WO2013027708A1 - 炭素繊維用サイジング剤、その水分散液、サイジング剤の付着した炭素繊維束、シート状物、および炭素繊維強化複合材 - Google Patents
炭素繊維用サイジング剤、その水分散液、サイジング剤の付着した炭素繊維束、シート状物、および炭素繊維強化複合材 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/11—Compounds containing epoxy groups or precursors thereof
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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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
- D06M13/2246—Esters of unsaturated carboxylic acids
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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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- 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
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/24—Thermosetting resins
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Definitions
- the present invention relates to a sizing agent for carbon fiber, an aqueous dispersion thereof, a carbon fiber bundle having a sizing agent attached thereto, a sheet-like material, and a carbon fiber reinforced composite material.
- Carbon fiber is used in a wide range of fields as a carbon fiber reinforced composite material formed by compounding with resin such as epoxy resin, unsaturated polyester resin, vinyl ester resin, acrylic resin (hereinafter referred to as matrix resin) and molding.
- resin such as epoxy resin, unsaturated polyester resin, vinyl ester resin, acrylic resin (hereinafter referred to as matrix resin) and molding.
- matrix resin acrylic resin
- a method for producing a carbon fiber reinforced composition a method of impregnating a fiber as a reinforcing material with a matrix resin is common.
- a method of impregnating the fiber with the matrix resin there are a prepreg method in which the matrix resin is thinly applied on the release paper and the fibers are arranged in one direction on the release paper, a dipping method in which the fiber is passed through the matrix resin bath, and the like.
- a sheet-like material is laminated and thermally cured by pressurization using an autoclave, or after one to several hundred carbon fiber bundles are aligned and impregnated with a matrix resin.
- a pultrusion method in which a matrix resin is cured through a die, a die, or the like, and a hand layup method in which a fiber base material such as a woven fabric or a sheet is impregnated with a resin at room temperature and cured as it is are known.
- a carbon fiber reinforced composite material using carbon fiber as a reinforcing material and formed of the carbon fiber and a matrix resin is lightweight and excellent in strength and elastic modulus.
- Such composite materials are being developed for use in a wide range of fields as components for sports / leisure products, vehicles / aerospace equipment, industrial materials for energy / civil engineering, and the like. Therefore, there is a strong demand for high performance of carbon fibers as a reinforcing material.
- carbon fibers used as structural materials and industrial materials in vehicles and aerospace applications are being developed for the purpose of increasing strength and increasing elastic modulus.
- Composite materials for use in such structural materials and industrial materials are required to have a high tensile strength in the longitudinal direction of the fiber.
- carbon fiber filaments are required.
- mechanical properties such as tensile strength as a carbon fiber reinforced composite material are hardly expressed.
- carbon fibers are filaments having a diameter of about 5 to 8 ⁇ m, and the single fibers are used in the form of a unit of thousands to tens of thousands (hereinafter referred to as “carbon fiber bundles”). . Since the carbon fiber itself has a low elongation and a brittle nature, fluff is likely to occur due to mechanical friction or the like, and fluff and thread breakage are likely to occur in the manufacturing process of the composite material. Therefore, in many cases, various sizing agents are applied to the carbon fiber and sizing treatment is performed for the purpose of suppressing fluffiness. In general, the carbon fiber is used in the form of a woven fabric obtained by processing the carbon fiber bundle with a loom.
- the carbon fiber is treated with a sizing agent.
- Patent Document 1 proposes a sizing agent using polyglycidyl ethers (hereinafter referred to as “sizing agent 1”), and Patent Document 2 and Patent Document 3 disclose an epoxy resin, an unsaturated dibasic acid, and bisphenol. Proposed is a sizing agent (hereinafter referred to as “sizing agent 2”), which comprises a condensate of an alkylene oxide adduct and a alkylene oxide adduct of a phenol selected from monocyclic phenols and polycyclic phenols. Has been.
- the sizing agent 1 is excellent in impregnation property and interfacial adhesion, but it cannot be said that it has good adhesion to radical polymerization resins such as unsaturated polyester resins, vinyl ester resins and acrylic resins.
- the sizing agent 2 can be expected to improve the adhesiveness with a matrix resin, particularly an unsaturated polyester resin, and can maintain the physical properties of the fiber-reinforced composite material when an epoxy resin is used as the matrix resin.
- a matrix resin particularly an unsaturated polyester resin
- the adhesion to the radical polymerization resin is not good.
- Patent Document 4 proposes a sizing agent (hereinafter referred to as “sizing agent 3”) comprising an ester resin containing one or more epoxy groups, a urethane acrylate, an anionic emulsifier, and a small amount of a nonionic emulsifier.
- sizing agent 3 a sizing agent comprising an ester resin containing one or more epoxy groups, a urethane acrylate, an anionic emulsifier, and a small amount of a nonionic emulsifier.
- the sizing agent 3 has excellent adhesion to radical polymerization resins such as unsaturated polyester resins, vinyl ester resins, and acrylic resins, and can provide the same performance as a composite material using an epoxy resin as a matrix resin. Moreover, compatibility with an epoxy resin may be good, and the composite material combined with a wide range of thermosetting resins can exhibit excellent mechanical strength.
- radical polymerization resins such as unsaturated polyester resins, vinyl ester resins, and acrylic resins
- this sizing agent has an excellent effect of suppressing the orientation disorder and meandering of the carbon fiber filaments during the molding process, which causes the strength reduction of the carbon fiber reinforced composite material.
- Patent Documents 5 and 6 propose a sizing agent containing a polyurethane resin (hereinafter referred to as “sizing agent 4”).
- sizing agent 4 a polyurethane resin
- it is effective in suppressing phenomena such as disordered alignment and meandering of carbon fiber filaments during molding, but the sizing agent 4 uses substantially 100% polyurethane resin.
- the sizing agent 4 is designed to reinforce the thermoplastic resin so that the softening temperature of the dry film of the sizing agent is 50 to 150 ° C, it is impregnated with resin near room temperature like a composite material using radical polymerization resin When work is performed, the resin impregnation property is poor.
- the present invention has been made in view of the above circumstances, and has excellent sizing process passability, a sizing agent is uniformly attached, and a machine when combined with a resin, particularly a radical polymerization resin. It is an object of the present invention to provide a carbon fiber sizing agent and an aqueous dispersion of a sizing agent that can obtain a carbon fiber bundle excellent in the effect of improving physical properties. Further, to provide a carbon fiber bundle excellent in the mechanical property improving effect of the composite material, a sheet-like material having the carbon fiber bundle, and a carbon fiber reinforced composite material excellent in mechanical property, particularly a pultruded composite material. Objective.
- the mass ratio of the content of the compound (A) and the urethane acrylate oligomer (B) is 1/3 or more and 2/1 or less as the ratio of urethane acrylate oligomer (B) / compound (A),
- the ratio of the total amount of the compound (A) and the urethane acrylate oligomer (B) in all sizing components is 20% by mass or more,
- the carbon fiber sizing agent of the present invention preferably has a tensile strength of the dry film of the polyurethane resin (C) of 10 MPa to 50 MPa.
- the polyurethane resin (C) preferably has a glass transition temperature of ⁇ 50 ° C. or more and 35 ° C. or less.
- An aqueous dispersion in which the carbon fiber sizing agent is dispersed in water, and an aqueous dispersion of the carbon fiber sizing agent in which the average particle size of dispersed particles of the sizing agent in the aqueous dispersion is 0.3 ⁇ m or less is provided.
- a carbon fiber bundle composed of carbon fibers to which the carbon fiber sizing agent is attached that is, a carbon fiber bundle to which the carbon fiber sizing agent is attached
- the amount of the sizing agent attached is 0.6 mass% or more.
- a carbon fiber bundle that is 0% by mass or less is provided.
- it is a carbon fiber bundle made of carbon fibers to which the sizing agent is attached, which is treated with the aqueous dispersion of the sizing agent for carbon fiber, and the attached amount of the sizing agent is 0.6% by mass or more.
- a carbon fiber bundle that is 3.0% by mass or less is provided.
- a sheet-like material including the carbon fiber bundle including the carbon fiber bundle
- a composite material including the sheet-like material and a pultruded composite material including the carbon fiber bundle.
- a carbon fiber bundle is obtained that is excellent in passing through a sizing treatment process, in which a sizing agent is uniformly attached, and that is excellent in mechanical properties when combined with a resin, particularly a radical polymerization resin.
- Carbon fiber sizing agents and aqueous dispersions of sizing agents are provided.
- a carbon fiber bundle excellent in the mechanical property improving effect of the composite material a sheet-like material having the carbon fiber bundle, a carbon fiber reinforced composite material excellent in mechanical property, particularly a pultruded composite material.
- the present invention by fixing the shape of the carbon fiber bundle, it becomes easy to maintain the straight holding property of the carbon fiber bundle, thereby optimizing the resin pickup in the resin impregnation step in pultrusion molding or filament winding molding.
- a carbon fiber bundle having significantly improved properties and a sheet-like material having the carbon fiber can be obtained.
- the sizing agent for carbon fiber of the present invention contains the components (A) to (C) described in detail below. This sizing agent can be obtained by appropriately mixing each component.
- Component (A) an ester of an epoxy compound having a plurality of epoxy groups in the molecule and an unsaturated monobasic acid, and a compound having at least one epoxy group in the molecule (A)
- the component (A) contained in the carbon fiber sizing agent of the present invention needs to have at least one epoxy group in the molecule.
- the epoxy group means a group having a ring skeleton having a three-membered ring composed of two carbon atoms and one carbon atom in its structure.
- Compound (A) having at least one epoxy group in the molecule examples of the epoxy group contained in the component (A) contained in the carbon fiber sizing agent of the present invention include a group represented by the following formula (e1) and a group represented by the following formula (e2) (glycidyl group). And other cycloaliphatic epoxy groups. Examples of other cycloaliphatic epoxy groups include groups having a cyclic structure formed by the three-membered ring and a monocyclic or polycyclic aliphatic ring in the structure. For example, the following formula (e3 ) To (e5).
- the epoxy compound having a plurality of epoxy groups in the molecule forming the ester is not particularly limited, and examples thereof include bisphenol epoxy compounds and bisphenols. Alkylene oxide addition epoxy compounds, hydrogenated bisphenols epoxy compounds, hydrogenated bisphenols alkylene oxide addition epoxy compounds, and the like. These bisphenols are not particularly limited, and examples thereof include bisphenol F type, bisphenol A type, and bisphenol S type. Epoxy resins such as phenol novolak type, cresol novolak type, diphenyl type, dicyclopentadiene type, naphthalene skeleton type other than epoxy compounds of bisphenols can also be used. Further, it may have a linear aliphatic skeleton.
- the unsaturated monobasic acid forming the ester is not particularly limited as long as it is a compound having one unsaturated group and one carboxyl group. good.
- the unsaturated group is not particularly limited, but is preferably a vinyl group or a propenyl group, more preferably a vinyl group, because it is not bulky and does not lower the rigidity of the main chain of the ester formed.
- Particularly preferred is acrylic acid or methacrylic acid. That is, the component (A) is preferably an ester of the epoxy compound and acrylic acid or methacrylic acid.
- the component (A) contained in the sizing agent for carbon fiber of the present invention is an ester obtained by reacting a compound having a plurality of epoxy groups with an unsaturated monobasic acid. In this reaction, a plurality of epoxy groups are contained. Of the epoxy groups of the compound having at least one, at least one epoxy group remains unreacted, and at least one epoxy group is ring-opened by an unsaturated monobasic acid to form a so-called half ester having an unsaturated group.
- the component (A) includes an epoxy group derived from a compound having a plurality of epoxy groups in the molecule and an unsaturated group derived from an unsaturated monobasic acid (for example, CH 2 ⁇ CH—COO— derived from acrylic acid).
- radical polymerization resins such as unsaturated polyester resins, vinyl ester resins, and acrylic resins can be strongly bonded to carbon fibers, and excellent interfacial adhesion can be exhibited.
- the radical polymerization resin and the carbon fiber can be strongly bonded, and excellent interfacial adhesiveness can be expressed.
- the compound having an epoxy group at both ends of the molecule one or both of a diepoxy compound of a bisphenol and an alkylene oxide-added diepoxy compound of a bisphenol are particularly preferable.
