferably has a fracture surface generation energy of 30 N / m or more. The fracture surface generation energy is determined by forming a hemispherical defect having a size within a predetermined range with a laser on the surface of a single fiber, and breaking the fiber at the hemispherical defect site by a tensile test. Is obtained from the following Griffith equation (1).

σ = (2E / πC) ^1/2 × (Fracture surface generation energy) ^1/2 (1)
Here, σ is the breaking strength, E is the ultrasonic elastic modulus of the carbon fiber bundle, and c is the size of the hemispherical defect. The fracture surface generation energy is more preferably 31 N / m or more, and even more preferably 32 N / m or more.

  Here, the fracture generation energy is an index of the difficulty of breaking the carbon fiber, and represents the substrate strength. Carbon fiber is a material that exhibits brittle fracture, and its tensile strength is governed by defect points. When the carbon fiber has the same defect point, the higher the substrate strength, the higher the breaking strength. In addition, many matrix resins for high-performance composite materials have high adhesion to carbon fibers, and as a result, the critical fiber length that serves as an index of stress transmission is shortened. As a result, the strength of the composite material reflects the strength at a shorter length, and the substrate strength is considered to be an important index. On the other hand, when it exceeds 50 N / m, it is necessary to lower the orientation in the fiber axis direction. Therefore, the fracture generation energy should be 50 N / m or less.

In the present invention, the ipa value obtained by an electrochemical measurement method (cyclic voltammetry) is preferably 0.05 to 0.25 μA / cm ² . This ipa value is influenced by the number of oxygen-containing functional groups of the carbon fiber, the degree of surface unevenness involved in forming the electric double layer, and the fine graphite structure on the surface of the carbon fiber. In particular, carbon fibers that have undergone large etching of the surface layer and carbon fibers that form an intercalation compound in which anion ions enter between graphite crystals have large values. In composite materials that exhibit excellent mechanical performance, the interface between carbon fiber and resin is important, especially carbon fiber with a suitable oxygen-containing functional group and a surface that forms a small electric double layer is optimal. It was found to form a new interface. When the ipa value is 0.05 μA / cm ² or more, it indicates that sufficient oxygen-containing functional groups are present on the surface, and has sufficient interfacial adhesion. On the other hand, when the ipa value is 0.25 μA / cm ² or less, the surface is not excessively etched, and no intercalation compound is formed. Such a surface can be firmly bonded to the matrix resin, and as a result, has sufficient interfacial adhesion to the resin. More preferably, it is 0.07-0.20 microampere / cm < ² >, More preferably, it is 0.10-0.18 microampere / cm < ² >.

  Furthermore, in the present invention, it is desirable that the carbon fiber has an oxygen-containing functional group amount (O1S / C1S) on the surface of the carbon fiber determined by X-ray photoelectron spectroscopy in the range of 0.05 to 0.15. This is because it is important to have an appropriate interfacial adhesion with the matrix resin.

  In the present invention, the Si amount measured by ICP emission analysis is desirably 200 ppm or less. In order to produce a high-strength carbon fiber, a silicone oil-containing oil agent is usually adhered to the precursor fiber bundle. Silicone oil is very excellent in heat resistance and can provide excellent release properties. For this reason, the filament diameter is very small, it has a form of a multifilament bundle formed by aggregating many of these filaments, and is further subjected to processing at a high temperature of 200 ° C. or more for several tens of minutes to several hours. It is considered to be the most suitable for the oil agent of the carbon fiber precursor fiber bundle. However, in the carbonization treatment performed after the flameproofing treatment, most of these silicone oils are decomposed and scattered, and the amount of the silicone compound remaining on the surface of the carbon fiber is very small. Further, it is known that the remaining silicone compound is present in the vicinity of the surface layer of the carbon fiber and causes void formation. Therefore, by reducing such a silicone compound as much as possible, carbon fibers with few voids can be produced, and as a result, the strength of the carbon fiber bundle can be increased. A more preferable amount of Si is 150 ppm or less, and a more preferable amount of Si is 100 ppm or less.

(Precursor fiber bundle and manufacturing method thereof)
Although there is no restriction | limiting in particular as a starting raw material which obtains the carbon fiber bundle of this invention, The thing obtained from an acrylonitrile type | system | group precursor fiber (henceforth "precursor fiber" suitably) is preferable from a viewpoint of mechanical performance expression.
The acrylonitrile copolymer constituting the precursor fiber is obtained from 96% by mass or more of acrylonitrile and several kinds of copolymerizable monomers. More preferably, the composition ratio of acrylonitrile is 97% by mass or more. Examples of copolymer components other than acrylonitrile include acrylic acid derivatives such as acrylic acid, methacrylic acid, itaconic acid, methyl acrylate, methyl methacrylate, acrylamide, methacrylamide, N-methylol acrylamide, N, N-dimethylacrylamide, and the like. Suitable are acrylamide derivatives and vinyl acetate. 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 the monomer mixture may be, for example, redox polymerization in an aqueous solution or suspension polymerization in a heterogeneous system and emulsion polymerization using a dispersing agent, or any other polymerization method. The present invention is not limited by the differences. The precursor fiber is preferably prepared by dissolving the acrylonitrile-based polymer described above in an organic solvent such as dimethylacetamide, dimethylsulfoxide, dimethylformamide or the like to prepare a spinning dope. Since these organic solvents do not contain a metal component, the content of the metal component in the obtained carbon fiber bundle can be lowered. The solid concentration of the spinning dope is preferably 20% by mass or more, and more preferably 21% by mass or more.

