WO2012081407A1 - 炭素繊維プリプレグおよびその製造方法、炭素繊維強化複合材料 - Google Patents
炭素繊維プリプレグおよびその製造方法、炭素繊維強化複合材料 Download PDFInfo
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- WO2012081407A1 WO2012081407A1 PCT/JP2011/077750 JP2011077750W WO2012081407A1 WO 2012081407 A1 WO2012081407 A1 WO 2012081407A1 JP 2011077750 W JP2011077750 W JP 2011077750W WO 2012081407 A1 WO2012081407 A1 WO 2012081407A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B11/00—Making preforms
- B29B11/14—Making preforms characterised by structure or composition
- B29B11/16—Making preforms characterised by structure or composition comprising fillers or reinforcement
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/10—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by a fibrous or filamentary layer reinforced with filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/12—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by the relative arrangement of fibres or filaments of different layers, e.g. the fibres or filaments being parallel or perpendicular to each other
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/248—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using pre-treated fibres
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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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
- B29K2105/0872—Prepregs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2307/00—Use of elements other than metals as reinforcement
- B29K2307/04—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
- B32B2260/023—Two or more layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
Definitions
- the present invention relates to a carbon fiber bundle composed of a large number of carbon fiber single yarns and a carbon fiber prepreg composed of a matrix resin, and a method for producing the same.
- the present invention also relates to a carbon fiber reinforced composite material obtained by molding the carbon fiber prepreg of the present invention.
- the carbon fiber prepreg of the present invention provides a carbon fiber reinforced composite material with good appearance quality.
- the dispersion spots of the carbon fiber single yarn due to the partial aggregation of the carbon fiber single yarn in the carbon fiber bundle generate lightness and shade on the surface of the molded body.
- disturbances in the orientation of the carbon fiber single yarn such as fluctuations and twists, change the appearance depending on the angle of incidence of light on the surface of the molded body, which gives the viewer an unpleasant feeling. This discomfort is often referred to as “irritation”, “glare”, “yuragi”, etc., and there has been a desire for a molded body that is avoided and has no such discomfort.
- Patent Documents 1 to 11 it is difficult to understand spots by a method of suppressing a resin flow by defining a resin flow at the time of molding or a method of concealing the surface with a translucent glass scrim cloth. There was a way. However, these are all improvements in moldability that suppress the occurrence of defects that greatly impair the appearance, and are not aimed at improving the designability of the carbon fiber reinforced composite material, but have been limited to the improvement of the molding defects.
- An object of the present invention is to provide a carbon fiber prepreg suitable for manufacturing a carbon fiber composite material in which visual spots on the surface are eliminated, that is, to provide a carbon fiber prepreg having a high uniformity in appearance, and to manufacture the same. It is another object of the present invention to provide a carbon fiber composite material having a good appearance quality.
- One of the carbon fiber prepregs of the present invention for achieving the object of the present invention is as follows.
- a carbon fiber prepreg composed of a carbon fiber bundle composed of a number of carbon fiber single yarns and a matrix resin impregnated in the carbon fiber bundle, cutting when the carbon fiber prepreg is cut at right angles to the arrangement direction of the carbon fiber bundle.
- the value of the coefficient of variation expressed as a percentage of the number of carbon fiber single yarns contained per unit area having a depth from the surface of the carbon fiber prepreg of 30 ⁇ m and a width of 100 ⁇ m is 10% or less.
- the arrangement direction of the carbon fiber bundle refers to the longitudinal direction of the carbon fiber bundle, that is, the fiber axis direction.
- this carbon fiber prepreg may be referred to as a first carbon fiber prepreg.
- Another one of the carbon fiber prepregs of the present invention for achieving the object of the present invention is as follows.
- the projected area of the carbon fiber single yarns having a fiber orientation angle of 0 ° ⁇ 3 ° or more is A carbon fiber prepreg that is 2% or less of the projected area of the entire carbon fiber single yarn.
- this carbon fiber prepreg may be referred to as a second carbon fiber prepreg.
- the projected area of the carbon fiber single yarn having a fiber orientation angle of 0 ° ⁇ 3 ° or more is preferably 2% or less of the projected area of the entire carbon fiber single yarn.
- the projected area of the carbon fiber single yarn having a fiber orientation angle of 0 ° ⁇ 3 ° or more is the total projected area of the carbon fiber single yarn. More preferably, it is 0.8% or less.
- the major axis / minor axis ratio of the carbon fiber single yarn is 1.00 to 1.10, and the carbon fiber single yarn is The surface smoothness is preferably 20 or less.
- the Si / C atomic ratio on the surface of the carbon fiber single yarn is preferably 0.01 or less.
- the basis weight of the carbon fiber in the carbon fiber prepreg is preferably 30 g / m 2 to 100 g / m 2 .
- the content of the matrix resin in the carbon fiber prepreg is preferably 15% by mass to 50% by mass.
- the matrix resin is preferably an epoxy resin composition.
- the method for producing the carbon fiber prepreg of the present invention for achieving the object of the present invention is as follows.
- a tension of 0.3 to 6 cN / tex is applied to the carbon fiber bundle before the carbon fiber bundle is impregnated with the matrix resin.
- a method for producing a carbon fiber prepreg comprising a step of widening the carbon fiber bundle to 80 to 98% of a target width in advance by aligning the multiple carbon fiber single yarns forming the carbon fiber bundle.
- the tension applied to the carbon fiber bundle is 0.5 to 6 cN / tex.
- the fiber entanglement degree of the carbon fiber bundle is preferably 10 or less.
- the drape value of the carbon fiber bundle is preferably 5 cm to 18 cm.
- the carbon fiber reinforced composite material of the present invention for achieving the object of the present invention is as follows.
- the target width in the step of expanding the carbon fiber bundle to 80 to 98% of the target width in advance means a width obtained by dividing the total width of the prepreg by the number of carbon fiber bundles in the prepreg. That is, the target width means the spread width per carbon fiber bundle in the prepreg.
- a carbon fiber prepreg in which the carbon fiber bundle is uniformly expanded over the entire prepreg width can be obtained by impregnating the carbon fiber bundle with a heated resin. .
- the value of the coefficient of variation (in the following, this value may be abbreviated as CV value), the fiber orientation angle and the rate of the disturbance are shown in the following method. Ask for.
- ⁇ CV value of the number of carbon fiber single yarn The carbon fiber prepreg to be measured for the CV value of the number of single carbon fiber yarns is left at 50 ° C under normal pressure for 2 weeks, and then left at each temperature in the order of 80 ° C, 110 ° C, 130 ° C, and 180 ° C for 30 minutes. Prepare a prepreg that is cured without flowing and the matrix resin is cured. The prepared prepreg obtained by curing the matrix resin is used as a prepreg for measuring the CV value of the number of single carbon fibers.
- a 10 mm ⁇ 10 mm rectangular sample is cut out from the measurement prepreg with the first axis as the fiber arrangement direction (fiber axis). Twenty samples are collected almost uniformly from the entire width of the prepreg. Each collected sample is cut at right angles to the first axis (fiber axis) to prepare 20 measurement samples.
- the prepared measurement sample is embedded with a position fixing resin so that the cut surface obtained by cutting can be seen, and the embedded resin is cured.
- the surface of the sample for measurement embedded in the obtained cured resin where the cut surface is visible is polished with # 800 sandpaper to prepare a measurement piece.
