WO2017038880A1 - エポキシ樹脂組成物、プリプレグおよび炭素繊維強化複合材料 - Google Patents
エポキシ樹脂組成物、プリプレグおよび炭素繊維強化複合材料 Download PDFInfo
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- WO2017038880A1 WO2017038880A1 PCT/JP2016/075520 JP2016075520W WO2017038880A1 WO 2017038880 A1 WO2017038880 A1 WO 2017038880A1 JP 2016075520 W JP2016075520 W JP 2016075520W WO 2017038880 A1 WO2017038880 A1 WO 2017038880A1
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- Prior art keywords
- epoxy resin
- resin composition
- mass
- carbon fiber
- general formula
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4035—Hydrazines; Hydrazides
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
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- 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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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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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
Definitions
- the present invention relates to an epoxy resin composition suitably used for a carbon fiber reinforced composite material. More specifically, the present invention relates to an epoxy resin composition that provides a carbon fiber reinforced composite material that is excellent in moldability and heat resistance and excellent in mechanical properties such as tensile strength and compressive strength.
- carbon fiber reinforced composite materials make use of their high specific strength and specific elastic modulus, such as aircraft, automobiles, sports equipment, fishing equipment, blades for wind power generation, PC housings, etc. Use is expanding to a wide range of applications.
- the shape of these structures is often a complex form, and can be used by laminating carbon fiber reinforced fiber woven prepregs, which can be made sheet-like and can be made thin while being thin. Many.
- thermosetting resin excellent in mechanical properties, heat resistance, and processability, especially an epoxy resin is widely used.
- mechanical properties required for weight reduction have been further increased for applications used as structures such as aircraft and automobiles. It is required to further increase the tensile strength and compressive strength, which are important properties, and to maintain the physical properties in a humid high temperature environment.
- the tensile strength of the composite material it is also effective to lower the crosslink density of a cured product of the epoxy resin composition (hereinafter sometimes abbreviated as a cured product) in addition to an improvement in the tensile strength of the carbon fiber serving as the base material.
- Patent Document 2 a resin composition in which two types of epoxy resins having a naphthalene skeleton are combined for the purpose of improving heat resistance and flame retardancy is used. However, no mechanical properties such as tensile strength and compressive strength of the composite material have been found.
- Patent Document 3 a trifunctional or higher functional bisnaphthalene type epoxy resin is used to improve mechanical properties, but the crosslink density is increased and sufficient tensile strength cannot be obtained.
- honeycomb sandwich structures are widely used for structures aimed at weight reduction.
- the honeycomb core and the prepreg are bonded with an adhesive film. If there is a lot of resin flow during bonding, molding defects may occur.
- Patent Document 4 discloses a composite material using an epoxy resin composition having a condensed polycyclic aromatic skeleton.
- the condensed polycyclic aromatic compound has problems such as a large resin flow in the molding temperature region of the adhesive film, which causes molding defects.
- an object of the present invention is to provide an epoxy resin composition that provides a carbon fiber reinforced composite material excellent in moldability, heat resistance, tensile strength, and compressive strength.
- the inventors of the present invention have made extensive studies on the above-mentioned problems and have clarified that the problems can be solved by mixing a specific epoxy resin component in a specific range as an epoxy resin component, and have reached the present invention.
- the epoxy resin composition of the present invention is an epoxy resin composition containing at least the following constituent elements [A] to [D], and the constituent element [A] is 5 parts per 100 parts by mass of the total epoxy resin.
- X represents either an alkylene group having 1 or 2 carbon atoms or a group represented by General Formula [2].
- R in General Formula [2] is , A glycidyl ether group, a group represented by the general formula [3], a hydrogen atom, a halogen atom, a phenyl group, or an alkyl group having 1 to 4 carbon atoms, Y represents one aromatic ring Alternatively, it represents a condensed polycyclic aromatic hydrocarbon, Z represents a condensed polycyclic aromatic hydrocarbon, and Y and Z each have one glycidyl ether group, or either Y or Z has the general formula [3]
- the repeating unit has a structure mainly having two epoxy groups in the repeating unit, and the bond between the aromatic ring of Y and Z and the main chain of the condensed polycyclic aromatic is in the ortho position or the meta position.
- T may be a condensed polycyclic aromatic hydrocarbon. Represents any of a hydrogen atom.
- the prepreg of the present invention is It is a prepreg formed by impregnating a reinforcing fiber with an epoxy resin composition, and the reinforcing fiber may be a base material in the form of a woven fabric.
- the fiber reinforced composite material of the present invention is a fiber reinforced composite material obtained by curing the prepreg.
- an epoxy resin composition that provides a carbon fiber reinforced composite material that is excellent in moldability and heat resistance and excellent in mechanical properties such as tensile strength and compressive strength.
- the epoxy resin [A] (the component [A] may be referred to as the epoxy resin [A]) is contained in one or more repeating units represented by the general formula [1] or [4]. It is an epoxy resin having a condensed polycyclic aromatic hydrocarbon skeleton and mainly two epoxy groups. “Mainly” means that the epoxy resin having two epoxy groups in the repeating unit is 40% by mass or more.
- the epoxy resin [A] contains an aromatic ring or condensed polycyclic aromatic hydrocarbon such as naphthalene or anthracene in one molecule. By introducing a molecular structure having an aromatic skeleton, rigidity is increased and high resin modulus and heat resistance are obtained.
- X in the formula represented by the general formula [1] or [4] connects the aromatic compound and the end group.
- T represents either a condensed polycyclic aromatic hydrocarbon or a hydrogen atom.
- X represents either an alkylene group having 1 to 2 carbon atoms or a substituent represented by the general formula [2].
- An alkylene group having a smaller carbon number has a smaller free volume and a higher elastic modulus.
- at least one condensed polycyclic aromatic hydrocarbon is required in the repeating unit in order to increase heat resistance and molecular rigidity.
- Y is one aromatic ring or a condensed polycyclic aromatic hydrocarbon
- Z is a condensed polycyclic aromatic hydrocarbon.
- Y and Z may be the same skeleton.
- each of Y and Z has one glycidyl ether group, or either Y or Z has a substituent represented by the general formula [3], and has two epoxy groups in the repeating unit.
