CN101426830A - Epoxy resin composition for fiber-reinforced composite material - Google Patents
Epoxy resin composition for fiber-reinforced composite material Download PDFInfo
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- CN101426830A CN101426830A CNA200780014731XA CN200780014731A CN101426830A CN 101426830 A CN101426830 A CN 101426830A CN A200780014731X A CNA200780014731X A CN A200780014731XA CN 200780014731 A CN200780014731 A CN 200780014731A CN 101426830 A CN101426830 A CN 101426830A
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- 239000000203 mixture Substances 0.000 title claims abstract description 86
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 83
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 83
- 239000003733 fiber-reinforced composite Substances 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 199
- 239000011347 resin Substances 0.000 claims abstract description 199
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 150000007524 organic acids Chemical class 0.000 claims abstract description 36
- 150000001412 amines Chemical class 0.000 claims abstract description 23
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 229920000768 polyamine Polymers 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 7
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 4
- 239000004593 Epoxy Substances 0.000 claims description 66
- 229920001187 thermosetting polymer Polymers 0.000 claims description 24
- 229920005992 thermoplastic resin Polymers 0.000 claims description 22
- 239000000835 fiber Substances 0.000 claims description 12
- 241001676573 Minium Species 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 238000005728 strengthening Methods 0.000 claims description 10
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- 230000006378 damage Effects 0.000 claims description 6
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- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims description 3
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- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
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- 239000002253 acid Substances 0.000 claims 1
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- -1 glycidyl group amine Chemical class 0.000 description 8
- 230000001464 adherent effect Effects 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 230000009975 flexible effect Effects 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 238000009998 heat setting Methods 0.000 description 3
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- 238000000465 moulding Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000011499 joint compound Substances 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 229940038384 octadecane Drugs 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
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- 239000009719 polyimide resin Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- 239000012943 hotmelt Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
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- 239000000049 pigment Substances 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
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- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
Abstract
Provided is an epoxy resin composition for fiber-reinforced composite materials, which serves as a matrix resin for a prepreg. This epoxy resin composition is improved in tackiness stability during storage, while maintaining mechanical characteristics. The epoxy resin composition for fiber-reinforced composite materials is characterized by containing 25 to 50 parts by weight of an amine curing agent (B) selected from aliphatic polyamines, alicyclic polyamines and aromatic polyamines, and 1 to 20 parts by weight of an organic acid dihydrazide compound (C) having a melting point of not less than 150 DEG C, per 100 parts by weight of an epoxy resin (A).
Description
Technical field
The present invention relates to epoxy resin composition for fiber-reinforced composite material, in more detail, relate to the composition epoxy resin of the panel that is suitable as perforated plate from the matrix resin of connectivity prepreg (prepreg).
Background technology
With the composition epoxy resin is the fiber reinforced composite of matrix resin, owing to its excellent mechanics rerum natura etc. is widely used in the industry purposes such as aircraft, automobile.Particularly for aircraft for structured material and interior dress material, consider from light-weighted viewpoint, use the example of fiber reinforced composite to increase as the panel of perforated plate.As its matrix resin, using with Resins, epoxy and amine mostly is the resin combination of solidifying agent as main body, and its cured article has the toughness height, characteristics such as heat-drawn wire height.But along with the expansion of matrix material purposes, higher mechanical characteristics is brought into play in strong request gradually.
As one of countermeasure, patent documentation 1 has proposed to improve the scheme of interlaminar shear strength and flexural strength by adding Dyhard RU 100 as solidifying agent in composition epoxy resin.But when using Dyhard RU 100, Dyhard RU 100 is dissolved in the Resins, epoxy easily in temperature-rise period, uprise with the reactive behavior of Resins, epoxy, so there is following problems, promptly when making resin film or during the prepreg infiltration, the temperature rising promotes the curing reaction with Resins, epoxy easily, makes the problem of the lasting rising of viscosity of resin combination.Also have following problems in addition, be about to prepreg under operating environment during keeping, curing reaction carries out, and loses the viscosity of prepreg and drape etc. easily.
People pursue on the other hand: in order to make the further lightweight of perforated plate, and reduce the moulding cost, when the prepreg of desiring to make fiber reinforced composite engages with honeycomb core, do not use the film joint compound, and directly joint from joining technique.
But otherwise use the film joint compound, need to improve prepreg matrix resin from bond strength, and to improve from bond strength, importantly improve the core skin adherent shape and the intensity that on the junction surface of honeycomb core and prepreg, form.Core skin adherent intensity is influenced by the toughness of the cured article of matrix resin, and the viscosity of the matrix resin of core skin adherent shape when being heating and curing is very relevant, and MV minium viscosity is high more, and the shape that obtains is just good more.That is, if do not make the toughness of resin cured matter and the resin viscosity when being heating and curing suitable, just can not be by the bonding sufficient joint strength that obtains of core skin.
In addition, before being heating and curing of prepreg, the side that the preferred substrate resin viscosity is low.At this moment because, if the resin viscosity in the normal temperature zone of handling prepreg is low, then can keep good viscosity and drape, in addition, in the resin film production process before the prepreg infiltration, if resin viscosity is low in the scope of about 60～90 ℃ of temperature, then can improve the cause of the production efficiency of prepreg.
