WO2011118106A1 - 炭素繊維強化複合材料用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
炭素繊維強化複合材料用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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- WO2011118106A1 WO2011118106A1 PCT/JP2010/073335 JP2010073335W WO2011118106A1 WO 2011118106 A1 WO2011118106 A1 WO 2011118106A1 JP 2010073335 W JP2010073335 W JP 2010073335W WO 2011118106 A1 WO2011118106 A1 WO 2011118106A1
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- epoxy resin
- carbon fiber
- resin composition
- reinforced composite
- composite material
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- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 1
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- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- NWZGJOMHAHVXMA-UHFFFAOYSA-N 4,6-bis(oxiran-2-ylmethyl)benzene-1,3-diol Chemical compound C(C1CO1)C1=CC(=C(C=C1O)O)CC1CO1 NWZGJOMHAHVXMA-UHFFFAOYSA-N 0.000 description 1
- CFXCQBWUMFAVSJ-UHFFFAOYSA-N 4-(2-cyclohexylphenoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC(OC=2C(=CC=CC=2)C2CCCCC2)=CC=1)CC1CO1 CFXCQBWUMFAVSJ-UHFFFAOYSA-N 0.000 description 1
- KDSOGCGQVJSTMA-UHFFFAOYSA-N 4-(2-ethylphenoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound CCC1=CC=CC=C1OC1=CC=C(N(CC2OC2)CC2OC2)C=C1 KDSOGCGQVJSTMA-UHFFFAOYSA-N 0.000 description 1
- WEWBGPFWVSMYMP-UHFFFAOYSA-N 4-(2-naphthalen-2-yloxyphenoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC(OC=2C(=CC=CC=2)OC=2C=C3C=CC=CC3=CC=2)=CC=1)CC1CO1 WEWBGPFWVSMYMP-UHFFFAOYSA-N 0.000 description 1
- CPGKPCYIDWWXEG-UHFFFAOYSA-N 4-(2-nitrophenoxy)-N,N-bis(oxiran-2-ylmethyl)aniline Chemical compound C(C1CO1)N(C1=CC=C(C=C1)OC1=C(C=CC=C1)[N+](=O)[O-])CC1CO1 CPGKPCYIDWWXEG-UHFFFAOYSA-N 0.000 description 1
- VMVFANPYDKVRDN-UHFFFAOYSA-N 4-(3-methoxyphenoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound COC1=CC=CC(OC=2C=CC(=CC=2)N(CC2OC2)CC2OC2)=C1 VMVFANPYDKVRDN-UHFFFAOYSA-N 0.000 description 1
- NYDZCRPJHGOGOC-UHFFFAOYSA-N 4-(3-nitrophenoxy)-N,N-bis(oxiran-2-ylmethyl)aniline Chemical compound C(C1CO1)N(C1=CC=C(C=C1)OC1=CC(=CC=C1)[N+](=O)[O-])CC1CO1 NYDZCRPJHGOGOC-UHFFFAOYSA-N 0.000 description 1
- HCHQQJNCKYNFEY-UHFFFAOYSA-N 4-(4-methoxyphenoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1=CC(OC)=CC=C1OC1=CC=C(N(CC2OC2)CC2OC2)C=C1 HCHQQJNCKYNFEY-UHFFFAOYSA-N 0.000 description 1
- LSSWPDUBLAOHKT-UHFFFAOYSA-N 4-(4-nitrophenoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC1=CC=C(N(CC2OC2)CC2OC2)C=C1 LSSWPDUBLAOHKT-UHFFFAOYSA-N 0.000 description 1
- HQGUZDWXCPWDFZ-UHFFFAOYSA-N 5-methoxy-2-methyl-3-(oxiran-2-ylmethyl)-1h-indole Chemical compound C12=CC(OC)=CC=C2NC(C)=C1CC1CO1 HQGUZDWXCPWDFZ-UHFFFAOYSA-N 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- DCILHLLIUXDBNR-UHFFFAOYSA-N [2-(oxiran-2-ylmethyl)-1h-indol-4-yl] acetate Chemical compound C=1C=2C(OC(=O)C)=CC=CC=2NC=1CC1CO1 DCILHLLIUXDBNR-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000005415 aminobenzoic acids Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 238000004883 computer application Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000009730 filament winding Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000009787 hand lay-up Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VQUBWUABRWJYCR-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)-4-(3-phenoxyphenoxy)aniline Chemical compound C1OC1CN(C=1C=CC(OC=2C=C(OC=3C=CC=CC=3)C=CC=2)=CC=1)CC1CO1 VQUBWUABRWJYCR-UHFFFAOYSA-N 0.000 description 1
- SQQCTLWZEJJCNB-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)-4-(4-phenoxyphenoxy)aniline Chemical compound C1OC1CN(C=1C=CC(OC=2C=CC(OC=3C=CC=CC=3)=CC=2)=CC=1)CC1CO1 SQQCTLWZEJJCNB-UHFFFAOYSA-N 0.000 description 1
- GJIHJADPBSMNFZ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)-4-(4-phenylphenoxy)aniline Chemical compound C1OC1CN(C=1C=CC(OC=2C=CC(=CC=2)C=2C=CC=CC=2)=CC=1)CC1CO1 GJIHJADPBSMNFZ-UHFFFAOYSA-N 0.000 description 1
- VJOHYQMELJCMGX-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)-4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N(CC2OC2)CC2OC2)C=C1 VJOHYQMELJCMGX-UHFFFAOYSA-N 0.000 description 1
- ZPEMUYUJMFRLFL-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)-4-[2-(trifluoromethyl)phenoxy]aniline Chemical compound FC(F)(F)C1=CC=CC=C1OC1=CC=C(N(CC2OC2)CC2OC2)C=C1 ZPEMUYUJMFRLFL-UHFFFAOYSA-N 0.000 description 1
- HPQDXWHEPFWTFQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)-4-[3-(trifluoromethyl)phenoxy]aniline Chemical compound FC(F)(F)C1=CC=CC(OC=2C=CC(=CC=2)N(CC2OC2)CC2OC2)=C1 HPQDXWHEPFWTFQ-UHFFFAOYSA-N 0.000 description 1
- NJPMKWAHFMFMTF-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)-4-[4-(trifluoromethyl)phenoxy]aniline Chemical compound C1=CC(C(F)(F)F)=CC=C1OC1=CC=C(N(CC2OC2)CC2OC2)C=C1 NJPMKWAHFMFMTF-UHFFFAOYSA-N 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical class C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- VAUOPRZOGIRSMI-UHFFFAOYSA-N n-(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CNC1=CC=CC=C1 VAUOPRZOGIRSMI-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005649 polyetherethersulfone Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Classifications
-
- 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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3227—Compounds containing acyclic nitrogen atoms
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- 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
-
- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Definitions
- the present invention relates to an epoxy resin composition for carbon fiber reinforced composite materials (hereinafter sometimes simply referred to as “epoxy resin composition”), a prepreg, and a carbon fiber 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 mechanical strength under severe conditions such as low temperature and high temperature moisture absorption and that is suitable as a structural material, and a prepreg and a carbon fiber reinforced composite material.