- the polished surface (prepreg cut surface) of the prepared measurement piece is photographed with a microscope: VHX-500 manufactured by Keyence Corporation.
- This photo was taken with a lens: VH-Z100R, field of view range: 1.02 ⁇ 0.76 mm, magnification: 300 ⁇ , resolution 1600 ⁇ 1200 pixels, number of measurement points: one point of each surface from each measurement piece Is done.
- a 200 mm ⁇ 200 mm rectangular sample is cut out from the carbon fiber prepreg with the first axis as the fiber arrangement direction (fiber axis direction), and used as a measurement piece. Five measurement pieces are collected almost uniformly from the entire width of the prepreg.
- the obtained measurement piece is a prepreg with a release paper
- the measurement piece is immersed in water to remove surface air.
- alcohol or a surfactant may be added to water so that the surface air is easily removed.
- the resulting measurement piece is photographed with a microscope manufactured by Keyence Corporation: VHX-500 such that the orientation of the carbon fiber single yarn is averagely oriented in the 0 ° direction (the first axis direction).
- lens VH-Z20R
- field of view range 3.04 ⁇ 2.28 mm
- magnification 100 ⁇
- number of measurement points positions of 5 points from any surface of each measurement piece This is done by randomly selecting and taking a picture of the selected location.
- the obtained photographs are subjected to image analysis using the image processing library HALCON (Ver. 8.0) manufactured by MVTec in the following procedure, and noise removal, contour enhancement, binarization, expansion / contraction, and thinning are performed. Then, after emphasizing each single carbon fiber yarn, after calculating the fiber orientation direction (0 °) of the average carbon fiber single yarn, the fiber orientation direction of the average carbon fiber single yarn obtained by the calculation The carbon fiber single yarn that is at a certain angle ( ⁇ 3 °) or more and a certain length (150 pixels, equivalent to 0.285 mm) or more is extracted, and the carbon fiber single yarn is disturbed according to the equation (1) Measure the percentage of
- the carbon fiber prepreg according to the present invention has good uniformity in the arrangement of carbon fiber single yarns.
- the carbon fiber composite material molded using this has excellent designability on the observed surface (design surface). That is, in the carbon fiber composite material formed using the carbon fiber prepreg according to the present invention, a state in which the dispersion and orientation variation of the carbon fiber single yarn is extremely small is observed on the surface and has an excellent appearance design. .
- the obtained carbon fiber reinforced composite material especially in products used for applications where its appearance is directly observed, greatly increases the product value of the product and further eliminates the need for surface coating. It is also useful for weight reduction.
- FIG. 1 is a schematic side view of a measuring device for the number of occurrences of yarn cracking in a carbon fiber bundle.
- FIG. 2 is a schematic side view of a fiber bundle pretreatment device for measuring the drape value of the fiber bundle.
- FIG. 3 is a schematic side view of an apparatus for measuring the drape value of a fiber bundle.
- FIG. 4 is a schematic side view of the prepregizing apparatus.
- the carbon fiber prepreg of the present invention will be further described using its embodiment.
- the carbon fiber prepreg of the present invention is characterized in that the CV value of the number of carbon fiber single yarns contained per unit area measured by the above method is 10% or less.
- the CV value of the number of single carbon fibers per unit area is preferably 8% or less.
- the projected area of the carbon fiber single yarn having a fiber orientation angle of 0 ° ⁇ 3 ° or more is 2% or less of the total projected area of the single yarn, preferably the fiber orientation angle is 0.
- the projected area of the carbon fiber single yarn of ° ⁇ 3 ° or more is 0.8% or less of the total single yarn projected area.
- the projected area of the carbon fiber single yarn whose fiber orientation angle is 0 ° ⁇ 3 ° or more 2% or less, preferably 0.8% or less it is possible to maintain the uniformity of the appearance of the prepreg and at the same time
- a molded product having a good appearance can be obtained.
- the number of carbon fiber single yarns per unit area is It is preferable that the projected area of the carbon fiber single yarn having a CV value of 10% or less and a fiber orientation angle of 0 ° ⁇ 3 ° or more is 2% or less of the entire single yarn projected area.
- the carbon fiber prepreg of the present invention preferably has a fiber basis weight of 30 g / m 2 to 100 g / m 2 , and more preferably 40 g / m 2 to 80 g / m 2 .
- the fiber basis weight By setting the fiber basis weight to 100 g / m 2 or less, it is possible not only to easily produce a low-weight molded product, but also to suppress the occurrence of fiber alignment spots due to the movement of the fiber in the thickness direction of the prepreg. From this viewpoint, a more preferable fiber basis weight is 80 g / m 2 or less. Moreover, when the fiber basis weight is 30 g / m 2 or more, when a large number of carbon fiber single yarns are spread uniformly, the single yarns can easily maintain straightness. From this viewpoint, a more preferable fiber basis weight is 40 g / m 2 or more.
- the content of the matrix resin of the carbon fiber prepreg of the present invention is preferably 15% by mass to 50% by mass, and more preferably 20% by mass to 40% by mass.
- the resin content When the resin content is set to 15% by mass or more, the resin can easily be uniformly present on the surface when the molded body is manufactured. From this viewpoint, a more preferable resin content is 20% by mass or more. Moreover, it can suppress that fiber orientation is disturb
- the matrix resin used in the carbon fiber prepreg of the present invention is not particularly limited, but a thermosetting resin is preferably used.
- thermosetting resins examples include polyester resins, vinyl ester resins, and epoxy resins. Curing agents, thickeners, shrinkage inhibitors and the like used for the thermosetting resin are appropriately used and are not particularly limited. As the thermosetting resin, an epoxy resin is preferable.
- the epoxy resin examples include a glycidyl ether obtained from a polyol, a glycidyl amine obtained from an amine having a plurality of active hydrogens, a glycidyl ester obtained from a polycarboxylic acid, and a compound having a plurality of double bonds in the molecule.
- examples include polyepoxide obtained by oxidation.
- bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol type epoxy resin such as tetrabromobisphenol A type epoxy resin, novolac type epoxy such as phenol novolac type epoxy resin, cresol novolac type epoxy resin Resins, glycidylamine type epoxy resins such as tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, tetraglycidylxylenediamine, and the like, or combinations thereof are preferably used.
- any compound having an active group capable of reacting with an epoxy group can be used.
- amine-based curing agents such as ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, aliphatic amines such as m-xylylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiethyldiphenylmethane, diaminodiethyldiphenylsulfone, etc.
- Tertiary amines such as aromatic amines, benzyldimethylamine, tetramethylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, basic active hydrogen compounds such as dicyandiamide, adipic acid dihydrazide, etc.
- imidazoles such as organic acid dihydrazide, 2-methylimidazole and 2-ethyl-4-methylimidazole.
- aliphatic acid anhydrides such as polyazibic acid anhydride, poly (ethyloctadecanedioic acid) anhydride, polysebacic acid anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene
- Alicyclic acid anhydrides such as dicarboxylic acid anhydrides, aromatic acid anhydrides such as phthalic anhydride, trimetic acid anhydride, pyromellitic anhydride, glycerol tristrimellitate, halogens such as het acid anhydride, tetrabromophthalic anhydride, etc.
- acid anhydrides such as polyazibic acid anhydride, poly (ethyloctadecanedioic acid) anhydride, polysebacic acid anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohe
- an amine-based curing agent particularly a basic active hydrogen compound can be preferably used as the curing agent because it is cured at a relatively low temperature and has good storage stability.
