WO2010143680A1 - 炭素繊維用アクリロニトリル膨潤糸、前駆体繊維束、耐炎化繊維束、炭素繊維束及びそれらの製造方法 - Google Patents
炭素繊維用アクリロニトリル膨潤糸、前駆体繊維束、耐炎化繊維束、炭素繊維束及びそれらの製造方法 Download PDFInfo
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- WO2010143680A1 WO2010143680A1 PCT/JP2010/059827 JP2010059827W WO2010143680A1 WO 2010143680 A1 WO2010143680 A1 WO 2010143680A1 JP 2010059827 W JP2010059827 W JP 2010059827W WO 2010143680 A1 WO2010143680 A1 WO 2010143680A1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
- D01D5/247—Discontinuous hollow structure or microporous structure
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2973—Particular cross section
- Y10T428/2975—Tubular or cellular
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2973—Particular cross section
- Y10T428/2978—Surface characteristic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/298—Physical dimension
Definitions
- the present invention has excellent mechanical properties, and in particular, a carbon fiber bundle for obtaining a high-quality and high-performance fiber-reinforced resin such as aircraft use and industrial use, and a swollen yarn and a precursor fiber bundle used for the production thereof And a flame-resistant fiber bundle.
- Patent Document 1 discloses a method of improving the uniformity of structure and orientation by drawing a coagulated yarn containing a solvent in a solvent-containing drawing bath when a precursor fiber bundle is obtained by a dry-wet spinning method. Proposed. 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.
- the technique for obtaining fibers with high uniformity in structure and orientation is very excellent.
- 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. As a result, it was difficult to obtain a carbon fiber bundle having high strength.
- 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.
- the pore distribution obtained by the mercury intrusion method reflects the bulk properties including the inside from the surface layer of the filament, and is an excellent method for evaluating the denseness of the overall structure of the fiber. It is.
- High-strength carbon fibers with suppressed defect point formation can be obtained from precursor fiber bundles having an overall denseness level or higher.
- the rupture state of the carbon fiber is observed, there is a very high proportion of the rupture start point near 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 having high denseness as a whole and extremely high density in the surface layer portion.
- Patent Document 4 proposes a technique for suppressing 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 and inhibits densification.
- 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
- 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 present inventors have clarified the appropriate form and properties of the acrylonitrile swollen yarn for carbon fiber and the precursor fiber bundle, and by optimizing the coagulation and drawing conditions of the spun fiber, A swollen yarn having a dense internal structure and capable of suppressing oil permeation was found in the vicinity of the surface layer.
- the above-mentioned problems are solved by the following present invention group.
- the first invention is treated with an oil agent having an opening having a width of 10 nm or more in the circumferential direction of the fiber on the surface of the single fiber in a range of 0.3 / ⁇ m 2 or more and 2 / ⁇ m 2 or less.
- the second invention is [1] 96.0% by mass or more and 99.7% by mass or less of acrylonitrile and 0.3% by mass or more and 4.0% by mass of unsaturated hydrocarbon having one or more carboxyl groups or ester groups.
- a step of coagulating in a coagulation bath comprising the following aqueous solution to obtain a coagulated yarn bundle containing the organic solvent; [3] A step of stretching the coagulated yarn bundle in air within a range of 1.0 to 1.25 times, and further stretching in a warm aqueous solution containing an organic solvent, and total stretching by both stretching Stretching at a magnification of 2.6 times to 4.0 times, [4] A method for producing a swollen yarn, further comprising a step of removing the solvent with warm water and further stretching it 0.98 times or more and 2.0 times or less in hot water.
- the third invention is required to contain 96.0% by mass or more and 99.7% by mass or less of acrylonitrile and 0.3% by mass or more and 4.0% by mass or less of unsaturated hydrocarbons having one or more carboxyl groups or ester groups.
- a precursor fiber bundle for carbon fibers comprising an acrylonitrile copolymer copolymerized as a component and treated with an oil containing a silicone compound as a main component and having a silicon content of 1700 ppm to 5000 ppm, comprising a Soxhlet extractor This is a precursor fiber bundle for carbon fiber having a silicon content of 50 ppm or more and 300 ppm or less after 8 hours of oil agent washing with methyl ethyl ketone used.
- an oil agent containing a silicone compound as a main component is attached to the bundle of swollen yarns by adhering 0.8 to 1.6% by mass of the oil agent component to 100% by mass of the swollen yarn.
- the carbon fiber precursor fiber bundle is then stretched by a heat stretching method or a steam stretching method in a range of 1.8 times to 6.0 times.
- the precursor fiber bundle is passed through a hot air circulation type flameproof furnace at 220 to 260 ° C. for 30 minutes or more and 100 minutes or less in an oxidizing atmosphere with an elongation rate of 0% or more and 10% or less.
- This is a method for producing a flame-resistant fiber bundle that satisfies the following four conditions by heat treatment.
- the resin impregnated strand strength is 6000 MPa or more
- the strand elastic modulus measured by the ASTM method is 250 to 380 GPa
- the ratio of the major axis to the minor axis in the cross section perpendicular to the fiber axis direction of the single fiber (major axis / short axis).
- (Diameter) is 1.00 to 1.01
- the diameter of the single fiber is 4.0 to 6.0 ⁇ m
- one or more voids having a diameter of 2 nm or more and 15 nm or less are 100 in the cross section perpendicular to the fiber axis direction of the single fiber. It is a carbon fiber bundle that exists in number or less.
- the precursor fiber bundle is made into a flame-resistant fiber bundle having a density of 1.335 g / cm 3 or more and 1.355 g / cm 3 or less by heat treatment in an oxidizing atmosphere, and then 300 in an inert atmosphere.
- heating is performed for not less than 1.0 to not more than 3.0 minutes while adding elongation of not less than 2% to not more than 7%, followed by firing from 1000 ° C in an inert atmosphere
- a method for producing a carbon fiber bundle wherein heat treatment is performed for 1.0 minute or more and 5.0 minutes or less while adding an elongation of -6.0% or more and 2.0% or less in one or more carbonization furnaces having a temperature gradient up to a temperature. It is.
- the swollen yarn of the present invention can suppress the penetration of silicone oil, which is the main component of the oil agent, into the surface layer portion of the precursor fiber.
- the carbon fiber bundle obtained by flameproofing and carbonizing the precursor fiber bundle has excellent mechanical performance, and a fiber reinforced resin having high mechanical properties can be obtained.
- the coagulated yarn is a process yarn that has been taken out of the coagulating liquid and not subjected to a drawing treatment.
- the swollen yarn is a process yarn obtained by subjecting the coagulated yarn to a drawing process and a washing process, and is a process yarn before the oil agent adhesion and the drying process.
- the acrylonitrile swelling yarn for carbon fiber of the present invention (hereinafter referred to as “swelling yarn” as appropriate) has 0.3 apertures having a width of 10 nm or more in the circumferential direction of the fiber in the state before the oil agent treatment. / ⁇ m 2 or more and 2 / ⁇ m 2 or less in the range of the single fiber.
- the swollen yarn is subjected to a process of attaching, drying and further stretching an oil agent having a silicone compound, and is formed into a precursor fiber bundle.
- the swollen yarn has such a surface. It becomes possible to greatly suppress penetration into the surface layer.
- the polymer constituting the swollen yarn is 96.0% by mass or more and 99.7% by mass or less of acrylonitrile units, and 0.3% by mass or more of unsaturated hydrocarbon units having one or more carboxyl groups or ester groups.
- An acrylonitrile-based copolymer having 0% by mass or less as an essential component is preferable.
- the unsaturated hydrocarbon component having a carboxyl group or an ester group serves as a starting point for the flameproofing reaction in the flameproofing step, and the content thereof is 0.3% by mass or more and 4.0% by mass.
- the swollen yarn is obtained by subjecting a predetermined amount of an oil containing a specific silicone compound to adhesion, drying and densifying, and then quantifying the remaining silicone compound after 8 hours of oil extraction and washing with methyl ethyl ketone. It is possible to evaluate whether it has a surface layer part which can suppress permeation of water.
- the oil agent permeability of the swollen yarn can be evaluated as follows. First, the following (1) amino-modified silicone oil and (2) emulsifier are mixed, and an aqueous dispersion (aqueous fiber oil) is prepared by a phase inversion emulsification method. This aqueous fiber oil is adhered to the swollen yarn.
- the swelling yarn of the present invention preferably has a silicon content (residual amount) of 50 ppm or more and 300 ppm or less in the oil agent extraction cleaning. This value is more preferably 50 ppm or more and 200 ppm or less.
- the fact that the silicon content of the fiber bundle after the oil agent extraction washing exceeds 300 ppm means that the denseness of the surface layer part that suppresses the penetration of the oil agent component into the surface layer part is insufficient, and is obtained through the firing step.
- the carbon fiber to be obtained includes a large number of voids in the surface layer portion. As a result, the intended high-strength carbon fiber cannot be obtained.
- this value is less than 50 ppm, it means that the amount of the oil agent penetrating into the surface layer portion of the swollen yarn is very small, and the cause is that an extremely dense skin layer is formed on the surface layer portion of the fiber in the coagulation bath. It is thought that it was formed.
- the degree of swelling measured by the method for measuring the degree of swelling of the swollen yarn] is more preferably 80% by mass or less.
- the swelling degree exceeding 80% by mass indicates that the denseness of the inner layer structure of the swollen yarn is slightly lowered. In this case, even if defect point formation can be suppressed in the surface layer portion, the possibility of defect point formation in the inner layer portion is increased, and as a result, a carbon fiber having high mechanical performance is obtained. I can't.
- a more preferable degree of swelling is 75% by mass or less.
- the denseness of the swollen yarn can be evaluated by measuring the pore distribution inside the fiber.