  The spinning method may be either wet spinning or wet and wet spinning. More preferred is dry and wet spinning. In dry and wet spinning, the prepared spinning solution is spun into air from a spinneret with a large number of discharge holes, and then discharged into a coagulating liquid filled with a mixed solution of temperature-controlled organic solvent and water for coagulation. The coagulated yarn is taken out and then washed and stretched. Any cleaning method may be used as long as the solvent can be removed. In addition, a fibril structure can be formed by extending | stretching in the pre-drawing tank with a solvent concentration lower than coagulation liquid and high temperature before wash | cleaning the taken-up coagulated yarn. When the coagulated yarn is drawn, the temperature of the drawing tank is preferably in the range of 40 to 80 ° C. If the temperature is less than 40 ° C., the stretchability cannot be ensured and the stretching becomes impossible, and a uniform fibril structure cannot be formed. On the other hand, when the temperature exceeds 80 ° C., the plasticizing action due to heat becomes too large, the solvent removal on the surface of the yarn proceeds rapidly, and the stretching becomes uneven, and the quality of the precursor fiber bundle deteriorates. . A more preferable temperature is 50 to 75 ° C. The concentration of the stretching tank is preferably 30 to 60% by mass. If it is less than 30% by mass, stable stretchability cannot be ensured, and if it exceeds 60% by mass, the plasticizing effect becomes too large and the stable stretchability is impaired. A more preferable concentration is 35 to 55% by mass.

  The stretching ratio in this stretching tank is preferably 2 to 4 times. If it is less than 2 times, the stretching is insufficient, and a desired fibril structure cannot be formed. On the other hand, if the stretching exceeds 4 times, the fibril structure itself is broken, resulting in a precursor fiber bundle having a very sparse structural form. A more preferable draw ratio is 2.2 to 3.8 times, and further preferably 2.5 to 3.5 times.

  In addition, after washing, it is possible to further enhance the fiber orientation by stretching the process fiber bundle in a swollen state with no solvent content in hot water. It is also possible to remove distortion. Preferably, the stretching is performed 1.1 to 2.0 times in hot water for the purpose of increasing the total stretching ratio and increasing the fiber orientation.

Next, an adhesion treatment is performed so that the oil agent composed of the silicone compound becomes 0.8 to 1.6% by mass, and the resultant is dried and densified. Dry densification is not particularly limited as long as it is dried and densified by a known drying method. A method of passing a plurality of heating rolls is preferable.
The acrylic fiber bundle after the drying and densification may be performed in a pressurized steam of 130 to 200 ° C., in a dry heat heating medium of 100 to 200 ° C., between heating rolls of 150 to 220 ° C. or on a heating plate as necessary. The film is stretched by 1.8 to 6.0 times, further improved in orientation and densified, and then wound up to obtain a precursor fiber bundle.

Further, the carbon fiber of the present invention can be produced from the precursor fiber bundle as follows. The precursor fiber bundle is passed through a hot air circulation type flameproofing furnace at 220 to 260 ° C. for 30 to 100 minutes to obtain a flameproofed yarn having a flameproofing yarn density of 1.335 to 1.360 g / cm ³ . At that time, an elongation operation of 0 to 10% is performed. The flameproofing reaction includes a cyclization reaction by heat and an oxidation reaction by oxygen, and it is important to balance these two reactions. In order to balance these two reactions, the flameproofing treatment time is preferably 30 to 100 minutes. In the case of less than 30 minutes, a portion where the oxidation reaction has not sufficiently occurred exists inside the single fiber, and a large structural spot is generated in the cross-sectional direction of the single fiber. As a result, the obtained carbon fiber has a non-uniform structure and does not exhibit high mechanical performance. On the other hand, when it exceeds 100 minutes, more oxygen comes to exist in the part near the surface of the single fiber, and a reaction in which excess oxygen disappears by a subsequent heat treatment at a high temperature occurs to form a defect point. For this reason, high strength cannot be obtained. A more preferable flameproofing treatment time is 40 to 80 minutes.

When the flame resistant yarn density is less than 1.335 g / cm ³ , the flame resistance becomes insufficient, and a decomposition reaction occurs due to the subsequent heat treatment at a high temperature, and a defect point is formed, so that high strength cannot be obtained. When the flameproof yarn density exceeds 1.360 g / cm ³ , because the oxygen content of the fiber increases, a reaction in which excess oxygen disappears due to the subsequent heat treatment at a high temperature occurs to form a defect point. High strength cannot be obtained. A more preferable range of flameproof yarn density is 1.340 to 1.350 g / cm ³ .

  Proper elongation in the flameproofing furnace is necessary to maintain and improve the orientation of the fibril structure forming the fibers. If the elongation is less than 0%, the orientation of the fibril structure cannot be maintained, the orientation at the fiber axis in the formation of the carbon fiber structure is not sufficient, and excellent mechanical performance cannot be exhibited. On the other hand, if the elongation exceeds 10%, the fibril structure itself breaks, and the subsequent formation of the carbon fiber structure is impaired. Further, the breaking point becomes a defect point, and a high-strength carbon fiber cannot be obtained. A more preferable elongation rate is 3 to 8%.