- these curing agents can be used in combination with an appropriate curing accelerator.
- Preferred examples include a combination of a curing agent such as dicyandiamide and a urea derivative or an imidazole derivative as a curing accelerator, a curing agent such as a carboxylic acid anhydride or a polyphenol compound, and a curing accelerator as 3 Examples include a combination of a secondary amine or an imidazole derivative.
- an amine curing agent particularly dicyandiamide
- a urea curing accelerator composed of a urea derivative is used as a curing accelerator. It is preferable to use together.
- urea curing accelerators include 3-phenyl-1,1 dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU), 1,1′-4 (methyl-m-phenylene).
- Bis (3,3′dimethylurea) and the like are preferably used, and among them, compounds having two urea groups in the molecule, such as 1,1′-4 (methyl-m-phenylene) bis (3,3 'Dimethylurea) is preferably used.
- the room temperature stability of the resin composition decreases.
- the above-mentioned curing agent is 4 to 8 parts by mass with respect to 100 parts by mass of the epoxy resin, and the curing accelerator is 0.5 to 5 parts by mass. It is preferable to add within the range of parts.
- curing agent curing accelerator
- other components such as polymer compounds, organic particles, and inorganic particles can be appropriately blended in the epoxy resin composition according to the purpose.
- thermoplastic resin is preferably used as such a polymer compound.
- a thermoplastic resin is blended, it is preferable to optimize the viscosity of the resin composition and the handleability of the prepreg and to have a high polarity because an effect of improving adhesiveness can be expected.
- the thermoplastic resin is selected from a carbon-carbon bond, amide bond, imide bond, ester bond, ether bond, carbonate bond, urethane bond, urea bond, thioether bond, sulfone bond, imidazole bond, and carbonyl bond in the main chain.
- a thermoplastic resin having such a bond is preferably used.
- thermoplastic resins a group of thermoplastic resins belonging to engineering plastics such as polyacrylate, polyamide, polyaramid, polyester, polycarbonate, polyphenylene sulfide, polybenzimidazole, polyimide, polyetherimide, polysulfone, polyethersulfone are more.
- polyimide, polyetherimide, polysulfone, polyethersulfone and the like are suitably used because of their excellent heat resistance.
- the blending amount of the thermoplastic resin is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total epoxy resin in the epoxy resin composition to give an appropriate viscoelasticity to the epoxy resin composition, and at the time of molding.
- the material may be easy to handle and may have an effect of increasing the mechanical strength of the obtained carbon fiber reinforced plastic.
- rubber particles and thermoplastic resin particles are preferably used as the organic particles blended in the epoxy resin composition. These particles are preferable because they have the effect of improving the toughness of the resin and the impact resistance of the carbon fiber reinforced plastic member.
- thermoplastic resin particles polyamide or polyimide particles are preferably used.
- cross-linked rubber particles and core-shell rubber particles obtained by graft polymerization of a different polymer on the surface of the cross-linked rubber particles are preferably used.
- inorganic particles blended in such an epoxy resin composition examples include silica, alumina, smectite, and synthetic mica. These inorganic particles are blended in the epoxy resin composition mainly for rheology control, that is, for thickening and thixotropy imparting.
- carbon fiber used for the carbon fiber prepreg pitch-based or polyacrylonitrile-based carbon fibers are used, and polyacrylonitrile-based carbon fibers are preferable because of their relatively high tensile strength.
- the tensile strength of the carbon fiber bundle is preferably 3500 MPa or more, and more preferably 4500 MPa or more. By selecting the tensile strength of the carbon fiber bundle in such a range, it is possible to reduce the weight of the obtained carbon fiber composite material.
- the elastic modulus of the carbon fiber bundle is preferably 200 to 450 GPa, more preferably 225 to 400 GPa.
- the thickness of the carbon fiber composite material (molded product) can be kept thin, and by setting it to 450 GPa or less, the composite properties of the molded product, particularly, the shear strength thereof can be kept high. it can.
- the fiber diameter of the carbon fiber single yarn is preferably 3 to 8 ⁇ m.
- the fiber diameter of the carbon fiber single yarn is more preferably 4 to 7.5 ⁇ m because a large number of single yarns can be easily aligned. From such a viewpoint, the fiber diameter of the carbon fiber single yarn is more preferably 4.5 to 6.5 ⁇ m.
- the carbon fiber bundle it is preferable that a large number of single yarns forming the carbon fiber bundle are aligned in the same direction.
- a carbon fiber bundle produced by non-twisting firing in a flameproofing and carbonizing process is used with less entanglement between carbon fiber single yarns.
- the degree of entanglement between single yarns in the carbon fiber bundle is preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less.
- the degree of entanglement is measured by the following method.
- the entanglement degree of the carbon fiber bundle is measured according to the entanglement degree measuring method of JIS L1013: 2010 “Chemical fiber filament yarn test method”.
- One end of the measurement sample of the carbon fiber bundle is attached to an upper grip portion of a drooping device having an appropriate performance, a load (100 g) is suspended at a position 1 m below the grip portion, and the measurement sample is suspended vertically.
- a hook (hook made of a wire having a diameter of 1 mm) is inserted at a point 1 cm below the upper grip portion of the measurement sample so as to divide the carbon fiber bundle into two.
- a predetermined load (10 g) is attached to the other end of the hook, and the hook is lowered at a speed of about 2 cm / second. Measure the descent distance L [mm] of the hook to the point where the hook stopped due to the entanglement of the yarn forming the fiber bundle.
- the degree of entanglement is obtained by the following equation using the measured hook drop distance L [mm].
- L 1000.
- the degree of entanglement is expressed as an average value obtained by repeating the above operation 50 times.
- the carbon fiber bundle to be used may be uniformly expanded in the carbon fiber prepreg manufacturing process while maintaining good yarn handling properties in the carbon fiber manufacturing process, in particular, the winding process and the carbon fiber prepreg manufacturing process. It is preferable to have both good convergence and spreadability. From such a viewpoint, it is preferable that the single yarn constituting the carbon fiber bundle has a circular cross-sectional shape and a smooth surface.
- a single yarn of a carbon fiber bundle was cut in a direction perpendicular to the fiber axis, and a cross section of 25 randomly selected single yarns was observed using an SEM, and the ratio of major axis / minor axis when approximated as an ellipse was It is preferably 1.00 to 1.10, more preferably 1.01 to 1.05, and still more preferably 1.02 to 1.04.
- the surface of the single yarn has an arithmetic average roughness Ra of the carbon fiber surface measured by the following method of preferably 20 or less, more preferably 10 or less, and even more preferably 7 or less.
- the major axis / minor axis ratio is preferably in the range of 1.00 to 1.10, more preferably 1.01 to 1.05, still more preferably 1.02 to 1.04, and the surface roughness Ra is preferably By setting it to 20 or less, more preferably 10 or less, and even more preferably 7 or less, the single yarns constituting the carbon fiber bundle are arranged compactly in the carbon fiber bundle, and the surface is smooth, so that the single yarn Since misalignment can be prevented, the convergence of the carbon fiber bundle becomes high, and the disturbance of the single yarn when an external force is applied is prevented, and the carbon fiber bundle spreads uniformly. As a result, the carbon fiber bundle with uniform single yarn orientation can be supplied to the matrix resin impregnation step for producing the prepreg.