- the average pore size of the swollen yarn of the present invention is preferably 55 nm or less, and the total pore volume is preferably 0.55 ml / g or less.
- the average pore size is more preferably 50 nm or less, and further preferably 45 nm or less.
- the total pore volume is more preferably 0.50 ml / g or less, and further preferably 0.45 ml / g or less.
- Such swollen yarn does not have large-sized voids inside the fibers, and the proportion of voids is low and dense.
- both the surface layer of the swollen yarn is densified as described above to suppress the penetration of the oil agent, and the fiber has a dense structure with few voids inside. It is preferable to do.
- the pore distribution of the swollen yarn is described in [4. Measurement method of pore distribution of swollen yarn].
- the swollen yarn of the present invention can be produced by wet spinning or wet and wet spinning of a spinning stock solution comprising an acrylonitrile copolymer and an organic solvent.
- the acrylonitrile-based copolymer include those obtained by copolymerizing acrylonitrile and an unsaturated hydrocarbon having one or more carboxyl groups or ester groups as an essential component.
- the unsaturated hydrocarbon having one or more carboxyl groups or ester groups include acrylic acid, methacrylic acid, itaconic acid, methyl acrylate, methyl methacrylate, and ethyl acrylate.
- the unsaturated hydrocarbon component having a carboxyl group or an ester group is known to be the starting point of the flameproofing reaction in the flameproofing process, and if its content is too small, the flameproofing reaction does not occur sufficiently, This will hinder the formation of the structure of the synthetic fiber. On the other hand, if the number is too large, a rapid reaction occurs due to the presence of a large number of reaction starting points, resulting in the formation of a rough structural form, and carbon fibers having high performance cannot be obtained. By making the content 0.3 mass% or more and 4.0 mass% or less, the balance between the flameproofing reaction start point and the reaction rate becomes good, the structure is dense, and it becomes a defect point in the carbonization process.
- acrylamide derivatives such as acrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, vinyl acetate, etc. may be used.
- 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.
- a spinning stock solution having a temperature of 50 to 70 ° C. in which an acrylonitrile copolymer is dissolved in an organic solvent at a concentration of 20 to 25% by mass is prepared.
- the solid concentration of the spinning dope is preferably 20% by mass or more, and more preferably 21% by mass or more.
- the temperature of the spinning dope by setting the temperature of the spinning dope to 50 ° C. or higher, it is possible to achieve an appropriate viscosity of the stock solution without lowering the solid content concentration, and by setting it to 70 ° C. or less, the temperature difference with the coagulating liquid is reduced. can do. That is, when the temperature of the spinning dope is 50 to 70 ° C., a coagulated yarn having a high density and a homogeneous structure can be stably produced.
- the organic solvent is not particularly limited, but dimethylformamide, dimethylacetamide or dimethyl sulfoxide is more preferably used. More preferably, it is dimethylformamide excellent in the dissolving ability of the acrylonitrile-based copolymer.
- the spinning method may be either wet spinning or wet and wet spinning. More preferred is dry and wet spinning. This is because it is easy to form a dense solidified yarn, and in particular, the denseness of the surface layer portion can be improved.
- dry-wet spinning the prepared spinning solution is spun into air from a spinneret with a large number of nozzle holes, and then discharged into a coagulating solution filled with a mixed solution of temperature-controlled organic solvent and water for coagulation. Take the coagulated yarn.
- the coagulation liquid preferably has a temperature of -5 to 20 ° C. and an organic solvent concentration of 78 to 82% by mass.
- a more preferable temperature range is ⁇ 5 ° C. to 10 ° C.
- a more preferable organic solvent concentration range is an aqueous solution having a concentration of 78.5% by mass or more and 81.0% by mass or less.
- the coagulated yarn is stretched and washed.
- the order of the stretching and washing treatment is not particularly limited, and the film may be washed after stretching, or the stretching and washing may be performed simultaneously.
- the cleaning method may be any method as long as the solvent can be removed.
- a particularly preferred drawing and washing treatment of the coagulated yarn is to draw in a predrawing tank having a lower solvent concentration and higher temperature than the coagulating liquid before washing. Thereby, a uniform fibril structure can be formed in the coagulated yarn.
- Stretching the coagulated yarn in a bath containing a solvent is a method generally known as a solvent stretching technique, which enables a stable stretching process by solvent plasticization, and as a result, both structure and orientation are uniform. You can get something expensive. However, by stretching the fiber bundle containing the solvent in a swollen state, the orientation of the structure by fibril structure formation and stretching becomes insufficient, and the filament obtained from the oil agent squeezed out from the filament abruptly It was easy to form a sparse structure, and it was impossible to have a desired dense structure.
- the temperature and concentration of the spinning dope and coagulation solution are set optimally, and then the solvent stretching process is performed with the optimum combination of the conditions of the solvent stretching tank and the stretching ratio, thereby forming a dense fibril structure.
- the solvent stretching process is performed with the optimum combination of the conditions of the solvent stretching tank and the stretching ratio, thereby forming a dense fibril structure.
- a coagulated yarn bundle containing an organic solvent is first drawn in air, and subsequently drawn in a drawing tank containing a warm aqueous solution containing an organic solvent.
- the temperature of the warm aqueous solution is preferably in the range of 40 ° C to 80 ° C.
- the temperature of the warm aqueous solution is preferably in the range of 40 ° C to 80 ° C.
- the temperature is set to 40 ° C. or higher, good stretchability can be ensured, and formation of a uniform fibril structure is facilitated.
- the temperature is set to 80 ° C. or less, an excessive plasticizing action is not caused, the solvent removal on the surface of the yarn proceeds appropriately, and the stretching becomes uniform. It becomes good.
- a more preferable temperature is 55 ° C. or higher and 75 ° C. or lower.
- the concentration of the organic solvent in the warm aqueous solution containing the organic solvent is preferably 30% by mass or more and 60% by mass or less. This concentration is within a range where a stable stretching treatment can be provided, and a dense and uniform fibril structure can be formed in the inside and the surface layer. A more preferable concentration is 40% by mass or more and 50% by mass or less.
- a preferred method of drawing the coagulated yarn is that the drawing in air is 1.0 to 1.25 times, and the total draw ratio in air and warm aqueous solution is 2.6 to 4.0 times. To do.
- the coagulated yarn has a fibril structure swollen with a large amount of solvent.
- the total draw ratio in air and warm aqueous solution 2.6 times or more, sufficient drawing can be performed and a fibril structure oriented in a desired fiber axis direction can be formed. . Further, by setting the total draw ratio to 4.0 times or less, it is possible to obtain a precursor fiber bundle having a dense structure form without causing breakage of the fibril structure itself. That is, a dense fibril structure oriented in the axial direction of the fiber can be formed in the range of 2.6 times to 4.0 times. A more preferable total draw ratio is 2.7 times or more and 3.5 times or less.
- the stretching ratio in the organic solvent warm aqueous solution is 2.5 times or more. This is because the stretching in the organic solvent warm aqueous solution is performed at a relatively high temperature and can be stretched without causing structural destruction. Therefore, it is preferable that the stretching distribution in the air and the organic solvent warm aqueous solution is set so that the stretching distribution in the organic solvent warm aqueous solution is set high. More preferable stretching in air is 1.0 times or more and 1.15 times or less. In this way, a swollen yarn having a dense surface layer portion can be obtained.
- the fiber bundle is washed with warm water of 50 ° C. or higher and 95 ° C. or lower to remove the organic solvent.
- it is possible to further enhance the orientation of the fiber by stretching a fiber bundle in a swollen state free from solvent in hot water, and it is possible to take strain in stretching by adding some relaxation.
- the stretching is performed at 0.98 times or more and 2.0 times or less in hot water at a temperature of 70 to 95 ° C.
- the draw ratio is 0.98 times or more and less than 1.0 time, the treatment is relaxed.
- the fiber bundle provided at a high draw ratio is effective for stable drawing in the subsequent drawing step by taking drawing strain.
- the draw ratio is in the range of 1.0 to 2.0, the degree of orientation of the fibril structure can be improved and the surface layer can be denser. More preferably, stretching is performed at a ratio of 0.99 times to 1.5 times. In this way, a swollen yarn can be obtained by subjecting the coagulated yarn to stretching and washing.
- 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 preferably used.
- the fiber bundle after drying and densification is further stretched in a pressurized steam at 130 to 200 ° C., in a dry heat heat medium at 100 to 200 ° C., between heating rolls at 150 to 220 ° C. or on a heating plate, and further After the orientation is improved and densified, it is wound up to obtain a precursor fiber bundle.
- the precursor fiber bundle for carbon fibers of the present invention (hereinafter appropriately referred to as “precursor fiber bundle”) has 96.0% by mass or more and 99.7% by mass or less of acrylonitrile and one or more carboxyl groups or ester groups. It consists of an acrylonitrile copolymer copolymerized with 0.3% by mass or more and 4.0% by mass or less of an unsaturated hydrocarbon as an essential component, and has a silicon content after being treated with an oil mainly composed of a silicone compound.
- the silicon content after 8 hours of oil cleaning with methyl ethyl ketone using a Soxhlet extractor is 50 ppm or more and 300 ppm or less.
- the silicon content is measured with a fluorescent X-ray apparatus. Further, the silicon content after the oil agent washing is a measured value based on the evaluation by the oil agent adhesion to the oil agent washing in [Evaluation of oil agent permeability of swollen yarn].
- the silicon content of the precursor fiber bundle after being treated with the oil agent is 1700 ppm or less and 5000 ppm or less, fusion between the filaments does not occur in the flameproofing process, while the surface layer has an excessive silicone compound to the inside of the filament. Oxygen diffusion is hindered, and there is no portion where the flameproofing reaction is insufficient, so that the occurrence of yarn breakage in the carbonization step, which is a higher temperature treatment, can be suppressed. As a result, stable process passability can be maintained.