  Next, the flame-resistant fiber is passed through an inert atmosphere such as nitrogen in a first carbonization furnace having a temperature gradient of 300 to 800 ° C. while applying elongation of 2 to 7%. A suitable processing temperature is 300 to 800 ° C., and processing is performed with a linear gradient. Considering the temperature of the flameproofing process, the starting temperature is preferably 300 ° C. or higher. When the maximum temperature exceeds 800 ° C., the process yarn becomes very brittle and it is difficult to shift to the next process. A more preferable temperature range is 300 to 750 ° C. The temperature gradient is not particularly limited, but it is preferable to set a linear gradient.

  If the elongation is less than 2%, the orientation of the fibril structure cannot be maintained, the orientation at the fiber axis in the formation of the carbon fiber structure is not sufficient, and excellent mechanical performance cannot be exhibited. On the other hand, if the elongation exceeds 7%, the fibril structure itself breaks, and the subsequent formation of the carbon fiber structure is impaired, and the break point becomes a defect point, and a high-strength carbon fiber cannot be obtained. A more preferable elongation rate is 3 to 5%.

  A suitable heat treatment time in the first carbonization furnace is 1.0 to 3.0 minutes. In the treatment for less than 1.0 minute, a violent decomposition reaction accompanying a rapid temperature rise occurs, and a high-strength carbon fiber cannot be obtained. If it exceeds 3.0 minutes, the influence of plasticization in the first stage of the process occurs, and the orientation of crystals tends to be lowered, resulting in the deterioration of the mechanical performance of the resulting carbon fiber. A more preferable heat treatment time is 1.2 to 2.5 minutes.

  Furthermore, it heat-processes under tension in the 2nd carbonization furnace which has a temperature gradient of 1000-1600 degreeC in inert atmosphere, such as nitrogen, and is set as carbon fiber. Further, if necessary, heat treatment is performed under tension in an inert atmosphere in a third carbonization furnace having an additional desired temperature gradient.

  The temperature of the carbonization treatment is set according to the desired elastic modulus of the carbon fiber. In order to obtain carbon fibers having high strength characteristics, it is preferable that the maximum carbonization temperature is low. Further, since the elastic modulus can be increased by extending the treatment time, the maximum temperature can be lowered as a result. Furthermore, by increasing the processing time, the temperature gradient can be set gently, which is effective in suppressing defect point formation. Although a 2nd carbonization furnace is based also on the temperature setting of a 1st carbonization furnace, what is necessary is just 1000 degreeC or more. Preferably it is 1050 degreeC or more. The temperature gradient is not particularly limited, but it is preferable to set a linear gradient.

  The heat treatment time in the second carbonization furnace is preferably 1.3 to 5.0 minutes. More preferably, it is 2.0 to 4.2 minutes. In this heat treatment, since the process fibers are accompanied by a large shrinkage, it is important to perform the heat treatment under tension.

  The elongation is preferably -6.0 to 0.0%. If it is less than -6.0%, the crystal orientation in the fiber axis direction is poor, and sufficient performance cannot be obtained. On the other hand, when it exceeds 0.0%, the structure itself that has been formed is destroyed, the formation of defect points becomes remarkable, and the strength is greatly reduced. A more preferred elongation is in the range of -5.0% to -1.0%.

Next, the carbon fiber bundle is subjected to a surface oxidation treatment. Examples of the surface treatment method include a known method, that is, an oxidation treatment such as electrolytic oxidation, chemical oxidation, and air oxidation. The electrolytic oxidation treatment that is widely practiced industrially is more preferable because stable surface oxidation treatment is possible. In order to control the ipa representing the surface treatment state suitable for the present invention within the above-described range, the simplest method is to use electrolytic oxidation treatment and change the amount of electricity. In this case, even if the amount of electricity is the same, ipa varies greatly depending on the electrolyte used and its concentration. In the present invention, it is preferable to carry out the electrolytic oxidation treatment in an alkaline aqueous solution having a pH higher than 7 by using a carbon fiber as an anode and flowing an electric quantity of 10 to 200 coulomb / g. By the oxidation treatment, ipa can be 0.05 to 0.25 μA / cm ² . As the electrolyte, it is preferable to use ammonium carbonate, ammonium bicarbonate, calcium hydroxide, sodium hydroxide, potassium hydroxide, or the like.

  Next, the carbon fiber bundle of the present invention is subjected to a sizing treatment. A sizing agent imparts to a carbon fiber bundle a solution dissolved in an organic solvent or an emulsion liquid dispersed in water with an emulsifier or the like by a roller dipping method, a roller contact method or the like. Subsequently, the sizing process can be performed by drying this. The amount of the sizing agent attached to the surface of the carbon fiber can be adjusted by adjusting the concentration of the sizing agent solution or adjusting the amount of drawing. Moreover, drying can be performed using hot air, a hot plate, a heating roller, various infrared heaters, and the like.