- carbon fiber reinforced composite materials using carbon fibers as reinforced fibers have utilized their high specific strength and specific elastic modulus to make structural materials such as aircraft and automobiles, sports such as tennis rackets, golf shafts and fishing rods, and It has been used for general industrial purposes.
- a prepreg which is a sheet-like intermediate material in which a reinforcing fiber is impregnated with an uncured matrix resin is used to cure the prepreg, or a reinforcing fiber disposed in a mold.
- a resin transfer molding method is used in which a liquid resin is poured to obtain an intermediate and then cured.
- a carbon fiber reinforced composite material is usually obtained by laminating a plurality of prepregs and then applying heat and pressure.
- a thermosetting resin, particularly an epoxy resin is often used from the viewpoint of productivity such as processability.
- carbon fiber reinforced composite materials are required to have high strength in more severe use environments such as high temperature and high humidity and low temperature.
- compressive strength is also an important physical property.
- the compressive strength is measured using a test piece such as a non-perforated plate, a perforated plate, or a cylinder. In actual use, it is often in the form of a plate with a bolt hole.
- the compressive strength of the hole plate especially the strength under high temperature and high humidity conditions, is important.
- the conventional composite material with a polymer matrix has the advantage of light weight, but the compressive strength may decrease greatly with the decrease in strength and elastic modulus under high-temperature and high-humidity conditions. There was something to be done.
- Examples of the resin composition that gives a carbon fiber composite material having excellent compressive strength include tetraglycidyl diaminodiphenylmethane, a bifunctional epoxy resin such as bisphenol A type epoxy resin and diglycidyl resorcinol, and an epoxy composed of 3,3′-diaminodiphenyl sulfone.
- a resin composition (see Patent Document 3), an epoxy resin composition comprising a polyfunctional epoxy resin and a diglycidylaniline derivative and 4,4′-diaminodiphenylsulfone (see Patent Document 4), a polyfunctional epoxy resin and a special skeleton And an epoxy resin composition comprising 3,3′-diaminodiphenylsulfone (see Patent Document 5). Although these can achieve an improvement in compressive strength, nothing is said about an improvement in tensile strength at low temperatures.
- an object of the present invention is to provide an epoxy resin composition that is excellent in mechanical strength of a tensile system and a compression system and provides a carbon fiber reinforced composite material suitable as a structural material, and a prepreg and a carbon fiber reinforced composite material. .
- the present invention has the following configuration in order to achieve the above object. That is, an epoxy resin composition comprising at least the following components [A] and [B], wherein [A] is 20 to 80% by mass with respect to 100% by mass of the total amount of the epoxy resin, [B ] 10 to 50% by mass of an epoxy resin composition for a carbon fiber reinforced composite material.
- [A] An epoxy resin having a structure represented by the general formula (1) and having one or more amine-type glycidyl groups at the meta position.
- an epoxy resin composition having excellent heat resistance and excellent processability when obtaining a prepreg can be obtained.
- a prepreg can be obtained by combining this epoxy resin composition and carbon fiber, and a carbon fiber reinforced composite material having excellent tensile strength and compressive strength can be obtained by curing this epoxy resin composition. .
- the epoxy resin [A] represented by the above formula (1) has a ring structure of four or more members.
- An epoxy resin [B] having two or more and one amine-type glycidyl group or one ether-type glycidyl group directly linked to the ring structure is included in the epoxy resin composition in a specific content ratio, thereby achieving a trade-off. It has been found that an optimal structure can be obtained to achieve both high tensile strength and compressive strength.
- R 1 , R 2 , R 3 and R 4 of the epoxy resin [A] having a structure represented by the formula (1) contained in the epoxy resin composition of the present invention are each a hydrogen atom and a carbon number of 1 to 4 aliphatic hydrocarbon groups and alicyclic hydrocarbon groups having 4 or less carbon atoms. If the structure of R 1 , R 2 , R 3 , or R 4 is too large, the viscosity of the epoxy resin composition becomes too high and handling properties are impaired, or compatibility with other components in the epoxy resin composition is impaired. The strength improving effect may not be obtained.
- the epoxy resin having an amine-type glycidyl group in the meta position as referred to in the present invention is the 3-position or 3'-position when the carbon on the benzene ring to which the ether group of the formula (1) is linked is the 1-position. Or an amine-type glycidyl group linked to the 5th or 5 'position carbon.
- epoxy resin [A] examples include tetraglycidyl-3,4′-diaminodiphenyl ether, tetraglycidyl-3,3′-diaminodiphenyl ether, tetraglycidyl-3,4′-diamino-2,2′-dimethyldiphenyl ether, Tetraglycidyl-3,4'-diamino-2,2'-dibromodiphenyl ether, tetraglycidyl-3,4'-diamino-5-methyldiphenyl ether, tetraglycidyl-3,4'-diamino-2'-methyldiphenyl ether, tetra Glycidyl-3,4′-diamino-3′-methyldiphenyl ether, tetraglycidyl-3,4′-diamino-5,2′-dimethyldiphenyl ether, tetraglycidyl-3,4′
- R 1 , R 2 , R 3 and R 4 are preferably hydrogen atoms from the viewpoint of compatibility with other epoxy resins, and tetraglycidyl-3,4′-diaminodiphenyl ether or from the viewpoint of heat resistance. Tetraglycidyl-3,3′-diaminodiphenyl ether is more preferred. From the viewpoint of flame retardancy, it is also a preferred form that is substituted with a halogen atom such as Cl or Br.
- the epoxy resin [A] used in the present invention is represented by the following general formula (2)
- R 1 to R 4 are at least one selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 4 or less carbon atoms, and a halogen atom.
- the method for producing an epoxy resin [A] is obtained by adding 4 molecules of epichlorohydrin to 1 molecule of a diaminodiphenyl ether derivative, and the following general formula (3)
- R 1 to R 4 are at least one selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 4 or less carbon atoms, and a halogen atom.
- the subsequent dichlorohydrin derivative is dehydrochlorinated with an alkali compound to produce a tetrafunctional epoxy compound represented by the following general formula (1).