- the precursor fiber bundle of the present invention has a silicon content of 300 ppm or less after fiber agent extraction cleaning.
- the fact that the silicon content exceeds 300 ppm indicates that the silicone compound oil penetrates into the surface layer portion and the abundance thereof increases.
- the flame resistance of the firing process the silicone oil present in the surface layer part remains in the surface carbonization process (800 ° C. or lower) without being scattered, and is scattered in the late carbonization process (above 800 ° C.).
- a large number of voids are formed in the surface layer portion of a typical carbon fiber. Therefore, the intended high-strength carbon fiber cannot be obtained.
- the silicon content of the fiber bundle after the oil agent extraction cleaning is 300 ppm or less means that the silicone compound adhering to the precursor fiber penetrates the surface layer portion and exists in the vicinity of the surface layer, but is difficult to be extracted.
- the ratio of the existing state is small, meaning that it exists in the outermost layer. If it is such a state, a silicone type compound will disperse
- the silicon content after the more preferable oil agent extraction washing is 200 mass ppm or less.
- This precursor fiber bundle has a single fiber fineness of 0.5 dtex or more and 1.0 dtex or less, and the ratio of the major axis to the minor axis (major axis / minor axis) of the fiber cross section of the monofilament is 1.00 or more and 1. 01 or less, there is no surface uneven structure extending in the fiber axis direction of single fibers, the height difference (Rp-v) between the highest and lowest parts is 30 nm to 100 nm, and the center line average roughness (Ra) is 3 nm to 10 nm. Preferably there is.
- the smoothness of the precursor fiber filament surface is not excessive. This is because the low stretchability in the spinning process derived from the skin layer formed in the solidification process does not cause small breakage of the surface layer fibrils, and the formation of minute defect points can be avoided. Furthermore, due to excessive convergence as a fiber bundle that is an aggregate of filaments, non-uniform flame resistance treatment due to inhibition of oxygen diffusion into the filament in the flame resistance process can be avoided.
- the denseness of the structure in the vicinity of the surface layer can be made to a sufficient level. That is, when the surface has a (Rp-v) value of 30 nm or more and 100 nm or less and a (Ra) value of 3 nm or more and 10 nm or less, the density of the structure in the vicinity of the surface layer is at a sufficient level, and sufficient stretching is achieved. It is possible to reduce the chance of forming defect points in the vicinity of the surface layer in the process from spinning to firing. As a result, a high-strength carbon fiber bundle can be obtained.
- the surface concavo-convex structure extending in the fiber axis direction means a ridge structure having a length of 0.6 ⁇ m or more that is substantially parallel to the fiber axis direction.
- the acrylonitrile fiber bundle usually undergoes volume shrinkage due to solidification and subsequent stretching treatment, and a wrinkle structure extending in the fiber axis direction is formed on the surface.
- a wrinkle structure extending in the fiber axis direction is formed on the surface.
- the formation of the ridge structure is suppressed.
- the formation of this wrinkle structure is greatly suppressed by dry and wet spinning. It is preferable that the precursor fiber bundle does not have such a wrinkle structure having a length of 0.6 ⁇ m or more.
- a fiber having a ratio of major axis to minor axis (major axis / minor axis) of a single fiber cross section of 1.00 to 1.01 is a single fiber having a perfect circle or a cross section close to a perfect circle, and has a structure near the fiber surface. Excellent uniformity.
- a more preferred ratio of major axis to minor axis (major axis / minor axis) is 1.00 to 1.005. Since the fiber having a single fiber fineness range of 0.5 to 1.0 dtex has a small fiber diameter, it is possible to reduce structural non-uniformity in the cross-sectional direction that occurs in the firing step. A more preferable range is 0.5 to 0.8 dtex.
- the precursor fiber bundle having the predetermined silicon content is dried by attaching an oil agent mainly composed of a silicone compound to the swollen yarn of the present invention, and then subjected to a stretching process by heat stretching or steam stretching. Can be manufactured by.
- the silicone compound as the main component of the oil is not particularly limited, but amino-modified polydimethylsiloxane or epoxy-modified polydimethylsiloxane is preferably used from the viewpoint of interaction with the acrylonitrile copolymer.
- the swollen yarn of the present invention is preferably an amino-modified polydimethylsiloxane from the viewpoint of ease of covering the surface layer and difficulty of detachment from the surface layer because the surface layer portion has high density.
- skeleton by the phenyl group is excellent from a heat resistant viewpoint.
- the most preferred amino-modified polydimethylsiloxane has a kinematic viscosity at 25 ° C. of 50 to 5,000 cst and an amino equivalent of 1,700 to 15,000 g / mol.
- the amino-modified type is not particularly limited, but a primary side chain type, a primary and secondary side chain type, and a both-end modified type are preferable. Moreover, these mixed types or a mixture of a plurality of types can also be used. If the kinematic viscosity at 25 ° C. is 50 cst or more, it has a sufficient molecular weight that does not volatilize, can be prevented from scattering from the fiber throughout the flameproofing process, and exhibits the function as an original process oil, stable. Carbon fiber can be manufactured. Further, by setting the kinematic viscosity at 25 ° C.
- the kinematic viscosity at 25 ° C. of the oil is in the range of 50 to 5,000 cst and the amino equivalent is in the range of 1,700 to 15,000 g / mol, the trouble of winding of the fiber due to the transfer of the oil to a roll or the like There is no sudden scattering of the oil agent in the flameproofing process, and the process from spinning to flameproofing can be carried out stably for a long time.
- Examples of the primary side chain type amino-modified polydimethylsiloxane include KF-864, KF-865, KF-868, and KF-8003 (all manufactured by Shin-Etsu Chemical Co., Ltd.).
- Examples of the primary and secondary side chain types include KF-859, KF-860, KF-869, and KF-8005 (all manufactured by Shin-Etsu Chemical Co., Ltd.).
- Examples of the both-end modified type include Silaplane FM-3311, FM-3221, FM-3325 (all manufactured by Chisso Corporation) and KF-8012 (manufactured by Shin-Etsu Chemical Co., Ltd.).
- the oil agent is composed of a compound such as a surfactant for forming an aqueous emulsion, a softening agent that imparts excellent processability, and a smoothing agent.
- Nonionic surfactants are mainly used, and pluronic or higher alcohol EO / PO adducts are used.
- Newpol PE-78, PE-108 and PE-128 (all of which are Sanyo Chemical Industries Co., Ltd.), which are polyoxyethylene / polyoxypropylene block polymers, are suitable.
- Softeners and smoothing agents use ester compounds and urethane compounds.
- Content of the silicone compound in an oil agent is 30 mass% to 90 mass%. If it is 30 mass% or more, the fusion suppression in a flame-proofing process is enough. Moreover, if it is 90 mass% or less, stability of an oil agent emulsion can be easily made into sufficient level, and a stable precursor fiber can be manufactured. That is, if the content of the silicone compound in the oil agent is 30% by mass to 90% by mass, even in the precursor fiber having a dense surface as in the present invention, the effect of suppressing the fusion in the flameproofing process is sufficient. This can be achieved, and the stability in the oil agent attaching process, and hence the uniformity of the attached state, can be realized, so that the performance expression of the obtained carbon fiber can be stabilized.
- the adhesion amount of the oil agent mainly composed of a silicone compound is 0.8% by mass to 1.6% by mass.
- 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 fiber bundle after drying and densification is stretched by 1.8 to 6.0 times in a pressurized steam or dry heat heating medium at 130 to 200 ° C. or between heating rolls or on a heating plate as necessary.
- the resulting orientation is improved and densified to obtain a precursor fiber bundle.
- a more preferable draw ratio is 2.4 to 6.0 times, and more preferably 2.6 to 6.0 times.
- Method for producing flame-resistant fiber bundle By passing the precursor fiber bundle through a hot air circulation type flameproofing furnace at 220 to 260 ° C. for 30 minutes or more and 100 minutes or less and heat-treating in an oxidizing atmosphere with an elongation rate of 0% or more and 10% or less, A flame-resistant fiber bundle having a particle size of 1.335 g / cm 3 or more and 1.360 g / cm 3 or less can be obtained.
- 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 between 30 minutes and 100 minutes.
- More preferable flameproofing treatment time is 40 minutes or more and 80 minutes or less.
- the flame resistant yarn density is less than 1.335 g / cm 3 , the flame resistance becomes insufficient, the decomposition reaction is caused by the subsequent heat treatment at a high temperature, and a high-strength carbon fiber cannot be obtained because defect points are formed.
- the flameproof yarn density exceeds 1.360 g / cm 3 , the oxygen content of the fiber increases, so that a reaction in which excess oxygen disappears due to the subsequent heat treatment at a high temperature occurs, so that a defect point is formed. A strong carbon fiber cannot be obtained.
- a more preferable range of the flame resistant yarn density is 1.340 g / cm 3 or more and 1.350 g / cm 3 or less.
- Appropriate elongation in the flameproofing furnace is necessary to maintain and improve the orientation of the fibril structure forming the fiber. 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 is not 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% or more and 8% or less.
- (100) indicates the crystal orientation.
- the structure of the precursor fiber is greatly changed, and further, it is a step of forming a graphite crystal group which is the basic structure of the carbon fiber.
- the degree of orientation is closely related to the crystallinity, and the crystallinity is significantly lowered as the degree of orientation is lowered.
- high orientation can be maintained, high crystallinity can be obtained accordingly.
- a flameproof fiber bundle having a crystal structure in which the intensity ratio (B / A) is 1.3 or more, the orientation degree of peak A is 79% or more, and the orientation degree of peak B is 80% or more is preferable. .