The most suitable sizing agent composition applied to the surface of the carbon fiber of the present invention is (a) an epoxy resin having a hydroxy group (hereinafter referred to as component (a) as appropriate), (b) a polyhydroxy compound (hereinafter referred to as appropriate ( b) component) and (c) urethane-modified epoxy resin which is a reaction product of diisocyanate containing an aromatic ring (hereinafter referred to as component (c) as appropriate). Moreover, the mixture of the urethane modified epoxy resin which is a reactive organism obtained by introduce | transducing (a) component into a reaction system more than the quantity required for reaction, and the unreacted material of (a) component is mentioned.
Furthermore, a mixture of a urethane-modified epoxy resin and a component (d) obtained by using an epoxy resin having no hydroxy group (hereinafter referred to as “component (d)” as appropriate) can be mentioned. Furthermore, a urethane-modified epoxy resin and a mixture of the component (a) and the component (d) can be mentioned.

  The epoxy group has a very strong interaction with the oxygen-containing functional group on the surface of the carbon fiber, and can firmly adhere the sizing agent component to the surface of the carbon fiber. In addition, by having a urethane bond unit produced from a polyhydroxy compound and a diisocyanate containing an aromatic ring, it is possible to impart flexibility and strong interaction with the carbon fiber surface due to the polarity of the urethane bond and the aromatic ring. Is possible. Therefore, the urethane-modified epoxy resin having an epoxy group and the urethane bond unit in the molecule is a compound that can adhere strongly to the carbon fiber surface and has flexibility. That is, since such a sizing agent composition forms a flexible interface layer firmly bonded to the carbon fiber surface, the mechanical performance of the composite material obtained by impregnating and curing the matrix resin in the carbon fiber is excellent. Can be.

Here, the component (a) is not particularly limited, and the number of hydroxy groups contained in the component (a) is not limited. For example, glycidol, methyl glycidol, bisphenol F type epoxy resin, bisphenol A type epoxy resin, oxycarboxylic acid glycidyl ester epoxy resin and the like can be used. Particularly preferred are bisphenol type epoxy resins. Since these have an aromatic ring, the interaction with the carbon fiber surface is strong. In addition, the matrix resin used for the composite material is often an epoxy resin having an aromatic ring from the viewpoint of heat resistance and rigidity, and is excellent in compatibility with these matrix resins.
As the component (a), two or more epoxy resins can be used.

  Moreover, it is preferable that (b) component is comprised from either the alkylene oxide adduct of bisphenol A, an aliphatic polyhydroxy compound, a polyhydroxymonocarboxy compound, or these mixtures. This is because these compounds can soften the urethane-modified epoxy resin. Specifically, bisphenol A ethylene oxide 4 mol to 14 mol adduct, bisphenol A propylene oxide 2 to 14 mol adduct, bisphenol A ethylene oxide, propylene oxide block copolymer adduct , Polyethylene glycol, trimethylolpropane, dimethylolpropionic acid and the like.

  Further, the component (c) is not particularly limited. Particularly preferred is toluene diisocyanate or xylene diisocyanate.

  Further, the epoxy resin as the component (d) is not particularly limited. Preferably, what has two or more epoxy groups in a molecule | numerator is good. This is because the interaction between the surface of the carbon fiber and the epoxy group is strong, and these compounds adhere firmly to the surface. There is no restriction | limiting in particular in the kind of epoxy group, A glycidyl type, an alicyclic epoxy group, etc. are employable. Preferred epoxy resins include bisphenol F type epoxy resin, bisphenol A type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin (Epiclon HP-7200 series: Dainippon Ink and Chemicals, Inc.), trishydroxyn phenylmethane. Type epoxy resin (Epicoat 1032H60, 1032S50: Japan Epoxy Resin Co., Ltd.), DPP novolac type epoxy resin (Epicoat 157S65, 157S70: Japan Epoxy Resin Co., Ltd.), bisphenol A alkylene oxide-added epoxy resin, and the like can be used.

  In the production of the mixture containing the component (d), the component (d) may be added simultaneously with the component (a) when the component (a), the component (b), and the component (c) are reacted. Further, after completion of the urethanization reaction, component (d) may be added. Examples of the aqueous dispersion composed of such a compound include Hydran N320 (manufactured by DIC Corporation).

  Since the carbon fiber of the present invention has a strand elastic modulus of 250 GPa or more, it is obtained by firing at a relatively high temperature. Therefore, it is advantageous to obtain from precursor fibers containing as little impurities as possible, such as metals. As a result, the metal component contained in the obtained carbon fiber bundle is preferably small. In particular, the total amount of metal components such as alkali metal, alkaline earth metal, zinc, iron and aluminum is preferably 50 ppm or less. These metals react with carbon at temperatures exceeding 1000 ° C., cause melting or evaporation, and cause the formation of defect points, making it impossible to produce high-strength carbon fibers.

  Hereinafter, the present invention will be specifically described by way of examples. In addition, the measurement of the performance of the carbon fiber bundle in a present Example and evaluation were performed with the following method.

"1. Measurement of surface uneven structure of single fiber"
Based on the surface shape, it can be measured as follows.
Place several single fibers of a carbon fiber bundle on a sample table, fix both ends, and apply dotite around the sample to make a measurement sample. Using a silicon nitride cantilever with an atomic force microscope (Seiko Instruments Inc., SPI3700 / SPA-300 (trade name)), in the AFM mode, the fiber axis has a range of 1000 nm in the circumferential direction of the single fiber. The scanning is repeated while gradually shifting over a direction length of 1000 nm, and the obtained measurement image is subjected to inverse transformation after the low-frequency component is cut by two-dimensional Fourier transformation. From the plane image of the cross section obtained by removing the curvature of the single fiber thus obtained, the difference in height between the highest part and the lowest part in a range surrounded by a circumferential length of 1.0 μm and a length of 1.0 μm in the fiber axis direction is obtained. Further, Ra calculated by the following formula (2) is measured.