- R 1 to R 4 are at least one selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 4 or less carbon atoms, and a halogen atom.
- generates the epoxy compound shown by this is shown.
- the compounding amount of the epoxy resin [A] needs to be 20 to 80% by mass, preferably 30 to 75% by mass with respect to 100% by mass of the total amount of the epoxy resin compounded.
- the epoxy resin [B] contained in the epoxy resin composition of the present invention has two or more four-membered ring structures, such as cyclohexane, benzene, pyridine, etc. Or having at least one condensed ring structure composed of 4 or more ring members such as phthalimide, naphthalene, and carbazole.
- the amine type glycidyl group or ether type glycidyl group directly linked to the ring structure of the epoxy resin [B] is a structure in which an N atom is bonded to a ring structure such as benzene or phthalimide, and an O atom is bonded to an ether type.
- the amine type is a monofunctional or bifunctional epoxy resin
- the ether type is a monofunctional epoxy resin.
- the blending amount of [B] needs to be 10 to 50% by mass with respect to the total blended epoxy resin.
- a monofunctional epoxy resin is more excellent in the effect of strength development, and a bifunctional epoxy resin is more excellent in heat resistance. Therefore, the blending amount of [B] is more preferably 10 to 40% by mass with respect to the total amount of the epoxy resin blended in the monofunctional epoxy resin, and 25 to 50% by mass with respect to the total epoxy resin blended in the bifunctional epoxy resin. % Is more preferable.
- epoxy resin [B] examples include glycidylphthalimide, glycidyl-1,8-naphthalimide, glycidylcarbazole, glycidyl-3,6-dibromocarbazole, glycidylindole, glycidyl-4-acetoxyindole, glycidyl-3-methylindole Glycidyl-3-acetylindole, glycidyl-5-methoxy-2-methylindole, o-phenylphenyl glycidyl ether, p-phenylphenyl glycidyl ether, p- (3-methylphenyl) phenyl glycidyl ether, 2,6-di Benzylphenyl glycidyl ether, 2-benzylphenyl glycidyl ether, 2,6-diphenylphenyl glycidyl ether, 4- ⁇ -
- epoxy resin [B] “Denacol (registered trademark)” Ex-731 (glycidyl phthalimide, manufactured by Nagase ChemteX Corp.), OPP-G (o-phenylphenyl glycidyl ether, manufactured by Sanko Co., Ltd.) ), PxGAN (diglycidyl-p-phenoxyaniline, manufactured by Toray Fine Chemical Co., Ltd.) and the like.
- thermosetting resin used by being copolymerized with an epoxy resin include unsaturated polyester resin, vinyl ester resin, epoxy resin, benzoxazine resin, phenol resin, urea resin, melamine resin, and polyimide resin. It is done. These resin compositions and compounds may be used alone or in combination as appropriate.
- the blending of at least another epoxy resin of [A] and [B] has both the fluidity of the resin and the heat resistance after curing.
- a glycidyl ether type epoxy resin having a phenol as a precursor is preferably used as the bifunctional epoxy resin.
- examples of such epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, urethane-modified epoxy resins, hydantoin type and resorcinol type epoxy resins. It is done.
- liquid bisphenol A type epoxy resin, bisphenol F type epoxy resin and resorcinol type epoxy resin are preferably used in combination with other epoxy resins because of their low viscosity.
- the solid bisphenol A type epoxy resin gives a structure having a lower crosslink density compared to the liquid bisphenol A type epoxy resin, so that the heat resistance is low, but a tougher structure is obtained, so that a glycidylamine type epoxy resin is obtained.
- liquid bisphenol A type epoxy resin or bisphenol F type epoxy resin is obtained.
- An epoxy resin having a naphthalene skeleton gives a cured resin having low water absorption and high heat resistance.
- Biphenyl type epoxy resins, dicyclopentadiene type epoxy resins, phenol aralkyl type epoxy resins and diphenylfluorene type epoxy resins are also preferably used because they give a cured resin having a low water absorption rate.
- Urethane-modified epoxy resins and isocyanate-modified epoxy resins give cured resins having high fracture toughness and high elongation.
- bisphenol A type epoxy resin examples include “EPON (registered trademark)” 825 (manufactured by Japan Epoxy Resin Co., Ltd.), “Epiclon (registered trademark)” 850 (manufactured by DIC Corporation), and “Epototo (registered trademark)” ) "YD-128 (manufactured by Tohto Kasei Co., Ltd.), DER-331 and DER-332 (above, manufactured by Dow Chemical Co.).
- Examples of commercially available resorcinol-type epoxy resins include “Deconal (registered trademark)” EX-201 (manufactured by Nagase ChemteX Corporation).
- Examples of commercially available glycidyl aniline type epoxy resins include GAN and GOT (manufactured by Nippon Kayaku Co., Ltd.).
- biphenyl type epoxy resins examples include NC-3000 (manufactured by Nippon Kayaku Co., Ltd.).
- Examples of commercially available urethane-modified epoxy resins include AER4152 (manufactured by Asahi Kasei Epoxy Corporation).
- a commercially available hydantoin type epoxy resin includes AY238 (manufactured by Huntsman Advanced Materials).
- epoxy resins used as epoxy resins other than [A] and [B] as tri- or higher functional glycidylamine type epoxy resins, for example, diaminodiphenylmethane type, diaminodiphenylsulfone type, aminophenol type, metaxylenediamine type 1,3-bisaminomethylcyclohexane type, isocyanurate type epoxy resins and the like.
- diaminodiphenylmethane type and aminophenol type epoxy resins are particularly preferably used because of a good balance of physical properties.
- Examples of the tri- or higher functional glycidyl ether type epoxy resin include epoxy resins such as phenol novolak type, orthocresol novolak type, trishydroxyphenylmethane type, and tetraphenylolethane type.
- the amount of the tri- or higher functional epoxy resin including the epoxy resin [A] is the amount of the epoxy resin [A] and [B] combined with the epoxy resin other than [A] and [B].
- the total amount of the epoxy resin) is preferably 40 to 80% by mass, more preferably 50 to 70% by mass with respect to 100% by mass.
- Diaminodiphenylmethane type epoxy resin as a commercial product of tri- or higher functional epoxy resin is ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), “Araldite (registered trademark)” MY720, “Araldite (registered trademark)” MY721, “Araldite (registered) Trademark) “MY9512”, “Araldite (registered trademark)” MY9663 (manufactured by Huntsman Advanced Materials), and “Epototo (registered trademark)” YH-434 (manufactured by Toto Kasei Co., Ltd.).