- the flame-resistant fiber bundle as described above can be obtained relatively easily by using the precursor fiber bundle of the present invention. Further, in the step of heat-treating the precursor fiber bundle in an oxidizing atmosphere, the decompression processing conditions and divided into at least three blocks, at a fiber density 1.200 g / cm 3 or more 1.260 g / cm 3 or less of the range, 3. Elongation of 0% or more and 8.0% or less is performed, and further, elongation of 0.0% or more and 3.0% or less is performed in a density range of 1.240 g / cm 3 or more and 1.310 g / cm 3 or less. It is preferable to set the 300 g / cm 3 or more 1.360g / cm 3 oxidization conditions such as to extend -1.0% to 2.0% or less in the range.
- the flame resistant fiber bundle is added in the first carbonization furnace having a temperature gradient of 300 ° C. or more and 800 ° C. or less in an inert atmosphere such as nitrogen while adding elongation of 2% or more and 7% or less to 1.0 to 3.0 minutes. Heat-treat for minutes.
- the preferred processing temperature is 300 ° C. to 800 ° C., with a linear temperature gradient.
- the starting temperature is preferably 300 ° C. or higher. If the maximum temperature exceeds 800 ° C., the fiber becomes very brittle and it is difficult to move to the next step.
- a more preferred temperature range is 300 to 750 ° C.
- a more preferable temperature range is 300 to 700 ° 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 expressed. 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% or more and 5% or less. The preferred treatment time is 1.0 to 3.0 minutes.
- heat treatment is performed under tension in a second carbonization furnace capable of setting a temperature gradient in the range of 1000 to 1600 ° C. in an inert atmosphere such as nitrogen to obtain carbon fibers. Further, if necessary, heat treatment is performed under tension in an inert atmosphere in a third carbonization furnace having an additionally desired temperature gradient.
- the temperature setting depends on the desired elastic modulus of the carbon fiber. In order to obtain carbon fibers with high mechanical performance, the maximum temperature of carbonization treatment should be low, and the elastic modulus can be increased by increasing the treatment time, so that the maximum temperature can be lowered as a result. it can. Furthermore, by increasing the processing time, the temperature gradient can be set gently, which is effective in suppressing defect point formation.
- the second carbonization furnace may be 1000 ° C. or more although it depends on the temperature setting of the first carbonization furnace. Preferably it is 1050 degreeC or more.
- the temperature gradient is not particularly limited, but it is preferable to set a linear gradient.
- the treatment time is preferably from 1.0 minute to 5.0 minutes. More preferably, it is 1.5 minutes to 4.2 minutes. In this heat treatment, since the fiber bundle is accompanied by a large shrinkage, it is important to perform the heat treatment under tension.
- the elongation is preferably -6.0% to 2.0%. 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, if it exceeds 2.0%, 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 0.5%.
- the carbon fiber bundle thus obtained is subjected to surface oxidation treatment.
- the surface treatment method include known methods, that is, oxidation treatment by electrolytic oxidation, chemical oxidation, air oxidation, and the like.
- the electrolytic oxidation treatment widely practiced industrially is the most suitable method from the viewpoint that stable surface oxidation treatment is possible and that the surface treatment state can be controlled by changing the amount of electricity.
- the amount of electricity is 10 to 200 coulomb / g with carbon fiber as the anode.
- the electrolyte it is preferable to use ammonium carbonate, ammonium bicarbonate, calcium hydroxide, sodium hydroxide, potassium hydroxide, or the like.
- the carbon fiber bundle is subjected to sizing treatment.
- the sizing agent can be obtained by applying a solution dissolved in an organic solvent or an emulsion liquid dispersed in water with an emulsifier or the like to a carbon fiber bundle by a roller dipping method, a roller contact method, or the like, and drying it. it can.
- 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. Drying can be performed using hot air, a hot plate, a heating roller, various infrared heaters, and the like.
- a sizing agent is attached and dried, and then wound around a bobbin to obtain a carbon fiber bundle.
- a carbon fiber bundle excellent in mechanical performance can be obtained by applying the above-described firing method using the precursor fiber bundle or the flameproof fiber bundle of the present invention.
- the carbon fiber bundle of the present invention has a resin-impregnated strand strength of 6000 MPa or more, a strand elastic modulus measured by the ASTM method of 250 to 380 GPa, and a ratio of a major axis to a minor axis of a cross section perpendicular to the fiber axis direction of a single fiber.
- (Major axis / minor axis) is 1.00 to 1.01
- the diameter of the single fiber is 4.0 to 6.0 ⁇ m
- Further preferred carbon fiber bundles are those in which the average diameter of voids in the range of 2 to 15 nm in diameter observed in a cross section perpendicular to the fiber axis direction of single fibers is 6 nm or less.
- An average diameter of 6 nm or less indicates that the oil agent was uniformly present in the precursor fiber bundle without much local penetration. By securing this 6 nm or less, it is possible to realize stable strength development of carbon fibers.
- the total area A (nm 2 ) of voids existing in a cross section perpendicular to the fiber axis direction of single fibers is preferably 2,000 nm 2 or less. Moreover, it is preferable that the space
- the single fiber having such a structure indicates that the oil agent was present only in the extreme surface layer portion in the vicinity of the surface layer in the precursor fiber bundle.
- the knot strength obtained by dividing the tensile breaking stress of the carbon fiber bundles knotted by the cross-sectional area of the fiber bundle is preferably 900 N / mm 2 or more. More preferably, it is 1000 N / mm 2 or more, and further preferably 1100 N / mm 2 or more.
- the knot strength can be an index that reflects the mechanical performance of the fiber bundle in a direction other than the fiber axis, 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.
- the sample after rough dehydration still contains a solvent, the sample is thoroughly washed and then dehydrated.
- the sample after rough dehydration or washing and dehydration is transferred to a weighing bottle, and dried in a dryer at 105 ° C. for 3 hours with the lid removed.
- the dried sample is transferred to a desiccator while being placed in a weighing bottle, slowly cooled for 20 to 30 minutes, and then the weight of the weighing bottle is weighed. This mass is defined as dry mass B.
- the swollen yarn collected from the spinning process is dried by the following method. That is, the swollen yarn is fixed at a constant length so as not to shrink and deform during the drying process, and is sequentially mixed in a mixed solution of water / t-butanol at 80/20, 50/50, 20/80, and 0/100 every 30 minutes. Immerse to replace the solvent contained in the swollen yarn with t-butanol. Next, the swollen yarn sample is placed in a flask, rapidly frozen in liquid nitrogen, and then freeze-dried for 24 to 72 hours under a reduced pressure of 100 Pa or less while maintaining the sample temperature at ⁇ 30 to ⁇ 20 ° C.
- the freeze-dried swollen yarn bundle sample was cut to a length of about 10 mm with a razor, weighed about 0.15 g, and weighed from mercury to a maximum pressure of 30,000 psia using a mercury porosimeter (Shimadzu Corporation, product name: Autopore IV).
- the pore distribution is measured under the following conditions.
- the average pore size (nm) is obtained as a volume average pore size obtained by weighting the pore volume to the pore size.
- the total pore volume V (ml / g) is the mercury intrusion amount V1 (ml / g) when the pore size is a pressure corresponding to 500 nm and the mercury intrusion when the pore size is a pressure corresponding to 10 nm. It calculates
- V V2-V1
- a precursor fiber bundle is uniformly wound around an acrylic resin plate having a length of 20 mm, a width of 40 mm, and a width of 5 mm so as not to leave a gap, and a measurement sample is prepared and set in this apparatus.
- Both ends of the single fiber of the precursor fiber bundle are fixed with a carbon paste on a metal sample holder plate attached to the scanning probe microscope apparatus, and measured with a scanning probe microscope under the following conditions.
- the shape image of a single fiber is measured with a scanning probe microscope.
- 10 cross-sectional profiles in the direction perpendicular to the fiber axis are measured by image analysis to determine the height difference (Rp ⁇ v) and the centerline average roughness Ra between the highest and lowest portions of the contour curve. Measurement is performed on 10 single fibers, and an average value is obtained.
- the obtained shape image is subjected to [Flat processing], [Median 8 processing] and [Third-order inclination correction] to obtain an image obtained by fitting the curved surface to a plane.
- [Flat processing] [Median 8 processing]
- [Third-order inclination correction] to obtain an image obtained by fitting the curved surface to a plane.
- the cross-sectional profile in the direction perpendicular to the fiber axis is measured, and the height difference (Rp ⁇ v) between the highest and lowest parts of the contour curve and the centerline average roughness Ra are obtained.
- Inclination correction is to correct the inclination by obtaining and fitting a curved surface by least square approximation from all data of the processing target image.
- (Primary), (Secondary), and (Cubic) indicate the order of the curved surface to be fitted, and in the cubic, the cubic curved surface is fitted.
- the cubic inclination correction process the curvature of the fiber of the data is eliminated and a flat image is obtained.
- the flame-resistant fiber bundle is cut into a fiber length of 5 cm at an arbitrary location, and 12 mg is precisely weighed and aligned so that the sample fiber axes are exactly parallel.
- a fiber bundle having a width in the direction perpendicular to the longitudinal direction of the fiber of 2 mm and a uniform thickness in a direction perpendicular to both the width direction and the longitudinal direction of the fiber is arranged.
- a sample fiber bundle to be measured is obtained by impregnating both ends of the fiber bundle with a vinyl acetate / methanol solution and fixing the fiber bundle so as not to lose its shape.
- the degree of crystal orientation is calculated by the following equation by measuring the diffraction profile in the azimuth direction at the peak position of each reflection to obtain the half width W (unit: °) of the peak.
- Crystal orientation (%) ⁇ (180 ⁇ W) / 180 ⁇ ⁇ 100
- the X-ray diffraction measurement uses a CuK ⁇ ray (using Ni filter) X-ray generator (trade name: TTR-III, rotating counter-cathode X-ray generator) manufactured by Rigaku Corporation as an X-ray source, and a diffraction intensity profile. Is detected by a scintillation counter manufactured by Rigaku. The output is 50 kV-300 mA.