- the component (A) is an ester of either one or both of a bisphenol diepoxy compound and a bisphenol alkylene oxide addition diepoxy compound and an unsaturated monobasic acid, and is one end of the molecular main chain. It is preferable that the compound has an unsaturated group at the other end and an epoxy group at the other end.
- (A) component may be used individually by 1 type, and may use 2 or more types together.
- the component (B) contained in the sizing agent for carbon fiber of the present invention has an effect of forming an interface phase excellent in flexibility at the interface between the matrix resin and the carbon fiber. Thereby, the interface adhesiveness between matrix resin and carbon fiber improves.
- a radical polymerization resin such as a vinyl ester resin or an unsaturated polyester resin
- many of these resins have low toughness, and soften the interface phase. The resulting increase in toughness dramatically improves interfacial adhesion.
- the sizing agent component on the carbon fiber surface diffuses into the matrix resin, and the sizing agent component is concentrated at a high concentration especially in the matrix resin near the interface. A region included in is formed. This region affects the mechanical properties of the composite material.
- component (B) component is an acrylate oligomer, when forming a fiber reinforced composite material, it will be integrated in the hardening reaction of a matrix resin, and integration of an interface phase and a matrix resin phase will be aimed at. Therefore, by including this component (B), the mechanical properties of the fiber reinforced composite material are at the same level as when the epoxy resin is used as the matrix resin even when the radical polymerization resin is used as the matrix resin. can do.
- the component (B) contained in the sizing agent for carbon fiber of the present invention needs to have a tensile elongation of 40% or more of the cured product obtained by the following measurement method, which is effective in increasing the toughness of the interface phase. Since it is excellent, the tensile elongation is more preferably 45% or more, and more preferably 50% or more.
- the upper limit of the tensile elongation rate (%) is preferably 900% or less, more preferably 700% or less in consideration of a significant reduction in the elastic modulus of the resin near the interface.
- the component (B) contained in the carbon fiber sizing agent of the present invention needs to be bifunctional. If it is a tri- or higher functional type, the crosslink density becomes too high and sufficient toughness is not exhibited. On the other hand, in the monofunctional type, the crosslinking reaction with the matrix resin is only on one side, and a sufficient toughening effect cannot be obtained.
- the viscosity at 60 ° C. is 5,000 mPa ⁇ s or more and the cured product has a tensile strength of 6 MPa or more.
- a large viscosity indicates that the molecular weight of the oligomer is large or that the cohesive force between oligomer molecules is large.
- the component (B) is unevenly distributed in the interface phase between the carbon fiber surface and the matrix resin without diffusing into the matrix resin, resulting in the effect of the interface phase. It is preferable because it can be made flexible.
- cured material can be calculated
- a mixture of 97 g of urethane acrylate oligomer (B) and 3 g of a curing agent (2-hydroxy-2-methyl-1-phenyl-propan-1-one) is applied on a glass plate to obtain a film having a thickness of 100 ⁇ m.
- the coating is cured by irradiating with ultraviolet rays for 5 seconds from a position 10 cm away from the coating using an ozone type lamp (80 W / cm).
- the tensile strength and the tensile elongation are measured at a tensile speed of 300 mm / min.
- the viscosity of component (B) at 60 ° C. is more preferably 10,000 mPa ⁇ s or more, and further preferably 20,000 mPa ⁇ s or more.
- the viscosity of component (B) can be measured with a B-type viscometer.
- the glass transition temperature (Tg) of the cured product (B) contained in the carbon fiber sizing agent of the present invention is preferably ⁇ 5 ° C. or higher, more preferably 5 ° C. or higher. If the Tg of the cured product is ⁇ 5 ° C. or more, not only can the appropriate softening be achieved by the interfacial phase, but also the value of the stress leading to fracture increases, so that a stronger interfacial phase can be formed and the above effects are achieved. improves. That is, the interfacial phase has a function of supporting the reinforcing fiber, and it becomes easy to keep the mechanical properties of the composite material favorable by appropriately suppressing the softening. As an upper limit of Tg of hardened
- the Tg of the cured product is a rate of 2 ° C./minute using a viscoelasticity measuring apparatus (manufactured by UBM, product name: Rheogel E4000) using a cured film obtained by the same method as the measurement of tensile elongation as a test piece.
- the dynamic viscoelasticity and loss tangent of the test piece are measured, and the peak temperature (tan ⁇ MAX) of the loss tangent can be obtained.
- the “urethane acrylate oligomer” is a compound having a urethane bond and an acryloyl group (CH 2 ⁇ CH—CO—) in the molecule.
- the structure of the urethane acrylate oligomer can be broadly classified into an aromatic type having an aromatic group in the structure and an aliphatic type having no aromatic group.
- the structure of the urethane acrylate oligomer used in the present invention is not particularly limited, and may be aromatic or aliphatic. Since the balance between the tensile elongation percentage and the tensile strength of the cured product is good, an aliphatic system is preferable.
- component (B) contained in the carbon fiber sizing agent of the present invention commercially available urethane acrylate oligomers may be used.
- urethane acrylate oligomers include CN-965, CN-981 manufactured by Sartomer, CN-9178, CN-9788, CN-9893, CN-971, CN-973, CN-9882, UF-8001 made by Kyoeisha Chemical, UA-122P made by Shin-Nakamura Chemical Co., Ltd. Name).
- (B) component may be used individually by 1 type, and may use 2 or more types together.
- the content of the component (B) is less than 1/3 of the content of the component (A)
- the interfacial phase is not sufficiently softened and toughened.
- the content exceeds 2/1, (A )
- the good adhesion expression effect that is a function of the component is inhibited, and the effect of improving the adhesion of the carbon fiber to the matrix resin cannot be sufficiently obtained.
- the ratio of the total amount of the component (A) and the component (B) in the total sizing component is 20% by mass or more. If it is less than 20% by mass, the functions of these two components are not sufficiently exhibited, and the effects of the present invention cannot be obtained.
- the “total sizing component” is the total amount of all components applied to the carbon fiber after the sizing treatment among the components contained in the sizing agent, and is removed after sizing, such as water or an organic solvent. Represents an active ingredient not included. That is, the “total sizing component” includes the components (A) and (B) described above, the component (C) described later, the components (D) and (E) described later as optional components, and other components. It can be obtained as a total amount.
- the ratio of the total amount of the component (A) and the component (B) is preferably 25% by mass or more, more preferably 30% by mass or more in all sizing components.
- the carbon fiber sizing agent of the present invention comprises the component (C) as an essential component.
- Component (C) is a polyurethane resin, which facilitates fixing the shape of the carbon fiber bundle. Since the shape of the carbon fiber bundle is fixed and it is easy to maintain the straight-line holding property, it becomes easy to optimize the resin pickup in the resin impregnation process in the pultrusion molding and the filament winding molding, and the resin is impregnated.
- the component (C) has an effect of forming a flexible and tough interface phase at the interface between the matrix resin and the carbon fiber, similarly to the component (B) described above.
- the component (C) one type may be used alone, or two or more types may be used in combination.
- the component (C) contained in the carbon fiber sizing agent of the present invention needs to have a dry elongation of 350% or more and 900% or less. If the tensile elongation of the dry film is within this range, the effect of fixing the shape of the carbon fiber bundle described above and maintaining the straight-running retention can be sufficiently obtained, and the interface between the matrix resin and the carbon fiber can be obtained. A tough interfacial phase can be formed.
- the component (C) preferably has a dry elongation of 420% or more and 750% or less, and more preferably 450% or more and 650% or less.
- the component (C) contained in the carbon fiber sizing agent of the present invention preferably has a dry film tensile strength of 10 MPa to 50 MPa. If it is 10 MPa or more, it is easy to obtain the effect of fixing the shape of the above-described carbon fiber bundle and maintaining the straight advanceability, and it is easy to form a tough interface phase at the interface between the matrix resin and the carbon fiber. On the other hand, if it is 50 MPa or less, the sizing agent hardly adheres to the surface of the carbon fiber, and good process passability is easily obtained in the winding process and molding process of the carbon fiber after the sizing treatment.
- the tensile strength of the dry film (C) is more preferably 15 MPa or more and 40 MPa or less, and further preferably 20 MPa or more and 35 MPa or less.
- the tensile elongation rate of a dry film can be calculated
- Polyurethane resin was applied on a glass plate, and the film was prepared under conditions of preliminary drying at room temperature for 15 hours and main drying at 80 ° C. for 6 hours, followed by heat treatment at 120 ° C. for 20 minutes, with a thickness of 500 ⁇ m. A film is obtained, and tensile strength and tensile elongation are measured at a pulling speed of 300 mm / min according to JIS K7127.
- the component (C) contained in the carbon fiber sizing agent of the present invention preferably has a glass transition temperature (Tg) of ⁇ 50 ° C. or more and 35 ° C. or less. If it is ⁇ 50 ° C. or higher, the above-described effect of fixing the shape of the carbon fiber bundle can be easily obtained, and a tough interface phase can be easily formed at the interface between the matrix resin and the carbon fiber. On the other hand, if it is 35 degrees C or less, the adhesion spot of a sizing agent will not produce easily on the carbon fiber surface, and it will become easy to obtain favorable process permeability in the winding process of carbon fiber after a sizing process, and a shaping
- Tg glass transition temperature
- the Tg of the dry film of component (C) is preferably from ⁇ 35 ° C. to 30 ° C., more preferably from ⁇ 20 ° C. to 20 ° C.
- Tg of (C) component can be measured with a dynamic viscoelasticity measuring apparatus.
- the proportion of the component (C) in all sizing components is 5% by mass or more and 50% by mass or less. If it is 5 mass% or more, the effect which fixes the shape of the carbon fiber bundle mentioned above will be easy to be acquired. If it is 50 mass% or less, the shape fixation of the carbon fiber bundle by the component (C) is likely to be good, and good handling properties and impregnation properties of the matrix resin are easily obtained.
- the proportion of the component (C) in the total sizing component is preferably 10% by mass or more and 45% by mass or less, more preferably 15% by mass or more and 40% by mass or less.
- Component E Ester compound (E) which is an ester of an alkylene oxide adduct of bisphenols and a dicarboxylic acid compound and has an acid value of 50 or more
- the sizing agent for carbon fiber of the present invention preferably further contains a component (E) in addition to the components (A), (B) and (C) described above.
- the ester (acid value of 50 or more) of an alkylene oxide adduct of bisphenols and a dicarboxylic acid compound that can be added to the sizing agent for carbon fibers of the present invention has a molecular weight of about 1000 and a carboxyl group at one end of the molecule. It is preferable to use a compound having a main component.
- a component (E) exhibits excellent compatibility with matrix resins, particularly epoxy resins and vinyl ester resins. Therefore, the wettability of the sized carbon fiber to the resin is improved, and the resin impregnation property is further improved.
- alkylene oxide adduct of bisphenols that forms the component (E) that can be added to the sizing agent for carbon fiber of the present invention
- 2 to 4 mol of ethylene oxide or propylene oxide is added to 1 mol of bisphenols. It is preferable that When the addition amount of ethylene oxide or propylene oxide to 1 mol of bisphenols is 4 mol or less, it is easy to improve the affinity with the matrix resin without impairing the rigidity of the molecular chain inherent to bisphenols. . More preferably, bisphenols are added with 2 mol of ethylene oxide or propylene oxide.
- the alkylene oxide adducts of bisphenols may be used alone or as a mixture of a plurality of compounds.
- the “dicarboxylic acid compound” that forms an ester with an alkylene oxide adduct of bisphenols is preferably an aliphatic compound having 4 to 6 carbon atoms.
- an aromatic compound is used as the dicarboxylic acid compound, the resulting ester compound has a relatively high melting point and tends to be relatively poor in solubility with the matrix resin. Therefore, an aliphatic compound is more preferable than an aromatic compound from the viewpoint of expressing good wettability.
- an aliphatic compound having 6 or less carbon atoms is used as the dicarboxylic acid compound, it is easy to improve the affinity with the matrix resin without impairing the rigidity of the resulting ester compound.
- dicarboxylic acid compound examples include fumaric acid, maleic acid, methyl fumaric acid, methyl maleic acid, ethyl fumaric acid, ethyl maleic acid, glutaconic acid, itaconic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, and adipic acid. It is done.
- the component (E) that can be added to the carbon fiber sizing agent of the present invention may be used alone or in combination of two or more.
- content of (E) component is 2.0 mass times or less with respect to the sum total of (A) component and (B) component.