Ra = {1 / (Lx × Ly)} · ∫ Ly 0 ∫ LX 0 | f (x, y) | dxdy ··· (2)
Center plane: A plane that is parallel to a plane that has a minimum height deviation from the actual surface and that divides the actual surface into two equal parts, that is, a portion that is surrounded by the plane and the actual surface. Planes with equal volumes V1 and V2 on both sides of
f (x, y): difference in height between the actual surface and the central surface,
Lx, Ly: XY plane size.

  Further, during measurement with an atomic force microscope, the presence or absence of a concavo-convex structure having a length of 0.6 μm or more and the length of a concavo-convex structure having a length of 300 nm or less were measured.

"2. Evaluation of cross-sectional shape of single fiber"
The ratio (major axis / minor axis) of the major axis to the minor axis of the fiber cross section of the single fiber constituting the carbon fiber bundle was determined as follows.
A carbon fiber bundle for measurement was passed through a tube made of vinyl chloride resin having an inner diameter of 1 mm, and this was then cut into round pieces with a knife to prepare a sample. Next, the sample was bonded to the SEM sample stage with the fiber cross-section facing upward, and Au was further sputtered to a thickness of about 10 nm, and then scanned with a scanning electron microscope (product name: XL20, manufactured by Philips). The fiber cross section was observed under the conditions of an acceleration voltage of 7.00 kV and a working distance of 31 mm, and the major axis and minor axis of the fiber cross section of the single fiber were measured.

“3. Strand property evaluation of carbon fiber bundles”
Preparation of strand test pieces of resin-impregnated carbon fiber bundles and measurement of strength were measured and evaluated according to JIS R7601. However, the elastic modulus was calculated using a strain range according to ASTM.

“4. Measurement of knot strength of carbon fiber bundles”
The nodule strength was measured as follows.
A grip part having a length of 25 mm was attached to both ends of a carbon fiber bundle having a length of 150 mm to obtain a test specimen. During the preparation of the test body, a carbon fiber bundle was aligned by applying a load of 0.1 × 10 ⁻³ N / denier. A single knot was formed on the test body at almost the center, and the crosshead speed during tension was 100 mm / min. The number of tests was 12 and the minimum and maximum values were removed, and the average value of 10 was used as the measurement value.

"5. Measurement of fracture surface formation energy of carbon fiber bundle"
Cut a single fiber of carbon fiber into 20 cm, and attach and fix the center of this single fiber to a single fiber tensile test mount for a sample length of 10 mm shown in JIS R7606, and cut off the excess part protruding from the mount. A sample was removed.

  Next, hemispherical defects were formed by irradiating these samples fixed to the mount with a laser. The laser interface system used was a micropoint (pulse energy 300 uJ) manufactured by Photonic Instruments. An ECLIPSE LV100 manufactured by Nikon Corporation was used as an optical microscope necessary for condensing the laser. The aperture stop of the optical microscope was set to the minimum, and the objective lens was set to 100 times. Under this condition, one pulse of a laser beam having a wavelength of 435 nm, which is attenuated by 10% of the laser intensity with an attenuator, is applied to the central portion in the fiber axis direction of the sample and the central portion in the direction perpendicular to the fiber axis. A sample in which a defect was formed was obtained.

  In order to prevent the carbon fiber as a sample from causing shrinkage failure, the sample attached to the mount was further sandwiched between films, and the film was filled with a viscous liquid to conduct a tensile test. Specifically, a film having a width of about 5 mm and a length of about 15 mm was prepared, the film was attached to the upper part of both sides of the sample mount, and the entire mount was sandwiched between the films so as to cover the sample. The space between the films was filled with a glycerin aqueous solution (the ratio of water 2 to glycerin 1), and then a tensile test was performed at a tensile speed of 0.5 mm / min to measure the breaking load.

  Then, the sample pair divided into two in the tensile test was taken out from the mount, carefully washed with water, and then air-dried. Next, an SEM observation sample was prepared by fixing it to the SEM sample stage with carbon paste so that the fracture surface of the sample was on top. The fracture surface of the obtained SEM observation sample was observed with JSM 6060 (acceleration voltage 10 to 15 kV, magnification 10000 to 15000) manufactured by JEOL Ltd.

  The obtained SEM image was taken into a personal computer and image analysis was performed with image analysis software, and the size of the hemispherical defect and the fiber cross-sectional area were measured.

  Next, breaking load / fiber cross-sectional area = breaking strength (σ) and hemispherical defect size (C) were plotted, and the slope of the data was calculated.

σ = (2E / πC) ^1/2 × (Fracture surface generation energy) ^1/2 (1)
From the formula (1), the fracture surface generation energy was determined from the calculated slope and the ultrasonic elastic modulus (E) of the carbon fiber bundle.