- ⁇ Long diameter / short diameter ratio of carbon fiber single yarn> The major axis and minor axis in the cross-sectional shape of the single yarn in the carbon fiber bundle are observed by observing the cross-section of the single yarn of the carbon fiber bundle with a scanning electron microscope.
- the shortest is the short diameter, and the ratio of the long diameter to the short diameter is determined by dividing the long diameter by the short diameter.
- the surface smoothness of the carbon fiber is evaluated by the arithmetic average roughness (Ra) of the surface.
- the arithmetic average surface roughness is measured as follows. As a measurement sample, a carbon fiber cut to a length of several millimeters is used, fixed on a substrate (silicon wafer) using a silver paste, and the center portion of each single yarn by an atomic force microscope (AFM). In this case, an image having a three-dimensional surface shape is obtained.
- ⁇ Scanning mode Tapping mode
- Probe Probe integrated silicon cantilever
- Scanning range 2.5 ⁇ m 2
- Scanning speed 0.3Hz -Number of pixels: 512 ⁇ 512
- Measurement environment Room temperature, in air.
- a substance that inhibits its spreadability such as a residue of silicon oil oxide or carbide such as soot, may remain on the surface of the carbon fiber, but it is desirable that these be removed.
- the carbonized carbon fiber surface is anodized with an alkaline aqueous solution. Then, by performing a surface treatment that is washed with an acidic aqueous solution or carbonizing at a high temperature, and then performing a surface treatment, the amount of Si on the carbon fiber surface, which is an index of foreign matter, is 0.01 or less in terms of the ESCA atomic ratio. It is preferable to do.
- ⁇ Atom ratio of Si and C on the fiber surface (Si / C)>
- the peak area ratio between the Si 2P peak and the C 1S peak observed near 100 eV is obtained under the measurement device and measurement conditions described below, and the measured value is multiplied by the device constant 0.814 of the device described next.
- Pre-processing method After refluxing with a Soxhlet extractor for 2 hours using a 2: 1 (weight ratio) mixture of methanol and chloroform, it is immersed in sulfuric acid at room temperature for 12 hours, thoroughly washed with methanol, and air-dried.
- the number of occurrences of yarn cracking measured by the method described below is preferably 3 or less / 100 m.
- the pretreatment step in the prepreg manufacturing process that is, the opening step of the carbon fiber bundle, and the carbon fiber bundle in the prepreg step in which the carbon fiber bundle is impregnated with the matrix resin. Opening can be performed without performing an unreasonable opening operation, and in these steps, a carbon fiber bundle having a uniform spread can be obtained. Thereby, a carbon fiber prepreg having good straightness of the carbon fiber single yarn is produced.
- a fiber bundle 2 to be measured is placed on a creel device 1 capable of adjusting tension, the fiber bundle 2 is unwound from the creel device 1, and a plurality of fixed guide bars 3 having a plurality of rolls arranged in a staggered manner.
- the fiber bundle 2 is widened and wound around the winder 5 at a speed of 5 m / min so that the total fiber fineness per 1 mm of the yarn width becomes 1100 dtex while applying a tension of 0.45 cN / tex.
- the fiber bundle 2 is continuously run for about 100 m, and a gap having a width of 1 mm or more generated between the fibers at the end position 4 of the widening downstream from the fixed guide bar 3 is visually regarded as “thread breakage”. Count the number (number of occurrences).
- the carbon fiber used in the present invention is to adjust the spinning conditions after determining the spinning conditions of the polyacrylonitrile precursor, that is, the solvent type of the spinning dope, the degree of polymerization of the polymer, the copolymer composition, and the concentration.
- This precursor adjusts the temperature and concentration of the coagulation bath and the concentration of the polymer stock solution, and sets the conditions for the coagulation rate to be relatively slow, so that when wet spinning is used, the take-up speed of the coagulated yarn and the die discharge linear velocity
- the ratio can be manufactured by keeping the so-called draft low.
- the draft is set higher than wet spinning, and by adopting the coagulation bath temperature and concentration conditions to obtain a uniform coagulated yarn, a precursor with a smooth surface and a circular cross-section is obtained. Can be manufactured.
- a surfactant is added to the precursor to prevent deterioration of the quality of the fiber bundle due to fusion between single yarns in the firing process and insufficient convergence of the fiber bundle, and to keep the properties of the resulting carbon fiber high.
- a silicone oil as the surfactant, and it is more preferable to use an oil containing an amino-modified silicone dispersed or dissolved in an aqueous system as a component.
- the precursor thus obtained is flame-resistant in a heated atmosphere of 200 to 300 ° C. under tension without being twisted, then carbonized in an inert gas atmosphere at a maximum temperature of 2000 ° C. or less, and then as necessary. Then, the carbon fiber bundle is manufactured by graphitizing at a maximum temperature of 3000 ° C. or less under an inert gas atmosphere, subjecting it to surface treatment and sizing treatment, drying and winding up on a drum or bobbin.
- the preferred tension in the carbonization step is 2 to 8 cN / carbonized yarn tex
- the preferred tension in the graphitization step is 4 to 8 cN / graphitized yarn tex
- the preferred tension in the post-treatment (surface treatment, sizing) step is 2 to 8 cN / final yarn tex.
- Sizing agents applied after surface treatment include sizing agents containing epoxy groups and urethane groups and other surfactants.
- the amount of sizing agent applied is preferably 0.1 to 2% by mass, more preferably 0.5 to 1.2% by mass with respect to the carbon fiber.
- the fiber bundle After applying the sizing agent, the fiber bundle can be dried while applying appropriate tension, and wound on a drum or bobbin to obtain a carbon fiber bundle.
- the amount of sizing agent applied and the sizing agent are applied so that the drape value of the carbon fiber bundle after the sizing treatment is 5 cm to 18 cm, preferably 8 cm to 15 cm. It is preferable to adjust the drying conditions of the obtained fiber bundle.
- the drape value of the carbon fiber bundle By setting the drape value of the carbon fiber bundle to be 5 cm or more, it is possible to secure the convergence of the carbon fiber bundles traveling on the yarn path, particularly the carbon fiber single yarns in the carbon fiber bundle, and the alignment spots of the carbon fiber single yarns. Can be prevented. Furthermore, it is possible to prevent the occurrence of fluff at the yarn path from the creel containing the carbon fiber bundle to the resin impregnation step when the prepreg is formed, that is, when the carbon fiber bundle is impregnated with the matrix resin to produce the prepreg. . In addition, by maintaining the drape value at 18 cm or less, it is possible to ensure good fiber opening between the carbon fiber single yarns.
- the upper end of the carbon fiber bundle F cut to about 50 cm is attached to the sample fixture 21, the weight W is attached to the lower end, and the carbon fiber bundle F is suspended.
- the sample is allowed to stand for 30 minutes or more at a tension of 0.0375 g / tex applied by the weight W in an atmosphere of a temperature of 23 ° C. and a humidity of 60% to prepare a measurement sample.
- a portion having a length of about 30 cm shown in FIG. 2 excluding the upper end side and the lower end side of the prepared measurement sample is cut out from the measurement sample to produce a measurement piece FP.
- Fig. 3 shows a drape value measuring device.
- the drape value measuring device 30 includes a measuring table 31 having a horizontal upper surface, a quadrangular column A fixed to the upper surface of the measuring table 31, and a flat plate B (not shown) prepared separately from these.