- this ratio is 2 times or less, the interaction between the (A) component and the carbon fiber surface is caused by the interaction between the epoxy group of the (A) component and the acidic group (carboxy group, etc.) of the (E) component. It is possible to easily prevent the action from being hindered. As a result, the coupling function between the carbon fiber and the matrix resin of the component (A) is easily exhibited, and it is easy to improve the adhesion.
- This ratio is more preferably 1.75 or less, and most preferably 1.55 or less.
- the lower limit value of this ratio is not particularly limited, but is preferably 0.2 or more in order to exert the effect of the component (E) that improves the wettability and resin impregnation property of the sized carbon fiber to the resin. 0.4 or more is more preferable.
- the sizing agent of the present invention preferably further contains a component (D).
- the component (D) contained in the carbon fiber sizing agent of the present invention includes the components (A), (B) and (C), the optional component (E), and other components in water. It is used to disperse.
- a component may be used individually by 1 type and may use 2 or more types together.
- Examples of the component (D) contained in the carbon fiber sizing agent of the present invention include nonionic surfactants and anionic surfactants.
- a surfactant such as an aliphatic nonion and a phenol nonionic can be used.
- Aliphatic nonionic surfactants include higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid esters ethylene oxide adducts, glycerol fatty acid esters, sorbitol and sorbitan fatty acid esters, and pentaerythritol fatty acid esters.
- Etc examples of the phenol-based nonionic surfactant include alkylphenol-based nonions and polycyclic phenol-based nonions.
- ethylene oxide adduct a type in which a propylene oxide unit is provided in a part of the polyethylene oxide chain in a random or block form is preferable.
- fatty acid ethylene oxide adduct or polyhydric alcohol fatty acid ester ethylene oxide adduct nonionic surfactants such as monoester type, diester type, triester type, and tetraester type can be used.
- an anionic surfactant (D-1) component having an ammonium ion as a counter ion, and a nonionic surfactant (D-2) component described later are preferably contained simultaneously.
- the anionic surfactant (D-1) component having an ammonium ion as a counter ion has a hydrophobic group and an ammonium ion as a counter ion, so that the carbon fiber sizing agent of the present invention is used as an aqueous dispersion.
- the component (D-2) has the effect of suppressing the reaction activity between the ammonium ion of the component (D-1) and the epoxy group of the component (A). Therefore, by containing appropriate amounts of the components (D-1) and (D-2) (contents will be described in detail later), the impregnation properties of various matrix resins are further improved and treated with a sizing agent.
- the change with time of the hardness of the carbon fiber formed can be made extremely small.
- the component (D-1) is not particularly limited, and examples thereof include carboxylate, sulfate ester salt, sulfonate salt, and phosphate ester salt. Among these, sulfate ester salts and sulfonates are more preferable because they are particularly excellent in the ability to emulsify the component (A) and the component (B).
- sulfate ester salt examples include higher alcohol sulfate ester salt, higher alkyl polyethylene glycol ether sulfate ester salt, alkylbenzene polyethylene glycol ether sulfate ester salt, polycyclic phenyl ether polyethylene glycol ether sulfate ester salt, and sulfated fatty acid ester salt.
- propylene oxide units are randomly or block-containing in part of the polyethylene oxide chain in the higher alkyl polyethylene glycol ether sulfate, alkylbenzene polyethylene glycol ether sulfate, and polycyclic phenyl ether polyethylene glycol ether sulfate. Can also be used.
- sulfonate examples include alkylbenzene sulfonate, alkyl naphthalene sulfonate, polycyclic phenyl ether sulfonate, alkyl sulfonate, ⁇ -olefin sulfonate, ⁇ -sulfonated fatty acid salt, dialkyl sulfosuccinate, and the like. Is mentioned.
- an anionic surfactant having a hydrophobic group represented by the following formula (1) or (2) is more preferably used as the component (D-1).
- the anionic surfactant having a hydrophobic group represented by the formula (1) or (2) is a relatively long alkyl such as nonylphenol or octylphenol from the viewpoint of preventing the diffusion of the exogenous endocrine disrupting substance derivative. It is also preferable because it has been desired to avoid the use of an anionic surfactant having a phenol group having a group.
- R 1 is a hydrogen atom or a monovalent chain hydrocarbon group having 1 to 3 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Alternatively, a methyl group is more preferable, and a hydrogen atom is more preferable from the viewpoint of an exogenous endocrine disrupting substance derivative.
- R 2 and R 3 are a hydrogen atom or a monovalent chain hydrocarbon group having 1 to 3 carbon atoms, and may be the same or different. As the chain hydrocarbon group for R 2 and R 3, the same chain hydrocarbon group as for R 1 can be used.
- R 4 is a divalent aliphatic hydrocarbon group such as a linear or branched alkylene group having 1 to 10 carbon atoms.
- m represents a positive integer, preferably an integer of 1 to 3, and more preferably 1 or 2. If m is 3 or less, the hydrophobic group itself can be easily prevented from becoming a bulky structure, and the affinity and compatibility with the (A) component, the (B) component, and the matrix resin can be improved. Is easy. As a result, it is easy to improve the stability of emulsification, the resin impregnation property, and the mechanical properties of the fiber-reinforced composite material.
- a group in parentheses with a subscript m is a benzyl group (a group in which both R 2 and R 3 are hydrogen atoms) or a styrene group (R 2 and R 2 ) from the viewpoint of the bulkiness of the hydrophobic group molecule. It is preferable that one of 3 is a hydrogen atom and the other is a methyl group. Moreover, when m is 2 or more, that is, when there are a plurality of groups in parentheses with a subscript m, these groups may be the same or different.
- nonionic surfactant examples include “New Coal 707”, “New Coal 723”, “New Coal 707-F” manufactured by Nippon Emulsifier Co., Ltd., and the like.
- anionic surfactant (component (D-1)) examples include “New Coal 707-SF” and “New Coal 723-SF” manufactured by Nippon Emulsifier Co., Ltd., and “Hitenol manufactured by Daiichi Kogyo Seiyaku Co., Ltd. NF-13 "," Hitenol NF-17 ", etc. (all are product names).
- the component (D-2) is not particularly limited, but an aliphatic nonionic surfactant is particularly preferable because the reaction activity reducing action is extremely excellent.
- Aliphatic nonionic surfactants include higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid esters ethylene oxide adducts, glycerol fatty acid esters, sorbitol and sorbitan fatty acid esters, and pentaerythritol fatty acid esters. Etc. In these ethylene oxide adducts, a type in which propylene oxide units are randomly or block-containing in a part of the polyethylene oxide chain is also preferably used.
- fatty acid ethylene oxide adducts As higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, those containing propylene oxide units randomly or in blocks in part of these polyethylene oxide chains are more preferred. . This is because these are excellent in the ability to reduce the reaction activity of ammonium ions on epoxy groups.
- fatty acid ethylene oxide adduct and polyhydric alcohol fatty acid ester ethylene oxide adduct monoester type, diester type, triester, tetraester type and the like can be used.
- component (D-2) a commercially available product can be used, and examples thereof include “Fine Surf FON180E06 (product name)” manufactured by Aoki Yushi Co., Ltd.
- the content of the component (D) can be appropriately determined in consideration of the stability of the aqueous dispersion in which the sizing agent is dispersed in water and the sizing effect of the sizing agent. -30% by mass is preferable, and 10-25% by mass is more preferable. If the surfactant content is 5% by mass or more, it is easy to improve the stability of the aqueous dispersion in which the sizing agent is dispersed in water, and if it is 30% by mass or less, the effect of the sizing agent is achieved. Is easy to express.
- the ratio (mass ratio) of the content of the component (D-1) and the component (D-2) is The component (D-2) / the component (D-1) is preferably in the range of 1/10 to 1/5. When this ratio is within this range, the reaction activity of the ammonium ion derived from the component (D) with respect to the epoxy group of the component (A) can be easily suppressed, and the change with time of the hardness of the carbon fiber to which the sizing agent is attached is remarkably increased. This is preferable because the emulsification stability when the sizing agent is emulsified using water or the like as a medium and the wettability of the sized sizing carbon fiber surface to the resin is improved.
- the sizing agent of the present invention when the component (D-1) and the component (D-2) are contained, the component (D-1) and the component (D-2) occupying in all the sizing components
- the ratio of the total amount is preferably 10 to 25% by mass.
- the emulsion stability of the sizing agent solution is very good, and it is easy to exert the effect of the sizing agent.
- the more preferable lower limit of the total amount of the component (D-1) and the component (D-2) is 13% by mass, and the more preferable upper limit is 20% by mass.
- the aqueous dispersion of the sizing agent for carbon fibers of the present invention can be obtained as an aqueous dispersion of one sizing agent for carbon fibers by mixing and stirring (emulsification, water dispersion) each component by a conventional method. Or what was processed separately and became a plurality of kinds of water dispersions can be mixed, and one water dispersion can also be obtained.
- the concentration of components other than the sizing agent concentration (non-volatile component concentration) in the aqueous dispersion of the sizing agent for carbon fiber of the present invention that is, volatile components (water removed by drying after sizing, etc.) in the aqueous dispersion for sizing.
- concentration of components other than the sizing agent concentration (non-volatile component concentration) in the aqueous dispersion of the sizing agent for carbon fiber of the present invention that is, volatile components (water removed by drying after sizing, etc.) in the aqueous dispersion for sizing.
- the average particle diameter of the dispersed particles in the aqueous dispersion of the sizing agent for carbon fiber of the present invention is preferably 0.3 ⁇ m or less. If it is 0.3 micrometer or less, the storage stability of the aqueous dispersion of the sizing agent for carbon fibers and the temporal stability of the aqueous dispersion of the sizing agent for carbon fibers can be easily secured. Furthermore, since it is possible to easily prevent the occurrence of sizing agent adhesion spots on the surface of the carbon fiber and to easily maintain the scuff resistance of the carbon fiber, the winding process of the carbon fiber after the sizing treatment, Fluff generation in the molding process can be easily prevented, which is preferable.
- the average particle diameter is measured by, for example, a laser diffraction / scattering particle size distribution measuring apparatus.
- the sizing agent may be dispersed in a solvent.
- the volume-based average particle diameter of the polyurethane resin dispersed particles is preferably 0.2 ⁇ m or less. If the volume-based average particle size of the dispersed particles of the polyurethane resin is 0.2 ⁇ m or less, it is possible to easily prevent the sizing agent from adhering to the surface of the carbon fiber, and to maintain good scuff resistance of the carbon fiber. Therefore, it is possible to easily prevent the occurrence of fuzz in the winding process and molding process of the carbon fiber after the sizing treatment, which is preferable. In addition, there is no restriction
- polyurethane resin used in the aqueous dispersion of the polyurethane (C) component many products are commercially available from various companies in which an urethane resin is an aqueous dispersion. As described above, the tensile elongation of the dry film is 350% or more. A polyurethane resin that is 900% or less is dispersed in water, and the polyurethane resin particles in the aqueous dispersion having a volume-based average particle diameter of 0.2 ⁇ m or less can be selected.
- Examples include “Yukot UWS-145” from Sanyo Chemical Industries, Ltd., “KP-2820” from Matsumoto Yushi Seiyaku Co., Ltd., “Superflex 150HS”, “Superflex 470” from Daiichi Kogyo Seiyaku Co., Ltd. Both are product names).
- An example of a polyurethane aqueous dispersion having a dry film tensile elongation within the above range is “Permarin UA-368” (product name) manufactured by Sanyo Chemical Industries, Ltd.
- the carbon fiber bundle that can be suitably used for the carbon fiber bundle to which the sizing agent for carbon fiber of the present invention is attached may be obtained from any raw material such as pitch, rayon or polyacrylonitrile, and has high strength. Any of a type (low elastic modulus carbon fiber), medium high elasticity carbon fiber, or ultra high elasticity carbon fiber may be sufficient.
- the carbon fiber sizing agent is attached by, for example, a method of attaching a dispersion of the sizing agent to the carbon fiber by a roller dipping method or a roller contact method, and a method of spraying the carbon fiber bundle directly by spraying. However, the roller dipping method is preferable in terms of productivity and uniform adhesion.
- the adhesion amount of the sizing agent in the carbon fiber bundle to which the sizing agent for carbon fiber of the present invention is adhered is preferably 0.6% by mass or more and 3.0% by mass or less with respect to the total mass of the carbon fiber and the sizing agent. 1.0 mass% or more and 2.4 mass% or less is more preferable.