In patent documentation 2, using amine simultaneously by the solidifying agent as the composition epoxy resin of the matrix resin of prepreg is solidifying agent and Dyhard RU 100, and it is bonding to form the good core skin of intensity when directly engaging with honeycomb core, improves bond strength.But it with such amine solidifying agent and Dyhard RU 100 and time spent, as mentioned above, uprise with the reactive behavior of Resins, epoxy, thus there is following problems, promptly, if temperature raises to a certain degree, with Resins, epoxy curing reaction takes place easily then, for example, when the making of resin film, resin viscosity raises continuously, so the production efficiency of prepreg reduces.In addition, when taking care of prepreg under operating environment, curing reaction carries out causing the viscosity of prepreg and the problem that drape loses easily.In addition, this matrix resin, although can to a certain degree improve the toughness of resin cured matter, in making honeycomb and situation that prepreg directly engages, the toughness that improves for the core skin adherent intensity that improves formation is insufficient, mechanical characteristics is insufficient.
Patent documentation 1: Japanese kokai publication hei 2-51538 communique
Patent documentation 2: Japanese kokai publication sho 58-83022 communique
Summary of the invention
The object of the present invention is to provide a kind of epoxy resin composition for fiber-reinforced composite material, it can be when maintenance be used the mechanical characteristics of matrix resin as prepreg, the storage stability of tackifying.In addition, also provide a kind of epoxy resin composition for fiber-reinforced composite material, it can improve the productivity and the storage stability of prepreg improving in bond strength.
Realize the epoxy resin composition for fiber-reinforced composite material of the present invention of above-mentioned purpose, it is characterized in that, with respect to Resins, epoxy (A) 100 weight parts, having cooperated the amine that is selected from aliphatic polyamine, alicyclic polyamine or the aromatic polyamine is that solidifying agent (B) 25～50 weight parts and fusing point are organic acid dihydrazide compound (C) 1～20 weight part more than 150 ℃.
Described composition epoxy resin contains Dyhard RU 100 (D), and described organic acid dihydrazide compound (C) is dispersed in the composition epoxy resin with granular simultaneously.
In addition, it is solid thermosetting resin (E) at normal temperatures that described composition epoxy resin contains, and this thermosetting resin (E) is dispersed in wherein with granular.
Epoxy resin composition for fiber-reinforced composite material of the present invention, by being that to add fusing point in the solidifying agent (B) be that organic acid dihydrazide compound (C) more than 150 ℃ replaces Dyhard RU 100 at Resins, epoxy (A) and amine, Resins, epoxy becomes and is difficult for dissolving in temperature-rise period, not with Resins, epoxy generation curing reaction, the stability of viscosity is high, when making prepreg, can keep viscosity and drape at normal temperatures for a long time, and the mechanical characteristics of resin cured matter is also identical with the situation of using Dyhard RU 100.
In addition, to use in the situation of Dyhard RU 100 (D) together, because the fusing point of organic acid dihydrazide compound (C) is more than 150 ℃, than Dyhard RU 100 (D), amine is the fusing point height of solidifying agent (B), so organic acid dihydrazide compound (C) can disperse in granular non-dissolved mode, hindered the curing reaction of be heating and curing preceding Dyhard RU 100 (D) and Resins, epoxy (A) thus, therefore, productivity in the time of can improving the making resin film before prepreg infiltrates can also improve the stability that prepreg is preserved at normal temperature in addition.
On the other hand, in being heating and curing of prepreg during with heat, organic acid dihydrazide compound (C) dissolving, amine is that the curing reaction of solidifying agent (B) and Dyhard RU 100 (D) and Resins, epoxy (A) begins, the resin MV minium viscosity is increased, the core skin that obtains excellent in shape is bonding, can improve the toughness of resin cured matter simultaneously.Therefore, when in the matrix resin of prepreg, using, can improve prepreg from bond strength.
Embodiment
For epoxy resin composition for fiber-reinforced composite material of the present invention, (A) is not particularly limited to Resins, epoxy, can use glycidyl ether type Resins, epoxy, glycidyl esters type Resins, epoxy, glycidyl group amine type Resins, epoxy etc., in addition, can also use urethane modified epoxy, rubber modified epoxy resin, alkyd modified Resins, epoxy etc.Wherein, preferred glycidyl ether type Resins, epoxy or glycidyl group amine type Resins, epoxy.Number to the functional group of Resins, epoxy does not have particular determination, is preferably 2～5, more preferably 2～3.
These Resins, epoxy, specifically, as glycidyl ether type Resins, epoxy, can preferably list bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolac-type Resins, epoxy, cresols novolac-type Resins, epoxy, Resorcinol novolac-type Resins, epoxy etc., as glycidyl group amine type Resins, epoxy, can preferably list the four glycidyl group diaminodiphenyl-methane, the triglycidyl group p-aminophenol, the amino cresols of triglycidyl group, four glycidyl group diaminodiphenyl-methane resin, four glycidyl group m-xylene polyimide resin, N, N-diamino cresol resin, Resins, epoxy with other various modifications, crystallinity Resins, epoxy etc.By these Resins, epoxy are used singly or two or more kinds in combination, can guarantee mechanical characteristicies such as the desired toughness of matrix resin, thermotolerance, viscosity and the drape that can regulate prepreg simultaneously.
Amine is that solidifying agent (B) is selected from aliphatic polyamine, alicyclic polyamine or aromatic polyamine, the optimization aromatic polyamines.As aromatic polyamine, preferred diamino diphenyl sulfone, diaminodiphenyl-methane, m-xylene diamine, mphenylenediamine etc., from improving the stable on heating viewpoint of cured article, preferred especially diamino diphenyl sulfone.Wherein preferred more especially 3,3 '-diamino diphenyl sulfone and 4,4 '-diamino diphenyl sulfone.These amine are that solidifying agent (B) can be used in combination more than 2 kinds.