- the ratio of the major axis to the minor axis (major axis / minor axis) of the fiber cross section of the single fiber constituting the fiber bundle is determined as follows. After passing a fiber bundle for measurement through a tube made of vinyl chloride resin having an inner diameter of 1 mm, the sample is prepared by cutting the fiber bundle with a knife. Next, this 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 an electron microscope (manufactured by Philips, product name: XL20 scanning type) was used. The cross section of the fiber is observed under conditions of an acceleration voltage of 7.00 kV and a working distance of 31 mm, and the major axis and the minor axis of the fiber section of the single fiber are measured.
- a single fiber is extracted from the carbon fiber bundle, and platinum is sputtered to a thickness of 2 to 5 nm by a sputtering apparatus, and then carbon is coated to a thickness of 100 to 150 nm by a carbon coater apparatus. Then, using a focused ion beam processing device (product name: FB-2000A, manufactured by Hitachi High-Technologies Corporation), a tungsten protective film was deposited to a thickness of about 500 nm, and then a focused ion beam with an acceleration voltage of 30 kV was used. By etching, a thin section (thickness 100 to 150 nm) of the cross section of the fiber is obtained.
- a cross section of the single fiber is observed with a transmission electron microscope (product name: H-7600, manufactured by Hitachi High-Technologies Corporation) at a magnification of 150,000 to 200,000 times under the condition of an acceleration voltage of 100 kV. . Furthermore, using image analysis software (manufactured by Nippon Roper Co., Ltd., product name: Image-Pro PLUS), a void portion that appears bright in a TEM image is extracted, and the number of voids N is counted over the entire cross section. The equivalent area diameter d (nm) is calculated by measuring the area of the voids. Further, the total sum A (nm2) of the void area and the average void diameter D (nm) are obtained.
- a gripping part having a length of 25 mm is attached to both ends of a carbon fiber bundle having a length of 150 mm and used as a test specimen.
- the carbon fiber bundle is aligned by applying a load of 0.1 ⁇ 10 ⁇ 3 N / denier.
- a single knot is formed on the test body at approximately the center, and the crosshead speed during tension is 100 mm / min.
- the value obtained by dividing the tensile breaking stress by the cross-sectional area of the fiber bundle (the mass and density of the bundle per unit length) is defined as the knot strength.
- the number of tests is 12, and the minimum and maximum values are removed and the average value of 10 is displayed.
- This spinning dope was once spun into air from a spinneret having a diameter of 0.13 mm and a discharge hole with 2000 holes, then passed through a space of about 4 mm, and then adjusted to 15 ° C. and 79.5% by mass. It was discharged into a coagulation liquid filled with an aqueous solution containing dimethylformamide and coagulated, and the coagulated yarn was taken up. Next, the film was stretched 1.1 to 1.3 times in air, and then stretched 1.1 to 2.9 times in a stretching tank filled with an aqueous solution containing 30% by mass dimethylformamide adjusted to 60 ° C. After stretching, the fiber bundle containing the solvent was washed with clean water, and then stretched 1.2 to 2.2 times in 95 ° C. hot water.
- 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 is stretched between 2.2 times and 3.0 times between heating rolls at 180 ° C., and after further improving the orientation and densification, it is wound up to obtain a precursor fiber bundle. It was.
- the fineness of the precursor fiber was 0.77 dtex.
- the ratio of the major axis to the minor axis (major axis / minor axis) of the fiber cross section of the single fiber was 1.005.
- the oil agent which has amino-modified silicone as a main component was used for the oil agent which has amino-modified silicone as a main component.
- Amino-modified silicone KF-865 (manufactured by Shin-Etsu Chemical Co., Ltd., primary side chain type, viscosity 110 cSt (25 ° C.), amino equivalent 5,000 g / mol, 85% by mass, Emulsifier: NIKKOL BL-9EX (manufactured by Nikko Chemicals, POE (9) lauryl ether), 15% by mass.
- 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 1.9 minutes.
- heat treatment was performed at a stretch rate of -3.8% using a second carbonization furnace in which a temperature gradient of 1000 to 1250 ° C. was set in a nitrogen atmosphere.
- a carbon fiber bundle was obtained by performing a heat treatment at an elongation of 0.1% using a third carbonization furnace in which a temperature gradient of 1250 to 1500 ° C. was set in a nitrogen atmosphere.
- the elongation ratio of the second and third carbonization furnaces was -3.9%, and the treatment time was 3.7 minutes.
- Carbon fiber surface treatment Subsequently, the carbon fiber bundle was run in an aqueous solution of 10% by weight of ammonium bicarbonate and the carbon fiber bundle was used as an anode, and an electric current treatment was performed between the counter electrode so that the amount of electricity was 40 coulombs per gram of carbon fiber to be treated. After washing with, dried. Next, 0.5% by mass of Hydran N320 (manufactured by DIC Corporation) was adhered and wound around a bobbin to obtain a carbon fiber bundle. In Example 1 and Comparative Examples 1 to 3, the ratio of the major axis to the minor axis (major axis / minor axis) of the carbon fiber single fiber was 1.005, and the diameter was 4.9 ⁇ m.
- 156 carbon fiber bundles unwound from the bobbin were arranged on a release paper coated with B-staged epoxy resin # 410 (180 ° C. curing type) and impregnated with epoxy resin through a thermocompression 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 density of 125 g / m 2 , and a width of 500 mm.
- Examples 2 to 16 and Comparative Examples 4 to 9 In the same manner as in Example 1, the spinning process conditions were partially changed to obtain swollen yarns and precursor fiber bundles.
- the fineness of the precursor fiber was 0.77 dtex, and the ratio (major axis / minor axis) of the major axis to the minor axis of the fiber cross section of the single fiber was 1.005.
- a carbon fiber bundle was produced under the same firing conditions.
- the ratio of the major axis to the minor axis (major axis / minor axis) of the fiber cross section of the single fiber of carbon fiber was 1.005, and the diameter was 4.9 ⁇ m.
- Table 1 shows the conditions of the spinning process
- Table 2 shows the evaluation results of various fiber bundles.
- Example 17 to 20 Using the precursor fiber bundle obtained in Example 14, only the heat treatment conditions were changed in the second and third carbonization furnaces, and other conditions were the same as in Example 14 to produce a carbon fiber bundle. . Table 3 shows the heat treatment conditions and the properties of the carbon fiber bundle.
- Examples 21 to 25 and Reference Examples 1 and 2 Using the precursor fiber bundle obtained by changing only the fineness of single fibers under the same spinning conditions as in Example 14, among the firing conditions of Example 15, only the heat treatment conditions in the second and third carbonization furnaces A carbon fiber bundle was produced under the same firing conditions as in Example 15 except for the change.
- Table 4 shows the properties of the precursor fiber, the heat treatment conditions, and the carbon fiber bundle.
- Example 26 to 28 and Reference Examples 3 and 4 A precursor fiber bundle and subsequently a carbon fiber bundle were produced under the same conditions as in Example 14 except that the type of amino-modified silicone as the oil agent was changed.
- Table 5 shows the properties of the amino-modified silicone species, precursor fibers and carbon fiber bundles used.
- Example 29 to 31 In the same manner as in Example 1, the spinning process conditions were partially changed to obtain swollen yarns and precursor fiber bundles.
- the fineness of the precursor fiber was 0.77 dtex, and the ratio (major axis / minor axis) of the major axis to the minor axis of the fiber cross section of the single fiber was 1.005.
- a carbon fiber bundle was produced under the same firing conditions.
- the ratio of the major axis to the minor axis (major axis / minor axis) of the fiber cross section of the single fiber of carbon fiber was 1.005, and the diameter was 4.9 ⁇ m.
- Table 1 shows the spinning process conditions
- Table 2 shows the evaluation results of various fiber bundles.
- the carbon fiber bundle of the present invention can be used as a structural material for aircraft, high-speed moving bodies, and the like.