- the adhesion amount of the sizing agent is 0.6% by mass or more, it becomes easy to cover the entire carbon fiber surface with the sizing agent.
- the sizing-treated carbon fiber and the matrix resin are mixed when producing the carbon fiber reinforced composite material, the above-described functions such as flexibility and toughness due to the interface resin layer can be fully exhibited. .
- the adhesion amount of the sizing agent is 3.0% by mass or less, the handling property of the sizing treatment carbon fiber and the impregnation of the matrix resin as a result of the sizing treatment carbon fiber being hardened by depositing a large amount of the sizing agent on the carbon fiber surface. It is possible to easily suppress the deterioration of the property.
- the amount of sizing agent attached is within the above range, in the carbon fiber reinforced composite material, a failure occurs in the transmission of stress transmitted from the matrix resin to the sizing carbon fiber through the interface resin layer, resulting in a decrease in mechanical properties. Can be suppressed.
- the carbon fiber will have excellent bundling properties and scratch resistance, as well as sufficient wettability to the matrix resin and interfacial adhesion to the matrix resin. And the resulting carbon fiber reinforced composite material is provided with good mechanical properties.
- the convergence of the carbon fiber bundle varies depending on the number of filaments, fiber diameter, surface wrinkles, etc. of the carbon fiber to be sized.
- the adhesion amount of the sizing agent can be adjusted by adjusting the sizing agent concentration of the sizing agent aqueous dispersion in the sizing process or adjusting the squeezing amount.
- the carbon fiber bundle to which the sizing agent for carbon fiber is attached is weighed (W1), and left in a muffle furnace (FP410 manufactured by Yamato Scientific Co., Ltd.) set at a temperature of 450 ° C. in a nitrogen stream of 50 liters / minute for 15 minutes.
- the sizing agent attached to the carbon fiber bundle is completely pyrolyzed.
- the cantilever value at 25 ° C. of the carbon fiber bundle to which the sizing agent for carbon fiber is attached is preferably 200 mm or more and 400 mm or less.
- the cantilever value at 25 ° C. is 200 mm or more and 400 mm or less, the woven fabric is less likely to lose its shape even in various molding processing environments using the unidirectional reinforced fabric made of the carbon fiber bundle. Regardless of the working environment when creating the carbon fiber reinforced resin composition obtained by impregnating the resin, the straightness of the carbon fiber is easily maintained, and the molded product obtained from the carbon fiber reinforced resin composition (carbon fiber reinforced The mechanical properties of the resin composite material) exhibit good mechanical properties.
- the cantilever value at 25 ° C. is preferably 220 mm or more and 380 mm or less, and more preferably 240 mm or more and 360 mm or less.
- the cantilever value at 25 ° C. of the carbon fiber bundle to which the sizing agent for carbon fiber in the present invention is adhered is measured by the following method.
- Test 2 Measurement is performed in an air atmosphere at 25 ° C.
- the test carbon fiber bundle is placed on the horizontal plane of a measuring table having a horizontal plane and a slope having an inclination angle of 45 degrees inclined downward from one end (linear shape) of the horizontal plane.
- the end portion (linear shape) of the fiber bundle is aligned with the boundary line A between the slope and the horizontal plane.
- a pressing plate is placed on the test carbon fiber bundle, and the end (straight line) of the pressing plate is aligned with the boundary line A.
- the average value of the numerical value x and the numerical value y is defined as a cantilever value of one carbon fiber bundle, and the simple average value obtained by measuring the number of measurements in steps 2 to 5 is 10 times as the cantilever value.
- the carbon fiber bundle to which the sizing agent for carbon fiber of the present invention is attached is less prone to fluff due to mechanical friction and the like due to the sizing agent, and also has good resin impregnation and adhesiveness. Excellent.
- the sizing agent contains the component (B) and the component (C) together with the component (A)
- the carbon fiber bundle to which the sizing agent for carbon fiber of the present invention is adhered and the matrix resin are combined to form a carbon fiber.
- the mechanical properties of a molded product (fiber reinforced composite material) obtained using the carbon fiber reinforced resin composition exhibit good mechanical properties.
- the sizing agent contains the component (E), it exhibits excellent compatibility with the matrix resin. Therefore, the wettability of the sized carbon fiber to the resin is improved, and the resin impregnation property is further improved.
- the carbon fiber bundle to which the sizing agent for carbon fiber of the present invention is attached has excellent processability such as weaving and can be suitably processed into a woven fabric and a sheet-like material of a unidirectionally arranged sheet. Particularly in weaving, carbon fibers are usually prone to fluff due to rubbing, but the carbon fiber bundle to which the sizing agent for carbon fiber of the present invention is attached can remarkably suppress fuzz by the sizing agent. It is also suitable for direct molding such as pultrusion molding and filament winding molding.
- the sheet-like material including the carbon fiber bundle to which the sizing agent for carbon fiber of the present invention is attached is characterized by using the carbon fiber bundle treated with the above-described sizing agent, and is woven, unidirectionally arranged A combination of these, such as a sheet, a non-woven fabric, and a mat, can be used.
- the sheet-like material may be composed of a carbon fiber bundle to which the carbon fiber sizing agent is attached, or may include other elements.
- Examples of the sheet-like material of the present invention include those in which a carbon fiber bundle to which the sizing agent for carbon fiber of the present invention is attached is aligned in one direction.
- the sheet-like material is simply arranged at regular intervals in one direction, or further wefts are arranged in the width direction of the sheet-like material, or heat-fusible fibers are used as the wefts.
- the sheet-like material formed by arranging the carbon fiber bundles to which the sizing agent for carbon fiber of the present invention is attached in one direction is at least (a) a carbon fiber sheet-like material aligned in one direction.
- heat-sealable fibers are arranged at predetermined intervals in a direction perpendicular to the carbon fibers and heat-sealed (hereinafter referred to as sheet-like material a), or (b) aligned in one direction.
- a fusion-bonded fiber cloth such as a net-like support or a web-like support made of a thermoplastic resin or coated with a thermoplastic resin is heat-sealed on at least one surface of a carbon fiber sheet (hereinafter referred to as “a carbon fiber sheet”). And sheet-like material b).
- the sheet-like material a is formed by aligning the carbon fiber bundles in one direction into a sheet shape, arranging heat-fusible fibers in the width direction of the reinforcing fibers (carbon fibers), heating, and heat-sealing with the carbon fibers. Manufactured by.
- the interval at which the heat-fusible fibers are arranged is preferably 3 mm or more and 150 mm or less, more preferably 3 mm or more and 15 mm or less. If the spacing is 3 mm or more, the handleability of the sheet-like material is good, the restraint of the carbon fiber is suitable, and it is easy to improve the resin impregnation property, and 150 mm or less. In this case, it is easy to improve the handleability as a sheet.
- the sheet-like material b is a net-like shape in which carbon fiber bundles are aligned in one direction to form a sheet, and at least one surface thereof is melted at room temperature or higher and exhibits adhesiveness or a thermoplastic resin or a thermoplastic resin. It is manufactured by heat-sealing a heat-fusible fiber cloth such as a support or a web-like support.
- the opening of the net of the net-like support is preferably wide from the viewpoint of resin impregnation, and the opening of the polygon is preferably 1 mm or more and the opening area is 10 mm 2 or more. More preferably, one side is 2.5 mm or more and the opening area is 15 mm 2 or more.
- the opening is small, and that one side is 20 mm or less and the opening area is 500 mm 2 or less.
- the web-like support is a sheet-like material in which short fibers or long fibers are intertwined.
- the basis weight of the net-like or web-like support is preferably 20 g / m 2 or less from the viewpoint of the mechanical properties of the resulting molded product, particularly the interlaminar shear strength retention and the resin impregnation property of the sheet-like product.
- the sheet-like product composed of the carbon fiber bundle to which the sizing agent for carbon fiber of the present invention is attached may be a woven fabric using the carbon fiber bundle to which the sizing agent for carbon fiber of the present invention is attached as a woven yarn.
- the fabric can also be used for reinforcing sheet materials such as bridges, piers, and building columns.
- the woven structure of the woven fabric is not particularly limited, and other than the plain weave, twill weave and satin weave, these original structures may be changed.
- both the weft and the warp may be a carbon fiber bundle to which the sizing agent for carbon fiber of the present invention is attached, or a mixed weave with other carbon fibers (bundles) or fibers (bundles) other than carbon fibers.
- fibers other than carbon fibers include inorganic fibers such as glass fibers, Tyranno fibers, and SiC fibers, and organic fibers such as aramid, polyester, polypropylene, polyamide, acrylic, polyimide, and vinylon.
- fibers having a tensile modulus lower than that of the warp as the weft because the warp is less likely to meander in the longitudinal direction and sufficient strength can be obtained when a woven fabric is used as the reinforcing sheet.
- the fiber other than the carbon fiber may be a composite fiber composed of two or more kinds.
- a composite system composed of two kinds of fibers having a melting point difference of 50 ° C. or more is particularly excellent.
- the high melting point fiber functions as an original weft, while the low melting point fiber integrates the warp and the weft after weaving to give excellent handling properties.
- fibers other than carbon fibers preferably have narrow latitude lines, and preferably have a mass per meter of 0.1 g or less.
- the weft spacing is preferably 3 to 15 mm. When the interval is 3 mm or more, it is easy to suppress meandering in the longitudinal direction of the warp, and good strength development can be easily obtained. On the other hand, when the interval is 15 mm or less, it is easy to improve the handleability as a sheet-like material.
- a more preferable interval between the latitude lines is 4 mm or more and 10 mm or less.
- Carbon fiber reinforced resin composition composite material including sheet
- the carbon fiber bundle to which the sizing agent for carbon fiber of the present invention is attached and the sheet-like material of the present invention are combined with a matrix resin, and are unidirectional prepreg, cross prepreg, tow prep, short fiber reinforced resin impregnated sheet, and short fiber mat reinforced.
- the carbon fiber reinforced resin composition can be configured in the form of a resin-impregnated sheet or the like.
- the matrix resin is not particularly limited, and examples thereof include epoxy resins, radical polymerization resins such as acrylic resins, vinyl ester resins, unsaturated polyester resins, thermoplastic acrylic resins, and phenol resins. .
- the carbon fiber reinforced resin composition can be produced by impregnating the above matrix resin into a carbon fiber bundle to which the sizing agent for carbon fiber of the present invention is attached or a sheet-like material of the present invention.
- a conventional method can be employed as a method for producing such a carbon fiber reinforced resin composition. Examples thereof include a method such as a hot melt method, a solvent method, a syrup method, or a thickening resin method used for a sheet mold compound (SMC).
- the carbon fiber reinforced resin composition using the carbon fiber bundle to which the sizing agent for carbon fiber of the present invention is adhered or the sheet-like material of the present invention is used as a matrix resin because the sizing treated carbon fiber is used as a reinforcing material.
- excellent in impregnation with radical polymerization resins such as epoxy resin, acrylic resin, unsaturated polyester resin, vinyl ester resin, and phenol resin, and strong interfacial adhesion between carbon fiber and matrix resin. It may be characteristic.
- the pultruded composite material using the carbon fiber bundle to which the sizing agent for carbon fiber of the present invention is attached can be used as either a rod-shaped material or a plate-shaped material.
- the rod-shaped material can be manufactured by impregnating a carbon fiber bundle with a matrix resin, molding the carbon fiber bundle with a die or a mold, and then heat-curing the carbon fiber bundle.
- the plate-like material can also be produced by impregnating a carbon fiber bundle with a matrix resin, forming it with a mold, and curing it by heating.
- the matrix resin is not particularly limited, and examples thereof include epoxy resins, radical polymerization resins such as acrylic resins, vinyl ester resins, unsaturated polyester resins, thermoplastic acrylic resins, and phenol resins. .
- the composite material including a pultruded composite material or a sheet-like material includes a thermosetting matrix resin.
- the tensile strength of a pultruded composite material is 5000 MPa or more and 6000 MPa or less.
- the average particle size of the aqueous dispersion of the carbon fiber sizing agent was measured by a concentrated particle size analyzer (product name: FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.).