Amine is the use level of solidifying agent (B), and with respect to Resins, epoxy (A) 100 weight parts, 25～50 weight parts are better, preferred 30～45 weight parts.By make amine be the use level of solidifying agent (B) in this scope, can fully guarantee the rerum natura such as mechanical characteristics, particularly intensity, toughness, thermotolerance of resin cured matter.
Composition epoxy resin of the present invention is also with the granular organic acid dihydrazide compound (C) that has cooperated as the latent curing agent of active Hydrogen in the solidifying agent (B) at Resins, epoxy (A) and amine.As organic acid dihydrazide compound (C), fusing point be more than 150 ℃ better, preferred fusing point is 160～200 ℃.By making fusing point is more than 150 ℃, can make excellent heat stability, is coated with operation and in the normal temperature keeping, can suppresses and Resins, epoxy generation curing reaction under about 60～90 ℃ of resin temperatures.That is to say that even be in 60～90 ℃ resin temperature state for a long time when the coating operation, also can control resin viscosity increases.For example, even in the resin storehouse of supplying tank or coating roll (dam), make resin temperature be 60～90 ℃ 1～2 hour, also the increase of resin viscosity can be controlled at than low degree therebetween, from supplying tank, discharge easily, and under the working conditions of not changing coating roll, produce resin film.
Organic acid dihydrazide compound fusing point is up to more than 150 ℃, owing to being difficult to dissolve in Resins, epoxy at low temperatures, so preferably use granulous.By using granulous organic acid dihydrazide compound, when being heating and curing, heat up easily, when reaching certain temperature, be dissolved in easily and be cured reaction in the Resins, epoxy.The particle of organic acid dihydrazide compound (C), median size are preferably below the 100 μ m, more preferably 5～50 μ m.If making median size is below the 100 μ m, heat up easily when then being heating and curing, be dissolved in the Resins, epoxy easily when reaching certain temperature, so preferred.Median size is the following fine particles of 100 μ m, can obtain from commercially available product aptly.And then, obtain fine particle, preferably come granular by impact grinding method, spray-drying process.In addition, in the present invention, " median size " is to measure the particle diameter and the size-grade distribution of the particle after pulverizing, thereby their value is calculated the value that obtains according to weighted average.
Organic acid dihydrazide compound (C) is carboxylic acid dihydrazide compound or diprotic acid dihydrazide compound preferably, more preferably the carboxylic acid dihydrazide compound.The carboxylic acid dihydrazide compound is that the compound shown in the following formula (I) is better.
In the following formula (I), X represents that phenyl or carbonatoms are 2～18 aliphatic group.Aliphatic group is the group that is formed by stable hydrocarbon or unsaturated hydrocarbons, in addition, can be in straight chain shape, chain or the ester ring type any.
As such organic acid dihydrazide compound, can preferably list adipic dihydrazide, amber acid dihydrazide, sebacic dihydrazide, dodecanedioic acid two hydrazides and octadecane diene-two carbohydrazide etc.
Wherein, organic acid dihydrazide compound (C) the carboxylic acid dihydrazide compound shown in the following formula (II) preferably.
Organic acid dihydrazide compound (C) with respect to Resins, epoxy (A) 100 weight parts, cooperates 1～20 weight part better, preferably cooperates 3～10 weight parts.By setting use level is more than 1 weight part, the effect of mechanics rerum natura of resin cured matter can be improved, by being set at below 20 weight parts, when thermofixation, can in Resins, epoxy, dissolve effectively, thereby can make the MV minium viscosity when being heating and curing suitable.
Composition epoxy resin of the present invention, when not using Dyhard RU 100, use organic acid dihydrazide compound (C), so can under the situation that the mechanical characteristic that makes the resin cured matter that obtains, particularly toughness and thermotolerance do not reduce, obtain the mechanical characteristic of peer-level excellence as active Hydrogen latent curing agent.Therefore, when the matrix resin as prepreg uses, can improve core skin adherent intensity, improve bond strength with honeycomb core.
Epoxy resin composition for fiber-reinforced composite material of the present invention is necessary composition with above-mentioned (A)～(C) composition, can also contain Dyhard RU 100 (D) in the scope of not damaging effect of the present invention.
Dyhard RU 100 (D), because the reactive behavior height, the physical properties excellent after the curing is used so be suitable for the solidifying agent of the composition epoxy resin used as prepreg.But owing to before being heating and curing, be cured reaction easily, so by making it and the coexistence of organic acid dihydrazide compound (C) particle the curing reaction before can suppressing to heat with Resins, epoxy.
Fusing point is at the organic acid dihydrazide compound (C) more than 150 ℃, to the obstruction character excellence of the Resins, epoxy (A) before being heating and curing with the curing reaction of Dyhard RU 100 (D).Therefore, the curing reaction of the Dyhard RU 100 (D) before can suppressing to be heating and curing carries out, and suppresses resin viscosity and rises, and viscosity reduces when being suppressed at normal temperature preservation prepreg.For example, if in situation about existing with Dyhard RU 100 (D), even resin temperature is 60～90 ℃ state for a long time when the coating operation, also can suppress the increase of resin viscosity, even in the resin storehouse of supplying tank or coating roll, placed 1～2 hour, also the increase of resin viscosity can be controlled at lower level, be easy to discharge, and can under the situation of the working conditions that changes coating roll not significantly, produce resin film from supplying tank.