- a structure is preferred. From the balance of the mechanical strength of the composite material to be obtained, it is preferable that 40% by mass or more of two glycidyl ether groups in one unit is contained as a main component.
- a compound having 3 or 4 glycidyl ether groups in the repeating unit may be contained.
- the compound having two epoxy functional groups in the compound of the general formula [1] or [4] is preferably 40 to 80% by mass in the epoxy resin [A].
- the bond between Y and the aromatic ring of Z and the condensed polycyclic aromatic main chain may be in the ortho position or the meta position.
- bonding at the ortho position where the molecular flexibility is greater is preferable.
- the repetition number n shown by general formula [1] or [4] shows a number of 1 or more. In the formula, as n is smaller, the crosslinking density is increased and the elastic modulus of the cured epoxy resin is improved. Therefore, n is preferably 1.
- the blending amount of the epoxy resin [A] is 5 to 40 parts by mass with respect to 100 parts by mass of the total amount of the epoxy resin, so that a prepreg having excellent handling properties such as tackiness and drapeability can be produced.
- epoxy resins [A] include “Epiclon (registered trademark)” HP-4770 (manufactured by DIC Corporation), NC-7300L (naphthol type epoxy, Nippon Kayaku Co., Ltd., epoxy equivalent: 220). Can be mentioned.
- the epoxy resin [B] used in the present invention (the component [B] may be referred to as epoxy resin [B]) is a glycidylamine type epoxy resin having three or more glycidyl groups in the molecule. It is preferable that the number of glycidyl groups in the molecule is 3 or 4 because the mechanical properties and heat resistance of the composite material can be balanced.
- diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, xylenediamine, aminophenol, structural isomers thereof, derivatives having halogen or an alkyl substituent having 3 or less carbon atoms, and glycidylation were used as precursors.
- tetraglycidyldiaminodiphenylmethane a glycidyl compound of xylenediamine, triglycidylaminophenol, tetraglycidyldiaminodiphenylsulfone, tetraglycidyldiaminodiphenylether and the like can be mentioned.
- Examples of commercially available epoxy resin [B] include the following.
- Commercially available products of tetraglycidyldiaminodiphenylmethane include “Sumiepoxy (registered trademark)” ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), “Araldite (registered trademark)” MY720, “Araldite (registered trademark)” MY721, “Araldite (registered) Trademarks) “MY9512”, “Araldite (registered trademark)” MY9612, “Araldite (registered trademark)” MY9634, “Araldite (registered trademark)” MY9663 (manufactured by Huntsman Advanced Material).
- Examples of commercially available glycidyl compounds of xylenediamine include TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Inc.).
- Commercially available products of triglycidylaminophenol include “Araldite (registered trademark)” MY0500 having “p-aminophenol” as a precursor, “Araldite (registered trademark)” MY0510 (manufactured by Huntsman Advanced Materials) and “jER (registered trademark)”.
- the epoxy resin [B] may be blended with two or more different epoxy resins selected from these.
- the blending amount of the epoxy resin [B] is 20 to 95 parts by mass, preferably 40 to 90 parts by mass with respect to the total amount of the epoxy resin in order to balance the mechanical properties at a high level.
- thermoplastic resin [C] used in the present invention is a thermoplastic resin that is soluble in an epoxy resin and imparts high heat resistance.
- the glass transition temperature (hereinafter sometimes abbreviated as Tg) is preferably 180 ° C. or higher, and preferably has an aromatic ring in the molecule.
- Tg glass transition temperature
- polyethersulfone, polyetherethersulfone, polyetherimide, polyphenylene oxide, and polysulfone are preferably used.
- polyethersulfone As a commercially available product of the sulfone-based or imide-based thermoplastic resin [C], as polyethersulfone, “Sumika Excel (registered trademark)” PES5003P (manufactured by Sumitomo Chemical Co., Ltd.) having a hydroxyl group at the terminal or “Virantage (registered) Trademark) "VW10700 (manufactured by Solvay Advanced Polymers)", “Sumika Excel (registered trademark)” PES7600P (manufactured by Sumitomo Chemical Co., Ltd.) chlorinated at the terminal, and polyetherimide with an acid anhydride or amino group at the terminal
- the polysulfone include “Ultem (registered trademark)” 1010 (manufactured by Sabic Strategic Plastics Co., Ltd.) and polysulfone include “Virantage (registered trademark)” VW30500 (manufactured by Solvay Advanced Polymers
- soluble in epoxy resin means that there is a temperature range in which a sulfone or imide thermoplastic resin [C] is mixed with an epoxy resin and heated and stirred to form a uniform phase.
- Melaking a homogeneous phase means that a state without visual separation is obtained. As long as a uniform phase can be formed in a certain temperature region, the separation may occur in other temperature regions, for example, 23 ° C. Moreover, you may judge with the following method that it melt
- a sulfone or imide thermoplastic resin [C] powder is mixed with an epoxy resin and kept isothermal at a temperature lower than the Tg of the sulfone or imide thermoplastic resin [C] for several hours, for example, 2 hours.
- an increase in viscosity of 10% or more with respect to the initial viscosity is observed when the change in viscosity is evaluated, it is determined that the sulfone or imide thermoplastic resin [C] can be dissolved in the epoxy resin. It's okay.
- the blending amount of the sulfone-based or imide-based thermoplastic resin [C] is preferably 1 to 25 parts by mass when the total amount of the epoxy resin is 100 parts by mass. Within this range, the tackiness and drapeability are excellent and the viscosity adjustment of the epoxy resin composition can be adjusted to an appropriate range.
- the epoxy resin curing agent [D] used in the present invention may be a compound having an active group capable of reacting with an epoxy resin.
- the active group capable of reacting with the epoxy resin include those having an amino group or an acid anhydride group.
- Epoxy resin curing agents are preferred as the storage stability is higher, but liquid curing agents are preferably solid at 23 ° C. because of high reactivity.
- the epoxy resin curing agent [D] is preferably an aromatic amine, and preferably has 1 to 4 phenyl groups in the molecule from the viewpoint of heat resistance and mechanical properties. Furthermore, by imparting flexibility of the molecular skeleton, the resin elastic modulus can be improved and it can contribute to the improvement of mechanical properties. Therefore, at least one phenyl group contained in the skeleton of the epoxy resin curing agent has an amino group at the ortho position or the meta position. More preferably, it is an aromatic polyamine compound which is a phenyl group having a group.