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Abstract
Description
第1の発明は、繊維の円周方向に10nm以上の幅がある開孔部を0.3個/μm2以上2個/μm2以下の範囲で単繊維の表面に有する、油剤処理されていない炭素繊維用アクリロニトリル膨潤糸である。
〔2〕この紡糸原液を、乾湿式紡糸法を用いて吐出孔から一旦空気中に吐出させた後、温度-5℃以上20℃以下、有機溶剤濃度78.0質量%以上82.0質量%以下の水溶液からなる凝固浴中で凝固させて前記有機溶剤を含む凝固糸束を得る工程、
〔3〕前記凝固糸束を空気中で1.0倍以上1.25倍以下の範囲で延伸した後、更に有機溶剤を含有する温水溶液中で延伸する工程であって、両延伸による合計延伸倍率を2.6倍以上4.0倍以下として延伸する工程、
〔4〕引き続き、温水にて脱溶剤し、さらに熱水中で0.98倍以上2.0倍以下延伸させる工程を有する膨潤糸の製造方法である。
(1)繊維束広角X線測定による赤道方向のピークA(2θ=25°)とピークB(2θ=17°)の強度比(B/A)1.3以上、(2)ピークBの配向度80%以上、(3)ピークAの配向度79%以上、(4)密度1.335g/cm3以上1.360g/cm3以下。
本発明の炭素繊維用アクリロニトリル膨潤糸(以下、適宜「膨潤糸」という)は、油剤処理を施す前の状態で、繊維の円周方向に10nm以上の幅がある開孔部を0.3個/μm2以上2個/μm2以下の範囲で、単繊維の表面に有するものである。この膨潤糸はシリコーン化合物を有する油剤を付着、乾燥させ、さらに延伸をさせる工程に供され、前駆体繊維束とされるが、膨潤糸がこのような表面を有することにより、油剤成分の膨潤糸表層部への浸透を大幅に抑制することが可能となる。
膨潤糸の油剤浸透性は以下のようにして評価できる。
先ず、以下の(1)アミノ変性シリコーンオイルと(2)乳化剤を混合し、転相乳化法により水分散液(水系繊維油剤)を調製する。この水系繊維油剤を膨潤糸に付着させる。
(1)アミノ変性シリコーン;KF-865(信越化学工業(株)製、1級側鎖タイプ、動粘度110cSt(25℃)、アミノ当量5,000g/mol)、85質量%、
(2)乳化剤;NIKKOL BL-9EX(日光ケミカルズ株式会社製、POE(9)ラウリルエーテル)、15質量%。
本発明の膨潤糸は、油剤抽出洗浄のケイ素含有量(残存量)が50ppm以上300ppm以下であることが好ましい。この値は、より好ましくは50ppm以上200ppm以下である。
本発明の膨潤糸はアクリロニトリル系共重合体と有機溶剤からなる紡糸原液を湿式紡糸または乾湿紡糸することによって製造することができる。
アクリロニトリル系共重合体としては、アクリロニトリルと一つ以上のカルボキシル基あるいはエステル基を有する不飽和炭化水素を必須成分として共重合させたものが挙げられる。一つ以上のカルボキシル基あるいはエステル基を有する不飽和炭化水素としては、アクリル酸、メタクリル酸、イタコン酸、アクリル酸メチル、メタクリル酸メチル、アクリル酸エチルが挙げられる。これらのいずれか、あるいはこれらの中から2種以上を0.3質量%以上4.0質量%以下とアクリロニトリル96.0質量%以上99.7質量%以下とを共重合したアクリルニトリル共重合体が好ましく用いられる。より好ましいアクリロニトリル含有量は、98質量%以上である。
また、有機溶剤を含有する温水溶液中の有機溶剤濃度は30質量%以上60質量%以下が好ましい。この濃度は、安定な延伸処理を供することができる範囲であり、緻密な均一なフィブリル構造を内部と表層において形成させることができる。より好適な濃度は、40質量%以上50質量%以下である。
このようにして表層部が緻密な膨潤糸を得ることができるが、より好ましい緻密な膨潤糸を得るには、膨潤度が160質量%以下である有機溶剤を含む凝固糸束を用いて上述した延伸方法により膨潤糸を製造することである。これは、凝固糸の内層構造が緻密であるからである。
このようにして凝固糸に延伸処理と洗浄処理を施すことによって膨潤糸が得られる。
膨潤糸に所定量の油剤を付着処理し、乾燥緻密化する。乾燥緻密化は公知の乾燥法により乾燥、緻密化させれば良く、特に制限はない。複数の加熱ロールを通過させる方法が好ましく用いられる。乾燥緻密化後の繊維束は、130~200℃の加圧スチーム中、100~200℃の乾熱熱媒中、あるいは150~220℃の加熱ロール間や加熱板上で延伸して、更なる配向の向上と緻密化を行った後に巻き取って前駆体繊維束を得る。
本発明の炭素繊維用前駆体繊維束(以下、適宜「前駆体繊維束」という)は、アクリロニトリル96.0質量%以上99.7質量%以下と、一つ以上のカルボキシル基あるいはエステル基を有する不飽和炭化水素0.3質量%以上4.0質量%以下を必須成分として共重合させたアクリロニトリル共重合体からなり、シリコーン系化合物を主成分とする油剤で処理された後のケイ素含有量が1700ppm以上5000ppm以下であって、ソックスレー抽出器を用いたメチルエチルケトンによる8時間油剤洗浄後のケイ素含有量が50ppm以上300ppm以下である。ケイ素含有量は蛍光X線装置にて測定される。また油剤洗浄後のケイ素含有量は前記〔膨潤糸の油剤浸透性の評価〕における油剤付着~油剤洗浄による評価に基づく測定値である。
単繊維の繊度範囲が0.5~1.0dtexである繊維は、繊維径が小さいので、焼成工程で生じる断面方向の構造不均一性を低減できる。より好ましい範囲は、0.5~0.8dtexである。
前記所定量のケイ素含有量の前駆体繊維束は、本発明の膨潤糸に、シリコーン化合物を主成分とする油剤を付着させて乾燥させた後、熱延伸もしくはスチーム延伸にて延伸処理を施すことによって製造することができる。
また、ポリジメチルシロキサン骨格のメチル基の一部がフェニル基に置換されているものは、耐熱性の観点から優れている。最も好適なアミノ変性ポリジメチルシロキサンは、25℃における動粘度が50~5,000cst、アミノ当量が1,700~15,000g/molのものである。
前駆体繊維束を、220~260℃の熱風循環型の耐炎化炉に30分以上100分以下の間通過せしめて、伸長率0%以上10%以下として酸化雰囲気下で熱処理することによって、密度1.335g/cm3以上1.360g/cm3以下の耐炎化繊維束を得ることができる。耐炎化反応には、熱による環化反応と酸素による酸化反応があり、この2つの反応をバランスさせることが重要である。この2つの反応をバランスさせるためには、耐炎化処理時間は30分以上100分以下の間が好適である。30分未満の場合、酸化反応が十分に生じていない部分が単繊維の内側に存在し、単繊維の断面方向で大きな構造斑が生じる。その結果、得られる炭素繊維は不均一な構造を有するものとなってしまい、高い機械的性能は発現しない。一方、100分を超える場合は、単繊維の表面に近い部分により多くの酸素が存在するようになり、その後の高温での熱処理により過剰の酸素が消失する反応が生じ、欠陥点を形成するために高強度の炭素繊維が得られない。
次に耐炎化繊維束を窒素などの不活性雰囲気中300℃以上800℃以下の温度勾配を有する第一炭素化炉にて2%以上7%以下の伸長を加えながら1.0分から3.0分間熱処理する。好適な処理温度は300℃から800℃で、直線的な温度勾配で処理する。前工程の耐炎化の温度を考えると開始温度は300℃以上が好ましい。最高温度が800℃を超えると、繊維が非常に脆くなり、次の工程への移行が困難になる。より好適な温度範囲は、300~750℃である。より好ましい温度範囲は、300~700℃である。
紡糸工程で走行している繊維束を採取し、密閉可能なポリエチレン製袋に入れ、直ちに5℃以下の冷蔵庫内に保管する。保管開始から膨潤度測定完了までの時間は8時間以内とする。
予め乾燥しておいた秤量瓶を直示天秤で計量した後、前記繊維束から約3gの試料を採取し、秤量瓶に入れ計量する。試料を卓上遠心機の脱水用円筒に入れ、遠心機にセットする。3000回転/分の回転数で10分間遠心処理(粗脱水)を行った後、脱水後の試料を秤量瓶に移し、計量する。この質量を湿質量Aとする。
以下の式より膨潤度を計算する。
膨潤度(%)=(A-B)/B×100%
紡糸工程で採取した膨潤糸を試料として用いる。凝固糸の膨潤度測定と同じ手法にて実施する。
紡糸工程で採取した膨潤糸を試料として用いる。膨潤糸に含まれる溶剤をt-ブタノールに置換して、膨潤糸を液体窒素で急速凍結した後、この繊維試料を、温度-30~-25℃に保持して約3Paの減圧下で24時間凍結乾燥する。乾燥した繊維試料をSEM観察用試料台にカーボンペーストで固定した後、スパッター装置で白金を約3nmの厚さにスパッターし、走査型電子顕微鏡(日本電子(株)、製品名:JSM-7400F)により、加速電圧3kV、観察倍率50,000倍の条件で表面形態を観察する。
繊維表面に開孔した空隙について円周方向の幅を計測し、幅が10nmを超える空隙の数を計数する。50本以上の膨潤糸について同様の計測を行って、合計の空隙数と観察面積を計測し、単位面積(1μm2)あたりの空隙の数の平均値(平均開孔数)を求める。
紡糸工程から採取した膨潤糸を次の方法で乾燥処理する。すなわち、膨潤糸が乾燥過程で収縮変形しないよう定長に固定し、水/t-ブタノールの混合比が80/20、50/50、20/80、0/100の混合液に30分ずつ順次浸漬して、膨潤糸に含まれる溶剤をt-ブタノールに置換する。次いで、この膨潤糸試料をフラスコに入れ、液体窒素中で急速凍結した後、試料温度を-30~-20℃に保ちながら100Pa以下の減圧下で24~72時間凍結乾燥する。
V=V2-V1
〔測定装置〕
蛍光X線分析装置:理学電機工業株式会社製、製品名:ZSX100e、
ターゲット:Rh(エンドウインドウ型)4.0kW、
分光結晶:RX4、
検出器:PC(プロポーショナルカウンター)、
スリット:Std.、
ダイアフラム:10mmφ、
2θ:144.681deg、
測定線:Si-Kα、
励起電圧:50kV、
励起電流:70mA。