Dyhard RU 100 (D) with respect to Resins, epoxy (A) 100 weight parts, preferably cooperates 1～5 weight part, more preferably the Dyhard RU 100 of 1～3 weight part (D).By the use level that makes Dyhard RU 100 (D) is more than 1 weight part, can obtain the effect that the mechanical characteristics of resin cured matter fully improves, and is below 5 weight parts by making it, and can make the curing reaction before the thermofixation operation be difficult for taking place.
In addition, when being heating and curing, composition epoxy resin is heated, organic acid dihydrazide compound (C) is when beginning to dissolve, amine is solidifying agent (B) and Dyhard RU 100 (D) and Resins, epoxy (A) beginning curing reaction, so can increase the MV minium viscosity of resin combination when being heating and curing, make core skin bond shapes good, improve the toughness of resin cured matter simultaneously.
Composition epoxy resin of the present invention, containing under the normal temperature is solid thermosetting resin (E), and makes this thermosetting resin (E) better with granular dispersion.By making under the normal temperature is that solid thermosetting resin (E) is not when reaching certain temperature, its particle dissolves in Resins, epoxy (A) not exclusively, when reaching certain temperature, and uniform dissolution, can make the viscosity of composition epoxy resin suitable, it is bonding to form good core skin.
In addition, by adding the particle of thermosetting resin (E), when cooperating thermoplastic resin described later (F), can reduce its use level, so can reduce the viscosity of the resin combination before the operation that is heating and curing, improve the viscosity and the drape of prepreg, obtain excellent operation.And then, when adding thermosetting resin (E) particle, with only cooperate the situation of thermoplastic resin particle to compare in undissolved mode, the toughness of composition epoxy resin improves the effect excellence, so can improve core skin adherent intensity, further the bond strength of raising and honeycomb core improves from connectivity.
Normal temperature is down solid thermosetting resin (E) particle, preferably temperature less than 90 ℃, more preferably under 60～90 ℃ in Resins, epoxy (A) dissolving incomplete, and softening temperature is preferably more than 120 ℃, more preferably 130～160 ℃.In addition, softening temperature is the value that records according to JISK-7234.
In the present invention, kind to thermosetting resin (E) particle is not particularly limited, preference such as normal temperature are solid Resins, epoxy, bimaleimide resin, isocyanate resin, phenol resins, unsaturated polyester resin or vinyl ester resin, and preferred especially normal temperature is solid Resins, epoxy, bismaleimides system or isocyanate-based resin down.Be solid Resins, epoxy at normal temperatures, can improve its molecular weight simultaneously and modulate by for example bisphenol A type epoxy resin being made with extra care to improve purity, normal temperature becomes and has crystalline solid, have the raising softening temperature, improve the operability of prepreg, improve the effect of concave-convex surface simultaneously.
In addition, thermosetting resin (E) particle, its particle diameter are preferably below the 100 μ m, more preferably 5～50 μ m.Particle diameter by making thermosetting resin (E) particle in such scope, can be in the operation that is heating and curing when reaching certain temperature uniform dissolution, so the viscosity that can regulate composition epoxy resin is to suitable.In addition, the modulator approach of thermosetting resin (E) particle and the measuring method of particle diameter, same with above-mentioned organic acid dihydrazide compound (C) particle, modulate and measure to pulverize.
Composition epoxy resin of the present invention, with respect to Resins, epoxy (A) 100 weight parts, preferably with 2～20 weight parts, more preferably the cooperation ratio of 5～15 weight parts contains thermosetting resin (E).By the use level that makes thermosetting resin (E) is more than 2 weight parts, can the viscosity adjustment of composition epoxy resin is extremely suitable, and resin cured matter flexible effect is improved.By being set at below 20 weight parts, can make prepreg have the hardness of appropriateness, tackify and drape, so preferred.
Composition epoxy resin of the present invention, it is better to contain thermoplastic resin (F).This be because, by thermoplastic resin (F) is dissolved in the Resins, epoxy (A), the viscosity that can regulate composition epoxy resin, the MV minium viscosity of resin combination when being heating and curing, the core skin that forms excellent in shape is bonding, improves the flexible cause of resin cured matter simultaneously.Therefore, thermoplastic resin (F) is preferably in temperature more than 90 ℃, may be dissolved in the Resins, epoxy (A) under more preferably 95 ℃～150 ℃.By in such temperature range, dissolving, can dissolve easily and uniformly, mix.
Kind to thermoplastic resin (F) is not particularly limited, be preferably selected from polyethersulfone resin, polyetherimide resin, polyimide resin, polyamide resin, polyether resin, vibrin, polysulfone resin, polyamide-imide resin, polyacrylate resin, polyarylether resin, polyphenylene oxide resin and the polyether-ether-ketone resin more than a kind.Thermoplastic resin (F) is preferred, polyethers sulphone resin or polyetherimide resin especially, they with the consistency of Resins, epoxy composition or affinity than other thermoplastic resin height, it is effective to improve the resin cured matter flexible.
Thermoplastic resin (F) preferably uses granulous, and its particle diameter is preferably below the 200 μ m, more preferably 5～100 μ m.Have the thermoplastic resin of the fine particle of such particle diameter by use, can prevent in the time of in being coupled to Resins, epoxy that macroparticle from can not all dissolve and residual, make the rapid uniform dissolution of particle, so can improve the viscosity characteristics and the toughness of resin combination.That is, the particle diameter of fine particle is set at 200 μ m when following, can solve homogeneously in the Resins, epoxy (A) rerum natura of the resin combination that is improved, particularly flexible effect.The modulator approach of the particle of thermoplastic resin (F) and the measuring method of particle diameter, same with the particle of above-mentioned organic acid dihydrazide compound (C), modulate and measure to pulverize.