“6. Measurement of ipa of carbon fiber bundle”
The ipa value was measured by the following method.
The electrolyte is adjusted to pH 3 with a 5% phosphoric acid aqueous solution, and nitrogen is bubbled to eliminate the influence of dissolved oxygen. A carbon electrode as a sample is immersed in an electrolytic solution as one electrode, and a platinum electrode having a sufficient surface area is used as a counter electrode. Here, an Ag / AgCl electrode was employed as the reference electrode. The sample form was 12000 filament tow with a length of 50 mm. The scanning range of the potential applied between the carbon fiber electrode and the platinum electrode was −0.2 V to +0.8 V, and the scanning speed was 2.0 mV / sec. Draw a current-voltage curve with an XY recorder, and when the curve is stabilized by sweeping three or more times, read the current value i with the potential at +0.4 V as the reference potential with respect to the Ag / AgCl reference electrode. Ipa was calculated according to (3).

ipa = 1 (μA) / sample length (cm) × {4π × weight per unit area (g / cm) × number of filaments / density (g / cm ³ )} ^1/2 (3)

  The apparent surface area was calculated from the sample length and the sample density and the basis weight determined by the method described in JIS R7601, and the current value i was divided into ipa. This measurement was performed using a cyclic voltametry analyzer model P-1100 manufactured by Yanagimoto Seisakusho.

“7. Measurement of Si content in carbon fiber bundles”
A sample of the carbon fiber bundle was put in a platinum crucible known as a tare and ashed in a muffle furnace at 600 to 700 ° C., and its mass was measured to obtain an ash content. Next, a prescribed amount of sodium carbonate was added, melted with a burner, and fixed in a 50 ml polymeas flask while dissolving with deionized water. This sample was quantified for Si by ICP emission spectrometry.

(Precursor fiber bundle production examples 1 to 7)
Precursor fiber (1)
An acrylonitrile polymer having a composition of 98% by mass of acrylonitrile and 2% by mass of methacrylic acid was dissolved in dimethylformamide to prepare a spinning stock solution of 23.5% by mass.
This spinning dope was spun from a spinneret having a discharge hole having a diameter of 0.15 mm and several thousands, and was subjected to dry and wet spinning. That is, it was spun into air and passed through a space of about 5 mm, and then coagulated in a coagulation liquid filled with an aqueous solution containing 79.0% by mass dimethylformamide adjusted to 10 ° C., and the coagulated yarn was taken up. . Next, the film was stretched 1.1 times in air, and then stretched 2.5 times in a stretching tank filled with an aqueous solution containing 35 mass% dimethylformamide adjusted to 60 ° C. After stretching, the process fiber bundle containing the solvent was washed with clean water, and then stretched 1.4 times in 95 ° C. hot water. Subsequently, an oil agent containing amino-modified silicone as a main component was applied to the fiber bundle so as to be 1.1% by mass, followed by drying and densification. The fiber bundle after drying and densification was stretched 2.6 times between heated rolls, and after further improving the orientation and densification, it was wound up to obtain an acrylonitrile-based precursor fiber bundle. The fineness of this fiber was 0.77 dtex.

Precursor fiber (2)
The precursor fiber bundle (2) under the same conditions as the precursor fiber bundle (1) except that the draw ratio before the water washing treatment was 2.9 times and the draw ratio in the hot water after washing was 1.2 times. Got.

Precursor fiber (3)
A precursor fiber bundle (3) was obtained under the same conditions as the precursor fiber bundle (2) except that the fineness of the precursor fiber was 0.67 dtex.

Precursor fiber (4)
A precursor fiber bundle (4) was obtained under the same conditions as the precursor fiber bundle (2) except that the fineness of the precursor fiber was 0.90 dtex.

Precursor fiber (5)
The precursor fiber bundle (1) except that the draw ratio before washing with water was 4.1 times, the draw ratio in hot water after washing was 0.99 times, and the drawing ratio was 2.4 times between heating rolls. A precursor fiber bundle (5) was obtained under the same conditions.

Precursor fiber (6)
The precursor fiber bundle (6) under the same conditions as the precursor fiber bundle (1) except that the draw ratio before the water washing treatment was 1.9 times and the draw ratio in the hot water after washing was 2.0 times. Got.

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 1.0 dtex.
The production conditions of the precursor fiber bundles (1) to (7) are shown in Table 1.

(Examples 1-7, Comparative Examples 1-4)
(Preparation of carbon fiber bundle)
A plurality of precursor fiber bundles (1), (2), (3), (4), (5), (6) or (7) are introduced into a flameproofing furnace in a state of being aligned in parallel, 220 to 280 The precursor fiber bundle was flameproofed by blowing air heated to 0 ° C. onto the precursor fiber bundle to obtain a flameproof fiber bundle having a density of 1.345 g / cm ³ . The elongation rate was 6%, and the flameproofing treatment time was 70 minutes.

Next, the flame-resistant fiber bundle was passed through nitrogen in a first carbonization furnace having a temperature gradient of 300 to 700 ° C. while adding 4.5% elongation. The temperature gradient was set to be linear. The processing time was 2.0 minutes.
Furthermore, it heat-processed at the predetermined | prescribed temperature shown in Table 2 or Table 3 using the 2nd carbonization furnace which can set the temperature gradient of 1000-1600 degreeC in nitrogen atmosphere. Subsequently, using a third carbonization furnace capable of setting a temperature gradient of 1200 to 2400 ° C. in a nitrogen atmosphere, heat treatment was performed at a predetermined temperature shown in Table 2 or Table 3 to obtain a carbon fiber bundle. The elongation ratio of the second carbonization furnace and the third carbonization furnace was -4.0%, and the treatment time was 3.5 minutes.
Subsequently, it was run in an aqueous solution of 10% by weight of ammonium bicarbonate, and with the carbon fiber bundle as the anode, an electric current treatment was carried out with the counter electrode so that the amount of electricity was 40 coulombs per 1 g of carbon fiber to be treated. And then dried.
Next, 0.5% by mass of hydran N320 (hereinafter referred to as “sizing agent 1”) was adhered and wound around a bobbin to obtain a carbon fiber bundle.