- the surface state of the carbon fiber to which the sizing agent for carbon fiber of the present invention was attached was measured at an acceleration voltage of 5 kV and a magnification of 2500 times using a scanning electron microscope (manufactured by JEOL Ltd., product name: JEOL JSM-6390). Observed. The case where the adhesion spot of the sizing agent was not observed was evaluated as ⁇ , and the case where the adhesion spot of the sizing agent was observed was evaluated as ⁇ .
- the carbon fiber bundles to which the sizing agent of the present invention is attached are aligned in one direction using a face plate and a comb at a spacing of 2.5 mm and a width of 300 mm, and both surfaces have glass fibers (tensile elastic modulus 72.5 GPa) and a low melting point.
- Nylon fiber (multifilament, melting point 125 ° C.) entangled yarn (0.03 g / m) is arranged at 25 mm intervals per side (sheets are arranged at 12.5 mm intervals and parallels are alternately arranged on both surfaces)
- the sheet was unidirectionally formed by heat fusion at 180 ° C. by pressing.
- the width (direction perpendicular to the fiber axis direction of the carbon fiber bundle) is about 2.5 cm (so that six carbon fiber bundles to which the sizing agent is attached) are long.
- the length (fiber axis direction) is about 15 cm, except that five pieces are collected and used as test pieces.
- the unidirectional sheet shape is in accordance with the stiffness test method A (45 ° cantilever method) described in JIS L1096.
- the bending resistance of the object was measured. Note that the measurement in the lateral direction of the sample as described in the pliability test method A (45 ° cantilever method) described in JIS L1096 is not performed.
- the unidirectional sheet-like material is impregnated with a mixture of an epoxy resin (manufactured by Konishi Co., Ltd., product name: E2500S) and a main agent in a ratio of 100 parts by weight of the main agent and 50 parts by weight of the hardener. Was cured in a stationary state for 7 days to obtain a unidirectional sheet-like composite.
- an epoxy resin manufactured by Konishi Co., Ltd., product name: E2500S
- the fiber volume content Vf of the unidirectional sheet-like composite is expressed by the following formula:
- the weft (5 / inch (2.54 cm)) and the warp (5 / inch (2.54 cm)) have a carbon fiber basis weight of 315 g / m 2 .
- a plain weave cloth was woven.
- the fiber volume content Vf of the woven fabric composite material can be calculated by the same method as that for the unidirectional sheet composite material described above.
- the woven fabric composite was subjected to a bending test in accordance with ASTM-D-790, which is a general evaluation method for mechanical properties of a laminated board, to obtain a bending strength.
- ASTM-D-790 is a general evaluation method for mechanical properties of a laminated board, to obtain a bending strength.
- ASTM-D-790 is a general evaluation method for mechanical properties of a laminated board.
- the evaluation of the woven laminate was carried out so that a film was placed between the indenter and the sample of the test piece so as not to break due to stress concentration.
- Example 1 (1. Preparation of sizing agent) A sizing agent was prepared by phase inversion emulsification using a mixer (manufactured by Tokushu Kika Kogyo Co., Ltd., product name: Hibis Disper Mix, homomixer specification: Model 3D-5).
- the component (C) in the state of an aqueous dispersion shown in the column of Example 1 in Table 1 (details of each component are shown in Table 4) are dried at 120 ° C. for 2 hours, What removed the water
- Components other than the component (D) in the types and blending amounts shown in the column of Example 1 in Table 1 were kneaded and mixed at 120 ° C. with a planetary mixer and a homomixer. Thereafter, the temperature was raised to 90 ° C. while kneading, and then an aqueous solution of component (D) was added little by little. During this process, the viscosity of the contents gradually increased. After all the aqueous solution of component (D) was added, the temperature was set to 60 ° C. while kneading for 10 minutes. Next, deionized water was dropped little by little and after passing through the phase inversion point, the amount of water dropped was increased.
- a sizing agent aqueous dispersion having a sizing agent concentration of about 40% by mass was obtained.
- Tables 1 to 3 the composition of the sizing agent is shown in parts by mass. However, for the components obtained in the form of an aqueous dispersion or an aqueous solution, the parts by mass excluding water are shown.
- the carbon fiber to which the sizing agent for carbon fiber was attached was produced by the following procedure.
- a carbon fiber bundle (manufactured by Mitsubishi Rayon Co., Ltd., product name: Pyrofil TR50S) filled with an aqueous dispersion of the above sizing agent in an immersion tank having an immersion roller inside and not provided with the sizing agent in the aqueous dispersion. 12,000 filaments, strand strength 5,000 MPa, strand elastic modulus 242 GPa, fiber density 1.81 g / cm 3 ).
- the carbon fiber bundle to which the sizing agent adhered was obtained by drying with hot air.
- the carbon fiber bundle was wound around a bobbin.
- the room temperature curable epoxy resin EP1 is a mixture of an epoxy resin (manufactured by Konishi, product name: E2500S) and a curing agent in a ratio of 100 parts by mass of the main agent and 50 parts by mass of the curing agent.
- the fiber volume content Vf of the woven fabric composite material was calculated by the same method as that for the unidirectional sheet composite material described above.
- Example 2 Except having shown the component in the column of Example 2 of Table 1, the aqueous dispersion of a sizing agent was prepared by the method similar to Example 1, and the sizing process of carbon fiber using this was prepared. The carbon fiber bundle to which the sizing agent was adhered was obtained, and a sheet-like product and a woven fabric were prepared and evaluated.
- (C) component what was obtained in the state of the water dispersion was used after drying similarly to Example 1. The results are shown in Table 1.
- Examples 3 to 17 In each example, the water-dispersed polyurethane resin was used as component (C). That is, the sizing agent was dispersed in water in the same manner as in Example 1 using components other than the component (C) among the compositions of the sizing agents shown in the columns of Examples 3 to 17 in Table 1 or Table 2. After preparing the liquid, the water dispersion of the polyurethane resin as the component (C) was mixed with the water dispersion of the sizing agent not containing the component (C) to obtain a water dispersion of the sizing agent. Other than that was carried out similarly to Example 1, the carbon fiber sizing process was performed, the carbon fiber bundle which the sizing agent adhered was obtained, and the sheet-like material and woven fabric which used this were produced and evaluated. The results are shown in Table 1 or Table 2.
- Example 18 The sizing treatment of the carbon fiber was performed using the aqueous dispersion of the sizing agent obtained in Example 3, and the adhesion amount of the sizing agent was set to 1.6% by mass. Other than that was carried out similarly to Example 1, obtained the carbon fiber bundle to which the sizing agent adhered, and produced and evaluated the sheet-like material and woven fabric using this. The results are shown in Table 2.
- Example 19 The sizing treatment of the carbon fiber was performed using the aqueous dispersion of the sizing agent obtained in Example 3, and the adhesion amount of the sizing agent was set to 0.8% by mass. Other than that was carried out similarly to Example 1, obtained the carbon fiber bundle to which the sizing agent adhered, and produced and evaluated the sheet-like material and woven fabric using this. The results are shown in Table 2.
- Example 20 The carbon fiber bundle to be sized was treated as in the following 2-2, and the sizing treatment of the carbon fiber bundle was performed using the aqueous dispersion of the sizing agent obtained in Example 1. Other than that was carried out similarly to Example 1, the carbon fiber bundle to which the sizing agent adhered was obtained, and the evaluation similar to Example 1 was performed about the carbon fiber bundle to which the sizing agent adhered. The results are shown in Table 2.
- Pyrofil TRH50 (product name, manufactured by Mitsubishi Rayon Co., Ltd., 18,000 filaments, strand strength 5,600 MPa, strand elastic modulus 256 GPa, fiber density 1.82 g / m 3 ) is used as a carbon fiber bundle with no sizing agent attached. Using.
- the tensile strength of the pultruded product obtained in 5-1 above was measured in accordance with “The Tensile Test Method Using Fixing Expansion Material” of the Japan Society of Civil Engineers. The tensile strength was converted to a fiber volume content of 100% using the fiber volume content Vf of the obtained pultruded product. The results are shown in Table 2. The fiber volume content (%) of the pultruded product was obtained using the following formula.
- Fiber volume content Vf of pultruded molded product Vf (fiber bundle weight ⁇ number of inputs / fiber density) ⁇ [(extracted molded product outer diameter ⁇ 2) 2 ⁇ 3.1416] ⁇ 100
- the outer diameter of the pultruded product was measured by measuring the outer diameter in the direction perpendicular to the longitudinal direction of the pultruded product at six locations using a micrometer, and using the average value. Further, the fiber basis weight in the above formula was obtained by measuring 12 fiber bundles out of 34 carbon fiber bundles inputted, and using the average value.
- the fiber density is the fiber density of Pyrofil TRH50.
- Example 21 The carbon fiber bundle to be sized was treated as the above 2-2, and the sizing treatment of the carbon fiber was performed using the aqueous dispersion of the sizing agent obtained in Example 2. Other than that was carried out similarly to Example 1, the carbon fiber bundle to which the sizing agent adhered was obtained, and the same evaluation as Example 1 was implemented about the carbon fiber bundle to which the sizing agent adhered. In addition, a pultruded composite material was prepared and evaluated in the same manner as in Example 20 using the obtained carbon fiber bundle to which the sizing agent was adhered. The results are shown in Table 2.
- Example 22 The carbon fiber bundle to be sized was treated as the above 2-2, and the sizing treatment of the carbon fiber was performed using the aqueous dispersion of the sizing agent obtained in Example 3. Other than that was carried out similarly to Example 1, the carbon fiber bundle to which the sizing agent adhered was obtained, and the same evaluation as Example 1 was implemented about the carbon fiber bundle to which the sizing agent adhered. In addition, a pultruded composite material was prepared and evaluated in the same manner as in Example 20 using the obtained carbon fiber bundle to which the sizing agent was adhered. The results are shown in Table 2.
- Example 23 The carbon fiber bundle to be sized was treated as the above 2-2, and the sizing treatment of the carbon fiber was performed using the aqueous dispersion of the sizing agent obtained in Example 12. Other than that was carried out similarly to Example 1, the carbon fiber bundle to which the sizing agent adhered was obtained, and the same evaluation as Example 1 was implemented about the carbon fiber bundle to which the sizing agent adhered. In addition, a pultruded composite material was prepared and evaluated in the same manner as in Example 20 using the obtained carbon fiber bundle to which the sizing agent was adhered. The results are shown in Table 2.
- Example 24 The carbon fiber bundle to be sized was treated as the above 2-2, and the sizing treatment of the carbon fiber was performed using the aqueous dispersion of the sizing agent obtained in Example 13. Other than that was carried out similarly to Example 1, the carbon fiber bundle to which the sizing agent adhered was obtained, and the same evaluation as Example 1 was implemented about the carbon fiber bundle to which the sizing agent adhered. In addition, a pultruded composite material was prepared and evaluated in the same manner as in Example 20 using the obtained carbon fiber bundle to which the sizing agent was adhered. The results are shown in Table 2.
- Tables 1 to 3 The components shown in Tables 1 to 3 are detailed in Table 4, respectively. Catalog values were adopted for the tensile elongation and glass transition temperature (Tg) of the cured product of urethane acrylate oligomer, and the particle diameter of the polyurethane emulsion, the tensile strength of the dry film, the tensile elongation of the dry film, and the glass transition temperature.
- Tg tensile elongation and glass transition temperature
- A1 to A2 and E1 to E3 in Table 3 are synthetic products obtained by the following procedure, respectively.
- the half ester component effective as the component (A) is 1/2, and the remaining 1/2 is an unreacted product and a diester product.
- the blending amounts of A1 to A2 shown in Tables 1 to 3 represent the total amount of the half ester component, the unreacted product, and the diester product. Therefore, the amount of the active ingredient as a half ester is 1 ⁇ 2 of the blending amount shown in Tables 1 to 3. That is, when calculating the content of the component (A) in the sizing agent, a value that is half the blending amount of A1 and A2 shown in the table is used.
- the amount of all sizing components includes not only the blending amount of the half ester component but also the blending amounts of the unreacted product and the diester product. That is, in order to calculate the amount of all sizing components, the values of the blending amounts of A1 and A2 shown in the table are used.
- A2 Addition of 86 parts by mass of acrylic acid, 1 part by mass of hydroquinone, and 1 part by mass of lithium chloride to 1000 parts by mass of bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin, product name: JER834).
- PO propylene oxide
- Newpol BP-3P product name
- PO product name: New Pole BP-3P, manufactured by Sanyo Chemical Industries, Ltd.