Composition epoxy resin of the present invention, with respect to Resins, epoxy (A) 100 weight parts, preferably with 20～60 weight parts, more preferably the cooperation ratio of 30～50 weight parts contains thermoplastic resin (F).Use level by making thermoplastic resin (F) can by being set at below 60 weight parts, can be tackified and drape with the viscosity adjustment of composition epoxy resin to suitable in the scope of 20～60 weight parts.
Epoxy resin composition for fiber-reinforced composite material of the present invention, above-mentioned (A)～(C) is necessary composition, and cooperated (D)～(F) composition arbitrarily, in the scope of harmless effect of the present invention, can also cooperate the various additives such as particle, viscosity modifier, weighting agent, stablizer, fire retardant, pigment of known solidifying agent except above-mentioned (A)～(F) composition, thermosetting resin as required.
Composition epoxy resin of the present invention, the MV minium viscosity that obtains by the Measurement of Dynamic Viscoelasticity of carrying out under 2 ℃/minute of heat-up rates is 10～150Pas, more preferably 20～150Pas preferably.The MV minium viscosity of Measurement of Dynamic Viscoelasticity is in the above-mentioned scope, for the productivity that improves prepreg with from connectivity is important, MV minium viscosity is that 10Pas is when above, it is bonding to form good core skin, raising is from connectivity, be 150Pas when following, can in the bonding formation of holding core skin, resin combination be infiltrated up in the reinforcing fiber easily when prepreg is made.In addition, the MV minium viscosity that obtains by Measurement of Dynamic Viscoelasticity among the present invention is meant with 2 ℃/second heat-up rate to make temperature when 25 ℃ are warming up to 200 ℃, frequency 10rad/ second, the Schwellenwert of the complex viscosity in the Measurement of Dynamic Viscoelasticity of distortion 1%.
Composition epoxy resin of the present invention, the destruction toughness value of the resin cured matter after the curing are the destruction toughness values of measuring according to ASTM D5045-91, are preferably
More than, more preferably
The destruction toughness value of resin cured matter exists
When above, can improve the intensity of core skin stick portion, comb core material begins to occur the such degree of partial rupture ground in panel (prepreg) and stripping test after honeycomb core engages, improves stripping strength.
In addition, composition epoxy resin of the present invention is characterized in that, even be in for a long time when the coating operation of making resin film under 60～90 ℃ the resin temperature state, resin viscosity changes still little.For example, the viscosity variable quantity under the state that is in 75 ℃ of resin temperatures in 2 hours is preferably below the 150Pas, more preferably below the 100Pas, and then is preferably below the 70Pas, is preferably below the 55Pas especially.The viscosity variable quantity is that 150Pas is when following, even in the situation about in the resin storehouse of supplying tank or coating roll, stopping for a long time, it is still little that resin viscosity changes, and institute is so that follow-up discharging from supplying tank becomes easy, makes resin film under the situation of the working conditions that does not need significantly to change coating roll.In addition, viscosity change is in Measurement of Dynamic Viscoelasticity, under the rigid condition of 75 ℃ of temperature, measure frequency 10rad/ second, distortion 1% complex viscosity through the time change, thereby the viscosity variable quantity of obtaining.
And then, composition epoxy resin of the present invention, the reaction when being heating and curing begins temperature and is preferably more than 100 ℃, and more preferably up to 110～145 ℃, the excellent heat stability before be heating and curing this moment can suppress resin viscosity increase in the solidify reaction process.Specifically, the reaction by differential scanning calorimetric measurement (DSC) begins temperature and uprises, and can suppress curing reaction during keeping under resin temperature (60～90 ℃) when common coating operation or the normal temperature and carry out.In addition, the reaction when being heating and curing begins temperature and is to use DSC to begin temperature with the reaction of 10 ℃/minute determination of heating rate, and the peak that promptly dispels the heat begins the intersection point temperature of rising place and baseline.
Manufacture method to epoxy resin composition for fiber-reinforced composite material of the present invention is not particularly limited, can be with Resins, epoxy (A) preferably 95～150 ℃ of temperature, more preferably under 100～125 ℃ of temperature, be mixed into resin solution.At this moment, in the situation that cooperates thermoplastic resin (F), preferably add thermoplastic resin (F), and make its dissolving, form hybrid resin.Then this hybrid resin preferably is cooled to 60～90 ℃ of temperature, more preferably 70～80 ℃, in this hybrid resin, add then and comprise that amine is other gradation composition of solidifying agent (B) and organic acid dihydrazide compound (C), be that interpolation amine is solidifying agent (B), organic acid dihydrazide compound (C) specifically, the particle of Dyhard RU 100 as required (D) and/or thermosetting resin (E), thus make the manufacturing of their homodisperse.
Preferred specifically following method: use temperature is set in 95～150 ℃ planet mixing machine, makes Resins, epoxy (A), preferably mixes about 0.5～3 hour with thermoplastic resin (F), until evenly dissolving effectively.Then, this hybrid resin is chilled to 60～90 ℃ of temperature, adding amine is the particle of solidifying agent (B), organic acid dihydrazide compound (C) and Dyhard RU 100 as required (D) and/or thermosetting resin (E), thereby homodisperse mixes modulation.