(Production of unidirectional prepreg)
156 carbon fiber bundles unwound from a bobbin are arranged on a release paper coated with B-staged epoxy resin # 410 (180 ° C curing type) (Mitsubishi Rayon Co., Ltd.), and thermocompression bonded. The epoxy resin was impregnated through a roller. A protective film was laminated thereon to produce a unidirectionally aligned prepreg (hereinafter referred to as “UD prepreg”) having a resin content of about 33% by mass, a carbon fiber basis weight of 125 g / m ² , and a width of 500 mm.

(Molding of laminates and mechanical performance evaluation)
A laminate was molded using the UD prepreg, and the 0 ° tensile strength of the laminate was measured by an evaluation method based on ASTM D3039.
Tables 2 and 3 show the production conditions and evaluation results of the carbon fiber bundle.
In any of the examples, there was no surface uneven structure having a length of 0.6 μm or more extending in the longitudinal direction of the fiber on the surface of the single fiber, and a minute size uneven structure having a length of 300 nm or less was confirmed.

(Precursor fiber bundle production example 8)
Using the spinning stock solution prepared in the same manner as in Production Example 1, spinning was performed from a spinneret in which discharge holes having a diameter of 0.13 mm and several 2,000 were arranged, and dry and wet spinning was performed. That is, it was spun into air and passed through a space of about 5 mm, and then coagulated in a coagulation liquid filled with an aqueous solution containing 77.0% by mass dimethylformamide adjusted to 5 ° C., and the coagulated yarn was taken up. It was. Next, the film was stretched 1.3 times in air and then stretched 2.0 times in a stretching tank filled with an aqueous solution adjusted to 60 ° C. After stretching, the process fiber bundle was washed with clean water, and then stretched 2.0 times in 95 ° C. hot water. Subsequently, an oil agent containing amino-modified silicone as a main component was applied to the fiber bundle so as to be 1.0% by mass, followed by drying and densification. The fiber bundle after drying and densification was drawn 1.9 times between heating rolls, and after further improving the orientation and densification, it was wound up to obtain a precursor fiber bundle. The fineness of this fiber was 0.77 dtex.

(Example 8)
A carbon fiber bundle was produced under the same firing conditions as in Example 5 except that the third carbonization furnace was not used. Moreover, the laminated board was produced similarly and mechanical performance evaluation was implemented and the result of Table 2 was obtained. In addition, there was no surface uneven structure with a length of 0.6 μm or more extending in the longitudinal direction of the fiber on the surface of the single fiber, and a minute uneven structure with a length of 300 nm or less was confirmed.

(Examples 9-11, Comparative Examples 6-8)
A carbon fiber bundle was obtained in the same manner as in Example 2 except that the firing conditions were changed. The evaluation results are shown in Table 4. In any of the examples, there was no surface uneven structure having a length of 0.6 μm or more extending in the longitudinal direction of the fiber on the surface of the single fiber, and a minute size uneven structure having a length of 300 nm or less was confirmed.

(Examples 12 and 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. In any of the examples, there was no surface uneven structure having a length of 0.6 μm or more extending in the longitudinal direction of the fiber on the surface of the single fiber, and a minute size uneven structure having a length of 300 nm or less was confirmed.

(Examples 14 to 16)
A carbon fiber bundle was obtained in the same manner as in Example 5 except that the type of sizing agent and the amount of adhesion were changed. The evaluation results are shown in Table 5. In any of the examples, there was no surface uneven structure having a length of 0.6 μm or more extending in the longitudinal direction of the fiber on the surface of the single fiber, and a minute size uneven structure having a length of 300 nm or less was confirmed.
Sizing agent 2, sizing 3 and sizing 4 were prepared as follows.

(Sizing agent 2)
80 parts by mass of “Epicoat 828” manufactured by Japan Epoxy Resin Co., Ltd. as the main agent and 20 parts by mass of “Pluronic F88” manufactured by Asahi Denka Co., Ltd. as the emulsifier were mixed, and an aqueous dispersion was prepared by phase inversion emulsification.

(Sizing agent 3)
The flask is charged with 1.8 mol of a bisphenol A propylene oxide 8 mol adduct, 0.8 mol of trimethylolpropane, and 3.2 mol of a polyol composed of 0.6 mol of dimethylolpropionic acid. , 6-Di (t-butyl) 4-methylphenol (BHT) 0.5 g and dibutyltin dilaurate 0.2 g as a reaction catalyst were added and stirred until the mixture became homogeneous. Here, methyl ethyl ketone was added as a viscosity modifier as needed. The urethane prepolymer was polymerized at a reaction temperature of 50 ° C. and a reaction time of 2 hours while stirring and adding 3.4 mol of metaxylene diisocyanate dropwise to the uniformly dissolved mixture. Next, 0.25 mol of Epikote 834 (manufactured by JER Co., Ltd.) was added, and an isocyanate group at the end of the urethane prepolymer was reacted to obtain an epoxy-modified urethane resin.
90 parts by mass of this epoxy-modified urethane resin and 10 parts by mass of “Pluronic F88” manufactured by Asahi Denka Co., Ltd. were mixed as an emulsifier to prepare an aqueous dispersion.