- One end of the prepared measurement piece FP is fixed to the upper surface of the quadrangular column A in a cantilever-supported state.
- the portion of the measuring piece FP fixed to the upper surface of the quadrangular column A is parallel to the upper surface of the measuring table 31 and is perpendicular to the side surface of the quadrangular column A.
- the flat plate B is attached to the lower surface of the measurement piece FP and held in the horizontal direction so that the length from the side surface of the square column A to the tip of the measurement piece FP is 25 cm.
- the fiber bundle passage route (yarn path) is formed using a yarn path guide so as not to cause false twisting, twisting or entanglement of the single yarn
- a yarn path guide that has a small single yarn converging effect with respect to the width of the fiber bundle and that has a small friction against the single yarn.
- a force in a direction different from the fiber arrangement direction (fiber axis direction) is not applied to the fiber bundle at the time of conversion.
- a carbon fiber bundle can be obtained in which the number of occurrences of yarn cracking in the fiber bundle is 3/100 m or less and the entanglement degree is 10 or less, preferably 5 or less, more preferably 3 or less.
- the number of single yarns in the carbon fiber bundle is preferably 15000 or less. . From this point of view, the number of single yarns is preferably smaller. However, when the number of single yarns decreases, it is necessary to use a larger number of carbon fiber bundles in order to obtain a target prepreg. In this case, the carbon fiber bundle must be manufactured by aligning the fibers with a uniform tension, which increases the industrial difficulty. Therefore, practically, the number of fiber single yarns in the fiber bundle is preferably 500 or more, and more preferably 1000 to 7000.
- the original yarn width of the carbon fiber bundle that forms the prepreg is equal to the width per carbon fiber bundle in the prepreg, that is, the target width. Narrow is preferred. Therefore, it is preferable to use a carbon fiber package wound up with such an original yarn width. In addition, by not using a fiber bundle having a very narrow original yarn width, a prepreg can be created without causing spots during fiber opening.
- the base yarn width is preferably 95% or less of the target width, and more preferably 90% or less. Further, the base yarn width is preferably 25% or more of the target width, and more preferably 30% or more.
- the original yarn width of the carbon fiber bundle less than 90% of the target width, even if the yarn width is increased during prepreg formation, there is less interference with the yarn in the adjacent carbon fiber bundle, and the straightness of the single yarn is improved.
- a prepreg that is maintained and has a uniform thickness and spreadability of the fiber bundle can be produced.
- the desired yarn width of the carbon fiber bundle is the fineness of the carbon fiber bundle, the number of single yarns forming the carbon fiber bundle (number of filaments), the process conditions after the surface treatment step in the manufacturing process of the carbon fiber bundle, particularly
- the carbon fiber bundle can be obtained by appropriately adjusting the conditions when winding the carbon fiber bundle on a bobbin or drum.
- the original yarn width of the carbon fiber bundle is determined by measuring the yarn width immediately before the carbon fiber bundle is separated from the package surface when the carbon fiber is pulled out in units of 0.1 mm with a ruler for all bobbins, and the average value is the original yarn width. It was.
- any apparatus can be used as long as it can apply tension to the fibers so as to align the fibers in one direction, and has a function of widening the carbon fiber bundle before the resin impregnation.
- equipment that blows the compressed air and widens the carbon fiber bundle may cause entanglement of the single yarn in the carbon fiber bundle, so it is preferable to use a widening means such as a roll.
- the width of the carbon fiber sheet composed of a plurality of carbon fiber bundles before impregnation with the resin is such that a tension of 0.3 to 6 cN / tex is applied to each carbon fiber bundle, preferably a tension of 0.5 to 6 cN / tex is applied. More preferably, by applying a tension of 1.5 to 3 cN / tex, the yarn width of the carbon fiber before resin impregnation / the target width (%) per carbon fiber bundle in the prepreg, that is, the width of each fiber bundle It is preferable that the ratio of the width of the total fiber bundle obtained by adding together to the width of the target prepreg sheet (hereinafter referred to as the widening ratio) is 80 to 98%, preferably 85 to 95%. .
- the carbon fiber sheet has a widening ratio of 98% or less, it is possible to prevent the carbon fibers from overlapping when obtaining the target width with the pressure during resin impregnation, and to suppress a decrease in dispersibility of the carbon fiber single yarn.
- the widening rate of a carbon fiber sheet it is more preferred that it is 95% or less.
- the carbon fiber sheet widening ratio it becomes possible to obtain the target width while preventing excessive widening by the pressure during resin impregnation. From this point of view, the more preferable width expansion ratio of the carbon fiber sheet is 85% or more.
- the tension applied to the fiber bundle By setting the tension applied to the fiber bundle to be 0.3 cN / tex or more, it is possible to prevent a phenomenon in which the single yarn in the carbon fiber bundle is largely moved by the resin forced into the resin during the resin impregnation. Furthermore, by setting the tension to 0.5 cN / tex or more, the movement in the thickness direction of the single yarn in the carbon fiber bundle during resin impregnation can be prevented, and the straightness of the carbon fiber single yarn can also be suppressed. From this viewpoint, a more preferable tension is 1.5 cN / tex or more. By setting the tension to 6 cN / tex or less, generation of fluff at the time of opening the carbon fiber bundle can be prevented. From this viewpoint, a more preferable tension is 3 cN / tex or less.
- the carbon fiber bundle When the carbon fiber bundle is widened by applying the above tension, the single yarn is abraded and cut, and there are many single yarns that are fuzzy and disturbed on the surface of the prepreg, resulting in a prepreg with deteriorated appearance quality. Sometimes. Therefore, it is desirable to gradually widen the carbon fiber bundle in multiple stages using a plurality of widening rolls.
- the widening width of the carbon fiber bundle per roll is [(yarn width after passing through the roll ⁇ yarn width before passing through the roll) / yarn width before passing through the roll] (%), it is preferable per roll per stage.
- the widening width of the carbon fiber bundle is 10% or less on an average per stage.
- the carbon fiber single yarn can be uniformly dispersed. From this point of view, the more preferable widening width per one widening roll is 7% or less on average.
- ⁇ Thread width of carbon fiber bundle before resin impregnation> For the yarn width of the carbon fiber bundle before resin impregnation, the yarn width on the pass line before resin impregnation was measured in units of 0.1 mm with a ruler for all the carbon fiber bundles passing through the pass line, and the average value was calculated as the resin width. The yarn width before impregnation was used.
- FIG. 4 is a schematic side view of an example of a prepreg forming apparatus used in the prepreg forming step.
- the prepreg forming apparatus 40 includes a pair of introduction rolls 7a and 7b, a heater 8, a pair of impregnation rolls 9a and 9b, and a pair of take-out along the pass line 41 from the side where the carbon fiber sheet 6 is introduced. Rolls 10a and 10b and a winding device 11 are arranged.
- the carbon fiber sheet 6 expanded to 80 to 98% of the target width is supplied between the pair of introduction rolls 7a and 7b, and the release sheet (release paper) 13 is supplied along the upper introduction roll 7a.
- the sheet 42 formed by stacking the three-layer sheets passes through the heater 8, during which the resin of the prepreg resin sheet 12 is fluidized and then fluidized between the pair of impregnating rolls 9 a and 9 b.
- the carbon fiber sheet 6 is impregnated with a resin (matrix resin).