Fiber strengthening prepreg of the present invention is to be matrix resin with above-mentioned epoxy resin composition for fiber-reinforced composite material, and this matrix resin and reinforcing fiber are composited.Reinforcing fiber can preferably list carbon fiber, graphite fibre, Kevlar, glass fibre etc., more preferably carbon fiber wherein, preferred especially carbon fibre fabric.
Fiber strengthening prepreg, the content of its matrix resin are preferably 30～50 weight %, more preferably 35～45 weight %.If the ratio of matrix resin is in such scope in the fiber strengthening prepreg, then can improve prepreg from connectivity, improve operability and exterior quality simultaneously, and then give full play to the mechanical characteristics of carbon fiber-reinforced composite material.
Make the method for fiber strengthening prepreg, preferred hot melt process is about to composition epoxy resin of the present invention and is coated on and becomes film like on the release paper, makes resin film, be stacked in the both sides up and down of reinforcing fiber then, composition epoxy resin be infiltrated up in the reinforcing fiber by heating and pressurization.The prepreg that obtains like this, excellent in stability in the prolonged preservation under operating environment and normal temperature atmosphere, viscosity and drape do not reduce.
Specifically, because fiber strengthening prepreg of the present invention do not cooperate Dyhard RU 100 or reduced the use level of Dyhard RU 100, and cooperated the organic acid dihydrazide compound (C) of fusing point more than 150 ℃, so excellent storage stability in the normal temperature.That is, in the situation of normal temperature prolonged preservation, the viscosity of matrix resin increases little, and the viscosity of prepreg is constantization substantially.Here, normal temperature is meant the temperature of the environment that carries out the prepreg processing operation, is about 10～35 ℃.Composition epoxy resin of the present invention, for example, even preferably left standstill 10 days in the room temperature of 20 ℃ of temperature, viscosity does not worsen yet, and can keep excellent viscosity after prepreg has just been made with good order and condition.
The fiber strengthening prepreg that obtains like this is stacked on two faces of honeycomb core, can produces fiber reinforced composite by common autoclave molding or thermofixation moulding such as hot-forming.It is bonding that the fiber reinforced composite that obtains not only has good core skin, the bond strength height, and have excellent mechanical characteristics.
The honeycomb core that uses among the present invention preferably is selected from any in aromatic poly honeycomb, aluminium honeycomb, paper wasp nest and the glass honeycomb, wherein more preferably aromatic poly honeycomb.
Below, further specify the present invention by embodiment, but scope of the present invention is not limited by these embodiment.
Embodiment
[embodiment 1～6 and comparative example 1～4]
As Resins, epoxy (A), amine is that solidifying agent (B), organic acid dihydrazide compound (C) and any composition Dyhard RU 100 (D), thermosetting resin (E), thermoplastic resin (F) use following substances with table 1 and 2 described cooperation ratios respectively, modulates composition epoxy resin.At first, use temperature is set in 125 ℃ planet mixing machine, the whole of Resins, epoxy (A) and thermoplastic resin (F) is mixed 75 minutes, until becoming even resin solution.Then, the temperature of this planet mixing machine is set in 70 ℃, when resin temperature becomes even, adding amine in this resin solution is the whole of solidifying agent (B), organic acid dihydrazide compound (C), Dyhard RU 100 (D) and thermosetting resin (E) particle, mixes and modulates composition epoxy resin.
Resins, epoxy (A)
Resin A-1:N, N, O-triglycidyl group-p-aminophenol (the system MY-0510 of Ha Application Star マ Application ア De バ Application ス ト マ テ リ ア Le ズ society)
Resin A-2: bisphenol f type epoxy resin (the system エ ピ コ-ト-806 of ジ ヤ パ Application エ Port キ シ レ ジ Application society)
Amine is solidifying agent (B)
Solidifying agent B:3,3 '-diamino diphenyl sulfone (the system ARADUR9719-1 of Ha Application Star マ Application ア De バ Application ス ト マ テ リ ア Le ズ society)
Dyhard RU 100 (D)
Solidifying agent D: Dyhard RU 100 (the system エ ピ キ ユ ア DICY15 of ジ ヤ パ Application エ Port キ シ レ ジ Application society)
Organic acid dihydrazide compound (C)
Solidifying agent C-1: 177～184 ℃ of adipic dihydrazide compound (the Japanese Off ア イ Application ケ system system ADH of society) fusing points, median size 13 μ m
Solidifying agent C-2: 185～190 ℃ of dodecanedioic acid two hydrazides (the Japanese Off ア イ Application ケ system system N-12 of society) fusing points, median size 9 μ m
Solidifying agent C-3: 185～189 ℃ of sebacic dihydrazide compound (the Japanese Off ア イ Application ケ system system SDH of society) fusing points, median size 21 μ m
Solidifying agent C-4:1,3-two (diazanyl carbonyl ethyl)-5-sec.-propyl glycolylurea (flavor
The system VDH of Off ア イ Application テ Network ノ society) fusing point: 118～124 ℃, median size 10 μ m
Solidifying agent C-5:7,11-octadecane diene-1,18-two carbohydrazides (flavor
The system UDH of Off ア イ Application テ Network ノ society) fusing point: 150～165 ℃, median size 20 μ m
Thermosetting resin (E)
Resin E: bisphenol A type epoxy resin (Dongdu change into society system YD-020N), 135 ℃～150 ℃ of softening temperatures are fine particle below the 100 μ m through the particle diameter that impact grinding obtains.