- metaxylenediamine type epoxy resins examples include TETRAD-X (Mitsubishi Gas Chemical Co., Ltd.).
- Examples of commercially available 1,3-bisaminomethylcyclohexane type epoxy resins include TETRAD-C (manufactured by Mitsubishi Gas Chemical Company).
- TEPIC-P (manufactured by Nissan Chemical Co., Ltd.) can be mentioned.
- trishydroxyphenylmethane type epoxy resins examples include Tactix 742 (manufactured by Huntsman Advanced Materials).
- phenol novolac epoxy resins examples include DEN431 and DEN438 (manufactured by Dow Chemical Co., Ltd.) and “jER (registered trademark)” 152 (manufactured by Japan Epoxy Resins Co., Ltd.).
- ortho-cresol novolak epoxy resins examples include EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) and “Epiclon (registered trademark)” N-660 (manufactured by DIC Corporation).
- Examples of commercially available dicyclopentadiene type epoxy resins include “Epiclon (registered trademark)” HP7200 (manufactured by DIC Corporation).
- the epoxy resin composition for carbon fiber reinforced composite material of the present invention may be used by blending a curing agent.
- curing agent demonstrated here is a hardening
- Specific examples of the curing agent include dicyandiamide, aromatic polyamine, aminobenzoic acid esters, various acid anhydrides, phenol novolac resin, cresol novolac resin, polyphenol compound, imidazole derivative, aliphatic amine, tetramethylguanidine.
- Thiourea addition amine carboxylic acid anhydride such as methylhexahydrophthalic anhydride, carboxylic acid hydrazide, carboxylic acid amide, polymercaptan and Lewis acid complex such as boron trifluoride ethylamine complex.
- an aromatic polyamine as a curing agent, a cured epoxy resin with good heat resistance can be obtained.
- various isomers of diaminodiphenylsulfone are the most suitable curing agents for obtaining a cured epoxy resin having good heat resistance.
- the optimum value for the amount of curing agent added depends on the type of epoxy resin and curing agent.
- the ratio of the active hydrogen amount of the aromatic amine curing agent to the epoxy group amount of the epoxy resin is 0.7 to 0.
- a high elastic modulus resin may be obtained as compared with the case where it is used in an equivalent amount, which is also a preferable embodiment.
- These curing agents may be used alone or in combination.
- 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)” W (Japan Epoxy Resin ( ), And 3,3′-DAS (Mitsui Chemicals), “Lonacure (registered trademark)” M-DEA (Lonza), “Lonzasure (registered trademark)” M-DIPA ( Lonza Corporation), “Lonzacure (registered trademark)” M-MIPA (Lonza Corporation), “Lonzacure (registered trademark)” DETDA 80 (Lonza Corporation), and the like.
- compositions obtained by pre-reacting these epoxy resin and curing agent, or a part of them can be blended in the composition.
- This method may be effective for viscosity adjustment and storage stability improvement.
- thermoplastic resin is mixed or dissolved in the above epoxy resin composition.
- thermoplastic resins are generally selected from the group consisting of a carbon-carbon bond, amide bond, imide bond, ester bond, ether bond, carbonate bond, urethane bond, thioether bond, sulfone bond and carbonyl bond in the main chain.
- a thermoplastic resin having a selected bond is preferred.
- this thermoplastic resin may have a partially crosslinked structure, and may be crystalline or amorphous.
- the glass transition temperature (Tg) of the thermoplastic resin is at least 150 ° C. or higher and preferably 170 ° C. or higher. If the glass transition temperature of the thermoplastic resin to be blended is less than 150 ° C., it may be easily deformed by heat when used as a molded body. Furthermore, as a terminal functional group of this thermoplastic resin, things, such as a hydroxyl group, a carboxyl group, a thiol group, and an acid anhydride, can react with a cationically polymerizable compound, and are used preferably.
- PES7600P (above, manufactured by Sumitomo Chemical Co., Ltd.) and the like, and a copolymer oligomer of polyethersulfone and polyetherethersulfone as described in JP-T-2004-506789, Furthermore, “Ultem (registered trademark)” 1000, “Ultem (registered trademark)” 1010, “Ultem (registered trademark)” 1040 (above, manufactured by Solvay Advanced Polymers Co., Ltd.) and the like, which are commercially available polyetherimides, may be mentioned. .
- the oligomer refers to a polymer having a relatively low molecular weight in which about 10 to 100 finite number of monomers are bonded.
- a mixture of epoxy resin and thermoplastic resin often gives better results than using them alone.
- the brittleness of the epoxy resin is covered with the toughness of the thermoplastic resin, and the molding difficulty of the thermoplastic resin is covered with the epoxy resin, thereby providing a balanced base resin.
- the use ratio (parts by mass) of the epoxy resin and the thermoplastic resin is preferably in the range of 2 to 40 parts by mass of the thermoplastic resin with respect to a total of 100 parts by mass of the blended epoxy resin in terms of balance. More preferably, it is in the range of 5 to 30 parts by mass.
- thermoplastic resin particles it is also preferable to mix thermoplastic resin particles with the epoxy resin composition of the present invention.
- thermoplastic resin particles By blending the thermoplastic resin particles, the toughness of the matrix resin is improved and the impact resistance is improved when a carbon fiber reinforced composite material is obtained.
- thermoplastic resin particles used in the present invention the same thermoplastic resins as those exemplified above can be used as the thermoplastic resin that can be mixed or dissolved in the epoxy resin composition. From the viewpoint of giving stable adhesive strength and impact resistance when a fiber reinforced composite material is obtained, it is preferable that the shape is maintained in the particles. Among them, polyamide is most preferable, and among polyamides, nylon 12, nylon 11 and nylon 6/12 copolymer give particularly good adhesive strength with a thermosetting resin.
- the shape of the 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.
- polyamide particles include SP-500 (manufactured by Toray Industries, Inc.), “Trepearl (registered trademark)” TN (manufactured by Toray Industries, Inc.), and “Orgasol (registered trademark)” 1002D (manufactured by ATOCHEM). ), “Orgasol (registered trademark)” 2002 (manufactured by ATOCHEM), “Orgasol (registered trademark)” 3202 (manufactured by ATOCHEM), and the like.
- the epoxy resin composition of the present invention is a coupling agent, a thermosetting resin particle, a thermoplastic resin that can be dissolved in an epoxy resin, or silica gel, carbon black, clay, carbon nanotube, as long as the effects of the present invention are not hindered.
- An inorganic filler such as a metal powder can be blended.