- aromatic polyamines include various derivatives such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, metaxylylenediamine, (p-phenylenemethylene) dianiline and their alkyl substituents, and the position of the amino group. Examples include different isomers. These curing agents can be used alone or in combination of two or more. Of these, diaminodiphenylmethane and diaminodiphenylsulfone are preferable from the viewpoint of imparting heat resistance to the composition.
- aromatic polyamine curing agents include Seika Cure S (manufactured by Wakayama Seika Kogyo Co., Ltd.), MDA-220 (manufactured by Mitsui Chemicals), “jER Cure (registered trademark)” (Mitsubishi Chemical Corporation) 3,3'-DAS (Mitsui Chemicals Fine Co., Ltd.), "Lonzacure (registered trademark)” M-DEA (manufactured by Lonza), “Lonzacure (registered trademark)” M-DIPA (Lonza) "Lonzacure (registered trademark)” M-MIPA (manufactured by Lonza), “Lonzacure (registered trademark)” DETDA 80 (manufactured by Lonza), and the like.
- the addition amount of the epoxy resin curing agent [D] varies depending on the combination with the epoxy resin.
- the ratio of the amount of active hydrogen of the epoxy resin curing agent [D] to the epoxy group of the epoxy resin is 0.6 to 1.4, the curing can be sufficiently advanced, and the adverse effect on the mechanical properties due to the excessive curing agent can be prevented. It is preferable because it can be reduced, and more preferably 0.65 to 1.4.
- an organic acid hydrazide compound can be used in combination with the epoxy resin curing agent [D] in the present invention.
- the organic acid hydrazide compound By using the organic acid hydrazide compound, it is possible to increase the resin viscosity in the honeycomb structure material forming temperature region and to suppress the resin flow. If the blending amount of the organic acid hydrazide compound is too small, the desired thickening effect of the viscosity cannot be obtained, and if it is too large, the mechanical properties deteriorate and the storage stability of the resin composition is impaired. It is preferable to blend 0.01 to 10% by mass with respect to the total amount of the product. When it exists in this range, it becomes possible to suppress the effect which improves the curing reactivity of a resin composition, the thermal stability of a resin composition, and the heat resistant fall of hardened
- a compound having a structural formula represented by the general formula [5] or the general formula [6] is particularly preferably used.
- A is a structure selected from a monocyclic aromatic structure, a polycyclic aromatic structure, a condensed polycyclic aromatic structure, and an aromatic heterocyclic structure. You may have either an alkyl group with 4 or less carbon atoms, a hydroxy group, and an amino group.
- the organic acid hydrazide compound represented by the general formula [5] or the general formula [6] has an aromatic ring structure in the molecule, it has a rigid molecular skeleton compared to the aliphatic hydrazide, and is cured with an epoxy resin. It is preferable because of its excellent heat resistance when used as a product. Moreover, the organic acid hydrazide compound represented by the general formula [5] or the general formula [6] is excellent in reactivity with an epoxy resin as compared with an aliphatic hydrazide, and has a high resin flow suppression when an epoxy resin composition is obtained. Since an effect is acquired, it is preferable.
- the monocyclic aromatic represented by A is a benzene ring
- the polycyclic aromatic is a biphenyl ring, a triphenyl ring, or a condensed polycyclic aromatic.
- the aromatic heterocycle represented by A includes a pyridine ring, a pyrazine ring, a pyrimidine ring, a quinoline ring, a quinoxaline ring, a naphthyridine ring, a pyrimidopyrimidine ring, and a benzoquinoline ring.
- organic acid hydrazide compound examples include 3-hydroxy-2-naphthoic acid hydrazide, 2,6-naphthalenedicarbodihydrazide, salicylic acid hydrazide, terephthalic acid dihydrazide, and isophthalic acid dihydrazide. These organic acid hydrazide compounds may be used by mixing and mixing two or more kinds as necessary.
- curing agent [D] and an organic acid hydrazide compound is an epoxy resin hardening
- the amount of the active hydrogen in the hydrazide compound is preferably in the range of 0.7 to 1.3, more preferably 0.8 to 1.2.
- active hydrogen refers to a highly reactive hydrogen atom that is bonded to nitrogen, oxygen, and sulfur in an organic compound. For example, there are two active hydrogens in an amino group. In the case of hydrazide, only hydrogen atoms bonded to the terminal nitrogen atom contribute to the reaction with the epoxy group. Therefore, the number of active hydrogens is calculated with respect to one hydrazide group. When the ratio of the epoxy group and the active hydrogen is within the predetermined range, it is preferable because a cured resin product having excellent heat resistance and elastic modulus can be obtained.
- a hydrazide compound other than the organic acid hydrazide compound described in the general formula [5] or the general formula [6] can be blended as necessary.
- examples thereof include carbodihydrazide, malonic hydrazide, succinic dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, propionic acid hydrazide and the like. These have the effect of improving the curing reactivity of the resin composition, like the organic acid hydrazide compound.
- the amount of the hydrazide compound other than those described in the general formula [5] or the general formula [6] is large, the heat resistance of the cured resin product may be lowered or the thermal stability may be lowered. Therefore, 10 mass% or less is preferable with respect to the total amount of the epoxy resin composition.
- a bifunctional epoxy resin may be used as the constituent element [E] in addition to the constituent elements [A] to [D].
- the component [E] is not particularly limited as long as it is a bifunctional epoxy resin, but it is a bisphenol type epoxy resin, an epoxy resin having a biphenyl skeleton, an epoxy resin having a naphthalene skeleton, an epoxy resin having a binaphthalene skeleton, a novolac type epoxy resin. Can be preferably exemplified.
- epoxy resin [E] As commercially available products of bisphenol A type epoxy resin of epoxy resin [E] (component [E] may be referred to as epoxy resin [E]), “jER (registered trademark)” 825, “jER (registered trademark) ) “826”, “jER (registered trademark)” 827, “jER (registered trademark)” 828, “jER (registered trademark)” 834, “jER (registered trademark)” 1001, “jER (registered trademark)” 1002, “ jER (registered trademark) 1003, jER (registered trademark) 1004, jER (registered trademark) 1004AF, jER (registered trademark) 1007, jER (registered trademark) 1009 (Mitsubishi Chemical Corporation) "Epicron (registered trademark)” 850 (manufactured by DIC Corporation), “Epototo (registered trademark)” YD-128 (manufactured by Nippon Steel &
- the compounding amount of the epoxy resin [E] is preferably 5 parts by mass or more and 40 parts by mass with respect to 100 parts by mass of the total epoxy resin, because a composite material having high mechanical properties is obtained.