- the carbon fiber sheet 6 impregnated with resin is taken up while being sandwiched between a pair of take-up rolls 10a and 10b.
- the release sheet 13 of the sheet 42 from the pair of take-up rolls 10a and 10b toward the winding device 11 is peeled off from the sheet 42 along the upper take-up roll 10a.
- the carbon fiber sheet (prepreg) 43 impregnated with the matrix resin is wound into a roll shape by the winding device 11.
- a roll of unidirectional prepreg in which a large number of carbon fiber single yarns are arranged in one direction is produced.
- the release sheet 13 supplied along the upper introduction roll 7 a may be replaced with a prepreg resin sheet similar to the prepreg resin sheet 12.
- the resin of the resin sheet 12 is heated to about 80 to 150 ° C. by the heater 8, and the sheet 42 is pressed at 40 to 150 N / cm in the pair of impregnating rolls 9 a and 9 b, and the resin to the carbon fiber sheet is Impregnation takes place. At this time, the heated resin is impregnated into the carbon fiber of the carbon fiber sheet, and the fiber is widened to a predetermined width by the action of the impregnating roll, and cooled in that form, thereby obtaining a uniform thickness and a uniform thickness. A prepreg having a single yarn orientation is produced.
- the prepreg thus obtained is molded into a cylindrical body used for fishing rods and golf shafts by sheet winding, and after the surface is fastened with a wrapping tape or the like, the matrix resin is cured in a heating furnace, and carbon A fiber composite material (molded body) is produced.
- a plurality of prepregs obtained in this manner are laminated at a predetermined fiber orientation angle, and the matrix resin is cured in an autoclave or a heating furnace while removing voids using a vacuum bag, and a carbon fiber composite material ( Molded body) is manufactured.
- the prepreg thus obtained is put into a mold and press-molded to produce a carbon fiber composite material (molded body), for example, a panel used for a housing or the like.
- the carbon fiber composite material produced in this way is excellent in the uniformity of its appearance.
- Example 1 A dimethyl sulfoxide solution containing 20% by mass of an acrylonitrile polymer having an intrinsic viscosity [ ⁇ ] of 1.80 consisting of 99.5 mol% of acrylonitrile and 0.5 mol% of itaconic acid was prepared as a spinning dope. This spinning dope is once discharged into the air from each spinning hole of a spinneret having 6000 spinning holes having a hole diameter of 0.15 mm, and then a coagulation bath comprising a 35% aqueous dimethyl sulfoxide solution adjusted to 10 ° C. To obtain a coagulated yarn. The obtained coagulated yarn was washed with water and then stretched.
- a surfactant mainly composed of an amino-modified silicone dispersion was applied to the stretched coagulated yarn, and then the coagulated yarn provided with the surfactant was dried and densified.
- the dried and densified coagulated yarn is drawn by using a steam drawing device to obtain a precursor fiber bundle consisting of 6000 single yarns having a circular cross section and a smooth surface, and the obtained precursor fiber bundle is bobbins. Rolled up.
- the roll or guide is devised and the yarn (precursor fiber bundle) is used as a bobbin. Winded up. The fiber entanglement degree of the obtained precursor fiber was 1.5.
- the precursor fiber was unwound from a bobbin so as not to be twisted, subjected to a carbonization process, flameproofed in a non-twisted state, and then carbonized at a maximum temperature of 1900 ° C. with a tension of 5 g / carbonized yarn tex. Thereafter, the obtained carbon fiber bundle was continuously anodized at the same tension to impart compatibility with the matrix resin. Next, a sizing agent was applied to the anodized carbon fiber bundle, and after drying, the carbon fiber bundle was wound around a bobbin.
- the obtained carbon fiber bundle had a fineness of 250 tex, a filament number of 6000, a strand strength of 5490 MPa measured according to JIS R7608: 2007, an elastic modulus of 295 GPa, and a thread width on the bobbin of 3.5 mm.
- the major axis / minor axis ratio of the carbon fiber single yarn was 1.03, and the surface smoothness was Ra 2.5.
- the fiber entanglement degree of this carbon fiber bundle is 2.7, Si / C by ESCA is 0.00 (0.001 or less), the drape value is 15.0 cm, and the number of occurrences of yarn cracking is 2.
- Bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd., jER1005F): 20 parts by mass, bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd., jER828): 80 parts by mass was melt kneaded and dicyandiamide at 40 to 60 ° C. (Mitsubishi Chemical Corporation, DICY-7): 5 parts by mass, dicyandiamide (CVC Specialty Chemicals, Omicure 24): 4.2 parts by mass were added and kneaded to obtain a resin composition.
- This resin composition was applied to a carrier sheet to obtain a prepreg resin sheet that forms a matrix resin in the prepreg.
- a plurality of the carbon fiber bundles obtained above were aligned by applying a tension of 1.9 cN / tex, and passed through a multistage widening device composed of a plurality of rolls to obtain a carbon fiber sheet.
- a carbon fiber prepreg sheet was obtained under the conditions shown in Table 1 using the obtained carbon fiber sheet and the obtained resin sheet for prepreg.
- the sample prepreg is cut from the obtained carbon fiber prepreg sheet, and left at 50 ° C under normal pressure for 2 weeks, and then left at each temperature in the order of 80 ° C, 110 ° C, 130 ° C, 180 ° C for 30 minutes to allow the matrix resin to flow. Without curing.
- a 10 mm ⁇ 10 mm rectangular sample was cut out from the resin-cured prepreg with the first axis as the fiber arrangement direction (fiber axis). Twenty samples were collected almost uniformly from the entire width of the prepreg. Each collected sample was cut at right angles to the first axis (fiber axis) to prepare 20 measurement samples.
- the prepared measurement sample was embedded with a position fixing resin so that the cut surface obtained by cutting was visible, and the embedded resin was cured. The surface where the cut surface of the measurement sample embedded in the obtained cured resin was visible was polished with # 800 sandpaper to prepare a measurement piece.
- the polished surface (prepreg cut surface) of the prepared measurement piece was photographed with a KEYENCE microscope: VHX-500. This photo was taken with a lens: VH-Z100R, field of view range: 1.02 x 0.76 mm, magnification: 300 times, resolution 1600 x 1200 pixels, number of measurement points: one photo of each surface from each sample. Done by shooting.
- a rectangular sample of 200 mm ⁇ 200 mm is cut out with the first axis as the fiber arrangement direction (fiber axis direction), and a measurement piece for measuring the fiber orientation angle and the rate of disturbance thereof Prepared. Five measurement pieces were collected almost uniformly from the full width of the prepreg in the width direction. And one measurement piece was immersed in water and surface air was removed.
- Photographs were taken with a KEYENCE microscope: VHX-500 such that the orientation of single yarns averaged in the 0 ° direction.
- This photograph is taken with a lens: VH-Z20R, field of view range: 3.04 ⁇ 2.28 mm, magnification: 100 ⁇ , resolution 1600 ⁇ 1200 pixels, number of measurement points: 5 points each from an arbitrary surface of one measurement piece The position was selected at random.