- the carbon fiber used in the present invention can be any type of carbon fiber depending on the application, but is preferably a carbon fiber having a tensile modulus of at most 400 GPa from the viewpoint of impact resistance. From the viewpoint of strength, a carbon fiber having a tensile strength of preferably 4.4 to 6.5 GPa is preferably used because a composite material having high rigidity and mechanical strength can be obtained. The tensile elongation is also an important factor, and it is preferably a carbon fiber having a high tensile strength and a high elongation of 1.7 to 2.3%. Accordingly, carbon fibers having the characteristics that the tensile elastic modulus is at least 230 GPa, the tensile strength is at least 4.4 GPa, and the tensile elongation is at least 1.7% are most suitable.
- Carbon fibers include “Torayca (registered trademark)” T800G-24K, “Torayca (registered trademark)” T800S-24K, “Torayca (registered trademark)” T810G-24K, and “Torayca (registered trademark)” T700G- 24K, “Torayca (registered trademark)” T300-3K, and “Torayca (registered trademark)” T700S-12K (manufactured by Toray Industries, Inc.).
- the form and arrangement of the carbon fibers can be appropriately selected from long fibers and woven fabrics arranged in one direction. However, in order to obtain a carbon fiber reinforced composite material that is lighter and more durable, It is preferably in the form of continuous fibers such as long fibers (fiber bundles) or woven fabrics arranged in one direction.
- the number of filaments in one fiber bundle is preferably in the range of 2500 to 50000.
- the number of filaments is less than 2500, the fiber arrangement tends to meander and easily cause a decrease in strength. If the number of filaments exceeds 50,000, resin impregnation may be difficult during prepreg production or molding.
- the number of filaments is more preferably in the range of 2800 to 36000.
- the prepreg according to the present invention is obtained by impregnating carbon fiber with the epoxy resin composition of the present invention.
- the carbon fiber mass fraction of the prepreg is preferably 40 to 90% by mass, more preferably 50 to 80% by mass. If the carbon fiber mass fraction is too low, the weight of the resulting composite material becomes excessive, and the advantages of the carbon fiber reinforced composite material having excellent specific strength and specific elastic modulus may be impaired. If it is too high, poor impregnation of the resin composition occurs, and the resulting composite material tends to have a lot of voids, and its mechanical properties may be greatly deteriorated.
- the prepreg of the present invention comprises a wet method in which the epoxy resin composition of the present invention is dissolved in a solvent such as methyl ethyl ketone and methanol to lower the viscosity and impregnated into a reinforcing fiber, and the epoxy resin composition is heated to lower the viscosity and strengthened. It can be suitably produced by a hot melt method for impregnating fibers.
- the wet method is a method of obtaining a prepreg by immersing a reinforcing fiber in a solution of an epoxy resin composition, then pulling it up and evaporating the solvent using an oven or the like.
- the hot melt method is a method in which a reinforcing fiber is impregnated directly with an epoxy resin composition whose viscosity has been reduced by heating, or a resin film in which an epoxy resin composition is coated on release paper or the like is prepared, and then a reinforcing fiber is prepared.
- This is a method of obtaining a prepreg by transferring and impregnating the epoxy resin composition by overlapping the resin film from both sides or one side and heating and pressurizing.
- This hot melt method is a preferred embodiment because substantially no solvent remains in the prepreg.
- the fiber reinforced composite material of the present invention is obtained by laminating a plurality of prepregs produced by such a method, and then heat-curing the epoxy resin composition while applying heat and pressure to the obtained laminate. Can be manufactured.
- a press molding method As a method for applying heat and pressure, a press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method, an internal pressure molding method, and the like are used.
- a wrapping tape method and an internal pressure molding method are preferably used for molding sports equipment.
- the wrapping tape method is a method in which a prepreg is wound around a mandrel or the like and a tubular body made of a fiber reinforced composite material is formed, and is a suitable method for producing a rod-like body such as a golf shaft or a fishing rod.
- the prepreg was wound around a mandrel, and a wrapping tape made of a thermoplastic resin film was wound outside the prepreg for fixing and applying pressure, and the epoxy resin composition was cured by heating in an oven. Thereafter, the core bar is removed 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 apply high pressure gas to the internal pressure applying body to apply pressure. At the same time, the mold is heated to form a tubular body.
- This internal pressure molding method is particularly preferably used when molding a complicated shape such as a golf shaft, a bat, and a racket such as tennis or badminton.
- the carbon fiber reinforced composite material of the present invention can be manufactured by, for example, a method of laminating the above-described prepreg of the present invention in a predetermined form and curing the epoxy resin by applying pressure and heating.
- the carbon fiber reinforced composite material of the present invention can also be produced by using the above-described epoxy resin composition by a method that does not go through a prepreg.
- Examples of such a method include a method of directly impregnating the epoxy resin composition of the present invention into a reinforcing fiber and then heat-curing, that is, a hand lay-up method, a filament winding method, a pultrusion method, a resin injection. -Molding method and resin transfer molding method are used.
- a method of preparing an epoxy resin composition by mixing one or more main agents composed of an epoxy resin and one or more curing agents immediately before use is preferably employed.
- the carbon fiber reinforced composite material of the present invention can have high compressive strength and high tensile properties, that is, high tensile strength utilization rate.
- the tensile strength utilization factor here is obtained by the following formula.
- (Tensile strength utilization rate of carbon fiber reinforced composite material) (Tensile strength of carbon fiber reinforced composite material) / ((Strand strength of carbon fiber) ⁇ (Volume content of carbon fiber)) Carbon fiber reinforced composites even under severe environmental conditions if the tensile strength utilization rate under low temperature (under -60 ° C) is 75% or more and the porous compressive strength (OHC) under high temperature moisture absorption conditions is 240 MPa or more It is preferable because the effect of reducing the weight of the material can be easily expressed. More preferably, the porous compressive strength (OHC) under a high temperature moisture absorption condition is 250 MPa or more because the degree of freedom in design when used for structural members such as aircraft and windmills is increased.
- the fiber volume content can be determined by the nitric acid decomposition method described in JIS K7075 (1991).
- the carbon fiber reinforced composite material of the present invention is preferable for aircraft structural members, windmill blades, automobile outer plates, and computer applications such as IC trays and laptop computer housings (housing), and sports applications such as golf shafts and tennis rackets. Used.
- the epoxy resin composition of the present invention and the prepreg and carbon fiber reinforced composite material using the epoxy resin composition of the present invention will be described more specifically with reference to examples.