縦20mm、横40mm、幅5mmのアクリル樹脂製板に前駆体繊維束を隙間のない様に均一に巻いて測定サンプル調製し、本装置にセットする。通常の蛍光X線分析方法によりケイ素の蛍光X線強度測定を実施する。得られた前駆体繊維束のケイ素の蛍光X線強度から、検量線を用いて繊維束のケイ素含有量を求める。測定数はn=10とし、それらの平均値を求めて測定値とする。
前駆体繊維束の単繊維の両端を、走査型プローブ顕微鏡装置付属の金属製サンプルホルダー板上にカーボンペーストで固定し、走査型プローブ顕微鏡にて以下の条件で測定する。先ず走査型プローブ顕微鏡により単繊維の形状像を測定する。測定画像について、画像解析により繊維軸に垂直な方向の断面プロファイルを10点計測して輪郭曲線の最高部と最低部の高低差(Rp-v)および中心線平均粗さRaを求める。単繊維10本について測定を行い、平均値を求める。
装置:エスアイアイナノテクノロジーズ社 SPI4000プローブステーション、SPA400(ユニット)、
走査モード:ダイナミックフォースモード(DFM)(形状像測定)、
探針:エスアイアイナノテクノロジーズ社製 SI-DF-20、
Rotation:90°(繊維軸方向に対して垂直方向にスキャン)、
走査速度:1.0Hz、
ピクセル数:512×512、
測定環境:室温、大気中。
単繊維1本に対して、上記条件にて1画像を得て、前記画像を画像解析ソフト(SPIWin)で以下条件にて画像解析する。
得られた形状像に、〔フラット処理〕、〔メディアン8処理〕、〔三次傾き補正〕を行い、曲面を平面にフィッティング補正した画像を得る。平面補正した画像の表面粗さ解析より、繊維軸に垂直な方向の断面プロファイルを計測し、輪郭曲線の最高部と最低部の高低差(Rp-v)および中心線平均粗さRaを求める。
リフト、振動、スキャナのクリープ等によってイメージデータに現れたZ軸方向の歪み、うねりを除去する処理であり、SPM測定上の装置因によるデータのひずみを除去する処理である。
処理するデータ点Sを中心とする3×3の窓(マトリクス)においてSおよびD1~D8の間で演算を行い、SのZデータを置き換えることで、スムージングやノイズ除去といったフィルタの効果を得るものである。
メディアン8処理は、SおよびD1~D8の9点のZデータの中央値を求めて、Sを置き換えるものである。
傾き補正は、処理対象イメージの全データから最小二乗近似によって曲面を求めてフィッティングし、傾きを補正するものである。(1次)(2次)(3次)はフィッティングする曲面の次数を示し、3次では3次曲面をフィッティングする。三次傾き補正処理によって、データの繊維の曲率をなくしフラットな像とする。
耐炎化繊維束を任意の箇所で繊維長5cmに切断して12mg精秤採取し、試料繊維軸が正確に平行になるようにして引き揃える。繊維の長手方向に対して垂直方向における幅が2mmで、かつ前記幅方向および繊維の長手方向の両方に対して垂直な方向における厚さが均一である繊維束に整える。この繊維束の両端に酢酸ビニル/メタノール溶液を含浸させて形態が崩れないように固定したものを被測定用のサンプル繊維束とする。
結晶配向度(%)={(180-W)/180}×100
結晶配向度の測定は、測定対象の繊維束の長手方向において3個のサンプル繊維束を採取し、それぞれ結晶配向度を測定して平均値を求める。
尚、X線回折測定は、X線源としてリガク社製のCuKα線(Niフィルター使用)X線発生装置(商品名:TTR-III、回転対陰極型X線発生装置)を用い、回折強度プロファイルはリガク社製のシンチレーションカウンターにより検出する。出力は50kV-300mAとする。
繊維束を構成する単繊維の繊維断面の長径と短径との比(長径/短径)は、以下のように決定する。
内径1mmの塩化ビニル樹脂製のチューブ内に測定用の繊維束を通した後、これをナイフで輪切りにして試料を準備する。ついで、この試料を繊維断面が上を向くようにしてSEM試料台に接着し、さらにAuを約10nmの厚さにスパッタリングしてから、電子顕微鏡(フィリップス社製、製品名:XL20走査型)により、加速電圧7.00kV、作動距離31mmの条件で繊維断面を観察し、単繊維の繊維断面の長径及び短径を測定する。
樹脂含浸炭素繊維束のストランド試験体の調製および強度の測定は、JIS R7608に準拠して実施する。ただし、弾性率の算出はASTMに準じたひずみ範囲を用いて実施する。
炭素繊維束から単繊維を抜き取り、スパッター装置により白金を2~5nmの厚さにスパッターしたのち、カーボンコーター装置によりカーボンを100~150nmの厚さにコーティングする。その後、集束イオンビーム加工装置((株)日立ハイテクノロジーズ製、製品名:FB-2000A)を用いて、タングステン保護膜を約500nmの厚さにデポジションしたのち、加速電圧30kVの集束イオンビームでエッチングすることにより、繊維の横断面の薄片(厚さ100~150nm)を得る。
さらに、画像解析ソフトウェア(日本ローパー(株)製、製品名:Image-Pro PLUS)を用いて、TEM画像で明るくみえる空隙部分を抽出し、横断面の全体にわたって空隙数Nを計数するとともに、個々の空隙の面積を計測して円相当径d(nm)を算出する。また、空隙の面積の総和A(nm2)及び平均空隙直径D(nm)を求める。
T=R-r。
上記の測定を5本の繊維について行い、平均値を求める。
150mm長の炭素繊維束の両端に長さ25mmの掴み部を取り付け試験体とする。試験体の作製の際、0.1×10-3N/デニールの荷重を掛けて炭素繊維束の引き揃えを行う。この試験体に結び目を1つほぼ中央部に形成し、引張時のクロスヘッド速度は100mm/minで実施する。引張破断応力を繊維束の断面積(単位長さ当たりの束の質量と密度)で除した値を結節強さとする。試験数は12本とし、最小と最大値を取り除き、10本の平均値で表示する。
〔膨潤糸および前駆体繊維の調製〕
アクリロニトリル、メタクリル酸を水系懸濁重合により重合し、アクリロニトリル単位/メタクリル酸単位=98/2質量%からなるアクリロニトリル系共重合体を得た。得られた重合体をジメチルホルムアミドに溶解して濃度23.5質量%の紡糸原液を調製した。
ここで、アミノ変性シリコーンを主成分とする油剤は以下のものを用いた。
・乳化剤;NIKKOL BL-9EX(日光ケミカルズ株式会社製、POE(9)ラウリルエーテル)、15質量%。
次いで、複数の前駆体繊維束を平行に揃えた状態で耐炎化炉に導入し、220℃~280℃に加熱された空気を前駆体繊維束に吹き付けることによって、前駆体繊維束を耐炎化して密度1.342g/cm3の耐炎繊維束を得た。ここで、密度1.200g/cm3から1.250g/cm3の範囲で、5.0%の伸長を行い、さらに密度1.250g/cm3から1.300g/cm3の範囲で1.5%の伸長を行い、さらに1.300g/cm3から1.340g/cm3の範囲で-0.5%伸長させた。合計の伸長率は6%とし、耐炎化処理時間は70分とした。
引き続いて、重炭酸アンモニウム10質量%の水溶液中を走行せしめ炭素繊維束を陽極として、被処理炭素繊維1g当り40クーロンの電気量となる様に対極との間で通電処理を行い、温水90℃で洗浄した後乾燥した。次に、ハイドランN320(DIC株式会社製)を0.5質量%付着させ、ボビンに巻きとり、炭素繊維束を得た。実施例1及び比較例1~3における、炭素繊維の単繊維の繊維断面の長径と短径との比(長径/短径)は1.005、直径は4.9μmであった。
Bステージ化したエポキシ樹脂#410(180℃硬化タイプ)を塗布した離型紙上にボビンから巻き出した炭素繊維束の156本を引き揃えて配置して、加熱圧着ローラを通して、エポキシ樹脂を含浸した。その上に保護フィルムを積層して、樹脂含有量約33質量%、炭素繊維密度125g/m2、幅500mmの一方向引揃えプリプレグ(以下、「UDプリプレグ」という)を作製した。
前記UDプリプレグを使用して積層板を成形し、積層板の0°引張強度をASTM D3039に準拠した評価法により測定した。
紡糸工程での延伸条件を表1に示した。
得られた凝固糸と膨潤糸の膨潤度、膨潤糸の表面開孔幅測定、前駆体繊維束の広角X線測定、TMA評価、および耐炎化糸の広角X線測定、炭素繊維のストランド強度、弾性率ならびに断面空隙観察、結節強度測定を実施した。その結果を表2に示した。実施例1は高い機械的性能を有する炭素繊維となっていることが確かめられた。
実施例1と同様にして、紡糸工程の条件を一部変更して、膨潤糸と前駆体繊維束を得た。前駆体繊維の繊度は、0.77dtexとし、また単繊維の繊維断面の長径と短径との比(長径/短径)は1.005であった。引き続き、同じ焼成条件で炭素繊維束を製造した。炭素繊維の単繊維の繊維断面の長径と短径との比(長径/短径)は1.005、直径は4.9μmであった。
表1に紡糸工程の条件、表2に各種繊維束の評価結果をまとめて示した。
実施例14で得られた前駆体繊維束を用いて、第2と第3炭素化炉で加熱処理条件のみを変更して、その他の条件は実施例14と同様にして炭素繊維束を作製した。表3にその熱処理条件及び炭素繊維束の性状を示した。
実施例14と同じ紡糸条件で単繊維の繊度のみ変更して得られた前駆体繊維束を用いて、実施例15の焼成条件のうち、第2と第3炭素化炉で加熱処理条件のみを変更した以外は実施例15と同じ焼成条件で炭素繊維束を作製した。前駆体繊維、熱処理条件、及び炭素繊維束の性状を表4に示した。
油剤のアミノ変性シリコーンの種類を変更した以外は実施例14と同様な条件で、前駆体繊維束、引き続き炭素繊維束を作製した。
用いたアミノ変性シリコーン種、前駆体繊維及び炭素繊維束の性状を表5に示した。
実施例1と同様にして、紡糸工程の条件を一部変更して、膨潤糸と前駆体繊維束を得た。前駆体繊維の繊度は、0.77dtexとし、また単繊維の繊維断面の長径と短径との比(長径/短径)は1.005であった。引き続き、同じ焼成条件で炭素繊維束を製造した。炭素繊維の単繊維の繊維断面の長径と短径との比(長径/短径)は1.005、直径は4.9μmであった。
表1に紡糸工程の条件、表2に各種繊維束の評価結果を示した。
Claims (21)