Thermoplastic resin (F)
Resin F: polyethersulfone resin (Sumitomo Chemical society system ス ミ カ エ Network セ Le PES5003P) is a fine particle below the 100 μ m through the particle diameter that impact grinding obtains.
Use following method, respectively the 10 kinds of composition epoxy resins (embodiment 1～6, comparative example 1～4) that obtain are estimated the viscosity variable quantity of composition epoxy resin, the destruction toughness value of reaction beginning temperature, viscosity and cured article, the results are shown in table 1 and the table 2.In addition, MV minium viscosity, the viscosity of prepreg and the stripping strength of perforated plate when using following method respectively 5 kinds of composition epoxy resins (embodiment 4～6, comparative example 3 and 4) wherein to be estimated the composition epoxy resin thermofixation, table 2 shows this measurement result.
[the viscosity variable quantity of composition epoxy resin]
Measure composition epoxy resin 75 ℃ of viscosity of 2 hours down of temperature through the time change, mensuration is with respect to the viscosity variable quantity behind 2 hours of initial stage viscosity.In addition, the viscosity of composition epoxy resin is that temperature is remained under the same terms of 75 ℃, the complex viscosity of measuring in the Measurement of Dynamic Viscoelasticity of frequency 10rad/ second, distortion 1%.
[reaction of composition epoxy resin begins temperature]
With the composition epoxy resin of about 5mg as sample, with 10 ℃/minute heat-up rates from 20 ℃ of temperature condition that are warming up to 350 ℃ of temperature, under the nitrogen atmosphere, (DSC, the テ イ-system DSC-2920 of エ イ イ Application ス Star Le メ Application ト society) carries out heat analysis by the differential scanning calorimetric measurement.Measure the intersection point temperature that the heat radiation peak begins the extended line and the baseline of rising place, it is begun temperature as reaction.
[MV minium viscosity of composition epoxy resin]
The composition epoxy resin that use obtains rises to 200 ℃ with 2 ℃ of/second heat-up rates from 25 ℃ of temperature as sample, is 10rad/ second in frequency, measures dynamic viscoelastic under the condition of distortion 1%, measures the Schwellenwert of complex viscosity.
[viscosity of prepreg]
The composition epoxy resin that use obtains forms resin film on release paper, make this film go up transfer printing to carbon fiber plain goods (DongレShe makes T-300-3K) by heating and pressurizing, and making resin content is 41 weight %, thereby obtains prepreg.
According to three following segment standard, touch by hand and to estimate firm making when intact and at room temperature expose the viscosity of the prepreg after 10 days.
O: feel sufficient binding property.
△: feel binding property a little.
*: fundamental sensation is less than binding property.
According to ASTM D5045-91, the sample of being produced by the resin cured matter that obtains is determined at 23 ℃ of destruction toughness values under (drying regime)
[the destruction toughness of cured article]
The composition epoxy resin that use obtains, temperature was solidified 2 hours down for 180 ℃ in program control baking oven, produced resin cured matter.
[stripping strength of perforated plate]
With 2 prepreg stacked arrangement obtaining on two faces of honeycomb core (the clear and system ノ-メ Star Network ス Ha ニ カ system SAH-1/8-8.0 of flying machine industry society), put into bag then, heat 2 hours (2.8 ℃/minute of heat-up rates) down 180 ℃ of high pressure temperature in the kettle and make its curing, thereby make perforated plate.Therebetween, make by pressurized air and be forced into 0.32MPa in the autoclave.
To the perforated plate that obtains according to ASTMD1781, in the operation that is heating and curing, will be formulated in the upside of honeycomb core and the panel of downside and be processed into a certain size respectively, in 23 ℃ of (drying regime) following stripping strengths (lb-in/3in) of measuring the test piece of upper panel and downside panel of temperature.
Table 1
As can be known from the results of Table 1, the viscosity variable quantity of composition epoxy resin of the present invention (embodiment 1～3) after 75 ℃, 2 hours of temperature is little.Find also that in addition the reaction of measuring by DSC begins the temperature height, the possibility that curing reaction carries out when resin temperature (60～90 ℃) when common coating operation or normal temperature keeping is little.In addition, even at room temperature expose 10 days, the viscosity of prepreg does not change substantially yet.
In contrast, in using Dyhard RU 100 (comparative example 2) or the situation of fusing point less than organic acid dihydrazide (comparative example 1) of 150 ℃, find at 75 ℃ of the temperature viscosity variable quantity after following 2 hours greatly, the temperature of reaction beginning simultaneously is low.And then also find, after at room temperature exposing 10 days, the viscosity of prepreg significantly reduces.
Table 2
Claims (21)
1. epoxy resin composition for fiber-reinforced composite material, with respect to Resins, epoxy (A) 100 weight parts, having cooperated the amine that is selected from aliphatic polyamine, alicyclic polyamine or the aromatic polyamine is that solidifying agent (B) 25～50 weight parts and fusing point are organic acid dihydrazide compound (C) 1～20 weight part more than 150 ℃.
2. epoxy resin composition for fiber-reinforced composite material according to claim 1, described composition epoxy resin contain Dyhard RU 100 (D), and described organic acid dihydrazide compound (C) is with granular dispersion simultaneously.
3. it is solid thermosetting resin (E) at normal temperatures that epoxy resin composition for fiber-reinforced composite material according to claim 1 and 2, described composition epoxy resin contain, and this thermosetting resin (E) is with granular dispersion.
4. according to each described epoxy resin composition for fiber-reinforced composite material of claim 1～3, also contain thermoplastic resin (F).