- the carbon fiber, the resin raw material, the preparation method of the prepreg and the carbon fiber reinforced composite material used in the examples, the evaluation method of the porous compressive strength, and the evaluation method of the tensile strength are shown below.
- the production environment and evaluation of the prepregs of the examples are performed in an atmosphere at a temperature of 25 ° C. ⁇ 2 ° C. and a relative humidity of 50% unless otherwise specified.
- Epoxy resin [A] 34TGDDE (tetraglycidyl-3,4′-diaminodiphenyl ether) and 33TGDDE (tetraglycidyl-3,3′-diaminodiphenyl ether) were synthesized by the following method.
- Epichlorohydrin 1221.2 g (13.2 mol) 610.6 g (6.6 mol) was charged into a four-necked flask equipped with a thermometer, dropping funnel, condenser and stirrer, and the temperature was adjusted to 70 with nitrogen purge.
- ⁇ Curing agent> ⁇ Seika Cure S (4,4'-diaminodiphenyl sulfone, manufactured by Wakayama Seika Kogyo Co., Ltd.) -3,3'-DAS (3,3'-diaminodiphenyl sulfone, manufactured by Mitsui Chemicals Fine Co., Ltd.).
- This test piece was subjected to a perforated compression test (measured at 82 ° C. after being immersed in warm water at 70 ° C. for 2 weeks) using an Instron universal testing machine according to the standard of ASTM-D6484.
- Example 1 In a kneader, 50 parts by weight of 34TGDDE, 30 parts by weight of PxGAN, and 20 parts by weight of “Araldite (registered trademark)” MY721 were kneaded at 160 ° C. for 2 hours, and then cooled to 80 ° C. to obtain 40 parts by weight of Seikacure S.
- An epoxy resin composition was prepared by kneading. Table 1 shows the composition and ratio (in Table 1, the numbers represent parts by mass). The obtained epoxy resin composition was coated on a release paper with a resin basis weight of 50 g / m 2 using a knife coater to prepare a resin film.
- This resin film is overlapped on both sides of carbon fibers (weight per unit area: 200 g / m 2 ) aligned in one direction, using a heat roll, and the epoxy resin composition is made into carbon fibers while heating and pressing at a temperature of 100 ° C. and 1 atm.
- a prepreg was obtained by impregnation.
- the carbon fiber volume content of the carbon fiber reinforced composite material obtained by curing the prepreg was 58.7%. Using this volume content, the subsequent utilization of tensile strength was calculated.
- Example 2 to 5 Comparative Examples 1 to 3
- a prepreg was produced in the same manner as in Example 1 except that the types and blending amounts of the epoxy resin and the curing agent were changed as shown in Tables 1 and 4. Similarly, the volume content of carbon fibers was 58.7%.
- Example 6 In a kneading apparatus, 60 parts by weight of 34TGDDE, 40 parts by weight of PxGAN, and 10 parts by weight of PES5003P were kneaded at 160 ° C. to visually confirm that PES5003P was dissolved, and then cooled to 80 ° C. to obtain 35 Seica Cure S.
- An epoxy resin composition was prepared by kneading parts by mass. Table 2 shows the composition and ratio (in Table 2, the numbers represent parts by mass). The obtained epoxy resin composition was coated on a release paper with a resin basis weight of 50 g / m 2 using a knife coater to prepare a resin film.
- This resin film is overlapped on both sides of carbon fibers (weight per unit area: 200 g / m 2 ) aligned in one direction, using a heat roll, and the epoxy resin composition is made into carbon fibers while heating and pressing at a temperature of 100 ° C. and 1 atm.
- a prepreg was obtained by impregnation.
- the volume content of carbon fibers in the carbon fiber subject composite material obtained by molding this prepreg was 58.7%.
- Example 7 to 18, Comparative Examples 4 to 5, 7 A prepreg was produced in the same manner as in Example 1 except that the types and blending amounts of the epoxy resin and the curing agent were changed as shown in Tables 2 to 5.
- the volume content of carbon fibers in the carbon fiber subject composite material obtained by molding this prepreg was 58.7%.
- This resin film is overlapped on both sides of carbon fibers (weight per unit area: 200 g / m 2 ) aligned in one direction, using a heat roll, and the epoxy resin composition is made into carbon fibers while heating and pressing at a temperature of 100 ° C. and 1 atm.
- a prepreg was obtained by impregnation.
- the carbon fiber reinforced composite material obtained by the epoxy resin composition of the present invention is excellent in mechanical strength in more severe use environments such as high temperature and high humidity and low temperature, and therefore is particularly suitable for structural materials.
- primary aircraft structural materials such as main wing, tail and floor beams
- secondary structural materials such as flaps, ailerons, cowls, fairings and interior materials, rocket motor cases and satellite structural materials
- structural materials for moving bodies such as automobiles, ships and railway vehicles, drive shafts, leaf springs, windmill blades, pressure vessels, flywheels, paper rollers, roofing materials, cables, reinforcing bars, and repair reinforcements
- civil engineering and building material applications such as materials.
- golf shafts fishing rods, tennis, badminton, squash and other racket applications, hockey and other stick applications, and ski pole applications.