- the carbon fiber bundles when the sizing agents of Examples 1 to 24 were applied had no fuzz in the process from the hot air drying treatment after the sizing treatment to the bobbin, and no winding around the roll.
- the process passability is very stable, and the molded product (one-way carbon fiber sheet composite, woven fabric composite, pultruded composite) produced using this carbon fiber bundle, It had good physical properties.
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Abstract
Description
分子中に複数個のエポキシ基を有するエポキシ化合物と不飽和一塩基酸とのエステルであって、分子中に少なくとも1つのエポキシ基を有する化合物(A)と、
硬化物の引張伸び率が40%以上の2官能タイプのウレタンアクリレートオリゴマー(B)と、
乾燥皮膜の引張伸び率が350%以上900%以下であるポリウレタン樹脂(C)とを含有し、
前記化合物(A)と前記ウレタンアクリレートオリゴマー(B)との含有量の質量比が、ウレタンアクリレートオリゴマー(B)/化合物(A)の比として、1/3以上2/1以下であり、
全サイジング成分中に占める前記化合物(A)および前記ウレタンアクリレートオリゴマー(B)の合計量の割合が20質量%以上であり、
かつ全サイジング成分中に占める前記ポリウレタン樹脂(C)の割合が、5質量%以上50質量%以下である炭素繊維用サイジング剤が提供される。
前記炭素繊維用サイジング剤が水中に分散した水分散液であって、水分散液中のサイジング剤の分散粒子の平均粒子径が0.3μm以下である炭素繊維サイジング剤の水分散液が提供される。
前記炭素繊維用サイジング剤が付着した炭素繊維からなる炭素繊維束(すなわち、炭素繊維用サイジング剤が付着した炭素繊維束)であって、該サイジング剤の付着量が0.6質量%以上3.0質量%以下である炭素繊維束が提供される。
本発明の炭素繊維用サイジング剤は以下に詳述する(A)~(C)の成分を含む。このサイジング剤は、各成分を適宜混合することにより得ることができる。
本発明の炭素繊維用サイジング剤に含まれる(A)成分は、分子中に少なくとも1つのエポキシ基を有することが必要である。なお、エポキシ基とは、本願発明では、環骨格が2個の炭素原子と1個の炭素原子とから構成される3員環をその構造中に有する基を意味する。
本発明の炭素繊維用サイジング剤に含まれる(A)成分に含まれるエポキシ基としては、例えば、下記式(e1)で表される基、下記式(e2)で表される基(グリシジル基)、その他の環式脂肪族エポキシ基などが挙げられる。その他の環式脂肪族エポキシ基としては、前記3員環と、単環または多環式の脂肪族環とで形成される環状構造をその構造中に有する基が挙げられ、たとえば下記式(e3)~(e5)で表される基が例示できる。
本発明の炭素繊維用サイジング剤に含まれる(A)成分において、エステルを形成する分子中に複数個のエポキシ基を有するエポキシ化合物としては、特に限定されず、たとえばビスフェノール類のエポキシ化合物、ビスフェノール類のアルキレンオキシド付加エポキシ化合物、水素化ビスフェノール類のエポキシ化合物、水素化ビスフェノール類のアルキレンオキシド付加エポキシ化合物等が挙げられる。これらビスフェノール類としては、特に限定されるものではなく、ビスフェノールF型、ビスフェノールA型、ビスフェノールS型などの化合物が挙げられる。ビスフェノール類のエポキシ化合物以外のフェノールノボラック型、クレゾールノボラック型、ジフェニル型、ジシクロペンタジエン型、ナフタレン骨格型などのエポキシ樹脂を用いることもできる。また、直鎖脂肪族系骨格を有するものであっても良い。
本発明の炭素繊維用サイジング剤に含まれる(A)成分において、エステルを形成する不飽和一塩基酸としては、特に限定はなく、一つの不飽和基と一つのカルボキシル基を有する化合物であれば良い。不飽和基としては、特に限定はないが、嵩高くないこと、形成されるエステルの主鎖の剛直性を低下させないことから、ビニル基あるいはプロペニル基が好ましく、より好ましくは、ビニル基である。特に好ましいのは、アクリル酸またはメタクリル酸である。すなわち、(A)成分は、前記エポキシ化合物とアクリル酸またはメタクリル酸とのエステルであることが好ましい。
本発明の炭素繊維用サイジング剤に含まれる(B)成分は、マトリックス樹脂と炭素繊維との界面に、柔軟性に優れた界面相を形成する効果を有する。これにより、マトリックス樹脂と炭素繊維との間の界面接着性が向上する。また、繊維強化複合材料用のマトリックス樹脂として、ビニルエステル樹脂、不飽和ポリエステル樹脂等のラジカル重合系樹脂が使用される場合、それらの樹脂には靭性の低いものが多く、界面相の柔軟化に起因する高靭性化により、飛躍的に界面接着性が向上する。
硬化物のTgは、引張伸び率の測定と同じ方法で得られた硬化皮膜を試験片として、粘弾性測定装置(UBM社製、製品名:Rheogel E4000)を用いて、2℃/分の割合で昇温させ、試験片の動的粘弾性および損失正接を測定し、損失正接のピーク温度(tanδMAX)から求めることができる。
本発明において、(B)成分は、1種を単独で用いてもよく、2種以上を併用してもよい。
本発明のサイジング剤においては、(A)成分と(B)成分との含有量の比(質量比)が、(B)成分/(A)成分=1/3~2/1の範囲内であることが必要である。
(B)成分の含有量が、(A)成分の含有量の1/3未満であると、界面相の柔軟化・高靭性化が不充分となり、一方、2/1を越えると、(A)成分の機能である良接着性発現効果が阻害され、炭素繊維の、マトリックス樹脂との接着性向上効果が充分に得られない。
本発明の炭素繊維用サイジング剤は(C)成分を必須成分とするものである。(C)成分はポリウレタン樹脂であり、これによって炭素繊維束の形状を固定化し易くなる。炭素繊維束の形状が固定化され、直進保持性が維持し易くなることで、引抜成型やフィラメントワインディング成型のおける樹脂含浸工程での樹脂ピックアップの最適化が容易となること、樹脂を含浸させた後のトウ形状の安定化が著しく向上すること、織物の型崩れ、目ずれが生じ難くなることの効果により、成型物での炭素繊維単繊維の配向荒れ、蛇行が抑制され、成型物の強度発現性を著しく向上させることができる。また、(C)成分は、上述した(B)成分と同様に、マトリックス樹脂と炭素繊維との界面に、柔軟かつ強靭な界面相を形成する効果を有する。
(C)成分は、1種を単独で用いてもよく、2種以上を併用してもよい。
本発明の炭素繊維用サイジング剤は、上述した(A)成分、(B)成分および(C)成分に加えて、さらに、(E)成分を含有することが好ましい。
本発明のサイジング剤は、さらに、(D)成分を含有することが好ましい。
脂肪酸エチレンオキサイド付加物や多価アルコール脂肪酸エステルエチレンオキサイド付加物としては、モノエステルタイプ、ジエステルタイプ、トリエステルタイプ、テトラエステルタイプなどのノニオン系界面活性剤を使用できる。
本発明のサイジング剤は、(D-1)成分と(D-2)成分とを含有する場合、(D-1)成分と(D-2)成分との含有量の比(質量比)が、(D-2)成分/(D-1)成分=1/10~1/5の範囲内であることが好ましい。
この比がこの範囲であると、(A)成分のエポキシ基に対する(D)成分由来のアンモニウムイオンの反応活性を容易に抑制でき、サイジング剤を付着させた炭素繊維の硬さの経時変化を著しく抑制することができ、また、水等を媒体としてサイジング剤を乳化させた際の乳化安定性や、サイジング処理された炭素繊維表面の、樹脂に対する濡れ性が向上するので好ましい。
本発明の炭素繊維用サイジング剤の水分散液は、各成分を常法により混合、撹拌(乳化、水分散化)することにより1つの炭素繊維用サイジング剤の水分散液として得ることができ、あるいは別々に処理されて複数種の水分散液となったものを混合して1つの水分散液を得ることもできる。
また、本サイズ剤は溶剤に分散させても良い。
(C)成分としてポリウレタン樹脂を水分散体としたものを用いる場合、ポリウレタン樹脂の分散粒子の体積基準の平均粒子径は、0.2μm以下とすることが好ましい。ポリウレタン樹脂の分散粒子の体積基準の平均粒子径が0.2μm以下であれば、炭素繊維表面においてサイジング剤の付着斑の発生を容易に防止でき、炭素繊維の耐擦過性を良好に維持することが容易であるので、サイジング処理後の炭素繊維の巻き取り工程や成型加工工程における毛羽発生を容易に防止でき、好ましい。なお、平均粒子径の下限には特に制限はない。なお、平均粒子径は、例えば、レーザー回折/散乱式の粒度分布測定装置で測定される。
本発明の炭素繊維用サイジング剤が付着した炭素繊維束に好適に用いることができる炭素繊維束は、ピッチ、レーヨンあるいはポリアクリロニトリルなどのいずれの原料物質から得られたものであってよく、高強度タイプ(低弾性率炭素繊維)、中高弾性炭素繊維又は超高弾性炭素繊維のいずれでもよい。炭素繊維用サイジング剤を付着させる方法は、例えば、ローラー浸漬法、ローラー接触法によりサイジング剤の分散液を炭素繊維に付着させ、乾燥する方法や、スプレーで直接炭素繊維束に吹き付ける方法によって行うことができるが、生産性、均一付着性の観点においては、ローラー浸漬法が好ましい。
炭素繊維用サイジング剤が付着した炭素繊維束を秤量(W1)し、50リットル/分の窒素気流中、温度450℃に設定したマッフル炉(ヤマト科学株式会社製FP410)に15分間静置し、炭素繊維束に付着したサイジング剤を完全に熱分解させる。そして、20リットル/分の乾燥窒素気流中の容器に移し、15分間冷却した後の炭素繊維束を秤量(W2)して、次式:
サイジング剤の付着量(質量%)=[W1(g)-W2(g)]/[W1(g)]×100
より付着量を求める。
(手順1)サイジング剤が付着した炭素繊維束をボビンに巻き取る前に、長さ80cm程度に切断し、この炭素繊維束に0.04g/Texのおもりを取り付けて、25℃の空気雰囲気下で1時間吊り下げる。次に、この炭素繊維束の両端10cm程度を切断し、長さ70cm程度の試験用炭素繊維束を得る。試験用炭素繊維束は10本用意する。このとき、炭素繊維束の形状を崩さないように注意して作業を行う。
本発明の炭素繊維用サイジング剤が付着した炭素繊維束を含むシート状物は、上述したサイジング剤で処理された炭素繊維束を用いたことを特徴とするものであり、織布、一方向配列シート、不織布、マット等、これらを組み合わせたものが挙げられる。前記シート状物は、前記炭素繊維用サイジング剤が付着した炭素繊維束からなってもよいし、他の要素を含んでもよい。
シート状物aは、上記炭素繊維束を一方向に引き揃えシート状とし、強化繊維(炭素繊維)の巾方向に熱融着性繊維を配置し、加熱し、炭素繊維と熱融着することにより製造される。熱融着性繊維を配置する間隔は、3mm以上150mm以下が好ましく、より好ましくは3mm以上15mm以下である。配置する間隔が3mm以上であれば、シート状物の取り扱い性が良好であるとともに、炭素繊維の拘束が好適になり樹脂の含浸性を良好にすることが容易であり、また、150mm以下であれば、シート状物としての取り扱い性を良好にすることが容易である。
シート状物bは、炭素繊維束を一方向に引き揃え、シート状とし、その少なくとも一方の表面に室温以上の温度で溶融し接着性を示す熱可塑性樹脂あるいは熱可塑性樹脂で被覆されたネット状支持体、ウェブ状支持体などの熱融着性繊維布を熱融着することにより製造される。ネット状支持体のネットの目開きは、樹脂含浸性の観点からは広い方が好ましく目開き部分の多角形の一辺が1mm以上、その目開き面積が10mm2以上のものが好ましい。一辺が2.5mm以上で、目開き面積が15mm2以上であればより好ましい。一方、炭素繊維のほつれ防止、裁断時の取り扱い性の観点からは、目開きは小さい方が好ましく、一辺が20mm以下で目開き面積が500mm2以下であることが好ましい。