(Sizing agent 4)
The flask was charged with 2.5 mol of polyethylene glycol 400 and 0.7 mol of Epicoat 834 (manufactured by JER Co., Ltd.), and 2,6-di (t-butyl) 4-methylphenol (BHT) as a reaction inhibitor. ) 0.25 g, dibutyltin dilaurate 0.1 g was added as a reaction catalyst, and the mixture was stirred until uniform. Here, methyl ethyl ketone was added as a viscosity modifier as needed. To the uniformly dissolved mixture, 2.7 mol of metaxylene diisocyanate was added dropwise, and an epoxy-modified urethane resin was obtained at a reaction temperature of 40 ° C. and a reaction time of 2 hours while stirring.
80 parts by mass of this epoxy-modified urethane resin and 20 parts by mass of “Pluronic F88” manufactured by Asahi Denka Co., Ltd. were mixed as an emulsifier to prepare an aqueous dispersion.

  The carbon fiber bundle of the present invention can be used as a structural material for aircraft, high-speed moving bodies, and the like.

Claims (10)

There is no surface uneven structure with a length of 0.6 μm or more extending in the longitudinal direction of the fiber on the surface of the single fiber, and the average unevenness is 5-25 nm in height difference (Rp-v) between the highest and lowest parts of the surface of the single fiber. Ra has a concavo-convex structure of 2 to 6 nm, and consists of a single fiber of carbon fiber having a ratio of a long diameter to a short diameter (long diameter / short diameter) of a single fiber of 1.00 to 1.01. The mass per unit length of the single fiber is in the range of 0.030 to 0.042 mg / m, the strand strength is 5900 MPa or more, the strand elastic modulus measured by the ASTM method is 250 to 380 GPa, and the knot strength is A carbon fiber bundle which is a carbon fiber of 900 N / mm ² or more. There is no concavo-convex structure having a length of 0.6 μm or more extending in the longitudinal direction of the fiber on the surface of the single fiber, and a concavo-convex structure having a length of 300 nm or less, and the height difference (Rp) -V) has a concavo-convex structure with an average concavoconvexity Ra of 2-6 nm, and the ratio of the major axis to the minor axis (major axis / minor axis) of the single fiber is 1.00-1. The strand elastic modulus is measured by the ASTM method, which is composed of a single carbon fiber of 01, the mass per unit length of the single fiber is in the range of 0.030 to 0.042 mg / m, the strand strength is 5900 MPa or more. Is a carbon fiber bundle having a knot strength of 900 N / mm ² or more. A hemispherical defect having a size within a predetermined range is formed on the surface of a single fiber with a laser, the fiber is broken at the hemispherical defect site by a tensile test, and Griffith is determined from the breaking strength of the fiber and the size of the hemispherical defect. The carbon fiber bundle according to claim 1 or 2, wherein the fracture surface generation energy obtained from the formula (1) is 30 N / m or more.
σ = (2E / πC) ^1/2 × (Fracture surface generation energy) ^1/2 (1)
Here, σ is the breaking strength, E is the ultrasonic elastic modulus of the carbon fiber bundle, and c is the size of the hemispherical defect. The amount of oxygen-containing functional groups on the surface of the carbon fiber determined by X-ray photoelectron spectroscopy has an ipa value determined by an electrochemical measurement method (cyclic voltametry) of 0.05 to 0.25 μA / cm ² ( The carbon fiber bundle according to any one of claims 1 to 3, wherein O1S / C1S) is in a range of 0.05 to 0.15. The carbon fiber bundle according to any one of claims 1 to 4, wherein the amount of Si measured by ICP emission analysis is 200 ppm or less. (A) an epoxy resin having a hydroxy group, (b) a sizing agent composition comprising a urethane-modified epoxy resin which is a reaction product of a polyhydroxy compound and (c) a diisocyanate containing an aromatic ring, or the urethane-modified epoxy The carbon fiber bundle according to any one of claims 1 to 5, which is sized with a sizing agent composition containing a mixture of a resin and (a) an epoxy resin having a hydroxy group and / or (d) an epoxy resin having no hydroxy group. .   The carbon fiber bundle according to claim 6, wherein (a) the epoxy resin having a hydroxy group is a bisphenol type epoxy resin.   The carbon fiber bundle according to claim 6 or 7, wherein the polyhydroxy compound is any one of an alkylene oxide adduct of bisphenol A, an aliphatic polyhydroxy compound, a polyhydroxy monocarboxy compound, or a mixture thereof. .   (C) The carbon fiber bundle according to any one of claims 6 to 8, wherein the diisocyanate containing an aromatic ring is toluene diisocyanate or xylene diisocyanate. The carbon fiber bundle according to any one of claims 1 to 9, wherein a total amount of metals including alkali metal, alkaline earth metal, zinc, iron, and aluminum is 50 ppm or less.