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Abstract
Description
[A]一般式(1)で表される構造を有し、1個以上のアミン型グリシジル基をメタ位に有するエポキシ樹脂。
(ただし式中、R1~R4は、水素原子、炭素数1~4の脂肪族炭化水素基、炭素数4以下の脂環式炭化水素基、ハロゲン原子からなる群から選ばれた少なくとも一つを表す。)。
低温下(-60℃下)での引張強度利用率が75%以上であり、かつ高温吸湿条件下での有孔圧縮強度(OHC)が240MPa以上であれば、厳しい環境条件でも炭素繊維強化複合材料の軽量化効果が発現しやすくできるため好ましい。さらに好ましくは高温吸湿条件下での有孔圧縮強度(OHC)が250MPa以上であると、航空機や風車など構造部材に用いる際の設計自由度があがるため好ましい。
繊維体積含有率は、JIS K7075(1991)に記載の硝酸分解法により求めることができる。
・“トレカ(登録商標)”T800G-24K-31E(フィラメント数24,000本、引張強度5.9GPa、引張弾性率294GPa、引張伸度2.0%の炭素繊維、東レ(株)製)。
(エポキシ樹脂[A])
・34TGDDE(テトラグリシジル-3,4’-ジアミノジフェニルエーテル)および33TGDDE(テトラグリシジル-3,3’-ジアミノジフェニルエーテル)は下記の方法で合成した。
温度計、滴下漏斗、冷却管および攪拌機を取り付けた四つ口フラスコに、エピクロロヒドリン1221.2g(13.2mol)610.6g(6.6mol)を仕込み、窒素パージを行いながら温度を70℃まで上げて、これにエタノール1020gに溶解させた3,4’-ジアミノジフェニルエーテル222.2g(1.1mol)を4時間かけて滴下した。さらに6時間撹拌し、付加反応を完結させ、N,N,N’,N’-テトラキス(2-ヒドロキシ-3-クロロプロピル)-3,4’-ジアミノジフェニルエーテルを得た。続いて、フラスコ内温度を25℃に下げてから、これに48%NaOH水溶液229g(2.75mol)を2時間で滴下してさらに1時間撹拌した。環化反応が終わってからエタノールを留去して、408gのトルエンで抽出を行い5%食塩水で2回洗浄を行った。有機層からトルエンとエピクロロヒドリンを減圧下で除くと、褐色の粘性液体が398g(収率85.2%)得られた。主生成物であるテトラグリシジル-3,4’-ジアミノジフェニルエーテルの純度は、84%(GCarea%)であった。
温度計、滴下漏斗、冷却管および攪拌機を取り付けた四つ口フラスコに、エピクロロヒドリン1221.2g(13.2mol)610.6g(6.6mol)を仕込み、窒素パージを行いながら温度を70℃まで上げて、これにエタノール1020gに溶解させた3,3’-ジアミノジフェニルエーテル222.2g(1.1mol)を4時間かけて滴下した。さらに6時間撹拌し、付加反応を完結させ、N,N,N’,N’-テトラキス(2-ヒドロキシ-3-クロロプロピル)-3,3’-ジアミノジフェニルエーテルを得た。続いて、フラスコ内温度を25℃に下げてから、これに48%NaOH水溶液229g(2.75mol)を2時間で滴下してさらに1時間撹拌した。環化反応が終わってからエタノールを留去して、408gのトルエンで抽出を行い5%食塩水で2回洗浄を行った。有機層からトルエンとエピクロロヒドリンを減圧下で除くと、褐色の粘性液体が395g(収率84.5%)得られた。主生成物であるテトラグリシジル-3,3’-ジアミノジフェニルエーテルの純度は、82%(GCarea%)であった。
・“デナコール(登録商標)”Ex-731(N-グリシジルフタルイミド、ナガセケムテックス(株)製)
・OPP-G(o-フェニルフェニルグリシジルエーテル、三光(株)製)
・PxGAN(ジグリシジル-p-フェノキシアニリン、東レ・ファインケミカル(株)製)
・下記方法で合成した4PxPOG(4-フェノキシフェニルグリシジルエーテル)
温度計、滴下漏斗、冷却管および攪拌機を取り付けた四つ口フラスコに、エピクロロヒドリン305.3g(3.3mol)を仕込み、窒素パージを行いながら温度を70℃まで上げて、これにエタノール1020gに溶解させた4-フェノキシフェノール204.8g(1.1mol)を4時間かけて滴下した。さらに6時間撹拌し、付加反応を完結させ、4-フェノキシ-O-(2-ヒドロキシ-3-クロロプロピル)フェノールを得た。続いて、フラスコ内温度を25℃に下げてから、これに48%NaOH水溶液229g(2.75mol)を2時間で滴下してさらに1時間撹拌した。環化反応が終わってからエタノールを留去して、410gのトルエンで抽出を行い5%食塩水で2回洗浄を行った。有機層からトルエンとエピクロロヒドリンを減圧下で除くと、粘性液体が215.6g(収率89%)得られた。主生成物である4-フェノキシフェニルグリシジルエーテルの純度は、92%(GCarea%)であった。
・下記方法で合成した4CmPOG(4-α-クミルフェニルグリシジルエーテル)
合成したエポキシ樹脂の前駆体となる化合物を4-α-クミルフェノールに変更したこと以外は、上記した4-フェノキシフェニルグリシジルエーテルと同様の反応条件と手順によりグリシジル化反応を行い4-α-クミルフェニルグリシジルエーテルを得た。
・“アラルダイト(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・アドバンスト・マテリアルズ(株)製)
・“EPICLON(登録商標)”830(ビスフェノールF型エポキシ樹脂、DIC(株)製)
・44TGDDE(テトラグリシジル-3,4’-ジアミノジフェニルエーテル)は下記の方法で合成した。
温度計、滴下漏斗、冷却管および攪拌機を取り付けた四つ口フラスコに、エピクロロヒドリン1221.2g(13.2mol)610.6g(6.6mol)を仕込み、窒素パージを行いながら温度を70℃まで上げて、これにエタノール1020gに溶解させた3,3’-ジアミノジフェニルエーテル222.2g(1.1mol)を4時間かけて滴下した。さらに6時間撹拌し、付加反応を完結させ、N,N,N’,N’-テトラキス(2-ヒドロキシ-3-クロロプロピル)-3,3’-ジアミノジフェニルエーテルを得た。続いて、フラスコ内温度を25℃に下げてから、これに48%NaOH水溶液229g(2.75mol)を2時間で滴下してさらに1時間撹拌した。環化反応が終わってからエタノールを留去して、408gのトルエンで抽出を行い5%食塩水で2回洗浄を行った。有機層からトルエンとエピクロロヒドリンを減圧下で除くと、褐色の粘性液体が416g(収率89%)得られた。主生成物であるテトラグリシジル-3,3’-ジアミノジフェニルエーテルの純度は、87%(GCarea%)であった。
・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)
・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)。
・PES5003P(ポリエーテルスルホン、住友化学(株)製)。
JIS K7017(1999)に記載されているとおり、一方向繊維強化複合材料の繊維方向を軸方向とし、軸方向を0°軸と定義したときの軸直交方向を90°と定義する。