5. according to each described epoxy resin composition for fiber-reinforced composite material of claim 1～4, described organic acid dihydrazide compound (C) is the carboxylic acid dihydrazide compound shown in binary acid dihydrazide or the following formula (I),
In the following formula, X represents that phenyl or carbonatoms are 2～18 aliphatic group.
6. according to each described epoxy resin composition for fiber-reinforced composite material of claim 1～5, described organic acid dihydrazide compound (C) is the carboxylic acid dihydrazide compound shown in the following formula (II).
7. according to each described epoxy resin composition for fiber-reinforced composite material of claim 1～6, the median size of described organic acid dihydrazide compound (C) is below the 100 μ m.
8. according to each described epoxy resin composition for fiber-reinforced composite material of claim 1～7, described amine is that solidifying agent (B) is 3,3 '-diamino diphenyl sulfone and/or 4,4 '-diamino diphenyl sulfone.
9. according to each described epoxy resin composition for fiber-reinforced composite material of claim 3～8, described thermosetting resin (E) contains and is selected from that not exclusively dissolving and normal temperature are that solid Resins, epoxy, bismaleimides are at least a in resin and the isocyanate-based resin in described Resins, epoxy below 90 ℃ in temperature.
10. according to each described epoxy resin composition for fiber-reinforced composite material of claim 4～9, described thermoplastic resin (F) is polyethersulfone resin or polyetherimide resin.
11.,, contain described Dyhard RU 100 (D) with the cooperation ratio of 1～5 weight part with respect to described Resins, epoxy (A) 100 weight parts according to each described epoxy resin composition for fiber-reinforced composite material of claim 2～10.
12.,, contain described thermosetting resin (E) with the cooperation ratio of 1～20 weight part with respect to described Resins, epoxy (A) 100 weight parts according to each described epoxy resin composition for fiber-reinforced composite material of claim 3～11.
13.,, contain described thermoplastic resin (F) with the cooperation ratio of 20～60 weight parts with respect to described Resins, epoxy (A) 100 weight parts according to each described epoxy resin composition for fiber-reinforced composite material of claim 4～12.
14. according to each described epoxy resin composition for fiber-reinforced composite material of claim 1～13, the MV minium viscosity of the described composition epoxy resin that obtains by the Measurement of Dynamic Viscoelasticity under 2 ℃/minute of heat-up rates is 10～150Pas.
15. according to each described epoxy resin composition for fiber-reinforced composite material of claim 1～14, described composition epoxy resin after curing according to the destruction toughness value that ASTM D5045-91 measures is
More than.
16. the manufacture method of an epoxy resin composition for fiber-reinforced composite material, it is the manufacture method of each described epoxy resin composition for fiber-reinforced composite material of claim 4～15, under 95～150 ℃, described thermoplastic resin (F) is dissolved in the described Resins, epoxy (A) and makes hybrid resin, be cooled to 60～90 ℃ then, interpolation comprises other gradation composition that described amine is solidifying agent (B) and organic acid dihydrazide compound (C) in this hybrid resin.
17. a fiber strengthening prepreg is that each the described composition epoxy resin with claim 1～15 is a matrix resin, is composited with reinforcing fiber.
18. fiber strengthening prepreg according to claim 17, the content of described matrix resin are 30～50 weight %.
19. according to claim 17 or 18 described fiber strengthening prepregs, described reinforcing fiber is a carbon fiber.
Each described fiber strengthening prepreg and honeycomb core of requirement 17～19 20. a honeycomb sandwich board, lamination are had the right.
21. honeycomb sandwich board according to claim 20, described honeycomb core are to be selected from aromatic poly honeycomb, aluminium honeycomb, paper wasp nest and the glass honeycomb any.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
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| JP120707/2006 | 2006-04-25 | ||
| JP120706/2006 | 2006-04-25 | ||
| JP2006120707A JP4141481B2 (en) | 2006-04-25 | 2006-04-25 | Epoxy resin composition for fiber reinforced composite materials |
| JP2006120706A JP4141480B2 (en) | 2006-04-25 | 2006-04-25 | Epoxy resin composition for fiber reinforced composite materials |
| JP120704/2006 | 2006-04-25 | ||
| JP2006120704A JP4141479B2 (en) | 2006-04-25 | 2006-04-25 | Epoxy resin composition for fiber reinforced composite materials |
| PCT/JP2007/058882 WO2007125929A1 (en) | 2006-04-25 | 2007-04-24 | Epoxy resin composition for fiber-reinforced composite material |
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| CN101426830A true CN101426830A (en) | 2009-05-06 |
| CN101426830B CN101426830B (en) | 2012-03-21 |
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| CN103140536A (en) * | 2010-09-28 | 2013-06-05 | 东丽株式会社 | Epoxy resin composition, prepreg and fiber enforced complex material |
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| ATE366772T1 (en) * | 1999-10-13 | 2007-08-15 | Toray Industries | PREPREG AND FIBER REINFORCED COMPOSITE |
| JP2003026768A (en) * | 2001-07-13 | 2003-01-29 | Toray Ind Inc | Epoxy resin composition, prepreg, and fiber-reinforced composite material |
| JP2004075914A (en) * | 2002-08-21 | 2004-03-11 | Toray Ind Inc | Epoxy resin composition and prepreg |
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2006
- 2006-04-25 JP JP2006120704A patent/JP4141479B2/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| CN101426830B (en) | 2012-03-21 |
| JP4141479B2 (en) | 2008-08-27 |
| JP2007291236A (en) | 2007-11-08 |
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