- the obtained photographs are subjected to image analysis using the image processing library HALCON (Ver. 8.0) manufactured by MVTec in the following procedure, and noise removal, contour enhancement, binarization, expansion / contraction, and thinning are performed. Then, after emphasizing each fiber, after calculating the fiber orientation direction of the average carbon fiber single yarn, with respect to the fiber orientation direction (0 °) of the average carbon fiber single yarn obtained by the calculation Extract carbon fiber yarns that are at a certain angle ( ⁇ 3 °) or more and a certain length (150 pixels, equivalent to 0.285 mm) or more, and follow the above equation (1) to disrupt the carbon fiber yarns. The ratio was calculated. The average value of the measured values at a total of 25 points was defined as the ratio of disorder of the fiber orientation angle.
- Table 1 shows the obtained ratio of the angle of 3 ° or more.
- Examples 2 to 9 and Comparative Examples 1 to 11 Using the same spinning dope as in Example 1, adjusting the number of spinning holes of the die, spinning method, spinning / firing conditions, the major axis / minor axis ratio of the single yarn cross section after firing, and the surface roughness Various carbon fibers having the values shown in Tables 1 to 3 and Tables 4 to 7 were produced.
- Tables 1 to 3 and Tables 4 to 7 show the results of prepreging these carbon fibers according to the conditions shown in Tables 1 to 3 and Tables 4 to 7, respectively.
- the CV value of the number of carbon fiber single yarns is 10% or less, a carbon fiber prepreg having excellent appearance characteristics is obtained, and there is no partial brightness gradation on the surface, and the fiber orientation angle is inclined by ⁇ 3 ° or more.
- the area ratio was 2% or less, a carbon fiber prepreg having more excellent appearance characteristics was obtained, and a prepreg that appeared uniform without any partial reflection abnormality on the surface.
- a carbon fiber prepreg having a poor appearance was obtained when the CV value of the number of single carbon fibers exceeded 10% and the area ratio of fibers whose fiber orientation angle was tilted by ⁇ 3 ° or more exceeded 2%.
- the evaluation of the appearance is that five inspectors determine the brightness of the prepreg surface and the uniformity of light reflection (spots), that is, whether the quality is good, good, or bad, and five are good for each item. Those judged were excellent, those judged good by four people were good, and those judged not good by three or less were judged as bad.
- Evaluation is made by placing the prepreg on a horizontal desk, for lightness, judging shading from the Z-axis direction (perpendicular to the prepreg surface), and for light reflection, from the Z-axis direction to the Y-axis direction. Reflection spots were determined by changing the angle to (carbon fiber axis direction).
- a carbon fiber reinforced composite material was formed using this carbon fiber prepreg.
- a plurality of carbon fiber prepregs were laminated and placed in a mold so that the thickness of the formed carbon fiber prepreg was 1 mm, and compression molding was performed.
- the mold shape was such that a flat surface could be molded, the molding conditions were a mold temperature of 150 ° C., a molding pressure of 2 MPa, and the time until demolding was 5 minutes.
- Carbon fiber prepregs (Comparative Examples 2 to 11) in which the CV value of the number of single carbon fiber yarns exceeds 10% and the ratio of the projected area of the fibers with the fiber orientation angle tilted by ⁇ 3 ° or more exceeds 2% (Comparative Examples 2 to 11) have poor appearance. It became a carbon fiber reinforced composite material. In Comparative Example 1 in which the yarn width of the carbon fiber bundle before impregnation / the target width (%) per carbon fiber bundle was set low, a carbon fiber prepreg could not be produced.
- Light-weight carbon fiber composite material (molded product) that gives a good appearance to the carbon fiber composite material, for example, improved design of carbon fiber composite material (molded product) for sports, industrial, and aircraft use, and simplified painting ) Can be obtained.
- Creel device 2 Fiber bundle to be measured 3: Fixed guide bar 4: End position of widening 5: Winder 6: Widened carbon fiber bundle 7a, 7b: Introduction roll 8: Heater 9a, 9b: Impregnation roll 10a, 10b : Take-up roll 11: winding device 12: resin sheet for prepreg 13: release paper 21: sample fixture 30: drape value measuring device 31: measuring table 40: prepreg forming device 41: pass line 42: carbon fiber sheet, prepreg 43: Carbon fiber prepreg A: Square column F: Carbon fiber bundle FP: Drape value measurement piece W: Weight