- the epoxy resin composition of the present invention may contain particles containing 50% by mass or more of a thermoplastic resin as a main component.
- the particles containing a thermoplastic resin as a main component are blended for imparting the impact resistance of the fiber-reinforced composite material of the present invention.
- a fiber reinforced composite material has a laminated structure. When an impact is applied to the fiber reinforced composite material, high stress is generated between the layers, and peeling damage occurs. Therefore, when improving impact resistance against external impact, a resin layer (hereinafter referred to as “interlayer resin layer”) formed between the layers made of reinforcing fibers of the fiber-reinforced composite material. ) Toughness may be improved.
- component [C] is blended, and this is because the interlayer resin layer of the fiber-reinforced composite material of the present invention is selectively made tough.
- the thermoplastic resin which is the main component of the particle may be the same as or different from the thermoplastic resin used for the component [C].
- thermoplastic resin which is a component of such particles
- polyamide or polyimide can be preferably used, and among them, polyamide which can greatly improve impact resistance due to excellent toughness is most preferable.
- polyamide polyamide 12, polyamide 11, polyamide 6, polyamide 66 or polyamide 6/12 copolymer, an epoxy compound described in Example 1 of JP-A-01-104624, semi-IPN (polymer interpenetrating network structure) Polyamide (semi-IPN polyamide) or the like can be suitably used.
- thermoplastic resin particles may be spherical particles, non-spherical particles, or porous particles, but the spherical shape is superior in viscoelasticity because it does not deteriorate the flow characteristics of the resin, and there is no origin of stress concentration. This is a preferred embodiment in terms of giving high impact resistance.
- polyamide particles include SP-500, SP-10, TR-1, TR-2, 842P-48, 842P-80 (above, manufactured by Toray Industries, Inc.), and “Orgasol (registered trademark)” 1002D. , 2001UD, 2001EXD, 2002D, 3202D, 3501D, 3502D (above, manufactured by Arkema Co., Ltd.), “Grillamide (registered trademark)” TR90, TR55 (above, manufactured by Ms Chemi), “TROGAMID (registered trademark)” CX7323, CX9701, CX9704, (Degussa Co., Ltd.) etc. can be used. These polyamide particles may be used alone or in combination.
- the number average particle diameter of particles mainly composed of a thermoplastic resin is preferably in the range of 5 to 50 ⁇ m, preferably in the range of 7 to 40 ⁇ m, more preferably in the range of 10 to 30 ⁇ m.
- the particles can remain on the carbon fiber surface of the fiber reinforced composite material obtained without entering the bundle of reinforcing fibers or in the epoxy interlayer resin composition layer.
- the average particle size By setting the average particle size to 50 ⁇ m or less, the thickness of the matrix resin layer on the surface of the prepreg can be optimized, and further, the fiber mass content can be optimized in the obtained fiber-reinforced composite material.
- the resin viscosity which is an index of resin fluidity
- a dynamic viscoelastic device was used
- a flat parallel plate having a diameter of 40 mm was used for the upper and lower jigs
- the epoxy resin composition was set so that the distance between the upper and lower plates was 1 mm, and the angular frequency was 3.14 rad.
- the viscosity at 80 ° C. measured at / s is 0.5 Pa ⁇ s or more, an excessive resin flow is less likely to occur during molding of the fiber-reinforced composite material, and variations in the reinforcing fiber content can be suppressed.
- the viscosity of the epoxy resin composition is preferably 0.5 to 200 Pa ⁇ s, and more preferably in the range of 5 to 100 Pa ⁇ s with good handleability.
- the resin flow at the time of forming the honeycomb structure is appropriate, a dynamic viscoelastic device is used, a flat parallel plate with a diameter of 25 mm is used for the upper and lower jigs, and the distance between the upper and lower plates is 1 mm.
- the temperature was increased from 40 ° C. to 120 ° C. at an angular frequency of 3.14 rad / s at a rate of 1.5 ° C./min, and the temperature was kept constant at 120 ° C. for 1 hour.
- the viscosity (hereinafter referred to as viscosity after holding at 120 ° C.
- the fluidity of the resin is appropriate, and the adhesiveness to the honeycomb core material and the mechanical properties of the final molded product are preferable.
- the epoxy resin composition of the present invention can be used as a carbon fiber reinforced composite material in combination with carbon fibers.
- the carbon fiber any carbon fiber can be used as long as it is a known carbon fiber, and those having a strand strength of 3000 MPa to 7500 MPa and an elastic modulus of 200 GPa to 450 GPa in the strand tensile test are preferable.
- the strand tensile test refers to a test carried out based on JIS R7601 (1986) after impregnating a bundle of carbon fibers with a matrix resin having the following composition and curing it at a temperature of 130 ° C. for 35 minutes.
- the number of carbon fiber filaments is preferably 1000 to 100,000, more preferably 3000 to 50,000. If the number of carbon fiber filaments is less than 1000, the operation for forming a prepreg becomes complicated, and if it exceeds 100,000, it is difficult to impregnate the resin between the filaments, and impregnation failure may occur.
- the form of carbon fiber is preferably used by arranging continuous fibers in one direction, or in the form of a woven fabric such as plain weave, satin weave, twill weave, etc., and the carbon fiber may form a layer.
- the continuous fiber means a fiber having an average length of 10 mm or more.
- a prepreg obtained by impregnating a fiber base material with a resin in advance may be used after being molded by the method described below.
- the prepreg of the present invention refers to a continuous carbon fiber arranged in one direction in a sheet shape, a carbon fiber fabric or other carbon fiber base material impregnated with an epoxy resin composition, or a carbon fiber base material.
- a resin layer made of an epoxy resin composition is disposed on at least one surface, or a part of the epoxy resin composition is impregnated and the remaining portion is disposed on at least one surface. It is preferable that the epoxy resin composition at the time of impregnation or placement has fluidity because workability is improved when it is molded into a predetermined shape.