本発明の炭素繊維用サイジング剤が付着した炭素繊維束からなるシート状物は、さらに本発明の炭素繊維用サイジング剤が付着した炭素繊維束を織糸として用いた織物であっても良い。前記織物は橋梁、橋脚、建造物の柱等の補強用シート材用途にも用いられ得る。前記織物の織り組織は特に限定はされず、平織り、綾織り、朱子織りの他、これら原組織を変化させたものでもよい。また、緯、経糸共に本発明の炭素繊維用サイジング剤が付着した炭素繊維束でもよく、また他の炭素繊維(束)あるいは炭素繊維以外の繊維(束)との混織でもよい。炭素繊維以外の繊維としては、ガラス繊維、チラノ繊維、SiC繊維などの無機繊維、アラミド、ポリエステル、ポリプロピレン、ポリアミド、アクリル、ポリイミド、ビニロンなどの有機繊維などがある。
本発明の炭素繊維用サイジング剤が付着した炭素繊維束および本発明のシート状物は、マトリックス樹脂と複合化され、一方向プリプレグ、クロスプリプレグ、トウプレグ、短繊維強化樹脂含浸シート、短繊維マット強化樹脂含浸シートなどの形態で、炭素繊維強化樹脂組成物を構成することができる。マトリックス樹脂としては、特に限定されるものではないが、例えば、エポキシ樹脂、ラジカル重合系樹脂であるアクリル樹脂、ビニルエステル樹脂、不飽和ポリエステル樹脂、熱可塑性アクリル樹脂、さらにはフェノール樹脂などが挙げられる。
本発明の炭素繊維用サイジング剤が付着した炭素繊維束を用いた引抜成型複合材は、棒状材、あるいは板状材として、どちらでも使用することができる。棒状材は、炭素繊維束にマトリックス樹脂を含浸した後、ダイスまたは金型を用いて成形し、その後加熱硬化させることにより製造することができる。また、板状材についても、炭素繊維束にマトリックス樹脂を含浸した後、金型を用いて成形し、加熱硬化させることにより製造することができる。マトリックス樹脂としては、特に限定されるものではないが、例えば、エポキシ樹脂、ラジカル重合系樹脂であるアクリル樹脂、ビニルエステル樹脂、不飽和ポリエステル樹脂、熱可塑性アクリル樹脂、さらにはフェノール樹脂などが挙げられる。
炭素繊維用サイジング剤の水分散液平均粒子径は、濃厚系粒径アナライザー(大塚電子株式会社製、製品名:FPAR-1000)によって測定した。
後述する熱風乾燥処理からボビンに巻き取るまでの工程において、毛羽の発生が無く、工程間のロールへの繊維の巻き付きが無い場合を○、毛羽の発生が有る、あるいは工程間のロールへの繊維の巻き付きがある場合を×としてサイジング処理工程通過性を評価した。
また、本発明の炭素繊維用サイジング剤が付着した炭素繊維の表面状態を走査型電子顕微鏡(日本電子株式会社製、製品名:JEOL JSM-6390)を用いて、加速電圧5kV、倍率2500倍で観察した。サイジング剤の付着斑が観察されない場合を○、サイジング剤の付着斑が観察された場合を×で評価した。
本発明のサイジング剤が付着した炭素繊維束を2.5mm間隔300mm巾で、目板及び櫛を用いて一方向に引き揃え、その両表面にガラス繊維(引張弾性率72.5GPa)と低融点ナイロン繊維(マルチフィラメント、融点125℃)の交絡糸(0.03g/m)を片面当たり25mm間隔(シートとしては12.5mm間隔で両表面に交互に緯線は配置される)で配置して熱プレスにより180℃で熱融着させることにより一方向のシート状物とした。
前記一方向のシート状物から、幅(炭素繊維束の繊維軸方向に垂直な方向)の寸法を約2.5cm(前記サイジング剤が付着した炭素繊維束が6本含まれるように)、長さ(繊維軸方向)の寸法を約15cmとして、5枚採取し、試験片としたこと以外は、JIS L1096に記載される剛軟性試験A法(45°カンチレバー法)に従って、前記一方向シート状物の剛軟度を測定した。なお、JIS L1096に記載される剛軟性試験A法(45°カンチレバー法)に記載されているような試料横方向の測定は行わない。
前記一方向のシート状物に、エポキシ樹脂(コニシ社製、製品名:E2500S)の主剤と硬化剤とを、主剤100質量部、硬化剤50質量部の比率で混合したものを含浸させ、室温にて7日間、静置状態で硬化させて一方向のシート状物の複合材を得た。
前記複合材を用いて、JIS A 1191(試験片形状A形)に準拠して、引張強度を測定した。引張強度は、得られた一方向のシート状物の複合材の繊維体積含有率Vfを用いて、繊維体積含有率100%に換算した。なお、一方向のシート状物の複合材の繊維体積含有率Vfは下記式:
一方向のシート状物の複合材の繊維体積含有率(Vf)
=一方向のシート状物の理論厚み(mm)÷一方向のシート状物の複合材から得た試験片の厚み(mm)
=[一方向のシート状物の目付(g/m2)÷炭素繊維束の密度(g/m3)]÷一方向のシート状物の複合材から得た試験片の厚み(mm)
を用いて得た。
本発明のサイジング剤が付着した炭素繊維束を使用し、緯糸(5本/インチ(2.54cm))と、経糸(5本/インチ(2.54cm))で炭素繊維目付315g/m2の平織クロス(織布)を織成した。
前記織布を、幅300mm、長さ300mmの大きさで5枚ずつ二組切り出し、液状のビニルエステル樹脂VE1を一方の組の5枚に、また不飽和ポリエステル樹脂UP1をもう一方の組の5枚に塗布することにより樹脂を含浸させた。繊維体積含有率(Vf)は40%程度であった。ここで、VE1およびUP1はそれぞれ下記のものである。
「VE1」:ネオポール8260(製品名。日本ユピカ社製)と、パーメックN(製品名。日本油脂株式会社製)と、6質量%ナフテン酸コバルト液とを、ネオポール8260/パーメックN/6質量%ナフテン酸コバルト=100/1/0.5(質量比)で混合したもの。
「UP1」:ユピカ4521PT(製品名。日本ユピカ社製)と、パーメックN(製品名。日本油脂株式会社製)とを、ユピカ4521PT/パーメックN=100/1(質量比)で混合したもの。
「VE1の硬化条件」:60℃で2時間、次いで80℃で2時間、次いで120℃で2時間加熱した。
「UP1の硬化条件」:室温で1晩放置し、次いで60℃で2時間、次いで80℃で2時間、次いで120℃で2時間加熱した。
前記織布複合材について、積層板の機械的特性の一般的な評価法であるASTM-D-790に準拠して曲げ試験を行い、曲げ強度を求めた。ここで、織物積層板の評価は、圧子と試験片のサンプルとの間にフィルムを入れ、応力集中による破壊が生じないように実施した。
(1.サイジング剤の調製)
ミキサー(特殊機化工業(株)製、製品名:ハイビスディスパーミックス、ホモミキサー仕様:型式3D-5型)を用い、以下の手順で、転相乳化することでサイジング剤を調製した。
以下の手順で炭素繊維用サイジング剤が付着した炭素繊維を製造した。内部に浸漬ローラーを有する浸漬槽内に、上記サイジング剤の水分散液を満たし、該水分散液中に、サイジング剤を付与していない炭素繊維束(三菱レイヨン株式会社製、製品名:パイロフィルTR50S、フィラメント数12000本、ストランド強度5,000MPa、ストランド弾性率242GPa、繊維密度1.81g/cm3)を浸漬した。その後、熱風乾燥することによってサイジング剤が付着した炭素繊維束を得た。なお、炭素繊維束はボビンに巻き取った。この際、熱風乾燥処理からボビンに巻き取るまでの工程の観察し、サイジング処理工程通過性の評価を行ったところ、毛羽・巻き付きともに発生がなく、非常に安定していた。また、サイジング剤の炭素繊維への付着量、及びサイジング剤が付着した炭素繊維束のカンチレバー値を、上記した方法により測定した。その結果を表1に示す。なお、上記したようにカンチレバー値測定用の炭素繊維束は、ボビンに巻き取る前に採取した。
上記2-1で得たサイジング剤が付着した炭素繊維束を2.5mm間隔300mm巾で、目板及び櫛を用いて一方向に引き揃え、その両表面にガラス繊維(引張弾性率72.5GPa)と低融点ナイロン繊維(マルチフィラメント、融点125℃)の交絡糸(0.03g/m)を片面当たり25mm間隔(シートとしては12.5mm間隔で両表面に交互に緯線は配置される)で配置して熱プレスにより180℃で熱融着させることにより一方向のシート状物を得た。また、得られた一方向シート状物の剛軟度を、上記した方法により測定した。その結果を表1に示す。
後述する室温硬化型エポキシ樹脂EP1を調製し、上記3-1で得た一方向のシート状物に含浸させ、室温にて7日間、静置状態で硬化させて一方向のシート状物の複合材を得た。なお、室温硬化型エポキシ樹脂EP1は、エポキシ樹脂(コニシ社製、製品名:E2500S)の主剤と硬化剤とを、主剤100質量部、硬化剤50質量部の比率で混合したものである。
上記2-1で得たサイジング剤が付着した炭素繊維束を使用し、緯糸(5本/インチ(2.54cm))と、経糸(5本/インチ(2.54cm))で炭素繊維目付315g/m2の平織クロス(織布)を織成した。
上記4-1で得た織布を、幅300mm、長さ300mmの大きさで5枚ずつ二組切り出し、液状のビニルエステル樹脂VE1を一方の組の5枚に、また不飽和ポリエステル樹脂UP1をもう一方の組の5枚に塗布することにより樹脂を含浸させた。繊維体積含有率(Vf)は40%程度であった。ここで、VE1およびUP1は前述のものである。
このとき、上記織布へ樹脂を塗布する工程での樹脂含浸性について、前述の基準で評価したところ、泡立ちがあり、樹脂吸い込みは良好であった。その結果を「樹脂含浸性」として表1に示す。
「VE1の硬化条件」:60℃で2時間、次いで80℃で2時間、次いで120℃で2時間加熱した。
「UP1の硬化条件」:室温で1晩放置し、次いで60℃で2時間、次いで80℃で2時間、次いで120℃で2時間加熱した。
上記4-2で得た織布とラジカル重合系樹脂との複合材について、前述の織布の複合材の曲げ強度評価を行った。その結果を表1に示す。
(C)成分を表1の実施例2の欄に示したものとした以外は、実施例1と同様の方法でサイジング剤の水分散液を調製し、これを用いた炭素繊維のサイジング処理を行い、サイジング剤が付着した炭素繊維束を得、これを用いたシート状物、及び織布の作成、評価を実施した。なお、(C)成分は、実施例1同様、水分散体の状態で入手したものを、乾燥して用いた。結果を表1に示す。
各例において、(C)成分としてポリウレタン樹脂が水分散化されたものをそのまま使用した。すなわち、表1もしくは表2の実施例3~17の欄にそれぞれに示したサイズ剤の組成の内、(C)成分以外の成分を用いて実施例1と同様の方法でサイジング剤の水分散液を調製した後、この(C)成分を含まないサイジング剤の水分散液に、(C)成分としてポリウレタン樹脂が水分散化されたものを混合して、サイジング剤水分散液を得た。それ以外は実施例1と同様にして、炭素繊維のサイジング処理を行い、サイジング剤が付着した炭素繊維束を得、これを用いたシート状物、及び織布の作成、評価を実施した。結果を表1もしくは表2に示す。
実施例3で得たサイジング剤の水分散液を用いて炭素繊維のサイジング処理を行い、サイジング剤の付着量を1.6質量%とした。それ以外は実施例1と同様にして、サイジング剤が付着した炭素繊維束を得、これを用いたシート状物、及び織布の作成、評価を実施した。結果を表2に示す。
実施例3で得たサイジング剤の水分散液を用いて炭素繊維のサイジング処理を行い、サイジング剤の付着量を0.8質量%とした。それ以外は実施例1と同様にして、サイジング剤が付着した炭素繊維束を得、これを用いたシート状物、及び織布の作成、評価を実施した。結果を表2に示す。
サイジング処理する炭素繊維束を下記2-2のものとし、実施例1で得たサイジング剤の水分散液を用いて炭素繊維束のサイジング処理を行った。それ以外は実施例1と同様にして、サイジング剤が付着した炭素繊維束を得、サイジング剤が付着した炭素繊維束について、実施例1と同様の評価を行った。結果を表2に示す。
サイジング剤が付着していない炭素繊維束として、パイロフィルTRH50(製品名、三菱レイヨン株式会社製、フィラメント数18000本、ストランド強度5,600MPa、ストランド弾性率256GPa、繊維密度1.82g/m3)を用いた。