- 繊維の円周方向に10nm以上の幅がある開孔部を0.3個/μm2以上2個/μm2以下の範囲で単繊維の表面に有する、油剤処理されていない炭素繊維用アクリロニトリル膨潤糸。
- 水銀圧入法により測定される細孔分布において、平均細孔サイズが55nm以下であり、総細孔体積が0.55ml/g以下である請求項1に記載の膨潤糸。
- 膨潤糸を構成する重合体が、アクリロニトリル単位96.0質量%以上99.7質量%以下と、一つ以上のカルボキシル基もしくはエステル基を有する不飽和炭化水素単位0.3質量%以上4.0質量%以下を必須成分とするアクリロニトリル系共重合体である請求項1または2に記載の膨潤糸。
- 〔1〕アクリロニトリル96.0質量%以上99.7質量%以下と、一つ以上のカルボキシル基もしくはエステル基を有する不飽和炭化水素0.3質量%以上4.0質量%以下を必須成分として共重合させたアクリロニトリル系共重合体を、20質量%以上25質量%以下の濃度範囲で有機溶剤に溶解させて温度50℃以上70℃以下の紡糸原液を調製する工程、
〔2〕この紡糸原液を、乾湿式紡糸法を用いて吐出孔から一旦空気中に吐出させた後、温度-5℃以上20℃以下、有機溶剤濃度78.0質量%以上82.0質量%以下の水溶液からなる凝固浴中で凝固させて前記有機溶剤を含む凝固糸束を得る工程、
〔3〕前記凝固糸束を空気中で1.0倍以上1.25倍以下の範囲で延伸した後、更に、有機溶剤を含有する温水溶液中で延伸する工程であって、両延伸による合計延伸倍率を2.6倍以上4.0倍以下として延伸する工程、
〔4〕引き続き、温水にて脱溶剤し、さらに熱水中で0.98倍以上2.0倍以下延伸させる工程を有する膨潤糸の製造方法。 - 有機溶剤がジメチルホルムアミドあるいはジメチルアセトアミドのいずれかである請求項4に記載の方法。
- 前記温水溶液中での延伸倍率を2.5倍以上4.0倍以下とする請求項4または5に記載の方法。
- アクリロニトリル96.0質量%以上99.7質量%以下と、一つ以上のカルボキシル基あるいはエステル基を有する不飽和炭化水素0.3質量%以上4.0質量%以下を必須成分として共重合させたアクリロニトリル共重合体からなり、シリコーン化合物を主成分とする油剤で処理されたケイ素含有量が1700ppm以上5000ppm以下である炭素繊維用前駆体繊維束であって、ソックスレー抽出器を用いたメチルエチルケトンによる8時間油剤洗浄後のケイ素含有量が50ppm以上300ppm以下である炭素繊維用前駆体繊維束。
- 単繊維の繊度が0.5dtex以上1.0dtex以下、単繊維の繊維断面の長径と短径との比(長径/短径)が1.00以上1.01以下、単繊維の繊維軸方向に延びる表面凹凸構造が無く、最高部と最低部の高低差(Rp-v)が30nm以上100nm以下であり、中心線平均粗さ(Ra)が3nm以上10nm以下である請求項7に記載の前駆体繊維束。
- 請求項4~6のいずれかの製法で得られた膨潤糸の束に、シリコーン化合物を主成分とする油剤を、膨潤糸100質量%に対して油剤成分0.8質量%以上1.6質量%以下を付着させて乾燥させ、次いで熱延伸法もしくはスチーム延伸法によって1.8倍以上6.0倍以下の範囲で延伸を施す炭素繊維用前駆体繊維束の製造方法。
- シリコーン化合物として、以下の条件(1)及び(2)を満たすアミノ変性シリコーン化合物を用いる請求項9に記載の方法。
(1)25℃における動粘度50cst以上5000cst以下、
(2)アミノ当量1,700g/mol以上15,000g/mol以下。 - シリコーン化合物を主成分とする油剤を、請求項1~3のいずれかに記載の膨潤糸の束に付着させる炭素繊維用前駆体繊維束の製造方法。
- 請求項11に記載の製法により得られた前駆体繊維束を220~260℃の熱風循環型の耐炎化炉に30分以上100分以下の間通過せしめて、伸長率0%以上10%以下として酸化雰囲気下で熱処理することによる、以下の条件を満足する耐炎化繊維束の製造方法。
(1)繊維束広角X線測定による赤道方向のピークA(2θ=25°)とピークB(2θ=17°)の強度比(B/A)1.3以上、
(2)ピークBの配向度80%以上、
(3)ピークAの配向度79%以上、
(4)密度1.335g/cm3以上1.360g/cm3以下。 - 請求項7または8に記載の前駆体繊維束を、220~260℃の熱風循環型の耐炎化炉に30分以上100分以下の間通過せしめて、伸長率0%以上10%以下として酸化雰囲気下で熱処理することによる、以下の条件を満足する耐炎化繊維束の製造方法。
(1)繊維束広角X線測定による赤道方向のピークA(2θ=25°)とピークB(2θ=17°)の強度比(B/A)1.3以上、
(2)ピークBの配向度80%以上、
(3)ピークAの配向度79%以上、
(4)密度1.335g/cm3以上1.360g/cm3以下。 - 請求項12または13に記載の耐炎化繊維束の製造方法において、伸長処理条件を少なくとも3つのブロックに分割し、繊維の密度が1.200g/cm3以上1.260g/cm3以下の範囲以下で3.0%以上8.0%以下の伸長、繊維の密度が1.240g/cm3以上1.310g/cm3以下の範囲で0.0%以上3.0%以下の伸長、繊維の密度が1.300g/cm3以上1.360g/cm3以下の範囲で-1.0%以上2.0%以下の伸長を施す方法。
- 樹脂含浸ストランド強度が6000MPa以上、ASTM法で測定されるストランド弾性率が250から380GPa、単繊維の繊維軸方向に垂直な断面の長径と短径との比(長径/短径)が1.00~1.01、単繊維の直径が4.0μmから6.0μmであり、単繊維の繊維軸方向に垂直な断面に直径が2nm以上15nm以下の空隙が1個以上100個以下存在する、炭素繊維束。
- 前記空隙の平均直径が、6nm以下である請求項15に記載の炭素繊維束。
- 前記空隙の面積の総和A(nm2)が2,000nm2以下である請求項15または16に記載の炭素繊維束。
- 単繊維の繊維軸方向に垂直な断面に存在する空隙の面積の総和A(nm2)の95%以上に当たる空隙が、繊維の表面から深さ150nmの位置の間に存在する請求項16または17に記載の炭素繊維束。
- 結節強さが900N/mm2以上の炭素繊維である請求項15から18のいずれかに記載の炭素繊維束。
- 請求項8に記載の前駆体繊維束を、酸化雰囲気下での熱処理により密度1.335g/cm3以上1.355g/cm3以下の耐炎化繊維束にした後、不活性雰囲気中300℃以上700℃以下の温度勾配を有する第一炭素化炉にて2%以上7%以下の伸長を加えながら1.0分以上3.0分以下加熱し、引き続き不活性雰囲気中1000℃から焼成温度までの温度勾配を有するひとつ以上の炭素化炉にて-6.0%以上2.0%以下の伸長を加えながら1.0分以上5.0分以下熱処理を行う炭素繊維束の製造方法。
- 請求項9または10に記載の製造方法により得られた前駆体繊維束を、酸化雰囲気下での熱処理により1.335g/cm3以上1.355g/cm3以下の耐炎化繊維束にした後、不活性雰囲気中300℃以上700℃以下の温度勾配を有する第一炭素化炉にて2%以上7%以下の伸長を加えながら1.0分以上3.0分以下加熱し、引き続き不活性雰囲気中1000℃から焼成温度までの温度勾配を有するひとつ以上の炭素化炉にて-6.0%以上2.0%以下の伸長を加えながら1.0分以上5.0分以下熱処理を行う炭素繊維束の製造方法。
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JP2015030942A (ja) * | 2013-08-05 | 2015-02-16 | 三菱レイヨン株式会社 | 炭素繊維用アクリロニトリル前駆体繊維束及びその製造方法 |
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JP2015161056A (ja) * | 2014-02-28 | 2015-09-07 | 三菱レイヨン株式会社 | 炭素繊維用アクリロニトリル前駆体繊維束及びその製造方法 |
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Also Published As
Publication number | Publication date |
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BRPI1012968A2 (pt) | 2018-01-16 |
JP4945684B2 (ja) | 2012-06-06 |
CN102459722A (zh) | 2012-05-16 |
TW201114960A (en) | 2011-05-01 |
CA2764661C (en) | 2013-10-01 |
CA2764661A1 (en) | 2010-12-16 |
TWI396785B (zh) | 2013-05-21 |
ES2534649T3 (es) | 2015-04-27 |
CA2820976A1 (en) | 2010-12-16 |
CA2820976C (en) | 2014-02-25 |
EP2441865A4 (en) | 2013-05-22 |
EP2441865B1 (en) | 2015-02-18 |
CA2820810A1 (en) | 2010-12-16 |
KR101340140B1 (ko) | 2013-12-10 |
US20190233975A1 (en) | 2019-08-01 |
KR20120023181A (ko) | 2012-03-12 |
US20120088104A1 (en) | 2012-04-12 |
CA2820810C (en) | 2014-01-28 |
EP2441865A1 (en) | 2012-04-18 |
JPWO2010143680A1 (ja) | 2012-11-29 |
CN102459722B (zh) | 2014-04-16 |
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