- the prepreg can be produced by a wet method, a hot melt method, or the like described below.
- the wet method is a method in which a reinforcing fiber substrate is immersed in a solution composed of an epoxy resin composition and a solvent, then lifted, and the solvent is evaporated using an oven or the like.
- the hot melt method reduces the viscosity by heating.
- the hot melt method is preferable because substantially no solvent remains in the prepreg.
- the carbon fiber mass per unit area of the prepreg is preferably 70 to 1000 g / m 2 .
- the carbon fiber content in the prepreg is preferably 30 to 90% by mass, more preferably 35 to 85% by mass, and further preferably 40 to 80% by mass.
- the carbon fiber content is 30% by mass or more, the high specific strength and specific elastic modulus, which are the characteristics of the carbon fiber reinforced composite material, can be effectively used. If the carbon fiber content is 90% by mass or less, a uniform molded product is easily obtained. Therefore, it is preferable.
- the gap portion generated in the entangled portion of the warp and weft of the carbon fiber woven fabric is 5% or less when the prepreg is manufactured. From the back side of the fabric prepreg, photograph the surface of the fabric prepreg with an actual microscope while shining light. The woven yarn portion is black, the gap portion is white, and the transmitted light pattern of the fabric is photographed. When the total area S1 and the area S2 of the white portion (gap portion) are obtained by image processing, the ratio of the gap portion can be measured by S2 / S1.
- the carbon fiber reinforced composite material of the present invention is produced by a method of heat curing the resin while applying pressure to the laminate.
- the method for applying heat and pressure include a press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method, and an internal pressure molding method.
- the wrapping tape method is a method of winding a prepreg on a mandrel or other core metal to form a tubular body made of a carbon fiber reinforced composite material, and is a method suitable for producing rod-shaped bodies such as golf shafts and fishing rods. is there.
- the prepreg is wound around a mandrel, and a wrapping tape made of a thermoplastic resin film is wound around the outside of the prepreg to fix and apply pressure to the prepreg.
- This is a method of extracting a gold to obtain a tubular body.
- the internal pressure molding method is to set a preform in which a prepreg is wound on an internal pressure applying body such as a tube made of a thermoplastic resin in a mold, and then introduce a high pressure gas into the internal pressure applying body to apply pressure. At the same time, the mold is heated and molded.
- This method is preferably used when molding a complicated shape such as a golf shaft, a bat, a racket such as tennis or badminton.
- the curing temperature and time when the carbon fiber reinforced composite material of the present invention is molded in an autoclave or an oven vary depending on the type and amount of the selected curing agent and curing catalyst, but the temperature and time are 130 ° C. or higher. For applications requiring heat resistance, curing at 120 to 220 ° C. for 0.5 to 8 hours is preferable.
- a temperature rising rate of 0.1 to 10 ° C./min is preferably used. When the rate of temperature increase is less than 0.1 ° C./min, the time required to reach the target curing temperature becomes very long and workability may be reduced. On the other hand, if the rate of temperature rise exceeds 10 ° C./min, a temperature difference occurs at various portions of the reinforcing fiber due to the influence of airflow and internal heat generation, and a uniform cured product may not be obtained.
- pressure increase / decrease is not essential, but pressure increase / decrease may be performed as necessary.
- effects such as improvement of surface quality, suppression of internal voids, improvement of adhesion to metal or plastic to be bonded at the time of curing, or parts made of fiber reinforced composite material may be obtained.
- the carbon fiber reinforced composite material of the present invention is preferably used for aircraft structural members, wind turbine blades, automobile outer plates, and computer applications such as IC trays and notebook PC housings, and sports applications such as golf shafts and tennis rackets. .
- Component [A] An epoxy resin in which X in the general formula [1] or [4] is a methylene group, Y is a naphthalene skeleton, and Z is a naphthalene skeleton.
- "Epiclon (registered trademark)” HP-4770 bisnaphthalene type epoxy, manufactured by DIC Corporation, epoxy equivalent: 205).
- “Epicron” HP-4770 includes trifunctional and tetrafunctional bisnaphthalene type epoxy resins according to the description of JP2011-213784.
- ARALDITE registered trademark
- MY721 tetraglycidyldiaminodiphenylmethane, manufactured by Huntsman Advanced Materials, epoxy equivalent: 112
- TGDDS tetraglycidyl diaminodiphenyl sulfone, manufactured by Konishi Chemical Co., Ltd., epoxy equivalent: 112
- ALALDITE registered trademark
- MY0510 triglycidyl-p-aminophenol, manufactured by Huntsman Advanced Materials, epoxy equivalent: 100
- ARALDITE registered trademark
- MY0600 triglycidyl-m-aminophenol, manufactured by Huntsman Advanced Materials, epoxy equivalent: 105).
- Organic acid hydrazide compound isophthalic acid dihydrazide, manufactured by Otsuka Chemical Co., Ltd.
- JER (registered trademark) 807 (bisphenol F type epoxy, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 170)
- JER (registered trademark) 825 (bisphenol A type epoxy, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 175).
- Thermoplastic resin particles “Grillamide (registered trademark)” TR55 manufactured by Ms Chemi were pulverized and classified by an impact pulverizer to obtain fine particles having a number average particle diameter of 20 ⁇ m.
- Tg Glass transition temperature of cured resin
- DSC differential scanning calorimeter
- a plain weave fabric made of “Torayca (registered trademark)” T400H-3K (3000 fibers, tensile strength 4410 MPa, tensile elastic modulus 250 MPa, tensile elongation 1.8%) was used.
- Tensile test of fiber reinforced composite material Nine sheets of woven prepregs are aligned and laminated, and heated and pressurized in an autoclave at a temperature of 180 ° C. and a pressure of 6.10 kgf / cm 2 Pa for 2 hours to cure the composite material. Produced. A test piece having a width of 25 ⁇ 0.5 mm, a length of 250 ⁇ 1.0 mm, and a span between tabs of 130 ⁇ 1.0 mm was produced from the obtained composite material, and the warp tensile strength was measured according to EN2597B.