上記2-2のサイジング剤が付着していない炭素繊維束に前記サイジング剤を付着させた炭素繊維束34本(投入本数:34本)を使用し、図1に示したような成形工程により、引抜成形を実施して引抜成型複合材を得た。サイジング剤が付着した炭素繊維束Fはそれぞれクリール1から巻き出し、ガイドロール2を介してシート状に配列された。その後、サイジング剤が付着した炭素繊維束Fをレジンバス3内において後述する熱硬化性樹脂EP2に浸漬し、同樹脂を付着させてから、ガイドバー4により擦過させて同樹脂をサイジング剤が付着した炭素繊維束Fに含浸させると共に、過剰の樹脂をある程度除去した。更に、プレートに多数の貫通孔5aが形成された孔あきガイド5の各孔5aにそれぞれ一本のサイジング剤が付着した炭素繊維束Fを通過させ、過剰の樹脂をある程度絞り取ってから、直径6mmの円形断面をなす引抜通路6aをもつ引抜成形用金型6へと導入し、最終的に過剰な樹脂を除去した。引抜成形用金型6の金型温度は200℃、成形速度は0.25m/分とした。
「EP2」:主剤(ナガセケムテック社製、製品名:XNR6830)と、硬化剤(ナガセケムテック社製、製品名:XNH6830(M))と、内部離型剤(AXEL社製、製品名:モールドウィズINT-1846N2)とを、主剤/硬化剤/内部離型剤=100/100/0.75の質量比で混合したもの。
上記5-1で得られた引抜成型物の引張強度を土木学会の「定着用膨張材を用いた引張試験方法」に従って測定を実施した。引張強度は、得られた引抜成型物の繊維体積含有率Vfを用いて、繊維体積含有率100%に換算した。その結果を表2に示す。なお、引抜成型物の繊維体積含有率(%)は下記式を用いて得た。
引抜成型物の繊維体積含有率Vf=(繊維束目付け×投入本数÷繊維密度)÷[(引抜成型物外径÷2)2×3.1416]×100
なお、引抜成型物外径は、引抜成型物の長手方向に垂直な方向の外径を、マイクロメーターを用い、6ヶ所測定し、その平均値を用いた。また、上式中の繊維束目付は投入した炭素繊維束34本の内の12本の繊維束測定を行い、その平均値を用いた。繊維密度は前記パイロフィルTRH50の繊維密度である。
サイジング処理する炭素繊維束を上記2-2のものとし、実施例2で得たサイジング剤の水分散液を用いて炭素繊維のサイジング処理を行った。それ以外は実施例1と同様にして、サイジング剤が付着した炭素繊維束を得、サイジング剤が付着した炭素繊維束について、実施例1と同様の評価を実施した。また、得られたサイジング剤が付着した炭素繊維束を用いて実施例20と同様に引抜成型複合材の作成、およびその評価を実施した。結果を表2に示す。
サイジング処理する炭素繊維束を上記2-2のものとし、実施例3で得たサイジング剤の水分散液を用いて炭素繊維のサイジング処理を行った。それ以外は実施例1と同様にして、サイジング剤が付着した炭素繊維束を得、サイジング剤が付着した炭素繊維束について、実施例1と同様の評価を実施した。また、得られたサイジング剤が付着した炭素繊維束を用いて実施例20と同様に引抜成型複合材の作成、およびその評価を実施した。結果を表2に示す。
サイジング処理する炭素繊維束を上記2-2のものとし、実施例12で得たサイジング剤の水分散液を用いて炭素繊維のサイジング処理を行った。それ以外は実施例1と同様にして、サイジング剤が付着した炭素繊維束を得、サイジング剤が付着した炭素繊維束について、実施例1と同様の評価を実施した。また、得られたサイジング剤が付着した炭素繊維束を用いて実施例20と同様に引抜成型複合材の作成、およびその評価を実施した。結果を表2に示す。
サイジング処理する炭素繊維束を上記2-2のものとし、実施例13で得たサイジング剤の水分散液を用いて炭素繊維のサイジング処理を行った。それ以外は実施例1と同様にして、サイジング剤が付着した炭素繊維束を得、サイジング剤が付着した炭素繊維束について、実施例1と同様の評価を実施した。また、得られたサイジング剤が付着した炭素繊維束を用いて実施例20と同様に引抜成型複合材の作成、およびその評価を実施した。結果を表2に示す。
各例において、サイジング剤の組成を表3の比較例1~10の欄に示したものとし、(C)成分としてポリウレタン樹脂が水分散化されたものをそのまま使用した。すなわち、表3の比較例1~10の欄にそれぞれに示したサイズ剤の組成の内、(C)成分以外の成分を用いて実施例1と同様の方法でサイジング剤の水分散液を調製した後、この(C)成分を含まないサイジング剤の水分散液に、(C)成分としてポリウレタン樹脂が水分散化されたものを混合してサイジング剤水分散液を得た。それ以外は実施例1と同様にして、サイジング剤が付着した炭素繊維束を得、これを用いたシート状物、及び織布の作成、評価を実施した。結果を表3の比較例1~10の欄に示す。
サイジング処理する炭素繊維束を上記2-2のものとし、比較例9で得たサイジング剤の水分散液を用いて炭素繊維のサイジング処理を行った。それ以外は実施例1と同様にして、サイジング剤が付着した炭素繊維束を得、サイジング剤が付着した炭素繊維束について評価を行った。また、得られた本発明のサイジング剤が付着した炭素繊維束を用いて実施例20と同様に引抜成型複合材の作成、およびその評価を実施した。結果を表3に示す。
ここで、A1~A2において、(A)成分として有効なハーフエステル成分は1/2であり、残り1/2は未反応物とジエステル物である。表1~3に示すA1~A2の配合量は、ハーフエステル成分、未反応物およびジエステル物の総量を表している。したがってハーフエステルとしての有効成分量は、表1~3の配合量の1/2である。すなわち、サイジング剤中の(A)成分の含有量を計算する際には、表に示されるA1およびA2の配合量の半分の値を用いる。ただし、全サイジング成分の量には、上記ハーフエステル成分の配合量だけでなく上記未反応物およびジエステル物の配合量も含まれる。すなわち、全サイジング成分の量を計算するためには、表に示されるA1およびA2の配合量の値を用いる。
E1:ビスフェノールA1モル部に対してPO(プロピレンオキサイド)3モル部が付加したビスフェノールAのPO付加物(三洋化成工業株式会社製、製品名:ニューポールBP-3P)800質量部、フマル酸278質量部(アルコール/酸=1/1.2モル比)及びテトライソポプロポキシチタネート1質量部を、ガラス反応容器中、窒素流通下180℃で-0.1MPa(ゲージ圧)まで減圧し水を留去しながら10時間反応させて得た。
2 ガイドロール
3 レジンバス
4 ガイドバー
5 孔あきガイド
6 引抜成形用金型
6a 引抜通路
F 補強繊維(炭素繊維束)
Claims (16)
- 分子中に複数個のエポキシ基を有するエポキシ化合物と不飽和一塩基酸とのエステルであって、分子中に少なくとも1つのエポキシ基を有する化合物(A)と、
硬化物の引張伸び率が40%以上の2官能タイプのウレタンアクリレートオリゴマー(B)と、
乾燥皮膜の引張伸び率が350%以上900%以下であるポリウレタン樹脂(C)と
を含有し、
前記化合物(A)と前記ウレタンアクリレートオリゴマー(B)との含有量の質量比が、ウレタンアクリレートオリゴマー(B)/化合物(A)の比として、1/3以上2/1以下であり、
全サイジング成分中に占める前記化合物(A)および前記ウレタンアクリレートオリゴマー(B)の合計量の割合が20質量%以上であり、
かつ全サイジング成分中に占める前記ポリウレタン樹脂(C)の割合が、5質量%以上50質量%以下である炭素繊維用サイジング剤。 - 前記ポリウレタン樹脂(C)の乾燥皮膜の引張強度が10MPa以上50MPa以下である請求項1に記載の炭素繊維用サイジング剤。
- 前記ポリウレタン樹脂(C)のガラス転移温度が-50℃以上35℃以下である請求項1または2に記載の炭素繊維用サイジング剤。
- ビスフェノール類のアルキレンオキシド付加物とジカルボン酸化合物とのエステルであって、その酸価が50以上であるエステル化合物(E)をさらに含み、
前記エステル化合物(E)の含有量が、前記化合物(A)および前記ウレタンアクリレートオリゴマー(B)の合計量の2.0質量倍以下である請求項1~3のいずれか一項に記載の炭素繊維用サイジング剤。 - さらに、界面活性剤(D)として、アンモニウムイオンを対イオンとして有するアニオン系界面活性剤(D-1)と、ノニオン系界面活性剤(D-2)とを含有し、
前記アニオン系界面活性剤(D-1)と前記ノニオン系界面活性剤(D-2)との含有量の質量比が、ノニオン系界面活性剤(D-2)/アニオン系界面活性剤(D-1)の比として、1/10以上1/5以下の範囲内であり、
全サイジング成分中に占める前記アニオン系界面活性剤(D-1)および前記ノニオン系界面活性剤(D-2)の合計量の割合が10質量%以上25質量%以下である請求項1~4のいずれか一項に記載の炭素繊維用サイジング剤。 - 請求項1~5のいずれかに記載の炭素繊維用サイジング剤が水中に分散した水分散液であって、水分散液中のサイジング剤の分散粒子の平均粒子径が0.3μm以下である炭素繊維用サイジング剤の水分散液。
- 前記ポリウレタン樹脂(C)成分が、水分散液中の分散粒子の平均粒子径が0.2μm以下であるポリウレタン樹脂の水分散液の形で混合されてなる請求項6に記載の炭素繊維用サイジング剤の水分散液。
- 請求項1~5のいずれか一項に記載の炭素繊維用サイジング剤が付着した炭素繊維からなる炭素繊維束であって、該サイジング剤の付着量が0.6質量%以上3.0質量%以下である炭素繊維束。
- 請求項6または7に記載の炭素繊維用サイジング剤の水分散液で処理された、該サイジング剤が付着した炭素繊維からなる炭素繊維束であって、サイジング剤の付着量が0.6質量%以上3.0質量%以下である炭素繊維束。
- 25℃におけるカンチレバー値が200mm以上400mm以下にある請求項8または9に記載の炭素繊維束。
- 請求項8~10のいずれか一項に記載の炭素繊維束を含む引抜成型複合材。
- 熱硬化性マトリックス樹脂を含む請求項11に記載の引抜成型複合材。
- 引張強度が5000MPa以上6000MPa以下である請求項11または12に記載の引抜成型複合材。
- 請求項8~10のいずれか一項に記載の炭素繊維束を含むシート状物。
- 請求項14に記載のシート状物を含む複合材。
- 熱硬化性マトリックス樹脂を含む請求項15に記載の複合材。
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- 2012-08-21 EP EP12826136.9A patent/EP2749690B1/en active Active
- 2012-08-21 KR KR1020137034114A patent/KR101557568B1/ko active IP Right Grant
- 2012-08-21 US US14/240,161 patent/US9862824B2/en active Active
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Also Published As
Publication number | Publication date |
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CN103748281B (zh) | 2016-01-20 |
EP2749690A4 (en) | 2015-04-22 |
JPWO2013027708A1 (ja) | 2015-03-19 |
CN103748281A (zh) | 2014-04-23 |
US9862824B2 (en) | 2018-01-09 |
KR101557568B1 (ko) | 2015-10-05 |
KR20140012759A (ko) | 2014-02-03 |
US20140256855A1 (en) | 2014-09-11 |
EP2749690B1 (en) | 2019-11-06 |
TWI475142B (zh) | 2015-03-01 |
JP5497908B2 (ja) | 2014-05-21 |
TW201313985A (zh) | 2013-04-01 |
EP2749690A1 (en) | 2014-07-02 |
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