一方向プリプレグを所定の大きさにカットし、一方向に6枚積層した後、真空バッグを行い、オートクレーブを用いて、温度180℃、圧力6kg/cm2、2時間で硬化させ、一方向強化材(炭素繊維強化複合材料)を得た。この一方向強化材を幅12.7mm、長さ230mmでカットし、両端に1.2mm、長さ50mmのガラス繊維強化プラスチック製のタブを接着し試験片を得た。この試験片はインストロン万能試験機を用いて、JISK7073-1988の規格に準じて0゜引張試験(測定温度-60℃)を行った。
一方向プリプレグを所定の大きさにカットし、(+45/0/-45/90度)2Sの構成となるように16枚積層した後、真空バッグを行い、オートクレーブを用いて、温度180℃、圧力6kg/cm2、2時間で硬化させ、擬似等方強化材(炭素繊維強化複合材料)を得た。この擬似等方強化材を0゜方向が304.8mm、90゜方向が38.1mmの長方形に切り出し、中央部に直径6.35mmの円形の孔を穿孔して有孔板に加工して試験片を得た。この試験片はインストロン万能試験機を用いて、ASTM-D6484の規格に準じて有孔圧縮試験(70℃の温水に2週間浸漬後、82℃で測定)を行った。
混練装置で、50質量部の34TGDDE、30質量部のPxGAN、および20質量部の“アラルダイト(登録商標)”MY721を160℃で2時間混練した後、80℃に冷ましてセイカキュアSを40質量部混練して、エポキシ樹脂組成物を作製した。表1に、組成と割合を示す(表1中、数字は質量部を表す。)
得られたエポキシ樹脂組成物を、ナイフコーターを用いて樹脂目付50g/m2で離型紙上にコーティングし、樹脂フィルムを作製した。この樹脂フィルムを、一方向に引き揃えた炭素繊維(目付200g/m2)の両側に重ね合せてヒートロールを用い、温度100℃、1気圧で加熱加圧しながらエポキシ樹脂組成物を炭素繊維に含浸させプリプレグを得た。このプリプレグを硬化させた炭素繊維強化複合材料の炭素繊維の体積含有率は58.7%であった。この体積含有率を用いて、これ以降の引張強度利用率を計算した。
エポキシ樹脂と硬化剤の種類および配合量を、表1、4に示すように変更したこと以外は、実施例1と同様にしてプリプレグを作製した。同様に炭素繊維の体積含有率は58.7%であった。
混練装置で、60質量部の34TGDDEと40質量部のPxGAN、および10質量部のPES5003Pを160℃で混練してPES5003Pが溶解したことを目視で確認した後、80℃に冷ましてセイカキュアSを35質量部混練して、エポキシ樹脂組成物を作製した。表2に、組成と割合を示す(表2中、数字は質量部を表す。)
得られたエポキシ樹脂組成物を、ナイフコーターを用いて樹脂目付50g/m2で離型紙上にコーティングし、樹脂フィルムを作製した。この樹脂フィルムを、一方向に引き揃えた炭素繊維(目付200g/m2)の両側に重ね合せてヒートロールを用い、温度100℃、1気圧で加熱加圧しながらエポキシ樹脂組成物を炭素繊維に含浸させプリプレグを得た。このプリプレグを成形した炭素繊維教科複合材料中の炭素繊維の体積含有率は58.7%であった。
エポキシ樹脂と硬化剤の種類および配合量を、表2~5に示すように変更したこと以外は、実施例1と同様にしてプリプレグを作製した。このプリプレグを成形した炭素繊維教科複合材料中の炭素繊維の体積含有率は58.7%であった。
混練装置で、40質量部の34TGDDE、および60質量部のPxGANを160℃で2時間混練した後、80℃に冷ましてセイカキュアSを25質量部混練して、エポキシ樹脂組成物を作製した。表4に、組成と割合を示す(表4中、数字は質量部を表す。)
得られたエポキシ樹脂組成物を、ナイフコーターを用いて樹脂目付50g/m2で離型紙上にコーティングし、樹脂フィルムを作製した。この樹脂フィルムを、一方向に引き揃えた炭素繊維(目付200g/m2)の両側に重ね合せてヒートロールを用い、温度100℃、1気圧で加熱加圧しながらエポキシ樹脂組成物を炭素繊維に含浸させプリプレグを得た。
Claims (10)
- 少なくとも次の構成要素[A]、[B]を含んでなるエポキシ樹脂組成物であって、配合したエポキシ樹脂総量100質量%に対して[A]を20~80質量%と、[B]を10~50重量%含むことを特徴とする炭素繊維強化複合材料用エポキシ樹脂組成物。
[A]:下記一般式(1)で表される構造を有し、1個以上のアミン型グリシジル基をメタ位に有するエポキシ樹脂。
[B]:4員環以上の環構造を2つ以上有し、かつ、環構造に直結したアミン型グリシジル基またはエーテル型グリシジル基を1つ有するエポキシ樹脂 - さらに下記[C]を含む、請求項1に記載の炭素繊維強化複合材料用エポキシ樹脂組成物。
[C]:エポキシ樹脂に溶解可能な熱可塑性樹脂 - [B]が4員環以上の環構造を2つ以上有し、かつ、環構造に直結したアミン型グリシジル基またはエーテル型グリシジル基を1個有する1官能エポキシ樹脂である、請求項1または2に記載の炭素繊維強化複合材料用エポキシ樹脂組成物。
- エポキシ樹脂組成物中のエポキシ樹脂総量100質量%に対して、[B]の配合量が10~40質量%である、請求項3に記載の炭素繊維強化複合材料用エポキシ樹脂組成物。
- [B]が4員環以上の環構造を2つ以上有し、かつ、環構造に直結したアミン型グリシジル基を有する2官能のエポキシ樹脂である、請求項1または2に記載の炭素繊維強化複合材料用エポキシ樹脂組成物。
- エポキシ樹脂組成物中のエポキシ樹脂総量100質量%に対して、[B]の配合量が25~50質量%である、請求項5に記載の炭素繊維強化複合材料用エポキシ樹脂組成物。
- [A]がテトラグリシジル-3,4’-ジアミノジフェニルエーテルである、請求項1~6のいずれかに記載の炭素繊維強化複合材料用エポキシ樹脂組成物。
- 請求項1~7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。
- 請求項8に記載のプリプレグを硬化させて得られる炭素繊維強化複合材料。
- 請求項1~9のいずれかに記載のエポキシ樹脂組成物を硬化してなる樹脂硬化物、および炭素繊維を含んでなる炭素繊維強化複合材料。
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Also Published As
Publication number | Publication date |
---|---|
CA2788525A1 (en) | 2011-09-29 |
EP2551288B1 (en) | 2016-06-01 |
CN102822227B (zh) | 2014-11-05 |
US20130005855A1 (en) | 2013-01-03 |
KR20130018698A (ko) | 2013-02-25 |
BR112012018769A2 (pt) | 2016-04-12 |
EP2551288A4 (en) | 2015-10-14 |
JP5003827B2 (ja) | 2012-08-15 |
EP2551288A1 (en) | 2013-01-30 |
CN102822227A (zh) | 2012-12-12 |
US9434811B2 (en) | 2016-09-06 |
JPWO2011118106A1 (ja) | 2013-07-04 |
KR101761439B1 (ko) | 2017-07-25 |
RU2012144811A (ru) | 2014-04-27 |
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