- the elastic modulus of the cured resin is 4.0 GPa or more
- the elastic modulus of the cured resin at a moisture absorption high temperature is 2.4 GPa or more
- the Tg of the cured resin is 180 ° C. or more
- the warp tensile strength is 700 MPa or more.
- the warp compression strength was 850 MPa or more.
- ⁇ 80 was within 0.5 to 200 MPa ⁇ s, and it was confirmed that the epoxy resin composition had good impregnation properties when the prepreg was produced, and the obtained prepreg was bonded between the prepregs. It was confirmed that the sticking property and the sticking property (tack property) to the metal plate were good.
- Examples 13 to 14> As shown in Table 2, the cured resin and the fiber reinforced composite material obtained in the same manner as in Examples 1 to 12 except that the component [B] was two components were tested, and excellent physical properties were obtained. .
- Examples 15 to 17, 19> As shown in Table 2, the cured resin obtained in the same manner as in Examples 1 to 12 except that the constituent element [E] was further added to the constituent elements [A], [B], [C], and [D]. Physical properties and fiber reinforced composite materials were tested, and excellent physical properties were obtained.
- Example 20 As shown in Table 4, a woven fabric prepreg was prepared in the same manner as in Example 1 except that thermoplastic resin particles were added during the preparation of the epoxy resin composition, an interlayer resin layer of a fiber reinforced composite material was formed, and a fiber reinforced composite The impact resistance of the material was compared with that in Example 1. In Example 20 to which the thermoplastic resin particles were added, it was confirmed that the impact resistance was improved as compared with Example 1.
- Example 21 As shown in Table 5, the constituent elements [A] [B] [C] [D] were the same as in Example 18 except that isophthalic acid dihydrazide was added as an organic acid hydrazide compound as an organic acid hydrazide compound during the preparation of the epoxy resin composition. ] was measured, and the viscosity of the epoxy resin composition was measured, and the resulting cured resin and fiber reinforced composite material were tested. The viscosity after holding for 1 hour at 120 ° C. ( ⁇ 120h) increased to 25 Pa ⁇ s in Example 21 in which the organic acid hydrazide compound was added, compared to Example 18, and the honeycomb formability was in a favorable viscosity range. By adding the organic acid hydrazide compound, the elastic modulus of the cured resin at a high hygroscopic temperature slightly decreased, but was within the acceptable range.
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Abstract
Description
[A]:一般式[1]または[4]で示される繰り返しユニット内に1つ以上の縮合多環芳香族炭化水素骨格と主として2つのエポキシ基を有するエポキシ樹脂
[B]:分子内に3個以上のグリシジル基を有するグリシジルアミン型エポキシ樹脂
[C]:スルホン系またはイミド系の熱可塑性樹脂
[D]:エポキシ樹脂硬化剤
また、本発明のプリプレグは、前記エポキシ樹脂組成物を強化繊維に含浸させてなるプリプレグであり、強化繊維は織物の形態である基材でもよい。さらに、本発明の繊維強化複合材料は、前記プリプレグを硬化させてなる繊維強化複合材料である。
・3フッ化ホウ素モノエチルアミン(例えば、ステラケミファ株式会社製):3質量部
・アセトン(例えば、和光純薬工業株式会社製):4質量部。
一般式[1]または[4]におけるXがメチレン基、Yがナフタレン骨格、Zがナフタレン骨格であるエポキシ樹脂。
・“エピクロン(登録商標)”HP-4770(ビスナフタレン型エポキシ、DIC(株)製、エポキシ当量:205)。なお“エピクロン”HP-4770は特開2011-213784公報記載によると、ビスナフタレン型エポキシ樹脂の3官能、4官能体も含まれている。
一般式[1]または[4]におけるXがメチレン基、Yがトルエン骨格、Zがナフタレン骨格であるエポキシ樹脂。
・NC-7300L(ナフトール型エポキシ、ナガセケムテックス(株)製、エポキシ当量:220)。