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Abstract
Description
炭素繊維単糸数のCV値の測定対象の炭素繊維プリプレグを、常圧下50℃で2週間、その後、80℃、110℃、130℃、180℃の順に各温度で30分放置し、マトリックス樹脂を流動させずに硬化させ、マトリックス樹脂が硬化したプリプレグを用意する。用意されたマトリックス樹脂が硬化したプリプレグを、炭素繊維単糸数のCV値の測定用プリプレグとして用いる。
炭素繊維プリプレグから、第1軸を繊維の配列方向(繊維軸の方向)として200mm×200mmの矩形状のサンプルを切り出し、測定片とする。測定片は、プリプレグ全幅からほぼ均一に5枚を採取する。
計測された合計25点の測定値の平均値を炭素繊維単糸の繊維配向角度の乱れの割合とする。
炭素繊維束の交絡度は、JIS L1013:2010「化学繊維フィラメント糸試験方法」の交絡度測定方法に準じて測定する。炭素繊維束の測定試料の一端を適当な性能を有する垂下装置の上部つかみ部に取り付け、つかみ部より1m下方の位置に荷重(100g)を吊り下げ、測定試料を垂直に垂らす。測定試料の上部つかみ部より1cm下部の点に、炭素繊維束を2分割するようにフック(直径1mmの針金からなるフック)を挿入する。フックの他端に所定の荷重(10g)を取り付け、約2cm/秒の速度でフックを降下させる。フックが繊維束を形成している糸の絡みにより停止した点までのフックの降下距離L[mm]を測定する。
使用される炭素繊維束は、炭素繊維製造工程、なかでも巻取工程、および炭素繊維プリプレグ製造工程において良好な糸取り扱い性を保持しつつ、炭素繊維プリプレグ製造工程で均一に拡がるものであることが好ましく、良好な収束性と拡がり性を兼ね備えていることが好ましい。このような観点から、炭素繊維束を構成する単糸は、その断面形状が円形であって、その表面が平滑であるものが好ましい。
炭素繊維束における単糸の断面形状における長径、短径は、走査型電子顕微鏡により炭素繊維束の単糸の横断面を観察し、そこで観察される断面形状の直径の内、最も長いものを長径とし、最も短いものを短径とし、これら長径と短径の比を、長径を短径で除して求める。
炭素繊維の表面平滑度は、表面の算術平均粗さ(Ra)によって評価する。算術平均表面粗さは、次のようにして測定する。測定試料としては、炭素繊維を長さ数ミリメートル程度にカットしたものを用い、銀ペーストを用いて基板(シリコンウエハ)上に固定し、原子間力顕微鏡(AFM)によって、各単糸の中央部において、3次元表面形状の像を得る。
・走査モード:タッピングモード
・探針:探針一体型シリコンカンチレバー
・走査範囲:2.5μm2
・走査速度:0.3Hz
・ピクセル数:512×512
・測定環境:室温、大気中。
次に説明する測定装置、測定条件で、100eV付近に観察されるSi2PのピークとC1Sピークとのピーク面積比を求め、次に説明する装置の装置定数0.814を測定値に乗じて原子数比(Si/C)とする。
(株)島津製作所製、ESCA750・励起X線:MgのKα1、2線・C1Sメインピークの結合エネルギー値:284.6eV。
メタノールとクロロホルムの2:1(重量比)の混合液を用いてソックスレー抽出器で2時間環流後、12時間、室温で硫酸に浸漬後、メタノールで充分洗浄、風乾する。
図1に示すように、被測定繊維束2を張力調整可能なクリール装置1に仕掛け、繊維束2をクリール装置1から巻き出し、複数のロールを千鳥配列とした複数本の固定ガイドバー3により、0.45cN/texの張力を付与しながら、糸幅1mm当たりの繊維総繊度が1100dtexになるよう、繊維束2を拡幅後、速度5m/分でワインダー5に巻き取る。このようにして繊維束2を約100m連続して走行させ、固定ガイドバー3より下流側における拡幅の終了位置4において、目視により繊維間に生じた幅1mm以上の隙間を、「糸割れ」として、その個数(発生数)を数える。
炭素繊維束のドレープ値は、図2、3に示す方法によって測定する。
炭素繊維束の元糸幅は、炭素繊維を引き出した際にパッケージ表面から炭素繊維束が離れる直前の糸幅を、全ボビンについて定規により0.1mm単位で測定し、その平均値を元糸幅とした。
樹脂含浸前の炭素繊維束の糸幅は、樹脂含浸前のパスライン上での糸幅を、パスラインを通過する全炭素繊維束について定規により0.1mm単位で測定し、その平均値を樹脂含浸前の糸幅とした。
アクリロニトリル99.5モル%、イタコン酸0.5モル%からなる固有粘度[η]が1.80のアクリロニトリル系重合体を20質量%含むジメチルスルホキシド溶液を紡糸原液として用意した。この紡糸原液を、孔径が0.15mmの6000個の紡糸孔を有する紡糸口金の各紡糸孔から一旦空気中に吐出し、次いで、10℃に温調されたジメチルスルホキシド35%水溶液から成る凝固浴に導入して、凝固糸を得た。得られた凝固糸を、水洗し、その後、延伸した。次いで、延伸された凝固糸に、アミノ変性シリコーン分散物を主成分とした界面活性剤を付与した後、界面活性剤が付与された凝固糸の乾燥緻密化を行った。次いで、乾燥緻密化された凝固糸を、スチーム延伸装置を用いて延伸し、円形断面で表面平滑な単糸の6000本からなる前駆体繊維束を得て、得られた前駆体繊維束をボビンに巻き取った。
実施例2乃至9、ならびに、比較例1乃至11
実施例1と同じ紡糸原液を使用して、口金の紡糸孔数、紡糸方法、紡糸・焼成条件を調整することによって、焼成後の単糸断面の長径/短径比、表面粗さが、表1乃至表3、ならびに、表4乃至表7に示される値を有する各種炭素繊維を製造した。
2:被測定繊維束
3:固定ガイドバー
4:拡幅の終了位置
5:ワインダー
6:拡幅された炭素繊維束
7a、7b:導入ロール
8:ヒーター
9a、9b:含浸ロール
10a、10b:引取ロール
11: 巻取装置
12:プリプレグ用樹脂シート
13:離型紙
21:試料固定具
30:ドレープ値の測定装置
31:測定台
40:プリプレグ化装置
41:パスライン
42:炭素繊維シート、プリプレグ用樹脂シート、離型紙を重ね合わせたもの
43:炭素繊維プリプレグ
A:四角柱
F:炭素繊維束
FP:ドレープ値の測定片
W:おもり
Claims (14)
- 多数の炭素繊維単糸からなる炭素繊維束と該炭素繊維束に含浸されているマトリックス樹脂からなる炭素繊維プリプレグにおいて、該炭素繊維プリプレグを前記炭素繊維束の配列方向と直角に切断したときの切断面における前記炭素繊維プリプレグの表面からの深さが30μmであり、幅が100μmである単位面積当たりに含まれる前記炭素繊維単糸の数の百分率で表示した変動係数の値が、10%以下である炭素繊維プリプレグ。
- 多数の炭素繊維単糸からなる炭素繊維束と該炭素繊維束に含浸されているマトリックス樹脂からなる炭素繊維プリプレグにおいて、繊維配向角度が0°±3°以上の前記炭素繊維単糸の投影面積が、全体の前記炭素繊維単糸の投影面積の2%以下である炭素繊維プリプレグ。
- 繊維配向角度が0°±3°以上の前記炭素繊維単糸の投影面積が、全体の前記炭素繊維単糸の投影面積の2%以下である請求項1に記載の炭素繊維プリプレグ。
- 繊維配向角度が0°±3°以上の前記炭素繊維単糸の投影面積が、全体の前記炭素繊維単糸の投影面積の0.8%以下である請求項2または3に記載の炭素繊維プリプレグ。
- 前記炭素繊維単糸の長径/短径比が、1.00乃至1.10であり、かつ、前記炭素繊維単糸の表面平滑度が、20以下である請求項1または2に記載の炭素繊維プリプレグ。
- 前記炭素繊維単糸の表面のSi/C原子数比率が、0.01以下である請求項1または2に記載の炭素繊維プリプレグ。
- 前記炭素繊維プリプレグにおける炭素繊維の目付が、30g/m2乃至100g/m2である請求項1または2に記載の炭素繊維プリプレグ。
- 前記炭素繊維プリプレグにおけるマトリックス樹脂の含有率が、15質量%乃至50質量%である請求項1または2に記載の炭素繊維プリプレグ。
- 前記マトリックス樹脂が、エポキシ樹脂組成物である請求項1または2に記載の炭素繊維プリプレグ。
- 請求項1乃至9のいずれかに記載の炭素繊維プリプレグを製造する炭素繊維プリプレグの製造方法において、前記炭素繊維束に前記マトリックス樹脂を含浸させる前に、前記炭素繊維束に0.3乃至6cN/texの張力を付与して当該炭素繊維束を形成している多数の炭素繊維単糸を引き揃えることによって、該炭素繊維束を予め目的幅の80乃至98%まで拡幅する工程を含む炭素繊維プリプレグの製造方法。
- 炭素繊維束に付与する前記張力が、0.5乃至6cN/texである請求項10に記載の炭素繊維プリプレグの製造方法。
- 前記炭素繊維束における繊維交絡度が、10以下である請求項10に記載の炭素繊維プリプレグの製造方法。
- 前記炭素繊維束のドレープ値が、5cm乃至18cmである請求項10に記載の炭素繊維プリプレグの製造方法。
- 請求項1乃至9のいずれかに記載の炭素繊維プリプレグ、または、請求項10乃至13のいずれかに記載の炭素繊維プリプレグの製造方法により製造された炭素繊維プリプレグにおける前記マトリックス樹脂を硬化させることにより得られる炭素繊維強化複合材料。
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Also Published As
Publication number | Publication date |
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CN103261290B (zh) | 2016-01-27 |
KR20130131391A (ko) | 2013-12-03 |
KR101841797B1 (ko) | 2018-03-23 |
US9074064B2 (en) | 2015-07-07 |
JP5834917B2 (ja) | 2015-12-24 |
EP2653493A4 (en) | 2017-05-03 |
US20130274413A1 (en) | 2013-10-17 |
JPWO2012081407A1 (ja) | 2014-05-22 |
EP2653493A1 (en) | 2013-10-23 |
TW201231256A (en) | 2012-08-01 |
CA2820131A1 (en) | 2012-06-21 |
TWI504501B (zh) | 2015-10-21 |
CN103261290A (zh) | 2013-08-21 |
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