・“ARALDITE(登録商標)”MY721(テトラグリシジルジアミノジフェニルメタン、ハンツマンアドバンスドマテリアル社製、エポキシ当量:112)
・TGDDS(テトラグリシジルジアミノジフェニルスルホン、小西化学(株)製、エポキシ当量:112)
・“ARALDITE(登録商標)”(登録商標)MY0510(トリグリシジル-p-アミノフェノール、ハンツマンアドバンスドマテリアル社製、エポキシ当量:100)
・“ARALDITE(登録商標)”登録商標)MY0600(トリグリシジル-m-アミノフェノール、ハンツマンアドバンスドマテリアル社製、エポキシ当量:105)。
・“スミカエクセル(登録商標)”PES5003P(水酸基末端ポリエーテルスルホン、住友化学(株)製、Tg=225℃)
・“Virantage(登録商標)”VW-10700RP(水酸基末端ポリエーテルスルホン、Solvay Advanced Polymers(株)製、Tg=220℃)
・“スミカエクセル(登録商標)”PES7600P(塩素末端ポリエーテルスルホン、住友化学(株)製、Tg=225℃)
・“Virantage(登録商標)”VW-30500RP(ポリスルホン、Solvay Advanced Polymers(株)製、Tg=205℃)
・“ULTEM(登録商標)”1010(ポリエーテルイミド、Sabic Innovative Plastics(株)製、Tg=215℃)。
・3,3’-DAS(3,3’-ジアミノジフェニルスルホン、三井化学ファイン(株)製、活性水素当量:62、23℃で固形)
・セイカキュアS(4,4’-ジアミノジフェニルスルホン、和歌山精化工業(株)製、活性水素当量:62、23℃で固形)
・“Lonzacure(登録商標)”MIPA(4,4’-メチレンビス(2-メチル-6-イソプロピル)ベンゼンアミン、Lonza(株)製、活性水素当量:78、23℃で固体)。
・イソフタル酸ジヒドラジド、大塚化学(株)製。
・“jER(登録商標)”807(ビスフェノールF型エポキシ、三菱化学(株)製、エポキシ当量:170)
・“jER(登録商標)”825(ビスフェノールA型エポキシ、三菱化学(株)製、エポキシ当量:175)。
“グリルアミド(登録商標)”TR55(エムスケミ社製)を衝撃式粉砕機により粉砕分級することにより数平均粒径20μmの粒径の微粒子とした。
ニーダー中に、構成要素[A]のエポキシ樹脂、構成要素[B]のエポキシ樹脂、構成要素[C]の熱可塑樹脂、構成要素[E]のエポキシ樹脂を加熱しつつ混練し、構成要素[C]を溶解させ透明な粘稠液を得た。この液に、構成要素[D]の硬化剤を添加混練し、エポキシ樹脂組成物を得た。各実施例、比較例の成分配合比は表1~5に示すとおりであった。
エポキシ樹脂組成物の粘度は、動的粘弾性装置ARES-G2(ティー・エイ・インスツルメント社製)を用いて測定した。上下部測定冶具に直径40mmの平板のパラレルプレートを用い、上部と下部の冶具間距離が1mmとなるように該エポキシ樹脂組成物をセット後、角周波数:3.14rad/sで測定した。40℃から120℃まで速度1.5℃/分で昇温し、80℃の粘度η80を読み取った。
直径25mmの平板のパラレルプレートを用いた以外は同様にして、40℃から120℃まで速度1.5℃/分で昇温し、120℃で1時間ホールドした後の120℃1時間ホールド後の粘度(η120h)を求めた。
未硬化の樹脂組成物を真空中で脱泡した後、2mm厚の“テフロン(登録商標)”製のスペーサーを用い、厚み2mmになるよう設定したモールド中で、180℃の温度で2時間硬化させた。得られた厚み2mmの樹脂硬化物を幅10±0.1mm、長さ60±1mmでカットし、試験片を得た。インストロン万能試験機(インストロン社製)を用いJIS-K7171(1994)に従い、スパン間32mmの3点曲げを実施し、弾性率を測定した。測定数はN=6とし、その平均値を求めた。
(3)に示す寸法に作成した試験片を98℃の恒温槽に20時間浸漬後、(3)に示すインストロン万能試験機(インストロン社製)に設置した恒温槽を121℃に設定し、3分間槽内の環境に保持した後、(3)と同様の測定条件で弾性率を測定した。
上記(3)で得られた樹脂硬化物のガラス転移温度について、示差走査熱量計(DSC)を用いて、JIS-K7121(1987)に基づいてもとめ、中間点温度をTgとした。
上記(1)で調製したエポキシ樹脂組成物を離型紙上にコーティングし、所定の樹脂目付の樹脂フィルムを作製した。この樹脂フィルムをプリプレグ作製機にセットし、強化繊維織物の両面から重ね、加熱加圧して熱硬化性樹脂組成物を含浸させ、繊維目付193g/m2、樹脂含有率が38質量%の織物プリプレグを作製した。なお、強化繊維織物は“トレカ(登録商標)”T400H-3K(繊維数3000本、引張強度4410MPa、引張弾性率250MPa、引張伸度1.8%)からなる平織織物を用いた。
織物プリプレグの経糸方向を揃え9枚積層してオートクレーブ中で温度180℃、圧力6.10kgf/cm2Paで2時間加熱加圧して硬化し、複合材料を作製した。得た複合材料から、幅25±0.5mm、長さ250±1.0mm、タブ間スパン130±1.0mmの試験片を作製し、EN2597Bに従い、経糸引張強度を測定した。
織物プリプレグの経糸方向を揃え9枚積層して、上記(7)の成形条件で成形した複合材料から、幅12.5±0.2mm、長さ75~80mm、タブ間スパン5.25±0.25mmの試験片を作製し、EN2850Bに従い、経糸圧縮強度を測定した。
織物プリプレグ24枚を経糸方向を0°として[45°/0°/-45°/90°]3s(記号sは、鏡面対称を示す)で疑似等方的に積層し、上記(7)の成形条件で成形した複合材料から、幅100±0.2mm、長さ150±0.2mmの試験片を作製した。この中央に落下高さ468mmで5.4kgの落錘衝撃を与えた後SACMA SRM 2R-94が示す圧縮治具用治具を用い、クロスヘッドスピード0.5mm/minで圧縮し、圧縮強度を求めた。測定数はN=6とし、その平均値を求めた。
表1~2に示すとおり、実施例1~12では構成要素[A]、[B]、[C]、[D]を配合し、得られた樹脂硬化物および繊維強化複合材料の試験を行い、各物性とも優れた弾性率、Tg、経糸引張強度および経糸圧縮強度が得られた。
表2に示すとおり、構成要素[B]を2成分とした以外は実施例1~12と同様にして得られた樹脂硬化物および繊維強化複合材料の試験を行い、優れた物性が得られた。
表2に示すとおり、構成要素[A]、[B]、[C]、[D]に、さらに構成要素[E]を加えた以外は実施例1~12と同様にして得られた樹脂硬化物および繊維強化複合材料の試験を行い、優れた物性が得られた。
表3に示すとおり、比較例1のように構成要素[A]を含まない場合、樹脂硬化物の弾性率および経糸圧縮強度が低下した。比較例2のように構成要素[B]を含まない場合、樹脂硬化物の弾性率および経糸圧縮強度が低下した。比較例3のように構成要素[B]を含む量が少ないとき、樹脂硬化物の弾性率および経糸圧縮強度が低下した。比較例4のように構成要素[C]を含まない場合、樹脂硬化物の弾性率、吸湿高温下での樹脂硬化物の弾性率、経糸引張強度、経糸圧縮強度ともに低下した。比較例5のように構成要素[A]と構成要素[C]を両方とも含まない場合、樹脂硬化物の弾性率が低く経糸圧縮強度も低下した。比較例6のように構成要素[A]が過多である場合、樹脂硬化物の弾性率、吸湿高温下での樹脂硬化物の弾性率、経糸圧縮強度ともに低下した。比較例7のように、構成要素[E]が過多であるとき、樹脂降下物の弾性率、吸湿高温下での樹脂硬化物の弾性率、経糸圧縮強度が低下した。
表4に示すとおり、エポキシ樹脂組成物の調製時に熱可塑性樹脂粒子を入れた以外は、実施例1と同様に織物プリプレグを作製し、繊維強化複合材料の層間樹脂層を形成し、繊維強化複合材料の耐衝撃性を実施例1の場合と比較した。熱可塑性樹脂粒子を付与した実施例20では、実施例1に比べ耐衝撃性が向上していることが確認できた。
表5に示すとおり、エポキシ樹脂組成物の調製時に有機酸ヒドラジド化合物として実施例21ではイソフタル酸ジヒドラジドを入れた以外は、実施例18と同様に構成要素[A][B][C][D]を配合し、エポキシ樹脂組成物の粘度測定、得られた樹脂硬化物および繊維強化複合材料の試験を行った。120℃1時間ホールド後の粘度(η120h)は実施例18に対し、有機酸ヒドラジド化合物を入れた実施例21では25Pa・s、まで上昇し、ハニカム成形性が良好な粘度範囲となった。有機酸ヒドラジド化合物を入れることで、吸湿高温下での樹脂硬化物弾性率はわずかに低下したが、合格範囲内であった。
Claims (18)
- 少なくとも次の構成要素[A]~[D]を含むエポキシ樹脂組成物であって、エポキシ樹脂総量100質量部に対して、構成要素[A]を5~40質量部と構成要素[B]を20~95質量部含み、さらに構成要素[C]を1~25質量部含むエポキシ樹脂組成物。
[A]:一般式[1]または[4]で示される繰り返しユニット内に1つ以上の縮合多環芳香族炭化水素骨格と主として2つのエポキシ基を有するエポキシ樹脂
[B]:分子内に3個以上のグリシジル基を有するグリシジルアミン型エポキシ樹脂
[C]:スルホン系またはイミド系の熱可塑性樹脂
[D]:エポキシ樹脂硬化剤 - 構成要素[D]に、有機酸ヒドラジド化合物を0.01~10質量%含む請求項1に記載のエポキシ樹脂組成物。
- 構成要素[A]の一般式[1]において、Xの炭素数が1であり、YとZがともにナフタレン骨格である、請求項1または2に記載のエポキシ樹脂組成物。
- 構成要素[A]の一般式[1]において、Xの炭素数が1であり、Yがトルエン骨格、Zがナフタレン骨格である、請求項1または2に記載のエポキシ樹脂組成物。
- 構成要素[C]のガラス転移温度が180℃以上である請求項1~4のいずれかに記載のエポキシ樹脂組成物。
- 構成要素[D]が、23℃で固形である請求項1~5のいずれかに記載のエポキシ樹脂組成物。
- 構成要素[D]が、芳香族アミンである請求項1~6のいずれかに記載のエポキシ樹脂組成物。
- 構成要素[D]が、分子内に1~4個のフェニル基を有し、そのうち少なくとも1個のフェニル基がオルト位またはメタ位にアミノ基を有する芳香族ポリアミンである請求項1~7のいずれかに記載のエポキシ樹脂組成物。
- さらに構成要素[E]:2官能エポキシ樹脂を含む請求項1~8のいずれかに記載のエポキシ樹脂組成物。
- 構成要素[E]がビスフェノールA型エポキシ樹脂またはビスフェノールF型エポキシ樹脂である請求項9に記載のエポキシ樹脂組成物。
- エポキシ樹脂総量100質量部中に、構成要素[E]を5質量部以上40質量部以下含む請求項9または10に記載のエポキシ樹脂組成物。
- 120℃1時間ホールド後の粘度η120hが10~50Pa・sである請求項1~11のいずれかに記載のエポキシ樹脂組成物。
- 請求項1~12のいずれかに記載のエポキシ樹脂組成物を炭素繊維に含浸させてなるプリプレグ。
- 炭素繊維表面上または樹脂中に数平均粒径が5~50μmの熱可塑性粒子を配置した請求項13に記載のプリプレグ。
- 炭素繊維が織物の形態である請求項13または14に記載のプリプレグ。
- 請求項1~12のいずれかに記載のエポキシ樹脂組成物および炭素繊維を含む炭素繊維強化複合材料。
- 炭素繊維が織物の形態である請求項16に記載の炭素繊維強化複合材料。
- 請求項13~15のいずれかに記載のプリプレグを硬化させてなる炭素繊維強化複合材料。
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EP16841910.9A EP3345949B1 (en) | 2015-09-03 | 2016-08-31 | Epoxy resin composition, prepreg, and carbon fiber-reinforced composite material |
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CN201680050088.5A CN107922591A (zh) | 2015-09-03 | 2016-08-31 | 环氧树脂组合物、预浸料坯以及碳纤维增强复合材料 |
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US15/756,815 US10851217B2 (en) | 2015-09-03 | 2016-08-31 | Epoxy resin composition, prepreg, and carbon fiber reinforced composite material |
ES16841910T ES2817409T3 (es) | 2015-09-03 | 2016-08-31 | Composición de resina epoxídica, material preimpregnado y material compuesto reforzado con fibra de carbono |
KR1020177036384A KR20180048454A (ko) | 2015-09-03 | 2016-08-31 | 에폭시 수지 조성물, 프리프레그 및 탄소섬유 강화 복합 재료 |
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EP3563927A1 (en) * | 2018-04-30 | 2019-11-06 | Hexion Research Belgium SA | Purification of high performance epoxy resins via membrane filtration technology |
KR102193671B1 (ko) | 2019-03-19 | 2020-12-21 | 한국과학기술연구원 | 벤젠 고리를 가지는 화합물로 코팅된 탄소섬유의 급속 플라즈마 처리를 통한 표면 처리 방법 및 장치, 이에 따른 탄소 섬유의 물성 향상 방법 및 물성이 향상된 탄소 섬유 |
CN112300537A (zh) * | 2020-11-10 | 2021-02-02 | 山东非金属材料研究所 | 一种环氧树脂基体组合物及其制备方法 |
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RU2736820C2 (ru) | 2020-11-20 |
JPWO2017038880A1 (ja) | 2018-06-14 |
EP3345949A4 (en) | 2019-03-27 |
RU2018111705A3 (ja) | 2019-12-27 |
RU2018111705A (ru) | 2019-10-04 |
US20180244880A1 (en) | 2018-08-30 |
ES2817409T3 (es) | 2021-04-07 |
JP6787130B2 (ja) | 2020-11-18 |
US10851217B2 (en) | 2020-12-01 |
EP3345949B1 (en) | 2020-07-29 |
KR20180048454A (ko) | 2018-05-10 |
EP3345949A1 (en) | 2018-07-11 |
CN107922591A (zh) | 2018-04-17 |
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